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New Concepts in Polymer Science

Polymers for Packaging and Containers


in Food Industry
New Concepts in Polymer Science
Previous titles in this book series:
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Radiation Chemistry of Biopolymers Polymeric Biomaterials.
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New Concepts in Polymer Science

Polymers for Packaging


and Containers
in Food Industry
L.A. Sukhareva, O.A. Legonkova and
V.S. Yakovlev.
Edited by G.E. Zaikov

LEIDEN BOSTON - 2008


Printed and bound In The Netherlands

ISSN 0928-1584
ISBN 978 90 04 16143 6

Copyright 2008 by Koninklijke Brill NV, Leiden, The Netherlands.


Koninklijke Brill NV incorporates the imprints Brill, Hotei Publishing,
IDC Publishers, Martinus Nijhoff Publishers and VSP.

All rights reserved. No part of this publication may be reproduced, translated, stored in a
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provided that the appropriate fees are paid directly to The Copyright Clearance Center,
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Fees are subject to change.
Contents

Introduction 1
1 Methods and technology of preserving the nutritive value of food 5
1.1 The nutritive value of foodstuffs 5
1.2 Methods and technology of preserving food products and raw materials 9
1.3 Technology of preserving the quality of foodstuffs in manufacturing,
transportation and sales 17
1.4 Application of chemical preservatives in food industry 24
1.4.1 General information on chemical food preservatives 24
1.4.2 Mechanism of action of chemical preservatives 26
1.4.3 Characteristics and application of chemical preservatives 28
1.4.4 Methods for identification of preservatives 34
1.4.5 Fat antioxidants 35
1.4.6 Effect of oxidation on the food value of fats 44
1.4.7 Inhibition of autooxidation processes 46
1.4.8 Characteristics and application of antioxidants and synergists 49
1.4.9 Comparative efficiency, methods of treatment and admissible
concentrations of antioxidants 63
1.4.10 Methods for identification of antioxidants 65
2 Polymer packaging materials for preservation of foodstuffs 71
2.1 Food polymers 71
2.2 Hygienic characteristics of packaging materials components 75
2.3 Methods of packaging foodstuffs 82
3 Combined packaging materials using cellulose and its derivatives 105
3.1 Internal stresses in coatings using cellulose 105
3.2 Moisture-resistant packaging materials based on cellophane 109
3.2.1 Justification of the composition of the coating 109
3.2.2 Copolymer-based coatings 112
3.2.3 Coatings based on lacquer compositions 115
3.2.4 Design of heat sealed seams 118
3.2.5 Justification of the choice of solvent 121
3.2.6 Wetting of hydrated cellulose film with some organic solvents
and solutions of SVN-80 on the basis of these solvents 123
3.2.7 Working-out of an optimal process regime for producing
cellophane SVN-80 125
vi CONTENTS

3.3 Modification of cellulose diacetate for packaging materials 127


3.4 Interaction of cellulose with water 130
4 Compositions for decorative finish and protection of packaging products 133
4.1 Bases of the formation of protective and decorative finish coatings 133
4.2 Application of aqueous dispersions of polymers for finishing products 139
4.3 The formation mechanism, structure and properties of finishing
packaging materials from aqueous dispersions 145
4.4 Characteristics of finishing packaging materials 151
4.5 Aqueous dispersions of polymers for finishing coatings, offset papers
and inks 154
4.6 Properties of finishing coatings from aqueous dispersions of acrylic
polymers 158
4.7 Specifics of forming coatings on paper and offprints 177
5 Technology of the development of canning containers 181
5.1 Purpose of canning containers 181
5.2 Field of application and efficiency of use 183
5.3 Requirements to the properties of coatings for canning containers 184
5.4 Coatings for protection of canning containers 186
5.5 Compositions based on oligomer systems 189
5.6 Oleo-resinous lacquers 191
5.7 Polyvinyl chloride-based lacquers 192
5.8 Oligoesters and water-base, water-soluble and water-dispersion binders 193
5.9 Compositions with high dry residue and ink powders 195
5.10 Coatings for protection of the outer surface of canning containers 196
6 Structure and properties of compositions for protection of canning
containers 201
6.1 Ways of improving the protective properties of coatings 201
6.2 Effect of the nature of the support on the structure and properties of
coatings 202
6.3 Structure formation in solutions of epoxyphenol compositions and
the properties of coatings 203
6.4 Dependence of the properties of can lacquers on the structure of
phenol-formaldehyde oligomers 208
6.5 Fields of application of canning containers and methods of their
modification 212
6.6 Structure and properties of coatings based on epoxy oligomers 216
6.7 Technology of producing protective polymer coatings 219
6.8 Specific features of forming epoxyphenol coatings for canning containers 222
7 Ways of increasing the protective properties of coatings for canning
containers 231
7.1 Coatings with enhanced adhesion to aluminium and its alloys 231
7.2 The role of solvent in the formation of the properties of coatings for
canning containers 232
7.3 Effect of the nature of epoxy oligomers on the properties of coatings 236
7.4 Water-base compositions for protection of canning containers 237
7.5 Modification of polyvinyl chloride compositions by thermoplastics 240
CONTENTS vii

7.6 Effect of the structure of the block copolymer chain on the properties
of coatings 241
7.7 Development of the method for improving the protective properties
of polyvinyl chloride compositions by modification with block copolymers 242
7.8 Studies of the relaxation properties of coatings from polyvinyl chloride
compositions modified by thermoplastics 246
7.9 Modified perchlorovinyl coatings with increased shelf-life 249
8 Ways of modifying the properties of metallized packaging materials 253
8.1 Purpose and fields of application 253
8.2 Methods of forming metallized layers on polymer materials 254
8.3 Protective coatings for metallized materials 258
8.4 Methods of modifying the structure and properties of epoxy coatings 260
8.5 Protective coatings from copolymers of regular structure 264
8.6 Combined metallized materials for dairy produce packing 267
8.6.1 Combined material based on polyethylene, paper and aluminium foil 267
8.6.2 Hermeticity of polymer packaging 269
8.6.3 Coextruded polyethylene films for packaging dairy produce and
their quality indices 272
9 Technology of forming and modifying multilayer metallized packaging
materials 277
9.1 Purpose and production of multilayer materials 277
9.2 Prospects of using metallized packaging materials 282
9.3 Polymer films as the base for metallization 284
9.4 Methods of modifying the properties of films 288
9.5 Structure and properties of film materials 290
9.6 Ways of protecting metallized packaging materials 293
9.7 Effect of modification on the properties of protective coatings from
epoxy compositions 294
9.8 Technology of producing protective coatings with improved performance
properties 298
9.9 Ways of thixotropic decrease of internal stresses in the formation of
coatings from polymer dispersions for finishing of packaging materials 299
9.10 Modification of finishing dispersions for paper and offprints by
polymer systems 305
9.11 Combined packaging materials with increased protective properties 313
9.12 Effect of pH of the medium on the specific features of structure formation
and the properties of coatings from polymer dispersions 315
9.13 Polyurethane chemically resistant coatings for protection of container
and packaging materials 321
9.14 Protective polyurethane coatings and adhesive compounds 325
10 Methods of developing polymer gas-selective systems for storage of fruits
and vegetables 333
10.1 Problems of storage of agricultural raw materials and foodstuffs 333
10.2 Selectively permeable polymer materials 334
10.3 Effect of diffusion characteristics of polymer materials on the formation
of a gas medium 335
viii CONTENTS

10.4 Methods of developing an optimal gas medium and the technology of


storage 340
10.5 Efficiency of using polymer materials and protective coatings in
long-time storage of fruits 340
11 Structure and properties of oligomer compositions for protection of transport
containers 345
11.1 Corrosion resistance of coatings for transport containers 345
11.2 Structural conversions in hardening of thermosetting oligomers 346
11.3 Formation kinetics of coatings from polymerization oligomers 351
11.4 Causes of internal stresses in formation of coatings 357
11.5 Effect of the nature of hardener and initiator on the formation and
properties of coatings for transport containers 366
11.6 Biodeterioration of container/packaging materials 381
11.7 Effect of the polymerization initiation method on the formation and
properties of coatings for transport containers 387
11.8 Studies of the possibility of using stabilized radicals in protective coatings 395
12 Biochemically stable coatings for protection of transport containers 401
12.1 Coatings based on Ftorlon copolymers 401
12.2 Structure of modified Ftorlon coatings 402
12.3 Coatings based on modified and ladder polyphenyl sesquioxanes 403
12.4 Photohardenable epoxy acrylates for protection of transport containers 405
12.5 Physicochemical bases of developing photohardenable coatings 406
12.6 Photochemical processes and structural transformations in formation
of coatings under the action of ultraviolet light 410
12.7 Properties of epoxy acrylate coatings for transport containers 421
12.8 Biocidal coatings based on styromal 425
13 Technology of the protection of large-tonnage foodstuff containers 431
13.1.1 Methods of protecting storage tanks for potable 96% ethyl alcohol 431
13.1.2 Objects and methods of studies 432
13.1.3 Results of studies 433
13.1.4 Technology of anticorrosion protection of the inner surface of
ethyl alcohol storage tanks 436
13.2 Bactericidal wear-resistant coatings for storage and processing of grain
and grain products 440
13.3.1 Modified coatings of tanks for storage of vegetable oil 444
13.3.2 Results of tests 448
13.4 Food-grade coatings resistant to the action of sign-variable temperatures 452
14 Ecology and safety of utilization of container/packaging materials 455
14.1 Methods of utilization of packaging materials 455
14.2 Accelerated degradation of polymers by biocides 456
14.3 Photodegradable polymers 456
14.4 Modified photodegradable polymers 458
14.5 Principles of developing modifiers for biodegradable materials 462
14.6 Industrial and domestic plastics wastes 464
14.6.1 Secondary plastic raw materials in the public reproduction process 464
14.6.2 Sources and turnarounds of secondary polymer raw materials 465
CONTENTS ix

14.6.3 Economic assessment of secondary plastic raw materials 468


14.6.4 Collection and use of thermoplastic wastes from domestic
consumption sphere 470
14.6.5 Separation of plastic wastes from domestic garbage 473
14.6.6 Application of plastic wastes as fillers and additives 475
14.6.7 Mechanism of degradation 477
14.6.8 Energy efficiency of incineration of plastic wastes 479
14.7 Secondary raw materials based on packaging material wastes 480
14.8 Use of secondary energy resources 480
14.9 Economic and ecological aspects of utilization of secondary raw materials 482
14.10 Self-degrading polymer materials 485
15 Packaging of meat and meat products 491
15.1 Range of single-layer packaging materials in meat packaging 492
15.2 Combined film materials 498
15.3 Modern trends in the development of chilled meat packaging technology 503
15.4 Methods and equipment for packaging of meat and meat products 508
15.5 Active packaging technology 512
Conclusion 517
References 519
x CONTENTS

Introduction

Development of the concept of long-term food storage is an independent field of scientific


and applied research using polymers of various chemical compositions and structures.
It includes elaboration of technology of storing food products and food staples using
advanced packaging materials. Their development is based on studies of temporal regular-
ities of the quality of products depending on chemical composition, properties and struc-
ture. External factors are to be considered, too; they include conditions and terms of storage,
air temperature and humidity, biocide properties of container/packaging materials, quality
assessment criteria in turning out/accepting products and in long-time storage.
Based on the studies of the dynamics of the process, analysis of numerous results of
research, it became possible to predict the regularities in the change of quality and terms of
product storage, as well as the criteria of the impact of containers and packaging on them.
Food products are a complex object; various physico-chemical processes occur in
them in production and storage, thus changing their properties and nutritive value. Such
basic ingredients as proteins, lipids, carbohydrates are polyfunctional compounds, which
are involved in diverse intra- and intercellular interactions.
Despite the diversity and complexity of food products, they are an integral biological
system with its characteristic features. The basis of the organization of biologically active
food systems are variability, preservation and stability.
A determining factor in the development of the scientific approach to storage of food
products is the variability of the properties, and storage appears to be the unity of changes
and preservation, variability and stability.
The properties of food products and their changes in storage should be considered
under conditions of the multi-factor relationship of internal and external effects.
Stability of food products in storage is characterized by processes, which lead to a de-
crease of the consumer properties of foodstuffs. The directedness of these processes is de-
termined by internal factors and initial properties of a product: the peculiarities of chemical
composition, ratio of the main components, activity of the enzyme systems, occurrence of
natural antioxidants. This system is affected by external factors capable of inhibiting or ac-
tivating the active processes in food products. There is an exchange between the medium
and the product an exchange of mass, energy and information.
A system becomes stable and reliable when it is capable of reacting to the influence
of an external medium by changing it in accordance with its inherent properties. Food prod-
ucts, which are biological systems, do not passively obey the influence of the external me-
dium but actively counteract it, following its own processes due to its potentialities, its
resistance to the effects of individual factors. Therefore, the ability of food products to react
to an external effect is considered to be an essential factor of self-preservation.
2 INTRODUCTION

Of great importance in long-time storage of food products are polymers for containers
and packaging. For an open system, a container is a barrier between a product and external
factors. The requirements to containers are dictated by the properties of a product and the
character of its mass exchange with the external medium.
In products suitable for long-time storage, biological (microbial, enzymic) processes
are completely or almost completely excluded. Products with low moisture content (not
higher than 10%) can be attributed to such products. Products with average (10 to 40%) and
high (over 40%) moisture content are capable of retaining their properties for a rather lim-
ited period of time. Preservation (sterilization, freezing, sublimation etc.) makes it possible
to considerably increase their storage time. Therefore, products suitable for long-time
storage are those with low moisture content or preserved in various ways.
The basis of long-time storage of food products is the maximum preservation of con-
sumer properties by regulating the initial-quality change as a result of product ageing, ef-
fects of external factors, choice of containers and packaging materials.
The main processes in food products in long-time storage, which govern the guarantee
storage times, are as follows:
for products with low moisture content: exchange of moisture with the external medi-
um and the oxidative process;
for frozen meat: heat exchange and oxidation reactions;
for sterilized preserves: changes in the protein and lipid composition as well as inter-
action of the product with containers metal.
Of great importance is the development of container/packaging materials for storage
and transportation of high-calorie foodstuffs under extreme conditions. They are manufac-
tured for persons whose activity is related to prolonged physical and neuro-emotional
stresses under unfavourable conditions.
The assortment of these foodstuffs comprises dairy, meat, fish, fruit-and-vegetable and
other products, preserved by methods of thermal sterilization, sublimation drying, partial
dehydration, including:
dairy products sources of readily assimilable calcium, complete protein and fat.
They include milk beverages and curd products of sublimation drying, with added coffee,
cocoa, nuts, sea-buckthorn oil; puree from dried apricots, cranberry etc.;
sublimation-dried sour-milk products providing normalization of intestinal micro-
flora, which is especially important in long-term consumption of preserved food;
high-fat sterilized milk preserves, including cheeses, sterilized curd products, which
are distinguished by a high content of readily assimilable protein, optimal calcium to phos-
phorus ratio, increased content of potassium, high energy value;
fish products (preserves and products of sublimation drying): sources of complete
readily assimilable protein, fats with a high content of polyunsaturated fatty acids, oil-
soluble vitamins, major nutrients and trace elements;
meat and meat-and-cereal products (preserves, lunch packs of sublimation drying):
sources of complete protein with a balanced amino acid content owing to a combination of
animal and plant protein, minerals, as well as fats with a sufficient amount of polyunsatu-
rated fatty acids and oil-soluble vitamins in their composition;
fruit-and-vegetable products (fruit concentrates, vegetable side dishes, juices, kissels
and compotes of sublimation drying): sources of readily assimilable carbohydrates, mine-
rals (potassium, trace elements), vitamins, pectins, organic acids;
confectionary products distinguished by a high nutritive value at a minimum weight
and volume;
INTRODUCTION 3

dehydrated beverages (tea, coffee) with readily assimilable carbohydrates added.


Ready-to-eat products need minimum preparation, are portioned and are convenient
to use directly from the packaging container.
Lately, an important role is allotted to the biological safety of products, which is relat-
ed to the consumption of food produced from genetically modified plants. Only in the recent
years, the global acreage of transgenic crops, such as soy, maize, tomatoes and potatoes in-
creased more than 20-fold. Food products from them are already supplied to the table of
American and Russian consumers.
Norms and methods for the integrated assessment of the safety of genetically modified
sources of food are intensively worked out at present. Much attention is also given to the
development of advanced containers and packaging materials.
Principles of creating active packaging for food production have been proposed. Tra-
ditional basic qualities of food packaging are usually related to its inertness due to the in-
trinsic barrier properties of the polymer matrix. At present, the functions of packaging are
much broader. The quality of a packaging is assessed by its involvement in the preservation
of the nutritive value of a product, by its activity determined by such functions as the ability
to regulate the speed and temperature of foodstuff heating in a microwave oven; to create
an optimal gas medium inside the envelope; to change directionally the intranutrient com-
position of a product; to introduce flavouring materials, preservatives, gas absorbents,
moisture adsorbents, antimicrobial preparations; as well as to use special coatings to im-
prove the appearance and decorative properties of a packaging.
The purpose and functions of polymer and combined aseptic packaging have broaden.
The modern approach to packaging engineering of the 21 century is considered with
account for three directions of the development of active packaging, which, as the result of
introducing special additives, affects the quality of food products.
The first way of creating active packaging is based on the principles of forming a reg-
ulated modified gas medium using special membranes, adsorbents of oxygen, ethylene, for
instance, in storage of fruits and vegetables.
The second way is to impart a biocide activity to the packaging with respect to patho-
genic microflora in the process of production and storage. The third way: in production of
food products (cheeses, uncooked dry-cured sausages) the packaging should regulate the
biochemical transformations in the product for directed regulation of its properties. In this
connection, immobilized bacterial cells and enzymes are introduced into the active
packaging.
A topical problem is to develop ecologically harmless container/packaging materials
and coatings due to the aggravated situation with providing healthy food in the right quan-
tities. A decrease in the level of production, crumbling of structural industrial links, the un-
favourable ecological situation stipulate a sharp increase of the losses of agricultural and
food products, generally lead to such negative consequences as the rise of the deficit of pro-
tein and vitamins in the food ration, pollution of food with metabolic products of pathogenic
bacteria, including with carcinogens.
Ecologically safe packaging materials are created by modifying traditional polymers
with polyfunctional additives, which perform the functions of structure formers, plastici-
zers, antibiotics, relaxants of internal stresses, and stabilizers. Scientific bases of creating
packaging materials for foodstuffs have been developed. Additives providing the produc-
tion of materials, which are biochemically resistant to the impact of microflora and aggres-
sive media of food productions, are introduced into the composition of their base. Methods
of regulating the processes of mass transfer and distribution of structure-forming additives
4 INTRODUCTION

along the thickness of the packaging materials with the aim to form an optimal structure
and operational properties have been developed.
Fundamental works have been carried out on the development of packaging materials
and coatings based on various polyolefins, ftorlons, epoxy polyesters and other polymers
of mesomorphic structure, which provide for the production of packagings with polyfunc-
tional properties.
Special attention is given to the development of scientific principles of creating
self-degrading packaging materials with regulated service life and biodegradation upon dis-
posal.
Valuable characteristics of these materials are determined by the necessity of com-
bining the biocide properties with respect to foods in storage with the ability to be degraded
in soil under the action of microflora.
1 Methods and Technology
of Preserving the Nutritive
Value of Food

1.1 The nutritive value of foodstuffs


Special attention should be paid to the control of losses of food products in their processing,
storage, transportation and sale. This could not be done without scientifically grounded
rational application of polymer materials, which are used to preserve food products. In this
connection, it is necessary to consider the specific properties of both food itself and of poly-
mers in contact with it (packaging materials, containers, various coatings).
To preserve food well, it is necessary to know which of its specific properties should
be retained until it reaches consumers table, bearing in mind the concepts healthy food
and tasty food from the viewpoint of food biochemistry. Man can not exist without food.
It provides the organism with necessary substances for growth and is a source of energy,
which is transformed into heat required for the bodily functions of the human organism.
For a long time, the only index of food value was its caloric value. Energy is constantly
consumed throughout human life to maintain the normal body temperature, for mental and
physical work. Usually, a human in normal condition should consume an amount of food,
which corresponds to energy consumption by its caloric value.
The amount of energy required for the human organism, internal consumption includ-
ing, is determined in special chambers used to measure the amount of heat evolving in the
lying position, during physical or mental activities. Naturally, depending on the intensity
of work, the amount of energy evolved and, therefore, the requirement of its replenishment
at the expense of the caloric value of food would be different.
The human organism receives energy mainly due to oxidation of food. Actually, food
is not assimilated completely, and its real caloric value is slightly less than the amount
of heat evolved in its oxidation. Carbohydrates and fats burn almost completely. In oxida-
tion of carbohydrates and proteins, the energy evolved per 1 kg is 16.8103 kJ; of fats,
37.8103 kJ.
The basis of food are proteins, fats and carbohydrates. All foods essential for health
consist of proteins, fats and carbohydrates, and also of some other components. For the
organism, it is not the same if it receives these calories by consuming carbohydrates or fats.
The latter are more difficult to assimilate, and they come to the blood flow later. Proteins
are indispensable for the organism. Apart from the fact that they replenish the energy
consumed, they provide for the restoration of expended cells and tissues and ensure the
development of the human organism at the young age.
6 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Food does not only deliver energy for work and is required for us to move, think, for
the heart to pump blood through the body, to maintain normal body temperature; it also pro-
vides material for the incessant regeneration of tissues and cells. The most active constituent
parts of cells and tissues, consisting of proteins, are to be regenerated first of all. Various
types of proteins can be distinguished. They perform various functions in the organism.
Proteins of connective tissues fasten muscles and bones in tendons. Proteins, of which
muscles consist, are capable of contracting and stretching, in accordance with orders from
the brain, to bring into motion organs of the human body. Proteins of the blood deliver
oxygen required for oxidation of tissues (without which the human organism is not capable
of maintaining life and performing work) and pick up the waste product, carbon dioxide.
Cutaneous coverings, hairs, mucous envelopes also consist of proteins.
Of no less importance in comparison with the above is the regulatory function of pro-
teins. They regulate the vital processes in cells and organs. From the point of view of chem-
istry, these proteins catalyze and regulate chemical processes. Digestion is also one of these
processes.
Proteins in question are enzymes. Participating in the regulation of vital processes,
protein molecules are subjected to changes, as a result of which they lose their valuable
properties. Thus, it is necessary that the replacement for spent proteins come with food.
Therefore, sources of energy fats and carbohydrates are interchangeable. From the view-
point of their energy functions, they can be replaced with proteins. Proteins themselves are
indispensable, as they are valuable for the organism not only as an energy source but also
as building material for cells and as catalysts and regulators of biochemical processes.
Therefore, the value of food products is determined not only by their caloric value but
also by the content of protein substances. The hierarchy of food products by this parameter
differs from that obtained from comparison of foodstuffs by their caloric value.
Consider the protein content in different food products consumed in this country, %:

Soy 34.9 Rice 7.6


Dry pea 23.8 Cow milk 2.8
Cheddar cheese 23 Potato 2.0
Boiled hen 20.6 Cabbage 1.8
Beef 17 Carrot 1.2
Cod 16.5 Butter 0.6
Mutton 15.7 Margarine 0.3
Pork 15.2 Marmalade traces
Eggs 12.8 Sunflower oil none
Wheat flour 10.5 Sugar none

Food products can not be characterized by their caloric value alone. Despite the high
caloric values of sunflower oil and sugar, the human organism would not function in a
normal way, however large amounts of these high-calorie products are consumed. It is im-
perative that food of man contains fats, carbohydrates and proteins. In the human organism,
protein molecules break up to form smaller molecules, amino acids. Amino acid molecules
can be of different size and structure. Their common feature is the presence of amino and
carboxyl groups in the molecule. It has been established that amino acids required for the
vital activities of the human organism can be divided into nonessential and essential. Non-
essential amino acids can be synthesized by the human organism from fragments of mole-
cules. Essential amino acids can not be synthesized and should be obtained with food.
CHAPTER 1 7

Apart from proteins, fats and carbohydrates, the human organism requires vitamins.
They are essential. Certainly, vitamins can be injected or swallowed in pill form. But the
most useful method is to introduce vitamins with food. As molecules of amino acids are
fragments of large molecules of proteins, so vitamins are ready-made fragments of the most
important enzymes regulating the metabolism. Vitamins are divided into water-soluble and
fat-soluble. For example, vitamin C ascorbic acid belongs to the former. The human or-
ganism is not capable of synthesizing it, despite its comparatively simple chemical struc-
ture, probably, because the mankind has been almost always surrounded by natural sources
of vitamin C, which occurs in almost all fresh vegetables and fruits. This vitamin is present
in dill (0.15%), horseradish (0.2%), red pepper (0.25%), black currant (0.3%), winter pine
needles (0.220.28%), dry briar (15%) and in other vegetables, fruits and greens. Ascor-
bic acid is unstable and is easily destroyed in cooking, drying, preservation and in long-time
storage in air. Deficiency of vitamin C in food causes a severe disease, scurvy.
One of fat-soluble vitamins is widely known vitamin A, which is involved in the syn-
thesis of rhodopsin required for good vision and is contained in fish liver oil, carrot and
other products. Vitamin A occurs mainly in products of animal origin. Its highest amount
is in beef liver and cod. The liver stores 90% of all vitamin A in the animal and human or-
ganism. Good sources of this vitamin are hens and quails eggs, butter, dairy cream and
sour cream. Though plant products contain no vitamin A, some of them (carrot, red moun-
tain ash, sea buckthorn berries) contain a large amount of carotene up to 10 mg per 100 g
product. Under the action of carotenase in the intestines, carotene is converted to vitamin
A. Carotene is a rather unstable, readily oxidizable compound. For this reason, chopped
vegetables and greens should not be left unused for a long time, as carotene in them would
lose biological activity. Greens and vegetables should be cut immediately before a meal.
As carotene does not dissolve in water but dissolves well in fats and oil, it would be assim-
ilated better if an edible fat is added to vegetable dishes. For instance, grated carrots could
be dressed with mayonnaise or sour cream.
The daily requirement of vitamin A is 0.50.7 mg for children aged from one up to
ten years old; 1 mg for older-age children and adults; 1.25 mg for pregnant women; 1.5 mg
for breastfeeding women.
For persons whose work is associated with a heavy load on the organs of vision, those
who work evening or night shifts or have contact with substances causing irritation of the
mucosa of the eye, the daily intake of vitamin A should be increased 1.52-fold.
Deficiency of vitamin B can cause polyneuritis. Vitamin B2 (riboflavin) is required for
normal sight. The absence or deficiency of PP (nicotinic acid) leads to a heavy disease, pel-
lagra, and vitamin B2 contains the element cobalt required for the vital activity of the cells.
Thus, besides fats and carbohydrates, the human organism should receive with food a
set of essential amino acids, vitamins, cellulose for normal functioning of the gastrointes-
tinal tract. But even this is not sufficient for food to be wholesome and to contain all ele-
ments required for the vital activities of the organism. The important components are salts,
which contain such elements as potassium, sodium, calcium, phosphorus, fluorine, as well
as various trace elements in small amounts. Sodium is an important constituent of the blood
and together with potassium is required for the normal functioning of the nervous system.
Human bones consist of calcium phosphate. Adenosine triphosphoric acid is a kind of an
energy storage device in the human organism. Phosphorus-containing nucleic acids code
for the program of building up and operating each cell of the organism and, therefore, the
program of constructing the entire organism, i.e., heredity. Protein molecules also include
sulfur. The absence of iodine makes impossible the normal functioning of the thyroid gland.
8 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Iron is a component of blood hemoglobin. Fluorine is required for the normal state of the
teeth.
However, food should be not only wholesome but also tasty and even attractive to the
eye. By its appearance and aroma, it should cause a reflectory secretion of the substances,
which contribute to the digestion and assimilation of food. Therefore, a broad diversity of
gastronomy should not be reduced to carbohydrates, fats, amino acids, vitamins and salts.
In spite of the seeming rationality of introducing a certain amount of nutrients into the or-
ganism, the human can not live on tablets or powders of even the most perfect and well-
balanced diet. It is not by chance that even at the dawn of cosmonautics, when each extra
gram of load in the spaceship significantly complicated the mission, even then cosmonauts
did not swallow powders or pills consisting of amino acids, carbohydrates, fats and other
components. The taste, smell and appearance of food is not a caprice but an essential re-
quirement of the human organism. The diversity of taste hues can be reduced to a combi-
nation of four main gustatory properties: sour, sweet, bitter and salty. The edges of the
tongue are the most sensitive to sour taste; the base, to bitter taste, the tip, to sweet and salty
tastes. All acids have a sour taste. Cooking salt, as is known, possesses a salty taste. How-
ever, salts of most metals are not salty in taste, but bitter. In general, the relation between
the chemical structure of a substance and its taste has been investigated to date obviously
insufficiently. Peptides have a taste, which depends on which amino acids they consist of.
High-molecular-mass compounds, whose molecules are characterized by molecular-mass
magnitudes of the order of tens and hundreds of thousands are, as a rule, tasteless. This per-
tains to polysaccharides and polypeptides (proteins). As for the taste of amino acids, the
sweet ones are D-tryptophane, D-histidine, D-phenylalanine, L-alanine, glycine (in de-
creasing order). L-Tryptophane, L-phenyl alanine and the so-called L-isomers are bitter.
D-Alanine, D- and L-aspartic acids, D-glutamic acid are tasteless or have a very weak taste.
Food products are sometimes artificially flavoured, for example, to add a sweet taste.
Herewith, it is known that sugar is not the very sweet substance. Saccharine, for instance,
is 400500 times as sweet as sugar, but is not assimilated by the human organism.
Glycine (an amino acid possessing a sweet taste) is agreeable to the taste and whole-
some. It is widely used in production of soups, condiments, marinades; it softens a bitter or
salty taste and eliminates an unpleasant off-flavour of some products. Glycine is present in
large amounts in fish, prawns, molluscs.
D-Tryptophane and maltol are used to enhance sweetness. Addition of maltol in the
amount of 15 ppm makes it possible to decrease the consumption of sugar by 15%.
Preparation of food boiling, broiling, roasting, fermenting, pickling, junketing etc.
is accompanied with complex chemical reactions, as the result of which a large amount of
various volatile compounds are formed. Their content in food is negligible but the flavour
of food changes depending on the ratio of these compounds in the steams.
In individual cooking, it is easier to follow the preservation of useful substances, taste,
colour and smell. It is far more difficult to bring the valuable properties of food to the con-
sumers table, when food products are mass produced in meat-, milk- or food-packaging
plants; when these products should be preserved in the process of production, transportation
and storage in refrigerators, in the process of selling them up to the moment when the food
gets into the human organism.
Considering the problem of food preservation, one should not be abstracted from the
fact that foodstuffs are involved in the common closed process of interaction of the human
organism with the environment. The late 1970s and early 1980s witnessed the formation of
a new interdisciplinary science of food and nutrition, trophology (the Greek word
CHAPTER 1 9

means aliment). Trophology combines together the earlier disconnected links of the chain
and various aspects of the science of food, such as the distribution of nutrient substances in
the cell or in the organism; the mechanism of the transfer of nutrient substances along the
food chains; the role of trophological processes in the circulation of substances in the bio-
sphere; evolution of species and evolution of the biosphere. As far as the life of each organ-
ism and the maintenance of life depend essentially on the equilibrium between the synthesis
and decomposition of nutrient substances, the biosphere can be considered as a troposphere,
and all organisms as links of the planetary food chain, a food hierarchy forming a closed
circle. The new science of trophology should combine together the earlier scattered links
of this chain.
An integrated view of the trophological process made one to approach the evaluation
of food in a new way. While it was believed earlier that the organism needed as much food
as it consumed, it was not food in general that was meant but the nutrients assimilated by
the organism amino acids, carbohydrates, fatty acids, vitamins, essential salts. All the
other components of foodstuffs were considered to be an unnecessary ballast, which com-
plicates the bodily functions of the human organism. At present, one of the fundamental
conclusions of trophology is that, apart from the main flow of nutrients, four more flows
come to the organism. One of the most important flows is that of physiologically active sub-
stances formed in the stomach and in the intestines. The so called hormones and mediators
are implied.
If one takes account of all hormone-producing cells in the human gastrointestinal tract,
the result would be the largest endocrine gland in the human organism. This gland secretes
hormones, which control the essential metabolic functions and assimilation of nutrients.
Three other flows are formed in the gastrointestinal tract with the participation of bacterial
flora. The bacterial flora is required for the human organism and higher animals to exist.
Only the proportional ratio of all four flows creates normal conditions for the vital activities
of the organism. The so-called ballast substances, which until recently were to be with-
drawn from food to make it closer to an ideal meal, are in reality also required for the
human organism. On removal of, e.g., food fibres cellulose or lignin from food, the cho-
lesterol metabolism is disturbed, which can cause stones in the gall bladder or else a stom-
ach or intestinal disease. Therefore, ballast-free elementary diets are applicable only in the
case of some defects of the enzyme systems.

1.2 Methods and technology of preserving food products and raw


materials
Large amounts of food products in the CIS countries are lost at the stages of raw-material
production, processing, transportation, storage and, finally, sales. A considerable amount
of potatoes, milk, grain, meat perishes as the result of losses in harvesting, transportation
and storage.
The use of polymer materials makes it possible to preserve the quality and significantly
reduce the losses of food products.
At the stages of raw-material production, polymer materials are mainly used in grow-
ing the agricultural produce, in raising and sagination of domestic animals. One of the im-
portant areas of polymer use to increase the crop yield is the presowing treatment of seeds.
It consists of spraying the seeds with a polymer suspension, which includes nutrients, trace
elements, plant-growth regulators, insecticides and other biologically active substances.
The basis of film-forming compositions are water-soluble polymers with specific
10 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

physicochemical and physicomechanical properties and the possibility of providing a


hydrophilic/hydrophobic balance in the system. Protective films reliably protect seeds from
the action of low temperatures, from premature germination under unfavourable conditions.
The properties of the coatings are programmed depending on the biological peculiarities of
plants. This is achieved by chemical modification of a polymer (e.g., polyvinyl alcohol) in
the process of film formation and polymer structure change both at the molecular and
supramolecular levels.
The climatic conditions in many cases make it necessary to grow fruits and vegetables
under coverage. The major factor, which limits the possibility of growing vegetables, ber-
ries, fruits and other crops in unprotected areas is insufficient warmth. The temperature con-
ditions can be adjusted using hothouses, hotbeds, covers and other cultivation
constructions. Only these agricultural constructions can significantly improve the temper-
ature conditions in the plant-vegetation zone. These constructions prove economically ef-
ficient if fabricated using polymer-film materials, which, though inferior than silicate glass
with respect to life time, are cheap, transportable and easy to erect. The major factor causing
the ageing of polymer films is solar radiation in the ultraviolet and infrared regions of the
spectrum.
Application of polymer-film materials in cultivation constructions in agriculture is
rather efficient; however, it creates the problem of utilization of used films. Upon use and
loss of consumer properties, the polymer film retains mainly a two-dimensional structure.
It pollutes the ground and is not degraded or assimilated by the environment for about 80
years. Therefore, the use of polymer films in agriculture leads to the necessity to solve the
problem of utilization of used films or their transfer into a state in which they are assimilated
by the environment, i.e., to control the polymer degradation processes. Photochemical deg-
radation of polyolefins leads to the formation of 2 and 2, which are assimilated by
plants. Some organometal compounds, as well as complexes of variable-valence metals
with dialkyl dithiocarbamate (usually used as thermostabilizers of plastics), catalytically
degrade products of photooxidation of polymers, e.g., hydroperoxides, in storage. Besides,
complex compounds of metals are capable of absorbing the light energy. In the interaction
of organometal compounds with hydroperoxides, the so-called Norrish reactions occur. De-
pending on the content of sensitizers (the ScottGilid system), polymer is subjected to deg-
radation or the system exerts a thermostabilizing action on it. The ScottGilid system is
easily introduced into polymer together with other additives and pigments.
The requirements imposed on photodegradable polymers used in agriculture and in in-
dustries are rather stringent. They should have a guaranteed service life, good mechanical
properties, be rapidly and completely degradable after the induction period, polymer deg-
radation products formed should not be toxic, polymers should not change their properties
in storage, the polymer composition should be easily processable into items produced.
These polymers should not be expensive.
Polymer films used to fabricate cultivation constructions strongly warm up (to a tem-
perature of 6085C) in places of the contact with the supporting structures of the frames.
Film covers on hothouses are subjected to the action of negative temperatures, which in the
North regions reach 19 to 40C. Calculations show that in the North-West and Central
European regions of the Russian Federation, in the Urals, in Western and Eastern Siberia,
in the Ukraine, Belarus, Uzbekistan, Latvia, Estonia, Moldova, Turkmenistan the thickness
of films from light-stabilized polyethylene for covering hothouses should be no less than
0.15 mm. Research showed that harvest quality and crop yield are practically the same at
different UV transmission degrees. Therefore, films with UV radiation-absorbing
CHAPTER 1 11

stabilizing additives can be used when growing most agricultural crops in hothouses. The
most widespread type of film used in hothouses in Western and Eastern Europe and the
USA are polyethylene films. This is due to their comparatively low cost, simple production
technology, possibility of manufacturing wide formats and other advantages, e.g., the sim-
plicity of introducing various modifying additives. For these purposes, polyethylene of spe-
cials brands was manufactured.
Of film materials used for growing agricultural produce under coverage, mention
should be made of heat-resistant polymer films for disinfection of hothouse grounds with
live steam. This is the basic method of disinfecting hothouse grounds. It was invented in
Holland, but a Russian development is also available. According to this method, to increase
the efficiency of steaming (which kills all kinds of pests of agricultural crops) the ground
to be steamed is covered with a polymer film, which contributes to faster and deeper steam-
ing. The ground is covered with the film, which is fixed with sand bags along the perimeter.
Live steam at a temperature of 115120C is fed under the film. The ground and the film
is acted upon with steam of a slightly lower temperature (90100C). One cycle of steaming
provides for holding the film at a high temperature (90100C) for 12 h, and then for
another 12 h to cooling.
Apart from growing fruits and vegetables in hothouses, films are also used to arrange
small-size covers cultivation constructions whose size does not allow the handling of
plants and harvesting inside these constructions. Such constructions include skeleton covers
for growing plants, tunnel film covers; to some extent, special perforated films are also ap-
plicable. In the latter case, the supply of heat to the ground in the spring and the warming-up
of the soil are much greater than in an open plot. A wide-format film 2030 m thick is
also efficiently used for covering sown crops and plantings without wireframes (the edges
of the film are buried into the ground 510 cm deep). The thin film does not prevent the
plant growth and provides for the hothouse effect required. Only perforated films are used
for this purpose. Though skeleton-free coverings are less efficient as compared with skele-
ton ones, their total economic efficiency is higher.
Removal of the films should be done by hand and is associated with pollution of the
environment, in connection with which a number of problems arises. One of the efficient
ways of solving them is to use films with a given lifetime, upon expiry of which the films
are degraded under the action of light, moisture and other natural factors to produce forms
assimilable by the environment. Degradation of the film on skeleton-free covers can start
in 20 to 70 days, but this time strongly depends on weather conditions.
Besides the described methods, polymer films are successfully used to make winter
coverings of fruits and berries, hay etc.
Mulching is an agrotechnical technique to prevent evaporation of moisture and forma-
tion of a soil crust, to maintain an optimal temperature of the soil and to suppress the growth
of weeds. Film mulching is used both in unprotected grounds, and inside film-covered hot-
houses and tunnels. Polyethylene films are the most widespread; they can be transparent,
semi-transparent, non-transparent, light- and heat-reflecting (white and aluminium-
metallized). The greatest warming-up of the soil is observed in mulching by light-
transparent films, the use of which ensures a 4050% greater heat supply to the soil than in
an open plot. Semi-transparent films decrease the soil warming-up from 50 to 8090% de-
pending on their integral light transparency. Reflecting films smooth the total amplitude of
soil temperature variations owing to the warming-up during the day and the delayed cooling
during the night. Coating the soil with cuts from metallized polyethylene films reduces the
extent of damage (owing to the illumination of the low side of the leaves) of undersized
12 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

vegetable plants by some species of insects (aphids, flea beetles and bugs). Black mulching
films detain evaporation of moisture, but prevent penetration of solar radiation to the soil
surface. Film mulching enhances the biological activity of the soil; herewith, the amount of
microorganisms in the soil and their activity change, the illuviation of readily soluble nitro-
gen fertilizers from the soil is delayed.
Mulching of the soil in cultivation constructions can be done most rationally by used
films for covering hothouses, as well as secondary polyethylene films.
Mulching by light-reflecting films in winter hothouses, when there is not enough light,
has become widespread. It improves the illumination conditions and increases the early har-
vest by 1525%. Additional illumination at the expense of the light reflected by the film
accelerates the ripening of strawberries, salads, kohlrabi in winter hothouses. A black film
for mulching, PE-157 brand SM (GOST 10354-82), was developed and is manufactured in
the CIS countries. Light-transparent photodegradable films PE-108-70 and PE-108-71 are
used for short-time mulching of vegetables and berries, potatoes and other crops. Besides
them, CIS industries also manufacture film materials of other types used for mulching in
unprotected and protected ground. In agriculture, fibre- and tissue-reinforced films are used
for growing and storing vegetables and fruits. By their optical characteristics, they are
slightly worse than polyethylene non-reinforced films. Reinforced films can be used at a
temperature from 60 up to +60C. They are mainly used for erecting cultivation construc-
tions of protected ground (greenhouses, hothouses, coverings). The service life of the con-
structions is in this case longer (as compared with non-reinforced coatings), especially in
regions with increased wind and snow loads. Buildings and constructions from reinforced
polymer film materials are conditionally divided into three types: awnings, pneumatic con-
structions, skeleton constructions.
Skeleton constructions are distinguished by large reliability and do not require the use
of high-strength air-impenetrable materials. They are best of all to be used for growing and
storing horticultural produce. Skeleton-film warehouses and storages of horticultural and
other agricultural produce can be built quickly (35 days) and require no large capital in-
vestments or additional lighting. If it is necessary to make the premises darker, two-layer
coatings are used, the lower layer of which is light-impenetrable and which are fabricated
from, e.g., polyethylene filled with carbon black.
Foodstuffs can be protected from harmful substances getting into them by correctly
using the protective properties of polymer materials. It is important not only to grow a heavy
crop, to harvest it, but, which is especially important, to preserve it (not only from the point
of view of quantity, but also quality) up to the very moment of food consumption.
The problem of food preservation interested the man since long time ago. It was solved
differently at different times by different peoples.
The problem of food preservation emerged in connection with the need to store up food
reserves for oneself, ones own tribe, equpping an expedition, equipping an army etc.
Subsequently, formation and development of microbiology made it possible to lay the
scientific foundation under various technological techniques of food preservation. It proved
that the vital activities of microorganisms, which contribute to the spoilage of food, mani-
fest themselves under conditions of a certain temperature regime, certain humidity, absence
of substances aggressively interacting with substances from which microorganisms consist,
etc. If the conditions do not correspond to those required for the development of microor-
ganisms, the latter perish or their vital activities are temporarily stopped and, therefore, the
process of food spoilage stops, too.
A widespread technological technique of preserving food products is drying. The
CHAPTER 1 13

technique is based on the fact that most chemical processes determining the vital activities
of bacteria occur in an aqueous medium. Removal of water leads to the inhibition or inter-
ruption of chemical reactions contributing to the development of microorganisms and ac-
companying food spoilage.
In cells of fresh products, the food substances are, as a rule, in solution. In the course
of drying, the concentration of this solution increases until it becomes so high that the so-
lution can not be absorbed by the cells of various microorganisms any more. At the extent
of drying, corresponding to the above situation, a food product can be stored without dete-
rioration of its quality for a long time. The content of moisture in it should be observed not
to be higher than a certain limit: 1214% for dried vegetables, 1825% for dried fruits. The
smaller is the moisture content in the product after drying, the greater the guarantee of its
preservation is, the less the conditions for spoilage are.
However, the lower the moisture content in a dried product is, the more complicated
and, therefore, expensive the process of drying is. Besides, some substances useful for the
organism can be destroyed in the process. During the drying, water is evaporated from par-
ticles of the product and vapours formed are carried away. Drying is performed most often
using hot air, which, being a heat carrier, communicates a heat energy to water molecules.
Owing to the acquired energy, water molecules overcome weak physical and physicochem-
ical bonds and pass from the product into the vapour. The higher the temperature of the air
is, the more water molecules pass into the vapour, i.e., into the heated air.
The moisture capacity of the air is different at different temperatures. This method is
used to increase the storage life of fruits, vegetables, milk, meat, fish and other foodstuffs.
In drying apples and pears, mainly early varieties are used. Primarily fruit drops are
dried. It is best to dry fruits of one variety. In the summer, fruits usually dry up in 34 days.
Before drying, fruits are washed. Washed fruits are examined to cut the damaged parts, the
cores are excised and the fruits are cut into slices not more than 1 cm thick. Small fruits and
pears can be cut into two or four parts.
A method of preserving products by drying at low temperature freeze-drying is of
an ever increasing importance at present.
The process of sublimation (removal of moisture at low temperature, when a product
is preliminarily frozen) can be greatly accelerated by removing water vapour by direct
pumping out (evacuation), condensation of vapours on a chilled surface, absorption of va-
pours by hygroscopic substances. The use of the method of freezing for preserving food
products revealed the phenomenon of structure breakdown of plant and animal tissues by
growing crystals of ice. To avoid this undesirable phenomenon accompanied by the loss of
a number of useful specific properties of food products, the following technique is used.
Products are chilled so rapidly that ice crystals have no time not even to grow but to be
formed. Products prepared for freeze-drying are frozen and placed into a chamber, from
which the air and vapours are pumped out. If pressure in the chamber decreases from the
initial magnitude (of the order of 760 mm Hg) down to 11.5 mm Hg, water could not be
in a liquid state under these conditions and passes from the solid state (ice) into the gaseous
state by omitting the liquid state, i.e., it evaporates. Transition of a substance from the solid
state into the gaseous state by omitting the liquid state is called sublimation. The vapours
formed are pumped out by vacuum pumps, and water is gradually removed from the frozen
product. It dries at a low temperature.
One of the main requirements to drying, as to the other preservation methods, is the
maximum preservation of the nutritive value of food products. Numerous studies of the bi-
ological and nutritive value of food products subjected to various methods of drying have
14 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

been carried out with this in mind. The results of studies convincingly showed that the best
integrity of food products and their nutritive value is provided for by the method of freeze
drying. This refers equally to products of both plant and animal origin.
Removal of water from a food product drying is a forced measure, which is due to
the necessity to inhibit the chemical reactions occurring in storage. After the storage, the
product should restore its initial properties and the initial content of moisture. Therefore,
the reversibility of the drying process is essentially determined by the capability of the dried
product to swell again in contact with water. A relative increment (with respect to the mass
of the dry product) of mass in swelling is called the extent of swelling. The extent of swell-
ing of freeze-dried mutton was 3.5%, whereas that of heat-dried mutton only 2%. In other
words, meat after freeze-drying increased its mass 4.5-fold in 4045 min, after which no
increment was observed: all water, which the freeze-dried meat was capable of absorbing,
was absorbed. The process of water absorption is also observed in heat-dried meat. How-
ever, this process was slower than in freeze-dried meat, and it was completed only after
2.53 hours of swelling. The mass of heat-dried meat, after it absorbed the maximally pos-
sible amount of water, increased only three times. This difference in the swelling of
freeze-dried and heat-dried mutton is explainable by the denaturation of proteins and thick-
ening of muscle tissue. Freeze-dried meat, being boiled after 12 months of storage, pre-
served its culinary and organoleptic properties. The caloric value of freeze-dried mutton is
3.5 times as large as that of raw meat. Heat-dried meat is close to freeze-dried meat by its
caloric value. However, by its organoleptic properties (taste, smell, appearance)
freeze-dried mutton is much better than that of heat drying. Fat on freeze-dried mutton
chops does not differ from raw meat. A heat-dried duck broth is usually turbid and has an
unpleasant taste. A broth from freeze-dried meat tastes good and has the specific flavour of
a duck broth.
A similar pattern is observed in comparison of freeze-dried and heat-dried fish. Thus,
proteins of freeze-dried meat of pike perch preserve their properties better than proteins of
heat-dried meat. Only insignificant changes in the composition of its proteins were ob-
served during the storage of freeze-dried pike-perch meat. The specific composition of liver
oil determines its oxidation susceptibility. After a 12-month storage of freeze-dried meat of
pike perch, vitamin B1 was totally preserved. The extent of swelling of freeze-dried
pike-perch meat reached an equilibrium value in 3040 min and was 3.5. The swelling
equilibrium of heat-dried meat was established only in 3 h and was characterized by the
swelling extent of 2.2. It is known that the culinary properties of heat-dried meat of pike
perch leave much to be desired. But the broth from freeze-dried pike-perch meat, obtained
by boiling for 1517 min, has a good taste and flavour. Similar results were also obtained
in comparative studies of heat-dried and freeze-dried fillet of common carp. The caloric val-
ue of freeze-dried common carp meat proved almost five times as high as that of raw meat.
Freeze drying involves freezing of a product. However, it should be noted that freezing
of food products is of independent significance, not necessarily associated with drying of a
product. Chilling of foodstuffs can be used both for drying and with the aim to inhibit the
spoilage process without freezing the product itself. This goal is pursued in storing products
in refrigerators. But cold can also be used for freezing products with the aim of their further
processing. In the former case, products should be kept intact during the chilling, having in
mind not only mechanical damage but also the integrity of cell viability. Herewith, the bio-
chemical processes continue in the products stored but, naturally, at a slower pace. The met-
abolic processes in, e.g., chilled fruits and berries are active, they breathe and ripen.
Freezing of foodstuffs is accompanied by significant changes in their tissues and cells. The
CHAPTER 1 15

moisture in them freezes and turns into crystals of ice, which grow and partially destroy
cells. Moisture freeze-out is, in turn, accompanied by dehydration of the liquid part, in
which the nutrient materials of the cells are dissolved. During the unfreezing of such prod-
ucts, the moisture formed in thawing of ice crystals can not be absorbed by the cells, which
underwent irreversible changes. Unfrozen products abundantly ooze juice. However, unde-
sirable phenomena associated with the growth of crystals in freezing could be avoided. For
this purpose, the process of freezing should be very quick not to let ice crystals to be formed.
The matter is that for crystals, in particular, ice crystals, to be formed, their constituent mol-
ecules and atoms should be arranged in space in a strict order relative to one another. The
lower the temperature, the larger the viscosity of the liquid is. Therefore, if the cooling is
performed quickly, then, starting from some temperature, the rearrangement of the structure
has no time to be completed. The temperature is so low that a crystal should have formed,
but the structure remains the one corresponding to the liquid state. Molecules can not move
in space, but perform vibratory heat motions. There are no crystals and, thus, no irreversible
changes of the cells and tissues of frozen products take place. Therefore, to obtain a higher
quality of frozen products in modern refrigerating industry, the freezing process should be
performed quickly, with an intensive removal of heat, at as low temperature as possible. In
rapidly frozen products, the cell envelopes mainly remain unbroken. Therefore, there is no
juice oozing out after such products are unfrozen. Modern freezing installations usually pro-
vide for the coolant temperature within 25 to 35C. A product is frozen to 18 and is
stored at this temperature. During the storage, periodic temperature increases should be
avoided, as an increase of even several degrees is accompanied by the recrystallization of
ice, growth of separate crystals with all ensuing consequences.
To manufacture high-quality fast-frozen products, it is necessary to provide for the
freezing of manufactured semi-finished products in a fast freezer, storage of frozen products
in a refrigerator chamber of the plant, transportation of the products in refrigerator railroad
cars or refrigerated road vehicles for their sales. In shops, these products should also be
stored in distribution refrigerators or chambers. After purchasing rapidly frozen produces,
consumers should keep them in refrigerators, without allowing even for a short-time thaw-
ing. Manufacturing of high-quality frozen products is associated with expenditures for com-
plex refrigerating equipment. However, when comparing various methods of foodstuff
preservation (sterilization, drying, pickling, marinading, addition of preservative agents), it
should be stated that in fast frozen foodstuffs the quality of the product preservation of
taste, culinary merits, vitamins, aromatic substances proves the highest.
At present, the domestic industries manufacture a broad range of fast-frozen food-
stuffs. They include various kinds of fruits and vegetables, as well as products of a high
degree of doneness, such as vegetable, meat-and-vegetable and fish first and second
courses, fruit juices.
The process of freezing proceeds the most qualitatively and efficiently in special fast-
freezing machines. Storage and transportation of frozen products requires their packaging
in hermetic and moisture-proof containers. If these conditions are not observed, during the
storage of frozen products in chambers at a temperature of 15 down to 18 the moisture
will be sublimed into the air bathing the products. The moisture that passed from the product
to the air is condensed at cold pipelines, walls, ceilings as frost. The layer of accumulating
frost prevents the transfer of heat from the freezing product to the coolant. Thus, non-
hermetic or moisture-permeable packagings will cause the loss of weight of a freezing prod-
uct, deterioration of its quality and worsening of heat-exchange parameters. Usually, loose
frozen products are poured onto tables covered with tin-plate sheets and packaged into
16 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

containers. Above, we mentioned the necessity to maintain the temperature of a frozen


product constant both in storage and in transportation, as otherwise ice-crystal growth will
take place with the ensuing consequences.
Fish meat is in most cases less prone to deterioration when frozen by traditional meth-
ods. However, during the storage in refrigerators evaporation of moisture takes place, which
is accompanied by the penetration of ice crystals into the tissues. To prevent losses and
quality deterioration of fish products, a new cryotechnology for processing polymers from
aqueous solutions was developed. A protective coating is formed on fish products without
any additional energy expenses. Two types of food coatings, Polyol-1 and Polyol-2, were
developed. The second coating contains preservative agents for the inhibitory action on mi-
croflora and a structure former to produce an elastic transparent coating with a long lifetime.
Fresh fish is to be coated, which makes it possible to preserve additionally large quantities
of a valuable product lost at the stage of preliminary freezing. The process for the Polyol-1
protective coating was implemented at the Gurievrybprom Production Enterprise of the
Kaspryba All-Russian Industrial Association for long-term refrigeration storage of frozen
fish.
An incorrect choice of material for containers and packagings of frozen products,
the same way as an incorrect packaging of a product, can render null all professional actions
of sorting, calibration, washing, cleaning, cutting, chopping, freezing and other process
operations.
Considering the methods of preserving food products, we can not but dwell on one of
the classical methods preservation by heat. Vegetables for preserves, the composition of
which includes, besides vegetables, only water and some salt and sugar for good taste, are
subjected to washing, calibration, cleaning, cutting and blanching. The caloric value of such
preserves is not high, but they keep almost all valuable properties of preserved vegetables.
This applies to their taste, flavour and food value. Most vegetable natural preserves are ster-
ilized by heating above 100C. For instance, green peas are preserved, when their grains
are green, soft and sugary. Usually at this stage of ripeness, their grains contain 57% sugar,
2030% vitamin C, proteins and mineral substances. Prepared grains of green peas are
blanched at 9098 for 34 min, after which the grains are immediately cooled to avoid
overcooking. Green-pea grains thus prepared are packaged into tin-plate or glass contain-
ers, and a hot filling is poured in. The filling consists of sugar (23%) and salt (23%) dis-
solved in hot water and should be filtered before use. Sealed containers are subjected to
sterilization by heating to kill microorganisms, which cause spoilage of the product. In in-
dustrial conditions, such a sterilization is performed in autoclaves hermetically closed cy-
lindrical steel boilers. The higher the sterilization temperature is, the sooner the sterilization
is completed, i.e., the less time is required to kill microbes. However, too high sterilization
temperature can lead to a deterioration of the quality of the preserves: darkening of the prod-
uct, an unpleasant flavour etc. These changes are usually due to undesirable chemical reac-
tions between the components of the product at too high temperatures, which do not occur
at lower temperatures. The sterilization temperature is determined by the resistance of mi-
crobes to high temperatures, which essentially depends on the acidity of the sterilized prod-
uct. Usually, bacteria not forming spores perish during the boiling. Sporulating bacteria
perish only at a long-time heating up to 110120. In an acidic medium, e.g., in tomato
or sorrel puree, bacteria do not develop. However, in such products spoilage is due to molds
and yeasts, which perish in boiling. Products with a low acidity are sterilized at tempera-
tures of 112120. Large containers are heated up slower, low flat cans are heated up
faster than high ones.
CHAPTER 1 17

Besides temperature, size and shape of cans, the sterilization time is also determined
by the consistence of the product. The more densely the product, e.g., paste, fills a can, the
more time is required for the necessary temperature to be established in the middle of the
packaging. Besides the thermal conductivity of the contents of the packagings, the steril-
ization time is also determined by the thermal conductivity of (iron, glass or polymer) con-
tainers, as well as the initial temperature of cans. Therefore, its own regime of thermal
sterilization should be chosen for each kind of preserves and each type of cans, based on
the above conditions.

1.3 Technology of preserving the quality of foodstuffs in manufacturing,


transportation and sales
In production of foodstuffs, of great importance for preventing losses and spoilage, as well
as corrosion of food equipment is the use of antiadhesion coatings.
An optimal coating for baking rye bread was developed and is used at the St.-Peters-
burg Bread-baking Plant No 12. Besides the economy of oil, the antiadhesion coating saves
a considerable amount of flour, eliminates expenses for oiling and cleaning of molds, facil-
itates the application of automatic machines and, which is of no small importance, enable
increasing the quality of baked goods. In molds free of burnt deposits the required temper-
ature is easier to maintain, losses of bread are much smaller, the work of oven operators is
much easier. Antiadhesion polymer coatings are applicable in other branches of food indus-
try, e.g., in meat and dairy industry. Some components of the equipment in food industry,
in particular, shelves and racks for storing and ripening cheese are made from wood and
have a number of disadvantages: they are short-lived, are characterized by a highly labour-
intensive service due to stickage of cheese and integrated sanitation treatment, during which
wood warps. Besides, labour-intensive process operations can not be mechanized in this
case. Shelves and racks can be fabricated from cheep carbon steel coated with a polymer
coating, which should possess a low adhesiveness to foodstuffs and necessary physico-
mechanical and sanitation properties. The most important requirements to such coatings in
operation are the stability of antiadhesion and physicomechanical properties, protection of
the metal equipment from corrosion under conditions of high humidity within the temper-
ature range of 10 up to 80. Material with the required properties can be produced by tar-
geted modification of non-critical and physiologically harmless polymers, e.g., high-
density polyethylene (HDPE). To eliminate the cracking of HDPE-based coatings in their
operation in aggressive moist media, HDPE was modified by polyethyl siloxan PES-5, as
the result of which HDPE was stabilized, and the antiadhesion properties of the coating im-
proved.
The most labour-intensive operations in fabrication of molded meat products include
dislodging of a product from the mold and the subsequent cleaning of its surface. Inter-
laying materials cellophane and cooking parchment paper are used inefficiently to pro-
vide for the separation of a product and a mold. Animal fat is used for greasing the molds
in production of meat loafs, as the result of which a deposit is formed on the molds. The
quality of the products and the sanitary condition of the production shop deteriorate in this
case, the molds should be subjected to systematic cleaning, which makes difficult the mech-
anization and automation of the processes. All these drawbacks can be eliminated by using
antiadhesion coatings.
In the process industries of the agroindustrial complex, of great significance is the pro-
tection of equipment from corrosion. In this respect, it is difficult to overestimate the role
18 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

of antiadhesion coatings which by their sanitary characteristics are permitted to be used in


contact with food products. The problem of corrosion is very significant, though achieve-
ments in this field are quite a few, the domestic developments including.
One should take into account the losses of manufactured food products in storage,
transportation and sales by commercial enterprises. Various compositions for the protective
coating of food products are known. Thus, a composition was invented, which protects
cheeses from drying and molding. A composition for coating sausages and a method of pro-
ducing a casing on them were proposed. A composition for applying a protective coating
on fish and fishery products was also developed.
The most promising method of long-time preservation of the nutritive properties of
food products is their low-temperature preservation. However, a considerable amount of
weight of a product is lost in freezing and subsequent storage due to evaporation of mois-
ture, the quality of a product deteriorates, oxidation of lipids and denaturation changes of
proteins occur. One of the rational ways to retain the quality of products is to create coatings
impermeable for oxygen and moisture on their surface. For this purpose, aqueous solutions
of biologically inert polymers, e.g., polyvinyl alcohol (PA) are used. PA acquires water re-
sistance in the process of film formation at low temperature. During the freezing of the
polymersolvent system, as the result of a phase transition accompanied by an abnormal
increase of its volume, PA undergoes mechanochemical transformations (cryolysis). Cryo-
cracking of macromolecules is accompanied by the emergence of active cryolyzates, whose
interaction leads to the formation of insoluble spatial structures.
The topicality of the problem of using advanced polymer materials determined the ne-
cessity of international forums exhibitions and symposia dedicated to this problem. The
cost of a packaging was on average 8% of the cost of product. There is a tendency in Euro-
pean countries to sell foodstuffs in packagings convenient for preparation of food in micro-
wave ovens.
Great attention is paid to the process evaluation of the packaging systems from the en-
vironment-protection point of view. Among the main tendencies of the packaging business
in the USA, it is necessary to note the development and commercial production of ecolog-
ically pure packagings, a decrease of pollution of the environment. There is a tendency to
move from multi-layer to single-layer packagings, e.g., single-layer bottles from poly-
ethylene terephthalate (PET), which are easy to identify and reprocess. Packagings are used,
in which deep-freeze dishes can be warmed in microwave ovens (PET). Thus, Gortons
place fish sticks into a packaging, which is equipped with elements from metallized PET
film above and below. The elements are susceptible to the absorption of microwaves, which
leads to the effect of a crunchy crust. Special attention is paid to the use of renewable re-
sources (wood, plants). In this respect, of interest is the packaging material based on ethrol,
which under certain processing conditions can be transferred to a liquid-crystalline state.
Packaging in a film material in liquid-crystalline state is rather promising.
Polymer packaging materials found wide use throughout the world, Russia including.
Expanded production of polymer film materials is restricted only by deficit of the initial
materials. For this reason, it is possible to organize production of polyisoprene hydro-
chloride-based polymer films with good sanitation parameters, in contact with fats includ-
ing, which easily yield to two-dimensional strain and shrink after orientation at 70C. The
initial materials are polyisoprene (whose output reaches several million tons per year), HCl
and methyl chloride (which should be subjected to recuperation), a small amount of sorbic
acid (used as food stabilizer at present). The method of producing a film-forming material
based on polyisoprene hydrochloride was developed well back in 1960s.
CHAPTER 1 19

Multilayer films became widespread in the world practice as packaging materials. The
first domestic multilayer film for packaging non-fat food products was a film from poly-
ethylene and cellophane, which was improved and found widely used for packaging food
products (not of increased fat content). Cellophane is produced from naturally renewable
raw materials, is biologically harmless (at a corresponding control of production), possesses
the barrier properties, which significantly deteriorate when it is moistened. A disadvantage
of cellophane is its incapability of heat sealing, which greatly worsens the packaging pro-
cess of food products. A combination of these materials produces a film heat-sealed mate-
rial with high barrier properties. However, as the inner layer is polyethylene, this material
can not be in contact with fatty food products. Progress in the development of multilayer
film materials in this and other countries was accompanied by the emergence of multilayer
films with different combinations of paper, foil, various polymer films and binders. The
problems one comes across in this case are pollution of the environment and interaction of
a foodstuff with the packaging. Regularities of the interaction of a foodstuff with the pack-
ing and with the environment are being revealed. The most important processes of this king
are penetration of oxygen, water vapours, light and carcinogens from the atmosphere into
a foodstuff through polymer films. Substances contained in the foodstuff can get to the en-
vironment through the packaging. These processes are undesirable.
In the recent years, the use of the vacuum freeze drying of food products has become
more widespread, and the popularity of this method has increased. Production of foodstuffs
by this method has both positive and negative aspects.
The positive aspects include the high quality of these products; by their nutritive and
gustatory properties, they are comparable only with natural deep-frozen products (studies
by E.I. Kaukhcheshvili). A positive quality is also the capability of long-time storage (up
to 1 year and more) under non-regulated conditions of the environment. A drawback is the
high cost of vacuum freeze preservation; as shown by B.P. Kamovnikov, average reduced
costs for the removal of moisture from an object of vacuum freeze drying exceed similar
expenses for heat drying 1520 times.
A quite natural and justified idea would be to reduce the costs of preserving freeze-
dried products several times without decreasing the high consumer properties. Calculations
show that, though this is difficult, this problem is quite realizable technically: to solve it,
the freeze-drying process should be performed not in a vacuum, but at an atmospheric pres-
sure. This would, first, make it possible to exclude the expensive and energy-intensive vac-
uum equipment from the process. Second, at an atmospheric pressure heat-and-mass
transfer could be intensified (especially at the final stage of drying) due to the convection
of the drying agent, which is out of the question under vacuum conditions. In other words,
for production of daily-consumed freeze-dried products the vacuum freeze-drying should
be replaced with atmospheric freeze-drying (AFD).
In a general case, the process of preservation by the AFD method includes the follow-
ing major operations: sorting and treatment of raw materials, freezing, removal of moisture
by freeze drying at negative temperatures, cold and hot completion of drying to a given final
moisture content, prepackaging and packaging of the dried product. The properties of the
preserved products crucially depend on the condition of raw materials and the quality of
performing each of the above operations. Herewith, the preservation process has its peculiar
features for each particular kind of product, depending on the properties of raw materials
and requirements to the final product.
It should be pointed out that materials dried by the AFD method are rather hygroscopic
and have a large specific surface of the dry carcass.
20 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Objects of drying

Raw materials for production of Foodstuffs


medical preparations / biostimulants
Foodstuffs of animal origin
Endocrine / enzyme raw
materials of animal origin
Foodstuffs of plant origin

Crude drugs of plant origin Sea foods

Figure 1 Classification of objects of drying.

For this reason, long-term storage without reduction of quality can be possible only in
a reliable hermetically sealed packaging. With any other conditions equal, the duration and
quality of storage are basically determined by the quality of packaging. For instance, the
use of metal tin-plate cans or multilayer metallized films for fabrication of packages and
the filling-up of these containers with a dry product with gaseous nitrogen makes it possible
to provide for the storage of plant products in the off-season period.
As the preservation by the AFD method is a sufficiently complex process, and the pre-
served products are usually intended for long-time storage, the requirements to the initial
raw materials are high. The nutritive value and vendibility, structural mechanical properties
and admissible terms of storage, the temperature level of processing and duration of indi-
vidual process operations all these are largely determined by the properties of the raw ma-
terials. Along with the diversity of the chemical composition of various food products, they
are characterized by one common property: they contain a considerable amount of water.
As objects of processing (including by preservation by the AFD method), products are
classified by their physical nature into objects of animal and plant origin and sea foods. By
their consumer properties, a separate group is endocrine / enzyme raw materials, which are
usually not used as a source of food, but are an essential source in production of medicines
and biologically active substance.
A classification of objects of drying is presented in Fig. 1. The purpose of products is
taken as the first-rank classification criterion. Two large groups are singled out here food-
stuffs and raw materials for production of medical preparations and biostimulants.
The second rank of classification is chosen to be the characteristic of dividing the
objects by their physical nature. Individual groups of objects of drying singled out at the
second-rank level differ significantly by their composition, physicochemical and other
properties (Table 1.1). For this reason, the possibility of using methods of vacuum or atmo-
spheric freeze drying for their preservation and the choice of drying regimes should be de-
cided upon separately for each group of products close by their properties.
A complex interaction of these components with water and with one another forms the
properties of food products. The amount of water in a product also determines the condi-
tions of its storage, which would not reduce its quality.
Meat used for preservation by the AFD method should conform to a number of require-
ments. Cartilages, large vessels and connective tissue are removed during the trimming in
the preparation of meat for drying. These inclusions considerably differ by their heat trans-
fer properties from muscle tissue, their presence would lead to nonuniform drying, worse
CHAPTER 1 21

rehydration of the dry product, would reduce vendibility and gustatory qualities of culinary
products made using the dry product. A high content of fatty tissue is inadmissible. The
melting temperatures of animal fats are rather low (e.g., beef fat, 3252C; pork fat,
2848C; chicken fat, 2338C). For this reason, at the stage of residual moisture removal
(completion of drying) fat can melt and fill free pores, which would sharply increase the
duration of drying and formation of non-drying inclusions (lenses) in the depth of the spec-
imen. Besides, at the stage of storage of dried meat the oxidative transformations of the lipid
fractions can drastically deteriorate the organoleptic parameters of the product. These
changes can be the largest in pork and poultry meat, as fats of these kinds of meat contain
many unsaturated fatty acids.

Table 1.1

Product Water, Proteins, Fats, Carbo- Fibre, Ash, Energy value,


% % % hydrates, % % 100 g/kJ
%

Pasteurized milk 88.5 2.8 3.2 4.7 0.7 243


No fat curd cheese 77.7 18.0 0.6 1.5 1.2 360
Common beef 71.7 20.2 7.0 1.1 602
1st category hens 61.9 18.2 18.4 0.7 0.8 1008
Hens eggs 74.0 12.7 11.7 0.7 1.0 657
Azov-sea carp 75.3 18.4 5.5 1.0 506
Potato 75.0 2.0 0.1 19.7 1.0 1.11 374
Cabbage 88.5 1.3 0.1 7.0 1.2 1.0 138
Mushrooms 88 1.8 0.8 1.1 1.5 0.4 79
Apples 85.6 0.4 11.3 0.6 0.5 192
Black currant 85 1.0 8.0 3.0 0.9 167
Apricots 86 0.9 10.5 0.8 0.7 192
Plums 87 0.8 9.9 0.5 1.3 180
Bulb onion 86 1.7 9.5 0.7 1.0 180

The requirements to the raw materials intended for preservation by AFD are satisfied
the most by meat of young animals. The muscle fibres of this meat are more thin and elastic,
meat possesses a relatively lower mechanical strength, the content of fat in it is small.
An important factor in producing a high-quality product is the dependence of the prop-
erties of meat not only on the tissue and chemical compositions, but also on the depth of
autolysis. According to the obtained recommendations, meat after a 3- or 4-day holding at
24C should be used for preservation by freeze drying.
When choosing the AFD regimes for milk and dairy products, it should be taken into
account that the properties of milk proteins change in heating and freezing. Thus, in freezing
(down to temperatures below 10C), the colloidal properties of milk proteins change, their
solubility decreases. Milk fat in the milk mass is distributed in the form of balls up to 5 m
in diameter, each of which is enclosed by an envelope containing a protein complex. In the
contact of lipid fractions with oxygen of the air during the AFD process or in storage of a
dry product, the product can rancidify and suffer a deterioration of taste. For this reason,
when packaging dry milk and dairy products it is necessary, as in the case of packaging dry
meat products, to use hermetic vapour- and light-impenetrable containers filled with inert
gas. Products prepared from no fat milk are more resistant.
22 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Milk sugar (lactose) is close by its nutritive value to common beetroot sugar. However,
a larger content of reducing sugars in milk and dairy products (e.g., in mare milk, up to 7%)
creates conditions for sugar-amine reactions in storage of dried products. For their maxi-
mum inhibition, it is necessary to remove moisture from dairy products in the process of
drying up to 23%. In practice, during the preservation by the AFD method this condition
is achieved by drying dairy products in air convector heaters (furnaces) at temperatures of
4050C upon completion of the moisture removal by the icevapour phase transition.
Freeze drying of milk, curd, many fermented milk products makes it possible to pre-
serve maximally the high quality of the product produced. And for such products as, e.g.,
acidophilic paste and Mechnikovs sour milk, it has no alternative.
The recent decade is characterized by an increased production of new kinds of prod-
ucts based on combinations of meat raw materials with proteins of plant and animal origin.
Among protein preparations used for partial replacement of meat raw materials, composi-
tions used the most are milk proteins (sodium caseinate, milkprotein concentrate etc.) as
well as soy proteins (soy isolate, soy concentrate, soy flour and grits). Numerous experi-
ments have proved that a rational level of the substitution of protein for meat raw materials
is from 10 up to 30%, depending on the kind of protein used.
Introduction of rehydrated protein preparations into the meat system raises the stability
of the dried meats lipid fraction to oxidation and increases the storage times, raises the re-
sistance to thermal denaturation, provides for the balance of the amino acid composition,
improves the organoleptic properties of culinary products prepared from reconstituted dry
products. An especially important fact is the possibility of drying and freeze drying of meat
products with protein additives at a higher temperature as compared with meat products
containing no protein fillers. A temperature increase could be 56C without the loss of
quality, which enables saving energy and in some cases using a simpler equipment.
Milk and soy proteins are widely used at present for enrichment of meat products. Milk
proteins are added into chopped meat as sodium caseinate. The substitution of sodium ions
for calcium available in milk has a positive effect on the increase of solubility of the protein
and imparting it with the properties of a water-binding and fat-emulsifying component.
Precipitation of casein with whey proteins yields preparations containing all milk pro-
teins, the so called coprecipitates with up to 80% protein in the dry residue.
Processing of soybeans to obtain food proteins is performed in several directions,
which enables production of soy flour and grits containing about 50% protein: soy concen-
trate (produced from soy grit, from which soluble carbohydrates are removed and protein
passes into an insoluble form), the content of protein up to 70%; soy isolate (highly purified
protein preparations without taste and smell), the content of protein up to 90%. Integrated
studies of the chemical composition of some kinds of protein preparations show that all pro-
tein preparations are characterized by a high protein content and a low fat content.
Soy protein preparations contain essential vitamins and mineral salts.
A comparative analysis of the amino acid composition indicates that plant protein
preparations are characterized by a lower content of sulfur-containing amino acids as com-
pared with proteins of animal origin. However, when soy proteins are used in a complex
with proteins of animal origin (muscle protein, caseinate, blood plasma) their biological ac-
tivity increases due to the mutual enrichment with essential amino acids.
In the freeze drying of eggs, a mixture of egg white and yolk (a melange) or only white
is used. A promising procedure is the use of eggs for preparing products with a whipped
structure meat, milk or fruit souffle, which are then preserved by the AFD method.
The presence of various enzyme systems in eggs leads to the development of autolytic
CHAPTER 1 23

changes in their storage, the general tendency of which is similar to the autolysis process
in animal tissues, so dietary or fresh eggs are used as the initial product. According to the
operating standard, the former are the eggs that come to the consumer no later than 7 days
from the day of laying and not kept in solutions. Fresh eggs are those that were kept at a
temperature of +2 to 2C for no more than 30 days.
Along with animal and poultry meat, fish is an essential source of complete proteins;
proteins of fish meat are easily assimilated by the human organism. Constituents of fish
meat are basically represented by proteins, lipids and water. The chemical composition of
tissues is rather inconstant and depends on the fish species, age, time of capture etc. Thus,
the relative moisture content is on average from 53 (eel) up to 81% (cod, pike perch); pro-
tein substances, 10 up to 24%. Variations are even larger in the fat content from 0.20.4
up to 30%. Fatty meat contains less water than lean meat. However, the total content of
water and fat in the fish body remains practically always a constant value close to 80%.
For atmospheric freeze drying, only the meat of fish with a minimum amount of fat
could be used, as it could be oxidized both during the drying and in storage. We should note
that, owing to a high degree of unsaturation, fish fats are easily oxidized; herewith, some
of these products can be toxic. As the result of postmortem processes, fish meat undergoes
significant physicochemical changes. The initial stage of rigor mortis is characterized by
intensive glycolysis of glycogen, accumulation of lactic acid in muscles and a pH decrease.
The further development of the processes finally leads to contraction and tension of mus-
cles. With the course of time, rigor occurs owing to the further irreversible protein changes,
determined as maturation and autolysis. Meat becomes more tender.
Sea is also a source of other valuable foodstuffs (e.g., prawns, crabs) and raw materials
for medical industry (various algae). Freshwater reservoirs are habitats of such a valuable
source of protein and biologically active substances as chlorella. These objects can be suc-
cessfully preserved by the AFD method. The qualitative indices of dry semi-finished prod-
ucts conformed to the imposed requirements.
A characteristic feature of all plant products is a large water content, 6696%. The
main carbohydrates of fruits and vegetables are sugars, starch, cellulose and pectin sub-
stances. Studies of plant-origin products show that the chemical composition of even one
species changes depending on the extent of ripeness, variety, growth conditions etc.
Fruits and vegetables contain all known vitamins, except vitamins B12 and D (calci-
pherol). Vitamins C, A (as provitamin A, carotene), vitamin K occur in largest amounts.
Plant products are the main source of vitamin C. The change of its content in the food ration
due to freezing, freeze drying and subsequent storage of the dry product is (together with
the organoleptic indices) an essential criterion of quality of the entire preservation process.
Vitamin C is easily destroyed by heating and under the action of oxygen of the air.
Thus, in the presence of oxygen of the air it breaks down already at a temperature of 50C.
This should be taken into account when choosing the temperature regime at the stage of
completion of the drying, as well as when choosing the design of the device for AFD.
Fruits and berries contain a considerable amount of sugars, from 79% (black currant,
garden strawberries, apples) up to 2025% (dog-rose, grapes). In vegetables, the content
of sugars is usually at a level of 46%. Sugars are represented by glucose, sucrose and fruc-
tose, the quantitative ratios between which are different for each kind of product. Changes
in the properties of sugars in the course of the process have a strong effect on the quality of
the ready-made product. The action of high temperatures is inadmissible, they can contrib-
ute to the caramelization of sugars, induce reactions of melanoidin formation as a conse-
quence of the interaction of sugars with amino acids. As the result, browning of the product
24 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

takes place. Note that plant products with a significant sugar content, e.g., bananas, are prac-
tically unsuitable for preservation by the AFD method.
Fruits and vegetables contain 0.23% of cellulose, which is mainly used for construc-
tion of envelopes and cell walls. The composition and content of the cell walls determine
the mechanical properties of tissue. Cellulose is characterized by a high chemical resis-
tance. Preservation of fruits and vegetables by the AFD method usually envisages the de-
struction of cellulose the preparation of purees and pastes, comminution.
The pectin substances of plant-origin products include complex polysaccharides. In
fruits and vegetables, they are 0.12% of the total mass of a product. Significant amounts
of pectin are in apples, quince, plums, apricots. Pectins have the property of forming stable
colloidal solutions. The condition of the pectin substances in a dry product largely deter-
mines the degree of its rehydration.
As shown by the experience of preserving a broad assortment of fruits, vegetables and
berries by the method of vacuum freeze drying, the ultimate choice of this or that variety
with the aim to obtain a high-quality dry product can be made only based on the experimen-
tal check in each particular case. It was found that particular varieties of plant-origin prod-
ucts, good by their initial quality parameters, were unsuitable for preservation (due to the
loss of shape in drying, instability in storage, bad rehydration). In full measure, this is also
valid in the case of the AFD method.
The AFD method has a great potential for preserving flavouring/spicy plants added to
foods for flavour and to excite appetite. Many savoury herbs in the form of spices have a
strong bactericidal action. In the European part of Russia, these are widely used dill, parsley,
parsnip, coriander (cilantro), peppermint and estragon (tarragon). Leaves of these plants
contain various aromatic oils, vitamin C, provitamin A, biologically active substances.

1.4 Application of chemical preservatives in food industry

1.4.1 General information on chemical food preservatives


Chemical preservatives are synthetic chemical substances used for slowing down or pre-
venting undesirable changes in foodstuffs and technical products of biological origin
caused by microorganisms bacteria, molds, yeasts.
Chemical food preservatives include sulfurous anhydride and some salts of sulfurous
acid; benzoic, sorbic, propionic acids and some of their salts; methyl, ethyl and propyl esters
of para-oxybenzoic acid. Hexamethylene tetramine; formic, boric and salicilic acids;
formaldehyde, hydrogen peroxide have not been used lately in most countries.
Preservatives make it possible to increase the storage times of ready-made products
and raw materials, as well as prevent spoilage of raw materials in processing. Preservatives
are usually used when other methods are not possible.
Application of chemical preservations is restricted as, being toxic for microorganisms,
they are harmful for man and animals. Therefore, they are used at very small concentrations,
harmless for higher organisms and man.
In food industry, chemical preservatives are used mainly in combination with heating,
freezing, drying, irradiation etc. Their actions add up.
The method of treating a product with preservatives depends on the kind of product
and its condition. Liquid and comminuted products are usually thoroughly mixed with the
preservative. Lump products are subjected to surface treatment, e.g., by immersing a prod-
uct into a solution or by sprinkling it with a solution.
CHAPTER 1 25

Treatment of the surface of a product is especially expedient when there are no micro-
organisms inside it.
Preservatives cause damage to microbial cells, reversible (bacteriostatic or fungistatic
action) or irreversible, as a consequence of which cells die (bacteriocidal or fungicidal
action).
At a bacteriostatic action, microorganisms remain alive, but are not capable of propa-
gation. If they are transferred to a favourable medium, propagation becomes possible again.
However, microorganisms gradually die even at a bacteriostasis, depending on the concen-
tration and duration of action of a preservative. In practice, bacteriocidally acting substanc-
es differ from bacteriostatic ones only by a greater pace of microbial die-off.
The rate of bactericidal action increases with the increase of the concentration of a
chemical substance and temperature.
Bacterial cells can develop, propagate, produce toxins only under certain conditions.
Bacteria, e.g., are sensitive to pH of the environment. A significant change of pH leads to
a change of the surface amphoteric structures of the cell and, owing to this, to a disturbance
of cell equilibrium followed by cell death. In particular, the osmotic exchange between the
cell and the environment is disturbed. In some microorganisms, a pH decrease causes an
activation of the ribonuclease autolytic system, which is unfavourable for cell viability.
Bacteria, with few exceptions, can develop in media with pH 4.29.4; yeasts develop
in a more narrow pH interval (4.06.8); and mold fungi, within even broader pH limits
(1.211.1).
Many preservatives of acidic type are more efficient at low pH, as a major part of them
are in a non-dissociated form (Table 1.2).
Table 1.2
Preservative acid Dissociation Non-dissociative (real) part, %, at pH
constant
2 3 4 5 6 7

Sulfurous 1.7102 37 5.5 0.55 0.04 0.001 0


Bromoacetic 2.05103 83.0 32.8 4.65 0.48 0.049 0.0049
Salicilic 1.06103 90 49 8.6 0.94 0.094 0.0094
Formic 1.77104 98.3 85.0 36.1 5.35 0.56 0.056
p-Chlorobenzoic 9.3105 99 91 52 9.7 1.06 0.107
Benzoic 6.46105 99.3 93.9 60.7 13.4 1.52 0.15
p-Oxybenzoic 3.3105 99.7 96.8 75.2 22.3 2.94 0.30
Acetic 1.8105 99.8 98.2 84.7 35.7 5.26 0.55
Sorbic 1.73105 99.8 98.3 85.2 36.6 5.46 0.57
Propionic 1.4105 100 99 88 42 6.7 0.71
Dehydroacetic 5.3108 100 100 95 65 15.8 1.9
Bisulfite 1.02107 100 100 99.9 99.0 90.7 49.5
Boric 7.31010 100 100 100 100 100 100

Owing to this, molecules of an acid can penetrate into microbial cells, whereas pene-
tration of ions into cells is impossible or barely possible.
As the dissociation constant of a preservative acid decreases, even at a neutral or weak-
ly acidic reaction, the number of non-dissociated molecules, which guarantee its action, in-
creases. The weaker a preservative acid, the closer the pH can be to the neutral point; the
preservative action of the preservative does not decrease. Non-dissociating preservatives,
26 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

e.g., esters of para-oxybenzoic acid, are relatively independent of pH and can change at the
neutral reaction.

1.4.2 Mechanism of action of chemical preservatives


The mechanism of action of chemical preservatives on microorganisms has been little stud-
ied to date.
Common methods of determining the inhibitory doses of chemical preservatives can
not reveal the mechanism of their action. They can only establish the concentrations, at
which the propagation of microorganisms slows down. In practice, it is believed that a pre-
servative is efficient if it prevents the growth and propagation of microorganisms.
The probable mechanism of action of chemical preservatives on microorganisms, pro-
posed comparatively recently and accepted at present, is presented below.

Compound Probable effect


Cationic and anionic surfactants Disturbance of cytoplasmic cell membrane. Denaturation
of enzyme protein
Phenols, chlorophenols, naphthol Disturbance of cytoplasmic cell membrane. Reaction
sulfonates, cinnamic acid with genetic-mechanism proteins
Fatty acids, alcohols and high-molecular- Disturbance of cytoplasmic cell membrane. Competitive
mass aldehydes inhibition of enzymes by low-molecular-mass acids
Chloroacetic acid Effect on the cell wall. Competitive inhibition
Benzoic acid, p-chlorobenzoic acid, Effect on the cell wall. Competition with coenzyme for
p-oxybenzoic acid and its esters apoenzyme
Salicilic acid Effect on the cell wall. Competition with nicotinamide
adenine dinucleotide. Competition with amino acids used
by enzyme
Boric acid Reaction with phosphorus metabolism enzymes
Sulfur dioxide, sodium sulfite, sodium Reaction with aldehydes formed in dissimilation of
bisulfite carbohydrates. Reduction of SS bonds in enzyme
protein
Chlorine, chloramines, nitrogen tri- Breakdown of sulfhydryl groups in enzyme proteins.
chloride, peroxides, nitrates and other Breakdown of sulfhydryl groups in genetic-mechanism
oxidants proteins.
Ethylene oxide and other epoxides Reaction with carboxyl and other active groups in
enzyme protein
Fluorides, fluorosilicon compounds and Reaction with prosthetic groups of enzymes. Reaction
fluoroborates with active groups of enzyme protein
Formaldehyde Reaction with active groups of enzyme protein. Reaction
with active groups of genetic-mechanism protein
Salts Precipitation of enzyme proteins

Exchange between the bacterial cell and the environment is on the level of a limiting
surface (the envelope); a number of differentiated protoplasmic structures, which create
conditions required for active exchange of the cell with the environment, also occur here.
Any substance violating this topography of the cell causes a disorganization of surface
structures, which is equivalent to cell damage. In these cases, we observe bacteriostasis, or
death, of the cell.
CHAPTER 1 27

Under the action of chemical compounds, the metabolism in the microbial cell chang-
es. Metabolism in any cell is inseparably linked with the activity of the enzymes.
The action of certain chemical substances on some enzymes can lead to the termination
of preparation of nutritive material for assimilation, to the associated lack of nutrients and,
therefore, to the interruption of the growth and propagation of microorganisms, i.e., to a
bacteriostatic effect. If the stores in the cell are depleted, it dies. The total damage of certain
enzymes, in particular, dehydrogenases, can lead to the cessation of the oxidative processes
and associated processes of synthesis, i.e., to the termination of life. Depending on the re-
versibility or irreversibility of the reaction, the effect will be bacteriostatic or bacteriocidal.
Chemical substances, depending on their specific reactivity, can affect cell enzymes
by interacting with the functional groups of an enzyme. The catalytic action of an enzyme
is determined by several functional groups sulfhydryl, disulfide, indole, imidazole etc.
The breakdown or blockage of a group interacting with substrate or coenzyme leads to the
cessation or deceleration of the catalytic reaction.
The mechanism of blockage of active groups of enzymes can be different. For in-
stance, the sulfhydryl group is blocked via oxidation

H
2R SH R S S R

or substitution of hydrogen

R SH + R'OH R S R' + H2O.

Formaldehyde is characterized by a small selective reactivity. Depending on pH of the


medium, it can block various functional groups: at pH 9.5, free amino acids; at pH 6.0, the
imidazole group of histidine, at pH 5.0 and lower, formaldehyde is predominantly bound
by amide and guanidine groups; it also reacts with indole and sulfhydryl groups.
The preserving action of sulfurous acid is also based on its capability of damaging the
enzymes of the microbial cell. Substances capable of acting as reducers and oxidizers in-
hibit the activity of the enzymes. The enzymes containing the functional SS group, on
whose presence their catalytic activity depends, are inactivated by such reducing substances
as SO2, H2S, HCN, dithionate or HCOH. The SS bonds are split to form HS groups.
Besides, sulfurous acids, by reacting with aldehydes formed in carbohydrate ex-
change, capture them and violate the normal metabolism in the microbial cell. Thus, ace-
taldehyde sulfonate formed in this reaction is not accessible to corresponding enzymes.
In this case, inhibition of activity of the enzyme system is achieved by blocking the
substrate, which becomes inaccessible to microbial enzymes.
A possible explanation of the mechanism of inhibiting the growth of mold was pro-
posed, proceeding from the supposition that sorbic acid is degraded to final products under
the influence of mold enzymes by the type of the -oxidation of fatty acids. At the same
time, it was established that cyanide selectively inhibits oxidation of butyric acid to -ke-
tobutyric acid under the action of mold enzymes. Dehydrogenase, which catalyzes the con-
version of butyric acid to crotonic acid, was not inactivated by cyanide, but the enzyme
system catalyzing the conversion of crotonic acid to -oxybutyric acid, was inactivated to-
tally. This means that ,-unsaturated fatty acids accumulate in the medium; this accumu-
lation inhibits the dehydrogenase system of molds. When sorbic acid is added to a food
product, the final product of the reaction catalyzed by mold dehydrogenase is in excess, and
dehydrogenase can not function.
28 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

At a high mold contamination, the concentration of all enzyme systems increases, ow-
ing to which the dehydrogenase activity can not be inhibited. Sorbic acid at a high mold
contamination of a product is not active.
Chemical substances can inhibit an enzyme reaction by acting on a prosthetic group
of the enzyme, by attaching themselves to coenzyme or else to the protein part of the en-
zyme in such a way that the bond between coenzyme and the protein component of the en-
zyme (apoenzyme) becomes impossible.
If a chemical substance is similar by its structure to coenzyme, it competes with coen-
zyme by capturing apoenzyme, as the result of which the enzyme is inactivated. This, in
particular, is one of the mechanisms of action of benzoic acid and its salts, which compete
with coenzyme for apoenzyme. The efficiency of action of benzoic acid in media with a
lower amino acid content is higher than in food products, and under certain conditions nic-
otinic acid interferes into inhibition by benzoate.
Both inhibition and die-off of microorganisms can depend on various reasons, on one
or several all at once. Therefore, when choosing a preservative, not only its concentration
and time of action should be taken into account, but also the possibility of a simultaneous
damage to a large number of vital mechanisms. To develop preservative formulae with an
extended range of action, one should know the causes of microbial die-off under the action
of a preservative.
As most preservatives possess a specific action with respect to various microbial spe-
cies, and spoilage of food products is determined by a large number of microbial species,
the development of combined compositions of preservatives has certain advantages. The
additive action of two substances is possible owing to the fact that one substance, by acting
on the cell envelope, facilitates penetration into the cell of another substance, or one of the
preservatives decreases pH, and then the efficiency of action of the other preservative in-
creases.
The efficiency of action of a composition made up from two or more preservatives can
be increased by adding synergists, i.e., the substances, which possess no preservative action
by themselves, but can enhance and maintain the preservative action of a preservative.
Citric, tartaric and malic acids, as well as inorganic acids, their salts etc. can serve as syn-
ergists.
The action of double and triple combinations, consisting of a preservative (sorbic,
formic, benzoic acids or para-oxybenzoic acid esters) and an antibiotic (nisin or tylosin, or
both), was studied. A preservative is used to expand the antimicrobial range.

1.4.3 Characteristics and application of chemical preservatives

All methods of increasing the resistance of food products by using chemical preservatives
have their advantages and disadvantages. First of all, taste can become worse, and the nu-
tritive value can decrease. For instance, sulfurous acid degrades vitamin 1 to a significant
extent. Some preservatives are capable of disguising the true quality of a product, and a stale
product can be passed off as a fresh product. For instance, formic acid possesses this capa-
bility with respect to meat products. Partially for this reason, preservatives of this kind are
banned in most countries.
Benzoic acid (benzenecarboxylic acid; phenylformic acid) is present in most berries
(0.5%).
CHAPTER 1 29

COOH

Benzoic acid
Benzoic acid is a colourless crystalline substance, difficult to dissolve in water and
rather easily dissolving in ethanol. It is used as a preservative; its efficiency increases in an
acidic medium. The activity of benzoic acid against yeast fungi is higher than against molds.
Sodium benzoate (the sodium salt of benzenecarboxylic acid; the sodium salt of phe-
nylformic acid) is an almost colourless crystalline substance.
COONa

Sodium benzoate
This salt dissolves well in water, worse in ethanol. The preservative activity is exhib-
ited best of all in an acidic medium at pH lower than 5.0.
In studies of acute toxicity of benzoic acid and its sodium salt, LD50 for rats was 2700
mg/kg body weight; for rabbits and dogs, 2000 mg/kg body weight in peroral introduction.
In rats, prolonged feeding of food containing 0.5 and 1% of benzoic acid was found to
have no harmful effect on their growth, fertility and life expectancy. No deviations from
the norm were found in autopsy, either.
The dose causing no significant toxic effect in rats is 1% benzoic acid or sodium ben-
zoate in food, which is equivalent to 500 mg/kg body weight per day.
Benzoic acid is used for preservation of food products usually at a concentration of up
to 0.1%; sodium benzoate, at a concentration not exceeding this amount in terms of benzoic
acid. Though the preservative action of benzoic acid is higher than that of sodium benzoate,
the latter is used more often due to its better solubility in water. The solution should have
pH lower than 4.5, then sodium benzoate is converted into free acid. Already at a 0.1% con-
centration, sodium benzoate is a strong preservative for many food products. It is efficient
for acidic or slightly acidified products, such as fruit juices, marinaded vegetables.
Benzoic acid and its salts found use mainly for preserving products of plant origin.
In some cases, they are used for preservation of fish products. For instance, in Italy the
use of benzoic acid and its sodium, potassium and calcium salts is permitted for processing
of semipreserved fish products, caviar etc.
Ice containing 0.1% benzoic acid is known to be used for preservation of fish and fish
fillet, and packaging of these products with ice containing 0.150.30% sodium benzoate
enables their storage fresh for several days more than in a packaging with common ice. To
avoid coagulation of fish surface layer proteins, pH of ice is maintained higher than 4.0.
Besides, benzoic acid or its salts added at a concentration of 0.3% to a 5% solution of cook-
ing salt with pH 4.05.0, into which a fish fillet is immersed for 2 min, considerably in-
creases its storage time. Besides, the saline solution improves the taste of fish.
In many countries, benzoic acid and its salts are used for preservation of liquid eggs
and egg yolk.
Sodium benzoate is considered to be a good preservative for oleomargarine. It does
not affect the vitamin content.
30 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Information on the use of benzoic acid or its salts for preservation of meat products is
scarce. Preservation of meat salads and protective gelatin coatings for meat products by
benzoic acid is known to be used.
There are indications that a 0.06% addition of benzoic acid increases twofold the sta-
bility of fresh sausages and other meat products. For their longer storage, it is recommended
to add 4 g of a preservative mixture per 1 kg of sausage: 8.5 parts of benzoic acid, 8.5 parts
of sodium benzoate, 8.3 parts of cooking salt. This method significantly inhibits the growth
of all bacterial species.
In Russia, of products having a relation to meat industry, benzoic acid is allowed for
preservation of food gelatin at a concentration of 0.07%.
Methyl, ethyl and propyl esters of p-oxybenzoic acid possess an ability to exhibit a pre-
servative action in a neutral medium.
COOR

OH
p -Oxybenzoic acid ester
In the formula, R is CH3, C2H5 or C3H7.
These esters are colourless crystalline substances with almost no smell. All of them
are hard to dissolve in water and are easily soluble in ethanol.
In acute experiments on mice, LD50 for methyl and propyl esters of p-oxybenzoic acid
was more than 8000, and for their sodium salts 2000 mg/kg of body weight. In similar ex-
periments for the sodium salt of ethyl ester of the same acid, LD50 was about 2500 mg/kg
body weight.
In chronic experiments (96 weeks), methyl ester of p-oxybenzoic acid was introduced
to rats with food in the amount of 2 and 8%. Animals given the feed containing 2% of the
preparation did not differ from controls. In rats, which received feed containing 8% of the
preparation the weight increase went down in the initial period of the experiment, and then
levelled out. Histological studies revealed no significant changes in organs of rats. The
same results were obtained in experiments with propyl ester.
The dose causing no significant toxic effect in rats is a 2% addition of each of the three
esters to food, which is equivalent to a daily dose of 1000 mg/kg body weight.
Esters of p-oxybenzoic acid, mainly ethyl and propyl esters, and their mixtures were
earlier rather broadly used in the West as preservatives for a number of confections marz-
ipan pastes, marmalades etc., mayonnaise, some fish semipreserves, caviar, especially crab
preserves etc. Lately, they are not used in most countries.
In some countries, for instance, Norway, esters of p-oxybenzoic acid and its sodium
salts are permitted to be used at a 0.05% concentration to increase the stability of some fish
semipreserves, special types of cheese, as well as for surface treatment of cheeses. How-
ever, before paraffin treatment of cheeses, the preservative should be removed. Preserva-
tives are introduced into compositions containing cellulose esters intended for the surface
coating of salty meat products.
In Italy, ethyl and propyl esters of p-oxybenzoic acid are permitted to be used for pre-
serving semipreserved fish products, caviar, mayonnaise etc. They are used instead of ben-
zoic acid for preservation of meat salads and edible gelatin coatings for meat products.
CHAPTER 1 31

Ethyl ester of p-oxybenzoic acid at a 0.75% concentration makes it possible to store edible
blood without its organoleptic properties changed.
Sorbic acid (1,3-pentadiene-1-carboxylic acid; ,-pentadiene-a-carboxylic acid;
trans-2, trans-4-hexadiene acid) is represented by colourless needlelike crystals with mod-
erately sharp smell:
CH 3CH CHCH CHCOOH
Sorbic acid
The technical requirements to edible sorbic acid abroad (in the USA) are as follows:

Melting temperature (dry sample) 133.0137.0C


Titration (dry sample) 99.0101.0% (w/w)
Water content 3.010.0% (w/w)
Heavy metal content 1 mg% (maximum)
Ash content 0.2% (maximum)
Transmission of light (5% methanol solution at 425 m) 95% (minimum) for a layer of 1 cm

Sorbic acid is soluble in cold water only slightly (0.15% at 20C), but is much more
soluble in hot water (3.8% at 100C). The salts of sorbic acid are better soluble in water.
The solubility of sodium sorbate in water is 32%, it does not essentially change depending
on temperature within the range of 060C. The solubility of potassium sorbate is more
than 50% at 20C, and calcium sorbate dissolves in the amount of 1.2% at 25C.
The solubility of sorbic acid in various solvents at 20C is shown in Table 1.3.
Table 1.3

Solvent Solubility, Solvent Solubility,


g/100 g solvent g/100 g solvent

Glacial acetic acid 11.5 Ethyl ester 5.0


Acetone 9.2 Glycerol 0.31
Benzene 2.3 Cottonseed oil 0.58
Carbon tetrachloride 1.3 Anhydrous propylene glycol 5.5
Cyclohexane 0.28 25% sodium acetate 2.1
Anhydrous ethanol 12.9 15% sodium chloride 0.038
20% ethanol 0.29 Water 0.15

Sorbic acid, having two unsaturated bonds in its structure, is a rather reactive com-
pound. Its autooxidation leads to the formation of peroxides. It should be especially pro-
tected from the action of sunlight, otherwise the quality of the crystalline preparation
worsens, which manifests itself in a melting temperature decrease, yellowing and rancidity.
Sorbic acid is used as an antimicrobial substance. It possesses a high activity against
molds and yeast fungi and, to a smaller extent, against bacteria. Its optimal pH is 4.5. The
fungistatic activity increases in the presence of acids and cooking salt. Sorbic acid is found
in berries of mountain ash Sorbus aucuparia L.
In peroral introduction to rats, the lethal dose (LD50) of sorbic acid was 10,500 mg/kg
body weight.
Chronic experiments on rats were conducted for 1000 days on two generations of
32 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

animals. Rats were given feed, which contained 5% of sorbic acid. No deviations in weight
increment and fertility from control animals were observed.
A dose causing no toxic effect in rats is 5% of sorbic acid in feed, which is equivalent
to 2500 mg/kg body weight per day.
In subacute and chronic experiments on animals, sorbic acid was found not only to be
non-toxic but possessed a number of favourable biological properties.
Sorbic acid is used to inhibit the growth of yeasts and against molding of fruit and veg-
etable juices, marinades, brines, smoked fish, flour confections etc., as well as to prevent
damage of cheeses and margarine by mold. It is also used to impregnate packaging paper
for food products.
Sorbic acid strongly inhibits the growth of molds and yeasts on smoked fish, if
0.050.1% of this preservative is absorbed by fish tissues during their soaking in a brine,
which contains sorbic acid.
Usually, sorbic acid is used at a concentration of 0.020.2% of the weight of a product
and has no influence on its colour and taste within these limits.
In meat industry, sorbic acid did not find wide use; however, there is information that
it is used to inhibit the growth of mold on fermented sausages, for preservation of meat sal-
ads and edible gelatin coatings of meat products. A number of studies on the use of sorbic
acid for increasing the stability of meat products yielded positive results.
An aqueous 0.5% solution of sorbic acid was used to remove mold from the surface
of semi-smoked sausages. Wiping and rinsing of sausages in a solution of the acid made it
possible to increase the storage time by 59 days. The loaves wiped with the solution and
kept in it for 15 min could be stored 20 days more than those wiped with water. By adding
0.2% sorbic acid to sausage goods, their storage times can be increased by three days.
Treatment of the surface of raw pork and beef sausages, raw fish fillet, eviscerated
poultry etc. by immersion for 0.12 min into an aqueous solution of 0.15.0% sorbic acid or
its water-soluble salt and up to 0.2% antioxidant impedes microbial and oxidative spoilage.
The treatment of packaged fresh meat by sorbic acid and an antibiotic in combination
with ionizing irradiation is also efficient in inhibiting microbial spoilage.
Deceleration of microbial growth in beef at 2C, achieved by combining ionizing ir-
radiation (105 rad), oxytetracycline (1 mg%) and sorbic acid (0.1%), is shown in Table 1.4.
Table 1.4
Treatment Tenfold population growth, days

yeasts and molds bacteria

Control >20 25.5


Irradiation 3.59.0 46
Oxytetracycline 3 78
Sorbic acid >20 35
Irradiation + oxytetracycline 4 14
Irradiation + sorbic acid 817 817
Irradiation + sorbic acid + oxytetracycline 1523 1633

However, meat treated in this way is of much lower quality, dehydration is observed,
as well as undesirable changes of colour and decreased flavour.
A promising way of increasing the storage times of eviscerated and cooled poultry car-
casses in packagings is a two-stage treatment, which included acid hydration and use of sor-
CHAPTER 1 33

bic acid. Part of a carcass is treated for 2 h in an ice-cooled solution of 2-substituted sodium
phosphate. Herewith, pH < 5.5 is achieved on the surface. Then, after excess liquid leaks
off, the carcass is treated with a hot (70C) solution of sorbic acid. A mixture consisting of
70% propylene glycol, 20% water and 10% glycerine is used as a solvent. The sorbic acid
concentration of 0.11 mg per 1 cm2 of the product surface is achieved in 210 sec of driz-
zling. Control samples were spoiled in 5 days of storage at 7C, while test samples were
not spoiled in up to 18 days.
In some countries, it is permitted to add 0.1% sorbic acid and its sodium salts, which
are used along with sorbic acid, into animal fats (except butter), margarine, egg yolk or a
mixture of yolk and white. The solubility of the potassium salt in cold and hot water and
wateralcohol mixtures can be considerably decreased in the presence of cooking salt and
saccharose. They are active at pH 6 and lower.
Methods of commercial synthesis of sorbic acid have been developed in this country
to date. Sorbic acid possesses a high efficiency with respect to molds and yeasts.
Sulfur dioxide (SO2), sodium sulfite (Na2S03), sodium metabisulfite (Na2S2O5), sodi-
um bisulfite (NaHSO3) are soluble in water and are used as antimicrobial substances, as well
as for preventing the browning of food products.
In acute experiments on mice at the intravenous injection, LD50 was 130 mg/kg body
weigh for sodium bisulfite and 175 mg/kg for sodium sulfite.
Chronic experiments were performed in several groups of rats, 1824 animals in each
group. The daily ration given to rats for 12 years included sodium bisulfite in the amount
of 0.0125, 0.025, 0.05, 0.1, 0.25, 0.5, 1 and 2% of the feed. No toxic phenomena were found
in rats given 0.05% sodium bisulfite for 2 years.
Addition of sulfite to the feed at concentrations of 0.1% or higher caused growth inhi-
bition in rats, possibly as the result of the degradation of thiamine in the feed.
The dose causing no significant toxic effect in rats is 0.05% sodium bisulfite in the
feed, which is equivalent to 15 mg/kg body weight per day in terms of sulfur dioxide.
Sulfur dioxide found wide use for preservation of fruits, juices etc., but its application
for products of animal origin is very limited. In Russia, this preservative is permitted to be
added into food gelatin. The content of sulfurous acid in dry product should not exceed
0.1%.
In Norway, the content of sodium bisulfite in vacuum-packaged salt fish fillet is per-
mitted to be up to 0.14%.
In England, sulfur dioxide is permitted to be used for preservation of raw sausages in
the amount of 45 mg% of the weight of a product. In Scotland this addition of sulfur dioxide
is permitted for chopped raw meat for the three summer months.
The treatment of sausage filling with sodium metabisulfite (in terms of 0.5 g SO2 per
kg of filling) increases its storage time at 5C 2- or 3-fold. One of the undesirable pheno-
mena in SO2 treatment is, as was pointed out earlier, a considerable degradation of vita-
min B1.
It has been proposed to treat the surface of hen and duck carcasses with metabisulfite.
Carcasses are to be immersed into a bath with a 1% metabisulfite solution at a temperature
of 6366C and be held for 1 min. Then the carcasses are dried on a dressing rail and pack-
aged into boxes. The treated carcasses are stored 35 times longer than controls at 810C.
A method was recommended to preserve gut raw material using a 0.5% solution of
metabisulfite. The method is of particular importance for enterprises located in the thermal
belt or those that prepare guts for long-time storage and transportation. Thus, a six-month
storage of beef casings, bungs, rounds, hog and sheep casings as raw materials at a temper-
34 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

ature of 1524C and beef, hog and sheep casings as semifinished products at 2940C did
not lead to any deviations from the norm during the subsequent use in sausage production.
To preserve non-food raw material and condemned materials (from non-infected ani-
mals), not processed by meat-processing plants for dry animal feeds in the period of mass
livestock dressing, it is recommended to add dry sodium or potassium pyrosulfite
((Na2S2O5 or K2S2O5) in the amount of 2% of the weight of raw materials.
The same preservatives are proposed to be used for preservation of blood intended for
feeding, which was earlier preserved by potassium oxide or diluted sulfuric acid in the pres-
ence of cooking salt. Defibrinated blood preserved using 1% potassium pyrosulfite to the
weight of the blood can be stored for two months in the summer time at room temperature.
In gelatin production, sulfurous acid or hydrogen peroxide or both substances consec-
utively are usually used for preserving and whitening of high-quality broths intended for
producing photographic gelatin.
For preservation of glue, a number of preservatives are used, including sulfur dioxide
and sodium bisulfite.
Aliphatic acids. Fatty acids containing from 1 up to 14 carbon atoms are efficient in-
hibitors of molds. Propionic acid and its sodium and potassium salts prevent molding of
bread and baked products. Salts of propionic acid found use in dairy industry, in particular
in preventing molding on some types of packaged cheeses.
In meat industry, propionic acid and its salts found no use, because they deteriorate
the organoleptic properties of meat products. However, it is possible that further research
in this direction would find a possibility of using propionic acid and its salts for mold con-
trol in sausage production.
Formaldehyde, formic acid, salicilic acid, boric acid, borax, mono-, di- and trichloro-
acetic acids, hexamethylene tetramine (urotropin) etc. found application as food preserva-
tives. At present, their use is banned in most countries, but in some countries hexamethylene
tetramine, formic and boric acids are still permitted to be used for preservation of caviar
and other fish products.

1.4.4 Methods for identification of preservatives


Quantitative determination of preservatives in products is made by gravimetric, titrometric,
spectrophotometric, chromatographic and other methods.
A number of methods have been proposed for determining the content of sorbic acid
in products. In most of them, the acid is isolated from a product by steam distillation. The
distillate is used for the assay directly or is used to extract sorbic acid with ether to reduce
the effect of minor impurities present in the distillate. In some cases, sorbic acid is isolated
by extraction. However, this method is not applicable for fats and products containing large
amounts of fat.
In the distillate or extract, sorbic acid can be determined titrometrically.
A simple method is the iodometric determination of sorbic acid in distillates or extracts
from margarine, dairy products etc. The error of the method is 2.25.0%.
The widespread spectrophotometric method of determining sorbic acid in products is
based on the ability of sorbic acid solutions to absorb light in the ultraviolet region of the
spectrum. The light absorption maximum of the solution at pH 5.9 corresponds to the wave-
length of 256 m, and at pH 4.0, 262 m.
The spectrophotometric method of determining sorbic acid, developed for cheese, was
applied for other food products (bread, cakes, syrups, meat produces etc.).
CHAPTER 1 35

Later, a more precise spectrophotometric method was recommended.


The content of sorbic acid in margarine was determined by the light absorption in the
ultraviolet region of the spectrum at 260 m.
The basis of one of the spectrophotometric methods is the reaction of sorbic acid with
2-methyl-mercaptobenzthiazol-p-ethyl toluene sulfonate (benzthiazol), which leads to the
formation of a green product, whose light absorption is measured at a wavelength of
652 m. Other chemical preservatives benzoic, sulfurous, salicilic, formic, cinnamylic,
propionic acids and a mixture of p-oxybenzoic acid esters give no green coloration with
benzthiazol and do not prevent the determination of sorbic acid. The method is recommend-
ed for determining sorbic acid in food products (cheese, butter etc.).
The method of paper chromatography was proposed for determining the content of
preservatives in bread and baked products. Formic, propionic, benzoic, salicilic, sorbic,
p-chlorobenzoic, p-oxybenzoic acids and p-oxybenzoic acid esters were identified.
For separation of p-oxybenzoic acid and some of its esters, methods of paper chroma-
tography were also described, but they are lengthy and are inferior to thin-layer-chroma-
tography methods in this respect.
The method of thin-layer chromatography was successfully used to separate p-oxy-
benzoic acid and its methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, octyl,
nonyl, dodecyl, phenyl and benzyl esters. A mixture of 10% acetylcellulose and polyamide
(1:1, w/w) was used as the stationary phase; a two-component system consisting of a
hydrocarbon solvent and glacial acetic acid (50:10, v/v), as a mobile phase.
The separation of methyl and propyl esters of p-oxybenzoic acid was achieved on a
thin layer of silica gel using a mobile phase from a mixture of pentane and glacial acetic
acid.
A major part of the methods of determining sulfurous acid is based on its capability of
being readily oxidized. There are volumetric and gravimetric method of determining sulfu-
rous acid.
A comparatively exact and fast assay is the iodometric method of determining sulfur
dioxide using formalin, which binds sulfurous acid.

1.4.5 Fat antioxidants


Under the action of oxygen of the air, fats undergo oxidative processes, which even at the
early stages are accompanied by a decrease of nutritive value and subsequently lead to
spoilage (unpleasant odour and taste, sometimes change of colour and consistency of fat).
The modern views on the mechanism of oxidative reactions of organic substances are
based on the BachEngler peroxide theory and the theory of degenerate branched chain re-
actions by N.N. Semenov.
In accordance with the peroxide theory, the first product of oxidation of most organic
and many inorganic substances are peroxides. When peroxide is formed, two atoms of the
oxygen molecule still remain bound to each other. Therefore, in the oxygen molecule there
is no complete rupture of bonds between atoms, which would require a large consumption
of energy (117 kcal/mol). Thus, oxidation of organic substances via peroxide formation
proceeds comparatively easily.
Peroxides were found even in freshly produced fats, because their oxidation begins al-
ready at the technological processing: in preparation of raw fat for rendering, during the ren-
dering and in subsequent operations. Formation and accumulation of peroxides is greatly
affected by the method of rat production. Comparison of the results of peroxide numbers
36 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

determination for pork rendered fats, obtained by various investigators, shows that the per-
oxide numbers of a fat rendered in an open heater are 0.0130.035, and for that rendered
on a centrifugal machine, 0.0000.025.
The chemical composition of initial raw material and the changes that occurred in tech-
nological processing determine subsequently the rate of spoilage of fats in storage. The
spoilage rate of a fat present in food products also depends to a great extent on these factors.
Many investigators, in particular, by the example of oxidation of fatty acid esters, have
convincingly shown that at least at the first stages of oxidation all peroxide products formed
are hydroperoxides
R1 CH CH CH R2
OOH
In the formation of hydroperoxide, oxygen attacks the CH bond at the -position to
the double CC bond, which possesses an increased reactivity in oxidation processes. Ab-
straction of the -methylene atom H from the compound containing double bonds between
carbon atoms leads to the formation of active free radical CHCH=CH, which requires
an energy consumption of about 80 kcal/mol. This energy is required in the onset of the re-
action for breaking the CH bonds. The further development of the reaction by the chain
mechanism requires a very small amount of energy or no energy at all.
It has been proven experimentally that with the abstraction of the hydrogen atom the
double bond is not broken, but that this phenomenon is accompanied by the displacement
of double bonds in fatty acid molecules. Herewith, coupled double bonds
C C C C C C C C C C
appear in the molecules of polyunsaturated fatty acids (containing two or more double
bonds), which initially contained only isolated double bonds.
The possibility of the presence of cyclic peroxides
R1 CH CH R2
O O
in oxidation products has not been proven to date by direct methods. While hydroperoxides
were isolated and studied, cyclic peroxides were not, possibly because of their extreme in-
stability or because they do not exist. In most cases, the proof of the emergence of cyclic
peroxides at the advanced stages of oxidation is based on the determination of the general
content of peroxide compounds by the iodometric method and the determination of only
hydroperoxides by the polarographic method. However, the quantitative differences ob-
tained are within the limits of error of the determination methods.
Hydroperoxides are comparatively unstable compounds easily undergoing various
conversions, which lead to the rupture of the OO bond and the formation of free radicals.
The bond rupture energy in peroxides is considerably lower than in the oxygen molecule
and makes 3040 kcal/mol. As the result of dissociation or other conversions of peroxides,
the system forms more stable oxidation products as compared with peroxides the so called
secondary oxidation products aldehydes, ketones, low-molecular-mass acids etc. While
hydroperoxides have no smell or taste, many of the secondary oxidation products of rela-
tively low molecular masses are involved in the formation of a specific smell and taste of
spoiled fats.
The quantum yields determined in photochemical oxidation prove to be much larger
CHAPTER 1 37

than unity (according to Einsteins law of photochemical equivalence, one quantum of light
induces only one chemical reaction), which is a direct proof of the chain nature of the oxi-
dation reactions.
Other proofs of the chain mechanism of the oxidation processes can be the phenomena
of initiation (excitation) and retardation (inhibition) of the oxidation reactions. In the former
case, oxidation is accelerated in the presence of substances capable of decomposition into
free radicals; in the latter, of being inhibited by addition of minor amounts of substances
capable of interrupting the chain reaction of oxidation by capturing free radicals that lead
the oxidation chain. Oxidation of fats proceeds via formation of free radicals and pertains
to the class of slowly evolving chain branched reactions.
Free radicals are highly active particles. Reactions between free radicals and between
free radicals and molecules proceed easily; new free radicals are formed in the process to
continue the chain reaction.
It is well known that the smaller the activation energy E, the easier the reaction be-
tween two reacting chemical compounds is. If two molecular compounds participate in the
reaction, the magnitude of the activation energy is usually several tens of kilocalories per
mole. In the case of the reaction of free radical with a molecule, the magnitude of the acti-
vation energy is not large or equals zero, i.e., E is within the range of 010 kcal/mol.
Besides the reaction product (in this case, hydroperoxide), a new free radical (R) is
formed in the chain reaction mechanism. This radical again enters into the reaction and con-
tinues the initiated chain of chemical conversions. Herewith, more new molecules of the
initial substance are involved into the oxidation reaction. Thus, the development of the ox-
idation chain occurs and the involvement of new molecules of the fatty acid or triglyceride.
The chain of oxidative conversions develops until the chain-leading free radicals R
and RO2 disappear from the system, i.e., as the result of recombination of two radicals. An
inactive compound is formed, and the chain terminates. The sooner this happens, the less
fatty-acid or triglyceride molecules get oxidized.
Occasionally, the molecular product of the chain reaction in the system where the ox-
idation process occurs hydroperoxide breaks down to form new free radicals, i.e., the
chain branches, as each newly formed free radical initiates a new oxidation chain.
The slow development of the oxidation reactions is due to the fact that the branchings
of the chain in these reactions are as if retarded and occur only at times when hydro-
peroxides break down to free radicals. These retarded branchings are called degenerate
branchings.
Below, we present a generally accepted scheme of a degenerate branched chain
reaction:

RH + O2 R + HO 2 Chain initiation (formation of free radical R)


R +O RO 2
Chain continuation
RO 2 + RH RO2H + R
RO2H RO + OH Degenerate chain branching
RO 2 + RO2
R +R Chain termination
RO 2 + R
Here RH is the molecule of an oxidizing substance, e.g., a fatty acid; RO2H is the
hydroperoxide molecule; R and RO2 are free radicals leading the oxidation chain; RO and
OH are free radicals formed in the breakdown of the hydroperoxide.
38 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

0.5

Peroxide numbers, % iodine


0.4

0.3

0.2

0.1

0
0 5 10 15 20 25
Time, h

Figure 1.2 A kinetic curve of peroxide accumulation in oxidation of pork rendered suet. Oxidation
temperature, 90C.

The slow development of fat oxidation in the initial stage is due to the delay of chain
branching. This stage of oxidation is known under the name of the induction period or
initiation period.
However, at later stages of oxidation, when a large amount of free radicals accumulate
in the system, the oxidation process is sharply speeded up. The typical autocatalytic char-
acter of the kinetic curves for oxidation of fats and related substances is clearly seen by the
example of the oxidation of pork rendered fat.
The ability of hydroperoxides to break down to form free radicals, as well as the de-
pendence of the oxidation rate on the extent of oxidation in the cases when hydroperoxides
are basically the only reaction products, indicates that degenerate branching in liquid-phase
oxidation reactions is due to the breakdown of hydroperoxides in the reaction
ROOH RO + OH or 2ROOH RO 2 + RO + H 2O .

Below, we will show that oxidation of both melted and solid animal fat proceeds ac-
cording to the same kinetic law.
The rate of fat autooxidation is commonly characterized, not only in research but also
in practice, by the length of induction period, i.e., the length of time during which no pro-
nounced changes in them are observed. This period serves as a preparation to fast oxidation.
In the beginning of the induction period, there is no sign of any oxidation products acces-
sible to chemical determination, then peroxides start to be found, and at their sufficient
amount, due to the autocatalytic character of the process, oxidation begins to develop at a
very high rate, the induction period ends. Upon completion of the induction period, the per-
oxide accumulation curve sharply rises (see Fig. 1.2).
It should be pointed out that, in an ideal representation, the induction period should be
understood to be only that part of the segment of the curve in which peroxides are not found
by common chemical (or physicochemical) methods. In practice, in modern production pro-
cesses, it is difficult to obtain fat not containing peroxides found analytically. In the main,
freshly produced fats always contain peroxides in minor amounts. Therefore, for practical
purposes a more suitable definition of induction period is that, which is given initially. It is
all the more correct as the notion of induction period is conventional, because oxidative
changes not registered by chemical methods are observed in fats in the cases when the pres-
ence of peroxides is not yet possible to detect by common analytical methods. It is known
CHAPTER 1 39

0.5
3

Peroxide numbers, % iodine


2
0.4 1

0.3

0.2

0.1

0 2 4 6 8 10 12 14
Time, h

Figure 1.3 Kinetic curves of accumulation of fat samples taken at different stages of the techno-
logical process (oxidation temperature, 100C): 1, after rendering; 2, from the collector; 3, from a
container.

that hydroperoxides at a concentration of 10 6 mol/l can not be found by common chemical


methods.
At the same time, the kinetic methods make it possible to register changes in fat at very
early stages of oxidation. Studies of fat samples taken from the same commercial batch at
different stages of the technological process and containing no peroxides determinable by
the iodometric method (peroxides were found in none of the samples) showed that the sta-
bility of fat to oxidation as determined by the kinetic method (Fig. 1.3) was different.
Secondary oxidation products include comparatively stable intermediate and end
products of oxidation alcohols, carbonyl compounds, esters, acids, as well as compounds
with mixed functions, such as oxy acids, epoxy compounds etc.
It could be said that all secondary products of oxidation emerge as the result of con-
versions of hydroperoxides; what is more, part of the secondary products are formed im-
mediately at the breakdown of hydroperoxides and the other part, as the result of further
reactions.
The primary character of hydroperoxides as the first molecular products of oxidation
and the secondary character of carbonyl compounds, alcohols, epoxy compounds and acids
is graphically illustrated by curves plotted based on the literature data on the oxidation of
methyl oleate under the action of ultraviolet light at 35C (Fig. 1.4).
The mechanism of formation of secondary oxidation products has been little studied.
Only with a small fraction of probability, it could be suggested that ketones are formed from
hydroperoxides:
R1 CH R 2 + R R1 C R2 + RH
OOH OOH

R1 C R2 R1 C R2 + OH ,
OOH O
where R is either radical OH or any of the radicals leading the main chain of oxidation.
It is probable that alcohols are formed from hydroperoxides in degenerate branching
of chains
40 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

nmol O2 / 100 g nonvolatile


50
1

oxidized substrate
2

5 4
3
0 100 200
Time, h

Figure 1.4 Kinetic curves of oxidation of methyl oleate at the action of ultraviolet light: 1, peroxide
oxygen; 2, carbonyl oxygen; 3, hydroxyl oxygen; 4, oxirane oxygen; 5, carboxyl oxygen.

ROOH RO + OH
RO + RH ROH + R
One of the possible routes of forming epoxy compounds is the intramolecular reaction
of the hydroperoxide of the unsaturated compound
R1 CH CH CH R2 R1 CH CH CH R2
OOH OH O
According to one of the most probable points of view, acids can be formed from ke-
tones by their oxidation to -ketohydroperoxide, which subsequently breaks down to form
aldehyde and acid
H
R1 C CH2 R2 R1 C CH R2 R1C OH + R2 C
O
O O OOH O
It has been proven experimentally that acids are not formed directly from hydroperox-
ides and emerge as the result of the further conversion of secondary oxidation products,
most probably, ketones. As seen from the above reaction, formation of acids proceeds with
the rupture of the carbon skeleton of the molecule. Studies of the composition of the acids
formed in oxidation of fatty acids and hydrocarbons confirm this, because in practice only
acids with a shorter carbon chain than in the initial compound could be isolated from the
oxidizing mixture.
The described mechanisms of formation of secondary oxidation products are basically
hypothetical and were proposed mainly based on the studies of hydrocarbons of the olefin
and paraffin series. However, they can be accepted with an equal degree of probability for
oxidation of fatty acids.
This can be done based on that in such acids being part of fats as, e.g., oleic, linolic or
linolenic acids, oxidation at the initial stages affects carbon atoms removed from the ester
group by a chain of at least six methylene groups. Therefore, the ester group can have no
influence on the oxidation process, and oxidation proceeds the way it does in the respective
unsaturated hydrocarbon.
CHAPTER 1 41

1.0

mol O2 / mol ester


0.8

0.6 4 3 2

0.4

0.2
1

50 100
Time, h

Figure 1.5 Dependence of the rate of oxidation of fatty acids in the air at a temperature of 37C on
the number of double bonds in them: 1, ethyl oleate; 2, ethyl linoleate; 3, ethyl linolenate; 4, methyl
arachidonate.

1.0
mol O2 / mol ester

0.8

0.6 4 3 2

0.4

0.2
1

50 100
Time, h

Figure 1.6 Kinetic curves of oxidation of pork suet at different temperatures: 1, 90C; 2, 100C; 3,
110C; 4, 120C.

Products of oxidation of fats and oils, as well as fatty acids and their derivatives are
found to have oxidation products belonging to the same groups of organic compounds,
which were found in hydrocarbons of the olefin and paraffin series, i.e., alcohols, carbonyl
compounds, epoxy compounds, acids etc.
For instance, carboxyl compounds of oxidized fats identified by chromatographic,
spectrophotometric and other methods include n-hexanal, 2,4-decadienal, propionic alde-
hyde, 2-hexanon, 2-octanon, 2-nonanon, 2-decanon, n-pentenal, acetaldehyde etc.
The reactivity of fatty acids increases with the increase of the number of double bonds
in the molecule. Figure 1.5 shows a dependence of the oxidation rate of unsaturated fatty
acid esters on the number of double bonds.
Formation of free radicals in the system is facilitated with the temperature increase.
Herewith, the chain initiating rate and, therefore, the oxidation rate, increases. Kinetic
curves of pork fat oxidation illustrating this are presented in Fig. 1.6.
If chain initiation occurs mainly according to the reaction RH + O2, then the rate of
42 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

1.0

mol O2 / mol ester


0.8

0.6 4 3 2

0.4

0.2
1

50 100
Time, h

Figure 1.7 Effect of oxygen pressure on the rate of oxidation of ethyl linoleate at 45C.

initiation should depend on oxygen pressure. The occurrence of this dependence at small
conversion rates has been established in oxidation of ethyl linoleate. From Fig. 1.7, it fol-
lows that the rate of ethyl linoleate oxidation on oxygen pressure becomes pronounced at a
pressure less than 200 mm Hg. However, it should be noted that the pressure range in which
a pronounced dependence of the oxidation rate on oxygen partial pressure is still pro-
nounced can change within broad limits in transition from one compound to another.
Processes of oxidative spoilage of fats, as well as other chain reactions, are also affect-
ed by light and ionizing radiation, which contribute to the emergence of free radicals in the
system.
The action of light of certain wavelengths and especially UV light on fats increases
the rate of emergence of free radicals, which leads to a fast oxidative spoilage of fats.
In the use of ionizing radiations to increase the stability of meat and meat or other food
products in storage, the most serious negative consequence of irradiation is oxidation of
fats. The emergence of free radicals in the presence of oxygen leads to the formation of per-
oxide radicals RO2 and, therefore, peroxides and products of their conversion.
Variable valence metals iron, copper and others, which get into fats from the equip-
ment in their processing, are efficient catalysts of oxidation processes.
The catalytic acceleration of the oxidation reactions by these metals is based on that,
depending on the valent state, they can either attach an electron or donate it to any valent
saturated particle, which leads to the activation of radical breakdown of hydroperoxides ac-
cording to the following mechanism:

ROOH + Fe2+ Fe3+ + RO + OH


ROOH + Fe3+ Fe2+ + ROO + OH+
Iron is not consumed in this process and, therefore, being present as traces, it contrib-
utes to the emergence of radicals RO and RO2, which initiate the chain process of oxida-
tion. By the example of metal-catalyzed oxidation of methyl linoleate, it has been shown
that metals accelerate the oxidation process only in the presence of the peroxides of oxi-
dized material or of specially added peroxides.
From literature data, it follows that lead has the largest catalytic efficiency, which is
followed by copper, iron, tin, zinc and, finally stainless steel.
Traces of metals contribute to spoilage of animal fats, which is called tallowiness. In
practice, tallowiness is observed, e.g., in excessive intensive mechanical treatment of fats,
CHAPTER 1 43

owing to a lengthy contact with metal apparatuses or long-time storage of fat in a metal con-
tainer. Tallowiness occurs without a significant accumulation of peroxides. The main oxi-
dation products in this case are oxy acids and, possibly, polymerization products.
The catalytic activity of variable-valence metals increases considerably if they enter
into the reaction with some specific organic compounds, especially proteins.
Meat and blood pigments myoglobin and hemoglobin, as well as their derivatives are
strong catalysts of oxidation of lipids of meat, meat products, fatback.
This, in particular, is confirmed by the acceleration of linoleate oxidation in the pres-
ence of extracts of hog muscle tissue. Coagulation of proteins considerably decreases the
catalytic activity of meat pigments. Hemoglobins of different animals differ insignificantly
by their catalytic action on the process of linoleate oxidation.
A decrease of temperature contributes only moderately to the decrease of the rate of
oxidation catalyzed by meat and blood pigments.
Fresh meat pigments, as well as their derivatives are nonspecific catalysts, e.g., hema-
tin also contributes well to oxidation of hydrocarbons and also fatty acids.
Though fat oxidation catalyzed by heme compounds has been known since long, the
mechanism and chemistry of this process have not been made clear until now, possibly ow-
ing to the exceptional complexity of this phenomenon.
There is no doubt that both forms of iron (Fe2+ and Fe3+), which are components of
heme compounds, initiate the breakdown of hydroperoxides and, thus, accelerate oxidation
of fat. But there is also no convincing proof that the Fe3+-containing pigment is capable of
accelerating oxidation of lipids in the absence of hydroperoxides, though, according to the
literature data, this is believed to be possible.
The presence of oxidation products in fats is revealed, as well as the extent of the ox-
idation process is assessed by using chemical, spectrophotometric, chromatographic, po-
larographic etc. methods.
Methods of determining compounds of peroxide character have become widespread.
Especially frequently, the iodometric method of determining peroxides is used. The
ironrhodanide, indophenol, ironchlorideindophenol, polarographic, stannochloride
etc. methods are used more rarely.
The content of peroxides in edible fats and oils, as well as in food products is expressed
in different way. In the Russian Federation, it is accepted to express the content of peroxides
in percent iodine; in the UK, in millilitres of a 0.002 N solution of thiosulfate per gram of
fat (Lee number). In the USA, the peroxide content is expressed predominantly in mil-
liequivalents or millomoles of active oxygen of peroxides per 1000 g of fat.
There is a certain dependence between the magnitude of the peroxide number and the
organoleptic rating of the quality of fats and fat-containing products, because peroxides in
them accumulate in parallel with the emergence and development of rancid smell and taste.
In fatty tissue separated from a freshly killed animal, it is impossible to find fatty per-
oxides, because they are not a normal metabolic product in the animal organism. However,
fatty peroxides can be formed in the organism of the alive animal in pathological cases, e.g.,
under the action of ionizing radiation.
As we pointed out, peroxides emerge in fat during the technological treatment and stor-
age. Delays of the raw materials before rendering, high temperature, the presence of atmo-
spheric oxygen, the contact with metal equipment, long-time treatment, effect of light,
incorrect condition of storing the final product all these contribute to the emergence and
further accumulation of peroxides in fat.
The relation between the organoleptic evaluation of the extent of fat spoilage and the
44 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

content of peroxide compounds in it has been discussed in the literature over a period of
many years. Investigators proposed various values of peroxide numbers, which, in their
opinion, corresponds to organoleptically established spoilage.
The values of peroxide numbers characterizing the extent of oxidative spoilage of an-
imal rendered fats are in most cases inapplicable for assessment of the extent of oxidative
spoilage of other types of fats and oils, as well as fat-containing products. While the perox-
ide number of 0.1 in percent iodine, as a rule, indicates that the spoilage of pork, beef, mut-
ton and bone rendered fats did occur, the same magnitude of the peroxide number for
fatback, vegetable oils and many fat-containing products, including meat products, will be
organoleptically assessed as good-quality foodstuffs.
Methods of determining carbonyl compounds in autooxidizing fats are of great impor-
tance, as, on the one hand, the presence of these compounds indicates the extent of oxidation
and, on the other hand, testifies the development of rancid taste determined organoleptical-
ly. It is commonly accepted that aldehydes and ketones, together with low-molecular-mass
acids, are a cause of rancid smell and taste. Heptyl, nonyl, hexyl and butyl aldehydes have
long been referred to as substances, which determine rancid smell and taste of fats.
An unpleasant smell of meat and meat products formed under the action of ionizing
radiations depends to a significant extent on the presence of carbonyl compounds.
Carbonyl compounds in oxidized fats and those that are components of meat, meat
products and other food products are determined by methods based on the conversion of
carbonyl compounds to their bisulfite, hydroxylamine, diphenylcarbazide, 2,4-dinitrophe-
nylhydrazine and other derivatives. The methods using 2,4-dinitrophenylhydrazine are the
most widespread. The formed 2,4-dinitrophenylhydrazones of monocarbonyl compounds
and corresponding osazones of dicarbonyl compounds are converted, by addition of alkali,
into intensively stained quinoid compounds, whose light absorption is measured. Separa-
tion of the mixtures of carbonyl compounds into classes or individual compounds is done
by methods of column, thin-layer, paper and gas chromatography.
The reaction with 2-thiobarbituric acid is used in determining such a product of oxi-
dative spoilage of fats as malonic dialdehyde.
The content of ,-dicarbonyl compounds, which are characterized by stability in
heat treatment of fats, is determined by treating the fat under study by alkali during the heat-
ing. Then the fluorescence or light absorption of the solution is measured.
Epoxy compounds, which were found to emerge in pork fat only in utmost stages of
oxidation, are determined using methods of splitting the oxirane ring with anhydrous hy-
drogen chloride in absolute ether or with hydrogen bromide in glacial acetic acid followed
by titration with excess hydrogen chloride or bromide. A method of determination by trim-
ethylamine hydrochloride was also described.
More detailed information on the methods of quantitative determination and identifi-
cation of products of oxidative spoilage of fats can be found in a number of literature sourc-
es, which contain references to original papers.

1.4.6 Effect of oxidation on the food value of fats


In long-time storage of fats their quality deteriorates, which leads to a decline of category
quality (in some cases, edible fats are transferred into the technical-grade category) and re-
lated material damage. The terms of refrigerator storage of frozen meat depend primarily
on oxidation of fats. Fat oxidation often affects the quality of long-stored smoked sausages,
fatback, as well as fat-containing dried meat and concentrated feeds.
CHAPTER 1 45

However, considerably earlier, long before oxidation can be detected organoleptically,


the food value of fats begins to decrease. As the action of oxygen of the air affects easiest
of all the unsaturated components of fats, the first to get oxidized are polyunsaturated fatty
acids vital for the human and animal organism. Essential polyunsaturated acids are linolic,
linolenic and arachidonic acids. All these natural acids have a cis-configuration. All of them
have a strong biological action, owing to which they are united under the name of vitamin F.
Of polyunsaturated acids, arachidonic acid has the largest biological activity. It occurs
only in lipids of animal origin. Linolic and linolenic acids are synthesized by plants. In the
animal organism, they are capable of converting into arachidonic acid.
Linolic and linolenic acids are contained in large amounts in vegetable oils. Of animal
fats, considerable amounts of linolic acid occur in pork fat.
The data on the content of polyunsaturated fatty acids in fats of slaughter cattle are giv-
en in Table 1.5.
Table 1.5
Product Content of acid, % Number of
samples
linolic linolenic arachidonic studied

Rendered pork fat 9.940.72 0.570.15 0.620.16 11


Pork fatback 11.221.24 0.660.22 0.630.35 38
Fat of salted cooked ham 10.002.35 0.620.26 0.670.25 15
Rendered beef fat 2.810.50 0.630.18 0.110.03 7
Rendered mutton fat 3.090.61 0.920.14 0.100.03 4
Bone fat 4.130.96 0.910.15 0.140.01 4
Rendered camel fat 4.320.14 1.480.10 0.390.02 4
Rendered horse fat 11.771.74 5.381.91 0.260.01 4

The absence of polyunsaturated fatty acids in the food of rats was found to lead to der-
matites, loss of weight, interruption of growth, loss of hair; affection of kidneys, mammary
glands and other organs. At a prolonged insufficiency of vitamin F, animals die. A timely
delivery of polyunsaturated fatty acids into the organism protects animals from death.
As we have already pointed out, autooxidation of fats leads to the formation of hydro-
peroxides and a related displacement of double bonds. Unsaturated fatty acids with conju-
gated double bonds, e.g., 9,11-octadiene acid, possess no biological activity.
Along with a decrease in the amount of polyunsaturated fatty acids in autooxidized
fats, the content of fat-soluble vitamins A and E decreases. In coloured animal fats, provi-
tamin A carotene breaks down. If oxidation affects the fat being in contact with meat
and blood pigments (myoglobin, hemoglobin) or their derivatives, then the B-complex vi-
tamins thiamin, riboflavin, pyridoxine, biotin etc. also break down.
The food value of fats decreases not only in long-time storage, but also in heat treat-
ment. Profound chemical changes have been established to occur in heat treatment of fats:
formation and breakdown of peroxides, formation of compounds with conjugated double
bonds, increase in the content of free fatty acids, decrease of iodine numbers, increase of
viscosity, formation of epoxy compounds etc.
Many investigators have proven the harmful effect of oxidized fats on the animal or-
ganism. This issue is dealt with in numerous reviews. Intensive research is under way in
this field. For instance, it has been found that feeding chickens small amounts of oxidized
animal fat leads to the retardation of growth and sexual development. Substances isolated
46 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

from the unsaponifiable fraction of oxidized beef fat were found to cause chicken diseases
(ascites, hydropericardium, oedema) at their amounts of 10 5 106% in food.
Some authors postulated a relationship between the activity of various enzymes and
their sulfhydryl groups. In living organisms, these groups are associated with the functions
of muscle contraction, nerve activity etc. Inhibition of sulfhydryl groups of enzymes by lip-
id peroxides has also been postulated.
It has been experimentally found that SH groups of cysteine, glutathione and also pa-
pain get totally oxidized in the presence of linolic acid peroxides.
It is believed that the harmful effect of oxidized fats on the organism is determined
mainly either by their direct toxic effect or by the degradation of vital components of food
they cause due to oxidation. There is no common point of view on this issue yet, and it is
still debated in the literature.
The toxicity of hydroperoxides isolated in pure form was established by direct exper-
iments. Besides, it is known that inclusion of more than 1% rancid fat into the ration of pig-
lets leads to the development of symptoms of vitamin E insufficiency. Inclusion of oxidized
(at 180C) soybean oil into the ration has the same effect as insufficiency of vitamin E, and
leads to the decrease of the content of polyunsaturated fatty acids in organs and tissues of
animals, which stipulates the vitamin E insufficiency.
Thus, there is no doubt as to the harmfulness of oxidized fats both as the consequence
of the loss of food value and of the accumulation of oxidation products which inflict harm
to the human and animal organism.

1.4.7 Inhibition of autooxidation processes


The oxidation reaction, as any chain reaction, can be inhibited by adding inhibitors, in this
case oxidation inhibitors, or antioxidants.
Antioxidants inhibit the chain process of oxidation by entering into reaction with free
radicals RO2 or R and, thus, break the oxidation chains.
Schematically, the mechanism of action of antioxidants can be presented as follows:

InH + RO 2 RO2H + In ,

where InH is antioxidant; RO2 is free hydroperoxide radical; RO2H is hydroperoxide of,
e.g., a fatty acid, In is free radical of the antioxidant.
As a consequence of the principle of the indestructibility of free valence, a new free
radical emerges from the antioxidant, but this radical possesses a very small activity and is
not capable of participating in chain continuation. The reaction is broken, and oxidation is
inhibited. The free radical enters into the recombination reaction with other low-active free
radicals to form a stable product, In + In In In.
Herewith, one molecule of antioxidant is consumed for each chain-breaking act, and,
therefore, its concentration constantly decreases in the process of oxidation. After all inhib-
itor is consumed, the chain process is resumed and will develop at almost the same rate as
before the inhibitor was introduced.
Figure 1.8 presents kinetic curves characterizing the accumulation of peroxides in pork
fat with an antioxidant and the decomposition of the antioxidant as the result of oxidation.
Another reaction of the death of low-active free radical In is possible in the case of its
emergence from substances of phenolic nature. If the concentration of free radicals RO2 or
R is large, they can interact with low-active free radicals of the inhibitor
CHAPTER 1 47

Content of antioxidant, mg %
Peroxide numbers, % iodine
0.30
1
0.25 25
0.20 20
0.15 15
0.10 10
0.05 2 5
0
2 4 6 8 10 12 14 16 18
Time, h

Figure 1.8 Kinetic curves, which characterize accumulation of peroxides in pork fat with an anti-
oxidant and its breakdown as the result of oxidation at 110C: 1, peroxide numbers; 2, content of
butyloxytolyene.

In + RO 2 InRO2
or
In + R InR.
From the chain theory of inhibition of oxidation processes it is seen that inhibitors
should be introduced at an earlier stage of the technological process of fat production, when
free radicals in the system are not many. Some antioxidants are capable of inhibiting the
process at sufficiently advanced stages of oxidation, but they are quickly consumed, so their
action is short.
By the example of inhibiting pork fat at the stage of rather well advanced oxidation,
the possibility of inhibiting the oxidation reaction was shown, but if the antioxidant were
introduced into fat at an earlier stage of oxidation, its efficiency would have been several
times larger. This is illustrated by the kinetic curves of Fig. 1.9.
The chain reaction of oxidation could be inhibited not only by increasing the break-
down of chains, as it takes places in the case of phenolic and some other antioxidants
(quinones, amines), but also by decreasing the rate of free radical formation by the degen-
erate branching reaction. Introduction of substances (e.g., some thio compounds), which in-
teract with hydroperoxides without forming free radicals, into the oxidizing system also
makes it possible to reduce the oxidation reaction rate.
Sulfurous compounds are much less active in inhibiting the oxidation processes than,
e.g., antioxidants of the type of alkylphenols, even if they are introduced in considerable
amounts. However, being added into the oxidizing system together with an antioxidant of
phenolic nature, they enhance the efficiency of its action significantly. Herewith, the length
of the induction period proves larger than the sum of the induction periods stipulated by
each substance separately.
This non-additive antioxidative action of a combined addition of two (or more) sub-
stances was called synergism.
In processes of inhibited oxidation, synergists are commonly substances, which by
themselves either possess no antioxidative action at all, or are weak antioxidants but en-
hance the efficiency of action of other inhibitors.
48 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Peroxide numbers, % iodine


0.16
1
4 3
0.12

0.08

0.04

0 2 4 6 8 10 12
Time, h

Figure 1.9 Kinetic curves of oxidation of pork fat at 100C in the presence of 0.01% butyloxyanisol
introduced into fat at various stages of oxidation: 1, initial, oxidized up to the peroxide number; 2,
0.008; 3, 0.026; 4, 0.045.

Synergists include thio compounds, phosphatides, some organic and inorganic acids,
amino acids, polyphosphates etc.
The listed groups of substances are so diverse from the chemical point of view that one
can not assume the existence of a synergic-action mechanism common for them.
One thing is considered to be undoubted, though, that in the case of a synergism each
of two components is involved in the oxidation inhibition process in a different way.
For some synergists, a credible view of the mechanism of their action is as of hydrogen
donors, which leads to the restoration of the initial form of the antioxidants. For instance,
the reversible conversion of quinones to hydroquinones creates a possibility, when the same
molecule of the inhibitor breaks several chains. This mechanism of the process is what ex-
plains a sharp increase of the efficiency of action of the inhibitor.
The synergic action of some amino acids is stipulated by their ability to reduce oxi-
dized phenolic antioxidants.
Ascorbic acid and its fatty-acid ethers are readily oxidized and reduced
OH OH O O
2H
C C C C
+2H

Due to their ability to donate hydrogen atoms, these compounds can regenerate oxi-
dized phenolic antioxidants. Simultaneously, ascorbic acid is a metal deactivator, forming
neutral monometal salts at the expense of one of the enol atoms of hydrogen.
Metal deactivators are substances, which inhibit the catalytic activity of metals. Deac-
tivators are used in the cases when the oxidizing system in the process of oxidation is in
contact with the metal surface and, corroding it, forms salt catalysts from variable-valence
metals.
A strong metal deactivator is citric acid, which forms complex compounds with metal
ions. These compounds are capable of binding iron traces occurring in fats and take them
out of the reaction. Polyoxycompounds sorbitol, sugars and their derivatives also pos-
sess an ability to bind metals.
CHAPTER 1 49

Owing to the synergism between oxidation inhibitors, there is a possibility of increas-


ing the antioxidative efficiency of a number of substances and, besides, decreasing their
concentration in the oxidizing system. The use of additives, which deactivate traces of
variable-valence metals in many cases getting into a product in the process of production,
enhances the inhibition of the oxidation process even more.
Thus, studies of the mechanism and chemistry of the oxidation processes and their in-
hibition enabled practical applications of particular antioxidants and efficient antioxidative
compositions for increasing the storage times of fats, and in some cases, of fat-containing
products.

1.4.8 Characteristics and application of antioxidants and synergists

At present, a large amount of substances possessing the properties of oxidation inhibitors


are used in practice.
Storage times of edible fats and technical fats, as well as fat-containing food products
are extended using individual antioxidants, mixtures of antioxidants, as well as composi-
tions of one or several antioxidants with various synergists and metal deactivators.
A commercial product butyloxyanisol (BOA) consists of a mixture of two isomers:
2- and 3-tert-butyl-4-oxyanisols (3- and 2-tert-butyl-4-methoxyphenols).
OCH3 CH OCH3
3

C CH3 CH3
C CH3
CH3
OH OH CH3
2-tert-butyl-4-oxyanisol 3-tert-butyl-4-oxyaniso

The ratio of the isomers depends on the manufacturing method of BOA. The 3-isomer
possesses a slightly larger antioxidative efficiency than the 2-isomer. Both isomers exhibit
some synergism, so that the mixtures containing a large amount of isomer are close to pure
3-tert-butyl-4-oxyanisol by their efficiency. In commercial mixtures, the content of 3-iso-
mer is no less than 85%. The antioxidative efficiency of butyloxyanisol increases up to a
concentration of 0.02% in the substrate.
Butyloxyanisol is represented by waxlike crystals of cream or rose-cream colour,
which possess a phenolic smell. The melting temperature of the mixture of isomers is
4855C. Each isomer melts at a temperature of about 65C.
Butyloxyanisol does not change the colour of food products and at small concentra-
tions has no effect on their taste and flavour. It is rather stable to the action of high temper-
atures and can be added into products subjected to searing, boiling and baking. It is also
capable of inhibiting oxidation of not only pure fats, but also fats added into products. The
solubility of butyloxyanisol at 25C is as follows (in percent): in water, 0; ethyl alcohol, 25;
pork rendered fat, 50; propylene glycol, 50; cotton oil, 30; peanut oil, 40.
At a concentration of 0.010.02%, butyloxyanisol was proved by several investigators
to protect pork rendered fat from oxidation well (Fig. 1.10).
Butyloxyanisol is widely used alone or in combination with other antioxidants
nordihydroguaiaretic acid, propyl gallate, butyloxytolyene, tocopherol to inhibit oxida-
tive processes in animal fats and fat-containing products. The efficiency of action of the
50 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

0.20

Peroxide numbers, % iodine


0.16 2

0.12

0.08

0.04

0
0 2 4 6 8
Time, h

Figure 1.10 Kinetic curves of oxidation of pork fat at 100C: 1, no antioxidant; 2, with 0.01% butyl-
oxyanisol.

antioxidant is enhanced by adding such synergists as citric acid, triethylphosphate,


methionine, lecitin and thiodipropionic acid.
An idea of the synergistic effect of a mixture of butyloxyanisol and thiodipropionic
acid added to lard can be given by the data presented below.

Inhibitor Induction period, h

No additives 2
0.01% butyloxyanisol 38
0.01% thiodipropionic acid 19
0.01% butyloxyanisol + 0.01% thiodipropionic acid 81

Butyloxyanisol in combination with other antioxidants and synergists inhibits rancid-


ification of fats in pork, turkey, in various fish-liver oils, and in diverse vegetable oils, in
fried potatoes, and in dough items.
Pork rendered fat used for frying some chips, alone or in combination with vegetable
oils, should be subjected to obligatory antioxidant treatment. Usually, a composition of bu-
tyloxyanisol, propyl gallate and citric acid is used, which is introduced either into the frying
fat, or into salt, or partially into the fat and salt. Approximately 0.1% of the antioxidant com-
position is added.
Butyloxyanisol proved an efficient antioxidant of packaging materials intended for
storage of fat-containing products, dehydrated soups, as well as frozen pork. A mixture con-
sisting of butyloxyanisol, nordihydroguaiaretic acid and ascorbic acid increases the stability
of chopped pork and turkey.
Addition of 0.003% butyloxyanisol and 0.001% citric acid to dry-cured sausages is
permitted in the USA.
Investigation of the toxicity of butyloxyanisol enables assigning it to the group of
CHAPTER 1 51

Peroxide numbers, % iodine


0.20
1 2
0.16
0.12
0.08
0.04
0
0 2 4 6 8 10 12 14 16 18 20
Time, h

Figure 1.11 Kinetic curves of accumulation of fat peroxides in oxidation of beef fat: 1, no antioxi-
dant; 2, in the presence of an antioxidant mixture (0.01% BOT + 0.005% PG + 0.005% citric acid).
Oxidation temperature, 122C.

low-toxic food supplements. The acute-toxicity test of this inhibitor showed its LD50 for
rats to be within 29005000 mg/kg weight and for mice 12502000 mg/kg weight.
A prolonged feeding of animals the food containing a moderate amount of butyloxy-
anisol did not lead to any deviations in their organism.
The dose causing no significant toxic effect in rats is 0.5% BOA in food, which is
equivalent to 250 mg/kg body weight per day.
Butyloxytolyene (2,6-di-tert-butyl-p-cresol; 2,6-di-tert-butyl-4-methylphenol) is a
screened phenol. Depending on its purity and manufacturer, it is known under the names of
BHT (BOT), Ionol CP (ionol), antioxidant AC-1, AC-3, topanols OC, A, O etc.
CH3
CH3 CH3
CH3 C C CH3
CH3 OH CH3
2,6-di-tert-butyl-p-cresol

Butyloxytolyene is represented by colourless crystals without taste and smell with the
melting temperature of 70C. Butyloxytolyene is not soluble in water and propylene glycol,
but is well soluble in fats. At 25C, 40% of the antioxidant dissolves in pork rendered fat
and beef fat. The presence of iron traces does not change the colour of products.
The crude preparation has a yellow colour and characteristic smell. It is purified by
vacuum distillation followed by recrystallization from ethanol or only recrystallization, de-
pending on the impurity of the antioxidant.
In the UV region of the spectrum, butyloxytolyene has two absorption maxima at
wavelengths of 284 and 277 m.
Butyloxytolyene alone or in a mixture with other antioxidants and synergists (buty-
loxyanisol, propyl gallate, citric acid) increases the resistance to oxidation of beef fat, pork
fat, milk fat and butter, cotton oil and shortenings.
An antioxidative mixture consisting of butyloxytolyene, propyl gallate and citric acid
increases the resistance to oxidation of beef fat ninefold (Fig. 1.11), as well as protects
against oxidation carotene contained in fat. A pronounced synergic effect is observed at the
combined presence of butyloxyanisol and butyloxytolyene in lard.
52 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Peroxide numbers, % iodine


0.7
1
0.6 2
0.5
0.4
0.3
0.2
0.1 3
0
0 2 4 6 8
Time, h

Figure 1.12 Kinetic curves of accumulation of peroxides in oxidation of a mixture of ethyl esters of
linolic and linolenic acids: 1, control; 2, with 0.02% BOT; 3, with 0.3% BOT. Oxidation temperature,
60C.

The antioxidative properties of BOT are carried over to products, e.g., biscuits con-
taining fats produced with this antioxidant; however, this effect is smaller than with BOA.
The efficiency of action of BOT increases with the increase of its concentration in the
substrate.
Butyloxytolyene inhibits the development of oxidation not only in edible fats but also
in most diverse systems subject to oxidation: resins, technical fats, waxes, oils, plastics etc.
At large concentrations, butyloxytolyene inhibits oxidation even in such readily oxi-
dizing systems as mixtures of linolic and linolenic acid esters (Fig. 1.12). It is also used as
an antioxidant of packaging materials intended for storage of fat-containing products.
Butyloxytolyene homologues 2,6-di-tert-hexyl-, 2,6-di-tert-heptyl- and 2,6-di-tert-
octyl-4-methylphenols are no less efficient, and 2,6-di-tert-amyl-4-methylphenol is more
efficient as an antioxidant of pork rendered fat than 2,6-di-tert-butyl-4-methylphenol.
Acute toxicity studies of BOT on rats showed its LD50 to be within the limits of
17002450 mg/kg weight; for mice this value was 2000 mg/kg body weight. The content
of up to 0.8% BOT in rat ration does not lead to significant pathological changes provided
the content of fat in the feed is less than 5%. Addition of 10 or 20% lard to the food enhanced
the harmful effect of BOT.
As the result of long-time toxic studies of this antioxidant on animals, it was concluded
that it can be used as a food supplement, though it is considered to be necessary to continue
studies, in particular, on the effect of BOT on lipid metabolism.
Gallic acid (3,4,5-trioxybenzoic acid) is a constituent part of tannin and is contained
in tea and pomegranate juice:
OH

HO OH

COOH
Gallic acid

Gallic acid is a white powderlike substance, which darkens in the light. It melts at a
temperature of 235C (to decomposition). It dissolves in water, ethyl alcohol and is poorly
soluble in fats. In the presence of iron, it stains blue-black.
CHAPTER 1 53

Gallic acid is a very strong phenolic antioxidant capable of acting synergistically with
other antioxidants. Its antioxidant efficiency in stabilization of carotene of animal fats and
vegetable oils proved to be high. In spite of this, its addition into edible fats is not permitted.
Possibly, this is due to the fact that, being well soluble in water, it dissolves in fats very
poorly. Esterification of the carboxyl group of gallic acid by normal aliphatic alcohols
makes it possible to improve its solubility in fats and to decrease its solubility in water.
Lower esters of gallic acid are poorly soluble in water and fats, higher esters are in fact in-
soluble in water but are comparatively well soluble in fats.
Propyl gallate PG (normal propyl ester of gallic acid):

OH

HO OH

CO OC3H7

Propyl gallate

Propyl gallate is a light-cream fine crystalline powder without smell with a light bitter
taste. Its melting temperature is 146148C. In concentrations applied, it does not affect
the organoleptic properties of fat. In the presence of iron traces, this antioxidant stains the
product. The emergence of a blue-black coloration it can be eliminated or weakened by cit-
ric acid or another metal deactivator. Propyl gallate dissolves in ethyl alcohol, propylene
glycol, glycerol and is rather poorly soluble in fats and oils. It inhibits efficiently the oxi-
dation of pork rendered fat, milk fat, herring oil, cotton oil. It is also successfully used in a
mixture with other antioxidants and synergists (BOA, citric acid). Propyl gallate lends a
high resistance to oxidation to neutral and slightly acidic fats and fatty products, not subject
to the action of high temperatures. It is unstable to heating and the action of weak alkali.
The decomposition rate of propyl gallate in lard was studied under conditions of broil-
ing. The data of this study are given in Table 1.6.
Table 1.6

Heating time, h Content of propyl gallate in lard, %, at temperature, C

162 190

0 0.0058 0.0058
1 0.0052 0.0048
2 0.0050 0.0037
8 0.0032 0.0008
16 0.0002 0.0000

The antioxidative activity of gallic acid ethers (isoamyl gallate, nonyl gallate, butyl
gallate, methyl gallate, propyl gallate) in pork fat are characterized by the data presented in
Fig. 1.13. Addition of 0.01% of each gallate increased the resistance of fat to oxidation
68-fold.
Octyl and dodecyl gallates (esters of gallic acid with n-higher fatty alcohols octyl
and dodecyl alcohols):
54 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

0.20

Peroxide numbers, % iodine


1 2 3
4
0.15 5
6

0.10

0.05

0
0 1 3 5 7 9 11 13 Time, h

Figure 1.13 Kinetic curves of accumulation of peroxides in oxidation of pork fat with additives of
different gallates: 1, control; 2, isoamyl gallate; 3, nonyl gallate; 4, butyl gallate; 5, methyl gallate; 6,
propyl gallate. Oxidation temperature, 110C.

OH OH

HO OH HO OH

CO O C6H17 CO O C12H25

Propyl gallate Dodecyl gallate

By their appearance, both antioxidants are crystalline substances of light-cream colour


without smell, with a weakly bitter taste. They have no effect on the organoleptic properties
of fat. The melting temperature of octyl gallate is 9495C; of dodecyl gallate, 96.597C.
These esters are almost insoluble in water, well soluble in glycerol, ethyl alcohol and
satisfactorily soluble in fat.
Octyl and dodecyl gallates in the presence of iron and its salts change the coloration
of food products. To eliminate the coloration, it is recommended to use metal deactivators.
Higher gallates are widely used for protection of fats and fat-containing products from
oxidation. They also inhibit the oxidation of fat-soluble vitamins and carotene.
Higher gallates are added to edible fats in various amounts depending on the purpose
of the product. Addition of 0.005% octyl gallate to lard increases its storage time up to ap-
proximately one year; and of 0.01%, up to two years.
Higher gallates inhibit well the oxidative processes in pure fat, as well as in fats present
in food products. They are efficient for protection from oxidation of dry dairy products.
The data on the toxicological studies of propyl, octyl and dodecyl gallates are consol-
idated in materials of the World Health Organization. According to these data, acute toxic-
ity of these compounds in peroral introduction to animals is as follows:

Antioxidants Animals LD50 (mg/kg weight)

Propyl gallate Mice 20003500


Propyl gallate Rats 36003800
Octyl gallate Mice/rats 4700
Dodecyl gallate Mice/rats 6500
CHAPTER 1 55

According to other data, LD50 for propyl gallate is 1700 mg/kg weight for mice and
2600 mg/kg weight for rats. However, chronic experiments have found a slight adverse ef-
fect of this compound. A retardation of growth and lower resistance to partial starvation was
observed in rats given fat with propyl gallate in their diet.
No essential differences were found between control and test groups of three genera-
tions of rats given a diet containing 7% of fat and 0.2% of octyl and dodecyl gallates.
Experiments on long-time feeding (over the space of 13 months) white rats a higher
dose of dodecyl gallate (0.4% in the ration) did not lead to a change in the behaviour and
appearance of rats; no difference in weight was observed, either.
The data of a morphological study of the blood as well as the hemoglobin content in
the blood varied in rats of the test and control groups within the same limits. No effect of
dodecyl gallate on the redox enzymes of the blood was found; there were no changes in the
organs of test-group animals.
Based on the studies conducted, no harmful effect of fat with dodecyl gallate on test
animals was revealed.
The dodecyl gallate concentration of 0.01% (twenty times smaller than in the test an-
imals) in edible fats can be considered permissible.
Nordihydroguaiaretic acid (NDGA) is contained in considerable amounts in leaves
and stems of the plant Larrea divaricata:

OH OH
CH3 CH3
HO CH2 CH CH CH2 OH

NDGA

NDGA 4,4(2,3-dimethyl tetramethylene)-dipyrocatechin.


NDGA is a white or yellow-gray crystalline powder with the melting temperature of
184185C. At a concentration of up to 0.1%, it does not change the colour, taste and smell
of pork rendered fat.
NDGA is weakly soluble in water and diluted acids. Its solubility in fats is about 0.5%,
but upon heating up to 125150C it reaches approximately 5%. In cooling, a major part
of NDGA is precipitated, but about 1% remains in fat in a dissolved form or in the form of
thin suspension. It can also be introduced into fat in ethyl alcohol or acetic acid followed
by their removal by heating under vacuum.
NDGA imparts high stability to oxidation to neutral and weakly acidic products, does
not form coloration in the presence of iron. In some cases, it lends a product a slightly bit-
terish taste in long-time storage. NDGA is unstable to the action of high temperatures (in
broiling) and weak alkali.
A number of works note a high antioxidative efficiency of NDGA in stabilization of
lard, beef fat, bacon, carotene, vitamin A, cow butter.
NDGA is used together with synergists (ascorbyl palmitate; phosphoric, ascorbic and
citric acids) to increase the stability of lard, bacon and other products. Introduction of
thousandth fractions of a percent of NDGA to the fat part of bacon ensures a significant
antioxidative effect.
Only to a very minor extent, the antioxidative efficiency of NDGA is transferred to the
product into which NDGA-containing fat is added. It inhibits very well the oxidation in
waterfat systems, especially in the presence of synergists. In this case, it inhibits the
56 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

0.15
Peroxide numbers, % iodine 1

0.10

0.05 2
3

0 4 8 12 16 20 24 28 32 36 40
Time, h

Figure 1.14 Kinetic curves of oxidation of pork fat at 90C): 1, no antioxidant; 2, with 1% toco-
pherol; 3, with 0.1% tocopherol.

development of oxidative spoilage catalyzed by meat and blood pigments and their
derivatives.
The toxicological study of NDGA has shown that LD50 for mice is within the limits
of 20004000; for rats, 20005000; for guinea pigs, 830 mg/kg body weight.
Chronic experiments carried out in limited quantities have not led to more or less un-
equivocal results, which does not make it possible to give a toxicological evaluation for
NDGA and at the same time to set a permissible daily dose for man.
Tocopherols (vitamin E). By their chemical structure, they are derivatives of 6-oxy-
chroman.
CH3
CH8 CH3
HO
CH2(CH2CH2CHCH2)2CH2CH2CHCH3
CH3 O CH3
CH3

-Tocopherol (5,7,8-trimethyl tocol)

Tocopherols are widespread in nature.


Besides -tocopherol, other tocopherols have been isolated from natural sources:
-tocopherol (5,8-dimethyl tocol), -tocopherol (7,8-dimethyl tocol), -tocopherol
(8-methyl tocol) etc.
Vitamin E is a rather stable compound. It is stable to the action of high temperatures,
prolonged boiling in water, but is decomposed by UV light and some oxidants.
Vitamin E is soluble in oils and fat solvents.
Tocopherols are natural antioxidants of fats, apparently, preventing the formation of
peroxides in the living organism.
Fats isolated from the animal organism or from plants is the stronger to rancidification,
the more tocopherols they contain.
Animal fats contain 0.23 mg% of tocopherols; in vegetable fats, they are 90280
mg%, i.e., the almost optimal concentrations. Therefore, tocopherols stabilize animal fats
well and are inefficient for vegetable oils.
CHAPTER 1 57

The antioxidative efficiency of tocopherols is higher at low concentrations. Their in-


troduction into fats at too high concentrations not only fails to enhance the antioxidative
effect, but in some cases leads to an adverse change of organoleptic parameters.
The increase of the stability of pork rendered fat, into which a 0.1% concentrate of vi-
tamin E obtained by the method of molecular distillation from soybean oil was added, is
indicated by the data presented in Fig. 1.14.
Tocopherol isomers are not equivalent by their antioxidative efficiency, and it is not
proportional to their vitamin activity. For pork fat, the most efficient antioxidant is -toco-
pherol, but -tocopherol is also successfully used for this purpose.
Feeding animals with tocopherols also increases the stability of fat and fatty meat to
oxidation. However, only a minor part of tocopherol is preserved in fat.
Tocopherols were found to stabilize fats present in baked and fried products.
A large number of works deal with stabilization of fats by various compositions of
plant origin, which contain vitamin E (extracts of vitamins from wheat, a petroleum-ether
extract from maize grains, oil of wheat and maize seedlings).
Soybean flour, maize and barley flour, rice bran, rye and pea flour, flour from cotton
seeds, cocoa seeds, oats flour possess antioxidative properties.
Oats have been found recently to contain aliphatic alcohol-esterified 3,4-dioxy-
cinnamoyl (caffeoyl), which possesses an antioxidative activity. The following esters were
isolated: 1-caffeoyl glycerol, 1-palmitoyl 2,3-dicaffeoyl glycerol and 1,2,3-tricaffeoyl gly-
cerol. Their antioxidative activity in oats oil is similar to the activity of propyl gallate and
BOT.
Besides these antioxidants, many other substances and groups of substances have been
proposed, which possess antioxidative properties.
Eugenol and its derivatives possess good antioxidative properties with respect to soy-
bean oil and citrus ether oils. The raw material for eugenol is ether oil of colluria and basil
oil. Sesamol attributed to the group of phenols (3,4-methylene dioxypenol) was obtained
from the unsaponifiable shelf fungus of gingili oil. By the efficiency of action in lard, it is
not inferior to nordihydroguaiaretic acid.
The antioxidative properties of 2,4,5-trioxyphenons have been studied. Antioxidants
of this type were proposed for fats, carotene and other products, as well as for preparing
feeds with fat for poultry and cattle. Ethoxyquine (2,2,4-trimethyl-6-ethoxy-1,2-dihydro-
quinolin) was proposed as a better feed antioxidant for protection of carotene of dried alfalfa
and carotene and vitamin A in mixed feeds. In the USA, it is permitted to be added into
poultry feed. Butyloxytolyene can also be used for inhibition of oxidation of animal fats
added into feeds, or to be added into feeds in a finely ground form.
Conidendrin is an antioxidant belonging to the group of polyphenols; it occurs in res-
inous trees. By its antioxidative efficiency for lard, it is close to nordihydroguaiaretic acid.
Guaiacum resin has been used for many years in some countries (USA, Austria, Canada
etc.). It also inhibits the oxidation of fats in dehydrated pork and frozen meat.
The antioxidative efficiency of tannins has been confirmed by patent applications and
research work. Many natural spices possess antioxidative properties; they slow down ran-
cidification of fats, including in chopped frozen pork and beef.
The antioxidative properties of many kinds of spices (cloves, rosemary, sage, ginger,
black pepper etc.) have been found. The lipid fractions of tomatoes and carrots possess an-
tioxidative properties.
The antioxidative properties of some substances belonging to the group of flavonoids
(quercitin, dihydroquercitin, pomiferin, catechin) have been studied. Upon addition of 0.1%
58 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

1.000

0.900

TBA numbers 0.800

0.700 1

0.600
2
0.500 3

5 4
0.400

0.300
10 20 30 40 50 60 70 80
Time, days

Figure 1.15 Dependence of the amount of oxidation products reacting with TBA on storage time of
sausages stabilized by (concentration of antioxidants, 0.02%): 1, control; 2, butyloxyanisol; 3, ascor-
bic acid; 4, sodium gentisate; 5, gentisic acid.

each of quercitin and propyl gallate to fats, the antioxidative effect was the same. Quercitin
inhibits the oxidation of pork fat in the presence of copper(II) no less satisfactorily than bu-
tyloxytoluene, owing to the ability of flavonoids to form complexes with heavy metals.
Crystalline amino hexose reductons obtained from hexoses and secondary amines
were found to have a high antioxidative activity in various animal fats.
Smoking fluids were found to possess rather strong antioxidative properties due to the
content of phenols in them.
In the recent years, gentisic acid (2,5-dioxybenzoic acid) and its sodium salt were
again proposed as antioxidants of lard and other edible fats. The efficiency of these sub-
stances in the inhibition of oxidation of lard is the same as that of butyloxyanisol. They in-
hibit the oxidative processes in unsalted frozen bacon and sausages. The comparative
evaluation of gentisic acid, sodium gentisate, ascorbic acid and butyloxyanisol are present-
ed in Fig. 1.15.
Esters of sorbic acid propyl, allyl, butyl, isoamyl, hexyl, nonyl and decyl were pro-
posed as substances inhibiting the oxidation of hydrogenated whale blubber. It is seen in
Fig. 1.16 that each of the esters studied possesses an ability to increase the stability of hy-
drogenated whale blubber in storage. There are yet no data as to whether these compounds
can be considered as antioxidants or should be attributed to synergists.
Frequently, additives possessing the properties of synergists are introduced into anti-
oxidative compositions. Many of them are metal deactivators.
Some acids and their derivatives. Citric acid. Many works note the positive effect
of citric acid on the stability of fats and oils in storage. Citric acid forms soluble complex
compounds with metal ions. Application of this acid is made difficult by the fact that it is
not soluble in fats and is to be introduced into fats in propylene glycol or ethyl alcohol.
Therefore, frequently fat-soluble esters of citric acid are used, e.g., isopropyl citrate, stearyl
citrate. These esters are used independently or with phenolic antioxidants. Besides citric
CHAPTER 1 59

0.10
1

0.08
Peroxide numbers, % iodine

0.06

0.04

2
5
6
0.02 8
3
4
7

0
5 10 15 25
Time, days

Figure 1.16 Change of the peroxide numbers in hydrogenated whale blubber during its storage at
room temperature: 1, control; upon addition of: 2, 0.02% propyl ester of sorbic acid; 3, 0.02% allyl
ester; 4, 0.02% butyl ester; 5, 0.02% isoamyl ester; 6, 0.02% hexyl ester; 7, 0.02% nonyl ester; 8,
0.02% decyl ester.

acid, it is recommended to use oxalic, malonic, maleic, fumaric and other organic acids, as
well as mineral acids phosphoric and sulfuric.
Ascorbic acid and its derivatives Ascorbic acid (vitamin C) is a crystalline com-
pound readily soluble in water.
Ascorbic acid and its dehydro derivative form a redox system, which can donate and
accept hydrogen atoms.
In the recent years, ascorbic acid and its stereoisomer D-iso-ascorbic acid became
widespread in food industry as synergist antioxidants:
O O
C C
HO C HO C
O O
HO C HO C
H C H C
HO C H H C OH

CH2OH CH2OH

Ascorbic acid D-iso-ascorbic acid


60 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Ascorbic acid is an oxidation inhibitor for lard and other fats. Together with -toco-
pherol, it has a very strong inhibitory effect. Besides, ascorbic acid can retard oxidative
changes of muscle tissue and blood pigments. There are indications that sometimes ascorbic
acid contributes to oxidation, e.g., when it is in contact with animal fat, in which the content
of tocopherol is insignificant.
Contrary to true antioxidants, which inhibit oxidation processes even at advanced
stages, ascorbic acid in similar cases not only fails to inhibit the development of oxidation
but even accelerates it. By the example of animal fats, it was shown that addition of ascorbic
acid at the stage of oxidation, when the peroxide number was higher than 0.05 (% iodine),
has a catalytic action. Ascorbic acid is recommended to be used for stabilization of those
fats, which contain natural or added antioxidants. Owing to its solubility in water, ascorbic
acid is used for inhibition of oxidative processes in emulsions of fats and oils, and its sodium
salt
O C
HO C
O
NaO C
H C
HO C H

CH2 OH
for inhibition of oxidation in packaged meat.
In introduction of both substances with food, LD50 for rats, mice and other animals
was found to be >5000 mg/kg body weight.
D-iso-ascorbic acid (3-keto-D-glucofuranolactone, erythorbic acid), which possesses
no vitamin C activity, found use as an oxidation inhibitor in emulsions of fats and oils, as
well as meat and meat products.
The sodium salt of erythorbic acid is used for treatment of fatback before smoking. It
retards oxidation and contributes to the development and fixation of a reddish tint.
A 1% content of erythorbic acid in food, which is equivalent to 500 mg/kg body weight
(rats) does not lead to any significant toxic effect.
Esters of ascorbic acid with high-molecular-mass fatty acids. Of special interest are
fat-soluble derivatives of ascorbic acid: esters with aliphatic acids palmitic, stearic, myris-
tinic, and others.
Esters of ascorbic acid do not impart fats with undesirable smell, taste and colour.
Ascorbyl palmitate is a white or yellow-white powder with a smell similar to that of citrus
fruits. The melting temperature of ascorbyl palmitate is 112113C:
OH OH OH
O C C C CH CH CH2 O CO(CH2)14 CH3.
O
Ascorbyl palmitate and other synthetic esters increase the stability of fats and oils to
oxidation. They are very efficient in vegetable oils; their synergist action manifests itself
well with phospholipids and -tocopherol.
The antioxidant efficiency of ascorbyl palmitate in pork fat containing natural inhibi-
CHAPTER 1 61

tors is close to the efficiency of butyloxyanisol. The combined application of ascorbyl


palmitate and butyloxyanisol is especially efficient.
The presence of ascorbyl palmitate in butyloxyanisol-stabilized beef fat retards the ap-
pearance of a greenish tint in it during refrigerator storage.
There have been no reports of acute toxicity of ascorbyl palmitate in the literature. A
0.25% content of this substance in daily diet, equivalent to 125 mg/kg body weight, has no
noticeable toxic effect on rats.
Many amino acids possess an ability to retard the oxidative spoilage of edible fats. His-
tidin and arginin inhibit well the oxidation of edible fat. They exhibit a significant syner-
gism with phenolic antioxidants -tocopherol, nordihydroguaiaretic acid and gallic acid
ethers.
Phosphatides are widespread in nature. In the literature, there are often contradictory
data on phosphatides as inhibitors of oxidation of fats and oils. This is, apparently, due to
the fact that phosphatides are a complex mixture of plant or animal phospholipids. Besides,
they include unsaturated fatty acids, which are readily oxidized when they get phosphatides.
Lecithin was one of the first antioxidants of edible fats to be used.
There are indications that phosphatides alone in the absence of phenolic-type anti-
oxidants weakly increase the stability of lard.
Some works indicate that a minor addition of commercial soy lecithin succeeded in
retarding the oxidation of lard, cotton oil and other fats, as well as vitamin A.
However, cases are known when storage of products with a lecithin addition led to
their darkening and unpleasant smell.
The lecithin and kephalin fractions of soybean, sunflower and flax phosphatides have
almost the same efficiency in stabilization of sunflower oil.
Kolamin a constituent part of kephalin has an inhibitory action on the oxidation of
some fats. There are recommendations on the application of ascorbic acid together with
kolamin for stabilizing fats and preserving vitamin A in them.
Mixtures of carbohydrates and phosphatides for stabilization of lard, bacon and other
products have been patented.
Addition of lecithin does not prevent uncooked smoked sausages from oxidative spoil-
age and deteriorates their taste. The synergic action of phosphatides is dealt with in a large
number of works.
It has been found that thiodipropionic and thiodiacetic acids are capable of inhibiting
oxidation.
CH2 CH2 COOH
S
CH2 CH2 COOH

Thiodipropionic acid

Thiodipropionic acid was proposed as a stabilizer of oxidation of fats and oils. This
acid in combination with butyloxyanisol exhibits a significant synergism. Its LD50 in
studies on mice was found to be 2000; in rats, it was 3000 mg/kg body weight (perorally).
For such derivatives of thiodipropionic acid as dilauryl thiodipropionate and distearyl thio-
dipropionate, which are also used as inhibitors of oxidation of fats and food products, LD50
for mice was >2000 mg/kg; and for rats, >2500 mg/kg body weight. A 3% content of these
substances in the diet, which is equivalent to 1500 mg/kg body weight per day, has no
noticeable toxic effect.
In a number of countries, thiodipropionic acid is permitted for addition to edible fats.
62 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Nevertheless, it has not found widespread use, as mercaptans or other sulfur-containing


products with an unpleasant smell can form during its decomposition.
Tetraalkyl tiuram disulfides are recommended as substances inhibiting the oxidation
processes in edible fats. This group of compounds includes tetraethyl tiuram disulfide
(TETD) or antabus:
CH3 CH2 CH2 CH3
N C S S C N
CH3 CH2 CH2 CH3
S S
The application of these preparations for increasing the stability of fats and oils has
been patented.
Besides, such sulfo compounds as thiourea, thiouracyl, cystin were studied as stabiliz-
ers of fats, fatback and other fat-containing products together with a rice-bran concentrate.
Phosphates. The salts of phosphoric acid have long been proposed to be used to in-
crease the stability of fats and fat-containing products to oxidation.
Polyphosphates belong to a very small number of oxidation inhibitors, which exhibit
their action in the presence of water. They inhibit oxidation even in the presence of heme
pigments.
Table 1.7 presents a comparative assessment of the antioxidative efficiency of various
polyphosphates added into chopped pork meat. For the assessment, the reaction with
2-thiobarbituric acid (TBA) was used; the results are expressed in units of optical density
at a wavelength of 538 m.
Table 1.7

Added phosphate (0.5% of the weight of a meat Optical density


product)
before storage one-week storage at
4.4C

No additives, control 1.200 5.500


Sodium tripolyphosphate 0.192 0.334
Sodium hexametapolyphosphate 0.168 0.270
Sodium tetrapyrophosphate 0.176 0.255
Orthophosphate 1.200 5.450

Tripolyphosphate, hexametaphosphate and tetrapyrophosphate are efficient additives


for pork. Their efficiency increases at the addition of ascorbic acid.
Polyposphates in combination with ascorbic acid were found to play a positive role in
inhibition of oxidation in boiled meat.
Studies of the antioxidative action of polyphosphates on meat products subjected to
brining have found that polyphosphates contribute to the preservation of their coloration
and retard the oxidation of fat.
For inhibiting the oxidative spoilage of fat in bacon and sausage products, it is recom-
mended to add polyphosphates into cover brines and syringe brines.
A significant antioxidant efficiency of action of a mixture of tripolyphosphate with so-
dium ascorbinate on roasted beef slices was established. Beef slices were immersed into a
solution containing 1% tripolyphosphate (Na5P3O10) and 0.27% sodium ascorbinate. The
effect of this treatment on the change of oxidation products reacting with 2-thiobarbituric
CHAPTER 1 63

acid (TBA) and the organoleptic parameters of the roasted beef slices during their storage
in a refrigerator and in a freezing chamber is seen from the data presented in Table 1.8.
Treatment of poultry carcasses with solutions of phosphates provides for the inhibition
of the oxidative processes in fat. Phosphates also decrease the losses of meat fluid in the
culinary treatment of the carcass. Depending on the size, the carcass is immersed into a 6%
phosphate solution for 624 h or into a 15% solution for 1.24 h.
Binding of traces of variable-valence metals is ever more recommended to be done by
using some salts of ethylene diamine tetraacetic acid (EDTA). The use of these compounds
in combination with antioxidants considerably increases the stability of lard and other food
products to oxidation.
Table 1.8

Storage Storage time, Controls Tested samples


temperature, days
C TBA number smell, score** TBA number smell, score*

1 1 11.5 0.3
4 15.2 2.5 0.4 5.6
7 19.5 2.6 0.3 5.3
11 21.1 1.9 0.3 4.7
18 21.2 0.3
26 11 3.5 2.7 0.2 5.4
31 2.3 2.4 0.2 5.5
45 3.2 0.2
81 4.9 2.2 0.2 5.9
164 4.1 3.5 0.2 5.8

* *Score 6 indicates the absence of smell, score 1, a strong rancid odour.

1.4.9 Comparative efficiency, methods of treatment and admissible concentrations


of antioxidants
A number of original works give a comparative evaluation of many antioxidants, synergists
and metal deactivators as applied to various fats and model systems, a major part of which
is dealt with in monographs. As as example, Fig. 1.17 compares the efficiencies of several
inhibitors of oxidation of pork rendered fat. As this kind of fat contains little natural inhib-
itors tocopherols addition of one synergist is the least efficient.
The most suitable inhibitors of animal rendered fats are phenolic antioxidants, prefer-
ably with addition of a synergist.
The choice of an antioxidant or an antioxidant mixture becomes much more compli-
cated if fat is a component of a food product, because in this case it is in contact with mois-
ture and various food components. If there is water in the system, the antioxidant should be
relatively soluble in fat and water. Water-insoluble inhibitors are more suitable for dry
fat-containing products.
When using antioxidants, a matter of importance is the moment of their introduction
into fat, so that to inhibit the development of the chain reaction of oxidation as soon as pos-
sible. Antioxidants can be introduced into raw materials before rendering, before settling
or draining off the fat into barrels. Below, we present the results of model experiments.
64 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

0.20
1 4

0.16 7
Peroxide numbers, % iodine
5 6

2 3
0.12

0.08

0.04

0 4 8 12 16 20 24
Time, h

Figure 1.17 Kinetic curves of accumulation of peroxides at a temperature of 110C during the oxi-
dation of pork pat in the presence of 0.01% antioxidant: 1, no antioxidant; 2, ascorbyl palmitate; 3,
dodecyl gallate; 4, octyl gallate; 5, butyloxytolyene; 6, butyloxyanisol; 7, propyl gallate.

Point of introduction of 0.01% BOA Induction period, h

Before rendering 10.0


Before settling 11.8
After settling 10.5

As seen, the greatest effect is achieved at the introduction of BOA into fat before set-
tling and the lowest effect before rendering, which can be explained by adsorption of the
antioxidant by proteins of connective tissue.
Therefore in rendering fat in kettles the antioxidant should be introduced before set-
tling.
For fats produced in automatic fat-rendering units (e.g., Titan), antioxidants can be in-
troduced only at one point of the technological process before draining off into barrels.
Pork fat or another animal fat is accumulated in the receiver. After filling the receiver,
the supply of fat to it is stopped. Fat (35 kg, temperature usually 80C) is poured from the
receiver into a small vessel, into which the antioxidant or antioxidative mixture is added;
the contents are mixed to dissolution, poured back into the receiver and mixed with the
entire bulk for 10 min, after which fat is drained off into barrels.
The surface treatment of slabs of meat and other products is performed by sprinkling
with solutions or suspensions of antioxidants or by immersion into them, but in some case
it is better to fine spray a solid antioxidant. If a product should be soaked, it is kept for a
long time in a solution of an antioxidant or the antioxidant is introduced into tissues by a
syringe.
Pieces of fatback can be treated by rubbing the antioxidant together with salt in dry
salting, or by adding the antioxidant in solution into the brine in brine salting.
CHAPTER 1 65

Dehydrated products are usually treated with solutions or a suspension of an antioxi-


dant before drying.
Into rendered fats and chopped products, antioxidants and antioxidative compositions
are also introduced in propylene glycol or in mono- or diglycerides; volatile solvents
alcohol or acetic acid can also be used; afterwards they are removed by a combined action
of temperature and vacuum. Salt, glucose and spices can also be used as antioxidant
carriers.
Some Western companies manufacture ready-made antioxidant compositions in
solutions.
The number of countries, in which the use of some antioxidants and synergists is per-
mitted, increases. Recently, the Committee on Food Additives (FAO/WHO) determined the
limits of unconditionally and conditionally permissible daily doses of antioxidants for man.
The largest unconditionally permissible should not be considered as the maximum val-
ue, which can be permitted from the point of view of toxicity of a food additive. Therefore,
the Committee found it expedient to set the limits of conditionally permissible daily doses
so that experts in each country could make a final decision on the permissibility of the doses
within the limits conditional for this or that food additive with consideration of special re-
quirements of their own country, groups of population, kinds of food into which additives
would be introduced, methods of their treatment, consumed amount of this food and other
peculiarities.
For some substances, only conditionally permissible doses are given due to the
absence of sufficient scientific data required for the toxicological evaluation of those
substances.

1.4.10 Methods for identification of antioxidants


The following methods are proposed for a quantitative determination of antioxidants, syn-
ergists and metal deactivators, as well as their mixtures: polarographic, colorimetric, spec-
trophotometric (in the visible, ultraviolet and infrared regions of the spectrum),
chromatographic (paper, gas and thin-layer chromatography) and other methods.
Polarographic methods and methods of determination in the infrared region of the
spectrum are not many and found no wide use.
Of considerably greater interest for practical purposes are spectrophotometric methods
of determining antioxidants in the ultraviolet region of the spectrum.
UV spectrophotometry is used for determining butyloxyanisol and butyloxytoluene in
edible fats.
In the presence of PG, BOA, NDGA, citric acid and monoisopropyl citrate, more than
93% butyloxytoluene was determined. Spectrophotometric curves of BOT and other inhib-
itors are given in Fig. 1.18.
Based on thorough studies of the spectrophotometric method of determining butyloxy-
anisol, higher and lower gallates in edible fats and oils, the authors consider it the simplest
and most reliable for quantitative determination.
Light absorption is measured at several wavelengths after extraction of antioxidants
by 72% ethyl alcohol. This method also makes it possible to determine the content of ascor-
bic acid in the presence of the above antioxidants.
A method of determining ethoxyquine in feeds from the absorption in the UV region
of the spectrum has been proposed.
Determination of ethoxyquine is based on its extraction with 0.5N HCl from the sol-
66 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

50

1
40

30
Absorptivity

20
3 2

10

4
5
0
240 260 280 300 320
, m

Figure 1.18 UV absorption spectra of antioxidants and synergists: 1, propyl gallate; 2, butyloxy-
anisol; 3, nordihydroguaiaretic acid; 4, butyloxytolyene; 5, citric acid.

vent and the measurement of the optical density of the solution at a wavelength of 296 m
(Fig. 1.19).
Other spectrophotometric methods of determining antioxidants in the UV region of the
spectrum have been also described.
Colorimetric methods, as spectrophotometric methods in the visible region of the spec-
trum, are used the most frequently for quantitative determination of antioxidants in edible
fats.
For carrying out the colour reaction, antioxidants are extracted from fat by a suitable
solvent or are distilled with superheated steam (in determining butyloxytolyene).
For quantitative determination of a number of antioxidants: butyloxyanisol, butyl-
oxytoluene, gallic acid ethers, nordihydroguaiaretic acid, tocopherols and others, use was
made of redox reactions. The colour reaction is performed with ,-dipyridyl or potassium
ferricyanide. These colorimetric methods are nonspecific.
A reagent 2,6-dichloroquinone chlorimide is widely used for antioxidant determina-
tion; this reagent is specific for butyloxyanisol.
Using 2,6-dichloroquinone chlorimide, the content of butyloxyanisol in the presence
of butyloxytoluene can be determined.
A spectrophotometric method was developed for quantitative determination of gal-
lates. Determination of propyl gallate is based on the colour reaction with the reagent fer-
rotartrate in the presence of an aqueous solution of sodium acetate and the measurement of
the coloration at a wavelength of 530 m with respect to water. When determining octyl
CHAPTER 1 67

1.0
1
0.9

0.8

Optical density 0.7

0.6

0.5
2
0.4

0.3
3
0.2

0.1

280 300 350 , m

Figure 1.19 UV absorption spectra of a standard solution of ethoxyquine in 0.5N HCl: 1, 0.0112
mg/ml; 2, 0,0056 mg/ml; 3, 0,0028 mg/ml.

and dodecyl gallates, the optical density of the solutions at 550 m with respect to isoamyl
alcohol is measured.
A simple and fast method of determining gallates is based on their isolation from fat
with a 95% alcohol and the determination of the amount of gallates in the extract by
measuring the coloration formed with Mohrs salt, at 580 m.
Recently, a complexometric method of determining antioxidants was developed. Mer-
cury acetate proved the best precipitation agent of gallates. This method yielded good re-
sults in determination of gallates soluble in water. At the determination of butyloxyanisol
by the complexometric method the author obtained more reliable data than in the determi-
nation by the colorimetric method.
Chromatographic methods make it possible to detect comparatively easily and in many
cases to determine quantitatively several substances at once, if an antioxidant composition
was added into the product assayed.
Using paper chromatography, antioxidants butyloxyanisol and butyloxytoluene can be
separated in the presence of gallates and butyloxyanisol isomers. Three-valent ferrous sul-
fate or potassium ferricyanide are used as developers. This method enables detection of
0.001% gallate, 0.005% butyloxyanisol and 0.01% butyloxytolyene in pork fat.
When separating a large number of antioxidants in pork fat or margarine, the chro-
matogram is sprayed with one of the two developers: (i) a 1% alcohol solution of silver ni-
trate and after drying a 1% solution of ammonia; (ii) a 2% aqueous solution of borax and
after drying a 0.01% alcohol solution of 2,6-dichloroquinone chlorimide. The separation is
done on paper SS20443b or Whatman No 1.
68 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Paper chromatography is used for separation of tocopherols over a period of several


years.
Using paper chromatography, the content of tocopherols in natural oils is determined.
In one-dimensional chromatography, paper is impregnated with zinc carbonate; in two-
dimensional chromatography, with paraffin. As a developer, ,-dipyridyl is used.
The method makes it possible to separate and determine -, -, -, -, and -toco-
pherols.
The literature gives results of separating methyl, ethyl, propyl, octyl, dodecyl gallates;
nordihydroguaiaretic acid, butyloxyanisol and butyloxytoluene using descending paper
chromatography. The antioxidants are isolated by 78% ethanol from a solution of fat in
petroleum ether; the extracts are evaporated to dryness and dissolved in ethyl acetate. For
their distribution, a mixture of chloroform with acetic acid (99:1) is used at a saturation of
the chamber with 50% acetic acid. All antioxidants separate well, besides butyloxyanisol
and butyloxytolyene, which have very close values of Rf.
Butyloxyanisol and butyloxytolyene can be separated most suitably by the method of
chromatography on Mitchell paper.
Thin-layer chromatography has found wide use in determination of food additive
owing to the exceptional speed of the analysis with all the other advantages of the chro-
matographic methods preserved.
Mixtures of pure antioxidants can be easily and quickly separated using thin layer
chromatography on kieselguhr. 2,6-Dichloroquinone chlorimide and diazotized sulfanilic
acid are used as developers. The method is very sensitive and reliable.
A method of quantitative determination of butyloxyanisol, butyloxytolyene, propyl
gallate and nordihydroguaiaretic acid in lard using two-dimensional thin layer chromato-
graphy has been described. Antioxidants are extracted with 80% ethyl alcohol and aceto-
nitrile from a solution of lard in n-hexane. Stains are separated using benzene and aceto-
nitrile. The quantitative determination is performed colorimetrically after extracting stains
from the plate.
This method determines the following amounts of antioxidants: BOA, 98101%;
BOT, 96101%; PG, 90101%; NDGA, 8298%. The method enables efficient separation
of butyloxyanisol isomers.
A method was proposed for determining nordihydroguaiaretic acid, propyl gallate,
ascorbyl palmitate, butyloxyanisol and butyloxytolyene in a thin layer on polyamide pow-
der. A mixture of methanol, acetone and water at 3:1:1 or 6:1:3 ratios is used as solvents.
Identification is performed with diazotized sulfanilic acid or phosphoric-molybdic acid.
Ascorbyl palmitate in the presence of other antioxidants can be determined even if it
is present in fats in the amount of 0.0010.002%. Ascorbyl palmitate extracted from fat is
treated with a solution of the sodium salt of 2,6-dichlorophenol indophenol in the presence
of trichloroacetic acid, heated at 70C with a solution of 2,4-dinitrophenyl hydrazine in sul-
furic acid. The reaction products formed are extracted with ethylacetate, separated on a thin
layer of silica gel in a chloroformethylacetate (1:1) system. The brick-red band of the
2,4-dinitrophenyl hydrazine derivative of the dehydro form of ascorbic acid taken from the
plate is eluted; the intensity of coloration of the solution is determined photometrically at
520525 m.
Thin layer chromatography can be used to separate methyl, ethyl, propyl, butyl, octyl
and dodecyl esters of gallic acid. A 10% acetylated cellulose is used as the stationary phase;
the solvent is a four-component system of a solution of Shell Soil A, n-propyl alcohol,
glacial acetic acid and formic acid at ratios of 45:6:3:6 (v/v).
CHAPTER 1 69

2
0.6

0.5

Detector signal, mV
1
0.4

0.3

0.2

0.1

0
10 5 0
Time, min

Figure 1.20 Chromatogram of a standard solution in petroleum ether: 1, butyloxyanisol; 2, butyl-


oxytolyene.

Thin layer chromatography on polyamide was applied in determination of flavonoids,


glucosides and fat-soluble vitamins.
A number of gallic acid ethers, butyloxyanisol, butyloxytolyene, sesamol and others
were analyzed on a starch-bound polyamide layer in a methanol/acetone/water solvent
(60:20:20).
On a thin layer of polyamide, the Rf values of a large number of antioxidants (methyl,
ethyl, propyl, butyl, octyl, dodecyl gallates; butyloxyanisol, butyloxytolyene, sesamol, nor-
dihydroguaiaretic acid, ascorbyl palmitate) with various solvents (methanolacetone
water, 60:20:20 and light petroleum etherbenzeneacetic aciddimethylformamide,
10:10:5:0.25) were determined.
The development of gas chromatography provided for the possibility of its use in the
field of antioxidant determination.
A method using gas-liquid chromatography has been developed for separation and
quantitative determination of butyloxyanisol, butyloxytolyene and ethoxyquine in samples
soluble in water and hydrocarbons. In combined occurrence of all of these antioxidants,
they are determined at a temperature of 188C on a column (1520.6 or 0.3 cm) filled with
20% silicon SE-30 on refractory brick (6080 mesh) at a helium flow rate of 185 ml/min;
detection, by heat conductance.
To determine traces of BOA, BOT and ethoxyquine, it is recommended to perform
chromatography at 185C on a column filled with 20% silicon SE-30 on chromosorb W at
a gas flow rate of 175 ml/min. An ionization detector is used.
For a quantitative determination of butyloxytolyene and butyloxyanisol in dehydrated
potato granules, a fast method of gas-liquid chromatography using a flame ionization
detector has been proposed. Figure 1.20 shows a chromatogram obtained in determination
of a mixture of both antioxidants.
70 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

A combination of rapid extraction with a gas-chromatographic assay enabled determi-


nation of traces of butyloxytolyene and butyloxyanisol in potato granules, vegetable oils
and packaging materials. The use of a column with a mixture of silicon SE-30 and Tween
80 at 150C provided a possibility of complete separation of assayed substances from in-
terfering impurities. 3,5-Di-tert-butyl-4-oxyanisol was used as an internal standard.
A method of determining butyloxyanisol and butyloxytolyene on a gas chromatograph
with temperature programming and use of 3,5-dibutyloxyanisol as an internal standard has
been described. A chromatograph equipped with a catharometer was applied. Initial tem-
perature of the column, 125C; final temperature, 190C; programming rate, 11 deg/min.
All existing methods of determining antioxidants, besides gas-liquid chromatography,
are low-sensitive at antioxidant concentrations below 1 mg%.
2 Polymer Packaging
Materials for Preservation
of Foodstuffs

2.1 Food polymers


One of the most important high-molecular-mass compounds is at present the class of poly-
mers. As compared with common substances, such as, e.g., water (molecular mass, 18),
benzene (molecular mass, 78), chalk (molecular mass, 100), the values of polymers
molecular masses vary within the range of tens of thousands up to millions. In polymers,
their giant molecules are built from consecutively bound groups of atoms forming a long
chain, which contains sometimes hundreds of thousands repeating structural units: ele-
ments, links. The word polymer means many parts and is derived from the Greek words
polys meaning many and meros meaning parts. An example of a polymer consist-
ing of atoms linked by chemical forces into a chain is plastic sulfur. As is known, it is pro-
duced by pouring molten sulfur into cold water. The structure of polymer sulfur is
represented by a chain of atoms linked by chemical bonds: S S S S . In this
state, the properties of sulfur differ from the properties of common crystalline sulfur. They
resemble rubberlike rather than solid bodies. For most polymers, the repeating elements of
the structure are usually small groups of atoms. One of the simplest (from the point of view
of its chemical structure) and widespread polymers polyethylene has the following
structure: CH2 CH2 CH2 CH2 CH2 ... .
Polyethylene is obtained by attaching molecules of ethylene CH2 CH2 to one
another. By means of corresponding catalyst and conditions, the double bonds are opened
and chains are formed from consecutively attached groups of CH2 CH2 . The initial
molecule, from which the polymer is formed, is called monomer. The word monomer
is derived from the Greek word monos meaning single. The number of monomer units
forming the chain molecule of the polymer is called the degree of polymerization. Another
widespread polymer, polypropylene, has a close structure:
...CH2 CH CH2 CH CH2 CH CH2 CH ...
CH3 CH3 CH3 CH3

It is obtained by attaching molecules of propylene CH2 CH to one another.


CH3
As polyvinyl chloride ... CH2 CHCl CH2 CHCl CH2 CHCl ... obtained
by polymerization of vinyl chloride CH2 CHCl , polyethylene pertains to large-scale
72 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

products. Large-scale polymers include synthetic rubbers (polyisoprene


... CH2 C CH CH2 , butadiene ... CH2 CH CH CH2 ... , and others),
CH3
polystyrene ... CH2 CH CH2 CH ... , cellulose hydrate and esters, as well as poly-

mers, which are used in contact with foods. Among polymer materials suitable for contact
with food products, of special importance are linear polyesters, whose links contain aro-
matic and aliphatic groups, e.g., polyethylene terephthalate or polyethylene glycol tere-

phthalate ...OCH2 CH2OOC CO ... .


This is a crystallizable polymer. Its polymerization rate is maximal at 180190C. It
does not crystallize below 97C. Crystallites of polyethylene terephthalate melt at 256C.
If the melt is rapidly cooled, it has no time to get crystallized and will be in a glass-transition
state. The temperature at which it begins to pass from the glass-transition to rubber-like
state is 81C. If, however, the polymer has time to get partially crystallized (at a slower
cooling), its glass-transition temperature increases. Thus, for instance, at the crystallinity
rate of 65% the glass-transition temperature increases up to 120C.
Films from polyethylene glycol terephthalate are 5 to 6 times stronger than oriented
films from polyethylene, possess a lower vapour and water permeability and a larger oxy-
gen and light resistance.
The breaking strain of this film is 175 MPa; relative elongation, 5070%; low-
temperature resistance, 160C; water absorption, 0.5%; melting temperature, 250C; tem-
perature of the total strength loss, 248C.
O
If the main chain of the macromolecule contains amide groups C NH , then the
polymer belongs to the class of polymer compounds under the general name polyamides;
in a general form, their chemical structure can be expressed by the general formula

... C R C NH R' NH ...


O O
where R and R are meant to be atomic groups ( CH2 )n and (CH2)m. Films from poly-
amides in combination with films from other materials have recently found use in packag-
ing of meat products.
Along with the required performance properties, such as chemical durability, a certain
level of the physicochemical, physicomechanical and technologocal properties, polymer
materials used in direct contact with foods should also meet high hygienic requirements.
Therefore, in accordance with the law, polymer materials can be used in contact with a
given type of food products only after a corresponding permission from the sanitary-
epidemiological bodies. Goods from polymers are subject to thorough organoleptic,
sanitary-chemical and toxicological studies.
Polymers are produced not only by chemical methods. They are widespread in nature
in the form of cellulose, starch, natural rubber, silk and various resins. Not only many kinds
of natural polymers can be reproduced by chemical methods and synthetic polymers
CHAPTER 2 73

developed (e.g., synthetic rubber), but also new polymer substances required for the econ-
omy can be created. Chemical methods can also be used to change the chemical nature of
a natural polymer, e.g., cellulose, by imparting it with the required properties. As a rule,
natural, synthetic and chemically changed natural polymers are used not in pure form, but
in various combinations both between themselves and with various substances added into
the polymer composition to impart it with properties required.
To date, there is a tendency not to expand the range of large-scale polymers used as
the basis for production and processing of plastics, but to search for rational ways of using
traditional polymers. This search proves the most productive in physicochemical, chemical
and physical modification of polymers or in combining various polymers and other mate-
rials in constructions, which optimally combine the properties of a component and the final
complex of the properties of material or article.
The simplest variant is a mixture of two or several polymers, which gives the required
combination of performance properties.
When choosing a polymer for fabricating an article, one should proceed from the pur-
pose of the article and conditions of its use. Herewith, one should be based on the values of
the characteristics, which determine the performance of the article, e.g., the value of break-
ing strain at the sterilization temperature or the strength of an adhesion seam in heat sealing
etc. These characteristics should correlate with conditions, under which the article would
be operated, e.g., the value of strength should not go below a given level under all perfor-
mance conditions. The successful fabrication of an article from polymers is possible only
if the characteristic properties of the plastics are taken into account depending on the oper-
ational conditions and methods of processing.
When choosing polymers, it is necessary to use their resources to a maximum, so that
an article not only conforms to its purpose but its fabrication from a chosen plastic is eco-
nomically more expedient than fabrication from another material. The chosen polymer and
other ingredients of a composition should conform to the sanitary-hygienic conditions.
Most polymer compositions used to produce plastics can include besides a polymer
binder hardeners, plasticizers, fillers, dyes, pore formers, lubricating agents and other
components. Each of the components of a polymer composition performs its specific
function.
Plasticizers are usually introduced into plastics to increase the plasticity of a compo-
sition and of a plastic produced from it. This change of properties (physical modification)
contributes to an easier processing of the plastics into articles, increases their low temper-
ature resistance, decreases the elasticity modulus. Introduction of plasticizers into a com-
position facilitates the mixing of a polymer with other ingredients, decreases the
temperature of processing a plastic into articles. In some cases, besides the above functions
plasticizers also impart plastics with such properties as, e.g., noncombustibility, increases
their heat resistance and light permanence.
Both low- and high-molecular-mass compounds can serve as plasticizers. The require-
ments they should meet are as follows: the ability to match with polymers to form an oper-
ationally stable system, low volatility; absence of colour, smell; the plasticizing action
should be preserved at the lowest operational temperatures; chemical stability should be no
less than in polymer components.
In some cases, additional requirements should also be met, such as an almost complete
absence of extractability from the polymer with liquid media, oils, solvents, detergents,
food products.
The most important plasticizers include esters of aromatic and aliphatic carboxylic
74 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

acids and phosphoric acid, epoxidized compounds, polyesters, esters of glycols and mono-
carboxylic acids.
Fillers of plastics are solid and gaseous substances, whose introduction makes plastics
stronger, less deformable and less shrinkable, or makes them to acquire other useful prop-
erties, such are incombustibility, larger friction coefficient, electrical conductivity etc. In
some cases, fillers do not improve the operational properties but, being a cheaper and more
available part of the plastics, reduce their cost. Fillers, which significantly improve the
operational properties of plastics are usually called active.
The content of fillers in plastics can change within broad limits and is usually 4550%
in terms of polymer weight. In high-filled plastics, the content of filler can exceed the poly-
mer content severalfold.
Of undoubted interest are the current works on production of high-filled thermo-
plastics directly in the synthesis process. The idea is to use the catalyst applied onto the car-
rier as a filler in the polymer composition. Thus, the filled composition is produced directly
in the reactor, which not only makes the mixing process simpler, easier and less energy-
intensive, but contributes to a stronger bonding between the components. Such materials
developed by academician N.S. Enikopolov et al. were given the name of norplastics.
The most widespread fillers are solid; they are divided into powdery and fibrous. In
some cases, such fillers as, e.g., graphite, glass, various metals etc., are used both as pow-
ders and fibres. Active fibrous fillers are called reinforcing fillers.
The general requirements imposed on fillers are primarily their ability to mix with
polymer to yield a given degree of homogeneity, the ability to be wetted by the polymer
melt or solution, the stability of the properties in storage of the filler, processing and use of
the plastic.
When using powdery fillers, the process engineer should solve a number of problems,
such as to determine the optimal size of particles, the concentration of filler and the desir-
able structure of the polymerfiller system. In the latter case, it is desirable to determine
which type of structures (a more or less uniform distribution of particles in the bulk of the
polymer composite, or formation of chain structures consisting of filler particles, or else,
e.g., formation of a three-dimensional network from the chain structures etc.) is the most
expedient for achieving a given set of properties.
It follows from the above that polymer materials are used in fabrication of articles not
as individual substances but as a polymer composition, a mixture of various polymer ingre-
dients, which confer a required shape upon the article and then fix this shape by various
technological techniques.
A great diversity of polymer types and polymer compositions makes it possible to
choose those the combinations of properties of which correspond to the conditions of op-
eration of an article. Especially specific are operational conditions of polymer materials
used for packaging of foods. Packaging is reduced to not only providing the possibility of
prepackaging and transporting the food products, but to protecting them from the impact of
the environment, pathogenic bacteria, preserving the nutritive value of a product, increasing
its expiry date and many other aspects. Thus, a polymer packaging is active with respect to
a food product. However, this activity can be not only useful but also harmful.
This is due to the fact that polymer material is a complex composition, which, besides
a polymer, i.e., a high-molecular-mass compound, includes many low-molecular-mass
chemical compounds.
As a rule, additives and low-molecular-mass impurities are chemically not bound to
the polymer. Under certain conditions, these substances can pass (migrate or diffuse) into
CHAPTER 2 75

the contacting medium: air, water, foodstuffs. This creates a potential hazard for man when
using polymer materials as food packaging, because migrating substances can be toxic and
have adverse effects on the human organism. Of special importance is that, getting into the
human organism in small concentrations but acting for a long time, they can evoke no fast
and acute diseases, but act slowly and sometimes not manifesting themselves for years.
Therefore, prevention of such pathological phenomena becomes the most important
hygienic and social problem.
This problem is being solved by a common effort of physicians, chemists and process
engineers. At present, physicians listen to a course of lectures on polymers, and process en-
gineers study the possible consequences of incorrect use of polymer materials and methods
of developing practically harmless polymer articles.
The hazardous action of polymer articles is usually determined by the toxicity of low-
molecular-mass substances present in them, but not by the polymer itself, which is practi-
cally insoluble in water and other food media. Therefore, two criteria determine the harm-
fulness of a polymer material: the toxicity of low-molecular-mass substances present in a
polymer or forming in it, and the amount of these substances passing into the contacting
medium. The certificate of toxicity, i.e., the extent of harmfullness for man, of chemical
substances is issued after toxicological studies; and the chemical composition, amount and
character of migration of individual substances from polymer materials are studied in the
course of sanitary and chemical tests.
In view of the importance of this problem, besides a certain set of physicochemical and
physicomechanical properties, polymer materials intended for contact with foods should
also satisfy hygienic requirements: the formulation of a polymer material should not include
substances possessing a toxicity, but only those substances that are permitted by the Min-
istry of Health bodies and are present in a corresponding list; articles from a polymer ma-
terial in contact with food products should not change their organoleptic properties (i.e.,
taste and smell) and should not evolve low-molecular-mass chemical substances in amounts
exceeding admissible levels, i.e., in amounts, which can have a harmful effect on humans
when taken up with food; at the impact of food media, the appearance of the articles should
not change. Physico-hygienic, physiologo-hygienic and microbiological studies can be also
necessary in some cases.

2.2 Hygienic characteristics of packaging materials components


Preliminary information on the hygienic characteristic of substances introduced into a poly-
mer composition can be obtained based on the physicochemical properties solubility in
various media, volatility etc. However, ultimately the possibility of using this or that chem-
ical substance in polymer materials can be decided upon only based on the data obtained in
experiments on animals. The aim of toxicological studies is to reveal the toxic action of
low-molecular-mass substances, evolved from polymer materials into the environment, on
the animal organism. The currently accepted scheme of toxicological studies is two-stage.
The first to be studied are the toxic properties of separate components, which are either ini-
tial substances for producing a polymer or are introduced into it subsequently to impart it
with certain properties. In each particular case, the need for the toxicological evaluation of
substances is determined based on the formulation of polymer material and the results of
the sanitary and chemical analysis. This toxicological evaluation is to establish the norms
of evolution of these low-molecular-mass components into the environment air, water,
food products or model media imitating them. If, as the result of a toxicological evaluation,
76 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

any of the additives is found to be practically nontoxic, no norms of evolution for it are es-
tablished, and its use is permitted in all-purpose plastics without any obligatory control of
its evolution.
The second stage of the toxicological evaluation is to study the toxic action of all poly-
mer material as a whole depending on its assumed application. This type of toxicological
research is to be carried out either when the evolution of separate components is close to
the established norms but the combined action of several components is anticipated to be
stronger, or when not all substances evolved from the plastic have been identified. It is es-
pecially important in this case to establish the amount of substances capable of evoking a
pathological effect.
Proceeding from the degree of the risk of possible pathogenic effects on the organism
to develop, taking into account the biological activity and extent of migration from polymer
materials, various additives can be divided into admissible, whose use for food brands of
polymer materials is permitted, and inadmissible.
The first group includes compounds, which do not change the organoleptic properties
of products, and also those whose harmlessness has been proven by many years of practice.
This group includes most major compounds used in production of polymer materials:
monomers, plasticizers, dyes. However, their use is regulated by hygienic norms the ad-
missible amount of migration (AAM) (e.g., for such monomers as styrene, epichlorohydrin,
formaldehyde) or by standardization of their content in a polymer composition on the lev-
el providing for the harmlessness for foods.
The group of inadmissible compounds includes those the use of which in production
of food-purpose polymer materials is totally banned.
This group incorporates compounds, which possess a high toxicity and pose a signif-
icant threat in the case of migration into the environment (e.g., arsenic and lead com-
pounds).
Based on the results of hygienic studies, the maximally admissible daily dose (Dm) is
established.
This coefficient is a major parameter for the calculation of the AAM for a given sub-
stance in the food brands of polymer materials.
Based on the results of the toxicological experiment of determining Dm and AAM, the
health bodies make a decision on the admissibility of using the substance studied in food
brands of polymer materials.
Let us dwell on the evaluation of the biological activity of compounds used the most
in production of polymer materials: monomers, catalysts, initiators, stabilizers, plasticizers.
Monomers. When producing polystyrene, the initial monomer is styrene (vinyl ben-
zene) a liquid with a characteristic smell, which boils at 146C. The norm of the admis-
sible amount of migration of styrene from polystyrene articles is 0.01 mg/l.
Epychlorohydrin is a colourless transparent liquid with a specific irritating smell. Pos-
sesses a high biological effect, which to a large extent is explained by the presence of chlo-
rine-containing groups in the molecule. AAM of epychlorohydrin is 0.1 mg/l.
Vinyl chloride is a colourless gas without a smell; boils at 13.8C. AAM of vinyl chlo-
ride is 0.01 mg/l.
Most polymerization catalysts are totally incorporated into the final product. The res-
idue of the inorganic compounds in the polymer can be characterized by the ash content.
Thus, the ash content of polyethylene intended for contact with foodstuffs should not ex-
ceed 0.02%. The presence of even insignificant amounts of catalysts in the finished article
may lead to a faster ageing of polymer material.
CHAPTER 2 77

Polymerization initiators are capable of decomposition during the heating to form free
radicals. Usually, oxygen-organic and -inorganic peroxides, hydroperoxides and diazo
compounds are used as initiators. Most of these substances possess an irritating action, have
an effect on the nervous system. Peroxide degradation products are also biologically active.
The content of polymerization initiators and products of their degradation in finished poly-
mer materials should not exceed 0.2%.
Stabilizers contribute to the long-term preservation of the properties of plastics. Sta-
bilizers enter into a chemical interaction with polymer. They readily diffuse from it into
contacting media. The proximity of the mechanisms determining the efficiency of stabiliz-
ers to the phenomena occurring in a living organism points to their biological activity.
Widespread heat stabilizers are stearates of metals calcium, zinc borate, lead etc. Calcium
and zinc stearates, as well as complex stabilizers, proved to be practically nontoxic sub-
stances. At the same time, stearates of cadmium, barium, lead possess a high toxicity.
For stabilization of PVC materials contacting with foodstuffs, epoxidized soybean oil
is used, which is a low-toxic compound. However, its introduction to the polymer compo-
sition in excess amounts may enhance migration of the other ingredients.
Plasticizers. All in all, 2000 various plasticizers are known; however, in production of
materials contacting with food products, a limited number is used: glycerol; paraffin oil;
ethanolamines; esters of phthalic, sebacinic, adipic and citric acids; as well as low-
molecular-mass polyesters. In the opinion of some investigators, esters of sebacinic and cit-
ric acids, as well as stearic acid and its salts (calcium and zinc stearates) can be considered
to be practically nontoxic plasticizers.
Glycerol, triacetin, castor oil, mono-, di- and triethanolamines and their salts are also
attributed to nontoxic plasticizers. Of great importance are acetyl tributyl citrate and ethyl-
hexyl phenyl phosphate, which are used to produce films intended for packaging of food
products. Both plasticizers are low-toxic, possess a high water, oil and low-temperature re-
sistance as well as insignificant volatility.
Fillers. Silicon dioxide, chalk, cellulose, wood veneer, titanium dioxide etc. are used
as fillers. For the most part, they are nontoxic.
Solvents. Organic solvents toluene, benzene, ethylacetate, hexane, petrol, methylene
chloride etc. are used in polymerization or polycondensation in solution. Certain amounts
of these solvents can remain in fabricated polymer materials both after the main process
operations and after some auxiliary operations. Chloroorganic and aromatic compounds
and alcohols can remain in the material owing to incomplete drying.
Migration of solvents into contacting media can have an impact on their taste and
smell, and also lend them toxic properties. Information on the toxicity of particular solvents
can be found in reference books PDK Vrednykh Veshchestv (=MPC of Harmful Sub-
stances) (in Russian) (Leningrad, Khimiya Publishers, 1975) and Vrednye Veshchestva v
Promyshlennosti (=Harmful Substances in Industries) (in Russian) ed. by N.V. Lazarev
(Leningrad, Khimiya Publishers, 1971).
Dyes. Synthetic or natural dyes soluble in most common solvents, as well as pigments
of organic and inorganic origin are used for colouring plastics. The dyes are usually insol-
uble. Migration of dyes can have a general toxic action during its penetration through the
skin, as well as in the stomach during its intake with water or with food products.
Various aminoanthraquinone and azo dyes are capable of evoking disturbances of the
functional state of the liver, kidneys, the central nervous system; to disturb redox processes
in the organism. A characteristic feature of most dyes is a low toxicity at a single introduc-
tion into the organism in large doses and the ability to cause intoxication during the chronic
78 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

intake of small doses.


As for inorganic dyes, their biological activity depends on the element occurring in the
compound. A general toxic action is characteristic of strontium- and chromium-based dyes.
Iron- and titanium-based dyes are practically harmless. To guarantee the harmfulness of
using coloured articles, the AAM for dyes is set to be with the safety margin of 1001000.
In operation of polymer materials, they age, i.e., their physicochemical and physico-
mechanical properties change under the action of external conditions. Ageing of polymers
is due to the degradation reactions owing to the rupture of the molecular chain. As the result
of the degradation, articles get deformed, crack and in some cases break. Some degradation
processes are accompanied with a change of the appearance of the articles, staining, yel-
lowing, blooming, warpage etc.
Degradation of polymers usually occurs under the action of chemical agents (water,
alcohols, acids, oxygen, ozone etc.) or under the action of physical impacts (heat, light, ion-
izing radiation, mechanical energy etc.). Polymers can also be degraded during their pro-
cessing owing to the violation of the technological regime. All these processes are
invariably associated with the evolution of harmful chemical substances degradation
products from plastics into the environment.
Decomposition of polyethylene is accompanied with evolution of such substances as
formaldehyde, acetaldehyde, acids, unsaturated hydrocarbons, low-molecular-mass oligo-
mers; in strongly pronounced decomposition, H2O and CO2 can evolve. Besides the above,
acetone, methyl alcohol and other alcohols are found among the degradation products of
polypropylene.
The most toxic are formaldehyde its AAM was set to be 0.1 mg/l and methyl alco-
hol (AAM, 1.0 mg/l).
Polystyrene in degradation evolves styrene, -methyl styrene, ethyl benzene and other
aromatic hydrocarbons, benzaldehyde, benzophenone and other aromatic aldehydes and
ketones. Aldehydes, alcohols, hydrogen chloride, chlorinated hydrocarbons, unsaturated
hydrocarbons are formed as the result of the degradation of PVC.
Ageing of methylacrylate is accompanied by the evolution of methyl alcohol, MMA,
methacrylic acid, unsaturated hydrocarbons. The AAM of MMA is 0.25 mg/l.
Amino plastics are degraded to form aldehydes (formaldehydes), ammonia; pheno-
plastics, to form phenol (AAM, 0.001 mg/l), aldehydes; epoxy resins evolve epichlorohy-
drin (AAM, 0.7 mg/l), phenol, chlorinated hydrocarbons, aromatic hydrocarbons. To
predict the potential hazard of plastics used for contact with foodstuffs, it is necessary to
have a real idea of the chemical nature of substances evolving from them, the level of their
migration and toxicological characteristics.
To establish the correspondence of the finished article to the hygienic requirements,
special studies should be carried out. They are based on modelling the real conditions under
which polymer materials would be used, followed by the determination of the organoleptic
properties of the contacting media and the level of migration of the chemical compounds.
In an ideal case, migrating substances should be determined directly in food products.
However, the compositions of food products are rather complex, so in most cases it is
impossible to determine particular chemical compounds in them. For instance, milk is a
complex chemically and biologically active system, which includes protein, fat, plasma;
these, in turn, consist of amino acids, casein, albumin etc. The presence of these substances
not only disturbs the determination of separate compounds migrating from plastics, but is
also capable of changing the initial shape of these substances, i.e., to enter into interaction
with them. Nevertheless, a number of highly sensitive assays for determining separate low-
CHAPTER 2 79

molecular-mass substances in food products (e.g., solvents, plasticizers, monomers in sun-


flower oil, milk, curd, cheese) have been developed to date; still, sanitary-chemical studies
are mainly carried out on model solutions, which simulate particular kinds of products by
the most characteristic features.
Solutions of some salts, acids, alcohols serve as model media to simulate the extract-
ability of various food products. In all cases, water is used as one of the model solutions as
the most universal and convenient medium for organoleptic studies and the determination
of the amount of chemical substances migrating from plastics.
Different countries use various sets of model media, which reflect more or less com-
pletely the character of major food products. An essential criterion in choosing a model me-
dium is to simulate the factors, which contribute to or prevent the migration of chemical
substances: the consistence of a product, its pH and composition of the salts; the content of
water, fat or alcohol. The greatest attention is paid to liquid and fatty products.
The requirements to plastics used for prepackaging solid food products are less strin-
gent. In some countries, they are permitted to be used without special studies.
In the Russian Federation, 9 model media are used; in the USA, 8; in France, 13; in
Czech Republic and Italy, 6; in Germany, 4. There are certain differences in the composi-
tion of model media simulating the same food products, especially of fats, which are pro-
posed to be replaced in tests by olive or sunflower oil, heptane, hexane, diethyl ester.
It is known that aggressivity of food products with respect to polymer materials de-
pends to a certain extent on the content of moisture in them. Therefore, the approaches to
the studies of articles intended for contact with food products of a moisture content of above
15% and below 15% are different.
Almost all model media include water, so for simplicity water-containing products are
simulated by water; fat-containing products, by sunflower or other vegetable oil. As the re-
sult of accumulation of experimental data, the principles of choosing simulators of food
products are being reconsidered at present.
The conditions of modelling polymer tests in this country have been accepted to de-
pend upon real conditions of their practical use with some exaggeration.
The specific surface of specimens of a material or articles should correspond to real
operating conditions.
The sanitary-chemical study is preceded by organoleptic studies. Their aim is to reveal
the possibility of transferring a foreign smell and flavour to food products, which are in con-
tact with a polymer material. The organoleptic parameters are determined by tasting and
are expressed in points of smell intensity. Changes of the organoleptic properties of food
products and model solutions contacting with articles studied are due to the transition of
polymer components into them. In this connection, the data obtained in the organoleptic
studies are one of the most important limiting parameters in the sanitary-chemical study of
articles from polymer materials. If the organoleptic examination reveals a change of smell
and taste of a food product or a model medium as the result of a contact with polymer ma-
terial, this is the reason for banning this material for packaging foodstuffs.
The subsequent sanitary-chemical studies isolate both the total amount of substances
that passed into model media from the polymer composition, and separate components.
Their qualitative composition is determined, i.e., chemical substances are identified and the
character of their migration is defined. The total amount of low-molecular-mass substances
that pass into the media is determined by the so called integral methods. They include the
methods of oxidizability, brominability, dry residue of the extracts. However, neither of the
methods gives the complete idea of all substances migrating into model media. In particular,
80 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

the oxidizability shows the total content of (organic and inorganic) reducers (in solution)
capable of oxidation under conditions of the experiment, and characterizes the resistance
of the material to water. The brominability testifies to the presence (in extracts) of substanc-
es capable of adding bromine, e.g., unsaturated compounds, phenol. The dry residue ob-
tained by evaporation of the extracts at 100105C contains no volatile substances, whose
boiling temperature is lower than these temperatures.
Therefore, major information in sanitary-chemical studies is obtained using the meth-
ods that make it possible to determine the migrating substances in a differentiated manner.
These methods include specific chemical reactions, which make use of the ability of
each individual compound to enter into interaction with certain reagents. Usually, such re-
actions are used, which yield coloured compounds absorbing light in the visible region of
the spectrum. Such a feature of these compounds makes it possible to register the intensity
of the coloration on a photoelectrocolorimeter type of instruments, and, therefore, to deter-
mine the concentration of an analyzed substance with greater accuracy.
Such instrumental methods as gas-liquid and thin-layer chromatography, spectroscopy
in the ultraviolet and infrared regions, mass spectrometry, spectrography are also widely
used.
Much attention is paid at present to the elucidation of the regularities of migration of
individual supramolecular components, which is especially important for packagings and
containers for long-term use. In a general case, the intensity of migration is affected by the
physicochemical impact of polymer and medium, the composition and technology of pro-
ducing and reprocessing a polymer, duration of contact of the product and the packaging.
The migration ability of particular components is described using the diffusion equation,
which gives a possibility of predicting the migration process at different operating condi-
tions. Migration of monomers is well described by the diffusion equations, as in this case
the determining factor is the solubility of the monomer in the polymer.
In a number of cases, migration processes of additives are described by two parame-
ters: D (diffusion coefficient) and S (solubility). When an additive in the model medium is
not very small, migration is determined by diffusion of the polymer additive and changes
proportionally to time raised to the power of 1/2. When additives are very small, the rate of
migration changes linearly.
In a number of cases, the migration process is described taking account of several fac-
tors (concentration of a component, temperature of the medium, time of contact), by making
up the regression equation. Mathematical models of migration of this or that component are
being developed.
The chemical nature of the model medium has a significant effect on the character of
migration. It has been found that water, weak solutions of acids and salts evoke a surface
cracking of PE at elevated temperatures, which leads to accelerated migration of low-
molecular-mass substances from these materials. In this connection, the use of such a ma-
terial as PE should be limited in time at temperatures higher than 60C due to possible
cracking. The amount of migrated substances (solvents, products of heat-oxidation decom-
position) often does not exceed the admissible level of migration. However, it deteriorates
the organoleptic properties of food media, which is also inadmissible from the hygienic
point of view.
An insignificant swelling in fats or fat-simulating media is not always a sufficient rea-
son for recommending a material as a packaging for fat. In a number of cases, the determin-
ing factor is oxygen permeability of the polymer film, because an increased oxygen
permeability leads to a rancidity of the packaged fat-containing product, as well as to a
CHAPTER 2 81

decrease of vitamins in it. Besides, one should pay attention to the fat solubility of poly-
mers low-molecular-mass ingredients: plasticizers, stabilizers, dyes. Only consideration of
all the above factors together enables a conclusion of the expediency of using a particular
material in contact with fat. Owing to a change of its composition, the same polymer can
be used in different applications. One of the oldest polymer materials cellophane has
been widely used in the recent years as a packaging for foodstuffs (owing to its low hydro-
philicity and gas permeability due to the application of a lacquer coating on the surface of
the film). This material can be heat sealed, so cellophane can be used as casings for sausages
and cheeses. But new problems have arisen: removal of the residual solvent in the lacquer,
especially from the adhesive layer, the purpose of which is to create a strong bonding of the
coating and the film. If the coating is formed directly on a product, one should take account
of the diffusion of the solvent not only in the air but also in the product. Thus, when applying
a latex coating on a cheese, the residual content of the solvents and monomers is controlled
both in the coating and in the cheese. The sanitary-chemical properties can be improved and
the range of application of the material could be expanded not only by changing the com-
position of the polymer material, but also by varying particular parameters of the techno-
logical process. For this purpose, the technological process is to be optimized with
consideration of definite sanitary-chemical parameters of significance for a given material.
This approach was used to modify the process of producing a combined material based on
polyethylene and cellophane. Besides the major technological parameters, the mathemati-
cal model of the process comprised the organoleptic parameter, which is the determining
parameter in this case, and the extent of oxidation of the polyethylene coating surface.
Mathematical treatment of the data made it possible to choose the temperature of PE extru-
sion on cellophane, at which the organoleptic and other sanitary-chemical parameters of the
material satisfy the generally accepted hygienic norms. The sanitary-chemical properties
often become a determining factor in deciding which of the materials is in this case the best.
The criterion of choosing the material has been developed, which takes into consider-
ation the sanitary-chemical parameters. This criterion is the ratio of the aggregate of the use-
ful properties to the total costs of all the life cycle, which adds up from the expenses for
development, production and operation. This or that hygienic parameter (e.g., oxidizability,
content of solvents, temperature at which a smell emerges) is assigned a certain numerical
value in the abstract scale (1 or 0) and the sum of values for one and the other material is
calculated. For instance, LDPE and HDPE are compared with respect to oxidizability (less
for HDPE), number of solvents (available for HDPE), migration of 3,4-benzpyrene (less in
HDPE), smell (appears in HDPE at a higher temperature). At the same costs, the preferred
material should be HDPE, whose complex parameters of the hygienic properties are 20%
higher than those of LDPE.
Owing to the studies carried out in the recent years, the quality of many polymer ma-
terials was significantly improved.
The major way of achieving this are:

increase of the purity of initial raw materials


introduction of nontoxic additives into the composition
selection of the formulations of polymer compositions, which ensure a sufficient
chemical stability of materials
choice of optimal polymer-processing regimes, which prevent the thermooxidative
degradation of material
application of coatings, preventing migration of low-molecular-mass substances, on
82 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

the surface of material


use of additional technological techniques improving the hygienic properties of ma-
terials (vacuum treatment, heat treatment, washing etc.).

It is very important that the technological protocol be strictly observed: ingredients of


the composition should not be replaced by others; raw materials should be of the extent of
purification required to produce a hygienically flawless material. The article obtained
should be used only for the intended purpose within the temperaturetime limits required.
The permit issued by the Ministry of Health stipulates the operating conditions of material
or fabricated packagings, and the violation of these recommendations is fraught with
serious consequences for human health.
Having obtained the results of the sanitary-chemical study, the hygienists make a con-
clusion of the possibility or impossibility of using the polymer material in contact with giv-
en products. If it can be used, the operating conditions are stipulated, i.e., the temperature
regime and time interval, as well as specifically the kind of a food product. The same poly-
mer can be suitable for one product and can not be used in contact with another product.
This is explainable by the chemical nature and physical structure of both the polymer itself
and additions in its composition. Such a widespread material as polyethylene is broadly
used for contact with water-containing products, but on a limited scale with fat-containing
materials. And such a polymer as polyamide is intended for fatty products and can not con-
tact with water. It should be noted that there are many ways to modify polymers: impart
them with water resistance or, vice versa, water solubility, fat resistance, gas impenetrabil-
ity etc. Due to the latter, materials not used previously for certain products can withstand a
contact with them without changing their properties and the properties of the product. Thus,
for instance, the higher homologs of polyolefins possess an increased fat resistance; appli-
cation of lacquers on cellophane imparts it with water resistance, while coating polyethyl-
ene with foil makes it gas-impermeable.
Unsatisfactory sanitary-chemical parameters are a signal for process engineers, who
correct the production process for polymer articles, change the composition of polymer ma-
terial, choosing such additives, which would not migrate during the contact of the packag-
ing with the contents. When developing new polymer materials, the technological process
should be optimized with account for the hygienic requirements, and this is a guarantee of
the safety of using polymer materials for food packaging.
At present, all regulatory documents for polymers intended for contact with food prod-
ucts include compulsory hygienic parameters, in accordance with which the material is con-
trolled at the stage of its final fabrication.

2.3 Methods of packaging foodstuffs


To preserve a product, it should be packaged in good condition. If it was getting spoiled,
the very perfect packaging would not restore its original properties. Contrarywise, favour-
able conditions for accelerated spoilage of the product can develop in the packaging. Thus,
for instance, each variety of fruits and vegetables has its most favourable harvest time.
Fruits and vegetables picked up too early do not reach their normal size. Their green
pulp has a grass acidic taste. The coloration and aroma of these fruits and vegetables are
weakly expressed. If prematurely picked fruits and vegetables are put into storage, they
droop and brown faster.
On the contrary, fruits and vegetables harvested too late are infected with various
CHAPTER 2 83

diseases and fungal rots. They are susceptible to damage, cold injury, development of floury
texture, have a tendency of rapid overripeness, loss of gustatory properties and vendibility.
On the strength of the above reasons, it is inappropriate to preserve fruits picked later than
the admissible harvesting time. They should be delivered to the consumer as soon as
possible.
The optimal time of harvesting many varieties of apples could be determined by their
colour. Thus, for long-term storage of many varieties of apples they should be picked when
they have a greenish-yellowish coloration with predominant green colour. Fruits intended
for mid-term storage have yellow-green colour, and totally yellowed fruits are not to be
stored.
The strength of attachment of fruits to the fruiting branch is also an indicator of their
ripeness. Overripe fruits are detached by a weak touch.
Experts determine the optimal time of picking fruits by the colour of seeds, content of
sugar and acid in them, taste and density of fruits and vegetables, content of starch etc.
Any damage (punctures, injuries, damage caused by codling moths and scabs, absence
of fruitstalk) are undesirable in putting fruits into storage. In accordance with the State Stan-
dards, only highest and first grade fruits are put into long-time storage. Though harvested
fruits and vegetables receive neither water nor nutrients, they absorb oxygen, evolve carbon
dioxide, water, heat and various volatile organic substances. This physiological process is
generally called respiration. The respiration intensity can also serve one of subjective pa-
rameters of ripening, ageing and possible duration of product storage. To make clearer how
the respiration intensity change data are used in such cases, consider an example of storing
apples at various temperatures. First of all, let us mention that it is customary to divide the
change of respiration intensity in the fruit ripening period into three phases. The first is char-
acterized by a low level of respiration. The second is characterized by an increased intensity
of respiration. An increase of respiration intensity implies that fruits have ripened. Subse-
quently, ageing and spoilage of products shall follow. Spoilage begins the sooner the more
intensive the respiration process is. As is usual, the rate of reversible chemical reactions can
be regulated by either changing the temperature or by changing the concentration of final
products in the reaction medium. Therefore, by decreasing the temperature to some limits
or by changing (modifying) the atmosphere, in which the biologically active products are
stored, we can extend the time during which they achieve optimal properties, i.e., extend
the storage time and improve the quality of the products.
Fresh fruits and vegetables are valuable foodstuffs, one of the major sources of pro-
viding the human organism with vitamins, mineral salts, organic acids, biologically active
substances essential for life. The output of these products increases each year; however,
their consumption is obviously of seasonal character.
Partly, the problem of long-time storage is solved by using special chambers and stor-
age facilities at a relatively low temperature of refrigerating chambers with artificial refrig-
eration.
However, storage of fruits and vegetables in refrigerators has a number of disadvan-
tages: losses are still high; storage is possible only to January or February, only some vari-
eties preserve the food merits in the spring period, when the human organism has a special
need for vitamins; too low temperatures cause irreversible biochemical processes in fruits.
Therefore, it is necessary to use advanced methods of storage. One of the promising
methods of storing fresh agricultural produce, which makes it possible to preserve consum-
er properties for a long period of time is to develop a gas medium, characterized by an in-
creased content of carbon dioxide and a decreased oxygen content.
84 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

This method is widely used abroad. However, construction of such chambers is asso-
ciated with difficulties of their air-tight sealing, development of special gas mixtures etc.
Development of a modified atmosphere is possible only in storage of fruits and vege-
tables in polymer films with a given gas, vapour and water permeability by natural accu-
mulation of carbon dioxide and increasing the content of oxygen in respiration of fruits and
vegetables. Harvested fruits and vegetables continue to grow, they absorb oxygen, evolve
carbon dioxide, heat and volatile organic substances. This physiological process of respi-
ration is described in a simplified way by the equation: C6H12O6 + 6O2 = 6CO2 + 6H2O +
674 kcal. However, the respiration process proceeds according to this scheme only if there
is a free access of oxygen, and oxidation proceeds up to the final products. During the stor-
age in a packaging little permeable for air, the access of oxygen to the product is hampered
and oxidation can proceed not to the end, which results in the emergence of visible signs of
the physiological disorder in the metabolism. Therefore, one of the main requirements to
polymer films for storage of fresh agricultural produce is absolute gas permeability.
However, an excessively high gas permeability makes the film little suitable for pack-
aging fruits, because in such films it is impossible to create an atmosphere with an increased
content of CO2 and decreased content of O2. In films with low gas permeability, free oxy-
gen present in the packaging is consumed for respiration over a short period of time, and
the concentration of CO2 may increase up to the limits dangerous for fruits and vegetables
(more than 610%). Therefore, such films are also unsuitable for packaging fruits and veg-
etables.
Many polymer films possess a sufficient gas permeability, a selectivity of permeabil-
ity, the extent of which depends not only on the chemical nature of a film, but also on its
thickness, temperature conditions, partial pressure of the gases and other factors. Films
from high-pressure polyethylene (up to 60 m thick) are used in practice; they possess a
certain permeability for CO2 and O2, weak vapour and water permeability and such impor-
tant properties as high elasticity, strength, chemical inertness, resistance to external factors,
heat sealability etc.
The idea of using film containers with gas-exchange membranes is a further develop-
ment of the method of storing fruits and vegetables in polymer packagings.
French scientists proposed and realized in practice a method of regulating the compo-
sition of the atmosphere in storage of fruits. The method is based on using the selective per-
meability of silicon elastomer (polysiloxane) for various gases.
The method comprises four steps: storage of fruits using diffusion exchangers, which
are located outside the storage chamber; storage of fruits using diffusion exchangers located
inside the storage chamber using gas-permeable walls from films (for very large premises);
storage of fruits using small storage tanks with windows closed off with a silicon film (soft
containers from polyethylene, of 5001000 kg holding capacity).
One of the technically simplest variants of using the selective permeability of film ma-
terials for regulating the gas composition of the atmosphere are soft polyethylene contain-
ers.
Fruits are put into storage in these containers in the same way as in common boxes.
Containers are equipped with inserts (windows) from silicon elastomer. The amount of elas-
tomer is the same as in the diffusion exchanger.
After putting boxes with fruits into the container, its top is tightly fastened, after which
the exchange with the outer atmosphere is predominantly through the silicon window.
Diffusion of gases through the window is a function of the partial gas pressure differ-
ential on both sides of the membrane, of the type of cloth used in the film and of the thick-
CHAPTER 2 85

ness of the coating of the cloth with silicon elastomer.


The choice of siloxane elastomer to be applied on the cloth is determined by the unique
properties of this material: the gas permeability of polydimethylsiloxane (PDMS) is 1520
times as high as that of natural rubber, which has the highest permeability of all-hydrocar-
bon elastomers.
By their gas solubility, both these rubbers are close, and a higher gas permeability of
PDMS as compared with natural rubber is explained by a considerable increase of the rate
of gas diffusion. This is also confirmed by the fact that the diffusion coefficient is largely
determined by the nature and structure of polymers, whereas the values of the solubility co-
efficient depend mainly on the nature of diffusing gas or vapour.
Storage of fruits in containers has a number of advantages: there is no need to seal the
premises, and products are stored at a temperature of +2 up to +7C. Therefore, containers
could be used both in artificially refrigerated and noncooled fruit storages. These features
of the container method of storage make it rather promising, in particular, for a broad use
in collective farms and state-owned farms.
The size of containers could be diverse. However, in each case, for a given area of the
membrane, there is a dependence between the weight of stored apples, storage temperature
and a given content of O2 and CO2 in the container. The violation of this dependence can
leads to unfavourable results of storage. Putting fruits for storage should be done as soon
as possible after harvesting.
Successful storage of food products can be ensured only at a correct choice and main-
tenance of the main factors of storage (temperature, relative humidity, composition of the
atmosphere) not only for fruits of each species and variety, but even for fruits of the same
variety depending on the growth conditions, picking time and duration of storage.
Provision of required temperature and humidity conditions of storage is done rather
successfully by constructing refrigerating chambers. However, even in perfect refrigerating
storage facilities the losses of fruit-and-vegetable produce are considerable, its vendibility
qualities and nutritive value are significantly decreased, all due to premature overripening,
ageing and damage caused by physiological and parasitic diseases.
Creation of a modified gas medium using selectively permeable film materials (SPFM)
deserves special attention, as this method of storage does not require constructing expensive
sealed storage facilities or reconstructing the existing refrigerating chambers. The method
can be also successfully used under conditions of noncooled storages (warehouses, cellars).
Additional expenses for polymer materials are not large and are totally paid off due to the
significant improvement of the quality of fruit-and-vegetable produce and a decrease of nat-
ural depletion of weight and losses. The use of this method makes it possible to put the pro-
duce for storage in a modified gas medium directly where it is harvested.
A container design has been developed, which enables a secure protection of the mem-
brane from mechanical impacts and its multiple use. The design makes it possible to carry
out tests of storing fresh agricultural raw materials using SPFM and to perform calculations
of the feasibility of this method as compared with the existing method of refrigerator storage
in open standard boxes and containers. When preparing SPFM for applying onto the base
of polymethylsiloxane composition, the so called spread coating method was used.
Package inserts with membranes and filters from SPFM are operated under conditions
of fruit and vegetable storages without the light; the temperature in storages is +2 up to
+7C. If refrigerator chambers are used for storage, the temperature is decreased to 0 to
2C. The further decrease of temperature leads to irreversible cold damage of the fruits
burns, scalds etc. Relative humidity in package inserts is maintained at a high level
86 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

(9599%), which in violations of storage technology leads to the condensation of moisture


on the walls. During the preparation of the membranes, their pasting, as well as in subse-
quent operation of package inserts, SPFM can be subjected to deformations and mechanical
damage. However, the main requirements to this type of materials is the high level of gas
permeability and the selectivity of permeability with respect to various gases, mainly to ox-
ygen and carbon dioxide.
SPFM are used for long-time storage of fruits and vegetables not independently but as
membranes. The design of vegetable and fruit containers can be different, which depends
on the kind of produce, charge volume and other factors, but they are fabricated mainly from
a food-grade polyethylene film 80200 m thick.
When fabricating package inserts with membranes, and subsequently gas-selective
heat diffusion devices (CSHD) the main problem was to join the gas-selective membrane
with polyethylene and polystyrene, because these materials are of different chemical nature.
Bonding of the membrane to polyethylene was done by two techniques pasting and
heat sealing; bonding to polystyrene was performed by pasting using intermediate materi-
als. As polyethylene packages with membranes are operated under conditions of high rel-
ative humidity (9599%) and even of moisture condensation of the walls of the container,
studies were carried out to determine the strength of pasting with adhesive sealant VGO-1
after holding the specimens in water. A prolonged holding in water proved not to have any
noticeable effect on the strength of pasting.
The second technique suitable for bonding a membrane from SPFM to polyethylene
is heat sealing, which consists of the following. A membrane with round holes 35 mm in
diameter along the perimeter with 5-mm spaces between the holes is put onto a polyethylene
package insert with a window in it. A polyethylene-film covering also with a window in it
is put on top of the membrane. They are pressed by a plate heated up to a temperature of
about 130C. Under the action of temperature and pressure, the fused polyethylene of the
covering is sealed through the holes to the material of the insert. The covering is slightly
larger than the membrane, owing to which the material of the membrane is sealed to the
polyethylene package.
The heat sealing method requires less hand labour as compared with the pasting meth-
od. Almost all operations can be mechanized. Besides, raw stuff and materials are saved
there are no expenses for undercollar cloth and adhesive sealant; additional expenses for
polyethylene coverings are insignificant.
Initially, tests of storage of fruit-and-vegetable produce were carried out using con-
tainers and package inserts with membranes fixed by the above methods. The design of the
package inserts is such that the membrane was located in one of the side walls of a container.
However, the use of such packages on a commercial scale is difficult due to the com-
plexity of their fabrication, difficulty of using mechanized automated lines.
Poor removal of biological heat of the respiration of fruit-and-vegetable produce in
large-volume containers (300-100 kg) leads to the increase of the temperature gradient in
the bulk of the produce.
All these necessitated a further improvement of the method. However, for storage of
small batches of fresh agricultural produce, as well as for special purposes, e.g., for equip-
ping deepwater ships, expeditions, the method of storage in small packages with mem-
branes remains acceptable.
Placement of a gas-selective membrane in the inner cavity of the device made it pos-
sible to protect it reliably from mechanical damage and ensure its multiple use. The design
of GSD enabled introduction of the membrane directly into the bulk of stored produce.
CHAPTER 2 87

The method of creating a modified gas medium by means of gas-selective devices us-
ing a hose polyethylene film is economical, simple and accessible for practical use in non-
hermetic storages of all types.
A gas-selective device has the shape of a funnel with shanks and blades, whose inner
cavity has gas-selective elements. The body of the device was fabricated from a food-grade
shock-proof polystyrene sheet 2.53 mm thick by the method of vacuum molding or pres-
sure casting from granulated polystyrene. The gas-exchange section of the device is perfo-
rated.
The device is universal and can be used with hose polyethylene film in all kinds of fruit
and vegetable containers manufactured by domestic industry.
During the storage, it is necessary to check daily the temperature regime in the storage
facilities and to sample and analyze the gases in sampled packages in two days for the first
six days and then once a month. Such kinds of produce as garlic, bulb onion and carrot are
stored at a temperature of 01C, and other kinds of produce, at 34C. At a stabilized re-
gime of the atmosphere in a packaging with produce in the visually normal state, the dura-
tion of storage is determined by the necessity related to the produce sales time. The
maximum storage time is 79 months. Storage can be terminated in the case of deteriora-
tion of the quality of fruits, as well as at a decrease of the oxygen content below 2% or at
an increase of the carbon dioxide content above 67%.
Activated charcoal absorbs ethers evolved in respiration of fruits, aldehydes and acids,
the formation of which is associated with the disturbance of their metabolism, the biochem-
ical and mechanical injuries of tissues, and ethylene which causes accelerated ripening of
fruits. In storage, fruits are subjected to microbial spoilage, one of the major means of con-
trolling which is to use substances suppressing the development of microorganisms.

Gathering the harvest into Stockpiling Modular storage Sales of produce


polymer containers with GSHD

Sorbic acid is the most efficient of acid antiseptics; it is absolutely tasteless and has no
smell. Its salts (e.g., potassium or sodium sorbate) as aqueous or aqueous-alcoholic solu-
tions are as efficient. Introduction of activated charcoal and any antimicrobial preparation
into the packaging makes it possible to remove excess ethylene and volatiles evolved by
fruits, and also to inhibit the processes of microbial spoilage. For this purpose, a porous hy-
drophilic material treated with a suspension of the antiseptic and activated charcoal is
placed at the point of fixation of the membrane, as the most suitable place; it is placed from
the inner side of the membrane facing the fruits. Papers of sufficient strength, e.g., kraft,
cloth, paperboard etc. can be used as a hydrophilic porous material. The suspension can be
applied by spraying, immersion or passing between rolls. When carrying out the works, cot-
ton calico impregnated by immersion into a suspension of activated charcoal and sorbic acid
in acetone was used as a porous hydrophilic material. After drying, a gasket was cut from
this material. The size of the gasket was equal to the size of the gas-selective membrane
used. The gasket was placed from the inner side of the membrane. In the case of using the
88 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

gas-selective device for storage, the gasket was placed between the membrane and perfo-
rated wall of the GSD. The gasket was fixed the way the membrane was fixed, by adhesive
sealant VGO-1. Storage was performed in unsealed facilities at a temperature of 13C.
Analyses established the food components of fruits to be better preserved in storage in
a modified atmosphere than in a common atmosphere. Noticeable changes were observed
to occur in the content of total sugar, pectins and tannins. The development of an anaerobic
exchange is indicated by the amount of alcohol and acetaldehyde. Under conditions of a
modified atmosphere, accumulation of alcohol and acetaldehyde was observed to be insig-
nificant, owing to which apples stored under these conditions had no physiological diseases.
The economic effect of storing apples in containers with GSD is due not only to the lower
expenses for storage, but mainly due to the increased vendibility of apples.
The recommendation to store food products of only good quality refers not exception-
ally to the storage of fruits and vegetables. It is equally valid with respect to other products:
meat, dairy, fish etc.
The meat of a just-killed animal usually has a glossy surface, dark red colour and rub-
berlike consistency.
After cooking, green meat is usually coarse and is difficult to chew. The smell of such
a meat is weakly expressed due to the absence of aromatic substances. Usually, this meat
is said to be tasteless. Therefore, fresh meat should be subjected to maturation, during which
it becomes tender, juicy and aromatic. Herewith, under the action of enzymes there occur
autolysis, degradation of proteins to polypeptides and amino acids, and breakdown of the
carbohydrate system of the muscle tissue to simpler substances. This leads to the accumu-
lation of lactic and phosphoric acids in the musculature and a shift of the reaction of the
medium to the acidic side. The pH values of the meat vary between 5.6 and 6.0. Part of tight-
ly bound water passes to loosely bound water. Only after biochemical changes in matura-
tion, meat acquires a tender consistency, becomes juicy, and has an expressed aroma and
taste.
The maturation time depends on the quality, integrity and assumed use of meat. The
course of the maturation process also depends on temperature, kind of animal, its age, sex,
on management and feeding conditions prior to slaughtering and its condition during the
slaughtering.
At present, carcasses, half-carcasses or quarters are first cooled for 2448 h at a tem-
perature of 0C and relative humidity of 8590% and air conditioning. At a low air ve-
locity, the temperature inside the meat should be from + to +2C. Herewith, a dried up layer
is formed on the surface of meat. After that, the carcasses are hung up and held in a refrig-
erator approximately at a temperature of +2C and 85% relative humidity. Air velocity
should be such that to prevent unnecessary losses of mass at these temperature and humidity
regimes. At a higher temperature, meat becomes more tender and matures faster. During
the maturation, it is necessary to observe hygienic conditions and, as far as possible, to
avoid temperature variations of more than 1C.
Under the above described conditions, beef matures in 814 days; pork, about 3 days;
veal and mutton, 37 days.
Losses of mass in maturation of meat according to the described method are rather sig-
nificant. They differ depending on the species of animal, its age and the properties of meat,
and make 2.55% on average. Dressing losses owing to the removal of dried and
dark-brown parts of carcass surface (facings) are to be added to losses of mass after mat-
uraion. The dressing losses are, as a rule, 1.52%. Thus, the total losses reach 47%, and
in hanging of individual slabs of meat, even 12%.
CHAPTER 2 89

After maturation, meat should be consumed as soon as possible; otherwise, it is diffi-


cult to prevent further losses.Veal and pork do not withstand a long-time storage at the given
temperature regimes. The storage time of meat at a temperature of 0 up to 2C in a refrig-
erator can be increased significantly owing to the introduction of 1015% carbon dioxide.
The above described method of preserving the quality of meat by its hanging and cool-
ing is widely used, e.g., in Germany.
In Germany, a special composition was developed, which makes it possible to preserve
meat fresh for five days even at a temperature of 35C. According to the proposed method,
a freshly slaughtered carcass is immersed for 10 sec into a solution of maize starch, cooking
salt, sugar and fruit acid. Experimental checks found this composition to prevent the activity
of salmonella, which cause food poisoning.
For more long-time preservation of the quality of meat, it is kept in frozen state. Deep
freezing is considered to be the best method of meat preservation. Freezing at a temperature
of 40C and strong air motion with high humidity, followed by storage at 18C in the
dark guarantees the preservation of the quality of cattle meat for 1012 and of pork for 46
months; when stored in the dark at 30C, cattle meat is preserved for 2224 months; and
pork, 1315 months without the change of quality. During the storage in a frozen form, the
losses of vitamins, especially vitamin B, are slowed down.
If unpackaged meat is stored in the frozen form, then in storage from 18 up to 20C,
relative humidity of about 90% and good air conditioning, the losses of mass of meat are
considerable.
In freezing, the losses of mass of cattle meat are from 1 up to 2%; and of pork, from 1
up to 1.6%. The losses of mass after 3 months of storage in the frozen form reach, as a rule,
2.23.2% in cattle meat, and in pork, 1.52.0%. The losses strongly vary and depend first
of all on the kind of meat, as well as on temperature and duration of freezing. During the
freezing in a frozen form, meat not only loses its mass but is subjected to other changes,
including the denaturation of proteins and oxidation of fats. These processes also depend
on temperature and time, as well as, in this case, on the action of light; herewith, the
short-range region of the spectrum is especially efficient. The freezing conditions are also
significant for the above processes. In deep freezing, the changes of products are little tan-
gible, because a thin structure of crystals is formed, and, owing to their small growth rate,
a smaller amount of water contained in the cells passes into the intercellular space. At
non-deep freezing, water contained mainly in the intercellular space freezes. Herewith, a
small amount of large crystals is formed, which grow at a large rate, and the muscle tissue
loses much water, and connective tissue is broken. The longer the freezing process is, the
more time it takes for water to diffuse from the muscle fibres or cell protoplasm owing to
the osmosis. The protein being in solution gets denatured owing to a change of the concen-
tration. Water permeability of the cell wall changes. These changes are largely irreversible,
and in the subsequent thawing the meat looses a large amount of cell sap, which contains
nutritive and flavouring substances.
Freezing of meat by liquid nitrogen (196C) is the fastest method of freezing, which
finds an ever wider application in Western practice. Due to evaporation of liquid nitrogen,
this type of freezing prevents the structural changes better, as the result of which the fresh-
ness and flavour of meat are preserved till thawing even after long-term storage. Colourless,
tasteless nitrogen changes neither the smell nor the taste nor the colour of meat. It does not
enter into chemical interaction with the product. Owing to an extremely large temperature
difference, the freezing lasts only several minutes.
Technically developed countries use the newest achievements in meat industry and
90 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

avoid losses of mass by means of storing and freezing meat in polymer films. The basic re-
quirements are reduced to the above mentioned sanitary-hygienic norms, which should be
observed in storage of meat.
Besides banning polymer films, from which ingredients of the polymer composition
can migrate into meat, a number of requirements are imposed upon films. They should pos-
sess the following properties: protect meat from harmful external effects; not to change the
taste and smell of meat; prevent the loss of flavour; possess a high mechanical strength, as
well as the capability of non-penetration of microorganisms; not to lose the operating prop-
erties with temperature changes; possess the required water and vapour permeability and
have the given values of gas impermeability and fat resistance; possess a flexibility and ac-
quire the shape of the packaged product; packaging into the film should be easy and eco-
nomical not only manually, but also in automatic machines; films should be transparent and
easily printable. Besides, they should be sufficiently cheap so that the economy from re-
ducing the losses exceeds the packaging costs.
The main requirements of foodstuffs hygiene, as well as the technical requirements are
satisfied with respect to polystyrene films, combined polyesterpolyethylene films, as well
as certain polyamidepolyethylene combined films and other films.
Polyester films have a number of advantages. Their mechanical strength is so high that
a thin film can not be torn by hand. Polyester films can be used for fabricating vacuum pack-
agings. They preserve their operating characteristics within admissible limits in the temper-
ature range from 200C up to +255C. This means that foodstuffs packaged into polyester
films can be sterilized by boiling in water or by steam heated up to 120C. Products pack-
aged into polyester films can be scalded, boiled, steamed, stewed, grilled, dried. Along with
this, these films can be used in freezing products by liquid nitrogen down to a temperature
of 196C. As polyester films possess a certain rigidity, air bubbles are inevitable in poly-
ester packages. The film should adhere tightly to meat along the entire surface, otherwise
air cavities with a high relative humidity emerge.
Polyester films belong to a few artificial packaging films, which have an insignificant
permeability for carbon dioxide.
Many polymer film materials are characterized by the dependence of gas permeability
on humidity. Thus, the oxygen permeability of combined (polyamide/polyethylene) films
with an increased relative humidity increases. The oxygen permeability of polyester films
is absolutely not affected.
Packaging of cattle meat into water-, vapour- and gas-impermeable films for matura-
tion and cold storage has significant advantages. Thus, for instance, the quality of meat can
be preserved especially completely during the storage in a refrigerator if the package is
filled with a gas of a certain composition: a mixture of 8590% nitrogen and 16-10% car-
bon dioxide. This composition favours the storage of meat at a temperature of 0 to +2C.
Nitrogen serves as an inert gas medium. Carbon dioxide evolved in maturation of meat be-
gins to act, preventing the spoilage at a low temperature and a weak concentration of CO2
only in several weeks.
A favourable effect of carbon dioxide is based on the inhibition of the development of
microorganisms. A possible change of coloration due to the microbial metabolism is slower
in this case.
The concentration of carbon dioxide greater than 1015% is undesirable, because the
further increase of the concentration is accompanied by an increase of CO2 diffusion
through the packaging film, owing to which only a limited part of carbon dioxide will be
absorbed by meat fluid.
CHAPTER 2 91

Application of polyethylene terephthalate (polyester) films for meat packaging makes


it possible to avoid the use of nitrogen. Meat can be separated from bones and cut into slabs
from a quarter carcass of a temperature plus 12C and pH 6.2 immediately after cooling.
This should be done if possible in 24 days after slaughtering.
Meat of only good quality should be used for storage in films.
Cutting and packaging should be performed in facilities with a temperature of plus
812C for 2040 min. Therefore, it is important that prepackaging and packaging pre-
mises be near refrigerators.
Meat of 3 up to 10 kg weight can be packaged into polyester thermosetting packages,
as well as packages from combined films, one of the layers of which is a polyester film.
Thermosetting films are those that shrink at a short heating up to a temperature of plus
685C.
Films acquire this property as the result of a preliminary biaxial stretching. After the
action of the deforming force is removed, the resultant structure of the films becomes un-
stable. Transition to the stable structure after the external mechanical action is removed can
be delayed either by keeping the film frozen under the operating conditions, so that it is
in a glass-transition state, or else the structure of the film formed in the process of orienta-
tion is fixed by rare crosslinks, which link the chain macromolecules into a three-dimen-
sional network. If this system is warmed up, the rare crosslinks would not withstand the
tendency of breaking down the segments of chain macromolecules under the action of the
heat development of microorganisms on the surface of meat. Simultaneously, the danger of
deterioration of the quality of meat (appearance, smell and taste) is decreased. Application
of absorbing pads contributes to the increase of storage time and improvement of the quality
of meat.
Herewith, it should be taken into account that, with a pad for absorbing meat fluid, the
loss of mass is approximately 0.8%. Addition of absorbing material should correspond to
the expected loss.
Packaging into films is also recommended for storing frozen meat. This prevents its
loss of mass, change of coloration etc. In this case, its aroma, vitamins and nutritive value
are preserved. In impermeable films, packaged slabs of frozen meat preserve their useful
properties longer. While packaging into dense films is acceptable for maturation and refrig-
erated storage of only cattle meat and, on a limited scale, of veal, packaging of frozen meat
into impermeable films is suitable for all kinds of meat. For meat to be well preserved in a
packaging, its quality should be perfect. Meat should be packaged into a proper film with
all rules observed, quickly frozen and properly stored (23 weeks at 02C, maturation and
storage).
Meat of cattle should be matured prior to freezing; the maturation process is almost
stopped by freezing, and thawed meat matures worse due to the known structural and bio-
chemical changes. At room temperature, such meat remains hard for a long time. Good mat-
uration before freezing is required, first and foremost, for slabs of meat intended for
cooking.
Packaging of meat in water-, vapour- and gas-impermeable packages from polyester
films or from polyester combined films for maturation, as well as for storage in frozen con-
dition is an especially effective technique for preserving the nutrients and reducing the loss-
es. Meat matured and stored in packages, as compared with that matured and stored without
packaging, has the following advantages: it is protected from contamination and microbes,
drying, oxidation, discoloration, loss of aroma. Besides, its storage time and quality in-
crease. Such a meat has a greater nutritive value, it is more succulent and tender, and has a
92 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

better aroma. Storage of packaged meat allows a stronger circulation of air in the refriger-
ator.
Losses of mass in maturation and storage of meat in a refrigerator are restricted to ex-
udation and make 12.5% on average, whereas in usual maturation and storage without a
film they reach 47%.
Due to the use of respective film packages, losses in maturation and storage of meat
can be decreased by two thirds on average with simultaneously better maturation and in-
creased storage time. Meat in impermeable film packages shows no considerable losses of
mass not only during the freezing, but also in storage.
Dressing of carcasses, as well as cutting of meat and its processes can be more rational
and with a relatively smaller labour input.
Storage and transportation of packaged meat in stacked boxes or dispatch in cases in-
crease the labour productivity, make it possible to use the premises more rationally and in-
crease the load-carrying capacity of vehicles by almost 22%.
Packaging of frozen meat into vacuumed packages enables hygienic lossless thawing
in a bath with cold water, which is economic from the point of view of time and energy ex-
penses.
Based on modern achievements of polymer chemistry, synthetic films and materials
on their basis have been created, the use of which for protection of meat and meat products
from spoilage in combination with artificial cold make it possible to significantly reduce
normal wastage and ensure the sanitary well-being of a product.
Fabrication of meat and meat products in a packaged form contributes to the solution
of an important social problem economy of socially useful labour during the sale and con-
sumption of prepackaged products on the market, in catering trade and in housekeeping.
Unfreezing of products in microwave ovens takes only several minutes, so meals should be
prepared in such ovens in packages from polyester films of the type of SP-2.
When using polymer packagings for meat and meat products, the effect of external fac-
tors vacuum or modified atmosphere with a low content of oxygen in the packaging on
the complex multicomponent biological system can vary depending on its state, which is
determined by the character of the physicochemical and biochemical processes in muscle
and fatty tissue.
The need to solve the problem of increasing the duration of refrigerator storage of
chilled meat invariably increases as the technological processes of meat production are im-
proved.
Apart from the general increase of meat production, volumes of stored meat in chilled
state increase, the assortment of semifinished meat and meat products becomes broader.
Storage in chilled state using film materials makes it possible to preserve the food nu-
tritive value of products, to decrease losses of mass, to improve the sanitary state of products
and sites of their production, storage and sale.
At present, great attention is paid to novel methods of storing chilled meat, which are
based on vacuumizing and use of modified atmosphere. This required the development of
novel film materials, which possess an increased gas, vapour and moisture permeability;
special equipment and qualified personnel.
From the practice of storing fresh agricultural raw materials and ripening of cheeses,
it is known that the gas composition inside polymer packagings can be modified using film
materials, which possess a selective permeability for carbon dioxide, oxygen, nitrogen and
other gases.
Selectively permeable film materials (SPFM) are used as membrane inserts of soft
CHAPTER 2 93

polymer containers.
Changes of the gas composition in packages occur in accordance with the generally
known gas diffusion law, whose driving power is the difference of partial pressures of the
gases on both sides of the material. Owing to this, gas is transferred from the zone with a
high partial pressure to that with a lower partial pressure up to a point of a certain equilib-
rium.
The rate of the onset of an equilibrium state of the gas phase inside a packaging de-
pends on the selectivity of material of the insert; the rate is assessed by the ratio of the
amount of one gas to that of the other, which pass per unit of time through a unit of 1 atm.
Thus, prerequisites are established for studying the possibility of using gas selective
materials for storage and transportation of chilled meat.
Some of the products, for instance, dry kissels, concentrates of first and second cours-
es, desserts, dry beverages (coffee, cocoa, etc.), freeze-dried food products, etc. readily ab-
sorb moisture. Even small amounts of moisture, oxygen and light cause spoilage of
freeze-dried products, instant coffee, babys formulas. These products are well preserved
in vapour-, gas- and light-impermeable packaging, best of all, under conditions of deep vac-
uum or in an inert gas atmosphere. Dry food products may disturb the integrity of a pack-
aging. Therefore, the requirements to their strength characteristics should be more stringent.
Thus, during the packaging of cereal concentrates into lacquered cellophane the layer of lac-
quer is damaged by particles of a cereal.
In vacuum packaging, the mechanical impact of a dry product on the material is no-
ticeably increased, which leads to the necessity of using multilayer films based on polyeth-
ylene terephthalate. Modern weighing-and-packaging machines exert a considerable
mechanical impact on polymer film materials. This equipment is intended to be used at high
speeds (their performance often exceeds 100 packagings per minute). Packaging material
for this equipment should be strong, have a smooth surface and low friction coefficient. In
most cases, the use of soft, low-strength polymer film materials is inadmissible on modern
weighing-and-packaging equipment. Materials should be sufficiently strong, such as com-
bined materials from paper, aluminium foil, cellophane, polypropylene, polyethylene
terephthalate etc. In a number of cases, e.g., in packaging cloves, cinnamon, coriander, lau-
rel leaf powder, food concentrates, instant coffee etc., a high air tightness is required. At-
tention should be paid to the fact that a high initial humidity of a product at its airtight
packaging leads to the condensation of moisture on the inner side of the packaging and the
development of mold. Therefore, before packaging, one should be sure that the concentrates
are sterile or else to add a preservative. Thus, it is recommended to add about 0.02% of sor-
bic acid to kissel concentrates. The maximum admissible moisture content for instant coffee
is 67%.
Packaging of food concentrates into paper or cellophane with a polyethylene coating
enables increasing their shelf lives 1.5-fold, and packaging into combined materials based
on aluminium foil, more than 2-fold as compared with packaging into parchment or imita-
tion parchment paper. The shelf lives of some milk concentrates, such as coffee with milk,
cocoa with milk, cocoa with cream, coffee with cream and scalded cream in paper or cel-
lophane with a polyethylene coating increase twofold as compared with those in imitation
parchment or in labelling paper.
At present, products with a high content of fat store well in combined packaging ma-
terials based on paper, cellophane, aluminium foil with a grease-resistant coating based on
copolymers of vinyl chloride with vinylidene chloride, ethylene with vinyl acetate. These
coatings are applied as a melt and water emulsions latexes. Fatty products store well in
94 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

containers from cellulose derivatives ethrols. Food concentrates of the first and second
courses are well stored in combined materials based on aluminium foil. Herewith, it is rec-
ommended to add into the fat-containing concentrate of a food product an oxidation-pre-
venting substance, e.g., dodecyl gallate (up to 0.01% of the weight of fat).
Application of paper with a coating from polyethylene (viscotene) or cellophane with
a polyethylene coating (PC-2, PC-3, PC-4) instead of imitation parchment makes it possible
to increase the shelf life of milk concentrates from 34 up to 68 months. For packaging
of dry products from potato, the following are successfully used: for semifinished crackers,
a polyethylene film and paper with the polyethylene coating; for roasted crackers, PC-2
film; for potato crisps, a film from a mixture of different grades of polyethylene, PC-2, etc.
For packaging of dried potato with a moisture content of 68%, four-layer kraft paper bags
with a double polyethylene coating were successfully used. In this packaging, the product
was stored up to 6 months without losing its edibility characteristics. Freeze-dried fruits,
berries, purees and other products store well in glass and tin cans. However, this kind of
containers have drawbacks: they are brittle, unsuitable for transportation (glass containers),
they corrode (tin cans), their weight is large (sometimes exceeding the weight of the con-
tents nine times). Therefore, more advanced containers for these products are made from
polymer films, e.g., lavsanpolyethylene (SP22), films based on aluminium foil plied up
with polypropylene or a mixture of certain brands of polyethylene (steralkon, lamister, fol-
goplen), polyethylenepaperfoil, etc. Materials based on foil with application of a poly-
ethylene film or SP-2 film possess the best protective properties.
As food products degrade, there occurs decomposition of vitamin C. The better a con-
tainer is, the slower the decomposition of ascorbic acid proceeds. The efficiency of the pro-
tective properties of containers could be judged by the change of coloration of products in
storage, as well as by the change of the composition of aromatic compounds present in the
food product.
Airtight packaging of food concentrates can be done into packages from polymer and
combined materials on packaging lines. For this purpose, both Russian equipment (e.g., of
the type of the KMKh-75 automatic machine) and Western equipment (e.g., of the company
Hassia GmbH) are used.
Granular food products, e.g., corn flakes and dry breakfasts, are packaged into rectan-
gular boxes from chrom-ersatz paperboard (240250 g/m2) with the inner package insert
from thin paper (4070 g/m2) coated with polyethylene. This line is manufactured by the
Swedish company Cristiagren.
The tendency of manufacturing food products both in this country and abroad is that
products of a high degree of preparedness become more widespread. In particular, frozen
ready-prepared meals, semifinished products, fruit-and-vegetable juices, etc., are offered
for sale in increasing amounts. Packaging of food products intended for freezing can be car-
ried out by various methods. Thus, for instance, trays fabricated from an aluminium alloy
with several divisions are used for this purpose. The inner surface of the trays was covered
with a corrosion-resistant lacquer; its upper surface was finished with lacquered aluminium
foil, which was sealed to the lips of the tray. For packaging of frozen products, containers
from polymer materials are used, sometimes in combination with traditional materials. At-
tempts are made to fabricate containers withholding the sterilization by boiling followed by
warming-up in hot water. Packages from a polyethylene terephthalate film plied with a
polyethylene film are used for this purpose the most. A package fabricated from such a ma-
terial (e.g., from SP-2 film) is transparent, which makes it possible to see its contents. The
main requirements to the material for packaging frozen ready-prepared meals are as
CHAPTER 2 95

follows: its use should be permitted by the State Sanitary Inspection for contact with a given
concrete product under concrete conditions of storage, transportation, sale and use; it should
be sufficiently processable and economical, airtight, strong and elastic.
For a material not to become brittle at a deep freezing to minus 5060C or refrigerator
storage at minus 2030C, it should be sufficiently elastic. Besides, packaging material in-
tended for prepackaging frozen ready-to-eat meals should withstand rapid defrostation and
warming-up of the packaged product in boiling water.
As the packaged food product is protected by polymer material, it proves to be possible
to use for its freezing the most progressive method of contact freezing. This method is per-
formed in contact plate freezers or in refrigeration brines. The packaging prevents the prod-
uct from spoilage by burns. Slowing-down of the chemical reactions at low temperatures
enables the use of polyolefins, such as polyethylene and polypropylene, in contact with fatty
products.
Frozen ready-prepared meals, as a rule, are packaged either into packages from
single-layer or multi-layer polymer materials, or else into boxes of various designs with
thermoplastic coatings.

Type of food product Recommended kinds of packing materials

Non-long-term storage Long-term storage,


stringent storage conditions

Dried fruits and vegetables Polyethylene-coated kraft paper Polyethylene-coated polyester


Polyethylene-coated cellophane (lavsan)
Corn products (popcorn, corn- Polyethylene-coated paper and Polyethylene-coated aluminium
flakes), oat diet products, paperboard foil (lacquered on the outside)
kissels, dried potato puree and Polyethylene-coated cellophane
other dry products containing Polyethylene film
no fat
Potato fried in oil (chips, Lacquered cellophane Lacquered aluminium foil with
crackers) Fat-resistant copolymer-coated fat-resistant copolymer coating
paper
Food concentrates (first and Polyethylene-coated paper. Lacquer aluminium foil,
second courses) containing Polyethylene-coated cellophane paper polyethylene
no more than 1015% fat Lacquer paper, aluminium
foil polyethylene
Food concentrates containing Fat-resistant copolymer-coated Lacquer aluminium foil,
more than 15% fat paper and paperboard paper fat-resistant copolymer
Fat-resistant copolymer-coated coating
cellophane Lacquer paper, aluminium
foil fat-resistant copolymer
coating
Milk concentrates (based on Polyethylene-coated cellophane Cellophane aluminium
coffee, cocoa) foil polyethylene
Instant coffee Cellophane aluminium foil Cellophane aluminium
polyethylene foil polyethylene
Spices and food additives Lacquered cellophane Cellophane aluminium foil
Polyethylene-coated cellophane polyethylene
Cellophane aluminium
foil copolymer coating
(of the type of CVC)
96 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

(continued)
Type of food product Recommended kinds of packing materials

Non-long-term storage Long-term storage,


stringent storage conditions

Freeze-dried food products Polyethylene-coated lavsan Lavsan aluminium foil


(humidity 23%) Cellophane aluminium foil polyethylene
polyethylene Polyethylene lavsan
adhesive lavsan poly-
ethylene; polyethylene lavsan
adhesive fluoroplastic
polyethylene; lavsan alumi-
nium foil polyethylene
aluminium foil polyethylene

Packages from polyethylene terephthalatepolyethylene SP-2 are characterized by the


range of working temperatures from 70 up to +120C. Ready-prepared meals are frozen
at these temperatures at a temperature of minus 6070C, and unfreezing and warming-up
can be performed directly in the package. It takes the customer a minimal time to prepare
the frozen product for consumption. If the frozen product, e.g., the first or second course,
is to be consumed in the hot state, its preparation would take a maximum of 12 min or less
if a microwave oven is used. If the frozen meal is to be consumed in the cold state, e.g., it
is a dessert, then its preparation requires about 1 min. After the preparation, the product can
be put from the package into dinnerware by cutting one of the sides of the package.
Frozen meals can be packaged into films either from high-density polyethylene or
from a mixture of low- and high-density polyethylenes. These films withstand sterilization
in boiling water at 120 and even 130C, they are more transparent and more resistant to fats.
Films from polypropylene are well heat-sealable. Films from polyethylene terephthalate are
characterized by even better protective properties. They withstand the action of low (minus
4460C) temperatures and boiling in water at 130C, are low-permeable for vapours and
gases; are characterized by a good resistance to attrition and impact loads. Their disadvan-
tage is poor heat sealability, which in practice makes impossible the use of these films on
automatic packaging lines. Therefore, the polyethylene terephthalate or, as it is often called,
polyester film is plied with a film from polyethylene or polypropylene. The polyethylene
terephthalate film provides for such properties of the material as strength, resistance to at-
trition, gas impermeability.
The inner layer from polyethylene or polypropylene ensures the heat sealability of the
material. Its disadvantage is that it is in short supply and expensive.
As we mentioned above, storage of the most biologically active products or in pro-
longed storage times of food products requires that packaging material has a combination
of high protective properties and light permeability. In these cases, multilayer polymer film
materials are successfully used, one layer in which is aluminium foil.
Such a type of packaging material, e.g., for packaging infants food, was developed at
the Moscow Technological Institute of Meat and Dairy Industry together with workers of
from the Paper-and-Packaging Plant of the Ministry for Meat and Dairy Industry. It was
called folgoplen. Cellophane from an unreeling roll is fed to the plying rolls of a Werner
and Pfleider line. Before the bands of cellophane and aluminium foil are pressed together
by the rolls, a thin layer of polyethylene melt is to be put between them on the cellophane
surface. This thin layer is to paste cellophane and foil together. This operation produces a
CHAPTER 2 97

three-layer (cellophanelow-density polyethylenefoil) film. This material is made heat


sealable by applying a polyethylene melt on the foil. The layers of polyethylene melt ap-
plied from above are not pressed one to another until the polyethylene melt hardens. There-
fore, to provide for a sufficiently good adhesion of the layers one to another, the
polyethylene melt is applied at a high temperature of the order of 270C. At this tempera-
ture, intensive oxidation of polyethylene is initiated. The active centres formed in polyeth-
ylene molecules are capable of interacting with the packaged product, causing undesirable
chemical reactions, which lead to spoilage of the packaged product. An example of these
reactions is the rancidification of fat. To avoid such phenomena, one more layer of poly-
ethylene is applied on the surface of the oxidized polyethylene layer at a temperature suf-
ficient for it to melt but insufficient to be oxidized.
To increase the strength of adhesion at as low temperature as possible, the surface of
films is treated by a corona electric discharge.
Besides folgoplen, other light-impermeable materials with high protective properties
are polyethylenefoilpaperpolyethylene, cellophanefoilpolyethylene and others.
As for boxes from paperboard, chrom-ersatz or dense paper coated with a layer of ther-
moplastic polymer, the following combinations are the most recognized: the outer layer
paraffinepaperthermoplast; paper can be replaced by chrom-ersatz. The material con-
sisting of paraffinepaperaluminium foilthermoplast is widespread. In all combinations
considered, the inner layer is a thermoplast, which is polyethylene or polyvinyl chloride,
polyisoprene hydrochloride, saran (copolymer of vinyl chloride CH2=CHCl with vi-
nylidene chloride CH2=CCl2), compositions of copolymers with paraffine.
Great importance is attached to the expansion of production of ready-prepared meals,
including frozen stuff. To date, many frozen ready-to-eat meals are manufactured, such as
meat balls in red sauce, stewed beef, beef goulash, minced beefsteak, kidneys in red sauce,
stewed pork. Two portions of these meals are packaged into paperboard boxes 1207050
mm in size. A similar packaging for four portions is also used. In this case, the paperboard
box is 1809050 mm in size. Inside, boxes are layered with lacquered cellophane. The
packaged product is frozen in fast freezers at temperatures of minus 3040C for 23 h.
Within this time, the temperature in the bulk of the product reaches 18C. At approximate-
ly this temperature, ready-to-eat meals are stored in refrigeration chambers for up to one
year. Frozen meals are transported at temperatures not higher than 15C. In trading net-
works, they are stored at a temperature of 18C. In five months of storage at minus
1820C, frozen ready-to-eat meals, packaged into a paperboard box with an insert from
lacquered cellophane and heat sealed, lose from 1 up to 3% of their initial weight.
Frozen fruit juices preserve well their valuable nutritive properties in polymer contain-
ers. Being packaged into bags from the polyethylenecellophane film PC-2, frozen fruit
juices preserved their taste, colour, flavour, vitamin content for three years of refrigeration
storage at a temperature of minus 1820C. These results were obtained in storage of frozen
apple, grape, tomato, cherry, black-currant etc. juices. Similar results were obtained in stor-
age of these juices in packages from paper with a polyethylene coating and from multilayer
film material (cellophanealuminium foilpolyethylene).
Commercial production of frozen juices tomato, apple and grape in Tetra Pack
packages was introduced. The packaging material was paper with a polyethylene coating
on one side and with a thin layer of paraffine on the other side. This material was first ster-
ilized by irradiation by a bactericidal lamp, and then was converted into a hose by wrapping
and heat sealing the longitudinal seam. Sterilized fruit juice was fed to the hose thus ob-
tained. The transverse sealable elements form a chain of tetrahedral packages cut from the
98 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

hose. The cut tetrahedra are put into transport containers. After packaging, the juices are
immediately frozen in fast freezers. The freezing takes 3.54 h.
The described freezing method, in contrast with thermal preservation of, e.g., tomato
juice, enables preserving a major part of vitamin C, whereas the microbiological character-
istics (bacterial content) in storage of frozen juices at 18C for one year do not change in
practice. Frozen juices are defrosted in the package. If the unfreezing is done in the air, its
duration is 56 h; in flowing water, it lasts 1.01.5 h. Unfrozen (defrosted) juices are stored
in the package in different ways depending on the conditions: at room temperature, no more
than 24 h after defrosting; in a domestic refrigerator, for up to one week; and in refrigeration
cabinets of trading networks (at a temperature of 8C), for up to two months.
Automatic lines similar to those described enable packaging of spreads (jams, creams,
concentrated fruit-and-vegetable juices) also in packages from polymer and combined ma-
terials of the type of PC-2. Packages from paper with a polyethylene coating are also used;
sometimes, even simply from polyethylene.
Concentrated and natural juices, sauces, syrups, fluid food concentrates in general are
at present packaged either into paper or paperboard containers with a polymer coating, or
else in bottles or canisters from polymer materials. Fluid preserved products are success-
fully packaged into rectangular and tetrahedral containers. The prepackaging of natural and
concentrated juices into these containers, which are characterized by a high airtightness, is
similar to that of long-storage milk into tetra packs. Such packaging lines (Tetra Pack Acep-
tic) were developed by the Swedish company Tetra Pack and found wide use not only for
packaging milk but also for aceptic filling of fruit-and-vegetable juices and other fluid food
products.
A combination of paraffinepaperaluminium foilpolyethylene is used as a material
for packaging fruit-and-vegetable juices. This material is passed as a band through a bath
with a hydrogen-peroxide solution and is used to form a continuous tube with the continu-
ous sealable seam. The inner surface of the tube is warmed up by an infrared source to elim-
inate the remaining hydrogen peroxide and for additional sterilization. A food product is
fed to the sterilized tube. Naturally, the bottom of the tube is sealed by the transverse seam.
The transverse sealable seams are implemented by means of sealable elements, as the tube
is filled with a food product. The continuous chain of tetrahedra formed in this way is cut
into separate packagings.
The packaging material used for these purposes it consists of the outer layer of par-
affine or lacquer, then paper, aluminium foil and the inner layer of polyethylene is char-
acterized by the capability of being heat-sealed and forming airtight packagings. It protects
well the packaged product from microorganisms, light, oxygen, air; and prevents the loss
of moisture. In such a packaging, it is possible to store natural or concentrated
fruit-and-vegetable juice under usual conditions for up to one year.
Polymer materials characterized by a high gas impermeability are also used for storage
of sterilized food products. In this case, the bactericidal action of gaseous chlorine, form-
aldehyde, propylene oxide, ethylene oxide and other gaseous substances is used. In preser-
vation of food products in polymer packagings, it is natural to use only hygienically
harmless gaseous ethylene oxide and propylene oxide, as well as a mixture consisting of
60% ethylene oxide and 40% carbon dioxide. Under usual conditions, inhibition of the mi-
croflora in such a gas mixture takes 46 h. To provide for the safety (to exclude the possi-
bility of explosion), mixtures of ethylene oxide or propylene oxide (no more than 17%) with
such inert gases as nitrogen, carbon dioxide, freon, etc. are used. The process is accelerated
by increasing the pressure of the gases up to 68 kgf/cm2. The thickness of the walls of the
CHAPTER 2 99

polymer packaging should not exceed 60 m.


Sterilization of food products by gaseous substances can be done not necessarily in
polymer packagings with good gas permeability. If a product is packaged in an airtight
package from polymer material with low gas permeability, the polymer package is vacu-
umized, filled with a bactericidal mixture of gases and sealed. In this case, the materials
used are based on foil, such as cellophanealuminium foilpolyethylene,
cellophanepolyethylene. The absence up to the present of domestic packaging materials
of the type of lavsanfoilpolyethylene mixtures, lavsanpolyethylene, etc. is due to the
lack of supply of polyethylene terephthalate. Its high cost as compared with cellophane is
compensated by the adaptability of the packaging process and a high quality of the pack-
aging.
The specific properties of these materials are especially pronounced in packaging ther-
mally preserved food products. This preservation can be performed both at 100C and at a
higher temperature. In the former case, the treatment process is called pasteurization; in the
latter, sterilization of the food product. In thermal preservation, the polymer packaging ma-
terial should be temperature-resistant. At a temperature higher than 100C, an increased
pressure is created inside the packaging, so special attention should be paid to the ability of
the material to form strong seams and to preserve airtightness of the packaging within the
entire range of working temperatures.
In practice, there is no individual polymer film, from which one could fabricate a pack-
age suitable for thermal preservation of food products in it. This is due to the fact that, as a
rule, heat-resistant polymer materials poorly yield to heat sealing. Besides, there are a num-
ber of other reasons, such as unsatisfactory sanitary-hygienic properties, strong deforma-
tion or thermosetting; high gas, vapour and aroma permeability, owing to which polymer
materials are used for the considered method in combination with other polymer materials
or with aluminium foil. In such combinations, high-density polyethylene and its mixtures,
polypropylene, polyamide, polyethylene terephthalate etc. are used for thermal preserva-
tion of food products in packages.
The most widespread combinations of individual films in combined film materials for
packages suitable for thermal preservation of food products are as follows.
Polyethylene terephthalatelow-density polyethylene is suitable for thermal preser-
vation at a temperature not higher than 105C and for packaging products containing no
more than 30% fat. If, instead of LDPE, a mixture of low- and high- (or medium-) density
polyethylenes is used, then the combination of polyethylene terephthalate and polyethylene
withstands sterilization at a temperature of 120C. The material described above but rein-
forced with the central layer of aluminium foil was found to be good in long-time storage
of sterilized products. In the recent decade, the most advanced material for storage of food
products proved to be a combination of polymer lacquerplastic aluminium
foiladhesivepolypropylene. As a rule, this material is used for fabrication of contain-
ers/packagings by the deep draw extrusion method. The polypropylene film in particular
cases can be used for sterilization of food products in the heat treatment up to 130C and
as an individual film. However, owing to its high oxygen permeability, the film from
polypropylene can not be used for storage of products sensitive to the action of oxygen, and
such products are numerous.
For sterilization of food products with a high content of fat at a heat treatment up to
130C the French company Organico manufactures a film material from polyamide under
the tradename of Rilsan. For heat treatment of any food products by heating up to 130C,
a film from polytrifluorochloroethylene can be used.
100 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

An example of the thermal preservation of food products in packages from a polymer


material is a method of pasteurization of dried fruits: plums, cherries with increased
moisture content of up to 30%. This method was developed in the Moldavian Research
Institute of Food Industry. Hermetically sealed into packages from polyethylene or
polyethylenecellophane film PC-2, dried fruits (200-gram portions) are passed through a
tunnel convection drier. The total time of holding a package in the drier is 12 h at a tem-
perature, which provides for the warming-up of the product up to 8085C. At this temper-
ature the product is pasteurized, which enables preserving products with up to 30% moisture
for no less than one year.
Above, we have already attracted the readers attention to the fact that in the described
methods of preservation special attention should be paid to the strength of sealed seams and
to the prevention of the loss of airtightness of the packaging owing to the increase of pres-
sure inside the package. Research has shown that the strength of sealed seams should be no
less than 80% of the strength of the base material. The maximal strength of the heat seal is
provided for at its width of 56 mm, and in the case of thermoshrink materials it should be
even smaller. At the width of 120 mm, the strength of the seal seam decreases owing to
the setting of the material and the emergence of internal stresses, which contribute to its
breakdown. To compensate for the pressure emerging inside the package at the thermal ster-
ilization in an autoclave or in a sterilization vessel, a counterpressure is created and main-
tained. During the sterilization of the products in packages from polymer materials, a
pressure exceeding that emerging inside the package is maintained in the autoclave. Other-
wise, packages inflate. As the autoclave begins to be cooled, the heat carrier cools down
quicker than the content of the package. Owing to this, the difference of pressures in the
package and outside it can prove to be larger than the value the package can withstand with-
out breaking down. To avoid the disturbance of airtightness of packages, special attention
should be paid to the maximally possible elimination of air from packages prior to their seal-
ing.
Sterilization studies of such products as tomato pulp and collops in polymer packages
showed an advantage of the steam-air method of thermal sterilization over the water meth-
od, because it is easier to maintain the set parameters of the process in the former case. The
external pressure in the course of the process should be 0.20.3 atm higher than the internal
pressure. At a temperature of 100C, the counterpressure should be of the order of 1.251.3
atm. At a higher temperature, excess pressure is increased by 0.3 atm for each 5C. In ster-
ilization by this method at 100C of fruit juices, at 117C of liver sausage and at 121C of
green beans and soup from champignons, the best results were obtained for films from
polypropylene and polyamide. The sterilization process took 1530 min. The quality of the
products was preserved for 6 months. Until now, heat treatment of food products in pack-
ages from polymer materials has been considered. However, thermal preservation of food
products in polymer containers can also be successful.
Herewith, thermal preservation of such fruit-and-vegetable products as juices, com-
pots, confiture, jam can be done at a temperature not higher than 100C. Packaging of these
products into polymer containers is sufficiently easy. In some cases, the product heated up
to the required temperature is poured into containers, and in other cases the packaged prod-
uct is heated in containers at a temperature of 80100C. The described method of steril-
izing food products in polymer containers is characterized by some features. As rigid and
semi-rigid containers are readily deformed both at excess internal and at excess external
pressure, the success of the process depends on the correct choice of the regime of applica-
tion and removal of the counterpressure.
CHAPTER 2 101

Fabrication of polymer containers is accompanied by the emergence of the so-called


internal stresses. Under the action of these stresses, a nonuniform shrinkage develops dur-
ing the heating of containers. The shrinkage is avoided by the correct choice of the regimes
of application and extent of counterpressure. This choice is required in transition from one
type of polymer containers to another, as well as in changing the sterilization regime. The
use of vacuumizing of the packaging should be specially accounted for. Shrinkage and the
related change of shape of the polymer containers are eliminated by warming the containers
before filling them. Thus, for instance, cups from high-density polyethylene or from
polypropylene should be warmed before filling for 30 min at a temperature 510C higher
than the sterilization temperature, i.e., for HDPE at 110C and for polypropylene at 130C.
The sterilization regime in such cups is characterized by a maximal temperature of
120125C.
Rigid polymer containers are closed either by metal or polymer lids. When using metal
lids, the sealing of polymer containers is done by mechanical methods similar to those used
in the case of tin or glass containers. These methods include vacuumizing. When using
polymer lids, the sealing is done by heating, and vacuum is created either by special means
or due to a decrease of volume of the product during its cooling. In sterilization of food
products in polymer packages with metal lids, it is recommended to use the following val-
ues of counterpressure: at the sterilization temperature of 105C, counterpressure of 0.7
atm; at 112113C, 0.8 atm; at 116117C, 0.9 atm; at 129C, 1.0 atm.
In the recent decade, another widespread method of sterilizing food products has been
sterilization by radiation. This method imposes special requirements on polymer materials,
such as resistance to ionizing radiation within the limits of the doses used in preservation;
absence of harmful substances emerging in this method of sterilization; absence of foreign
taste and smell. Tests have shown that in sterilization of food products by gamma rays from
a cobalt source at doses common for preservation of food products (0.55.0 Mrad), the ma-
jor characteristics of a number of polymer materials do not undergo noticeable changes.
Such materials include, for instance, films from polyethylene, polypropylene, polyamide,
polyethylene terephthalate. The characteristics of strength, gas and vapour permeability,
as well as specific characteristics mentioned above remain within the normal limits. Such
films as from polyvinyl chloride, from copolymers of vinyl chloride with vinylidene chlo-
ride, from polyisoprene hydrochloride have a foreign smell when irradiated even by the dos-
es of 0.10.2 Mrad. The most resistant to radiation sterilization of food products are
considered to be cellophane lacquered with nitrocellulose lacquer, nonlacquered cello-
phane, polyethylene terephthalate and polyamide films.
At the radiation impact on multilayer polymer and combined materials, the endurance
of the least-resistant components increased about 1.5-fold. A foreign smell emerging in ir-
radiation of polyethylene is due to the evolution of gaseous products: carbon dioxide, hy-
drogen, ethylene, propane, butane. In irradiation of polyethylene terephthalate, the evolved
gases were carbon dioxide, nitrogen, oxygen, water vapours and other volatiles. Irradiation
of films from copolymer of vinyl chloride and vinylidene chloride yielded a number of gas-
eous products with a sharp smell: chlorine, hydrogen chloride, hydrocarbons and some car-
cinogenic products.
In domestic practice, good results were obtained in radiation preservation of a number
of fresh fruits and vegetables, raw meat, meat culinary products, poultry and other food
products in polymer packagings. As a rule, products were subjected to small radiation doses
(0.51.2 Mrad). The most promising in this respect proved to be films of the type of PC,
paper with a polyethylene coating, polyethylene terephthalate films. In this case we mean
102 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

domestic polymer materials, to which we should also add lacquered cellophane suitable for
this kind of sterilization of products not containing a large amount of moisture. Polyamide
films of the type of rilsan and nylon showed good characteristics. Of special interest are the
results of radiation treatment (0.6 Mrad) of beef meat packaged into cellophane with a poly-
ethylene coating. Meat treated in this way had no foreign smell and stored well under room
conditions for up to two weeks. Pork at the same method of preservation stored for up to
three weeks. Hens and ducks, at a slightly large irradiation dose (1.0 Mrad), stored under
room conditions for up to one month. Meat culinary products irradiated with 0.8 Mrad
stored in this packaging for up to four months.
The described method of storage is also applicable for fish and fish products. Irradia-
tion by a dose of 1.0 Mrad at a temperature of 05C made it possible to store unfrozen
herring for 60 days, fresh pike for 60 days, unfrozen cod for 120 days, fried fish for 60 days,
fish in tomato sauce and in vegetable marinade for 365 days.
With the rise of production and due to the appearance of polymer materials exceeding
the traditional materials (wood, tin, cardboard, paper, glass, natural cotton fibres, tarpaulins
etc.) fish industry came across the problem of using these advanced materials as packaging
and containers for transportation and storage of fish products; consumer containers for
packaging and sales of various fish products, including culinary products.
To provide for the introduction of new materials in fish industry, R&D and process
design units were organized to carry out work in the following directions:

research into polymer materials satisfying the physicomechanical and sanitary-


hygienic requirements to packagings and containers for fish products and to synthetic fibres
for fishing nets and tackles
development of polymer containers designs
mechanization of prepackaging/packaging of fish products into polymer containers
R&D works for the organization of enterprises and plants for production of polymer
containers.

These measures made it possible to organize production of polyethylene boxes of


1025 litres in capacity; polyethylene barrels of 50 litres in capacity; small packages with
overprinting; inserts, bags and packages for whale meat, salt fish, frozen fish; 1.5-litre poly-
ethylene cans with overprinting; polyethylene cans of 0.10.4 litres; trays from polyvinyl
chloride.
Production of goods in small packages was increased. For processing of marketable
fish products, new fish-processing complexes were put into operation for production of fish
delicacies in places of consumption.
For packaging of products into consumer containers, use is made of polymer films,
cartons and combined materials based on paperboard, paper, foil with a polymer coating.
The use of polymer materials for packaging, transportation and storage of fish products
makes it possible to free traditional materials woods, white tin, aluminium, glass, etc. This
decreases the costs and consumption of materials in production of containers/packagings.
For instance, production of a 50-litre barrel from polyethylene for packaging cod liver oil
requires three times as less materials as compared with 10-litre glass flasks.
New combined packaging materials used in fish industry are aluminium foil poly-
propylene (of the type of steralkon) and aluminium foil coated with heat sealable lacquers.
The steralkon packaging is strong, light, glossy; makes it possible to produce solid-drawn
cans of various configurations, which possess airtightness and enable sterilization of the
CHAPTER 2 103

product. There are several lines manufacturing these cans for fish industry.
Domestic industry assimilated the filling and closing equipment operated on polyvinyl
chloride and polystyrene (cases of packagings) and aluminium foil with heat sealable
lacquer (lids of packagings).
104 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY
3 Combined Packaging
Materials Using Cellulose
and Its Derivatives

3.1 Internal stresses in coatings using cellulose


Polymer coatings find wide use for protection and decorative finishing of traditional mate-
rials (metal, woods, glass, paper, etc.), as well as in the development of plied and combined
materials of various purposes.
In developing the physicochemical bases for production of these materials, of great im-
portance is to study the effect of structural transformations on the properties of polymer sys-
tems in their transition from the liquid to the solid state. A peculiar feature of this transition
for polymer coatings is that their formation mechanism passes the stage of gelation and is
accompanied with a sharp inhibition of relaxation processes, which lead to the emergence
of internal stresses (BH).
Studies of the durability of polymer coatings have established that their service life is
largely determined by BH, capable of inducing the spontaneous exfoliation and decompo-
sition of polymer coatings on rigid and elastic supports. Therefore, of great scientific and
applied importance is to develop the physicochemical ways of decreasing BH. This prob-
lem is topical in developing packaging materials for food products, as they affect the pro-
tective properties of packagings.
Usually, low-molecular-mass plasticizers are used for this purpose. Their mechanism
of action is related to the weakening of intermolecular interaction between structural ele-
ments and to the increase of their mobility, which leads to the relaxation of stresses. This
effect is also achieved in the formation of polymer coatings under more mild conditions,
e.g., at (relatively) low temperatures. However, the use of these regularities for monitoring
structure formation in polymer systems is not always efficient, as, along with the decrease
of BH, the physicomechanical, adhesion, thermophysical, dielectric and other properties
are considerably worsened in this case.
In this connection, it is important to decrease BH not during the weakening but during
the intensification of intermolecular interaction between the structural elements. This
would also make possible a considerable improvement of the performance properties. This
effect is achieved by forming a three-dimensional network from supramolecular compo-
nents available in the liquid system before the onset of its solidification due to the emer-
gence of local bonds, whose strength is commensurable with the energy of thermal motion.
The appropriateness of forming such a network ensues from the new views of the mecha-
nism of BH in polymer systems. The regularities establishing the interaction between the
106 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

character of structural transformations in liquid systems and the incompleteness of relax-


ation processes were the basis for developing new physicochemical views of the ways to
decrease BH in polymer coatings, based on the development of an ordered thixotropic
structure in film formers and fixing it in ready-prepared products. This is the essence of the
phenomenon of a decrease of BH.
Thixotropy is one of the forms of gelation: such a gel is transformed into a fluid at a
weak mechanical impact, e.g., in mixing, and in a quiescent state a network again emerges
in the fluid; the peculiar feature of the network is that overstresses in it rapidly relax, which
enables formation of products with higher performance characteristics. The effect of a thix-
otropic decrease of BH is universal and is observed during the formation of polymer coat-
ings, adhesive layers, filled and reinforced systems from monomer and oligomer
compositions, solutions and dispersions of polymers of different chemical composition.
However, not all polymers are readily transformed into thixotropic gels, so new
methods of creating them in various film-forming systems were developed. This is achieved
by introducing special additives to liquid systems. In some cases, these are oligomers form-
ing bridges between supramolecular structures; in other cases, polymers creating a three-
dimensional network in monomers, oligomers, dispersions and solutions of polymers.
For polymer dispersions with large particles, universal modifiers are efficient: first
they break particles into more fine structural elements, and then crosslink them into a
three-dimensional network. The role of these modifiers can be played by monomers and oli-
gomers, polymer electrolytes adsorbed by particles of dispersions, surfactants.
The gel formation mechanism was studied by various physicochemical methods:
infrared spectroscopy, high-resolution nuclear magnetic resonance, electron paramagnetic
resonance, scanning and transmission electron microscopy; rheological, thermophysical,
physicomechanical etc. methods.
The phenomenon of a thixotropic decrease of BH does not depend on the method by
which the thixotropic structure is created; it can be produced as the result of adding poor
solvents, branched oligomers, crosslinking agents, structuring systems, surfactants, dis-
persants.
In many cases, it is much more convenient to work with thixotropic systems than with
liquid or solid systems. They are processable, impregnate fibrous materials less and do not
bleed on paper, which is important in printing production and other industries.
The development of a thixotropic structure makes it possible not only to considerably
improve the performance characteristics of polymer coatings. In a number of cases, it en-
ables the complete exclusion of low-molecular-mass plasticizers (readily dropping out in
the process of ageing and, thus, sharply decreasing the durability of the coating) from the
formulation of rigid-chain polymers. The authors used the phenomenon of a thixotropic de-
crease of BH to develop elastic polymer coatings based on nitrocellulose (NC) with high
physicomechanical properties. Usually, plasticizers are used for this purpose in polymer
coatings from NC, in particular, castor oil, which is in short supply, at a 1:1 ratio. Grafting
of other polymers to NC does not exclude plasticizers, either. NC was modified by poly-
urethane oligomers with a 0.30.5 ratio of the isocyanate and hydroxyl groups. The extent
of oligomer branching was regulated by introduction of different amounts of triol. Figure
3.1 presents the kinetics of BH changes during the formation and ageing of polymer coat-
ings. It is seen that significant BH emerge in polymer coatings from nonplasticized NC.
Introduction of castor oil at a ratio of 1:1 decreases BH by an order of magnitude. However,
the properties of such polymer coatings are unstable, which is indicated by a sharp increase
of BH during the thermal ageing of polymer coatings. A significant decrease of stresses is
CHAPTER 3 107

5 1.0
1

in, MPa
3 0.6
2
3
4
1 0.2 5

4 8 12 40 80 120
Time, h

Figure 3.1 Kinetics of the buildup of internal stresses during the formation and thermal ageing of
polymer coatings from a 10% solution of NC in butyl acetate: initial (1), plasticized by castor oil (2),
modified by weakly (3), medium (4) and strongly (5) branched oligomer.

observed as a thixotropic structure is created in polymer coatings by means of highly


branched oligomers. Polymer coatings from such systems are distinguished by good phys-
icomechanical properties (see Table 3.1) before and after the ageing.
Table 3.1

Additive NCO/OH Content of Tensile strength, Breaking elongation,


additive, MPa %
weight
fraction before after before after
ageing ageing ageing ageing

Polyurethane oligomer,
weakly branched 0.3 90 24.0 23.4 48 50
0.5 90 28.1 28.0 80 81
0.5 110 8.5 8.8 91 96
strongly branched 0.3 90 28.6 29.3 60 60
0.4 90 32.4 31.5 60 60
0.5 90 43.7 39.2 20 22
medium branched 0.0 100 0.06 0.03 640 600
0.1 100 2.0 3.3 247 213
0.3 100 7.6 8.3 95 88
0.5 100 8.7 10.0 76 72
0.7 100 10.0 15.0 48 41
Castor oil 90 16.7 60
100 14.7 13.1 51 30
110 14.6 11.8 68 50

Polymer coatings from NC are characterized by an inhomogeneous globular structure.


The globular morphology of the structural elements is preserved in the presence of castor
108 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

a b

Figure 3.2 Structure of polymer coatings from initial NC (a) and NC modified by a thixotropic
additive (b).

oil. The character of structure formation is changed significantly in the development of a


thixotropic structure, which is also indicated by the change of the rheological properties. It
is seen that solutions of initial NC and polyurethane oligomers represent weakly-structured
or Newton-type systems. Their modification by castor oil and weakly branched oligomers
does not change the character of the rheological curves. Formation of a thixotropic structure
is observed in a solution of NC in the presence of a highly branched oligomer. The cause
of this phenomenon was shown by the method of IRS to be related to the formation of hy-
drogen bonds between hydroxyl groups of NC and the modifier.
These regularities were used to produce a thixotropic structure in solutions of poly-
mers of different chemical composition with the view to improve the properties of polymer
coatings: polyurethanes, polyester amidourethanes, chlorinated rubbers, nairites and chlo-
rinated nairites, block copolymers (Fig. 3.2) .
Depending on the purpose of polymer coatings, the thixotropic structure can be formed
by choosing the nature of solvent; introducing a surfactant with a definite structure of mol-

4
1

2
3
3 5

1
log

2 2
4
3
1
a b
0
1 2 3 4 1 2 3 4
log p

Figure 3.3 Dependence of viscosity on shearing stress for 10% solutions of the initial components
(a) and modified NC (b): a, for strongly (1), medium (2), weakly (3) branched oligomers and initial
NC (4); b, for NC modified by weakly (1), medium (2), strongly (3) branched oligomer and castor
oil (5).
CHAPTER 3 109

ecules, bifunctional compounds of polymers forming a network skeleton on solutions of the


base polymer, monomer or oligomer (Fig. 3.3).

3.2 Moisture-resistant packaging materials based on cellophane

3.2.1 Justification of the composition of the coating


Compositions based on modified cellulose became widespread in food industry as packag-
ing materials. This is due to the fact that packaging of food products into polymer materials
significantly extends their shelf life, reduces losses in transportation and its costs. Besides,
most film materials are transparent, they colour well and take up ink printing, which enables
presenting a packaging in a good marketable state.
One of the most widespread film polymer materials is hydrated cellulose film, cello-
phane. It has such valuable properties as a high mechanical strength, gas impermeability,
grease resistance and transparency. However, it also has a number of drawbacks, which sig-
nificantly restrict its applications. In an elementary link, the hydrated cellulose macromol-
ecule has three hydroxyl groups, which is the cause of a large affinity of cellophane to water.

CH2OH H OH
C O C C
H H
H OH H
C C O C C O
OH H
H H
C C C O
H OH CH2OH
n

A film from hydrated cellulose contains up to 12% of water and about 11% of glycerol.
Its thickness is from 20 up to 50 m and its mass is 30100 g. To make cellophane hydro-
phobic, films are lacquered with a layer of 24 m cellulose ester or a synthetic polymer.
Swelling in water for 1 h by about 50%, cellophane loses its mechanical strength two-
fold. Besides, not being a thermoplast (and degrading when heated up to 170180C), cel-
lophane is not capable of heat sealing, which makes impossible its use for vacuum
packaging. Various currently used modifications of cellophane are devoid of its major
drawbacks. Until recently, the basic coating for cellophane was nitrocellulose. However,
these coatings have a comparatively low adhesion to hydrated cellulose (especially in a hu-
mid atmosphere); low heat sealability, grease and oil resistance; become more vapour- and
moisture-permeable upon application of labels.
Lacquered cellophane used in Russia, by the company Meyer, also has nitrocellulose
as the base for the coating. Along with the general drawbacks characteristic of cellophane
with such a kind of coatings, cellophane by Meyer also has the following drawbacks. The
lacquer composition is multi-component (over 10 components), many of the components
have not been disclosed by the company and are not manufactured by Russian industries.
Domestic research yielded a moisture-resistant, heat-sealable cellophane with a coat-
ing based on domestic raw materials; optimal processes for it have been worked out.
To develop moisture-resistant heat-sealable cellophane, thermoplastic polymers with
high parameters of moisture resistance were used as modifiers: copolymers of vinylidene
110 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

chloride and vinyl chloride, epoxy oligomers with molecular masses from 600 up to 3000
and various compositions on their basis.
Tables 3.23.6 present the properties of modifying polymers.
Table 3.2 Properties of films from copolymers of vinylidene chloride with acrylonitrile at ratios
of 80:20 and 60:40.

F-218 F-220

Ratio of monomers in initial mixture


(vinylidene:acrylonitrile) 80:20 60:40
Content of nitrogen in copolymer, % 6.1 1.2
Content of acrylonitrile, wt. % 23.1 42.4
Characteristic viscosity in cyclohexanone 0.95 1.87
Gas permeability of 25-m film, ml/645 cm2 /24 h/atm
for N2 0.084 0.422
for O2 0.710 3.420
for CO2 1.770 7.910

Table 3.3 Basic properties of resin Saran F-120 (copolymer with a high content of vinylidene
chloride and low content of acrylonitrile).

Properties Grades of different viscosity

210 3 Pas 10 3 Pa h

Viscosity limits, cp 180220 10120


Specific weight at 25C 1.60 1.60
Refractive index at 25C 1.580 1.580
Tensile strength, MPa 56 70.3
Elongation, % 8 8
Moisture permeability of films, g/dm2 24 h at 37C 0.023 0.023
Permeability of toluene vapours, g/dm2 24 h 0.0403 0.0403

Table 3.4 Properties of films from copolymers of vinyl chloride, vinylidene chloride, and from
epoxy oligomers.

Material Water Gas permeability Heat Water Oil/grease


permeability, for O2, 10 6 g sealability resistance resistance
g mm/244 m2 mm/244 m2 cmN temperature,
cm Hg at 25C at 21C, 0% rel. C
humidity

Copolymer of 0.20 80100 excellent good


vinylidene chloride
with vinyl acetate
Copolymer of 0.01 2 100150 excellent excellent
vinylidene chloride
with vinyl chloride
Epoxy oligomers excellent excellent
Low-density poly- 0.06 2000 115160 excellent unstable
ethylene
CHAPTER 3 111

Table 3.5 Characteristics of copolymers.

Name of polymer Relative humidity Content of C, %

Copolymer of vinylidene chloride with 1.59 57.98


acrylonitrile at a ratio of 80:20 [SVN-80]
60:40 [SVN-60] 2.49
Copolymer of vinylidene chloride with
vinyl chloride at a ratio of 60:40 [SVKh-40]
Copolymer of vinyl chloride with vinyl 1.29 50.88
acetate [VKh+VA]

Table 3.6 Characteristics of epoxy oligomers.

Epoxy Mol. mass Epoxy Viscosity*, Amount of hardener Melting Elasticity Solvents
grade value, sec per 100 g of tempera- by the
% oligomer ture (ring NIILK
and ball scale**
hardener adduct test),
No 1 C

ED-5 1620 10 ketones


ED-15 57 710 ketones
E-40 600 1820 12 18 54 25 by 510 toluene
Ubbelode
E-41 900 910 60 10 30 7280 150 acetates
E-44 1500 67 7080 6 18 8590 150 ketones
E-49 2500 24 150 3 9 105 540 ketones,
3000 ethyl
cellosolve

*of a 40% solution in cellosolve, as measured by a VZ-4 viscosimeter.


**NIILK = Nauchno-Issledovatelsky Institut Lakov i Krasok = Research Institute of Lacquers and
Paints

Polyvinylidene chloride is a very strong and robust material with exceptionally good
water resistance, it has a high softening point, as well as a limited compatibility and solu-
bility. Copolymers of vinylidene chloride with such monomers as acrylonitrile or vinyl
chloride have a slightly lower water resistance and chemical resistance than polyvinylidene
chloride; however, they possess a good solubility and compatibility. These copolymers are
applicable for production of coatings, films, sheets and plastics.
Table 3.7 presents the properties of films from copolymer SVN-80 produced by cast-
ing from solution in methyl ethyl ketone.

Table 3.7 Properties of CVN-80 films (thickness, 70 m).

Tensile strength, Relative Vapour / moisture Air permeability, Swelling in water,


MPa elongation, permeability, cm3 cm/cm2 sec atm % (24 h)
% g/dm2 (48 h)

20 280 0.035 0.04010 8


112 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

3.2.2 Copolymer-based coatings


O
Copolymers having in their composition the polar groups Cl ; C N C and
others were used as coatings for cellophane. CH3
The 5% solutions of these copolymers in a mixture of acetone and cyclohexane (1:1)
were used. Lacquering was done by dipping followed by drying in the air. The material ob-
tained was tested for vapour and moisture permeability (Table 3.8) and swelling in water
(Table 3.9).
Table 3.8 Vapour/moisture permeability of cellophane lacquered with various copolymers.

Copolymer used as a coating for Thickness of coating, m Vapour Moisture


cellophane
permeability, g/dm2 (48 h)

SVN-80 5 0.72 0.82


SVN-60 5 2.50 2.00
SVKh-40 4.5 0.45 0.65
VKh+VA 4.5 4.00 16.00
Common cellophane 17 25

As it follows from Table 3.8, the greatest effect in decreasing vapour and moisture per-
meability of cellophane was rendered by copolymers SVN-80 and SVKh-40.

Table 3.9 Kinetics of swelling in water of cellophane lacquered by various copolymers.

Copolymer used as a Thickness Weight increment, % Film


coating for cellophane of coating, peeling
m 1h 2h 3h 5h 24 h time

SVN-80 5 17.0 29.0 34.5 34.5 60.0 48 h


SVN-60 5 25.0 32.5 38.0 45.0 70.0 24 h
SVKh-40 4.5 60.0 20 min
VKh+VA 4.5 48.0 75.0 2h
Common cellophane 70.0 75.0 78.0 80.0 85.0

As it follows from Table 3.9, cellophane with a lacquered coating from SVN-80 pos-
sesses a lower degree of swelling in water in 24 h. The film of this copolymer peels off cel-
lophane in 48 h, whereas the film SVKh-40, which also provides for a sufficiently low
vapour and moisture permeability of cellophane, peels off in 20 min of swelling in water.
Figure 3.4 presents the kinetics of swelling in water of common cellophane and cello-
phane lacquered with copolymers SVN-80 and SVN-60. Common cellophane swells in 1
h almost to a maximum, and then in 24 h the amount of absorbed moisture increases insig-
nificantly. In the case of coating with lacquers, the swelling in 1 h decreases by about 5
times for the coating from SVN-80 and by about 3 times for the coating from SVN-60. In
only 24 h the swelling of lacquered cellophane reaches a maximum of 6070%.
Studies have shown that lacquered coating from copolymer SVN-80 is the most expe-
dient material to be used as a hydrophobic coating for cellophane.
Various epoxy polymers with molecular masses from 600 up to 3000 were used to ob-
tain water-resistant coatings for cellophane. Various solutions of epoxy oligomers (10, 15
CHAPTER 3 113

100
1

Weight increment, %
80
2
3
60

40

20

0
2 4 6 8 10 12 14 16 18 20 22
Swelling time, h

Figure 3.4 Kinetics of swelling in water of common cellophane and cellophane lacquered with
SVN: 1, common; 2, SVN-60; 3, SVN-80.

and 20%) in a mixture of acetone and cyclohexane (1:1) were prepared. Cellophane was
lacquered by dipping followed by drying in the air. The hardeners used were polyethylene
polyamine, hardener No 1 (a 50% solution of hexamethylene diamine in alcohol) and ad-
duct. The materials produced were tested for vapour and moisture permeability and swell-
ing in water (see Table 3.10, Figs. 3.53.8).

Table 3.10 Vapour/moisture permeability of cellophane with epoxy coatings.

Epoxy grade Molecular mass Concentration Vapour Moisture


of lacquer, %
permeability, g/dm2 (48 h)

20 1.60 1.45
E-40 600 15 1.73 1.70
10 1.80 1.63
20 1.59 1.40
E-41 900 15 2.00 1.80
10 2.50 2.08
20 1.82 1.45
E-44 1500 15 2.22 1.80
10 2.70 2.60
20 1.50 1.45
E-49 3000 15 2.10 2.04
10 2.70 2.96

Cellophane with coatings from epoxy oligomers possesses a good heat sealability.
However, it appears not possible to recommend epoxy coatings for cellophane, as thicker
coatings (~10 m) are required to achieve the required hydrophobic properties, which leads
to a considerable decrease of the elasticity of material on the whole and, besides, to cracking
and pitting of the coating, both in the sites of sealing and on the surface of the material in
comparatively small storage times.
114 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Gas permeability, g/dm2 48 h


2

1
4 6 8 10
Thickness of coating, m

Figure 3.5 Dependence of vapour permeability of cellophane with coatings from various epoxy oli-
gomers on the thickness of a coating.

3
Moisture permeability, g/dm2

E-49
E-40
E-41
E-44
2

2.5 5 7.5 10
Thickness of coating, m

Figure 3.6 Dependence of moisture permeability of cellophane with coatings from various epoxy
oligomers on the thickness of a coating.

E-40
Weight increment, %

40 E-44
E-49
30

20

10

0
0 10 15 20
Concentration of lacquer, %

Figure 3.7 Dependence of the swelling in water for 1 h of cellophane with various epoxy coatings
on the thickness of a coating.
CHAPTER 3 115

50

Swelling, %
40

30
E-40
E-41
20 E-44
E-49
10
1 2 3 4 5 24
Swelling time, h

Figure 3.8 Kinetics of the swelling in water of cellophane with an epoxy coating; concentration of
a lacquer, 20%.

3.2.3 Coatings based on lacquer compositions


With the aim to eliminate the drawbacks specific to copolymer coatings and those based on
epoxy polymers, works were carried out to develop and adjust lacquer compositions based
on SVN-80 and E-49 polymers imparting cellophane with the most hydrophobic proper-
ties as compared with other polymers studied.
Lacquer compositions were prepared as follows. Dry resin E-49 in the amount of 50,
30, 20, 10 and 5% of the weight of dry copolymer was added into a 3% solution of SVN-80
in a mixture of acetone and cyclohexanone (1:1). Cellophane was lacquered by dipping and
dried in the air. The coating produced had (depending on the amount of epoxy oligomer
added, see above) the following weight per 1 m2: 7.0 g, 5.0 g, 5.0 g, 5.0 g, 4.5 g.
If the specific weight of the coating is taken to be ~1 g/cm3, then the thickness of the
lacquer layer (on two sides) is equal, respectively, to 7 m, 5 m, 5 m, 5 m, 4.5 m. The
coating obtained was thin, elastic, transparent and was even along the thickness. Tables
3.11, 3.12 and Figs. 3.9, 3.10 present the data of the tests of produced material for vapour
and moisture permeability and swelling in water.
Table 3.11 Vapour and moisture permeability of cellophane lacquered with compositions from
SVN-80 and E-49.

Amount of epoxy E-49 in the Vapour Moisture Note


lacquer composition, %
permeability, g/dm2 (48 h)

50 2.00 2.14 E-49 is introduced as a


30 2.05 2.21 percentage of the weight of
20 2.01 2.02 dry copolymer SVN-80.
Lacquer SVN-80, of 3%
10 1.80 1.60
concentration
5 1.89 1.25
Nonlacquered cellophane 1618 2225
116 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Vapour / water permeability,


4

g/dm2
2
Water permeability
Vapour permeability
1

0 10 20 30 40 50
Amount of resin E-49, %

Figure 3.9 Dependence of the vapour/moisture permeability of lacquered cellophane on the com-
position.
Weight increment, %

60

50 1

20
2
10

0 10 20 30 40 50
Content of resin E-49 in the composition, %

Figure 3.10 Change of swelling of lacquered cellophane depending on the content of resin E-49 in
the lacquer composition. 1, Swelling in 24 h; 2, swelling in 1 h.

Table 3.12 Swelling kinetics of cellophane lacquered with compositions from SVN-80 and E-49.

Amount of epoxy E-49 in the lacquer Weight increment, %


composition, %
1h 2h 3h 5h 24 h

50 12 15 21 26 50
30 11 15 20 26 48
20 9.5 14 20 26 47
10 9.0 14 19 24 47
5 11 20 23 30 53
Nonlacquered cellophane 68 68 71 75 80
CHAPTER 3 117

160

Seam strength, g/25 cm


140
120
100
80
60
40
20

110 130 150 170 190 210 230


Temperature, C

Figure 3.11 Dependence of the seam strength of the lacquered cellophane-based composition on
temperature.

As it follows from the presented tables and figures, an optimal amount of resin E-49
in the lacquer composition, providing for the best hydrophobic properties of cellophane, is
10% of the weight of copolymer. An increase of the concentration of E-49 in the lacquer
composition leads to a deterioration of the moisture resistance of cellophane, probably, due
to a reduction of compatibility of the resin with SVN-80. A decrease of the content of E-49
down to 5% and less leads to a decrease of adhesion of the coating to cellophane (peeling
of the lacquer film on the second day, as compared with five days for compositions with
10% of E-49 and more), which, in turn, causes a deterioration of the moisture resistance of
lacquered cellophane.
Table 3.13 Dependence of the heat-seal strength of lacquered cellophane on heat sealing
temperature.

Voltage at the heat sealing Sealing temperature, C Seam strength,


device, volts g/25 cm

80 130 80
85
90 160 135
95
100 180 149
110 170
120 205 131

Cellophane lacquered with a composition from SVN-80+E-49 heat seals well. An op-
timal heat sealing temperature is 180C (see Fig. 3.11 and Table 3.13).
118 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

3.2.4 Design of heat sealed seams


The effect of temperature on the strength of various designs of seams was studied. Two de-
signs of heat sealed seams are known to be available: butt sealed and lap sealed (Fig. 3.12).
The former work in exfoliation; the latter, in shear.

a Butt sealed

b Lap sealed

Figure 3.12 Types of heat sealed seams.

Studies of the temperature dependence of the strength of heat sealed seams of these
designs showed (Fig. 3.13) the strength of seams working in shearto exceed 40130 times
the strength of seams working in exfoliation. The character of the temperature dependence
is in both cases the same: with temperature increasing the strength of the seams decreases
monotonically, which is, probably, due to the increase of the number of coating-to-base
intermolecular bonds broken per unit of time under the action of heat motion.
Breaking strength of seam, kg/cm

b 1 2

4
a
2

20 40 60 80 100 120 140


Temperature, C

Figure 3.13 Effect of temperature on the heat-seal strength of lacquered cellophane in exfoliation
(1) and in shear (2).

Seams working in shear when loaded are feasible only for longitudinal seams of most
items; butt seams work in exfoliation, thus weakening the item on the whole. It is recom-
mended to use tucked seams (Fig. 3.14) working in shear, as they present no problems in
processing.
The diagram for the adhesion breakdown of tucked seams and a dependence of their
strength on temperature are presented in Fig. 3.15.
As it follows from Figs. 3.133.15, the breakdown character of the seams of compared
designs and the shape of the breakdown adhesiogram is absolutely the same; the absolute
CHAPTER 3 119

Initial appearance
of sealed films

Tuck

Sealing

After loading

Figure 3.14

4
Breaking strength of seam,

3
kg/cm

20 40 60 80 100 120 140


Temperature, C

Figure 3.15 Effect of temperature on the strength of tucked seams.

values of the adhesion strength of the seams are also very close.
By the performance properties and breakdown mechanism, the recommended seam
design does not practically differ from the characteristics obtained in seam shear tests.
Thus, the most rational composition from the viewpoint of heat sealability and hydro-
phobicity of cellophane out of copolymers with epoxy resins studied as coatings is the
lacquer composition from copolymer SVN-80 and epoxy resin E-49 in the amount of 10%
of the weight of copolymer. Cellophane with this coating was called cellophane SVN-80.
As it follows from the data of Table 3.14, the composition of copolymers SVN-80 from
various test batches is sufficiently homogeneous by its main characteristics. Thus, the ulti-
Table 3.14 Chlorine content and characteristic viscosity of various test batches of copolymer
SVN-80.

Batch numbers Chlorine content, Characteristic Note


of SVN-80 % viscosity, m2/sec

266/1 56.50 1.22 The characteristic viscosity of


copolymers was determined from
267/1 55.72 1.20
0.5% solutions in cyclohexane at
267/5 55.77 1.11 T = 25C
270/5 56.85 1.27
120 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY
Table 3.14 Chlorine content and characteristic viscosity of various test batches of copolymer
SVN-80.
Table 3.14 (continued)

Batch numbers Chlorine content, Characteristic Note


of SVN-80 % viscosity, m2/sec

334/5 54.47 1.10


341/5 57.10 1.13

341/5 56.61 1.22

544/5 56.27 1.15

545/5 56.85 1.08

548/5 59.74 1.18

550/5 58.78 1.12

mate difference in the characteristic viscosity is about 0.2, and in the content of chlorine
about 5%. For this reason, the properties of cellophane lacquered with copolymer SVN-80
in these test batches are also sufficiently homogeneous (see Table 3.15).

Table 3.15 Properties of cellophane lacquered with copolymer SVN-80 from various test batches.

SVN-80 Vapour Moisture Swelling Time to Seam Note


batch nos in water, peeling, strength,
permeability, g/dm2 % min g/2.5 cm
(48 h) (24 h)

1. Cellophane was
266/1 0.16 0.17 30 50 200
lacquered with 5%
267/1 0.18 0.16 35 60 200 solutions of SVN-80 =
E-49 in cyclohexane
267/5 0.11 0.13 30 50 150 (viscosity, sec, by VZ-4
270/5 0.12 0.17 30 60 150 viscosimeter)
2. Tensile strength and
334/5 0.10 0.10 30 60 150 relative elongation of
341/5 0.12 0.13 35 60 200 cellophane lacquered
with SVN-80 was within
541/5 0.17 0.19 25 50 110 the limits of GOST (State
Standards) in all batches
544/5 0.17 0.20 35 60 100
studied
545/5 0.18 0.20 35 60 110 3. Time to peeling in
minutes was determined
548/5 0.20 0.25 35 60 120 by the method of GOST
550/5 0.14 0.17 30 60 150 7730-63

Thus, the studies conducted make it possible to conclude that the test batches of co-
polymer SVN-80 manufactured by the plant of the V.A. Kargin Institute of Chloroorganic
Products and Acrylates differ little from one another by their main characteristics, which
provides for the production of lacquered cellophane with sufficiently close values of the
major physicochemical and physicomechanical characteristics.
CHAPTER 3 121

3.2.5 Justification of the choice of solvent


The properties of the produced coating are known to depend largely on the quality of the
main film-forming material. However, a number of technological factors, the formulation
of the coating including, also have a significant effect on the properties of the film.
When developing the formulation of a lacquer coating, special attention should be paid
to the correct choice of the solvent for the film-forming polymer.
As it follows from the literature data, the most suitable solvents for copolymers of vi-
nylidene chloride with acrylonitrile are ketones: methyl ethyl ketone, acetone, cyclohex-
anone, as well as 1,4-dioxane, dimethylformamide, mesityl oxide.
A number of solvents and solvent mixtures were tested in order to choose solvents for
the lacquer composition based on SVN-80. As expected, ketones proved to be the best; what
is more, acetones or aromatic hydrocarbons could replace 60% of ketones in the solvent
mixture. The composition would not dissolve in acetones only. The data on the choice of
solvents are given in Table 3.16.
Table 3.16 Solubility of the composition SVN-80+E-49 in various solvents (concentration was
taken in terms of three parts of SVN-80 plus 0.3 g E-49 for 100 ml solvent).

Solvents Ratio Solvent Dissolution Note


boiling
tempe- in 1 h in 24 h
rature, C

Acetone 56 slight residue total dissolution 1. Dissolution


temperature,
1518C
Methyl ethyl ketone 80 total dissolution ditto 2. Introduction
Cyclohexanone 156 slight residue ditto of butyl acetate
Ethyl acetate 75 partial partial into the mixture
dissolution dissolution of solvents leads
to an opaque
Butyl acetate 125 ditto ditto
coating on
Ethyl cellosolve 130140 not dissolved not dissolved cellophane
Ethyl cellosolve 78 ditto ditto
Methyl ethyl ketone: 1:1 80 total dissolution
ethyl acetate 75
Methyl ethyl ketone: 1:4 80 almost total total dissolution
ethyl acetate dissolution
75
Methyl ethyl ketone: 80 incomplete dissolution, slight
ethyl acetate: 75 residue
butyl acetate 1:1:3 125
Methyl ethyl ketone: 80 almost total total dissolution
ethyl acetate: 75 dissolution
butyl acetate: 125
cyclohexanone 1:2:1:1 156
Methyl ethyl ketone: 80 total dissolution
ethyl acetate: 75
122 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY
Table 3.16 Solubility of the composition SVN-80+E-49 in various solvents (concentration was
taken
Tablein3.16
terms(continued)
of three parts of SVN-80 plus 0.3 g E-49 for 100 ml solvent).

Solvents Ratio Solvent Dissolution Note


boiling
tempe- in 1 h in 24 h
rature, C

butyl acetate: 125


acetone 3:2:3:2 56
Acetone: 56 ditto
cyclohexanone: 156
butyl acetate: 125
toluene 1:1:2:1

To find a good solvent for SVN-80, we plotted the kinetics of its swelling in vapours
of such organic solvents as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate and
some mixtures of these solvents. The data are given in Table 3.17.
Table 3.17

Solvents Weight increment, % per hour Note

1 2 3 4 5 6 7 8

Acetone 41.5 49.0 53.5 60 92.7 100 110 118 Swelling


Methyl ethyl ketone 33.5 42 45.5 52.5 86 95 98.5 tempe-
Cyclohexanone 2.5 4.2 5.4 7.5 27.5 42 52 60 rature,
20C
Ethyl acetate 18.2 25.5 27 29 33 33 33 33
Acetone:cyclohexanone = 12.2 14.2 15.1 17.7 32.2 43.2 57.0 64.0
1:1 (mixture No 1)
Acetone:cyclohexanone: 15.1 20.5 22.9 42.7 52.7 68.5
butyl acetate: ethyl acetate
= 2:2:2:4 (mixture No 2)
Weight increment, % per hour Swelling
tempe-
Cyclo- 1 3 5 8 12 16 22 27 32 36 rature,
hexanone 55C
17.0 39.2 47.4 69.3 84.0 108 132 149.5 188 212

In all solvents studied, except ethyl acetale, SVN-80 swells unrestrictedly. The extent
of its swelling in ethyl acetate vapours is 33%.
The swelling of SVN-80 in vapours of methyl ethyl ketone (without comparison with
its swelling in acetone) is characterized by the highest rate in the first 24 h.
The swelling rates of SVN-80 in vapours of all solvents studied (except ethyl acetate)
become approximately the same in 24 h (Fig. 3.16).
The SVN-80 swelling rate in acetone vapours is maximal. However, the use of acetone
as a solvent of SVN-80 is not expedient owing to its high volatility and, therefore, worse
conditions of film forming. The latter statement confirmed experimentally is consistent
with the literature data.
An increase of temperature leads to an intensification of the swelling process. Thus,
CHAPTER 3 123

1
130
2
110
3
90
Weight gain, %

70 4
5
6
50

30 7

10

8 16 24 48 56 64 72 80 88 96
Swelling time, h

Figure 3.16 Kinetics of swelling of copolymer SVN-80 in vapours of some organic solvents: 1,
cyclohexanone (T = 55C); 2, acetone; 3, methyl ethyl ketone; 4, mixture No 2; 5, mixture No 1; 6,
cyclohexanone; 7, ethyl acetate.

the swelling rate of SVN-80 in cyclohexanone at a temperature of 55C exceeds that in ac-
etone at room temperature more than twofold.
As the result of the studies, and also because
the method of drying by infrared beams, as a more advanced method as compared
with convective drying, rules out the large duration of the drying process and the possibility
of insufficient drying of the coating
application of solvents with a high boiling temperature improves the film-forming
conditions, and the use of a mixture of solvent complicates the process at the stage of recu-
peration of the solvents
we believe that the use of cyclohexanone as a solvent of SVN-80 is the most expedient.

3.2.6 Wetting of hydrated cellulose film with some organic solvents and solutions of
SVN-80 on the basis of these solvents
As indicated by the results of recent studies, the value of adhesion is largely affected by the
wetting of substrate with a fluid adhesion-promoting agent. By conducting studies of the
wetting of a hydrated cellulose film with such organic solvents as cyclohexanone, acetone,
some mixtures of solvents, as well as solvents of SVN-80, we thought it possible to confirm
the choice of a solvent for SVN-80, i.e., to obtain the minimal values of the contact angle
of wetting ( ) and the time of its complete spreading (Tmax) for a good solvent for
SVN-80. The study conducted has shown that in the case of the above solvents we have an
ideal wetting of the base: is practically equal to zero, and the spreading of a drop of a
solvent is almost instantaneous. Based on these data, it was natural to assume that the af-
finity of the studied solvents to cellophane is almost the same, which was confirmed by the
124 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

study of the wetting of a nonpolar (paraffin) support by the same solvents. The data of the
study are summed up in Table 3.18.
Table 3.18 Contact angle of wetting of paraffin by some organic solvents.

Solvents Acetone Cyclohexanone Mixture No 1 Mixture No 2

eq 37 40 43 40

As seen in the table, the values of in all four cases are rather close.
As the study of the wetting of cellophane by pure solvents gave us no possibility to
determine, which solvent is the best for SVN-80, we studied the wetting of cellophane by
solutions of SVN-80 on cyclohexanone and mixture No 1. Acetonic solutions of SVN-80
were not studied as solutions on a volatile solvent, which deteriorated film formation. The
purpose of this study also aimed at establishing the effect of the concentration of the solu-
tion on the wettability of the support. The results are presented in Tables 3.19 and 3.20 and
in Fig. 3.17.
Table 3.19 Contact angles of wetting of cellophane by solutions of SVN-80.

Contact angle of wetting, deg

T, sec Solution of SVN-80 in cyclohexanone Solution of SVN-80 in mixture No 1

20% 15% 10% 7.5% 5% 15% 10%

10 45 39 23 [15] 15 38 26
30 32 21 20 16 [25] 10 27 [25] 19
60 28 16.5 [75] 15 10 [35] 8.5 [35] 12
90 24 11.5 12 7 [40] 6.0 20 [45] 9
120 20 12.4 9 [135] 6 [50] 4.0 [55] 8
150 10.0 7 [60] 3.5 [110] 7
180 18 7.5 5 [90] 2.5 17
210 3.5
240 16.5 7.3 4 12
300 15.0
360 7.2 11
420
480 7.2
510 14.5

Table 3.20 Dependence of the contact angle of wetting and time of complete spreading on the
concentration of SVN-80 solutions.
Concentration eq, deg Teq, min
of solution,
% SVN-80 in SVN-80 SVN-80 in SVN-80
cyclohexanone in mixture 1 cyclohexanone in mixture 1

20 15 5
15 7.5 11.0 4 4
CHAPTER 3 125
Table 3.20 Dependence of the contact angle of wetting and time of complete spreading on the
Table 3.20 (continued)
concentration of SVN-80 solutions.
Concentration eq, deg Teq, min
of solution,
% SVN-80 in SVN-80 SVN-80 in SVN-80
cyclohexanone in mixture 1 cyclohexanone in mixture 1

10 4 7.0 3 1
7.5 3 2.5
5 2.5 1

As it follows from Fig. 3.17, the rate of reaching eq is higher for the solution of
SVN-80 in mixture No 1. This is explainable by a decrease of the viscosity of the solution
at the addition of acetone to cyclohexanone. However, an increase of the rate of spreading
does not lead to an improvement of wetting. What is more, introduction of acetone worsens
the wettability of the solution. Indeed, if the value of eq in the case of the solution of
SVN-80 on cyclohexanone at a concentration of the solution of 15 and 10% is, respectively,
7.2 and 4.0, then for solutions of SVN-80 of the same concentration on a mixture of solu-
tions, eq is 11 and 7.

50
In cyclohexane
Contact angle of wetting, deg

40 In mixture

30

20

10 15%
10% 10% 15%
5% 7.5%
1 2 3 4 5 6
Spreading time, min

Figure 3.17

This, we have shown that solutions prepared using a mixture of solvents have a worse
wettability as compared with solutions of cyclohexanone.

3.2.7 Working-out of an optimal process regime for producing cellophane SVN-80

The effect of drying time on the properties of lacquered cellophane was initially studied on
specimens obtained in the laboratory. Cellophane was lacquered by dipping*, dried in the

*3% solutions of SVN-80 and E-49 in a mixture of cyclohexanone:acetone (1:1) were used for the
coating.
126 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

air until tack-free, and then held at a temperature of 8085C for 15, 30, 45, 60 and 90 min.
It was noted that only the specimens dried for no more than 1520 min preserve their
elasticity; the others become brittle and, when allowed to swell in water, the lacquer film
in them exfoliates in several hours.
The initial variant of the pilot-plant lacquer installation for drying the coating made
use of the convective method. However, attempts to produce material with a desirable set
of properties failed: at comparatively low drying temperatures (70C) the coating peeled
off from cellophane swollen in water for 13 h; at higher drying temperatures, the coating
possessed a sufficiently good moisture resistance but was not heat sealable. Exfoliation of
the lacquer coating from cellophane swollen in water (in the case of its drying at low tem-
peratures) can, probably, be explained by the presence of traces of solvent; the same is in-
dicated by the opacity of lacquered cellophane in swelling. The inability of lacquered
cellophane dried at increased temperatures to be heat sealed is, probably, due to the
crosslinking of the polymer at these temperatures. At some intermediate temperatures there
is no crosslinking and no traces of solvent in the film; still, swelling in water for a short time
leads to exfoliation of the lacquer coating from cellophane.
Using the convective method, the coating is dried unevenly with respect to the thick-
ness; the rate of diffusion of the solvent from the deep layers of the coating to the surface
layers is much smaller than the rate with which the solvent evaporates from the surface. As
the result, the surface layer dries up faster, and the solvent, which continues to diffuse to
the surface, disturbs the integrity of the coating. Micropores are produced, via which mol-
ecules of water during the swelling freely penetrate into the coating, to cellophane; its swell-
ing exfoliation of the lacquer film occur. In the given case, these phenomena play an even
greater role owing to the fact that the solvent for the lacquer composition was a mixture of
acetone and cyclohexanone (1:1) with different boiling and evaporation temperatures.
On the other hand, the film-formation conditions are, probably, such that adhesion
forces are commensurable with internal stresses generated in the lacquer film in its forma-
tion, which can lead to rapid exfoliation of the coating in swelling.
In view of this, the convective method of drying the coating in the pilot-plant installa-
tion was replaced by a more advanced method of drying with infrared beams, which provide
for the heating of the lacquer layer along its thickness and an increased solvent diffusion
rate from the depth of the coating to the surface. Besides, IR drying removes the necessity
of using mixtures of solvents with different boiling temperatures. The high drying rates
in this method enable using cyclohexanone to produce a lacquer composition; cyclo-
hexanone provides for good film-forming conditions and end material with an optimal set
of properties.
Preliminary works on IR drying of lacquered cellophane showed the appropriateness
of using this method of drying. Lacquered cellophane dried for 23 min by plate-type IR
radiators at an optimal distance of 5 cm between the film and the plates, at a supplied voltage
of 100 V (approximately, a temperature of 10120C corresponds to this voltage) swells
in water in 24 h up to 2023% as compared with 3540% for lacquered cellophane dried
by the convective method. The lacquered film does not peel off from cellophane swollen in
water for 5 days; the lacquered cellophane is heat sealable.
A technological scheme for producing lacquered cellophane was developed.
Cellophane from the unreeling device via the guiding rolls is fed to the lacquer bath,
where it is covered with lacquer on one or both sides as required, is then supplied to the
drying section, and after drying of the end material is supplied by a special tensioning
device to the reeling roll.
CHAPTER 3 127

3.3 Modification of cellulose diacetate for packaging materials

Films and consumer containers based on cellulose diacetate (CDA) are promising ecolog-
ically safe materials intended for contact with high fat-content spreads, confections and in-
fants food products. Great importance of these materials for food industry and the diversity
of requirements imposed on them makes it necessary to develop new formulations of ethrols
with specific balanced sets of properties.
The possibility of targeted regulation of the properties of cellulose acetate composi-
tions was studied. The aim of the studies was to obtain food-grade ethrols with a wide range
of plasticity properties, MFI (melt fluidity index), a wide interval between the yield tem-
perature and breakdown temperature, a high tensile yield strength, a certain set of perfor-
mance characteristics. Therefore, it was necessary to develop ethrol whose process
characteristics would enable its reprocessing into consumer containers by injection mold-
ing, by methods of blow molding and pressure forming.
We studied triacetine (TA)-placticized CDA with the content of combined acetic acid
of 55.8% and molecular mass of 45,000 (as determined from the viscosity of solutions in
acetone). Dibutyl esters of the general formula

C4H9 O [ ROC ( CH2 )n C ]m OC4H9,


O O

where R = CH2CH2 O CH2CH2 or CH2 CH


CH3

served as modifiers of the plasticizing system. Namely, they are dibutyl esters of polydi-
ethylene glycol adipinate (PDEA), of polyethylene glycol cebacinate (PAC-22) and of
polypropylene glycol adipinate (PPA-4). The amount of modifier in the plasticizing system
of TA + oligoester was varied from 0.1 up to 10%; the amount of mixed plasticizer was
constant and equaled to 35% per 100% CDA. The ingredients were mixed in a high-speed
turbomixer at a temperature of 343 K; the mixing time of dry components was 8 min; of
dry components with liquids, 12 min. The mixture obtained was homogenized in an extrud-
ing-and-kneading machine at a melt temperature of 453 K at the outlet from the head of the
extruding machine. The straps obtained were cooled, cut into granules and used to form a
band 3540 m thick on an extruder with the orifice slit, at a temperature for the cylinder
zones of 438451468 K, orifice temperature of 468 K, temperature at the output 453 K.
Test specimens of corresponding sizes were cut from the band in longitudinal and trans-
verse directions. Model thin films (20 m thick) from the CDA + TA + oligoester system
were prepared by hot pressing at 423 K and pressure of 12 MPa.
The phase transitions in plasticized compositions were determined by the refractomet-
ric method by finding the temperature dependence of the refractive index for thin (20 m)
films in an URL-1 refractometer at a continuous change of temperature at a rate of 1 K/min.
The glass transition temperature was determined by the thermomechanical method at a con-
stant strain on a specimen (1.410 2 Pa) and a rate of 1 K/min and also refractometrically.
Preliminarily, the data obtained by both methods were shown to correspond one to the other.
The thermomechanical characteristics of the compositions were determined using a tensile
creep-measuring instrument according to State Standard GOST 18197-72 at a constant
strain (110 Pa) and heating rate of 5 K/min on specimens of 1.82.00.3)10 4 m.
128 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The mechanical properties of model thin films were assessed on an N-2001 R-0.5 ten-
sile tester at a strain rate of 0.3210 3 m/h with the automatic recording of the strain curve.
The mechanical indices of the extrusion films were determined at temperatures of 293 and
393 K on an Instron tensile tester according to GOST 14236-81 at a strain rate of 10 2 m/h
on specimens with the working area parameters of (5100.4)10 3 m.
The melt fluidity index MFI was determined by GOST 11645-73 on an IIRT instru-
ment at a temperature of 463 K, load of 100 N, standard capillary of 0.948 mm in diameter
and 8 mm in length. The rheological properties of the material were studied on a capillary
constant-pressure viscosimeter at temperatures of 453, 463, 473 K and the rate of shear from
10 3 up to 10 4 s 1.
Due to the great importance of the performance stability at given temperatures in con-
tact with biochemically active media during the development of plasticized compositions,
one should account for their thermodynamic stability. It provides for a long-time invariabil-
ity of the properties not only in reprocessing, but also in long-term storage. In this connec-
tion, phase diagrams were obtained for triple CDA+TA+oligoester system of different
molecular nature (PDEA, PAC-22, PDEC, PPA-4), which made it possible to single out re-
gions of homogeneity at various temperatures. Studies of the isothermal cross sections of
phase-equilibrium bulk diagrams have established that the homogeneity region for all sys-
tems studied expands with temperature increasing. Comparison of the phase diagrams of
the systems containing various-structure oligomers shows that an increase of the length of
aliphatic segments between ester groupings, which provide for the interaction with polar
groups of the polymer, leads to the deterioration of compatibility. Compatibility of the com-
ponents of the CDA+TA+oligoester triple systems decreases in the sequence PPA-4 >
PAC-22 > PDEA. Analysis of the phase diagrams shows that at room temperature the sys-
tems comprising >57% of oligoester in the mixture are microheterogeneous.
By the example of the CDA+TA+oligoester systems, we considered the effect of oli-
goester on the efficiency of the plasticizing action of the TA+oligoester mixture with re-
spect to CDA. For this purpose, we studied the concentration dependence of Tg and the
mechanical properties of the films. As the content of oligoester in the plasticizing system
increases, its plasticizing action rises. Herewith, addition of oligoester, which contains res-
idues of molecules of sebacinic acid (up to 50% PAC-22), decreases Tg of the polymer to
a greater extent. Comparison of the phase diagrams and of the dependence Tg = f(Cm) shows
that interstructural plastification in the microheterogeneous system begins at the introduc-
tion of oligoesters. Therefore, a decrease of the extent of polarity of the components as the
result of the increase of the length of aliphatic fragments or a change of their branching in
the oligoester enhances the action of the second plasticizer, which plays the role of an in-
terstructural lubricant leading to a large decrease of Tg.
When analysizing the data for the mechanical properties of model films from
three-component systems (Table 3.21), it is seen that the systems containing PDEA and
PPA-4 have the greatest breaking strength p; while the systems with PAC-22 are more
elastic (have a greater relative breaking elongation ). The studies conducted enabled sin-
gling out homogeneity regions for all systems studied. The regularities obtained were used
in developing food grades of ethrol with given rheological, strain-resistant and sani-
tary-chemical properties. Modified ethrols were fabricated by the traditional process.
The set of technological and performance properties of films fabricated from ethrol
compositions of various formulations (Table 3.22) was studied. In the general case, intro-
duction of oligoester to an ethrol composition at the stage of its preparation significantly
(by an order of magnitude) decreases the effective viscosity of the melt, shifts Tg and Tm to
CHAPTER 3 129

the region of higher temperatures practically without changing the plasticity interval. As the
result of the decreased strength of the intermolecular bonds the deformability of the material
at increased temperatures increases. The obtained regularities were used when choosing the
optimal content of modifier in the plasticizing system to provide for a balanced set of tech-
nological and operational properties of ethrols of various purposes.

Table 3.21 Strength properties of CDA films plasticized by TA in a mixture with oligoesters
(15%).

Oligoester TA:oligoester mass ratio p, MPa , %

PDEA 3:1 5.6 4.5


PDEA 1:1 4.2 13.0
PDEA 1:3 8.7 6.0
PPA-4 3:1 7.1 4.5
PAC-22 3:1 4.1 12.0

Comparative analysis of the rheological properties of base ethrol and ethrol modified
by PPA-4 showed that the optimal temperature of plasticizing material in an extruder was
438 K for the extrusion grade and 463 K for the blow-molding grade. These temperatures
provide for an intensive agitation of the melt at lower loads. It should be noted that MFI for
all modified compositions is much higher than the rated values. Such compositions can be
reprocessed at lower temperatures and smaller shear loads, which is confirmed by the data
obtained in reprocessing of modified compositions on industrial equipment.
Table 3.22 Process characteristics of modified ethrols.

Plasticizer and Melt viscosity, p, MPa , %


its content, % 102, Pa s
at 293 K at 393 K at 293 K at 393 K

TA (35) 24.0 60 2 48 100


TA(25) 3.5 40 4 42 140
PPA-4 (10)
TA (25) 5.2 45 7 20 140
PAC (25)
TA (25) 5.8 45 4 30 130
PDEA (10)

Note: Polymer, CDA; plasticity range (Tpl Tg), 315 K.

The established anomalous dependence of the rheological, physicomechanical and


strain characteristics of modified ethrols suggests that the effect of strengthening of plasti-
cized CDA at the introduction of small additions of oligoester is determined by structural
changes at the supramolecular level. An increase of the mobility of the structural elements
and the acceleration of relaxation processes in modified material provides for the formation
of a more homogeneous structure, which is confirmed by the data of electron-microscopy
analysis.
To determine the rational applications of packaging/container materials and consumer
containers on their basis, we determined the endurance and service time of articles in
130 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

contact with a product or a medium modelling this product (Table 3.23).


Table 3.23 Long-term strength of CDA-based specimens.

Temperature, K Time to rupture, min

in air in distilled water in sunflower oil in 3% solution of


lactic acid

293 6070 40 1200 50


323 30 25 1200 20

Note: Testing stress, 3.0 MPa.

Estimation of sanitary-chemical properties of test batches of materials and articles


from them, obtained by vacuforming and deep drawing, showed that more than 92% of the
specimens had satisfactory organoleptic parameters: a small (0.5 mg/l) dry residue, a small
amount of brominated compounds (1.55.6 mg Br/l). The amount of TA migrating to water
from ethrol-based material is 0.05 g/l; that of acetic acid, 5 mg/l; which do not exceed the
maximum permissible levels of migration.
Thus, consumer containers based on ethrol should be recommended for prepackaging
of spreads with an increased content of fat; lactic-acid products, as well as hot beverages at
their short-time effect.

3.4 Interaction of cellulose with water


Chemically, cellulose is a polymer whose elementary link is anhydro-D-glucose. The struc-
ture of the cellulose macromolecule can be represented by the following formula:

CH2OH CH2OH CH2OH


CH O CH O CH O

HOHC CH OHC CH OHC CHOH

H HC CH HC CH HC
OH OH OH OH OH OH
n

Each elementary link contains three hydroxyl groups. Two of them are secondary; one
is primary. This explains the different reactivities of the hydroxyl groups. The interaction
energies of these groups with water molecules are different, too, which would be discussed
in detail in Chapters 2 and 3. Here, we would like to note that the high hydrophilicity cel-
lulose is due namely to the presence of three hydroxyl groups in the elementary link; these
groups interact with water molecules by forming strong hydrogen bonds.
Sorption of water by cellulose can be radically changed only by substitution of the hy-
droxyl groups. Indeed, a gradual substitution of the hydroxyl groups for other groups of at-
oms changes the sorption properties of cellulose. Thus, unetherified cellulose at 65%
relative humidity absorbs 1112% of water; cellulose diacetate, 6.5%; and triacetate, 3.2%.
Cellulose esters with a longer aliphatic residue absorb only fractions of a percent of water.
CHAPTER 3 131

The effect of the end groups of cellulose macromolecules of the sorption of water is
small, as the (number-average) extent of polymerization for common specimens of cellu-
lose is comparatively large (greater than 200300).
Cellulose materials used in practice have natural contaminants of other polysaccha-
rides and lignin (the satellite of cellulose in wood), which have some influence on the sorp-
tion of cellulose water; besides, there are disturbances in the chemical composition of
macromolecules of cellulose proper. These disturbances mainly consist of a partial oxida-
tion of the hydroxyl groups in the links of chains up to carboxyl groups (without or with the
rupture of the anhydro-D-glucose ring). These partial disturbances have a small influence
on the sorption of water, but the sorption of cations from the aqueous solutions of metal
salts, e.g., the sorption of iron ions, may increase substantially.
Partial destruction of cellulose in its purification leads to a decrease of the extent of
polymerization and to the emergence of low-molecular-mass products, which can be par-
tially soluble in water, especially at increased temperatures. Without having a noticeable
direct effect on the equilibrium values of water sorption by cellulose materials, under cer-
tain conditions this can affect the water sorption kinetics. One of the hypotheses explaining
the differences in the reactivity (kinetics of the process) during the etherification of vari-
ous-origin cellulose materials is related to the account for the physical transformations of
low-molecular-mass admixtures during the drying of cellulose at high temperatures.
Though the presence of the hydroxyl groups in cellulose is a factor, which mainly de-
termines its sorptivity with respect to water, a significant role is also played by the physical
structure of cellulose material, which has an effect on both the equilibrium values of water
absorption and on the kinetics of the sorptiondesorption processes.
First of all, it should be noted that cellulose is a crystallizable polymer. The energy of
hydrogen bonds emerging between water molecules and hydroxyl groups of cellulose
proves to be insufficient to break the crystalline lattice. Therefore, the sorption of water oc-
curs only in amorphous regions and does not affect the crystalline regions (except the hy-
droxyl groups, which are on the surface and in the defect regions of the crystallites). The
extent of crystallinity of cellulose depends on the origin (prehistory) of the specimen. Nat-
ural cellulose (cotton, ramie) has the greatest degree of crystallinity. Cellulose regenerated
from solutions of cellulose and its ethers (following the saponification of the latter) has a
much lower crystallinity. Usually, the extent of crystallinity estimated from X-ray diffrac-
tion measurements is 6070% for natural cellulose and about 2540% for regenerated cel-
lulose.
The values of water sorption differ accordingly. As a rule, the sorption of water by re-
generated cellulose (viscose fibres) is approximately two times as high as that of natural
cellulose (e.g., cotton or ramie).
Alkaline and temperature treatments of cellulose can cause transitions between partic-
ular types of crystal lattices. Thus, a cellulose modification I, which occurs in natural spec-
imens, during the transfer of cellulose into the solution followed by regeneration from
solution or during the treatment in moderate-concentration alkali and then the washout of
alkali passes into a crystalline modification of cellulose II, which differs from cellulose I
by interplane distances and angular ratios in the lattice. At increased temperatures, cellulose
II passes to a modification of cellulose IV. All these transformations, apparently, would not
have a strong effect on the sorption of water by cellulose, if they would not have been ac-
companied by the simultaneous changes in crystallinity. During the mercerization (alkaline
treatment) and at the regeneration of cellulose from solutions the extent of crystallinity de-
creases significantly, as we mentioned above. Some increase of the extent of crystallinity
132 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

occurs during the temperature treatments of regenerated cellulose in moist state, which is
accompanied by a partial transition of cellulose II to cellulose IV. This treatment leads to a
cellulose sorptivity decrease with respect to water, though the isomorphic conversion
proves to be not the determining event but a process occurring in parallel.
Cellulose can be totally amorphized by dry mechanical grinding. This can be seen from
the results of the X-ray diffraction study and from the fact that the heat of the interaction of
this cellulose with water is three to four times as high as the heat of wetting the nonground
cellulose. But the interaction with water is followed by the crystallization process, and cel-
lulose again becomes insoluble. Incidentally, during the formation of viscose fibres in the
initial stage after the saponification of cellulose xanthogenate these fibres very strongly
swell in water (after the washout of precipitation-bath salts), but after some time the swell-
ing strongly decreases as the result of the completion of the crystallization processes.
Besides the important role of the phase state in determining the sorption properties of
cellulose, we should also note the effect of such a factor as the physical structure of cellulose
material. The matter is that besides the true sorption of water (absorption) determined by
the amount of the amorphous component of polymer, there occurs a capillary uptake of wa-
ter by cellulose materials due to porosity, which can be obvious (capillaries in natural fibres,
interfibrillar spaces in wood, pores in cells of plant cellulose and in artificial cellulose fi-
bres, capillaries and pores in paper and textile materials) and hidden, revealed during the
wetting in water and representing the pores and capillaries, which are collapsed in the dry-
ing of moist cellulose materials and are capable of being restored due to the relaxation of
internal stresses remaining in the dry specimen.
Experiments confirming the thermodynamic nonequilibrium of real cellulose materi-
als, which determines the dependence of the sorption properties on their prehistory, were
described.
It should be noted that this nonequilibrium renders an especially serious effect on the
kinetics of absorption processes.
4 Compositions for Decorative
Finish and Protection of
Packaging Products

4.1 Bases of the formation of protective and decorative finish coatings


Aqueous dispersions of polymers are the most promising class of film formers in paper and
printing industries, applicable for fabrication of protective and decorative coatings on pack-
aging products.
The use of polymers aqueous dispersions has a number of advantages as compared
with solutions of polymers in organic solvents, making it possible:
to eliminate the danger of fire and to decrease occupational hazards of work
to decrease considerably the power intensity of production and to eliminate the use
of heavy equipment
in a number of cases to achieve a higher quality of articles produced.
Fabrication of polymer coatings for packaging products with a required set of proper-
ties is the final aim of using latexes or aqueous dispersions of polymers for finishing print-
ing products. In this connection, of great importance is the quality of polymer coatings and
the mechanism of their formation.
Formation of films from polymer solutions has been studied by many researchers,
primarily by Russian scientists V.A. Kargin, P.V. Kozlov, A.Ya. Drinberg, P.I. Zubov,
S.S. Voyutsky and others.
In contrast, the formation mechanism and structure of films from polymer dispersions
have been studied insufficiently. The effect of the chemical composition, structure of latex
particles and coatings on the decorative and protective properties has not been studied; the
impact of the nature of the support, especially of fibrous materials, on the formation and
properties of latex coatings has not been studied sufficiently enough.
In works of the recent years the physicomechanical properties of the coatings have
been shown to depend not only on the chemical structure of the film former, but also on the
colloidalchemical nature of latex, size and structure of latex particles, nature and concen-
tration of polar groups.
It follows from these data that the complex structure of latex particles, which are su-
pramolecular formations consisting of simpler structural elements, determines the incom-
pleteness of the relaxation processes and has an effect on the values of internal stresses, the
kinetics of their buildup and relaxation.
The specific features of polymer coatings used for finishing printing products are that,
134 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

along with good physicomechanical properties, they should have a high light resistance,
gloss and have no tackiness.
The dependence of these parameters on the structure and chemical composition of a
polymer has not been studied sufficiently. This impedes the correct scientifically grounded
choice of film formers for finishing the printing products and does not make it possible to
formulate the requirements for finishing compositions.
The effect of the chemical composition of polymer, the structure of latex particles, the
nature and concentration of polar groups, the colloidalchemical nature of latex on the for-
mation of the coatings, decorative and physicomechanical properties (strength, adhesion,
relative strain, internal stresses) was studied. This was done by comparing the kinetics of
forming the structure and properties of the coatings on a model non-porous glass support
with the mechanisms of forming the coatings on fibrous bases of the type of offset paper
and offprints.
One of the ways to increase the quality of printed matter is application of transparent
polymer coatings on printed material, which improves its decorative appearance and in-
creases mechanical strength.
The following requirements are imposed on polymer films on printed matter (off-
prints): high gloss, elasticity, transparency, absence of tack, water resistance, light perma-
nence, stability and mechanical strength.
Application of protective and decorative coatings to the surface of printed matter is
done in two different techniques: lamination of the end polymer film to offprints and direct
application of a film former to offprints.
In application of coatings to printed matter by the latter technique, film formers of
three different types can be used, which differ significantly by their film-formation mech-
anism:

solutions of polymers
compositions of oligomers
dispersions of polymers.

The method of producing coatings from polymer solutions is used the most for finish-
ing printed matter in Russia and abroad. This is due to the simplicity of producing coatings
and the absence of additional components in their composition (emulsifiers, hardeners,
etc.), which in some cases worsen the properties of the coatings.
The chemical composition of these lacquers is approximately as follows (in %):

Polymer 4050
Plasticizer 25
Solvent 5845

Amorphous polymers of the type of polyvinyl acetate, polyvinyl butyral, polyvinyl al-
cohol, cellulose esters etc. are mainly used as film formers.
Coatings from polymers with a large extent of crystallinity are distinguished by a high
strength, but they have not found use in finishing printed matter due to poor adhesion to the
coated surface.
The decorative and protective properties of the coatings are affected by the nature of
solvents used. The most widespread classes of solvents are alcohols, ethers and esters,
hydrocarbons, etc.
CHAPTER 4 135

The hydroxyl group confers a greater polarity and strong hydrophilicity to alcohols.
Methyl, ethyl and propyl alcohols are totally mixed with water. A decrease of hydrophilicity
with the molecular mass increasing affects the dissolving capacity. The higher members of
the homologous series, e.g., butyl alcohol, improve the flow behaviour and prevent the
blooming of films produced by application of nitrocellulose lacquers. Alcohols are rather
stable compounds and find application for many types of lacquer-and-paint materials.
Ethers, such as ethyl ether and propyl ether, in a mixture with other solvents, for in-
stance, dissolve cellulose. These ethers are too volatile, readily form peroxides, and are used
in compositions of lacquer-and-paint materials on a limited scale.
Esters are similar to ketones by polarity, but are less hydrophilic. Formates, which are
esters of lower molecular masses than acetates, are unsuitable due to their instability, are
easily hydrolyzed by water and are too volatile. Acetates (ethyl acetate, butyl acetate, iso-
propyl acetate) are very widely used, especially in nitrocellulose materials.
To impart elasticity to the film, plasticizers are introduced into the solution of a film
former. Fluids with a relatively small molecular mass are usually used as plasticizers.
Earlier printed-matter finishes made use of lacquers based on natural resins of the type
of copal, wood rosin and sandarac in ethyl alcohol.
Copal is a hard resin of plant origin, of transparent yellow or reddish colour. The heat
treatment of copal at 280320C improves its solubility in ethyl alcohol as the result of
stripping volatile substances. Manila copal, completely dissolvable in ethyl alcohol, is used
for fabrication of lacquers.
Wood rosin is conifer resin; it can be of two types depending on the method of pro-
duction: gum rosin and wet-process rosin. Gum rosin is produced from raw gum of conifers,
wet-process rosin is extracted from resinous wood with alkali. Wood rosin is a mixture of
isomeric monobasic rosin acids of the general formula C20H30O2. Rosin acids present in
wood rosin are a mixture of dextropimaric acid with conversion products of levopimaric
and -sapinic acids, the major of which is abietinic acid. The structure of abietinic acid is
expressed by the formula:
H3C COOH

CH3
CH3
CH
CH3
Sandarac is an thick aromatic resin of the North-African Sandarac tree.
The approximate composition of these lacquers, in %:

Copal 25.525.0
Wood rosin 17.510.0
Sandarac 5.0
Ethyl alcohol 5760.0

Lacquers were also used for lacquering dust wrappers and other kinds of printed mat-
ter. Lacquers from imported natural resins are expensive, are produced in minor amounts
and have not found wide use in printed-matter finishing.
Finishing of printed matter in the West is done using nitrocellulose lacquers. Their for-
mulation includes nitrocellulose, a plasticizer and organic solvents methyl alcohol,
136 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

methyl acetate, ethyl acetate, butyl alcohol, toluene, xylene.


These lacquers give high-quality coatings on chalk-coated paper. Nitrocellulose lac-
quers are toxic and explosive. In spite of this, they are manufactured as modified composi-
tions on a large scale by a number of companies: Grafisk Farg (Sweden), Sadolin (Finland),
lacquer L-186; Sicpa (Switzerland), rapid-setting lacquer intended for application to off-
prints printed on chalk-coated paper; Herbol (Germany), gloss lacquer with high gloss of
the coating; Herberts (Germany), brilliant lacquer GL; Lorilleux-Lefrans (France), delta
lacquer and lacquer for finishing offprints printed by high-print and offset methods.
Iditol lacquer is an ethyl-alcohol solution of the product of polycondensation of phenol
with formaldehyde in the presence of a catalyst (oxalic or hydrochloric acids).
OH OH OH OH
O
CH2 CH2 CH2 ...
n + n HC
n H2O
O
Coatings based on this resin are light non-permanent.
Carbinol lacquer is a solution of MBK-10 resin in ethyl alcohol. Products of polymer-
ization and copolymerization of vinyl ethyl carbinol are called carbinol resins. Resin
MBK-10 is produced by copolymerization of dimethyl vinyl ethynyl carbinol containing
no inhibitor, with technical-grade methyl methacrylate and butyl methacrylate in the pres-
ence of benzoyl in ethyl cellosolve. Carbinol lacquer forms a glossy film with a yellowish
tint on the offprint. The lacquer has a sharp unpleasant smell, preserved in the coating even
after a prolonged drying at 80C.
Lacquer KS-235 is a solution of low-molecular-mass carbinol resin and cyclo-
hexanone-formaldehyde resin in hydrazite. The film of this lacquer is light-permanent, elas-
tic, but has an increased tackiness, which leads to the agglutination of offprints in a paper
sheet stack.
For finishing printed materials, home industries manufacture polyvinyl acetate
lacquer, which is a 40% solution of polyvinyl acetate in ethyl alcohol. Polyvinyl acetate is
a thermoplastic colourless transparent solid product obtained by polymerization of vinyl
acetate.

n CH2 CH CH2 CH
O CO CH3 O CO CH3 n

To impart polyvinyl acetate with rubberlike properties, it is plasticized with dibutyl


phthalate. The alcoholic solution of polyvinyl acetate is used as a lacquer for lacquering off-
prints; it forms a light-permanent, transparent, elastic, colourless film without smell but
with a low gloss, even on chalk-coated paper.
Formation of the film from polymer solutions on the surface of printed matter is ac-
companied by the emergence of local physical links between the most active groups of
structural elements as the result of the evaporation of the solvent and the slowdown of the
relaxation processes.
It has been shown that the incompleteness of the relaxation processes during the for-
mation of coatings from polymer solutions (polyvinyl alcohol and its derivatives, nitrocel-
lulose and others) leads to the emergence of significant internal stresses reducing the service
life of the coatings.
CHAPTER 4 137

Coatings from lacquers based on polymer solutions, along with good decorative and
high physicomechanical properties, have a number of drawbacks. They contain toxic and
fire-hazardous solvents, are distinguished by the low content of dry matter at a working vis-
cosity, poor light permanence; evoke the dissolution of alcohol-nonresistant pigments.
Organic solvents in lacquers are, as a rule, lost irreversibly, they pollute the air in pro-
duction facilities and necessitate special measures to be taken on safety regulations and oc-
cupational sanitation (among solvents, aromatic hydrocarbons are poisonous).
According to the data of Western statistics, the level of occupational diseases in work-
ers of paint shops and bays is five times and more higher than the average level in industries.
In this country, where human health is given great attention, abandonment of organic
solvents in protective coatings technology is not only a technical but also a social problem.
The use of organic solvents is a critical drawback of lacquer-and-paint materials also
because it creates problems of technological character lacquers should be diluted with or-
ganic solvents before application; this makes their compositions, dissolving capability, vol-
atility, viscosity etc. variable.
One of the directions in solving the problem of excluding organic solvents from the
formulations of lacquer-and-paint materials is to develop aqueous lacquer-and-paint com-
positions, i.e., such systems, where the role of a medium determining the required condi-
tions of applying and forming a coating is played by water.
When using aqueous lacquer-and-paint systems, it becomes possible not only to save
on the cost of irrevocably lost organic solvents, on ventilation and safety measures, to make
the painting process safe and flame-proof, but also to receive a number of technical advan-
tages:
possibility of applying the coating at increased humidity
use of electrophoretic sedimentation, a method special for aqueous systems; in the
West, this method found use in paper-making plants in fabrication of high-gloss paper rolls
harmlessness and smaller labour intensity of cleaning the equipment
water as a solvent or dispersant is extremely convenient.

In this country, some printing plants attempted to use alcoholwater solutions of poly-
mers, whose composition is approximately as follows (in %):

Polymer (alcohol/water-soluble) 1015


Additives 510
Solvent (a mixture of water and alcohol, 1:2) 8575

Special additives are meant to be materials, which are introduced into the composition
for hardening, crosslinking of the polymer (e.g., boric acid for polyvinyl alcohol, etc.). They
form films of high strength and good decorative properties, but the use of these polymer
solutions for finishing printed matter is made difficult due to the sharply increased viscosity
of film formers at a comparatively low percentage of polymer in the lacquer. In some cases,
this considerably affects the gloss of the film. Special additives should be introduced into
the lacquer immediately before its application to offprints, as the life time of such a lacquer
is several hours. A large amount of water in the formulation leads to the notwettability of
the most ink-saturated regions of the offprint, to a decreased adhesion to the substrate and
to a deformation of the products as the result of strong wetting. A considerable energy is
required to remove such a large amount of water, and the rate of the drying process of lac-
quered offprints does not correspond to the general rate of the lacquering process.
138 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

For instance, a nonexplosive and nontoxic lacquer PVSK based on polyvinyl alcohol
... CH2 CH CH2 CH ...
OH OH
has been developed, with an addition of boric acid and emulsifier OP-7. The lacquer is not
in use due to the duration of drying of lacquered offprints at high temperature and their curl-
ing, although it has good decorative and physicomechanical properties (high gloss, resis-
tance to abrasion, transparency, light permanence of the film).
Lacquers based on vinyl resins have been developed for lacquering specific kinds of
production labels and others. The lacquer PVM-1 is a solution of polyvinyl butyral with
an addition of water-soluble phenol formaldehyde film VMCh-4, whose formula is as fol-
lows:
HOH2C N CH2 N CH2 N H
C O C O
HOH2C N H HN CH2O(CH)2OC2H5
This resin is added as a crosslinking agent to increase the water resistance of the film.
A special class of compounds for production of coatings are oligomers. Their specific
features are that the monomer present in them performs the role of a polymerizing solvent.
In film formation, it is involved in the polymerization proceeding on the support and leading
to the formation of a three-dimensional network structure. This provides for the production
of materials with a low initial viscosity at an increased concentration of the film former.
The use of oligomer systems enables a sharp decrease of the content of volatile solvents and
yields coatings with high mechanical and adhesion properties.
Oligomer compositions include oligomers and polymerizing solvents and, in some
cases, evaporating solvents. Synthetic resins (condensation polymers alkides, phenol
formaldehyde polyesters, amino formaldehyde esters, and others) are used as oligomers.
Oligomer systems are not used in pure form in printing industry for finishing printed
matter. They are used in a mixture with natural resins of the type of wood rosin, copal, san-
darac and vegetable oils. Hard resins, used since long time ago in production of oil lacquers,
interact with oils by way of reetherification to form products similar to alkyds in their struc-
ture.
Thus, for instance, the lacquer for overprinting is a solution of hard resin in a mixture
with vegetable and mineral oils. Fixation of the lacquer on offprints occurs due to a partial
soaking-in of oils followed by the formation of a strong film as the result of oxidative po-
lymerization. In spite of a number of advantages such lacquers present (lacquering can be
done typographically and by the offset method, sometimes selectively from the printed el-
ements of the mold), they do not make it possible to produce films with high mechanical
and decorative properties in one run on papers with high absorptivity and low smoothness.
Formation of the film under normal conditions of drying is very slow, so anti-setoff prep-
arations have to be used, offprints have to be kept in stacks not higher than 3040 cm and
shook every hour to avoid tackiness. To produce a continuous film, high drying temperature
and long drying time are required, as the mechanism of coating formation from these com-
positions is complex and is accompanied by the removal of solvent, by the oxidation and
polymerization processes to form the three-dimensional network. It is reported that electro-
magnetic waves of a frequency fro 0.3 up to 3000 Hz are used to accelerate stacking of print-
ed materials with the aim to rapidly obtain a dry protective lacquer film on offprints.
CHAPTER 4 139

The most widespread in home industry is a lacquer (CF-1) based on an oligomer film
former the cyclohexanoneformaldehyde resin. The CF-1 lacquer is a solution of the fol-
lowing composition (in %):

Cyclohexanoneformaldehyde resin 52
Plasticizer 2
Colophony (pine wood rosin) 5
Ethyl alcohol 41

When used to lacquer papers with high absorptivity (e.g., offset papers), this lacquer
does not form a film with good physicomechanical and decorative properties. To impart the
coating with gloss and to increase the abrasion resistance of the offprint, two layers of lac-
quer should be applied, which is extremely unproductive and uneconomical.

4.2 Application of aqueous dispersions of polymers for finishing products


Aqueous dispersions of polymers have advantages in comparison with aqueous solutions
of polymers, as they enable production of film formers with a greater concentration of poly-
mer (4050%) at a comparatively low viscosity and rapidly dry to form the film. The vis-
cosity of dispersions does not depend on the extent of polymerization of resins.
Film formers for finishing packaging materials were chosen in two directions:

first, Russian-make aqueous dispersions of polymers were used for finishing; the dec-
orative properties of coatings on their basis were studied
based on the analysis and studies of Western patents and literature, the most prom-
ising aqueous dispersions of polymers were chosen and recommended to Russian chemical
enterprises for the development of special compositions of latexes with account for the re-
quirements of the qualitative finishing of printed materials and for availability of Russian
raw materials for production of latexes.

Aqueous dispersions consists of an aqueous dispersion medium and polymer dispersed


in it. Polymer dispersions used for coatings on paper are obtained predominantly in the re-
action yielding high-molecular-mass substances in an aqueous medium in the process of
emulsion polymerization: in the presence of an emulsifier and an initiator.
Dispersions used the most for application of surface coatings to paper are vinyl acetate
dispersions, copolymers of this type, as well as acrylate dispersions. The company Hoechst
(Germany) manufactures an aqueous dispersion of polyvinyl acetate under the name of
Movilit for fabricating decorative coatings on paper.
Many researchers deal with synthesizing novel compositions of aqueous dispersions.
Western patents recommend an aqueous dispersion containing a linear polymer and the am-
monium salt of the copolymer of diisobutylene with maleic acid monoamide. The quality
of this coating is good: butadienepolystyrene copolymers and polyacrylates can be used
for coatings on paper; DuPont (USA) manufactures a dispersion of blended polymers of
polyvinyl acetate and polyethylene under the trademarks of Elvax 150 and Elvax 250,
which form a glossy coating on printed material.
Methods of producing aqueous dispersions of polymers are different. Bayer et al. pro-
pose the following method: vinyl esters (e.g., vinyl acetate, vinyl propionate) as well as
mixtures with other polymerizing esters (e.g., esters of acrylic, maleic and fumaric acids)
140 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

are polymerized in a neutral or weakly acidic medium in the presence of water-soluble ac-
tivators and protective colloids.
A method for producing polyvinyl acetate dispersions stable at low temperatures was
developed. The release of an aqueous dispersion of a copolymer of vinyl acetate with other
monomers under the trademark of Wallpol 9120 is reported; the formulation is used for lac-
quer coatings. This dispersion is produced using esters of unsaturated (maleic, fumaric) ac-
ids and acrylic-acid esters as a copolymerization monomer.
Films of polymer aqueous dispersions on paper, as well as lacquer films for finishing
printed materials, should possess certain properties: gloss, elasticity, transparency, water
resistance, light permanence, mechanical strength, stability and low-temperature resistance.
Low-viscous dispersions forming thin films (1015 m) on paper can be used for coat-
ing printed and packaging materials. The gloss of films of vinyl-polymer and polyvinyl ac-
etate dispersions depends on the size of their particles. Coarse dispersions with particle size
of 0.52.0 m form mat coatings. Fine dispersions with particle size of 0.050.2 m form
glossy elastic coatings. Films of polymer coatings on paper are transparent.
Water resistance of polymer coatings is of great significance. Water-resistant coatings
can be produced using polymers obtained by polymerization of vinyl acetate with additions
of acrylic- or nitrile acrylic-acid esters.
Coatings from aqueous dispersions of polyvinyl acetate have a high light permanence.
A polymer coating for single- and multicolour offprints, which possesses a mechanical
strength, has been developed.
There are stable and low-temperature-resistance aqueous dispersions of polymers. The
stability of the dispersions at a temperature of 15C for six months is achieved by using
a mixture of water and (ethyl, methyl) alcohol at weight ratios of 190:10100:100 as an
emulsion medium.
It is proposed to introduce synthetic (acryl, butadiene styrene, polyvinyl acetate) resins
into dispersions of epoxy esters to produce stable dispersions. A dispersion possessing both
a stability and low-temperature resistance was produced. The patent literature also recom-
mends stable and low-temperature-resistant dispersions consisting of a homogeneous poly-
mer or copolymer (e.g., ethylene and alkylacrylate, in the hydrocarbon chain of which
2.525% of carbon atoms are substituted by carboxyl, carboxylate or carbamyl.
Viscosity is of great significance in application of dispersions to paper. It has been
found that at the same dry residue a coarse dispersion of polyvinyl acetate has a viscosity
of 100 ps; a fine dispersion, several poise. It is proposed to regulate the viscosity of the dis-
persion of vinyl resins with crotonic acid. For this purpose, crotonic acid is added to the
dispersion of vinyl acetate, and copolymerization is carried out. By changing pH of the co-
polymer obtained, the viscosity of the dispersion is regulated within the required limits.
The dependence of viscosity and temperature has been studied; the viscosity of a poly-
vinyl acetate dispersion with particle size of 0.22.0 m was found to decrease with its tem-
perature increasing.
Divinyl styrene latexes are used as coatings for paper to increase its printing properties
and the quality of typographic and offset printing; herewith, the resistance of the offprint to
abrasion in dry and moist state increases.
Divinyl styrene latex SKE-30, modified by an aqueous solution of polyvinyl alcohol,
is used to produce special lacquer-and-paint materials for the printing industry. Special
primers for producing paper-based binder materials were developed on the basis of this
latex.
However, coatings from these latexes are characterized by low decorative properties.
CHAPTER 4 141

A latex based on the copolymer of acrylate with vinylidene chloride Rhoplex A-9
is widely used for coatings on paper for packaging materials. This latex is colourless, pre-
serves the flexibility of paper, causes no sticking, yields well to dyeing, but its film is not
light-permanent. Copolymers of vinyl chloride and vinylidene chloride are used for finish-
ing packaging materials, paper and paperboard.
A possibility of using latexes manufactured by Russian industries for finishing printed
materials has been studied.
With this in mind, a large set of fine dispersions of polyvinyl acetate,
... CH2 CH ...
OCOCH3 n

obtained under diverse conditions of synthesis (Table 4.1) and differing by their molecular
masses (Table 4.2), was synthesized in the presence of various emulsifiers (Table 4.3), with
introduction of phenol-formaldehyde resins. Analysis of the data presented in the tables
shows that PVA dispersions synthesized under various conditions yield no coatings with
the required set of mechanical and decorative properties. Regulation of the molecular mass
of polymer and the nature of emulsifier (Tables 4.2 and 4.3) failed to improve the decorative
properties of coatings. Modification of the PVA dispersion by phenol-formaldehyde resin
improves the decorative properties, but leads to a sharp increase of brittleness of the film
and to light nonpermanence.
Table 4.1

Type of latex Dry residue, % Characteristics of dispersion and quality


of coating on offset imprint

Fine-particle 48 Slightly sticky, light nonpermanent; grains in the


polyvinyl acetate coating
(PVA) dispersion 49 nonsticky; good gloss but light nonpermanent
47.8 mat nonsticky film
48.7 low gloss; dispersion does not wet saturated areas
of offprints
49.0 dispersion soaks into the offprint without forming
a glossy coating even after two layers of coat
48.5 high gloss, coating non-sticky; dispersion unstable
(coagulates on day 3)
47.9 high gloss, coating non-sticky; dispersion unstable
(coagulates on day 3)
49.2 high gloss, coating non-sticky; dispersion unstable
(coagulates on day 3)

Table 4.2

Type of Dry residue, Emulsifier Characteristics of coating on offset imprint


latex %

Fine-particle 48.7 OP-7 no gloss; dispersion does not moisten black


PVA ink
49.1 OP-10 with 0.2% no glossy film is formed; dispersion does not
sulfanol addition moisten saturated areas of offprint
142 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 4.2 (continued)


Type of Dry residue, Emulsifier Characteristics of coating on offset imprint
latex %

49.5 OP-10 cast film is lusterless; dispersion does not


moisten black ink
48.3 technical-grade cast film is lusterless; dispersion does not
proxanol 228 moisten black ink
48.5 16% proxanol no film is formed
47.9 alphanol 12 film is lusterless but non-sticky

Note: PVA, polyvinyl acetate dispersion; alphanol and sulfanol, anionogenic preparations; OP-8,
OP-10 and proxanol, nonionogenic preparations.

According to the data of patents, PVA dispersions have found wide use owing to their
relatively low cost.
Their major drawback is that at a normal temperature they are incapable of forming a
continuous film and, thus, need plasticizers to be added. Due to the volatility and migration
of plasticizers, the film is rapidly aged and becomes brittle. Besides, vinyl acetate ester is
apt to saponify. By introducing various additives, we succeeded in obtaining a composition
for finishing printed products; however, its use on the existing equipment is associated with
a number of technological difficulties.
To avoid introducing a plasticizer into the ready polyvinyl-acetate dispersion, a meth-
od of internal plasticization was used, namely, fabrication of copolymers of vinyl acetate
with other monomers (esters of unsaturated acids maleic, fumaric; esters of acrylic acid).
Table 4.3

Type of latex Dry residue, Molecular mass Characteristics of coating


% on offset imprint

Fine-particle PVA 43.7 96.600 non-sticky, with good gloss; dispersion


does not moisten black ink
45.6 79.700 dispersion coagulates on day 3
47.3 67.900 low gloss
45.2 53.300 no gloss at all; dispersion unstable
48.3 90.600 dispersion coagulates on day 2
Fine-particle PVA hydrocarbon: H2O Monomer cast film has high gloss
with different ratio dosage but is very brittle
proportions of
monomer
43.7 2:3 1/20
44.3 1:1 1/10 cast film is lusterless
Fine-particle PVA with addition of water-soluble rigidity of film increases and
phenol-formaldehyde resin non-light-resistance appears; in time,
introduction of resin causes coagulation of
dispersion
Specimen of aqueous forms nonsticky coating, with high gloss;
dispersion from cast film grows turbid in the light (on day
Germany 3); opacity increases in time
CHAPTER 4 143

Copolymers of vinyl acetate (VA) with ethylene grafted in several cases with acryla-
mide were tested. Aqueous solutions of solvars with various ratios of the hydroxyl and ac-
etate groups, and dispersions of copolymers of polyvinyl alcohol with acrylonitrile and
acrylic acid (Table 4.4) form coatings with poor decorative properties. The decrease of the
number of acetate groups in solvar increases the gloss, but the adhesion of coatings becomes
worse in this case.
Table 4.4

Type of latex Ratio of Dry Content of Characteristics of coatings


components residue, acetate on offset imprint
% groups, %

PA copolymer : AAN 64:36 Latex rapidly soaks to form a


low-gloss film
PA:PVA (solvar) 21 Gloss increases with decrease of
18.2 acetate groups, viscosity of solutions
9 increases

PA copolymer : AA Content of AA Coating has no gloss; viscosity of latex


7.6% 10.5 increases with percentage of AA,
38% 7.4 causing warpage of imprint
25% 8.4
VA copolymer : DAC 96:4 47.5 Cast films are yellow and
94:6 46.7 nontransparent; latexes are unstable
90:10 35.8 (peel off with time)
88:12 42.3
emulsion N-542 Film light-nonpermanent; gloss is
high after two coatings; lacquer film
can be calendered
NC with different Initial suspensions are very viscous;
degrees of branching when diluted, soak into imprint
without forming a glossy film

Note: PA, polyvinyl alcohol; AAN, acetic acid nitride; PVA, polyvinyl acetate; AA, acrylic acid;
VA, vinyl acetate; DAC, diallyl cyanamide; NC, nitrocellulose.

According to the literature data, at a certain ratio of components the copolymer of vinyl
acetate with ethylene has a higher strength and elasticity as compared with high-pressure
polyethylene; is resistant to cracking, action of ultraviolet rays; has good adhesion proper-
ties; is resistant to alcohols, glycols, organic acids and is used in a paper-finishing compo-
sition. The copolymer of vinyl acetate, ethylene and triallyl cyanurate is used to form a
smooth glossy coating on paper and paperboard.
Coatings with unsatisfactory decorative properties also form dispersions of vinyl ace-
tate with diallyl cyanamide. Coatings from the emulsion based on nitrocellulose are distin-
guished with a low light permanence.
Aqueous dispersions based on copolymers of vinyl acetate with ethylene, grafted in
several cases with acrylamide, and introduced polymethyl siloxane (Table 4.5), as well as
copolymers of divinyl with methacrylic acid or methacrylamide fabricated at the S.V. Leb-
edev All-Russian Institute of Synthetic Rubber were tested as film formers for finishing
144 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

printed products. As seen, coatings based on these dispersions have poor decorative prop-
erties and low strength.

Table 4.5

Type of aqueous Colloidal characteristic Surface Characteristic of Characteristic of


dispersion tension, free film coating on offset
dyn/cm imprint
dry pH ratio of elong- tensile
residue, components ation, % strength,
% MPa

VA copolymer:ET 49 3.9 80:15 900 0.079 Very sticky


49 3.9 82:12 500 0.10 Very sticky
VA copolymer: 47.4 3.5 80.5:17:2.5 47.1 500 0.42 Coating is sticky,
ET:AA dispersion does not wet
saturated areas
of imprint
48.2 3.4 82:17:1 43 570 1.5 Ditto
47.8 3.6 79:20:1 41.7 550 2.4 Ditto
VA copolymer:ET 57.7 5.3 80:20 and 39.3 550 2.7 Sticky due to residual
with addition of 10% monomer (6.5%)
PMS-200
VA:ET with 44.3 5.5 90:10 and 39 400 6.9 Grains in dispersion
addition of SiO2 20% make coating rough,
latex does not wet black
ink
copolymer 43.0 8.5 Gloss not high; latex
DMMA-65-1GP does not wet black ink
DMMA-65(60)-2 42.0 8.3 Gloss not high; total
wetting of black ink

Note: VA, vinyl acetate; ET, ethylene; AA, acrylamide; PMS, polymethyl siloxane; DMMA-65-1GP,
divinyl and methacrylic acid; DMMA-65(60)-2, divinyl and methacrylamide.

As shown by the preliminary selection of dispersions and analysis of Western litera-


ture, acrylic dispersions of polymers proved to be the most promising for finishing coatings.
Acrylates begin to exhibit a film-forming ability almost at 0C; what is more, the produced
films are distinguished with a sufficient mechanical strength, as well as a high light and at-
mospheric resistance. A characteristic property of polyalkylacrylate films is their high
gloss, resistance to the action of UV light and molds.
Good results using these dispersions for finishing reel paper suggest that there is a ten-
dency to use aqueous dispersions of polymers for finishing printed packaging material.
The employment of aqueous dispersions of polymers requires special equipment for
their application, development of special process regimes and method of drying polymer
coatings. These important issues are being dealt with for several years now by many ad-
vanced companies in developed countries.
Dispersions based on triple copolymers of ethylacrylate, nitrile acrylate, -m-styrene
with various ratios of the components were obtained (Table 4.6), as well as copolymers
based on ethylacrylate, nitrile acrylate, -m-styrene and 2-ethyl hexyl acrylate. It is seen
CHAPTER 4 145

that coatings based on these copolymers have poor gloss and do not wet the saturated re-
gions of offprints.
Table 4.6

Ratio of components Colloidal characteristic of Condition of Characteristic of coating


latex synthesis

dry residue, sp pH
%

EA:NAC:-m-styrene 37.5 2.6 3.45 Emulsifier was Coating has a pungent smell,
75:20:5 fed batchwise bad gloss; latex does not
moisten greasy areas of imprint
EA:NAC:-m-styrene 37. 5 2.0 3.65 Emulsifier was Ditto
75:20:5 batched
EA: 2-EHA: NAC: 37.6 3.4 4.7 Ditto Ditto
-m-styrene 50:25:20:5
EA:NAC:-m-styrene 38.1 1.9 3.6 Ditto Ditto
65:20:15
EA:NAC:-m-styrene 37.6 1.9 2.7 Emulsifier was
80:5:15 fed batchwise Ditto

Note: EA, ethyl acrylate; NAC, nitrile acrylate; 2-EHA, 2-ethyl hexyl acrylate.

Thus, latexes produced by home industries and specially synthesized with the view of
using them for finishing printed products, do not form coatings satisfying the required set
of decorative and physicomechanical properties. Coatings based on these systems, as is
seen from the presented data, are sticky, with low gloss; they crack and have a smell.

4.3 The formation mechanism, structure and properties of finishing


packaging materials from aqueous dispersions
The mechanism of forming coatings from aqueous dispersions of polymers has not been
sufficiently studied until now. Most works in this field deal with the synthesis of latexes
and the development of the technological bases of their use. The reason for this is that the
processes of film formation from latexes have been studied using the methods, which do
not make it possible to investigate the kinetics of the process and the character of structural
transformations at particular stages of film formation. Methods of studying the kinetics of
moisture removing and electrical-conductivity changes were the most widespread. These
methods are not sensitive to the changes of the properties of films after moisture is removed.
It is known that the process of coatings and films formation does not end at this stage and
is accompanied by further structural transformations after the removal of moisture.
Most works analysing the film-formation mechanism consider latexes as typical
colloidal systems without taking into account the polymer specifics of the disperse-phase
material. It is assumed that certain conditions different from those in production of films
from polymer solutions should be met to produce a continuous film from latex.
This is due to the fact that a polymer in latex is distributed not in the form of more or
less associated molecules, but in the form of particles containing sometimes tens of
thousands of macromolecules.
146 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

1-3

F2 F

1-3

Figure 4.1 An action pattern of forces contributing to the coalescence of latex particles.

Film formation from latexes is associated with the consideration of factors, which
affect the rate of deformation and coalescence of latex particles, such as surface tension,
capillary forces, diffusion, nature of polar groups, film formation temperature, etc.
In a number of works, the driving force of film formation is taken to be the surface
tension at the polymerair interface, which tends to reduce the surface of the polymer
phase.
It is assumed that after the evaporation of water latex particles flow in under the
action of the surface tension force, which depends on angle (Fig. 4.1), the value of which
is determined from the Frenkel equation

2 3 13 t
= ---------------- ,
2 r

where 13 is the surface tension at the polymerair interface, t is the contact time of par-
ticles, is the viscosity of polymer and r is the radius of a polymer particle.
It is assumed that the force of interaction between latex particles depends on their size;
herewith, it is not taken into account that particles themselves can have diverse shapes.
In works by Brown, of crucial importance in the film formation process are capillary
forces, which act against forces of electrostatic repulsion and forces of strain (deformation)
resistance identified with polymers elasticity modulus. At a certain value of the modulus,
particles are not able to get deformed, so no film is produced.
The capillary forces depend on the surface tension at the polymerair interface and
the capillary radius rc

2
F = --------1- .
rc

Assuming that aqueous streaks between latex particles have the form of a cylinder
(Fig. 4.2a), we can determine the radius of a capillary

r ( 1 cos 30 )
r c = ---------------------------------- ,
cos 30

where r is the radius of a latex particle.


CHAPTER 4 147

FH
rc
Fn
30 rc
r

a b

Figure 4.2 An initiation pattern of capillary forces during the drying of latex: a, initiation pattern of
capillary forces; b, resolution pattern of capillary forces.

According to Brown, the film-formation process occurs when

F1 + F2 + F3 + F4 > F5 + F6 ,

where F1 are the capillary pressure forces, F2 is the force depending on the surface tension
at the polymerwater interface, F3 are the forces of molecular interaction, F4 the force of
gravity, F5 is the resistance to strain, F6 the force of electrostatic repulsion.
At the same time, it has been found that the size of particles, on which the capillary
pressure depends, has no effect on the film formation process, and the last stage of film for-
mation from latex can be determined by its polarity or autoadhesion.
Film formation can have the diffusion-osmotic mechanism. In this case, it is assumed
that water is fed to the surface not only through capillaries, but also via latex particles them-
selves, proceeding from the assumption that for real latexes the surface tension at the water
phaseair interface is greater than 30 dyn/cm and the wetting angle is greater than 0.
Therefore, a force applied to the wall of a capillary can be resolved into two components
(Fig. 4.2b): normal, Fn = 2 rc 23cos and tangential, FH = 2 rc 23sin , where Fn is
the compressing force directed inside the specimen and FH is the force directed along the
surface and tending to close the openings of the capillary. For synthetic latexes, FH > Fn.
The polymer film formed on the surface of drying latex is permeable for water vapours,
not impermeable for water itself; because of this, an osmotic pressure emerges, which is
directed inside the film and is compacting its structure. It is concluded that the main source
of energy in film formation is ambient heat transformed into effective work in the evapo-
ration of water via latex particles. The action of capillary forces has to do with faster drying
of latex films if the polymer is in a rubberlike state as compared with the polymer in a vis-
coelastic state.
The main criterion of film formation in a number of cases is taken to be the minimum
film formation temperature (MFFT), i.e., the temperature above which globules of thermo-
plastic polymer are capable of deformation to form a continuous film. MFFT is an essential
characteristic of the film-forming latex. It is assumed to correspond to the temperature of
the transition from the glassy to the rubberlike state. However, it has been shown that for-
mation of films can occur at temperatures lower than the glass transition temperature of a
polymer; as the result of the contact of latex particles one with another, there will be the
148 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

interpenetration of macromolecular segments on their surface, possessing a significant free-


dom of rotation. Therefore, it is suggested that the temperature of film formation should be
the function of the ratio of the surface to the volume of the polymer phase. On the other
hand, one of the works showed not only the feasibility of film formation but also its kinetics
to depend on the physical state of the polymer.
Film formation depends not only on the colloidal and rheological properties of latex
but also on the chemical composition of the polymer.
Studies of the effect of polymer polarity on the rate of film formation by the example
of latexes of various copolymers of ethylacrylate have shown that the rate increases with
the polarity of the polymer going up.
An essential drawback of those works is that they fail to take into account the crucial
role of structural transformations during the formation of the properties of latex films. This
was first noted in the works by S.S. Voyutsky and coworkers, who considered formation of
films from latexes as a multistage process. Of crucial significance is the last stage of film
formation associated with the redistribution of emulsifier, the deformation and coalescence
of latex particles. The redistribution of emulsifier and its dissolution in the polymer can be
contributed to by the diffusion of macromolecules similar to how it takes place in the for-
mation of films from other systems. Even at a very low content of emulsifier in the latex
film, its water absorption was shown to depend on the structure of the latter. Water absorp-
tion of acrylate latexes synthesized at the same consumption of the initiator and emulsifier
decreases with the increase of the elasticity modulus of the polymer and an increase of its
molecular mass. This can be explained by the increase of the intermolecular interaction, at
which the number of holes, formed in the thermal motion of polymer macromolecules
and responsible for water absorption, decreases. A similar dependence of water absorption
of latex films from polyvinyl acetate and its copolymers with butyl acrylate on polymers
deformation resistance was obtained.
In all these works, latex particles were considered as a ball of irregularly intertwined
macromolecules kept together by the forces of intermolecular interaction.
Studies of the fine structure of latex coatings and its effect on the properties of the latter
have not been given due attention. Studies of latex particles were mainly reduced to the rev-
elation of their size; and studies of structures of films, to observations of replicas from their
surfaces in an electronic microscope.
We investigated the structure of latex particles and its effect on the structure and prop-
erties of coatings by the example of commercial latexes. For electron-microscopy studies
of the fine structure of latex particles, we used the method of oxygen etching.
As a result of these studies, we found latex particles to be complex supramolecular for-
mations consisting of simpler structural elements. The size and morphology of the struc-
tures occurring in latex particles depends on the chemical composition of the polymer, the
nature of the functional groups, the colloidalchemical nature of latex.
To study the mechanism of formation of latex coatings, in these works we used new
methods enabling us to investigate the properties of latex coatings at various stages of film
formation and to assess the emerging internal stresses in the coatings, which cause sponta-
neous curling and warping of the materials. A relationship between the structure and prop-
erties of latex coatings was established.
Internal stresses emerging in the formation of coatings are determined by the rate of
inhibition of the relaxation processes, which depends on the architecture of molecules and
the character of supramolecular structures they form.
The significance of the relaxation processes in drying was first noted in the works by
CHAPTER 4 149

Academician A.V. Lykov, who proposed methods for the calculation of internal stresses,
with account for the fields of temperature and moisture content, and deduced a dimension-
less criterion of crack formation depending on the operational parameters of drying.
V.A. Kargin et al., G.L. Slonimsky, P.I. Zubov and T.I. Sogolova investigated the na-
ture of the relaxation processes in polymers and their role in the formation of coatings; this
process was shown to be accompanied by the emergence of local links between the most
active groups of polymer molecules. The number and nature of these links, as well as the
conformation of macromolecules, render an effect on the rate of the relaxation processes
and the value of internal stresses.
A peculiar feature of the formation of latex coatings is the nonmonotonic change of
internal stresses in the film-forming process. First they increase and reach a maximum after
the removal of moisture, and then relax to a constant value.
Studies of the structure of the initial dispersions and coatings on their basis revealed
that after moisture removal the coatings preserved latex particles whose diameter, depend-
ing on the nature of polymer, changed little within the limits of 0.15 up to 0.17 m. With
this in mind, special attention was paid to studies of the structure of latex particles; it was
shown that they were complex supramolecular formations consisting of simpler and finer
supramolecular structures.
A direct relationship was established between the structure of latex particles and the
rate of the relaxation processes; the relaxation processes are completed the fastest in coat-
ings with the least number of globules (equal to 50, of about 30 nm in diameter) in a latex
particle. As the number of globules in a latex particle increased by two orders of magnitude
and their diameter decreased to 910 nm, the relaxation processes were sharply slowed
down and were completed in 30 days of formation.
Studies of the supramolecular structure at particular stages of formation of latex coat-
ings have established that the removal of moisture was accompanied by the preservation of
latex particles with the emergence of local links between them and structural elements that
form them.
The subsequent relaxation processes are associated with the breakdown of latex parti-
cles and the rearrangement of their constitutive structural elements.
Thus, formation of latex coatings is not completed after moisture removal and consists
of two stages. The first stage is associated with the increment of internal stresses as the re-
sult of establishing local links between latex particles and their constituent structural ele-
ments during the removal of moisture from the system.
The second, longer stage is to break down latex particles and to rearrange their consti-
tutive structural elements, which leads to the relaxation of internal stresses.
The methods of measuring the kinetics of increment and relaxation of internal stresses
and measuring the thermal and physical properties of coatings, proposed in these works, are
of significant interest for coating formation studies and of great practical importance.
In contrast with the methods of studies of other mechanical and electrical parameters,
they make it possible to follow the complete process of forming films on the support on one
specimen and to assess the change of the properties of latex coatings after moisture removal.
The earlier used methods of studying the film-formation kinetics by the change of
moisture and electrical resistance failed to detect structural transformations in latex coat-
ings after removal of moisture from them.
Using this method for studies of internal stresses, it has been shown that the character
of the kinetic curves of the increment and relaxation of internal stresses does not depend on
the nature of the support, which has a significant effect on the value of internal stresses.
150 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Ways to decrease internal stresses during the formation of latex coatings were pro-
posed by regulating the character of structural transformations and by forming an ordered
supramolecular fibrillar-type structure in latexes and coatings on their basis, using modified
additives and changing the colloidalchemical nature.
This made it possible not only to reduce internal stresses in the system, but also to con-
siderably decrease their formation period, to sharply increase adhesion and strength of latex
films.
Studies of the effect of structural transformations in latex films on the decorative prop-
erties of coatings have not been given due attention. This complicates the choice of latex
systems for finishing packaging and printed products and does not make it possible to define
the main requirements to the structure and chemical composition of a latex formulation,
which provide for the required set of mechanical and decorative properties of coatings.
The process of forming coatings from aqueous dispersions of polymers on fibrous
bases of the type of paper and printed products has been little studied. The effect of the
chemical composition of the dispersion, the nature and concentration of polar groups, the
colloidalchemical nature of latex has not been investigated.
The most promising class of film formers for finishing printed products are aqueous
dispersions of polymers.
To develop aqueous dispersions of polymers used for finishing printed products, the
effect of various physicochemical factors on the decorative properties of the coatings, such
as the structure of latex particles and coatings, the nature of the functional groups and their
distribution on the surface of latex particles, the colloidalchemical nature of latex has been
studied.
These studies made it possible to develop the physicochemical bases of the synthesis
of latexes forming the coatings with high decorative and protective properties.

4.4 Characteristics of finishing packaging materials


The mechanism of film formation from aqueous dispersions of polymers has not been stud-
ied sufficiently. The earlier used methods of studying the kinetics of moisture removal, the
changes of electrical conductivity; of plotting the thermomechanical curves, do not make it
possible to investigate completely the kinetics of the process and the character of structural
transformations occurring as the result of incompletion of the relaxation processes.
To study the process of coating formation from latexes, we investigated the kinetics
of the increment and relaxation of internal stresses. The internal stresses were determined
by the polarization-optical method broadly used in various industries.
The peculiar feature of the method we used is that stresses are assessed by the value
of the birefringence in the support at the interface with the film. This excludes the need for
measuring additional physicomechanical characteristics for calculating internal stresses,
which change during the formation and ageing of the coatings.
Glass isotropic prisms in the form of parallelepipeds, 102030 mm in size, which are
an optically sensitive material with a linear dependence between voltages and birefringenc-
es within a broad range of voltages and temperatures were used as a support. The error of
the method does not exceed 510%. The value of the method is also that, along with internal
stresses, it determines adhesion of coatings, which is assessed by the maximum critical
stresses causing the spontaneous delamination of the film from the support at a certain
thickness of the coatings. The critical stresses were developed by forming an epoxy coating
on the latex coating obtained on a glass support. The optical schematic of the recording
CHAPTER 4 151

8
3 4 7 +
2 5 6
1

9 V
10 +

11 Rcr

Figure 4.3 The electro-optical schematic of the instrument.

instrument is given in Fig. 4.3.


A beam of light from incandescent lamp 1 (170 W, 17 V) passes through condenser 2
and is fed via polarizer 3 to measured specimen 4. Through slit 5 (0.50.5 mm in size) and
object lens 6 the light comes to analyzer 7 crossed with polarizer 3 and goes to measuring
photocell 8. Compensation photocell 9 is connected in parallel to the measuring photocell.
A light beam from source 11, which has a system of diaphragms and neutral wedge 10, is
incident on the compensation photocell. The compensation part of the circuit, connected to-
ward the measuring photocell, serves for the exact zero point adjustment in the electric cir-
cuit. Internal stresses in various planes are measured by automatic displacement of the table
with the specimen at a rate of 4 mm/min.
Studies of stresses by the optical method during the formation of coatings on various
supports can be done by preliminary pasting or depositing a support in the form of a layer
10 to 100 m thick on the surface of the glass prism, followed by the application of a poly-
mer coating to this support. Various supports were pasted by a glue based on epoxy resin
ED-5 applied as a thin layer 36 m. Using this method of pasting, there were practically
no internal stresses in the glass prism before the application of coatings.
Using the optical method, we studied the effect of various factors on the value and
increment/relaxation kinetics of internal stresses, such as the chemical composition of film
formers, the colloidalchemical nature of latex, the nature and polarity of the functional
groups, the effect of the nature and structure of the support, the formation conditions and
methods of drying the coatings.
The kinetics of drying latex coatings was studied by the weight method. The same
amounts of latex of a known concentration (in our experiments, it was 0.010.015 g at a
latex concentration of about 50%) were applied to glass plates of 1020 mm. The glass
plates were periodically weighed at room conditions (at a temperature of 20C and relative
humidity) at certain time intervals on an analytical balance until a constant weight was
reached.
Penetration of polymer into the fibrous support in the process of drying of the coatings
was determined by the fluorescence of transverse sections of papers (offprints) with a coat-
ing in an ML-2 ultraviolet microscope. The source of light is a DPSh-250 mercury lamp,
which gives an intensive radiation in the blue-violet region of the spectrum up to the wave-
length of 340 nm. The operation of the instrument is based on the use of the fluorescence
of belofors, which occurs under the action of beams of a certain spectral composition. The
152 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

to pressure gauge
1
6

5
2 3 4

cooling

to pump

Figure 4.4

light of the fluorescence has a longer wavelength than the light exciting the fluorescence.
Belofors having an affinity to the polymer (Belofor SNPA) were used as optically bleaching
substances. A minor amount of belofor (0.0054 g per 50 g latex) was introduced into the
initial dispersion, and then the dispersion was evenly applied to the supports by means of a
spreading knife; the weight of the applied dispersion was controlled.
The supramolecular structure of latex coatings was studied using an electron micro-
scope by means of the method of carbon replicas. In some cases, the specimens were sub-
jected to oxygen etching to reveal the structure more clearly.
Activation of oxygen was performed in an electromagnetic high-frequency field. The
advantage of this method of etching is that the substance is treated not for a long time and
evenly without increasing the temperature or increasing it comparatively little within the
limits of 24C.
The specimen was etched in a tube presented schematically in Fig. 4.4.
After specimen 2 is introduced through the side tap, a vacuum of up to 10 3 mm Hg
is created and an oxygen flow at a pressure of 34 10 2 mm Hg is set by means of a needle
valve. Then a discharge is carried out. The etching time was adjusted experimentally to
810 min.
Oxygen etching contributes to a more pronounced revelation of the structure, without
changing its character, as the result of the elimination of a low-molecular-mass less ordered
structure.
Preparations were observed at an UEMB-100 electron microscope.
The molecular structure of the coatings, with account for the distribution of the polar
groups on the surface of latex particles and the formation of hydrogen bonds between them,
was studied by the method of IR spectroscopy. Formation of films from latexes was
performed on fluorite plates. IR spectra of the latex coatings were recorded by an UR-20
instrument.
CHAPTER 4 153

The size of latex particles was determined by the method of electron microscopy by
preparing preparations from very dilute dispersions at a concentration of 0.001%; these data
were simultaneously compared with those of the diameter of particles obtained by means
of an FEKN-57 nephelometer.
The macrostructure of the initial papers was examined in reflected light on an MIM-7
microscope. Specimens of papers studied were preliminarily contrasted.
The microstucture of the initial papers was examined in an UEMB-100 electron
microscope. Specimens were obtained by dispersing papers by means of an UZDN-1 ultra-
sonic disperser at a frequency of 15 kHz for 30 sec.
The rheological properties of latexes, depending on their composition and colloidal
chemical nature were studied on a viscosimeter with Shvedov-type coaxial cylinders and
were assessed by the character of the viscosityshearing stress curves.
Stressstrain characteristics were recorded at room temperature by a Polyani instru-
ment to characterize the mechanical properties of films. Specimens for tests were cut as
rectangles 455 mm in size from the most even-thickness part of a film. The area of the
working part was 105 mm2; the loading rate, 610 mm/min. The mean values of the
stress-strain characteristics were obtained from 910 parallel determinations.
The thermomechanical properties of polymers were assessed by the change of strain
on temperature. The thermomechanical curves were registered on a Kargin balance at a con-
stant load and heating rate.
Factors affecting the quality of lacquering printed offprints at various types of papers
were studied. The method of determining the extent of lacquering is based on the assess-
ment of the rate of lacquer penetration into the support and depends on the absorption prop-
erties of the support.
To assess the extent of lacquering of saturated regions of an offprint with dispersions
studied, we measured the contact angle of wetting at the offprint surface /drop of
dispersion/air interface and determined the wetting as a function of time (rate of absorption)
by the drop contour projection method.
The character of the kinetic curves of wetting is similar, so the data of measurements
are summed in the table.
The gloss of the coating is one of the major decorative parameters of the coating qual-
ity. Objective methods of measuring the gloss have been developed. The Fairchild gloss-
meter is the most advanced, as it enables measuring the gloss of paper continuously by
means of a comparative method, can be used at a high temperature, humidity in the presence
of corroding chemicals and vapour, has a number of design advantages. The gloss of coat-
ings under study was measured by a glossmeter, was assessed with respect to black glass
and was expressed in percent.
Cohesion of lacquered offprints was determined by the method proposed for binding
fabrics. The method consists in determining the force of cohesion emerging as the result of
the contact of the face surfaces of lacquered offprints at a certain temperature, pressure and
time. Specimens were prepared as follows. Straps of lacquered products of 3050 mm in
size were preliminarily held at a 100% relative humidity on an exciccator mesh (with the
face part up) for 30 min, them placed into a press mold heated up to 302C, were subjected
to compression at a pressure of 2005 kgf for 1 min, removed from the press mold and put
between glass plates under a load of 1 kg for 24 h. Then the specimens were subjected to a
load, required for a shift of the surfaces, in a tensile tester.
The force of cohesion (B) in kg/cm2 was determined by the formula:
154 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

P
B = --- ,
S

where P is the load at the shift of the surfaces in kg and S is the contact area of the specimens
in cm2 (of 57 parallel tests to an accuracy of up to 0.1).
The lacquer film on an offprint should have an abrasion resistance and elasticity. The
resistance of a coating to abrasion can be defined by the length of a path, in passing which
the coating is being broken, and be characterized by the number of turns of a prism before
the appearance of the paper base. Specimens studied are fixed on to the prisms; the speci-
mens are in contact with a closed band made from the fabric used as a counterbody in abra-
sion. The fabric band is cut of the same size as the base, is pulled tight by a load of 3 kg,
and then the cross with the prisms is rotated at a speed of 60 revolutions per minute. The
mean arithmetic of six parallel determinations was taken as the abrasion result.
Elasticity of the coating was assessed by the number of double bends in tests on an
MIDP-1 instrument used in printing industry. The method consists in determining the num-
ber of double bends to an angle of 150 to each side from the vertical position of the material
being under tension, up to the emergence of cracks on the film coating or the break of the
specimen.
Durability of coatings on paper is assessed not only by the values of internal stresses,
but also by its resistance to ultraviolet radiation. The light permanence of coatings was es-
timated by a faster method from the change of the colour of the specimens as compared with
the reference methods under the action of ultraviolet radiation of a PRK-4 lamp. A corre-
lation between the data obtained by the faster method and under natural testing conditions
was established.

4.5 Aqueous dispersions of polymers for finishing coatings, offset papers


and inks
To enable the use of aqueous dispersions of polymers for finishing printing products, the
mechanism of forming coatings from latexes was studied with the aim to establish relations
between the chemical composition of the dispersion, structure of latex particles and deco-
rative properties of coatings.
Latexes manufactured by home industry were tested. However, the coating produced
from these compositions on offprints does not conform to the requirements imposed on the
quality of lacquered products. These were systems based on copolymers of vinyl acetate
and other monomers (coatings possess a high tackiness, low gloss; and dispersions them-
selves, unstable properties). The major characteristics of tested latexes are given in the ta-
ble. Taking account of this, acrylic dispersions both commercially manufactured and
specially synthesized were chosen as promising film formers.
Of commercial dispersions, the latexes tested were polyalkyl acrylates based on acryl-
CH3
ic acid CH2 CH and methacrylic acid CH2 C and their esters, where R H1CH3
COOR COOR
R ,
namely:
copolymer of butyl acrylate with meth- or ethacrylate and MAA
CHAPTER 4 155

CH3 CH3
MBM-5s ... CH2 CH ... CH2 C ... CH2 C ...

COOC4H9 COOCH3 COOH


n
copolymer of butyl acrylate with methyl acrylate and MAA

CH3
MBM-3 ... CH2 CH ... CH2 CH ... CH2 C ...
COOC4H9 COOCH3 COOH
n
copolymer of methyl acrylate with vinyl acetate and MAA

CH3
MVM-1.5s ... CH2 CH ... CH2 CH ... CH2 C ...

COOCH3 OCOCH3 COOH


n
the composition and colloidal characteristic of which are given in the table.
Coatings from these latexes on offprints possess a tackiness and low gloss.
A dispersion based on polyalkyl acrylates, which forms coatings with high decorative
and physicomechanical properties, was developed. As the result of the studies, it was found
that latex BM-12, of the structure

CH3 CH3
... CH2 CH ... CH2 C ... CH2 C ...

COOC4H9 COOC4H9 COOH


n
forms a glossy, nonsticky coating with high adhesion and physicomechanical properties.
This latex is produced in the presence of an emulsifier (sulfanol) and an initiator (ammoni-
um persulfate, 0.15 parts by weight).
Dispersions of the BM-12 formulation with pH from 2.5 up to 8.4 were synthesized to
study the effect of the colloidalchemical nature of latex, namely, pH of the medium. These
latexes were produced by the method of hot neutralization by introducing various amounts
of ammonia (Table 4.12) into the latex.
Latexes with various polar groups carboxylic (COOH), amide (CONH2) and
nitrile (CN) are obtained by the method of emulsion polarization with equal amounts of
the same emulsifier (sulfanol), with the other similar conditions observed, by introducing
12 wt.% monomers with various functional groups: methacrylic acid, methacrylic-acid
amide and a mixture of methacrylic acid and acrylic-acid nitrile (Table 4.13).
A peculiar feature of investigated latexes with various amounts of methacrylic acid
from 2 up to 15 wt.% is that it was introduced as a monomer in emulsion polarization per-
formed by a semicontinuous method with the triple dosage of monomer and emulsifier. The
colloidal characteristic of synthesized latexes is given in the table.
To study the formation process of polymer coatings on offset papers and offprints, the
following were chosen: plain offset paper and an offprint obtained under production
156 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

conditions by the offset method during the application of inks of the 2513 series. Papers for
different methods of printing differ mainly by their moisture resistance (degree of sizing),
smoothness, elasto-plastic properties, absorptivity (porosity and capillarity) and strength of
the surface. These are the essential printing properties of a paper, on which its behaviour in
the printing process depends.
A number of requirements are imposed on offset paper; these are stipulated by the spe-
cific features of offset printing, when an ink image is transferred from the offset plate to
paper by means of the offset rubber cylinder, and the offset plate is systematically moist-
ened with water in the process of printing.
Therefore, offset paper should be sufficiently moisture-resistant, i.e., well sized with
rosin size, and sometimes additionally with starch. Highest quality offset paper, e.g., map
paper, is obtained by using melamine-aldehyde resin in combination with wood rosin as
size. A high degree of sizing of offset paper (1.25 mm) is required, first, to avoid excessive
deformation of paper in its contact with the moistened offset cylinder and, second, so that
there is no decrease of strength of the surface of paper in moistening and an associated fluff-
ing of paper by ink.
The elastic and plastic properties of offset paper are undesirable, as in printing they
cause ink squeezing on the offprint. For this reason, the content of filler in the offset paper
is always lower than in printing paper or in intaglio paper.
The absorptivity of offset paper can be limited, if the inks used are fixed by oxidative
polymerization or evaporation of a high-boiling solvent, especially in gas-flame drying of
offprints. However, when using inks fixed by selective absorption of the bonding adhesive,
the absorptivity of offset paper should be high, which is achieved by increasing the capil-
larity of the paper owing to the increased content of filler (more than 15%) and preservation
of porosity and capillarity of the paper in its fabrication on a paper-making machine. Be-
sides, in offset printing some roughness of paper prevents ink scuffing.
The major types of plain papers, depending on their purpose, composition with respect
to fibre content and technical parameters, are produced as numbers 1, 2 and 3, which denote
certain compositions (Table 4.7).
Papers of each number are divided into several grades denoted by letters A, B, C and
D for the same composition, having slightly different degrees of smoothness, ash content
and bulk density.

Table 4.7 Composition of printing paper (in %).

Fibrous semi-finished products Paper

No 1 No 2 No 3

Bleached sulfite cellulose, no less than 100 50


Unbleached sulfite cellulose, no less than 35
White woodpulp, no more than 50 65

Map paper is a high-grade offset paper intended for printing topographic, hydro-
graphic and geographic maps. The requirements to map paper include those for offset paper
and some additional requirements due to the specific features of map production and con-
ditions of map use. Map paper should have a high degree of whiteness (without any addi-
tional tint), the homogeneous smooth, closed-up surface, additional abrasion resistance,
resistance to moisture and atmospheric effects (rain, snow), minimal and even deformation
CHAPTER 4 157

in moisturing, minimal speckiness (specks of more than 15 mm are inadmissible), high light
permanence.
Map paper is fabricated from bleached sulfite cellulose and linen rag pulp (Table 4.8),
has a wood resinmelamine sizing of no less than 1.75 mm, i.e., much greater than common
offset papers.
Table 4.8 Composition of atlas paper.

Fibrous semi-finished products Grade A (hydrographic Grade B Grade C


and topographic) (geographic) (geographic)

Bleached linen rag pulp, no less 30 50


than
Bleached sulfite cellulose, no more 70 50 100
than

With this in mind, to study the formation mechanism of coatings from polyalkyl acry-
late latexes, we chose different papers, whose properties are given in the table.
As ink sublayers, printing inks intended for offset printing were used.
When fabricating offset colour inks, account should be made of the offset printing pro-
cess and, mainly, the character of the printing plate and regime of its moistening in printing.
Therefore, offset colour inks are usually fabricated on viscous and sticky bonding adhesives
from absolutely water-proof pigments (or lacquers).
Earlier, offset inks were produced predominantly on alkid and natural drying oils;
nowadays, on composition drying oils.
Composition drying oil is a mixture (composition) of specially selected resins, syn-
thetic polymers, highly viscous drying oils, mineral or vegetable oils, and high-boiling or-
ganic solvents. To accelerate ink fixation, the formulation of inks is supplemented with a
siccative a catalyst of oxidative polymerization of the bonding adhesive.
The inks of the series used are the most advanced. The composition of the ink is
approximately as follows:
pigment
composition drying oil
thinner
siccative.

Depending on the colour of the ink, respective pigments are used:

Ink number Ink colour Pigment name

011 black channel carbon black


231 magenta ruby lacquer SK
331 cyan heliogen blau LBGN
531 yellow yellow clear 0

Offset inks of this series are fixed on paper due to the partial selective ink penetration
and oxidative polymerization of the bonding adhesive.
Polyalkyl acrylate dispersions were applied to dry offprints.
Conducted research in the field of printed-matter finishing enabled the major
158 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

conclusion that the finishing material should be chosen to match paper and inks. It is not by
chance that in the West acrylic dispersions are used in the paper-making process with the
aim to improve their printing properties; printing aqueous acrylic inks are being developed.

4.6 Properties of finishing coatings from aqueous dispersions of acrylic


polymers
Studies of the formation of coatings from industrial latexes have established that the struc-
ture of latex particles has a significant effect on the rate of relaxation processes, kinetics of
increment of internal stresses, adhesion and other physicomechanical properties of the
coatings.
It could be expected that the structure of latex particles, which depends on the chemical
composition of a polymer, the nature and concentration of polar groups, the colloidal
chemical nature of a latex, should also have a significant effect on the decorative properties
of the coatings, determining the quality of finish of printing products.
With account for this, we studied the effect of the chemical composition of polyalkyl
acrylates on the structure of latex particles and coatings, established the relationship
between the character of structural transformations in the formation of latex coatings, dec-
orative and physicomechanical properties of the coatings.
For solving this problem, we studied the effect of the chemical composition of poly-
alkyl acrylates on the structure and properties of coatings, chose the composition forming
a coating with the required set of properties.
The latex coating formation process was studied by investigating the kinetics of incre-
ment and relaxation of internal stresses.
It follows from the analysis of the data on the kinetics of increment and relaxation of
internal stresses in the formation of coatings from latexes of acrylic copolymers of various
chemical composition (Table 4.9) that for coatings from latexes MBM-3, MBM-5s,
MVM-1.5s the internal stresses change nonmonotonically: first they increase and then re-
lax. A specific feature of the hardening of coatings from latex BM-12 is associated with a
rapid increment of internal stresses in the initial stage of formation and their stability in the
subsequent formation of the coatings (Fig. 4.5).

Table 4.9 Characteristics of various latexes.

Synthesis Latex Ratio of components, wt. % Colloidal characteristic


No name of latex

BA MA VA BMA MMA MAA dry sp pH


residue,
%

50 shopfloor MBS-5s 55 40 5 49.0 2.5 4.5


278 shopfloor MBM-3 62 35 3 40 7.4 6.0
133-1 MVM-1.5s 70 28.5 1.5 48.0 2.5 3.0
112 BM-12 30 70 12 49.0 3.6 3.0
experimental

Note: BA, butyl acrylate; MA, methyl acrylate; VA, vinyl acetate; BMA, butyl methacrylate; MMA,
methyl methacrylate; MAA, methacrylic acid.
CHAPTER 4 159

16

b10, MPa
12

4
8 3
1
4 2

4 8 12 400 600 800 1000


, h

Figure 4.5 Kinetics of increment and relaxation of internal stresses in the formation of coatings
from latexes of various chemical compositions: 1, BM-12; 2, MBM-3; 3, MBM-5s; 4, MVM-1.5s.

u, %
100

80

60

40
4
2
20 3
1

2 4 6 8 10 , min

Figure 4.6 Kinetics of drying of coatings from latexes of various chemical compositions: 1,
BM-12; 2, MVM-1.5s; 3, MBM-3; 4, MBM-5s.

Analysis of the curves of drying of various-composition latexes indicates that the most
rapidly drying coatings are those from BM-12 and MVM-1.5s (Fig. 4.6). Comparison of
the kinetics of drying of the coatings with the kinetics of increment of internal stresses in-
dicates that the most sharp inhibition of the relaxation processes is observed in the period
of the dropping rate of drying and is due to the formation of local physical links between
structural elements. Significant differences in the mechanism of formation of the coatings
from latexes of acrylic copolymers, differing by their chemical composition, are determined
by the specific features of the structure of latex particles and the distribution of polar groups
on their surface. These factors determine not only the mechanism of formation of the coat-
ings from latexes, but also the properties of polymer dispersions.
Figure 4.7 presents a dependence of viscosity on shearing stress for dispersions of var-
ious chemical compositions. It is seen that dispersions from copolymers MBM-3 and
MBM-5s are weakly structured systems passing to a state of viscous flow at a comparatively
small shearing stress. The system of copolymer BM-12 is more structured and breaks down
160 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

, 10 Pa . s
24

20

12

8
3
1
4 2

2 4 40 80 120 160
P, 10 Pa

Figure 4.7 Dependence of viscosity on shearing stresses for latexes of various chemical composi-
tions: 1, MBM-3; 2, MBM-5s; 3, BM-12.

at a shearing stress by an order of magnitude higher than BM-type latexes.


This is, evidently, due to the smaller size of latex particles in the BM-12 dispersion,
determined by the results of electron-microscopy studies (Table 4.10), and also by the con-
centration of a significant amount of polar groups on their surface. For this reason, coatings
from the dispersion of BM-12 are characterized by a considerably smaller formation time.

Table 4.10

Copolymer Particle size, Adhesiveness Gloss relative Strength p, Relative Adhesion A,


m of coating, to black glass, MPa elongation , MPa
MPa % %

MBM-5s 0.175 sticky 12 7 400 1.8


MBM-3 0.225 very sticky 14 4.6 1500 1.6
MVM-1.5s 0.22 0.34 11 8.0 500
BM-12 0.14 0.100.12 49 8.0 90 4.0

IR spectra recorded for films from latexes of various chemical compositions have a
broad band in the region of 3300 cm 1, characteristic of a hydrogen bond, apparently form-
ing as the result of intermolecular interaction of polar groups. The largest intensity of this
band is indicative of a larger concentration of hydrogen bonds in the system for a coating
from test latex BM-12 (Fig. 4.9).
Studies of the adhesion of latex coatings to glass by the value of ultimate critical stress-
es causing the spontaneous delamination of the film from the support have found that coat-
ings from latex BM-12 are characterized by a greater adhesion of about 4 MPa. In coatings
from MBM-type latexes the relaxation processes determined by the disturbance of adhesion
interaction are observed at stresses of about 1.62 MPa (Table 4.10).
Figure 4.8 presents the stressstrain characteristics of coatings formed from latexes of
various copolymers. It is seen that films from latex MBM-3 are characterized by a very high
CHAPTER 4 161

1
80

p 10, MPa
60
2
40 3
4
20

40 80 120 400 800 1200 1600


, %

Figure 4.8 Stress strain characteristics of films formed from latexes of various chemical compo-
sitions: 1, BM-12; 2, MVM-1.5s; 3, MBM-5s; 4, MBM-3.

1 23 4

3460
Transmission, %

3300

2990

3600 3400 3200 3000 2800 2600 2400


cm1

Figure 4.9 Spectrogram for films from latexes of various chemical compositions: 1, MVM-1.5s; 2,
MBM-3; 3, MBM-5s; 4, BM-12.

relative breaking elongation and the smallest strength as compared with films from the other
systems studied. Introduction of methyl methacrylate considerably increases the strength
of the system and contributes to the decrease of relative elongation.
Films from latex MVM-1.5s become hazy in the process of deformation and change
their structure, which stipulates the complex character of the stressstrain dependence. The
physicomechanical properties of coatings from latexes of various chemical compositions
were compared with the process parameters characterizing the decorative properties of
coatings (Table 4.10). It is seen that coatings from latexes MBM-5s, MBM-3, MVM-1.5s
are distinguished by a high tackiness and low gloss.
Coatings from test latex BM-12 were found to have the best decorative properties.
The thermomechanical curves taken on a Korgin balance (Fig. 4.10) show that the
162 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

70
60
50
40
30 1 2
20
10

-10 0 +10 +30 +50 +70 +90 +110


T, C

Figure 4.10 Thermomechanical curves plotted for films from latexes: 1, MVM-1.5s; 2, BM-12.

copolymer MVM-1.5s has a low glass-transition temperature and passes into the rubberlike
state at a lower temperature as compared with copolymer BM-12.
Films from MBM latexes start to exhibit a plastic flow at a temperature of +10C.
Comparison of the kinetics of the formation of coatings with their process parameters
and physicomechanical properties indicates that the high tackiness of coatings from MBM-
and MVM-type latexes and low gloss are related to the instability of their properties in the
formation process, to the incompleteness of the structural transformations and the pro-
longed formation time.
The supramolecular structure of latex coatings was studied using the method of oxy-
gen etching to elucidate the causes of such significant differences in the formation mecha-
nism, in the physicomechanical and decorative properties (Fig. 4.11).
The structure of coatings produced from MBM-, MVM- and BM-12-type latexes was
studied. Coatings from MBM latexes were found to be characterized by a globular structure
with globules of about 30 nm in diameter. For coatings from MVM latex, the structure was
observed to be inhomogeneous, more dense by the borders of latex particles and with a
loose packing of anisodiametric structural elements inside each particle. A specific feature
of coatings formed from a dispersion of BM-12 is that they are characterized by a very fine
structure, which is not revealed using an electron microscope even when oxygen etching is
applied. The presence of this structure facilitates the coalescence of latex particles, consid-
erably shortens the formation time of coatings, increases their strength and significantly im-
proves their decorative properties by providing for a high gloss in the finishing of printed
matter.
These data suggest that coatings, which meet the requirements of the printing industry
small formation time, high gloss, absence of tack can be produced from polymer dis-
persions of the type of BM-12, which are characterized by a very fine structure of latex par-
ticles consisting of separate molecules and the occurrence of a large amount of polar groups
in their surface.
As the result of studies of the effect of the chemical composition of polyalkyl acrylates
on the structure and properties of coatings, the chemical composition of a latex was chosen,
which forms coatings with an optimal set of decorative and physicomechanical properties
satisfying the requirements of the printing products.
The effect of various physicochemical factors (pH of the medium, nature and concen-
tration of polar groups) enabling the regulation of the decorative and protective properties
CHAPTER 4 163

Figure 4.11 Structure of latex coatings from MBM (a), BM-12 (b) and MVM (c).

5 6
6
1
b 10, MPa

4 2
4
2 3

1 2 4 6 8 50 100
, h

Figure 4.12 Kinetics of increment and relaxation of internal stresses for coatings from latexes with
different pH at 20C: 1, pH 2.5; 2, pH 5.3; 3, pH 7.7; 4, pH 7.9; 5, pH 8.2; 6, pH 8.4.

of coatings from latex with an optimal chemical composition on the formation and proper-
ties of the coatings was studied.
Dispersions with pH from 2.5 up to 8.4 were obtained by the method of hot neutral-
ization by introducing various amounts of ammonia into the latex.
Figure 4.12 presents the data on the kinetics of increment and relaxation of internal
stresses in the formation of coatings at 20C. It is seen that the character of the kinetic curves
and the value of internal stresses depend on pH of the medium.
164 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

, 10 Pa
2
100

80 4

60

40
3 1
20

20 40 60 80
P, 10 Pa

Figure 4.13 Dependence of viscosity on shearing stress for latexes with different pH: 1, pH 3.2; 2,
pH 7.7; 3, pH 7.9; 4, pH 8.2.

The internal stresses first increase up to an ultimate value and then relax. The forma-
tion period of coatings up to extreme and equilibrium values of internal stresses increases
with pH of the medium going up. At pH from 2.5 up to 5, the formation of coatings is com-
pleted very rapidly in 1530 min, however, the internal stresses in this case are compara-
tively high to make 0.40.5 MPa. As pH is increased up to 7.7, the coating formation period
increases up to 4 h at considerably smaller equilibrium magnitudes of internal stresses, not
exceeding 0.3 MPa. In the subsequent increase of pH up to 8.28.4, the equilibrium values
of internal stresses are reached in 5070 h at a simultaneous increment of their magnitudes.
Figure 4.13 shows a dependence of viscosity on shearing stress for latexes with various
pH. It is seen that dispersions of acrylic copolymers at various pH values are structured sys-
tems. As pH is increased from 2.5 to 7.7, the ultimate shearing stress and viscosity of the
broken structure increase. In the subsequent increase of pH, the ultimate shearing stress de-
creases and the character of the rheological curves changes. At pH equal to 8.2, a sharp dif-
ferential is observed between the upper and lower levels of viscosity, which is indicative of
a small number of contacts between the structural elements and a weak intermolecular in-
teraction between them. The most structured dispersion is a latex with pH equal to 7.7. As
seen in Fig. 4.12, coatings produced from this dispersion reveal the least internal stresses.
The data on the rheological properties of dispersions were compared with the size of
latex particles determined by the method of electron microscopy.
The microstructure of latex particles obtained from very diluted dispersions of a con-
centration of 0.001% was studied. The diameter of latex particles was found to change non-
monotonically. As pH was increased from 3 up to 7.7, the diameter of latex particles
decreased from 0.15 down to 0.06 m and then, at a subsequent increase of pH up to 8.4,
rose up to 0.2 m.
CHAPTER 4 165

0.5 m
a b

0.5 m
c d

0.2 m

e f

Figure 4.14

A peculiar feature of dispersions studied is that, starting from pH 7.7, the polydisper-
sity of latex increases significantly, and, along with large particles of 0.06 up to 0.2 m,
globules of 1520 nm in diameter, corresponding to the size of separate coiled molecules,
were found.
These data suggest that the most structured dispersions are latexes with particle size
of 15 up to 60 nm. As the diameter of particles increases up to 200 nm, the ultimate shearing
stress decreases and the character of the rheological curves changes, which is indicative of
the fast degradation of this structure at a small increase of the shearing stress.
The occurrence of globules in dispersions commensurable with the size of coiled mol-
ecules at pH larger than 7, and a significant effect of pH on the physicomechanical proper-
ties of dispersions and coatings on their basis indicates the interaction of ammonia atoms
with carboxylic groups of polymer molecules, a decrease of the intermolecular interaction
and dispersion of latex particles at optimal pH. At a further increase of pH, ammonia acts
as an astabilizing agent promoting the coalescence of latex particles.
To elucidate the peculiar features of structure formation in the dispersion depending
on pH of the medium, the structure of coatings corresponding to the equilibrium values of
internal stresses depending on pH of the medium was studied (Fig. 4.14).
It has been found that for coatings from dispersions with pH from 2.5 up to 7 the fine
structure of latex particles is not revealed, which indicates that they are formed by uncoiled
166 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

80
2
1
60 4
b 10, MPa

3
40

20

40 80 100 200 300 400


, %

Figure 4.15 Stress strain characteristics of films from latexes with different pH: 1, pH 3; 2, pH 7.7;
3, pH 7.9; 4, pH 8.2.

densely packed molecules. At a small pH value, the capability of coalescence of latex par-
ticles becomes worse. At pH equal to 7.7, a network structure of anisodiametric structural
elements is observed. At the further increase of pH, an inhomogeneous globular structure
is formed, with the diameter of globules commensurable with the size of coiled macromol-
ecules and their clusters. two lines
Thus, introduction of alkali contributes to the decrease of the intermolecular interac-
tion, dispersion of latex particles and rearrangement of their constituent macromolecules.
The presence of a set of supramolecular different-size structures in dispersions with
an alkaline medium extends the formation time of coatings owing to the incompleteness of
the relaxation processes in these systems, and contributes to the nonmonotonic change of
internal stresses in the formation of coatings.
Formation of an ordered structure in dispersions with pH equal to 7.7 and coatings on
their basis promotes a sharp decrease of internal stresses and an improvement of the phys-
icomechanical properties of latex films.
Figure 4.15 presents stress-strain characteristics of films from acrylic latexes with dif-
ferent pH. It is seen that films from the latex with pH equal to 7.7 have the greatest strength
at a relative elongation. The dependence of strength and relative elongation on pH of the
medium is nonmonotonic and reveals a maximum at pH 7.7. A similar nonmonotonic de-
pendence on pH of the medium is revealed for the adhesion of coatings (Table 4.11). The
greatest adhesion is seen to be observed for coatings from a dispersion with pH 7.7.
To elucidate the cause of a sharp increase of adhesion of coatings at pH 7.7, the effect
of pH of latex on IR spectra of the coatings was studied. As the result of those studied, it
was found that a new band in the region of 1560 cm1 characteristic of free carboxyl groups
emerged on the spectrograms with the increase of pH up to 7. It is seen in Fig. 4.16, which
presents the data on the effect of pH on the concentration of carboxyl groups, that the
amount of these groups increases significantly at pH equal to 7.78.2. It follows from the
comparison of these data with the structure of coatings that at pH 7.7 the coatings feature
ooooo
CHAPTER 4 167

Table 4.11 Effect of pH of latex on the physicomechanical and decorative properties of coatings.

pH of latex Strength p, Relative Adhesion A, Gloss, Agglutination,


MPa elongation , % MPa % MPa

3.0 6.8 210 4.0 3540 0.100.12


5.3 7.8 3540 0.150.18
7.7 8.3 310 14.0 4045 0.070.09
7.9 6.5 320 12.0 2530 0.150.18
8.2 6.8 305 11.0 2328 0.100.13

the most ordered structure from anisodiametric structural elements. A sharp increase of
adhesion at pH 7.7 is, apparently, due to the concentration of free carboxyl groups on the
surface of these structures.

100

75
Transmission, %

50

25

0
0 2 4 6 8 pH

Figure 4.16 Effect of pH of latex on the concentration of carboxyl groups.

The effect of pH on the kinetics of film formation is also revealed in the formation of
coatings at a higher temperature (6070C). Figure 4.17 presents the data on the kinetics
of increment of internal stresses in the formation of latex coatings at 70C from dispersions
with different pH. It is seen that the rate of the formation of coatings under these conditions
increases considerably irrespective of the pH value of the medium. However, in coatings
from dispersions with pH from 3 up to 7.7, internal stresses were observed to have some
rise as compared with coatings formed at 20C.
The effect of the nature of the polar groups on the formation process, supramolecular
structure, physicomechanical and decorative properties of coatings from latexes based on
polyalkyl acrylate was studied.
Latexes with various (carboxyl, amide, nitrile) polar groups were produced by the
method of emulsion polymerization with an equal amount of the same emulsifier (sulfanol)
and the other conditions equal by introducing 12 wt.% monomers with various functional
groups: methacrylic acid, methacrylic acid amide, acrylic acid nitrile and a mixture of
168 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

3
6

2
b 10, MPa 4
5 6 4
1

1 2 4 6 8
, h

Figure 4.17 Kinetics of increment of internal stresses for latexes with various pH at 70C: 1, pH
2.5; 2, pH 3.0; 3, pH 7.7; 4, pH 7.9; 5, pH 8.2; 6, pH 8.4.

methacrylic acid and acrylic-acid nitride (Table 4.13).


Table 4.12 Characteristics of latexes of different colloidal and chemical nature.

Latex Composition and ratio of Dry sp pH viscosity by


components, wt. % residue, % VZ-4, sec

BA BMA MAA 46 2.9 2.55 13


BM-12 30 70 12 49.0 3.6 3.0 15
40 6.1 5.0 20
40 6.1 7.7 16
40 6.1 7.9 41
40 6.1 8.2 210
40 6.1 8.4 24

Table 4.13 Characteristics of latexes of different nature of polar groups.

Chemical composition and ratio of Dry residue, pH Particle size, Surface


components, wt. % % m tension, ,
103 N/m
BA BMA MAA AAN AAA

30 70 12 49.7 2.65 0.131 53.5


30 70 12 38.5 6.3 0.808 50.9
30 70 12 46.2 3.1 0.925 57.0
30 70 12 12 50.4 3.4 0.102 49.1

Note: BA, butyl acrylate; BMA, butyl methacrylate; MAA, methacrylic acid; AAN, acrylic acid
nitrile; AAA, acrylic acid amide.

methacrylic acid and acrylic-acid nitride (Table 4.13).


Figures 4.18 and 4.19 present the data on the kinetics of increment and relaxation of
internal stresses in the formation of coatings from latexes of acrylic copolymers with
CHAPTER 4 169

2
4 1

b 10, MPa
3

2
4

2 4 6 8 10 , h

Figure 4.18 Kinetics of increment and relaxation of internal stresses in the formation of coatings
from latexes with various functional groups: 1, COOH; 2, CONH2; 3, COOH, CN; 4, CN.

6
2
1
4 3
b 10, MPa

2 4

1 2 3 4 6 8 , h

Figure 4.19 Kinetics of increment and relaxation of internal stresses in the formation of coatings
from latexes with various functional groups at 70C: 1, COOH; 2, CONH2; 3, COOH, CN; 4, CN.

various functional groups. It is seen that the formation at 20 and 70C is completed the most
quickly for coatings from latexes containing the carboxyl groups. The greatest internal
stresses at the initial stage of coating formation emerge in the system from a latex containing
the amide groups. However, as the result of the relaxation processes during the storage of
coatings under room conditions, the internal stresses decrease significantly. By the equilib-
rium values of internal stresses, the coatings can be arranged in the following sequence. The
internal stresses are the greatest in the formation of coatings from a latex with the carboxyl
groups; the smallest, in coatings from a latex with the nitrile groups. Latexes with the amide
groups and a mixture of carboxyl and nitrile groups form coatings with intermediate values
of internal stresses.
These data are well consistent with the results of studies of the stresses for coatings
from a latex based on the copolymer of butyl acrylate and methyl acrylate with various polar
groups. However, the effect of the nature of the functional groups manifests itself different-
ly on the character of the kinetic curves depending on the chemical composition of the co-
polymer.
The data on the kinetics of the change of internal stresses in the formation of coatings
170 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

u, % 50

40

30
CN
20
CONH2

10

COOH

0.1 0.2 1 2 3 , h

Figure 4.20 Curves of the drying of coatings of various chemical compositions.

from latexes with various functional groups were compared with their drying kinetics. Fig-
ure 4.20 presents the drying curves for coatings of various chemical compositions. It is seen
that the drying process is completed the most quickly for coatings from latexes with the car-
boxyl groups; the slowest drying coatings were those from a latex with the nitrile groups.
Internal stresses reach a maximum after the removal of moisture from the latex and the
emergence of the largest number of bonds between latex particles.
To elucidate the cause of the nonmonotonic change of internal stresses in the formation
of coatings from latexes with various functional groups, the structure of the film was studied
at particular stages of the film formation process by the method of replicas without their
additional treatment and using oxygen etching to reveal the fine structure of latex particles.
From the data on the structure of coatings from latexes with the carboxyl groups at the
stage corresponding to the maximum internal stresses and their equilibrium value, it follows
that in coatings from latexes with the carboxyl groups latex particles are found on unetched
specimens at the initial stage of coating formation.
In coatings from a latex with the nitrile groups under the same formation conditions,
a more dense structure is observed by the interfaces of the latex particles.
The structure of latex particles was revealed using the method of oxygen etching.
Coatings from latex with the carboxyl groups reveal a fine structure, which is indi-
cative of the presence of a homogeneous molecular structure of latex particles. In coatings
from a latex with the nitrile groups, an inhomogeneous globular structure is observed
(Fig. 4.21).
As the result of their coalescence, no latex particles were observed in coatings from
latexes with the carboxyl groups at the final stage of formation, corresponding to the equi-
librium value of internal stresses.
For coatings from latexes with the nitrile groups, owing to the rearrangement of the
structural elements, a homogeneous globular structure (revealed by the method of oxygen
etching) is observed at the final stage of formation.
The structure of latex particles, nature of polar groups and their distribution on the
surface of particles renders a significant effect on the adhesion of coatings (Table 4.14).
CHAPTER 4 171

Mixture of CN
with COOH

0.4 m

Mixture of CONH2
with CN

Figure 4.21

Table 4.14 Effect of the nature and concentration of functional groups on the properties of films.

Characteristic Breaking Abrasion, Strength Relative Adhesion Agglutination, Gloss, %


of latex number turns of p, MPa elongation, A, MPa MPa***
of bends* prisms** , %
Functional group
Carboxyl 50 300 0.80 90 0.55 0.0850.10 4055
COOH
Amide CONH2 65 400 0.58 400 0.70 0.170.20 2030
(rupture of
paper)
Nitrile CN 75 0.52 630 0.15 very sticky 1517
coating
Mixed (COOH, 55 350 0.80 130 0.40 0.0120.014 3045
CN)
offprint without 1520 1015
coating
Amount of
methacrylic acid
(MAA), %:
172 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 4.14 Effect of the nature and concentration of functional groups on the properties of films.
(continued)
Characteristic Breaking Abrasion, Strength Relative Adhesion Agglutination, Gloss, %
of latex number turns of p, MPa elongation, A, MPa MPa***
of bends* prisms** , %

4 80 3.0 700 1.0 very sticky low


coating
6 75 4.5 520 1.6 ditto ditto
8 62 7.5 400 2.0 sticky ditto
10 58 230 9.0 350 3.0 0.120.14 1520
12 50 300 8.2 110 4.5 0.0950.10 4555
15 35 280 8.0 0.0850.10 4045

*By preliminary requirements, no less than 30.


**By preliminary requirements, no less than 20.
***By preliminary requirements, no more than 0.12.

As seen in the table, coatings with the amide and carboxyl groups are characterized by
the highest adhesion equal to 0.507 MPa. The lowest adhesion is observed for coatings
from a latex with the nitrile groups. A sharp decrease of adhesion was also observed in the
introduction of nitrile groups to the copolymer of butyl acrylate and methyl acrylate. How-
ever, unlike the system we studied, this copolymer formed coatings with the highest adhe-
sion in the presence of carboxyl not amide groups, To elucidate the cause of the high
adhesion of coatings with amide groups, we studied IR spectra of coatings from latexes with
various functional groups.
Figure 4.23 presents spectrograms of coatings. It is seen that a sharp increase of inten-
sity of the absorption bands in the region of 3340 cm 1 and their shift towards lower fre-
quencies for coatings from latexes with the amide groups indicates a high concentration of
the polar groups, forming the hydrogen bonds, on the surface of latex particles as compared
with latexes containing the nitrile and carboxyl groups. However, the high concentration of

1
80 2
10, MPa

3
60
4
40

20

50 100 150 300 400 500 600 , %

Figure 4.22 Stress strain characteristics of acryl coatings with different groups: 1, COOH; 2,
COOH, CN; 3, CONH2; 4, CN.
CHAPTER 4 173

100
1
2

Transmission, %
3

0
3600 3400 3200 cm1

Figure 4.23 A spectrogram for films from latexes with various functional groups: 1, CN; 2, COOH;
3, CONH2.

amide groups on the surface of latex particles not only increases adhesion of coatings on
their basis, but also leads to an instability of the system and to the formation of an inhomo-
geneous defect structure, which stipulates their comparatively low strength as compared
with coatings from latexes with the carboxyl groups.
Figure 4.22 presents the stressstrain curves for films from latexes with various polar
groups. As seen, the lowest strength and high relative breaking elongation is observed for
coatings from latexes containing nitrile and amide groups. The highest strength is charac-
teristic of films from latex with carboxyl groups. The nature of the functional groups proves
to have a significant effect on the decorative properties of coatings and their tackiness.
As seen in Table 4.14, coatings from latexes with the carboxyl groups and a mixture
of the carboxyl and nitrile groups are characterized by the highest decorative properties. The
greatest tackiness and low gloss are observed for coatings from latexes with the nitrile and
amide groups. One of the most important characteristics of a decorative coating on a print-
ing product is the transparency and light permanence of the lacquer film. Acrylic copoly-
mers are known to form films with a high transparency and light permanence. The latexes
studied are characterized not only by a high light permanence but also form coatings capa-
ble of protecting paper from yellowing under the action of ultraviolet radiation. The latter
is very important, as photodegradation of cellulose is a surface phenomenon. Films with the
carboxyl and amide groups remained the same after 8 h of irradiation by a PRK-4 lamp
those with the nitrile groups, yellowed.
Absorption of water by a film from a latex with the carboxyl groups was significantly
lower than that from latexes with the amide and nitrile groups, and made 2% in 24 h.
Coatings on offprints from latexes with the nitrile groups have a smell inadmissible
for printing products.
Thus, coatings with the COOH group are distinguished by the lowest internal stresses
and formation time, high adhesion and good decorative properties; so it was of interest to
study the effect of the concentration of methacrylic acid on the formation process and prop-
erties of coatings.
In studies of the effect of the concentration of methacrylic acid on the formation mech-
anism of coatings from industrial specimens of divinyl latexes, we found that introduction
of an additional amount of methacrylic acid into the ready latex is accompanied by a non-
monotonic change of adhesion of the coatings. Adhesion is observed to be maximal at a
174 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

1
4

b 10, MPa
2
3 3
2 4
1 5

1 2 3 4 10 20
, h

Figure 4.24 Kinetics of increment and relaxation of internal stresses in the formation of coatings
from latexes with various percentage contents of MAA: 1, 15%; 2, 12%; 3, 10%; 4, 86%; 5, 4%.

small concentration of methacrylic acid of about 3%.


The further increase of the concentration of methacrylic acid was found to slow down
the rate of the relaxation processes and a sharp increment of internal stresses in the system.
The cause of this phenomenon is, apparently, due to the fact that methacrylic acid intro-
duced in the latex adsorbs mainly on the surface of latex particles. At a large concentration
of methacrylic acid, the coalescence of latex particles becomes worse and the rigidity of the
system increases. Similar regularities in the change of adhesion depending on the concen-
tration of methacrylic acid are observed for films based on natural rubber and divinyl sty-
rene latexes.
A specific feature of latexes studied is that different amounts of methacrylic acid (from
2 up to 15%) were introduced as a monomer in the course of emulsion polymerization per-
formed by the semicontinuous method with the triple dosage of monomer and emulsifier.
In this section, we studied structural transformations, physicomechanical and techno-
logical properties of coatings based on latexes from alkyl acrylates containing various
amounts of carboxyl groups in the polymer chain.
Figure 4.24 presents the data on the kinetics of increment and relaxation of internal
stresses in the formation of coatings at 20C. It is seen that coatings from latexes with a
small concentration of methacrylic acid (46%) are characterized by minor internal stress-
es. Owing to the incompleteness of the relaxation processes, their formation proceeds com-
paratively slowly and completes in 34 h. A lower content of methacrylic acid yields
unstable latexes forming very sticky coatings. As the concentration of methacrylic acid is
increased, the coating formation time becomes smaller and the character of the kinetic
curves of increment and relaxation of internal stresses changes. At the introduction of
1012% methacrylic acid into the reaction system the formation of coatings is completed
practically in 3040 min of drying. At a large concentration of methacrylic acid, along with
the increase of the stability of the physicomechanical properties, the internal stresses in the
coatings are observed to increase.
As the concentration of methacrylic acid is increased up to 15%, internal stresses be-
come commensurable with the strength of the coatings and induce their spontaneous crack-
ing in the process of formation.
Formation of the coatings at 70C (Fig. 4.25) is accompanied by similar regularities
in the change of the kinetics of increment of internal stresses depending on the concentra-
tion of methacrylic acid in the system; herewith, the relaxation processes in the coatings
from latexes with a greater concentration of methacrylic acid (812%) proceed faster than
CHAPTER 4 175

b 10, MPa
4
2 3

2 4 5

1 2 1 3 5 7
, h

Figure 4.25 Effect of the concentration of MAA on the kinetics of increment and relaxation of
internal stresses at 70C: 1, 15% MAA; 2, 12%; 3, 10%; 4, 86%; 5, 4%.

under conditions of hardening at 20C.


A significant rate of the increment of internal stresses in the formation of coatings from
latexes with a large concentration of methacrylic acid is stipulated by the slowdown of the
relaxation processes, which is related to a more intensive removal of moisture from these
systems. This is indicated by the data presented in Fig. 4.26 on the drying kinetics of coat-
ings at 20C. From the comparison of the data on the kinetics of increment of internal stress-
es and drying of coatings, it follows that internal stresses in latex coatings sharply increase
in the second period of drying and reach a maximum after removal of moisture.
Table 4.15 Characteristics of latexes with various amounts of the third component MAA at a
constant ratio of two monomers BA:BMA (30:70).

Colloidal Amount of methacrylic acid, wt. %


characteristic of
copolymer 15 12 10 8 6 4 2 0

Dry residue, % 49.9 49.7 49.3 49.2 49.4 49.9 49.3 48.9
pH 2.5 2.65 2.55 2.8 3.0 2.65 2.5 2.7
Specific viscosity 1.74 1.98 1.9 1.82 1.73 1.68 1.48 1.36
Size of particles, m 0.086 0.097 0.082 0.09 0.087 0.063 unstable
Surface tension, , 56 55 57 57.5 58.5 59.7 ditto ditto
103 N/m

Note: (1) Dispersions with MAA of 0 to 2% are unstable and coagulate already on day 5. Films from
these latexes are very sticky. (2) In all specimens, the same amount of emulsifier sulfanol was used
during the synthesis.

Under coating formation conditions at 70C, the drying process (Fig. 4.26) is complete
in 20 min; herewith, the concentration of methacrylic acid in the system has no significant
effect on the character of the kinetic curves and the rate of drying.
As the concentration of carboxyl groups in the polymer chain increases, adhesion and
strength are observed to increase monotonically (Table 4.14). The concentration of meth-
acrylic acid in the latex changes the stressstrain properties of the coatings. Figure 4.27
176 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

urel, % 100
80 1
60
at 70C 2
40 3 4
20
0
2 4 6 8 10 25 , min

urel, % 100
1

at 20C 60 2
3
4
20

10 20 30 40 60 , min

Figure 4.26 Kinetics of drying of coatings from latexes with various percentage contents of MAA:
1, 4%; 2, 8%; 3, 12%; 4, 15%.

100
1
80
2
p 10, MPa

60

40
3

20 4 5

50 100 200 400 600 800 , %

Figure 4.27 Effect of the concentration of MAA on the stressstrain properties of films: 1, 12%
MAA; 2, 10%; 3, 8%; 4, 6%; 5, 4%.

presents the data on the effect of the concentration of methacrylic acid on the character of
the stressstrain curves of the films.
It is seen that at a small concentration of methacrylic acid the films are distinguished
by a high relative elongation and low elasticity modulus. The change of the character of the
strainstress curves is observed for films from latexes with 12% methacrylic acid, which
are characterized by a high elasticity modulus and strength at a comparatively large relative
CHAPTER 4 177

breaking elongation. Films from latexes with 15% methacrylic acid spontaneously crack in
the formation process at stresses not exceeding 1 MPa. To elucidate the cause of this phe-
nomenon, we studied the structure of coatings from latexes synthesized with different
amounts of methacrylic acid.
The structure of latex coatings from alkyl acrylates with various concentrations of
methacrylic acid was studied by the method of electron microscopy. It is seen that coatings
from latexes with 4% methacrylic acid reveal no supramolecular structure. At a methacrylic
acid concentration of 6%, separate globules of 25-40 nm in diameter and their aggregates
are observed. At the further increase of the concentration of methacrylic acid in the system,
the number of globules per surface unit increases. At a methacrylic-acid concentration of
15% striped structures are found, by the boundaries of which, owing to the concentration
of internal stresses, a spontaneous cracking of the coatings is observed.
It follows from these data that during the formation of coatings from latexes synthe-
sized in the presence of a minor amount of methacrylic acid, no supramolecular structures
are formed in latex particles and coatings as the result of a strong branching of molecules
of other constituent monomers. As the concentration of methacrylic acid in the system is
increased, the intermolecular interaction goes up and, along with the fine molecular struc-
ture not revealed by electron microscopy, separate globules of 25 up to 50 nm in diameter
are observed, probably formed as the consequence of the aggregation of macromolecules.
In studies of the effect of the concentration of methacrylic acid on the coatings deco-
rative properties determining the possibility of their use for finishing printing products, the
best gloss and absence of tack were found to occur in coatings with a high concentration of
methacrylic acid (1215%) (Table 4.14).
The entire set of data obtained indicates that coatings from latexes with 12% meth-
acrylic acid are characterized by the best physicomechanical and decorative properties.

4.7 Specifics of forming coatings on paper and offprints


The physicomechanical and decorative properties of coatings used for finishing printed
products have been shown to depend on the structure of latex particles and coatings. High
gloss, strength, adhesion, the absence of tack, the small formation period of latex coatings
and minor internal stresses are characteristic of coatings from latexes with the homoge-
neous molecular structure of latex particles and a large concentration of the carboxyl groups
on their surface, which contributes to the fast coalescence of latex particles in the formation
of coatings.
When working out the formulation of compositions for coatings with optimal physi-
comechanical and decorative properties, suitable for finishing packaging products, devel-
opers studied the effect of the chemical composition of copolymers based on alkyl acrylates,
the colloidalchemical nature of latex, the nature and concentration of polar groups on the
structure and properties of coatings.
However, all those studies were performed in the formation of coatings on a glass sup-
port. The glass support was chosen as a model containing a considerable amount of hydrox-
yl groups on the surface and differing from the supports used in the printing and packaging
industry (paper, offprints) by the absence of a fibrous porous structure. This model made it
possible to exclude the effect of a specific structure of the support and its inhomogeneity
on the formation of latex coatings.
This section investigated the effect of the nature of the supports surface and the
character of its structure on the formation of latex coatings by comparing the kinetics of
178 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

increment and relaxation of internal stresses with the drying rate, depth of impregnation,
rate of absorption and the contact angle of wetting, and the decorative properties of
coatings.
The physicochemical ways for decreasing the internal stresses in the formation of latex
coatings on paper and offprints were developed by studying the effect of structuring addi-
tives and the drying method on the formation of latex coatings.
The object of the study was the latex based on polyalkyl acrylate BM-12.
As supports, we used offset papers of various densities and types (see Table) and off-
prints. Halftone prints were obtained under production conditions by the offset method by
applying four inks (series 2513) on paper (of the Goznak Paper Plant). The most saturated
sections of the prints were used for the study.
It is seen in Table 4.16 that the most porous papers with low sizing and large uneven-
ness of the surface are those of the Kamenogorsk Paper Plant and the Goznak Paper Plant.
A more dense paper with the closed-up structure of pores, small porosity and high smooth-
ness is map paper.
Table 4.16 Characteristics of papers studied.

Parameter State standard Offset paper Offset paper GOST for Cartographic
(GOST) for No 1 (Goznak No 1 grade G cartographic paper,
offset paper Paper Plant) (Kamenogorsky paper grade C
Offset Paper
Plant)

Bulk weight in g/cm3, no 0.75 0.8 0.78 0.87


less than
Mass of 1 cm2 in g 100,120 120 120 120 120
Breaking length (on 2400 2905 2500 2300
average in two
directions) in meters, no
less than
Fracture (number of 5 44 30 on average in 62
breaking bends) in two directions
transversal direction, no no less than
less than 50
Sizing in mm, no less 1.25 1.25 1.25 1.75 1.75
than
Ash content in %, no less 10 12 16 no less than 4 4.8
than
Smoothness on average 30 3762 3853 no less than 90110
on the face side and grid 35
side in sec, no less than
Strain after soaking in %, +2.5 +1.6 +1.8 +2.2 +1.5
no more (in transversal
direction)
Moisture in % (VEB-36) 5.57.0 5.8 5.7 6.51 4.7
Porosity in sec 27.3 21 17

Note: In all papers, the fibre is directed longitudinally. Acclimatized conditions: equilibrium air
moisture 5560%, temperature 21C.
CHAPTER 4 179

24
1
20

b 10, MPa
16 2
3
12
8 4
4

2 4 6 8 10 12 14 , h

Figure 4.28 Formation of latex coatings on various papers and offprints at 20C: 1, Kamenogorsk
Paper-Plant paper; 2, Goznak paper; 3, map paper; 4, offprint.

Films from blue and black inks (included in the series 2513) applied to the surface of
glass prisms as a sublayer of 5-7 m thick were also used as supports to elucidate the effect
on the values of internal stresses and adhesion of the lacquer film to the surface of offprints.
Internal stresses in the formation of coatings on fibrous supports (paper, offprints)
were studied by the polarizationoptical method using the earlier developed technique for
preparing specimens, which consists in pasting paper onto the surface of glass prisms fol-
lowed by the application of a film former onto it.
Adhesion was assessed by the values of ultimate critical stresses causing the sponta-
neous delamination of the film from the support. The effect of the nature of nonporous sup-
ports of the type of glass, black and blue inks on the kinetics of increment and relaxation of
internal stresses in the formation of coatings. It is seen that coatings are formed the most
rapidly on a blue ink sublayer, with the stable properties settled. Formation of coatings on
a blue and black ink sublayer is accompanied with a decrease of the internal stresses in the
system. However, the adhesion of coatings decreases simultaneously from 5 MPa on glass
down to 1.82.2 MPa on an ink sublayer, respectively, black and blue.
Worse adhesion of coatings to the ink sublayer is due to the fact that offset inks include
polymerizing composition drying oils based on wood rosinmaleic or phenol-aldehyde
resins, which contain in a hardened state a much smaller amount of active polar groups ca-
pable of specific interaction with the latex coating.
Figures 4.284.29 present the data on the kinetics of increment and relaxation of in-
ternal stresses in the formation of latex coatings on the surface of various kinds of papers
and offprints at 70 and 20C. It is seen that internal stresses in the formation of coatings
both at 20C and 70C on offprints and paper change nonmonotonically, the way they do
on glass. Figure 4.30 presents the drying curves of latex coatings on various papers and on
an offprint. It is seen that drying to a constant weight is completed the most quickly in an
offprint and in map paper. It is seen from the comparison of Figs. 4.25 and 4.27 that con-
siderable internal stresses emerge at the initial coating-formation stage associated with the
elimination of moisture and the emergence of local links between latex particles. A sharp
increase of internal stresses in the formation of coatings on fibrous supports is, apparently,
due to a partial impregnation of the fibrous base and the reinforcement of the boundary lay-
ers of the coatings. However, during the storage of coatings under room conditions, owing
to the relaxation processes, the internal stresses are sharply decreased and do not exceed
0.40.5 MPa. From the comparison of Figs. 4.24 and 4.26, it follows that the relaxation pro-
cesses in coatings formed on glass are completed much faster than in coatings on paper and
on an offprint.
180 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

32
1
24
b 10, MPa 4
2
16
3

1 2 3 5 7 9 , h

Figure 4.29 Formation of latex coatings on various papers and offprints at 70C: 1, Kamenogorsk
Paper-Plant paper; 2, Goznak paper; 3, map paper; 4, offprint.

u, % 100
80
60
1
40 2
3 4
20

5 10 15 20 25 30 45 60 , min

Figure 4.30 Kinetics of drying of latex coatings on various papers and offprints: 1, map paper; 2,
Goznak paper; 3, Kamenogorsk Paper-Plant paper; 4, offprint.

The cause of this phenomenon is, probably, due to a partial reinforcement of the coat-
ing by the fibrous support and to the effect of its structure on the rate of the relaxation pro-
cesses. When specimens are dried under room conditions, the relaxation processes are
completed the fastest in coatings applied on to offprints.
Thus, it follows from these data that the character of the kinetic curves of the change
of internal stresses during the formation of latex coatings does not significantly depend on
the nature of the support. The nature of the surface of the support, its structure and porosity
render a considerable effect on the increment and relaxation rates, the values of internal
stresses, the formation period, the decorative properties of coatings.
The structure of various types of papers and its effect on the impregnation of paper and
offprint with latex was studied using optical and electron microscopies with the view to elu-
cidate the specific features of latex coating formation on fibrous supports.
5 Technology
of the Development
of Canning Containers

5.1 Purpose of canning containers


Despite the development of new methods, equipment and technologies for processing food
products, canning still remains one of the methods of preserving perishable products during
the mass slaughter of livestock and delivery of milk. A broad use of canning makes possible
a gradual supply of meat and dairy products over the year and their delivery to regions dis-
tant from processing plants.
Metal containers from aluminium, chrome-plated steel or tinplate are the traditional
type of packaging for canned products in meat and dairy industry, in production of canned
fruits, juices, drinks, stewed fruits. Application of metal containers reduces labour intensity
and sterilization time, increases labour efficiency, decreases the requirement in storage
facilities.
The progress of canning industry is closely related to the development and manufac-
ture of advanced, mainly metal, canning containers. Though they give way to polymer con-
tainers in the assortment and production rates of new types, metal containers are
nevertheless successfully used and their output is predicted to double by the turn of the
century.
In Russia, annual output of tinplate cans is 34.6 bln; of them, 26.3 bln for packaging
various food products; for alcohol-free beverages, 4.4 bln; and for non-food purposes, 3.9
bln.
In the UK, one of the leading European countries manufacturing metal food contain-
ers, production of canning containers was 3.6 bln cans for foodstuffs; 2.2 bln cans, for an-
imal food; and 7.38 bln cans, for drinks.
According to the data by the American Iron and Steel Institute, eight leading US com-
panies members of this institute manufacture annually 3715 thousand tons of
light-gauge tinplate, used mainly in fabrication of metal cans; including tinplate, 2611 thou-
sand; tin-free plate, 889 thousand, and black plate, 215 thousand. On the whole, the world
demand is over 50 bln cans. The development of a new metal can takes three years on
average. This time is required to solve numerous issues: fabrication of a container and a set
of equipment; filling of the container; processing of the packaged product; reliability; air
tightness.
182 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

In Russia and Kazakhstan, electrolytical tinplate is manufactured on five lines; in par-


ticular, in Magnitogorsk Integrated Works of Metal Containers and Ispat-Karmet Steel
Works.
Owing to the change in the level of requirements to tinplate by processing plants,
which is due to the implementation of advanced can-producing lines and the development
of new canning container-producing technologies, these enterprises can not meet the de-
mand on some items of assortment and quality. First and foremost, this is high-plasticity
tinplate for production of beverage cans by the deep-drawing method. There is also a deficit
of wide-format (more than 850 mm), thin-gauge and fine (0.20 and less) tinplate. Manufac-
turing of these types of tinplate in Russia is impossible due to the absence of respective
equipment.
The ecological and technological problems of tinplate production have been solved in
the recent decade. The quality of tinplate has been significantly improved due to the in-
crease of the uniformity of distribution of the tin coating over the width of the band by
2535% or 0.30.4 g/m2 depending on the mean thickness of the coating; elimination of
some characteristic defects of the coatings, affecting the consumer properties of tinplate,
such as non-reflown edge and matte appearance; increase of the corrosion resistance
of tinplate by 3040% depending on the mean thickness of the coating.
An important problem is also a limited assortment. The system of assessing the quality
of tinplate does not include the set of issues related to corrosion resistance and other per-
formance characteristics of material. Of all parameters affecting the corrosion and opera-
tional behaviour of material (lacquering, soldering, integrity), in practice only the
roughness is rated and checked. Totally excluded from the rating system are such parame-
ters as corrosion resistance, composition of the chromate film, thickness variation of the
coating. These parameters are especially important for tinplate.
Traditional types of containers used for production of canned products are glass jars
with lids from tinplate or chrome-plated steel or aluminium. Production of canned products
in metal canning containers ensures the rise of the productivity of the process equipment,
the decrease of labour intensity and sterilization time, the reduction of the demand for
storage facilities.
In the recent years, aluminium, chrome-plated steel, aluminized steel are widely used
along with tinplate, which is in short supply. New materials are characterized by a lower
corrosion resistance as compared with hot-dip tinning and electrolytic tinning tinplate. In
this connection, other oligomers and polymers are used for protection of canning containers
along with traditional film formers, such as oil systems and epoxyphenol lacquers. The re-
quirement in new lacquer-and-paint materials is also due to the production of metal canning
containers of changed design (deep-drawn cans, composite cans with soldered seam, two-
piece stamped and composite cans, readily opened lids, special lids for glass containers,
tubes).
All this specifies the high requirements to lacquer-and-paint coatings intended for pro-
tection of containers, with respect to adhesion, physicomechanical properties and resistance
to the action by canned products in their long-time storage. At present, coatings of canning
containers are produced using phenolic-oil, epoxy, acrylic, polyester etc. bonding adhe-
sives as film formers.
A broad assortment of lacquer-and-paint materials for protection of metal canning con-
tainers is due to the fact that at present there is no universal paintwork material suitable for
any metal support and canned product. The diversity of materials used to produce canning
containers and the difference of the properties of products packaged into them make it
CHAPTER 5 183

necessary to develop diverse lacquer coatings ensuring the protection of containers and
products under various technological conditions of production, canning and storage.

5.2 Field of application and efficiency of use


When producing containers for packaging meat, dairy, fish, juices and fruit-and-vegetable
canned products, tinplate due to the deficit and appreciation of tin is increasingly more
often replaced with aluminium and its alloys, although they are more expensive than tin-
plate (1015% or, by some other information, 25%).
Aluminium possesses a number of properties, which make it indispensable container
material: light weight (density of aluminium is almost 3 times larger than that of tinplate),
good formability, plasticity, high protective properties, heat resistance; resistance to water,
gases, smells, fats, action of bacteria and pests; high reflectivity; good protection of the
product from the action of heat and cold; possibility of combining it with other materials.
Increased use of aluminium materials is also stipulated by the development of aceptic
canning, increased production of frozen foods, increased demand of extended storage time.
Prospects of the further application of aluminium are determined not only by its merits,
but also by the reduction of costs for reprocessing of discarded containers. On average, 1
ton of aluminium is required to fabricate 32 thousand cans; 1 ton of tinplate, only 15 thou-
sand. Expenses for the fabrication of an aluminium container are on average 1% of the cost
of canned product it contains.
According to the data by US companies, production of 1 kg aluminium from bauxites
requires 18.6 kW h of electric energy and 57.1 kJ of thermal energy. These data also include
total energy costs for extraction of ore, its processing and melting, as well as transportation,
heating, illumination, collection and utilization of wastes.
In production of an aluminium sheet, a considerable part of material charged into the
melting furnace is scrap of all sorts, including used aluminium containers. This type of sec-
ondary raw materials should be subjected to pretreatment, which includes its cleaning and
removal of the lacquer coating. With the required energy expenses in mind, as well as ad-
ditional consumption of energy for transportation, illumination and heating, the total con-
sumption of energy for melting of 1 kg of aluminium from scrap is 0.11 kW h of electric
energy and 8.0 kJ of thermal energy. Therefore, production of aluminium from secondary
raw materials requires only 0.6% of electric energy and 13.8% of thermal energy necessary
for production of this material from ore.
The ratio between the total reduced energy intensity of the treatment of primary and
secondary aluminium raw materials is 28.5:1. Calculations performed by US companies
have shown that collection and reprocessing of 60% of used aluminium containers reduces
the total energy intensity of container production almost two times. Two major US compa-
nies Reynolds Metals and Alcoa annually collect and reprocess over 200 thousand tons of
used aluminium containers, which enables the output of about 9.6 bln cans. These compa-
nies utilize about 75% of containers produced. On the whole in the USA, about 60% of alu-
minium cans and packs are utilized annually, which makes possible the re-use of 650
thousand tons of aluminium.
In France, 27% of aluminium is produced from secondary raw materials. In Sweden,
about 80% of manufactured aluminium packs are reprocessed. However, there are organi-
zational problems of collecting, sorting out and transporting the used aluminium packs. On
the whole, the return of this metal to the production cycle can reach 50150 bln tons per
year.
184 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

5.3 Requirements to the properties of coatings for canning containers

The purpose of a lacquer-and-paint coating is to protect the surface of canning containers


from the action of food products. The larger is the continuity of a lacquer-and-paint coating,
the lower its permeability is, and, therefore, the more reliable its protection properties are.
The major requirement to lacquer-and-paint coatings is their continuity, as well as chemical
endurance, mechanical strength and high adhesion.
The performance properties of coatings for protection of metal canning containers de-
pend on the composition of their ingredients, the physicochemical and technological prop-
erties of lacquers and enamels.
Of great importance is the ability of film-forming solutions to spread well and be well
distributable on metal upon application. Viscosity of the lacquer-and-paint materials and
the dry residue content are also of great significance.
Protection of the inner and outer surface of canning containers is provided for by the
use of mainly lacquer-and-paint materials, which harden at high temperatures from 180 up
to 360C.
The physicomechanical properties of coatings are determined by the structure of poly-
mer macromolecules. Linear and network polymers under the action of an external force
change their properties differently. Network polymers extend in tension insignificantly and
then break down. Linear polymers are deformed in tension, then a thickening appears on
specimens at the further increase of stresses, and polymer extends four and more times with
the orientation along the extension axis of macromolecules and their aggregates.
Linear polymers are characterized by three major types of strain: elastic, rubberlike
and plastic. Elastic strain is caused by large stresses and is due to the change of interatomic
distances in polymer crystals or molecules. They are totally reversible and do not exceed
1%. Rubberlike strains can reach 1000% and are totally reversible; however, the initial
shape is recovered not immediately but in time.
Plastic strain of polymers is irreversible. It is associated with the regrouping of mac-
romolecules or their aggregates relative to one another. The process of changing the state
of stress in transition from an inequilibrium arrangement of its structural elements to the
equilibrium state is stipulated by the relaxation of stresses. Relaxation phenomena are es-
pecially dangerous for those technological processes, where the strongly deformed coating
is under the action of high temperatures.
The disturbance of a polymer coating, due to the formation of cracks, a partial delam-
ination and other defects can be observed in thermal sterilization in the container fabricated
by deep drawing from lacquered tinplate or aluminium, as well as in drying of the sealing
paste on lids pressed from lacquered tinplate.
Internal stresses can occur in coatings not only as the result of their deformation upon
film formation, in particular in drying of coatings, but also as the consequence of inhomo-
geneity and imperfection of the structure. Inadmissible shrinkage of a polymer coating in
the process of drying is determined by the decrease of its volume at an invariable surface
area of the material. The cause of shrinkage is the removal of solvent and the polyconden-
sation reaction in coatings with evolution of side products of the reaction. An increase of
the molecular mass of the film former leads to a larger shrinkage of the film; solvents with
a smaller vapour pressure, as less volatile ones, contribute to the decrease of shrinkage of
the coatings.
To reduce the shrinkage of coatings in fabrication of metal container materials, their
thickness should be decreased down to 36 m. If thicker coatings up to 1218 m
CHAPTER 5 185

are to be applied, for instance, for protection of black plate, they are applied, as a rule, in
two or three layers.
A large role in defining the protective properties of coatings is played by the adhesion
properties. Adhesion is determined by the force of interaction of two contacting surfaces of
materials different by their nature. The extent of adhesion of a film to a solid surface is as-
sessed by the force spent for its delamination from the support. At strong deformations of
material in fabrication of containers and partial destruction of the coating, three types of
adhesion disturbances are observed:
adhesion forces are stronger than cohesion forces, peeling-off occurs by the material
of the coating; this is the cohesion detachment of the film;
adhesion forces are smaller than cohesion forces, peeling-off occurs by the area of
the contact of the film with the support; this is the adhesion detachment of the film;
adhesion forces are approximately equal to cohesion forces, the mixed peeling-off
occurs; this is the adhesioncohesion detachment of the film.
When applying a lacquer-and-paint coating to the metal surface at the first stage of the
process in the liquidsolid system, adhesion forces exceed cohesion forces significantly.
However, as the film-formation process proceeds further, cohesion forces increase and in
most cases start to exceed those of adhesion.
Formation of a polymer film includes a complex of processes chemical, physico-
chemical, electrostatic, as well as mechanical interaction of the polymer coating with metal.
The value of adhesion is greatly affected by the state of the surface and its microgeometry,
as well as the nature of the film former. The more the amount of active polar groups in the
composition, such as hydroxyl, carboxyl, epoxy etc. groups, the stronger the interaction of
the polymer coating with metal is.
Lacquers based on comparatively low-molecular-mass substances (phenol formalde-
hyde and epoxy oligomers) form films with good adhesion owing to the high mobility of
molecules and their orientation at the interface.
The nature of forces responsible for adhesion is defined differently in works by differ-
ent authors. According to the electrostatic theory, adhesion of polymer coatings to metal is
explained by the electrostatic attraction of the charges of the double electrical layer by anal-
ogy with microcapacitors, whose interfaces are films of polymer and metal. Considering
that adhesion of various kinds of lacquer-and-paint materials is different and depends on
the nature of metal, the method used in practice consists in using special systems of coat-
ings, such as primercoating systems. In this case, the coating consisting of two layers of
polymer provides for adhesion to any of these materials. Of crucial significance in this case
is the diffusion phenomenon, which provides for a strong cohesion of two polymer film
formers. When considering the phenomena at the metalpolymer interface, the crucial fac-
tor in its determination is the formation of special bonds providing for the chemical inter-
action.
Permeability of polymer coatings is one of the main characteristics determining its
protective properties. It depends on the following major factors:
molecular permeability, which is determined by the nature of polymer, molecular
structure, packing density of molecules;
nature of a lacquer-and-paint material and its preparation;
process procedures in application and formation of coatings.
Chemical endurance of polymer coatings depends on the nature of a film former, as
well as on the conditions of chemical reactions leading to the formation of a crosslinked
molecular structure.
186 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Oleo-resinous lacquers are characterized by an insufficient chemical resistance, which


is affected by the drying oils in their compositions, owing to the large content of ester
groups subjected to oxidation and determining the swelling of coatings in aggressive media.
Resistance of coatings to ageing in the process of operation is determined by the extent
of deterioration of the mechanical properties, such as elasticity and shock resistance. This
process is determined by the following factors: destruction of the film former, occurrence
of chemical reactions, loss of the plasticizer or residual solvent by the film, rate of the re-
laxation processes.
The film former can be destroyed under the action of light, oxygen, high temperatures
or aggressive media. As the result of the destruction, the molecular mass decreases, the
strength and elasticity of the coating go down. Ageing of the films due to the erosion or
blooming of plasticizers and residues of solvents is of no great significance for can var-
nishes, as they are not used in formulations of varnishes, and the coatings are dried at high
temperatures.
The effect of factors that accelerate ageing is attenuated by using antioxidants as ad-
ditives. Introduction of pigments, such as aluminium powder, titanium and zinc dioxide
slows down the ageing process, as the formation of various aggressive substances in liquid
and gaseous state is made difficult.

5.4 Coatings for protection of canning containers


The corrosion resistance of aluminium is insufficient for most food media; an additional
protection is required, which is done by anodization followed by lacquering the metal. The
type and stability of can varnishes mainly determine the possibilities of using metal con-
tainer materials. Owing to the protective property of a varnish, the canned product is sepa-
rated from the metal of the can. If metal is not lacquered, then sweet, sour, salt- or
protein-containing food products cause its corrosion. The action of metal compounds
formed as the result causes changes of the appearance, colour and taste of ready-prepared
products, reduce the integrity of sterilized preserves. Application of a lacquer coating on
the surface of chrome-plated plate decreases the rate of penetration of iron and chromium
into the product tenfold.
The protective lacquer coating should have the following properties: a good adhesive-
ness to metal and a corrosion resistance; inertness with respect to a food product; a good
capability of deep drawing; a maximal resistance to strain, action of hot water and acids, as
well as to sterilization and pasteurization; a large range of applications for various food
products; processibility, stability of the properties of compositions in storage (no less than
1 year); the possibility of coating thickness variation within wide limits; formation of an
almost pore-free lacquer film with a high scratch resistance at its weight of 58 g/m2 of the
film; a small duration of hot drying, no more than 3060 sec to achieve an optimal
crosslinking of the polymer using a high-capacity equipment; a possibility of endowing the
antiadhesion properties, preventing the adhesion of the contents to the can.
These requirements are met using epoxyphenol and oleo-resinous lacquers; enamels
with zinc oxide, titanium dioxide and based on polyvinyl chloride and copolymer of vinyl
chloride; lacquer-and-paint materials from water-diluted, -soluble, -dispersion bonding ad-
hesives, as well as systems with a high content of film former; powder inks.
Various raw materials and semi-finished products mainly synthetic oligomers and
polymers are used to produce lacquer-and-paint materials intended for protection of metal
canning containers. To modify some of them, natural products are used plant oils,
CHAPTER 5 187

products of wood rosin reprocessing. Enamels are prepared with application of mineral pig-
ments, such as zinc oxide, titanium dioxide and aluminium powder. To dissolve
lacquer-and-paint materials, organic solvents are used.
Plant oils are produced from seeds or fruits of oil-bearing crops. The major component
of plant oils (over 95%) are glycerol esters of fatty acids (triglycerides) containing from 14
up to 18 carbon atoms.
The properties of oils depend on the composition and structure of fatty acid radicals,
which are components of the esters. In particular, the ability to dry is determined by the
number of double bonds in the triglyceride molecule, as well as by their mutual position.
By the drying ability, oils are divided into the following groups: oils with the greatest drying
ability, drying oils and semidrying oils.
Castor oil is used in production of lacquers in dehydrated form. It is distinguished by
a number of valuable properties and is close to Chinese wood oil. It is widely used abroad
in production of can varnishes, in particular, to produce protein-resistant coatings. It is also
used to produce dimerized acids, which are used in the synthesis of epoxy esters.
Maleinized oil is obtained by the interaction of oil with maleic anhydride; it is attached
to the fatty acid radical by the side of the coupled bond. As the result of maleinization, the
oxidation of oils slows down, and they dry slower in the air than the initial products.
For protective coatings, wood rosin modification products are used. By its chemical
composition, wood rosin of plant origin is a mixture of resin acids. The most stable isomers
are abietinic, dextropimaric and levopimaric acids. In lacquer-and-paint industry, mainly
wood rosin ethers are used, which are a product of etherification of resin acids of wood rosin
by pentaerythritol.
As film formers, epoxy oligomers are used, which are compounds whose molecule
contains no less than two epoxy or glycide groups, at the expense of which there occurs the
formation of a three-dimensional network structure in the hardening of coatings.
The main advantage of epoxides is high adhesion to most materials, the physico-
mechanical properties and chemical endurance, determined by the absence of readily
hydrolyzed functional groups in their composition.
As hardeners of the compositions, the most frequently used substances contain amino
groups, anhydrides of organic acids, phenol- and aminoformaldehyde oligomers, isocyan-
ates. A disadvantage of the epoxy coatings is their low stability to stamping.
Epoxy ester oligomers are used to fabricate lacquer-and-paint materials, including can
varnishes. Widespread materials are epoxy esters of fatty acids of plant oils, as well as syn-
thetic fatty acids with the radical length C10 C13 and C10 C16 in a mixture with fatty acids
of flax oil. Modified oligomers in production of can varnishes include alkyd epoxy resin of
grade E-30. It contains glycerophosphate GF-019 and epoxy resin E-40. Resin E-30 is used
as a bonding adhesive in epoxyphenol lacquers.
Lacquer EF-0188 belongs to epoxy esters. It is the product of etherification of epoxy
resin E-44 by fatty acids of flax oil.
The same group of film formers includes epoxy ester of grade EM-34. It is a ester ob-
tained in the interaction of epoxy resin E-40 with monomer methyl esters of acids. This
composition is used to produce white enamel.
Production of can varnishes, along with melamine-formaldehyde oligomers, makes
use of the derivatives melamine-acetoguanamine and benzguanamine. A complex of high
physicochemical and technological characteristics of these oligomers, as well as the admis-
sibility of their contact with food media specify the possibility of their use for production
of can varnishes.
188 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Epoxy esters based on dimerized acids of dehydrated castor oil are used in epoxyphe-
nol can varnishes to increase their flowability. The coatings on their basis are characterized
by high adhesion, elasticity and chemical endurance.
Phenol-formaldehyde oligomers used to form coatings of canning containers are a
product of polycondensation of mono- and polybasic phenols with aldehydes, mainly with
formaldehyde.
Phenol-formaldehyde oligomers based on a mixture of phenol with o-cresol, n-tert-
butyl phenol and technical-grade xynenols are produced under industrial conditions.
Carbamide-, melamine- and benzguanamine-formaldehyde oligomers for canning
containers are obtained by polycondensation of carbamide, melamine or benzguanamine
with formaldehyde in a neutral or weakly alkaline medium. These oligomers are widely
used in lacquer-and-paint industry as a constituent part of many canning materials.
Oligoesters are used to produce can varnishes. They are obtained by the polyconden-
sation reaction of polyatomic alcohols with polycarboxylic acids or their derivatives. Can
varnishes based on oligoesters are synthesized using benzguanamine or melamine-formal-
dehyde resins, which contribute to the increase of chemical resistance of films. Coatings
hardened at 180200C for 10 min withstand boiling and sterilization.
Polyvinyl chloride and its copolymers have lately found wide use, especially abroad,
in production of can varnishes. Copolymers of vinyl chloride with vinyl acetate or with mix-
tures of vinyl acetate with maleic anhydride or acrylic acid, as well as copolymers of vinyl
chloride with partially saponified vinyl acetate, are used the most frequently. Coatings
based on these copolymers should satisfy stringent requirements to the content of residual
monomers and emulsifiers in products, absence of off-flavour and smell, which determines
their sanitary-hygienic properties.
For coating the outer surface of canning containers of food purpose, lacquers based on
polyacrylates are used. They represent copolymers based on acrylic CH2 =CHCOOH and
methacrylic CH2 =C(CH3)COOH acids and their derivatives, such as methyl methacry-
late, butyl methacrylate, acrylamide with the general formula CH2 =rC(CH3)COR. Acrylic
copolymers are well soluble in esters of aromatic hydrocarbons, ketones.
Coatings on their basis are characterized by a high thermal stability, hardness, resis-
tance to mechanical loads.
Polyvinyl acetals are also used for production of canning containers. They are pro-
duced by the interaction of polyvinyl alcohol with aldehydes. They are a valuable raw ma-
terial for lacquer-and-paint industry. For this purpose, polyvinyl butyral a product of the
interaction of polyvinyl alcohol and butyl aldehyde - is produced in this country on an in-
dustrial scale. Polyvinyl butyral combines with alkyds; phenol-, carbamide- and
melamine-formaldehyde; epoxy oligomers, cellulose nitrate, natural resins, various plasti-
cizers. In this connection, polyvinyl butyral is widely used in production of lacquers, enam-
els, primers and powder inks for protection of canning containers, items from steel and
aluminium.
Along with film formers, the composition for coating canning containers includes sol-
vents, pigments, hardeners, modifiers. Most polymer coatings are applied from solutions.
By their chemical composition, solvents are divided into several classes: aliphatic and naph-
thenic hydrocarbons, for instance, white spirit; aromatic hydrocarbons (toluene, xyol, sol-
vent naphtha); terpenic hydrocarbons (turpentine); alcohols (ethanol, butanol, etc.); ketones
(acetone, methyl ethyl ketone, cyclosanone); ethers and esters (ethyl acetate, butyl acetate,
cellosolve).
The most important requirements to solvents are their dissolving power, incombusti-
CHAPTER 5 189

bility and toxicity. Upon evaporation of the solvent, the film should have no smell.
Pigments are introduced into lacquer-and-paint materials to obtain filled coatings. In
most cases, they endow the coatings with a corrosion resistance and can be corrosion inhib-
itors. Pigments also contributed to fabrication of coatings resistant to processes of atmo-
spheric ageing and possessing decorative properties.
Aluminium powder produced from aluminium-containing raw materials looks like
scales 0.20.5 m thick and 250 m wide. The content of aluminium in the raw material
should be no less than 99%. For lacquer-and-paint industry, aluminium powder is manu-
factured as paste. It is fabricated from aluminium powder of grades A-5E, A-5, A-6, A-7.
White spirit is used as a solvent.
Zinc white paint by its chemical composition is zinc oxide a white crystalline pow-
der with the size of particles of 0.11 m. The content of zinc oxide in the pigment is
98.099.7%. Being a weakly basic pigment, zinc white dissolves in acids and alkali. It re-
acts to free fatty acids of oil-containing film formers.
Colloidal zinc oxide is used in production of protein-resistant enamels for protection
of canning containers.
Titanium dioxide is a white pigment. It is produced in two rutile and anatase mod-
ifications. The content of the base substance in titanium dioxide manufactured by the in-
dustry should be no less than 9598%.
Titanium dioxide is used in production of lacquer-and-paint materials for external and
internal protection of metal canning containers. Coatings based on these compositions are
resistant to aggressive canning media and external effects.
An important component of the compositions are hardeners. In production of canning
containers, the hardeners used are reactive compounds introduced into lacquers and enam-
els based on various film formers (epoxy, acrylic, polyester ones and copolymers of various
chemical compositions). Phenol-formaldehyde and aminoformaldehyde oligomers, polyes-
ters, anhydrides of carboxylic acids, isocyanates are used as hardeners.
Catalysts are introduced into the compositions in minor amounts to accelerate the
hardening process. In some cases, they make it possible to reduce the temperature of hot
drying. In some cases, catalysts are used together with hardeners; for instance, orthophos-
phoric acid, mono- and dibutyl esters of phosphoric acid are used for epoxyphenol lacquers,
as well as tetrabutoxytitanium, para- and orthotoluene sulphoacid, aluminium alcoholate.
One of the components of a film former are gliding additives. They are introduced to
endow the coating with a resistance to scratching in the mechanical treatment of lacquered
tinplate in fabrication of metal container from it; for instance, additive PVO-30. It is oxi-
dized polyethylene wax and is used as a 5% solution in xylol.
To improve the flow behaviour of lacquers and to eliminate crates on the surface of
coatings in the application of lacquers and enamels, special additives are introduced into
them, for instance, lacquer KO-815. Abroad, the formulations of lacquers include additives
on an acrylic or silicone basis to improve the flow behaviour, for instance, products of
grades BIK-304 or BIK-344 manufactured by German firms.

5.5 Compositions based on oligomer systems


A number of requirements are imposed on the lacquer-and-paint materials intended for in-
ternal coating of canning containers: they should not contain toxic components, be suffi-
ciently stable in storage and provide for an even and smooth film on the surface of metal at
the application and drying of lacquer-and-paint materials. Coatings on the basis of these
190 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

systems should possess a good adhesion to metal, elasticity, hardness and strength to be able
to withstand die stamping, seaming, sealing and other mechanical operations in production
of cans and lids.
Home industries manufacture epoxyphenol lacquers used for protection of canning
containers from tinplate, aluminium alloys and chrome-plated steel. The composition of
these lacquers includes various epoxy oligomers, differing by their molecular mass; phe-
nol-formaldehyde oligomers based on various phenols and their mixtures. The high content
of phenol-formaldehyde oligomers contributes to high chemical endurance of the coatings.
Phenol-epoxy lacquer FP-559 is a solution of a mixture of resins xylene phenol
formaldehyde KFE, epoxy E-05K and alkyd epoxy E-30 in a mixture of organic solvents.
The lacquer is applied on tinplate sheets on roller-type lacquering machines; and on the in-
ner surface of one-piece cans, on spray-type lacquering machines.
The predominant component of lacquer FP-559 is phenol formaldehyde, so at a high
chemical stability of coatings on its basis they are distinguished by a low elasticity. For this
reason, it can not be used in production of one-piece cans.
Epoxyphenol lacquer EP-547 is a solution of a mixture of epoxy E-05K and phe-
nol-formaldehyde FP-1 resins in a mixture of organic solvents. It is used mainly for coating
tinplate in production of canning containers. The lacquer is applied on tinplate sheets on
roller-type lacquering machines and is hardened in convection-type furnaces at 200210C
in 1215 min.
As compared with FP-559, lacquer EP-547 forms films of better elasticity, which en-
ables its use in production of one-piece containers. However, the chemical endurance of
coatings based on this lacquer, especially in an acidic medium, is lower than that of coatings
from lacquer FP-559, which restricts the areas of its application.
Lacquer EP-547 is widely used also for lacquering tubes for food and perfumery prod-
ucts. In fabrication of canning containers for strongly aggressive food media, tomato paste
and tinted stewed fruits, lacquer EP-547 is used in combination with other lacquers and
enamels, such as FP-559, EP-5147al, EP-5195p. Coatings on the basis of these composi-
tions play the role of a sublayer. Chemical endurance of coatings based on lacquer EP-54
is increased by introduction of hardening catalysts of the type of tetrabutoxytitanium or che-
late compounds of aluminium.
Epoxy phenol lacquer EP-527x is a solution of epoxy E-05K, phenol-formaldehyde
FPF-1 and alkyd epoxy E-30 resins in a mixture of organic solvents. This lacquer is used
mainly for coating chrome-plated steel.
Drying of the lacquer film is performed by high-frequency currents in inductors at a
temperature of up to 350C for 35 s. To increase the chemical endurance of the coating
and extend the applications of containers from lacquered chrome-plated steel, two-layer
coating is recommended to be done.
Epoxy phenol lacquer EP-5118 is a solution of epoxy E-04kr and phenol-formalde-
hyde FKoF-4 resins in a mixture of organic solvents. The lacquer is characterized by a high
content of epoxy resin. The lacquer is used for inner and outer coating of the band from
aluminium alloys. On the surface of metal, the lacquer is applied by the roller method. The
regime of its drying is 30 s at 340C. The advance rate of the band during the application
of the lacquer is 60 m/s.
Aluminium enamel EP-5147al is a solution of a mixture of epoxy E-05K, phe-
nol-formaldehyde FPF-1, alkyd epoxy E-30 resins; aluminium paste, polyvinyl butyral and
special additives.
Coatings based on this enamel are resistant to the action of protein-containing
CHAPTER 5 191

products. It is used for coating cans for meat, fish and vegetable canned products.
To improve the physicomechanical parameters of coatings, primarily, scratch resis-
tance, the enamel is applied over a thin layer of lacquer EP-547. This coating is used for
protection of containers for most types of fish preserves.
Seam lacquer EP-5186 is a mixture of solutions of epoxy E-05K and E-30 and phe-
nol-formaldehyde FPF-1 and FKoF-4 resins in organic solvents. This seam lacquer is used
for protection of the soldered side seam of composite electrolytic-tinplate cans. The lacquer
is applied after soldering the seam, by means of pneumatic spraying and a working viscosity
of 1315 s by VZ-4. This viscosity provides for a lacquer film of 34 g/m2 thick; the width
of the lacquer coating lane is 1520 mm. The lacquer dries up due to the residual heat after
soldering and additional drying together with lacquer of grade EP-5194 at 175C for 15
min.
Lacquer EP-5194 is a mixture of solutions of epoxy resins EO-4kr and E-30 with phe-
nol-formaldehyde resin FPF-1 in organic solvents. This lacquer is used for additional pro-
tection from corrosion of the entire inner surface of two-piece canning containers, as well
as for covering the lead-containing solder. This lacquer is applied by pneumatic spraying
and is dried for 15 min at 175C.

5.6 Oleo-resinous lacquers


An advantage of coatings based on these lacquers are their high physicomechanical prop-
erties, water and salt resistance. A disadvantage of the coatings is the low stability as com-
pared with epoxyphenol materials. These lacquers are used for protection of containers for
certain type of preserves, for instance, crabs.
Lacquer FL-560 is a solution of the product of condensation of phenol-formaldehyde
resin 101 with Chinese wood oil. A mixture of turpentine with white spirit is used as a sol-
vent. The drying is accelerated by using a manganese resinate siccative.
The lacquer is used for coating tinplate cans for crab preserves. This lacquer is char-
acterized by the following technical parameters: a homogeneous and clear solution, viscos-
ity by VZ-4 at 20C, 95120 s; drying time at 185190C, no more than 30 min.
Lacquer FL-561 is a solution of the product of condensation of phenol-formaldehyde
resin with a mixture of oxidized flax oil and dehydrated castor oil in turpentine. A co-
balt-manganese siccative is used to accelerate the drying of the lacquer.
This lacquer is used for coating tinplate, which is applied in fabrication of canning con-
tainers for preserves with a neutral medium. The drying time of the lacquer at 185190C
is 30 min.
Lacquer FL-5157 is used in production of protein-resistant enamel for protection of
canning containers from tinplate, intended for crab and neural-medium fish preserves. The
cobalt-manganese siccative is used to accelerate the drying of the lacquer. The viscosity of
this lacquer is 7080 s, the content of volatiles is about 55%, the duration of hardening at
180C is 2630 min.
Lacquer KF-281 is used as a protective coating of an enamel composition based on
lacquer FL-5157. It is the product of condensation of fatty acids of flax oil and Chinese
wood oil with pentaerythritol ester of wood rosin. The lacquer contains the cobalt-manga-
nese siccative. The viscosity of the ready-to-use lacquer is 1830 s, the content of volatiles
is about 64%, the drying time at 180C is 2630 min.
Enamels with zinc oxide are manufactured as protein-resistant ones. They are distin-
guished by an increased resistance to canned protein media, as zinc oxide is dispersed into
192 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

lacquers and binds sulfurous compounds evolving in sterilization and storage of pro-
tein-containing preserves.
To increase the decorative, hygienic and anticorrosion properties of coatings, use is
made of lacquer-and-paint materials with the anticorrosion neutral pigment titanium diox-
ide. The major parameters of lacquer-and-paint materials for internal protection of canning
containers are given in Table 5.6.1.
Table 5.6.1 Comparative characteristics of canning containers.

Lacquer Viscosity Content of Hardening Duration of Field of application


(by VZ-4), nonvolatiles, temperature, hardening,
sec % C min

FL-559 80115 4550 180185 1215 Glass-container lids, tinplate


containers
EP-547 90120 3842 205210 1215 Composite containers from tinplate
(elongation ratio, up to 0.4)
EP-527h 100150 3845 375385 40 (45) Lids and cans from chrome-plated
steel
EP-5118 110180 3640 335345 3540 Aluminium lids and cans
(elongation ratio, up to 0.6)
FP-560 95120 5054 185190 30 Composite tinplate containers
FP-561 140170 4952 185190 30 Ditto
EP-5186 5080 4248 175180 15 For lacquered seam
EP-5147 100150 3845 210215 15 Composite and pressed/punched
containers
EP-5194 90130 4550 190200 15 Cans and tubes

Note: Thickness of film in these coatings changes from 4 up to 8 m depending on the chemical
composition of a lacquer.

5.7 Polyvinyl chloride-based lacquers


These lacquers also include other bonding adhesives, in particular, alkyd, phenol and epoxy
resins. The major advantages of coatings based on these copolymers is their high elasticity,
good adhesion, especially to aluminium and alloys, as well as an almost complete absence
of the transfer of off-flavours from the coating to the canned products.
Hardening of films based on vinyl copolymers occurs as the result of evaporation of
the solvents and during the lacquering of tinplate in convection-type conveyor furnaces.
The duration of drying is 10-12 min at 120185C. In application of vinyl lacquers on the
aluminium band the drying is usually accelerated 3040 s at 250275C. When using
lacquers based on vinyl copolymers, it is necessary to take into consideration the possibility
of destruction of the bonding adhesive at a drying temperature above 185C. Primarily they
are used for lacquering cans for beverages.
Coatings practically do not transfer foreign smells and off-flavour to the contents of
the can. Another important application are lids for glass containers.
A disadvantage of lacquer-and-paint materials on vinyl basis is the inconstancy of their
properties in storage of no more than 46 months. The difficulty of preparing stable dis-
persions is the complexity of purification and scarcity of components, a higher consumption
of lacquers on vinyl basis as compared with epoxyphenol compositions, as well as in most
CHAPTER 5 193

cases a low chemical stability due to the difficulty of achieving a high and stable adhesion
of vinyl lacquers to the protected surface.

5.8 Oligoesters and water-base, water-soluble and water-dispersion


binders
A promising trend in the development of lacquer-and-paint materials for protection of the
outer and inner surface of canning containers is the creation of lacquer and pigment systems
based on saturated oligoesters. Such materials combined advantages characteristic of ep-
oxyphenol and generic systems. Coatings based on oligoesters, along with high adhesion,
thermal and corrosion resistance, possess a high elasticity, hardness and resistance to me-
chanical loads.
Oligoesters are used as film formers for can varnishes independently or in combination
with thermosetting oligomers, for instance, epoxy, phenol, melamine- and benzguanoform-
aldehyde and thermoplastic polymers (vinylic, acrylic).
Water-based lacquer-and-paint materials occupy one of the leading places in the as-
sortment of ecologically adequate kinds of lacquer-and-paint products in most developed
countries. A significant part of the total volume of lacquer-and-paint materials on water ba-
sis are supplied to the US canning industry and are used for anticorrosion protection of con-
tainers intended for packaging beer and alcohol-free beverages. Western companies
manufacture a wide assortment of water-based lacquer-and-paint materials based on epoxy,
vinyl, acrylic polyester and other resins used in formulations of lacquers for protection of
canning containers.
In the recent years, great attention is given to the development of water-dispersion sys-
tems for protection of canning containers based on carboxyl-containing epoxyacrylic film
formers, obtained by way of physical or chemical modification of epoxy oligomers by acry-
lates. These lacquers were first introduced in the US canning industry, and at present more
than half of all beer cans are manufactured using water epoxyacrylic systems. Phenol- or
melamine-formaldehyde resins are used as hardeners; herewith, tertiary amines serve as a
neutralizing agent. Coatings are hardened in several seconds at a temperature of about
200C. Their advantages are high elasticity and correspondence to the sanitary-hygienic re-
quirements to food-purpose coatings.
Changes in the recent years in the assortment of lacquer-and-paint production under
the influence of causes of economic and ecological character affected the canning industry
to a significant extent. Ecologically adequate lacquer-and-paint materials powder mate-
rials, with high content of nonvolatile components, aqueous, of radiation hardening start-
ed to be widely used for protection of the inner and outer surface of metal canning
containers. Thus, demand for such materials in the USA is over 20%; herewith, water-di-
luted materials are used to cover over half of beer and drink cans. In the nearest years, this
index would reach 100%.
A significant growth of demand for such compositions is due to the decreased content
of solvent, whose amount does not exceed 1520% as compared with traditional lacquers.
Their advantages are also low toxicity, fire safety, simplicity of application methods. How-
ever, for protection of canning containers only those systems are suitable, which satisfy spe-
cific requirements to materials in contact with food products. The major of them are
inertness of the coating as compared with the canned product, stability of materials in stor-
age for no less than 12 months, processibility, high adhesion to metal supports, stability to
the action of hot water and acids, stability to sterilization and pasteurization. Coatings from
194 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

water-diluted materials should be of high quality, should not be inferior than traditional lac-
quer coatings by their performance characteristics and economical efficiency.
The most widespread water-diluted canning materials are carboxyl-containing epoxy
oligomers and epoxyacrylates. These oligomers are synthesized by various methods. The
simplest of them envisages the interaction of an epoxy oligomer with dibasic acids or their
anhydrides. Disadvantages of these methods are process problems associated with the
two-stage character of the synthesis, large duration of the process, and high cost of the prod-
uct. Aqueous materials, which are distinguished by a high stability and processibility, are
obtained in the reaction of epoxy oligomers with various aromatic amino acids. These com-
positions are hardened in 10 min at 204C to form coatings stable to the action of acidic
and protein food products.
As a phenolic component, use is made of epoxy oligomers modified by polyfunctional
phenols. In the West, such oligomers are hardened using amino-, urea- or phenol-formal-
dehyde resins. Compositions are hardened in 212 min at 200215C to form coatings sta-
ble to pasteurization, sterilization; action of acids, alkali and solvents. However, the most
widely used materials for protection of canning containers are water-diluted materials based
on epoxy oligomers modified by acrylates. According to estimates by experts, these mate-
rials are used to cover over 60 bln cans.
A number of works note that aqueous materials based on mixtures of epoxy oligomers
with acrylates do not always satisfy manufacturers of canning containers with respect to
their water resistance, chemical stability and other characteristics. Considerably higher per-
formance characteristics are found to have systems containing grafted epoxyacrylates with
carboxyl groups in the side chain as film formers. Dispersions are hardened in the presence
of hexamethoxymethyl melamine at 188C in 60 s. Coatings are distinguished with a high
adhesion to aluminium and stability in hot water.
Carboxyl-containing epoxy oligomers and epoxyacrylates are of interest as potential
film formers for electrophoretic materials for coating the inner and outer surfaces of cans.
Phenol-formaldehyde or nitrogen-containing resins are used as hardeners. Such modified
compositions are used also for coating drawn cans or rolled metal to be used for fabrication
of three-piece composite cans.
Epoxy oligomers modified by polyesters and polyurethanes are used as film formers
of water-diluted materials for coating canning containers. For instance, aluminium and steel
beer cans are recommended to be coated with an aqueous dispersion, which includes
7095% of carboxyl-containing polyester based on trimellitic anhydride and adipic acid
with 530% epoxy dianic oligomer. Upon neutralization with ammonia, the dispersion is
applied to the surface of cans and is hardened for 10 min at 200C. The coating does not
affect the taste of the packaged product.
When producing such compositions, the polyurethane forpolymer is used, which is ob-
tained by the interaction of a mixture of polyester polyol and carboxyl-containing polyol
with polyisocyanate. The latter plays the role of a crosslinking agent. Coatings from these
materials are distinguished by a high chemical endurance, elasticity and adhesion to metal.
Water-diluted materials based on acrylic resins make it possible to obtain coatings
with high durability, light permanence and heat resistance. However, due to the negative
effect on the taste qualities, they are used only for coating the external surface of the con-
tainer and as coating lacquers for protection of lithographic printing. Such compositions are
produced using alkyl acrylates, methacrylic acid, methacrylates and vinyl acetate.
Coatings based on vinyl materials are distinguished by a high corrosion resistance and
elasticity. However, due to an insufficient heat resistance, they are unsuitable in the cases
CHAPTER 5 195

when products are subjected to long-time heat treatment. Copolymers of vinyl chloride or
vinylidene chloride with acrylate or other monomers are used the most frequently to pro-
duce these compositions.
For protection of the inner surface, use is made of copolymers of methacrylic acid, eth-
yl acrylate and styrene in a mixture of cyclohexanol and butyl cellosolve containing vinyl
copolymer and epoxy oligomer. Coatings on the basis of water-diluted compositions of this
kind have a high adhesion and render no effect on the properties of canned product.
Aqueous emulsions for coating cans based on polymer of vinyl chloride, ethylene and
acrylic acid have been developed. Copolymerization is carried out in the presence of poly-
vinyl alcohol, which plays the role of a dispersant. Compositions are used in combination
with melamine-formaldehyde resin for thermosetting coatings.
Aqueous pigmented materials are used for external coating and lithography of cans.
Alkyd, polyester, acrylic or epoxyphenol oligomers are used as film formers in such mate-
rials.
Water-diluted materials for coating canning containers are applied on the surface by
rolls, spraying or pouring. The choice of the application method is determined by the type
of container and the process of its fabrication. When producing composite or two-piece cans
by the multiple drawing method, use is made of rolled or sheet material preliminarily paint-
ed by any method on a standard equipment. Before formation of cans, the surface of metal
is coated with a layer of lubricant, which facilitates the process of fabrication and protects
the lacquer-and-paint coating from destruction. Two-piece cans produced by the ironing
method are decorated from the outer side and are painted from the inside by spraying. In
this case, the best results are obtained by using double-nozzle sprayers or those with two
mixed nozzles, which enable application of two-layer coatings.

5.9 Compositions with high dry residue and ink powders


An advanced direction of studies in the field of ecologically adequate lacquer-and-paint ma-
terials for protection of canning containers is the development of systems with high dry res-
idue. Unlike aqueous compositions, lacquer-and-paint materials with high dry residue wet
the metal support well and do not require special surfactants or other additives. The use of
lacquers with high dry residue has begun from the application of oil-phenolic systems with
dry residue content of 7075%. For instance, lacquers with high dry residue were proposed
for protection of canning containers; as the bonding adhesive, they contain an adduct of an
epoxy oligomer with another oligomer, having amino groups, which perform the function
of a reactive diluter and plasticizer.
Ink powders are a progressive type of ecologically adequate lacquer-and-paint mate-
rials; coatings on their basis are characterized by high physicomechanical and protective
properties.
Studies of the use of ink powders for protection of canning containers are carried out
by a number of leading Western companies in the USA, the UK, Germany etc.
However, the use of powder lacquer-and-paint materials for protection of bodies of
canning containers is of limited character due to the high costs of coatings and the complex-
ity of regulating their thickness in the high-speed application process. These drawbacks can
be overcome by using aqueous powder suspensions, which combine the advantages of wa-
ter-diluted systems and ink powders. Powder suspensions, which make it possible to obtain
coatings of any given thickness, are widely used in the recent years in Japan for protection
of canning containers.
196 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

5.10 Coatings for protection of the outer surface of canning containers

The following materials are used for protection of the outer surface of containers and ap-
plication of colour or black-and-white patterns on it:
silver or golden primer lacquers intended for creating the background as well as for
improving the elasticity and formability of the whole coating;
white or colour primer enamels for creating the continuous background for the print-
ed pattern;
white, colour and black printing inks intended for protection of a printed image from
mechanical damage, for offset printing on tinplate from flat plates of figures, background
and text in accordance with the reproduced original;
transparent colourless coating lacquers intended for protection of a printed image
from mechanical damage, for giving the coating a gloss, formability and resistance to ster-
ilization in production of canning containers.
The silver background under the pattern applied by printing is created by using colour-
less transparent lacquers of various grades: AS-548, EP-5190,EP-547; the golden back-
ground is created using lacquers EP-559, FL-561, FL-560.
Enamel AS-576 is a suspension of titanium dioxide in a solution of acrylic copolymer
and epoxy resin in a mixture of solvents xylene, butyl acetate and ethyl cellosolve.
White enamel EP-5239 is a suspension of titanium dioxide in a solution of epoxy resin
E-05K, melamine-formaldehyde resin K-421-04, glycerol polyester of sebacinic acid PE-5
and epoxyester EM-34. A mixture of ethyl cellosolve, butanol and xylol is used as a solvent.
Coating lacquers are intended for application over ink impressions; they can be applied both
over preliminarily dried and raw imprints immediately after printing.
Coating lacquers are produced using various resins and their modifications, such as
alkyd, acrylic, epoxy, epoxyester, phenol-formaldehyde, melamine-formaldehyde, polyes-
ter. Aromatic hydrocarbons, esters, ketones, alcohols are used as solvents.
To endow the lacquer coating with a gliding ability and strength to scratches, waxes
and silicon additives are introduced into the composition of the lacquer. The table gives the
process parameters of coating lacquers and enamels.
Coating lacquer AS-548 is a solution of acrylic copolymer 5BV in a mixture with ep-
oxy lacquer E-33R in ethyl cellosolve and propylene carbonate. The lacquer is applied on
a roller-type lacquering machine; the thickness of the dried layer is 6 g/m2. The lacquer
coating has a good gloss, hardness, stability to sterilization in combination with protective
primer enamels, for instance, with acrylic enamel AS-576. The coating has the required
elasticity and stability to the stamping of lids and cans with the drawing depth of up to 36
mm.
Lacquer EP-5190 is a solution of epoxy resin E-05K, melamine-formaldehyde resin
K-421-04 and glycerol ester of sebacinic acid PE-5 in a mixture of solvents ethyl cellosolve,
butanol and xylol.
Upon application over dried inks, the lacquer forms a glossy solid coating and is stable
to stamping. Is recommended in combination with enamel EP-5239 for the outer coating of
containers for nonsterilized products.
Printing of labels directly on metal containers as compared with pasting paper labels
significantly increases the quality of the design of the container and reduces its cost 1.82.6
times.
Formulations of new highly efficient lacquer-and-paint materials for printing on met-
als and the monitored technological process of their application have been worked out. The
CHAPTER 5 197

development of rapidly setting materials and technological processes of their application


considerably reduces the costs and increases the quality of printing on metals (Table 5.6.2).
Table 5.6.2 Characteristics of lacquers and coatings.

Material Viscosity by VZ-4 Drying regime, Thickness of Field of


at 20C C coating, m application

Lacquer AS-548 80120 1215 min at 56 Lacquering of ink


70180C imprints for
canning containers
Lacquer EP-5190 5070 1518 min at Lacquering of ink
170175C imprints for bodies
of nonsterilized
containers
Enamel AS-576 100140 1215 min at 1518 Bodies of
clear 150160C composite cans,
stamped cans
(diameter up to 36
mm), can lids
Enamel EP-5239 110180 1518 min at 1518 Bodies of
white 150160C nonsterilized
containers

Note: Content of volatiles in the film is from 45 up to 58%.

The technological process of producing an offprint on the metal surface includes three
stages: application of the primer film; printing of an image on the primer film; coating lac-
quering of the offprint. Formation of lacquer-and-paint films at each of these stages is done
at high temperatures up to 180C for a prolonged time of up to 20 min in large-sized drying
furnaces of up to 10 m in length with large energy intensity up to 1000 kW.
The printing sheet metal is used to fabricate containers for various purposes. The larg-
est thermal, mechanical and hydrothermal impacts to which an offprint on metal is subject-
ed occur in the fabrication of one-piece canning containers. Lacquer-and-paint materials
used to produce an offprint on metal should be stable to these impacts and possess a set of
high adhesion, physicomechanical, waterproof, technological, optical and economic pa-
rameters. A number of essential performance properties of lacquer-and-paint materials are
determined not only by the quality composition but also depend significantly on conditions
of their formation. In this connection, the correct protocol of the technological process for
metals is of no less importance as compared with the composition of lacquer-and-paint ma-
terials. Most of the recommended compositions for printing on metals do not possess the
set of required properties. They are characterized by a long setting time of 1040 min at
temperatures of 120200C. Many of them become yellow or hydrolyzed, others are not
satisfactory by their mechanical and adhesion properties, which can change depending on
the setting conditions. Due to the multicomponent nature of the recommended materials for
printing on various metals the process of their setting on the offprint is very complex and
is insufficiently studied.
In printing production, two drastically different methods of film formation in printing
on metals are used, such as the removal of solvent and other low-molecular-mass compo-
nents from the ink and film formation to form a three-dimensional network. Printing inks
for metals are set on the offprint as the result of oxidative polymerization of plant drying
198 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

oils, natural and synthetic drying oils. For setting primer and coating lacquer-and-paint ma-
terials, both hardening methods can be used, i.e., polymerization and polycondensation in
combination with the evaporation of solvent.
To accelerate the processes of film formation of lacquer-and-paint materials on an off-
print, various types of irradiation are used thermal, infrared, ultraviolet, electronic the
most widespread of which for printing on sheet metal is the method of thermal intensifica-
tion. Intensification of the setting of materials in printing on metals requires the use of ex-
pensive equipment and a large consumption of thermal energy. About 25% of all production
expenses are used for setting the printing.
A major problem in the considerable improvement of printing-on-metal technologies
is the development of a set of rapidly setting lacquer-and-paint materials and a scientifically
grounded regimes of priming, printing and coating lacquering.
Owing to the specific feature of the technological process, the printing is carried out
not on metal, but on the priming layer, the base of which is a polymer film former. This
technological feature is considered as a prerequisite for constructing the printing ink, whose
setting on the offprint should be performed as the result of the interaction of its components
with the priming film. The basic requirement to the priming film is its high permeability
with respect to the solvent of the printing ink.
Priming compositions were developed based on resin PMK-5, which is a linear amor-
phous copolymer of butyl methacrylate and methacrylic acid. Modifying additives used
were epoxy resins ED-8 and ED-20, n-tert-butyl-phenol-formaldehyde resin 101l, polyalu-
mophenyl syloxane representing a lacquer of grade KO-810. The compositions were dis-
tinguished by ratios of these components. The coatings consisting of 7.5% BMK-5 and
2.5% ED-8 had the optimal properties. As a solvent, the lacquer compositions used a mix-
ture of ethyl cellosolve and butyl acetate at a ratio of 1:1.
Priming films of lacquer compositions of about 10 m thick were formed on supports
at three temperatures of 160, 180 and 200C within the time interval of 1120 min. De-
struction of splices was performed on a tensile tester at a displacement rate of the lower
clamp of 30 mm/min. The measurement of adhesion strength was carried out by the method
of shear, which makes it possible to use supports used directly in printing and corresponding
to the conditions of force impact on the film in stamping. In adhesion strength studies, hot
dipped tinplate GZhK-25 fabricated from low-carbon steel band coated with tin on both
sides was used as a support.
Printing inks with the diffusion mechanism of setting on the priming film have been
developed; their basis is a lacquer composition of copolymer BMK-5. The regularities of
migration of free plasticizers based on esters of o-phthalic acid and from solutions of phe-
nol-formaldehyde resins to priming films, as well as the kinetics of ink setting on priming
films of various compositions have been studied. o-Phthalic esters of various compositions,
such as dimethyl phthalate, dibutyl phthalate, dioctyl phthalate have been studied. These
plasticizers are characterized by the largest diffusivity.
Phenol-formaldehyde resins, such as F-60 based on para-tert-butyl phenol and form-
aldehyde; E-12 based on diphenyl propane and formaldehyde; FT-1 based on para-tert-bu-
tyl phenol, diphenyl propane and formaldehyde; modified by various compounds, were
chosen as the film-forming basis of the compositions of printing inks. The absorption ki-
netics of free phthalates by the priming film of lacquer AE-1 has an exponential character,
and the diffusion increases in the series of the plasticizers dioctyl phthalate, dibutyl phtha-
late, dimethyl phthalate. The character of the regularity of absorption by the priming film
of phthalates from solutions of resins and the ratio of the diffusion activity between
CHAPTER 5 199

phthalates remain the same as in the case of free phthalates. The studied regularities are the
basis for developing formulations of printing inks with the diffusion mechanism of setting.
The setting rate on epoxyacrylic and epoxyphenol priming films is considerably lower
when using materials and inks based on dioctyl phthalate F-60 as compared with acrylic
priming lacquer AE-1. This is due to the lower permeability of these materials determined
by the significant differences in the structure-formation mechanism in the formation of
films. With these regularities in mind, a mechanism of setting printing inks on priming films
has been proposed.
Owing to the diffusion of plasticizer to the priming film, a solid film of the printing
ink is formed on the surface of the priming film; this solid film is adhesionally bound to the
priming film. The strength of the adhesion bond is determined by the interaction of free
functional groups, available on the surface of the films. The largest adhesion strength is ob-
served in films of the printing ink and the priming lacquer AE-1, as by the moment of print-
ing the film there occurs a partial formation of a three-dimensional structure. Owing to this,
carboxyl groups of BMK-5, which were not consumed totally, interact chemically with the
hydroxyl groups of phenol-formaldehyde resin F-60, and their macromolecules preserve
the capability of intensive mutual diffusion. Studies of the effect of the printing and finish-
ing processes on the adhesion strength of priming films have been carried out. The priming
film, applied to metal and formed in the process of the first technological operation, expe-
riences various effects of the subsequent technological operations. In this connection, the
effect of such factors as the action of printing inks and coating lacquers, deformation rate
and value of deformation of the priming filmmetal system has been studied. Objects of
study were the following: acrylic lacquer AE-1, epoxyacrylic enamel AS-576, epoxyphenol
lacquer EP-547 and alkyd priming enamel, as well as alkyd inks the basis of the bonding
adhesive of which is F-60 with dioctyl phthalate, coating epoxyacrylic lacquers AS-548, as
well as coating systems from Germany and Japan.
The general regularity of the effect of an ink is a decrease of adhesion and strength, an
increase of the ultimate relative elongation of priming films. A depletion of these charac-
teristics is observed in the series of priming materials AE-1, AS-576, EP-547. A decrease
of the adhesion and strength parameters is observed within the range of 1419 down to
710%; herewith, the relative elongation increases by 718%. The change of these param-
eters correlates with the permeability of priming films with respect to the solvent. The
mechanism of change of the properties of priming films during the impact of solvent or plas-
ticizer on them is the predominant adsorption of the liquid phase on the surface of metal
and the simultaneous plastification of the bulk of the film. The adhesion strength of priming
films in combination with epoxyacrylic lacquer AS-548 increases especially significantly;
herewith, the adhesion strength of the priming film of lacquer AE-1 increases under the ac-
tion of the coating lacquer, having one film-forming base, which is used for creating a set
of rapidly setting materials.
An increase of the adhesion strength of priming films occurs owing to the diffusion of
the film-forming components of the coating lacquer through them with the solvent, which
at high temperature contributes to the increase of the concentration of reactive groups on
the surface of the support. These groups can be sorbed on the surface of the support to form
intermolecular hydrogen bonds also by way of iondipole interaction of polymer molecules
with the surface groups of the passivation film of metal.
The results of studies of the effect of film-forming and hydrothermal-treatment condi-
tions on the adhesion and physicomechanical properties of compositions made it possible
to develop formulations of priming lacquers based on acrylic copolymers, as well as rapidly
200 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

setting acrylic priming enamels and a rapidly setting coating lacquer on the same film-
forming base.
The regularities of the studies of the diffusion properties of the priming layers and dis-
solving plasticizers enabled the development of printing inks of a new type with the diffu-
sion setting mechanism. On this basis, special purpose inks have been developed, for
printing on metals and ready-prepared items from metal and glass. A feature of the devel-
oped compositions is that at the initial stage of film formation, simultaneously with the
evaporation of the solvent, an adsorption layer is created; further on, the reaction of hard-
ening proceeds in the bulk of the films and on the surface of metal to form a three-dimen-
sional structure. The setting rate of inks is determined by the rate of solvent diffusion from
resin to the priming film; an increase of temperature sharply increases the rate. The chem-
ical nature and supramolecular structure of the priming film has a significant effect on the
ink setting rate. An increase of the extent of crosslinking of molecules and a rise of density
of packing of supramolecular formations decrease the permeability of priming films with
respect to phthalates, which reduces the ink-setting rate.
Inks set on priming films by the oxidative polymerization mechanism cause no change
in the adhesion and physicomechanical properties of priming films. Inks containing dioctyl
phthalate decrease adhesion and tensile strength of priming films and increase their ultimate
relative elongation. These regularities in the change of properties of priming films depend
on their permeability with respect to the solvent. However, they do not lead to a critical
change of the performance properties of priming films. Coating lacquers containing free
functional groups increase the adhesion strength of priming films.
6 Structure and Properties of
Compositions for Protection
of Canning Containers

6.1 Ways of improving the protective properties of coatings


Despite the broad range of materials for protection of canning containers, most lacquers
used at present are produced on the basis of epoxyphenol oligomers. However, the diversity
and complexity of the technological processes of fabricating modern types of canning con-
tainers, various sterilization regimes of canned products, high requirements to the terms of
their storage compel researchers to search for ways to improve the properties of epoxy-
phenol compositions. Work is under way mainly in two directions: chemical modification
of particular components of epoxyphenol compositions, mainly phenol-formaldehyde
oligomers, and modification of epoxyphenol compositions by various additives.
To improve the physicomechanical characteristics of phenol-formaldehyde oligomers
and coatings on their basis, these oligomers are modified and plasticized. The modifier for
resol oligomers is chosen of such a structure, so that to ensure the chemical interaction of
the components of the phenol fragment by the hydroxyl and methylol groups.
Phenol-formaldehyde oligomers (PFO) on the basis of glycerol esters of parasubsti-
tuted phenols, which contain no free phenol hydroxyl groups, are known. In this case, coat-
ings have high adhesion properties and elasticity.
Of great commercial importance is etherification of methylol groups by unsaturated
fatty acids or high-molecular-mass polyesters containing hydroxyl and carboxyl groups, as
well as by unsaturated, e.g., acrylic and methacrylic, acids. A significant effect of plastifi-
cation is achieved by introduction of long-chain polyoxy compounds into the structure of
PFO. However, the chemical endurance of coatings on their basis is reduced in this case.
The most widespread way of increasing the elasticity of PFO is their etherification by
alcohols, mainly n-butyl and isobutyl alcohols. Exactly these oligomers are used in ep-
oxyphenol compositions for protection of canning containers. Epoxy-phenol coatings based
on butanolized PFO possess a set of such valuable properties as high chemical endurance
and elasticity, determined to a great extent by the level of PFO butanolization. Coatings
with a high resistance to stamping can be formed from lacquers with etherified phe-
nol-formaldehyde oligomer with a molecular mass of 250500, containing 6.011.0 wt. %
methylol groups and 18.032.9 wt. % etherified groups.
A no less efficient way to improve the protective properties of coatings is structural
modification of initial epoxyphenol compositions by various additives, in particular, by
other oligomers. It has been shown that introduction of oligourethane triisocyanate or
202 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

oligodieneurethane isocyanate in the amount of 0.120.32 wt. % as a crosslinking agent to


the composition based on epoxy and butanolized phenol-formaldehyde resin leads to an in-
crease of elasticity, adhesion and resistance of coatings to the action of organic solvents.
To increase the adhesion strength and especially stability of coatings to sterilization, a mod-
ifying additive the product of interaction of epoxy dianic oligomer with a molecular mass
of 5001100 and monopropargyl urethane taken at a molar ratio of 1:(0.21.0) is intro-
duced to the epoxyphenol composition.
Positive results were obtained in modification of commercial lacquer EP-5118 by spe-
cial additives containing various functional groups (amine, hydroxyl, cyan etc.). The com-
position obtained in this case forms coatings with internal stresses reduced 25 times as
compared with films from the initial lacquer; high chemical endurance in model food me-
dia, as well as increased stability to stamping; the amount of rejects in this case is reduced
by 2030%.
Introduction of low-molecular-mass condensate of fluorinated organosilicon com-
pounds with alkoxylyl groups into compositions makes it possible to obtain coatings for the
internal surface of containers, which prevent deposition of dairy products, oils, vinegar etc.
poured into the containers.
Hardening of epoxy resins by phenol-formaldehyde condensates is accompanied with
a number of reactions, in particular, interaction of methylol and butoxyl groups of phenol
condensate with epoxy and hydroxyl groups of epoxy resin, affecting the quality of the final
product. Therefore, the choice of the optimal ratios of the components and hardening re-
gimes of compositions presents significant problems and is mainly performed empirically.
According to the literature data, acid-resistant coatings are produced using high-
molecular-mass epoxy resins with molecular masses above 2500 and alcohol-soluble
resols, for instance, phenol and 1-cresol, both butanolized and nonbutanolized. Novolac
resins and 100% reactive resins can be used as phenol resins. Hardening of epoxyphenol
compositions proceeds better upon addition of 12% phosphoric acid; herewith, epoxy-
phenol lacquers dry at 180200C for 2030 min. To increase the quality of epoxyphenol
coatings, it is recommended to warm up the mixture of resin solutions preliminarily at
100150C.
The possibility of modifying epoxy resins with phenol-formaldehyde condensates has
been studied, and the properties of coatings on their basis have been investigated.
Low-molecular-mass resins E-40 and E-41, medium- and high-molecular-mass
epoxides E-44 and E-49, as well as resins E-15 and E-05, were used.
Modified and nonmodified resol resins cresol-formaldehyde resin K-212-01, 100%
phenol-formaldehyde resin, phenol-formaldehyde butanolized condensate modified by
Chinese wood oil, as well as xylenolphenol-formaldehyde butanolized resin and maximally
butanolized phenol-formaldehyde condensate were used as phenol-formaldehyde resins.
It has been found that all the above epoxyphenol compositions form water-resistant
coatings. Only coatings with a high-molecular-mass epoxy resin in the amount of no more
than 40% proved to be acid-resistant. Coatings on the basis of low- and medium-molecular-
mass epoxy resins proved to be non-acid-resistant.

6.2 Effect of the nature of the support on the structure and properties of
coatings
When choosing lacquer-and-paint materials for protection of canning containers, it is
necessary to take into account not only the properties of polymer materials themselves, but
CHAPTER 6 203

also the characteristics of the metal support. This is explained by the fact that the structure
and properties of the polymer coatings formed depend significantly on the nature of the
solid surface and on their thickness. The effect of the support is especially significant at a
small thickness of the coating (46 m) for canning containers.
It has been shown by example of epoxyphenol lacquer EP-547 and supports from elec-
trolytic tinplate (EZhK), chrome-plated steel (KhZhK), aluminium anodized alloy AMG-2
that the microhardness of coatings essentially depends on their thickness and nature of the
support.
The experimental data obtained indicate the predominant influence of the nature of
supports as compared with the microgeometry of their surface (the character of the distri-
bution and size of defects) on the properties of coatings formed on them. Coatings applied
on KhZhK have greater values of hardness, gradient of its change in particular layers by the
thickness of the film and the strength of the adhesion bond as compared with coatings ap-
plied on EZhK and AMG-2. This is due to the differences in the size of structural elements,
in the density of their packing, as well as in the morphology of supramolecular structures,
which differ depending on the nature of the support and thickness of coatings. It has been
found that macromolecules of the phenol-formaldehyde components are sorbed from the
lacquer mixture predominantly on the surface of KhZhK and AMG-2 in the process of hard-
ening on the surface of the support, thus forming the structure of the network framework,
whose cells are filled mainly with the epoxy component. On the contrary, in coatings from
EZhK the basis of the structure is made by the epoxy oligomer with the phenol-formalde-
hyde component evenly distributed in it.
When the thickness of the lacquer layer is increased, coatings on KhZhK and AMG-2
approach those on EZhK by their structure and properties.
The results obtained indicate that a harder and stronger coating with lacquer EP-547
on KhZhK is more stable to the action of aggressive media as compared with coatings on
EZhK, but is less stable to impact loads in stamping as the result of layer-by-layer inhomo-
geneity determined by the hardness gradient.
With account for these results, protective lacquer compositions should be chosen for
particular types of metal, used to produce canning containers, and the composition of
canned product.

6.3 Structure formation in solutions of epoxyphenol compositions and


the properties of coatings
The results of studies of chemical transformations occurring in fabrication and hardening
of epoxyphenol systems are contradictory and have not been studied sufficiently.
It is pointed out that the reactions of epoxy groups proper, considering their minor con-
tent in a real composition, do not contributed significantly to the formation of the molecular
structure and properties of a polymer. Presumably, the greatest role is played by the reac-
tions of the functional groups of phenol-formaldehyde oligomer, of partially butanolized
resol type on the basis of phenol, and substituted with phenol (-resol, n-tert-butyl phenol
etc.). The kinetics of the reactions was studied by the methods of isothermal calorimetry
and chemical analysis, as well as IRS and NMR.
Interaction of PFO and EO during the hardening of compositions occurs by methylol
and butoxyl groups of PFO with secondary hydroxyl groups and o-hydrogen atoms of phe-
nyl cycles of EO.
It is assumed that the instable quality of coatings is due to dissimilar chemical
204 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

endurances of films when using different batches of epoxy oligomer. The low chemical
endurance of coatings is related in a number of works to an insufficient crosslinking when
using different batches of epoxy oligomer.
These regularities are explained by the association of epoxy oligomer in solution. To
decrease the extent of association of epoxy oligomers, use is made of better-quality sol-
vents, which leads to a greater density of the polymer network.
An indirect characteristic of the quality of solvent and the extent of associations is con-
sidered to be the critical concentration of associate formation. It is determined using rheo-
logical methods.
It has been found that for phenol oligomer the critical concentration in ethyl cellosolve
is two times higher than that for epoxy oligomer. It is assumed that the main contribution
to the formation of associates is made by molecules of epoxy oligomer.
A decrease of the extent of association of epoxy oligomer in solution contributes to a
more even distribution of the phenol component in it and leads to an increase in the density
of the three-dimensional network. However, this worsens the performance properties of
coatings, internal stresses increase, chemical endurance goes down. This is assumed to be
due to the formation of an inhomogeneous defect structure.
The increase of internal stresses contributes to the destruction of coatings in stamping
of workpieces of canning containers.
To improve the performance properties, it is customary to perform the preliminary
forcondensation by heating the mixture of solutions of oligomers in ethyl cellosolve for sev-
eral hours. However, the mechanism of the occurring physicochemical processes in solu-
tions of mixture compositions and coatings on their basis has not been studied.
Using the method of electron microscopy, it has been found that a homogeneous glob-
ular structure is formed in coatings from forcondensates, and the size of structural elements
decreases from 500 to 50 nm.
To elucidate the case of this phenomenon, the method of light scattering was used to
study the features of structure formation in solutions of epoxyphenol compositions depend-
ing on the forcondensation conditions.
As initial components, use was made of epoxy dianic oligomer E-04Kr and butano-
lized phenol-o-cresol-formaldehyde oligomer FKoF-4.
Comparing the parameters of the chromatographically determined molecular-mass
distribution of oligomers and the molecular-structural parameters of their solutions, one can
assume the existence of particles in the form of associated molecules in solutions. Close
values of these parameters testify to a sufficiently narrow distribution of associates by mass.
Studies of the structure of forcondensate solutions has shown that the mass of particles
present in solution decreases in the course of forcondensation to reach a minimum in 1 to
1.5 h. Further on, as the duration of the heating increases, the mass of particles grows. A
change of the mean radius of inertia of particles also corresponds to this change of mass.
The thermodynamic characteristic of the affinity of the solvent to polymer is deter-
mined by the value of the second virial coefficient. Its negative value, obtained for solutions
of the initial epoxy and phenol-formaldehyde oligomer, indicates a weak oligomerethyl
cellosolve interaction. An increase of this coefficient with the duration of forcondensation
increasing is, evidently, a consequence of an improved compatibility of the components in
the process of forcondensation.
It follows from the electron-microscopy data on the change of the average size of the
structural elements in coatings depending on the forcondensation time that this regularity
is nonmonotonic and has an extremum at an optimal forcondensation time, to which the
CHAPTER 6 205

smallest size of the globular structures corresponds.


From comparison of the data on the effect of the forcondensation time on the structure
of solutions and coatings, it follows that the character of the change of size of structural el-
ements is the same both in the liquid phase and in coatings. Higher physicomechanical and
performance parameters correspond to the smallest size of the structural elements.
The method of light scattering was used to study the effect of the moment of introduc-
ing orthophosphoric acid as a structure former on the properties of epoxyphenol composi-
tions. The role of the catalyst on the structural parameters of forcondensates was studied in
solutions of ethyl cellosolve with the initial concentration of 0.4 wt. %. Forcondensation
was carried out at 120C for 1.5 h.
It follows from the data obtained that forcondensation in the presence of orthophos-
phoric acid leads to an increase by almost an order of magnitude of the mass of associates
as compared with solutions without a catalyst.
The data obtained using the light-scattering method made it possible to establish some
features of structure formation in the process of forcondensation in solutions of epoxyphe-
nol compositions. However, the regularities for diluted solutions of compositions estab-
lished using this method should have been checked in concentrated solutions.
Structural features of compositions determine their optical properties, which depend
on the transparency and refractive indices of mixed components, as well as the extent of
their dispersiveness. However, the close values of the refractive indices of solutions studied
(for epoxy oligomer 1.416 and for phenol-formaldehyde oligomer 1.409) provide for the
transparency of the mixture irrespective of its morphology in the entire range of composi-
tions, exclude the possibility of assessing the structure of the epoxyphenol composition by
controlling its optical properties.
For this reason, the rheological properties of concentrated solutions of initial oligo-
mers and epoxyphenol compositions, depending on conditions of their formation, were
studied, which reflect the occurring structural transformations.
The character of the rheological curves suggests that within concentrations up to 20%
the solutions of initial oligomers and compositions on their basis are Newton-type systems,
i.e., the dependence of viscosity on shearing stress is a straight line parallel to the abscissa
axis.
As the concentration of solutions is increased up to 4050%, their viscosity is ob-
served to rise; there are some changes in the character of the rheological curves, on which
an area of structural viscosity appears. However, the absence of a region of constant vis-
cosity indicates that in this area of concentrations solutions are weakly structured systems,
in which the number of contacts between structural elements is insignificant.
Evidently, in this case the major part of intermolecular bonds is used to form primary
aggregates of macromolecules, and only an insignificant part of them is consumed for the
bulk structuring of the system. Already at small loads there is the rupture of bonds involved
in the formation of the three-dimensional network and the breakdown of the structure to the
primary associates of macromolecules.
Thus, in the range of working concentrations of solutions from 15 upto 40% the rheo-
logical parameters of epoxyphenol compositions are characterized mainly by the lowest
Newton viscosity, whose value is determined predominantly by the size of the primary
structural elements.
The rheological characteristics of solutions of epoxyphenol compositions change sim-
ilar to the way they change in solutions of individual oligomers. Apparently, the character
of structure formation and peculiarities of interaction of oligomers with the solvent in the
206 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

mixture composition does not change.


The regularities in the character of interaction of the epoxyphenol-composition com-
ponents depending on the conditions of their compatibility is well traced in studies of the
rheological characteristics of the composition-dependent solutions assessed by the change
of the relative viscosity of the system. The curve of the viscositycomposition dependence
obtained for a mechanical mixture of epoxy and phenol-formaldehyde oligomers goes
above the additive line, which indicates a more intensive interaction in the mixture as com-
pared with solutions of individual oligomers. This deviation is much more pronounced for
solutions of forcondensates.
The viscosity of a composition changes nonmonotonically depending on the forcon-
densation conditions and reveals a minimum in the point corresponding to the smallest size
of structural formations. Evidently, an improvement of the thermodynamic compatibility
of the components in the process of forcondensation and a decrease of the size of the struc-
tural elements in the solution at a certain warmup time lead to a decrease of the system vis-
cosity. The subsequent increase of the extent of association and the worsening of the
interaction of oligomers with the solvent are accompanied with an increase of viscosity.
As the molecular mass of epoxy oligomer is increased, the regularities in the change
of the rheological properties are preserved; however, the optimal time of warming up the
composition slightly increases.
To establish the relationship between the processes of structure formation in solutions
of epoxyphenol compositions and in the formation of coatings on their basis, as well as to
study the effect of the supramolecular structure of the coatings on their properties, the struc-
ture of films was studied by the method of electron microscopy. It has been found that coat-
ings from a mechanical mixture of epoxy oligomer and phenol-formaldehyde oligomer
reveal an inhomogeneous defect structure from large structural elements of 500700 nm in
size, which form a sparse three-dimensional network. A preliminary warming-up of the
composition contributes to an increase of the structural homogeneity of films and a decrease
of the size of supramolecular formations; the more homogeneous structure is formed in
coatings from forcondensates obtained at an optimal warmup time. The size of globular for-
mations in such coatings is 5070 nm. An increase of the forcondensation time as compared
with the optimal time leads to the aggregation of structural elements and the formation of
large associates 0.20.3 m in diameter.
The structural features of films determine the value of vapour permeability and the ex-
tent of their swelling in butyl acetate. The lowest value of vapour permeability corresponds
to films with the finest globular structure. The extent of hardening of coatings in this case
is at its maximum, so they are less prone to swelling. An increase of the size of structural
elements with the forcondensation time greater than the optimal value leads to a rise of va-
pour permeability of the films and a decrease of the extent of their hardening.
Comparison of the data of structural transformations in solutions of epoxyphenol com-
positions and the results of structure studies suggests that the regularities of structure for-
mation in the liquid phase are well consistent with the structural changes in the formation
of coatings. Evidently, the formation of an ordered structure of the coatings is a con-
sequence of an increased structural homogeneity and an improvement of compatibility of
epoxyphenol-composition components in forcondensation in an optimal temperaturetime
regime.
Structural features of coatings are closely related to the value of internal stresses,
which, in turn, has an effect on the main performance properties of the coatings, for in-
stance, adhesion and mechanical stress. The kinetics of change of internal stresses in the
CHAPTER 6 207

formation of coatings and the effect of various physicochemical factors on their value,
including the regime and compatibility of components in production of epoxyphenol
lacquers, have been studied.
The kinetics of change of internal stresses in the formation of coatings from epoxy-
phenol compositions depending on the conditions of matching the initial components has
been studied; it has been found that the rate of increment and the value of internal stresses
depend on temperature and time of forcondensation.
The ultimate values of internal stresses in coatings from a mixture of epoxy oligomer
and phenol-formaldehyde oligomer not subjected to forcondensation settle in 0.51.0 h
after the onset of hardening, and subsequently remain invariable. Forcondensation leads to
a significant acceleration of the coating formation process, which is completed in 1520
min.
The value of internal stresses decreases with the increase of the warmup time of the
compositions up to 11.5 h. The further increase of the forcondensation time increases the
internal stresses. Similar regularities in their change are also observed in the formation of
coatings from forcondensates obtained at lower temperatures; however, in this case the min-
imum shifts towards larger warmup times and the value of the ultimate stresses slightly in-
crease. An increase of the forcondensation temperature above 120C also leads to the
increment of internal stresses in hardened films.
Comparative characteristics of coatings from epoxyphenol compositions with ratios of
the components E-04Kr : FKoF-4 = 80 : 20 wt. % depending on the heating time are given
in Table 6.1.
Table 6.1

Duration of Content of gel Internal stress, Tensile Chemical endurance in 3%


heating, h fraction, % MPa strength, MPa CH3COOH at 100C, h

0 76.1 4.55.0 6.8 3.5


0.5 78.0 3.53.8 7.3 3.5
1.5 80.4 2.8 8.0 4.5
6.0 67.2 4.24.5 7.1 3.5

Comparison of the results of structural studies with the data of the change of the prop-
erties of coatings shows that the increase of the structural homogeneity of films in forcon-
densation in an optimal regime contributes to the increment of the strength and protection
characteristics of the coatings, as well as to a decrease of internal stresses.
The correct choice of the temperaturetime conditions of forming the coatings makes
it possible to create an optimal supramolecular structure, which provides for high perfor-
mance parameters.
The effect of the hardening regime of epoxyphenol coatings on their structural features
and physicomechanical characteristics was studied. Coatings based on epoxyphenol com-
positions with the ratio of components E-04Kr with the average molecular mass of 5 103
and FKoF-4 equal to 80:20, heated under optimal conditions at 120C for 1.5 h, were
formed within the temperature range of 200400C. The coating formation process was
studied by the kinetics of change of internal stresses in the process of their hardening. It was
found that the hardening rate increased significantly with the formation temperature rising.
At 300C, this process takes several seconds; herewith, the dependence of ultimate values
of internal stresses is of extremal character and reaches its highest value at 250300C.
208 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The dependence of internal stresses on hardening time is also nonmonotonic. Upon


reaching a maximum, they decrease the larger, the higher the temperature is. The complete-
ness of coatings hardening was controlled by the content of gel fraction after extraction in
Soxhlet extraction apparatus, because the theoretical calculation of the crosslinking density
is difficult to make for the systems studied due to the high molecular mass and functional
polydispersity of the components. It has been found that the most complete hardening of
the system is achieved at a temperature of 250300C.
The results of the differential thermogravimetric analysis have shown that in the tem-
perature range of 280300C the polymer is subjected to thermodestruction; with the con-
tent of epoxy oligomer in the composition increasing the temperature of the onset of thermo-
destruction decreases.
It follows from the electron-microscopic studies of the structure of coatings hardened
at various temperature regimes that coatings hardened at 200250C have a homogeneous
structure with the size of supramolecular formations of 5070 nm. Herewith, the features
of structure formation correlate with the structure observed in the solution of epoxyphenol
compositions in the process of forcondensation.
An increase of the coating formation temperature leads to the emergence of more com-
plex structural forms of various morphologies; herewith, globules and associates of
globules are distributed unevenly in the general mass of the film.
Intensive destruction processes at temperatures above 300C lead to the rupture of
chemical and physical bonds to form low-molecular-mass products and the formation of an
uneven network from chain-type structures; herewith, the physicomechanical and protec-
tive characteristics worsen (Table 6.2).
Table 6.2

Hardening regime Characteristics of coatings

Temperature, Duration Content of gel Internal stress, Chemical endurance in 3%


C fraction, % MPa CH3COOH at 100C, h

200 20 min 75.6 2.83.0 4.0


250 10 min 80.4 3.53.8 4.5
300 2 min 81.1 3.84.0 4.5
390 40 sec 49.5 2.52.8 3.5

Analysis of the obtained results suggests that the warming up of a mixture of oligomers
at 120C contributes to the formation of a homogeneous ordered structure at the coating-
hardening temperature of 250300C.

6.4 Dependence of the properties of can lacquers on the structure of


phenol-formaldehyde oligomers
The hardening regime of coatings based on epoxyphenol lacquers depends on the type of
metal, the support. For tinplate, it is 210C for 1015 min; for aluminium, 360390C for
3040 sec. In the latter case, owing to the strong thermal shock, the properties of coatings
worsen in the process of hardening. With account for this, a wide range of epoxyphenol lac-
quers, for instance, EP-527, EP-547, EP-5118, etc. are manufactured by Russian industry;
mainly lacquer EP-5118 is used, which does not always provide for the required properties
CHAPTER 6 209

of the coatings, which should combine the high chemical endurance to sterilization in so-
lutions of tartaric and acetic acids and sodium chloride and withstand stamping.
The phenol-formaldehyde component imparts chemical endurance to coatings based
on epoxyphenol compositions, as well as determines the stability of coatings at stringent
hardening regimes 360390C for 3040 sec.
It has been found that the properties of coatings are significantly affected by the char-
acteristics of phenol in synthesis of phenol-formaldehyde oligomer, such as molecular
mass, molecular-mass distribution, content of methylol groups, extent of their butanoliza-
tion. The currently existing technology for production of these oligomers does not make
possible the directed regulation and qualitative assessment of their characteristics. Using
this process, a large amount of waste waters is produced up to 3000 kg/t; herewith, com-
mercial oligomers contain no more than 10% (by weight) of butoxyl groups.
A new technology of producing phenol-formaldehyde oligomers has been developed.
The process makes it possible to separate in time the reactions occurring in their synthesis
(hydroxymethylation of phenol, polycondensation of methylol derivatives of phenol, ether-
ification of methylol groups) and to decrease the amount of waste waters to no more than
120 kg/t.
The process developed was used to synthesize butoxylated oligomers on various phe-
nols: phenol proper, cresols, xylenols and diphenylol propane. The latter were tested in
epoxyphenol lacquers for internal protection of canning containers.
The choice of this phenol was due to a number of reasons:
use of phenol with the hinged link contributes to the increase of the physicome-
chanical properties;
high functionality of diphenylol propane with respect to formaldehyde makes it pos-
sible to produce oligomers with a sufficiently high content of butoxyl and free methylol
groups;
decrease of the relative share of methylol bridges in these oligomers as compared
with oligomers based on other phenols makes it possible to increase the resistance to
thermal shock.
A new type of high temperature-hardened epoxyphenol compositions based on o-alky-
lated phenol-formaldehyde oligomers for fabrication of rapidly drying lacquers to form
coatings with high physicomechanical and protective properties has been developed. These
oligomers of grade OAPFO are characterized by a low reactivity of methylol groups at room
temperature and a practically unlimited stability in storage. After 1224 months of storage
they do not change their properties, whereas in other phenol oligomers the formation of gel
particles and delamination are observed. The reactivity of OAPFO strongly changes with
the rise of temperature, owing to which at temperatures greater than 350C the coatings on
their basis are distinguished by a high degree of hardening, thus providing for a good hard-
ness and thermal stability (Table 6.3).
The effect of the features of structure formation in solutions of epoxyphenol compo-
sitions has been studied.
It has been shown that epoxyphenol compositions with OAPFO on the basis of me-
chanical mixtures are not inferior than and sometimes even exceed coatings based on tra-
ditional forcondensates with the component matching regime optimal for butanolized PFO.
Based on the data on the studies of the hardening process of epoxyphenol coatings, a general
scheme of the process has been proposed for OAPFO-based compositions. It has been
shown that the determining reaction in hardening, as in the case of coatings based on
210 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

butanolized phenol-formaldehyde resol oligomers, is the interaction of methylol groups one


with another.

Table 6.3 Optimization of hardening regimes.

Hardening regime Content of gel fraction, wt. %

Time, min Temperature, C PFO-based coatings OAPFO-based coatings

60 100 10.4
90 100 12.4
120 100 19.8
15 210 75.6 82.5
10 250 80.4 83.9
2 300 81.1 52.1
40 sec 360 83.9
40 sec 390 49.5 88.0

Comparative studies of epoxyphenol coatings, hardened at 360C for 3060 sec,


based on etherified and nonetherified phenol formaldehyde oligomers o-alkylated with
dimethyl sulfate, butyl glycidyl ester and glycilyl ester of higher isomeric carboxylic acids,
as well as commercial oligomer FPF-1 show that coatings based on OAPFO are character-
ized by a higher adhesion strength, elasticity, chemical endurance and lower vapour perme-
ability as compared with coatings from compositions with butanolized phenol-
formaldehyde oligomer as the result of the decreased contribution of side reactions.
In the series of epoxyphenol coatings based on those o-alkylated with butyl glycidyl
ester the best set of properties is with coatings with butanolized o-alkylated phenol-
formaldehyde oligomer synthesized at a phenol : formaldehyde : butyl glycidyl ester molar
ratios of 1.0 : 1.78 : 0.33 and 1.0 : 2.5 : 0.33. In the latter case, coatings have a higher extent
of hardening and low vapour permeability (Table 6.4).

Table 6.4 Properties of epoxy phenol coatings based on forcondensates and mechanical mixtures
of epoxy oligomer and OAPFO oligomer (at ratios 80:20, wt. %), hardened at 360C.

Ratio, mol/mol Content, mol/mol OAPFO Mn Fabrication Chemical


phenol technique endurance,
points
Formal- BGE Phenol CH2OH CH2 OC4H9
dehyde OH group

1.78 0.33 1.779 0.908 0.959 540 mm* 5.0


1.78 0.33 1.779 0.908 0.959 540 fc** 5.0
2.50 0.33 1.659 1.200 1.007 620 mm 5.0
2.50 0.33 1.659 1.200 1.007 620 fc 5.0
1.78 0.50 0.727 0.894 0.946 580 mm 3.0
1.78 0.50 0.727 0.894 0.946 580 fc 3.0
2.50 0.50 0.709 1.200 1.005 670 mm 3.0
2.50 0.50 0.709 1.200 1.005 670 pc 3.5

*mm, mechanical mixture; **fc, forcondensate.


CHAPTER 6 211

For coatings mentioned in the table, the adhesion strength in bending is, in millimeters,
1 (according to a ShG-1 curvimeter), besides coatings from composition 4, for which this
parameter is equal to 3.
Epoxy-phenol lacquers based on diphenylol propane-formaldehyde oligomers with a
high content of butoxyl groups form coatings, satisfying all the requirements imposed on
can varnishes. At any hardening regime, including the rapid high-temperature drying, they
form chemically stable coatings withholding stamping and suitable for fabrication of cans
with the drawing coefficient up to 1.7.
For coatings from lacquer EP-5118 and a composition based on OAPFO, the effect of
the stage of forcondensation on the internal stresses in the formation of coatings was
studied. Forcondensations were shown to contribute to a decrease of stresses in coatings
from lacquer EP-5118; herewith, the forcondensation stage has no effect on internal stresses
and is not required.
Coatings from a composition based on OAPFO without forcondensation are charac-
terized by a higher adhesion strength, chemical endurance in water and acetic acid as com-
pared with coatings from compositions obtained via the forcondensation stage, as well as
by a higher adhesion and stability to stamping unlike coatings from composition EP-5118
(Table 6.5).
Table 6.5 Effect of the forcondensation stage on the properties of epoxy phenol coatings (at an EO
and PFO ratio of 80:20).

Composition Adhesion Chemical endurance, points Stampability,


strength, points
points H2O 3% solution of CH3COOH

EP-5118 with fc 3 5 4 4
OAPFO-based without fc 1 5 4 5
OAPFO-based with fc 2 4 3 5

The effect of the ratio of epoxy oligomer and OAPFO on the properties of coatings
was studied. It has been shown that at a component ratio of 80:20, 75:25 and 70:30 the coat-
ings are characterized by the same values of internal stresses. The difference is that at a ratio
of 75:25 and 70:30 coatings harden for 10 sec at 350C, and at a ratio of 80:20, for 1.5 min.
Coatings from compositions with the ratio of 80:20, though they have lower stresses, by
their protective properties and strength are inferior to compositions with the ratio of 75:25
(Table 6.6).

Table 6.6 Effect of the ratio of epoxy oligomer and phenol-formaldehyde oligomer on the
properties of coatings.

Ratio of EP Properties of coatings


and OAPFO,
wt. % Content of gel Bending Adhesion Chemical endurance, points
fraction, strength, strength,
wt. % mm points H2O 3% solution of CH3COOH

80 : 20 84.0 1 2 5 4
75 : 25 86.1 1 1 4 5
70 : 30 81.3 3 2 4 3
212 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The use of novel chemically modified epoxyphenol lacquers makes it possible to sig-
nificantly reduce rejects in container fabrication, to expand the range of packaged products,
to increase storage times of canned products due to a better protection of the inner surface
of metal stamped containers form the impact of biochemically active media.
The effect of chemical composition and synthesis conditions on the molecular charac-
teristic of PFO was studied. As initial components in their synthesis, use was made of phe-
nol, cresols, n-tert-butyl phenol, 3,4-xylenol and mixtures of phenol with these compounds.
The best results using linear PFO were obtained on the basis of n- and o-cresol-formalde-
hyde oligomers (Table 6.7).

Table 6.7 Properties of coatings.

Base of PFO Mn of PFO CH2OH, A, b, P108, Chemical endurance,


PFO mol points MPa g/(cm2 h) points

p-cresol 280 0.92 1 3.8 3.0 4.2


o-cresol 355 0.98 1 3.1 3.5 3.8
n-TBP 350 0.98 3 2.0 7.0 1.5
3,4-xylenol 375 0.96 2 2.8 4.5 2.4
p-cresol 290 0.75 2 2.5 3.5 3.5
p-cresol 250 0.90 2.9 3.2 4.5
p-cresol 290 0.96 3.1 3.0 4.5
o-cresol 460 1.35 5.0 2.5 4.0
o-cresol 500 1.48 5.4 2.7 4.0
phenol 490 1.68 6.8 2.0 4.0

6.5 Fields of application of canning containers and methods of their


modification
Diversification of canning products is accompanied by the improvement of packagings. The
relative share of metal containers increases, as well as that of small consumer containers in
the form of tinplate cans, packagings from combined materials on the basis of aluminium
foil for ready-prepared sterilized and frozen meals.
Sterilized ready-prepared meals and semi-finished convenience products are produced
in tinplate cans of various sizes. They contain several gobbets and by their taste are not in-
ferior than the meals prepared by traditional cooking methods. Before use, they are warmed
up and portioned.
A wide assortment of sterilized ready-prepared meals and convenience foods have
been mastered, for instance, stuffed pepper with meat, stuffed cabbage leaves with meat,
veal with garnish, etc. packaged using metal containers.
Tinplate containers are used for packaging convenience foods, which passed a culinary
treatment and can be used after a small additional processing mixing, addition of spices,
warming-up, roasting. Meat semi-finished products are usually combined with canned veg-
etable semiproducts.
Tinplate cans are used to package dietary foods, whose output continuously increases.
A ranking place in using this group of packagings is occupied by medicated food products
beverages enriched with pectin, fruit desserts from natural fruit puree apricots, apples,
pears, quince or carrots with addition of sugar syrup. These products are recommended
CHAPTER 6 213

in prophylaxis and therapy of diseases related to the increased content of fats and choles-
terol in the blood, chronic coronary insufficiency after infarction.
Metal containers are widely used in production of fruit preserves juices, stewed
fruits, drinks based on fruit syrups, apple concentrates and other fruits with natural aroma-
tizers. Aceptic packagings for tomato concentrate are introduced, as well as special tubes
based on metallized materials.
Traditional types of containers for production of canned food in this country are metal
cans from tinplate and aluminium, as well as glass jars with lids from tinplate, chrome-
plated steel or aluminium. In the case of glass containers, expenses for transportation and
storage of canned products as well as due to breakage of jars, are much greater. Use of metal
containers decreases the labour intensity and duration of sterilization, increases labour pro-
ductivity, reduces the requirement in storage facilities.
Production of canning containers in the recent years makes use of advanced materials,
such as aluminium, chrome-plated and aluminized steel instead of deficit tinplate, as well
as materials with a reduced thickness of the tin layer on tinplate.
Protective coatings on rolled metal materials are produced using high-speed lines,
which provide for hardening of the lacquer in several seconds at 350390C. The design
and assortment of produced canning containers have changed. Widely used are deep drawn
cans, welded-seam composite cans, stamped and composite cans from two different metals,
tubes, etc.
Resource-saving technologies and equipment for production of metal containers have
been developed. Machines for fabrication of two-piece aluminium cans provide for the
economy of materials without decreasing the parameters of strength in compression. This
is achieved due to the improvement of the shape of the bottom, which, in turn, makes it pos-
sible to decrease the thickness of the walls to 0.28 mm. Based on the use of new equipment,
the extent of the change of can volume in the process of pasteurization is significantly de-
creased.
Introduction of new types of technological and transport containers, as well as
advanced technologies of their fabrication from preliminarily lacquered aluminium band by
the method of deep drawing impose stringent requirements to the quality of
lacquer-and-paint coatings, especially for its internal protection, and an increase of shelf
life. The major of them are biochemical stability, high strength and elasticity, which provide
for a sharp decrease of internal stresses in the formation of coatings and the impact of me-
chanical fields in stamping.
Compositions widely used in industry for protection of canning containers are
epoxyphenol compositions based on high-molecular-mass oligomer hardened with
phenol-formaldehyde oligomer EP-5118, modified with a mixture of glyptal and poly-
phenyl silaxane resin Ko-815. A significant drawback of coatings based on this lacquer are
high internal stresses, small elasticity and low chemical endurance, which hinders their use
in production of one-piece canning containers.
Methods of modifying epoxyphenol lacquers have been developed, which make it pos-
sible to increase the resistance of protective coatings to the action of biochemically active
media and mechanical fields in stamping. The modification methods are based on introduc-
tion of special texturing agents into compositions.
The object of study were epoxyphenol compositions with the epoxy oligomer and
phenol-formaldehyde oligomer ratio of 80:20, as for commercial lacquer EP-5118. To
make the components compatible, forcondensation at 120C for 1 h was carried out. In the
subsequent mixing, orthophosphoric acid was added as a catalyst, as well as modifying
214 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

agents, containing various functional groups, such as amine, hydroxyl, cyan etc. As the re-
sult, a modified composition with higher protective properties and chemical endurance as
compared with the initial composition was developed. The thickness of coatings, stability
to stamping, chemical endurance and internal stresses were studied.
In accordance with technical specifications, the thickness of coatings was determined
by a micrometer gauge and by the weight method; it was 5 mm. The endurance of coatings
to mechanical impacts was assessed in stamping of cylindrical cups 33 mm in diameter with
the elongation coefficient of 0.6 (the ratio of height to diameter) and was expressed as a
percentage of destroyed coating. The chemical endurance of stamped specimens was stud-
ied under standard conditions in model media for 60 min at a pressure of 100 kPa (1 atm)
and 120C. It was assessed in points:
5 points lacquer coatings without changes;
4 points the inner surface with barely noticeable changes in the form of separate
strokes or points by the angles of drawing;
3 points insignificant change of colour and gloss, barely noticeable peeling;
2 points change of colour and gloss, peeling, spots of curling of lacquer;
1 points curling of lacquer over the entire surface.

Chemical endurance of lacquer coatings was assessed by the change of electrochemi-


cal potential on a potentiostat P-5827 in an electrolytic cell for electrochemical studies
with the determination of the breakdown potential. The specimen was held in solution for
10 min. In the process of polarization, the current density was measured after each 50 mV.
Internal stresses were measured by the photoelastic method (Table 6.8).
Table 6.8 Protective properties of coatings.

Composition Chemical endurance, points , Extent of b,


of lacquer, mV breakdown MPa
% 3% solution 2% solution 3% solution Distilled of coatings,
of acetic of tartaric of sodium water %
acid acid chloride

No additives 3/2 3/2 3/2 3/2 450 2030 1.0


2.1 4 4/5 4/5 5 +400 Abrasions 0.5
3.2 5/4 5 5 5 +813 No abrasions 0.2
4.5 4/5 5 4/5 5 +450 Abrasions 0.4

Note: The slashed numbers indicate the limits of measured values for a series of 10 specimens.

It is seen from the table that coatings based on basic commercial lacquers are charac-
terized by a low stability to stamping and protective properties in various media within the
range of 3 and 3/2 points. Chemical endurance of coatings from compositions modified by
organosilicon compounds increased significantly up to 5 and 5/4 points. For modified
coatings, the breakdown potential is significantly shifted to the positive side, the stability
of coatings to stamping increases as the result of the decrease of internal stresses. The su-
pramolecular structure of coatings was studied by the method of electron microscopy; it was
shown that the size of structural elements decreased as the result of modification to 0.4 m.
For nonmodified coatings, larger supramolecular formations of up to 0.85 m in size were
observed. It follows from these data that introduction of a modifier leads to the formation
CHAPTER 6 215

of coatings with an ordered structure.


To improve the performance properties of can varnishes and to impart a high elasticity
to coatings on their basis, they are modified by epoxyesters of various molecular masses.
The properties of coatings based on epoxyphenol compositions from the mixture of epoxy
oligomer E-04kr and phenol-formaldehyde resin FPF-1 at a ratio of 1.5:1 were studied.
The epoxyesters used were synthesized from epoxy oligomers ED-20 with an average
molecular mass of 400; E-44, with a molecular mass1600; E-05k, with a molecular mass of
3000; and oleic acid, taken at an equimolar ratio of 1:1, and in the base of E-05k also at a
ratio of 1:2. The former epoxyesters are monoepoxyesters; the latter, a diester.
The most significant barrier effect for the diffusion of corrosion agents through the
protective film was observed for coatings modified by monoepoxyesters based on the most
low molecular-mass oligomer ED-20 in the amount of 20%.
The effect of epoxyesters on the protective properties of coatings is confirmed also by
the results of the assessment of chemical endurance in sterilization in model media. The
protective action of coatings is determined not only by the barrier properties of polymer
films, but also by the adhesion strength. The results of determining the character of coat-
ings adhesion strength change after sterilization have shown that coatings containing a
modifier based on E-05k have a greater stability of adhesion properties.
The effect of film polarity decrease affecting the diffusion of the corrosion medium
increases with the rise of the concentration of monoepoxyester. This is, evidently, due to
the distribution of weakly polar fatty radicals in the bulk of the polar epoxyphenol matrix.
Studies of epoxy polymers have shown that a decrease of their polarity is accompanied with
a decrease of the sorption of water molecules and electrolyte ions.
By the example of epoxyphenol lacquers EP-547 and EP-547M, it has been found that
a decrease of polarity of coatings using higher-molecular-mass epoxy oligomers leads to an
increased stability at the action of aggressive sterilization media.
When passing from monoepoxyester to diester, the dielectric permeability of coatings
increases. We suggest that this is due to an increase of the volume content of strongly polar
ester groupings, whose dipole moment is 2.5D. Presumably, this explains an increase of the
value of cathodic current in substitution of monoepoxyester (MEE) to diester in composi-
tions based on E-05k. The level of dielectric losses of coatings in the introduction of
epoxyesters increases in all cases because of the rise of mobility of small fragments of ster-
ically structured molecules owing to the plasticizing action of modifiers (Table 6.9).
Thus, introduction of plasticizing epoxyester modifiers into the epoxyphenol compo-
sition enhances the mechanical and protective properties of coatings. This effects is more
Table 6.9 Effect of modifiers on the adhesion of epoxy coatings in aggressive media.

Medium Preservation of adhesion (%) of coatings,


with 20 wt. % modifier

No modifier MEE DE

ED-20 E-14 E-05k E-05k

Distilled water 60 100 98 98 100


3% solution of tartaric acid 50 98 95 98 98
3% solution of acetic acid 70 100 95 98 98
3% solution of sodium chloride 80 100 99 98 100
216 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

pronounced when using low-molecular-mass epoxyesters as modifiers.


The properties of epoxyphenol coatings depend on the structure and optimal ratio of
the functional groups in phenol oligomer. Mixtures of phenol and n-tert-butyl phenol of the
type of FPF-1 within a broad range of values of functional groups, bridging linkages, aver-
age molecular masses were synthesized. The range of values in wt. % of oxymethyl groups
was 2.514.6; of butoxymethyl groups, 9.022.0; methylene bridges, from 1.3 up to 5.6;
oxymethyl bonds, from 0.3 up to 4.4; the molecular mass of the oligomers was changed
within the limits of 290650.
It has been found that epoxyphenol compositions based on the given mixture phenols
with the mass fraction of butoxymethyl groups of 913% do not provide for the required
stability of coatings to stamping, at an increase of their content to 1822% the elasticity of
the coatings was significantly improved. An increase of the mass fraction of the oxymethyl
groups from 2.55.6% up to 814% worsens the elasticity and stability of specimens to
stamping.
It has been shown that coatings from lacquer EP-547 on tinplate provide for a relative-
ly high stability to stamping, combined with the acceptable chemical endurance and adhe-
sion. These oligomers are distinguished with a high content of butoxymethyl groups
(1618%) and methylene bridges (3.24.1%) at a comparatively low content of the oxym-
ethyl groups within the range of 6.110% and dimethylene oxide bridging linkages of
1.02.3%. Herewith, the residual content of free phenols in individual specimens was about
8% and had no negative effect on the quality of the coatings.
It follows from these data that variation of the structure of phenol oligomer within suf-
ficiently wide limits of the functional groups and bridging linkages does not make it possi-
ble to produce lacquer coatings, which would combine a high chemical endurance with
mechanical properties. When designing compositions, it is necessary to take into account
which characteristics of coatings are preferable for a particular purpose composite or
stamped containers, aggressiveness of the product stored.

6.6 Structure and properties of coatings based on epoxy oligomers


Protective and decorative polymer coatings are distinguished by a diversity of properties
depending on their purpose and performance conditions. Their specific features are that
they are formed as thin films on the surface of solid bodies (rigid and soft supports). De-
pending on the purpose, polymer coatings should satisfy various mechanical, adhesive,
thermophysical and electrophysical properties, and in some cases also such specific param-
eters as the sensitivity to a definite radiation range, bactericidal and fungicidal properties,
certain porosity, thermal stability, incombustibility etc. A combination of these properties
is achieved mainly by synthesizing polymers with certain functional groups and chain struc-
ture, molecular and supramolecular structure, as well as the result of their physical and
chemical modification.
Depending on the chemical composition of film formers, the nature of the functional
groups and formation conditions, the coatings produced can have a linear, branched and net-
work structure.
The decorative properties of coatings are changed and the protective properties are in-
creased also by adding organic dies, mineral pigments and reinforcing fillers. The proper-
ties of coatings can be regulated within broad ranges by their physical modification with
the aim to form a homogeneous structure.
To develop the physicochemical bases of forming polymer coatings, it is necessary to
CHAPTER 6 217

study the peculiar features of structure formation and properties of various types of film
formers, their effect on the specific features of structural transformations at various stages
of polymer coatings and their properties formation.
The process of forming coatings is accompanied with the emergence of local bonds
between the most active groups of macromolecules and other structural elements, and has
much in common with the mechanism of gel formation. When conducting these studies,
special attention was paid to the effect of the nature of the support on the structure and prop-
erties of coatings and interphase layers, as well as to the process of their formation. Mani-
festation of the special properties of the boundary layers, determined by the orienting effect
of the support, particles of the filler or fibrous reinforcing materials, is not restricted by the
bounds of one or several molecular layers, but significantly affects the structure and prop-
erties of the coatings on the whole. The specific features of polymer coatings are that they
are formed as comparatively thin films on the supports that adhere well to polymer, so the
surface phenomena play an important role in the formation of their structure and properties.
The structure of coatings from epoxy resin ED-20 obtained on a glass support at 80C
was studied. It has been found that a sharp change in the structure of the layers is observed
in the layers bordering with the support and the air. Away from the border (100200 nm)
the structure of middle layers is stabilized and does not change significantly in passing from
one layer to another. At the interface with the support, the structure was homogeneous and
globular owing to the adsorption interaction of the film former with the surface of the sup-
port and a sharply slowed-down mobility of the structural elements. Away from the inter-
face with the support, owing to the increase of the mobility of structural elements, they are
observed to aggregate to form more complex structures up to 100200 nm in size.
The inhomogeneity of the structure of coatings is preserved during their formation at
various supports and under different hardening conditions. Addition of active fillers to the
system increases the inhomogeneity of the structure. The authors studied the structure of
various layers of coatings 200 mm thick from epoxy resin ED-20 formed on a glass support
at 150C. It has been shown that in surface layers bordering the air the polymerization is
the most rapid, and a thin homogeneous structure is fixed, which coincides by its size with
the associates observed in the initial oligomer. The largest aggregation of structural ele-
ments, which accompanies the formation of a complex secondary supramolecular structure,
is observed in middle layers of the coatings. The change of the nature of the support renders
a specific effect on the structure of individual layers of the coatings, not eliminating its in-
homogeneity by the thickness of the film. From the data on the structure of epoxy coatings,
but formed on block copper, it follows that in layers bordering with the support there occurs
a structure, which reflects the granular texture of the support. In the surface layers, struc-
tural elements are observed to aggregate to form more complex secondary structures. At
the introduction of active fillers, in particular 4 wt. % rutile, the structural inhomogeneity
of these coatings is significantly increased.
A substantial feature of polymer coatings is that surface phenomena have a significant
effect not only on the character of the structural transformations, but also on the rate of re-
laxation processes and the properties of coatings. The retardation of relaxation processes in
the formation of coatings, which is due to local links between structural elements and ad-
sorption interaction of the film former with the surface of the support, is accompanied by a
sharp increment of internal stresses.
Internal stresses are determined by the shrinkage of gels produced in the formation of
coatings; they start to manifest themselves after the coatings are formed owing to the
inhibition of the relaxation processes. In this connection, internal stresses in coatings are
218 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

affected by the factors determining the rate of the gel formation process. These factors, be-
sides the concentration of the initial solution, also include the effect of the nature of solvent
and various texturing agents.
One of the ways of decreasing internal stresses is regulation of the relaxation processes
at the polymersupport and polymerfiller interfaces, which enables creating a homoge-
neous ordered structure in coatings.
Internal stresses emerging in the formation of coatings have a significant effect of the
mechanical, adhesion, electrophysical, thermophysical and other properties of coatings and
are a criterion, which determines their durability. In this connection, of special importance
are studies of the effect of various physicochemical and technological factors on the value
of stress in the formation and ageing of polymer, in particular, epoxy, coatings.
The value of internal stresses is significantly affected by the molecular mass of mole-
cules of a film former; it has an effect on their flexibility, conformation and structure-
mechanical properties of the system, as well as the number and nature of bonds, the char-
acter of their distribution in the system.
One of the features of polymer coatings is that their structure and properties are inho-
mogeneous along the thickness of the film and depend on it. The cause of this phenomenon
is due to the uneven hardening of coatings along the thickness of the film and to the effect
of adsorption interaction of the film former with the support. The work presents the data on
the study of the supramolecular structure of various layers of epoxy coatings 50, 200 and
400 m in thickness. The greatest differences in the structure along the thickness of the film
are found for coatings of 50 and 200 m in thickness. As the thickness of epoxy coatings
increases up to 400 m, the inhomogeneity of the structure along the thickness of the coat-
ing is preserved, but the size of the structural elements in middle layers ana those bordering
with the air decreases from 300 to 3040 nm, as the result of which the structure becomes
more homogeneous along the thickness of the coatings than for coatings of smaller thick-
ness. A decrease of the size of structural elements, apparently, leads to an increase of the
intermolecular interaction. This is accompanied with an increment of internal stresses with
the increase of the film thickness and decrease of the thermophysical parameters.
Rheological, thermophysical, physicomechanical and structural studies have shown
that at the first stage of coatings formation from oligomer systems local bonds are formed
within the limits of a small number of molecules or between individual associates. The pro-
cess is accompanied by the formation of supramolecular structures or aggregation of the
available structural elements. At the second stage, links emerge between these structures,
which lead to a sharp inhibition of relaxation processes and increment of internal stresses.
This character of structure formation was observed in the development of the three-
dimensional network from epoxides and solutions of epoxides.
In production of coatings from solutions of polymers and oligomer systems, to prevent
the formation of an inhomogeneous structure consisting of large aggregated structural ele-
ments, at the initial stage of their formation film formers were modified by texturing agents.
These agents contain functional groups capable of chemically interacting with molecules
of the film former and with the surface of solid bodies used as supports and fillers.
-Aminopropyltriethoxysilane (AGM-9) was used as a structural additive to improve
the properties of epoxy coatings. Introduction of a texturing agent in an optimal amount
(0.070.25%) to epoxides was shown to contribute to the decrease of internal stresses in
the system at a simultaneous increase of strength, adhesion and durability of the coatings.
At a large concentration of a modifier (more than 1%), other properties were noted to wors-
en together with the decrease of internal stresses.
CHAPTER 6 219

One of the ways to decrease internal stresses in the formation of coatings is the action
of a magnetic field on the system. Under optimal conditions, the magnetic field plays the
role of a dispersant preventing the aggregation of structural elements and contributing to
the formation of a homogeneous three-dimensional network from associated macromole-
cules. The effect of a magnetic field on structure formation in solutions of epoxy oligomer,
the formation of coatings and their physicomechanical properties have been studied. A
homogeneous globular structure with globules 1520 nm in size was found to be formed
at the action of a magnetic field with the optimal parameters. It was concluded that the ac-
tion of a magnetic field under these conditions is related not to the orientation of structural
elements along the direction of the force lines, but to the fixation of associates in the oligo-
mer system and to the elimination of the effect of their aggregation in the process of hard-
ening. This character of structure formation contributes to the sharp decrease of internal
stresses, a significant (1.53-fold) increase of adhesion and strength of coatings.
The effect of structuring of the system under the action of a magnetic field, which pre-
vents the aggregation of structural elements in the process of their hardening and contrib-
utes to the significant improvement of the physicomechanical characteristics is observed
both for unfilled systems and for systems filled with ferromagnetics and diamagnetics.

6.7 Technology of producing protective polymer coatings


The process of producing polymer coatings consists of main and auxiliary operations. The
former include processes determining the quality of coatings produced: preparation of the
surface of an article prior to the application of material, application of material, hardening
(drying) of material. The auxiliary operations include additional processes improving the
decorative properties of some coatings. For instance, grinding of intermediate layers and
polishing of the upper layers of coatings formed.
Preparation of the surface of an article largely determines the service life of the coat-
ings. Lacquer-and-paint material of even the best quality would not provide for the protec-
tion of metal from corrosion, if it is applied to an unprepared surface.
Preparation of the surface of an article for painting is the first operation in the process
of producing coatings.
Performance properties of coatings largely depend on the method of preparation and
the purity of treatment of the surface. The more aggressive the medium in which the article
used is, the more thoroughly its surface should be prepared for painting.
Durability and other performance properties of coatings from the same lacquer-
and-paint material depend on the process of its production, which is due to the corrosion
resistance of metal, composition of corrosion products formed on the metal surface, tech-
nology of fabricating the articles (its shape, configuration, size) and preparation of the sur-
face before painting.
Lacquer-and-paint coatings protect the surfaces of black metals (articles from rolled
steel, iron and steel castings) and nonferrous metals (items from galvanized and cadmium-
plated steel; magnesium, aluminium, copper and their alloys).
Preparation of the surface consists in the removal of metal corrosion products (rust),
oxide scale, contamination by fats and conservation agents, by other accretions preventing
a good adhesion of metal to material applied.
The preparation method is chosen depending on the metal from which the item is fab-
ricated, its size and design, the initial state of the surface, the requirements to the class of
coatings and performance conditions of the item.
220 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

In industry, for items from black metals, use is made of mechanical, thermal and chem-
ical methods of surface preparation. For surfaces from nonferrous metals, treatment with
thermal and partially mechanical methods is totally ruled out. Chemical methods of surface
purification of metal items include degreasing, etching, removal of old coatings, as well as
methods of rust removal and phosphatizing.
An important operation in the coating production process is application of material.
Only the use of advanced, automated methods of application makes it possible to complete-
ly realize all the potential possibilities inherent in material itself, and also to prevent the loss
of material, which is especially important in the current deficit of lacquer-and-paint mate-
rials.
Progress in the chemistry of high-molecular-mass compounds contributed to the com-
mercial production of various oligomers and polymers and led to the development of
high-quality lacquer-and-paint materials and polymer coatings on their basis. The improve-
ment of the quality of materials and expansion of their range was accompanied with the im-
provement of the existing and development of new application methods. From manual
methods, such as using brushes, swaps, the industry moved to modern methods: pneumatic,
electrostatic and airless spraying, jet glazing, electrodeposition.
Application of fluid lacquer-and-paint materials on a solid surface is based on:
(a) their conversion to aerosols followed by deposition and coagulation in a thin layer;
(b) wetting of the surface (adsorption);
(c) deposition (sedimentation) of a substance from the liquid medium (solution or dis-
persion) at the action of an electric current, heating;
(d) adsorption from the gaseous or vapour phase.
The most frequently used method of applying lacquer-and-paint materials is spraying.
Depending on the type of dispersant, there are the following dispersion methods:
pneumatic or aerodynamic spraying without or with heating; in this case, material is
atomized by a jet of compressed air;
hydraulic or hydrodynamic spraying at low and high pressure, with or without heat-
ing; in this method, material is supplied under a high pressure via the nozzle of a sprayer as
the result of a sharp pressure differential;
electrostatic spraying, which leads to the formation of aerosol due to the action of
electrical forces.
The second group of methods are dipping, glazing; painting by rolls, in drums, by
brushes and other manual implements. Their performance requires a direct contact of the
solid surface with the liquid lacquer-and-paint material and as complete as possible inter-
action (wetting).
The recent years witness a noticeably increased interest in the roller method due to the
sharply expanded production of painted sheets and rolls. The roller method compares
favourably with other methods by its high performance, a high coefficient of utilization of
lacquer-and-paint materials, a relatively good quality of coatings (even thickness, absence
of chagrin). Application of materials by this method is an automated process performed on
special roller-type machines.
The electrodeposition method is used to apply water-base lacquer-and-paint materials:
water-borne and water-soluble.
One of the stages of the production of coatings, which determines their quality, is the
hardening of the applied lacquer-and-paint material, which in practice is called drying.
Drying is the process of converting a liquid material into a solid state to form a film.
The state of a lacquer-and-paint coating depending on the duration and temperature of
CHAPTER 6 221

the drying is characterized by the extent of dryout. By the mechanism of coatings harden-
ing, film formers are divided into two classes. The first class includes film formers, the for-
mation of films from which occurs without chemical reactions due to the physical
dryout determined by the evaporation of the liquid phase. One of the main conditions of
producing coatings based on film formers of the first class is the slow increment of the vis-
cosity of the system. At a rapid evaporation of the solvent, not only surface defects of the
film can be possible in the formed coatings but also large internal stresses, which lead to a
significant decrease of the physicomechanical characteristics of coatings. Besides, in rapid
evaporation of the solvent the different viscosities of the surface and internal layers con-
tribute to the formation of unstable supramolecular structures in the film, which stipulate a
decrease of the physicomechanical and protective properties of coatings. Lacquer-and-paint
materials hardened by the mechanism of physical drying include coatings based on solu-
tions and dispersions of polymers of various chemical composition, cellulose ethers and es-
ters, and other film formers.
The second class of materials hardened by chemical drying includes film formers,
the formation of coatings from which occurs due to the chemical interaction of the systems
components. The hardening process of such coatings is a rather complex phenomenon, as
along with the removal of solvent, it involves chemical reactions contributing to the forma-
tion of a spatially crosslinked polymer. This class includes materials based on reactive oli-
gomer, oil-containing film formers and other materials coatings from which in most cases
represent spatially crosslinked polymers.
When choosing the kind, method and regime of coatings hardening, the factors to be
mainly considered are the type of lacquer-and-paint material, type of support, size and con-
figuration of articles, performance and energy intensity.
There are two types of coatings hardening: natural and artificial. In natural hardening,
coatings are dried in the open or indoors at an ambient temperature of 1225C and relative
humidity of no more than 65%. Advantages of natural hardening are the possibility to form
a coating on large-sized articles, simplicity of equipment and low power consumption; how-
ever, natural drying is, as a rule, long-term and can not be used commercially for
alkyd-melamine, epoxy, phenol-formaldehyde and other film formers; it also totally rules
out the possibility of automation of the process.
Artificial hardening of coatings is the impact of heat, light, radiation on the material;
they provide for the conversion of liquid material to the solid state prior to the formation of
the film. Depending on the method of impact, the following methods of coatings hardening
are to be distinguished: thermal, ultraviolet light, radiation. Production of aluminium can-
ning strip includes the following process operations: casting of ingots in an electromagnetic
crystallizer, machining of the ingots, heating of the ingots, hot rolling to produce rolled
products, cutting of the side edge, cold rolling, stretch flattening, anodizing and lacquering,
longitudinal cutting of the strip or transverse cutting for sheets, packaging of the final ma-
terial. The quality of the surface of aluminium plays the main role in its use for fabrication
of canning containers. If the surface of aluminium does not correspond to the imposed re-
quirements, all advantages of its use lose importance. Therefore, cold-rolled metal is sub-
jected to a special surface treatment, as the result of which the natural oxide film is
substituted for the artificially created one, with a certain structure and properties. This is
achieved by the method of anodic treatment.
Formation of the anodic film is the result of two simultaneous processes: electrochem-
ical formation of the film and its chemical dissolution. At the initial stage, when current
passes through the electrolyte in which aluminium serves as an anode, negatively charged
222 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

oxygen ions move to the anode, where they discharge by coupling with aluminium. As the
result of this reaction, a thin continuous film of aluminium oxide is formed on the surface.
Under the dissolving action of the electrolyte, this continuous film is converted to a porous
film. Oxygen ions penetrate through the porous film, and a continuous film again is formed
under it. Thus, in the anodizing process the porous film gradually becomes thicker to form
a cellular structure.
The thin film under the pores is also called the barrier layer and is a protection from
corrosion. To increase its protective functions, the pores are to be occluded. The pore oc-
clusion process is called consolidation and is achieved by a special treatment or application
of a lacquer-and-paint coating.
Anodizing of the aluminium canning strip is performed on a complex continuous line,
where the anodizing and lacquering processes are carried out consecutively.
Depending on the purpose of canning aluminium, one or both sides of the strip are lac-
quered. In the two-side process, the lacquer is applied simultaneously on both sides of the
continuously moving strip by means of rubber rollers. The thickness of the lacquer film is
regulated from 2.5 up to 6 m. The thin coating is applied on the side, which will be outer
after the cans are fabricated. The thickness of the applied layer is determined by many pa-
rameters: the gaps between the rollers, the ratio of the peripheral speeds of rotation of the
rollers and the transport of the covered surface, the distribution of the lacquer-and-paint ma-
terial between the surfaces after the gaps are passed.
Drying of the lacquer is performed in a convection-type tunnel drying furnace. As lac-
quer is applied simultaneously on both sides, when passing through the furnace the strip is
not supported but is held due to the tension. The maximally admissible sag of the strip and
the strength of metal determine the length of the drying furnace, and, therefore, at a fixed
velocity of the strip transport equal to 60 m/min, the drying time, which is 3040 sec. Spe-
cial lacquers prepared based on epoxy, phenol and vinyl resins and capable of being dried
at a temperature of 250350C, are used for coatings of canning containers. When choosing
the type of lacquer, one should take into account the performance conditions of the coatings.

6.8 Specific features of forming epoxyphenol coatings for canning


containers
Introduction of aluminium alloys in canning industry instead of tinplate opens wide possi-
bilities for manufacturers of cans. Such, for instance, as fabrication of cans of various con-
figurations by stamping, decrease of their weight, increase of the productivity of stamping
automatic machines, due to the fabrication of cans directly from rolls, development of new
types of closure, in particular easily opened lids. However, aluminium alloys, in contrast
with, for instance, hot-dipped tinplate, could not be used in canning industry without a pro-
tective lacquer-and-paint coating.
Compositions used the most for protection of canned food containers are epoxyphenol
lacquers. A combination of epoxy oligomer and phenol-formaldehyde oligomer in these
lacquers enables production of coatings with high adhesion to the support and good physi-
comechanical properties, inherent in epoxy materials, and high protective properties char-
acteristic of phenol-formaldehyde lacquers.
Until recently, epoxyphenol compositions were made up mainly empirically, because
the processes occurring in the interaction of epoxy and phenol-formaldehyde oligomers
were studied insufficiently. Up to the present, the scientific bases of creating compositions
from epoxyphenol systems and protective coatings resistant to biochemically active media
CHAPTER 6 223

2 1

b.10, MPa
3

0 5 10 1 2 3 4 , min

Figure 6.1 Effect of the ratio of the epoxy and phenol components on internal stresses: 1,
EO/OAPFO = 75:25; 2, EO/OAPFO = 70:30; 3, EO/OAPFO = 80:20.

have not been developed. In this connection, epoxy and epoxyphenol lacquers for chemi-
cally stable protective coatings produced in this country are characterized by a low stability
to biochemical media, in particular, to solutions of organic acids (acetic, lactic, malic), to
enzymes, amino acids and other components of food media. Interaction of epoxy and phe-
nol oligomers has been shown to be of a complex character due to the presence in them of
various functional groups, which can react one with another. Herewith, the probability of
some or other reactions, and, therefore, the properties of coatings depend both on the initial
composition and on the conditions of coatings formation: the presence of catalysts, plasti-
cizing additives, application and drying of lacquer compositions, type of solvent, character
of the support (Fig. 6.1).
Most often, epoxy lacquers are produced based on high-molecular-mass epoxy dianic
oligomer. It has been shown that the optimal set of coatings properties is provided for by
the use of epoxy oligomers (EO) with the molecular mass Mn ~ 3500. Herewith, it has been
found that the elasticity of coatings increases with the rise of molecular mass of EO, but
their chemical endurance to acidic media decreases.
Coatings based on low- and medium-molecular-mass (molecular mass up to 2000) EO
proved to be non-acid-resistant. Only introduction of high-molecular-mass oligomer (Mn
~ 3500), but in the amount of no more than 40%, provided for a sufficient acid resistance
of the coatings. It has also been shown that introduction of high-molecular-mass EO into
epoxyphenol compositions based on low-molecular-mass EO leads to an increase of the ad-
hesion strength of the coatings.
As a rule, PFO of resol type are used to produce can varnishes. Minor amounts of
cresols, xylenols, naphthols are used as the phenol component. Introduction of PFO on sub-
stituted phenols, for instance, p-tert-butyl phenol, to epoxyphenol compositions contributes
to the increase of the physicomechanical properties of coatings. However, chemical endur-
ance and the depth of hardening of the coatings increase at the increase of the content of
unsubstituted phenol in PFO. With the increase of the share of EO in the system, the elas-
ticity of the coatings was found to rise; and as the share of PFO increased, chemical endur-
ance increased, which is of special importance in production of canning strip.
224 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

5
1
4

3 2
b.10, MPa

3
1

0 10 5 10 20 30 , min

Figure 6.2 Kinetics of the change of internal stresses in hardening of epoxyphenol compositions: 1,
EP-5118 without fc; 2, EP-5118 with fc; 3, EPC based on OAPFO with fc; 4, EPC based on OAPFO
without fc.

In most cases, to produce lacquers, initial EO and PFO are mixed at a given ratio and
are subjected to a preliminary heating forcondensation. The purpose of forcondensation
is to improve the compatibility of EO and PFO, which are poorly compatible at the usual
temperature. It has been noted that a preheating improves the properties of coatings of even
well compatible oligomers, decreases internal stresses (Fig. 6.2). A relationship between
the processes of structure formation in solutions and the structure and properties of coatings
has been established. It has been shown that the structural features and performance prop-
erties of coatings based on epoxyphenol compositions are determined to a significant extent
by structural transformations, occurring at the stage of matching EO and PFO solutions
their forcondensation.
In diluted solutions (in ethyl cellosolve) of EO and PFO and compositions on their ba-
sis, the primary structural formations are associates of molecules. The affinity to association
is sufficiently pronounced in such solutions owing to the high molecular mass and polarity
of the initial components.
As the molecular mass of EO rises, the extent of structuring of solutions considerably
increases. The structures emerging in concentrated solutions of epoxyphenol compositions
have the character of a fluctuation network from associates of macromolecules.
Forcondensation leads to the change in the character of interaction in solutions of ep-
oxyphenol compositions, which is due to the accompanying chemical and physicomechan-
ical processes. It has been found that in forcondensation owing to intensive thermal motion
of macromolecules and mechanical impact on the solution, there occurs the dispersion of
macromolecule associates, which is accompanied with a decrease of the viscosity of the so-
lution. Disruption of the structure in the process of heatup also leads to the change of the
composition of associates.
An increase of the structural inhomogeneity of forcondensates heated under optimal
conditions leads to an increase of the uniformity of the distribution of the structural
CHAPTER 6 225

5 1
3
2
4
in, MPa
3

1
0 1.0 2.0 3.0 4.0
Forcondensation time, h

Figure 6.3 Dependence of the ultimate values of internal stresses in coatings from epoxyphenol
forcondensates heated at 100C (1), 120C (2) and 130C (3), on the duration of forcondensation.

elements in hardened coatings, which, in turn, contributes to the decrease of internal stresses
and an improvement of performance characteristics of coatings. Evidently, the formation
of a homogeneous small-globular structure, where the formation of chemical and physical
bonds is maximally realized, provides for the rigidity and stability of the spatial structure
of a highly crosslinked polymer. This, in turn, determines the high strength and protection
properties of coatings.
The further heating leads to the aggregation of structural elements to larger associates,
as the result of which a defect network is formed. Internal stresses in such coatings are twice
as large as in coatings with the homogeneous small-globular structure, which can be due to
the emergence of large structural elements, at the interface of which an internal stress is con-
centrated (Fig. 6.3).
Thus, the properties of coatings can be regulated by changing the size of the structural
elements in solutions of forcondensates. Optimal from the point of view of achieving the
homogeneity of solutions, and, therefore, hardened coatings, is the heating at 120C for
1.52.0 h depending on the molecular mass of the EO used; its increase leads to the increase
of the optimal time of forcondensation (Fig. 6.4).
The choice of the forcondensate hardening regime is of great significance. It is known
that the correct choice of the temperaturetime conditions of forming coatings would make
it possible to produce coatings with an optimal supramolecular structure, which provides
for their high performance properties. In this connection, the authors studied the effect of
the hardening regime of epoxyphenol coatings on their structural features and physicome-
chanical characteristics. It was found that the process of forming coatings was considerably
accelerated with the rise of temperature and at the hardening at higher than 300C occurred
within several seconds (3040 sec). The completeness of the coatings hardening was con-
trolled by the content of the gel fraction. The most complete hardening of the system is
achieved at 280300C (the content of the gel fraction, 7580%). Within the temperature
range above 300C, thermooxidative destruction of polymer begins; it is accompanied with
an intensive loss of the mass, and with the increase of the content of EO in the composition
the thermodestruction onset temperature slightly decreased.
226 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

5
4
4 1
2
3

in, MPa
3

0 1.0 2.0 3.0 4.0 5.0 6.0


Hardening time, h

Figure 6.4 Change of internal stresses in the formation of coatings from epoxyphenol compositions
heated at 100C (1), 110C (2), 120C (3) and 130C (4), Thard = 200C.

6 5
1
5

4 2
4
in, MPa

3
3
2

0 1.0 2.0 3.0 4.0 5.0 6.0


Hardening time, h

Figure 6.5 Change of internal stresses in the hardening at 200C of coatings produced from: 1, A
mechanical mixture of epoxy and phenol-formaldehyde oligomers (E-04Kr:FKoF-4 = 80:20 wt. %);
2 4, forcondensates heated for 0.5 h (2), 1.0 1.5 h (3) and 3 6 h (4); 5, forcondensation without cat-
alyst, hardened with H3PO4.

We also showed how the change of the temperature regime of formation affects the
structural features of coatings. It was concluded that the high-temperature hardening of ep-
oxyphenol coatings (at 350390C) is undesirable, as intensive destruction processes lead
to a worsening of the performance properties of coatings. The conclusion was made that the
optimal formation temperature of epoxyphenol coatings is 250300C (Fig. 6.5).
As we already said, coatings are formed based on a preliminarily obtained forconden-
sate by heating a mixture of alcohol solutions of oligomers at 100120C for several hours.
Due to the diversity of combinations of functional groups in epoxyphenol composi-
tions, the chemical reactions occurring in forcondensation and hardening are rather diverse.
Herewith, the probability of this or that reaction depends both on the composition and
CHAPTER 6 227

conditions of these processes their temperature, duration, presence and type of catalyst.
Studies carried out at the Chair of the Chemistry and Technology of Lacquers, Paints
and Coating Compositions, D.I. Mendeleyev University of Chemical Technology,
Moscow, made it possible to establish the main schemes and kinetic regularities of the re-
actions proceeding in forcondensation and hardening of such compositions.
It has been shown that under conditions of acid catalysis in forcondensation there is
no chemical interaction between epoxy and phenol-formaldehyde oligomers. Epoxy oligo-
mer reacts to the catalyst orthophosphoric acid by the scheme
OH OH
CH CH2 + HO P O CH CH2O P O (I)
OH OH OH

OH
CH CH2 + CH CH2 O P O
O
OH OH
OH O
CH CH2O P O CH CH2O P O CH2 CH (II)
OH OH OH

O
CH CH2 + HO P (O CH2 CH)2 (CH CH2O)3 P O (III)
O
OH OH OH
Herewith, all three hydroxyl groups prove to be reactive with respect to the a-oxide
groups of epoxy oligomer.
Phosphate groupings formed by reaction (I)(III) in the presence of orthophosphoric
acid and partial organic phosphates are readily subjected to hydrolysis, owing to which
a-oxide groups of epoxy oligomer turn to glycol ones.
The presence of orthophosphoric acid and partial phosphates also contributes to the
interaction (proceeding at a sufficiently high rate) of a-oxide groups of epoxy oligomer with
the dissolving alcohol (ethyl cellosolve or n-butyl alcohol introduced into the reaction mix-
ture together with phenol-formaldehyde oligomer):
CH CH2 + HOR CH(OH)CH2OR, (IV)
O
where R is C2H5OCH2CH2 or HC4H9 .
Phenol-formaldehyde oligomer in the presence of orthophosphoric acid is subjected
to etherification by the same alcohols.
OH OH

+ HOR (V)

CH2OH CH2OR
228 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Forcondensation under conditions of the basic (in particular KOH) catalysis, efficient
for the reaction of a-oxides with alcohols, leads to the formation of epoxyphenol-
formaldehyde copolymers. In this case, there also occurs condensation of methylol groups
of resol oligomer

2 HO CH2 OH + CH2O + H2O (VI)

CH2OH
and their etherification, predominantly by ethyl cellosolve
OH OH

+ HOCH2CH2OC2H5 (VII)

CH2OH CH2OCH2CH2OC2H5
The features of hardening of the epoxyphenol composition are determined by the na-
ture and ratio of the functional groups remaining after forcondensation, as well as the hard-
ening conditions (temperature, type and concentration of the catalyst used). In industry,
epoxyphenol coatings are usually hardened at high temperatures. Thus, for instance, can
varnishes on tinplate are hardened at temperatures of 473523 K (200250%) for 10 min;
and on aluminium, at 633 K (360C) and higher for 3040 sec.
As a hardening catalyst of epoxyphenol compositions, orthophosphoric acid is used
the most often.
The study of the hardening process (T = 473 K) has shown that in this case a-oxide
groups of epoxy oligomer react with phenol hydroxyl groups:

CH CH2 + HO CH CH2 O (VIII)


O
OH

and with secondary hydroxyl groups:


CH2
CH CH2 + CH2 CH CH2 CH CH2 O CH (IX)
O
OH CH2
Besides, secondary hydroxyl groups enter into a re-etherification reaction with phos-
phate groupings formed in the reaction of orthophosphoric acid with epoxy oligomer at the
stage of forcondensation. However, the greatest rate in the hardening is with the reactions
of methylol groups of resol between one another and with etherified methylol groups:

2 HO CH2OH HO CH2OCH2 OH (X)


CHAPTER 6 229

HO CH2OH + ROCH2 OH

HO CH2OCH2 OH (XI)

All reactions with participation of methylol groups are catalyzed by orthophosphoric


acid and its partial esters.
Besides, it has been found that under conditions of high (473 K) temperatures the hard-
ening can not occur due to the interaction of secondary hydroxyl groups with methylol ones,
because the groupings formed in this reaction are unstable at temperatures higher than
175C and are subjected to further conversions as follows:
CH2 CH CH2 CH2 CH CH2
OH O
+
CH2OH CH2 CH2 (XII)

Products of further
OH OH conversions
(oxidation, polymerization)

As a catalyst of hardening of epoxyphenol compositions, the most frequently used


agent is orthophosphoric acid, whose introduction accelerates the hardening process. This
is supported by experimental data. Thus, introduction of an additional amount of catalyst
orthophosphoric acid increases the content of the gel fraction in the hardened film. How-
ever, the amount of orthophosphoric acid added should be minimal as far as possible, be-
cause in this case lacquers are distinguished by a better stability, and their hardening
(especially under high-temperature conditions, at 360C) would be complicated to a smaller
degree by undesirable oxidative side reactions of phenol-formaldehyde oligomer, which de-
teriorate the quality of coatings.
It is noted that the considerable change of the properties of epoxyphenol coatings can
be achieved by introduction of minor amounts (35%) of oligomer modifiers into initial
compositions. Introduction of such additives makes it possible to create an ordered structure
in epoxyphenol systems and coatings on their basis and to improve significantly their prop-
erties. The structural transformations occurring in epoxyphenol compositions depend on the
type and functionality of the modifying oligomer, as well as on the ratio of viscosities of
oligomers and their matching conditions.
230 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY
7 Ways of Increasing
the Protective Properties
of Coatings for Canning
Containers

7.1 Coatings with enhanced adhesion to aluminium and its alloys


It is much more difficult to obtain a coating with a high adhesion to aluminium and its alloys
than to most other metals, because at other equal conditions adhesion of polymers decreases
in the sequence: nickel, steel, iron, copper, brass, aluminium, tin, lead.
Special attention is paid to the possibility of producing coatings, which satisfy the
stringent requirements for adhesion, water resistance and capability of hardening under
conditions of comparatively low temperatures up to 120C. One of the major ways to in-
crease adhesion and water resistance of coatings based on epoxy compositions is modifica-
tion of oligomers or introduction of various additives, improving adhesion and water
resistance, into compositions. To improve the adhesion properties, it is proposed to intro-
duce up to 20% modifying polymers, which possess a lower surface tension as compared
with the main polymer, as well as various organosilicon compounds in the amount from
0.01 up to 20%. Among other substances, modifying polymers include (CH2)3Si(OCH3)3,
Br2C6H3Si(OCH3)3, (CH3)2N(CH2)3Si(OCH3)3.
It has been shown that minor amounts of polymethyl silazan significantly improve ad-
hesion, water resistance and other performance parameters. As active thinners, it is recom-
mended to add glycidoxysilanes. The effect of increasing adhesion to metals, especially to
aluminium and its alloys, as well as an improvement of water resistance is revealed in mod-
ification of epoxy compositions by epoxysilane in the amount of 0.15%; this modification
increases the strength of coatings.
Silicon-containing compounds are used as modifiers of epoxy oligomers; herewith,
mixture compositions are used. Good results are observed in introduction of 3070% of
epoxy oligomer modified by siloxane compounds.
An increase of adhesion to aluminium and resistance of coatings to the action of boil-
ing water and 5% alkali liquor is observed in modification of epoxy coatings by epoxyure-
thane oligomers or polyurethanes with terminal isocyanate groups, which are produced by
the interaction of various diisocyanates with diols having molecular masses up to 200, at a
ratio of diisocyanate to diol from 1.2:1 up to 1.75:1. These compositions are recommended
as primers with increased adhesion to aluminium. For this purpose, epoxyurethane oligo-
mers, containing aliphatic epoxy oligomer were developed.
232 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Polymers, which are products of combined modification of epoxy oligomers with acry-
lates and diisocyanates, were found to have similar properties. These compounds contain a
set of active groups, such as carboxyl, hydroxyl, epoxy, methylol, amide and amine ones.
Polyisocyanates are capable of hardening at room temperature to form coatings with
high mechanical properties and adhesion to metals, as epoxyurethanes with a three-dimen-
sional structure are formed in the process of their hardening. From the comparison of po-
tentially possible ways of introducing urethane groups into epoxy oligomer as the result of
their modification and hardening of epoxy compositions by polyisocyanates, the former
should be recognized to be the best approach, because it is not associated with the use of
toxic isocyanates in preparation of lacquer compositions. In this case, the application pro-
cess is harmless and yields compositions stable in storage and air moisture-resistant. A
promising way is to use as hardeners compounds with urethane groups, containing no free
isocyanate groups. In this case, the reaction of hardening is provided for by the presence of
other functional groups capable of reacting with epoxy oligomer in the hardener. Coatings
of this composition are hardened at room temperature for seven days and are distinguished
by good adhesion and mechanical properties and low water absorption. Similar parameters
are characteristic of coatings from epoxy oligomers with hardener Versamide A-115.
Epoxy coatings hardened by compounds in which the silicon atom is bound to amino
or aminosubstituted groups, as well as compounds of the type of alkoxysilyl propylamine
have been shown to have high performance properties. These compositions are used for pro-
tection of metal surfaces in contact with hot water. Their structure is
R1
H2N R2O Si O R2 NH2,
R2

where R1 (CH3)n , C2H5 , C3H7 , C6H5, R 2 (CH2)x , x = 2 4; n = 1 30.


An increase of adhesion of coatings to aluminium was achieved by a special treatment
of metal before lacquering. For this purpose, use is made of primers based on products of
the interaction of oxyalkyl(meth)acrylates with anhydrides of dicarboxylic acids. They are
best to be applied to the metal surface before lacquering.
The formulation of similar compositions often includes silicon-containing com-
pounds, such as epoxysilanes and aminosilanes. These additives make it possible to in-
crease two times the adhesion of coatings to aluminium. Application of these compounds
improves the properties in painting metals with compositions based on other polymers.

7.2 The role of solvent in the formation of the properties of coatings for
canning containers
Polymer compositions based on epoxy oligomers are widely used in production of protec-
tive and decorative coatings on canning containers. Along with a rich set of properties (high
adhesion and cohesion strength, resistance to alkali liquors), they possess an insufficient
chemical endurance to organic acids (acetic, lactic, tartaric etc.), stamping, as well as insta-
bility of the performance properties. It has been shown that the instability is due to the emer-
gence of internal stresses owing to the slowdown of the relaxation processes in the
formation and operation of coatings. A significant effect on the value of internal stresses
and the kinetics of their increment is rendered by the specific features of the structure
CHAPTER 7 233

formation in oligomer systems. This is stipulated by the fact that dilute and concentrated
solutions of oligomers are strongly associated systems.
It has been found that the structure of associates, their size and morphology depend on
the chemical composition of oligomer, the nature of solvent, the conditions of coatings for-
mation and other physicochemical factors. In particular, a significant effect on structural
transformations in epoxy compositions, as well as on the structure and properties of coat-
ings, is rendered by the nature of solvent.
The effect of the nature of solvent on structure formation in epoxy and epoxyalkyd
compositions, as well on the structure and properties of coatings on their basis, used for can-
ning containers to improve their performance properties, was studied.
Compositions were produced on the basis of epoxy oligomer E-33 and its mixture with
alkyd oligomer at a ratio of 70:30. Orthophosphoric acid was used as a catalyst of harden-
ing. Coatings were applied using 50% solutions in solvents widely used in industry and dis-
tinguished with the affinity to oligomer systems: xylol, tributyl phosphate, ethyl cellosolve,
carbitol, butyl glycol.
The rheological properties were studied on a Shvedov-type instrument with coaxial
cylinders. The structure of coatings was studied by the method of electron microscopy by
taking carbon-platinum replicas from the surface of coatings subjected to oxygen etching
in the optimal mode. The adhesion strength of coatings to aluminium was determined by
the detachment method. The stressstrain parameters were studied on an Instron instru-
ment.
The gloss of coatings was assessed on a goniophotometer. The coating-formation pro-
cess was studied by comparing the kinetics of increment of internal stresses with that of po-
lymerization and release of the solvent at various stages of hardening. The quality of the
solvent was assessed by the rheological properties of the solutions of oligomers.
From the data on the dependence of viscosity on shearing stress for solutions of epoxy
oligomer in various solvents and in mixtures of tributyl phosphate with butyl carbitol (BC)
and butyl glycol (BG) at a ratio of 1:2, it follows that all solvents are in practice semistruc-
tured systems or Newton-type compositions. The lowest viscosity was observed for solu-
tions of oligomer in butylene glycol. Solutions of oligomer in tributyl phosphate (TBP) and
carbitol (C) are distinguished with a much higher viscosity. Herewith, the initial solvents
are semistructured systems, which differ little one from another by the character of the rheo-
logical curves.
In accordance with the HildebrandScatchard theory, the quality of a solvent with re-
spect to a polymer can be assessed by the similarity of the values of their solubility param-
eters; it is the square root of the cohesion energy density. When assessing the affinity of a
solvent to a polymer, it is also desirable to take into account the contribution to the cohesion
energy density of intermolecular forces of diverse nature (dispersion, polar, hydrogen, as-
sociation interaction). The interaction of each of these types is taken account of by deter-
mining, respectively, parameters d, p, h, a).
The characteristics of epoxy compositions studied and solvents used are presented in
Table 7.1.
By the proximity of the parameters of solvents solubility and epoxy composition, all
systems can be arranged in the sequence: butylene glycol, ethyl cellosolve, carbitol, tributyl
phosphate, xylol.
Butylene glycol and ethyl cellosolve, along with dispersion interaction, also exhibit
other types of intermolecular interaction characteristic of a film former. This is indicative
of a better quality of these solvents as compared with others.
234 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 7.1 Solubility characteristics of epoxy oligomer and solvents.

Compounds Thard, C Solubility parameters (MJ/m3)1/2

d p h a

Epoxy composition 23.5 17.3 11.2 11.2 15.9


Butylene glycol 230 23.0 15.9 5.7 15.7 16.7
Ethyl cellosolve 130 24.1 16.0 9.3 14.3 17.4
Carbitol 202 22.4 15.4 16.3
Tributyl phosphate 177 18.6
Xylol 138 17.8 17.2

The quality of a solvent was also assessed by the rheological properties of the solutions
of oligomers. From the data on the dependence of viscosity on shearing stress for solutions
of oligomers in various solvents and in mixtures of tributyl phosphate with carbitol and
butylene glycol at a 1:2 ratio, it follows that all solutions represent semistructured or
Newton-type systems. It could be suggested that solutions of oligomer in a good solvent
would form coatings with the finest and homogeneous structure and, respectively, with a
greater density of the three-dimensional network and better physicomechanical character-
istics. However, the obtained experimental data on the effect of the nature of solvent on the
network density, structure and properties of coatings failed to confirm this suggestion. By
the method of electron microscopy, it has been found that coatings from solutions of oligo-
mer in tributyl phosphate are distinguished by the most homogeneous structure with the size
of morphologically anisodiametric structural elements of 1015 nm. With the quality of the
solvent improved, structural elements are observed to aggregate to form a nonhomogeneous
globular structure. The size of aggregates increases in passing from carbitol to butylene gly-
col and xylol up to 0.20.5 m.
To elucidate the causes of this phenomenon, the process of coatings formation from
solutions of oligomer in various solvents was studied by comparing the data on the kinetics
of the release of solvent and the kinetics of polymerization of compositions with the change
of internal stresses in the process of hardening. From the kinetics of increment of internal
stresses in the formation of coatings at 180C from solutions of oligomer in various sol-
vents, it follows that the least internal stresses are observed in the formation of coatings
from solutions of oligomer in tributyl phosphate, as well as in its mixture with other sol-
vents. With the quality of the solvent improving or worsening, internal stresses increase;
what is more, spontaneous delamination of coatings is observed for coatings from solutions
in xylol. From the data on the kinetics of the release of the solvent in the formation of epoxy
coatings under the same conditions from solutions of oligomer in various solvents, it fol-
lows that the solvent is eliminated the most rapidly in the formation of coatings from solu-
tions of oligomer in butylene glycol. With the quality of the solvent worsening, the time up
to its equilibrium concentration in the system increases and the rate of its evaporation sharp-
ly slows down. This indicates that the chosen solvents interact with oligomer differently,
though its boiling temperature is the same as the boiling temperature of butylene glycol.
When studying the effect of the nature of the solvent on the polymerization kinetics of
compositions, a significant part of chemical bonds has been found to emerge after the sol-
vent is released. This indicates the occurrence of polymerization in the solid phase, i.e., after
the solvent release. With the release rate increasing, the incompleteness of the relaxation
processes also rises, which is accompanied by a sharp increment of internal stresses.
CHAPTER 7 235

Similar regularities were obtained in studies of structure formation in solutions of


epoxyalkyd compositions filled with rutile dioxide. From the data on the dependence of vis-
cosity on shearing stress for solutions of an epoxyalkyd composition in various solvents, it
follows that by the absolute value their viscosity is larger than that of epoxy oligomers.
However, the regularities of the effect on the nature of the solvent on the rheological prop-
erties of compositions remain the same. Solutions of compositions in a good solvent are dis-
tinguished with the lowest viscosity. With the worsening of the quality of a solvent, the
viscosity increases. Similar regularities are also observed in the kinetics of solvent release
in the formation of epoxyalkyd compositions.
From the data on the effect on the nature of solvent on the kinetics of increment of in-
ternal stresses in the formation of coatings from epoxyalkyd compositions, it follows that
the lowest internal stresses emerge in coatings from solutions of oligomer in tributyl phos-
phate and its mixture with other solvents. The disturbance of the law of additivity in the
change of internal stresses in coatings from mixture compositions based on butylene glycol
and tributyl phosphate is due to the worsening of adhesion properties of coatings and their
spontaneous delamination.
Coatings from compositions with an optimal affinity of oligomer to solvent and the
rheological properties are characterized by the highest strength parameters and adhesion
strength, which was used in the development of systems for canning containers (Table 7.2).
Table 7.2 Effect of a solvent on tensile strength (p), adhesion strength (A) and gloss of epoxy
alkyd coatings.

Solvent A, MPa p, MPa Gloss, %

TBP 1.0 29 80
C 2.3 27 60
TBP:BK (1:2) 3.8 27 65
BG 4.0 15 5
TBP:BG (1:2) 3.6 20 30

To improve the quality of epoxyphenol coatings, it is recommended to subject the mix-


ture of solutions of oligomers in ethyl cellosolve to forcondensation, i.e., heating at
373393 K for several hours. Epoxy and phenol-formaldehyde oligomers do not interact
in the course of forcondensation.
The changes occurring in ethyl cellosolve in the process of forcondensation were stud-
ied with the view to establish the relation between the optimal duration of forcondensation
and the properties of initial epoxy oligomers and to elucidate the causes of coatings prop-
erties worsening at a prolonged forcondensation exceeding the optimal value. No changes
occur in epoxy oligomers heated without solvents, whereas in phenol-formaldehyde oligo-
mers changes are in principle possible due to their large reactivity. As an object of study,
use was made of a mixture of epoxy oligomer E-05k (molecular mass, 20003000) in ethyl
cellosolve. Changes occurring during the heating of this system were studied by calorimetry
and by the method of dielectric characteristics measurements. Changes in ethyl cellosolve
during the heating were determined by the spectroscopy method.
A sharp decrease of heat liberation at the final stage of forcondensation for solutions
of epoxy oligomer in ethyl cellosolve, absent in pure solvent, implies the emergence of an
additional endothermic process superimposed on the exothermic process of regrouping of
the elements of the ethyl cellosolve structure. This phenomenon is explained by that the
236 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

time of disaggregation of associates depends on the initial structure of epoxy oligomer.


Using the fractionation method, a fraction containing mainly large structural elements was
isolated in epoxy oligomer as the lower phase. Between two phases close by their molecular
mass distribution and chemical structure, the solvent was distributed differently. The con-
tent of nonvolatiles in the lower phase exceeds the concentration in the upper phase approx-
imately sixfold, whereas for other specimens only 1.6-fold. This indicates that the
associated lower phase is in fact matched with a smaller amount of solvent than the initial
oligomer, which requires a larger heating time to disaggregate the structure. For the other
phases, the affinity to the solvent differs insignificantly. The suggestion on the effect of the
redistribution of the solvent between two phases on forcondensation time is confirmed by
the fact that for lacquers, obtained separately from the lower phase or upper phase, the
optimal time of forcondensation does not exceed 2 h irrespective of the optimal time of
forcondensation for the initial oligomer.
After the endothermic process, calorimetric studies fail to find the existence of any
exoprocess, which could be treated as a disaggregation of associates. It is assumed that the
extreme character of the dependence of the coating quality on forcondensation time can be
explained by an antiplasticizing, association-contributing action of the phenol formalde-
hyde oligomer.

7.3 Effect of the nature of epoxy oligomers on the properties of coatings


Possessing a high resistance to various aggressive canned media, coatings based on epoxy
resins etherified by fatty acids of various plant oils as well as isocyanates are insufficiently
stable to organic acids (acetic, etc.), so they can not be used for protection of canning con-
tainers from corrosion.
Hardening of epoxy resin-based can varnishes by phenol-formaldehyde forcondensa-
tors is accompanied with a number of reactions (interaction of methylol and butoxyl groups
of phenol condensate with epoxy and hydroxyl groups of epoxy resin, which affect the qual-
ity of the final product). The choice of the optimal ratios of the components and regimes of
hardening of compositions presents significant problems and is in many cases empirical.
To produce acid-resistant coatings, high-molecular-mass epoxy resins are used, with
molecular masses higher than 12,500 and alcohol-soluble resols (phenol resols or cresol
resols), both butanolized and non-butanolized. As phenol resols, Novolac resins and 100%
reactive resins can be used. For better hardening of epoxyphenol compositions, 12% phos-
phoric acid is added. Epoxy-phenol lacquers dry up at a temperature of 180200C for
2030 min. To increase the quality of epoxyphenol coatings, the mixture of resin solutions
is subjected to forcondensation under optimal conditions.
In Czech Republic, epoxyphenol compositions are used for coating tinplate sheets.
Compositions have been developed, which dry up at 200205C for 15 min. The properties
of coatings based on low-molecular-mass epoxy resins E-40 and E-41, as well as medium-
and high-molecular-mass epoxy resins, obtained from fusing low-molecular-mass resins
with diphenylol propane (resins E-44 and E-49) and emulsion condensation of diphenylol
propane with epichlorohydrin (resins E-15 and E-0.5) have been studied.
Modified and non-modified resol resins were used as phenol-formaldehyde resins.
Each epoxy resin as a 50% solution in a solvent matched with one of the phenol resins at
70:30, 60:40, 50:50, 40:60 and 30:70 ratios. The complete match of the resins was assessed
by the transparency of the film after the drying at 150160C of the mixture of resins
applied to glass.
CHAPTER 7 237

It has been found that at room temperature low-molecular-mass epoxy resins match
with phenol resins, as cresol-formaldehyde resin K-212-01 with the softening temperature
of 6266C matches with the content of methylol groups 5.05.5% and with the 100% phe-
nol formaldehyde resin No 101 with the similar softening temperature and with the 80%
content of methylol groups (produced based on n-tert-butyl phenol), as well as with phenol
formaldehyde butanolized by condensate modified by Chinese wood oil (resin No 241).
With these resins, low-molecular-mass epoxy oligomers almost do not match. The com-
plete match of these components is achieved only after their heating at 120125C for 1.5
h. Medium- molecular-mass epoxy resins match at room temperature with all phenol-
formaldehyde resins at given ratios. High-molecular-mass epoxy oligomers E-49 and E-0.5
match with resins K-212-01 and No 101 at all ratios at room temperatures, and with resin
No 241 only after a heating up to 100125C for 1.52 h. With resin based on xyle-
nol-formaldehyde butanolized KF and the product maximally butanolized with phe-
nol-formaldehyde condensate MBP, high-molecular-mass epoxy resins match both at room
temperature and after heating at 120130C, but not at all ratios. At ratios of these compo-
nents of 70:30, 60:40 and 30:70, the matching occurs at room temperature, and at ratios of
50:50 and 40:60 they do not match even after heating.
To produce coatings, lacquers were applied by the pouring or dipping method on
hot-dipped or electrolytic tinplate preliminarily degreased by a solvent and calcined at
180C for 1530 min. The thickness of the film was 46 m.
Chemical endurance of coatings was determined by boiling lacquer plates in a 3%
solution of acetic acid, 3% cooking salt, 2% solution of tartaric acid. Additionally, the coat-
ings were held in these solutions in autoclaves at 121C and pressure from 2.5 atm for 1 h.
Those coatings, which had no blisters, delamination or leadiness after boiling in acetic acid
were considered to be chemically stable.
Coatings having an impact strength of no less than 50 kgcm (a U-1 instrument), an
elasticity no less than 6 mm (an E press), a pendulum hardness no less than 0.8 and a bend
no more than 1 mm, were considered to be mechanically strong.
It has been found that all these epoxyphenol compositions form water-resistant coat-
ings. Acid-resistant proved to be only coatings based on compositions with high molecu-
lar-mass epoxy oligomer in the amount of no more than 40%.
Coatings based on low- and medium-molecular-mass epoxy oligomers are non-acid-
resistant. The greatest stability was shown for coatings based on resins E-0.5 in a combina-
tion with KF at a ratio of components 40:60, 30:70; resins E-0.5 and K-212-01 at a ratio of
30:70; E-49 and KF at a ratio of 40:60, 30:70. The results of storage of preserves with acid
media for 1 year have shown that coatings based on an epoxyphenol composition possess
much higher protective properties as compared with oil-based materials.

7.4 Water-base compositions for protection of canning containers


The inner and outer surfaces of metal canning containers are protected using ecologically
benign lacquer-and-paint materials: powder, with a high content of nonvolatiles, aqueous,
of radiation hardening.
Special attention is given to canning containers with protective coatings based on
water-base systems. The priority in this field is with the USA, where the demand for aque-
ous materials in production of canning containers increases annually by more than 19%. In
the years coming this parameter is assumed to reach 100%. The major reasons for the in-
creasing demand of aqueous compositions is a decreased content of organic solvents
238 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

(2025% less as compared with traditional lacquers), lower toxicity and fire hazard, sim-
plicity and accessibility of application methods. The world market offers a wide range of
water-base materials. However, only the systems, which satisfy the specific requirements
to materials in contact with food products, are suitable for protection of canning containers.
The major of them is inertness of coatings with respect to a canned product, the stability in
storage for no less than 12 months, the processibility, a high adhesion of coatings to the met-
al surface, the stability to the effect of hot water and acids, the stability to sterilization and
pasteurization. Coatings based on water-base systems should be of high quality, and their
performance properties and efficiency should not be worse than those of traditional lacquer
coatings.
Water-base compositions based on epoxy, acryl, epoxyacryl, vinyl etc. film formers
satisfy these requirements to different degrees. The choice of material is determined in each
particular case by the type of metal used, container fabrication method, type of canned prod-
uct. The most widespread film formers for water-base canning materials are carboxyl-
containing epoxy oligomers and epoxyacrylates. Various methods are used for their syn-
thesis. The simplest of them is the interaction of epoxy oligomers with dibasic acids or their
anhydrides. The drawbacks of these methods are the process difficulties related to the
two-stage synthesis, a large duration of the process and a high cost of the product.
Aqueous materials having a high stability and processibility are obtained in the reac-
tion of epoxy oligomer with aromatic amino acids; oligomers formed possess an increased
stability.
A promising method of the synthesis of carboxyl-containing epoxy oligomers with a
nonhydrolyzing ester bond is the interaction of phenol-containing epoxy oligomers with
formaldehyde and amino acids. Epoxy oligomers modified by polyfunctional phenols are
used as a phenol component. The reasonable cost and a sufficiently large choice of ep-
oxyphenol oligomers open wide possibilities for producing film formers with a diverse set
of properties. In combination with hardeners from amino-, urea- or phenol-formaldehyde
resins, such oligomers are used in formulations of water-base materials for protection for
the internal surface of canning containers. Compositions are hardened for 212 min at
200215C to form coatings resistant to pasteurization and sterilization, the action of acids,
alkali and solvents. In industry, use is made of water-base materials based on epoxy oligo-
mers modified by acrylates. One of the most widespread types of epoxyacrylic film formers
for aqueous systems is a mixture of epoxy oligomer and carboxyl-containing acrylate. Com-
positions are hardened in the presence of amino-aldehyde resin at 150370C to form a
high-quality coating resistant to the action of acids. Aqueous materials based on mixtures
of epoxy oligomers with acrylates do not always satisfy manufacturers of canning contain-
ers by their water and chemical resistance and other properties. Coatings based on epoxy-
acrylates with carboxyl groups in the side chains possess better performance parameters.
Water-base canning materials are produced using epoxyacrylates obtained by the re-
action of epoxy oligomers or modified epoxy oligomers with carboxyl-containing acrylic
systems, in particular, film formers containing products of interaction of dianic epoxy oli-
gomer with the mixture of methacrylic acid, styrene and epoxyacrylate. The dispersion is
hardened in the presence of hexamethoxymethyl melamine at 188C for 60 sec. The coat-
ings are distinguished by high adhesion to aluminium and the resistance to hot water.
Carboxyl-containing epoxy oligomers and epoxyacrylates are of interest as potential
film formers for electrophoretic materials. In the USA, water-base compositions have been
developed, intended for anaphoretic coatings of the internal and external surfaces of cans.
The composition contains the reaction product of epoxy oligomer with carboxyl-containing
CHAPTER 7 239

acrylic copolymer. For hardening, phenol-formaldehyde resin or nitrogen-containing resin


are used. After neutralization by tertiary amines of the type of pyridine, morpholine, methyl
pyrrole etc., the composition is used for coating of drawn cans or rolled metal to be used
for the fabrication of composite cans. Coatings are distinguished by an increased elasticity.
A special place among water-base materials is occupied by compositions based on ep-
oxy oligomers modified by phosphoric acid. Protection of canning containers by such ma-
terials makes it possible to provide for chemical and water resistance, strength and other
properties of coatings based on epoxyphenol lacquers. Hardeners for phosphorus-contain-
ing epoxy oligomers can be melamine-formaldehyde resins or their mixtures. Catalysts of
hardening are usually not used, because phosphoric acid present in the film former plays
the role of an inner crosslinking catalyst. Water-base epoxyphosphate compositions are ap-
plied to a metal support in one or two layers of the total thickness 0.002 mm and hardened
at 200C. The coating has a high resistance to hot water and solvents. Water-base materials
with the content of nonvolatile components up to 35%, based on phosphorus-containing ep-
oxy oligomer having OPO(OH)2 groups, are used for protection of canning containers.
The coatings are distinguished by an increased resistance to sterilization and pasteurization.
The assortment of phosphorus-containing film formers for aqueous compositions is ex-
panded due to the phasing in of epoxyphosphate oligomers modified by acrylates or their
mixture with other unsaturated monomers.
For painting canning containers, use is made of epoxy oligomers modified with poly-
esters and polyurethanes. Aluminium and steel beer cans are recommended to be painted
by an aqueous dispersion; the composition includes 70 95% of carboxyl-containing poly-
ester based on trimellitic anhydride, adipic acid and 530% epoxy dianic oligomer. After
the neutralization with ammonia, the dispersion is applied to the inner surface of cans and
is hardened for 10 min at 200C. The coatings do not affect the taste qualities of the pack-
aged product.
Epoxypolyurethane water-base materials for painting of the inner surface of beer cans
contain epoxy oligomer and polyurethane forpolymer, which is obtained by the interaction
of a mixture of polyester polyol and carboxyl-containing oligomer with polyisocyanate;
polyisocyanate plays the role of a crosslinking agent. Coatings are distinguished by chem-
ical endurance, elasticity and good adhesion to metal.
Water-base materials based on acrylic resins are of interest for production of canning
containers with high durability, light permanence and heat resistance of coatings. However,
due to the negative effect on the taste qualities of products, pure acrylates are used mainly
for painting of the outer surface of containers and as coating lacquers for protection of litho-
graphic printing. Compositions based on alkyl acrylates, methacrylic acid, methacrylate
and vinyl acetate are widely used for this purpose. Coatings based on these copolymers are
hardened at 200220C for 12 min.
Coatings based on vinyl materials are distinguished by a high corrosion resistance and
elasticity. However, owing to the insufficient thermal resistance they are unsuitable in the
cases when products are subjected to prolonged heat treatment. As film formers in vinyl
systems, use is made the most frequently of copolymers of vinyl chloride and vinylidene
chloride with acrylate or other monomers. Stable aqueous dispersions for protection of the
inner surface of metal cans for beer and drinks are obtained based on copolymer of vinyl
chloride and vinylidene chloride with vinyl monomers, which contain carboxyl or sulfonyl
groups. The most frequently used formulation of this type is based on copolymer from
3085% vinyl chloride, 1050% methyl acrylate, 0.120% acrylic acid and 0.57% vinyl
sulfonic acid. The inner surface of metal cans is protected by a water-base composition
240 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

based on a film former obtained by radical copolymerization of acrylic acid, ethylacrylate


and styrene in a mixture with cyclohexanone with butyl cellosolve, containing vinyl copol-
ymer and epoxy oligomer.
Aqueous pigmented materials serve for exterior painting and lithography of cans. As
film formers, use is made of alkyd, polyester, acryl or epoxyphenol oligomers. Water-base
compositions for this purpose are obtained based on hydroxyl-containing polyester, which
represents the product of polycondensation of a mixture of fatty alcohols with a mixture of
cycloaliphatic, aromatic or aliphatic 1-, 2-, 3-basic carboxylic acids.
Water-base materials intended for painting of canning containers are applied to the
surface using rolls or by spraying. The choice of the application method is determined in
each particular case by the type of container and its fabrication process. In production of
multiply-drawn composite or two-piece cans, use is made of rolls or sheet metal painted
preliminarily on the standard equipment. Before formation of cans, the metal surface is
coated with a layer of lubricant, which facilitates the fabrication and protects the coatings
from deterioration. If necessary, one or two layers of material are applied by spraying on
the inner surface of composite cans. Two-piece cans fabricated by the ironing technology
are decorated from the outside and painted by spraying using two-nozzle sprayers or spray-
ers with nozzles displaced relative to each other, which makes it possible to apply a two-
layer coating.

7.5 Modification of polyvinyl chloride compositions by thermoplastics


The use of regular-structure compounds as modifiers makes it possible to improve signifi-
cantly the performance properties of coatings in biochemically active media. To improve
the performance properties of perchlorovinyl coatings, we studied the effect of various
physicochemical factors on the properties of block copolymers based on styrene and buta-
diene for their subsequent use to increase the adhesion and protective properties of perchlo-
rovinyl systems for protection of canning containers.
The effect of the concentration of styrene in block copolymers on the properties of
coatings has been studied (Table 7.3).
Table 7.3 Effect of the concentration of -methyl styrene on the properties of coatings.

Concentration of Stress (MPa) at elongation, % E0 /E, Maximum swelling


-methyl styrene E = 100%, in isooctane,
50 100 200 300 I = 1 min %

31.5 1.47 1.60 1.76 2.04 4.76 132


34.5 1.87 1.98 2.12 2.52 4.76 136
42.5 2.55 2.59 2.70 3.47 3.71 105
44.5 2.21 2.35 2.65 3.74 3.85 110
52.0 5.37 5.29 6.04 8.95 2.70 81
DMST-35 2.18 2.17 2.21 2.59 4.55 126

Stresses characterizing the stressstrain properties of systems have been studied at


different degrees of strain. The maximal swelling of specimens in isooctane enables a
judgement of the density of the three-dimensional network of block copolymers. The rigid-
ity of specimens was assessed by the relative change of the initial modulus to the value of
its change at a relative deformation of 100% for 1 min. It has been shown that, as the
CHAPTER 7 241

concentration of -methyl styrene in the block copolymer DMST increases, the rigidity of
specimens is observed to rise monotonically and the rate of the relaxation processes to de-
crease. The deformation properties of specimens are characterized by the value of stress at
a fixed elongation determined from the curve of the dependence of stress on the values of
strain. The rate of the relaxation processes was assessed by the inverse value of the relative
drop of the modulus in the process of relaxation at a constant elongation of 100% for 1 min.
Thermoelastoplastic specimens were swollen at room temperature in isooctane. The maxi-
mal swelling was achieved in 34 days.
These results are agree with the regularities in the change of internal stresses, from
which it also follows that as the concentration of -methyl styrene in block copolymers in-
creases, internal stresses rise 23 times. A decrease of swelling of specimens is determined
by the increase of the density of the three-dimensional network with the increase of the me-
thyl styrene content.
To study the particular features of structure formation in regular-structure polymers
depending on their chemical composition, use was made of the method of electron micros-
copy. Films were prepared from solutions of specimens in benzene at a concentration of
0.003 g/mm. Films were contrasted in vapours of osmium tetroxides.
Analysis of the data obtained indicates that thermo- and elastoplastics are two-phase
systems. Owing to the significant rigidity of polystyrene blocks, they interact one with an-
other to form domains with parallel orientation of anisodiametric-type chains. With the con-
centration of styrene blocks rising, the size of the domains increases. The thickness of
polystyrene domains in the concentration range from 30 up to 50% is 3035 nm. Polysty-
rene domains interact to form networks, the cells of which comprise the elastomer part of
the compositions. The optimal properties of block copolymers, enabling their use as mod-
ifiers of perchlorovinyl compositions, are observed at 3035% polystyrene in the chain.

7.6 Effect of the structure of the block copolymer chain on the properties
of coatings
Thermoelastoplastics with the regular structure of the chain are characterized by higher
physicomechanical properties. The strength of films from thermoplastic DMST-35 in ten-
sion was 23.0 MPa, relative breaking elongation was 860%, the modulus at 50% was 2.1
MPa, p = 1.0 MPa.
Thermoelastoplastics with a similar ratio of irregular-structure components even after
introduction of a Zn atom into their chain and using various hardeners were distinguished
by lower physicomechanical properties (Table 7.4).
Table 7.4 Effect of the nature of the hardener on the physicomechanical properties of Zn-TEP.

Hardener Deformation strength p, p, % Adelam


MPa
f50, MPa f100, MPa

Initial composition 13.7 20.0 202 3.3


Altax+paraquinone dioxyl 10.6 14.3 18.8 195 0.6
Sulfur+chloxyl 9.5 12.4 16.4 188 0.7
Sulfur+santokur 10.5 13.8 95 1.1
Chloxyl 9.8 12.6 18.0 246 0.9
Diazo amino benzene 9.1 12.0 16.8 229 0.9
242 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

It is seen from the table that for films from irregular-structure thermoelastoplastics the
values of elasticity, adhesion strength and breaking strength are considerably decreased.
Use of various oligomers (epoxyphenol, epoxyphenol acryl) and compositions on their
basis as modifiers makes it possible to increase the elasticity of coatings without signifi-
cantly changing the strength parameters. Table 7.5 presents the data on the effect of various
modifiers on the mechanical properties of coatings from thermoelastoplastic Zn-TEP.

Table 7.5 Properties of modified thermoplastics.

Modifier f100, MPa f200, MPa fn, MPa p, %

EF 12.2 16.7 16.7 210


EF1 8.7 12.4 16.2 270
EF2 9.0 12.8 17.8 460
EFA-2 9.8 13.2 15.3 287
EFA-2 + 5 wt.% acetur 8.3 11.1 14.5 375
EFA-2 + 10 wt.% acetur 7.0 9.8 12.9 365
EFA-2 + b-cyanoethyl acrylate 10.2 13.6 16.9 370
FP-326 8.9 11.3 13.9 450

From the analysis of the table data, it follows that modification of butadiene styrene
compositions by epoxyphenol compositions makes it possible to improve the physico-
mechanical properties of coatings (strength, elasticity). However, the adhesion strength of
irregular-structure copolymers is more than 3 times as low as for block copolymers with
the similar ratio of regular-structure components.
For this reason, further studies were carried out using regular-structure block copoly-
mers as modifiers.

7.7 Development of the method for improving the protective properties


of polyvinyl chloride compositions by modification with block
copolymers
Block copolymers are widely used in developing polymer materials of various purposes.
This is due to the fact that they are characterized by a single-phase ordered structure. The
size of structural elements, their morphology, and, therefore, the properties of polymers can
be regulated within broad ranges by changing the length, chemical composition, molecular
mass of particular blocks.
In this connection, we used regular-structure block copolymers as modifiers to im-
prove the biochemical resistance of perchlorovinyl (PVC) coatings.
A characteristic feature of perchlorovinyl coatings is that they possess a high weath-
erability, resistance to the action of acids, strength and plasticity. At the same time, they
dissolve poorly in organic solvents, which is accompanied by the formation of an inhomo-
geneous imperfection structure and low strength of adhesion to various materials. To im-
prove the structure and properties of the coatings, 1025% solutions of PVC are
supplemented with plasticizers and various modifying additives.
The most widespread components in fabrication of compositions are mixtures of var-
ious solvents: ethyl acetate and butyl acetate, ketones, chlorinated lower aromatic and ali-
phatic hydrocarbons.
CHAPTER 7 243

Dibutyl phthalate, tricresyl phosphate, sovol (polychlorobiphenyl) are used as plasti-


cizers. An increase of the heat resistance of protective coatings is performed by way of in-
troducing various stabilizers, in particular, epoxidized oils (soybean, sunflower), low-
molecular-mass epoxy oligomers. They serve as acceptors of HCl, which is evolved in the
decomposition of a polymer.
For regulation of the structure and properties of polyvinyl chloride coatings, used was
made of divinyl styrene thermoelastoplastics, which are distinguished by the nature of the
end groups (styrene and -methyl styrene), the structure (linear and branched), by various
contents of polystyrene blocks, as well as the ones with different molecular masses.
Coatings were formed both from solutions of PVC compositions and from powder sys-
tems.
The characteristics of thermoelastoplastics used in the formation of coatings from
powder systems is given in Table 7.6.
Table 7.6 Characteristics of thermoelastoplastics.

Name Chemical formula Content Physicochemical Hard- Melt


of poly- characteristics ness index
styrene f0 T = 90C,
Tensile Relative 216 H,
strength, elongation, g/10 min
MPa %

Divinyl--methyl styrene P-2MS-PB-P--MS 30 31.5 890 68 51.5


DMST-30L
Divinyl--methyl styrene Si-PBP-2MS 30 28.5 855 65 39.0
DMST-30-R
Divinyl styrene DST-30L1 PS-PB-PS 28 144.0 935 66 48.0
DST-30L2 PS-PB-PS 28 255.0 847 66 24.0
Divinyl styrene DST-20-R 20 159.0 760 50 31.0
Si
DSG-30-R (PS-PB)4Si 31 211.0 910 70 37.0
DST-50-R (PS-PB)4Si 50 105.0 765 89 48.1

Based on the performed studies, it has been found that the best set of performance
properties is observed in modification of perchlorovinyl compositions using as modifier
-methyl butadiene styrene DMST-30L or DMST-35L in the presence of plasticizer
PPA-7.
Table 7.7 presents the physicomechanical properties of coatings produced at various
ratios of the main components polyvinyl chloride (PVC), block copolymer thermoplastic
DMST-35L and plasticizer (polypropylene glycol).
The stressstrain properties of films from mixture compositions were studied at an ex-
tension rate of 25 mm/min.
It is seen from Table 7.7 that the dependence of breaking strength on TEP concentra-
tion is nonmonononic. First, as the concentration of TEP is increased up to 50%, it goes
down sharply, and then at a further increase in the content of TEP it increases, staying lower
than the strength of the initial PVC and TEP components. The elasticity modulus increases
with the increase of the concentration of PVC. The ratio of the ingredients in the composi-
tion has a significant effect on the value of internal stresses. The results of the study are
presented in Table 7.8.
244 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 7.7 Deformation/strength properties of modified polyvinyl chloride films.

Composition E at = 50%, GPa p, MPa p, %

TEP PVC PPA

0 100 0 55.4 52
25 75 0 15.7 22
25 75 25 15.9 132
50 50 0 9.8 5.9 366
50 50 10 14.6 6.8 77
50 50 20 12.0 6.1 157
50 50 25 10.8 6.2 157
50 50 30 9.6 5.2 128
50 50 50 5.3 2.9 113
50 50 70 4.9 2.4 105
70 30 0 5.3 15.7 1070
100 0 0 2.1 23.0 860

Table 7.8 Effect of the ratio of individual ingredients on internal stresses in the formation of films
from mixture compositions.

Composition p, MPa

TEP PVC PPA-7

0 100 0 18.0
25 75 0 10.5
25 75 25 0.9
50 50 0 2.4
50 50 10 2.1
50 50 20 1.1
50 50 25 1.0
50 50 30 0.9
50 50 50 0.9
50 50 70 0.7
70 30 0 1.1
100 0 0 0.9

It is seen from the table that significant internal stresses occur in films from PVC. In-
troduction of thermoplastics decreases them more than 1.5-fold at a TEP content of 2%. The
most sharp decrease of internal stresses, more than 8 times, is also observed at an increase
of the concentration of TEP up to 50%.
The further decrease of internal stresses was performed by introducing the plasticizer
PPA-7.
Also noteworthy is a sharply increased adhesion of coatings from modified PVC,
which was 180200 MPa, whereas films from nonmodified PVC peel off at critical internal
stresses of 1.41.6 MPa.
As the concentration of the plasticizer in the mixture is increased, internal stresses go
down. For films from a mixture composition with the PVC to TEP ratio of 50:50, internal
CHAPTER 7 245

stresses decrease by about 2 times at a plasticizer concentration of 20%. The further in-
crease of plasticizer concentration has no significant effect on the value of internal stresses.
Their sharp (3-fold) decrease is found to occur at a plasticizer concentration of 70%.
The effect of the plasticizer concentration of the adhesion properties of compositions
was studied by the peeling method at a testing rate of 575 mm/min.
Table 7.9 presents the data on the adhesion strength of coatings with the 50:50 ratio of
the components (PVC:TEP) as a function of the concentration of plasticizer (PPA-7).
Table 7.9

PVC/TEP ratio Content of plasticizer PPA-7, wt. % Adhesion strength, MPa

50/50 0.445
50/50 20 0.350
50/50 30 0.345
TEP 0.221

It is seen from the table that introduction of a plasticizer up to 2030 wt. % has no
significant effect on the adhesion strength of modified polyvinyl chloride specimens.
The change of the ratio of the ingredients renders a significant effect not only on the
rate of the relaxation processes in the formation of coatings from mixture compositions, but
also on the relaxation processes in formed coatings in their operation.
The rate of the relaxation processes in formed coatings from mixture compositions was
assessed at different temperatures by the change of the elasticity modulus at a constant load
in 10 and 100 sec. The relaxation coefficient

E ( 10 sec ) E ( 100 sec )


K = ------------------------------------------------------------- 100% .
E ( 10 sec )

The results of the study are presented in Table 7.10, E in 103 MPa.

Table 7.10 Effect of the ratio of PVC and TEP in mixture compositions on the film relaxation
constant at different temperatures.

TEP/PVC Parameters Temperature, C

20 30 40 50 60

100/0 E = 30% 43.5 40.5 37.7 34.8 29.8


Kp 9.0 10.7 13.4 20.2 19.1
70/30 E = 30% 90.9 82.2 74.9 66.8 57.1
Kp 13.2 16.4 20.4 26.4 36.2
50/50 E = 30% 191.0 172.0 156.0 143.0 122.0
Kp 14.4 16.3 21.0 29.0 37.8

It is seen from the table that the rate of the relaxation processes increases for films from
all compositions with the temperature increasing. At the same time, the rate of the relaxation
processes also significantly rises with the increase of the content of PVC.
Comparison of these data with the results of the study of internal stresses as a function
of the concentration of PVC in mixture compositions indicates the absence of their
246 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

correlation, because internal stresses increase significantly due to the retardation of the re-
laxation processes in the formation of coatings with the content of PVC increasing.
Using the method of electron microscopy, it has been found that the specific change
of the relaxation characteristics depending on the ratio of ingredients in mixture composi-
tions is due to the features of structure formation in the fabrication and operation of coat-
ings.
In studies of the structure of coatings from PVC by the method of electron microscopy
it has been found to be inhomogeneous by the size of globules, which change within the
range of 3080 nm.
The structure of the block copolymer of -methyl styrene thermoplastic is character-
ized by the occurrence of domain-morphology structural elements with the domain width
of 20 nm.
At a 30% content of PVC, the composition is found to have a more homogeneous glob-
ular structure with the structural elements of 2550 nm in size. An increase of the concen-
tration of PVC up to 50% significantly increases the inhomogeneity of the structure. The
structural elements of PVC are distributed in the film unevenly in the form of aggregates
0.20.3 m in diameter. A further increase of the concentration of PVC up to 75% increases
the inhomogeneity even more. Separate regions of structural elements characteristic of PVC
and TEP are observed.
The distribution of ingredients in mixture compositions was regulated by introducing
a plasticizer.
Thus, at a PVC to TEP ratio of 30:70, one observes a good match of ingredients on the
level of their supramolecular structure. Production of coatings with the homogeneous struc-
ture and a good match of ingredients on the level of supramolecular structures can be done
in the presence of a plasticizer at a PVC to TEP ratio of 50:50.
It follows from these results that the rise of the relaxation constant for films from mix-
ture compositions with the PVC concentration increasing is due to the worsening of the
compatibility of components on the supramolecular level and the formation of a defect
structure more readily destroyed under the action of an applied load.
Based on the results of these studied, compositions containing 50% PVC and 50%
thermoelastoplastics with an optimal concentration of the plasticizer were chosen, which
provide for the fabrication of coatings with the best protective properties.

7.8 Studies of the relaxation properties of coatings from polyvinyl chloride


compositions modified by thermoplastics
The relaxation properties of coatings were assessed by studying the temperature depen-
dence of the stressstrain properties of compositions at an optimal ratio of PVC/TEP =
50:50 and different contents of plasticizer PPA-7. The tests were carried out at an extension
rate of 25 mm/min within the temperature range of 2080C.
The results of the study are presented in Table 7.11.
Figure 7.1 presents a temperature dependence of strength and relative breaking elon-
gation on the testing temperature. Analysis of these results suggests that the resistance to
rupture and breaking elongation decreases at an increase of temperature for nonplasticized
specimens.
For plasticized specimens, p changes nonmonotonically depending on the concentra-
tion of plasticizer. An exception is the initial composition, for which the maximum in the
change of p is not observed.
CHAPTER 7 247

70 p, %

60
1
50 400 1
2
2
p10, MPa

40
3 300
3
30
4
200
20

10 4
100

10 30 50 70 90 10 30 50 70 90
T, C T, C

Figure 7.1 Dependence of strength (a) and relative elongation (b) on testing temperature for spe-
cimens plasticized with PPA-7 and nonplasticized specimens of coatings. a: 1, no PPA-7; 2, 10 wt. %
PPA-7; 3, 20 wt. % PPA-7; b: 1, no PPA-7; 2, 10 wt. % PPA-7; 3, 20 wt. % PPA-7; 4, 30 wt. %
PPA-7.

Table 7.11 Effect of the testing temperature and the concentration of plasticizer on the
physicomechanical properties (tensile strength p, ultimate elongation p).

Concentration of Properties Testing temperature, C


PPA-7, wt. %
20 35 50 65 80

0 p, MPa 5.9 5.3 4.2 3.3 1.7


p 370 340 352 277 134
10 p, MPa 6.8 5.6 3.1 1.0 0.5
p 93 134 283 245 165
20 p, MPa 6.1 3.8 2.3 1.1 0.6
p 180 250 246 214 155
30 p, MPa 5.2 3.0 2.0 0.9 0.5
p 146 142 175 156 143

To elucidate the mechanism of interaction of the components in a modified polyvinyl


chloride system, the activation energy of the breakdown process was calculated.
It is known that the tensile stress calculated for the real transverse cross section of a
specimen at the moment of rupture [p = Pp (E + 1)] changes for many polymers, depending
on temperature, according to an equation similar to the Arrhenius equation:

p = BeU/RT,

where p is the rupture stress, B is a constant, R is a gas constant, T is temperature in degrees


Kelvin and U is activation energy.
248 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

logp
2.6 1

2.2
2
1.8
3

1.4 4

1.0

2.8 3.0 3.2 3.4 1000/T, K

Figure 7.2 Dependence of breaking stress in the logarithmic coordinate on inverse temperature for
specimens with different concentrations of plasticizer PPA-7 obtained from solutions. 1, 0 wt. %
PPA-7; 2, 10 wt. % PPA-7; 3, 20 wt. % PPA-7; 4, 30 wt. % PPA-7.

In (log p 1/T) coordinates, this dependence has the shape of a straight line, whose
slope to the abscissa axis is proportional to the activation energy.
Figure 7.2 presents a dependence of log p on 1000/T for four systems studied. This
dependence is seen to be not linear but to present a jogged line in the temperature range
studied (2080C). The inflection points of these lines are in the temperature range of
4550C. An exception is the initial system, for which this point is at 60C.
The fact that the dependence of log p on inverse temperature for the compositions
studied is a jogged line suggests that, depending on the temperature range of studies, the
breakdown of modified polyvinyl chloride compositions is determined by different mech-
anisms characterized by their own activation energies. In turn, these regularities are deter-
mined by the different character of structure formation and the level of match of the
components at the impact of temperature.
Table 7.12 gives the results of calculating the activation energy for the systems studied.
Table 7.12 Effect of the concentration of plasticizer on the activation energy of modified polyvinyl
chloride compositions at different testing temperatures.

Concentration Testing temperature range within which the dependence


of plasticizer log p 1/T is linear

2050C U1, kcal/mol 5080C U2, kcal/mol

0 2.29 8.85
10 1.22 8.92
20 3.23 6.16
30 6.01 6.38

It is seen from the table that at higher temperatures (5080C) the activation energy
is larger than at decreased temperatures (2050C).
CHAPTER 7 249

The differences in the activation energies are smoothed with temperature increasing,
and at 30 wt. % of plasticizer the values of U1 and U2 are almost equal. Similar regularities
in the change of activation energy depending on the testing temperature were observed for
specimens obtained not by forming films from solutions, but by calendering a mixture of
PVC with modifier TEP.
The results of the tests of the mechanical properties of this composition are presented
in Table 7.13.
Table 7.13 Mechanical properties of PVC modified by TEP.

Parameter Testing temperature, C

20 30 40 50 60 70 80

f30, MPa 7.26 5.71 3.97 2.55 1.65 1.16 0.80


p, MPa 9.90 8.39 6.39 4.56 3.08 2.10 1.36
p, % 90.0 106.0 126.0 143.0 123.0 118.0 116.0

It is seen from the table that for this batch of specimens, also with the testing temper-
ature increasing, the resistance to rupture decreases monotonically, and the breaking elon-
gation passes through a maximum revealed at approximately 50C.
The processing of experimental results with the view to determine the activation en-
ergy of the breakdown for this composition again showed a similar character of the depen-
dence of log p on inverse temperature in the shape of a jogged line, whose inflection is at
about 45C (Fig. 7.3). The values of the activation energy calculated by the slope of, re-
spectively, the gradual and steep segments of this jogged line are 2.7 and 10.3 kcal/mol.
From the analysis of the results of the studies, it follows that the formation of modified
perchlorovinyl compositions at a temperature of 4060C is accompanied with a signifi-
cant increase of the intermolecular specific interaction between structural elements and an
improvement of performance properties of coatings.

7.9 Modified perchlorovinyl coatings with increased shelf-life


Coatings based on perchlorovinyl compositions are characterized by a valuable set of prop-
erties. The most important of them are weatherability and the possibility of preserving the
protective properties in operation under conditions of the action of organic and inorganic
acids.
However, under operation conditions, owing to the imperfection and inhomogeneity
of their structure, the service life of coatings does not exceed 23 years.
To improve their protective properties and to increase durability, structure formers are
proposed to be used as modifiers; they increase the adhesion strength and stability of adhe-
sion of coatings to metal in contact with elements, water, and high-humidity atmosphere.
To increase the adhesion/cohesion strength and protective properties of coatings based
on perchlorovinyl compositions, use is made of modifiers containing coordination organic
compounds with plane-oriented structure and coordination ions of various metals in mac-
romolecules. These compounds increase the adhesion strength 23-fold and simultaneous-
ly improve the protective properties of coatings in aggressive media.
However, due to the complexity of their synthesis, they have not found wide use in
industry. Because of this, compounds with various functional groups are used as modifiers
250 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

log p
2.6

2.2
1

1.8
2

1.4
3.0 3.2 3.4 1000/T, K

Figure 7.3 Dependence of the logarithm of the breaking stress on inverse temperature for TEP-
modified PVC specimens obtained by calendering of the mixtures. 1, U = 2.7 kcal/mol; 2, U = 10.3
kcal/mol.

contributing to the increase of the adhesion strength of coatings from resin based on chlo-
rinated polyvinyl chloride resin PSKh-LS and its stabilizers in operation in liquid media.
The adhesion strength was measured by the method of irregular peeling of coatings
applied to plates from low-carbon steel 08kp, at a peeling rate of 2.4 mm/min.
Holding of coatings in a medium significantly reduces their adhesion strength. After
their removal from a medium, specimens were held for 24 h at 20C, and their adhesion
was measured. At a small exposure in the medium, the adhesion of coatings is partially re-
stored. An irreversible decrease of adhesion strength is due to the uneven distribution of
adhesion bonds in the boundary layers of the coatings due to the inhomogeneity and imper-
fection of their structure, which leads to the development of corrosion processes.
The level of the recovery of the adhesion strength is significantly affected by modifi-
ers. Owing to the larger surface energy and the presence of active functional groups, mod-
ifiers are adsorbed in the boundary layers of coatings to improve their physicomechanical
properties. Modifiers were introduced in an optimal amount of 12% to the resin prior to
the application of coatings. Table 7.14 presents the data on the effect of the time of exposing
Table 7.14

Medium Exposure, min Adhesion, g/cm

initial after exposure recovered % of recovery

Distilled water 0 333


10 333 92 185 55
40 333 31 59 17
60 333 0 0 0
HCl, 5% 0 304
15 304 36 157 51
30 304 0 96 31
H2SO4, 5% 0 312
15 312 12 99 31
10 312 10 53 16
CHAPTER 7 251

coatings to different media on the adhesion strength of the initial coatings after holding
them in media and the restored strength.
The effect of modifiers on the adhesion strength of perchlorovinyl coatings was stud-
ied. As additives, used was made of alkoxysilanes A-2 and ASOT-2 containing various
functional groups, additions of MHU and PMHU containing hydroxyl and ester groups,
regular-structure aromatic stabilizers with active radicals of CPA.
The results of studies of the adhesion strength of perchlorovinyl coatings are presented
in Table 7.15.
Table 7.15

Modifier Adhesion strength, g/cm

310 35
A-2 680 15
CPA 325 75
MHU 295 15
PMHU 295 15
ASOT-2 550 25

It is seen in the table that additions of CPA, MHU, PMHU change little the value of
the adhesion strength of perchlorovinyl coatings. Additions of MHU, PMHU decrease the
adhesion strength as compared with this parameter for nonmodified coatings.
Modifiers A-2 and ASOT-2 increase approximately twofold the adhesion strength of
initial coatings prior to the action of aggressive media on them. However, after keeping the
coatings in liquid media, probably, due to the ability of alkoxysilanes to be hydrolyzed un-
der these conditions, the adhesion strength of the coatings decreases.
At the action of electrolytes, the highest adhesion strength is observed for perchlorovi-
nyl coatings modified by antioxidant CPA.
252 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY
8 Ways of Modifying the
Properties of Metallized
Packaging Materials

8.1 Purpose and fields of application


Articles from plastics, ceramics and composite materials with metallized surface are used
at present in many industries and are widespread in households. The low specific mass,
good mechanical parameters, the absence of corrosion problems make it possible in a num-
ber of cases to give them the preference over traditional metals.
Abroad, metallized film materials are widely used in fabrication of various packagings
in food industry and other industrial spheres. This is due not only to the improved decorative
properties of packaging materials in metallization, but also a significant (several orders of
magnitude) reduction of vapour permeability and an increase of the barrier properties of
combined films.
New applications of synthetic materials (automotive industry, production of house-
hold appliances and electronics, etc.) put forward increased demands to their appearance
and service life. In this connection, a topical problem are the specific properties of the sur-
face of such materials, whose purpose is to conceal the formation defects, to increase the
resistance to cracking, scratching, as well as atmospheric and chemical endurance, to im-
prove the decorative properties. There are two ways of finishing nonmetal materials met-
allization and painting with lacquer-and-paint materials.
Metallized dielectrics, whose surface is partially or totally coated with a metal, possess
an increased resistance to the action of organic solvents, moisture, boiling and high temper-
atures; have high physicomechanical and decorative properties, as well as can endow arti-
cles with specific properties (for instance, metallized coatings in electronics are used to
shield the bodies of equipment from interference noise, for elimination of statics, protection
from the impact of various short-wave radiations). For metallization of dielectrics, such
metals are used as aluminium, copper, nickel, platinum, tin, lead, zinc, iron etc., as well as
metal alloys. The choice of a metal is determined by the purpose of a metallized item and
the technological features of the metallization method.
In finishing the surface of dielectrics with lacquer-and-paint materials, there are a
number of problems related to the adhesion strength of coatings to plastics, a relatively low
resistance of plastics to the action of increased humidity, high temperatures and organic sol-
vents, as well as to the provision of the required decorative, physicomechanical and adhe-
sion properties.
To endow articles from nonmetal materials with high decorative and performance
254 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

properties, a promising way is to combine two methods of surface finishing to produce a


combined coating: by applying a metal layer and by colour printing. In this case, besides
the decorative properties, metal endows an article with an increased resistance to the action
of high temperatures, moisture, organic solvents, as well as hardness and wear resistance.
A lacquer-and-paint material can not only be used to provide for high decorative and
performance properties, but protect the metal film from oxidation. Besides, a metallized
coating enables the use of electrodeposition for painting various dielectrics (polymer films,
plastics).
Electrodeposition of water-base lacquer-and-paint materials is one of the most wide-
spread methods of producing single-layer and primer coatings on metal articles under con-
ditions of large-series production. This method conforms the most completely to the
requirements imposed on the modern conditions and processes of chemical technology, is
a practically closed technological cycle with total automation and mechanization of the pro-
duction process.
However, many problems associated with the use of the electrodeposition method for
painting of metallized dielectrics have not been solved. The particular features of forming
coatings on a metallized sublayer have not been sufficiently studied in painting by the
electrodeposition method, the chemical nature of the surface of the metal support and the
structure of the surface of the metallized layer have a significant effect both on the techno-
logical regimes of the process and on the structure and properties of protective coatings.
Recently, to increase the corrosion resistance of steel, Western companies in various
machine-building industries make use of steel workpieces with various kinds of galvanic
coatings, mainly zinc nickel, zincaluminium, nickelcadmium, chemical or galvanic
nickel followed by the application of protective lacquer-and-paint materials.
A large cycle of works is under way in solving the problem of decreasing the hardening
temperature and time of materials manufactured by Russian industries. The main water-
base compositions, which can be applied to metallized film materials, harden at 180C.
Works in this field are carried out in several directions based on the introduction of
hardening catalysts, special low-temperature hardeners, into film formers, as well as by syn-
thesizing bonding adhesives with the low temperature of hardening.
Such additives include siccatives of metals, organic accelerators, modifiers based on
epoxy and isocyanate oligoesters. Usually, a significant drawback of such additives is a de-
crease of the stability of performance properties of the working solutions of polymer com-
positions prior to their application and, respectively, a deterioration of the properties of such
coatings.

8.2 Methods of forming metallized layers on polymer materials


The performance properties of metallized polymer materials with a protective lac-
quer-and-paint coating should be determined first of all by the adhesion of the metallized
sublayer to the polymer film and protective coating to metallization.
At present, three groups of methods are used for metallization in Russian and Western
industries:
mechanical (conformal coating, hot embossing);
physical (gas-thermal deposition of melted metal and metallization under vacuum);
chemical (chemical and chemico-galvanic metallization).
Some results of using various methods of metallization in this country are given in
Table 8.1.
CHAPTER 8 255

Table 8.1 Effect of the method of metallization on adhesion of coatings.

Metallization method Metallized dielectrics Type of coating Total thickness Adhesion


of coating, m

Chemical Almost all kinds of plastics, Copper, nickel, 0.0110 Good


ceramics silver
Chemico-galvanic ABS plastic, polystyrene, Copper, 3065 High
polypropylene, polysulfone, chromium, nickel,
glass fibre lead, silver, tin
Vacuum Polyamide, aminoplastics, Aluminium, 0.11 Low
epoxides copper

Under conditions of series production, the most widespread methods of metallization


of complex-shape items are chemical methods.
The method of chemical metallization by precipitation from solution consists in the
formation of a metal coating on the surface of a polymer material owing to the autocatalytic
chemical reactions at the interface. Before metallization, articles are subjected to activation
with the view to apply the catalyst of the reduction reaction of the base metal on the surface
of the support.
The process of chemical metallization is used the most frequently in coppering and
nickeling. The use of other metals is limited by the low stability of their solutions.
Activation can be performed according to two protocols: sensitization and direct acti-
vation. In sensitization, articles are first subjected to treatment in acidic, alkaline or alco-
holic solutions of divalent tin salts. After the treatment, the surface is activated by solutions
of salts or complex compounds. Usually, acidic solutions of palladium chloride or alkaline
solutions of silver nitrate are used for this.
For direct activation, use is made most often of combined solutions containing tin and
palladium salts and solutions of accelerators. Accelerators used the most are solutions of
mineral acids, alkali and salts of alkaline metals.
The process of chemical metallization proper is performed in solutions containing the
salt of applied metal, the reducer, the complex former for binding ions of reduced metal into
a complex, buffer additions to regulate pH of the solution, stabilizers, gloss formers, etc.
For coppering, use is made of solutions containing copper sulfate, a complex former
(potassiumsodium tartrate, glycerol, etc.), a reducer (formaldehyde).
Nickeling is performed in acidic or alkaline solutions of nickel chloride or sulfate; lay-
ers of reducer 0.0110 m thick are usually applied, which are then reinforced by applying
a thicker layer of metal by a galvanic method.
Deficit and high cost of precious metals were the reason for developing the activation
processes without using palladium or with its decreased content in activating solutions.
To decrease the concentration of palladium in solution, it was proposed to treat the sur-
face in sols based on silicon or iron oxides before the activation stage.
This treatment results in the creation of a developed surface, which significantly de-
creases the energy of the formation of active sites of palladium and its consumption. This
process is used in the metallization of printed circuit boards.
A method was developed of forming a catalytically active copper film by reducing its
hard-to-dissolve compound on a metallized surface by such efficient reducers as formalde-
hyde and hydrazine. The process proceeds in two stages: first the copper(I) oxide is formed
in a hydrazine medium, then a catalytic copper film is formed in a formaldehyde medium.
256 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

A method has been proposed of activating dielectrics in solutions, which represent a


stable colloidal system consisting of salts of basic metals with complexons. Reduction of
sorbed ions is performed using boron hydrides of alkaline metals or their derivatives.
Methods have been developed of substituting activated solutions based on palladium
for solutions of sodium boron hydrides containing organic solvents (monobasic alcohols,
hexachloroethane, dimethylformamide etc.) for chemical nickeling of small items with in-
creased adhesion of applied coating.
To increase adhesion of copper to polymers, the surface is activated by application and
subsequent thermolysis of copper hypophosphite. The surface is first treated with a solution
of thermosensitive copper salt. The subsequent heat treatment at 100140C leads to the
formation of metal copper particles, which are initiators of chemical precipitation of copper
from solution instead of palladium particles.
Chemico-galvanic metallization of dielectrics is widely used in formation of current-
conducting layers of a sulfide coating. The method consists in the subsequent treatment of
the surface in a solution of copper salts and in a solution of a sulfonating agent, for instance,
sodium sulfide. Treatment with water leads to the hydrolysis of the copper salt and to the
sorption of partially soluble hydrolysis products on the surface. In the subsequent treatment
in a solution of the sulfonating agent, the copper-salt hydrolysis products are converted to
copper sulfide.
Electrical conductivity of copper-sulfide layers can be regulated by their multiple ap-
plication, after which the cycle is repeated several times.
An increase of electrical conductivity of the coating is also achieved by adding copper
salts, zinc salts, metal copper or monovalent copper compounds to the solution.
To provide for the subsequent application of nickel by the galvanic method, the elec-
trical resistance of the current-conducting sulfide layer should not exceed 103 Ohm/m.
A significant advantage of this method is the stability of solutions and properties of
the produced current-conducting layers due to the use of separately stable solutions of cop-
per salts and the sulfonating agent, as well as to the removal of hydrolysis products (copper
salts), not bound to the surface, by washing.
The metallization process of dielectrics and the quality of metallized material are af-
fected by the surface preparation. The quality of metallized material is determined by the
strength of adhesion of the metal coating to the polymer film, so the process is carried out
under conditions providing for the maximal and uniform strength of adhesion interaction.
Several theories explain adhesion of the metal layer to polymer. The theory of mechan-
ical engagement pays main attention to the geometry of the surface. Adhesion is associated
with the number of micropits on the surface of well-etched polymers, into which deposited
metal penetrates. This theory explains well the formation of a strong bond of metal to het-
erogeneous-structure polymer, from the surface of which one of the phases is easily re-
moved during the etching. For ABS block copolymers, these are globules of polybutadiene;
for polypropylene and polyethylene, the amorphous phase. In accordance with these views,
the force of adhesion of metal to polymer depends on the content of the phase easily re-
moved in etching and its strength on the whole.
Chemical theory assumes the influence of the nature and concentration of functional
groups, for instance, the adhesion of a sulfite coating to chemically iodified polystyrene.
Wettability theory (surface-energy theory) considers adhesion as the adsorption pro-
cess, in which the forces of attraction depend on the distance between two plane bodies,
i.e., the complete mutual wettability specifies a better adhesion.
Diffusion theory assumes an increase of adhesion as the result of the diffusion of one
CHAPTER 8 257

substance into the other. The diffusive character of the formation of the copper sulfide layer
enhances its adhesion properties.
According to electrostatic theory, adhesion is also affected by electrochemical reac-
tions occurring near the interfaces between the polymer and working solution in the process
of metallization.
Thus, adhesion of the metal coating to the polymer film is affected by the state of the
surface and the strength of the polymer film, the presence of active functional groups on its
surface, its roughness, the nature and conditions of precipitation of the metal coating.
An optimal state of the surface of the polymer film before metallization depends both
on the method of processing the polymer into the film and the production of combined ma-
terials, and on the surface preparation processes, which include mainly degreasing and etch-
ing.
Degreasing is the initial stage of surface preparation to remove all organic impurities
possessing a large affinity to polymer. Most polymers are not wetted by water; therefore,
depending on the physicochemical properties of polymers, degreasing is done using organic
solvents or solutions of surfactants. Pure organic solvents are used rarely, because most of
them cause swelling of polymers, make the process more expensive and are harmful for the
environment. Commercially, aqueous emulsions are used the most; their compositions in-
clude organic solvents and synthetic emulsifiers. For degreasing, acidic or alkaline solu-
tions of the type of KM-1 are also used. Besides the removal of contamination, this
treatment causes a change of the structure of the surface layers of polymers owing to their
partial dissolution and swelling. This increases the etching capability of polymer and makes
it possible to increase adhesion of coatings.
Most polymers are etched using chrome mixtures. The regime and composition of
etching solutions for particular polymers are found experimentally, taking into account the
grade of polymer, fabrication conditions, roughness and other factors.
Processes occurring on the surface of ABS resins during the etching in a solution of
chromic anhydride and sulfuric acid have been studied. Under the action of etching solu-
tions, butadiene is oxidized by the double bonds to form carboxyl groups at a depth of sev-
eral micrometres. Herewith, butadiene dissolves to form pits of the shape of spherical
micro- and macrocavities.
An important role is also played by the composition of the polymer matrix. Owing to
the presence of acrylonitrile in the structure of ABS polymer, a better hydrophilicity of the
surface is achieved than in polystyrene, which has no polar component in its structure.
Another etching mechanism is observed using organic solvents. For this block copol-
ymer, particles of polybutadiene are embedded into the structure of styrene acrylonitrile and
swell to a greater extent than styrene acrylonitrile. Precipitation of metal occurs by the de-
fects emerging under the action of internal stresses determined by the different extent of
swelling and deformation of separate fragments of the polymer chain in the block copoly-
mer.
During the metallization of modified polypropylene subjected to etching, the quality
of the metal coating was shown to depend on the value and character of the distribution of
stresses in the surface layer, the extent of crystallization and size of supramolecular struc-
tures before and after the etching.
The use of minor amounts of finely dispersed additives and special surfactants has an
effect on the structural transformations during the etching, the stressed state on the surface,
amount and distribution of the amorphous phase, makes it possible to provide for the high
quality of coatings.
258 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Processes of etching some polymers in solutions containing no chromium compounds


have been developed. To ensure adhesion of the metal coating to polyamide, the material
is subjected to etching in aqueous solutions of organic bases (ethylene diamine and mono-
ethanolamine), and then is treated in a solution of potassium hydroxide.
Polyethylene and polyamides are recommended to be etched in acidic or alkaline so-
lutions of potassium permanganate.
In view of more rigorous ecological requirements, there is a tendency of using more
ecologically pure methods of modifying the surface of polymers, such as plasma etching,
corona discharge treatment, oxidative action of ozone and UV radiation.
In the preparation of the surface of polyethylene for metallization, it is efficient to use
combined methods, for instance, etching with a chromium mixture or with an acidic solu-
tion of potassium permanganate followed by the treatment with an electric discharge. High
adhesion of metallization in this case is explained by a favourable combination of the chem-
ical and microgeometrical structures of the film surface.
The effect of the nature of the support with the general tendencies preserved has its
own features for various polymer film-forming systems. There is no data in the literature
on the effect of the nature of metallized support on polymer coatings formation. In this con-
nection, for the development of polymer compositions and processes of their application to
metallized film materials, it is necessary to carry out studies to understand the mechanisms
of forming polymer coatings on metallized film materials and to develop methods of in-
creasing the adhesion strength of coatings to nonpolar and weakly polar film materials.
Polymer systems have a low adhesion strength to nonpolar or weakly polar film com-
bined packaging materials. Such materials also include metallized combined films.
A way of protecting the metallized layer from powdering under the action of a me-
chanical load and boiling is to form a thin polymer coating several micrometres thick on its
surface. To create such coatings, it is necessary to develop the physicochemical methods of
producing protective layers with high adhesion strength and resistance to sterilization.
The aim of the present work was to develop methods of modification of polymer com-
positions with high protective properties for metallized combined materials.

8.3 Protective coatings for metallized materials

High adhesion properties and resistance to the action of aggressive media are characteristic
of coatings based on low-molecular-mass epoxides ED-16 and ED-20. In this connection,
the epoxy bonding adhesive is chosen as the main component in developing a lacquer com-
position for protection of metallized packaging materials.
Studies of the regularities of forming the structure of epoxy network polymers contrib-
ute to the rational approach to monitoring the technological process for production and pro-
cessing of polymer materials on their basis, because the formation of these polymers occurs,
in contrast with linear ones, in the hardening of coatings.
Network (cross-linked, three-dimensional) polymers, according to the definition given
well back by Schtaudinger, are high-molecular-mass compounds, in which the constituent
chains are linked in three directions by chemical bonds, from which, however, covalent
bonds are capable of forming a three-dimensional network structure.
Other types of interaction (ion, coordination, hydrogen or intermolecular) introduce a
significant and sometimes even prevailing contribution to the formation, structure and prop-
erties of the polymer network.
CHAPTER 8 259

The occurrence of chemical bonds specifies a distinctive feature of network polymers


their insolubility in organic solvents and infusibility. The significant role of physical
bonds in the formation of the three-dimensional network of thermoreactive polymers is in-
dicated by the reversible change of the properties in repeated heating and cooling.
Based on the performed studies, it has been found that real network epoxy polymers
represent systems inhomogeneous by the size of structural elements, by the distribution of
chemical and physical bonds.
Epoxy oligomers consist of structural elements of globular morphology already in the
liquid phase. During the hardening, their polymerization proceeds first inside the globular
structures, which represent complex supramolecular formations consisting of more fine
structural elements.
Then links between these structures are formed. Chemical and physical bonds are dis-
tributed in the system unevenly. About 70% of them are formed inside the supramolecular
structures, which are characterized by a denser packing and orientation of polymer chains.
With this taken into account, the physicomechanical and protective properties of net-
work polymers are by several orders of magnitude lower than their calculated values ob-
tained with account for the strength of chemical bonds evenly distributed in the system.
Data of electron-microscopy studies of structure formation in hardening of network
polymers, including epoxy ones, also support the formation of an inhomogeneous defect
structure of the network, in which aggregates of colloidal size are separated by a structure
of lower-molecular-mass fractions.
Analysis of experimental data of the structure of epoxy coatings indicates that the
structural organization of polymers should be divided into three levels: molecular, topolog-
ical and supramolecular.
The molecular level of the structure reflects the chemical architecture of polymer, the
stereochemical organization of the chain, the character of the attachment of links one to an-
other. All parameters characterizing the molecular level of the structural organization can
be unambiguously related to the conditions of synthesis. The topological structure of poly-
mer describes the organization and structure of the chain as a whole. The supramolecular
level of organization of the polymer system reflects the character of intermolecular inter-
action of macromolecules and the extent of order in their mutual arrangement.
It is established at present that all polymers both amorphous and crystalline possess
an extent of order determined both by the molecular structure of polymer and the methods
of its production and reprocessing.
Studies of epoxy coatings have shown that the structure is formed already in initial oli-
gomer in the process of their synthesis. Similar data have been obtained by Catrell. He has
found that the structure emerges prior to the time of the loss of fluidity and is then fixed in
the process of hardening owing to a sharp decrease of mobility of the structural elements.
Studies of the formation specifics of coatings based on oligomers, solutions and dis-
persions of polymers have shown that the mechanism of this process is related to the tran-
sition of the system to a gelated state owing to the formation of local physical or chemical
bonds between structural elements and the inhibition of relaxation processes leading to the
emergence of internal stresses. Herewith, a view has been put forward and experimentally
substantiated that the formation process of epoxy coatings consists of two stages:
formation of local bonds within the limits of a small number of macromolecules,
which is accompanied with the formation of a supramolecular structure;
emergence of links between these structures and formation of the three-dimensional
network.
260 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

At the first stage, despite a significant number of groups involved in the formation pro-
cess, an induction period is observed on the kinetic curves for the change of the physico-
mechanical properties of coatings; the induction period is characterized by low physico-
mechanical properties and internal stresses in coatings. At the second stage, a sharp slow-
down of the relaxation process and the emergence of internal stresses are observed. This
character of structural transformations is common for network polymers and is found in
studies of the hardening of coatings based on oligoester urethanes, epoxides, phenol form-
aldehyde, organosilicon and other polymers.
By the method of NMR, it has been shown that, depending on the chemical composi-
tion of oligomer, folding of macromolecules into supramolecular structures can be differ-
ent, which, in turn, determines the distribution (on their surface) of active groups involved
in the film formation process and in the interaction with the support. To realize the largest
number of functional groups in the formation of adhesion and cohesion bonds, it is neces-
sary to develop in oligomer systems ordered structures of anisodiametric or clustered type
from unfolded molecules.
Electron-microscopy studies of polymers showed the morphology of sparsely cross-
linked polymers to differ little from the character of structural elements for linear polymers.
The major structural elements can be all morphological types (globules, spherolites,
crystallites, fibrillae, etc.) characteristic of linear polymers.
For densely crosslinked epoxy polymers obtained from oligomers with the static dis-
tribution of the functional groups, the main structural element are globules.
Variation of the structure of the initial reagents (oligomers, hardeners, solvents),
change of the formation conditions or the effect of thermal or mechanical fields on the al-
ready formed polymer do not change the morphology of the structure of a densely
crosslinked polymer: in all case, it remains globular, only the size of globules and the den-
sity of their packing do change.
Oligomers with the regular structure of the chain form associates of anisodiametric
shape from macromolecules of unfolded conformation, as well as highly organized crystals
of various morphologies. The number and size of globules change depending on the hard-
ening conditions.
Hardening of epoxy coatings at low temperatures is accompanied with the develop-
ment of large globular formation in the structureless matrix.
The subsequent heating of coatings up to 343353 K at the second stage of hardening
leads to the emergence of small globular formations and an increase of their number. Here-
with, chain and band structures are formed in epoxy coatings, which is indicative of the de-
struction of some bonds between structural elements and their regrouping into more
complex structural elements.
According to the data by Catrell, formation of supramolecular structures is determined
both by hardening temperature and rate. At a large rate of hardening, the size of globules
formed is 2010 6 m, whereas the slow hardening at low initial temperatures is accompa-
nied with the formation of globules of up to 9010 6 m.

8.4 Methods of modifying the structure and properties of epoxy coatings


Coatings used for protection of metallization should have a high resistance to the action of
water in boiling. The performance properties of epoxy coatings significantly depend on the
nature and concentration of hardeners. The resistance of coatings to the action of aggressive
media is significantly affected by the ratio between the value of internal stresses and adhe-
CHAPTER 8 261

sion strength of coatings. In this connection, the issues related to the development of phys-
icochemical way of decreasing internal stresses are of great scientific and practical
significance. One of the ways to decrease them is to develop methods of modifying com-
positions in the process of their synthesis. Internal stresses emerging in the formation and
performance of coatings are a measure of imperfection of their structure. In this connection,
targeted synthesis of oligomers with a regular structure of the chain or their modification
by special additives make it possible to significantly reduce internal stresses in coatings.
The effect of the structure of epoxy oligomer molecules on the protective properties
of coatings based on oligomer ED-20 was studied by using compounds of various chemical
compositions and molecular structures as hardeners. Along with polyethylene polyamine,
which makes epoxy oligomers harden as the result of copolymerization by epoxy and amino
groups by way of opening the oxide rings and substituting hydrogen atoms of hydroxyl
groups, ester acids with different chain structures were used as hardeners.
Regularities in the change of internal stresses depending on the main factors, which
determine the film formation process (formation conditions, film thickness, strength of in-
teraction at the polymersupport interface, etc.) proved to be common for coatings based
on various oligomer systems.
The rate of increment and the value of internal stresses in the formation of epoxy coat-
ings depend on the hardening conditions. At 20C, internal stresses rise comparatively
slowly and reach an ultimate equilibrium value in 2030 days.
As the formation temperature rises, the internal stress increment rate goes up, espe-
cially significantly in the range equal to or greater than the glass-transition temperature.
When comparing the kinetics of using the functional groups of epoxy oligomer in the
formation of coatings with the internal stress increment rate, it was found that there was no
symbasis in their increment. The rate of using the functional groups in the formation of the
three-dimensional network is much faster than the rate of increment of internal stresses.
The number of epoxy groups entering into the polymerization reaction was assessed
by IR spectroscopy from the change of intensity of the absorption bands in the region of
918 and 1247 cm 1, characteristic of epoxy groups; and 3350 cm 1, for amino groups.
The structure of epoxy coatings was studied by the method of electron microscopy by
taking carbon-platinum replicas at various stages of coating formation.
The regularities obtained suggest that at 20C more than 50% of all functional groups
enter into interaction for 57 h; in 1020 h, the polymerization process is totally complete;
herewith, 5075% of epoxy groups enter into the reaction. Internal stresses under these
conditions of hardening reach the ultimate value in 2530 days.
At 80C, the number of functional groups involved in the interaction increases up to
85%, and the polymerization process ends up in 6090 min of coating formation. Internal
stresses under these formation conditions reach an ultimate value in 1012 hours of hard-
ening.
Despite the small value of shrinkage of epoxy coatings in hardening (not more than
12%), they feature significant internal stresses up to 1015 MPa which at a film thick-
ness of 300400 m induce a spontaneous peeling and cracking of coatings.
Internal stresses were decreased by changing the nature of hardener for epoxy systems.
The dependence of internal stresses and other mechanical properties of films on the
amount of hardener in the composition is nonmonotonous and exhibits a maximum corre-
sponding to the formation of the largest number of crosslinks, therefore the decrease of in-
ternal stresses by changing the amount of hardener is accompanied with the worsening of
the other mechanical properties.
262 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

14.0

12.0 1

10.0
2
3
8.0
b10, MPa

6.0
4

4.0

2.0

400 800 1200 h, m

Figure 8.1 Dependence of internal stresses on the thickness of coatings from composite epoxides
hardened by polyethylene polyamine (1), glycerol trisuccinate (2), glycerol triadipinate (4) at 120C,
as well as glycerol tricebacinate at 200C (3).

To improve the mechanical properties of coatings, use was made of ester acids with
different chain structures as a hardener. The properties of coatings from epoxy oligomer
ED-20 changed depending on the nature of trifunctional ester acid. As the length of ester
acid branchings increased, the elasticity of coatings increased too.
Coatings were formed from 6085% alcohol-acetone solutions of epoxy oligomer
and, respectively, 70% acetone solutions of glycerol trisuccinate, triadipinate and triceba-
cinate at a ratio 1:1. Coatings were hardened at 120C. If coatings based on glycerol trice-
bacinate were hardened not at 120C but at 200C, their elasticity was smaller than for films
based on triadipinate formed at 120C. This is due to the fact that at this temperature, along
with the reaction between carboxyl groups and epoxy groups, there is probably a side reac-
tion of carboxyl and hydroxyl groups, which, in turn, leads to an additional crosslinking.
From the data on the kinetics of increment and relaxation of internal stresses, the
changes of hardness in the formation of coatings from these compositions at 120C and sub-
sequent operation of coatings at 20C, it follows that compositions based on glycerol trisuc-
cinate and triadipinate harden well under these conditions, and compositions with glycerol
tricebacinate harden very slowly, so that the formation of coatings from them can be per-
formed only at 200C.
The largest internal stresses emerge in coatings hardened by glycerol trisuccinate.
These data indicate that, as the length of branchings in ester acids, which harden the epoxy
oligomer, increases, internal stresses decrease, and elasticity of coatings goes up. If the
length of branchings is higher than the optimal value, which takes place in the introduction
of glycerol tricebacinate, the hardening of the composition at 120C is not observed. With
CHAPTER 8 263

b, MPa
1
6.0

5.0

4.0

3.0
3
2.0
2
1.0

2 4 6 8 10 12 , h

Figure 8.2 Kinetics of increment of internal stresses in the formation of epoxy coatings with glyc-
erol trisuccinate (1), glycerol triadipinate (2) at 120C, with glycerol tricebacinate (3) at 200C.

E .10, MPa

1.2 3
4
1
Hardness, arb. u.

0.5 1.0

0.4 0.8 6
5
0.3 0.6

0.2 0.4 2

0.1 0.2

5 10 15 20 25 30 , h

Figure 8.3 Kinetics of increment of the elasticity modulus (13), hardness (46) in the formation
of epoxy coatings with glycerol trisuccinate (14) and glycerol triadipinate (25) at 120C, with
glycerol tricebacinate (36) at 200C, amounts of E in GPa.

the formation temperature increasing up to 200C, coatings based on this composition re-
veal the highest physicomechanical properties.
Coatings from a composition with a hardener based on glycerol trisuccinate and tria-
dipinate under conditions of hardening at 200C spontaneously break down due to their
high embrittlement. Figure 8.1 presents a dependence of internal stresses for coatings of dif-
ferent chemical compositions on the thickness of the film. It is seen in the figure that coat-
ings based on glycerol trisuccinate and triadipinate (hardened under optimal conditions),
are characterized by a high adhesion strength within a wide range of film thicknesses.
Figures 8.2 and 8.3 present the kinetics of internal stresses, elasticity modulus and
264 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

hardness in the formation of coatings based on epoxy copolymers with various hardeners.
It is seen that the formation of coatings at 120C ends up practically in 56 h, when the
physicomechanical characteristics reach their ultimate maximal value.
Table 8.2 presents the data on the effect of the nature of hardener on the maximal in-
ternal stresses, elasticity modulus, tensile strength and adhesion strength of coatings.
Table 8.2

Hardener b, MPa E, MPa p, MPa A, MPa

Glycerol trisuccinate 6.0 0.9 15.0 13.0


Glycerol triadipinate 1.5 0.4 5.0 10.0
Glycerol tricebacinate 2.5 1.2 35.0 15.0

A specific feature of coatings based on glycerol tricebacinate is that at a high adhesion


strength, hardness, tensile strength they reveal comparatively small internal stresses.

8.5 Protective coatings from copolymers of regular structure


To improve the performance properties of coatings to decrease internal stresses in them
at a simultaneous improvement of the other physicomechanical characteristics (adhesion,
strength) techniques have been developed to produce regular-structure epoxy copolymers.
The effect of the structure of macromolecules on the structure and properties of coat-
ings from polyester-epoxy and silicon-containing polyester-epoxy polymers of irregular
(III) and regular (I, II) structure has been studied.
Polyester-epoxy oligomers were synthesized according to the following scheme:
O O
C[CH2OC(CH2)nCOOH]4 + 2CH2 CHCH2ORCH CH2

C CH2OC(CH2 )nCOCH2CHCH2OROCH2CHCH2OC(CH2)nCOCH2 C
O OH OH O O
As the diglycidyl component, use was made of hydroquinone diglycidyl and dipheny-
lol propane diglycidyl. Organosilicon polyester amidoepoxy polymers of regular structure
were produced in two stages. At the first stage, pentaerythrite tetraadipinate was condensed
with bis-(phenyl aminomethyl)tetramethyl disiloxane:
[CH2OC(CH2)4COOH]4 + 2HNCH2Si(CH3)2OSi(CH3)2CH2N H2O

C CH2OC(CH2)4C N CH2Si(CH3)2CH2N C(CH2)4COCH2 C


O O O O

The produced copolymers, which contained phenylamino methyl xylyl and carboxyl
groups, were converted to copolymers with the regular distribution of carbon atoms in the
network by the interaction with diglycidyl esters.
CHAPTER 8 265

130
1

100

80
b10, MPa
2
60

40
3

20 4

6 12 18 24 30 36 , h

Figure 8.4 Kinetics of internal stresses in the formation of coatings at 160C from copolymers I (2),
II (3), III (4) and epoxy oligomer (1).

We investigated the performance properties of coatings based on copolymers of the


following chemical composition:
O O OH CH3
C CH2OC(CH2)4COCH2CHCH2O C

CH3

OH O O CH3 CH3
OCH2C CHCCH2OC(CH2)4COCH2C CH2 OC(CH2)4CNCH2SiOSi

CH3 CH3

CH2NCH2CHCH2OROCH2CHCH2C(CH2)4OCH2C

OH OH O
Copolymer III represented a product obtained by the condensation of pentaerythrite
with adipic acid and diglycidyl ester of diphenylol propane at a simultaneous charging of
the components, and was distinguished by an irregularity of the structure.
To elucidate the effect of the composition and structure of polymers on the properties
of coatings, the kinetics of increment of internal stresses and other characteristics in the
hardening of compositions was studied.
From these data, it follows that the ordering of the structure of regular-structure oligo-
mers contributes to a 23-fold decrease of internal stresses in the formation of coatings as
the result of relaxation processes prior to the formation of adhesion bonds in the formation
of coatings. Coatings from regular-structure copolymers are also distinguished by the sta-
bility of the properties (Figs. 8.4 and 8.5).
266 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

E .104, MPa
4
24 1

Hardness, arb. u.
0.6
5

0.4 16 6
2
3
0.2 8

5 10 15 20 25 , h

Figure 8.5 Change of the elasticity modulus (1 3) and hardness (4 6) in the formation of coatings
from copolymers I (1, 4), II (2), III (3, 6) at 160C.

From the analysis of the results on the kinetics of increment of the elasticity modulus
of these same films in the formation of coatings, it follows that the elasticity modulus reach-
es an ultimate value in 1015 hour of formation.
Films from copolymer II harden the most rapidly at 160C. The character of the de-
pendence of internal stresses on the thickness of films for coatings from compositions of
various chemical compositions is linear.
Along with small internal stresses, coatings from regular-structure copolymers are
characterized by a high adhesion strength. From the comparison of the properties of coat-
ings obtained from various copolymers based on oligomer ED-20, it follows that internal
stresses in coatings from compositions 1 and 2 are 4 to 10 times less than in coatings from
the initial epoxy oligomer hardened with polyethylene polyamine. Herewith, coatings
based on ED-20 peel off at a comparatively small thickness of 400 m. Films based on co-
polymers peel off at the same value of internal stresses at a thickness larger than 2500 m.
This is indicative of a much larger adhesion strength of coatings from copolymers as com-
pared with coatings from the initial epoxy oligomer.
Table 8.3 presents the data on the physicomechanical characteristics of coatings from
regular-structure copolymers.
Table 8.3 Effect of chemical composition on the physicomechanical properties of coatings.

Film-forming p, MPa E, GPa b, MPa A, MPa Margin of cohesion


component strength

Copolymer I 25.2 1.5 1.4 150 18


Copolymer II 34.3 2.4 0.7 150 49
Copolymer III 21.5 1.2 2.2 9
ED-20 60.0 2.4 7.0 130 8

The tensile strength of films from regular-structure copolymers is 2050% larger than
for irregular-structure films, but 1.52 times smaller than the strength of films from ED-20.
However, in view of the small magnitude of internal stresses for coatings from regu-
lar-structure copolymers, their cohesion strength is 26 times higher than that of films from
oligomer ED-20. As the result, coatings from regular-structure copolymers are more dura-
ble than coatings from ED-20.
CHAPTER 8 267

Based on the regularities obtained, a composition based on epoxy oligomer ED-20 was
developed and a hardener with the regular structure of molecules; the composition hardens
for several minutes to form coatings with a high adhesion strength to metallized combined
materials from polypropylene and lavsan.

8.6 Combined metallized materials for dairy produce packing

8.6.1 Combined material based on polyethylene, paper and aluminium foil


Combined material consists of five layers, each of which has its own functionality:
the first (outer) layer from polyethylene; it is intended for protection of the paper base
from moisture and contamination;
the second layer from base paper of pure cellulose; density, 200250 g/m2. This lay-
er is the load-bearing structure of a packaging to provide its good rigidity and to give it a
geometrically constant shape. These characteristics are obtained owing to long fibres, from
which paper consists. Besides, paper is a protective layer;
the third layer from polyethylene; it serves for glueing the paper base and aluminium
foil;
the fourth layer from aluminium foil 9 m thick. It is the most essential barrier for
the action of atmospheric agents and gases. Even at this thickness, there are almost no
microholes on the surface of foil. This layer also protects well the contents of a packaging
from the light, thus preserving for a long time the primary organoleptic characteristics of
products. Besides, the plasticity of this layer makes it possible to bend the edges of a pack-
age and its angles without flaws. This layer is required for induction heat sealing;
the fifth (internal) layer from polyethylene. Its thickness is much larger than that of
the first and third layers. It consists of two sublayers: the adhesion oxidized sublayer and
the unoxidized sublayer, which is in contact with the product. The main aim of this layer is
to enhance the protective barrier and to facilitate the sealing (longitudinal and two trans-
verse ones).
Fabrication of a five-layer combined material includes the following operations: un-
winding of the base paper, gas-flame treatment of the base paper, coating of the external
side of the paper with decorative printing and a layer of polyethylene, corona treatment of
aluminium band, application of the intermediate polyethylene layer between aluminium foil
and base paper, application of the bilayer inner coating from the melt of polyethylene on
the side of aluminium foil, cutting of edges, winding of ready material to rolls.
When elaborating the process regimes for production of combined material, the main
parameters of the lamination process were varied: temperature by the extruders zones,
working speed of the base sheet, temperature of cooling water at the input to the pressure
rollers of the laminators, frequency of rotation of augers at the startup, melting temperature
of polyethylene in the flat-die drawhole of the extruders, pressure of the melt of polyethyl-
ene before the package of the filtering meshes, working pressure of gas and air fed to the
burners of the gas-flame station, unit force of the laminators at the winding and unwinding
units, parameters of corona treatment of the surface of the base.
The parameters of the process were chosen such that to provide for good adhesion of
all five layers of combined material, to achieve the required mass of the polyethylene coat-
ing in an area of 1 m2 at a high rate of the process, to exclude the oxidation of the inner
polyethylene coating in contact with the product.
268 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The following regime of the technological process for fabrication of combined mate-
rial was established and used in production of pilot batches at the Enterprise for Production
of Packagings and Containers of the Kuban Agroindustrial Complex:
the temperature of the polyethylene melt applied to the base paper and foil is within
305312C for the external coating; 305318C, for the intermediate layer; 303324C,
for the oxidized layer; and 275281C, for the unoxidized layer of the internal coating;
the speed of travel of the base sheet, 10010 m/min;
the number of blocks on the corona discharge units, 4345;
the ratio of air and gas pressure in the installation, 37%;
the temperature of cooling water at the output to the pressure rolls of the laminators,
22C.
Good quality of the combined material is one of the essential conditions for the stable
operation of automatic filling machines at dairy plants. It provides for minimal losses of
packaged dairy produce in its transportation, storage and sales. Therefore, the correct choice
of the main parameters for the output control at the combined-material manufacturing
plants and the input control at the dairy enterprises is one of the major issues in the
producerconsumer chain.
When phasing in to the optimal regime of production, making it possible to produce
combined material of required quality, specimens from 22 pilot batches were chosen and
their physicomechanical tests carried out. The following parameters were taken into ac-
count: the mass of 1 m2 of polyethylene coatings (layer-by-layer), the thickness of com-
bined material, adhesion of the polyethylene layers to the paper base, resistance to peeling
(aluminium foilpolyethylene).
Control of the mass of 1 m2 polyethylene coatings and bonding layer is required for
the correct monitoring of the production of combined packaging material based on paper
(paperboard) and aluminium foil and is of great significance for production of packaging
material of required quality.
A method of determining the mass of a 1 m2 polyethylene layer in the combined ma-
terial based on paper and aluminium foil has been developed; the method was submitted as
the application for an invention and became the basis of a new methodology of determining
the mass of the polyethylene layer.
Simultaneously with the physicomechanical tests, the sanitary and chemical assess-
ment of pilot batches of combined material was carried out in accordance with the Instruc-
tion and Recommendations of the Ministry of Health. Distilled water and a 0.3% solution
of lactic acid were used as model media. Extracts for studies were obtained under conditions
close to the operational conditions of packaging material. Model media were poured into
packs from the investigated material of 1 litre capacity. Upon filling, packs were hermeti-
cally sealed on a laboratory sealing machine at the regimes similar to the conditions of seal-
ing in commercial automatic machines. Extracts were kept for 1 and 3 days at room
temperature. The organoleptic assessment of aqueous extracts was carried out by the meth-
od of extended triangle by the five-point scale at room and elevated temperatures
(4060C).
Sanitary and chemical investigations of test specimens of the material were also car-
ried out with the aim to determine the extent of migration in extracts of low-molecular-mass
substances. The oxidizability of aqueous extracts was determined by the dichromate meth-
od. The content of brominated substances in aqueous extracts and lactic extracts was found
by the method of volumetric iodometry. The content of formaldehyde was assessed by the
method of thin-layer chromatography.
CHAPTER 8 269

The results of the studies have shown that in specimens of the final test batches of com-
bined material the total migration of low-molecular-mass substances is insignificant; the
presence of formaldehyde was not found. The regimes at which the final batches were pro-
duced, satisfying the requirements of dairy industry by the sanitarychemical and perfor-
mance properties, have been entered into the technical documents for the production of
combined material.
Thus, the effect of the process parameters on the quality parameters of combined ma-
terial has been studied; the method of determining the mass of 1 m2 of the polyethylene lay-
er has been determined; the nominal values of the parameters and tolerances for them have
been found; sanitary-chemical studies of the test specimens of combined material have been
carried out; the technological regulations for the production of combined material has been
developed; the technical specifications for a combined material based on paper and alu-
minium foil for packaging milk and dairy products have been developed and approved.

8.6.2 Hermeticity of polymer packaging


One of the main conditions for preserving the quality of a packaged product and preventing
its losses is the air-tightness of the packaging, which should not be disturbed on the way of
the product from producer to consumer.
At present, the air-tightness of various kinds of consumer containers from polymer ma-
terials in dairy industry enterprises is controlled visually. This control fails to provide an
objective assessment of quality and leads to losses of milk and dairy products during the
storage, transportation and sales.
Based on the literary and patent data in the field of nondestructive methods of control,
it is proposed to use the filled-system and optical methods of leakage detection for the as-
sessment of the air-tightness of consumer containers used for packaging milk and dairy
products. These methods are informative, do not require complex equipment, are simple
and provide express information.
Two instrumental methods of operational air-tightness control have been developed:
the method of determining the air-tightness of consumer containers capped with foil with a
thermolacquer coating (the method of TL measurements) and the method of determining
the air-tightness of polyethylene packets of the type of Elecster and Finnpack using a pho-
toelectric colorimeter (the method of PC measurements).
The essence of the TL method is to create a certain vacuum in a hermetically sealed
chamber with a capped (unfilled) consumer container. Due to the pressure difference inside
and outside the tested package, its shape and size change (it swells). If the package is
air-tight, after the removal of vacuum it acquires its initial shape. If the air-tightness of the
package is disturbed, no change of size is observed under the action of vacuum. When the
integrity of the package is violated during its exposure to vacuum, the leakage is determined
visually (breakdown, peeling and other defects) or (if there are microdefects) the package
is compressed after the vacuum is removed.
Tests of the consumer containers capped with foil with a thermolacquer coating were
carried out in a vacuum exciccator and in a vacuum cabinet at a maximum vacuum of 0.09
MPa. To determine the optimal conditions required for the assessment of the air-tightness
of consumer containers of 250 g capacity, the value of vacuum was varied within the range
of 0.0650.015 MPa, exposure time was from 1 up 10 min (Table 8.6.1). The result of the
experiment was taken to be the share of packages with violated air-tightness in percent.
At a vacuum of 0.0630.065 MPa, practically 100% of the specimens break down.
270 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The vacuum of 0.0630.065 MPa for this type of packagings is critical and can be used as
a characteristic of strength of sealed thermoformed containers. It should be noted that the
parameter depends on the kind and quality of raw materials used to produce polymer sheet
materials (granulated polymer), on the geometric size and shape of the package, on the cor-
rect observance of the process regime of the fabrication of consumer containers.

Table 8.6.1 Data on the air-tightness of polystyrene containers.

Vacuum, MPa Non-airtightness, in %, at exposure time (in min)

1 3 5 7 10

0.065 100
0.063 100
0.060 81.25 75 94
0.055 37.5 43.75
0.050 25 18.75 25 68.75 31.25
0.040 37.5 6.25 12.5 37.5
0.030 20.5 12.5 18.75 50
0.025 6.25 18.75 6.25 12.5 18.75
0.020 0 12.5 6.25 12.5 12.5
0.015 0 6.25 12.5 12.5 12.5

Note: The result was taken to be the mean arithmetic test of 16 specimens.

Analysis of the dependence of the share of non-air-tight containers on the value of vac-
uum at different exposures (Fig. 8.6.1) and that of the share of non-air-tight containers on
the exposure time at fixed values of vacuum (Fig. 8.6.2) made it possible to find the optimal
exposure time of specimens to be 5 min and the value of vacuum, 0.0150.04 MPa.
N, %
100

80 1

60

40 2

4 3
20 5
6
7

0 2 4 6 8 10 , min

Figure 8.6.1 Dependence of the share of unsealed containers (N) on exposure time. Residual pres-
sure, MPa: 1, 0.06; 2, 0.05; 3, 0.04; 4, 0.03; 5, 0.025; 6, 0.02; 7, 0.015.
CHAPTER 8 271

N, %
100

80

60

40

3 2 1
20

4
0
0.01 0.02 0.03 0.04 0.05 P, MPa

Figure 8.6.2 Dependence of the share of unsealed containers (N) on pressure. Exposure time, min:
1, 10; 2, 5; 3, 3, 4, 1.

The final conclusion on the optimal characteristics was made based on the determina-
tion of the maximal load acting on a package in transportation, storage and sales.
To monitor the air-tightness of Elecster- and Finnpack-type packages, it was proposed
to test the optical method of nondestructive control. The method is based on the determina-
tion of traces of milk in water by the results of optical-density changes of water, in which
packs with milk were kept under a load. This approach makes it possible to reveal the pres-
ence of microdefects in milk packages in the case when it does not appear possible to assess
the absence of air-tightness visually. To reveal the presence of milk in water, use was made
of refractometers of RPL-3 and IRP-4 type (measurement of the refractive index), and also
a FEK-M photocolorimeter (measurement of optical density).
It has been found that the refractometric method can not be used for these purposes,
because the experimental data are within the error of the experiment.
Positive results were obtained using a FEK-M photocolorimeter. The maximal sensi-
tivity of the instrument in this range of concentrations is observed when using cuvettes with
the working length of 3 cm and a yellow light filter.
The elaboration of the proposed method of monitoring the air-tightness was carried out
on 500-ml Elecster packages filled with milk; the packages were fabricated from imported
black-and-white bilayer coextruded polyethylene film. A washed and dried package with
milk was placed into a bath, into which 1 litre of water was poured; after that a load was
applied to the package, under which the specimen package was held for a certain time. Then
the package was removed from the bath, a sample of water was taken and its optical density
was determined on an FEK-M. It proved that for determining the optimal conditions of us-
ing the leakage-search method developed it is expedient to use packages with microdefects.
To determine under optimal condition the air-tightness of Elecster-type packages of 500
cm3 capacity, the load was varied within the range of 30 up to 70 N; exposure time, from
0.5 up to 2 min (Table 8.6.2).
272 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 8.6.2 Results of the air-tightness control of Elecster-type packs (with microdefects).

Load, N Exposure time, min Optimal density Content of milk in water, %

30 0.5 0.02 0.003


30 1 0.087 0.014
30 2 0.02 0.003
50 0.5 0.03 0.006
50 1 0.089 0.015
70 0.5 0.11 0.02
70 1 0.11 0.02
70 2 0.11 0.02

Note: In all cases the solution was clear.

Analysis of the experimental data and their recalculation for an additional load emerg-
ing in transportation, would enable making the optimal conditions of monitoring the
air-tightness of polyethylene milk packages of the type of Elecster and Finnpack more con-
crete.
These parameters were used to develop the protocol for determining the air-tightness
of polyethylene bags of the type of Elecster and Finnpack using a photoelectric colorimeter.
The developed methods of monitoring the air-tightness passed the metrological certifica-
tion and were assigned the state register numbers.
The methods considered were included in The Book of Methods of Input and Produc-
tion Control of Packaging Materials and Consumer Containers developed by the Labora-
tory of Packaging, All-Russian Research Institute of Dairy Industry (VNIKMI).

8.6.3 Coextruded polyethylene films for packaging dairy produce and


their quality indices
A widespread method of packaging milk at present is using disposable containers, which
became an integral part of the production process. The development and improvement of
the kinds of packaging is aimed mainly to preserve the quality and nutritive value of the
product.
The modern milk packaging should satisfy a whole range of requirements: it should
be harmless for man; to protect milk from spoilage, contamination and the effect of external
factors, such as moisture and foreign smells; to provide for the preservation of the product
in transportation and storage; to have a small mass and area; to have an attractive appear-
ance; to be cheap and easy to handle.
One of the widespread methods of packaging milk is its production in soft polyethyl-
ene packs. Polyethylene film as a packaging material conforms to all the above require-
ments. Such of its properties as nontoxicity, strength, elasticity; vapour, water and gas
impermeability; chemical inertness, relative simplicity of the production process stipulated
the wide use of this material in dairy industry. Besides, polyethylene film is the cheapest as
compared with other packaging materials.
In this country, packaging of milk and dairy products is performed using filled poly-
ethylene film produced by coextrusion from low-density polyethylene (LDPE), mainly of
grade 17504-006, with addition of 3% titanium dioxide and 0.08% slip additive Armide O.
CHAPTER 8 273

Titanium dioxide used as a filler is imported. In this connection, an important task is mod-
ification of coextruded films with the view to exclude or reduce the content of titanium di-
oxide.
The possibility of increasing the volume of production of this film and its modification
with the view of expanding the range of packaging materials has been studied.
Analysis of the home raw-material base and process equipment for production of films
made it possible to pinpoint the real directions of modification. Reduction of the consump-
tion of materials in production of the film without deteriorating its properties is possible ow-
ing to the use of the features of the coextrusion method of production. The bilayer
polyethylene film produced by the extrusion method has no drawbacks characteristic of in-
dividual films; the use of this method reduces the probability of random defects. Also, it
makes possible the protection from the light due to the introduction of pigment into the outer
layer of the film.
Considering the above-said, and also based on the analysis of the existing range of
grades of LDPE compositions permitted for use by the Ministry of Health, new construc-
tions of films have been proposed.
Test batches of films were produced at the Borisov Plant Polimiz on the Finnpack
equipment of the firm Tuomo Halonen (Finland) and Rotex 40 D (Germany). Four types of
coextrusion polyethylene film were produced (2, transparent; 2, semitransparent); LDPE
(base grade 17504006) and its compositions for them were fabricated by the Novopolotsk
Industrial Association Polimir (see Table 8.6.3).
Table 8.6.3 LDPE compositions for manufacturing coextrusion films.

LDPE grade Content, %

titanium dioxide Armide O

17504006
175132 0.08
175225 3.0 0.08

Regimes for the production of the films were identical for all their types (Table 8.6.4).
The types of the films are given in Table 8.6.5.
Table 8.6.4 Regimes of production of coextruded polyethylene films.

Specimen no Equipment Temperature at exit Auger Extrusion rate,


from auger head, C rotation frequency, m/min
rpm

1 Finnpack 190 6010 282


2 Rotex 40D 190 400500 2226
3 Finnpack 190 6010 282
4 Finnpack 190200 6070 2530

It is known that the possibility of phasing in novel packaging materials intended for
contact with food products depends on a range of conditions. They include the results of
studies of the quality of films with the aim to assess their effect on the human organism, the
determination of the physicomechanical characteristics and the possibility of their use on
274 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

the packaging equipment. In this connection, the Laboratory of Packaging, All-Russian Re-
search Institute of Dairy Industry (VNIKMI) conducted the sanitary-hygienic and physico-
mechanical tests of pilot batches of films.

Table 8.6.5 Design of experimental films.

Specimen no Design of films Polyethylene grade

for inner layer for outer layer

1 Transparent (no additives) / transparent 17504006 17504006


(no additives)
2 Transparent (with slip additive) / 175132 175132
transparent (with slip additive)
3 Transparent (no additives) / white 17504006 175225
(with slip additive and titanium dioxide)
4 Transparent (with slip additive) / white 175132 175225
(with slip additive and titanium dioxide)

The sanitary-hygienic studies were conducted in accordance with the methodological


recommendations and the Instruction for Sanitary-chemical Study of Articles Fabricated
from Polymer and Other Synthetic Materials Intended for Contact with Food Products.
They included organoleptic and chemical studies of extracts of model media specimens of
a test bilayer coextruded polyethylene film, whose conditions corresponded to the
temperaturetime regimes of packaging from filled films with increased severity. Model
media were 0.3% distilled water and 3% lactic acid. The ratio of the inner surface of a pack
and the volume of the model medium was 1:1. Extracts were held at room temperature in
hermetically sealed packages for 1, 3 and 10 days. After exposure, the appearance of the
extracts was studied and their organoleptic assessment was performed.
Studies of the appearance of extracts showed them in all cases to be nonturbid and con-
tain no residue. According to the results of an organoleptic assessment, at all temperature
time conditions of the experiment the intensity of smell of aqueous extracts did not exceed
1 point, i.e., the organoleptic properties of the film were stable.
Chemical studies of model media have been conducted with the view to investigate
migration of low-molecular-mass compounds in them. Migration of oxidizable and bromi-
natable substances into model media was insignificant; no formaldehyde was found.
The strength characteristics were determined on an Instron tensile tester. The breaking
strength and relative breaking elongation were determined according to the State Standard
(GOST); the strength of the heat seal, in accordance with the procedure. Tests were carried
out in longitudinal and transverse directions. The static coefficient of friction was deter-
mined by the method of inclined plane.
Analysis of the obtained experimental data made it possible to assess the quality of the
bilayer coextruded polyethylene film in pilot batches and to give recommendations on the
changes to be introduced into the technical specifications.
To solve the issue of the suitability of unfilled (both transparent and semifilled) poly-
ethylene film for filling milk and dairy products, it was tested in dairy enterprises. Based
on the results of integrated studies, recommendations were issued to use for packaging milk
and fermented milk drinks the unfilled (transparent) polyethylene film with sliding additive
in both layers and the semifilled polyethylene film with sliding additive in both layers and
titanium dioxide in one layer. These films combine the required physicomechanical and
CHAPTER 8 275

sanitary-hygienic properties and can be used in the dairy industry on M6-ORZE and Finn-
pack automatic packaging machines.
276 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY
9 Technology of Forming
and Modifying Multilayer
Metallized Packaging
Materials

9.1 Purpose and production of multilayer materials


Packagings from composite plastics, including metallized plastics, find ever wider use in
meat and food industries. Often they are given the preference over traditional articles from
metal and plastics owing to their low specific mass, high mechanical strength and corrosion
resistance. Metallized polymer materials are dielectrics. They possess an increased resis-
tance to the action of moisture, organic solvents, high temperatures, gas and vapour perme-
ability during the boiling of packagings, as well as endow materials and articles with
specific performance properties resistance to the action of bacteria and molds, protection
of food products from ionizing radiation. To obtain a metal layer, use is made of such metals
as aluminium, copper, nickel, platinum, tin, lead, zinc, as well as metal alloys. A topical
problem is protection of the surface of these materials, the purpose of which is to decrease
the number of formation defects, to increase the resistance to cracking, scratching, as well
as atmospheric and biochemical resistance of materials, to improve the decorative proper-
ties. One of the promising and non-traditional ways of solving this problem is to develop
polymer composite materials with high adhesion to the metallized layer, resistant to the ac-
tion of sterilization. This makes it possible to simplify the technological process of fabri-
cating multilayer packaging materials as the result of reducing the number of layers and,
respectively, stages of extrusion lamination and adhesive bonding of film materials with foil
or the metallized layer, as well as to rule out the labour-intensive and expensive treatment
of the surface of substrate with a metallized layer and to reduce the treatment temperature.
The use of a lacquer layer for protection of combined packaging materials makes it possible
to develop systems, which can successfully compete with foiled packagings by their prop-
erties, technical and economic parameters and fields of applications. Calculations based on
the data by Russian enterprises show that transition from the production of combined ma-
terials based on foil to metallized packagings ensures a significant economy of raw mate-
rials.
In Russia, fabrication of packaging materials for food products had not received due
development, and sharply decreased in the recent years. At the international symposium
Food Packaging in Russia reports of experts on the TACIS program A strategic review
278 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

of packaging food products were discussed. It was noted that a significant drawback of the
Russian packaging branch of food industry was the absence of stable links in the raw-ma-
terials manufacturerpackaging manufacturerconsumer chain. The disruption of these
links is one of the main causes of the growing import of packaging materials and the low
level of home packaging production.
Domestic packagings were assessed from the point of view of their correspondence to
the main functions they should perform: integrity in transportation and storage, as well as
quality appearance to attract attention of consumers. Analysis of the statistical data on the
industrial-branch and regional level has shown that none of the regions in Russia produces
a sufficient quantity of packagings. Glass is predominant in fabrication of packagings for
food products (55% of the total volume), whereas in Europe and the USA its production
occupies only the third place in the packaging nomenclature. Plastic packagings and those
from corrugated paper make only a minor percentage in Russia, whereas in Europe and the
USA they occupy the first place. In Russia as compared with these countries, tin cans are
manufactured 4.5 times less; steel cans, 55 and 47.5 times; aluminium cans, 18.6 and 5.3
times less; films, 21.3 and 7 times; glass containers, 4.7 and 4.8 times; corrugated paper, 90
and 55 times; plastic packagings, 14 and 21 times less, respectively.
The volume of production of the main packaging materials in Russia, thousand tons:
polyesters, 67; thermoshrinkable polyethylene terephthalate, 2.9; thermoplastics, 20.3; ma-
terials from polystyrene, 17.5; A-grade paper for granular products, 10.6; base paper for
laminate used for milk and dairy products, 9.6; pergamyn, 3.7; supergomin, 4.4. Over the
recent years, there was a further decline in the production of packaging materials by about
30% per year.
Restoration of the production of packaging materials in Russia should be done by the
priority manufacturing of the most competitive and ecological packagings, which include
metallized materials. A number of industry-specific research institutes analyzed the major
directions and prospects of using polymer packaging materials, coatings and polyfunctional
layers. In the Russian state sector, the share of packaged meat foods is only 2.7%. By the
estimates of experts, losses of cattle and poultry meat due to the low level of packaging are
in Russia 1.6 mln tons, which exceeds their imports two times. A similar situation is ob-
served for other kinds of foodstuffs.
Among polymer packaging materials, one of the most promising groups are metallized
packagings. They are economical: consumption of aluminium for their production is by two
orders of magnitude lower than for production of foil; they provide high protective and mar-
keting characteristics, are maximally adapted both to modern food technologies and to pro-
cesses of household culinary treatment of packaged products, for instance, in microwave
ovens. Herewith, the cost of the most expensive packagings does not exceed 58% of the
cost of packaged product, which is significantly lower than the cost of the losses of unpack-
aged products. In countries with the developed processing and chemical industries, the de-
mand in metallized multilayer materials is permanently greater than the volume of their
production. This is due to the orientation of the processing industry to produce ready-pre-
pared food products, for which metallized packagings provide optimal properties, such as
high barrier characteristics, excellent decorative properties and economic efficiency.
One of the largest potential consumers of containers with the coating based on modi-
fied polymer compositions is canning industry. At present, due to the general drop in pro-
duction of foodstuffs, the output of canning containers decreased approximately two times.
Though sheet tinplate production is in Russia only 700800 thousand tons, in the USA
3600 thousand tons and in Western Europe 3500, it is still considerable and will increase
CHAPTER 9 279

with the stabilization of the economy. With this in mind, the issue of the development and
use of modified polymer compositions for metal containers is rather topical. Analysis of the
major technico-economic and ecological parameters of the production of modified compo-
sitions as compared with base systems and containers with these coatings shows that, at the
corresponding hardening conditions (rate and time) of the developed compositions, the ba-
sic expenses for production of containers shall differ from the base version only by the ex-
penses for raw materials, which can be brought down by reducing the number of applied
layers. Herewith, containers with the developed types of coatings shall have higher deco-
rative and performance characteristics.
The above-said supports the necessity and topicality of developing efficient methods
for protection of meat semifinished and ready-prepared products. Only by the wide use of
the practice of the developed industrial countries, it is possible to reduce the losses of food-
stuffs during their delivery to the consumer by 5066%. An expansion of the output of such
types of polymer packagings as aseptic, sterilized, with preset barrier properties etc., would
make it possible to introduce progressive technologies of manufacturing food products of
high degree of preparedness and long-time storage; fast-frozen, freeze-dried, ready-to-eat
meals. Besides, this provides for the preservation of high consumer properties and reduction
of the mass of meat foods at the stages of their output, storage, use in public catering and
housekeeping.
More advanced processing of raw materials, realization of ready-to-use products and
with extended shelf life are considered in the West as the major direction of development
of food industry. Expenses for the production with extended shelf life are considered to be
5 times as low as for perishable products. It has been found that capital investment to pre-
vent losses of mass of products are 23 times as low as those required to expand production
in the volume equal to the losses to be eliminated.
The possible increase of foodstuff reserves due to increased production of foods is lim-
ited. It is determined not only by the volume of resources directed to agricultural produc-
tion, but also by limitations in environmental management. This stipulates to a significant
degree a lower dynamics of agricultural production as compared with industrial production.
For packaging of meat products, including frozen foods, use is made of consumer contain-
ers in the shape of trays from polyurethane foam, polystyrene foam, polyethylene foam,
polyvinyl chloride foam. Consumer containers from gas-filled foamed plastics are distin-
guished with a low density not exceeding 1560 kg/m3, with an ability to withstand signif-
icant specific loads without residual deformation, with a damping ability, elastic properties,
moisture resistance, chemical inertness, good hygienic parameters and low cost. Such con-
tainers make it possible to protect products from shocks, mechanical damage, temperature
variations, penetration of moisture and microorganisms; they have a low weight, increased
durability and low cost. Containers form gas-filled materials are fabricated by injection
molding, pressing, extrusion. Economy of materials is 3040%. The surface layer of a
packaging can be monolythic and rather strong. These containers can be overprinted, cov-
ered with lacquers and paints, glued with various glues. Gas-filled sheet materials are used
for fabrication of trays for meat by methods of pneumatic and vacuum formation.
Combined polymer materials with paperboard, paper and aluminium foil found wide
use for fabrication of consumer containers and food-purpose packagings. By their protec-
tive and shock-absorbing properties, they exceed significantly containers from wood, card-
board and other materials. Combined consumer containers and packagings from sheet and
film materials based on polymers provide for the high preservation of products, as well as
good consumer properties. Skin packagings are used for packing meat, fish and other goods.
280 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

They represent a paperboard support, on which an article close-wrapped on all sides


by a thermoshrink polymer film 30120 m in thickness is put. In packaging, the ends of
the film are fastened to the support by heat sealing, staples or glue. For shrinkage and close
wrapping, the film is heated. Additional stretching of material is done by vacuumizing or
by creating a pressure difference on both sides of the film. For this packaging, use is made
of thermoshrink films based on polyvinyl chloride, polyethylene, cellulose esters, polyvi-
nylidene chloride.
Food products are transported in shipping containers produced by injection molding,
rotational molding from polypropylene or polyethylene, as well as trays from the same ma-
terials with low walls. These containers are also used as returnables in transportation inside
plant premises and within stores. Containers of this type are widely used for transporting
meat and dairy products. For packaging and transportation of moisture-capacity and frozen
products, including meat, use is made of polymers from corrugated plastic board. Packaging
is chosen with optimal protective properties, which provide for the required shelf lives of
goods and do not lead to excessive expenses. When choosing packagings, a range of phys-
icochemical factors is also taken into account: temperature difference, effects of solar radi-
ation, biological and aggressive media (sulfur dioxide, chlorides, ozone, hydrogen sulfide),
the possibility of moisture getting into products, aggressive chemical substances in products
themselves, the action of oxygen and air, the loss of volatiles by products (flavouring
agents, acquirement of foreign smells owing to evaporation of solvents and absorption of
foreign substances).
Stringent hygienic requirements are imposed on materials in the development of pack-
agings for food products. Account is taken of the state of the product (powder, paste, liquid,
flocks, granules), its chemical activity (pH of the medium; occurrence of solvents, esters,
alcohols), as well as the physical activity (evolution of vapours and gases, their sorption,
delamination, change of tissue structure) and ability to change properties under the action
of temperature, light, moisture, oxygen, air. When choosing the shape and size of contain-
ers, account is also made of the consumption of polymer materials and the packing factor
of the packaging. Polymers, depending on the stress strain characteristics, can be rigid,
with the elasticity modulus greater than 1000 MPa; semirigid, with the elasticity modulus
greater than 400 MPa; and elastic or soft, with the elasticity modulus, respectively, greater
or smaller than 20 MPa.
When solving the issues of the possibility of packaging various types of products and
their preservation in transportation and sales, account is taken of a set of chemical and phys-
ical characteristics of polymers, the technological regimes of processing with consideration
of the thermophysical parameters, biostability, inflammability and vapour permeability. In
most cases, a whole range of ingredients are introduced into the polymer composition
plasticizer, thermostabilizer, stabilizerplasticizer, modifier of shock resistance and repro-
ducibility, fillers, inks, optical bleachers, flavouring agents, lubricants.
When fabricating polymer film materials, use is made of single films from polyethyl-
ene, polyvinyl chloride, multilayer polymer films, such as polyethylene with polyamide as
well as polymer combined film materials based on polymers, paper, aluminium. Combined
film materials provide for properties of polymers and traditional materials, which makes
possible their wide use for packaging of practically all consumer goods. By the utilization
capacity, the first place is occupied by polyethylene, which has good process and perfor-
mance properties (shock resistance, low temperature resistance, processibility of the article
on common equipment, as well as the lowest cost as compared with other polymer materials
produced in large volumes). The second place is occupied by polyvinyl chloride owing to
CHAPTER 9 281

its stability of shape, possibility of obtaining highly transparent packagings, good adhesion
of paints to the surface. Their drawback is a comparatively high brittleness, especially at
low temperatures. Besides, processing of polyvinyl chloride requires special equipment.
Strong, thin-walled and economical packagings based on single- and multilayer materials
are produced from polypropylene; however, it is used on a limited scale due to a small
low-temperature resistance. Other polymer materials are used for production of packagings
to a much smaller extent.
Protective polymer coatings are used for protecting the surface of packaging from cor-
rosion, for instance, in packaging of meat preserves and sausage filling. They protect metal
from erosion during the action of atmospheric conditions, contacting media, mechanical
impacts. The use of protective coatings makes it possible to prevent the destruction in the
metallization of packagings from multilayer materials. For this purpose, use is usually made
of compositions based on modified epoxides, epoxy elastomers, epoxyphenol and other
systems. Bactericidal coatings are of great interest for protection from the impact of the mi-
croflora of meat and other products. Chemical preservatives are used for this purpose, for
instance, those based on glutaric, sorbic, benzoic and nitrobenzoic acids, their salts and es-
ters. Preservatives are introduced into the lacquer composition, which is applied to the pack-
aging material. However, commercially produced food-purpose lacquer-and-paint
materials, when applied to multilayer or combined films, reveal a low adhesion strength and
fail to provide for the required performance parameters. Protective antimicrobial coatings
on food products are also obtained by introducing antibiotics (nisin, tetracyclin and its de-
rivatives) and chemical preservatives in the form of a solution in ethyl alcohol and a poly-
mer film former followed by the dipping of food products (meat articles, fish) into the
prepared solution.
To prepare antimicrobial preparations, ions of metals with bactericidal properties (sil-
ver, manganese, magnesium) are introduced into carboxyl and hydroxyl groups of grafted
homopolymers, for instance, those based on polyester acrylates; then coatings on food ob-
jects are formed. This method requires special metal-containing food-purpose polymers to
be synthesized, and failed to find wise use.
When producing multilayer and combined packaging materials, use is made of surface
pretreatment for fixing individual layers of polymer. Physical and chemical methods are
used for this purpose, such as chemical degreasing, etching and the treatment of the surface
of articles with solvents, oxidants and halogens, as well as the chemical modification of the
treated material during its production. The most widely used techniques are the physical
methods of surface preparation of polymer materials, treatment by ionizing radiations and
electric charges; flame, thermal and mechanical treatments. In activation by corona glow
discharge, the surface of articles remains active for several weeks at a temperature of 5
up to +60C. Chemical etching is done before metallization and painting of the surface. It
is carried out at normal and elevated temperature by oleum, halogens, ozone, chromic mix-
ture, nitric acid and other reagents.
To prevent inflammation during the production of film materials, antistatic treatment
is carried out, which contributes to the formation of an antistatic layer with increased elec-
trical conductivity on the surface of the film to prevent accumulation of static electricity
charges. As antistatic agents, special surfactants and metal chlorides are used. In many cas-
es, they worsen the performance properties of containers. More efficient agents are
high-frequency induction radioactive neutralyzersionizers.
The physiological harmlessness of polymer packaging materials is provided for by
their inertness with respect to the product with which they are in contact; by the absence of
282 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

a chemical interaction and nontoxicity of substances evolved by the polymer. To determine


the harmful components washed out of packaging materials, the most efficient methods are
chromatography and mass spectrometry. The toxicological tests are carried out no less than
on two types of warm-blooded animals. Under conditions of the hygienic assessment of
polymer materials for packaging meat and fish products, a 5% aqueous solution of sodium
chloride at 20C is used as a model medium. The duration of the tests of polymer materials
is 5 days.

9.2 Prospects of using metallized packaging materials


To impart articles from nonmetal materials with high decorative and performance proper-
ties, a promising approach is to use a combination of two methods of finishing to obtain a
multilayer combined coating: first the application of the metal sublayer, then of the lac-
quer-and-paint material or only a colour pattern. In this case, the metal layer confers the
article an enhanced resistance to the action of high temperatures, moisture, organic solvents,
hardness and wear resistance. The lacquer-and-paint coating provides for the required dec-
orative and performance properties, protects the metal film from oxidation. Besides, the
metallized coating makes it possible to use advanced methods of applying coatings to di-
electrics, for instance, the electrodeposition method, formation of coatings by spraying the
polymer in an electric field, i.e., the most advanced methods under conditions of large-scale
production.
The range of rolled coating materials to obtain air-tight capping of consumer contain-
ers is limited. In world practice, mainly materials based on foil are used. According to the
data by the European Aluminium Foil Association, demand in the member countries of the
Association is increasing, its annual rise for the last 30 years was more than 7%. In spite of
the retardation of the general economic growth in the European countries, consumption of
foil per capita constantly increases. Analysis of statistical data confirms the stability of the
market for aluminium foil, high barrier properties of this material, which is used mainly for
packaging food products, drinks; pharmaceutical, hygienic and tobacco articles.
In connection with the necessity of improving the ecological situation, campaigns are
run in many countries to reduce the weight of packaging materials per unit. In the USA, for
instance, by the beginning of 2000 the aim was to reach more than a 25% decrease of the
weight of packagings. These tendencies also affected the production of materials with alu-
minium foil; the thickness of laminate in the recent years was decreased from 9 to 7 m.
As aluminium foils becomes more expensive on the world market, and due to in-
creased requirements of consumers and developers of new types of containers to the ap-
pearance, weight and shape of packagings, in recent years significant attention has been
paid to production of metallized film materials. In the USA, their annual output is over 9
mln tons. Metallization makes it possible to significantly increase the protective and deco-
rative properties of packagings at a small consumption of aluminium (100 times less than
foiled materials). In Russia, metallized films produced are based on polyesters and polypro-
pylene, which possess a high density, impermeability for vapours, water, gases, aromatic
substances, ultraviolet rays. They are used for packaging the most expensive food products,
integrated diets, which are stored under severe conditions and are warmed up in the pack-
aging.
Laminated materials based on metallized films can successfully replace glass and met-
al containers for packaging products subjected to sterilization, as well as for packaging of
cold drinks and juices. Drawbacks of the existing metallized packaging materials are low
CHAPTER 9 283

adhesion of the deposited metal layer to the polymer base, as well as its rapid breakdown
during the sterilization of packagings. Of great practical significance is the development of
the method of protecting the metallized layer in combined packaging materials. In world
practice, a drastically new type of packaging materials is widespread at present; the mate-
rials are produced by vacuum evaporation and condensation of metal layers 0.020.03 m
thick on polymer film, paper, paperboard. Material aluminized in vacuum is a competitor
of traditional aluminium foil, which has been produced by the rolling method for over 70
years. Metallization of the film or paper in vacuum gives a large economy of aluminium.
Metallization of 10 m2 of paper requires only 33 g of aluminium. To produce the same
amount of foil, 2.9 kg of aluminium is required. The use of packagings from metallized ma-
terial enables the economy of 99% of aluminium at the same area of packaging material.
To endow metallized materials with the barrier properties and rigidity of aluminium foil,
they are laminated. As the result, the permeability of water vapours is decreased 46 times;
of oxygen, 3040 times.
The use of metallized films has a number of advantages as compared with common
materials. Packaging of products with a high content of fat into aluminized polypropylene
films increases the storage time up to 20 weeks. The use of only polymer films for this pur-
pose leads to the emergence of static electricity, which worsens the air-tightness of the
package seam; a thin aluminium layer applied in vacuum decreases the charge of this elec-
tricity. Consumption of metallized films for packaging purposes is constantly increasing.
In the USA, the share of this packaging material is about 21% of the total production of
similar materials. The largest amount about 53% of the total production of packaging ma-
terials is the manufacture of metallized papers; 15% is the share of oriented polypropy-
lene; 6, polyethylene; 2, biaxially oriented nylon and 3%, other metallized materials.
In Western European countries, manufactured metallized materials are used to pro-
duce (approximately in %): polymer films, 72; cellophane, 5; paper and cardboard, 22.
Their greatest part (about 31%) is used for fabrication of soft packagings of food products
and up to 25% goes for labels. Metallized materials are used especially extensively for pro-
duction of ready-to-eat meals and entrs.
By their appearance, metallized packagings resemble aluminium foil, but their cost is
much lower. In recent years, the tendency is to use metallized materials with high barrier
properties with respect to oxygen and ultraviolet radiation, which is achieved by a signifi-
cant improvement of the metallization process with the aim to increase the resistance to
multiple bends, elimination of micropores and of the tendency to cracking. There is a ten-
dency to increase the output of multilayer materials for packaging of food products, which
is stipulated by the diversity of the physicochemical and mechanical properties of polymer
packagings, simplicity of processing, reliability of the raw material base, low energy con-
sumption as compared with production of packagings from other materials of similar ca-
pacity, for instance, glass containers. The small density of polymer materials from 0.9 up
to 1.5 g/cm3 makes it possible to save on transport expenses. The cost of packagings from
polymer materials is lower.
At present in Germany the consumption of multilayer packaging materials is about
27%; only the demand for glass is greater 39% with respect to the total volume of pro-
duction of packaging materials. The most widely used are multilayer polymer materials,
90% of which is for packaging. This is due to the fact that single-layer films do not satisfy
the ever increasing requirements to packagings; in particular, the guaranty period of storage
of food products, the preservation of their taste qualities, reliability in transportation. To in-
crease the storage times of meat products, the number of layers in packaging materials, met-
284 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

allized materials including, is significantly increased. Multilayer films include from 2 up to


7 layers. The average thickness of one layer is about 10 m, including with the metallized
layer. The lower layer of the material about 20 m in thickness are mainly polyolefins
(polyethylene, more rarely polypropylene). For this layer, low-density polyethylene is used,
owing to its low melting temperature, capability of thermal treatment, reasonable cost. Mul-
tilayer materials with the lower layer from low-density polyethylene are used for packaging
products subjected to pasteurization at 85C. At the sterilization of packaged products at
100C and deep freezing, use is made of multilayer packagings with the lower layer from
medium-density polyethylene. Frozen products can be warmed up at 100C. High-density
polyethylene is used for the lower layer of multilayer packagings for preserved products,
sterilized at temperatures no less than 121C. The average thickness of multilayer films is
from 20 up to 1500 m. Depending on the purpose and properties of individual layers, mul-
tilayer films can be used within the temperature range of 60 up to +135C. They possess
a high strength of the heat seal, moisture resistance; fat and oil impermeability; resistance
to acids and alkali, solvents, microbial impermeability. For packaging of meat, meat prod-
ucts, semi-finished products and ready-prepared meals, the company Vipack, which is
part of the Finnish concern, manufactures multilayer polymer films. At the exhibition In-
terpack-90, Germany presented packagings for processing foods in microwave ovens; the
packagings are fabricated from pressed polyesters filled with nylon, polysulfone, polyacry-
late, polyoxyphylene with polystyrene. Their surface is metallized with aluminium or al-
loyed steel. In such a packaging, a food product after its treatment in the microwave oven
acquires a crispy crust. Metallized multilayer packaging materials are used for packaging
and storing meat-and-vegetable preserves for 2430 months. For this purpose, use is made
of metallized materials based on polyamide and polypropylene, oriented polypropylene and
polyethylene films. They are characterized by high performance properties, their resistance
to delamination is 290196 N/m, the breaking strength 4934 MPa, relative breaking elon-
gation greater than 10%, resistance to puncture greater than 9.8 MPa, strength of the heat
seal 15001200 N/m, resistance to delamination after sterilization in an aqueous medium
greater than 147 N/m, strength of the heat seal after sterilization in an aqueous medium is
1050840 N/m.

9.3 Polymer films as the base for metallization


Film materials used for packaging of food products require a set of the following charac-
teristics: technical-grade strength in monoaxial and biaxial stretching, resistance to multiple
bending, to temperatures increased in sterilization of products and decreased in freezing
products; protective permeability for gases and vapours; radiation resistance; process fac-
tors resistance associated with the packaging process at a high-speed automated equip-
ment with account for the friction coefficient, static coefficient, caking property, capability
of heat sealing; sanitary and hygienic factors extractability in various model media; extent
of toxicity; aesthetic factors appearance, overprinting capability.
The properties of films are determined by many factors and, first and foremost, by
compositions of initial polymer and of the composite as a whole, by processing conditions.
Usually, the film is produced from polymer by the method most efficient for the polymer:
from low-density polyethylene, by extrusion blowing; from polyvinyl chloride, by calen-
dering; from rubber hydrochloride, by solution casting. Considering the peculiar features
of the structure and properties of film material, the most efficient method of creating a pack-
aging material with a set of required performance properties is by combining. Combining
CHAPTER 9 285

films and coatings, it is possible to produce packaging materials with required properties,
which are impossible to obtain using one polymer in pure form. For instance, a coating from
a thin layer of lacquer considerably decreases the rate of removal of a plasticizer, increases
moisture resistance, can ensure heat sealability. Coextruded bilayer films for milk packag-
ing are fabricated based on low-density polyethylene filled with titanium dioxide and car-
bon black. An advantage of multilayer film materials is their low weight. Containers from
them are 410 times lighter than metal containers and 20 times lighter than glass containers;
they withstand a rapid heating, easily open, are economical, are distinguished with small
energy intensity.
Containers and packagings should be air-tight and resistant to the action of preserva-
tives, such as solutions of sorbic acid, sodium acid or potassium acid. Polymer containers
for freezing products from 12C to 40C and lower should withstand the heating before
the products are used. Polymer packaging material should satisfy some or other require-
ments depending on the packaging and the properties of products. Food industry consumes
about 50% of all polymer materials used for containers and packagings. Along with general
requirements (mechanical strength, chemical endurance to the action of food products and
the environment, physiological harmlessness), additional requirements imposed on them
are manufacturability, processibility on modern packaging equipment operated in speed re-
gimes, resistance to sterilization and pasteurization, as well as capability of forming a strong
seam in heat sealing.
A promising approach is to use polymer packagings in combination with aseptic can-
ning. This method is applicable for products and containers, which do not withstand a pro-
longed impact of high temperatures. To increase the storage times and obtain film materials
with the required set of properties, food products in polymer containers are treated using
high energies. Sometimes, a mixed treatment by irradiation with high-energy frequencies
and the action of temperature is used. For rapid warming-up of the product in a microwave
oven, metallized materials are used. The process is performed as the result of intensive ab-
sorption of electromagnetic energy by metal. The high melting temperature of polyethylene
terephthalate provides for the preservation of the strength of films. The same role is played
by this film in packagings of frozen products when they are cooked or warmed up in mi-
crowave ovens; herewith, a crispy crust is formed on food products, which is not observed
using polymer nonmetallized packagings. To produce similar products, use is made of com-
bined packaging materials, on particular sections of which a different number of layers is
formed. Packaging materials intended for warming up meals in microwave ovens have high
barrier properties with a regulated layer, which determines the intensity of warming-up. The
packaging with a metallized layer, as compared with foil, protects the product better and
has higher decorative properties, as it does not crack or crease.
Films of metallized metapropylene are produced. Also, combined packaging material
is fabricated, using the method of coextrusion of metallized film with transparent polypro-
pylene film. Both films form a strong heat-sealed seam. When fabricating packagings, met-
allized films are additionally coated with a layer of ink printing and are laminated with a
layer of transparent polypropylene film. In the USA, metallized laminated polymer pack-
aging material for food industry has been developed, which possesses a high elasticity,
strength, is impermeable for gases and vapours, aromatic substances and UV rays. An ad-
vantage of this material is also its small weight.
Material in the form of one or two layers of polyolefin film with a metallized coating
is used for fabrication of canisters 320 litres in capacity. Materials produced by forming a
metallized coating on paperboard and other polymers are used for aseptic packaging of food
286 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

products. For production of metallized materials, use is made of the method of transferring
metallization on paper and cardboard. First, the film support is coated with lacquer, on
which a layer of metal is applied by the vacuum method. Then the surface of metal is cov-
ered with a layer of glue, on the other side of which paper is rolled on. After that, the initial
film support is removed. This method is used for metallization of films, which can not be
decorated with metal using the usual vacuum method, or the preparation of the surface of
which requires significant expenses and auxiliary substances. The transfer method is used
to metallize materials of the type of pack in box for wrapping meat and products to be
warmed up in microwave ovens, as well as for packaging confections and coffee.
A method of producing metallized materials has been developed in Germany. The
method provides for spraying of a metal layer on one of the films of a multilayer material
formed; the films are then joined by glueing followed by thermoflattening of the multilayer
film.
To produce material with selective gas permeability, a layer of palladium is sprayed
onto the base under vacuum. The metallized coating is protected with a layer of organic
polymer, which possesses a selective gas permeability; the polymer is based on low- or
high-density polyethylene, polypropylene, copolymer of ethylene with propylene or with
ethylacrylate, polybutene-1, ionomer of poly-4 methyl pentane-1 and (or) polybutadiene.
Copper-foil film materials are produced by applying first a 280 m-thick layer of zinc on
the copper support by vacuum spraying, and then layers of silicon oxide or aluminium ox-
ide. After that, copper with a two-layer coating applied to it is laminated with the film base.
The method provides for high adhesion of copper to the film base via an intermediate
two-layer coating. When producing the intermediate polymer film, glueing of the layers can
be done by sulfated copolyester containing an alkaline metal.
To protect films from UV rays, a stabilized transparent combined material has been
proposed, which is a biaxially oriented polyester film joined with a metallized film from
polyethylene terephthalate coated with colour lacquer.
Material capable of heat sealing represents a thermoplastic polymer layer and metal
foil or metallized flexible sheet.
Films from plasticized polyvinyl chloride 0.5 mm in thickness, used for packaging
food products, have a layer of primer with aluminium 50 m in thickness sprayed on it. To
protect the metal layer, use is made of polymer coatings from acrylic copolymers, modified
polyisocyanates containing inks, which harden at the action of UV radiation.
In packages from oriented polypropylene and metallized polyethylene terephthalate
film, food products can be stored for 68 months.
Materials subjected to metallization include crystalline polyolefins (oriented polypro-
pylene, polyethylene), polyester films (polyethylene terephthalate). To improve the adhe-
sion and decorative properties of metallized coatings, use can additionally be made of
various compositions applied directly to the coating, for instance, sulfated copolyester con-
taining alkaline metals, colour lacquers.
Metallized polyester films widely used for various purposes are more resistant to fric-
tion and stretching, which provides for a high stability of shape of the packagings. The use
of these films makes it possible to increase the speed of overprinting and to reduce the con-
sumption of ink by 30%.
The use of metallized polymer materials increases annually not only owing to good
decorative properties, but also due to the vapour and water impermeability, decreased heat
and light transmission, as the result of which the service life of food products, especially
meat and dairy, is significantly increased.
CHAPTER 9 287

Metallized materials are used in fabrication of containers for transporting the products.
An advantage of a thin metal layer is the absence of thermal conductivity outside the con-
tainer owing to its small mass. Losses of heat are absent even in the contact of the metallized
surface with components of the outer walls of the container.
The metallized film proposed by the company Kraun Sellerbach (USA) is used for
packaging of food products. Its main part is a multilayer polyethylene film, which provides
for thermal insulation. Aluminium is applied to the base by vacuum metallization, which
prevents the penetration of moisture, gaseous and aromatic substances, as well as light. By
means of extrusion or adhesion, the metallized film is layered onto paper or films, for in-
stance, polyester, nylon, cellophane or polyethylene ones depending on the requirements.
Such a film has various advantages, the major of which is its universal properties. For in-
stance, if it is required to exclude the penetration of gaseous substances, the film can be
joined with cellophane. The use of only one layer of cellophane provides for the resistance
to the penetration of gas up to a level equal to 0.3 cm3 for 24 h at 40.5C and relative hu-
midity 45%. Herewith, the moisture permeability does not exceed 0.03 g for 24 h for a sur-
face area of 645 cm2 (100 square inches). Another example of the universal properties are
high thermal insulation parameters of the film, which is provided for by the introduction of
an additional thermal insulation material 0.025 mm in thickness, for instance, polyethylene,
films from latex or other resins. This characteristic was revealed in the tests of wrappings.
An insignificant time of contact of the thermal insulation with the metallized base at a pro-
ductivity of 180 packagings per minute weakens the insulation on the edges. Addition of a
layer from the monomer eliminated this drawback.
The film possesses isolating properties characteristic of foil, thus preventing the pas-
sage of moisture, whose amount does not exceed 0.05 g per 645 cm2 of the surface for 24 h.
The penetration rate of oxygen is 10 cm3 per the given surface area at the deposition of this
material on paper and less than 4 cm3 at the deposition on film. The extent of penetration
of the light corresponds to 1%. The film can be easily bent. The metallized surface is be-
tween two layers, which protect the film from the emergence of holes and cracks at pressing.
A major advantage are constant insulation characteristics of the film at the action of pres-
sure on it. The film is used for packaging of meat products.
Examples of packagings from the film by US companies for retail goods are bags lined
with paper, intended, in particular, for nonfat dry milk, packaged meat products, for solid
spice mixtures and fried potatoes. A laminated bag based on this film for packaging acidic
appetizer spreads received a highest award at an exhibition held in Moscow at the Red
Presnya Exhibition Centre. For a more attractive appearance, metallized bags are fabricated
in various colours (blue, yellow, red) and are overprinted with four-colour images of snacks.
The company also fabricated various packaging shapes for aroma drinks, ground coffee and
lining for boxes with articles from crushed grain.
The US food industry also makes use of metallized films: cellulose, coextruded
polypropylene and polyester. The metallized cellulose film has an excellent appearance, is
used for packaging meat and other products. The relative breaking elongation of metallized
polypropylene is 6575% (longitudinal) and 8090% (transverse); of metallized cellulose
film, 2025 and 5565%, respectively.
The low specific weight, good mechanical and protective properties stipulate the wide
use of metallized polymer film materials. Unlike plastics, they are characterized by a large
value of surface with respect to volume and a capability of adhesion interaction with applied
layers of other materials. The structure and properties of polymer films vary along the thick-
ness and depend both on the chemical composition of the polymer and on their production
288 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

process. These parameters have a significant effect on the structure and properties of poly-
mer and metal coatings applied to the films. Regulation of the processes at the filmcoating
interface makes it possible to reduce significantly internal stresses, to improve the physico-
mechanical and other performance properties of materials.
Films used for metallization should satisfy a number of requirements. Thus, to obtain
high-purity metal coatings it is necessary to use polymer materials with an insignificant gas
evolution and as low as possible content of volatile components in the polymer. A necessary
requirement is also the high thermal resistance of films relative to the heat radiation from
the source of spraying, good adhesion properties to deposited metal, high strength.
The depth of vacuum, quality of film, formation of folds, displacement and density of
the roll in production of the film in metallization units with the rolling mechanism are af-
fected by the nonuniform thickness of the film, friction coefficient, mechanical properties,
thermal resistance, conditions of charging with static electricity, as well as the dose of gas
separation. At a high gas evolution by the film, preliminary degassing or lacquering are
used, which prevent evolution of volatiles from the film in the process of metallization. Su-
perthin films with a large surface area with respect to volume are in high demand. Polyeth-
ylene terephthalate films have the specific surface 600 m2/kg at a thickness of 2.5 m.
However, thin films are more difficult to process into articles. The processibility of the film
in rolling is greatly affected by its unevenness. Before its use for packaging, the film is pow-
dered; the powder should be uniformly distributed along its surface, which provides for its
better winding as compared with smooth films.
Apart from the main physicomechanical characteristics, such as ultimate tensile
strength, relative breaking elongation, the films are also characterized by tear resistance and
tear propagation resistance, resistance to bends, elasticity, coefficients of thermal expansion
and swelling, extent of transparency. Special grades of polymer films are produced to fab-
ricate quality metallized materials of particular purpose.
Stronger but less transparent films are used to fabricate coloured embossing foils. To
increase adhesion to lacquer and metal coatings, the surface of the polymer film is activated
mainly by corona discharge. Activation contributes to the increase of the surface tension of
films by 40% as compared with nonactivated films.
Practically all polymers capable of yielding solutions or passing into a viscoelastic
state in heating possess the film-forming properties. Films are usually produced by evapo-
rating the solvent from the thin layer of a solution applied to the support (sometimes with
the separating layer to facilitate the removal of the film from the support), or from the melt
using a forming tool followed by cooling of the film.
Linear polymers are used to produce films. The minimal degree of polymerization, i.e.,
the number of homotypic links in the polymer chain, at which strong films are produced
from polyvinyl chloride, is 500700; from polyamides, 100200. With the decrease of the
intensity of intermolecular interaction and flexibility of the chain, stronger films are pro-
duced at a smaller molecular mass.
A significant increase of the extent of polymerization does not lead to any significant
increase of strength, but only hinders the processing of polymer owing to the low yield in
heating and poor solubility.

9.4 Methods of modifying the properties of films


Most film materials usually contain auxiliary substances: stabilizers, plasticizers, inks and
pigments, antistatic additives. The purpose of stabilizers is to preserve the properties of the
CHAPTER 9 289

polymer film invariable and to prevent the occurrence of chemical reactions under the ac-
tion of the environment.
The role of other auxiliary substances is to impart the polymer film with additional
properties required for processing it into articles. Stabilizers are artificial nuclei of crystal-
lization and significantly affect the structure of the film. Structural transformations are reg-
ulated by introducing surfactants into melts; surfactants decrease the rate of crystallization
as the result of a surface energy decrease at the spherolitemelt interface. This impedes the
growth of spherolites, but increases the rate of nucleus formation owing to the decrease of
the size of crystalline nuclei. The rates of these processes depend on the nature of surfac-
tants and their concentration.
Of great practical importance are plasticizers. Plasticizers used are organic compounds
imparting polymers with plasticity and extending the range of their rubberlike state. They
increase the low-temperature resistance of polymer, resistance to impact loads; facilitate the
processing conditions. Introduction of plasticizers causes an increased mobility of poly-
mers structural elements due to the decrease of intra- and intermolecular interaction. The
chemical nature and quality of plasticizer introduced render a significant effect on the struc-
ture, physicochemical properties, permeability of films to various vapours, liquids and gas-
es; on the resistance to atmospheric conditions and microorganisms.
Migration of the plasticizer, owing to the impact of the external medium, also leads to
undesirable changes of the structure, especially of films, because they have a large surface
area and small thickness. In production of polymer films, polymers to be plasticized are
those that are used for fabrication of packagings, such as polyvinyl chloride, copolymer of
vinylidene chloride with vinyl chloride, cellulose and its esters.
Specific requirements to films for various purposes stipulate the choice of plasticizer.
The main requirements to all plasticizers are compatibility with polymer, small volatility,
high chemical endurance at various temperatures. The minimal temperature at which ma-
terial preserves its performance properties characterizes its low-temperature resistance. The
presence of aromatic fragments in the plasticizer molecule negatively affects its own
low-temperature resistance.
Polymer plasticizers are oligomers with molecular masses from 1000 up to 8000 and
are polyesters of dibasic alcohols. They endow film materials with valuable performance
properties. Polymer cebacinates possess a good resistance to oils, water, detergents,; an in-
significant yield, absence of migration, high dielectric properties, compatibility with poly-
vinyl chloride. However, they are expensive.
Adipinates are less expensive, possess a small yield, migration, good dielectric prop-
erties, but are less efficient, leached with water, impart PVC films with a smaller low-tem-
perature resistance.
Phthalates are well matched with polyvinyl chloride and improve its processing; do
not migrate and are not extractable with oils. However, at low temperatures they worsen
the properties of films. Other polymers are also used for plastification. Thus, for polyeth-
ylene and polypropylene, it is polyisobutylene; for polyvinyl chloride, chlorinated polyeth-
ylene and copolymers of butadiene and acrylonitrile. The efficiency of their plasticizing
action is higher for restrictedly compatible copolymers.
Low-molecular-mass plasticizers increase elasticity and low-temperature resistance of
the film, but worsen its resistance in liquid media; decrease tensile strength, increase the
permeability of vapours and gases through plasticized film, which is indicative of the for-
mation of a defect inhomogeneous structure.
Physiologically safe plasticizers (permitted to be used in polymer films of food
290 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

purpose) are used in fabrication of packagings for food products. However, even in the case
of using nontoxic plasticizers it is necessary to take into account their volatility and the pos-
sibility of extraction by food media, which leads not only to the change of properties of the
film itself, but also to the emergence of foreign taste and smell in food products.
Inert high-molecular-mass compounds are used for packaging. A source of hazard in
them are low-molecular-mass components, such as the residual monomer, emulsifiers, sta-
bilizing plasticizers, as well as substances formed as the result of decomposition in process-
ing and operation of articles. Harmlessness of all ingredients introduced should be taken
into account in production of packagings. However, even in this case it is impossible to
guarantee the inertness of the material due to the difficulty of determining the interaction
of all its constituents between themselves and with the medium. With account for this, it is
necessary to carry out the sanitary-hygienic and toxicological assessment of the material.
The conclusion of the possibility of its use is made based on tests in individual media imi-
tating the composition of the liquid phase for food products (bottled water, vegetable oil,
weak solutions of cooking salt, bicarbonate of soda, hydrochloric acid, 50% ethyl alcohol
etc.).
Determination of the extractability of particular components with model media is pre-
ceded by the organoleptic assessment of the material and the aqueous extract on the absence
of taste and smell, as well as by the establishment of the character and amount of substances
migrating into these media.
Introduction of low-molecular-mass substances into the composition, as a rule, affects
unfavourably the sanitary-hygienic characteristics of film materials. Plasticizers, by in-
creasing the flexibility of chain macromolecules, improve the low-temperature resistance
of the film but can migrate and contribute to migration of other components in the liquid
medium, thus worsening its protective and mechanical properties, as well as the quality of
overprinting. The small thickness of films hinders the modification of their structure by fill-
ers and powdered additives (pigments, modifiers etc.); the latter should be finely dispersed
and actively interact with the polymer.

9.5 Structure and properties of film materials


The peculiar feature of polymer films, including those used for packaging, is that they are
characterized by a structure, which is inhomogeneous along the thickness of the film. This
is typical in the formation of films from crystalline polymers on various supports. In pro-
duction of films from the polyethylene melt, the adsorption interaction of polymer with the
surface of the support prevents the formation by crystallites of more complex lamellar-type
supramolecular structures, which are formed in layers bordering with the air. However, the
mobility of structural elements, which is required for complex supramolecular structures to
be formed should, apparently, be optimal. This is indicated by the data in the formation of
films from powdered compositions of low-density polyethylene, obtained by preliminary
holding over vapours of a solvent (xylol). Swelling of the surface layers in vapours of the
solvent contributes to the decomposition of their lamellar structure and its formation in lay-
ers bordering with the surface of solid bodies.
Optical studies of thin transverse sections (1520 mm) of films from powdered poly-
trifluorochloroethylene revealed an inhomogeneous supramolecular structure along the
cross section. Hardened films, in the zone of contact of polymer with the support, were
found to have fine supramolecular formations. Large-spherolite films formed at a melt cool-
ing rate of 1 deg/min were found to have a 5070-m-thick layer of structural elements,
CHAPTER 9 291

occurring in spherolites, at the interface with the support. Studies of the structure of longi-
tudinal cross sections in this zone found it to be homogeneous fine-spherolite one in the
polymer. The size of spherolites increases by an order of magnitude in passing to the layers
bordering the air. The support plays the role of a nucleating agent and contributes to a faster
and more complete ordering of the structure. The effect of structural inhomogeneity on the
melting and crystallization temperatures of polytrifluorochloroethylene along the cross sec-
tion of the film was studied. It was found that polymer begins to melt in the surface layers
of the film. The layer at the interface with the support melts 1015 min later at a tempera-
ture 12C higher than the subsequent layer, and crystallizes 4060 min earlier than they
at a temperature 46C higher. Thus, the texturing influence of the support leads to the
two-stage process of crystallization of films and to the inhomogeneity of the structure along
the thickness.
An inhomogeneous structure (along the thickness) is formed in films from solutions
of polystyrene (PS). When they are produced from solutions of PS in carbon tetrachloride
in layers bordering with the air, a structure of the type of quasicrystals is formed, which
group into networks. However, X-ray patterns of tactic polystyrene indicate that the poly-
mer is amorphous. Etching of films reveals a globular structure with a denser packing of
structural elements at the interface with the support. In the surface layers of the films, along
with the globular structure characteristic of polystyrene blocks, we observe secondary su-
pramolecular structures. The character of the arrangement, the morphology and extent of
ordering of these structures depend on the nature of solvent. This is, evidently, due to dif-
ferent solubilities of polystyrene in solvent naphtha, xylol, carbon tetrachloride; different
rates of their evaporation in the formation of films; as well as to the effect of the values of
internal stresses and strength of interaction at the polymersupport interface on the orien-
tation of structural elements. The largest secondary supramolecular structures of up to 45
m in size are observed in films formed from solutions of polystyrene in xylol, which is
distinguished by the highest boiling temperature. In films from solutions of polystyrene in
solvent naphtha, the size of the secondary needle-type structures decreases down to 34
m. The smallest size of the structural elements forming a network (0.20.3 m) is ob-
served to occur in films obtained from solutions in carbon tetrachloride. The size of the pre-
dominant globular structure also depends on the nature of solvent.
The finest globules 3070 nm in diameter are found in films formed from solutions in
xylol. With the quality of solvent worsening, their size increases up to 50100 nm for films
obtained from solutions in solvent naphtha; up to 80400 nm, from solutions in carbon tet-
rachloride.
To elucidate the role of solvent in the formation of the properties of coatings, we in-
vestigated the influence of its nature on the drying process, the change of internal stresses,
the physicochemical characteristics. It was found that the drying of films from solutions of
PS in carbon tetrachloride is completed sooner than of those from solutions in o-xylol; here-
with, the solvent elimination rate, irrespective of the nature of solvent, is much higher than
the rate of increment of internal stresses. Upon removal of 7080% solvent from the sys-
tem, comparatively small internal stresses emerge in the films. They reach an ultimate value
at no more than 13% of the solvent. The thermal conductivity coefficient of films decreas-
es with internal stresses increasing. Its value and kinetics also depend on the nature of sol-
vent.
Structural transformations at different stages of solvent elimination were studied. The
size of globules found at the early stages of solvent elimination at 80C in 510 min was
found to be about 30 m and gradually increased owing to their aggregation. A sharp in-
292 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

crement of internal stresses was observed upon completion of this process owing to the for-
mation of local bonds between these elements.
The high mechanical, adhesion and thermophysical parameters are observed for films
formed from in xylol; they feature a more homogeneous fine-globular structure with a small
content of secondary associates.
Tables 9.1 and 9.2 present the data on the nature of solvent on, respectively, the phys-
icomechanical and thermophysical characteristics of polystyrene films and on the shearing
and tearing strengths of glue layers produced from solutions of PS.
Table 9.1

Solvent Rupture Internal Adhesion, Thermal Thermal


strength, stress, MPa conductivity, diffusivity,
MPa MPa W/(mK) 108 m2/s

Xylol 13.5 1.0 1.6 0.28 5.15


Solvent naphtha 12.8 0.7 1.0 0.27 4.84
Carbon tetrachloride 12.0 0.4 0.7 0.24 4.70

Table 9.2

Solvent Type of failure Strength of films (MPa) at testing temperatures, C

40 20 20 40 60

Xylol Shear 3.44 6.45 5.90 5.47 2.30


Tear 0.78 0.94 0.90 1.83 2.50
Solvent naphtha Shear 3.96 5.84 4.52 2.70 0.68
Tear 0.75 0.85 0.90 1.72 1.32
Carbon tetrachloride Shear 3.22 5.05 4.60 3.40 2.14
Tear 0.78 0.58 0.82 1.35 1.80

Specimens were prepared as follows. A solution of polystyrene was applied to the sur-
face of aluminium plates, the coatings were dried at 20C for 25 h, then bonded under a
pressure of 1 MPa during 10 min at 100C. From the data of Table 9.2, it is seen that at a
testing temperature higher than 40C both in tearing and shearing tests the highest values
of adhesion strength are observed in most cases for glue layers of films produced from so-
lutions of PS in xylol.
Internal stresses in polystyrene films significantly depend on the chemical composi-
tion and structure of the material on which it is formed. We investigated the kinetics of in-
crement of internal stresses in the formation of films from solutions of PS in xylol, solvent
naphtha on steel and copper supports obtained by metallization in vacuum. Depending on
the nature of the support, the values of internal stresses and the rate of their increment
change significantly. Stresses increased with the quality of solvent and the strength of ad-
hesion interaction improved. These data indicate that polymer coatings with optimal pro-
tective properties, internal stresses and adhesion strength can be produced by regulating
their structure by means of modifiers.
Methods of decreasing internal stresses and improving the performance properties of
combined polyvinyl chloride films were developed.
Particles of powdered PVC used for fabrication of films represent complex secondary
CHAPTER 9 293

supramolecular formations. They are not destroyed completely during the swelling in plas-
ticizers and the heating of compositions in processing. To improve the performance prop-
erties of films, an efficient method is to modify compositions by structure formers, which
disperse particles in plastisols. Dispersions of polyvinyl chloride are modified using syn-
thetic fatty acids (SFA); the effect of the molecular mass of their hydrocarbon radical and
of the valency of the cation of the salts on the character of structural transformations and
properties of films was studied. PVC plasticized by dioctyl phthalate was modified by mag-
nesium salts of SFA with hydrocarbon radical of various molecular masses (C7 C9,
C10 C16, C17 C20), as well as by a sodium salt of SFA of the series C10 C16 and alumin-
ium stearate. The composition was held at 90C for 1.5 h and processed into films on rolls
at 130135C for 10 min.
It was found that, with the molecular mass of the hydrocarbon radical increasing, the
contact angle of wetting PVC by glycerol does not practically change. Wettability depletes
in the series Na > Mg > Al. In accordance with this, the modifier, depending on the valency
of the cation, renders different effects on the character of structure formation in films.
The structure of films from PVC dispersions is inhomogeneous and consists of glob-
ules of various sizes. This indicates that particles of the dispersion are not totally broken
down into initial structural elements even at a significant content of plasticizer in the system
and the effect of high temperature. Introduction of the SFA sodium salt of the series
C10 C16 contributes to additional aggregation of structural elements, and modification of
the dispersion by the SFA magnesium salt promotes the dispersing of structural elements
and forming of a homogeneous structure; herewith, the size of the structural elements de-
pends on the length of hydrocarbon radical and decreases as it is increased. At the introduc-
tion of modifiers, internal stresses decrease the greater, the longer the SFA hydrocarbon
radical is.
Introduction of SFA makes it possible to significantly improve the properties of filled
films by regulating the structure formation conditions. Most mineral fillers and pigments
usually introduced into PVC films are more hydrophilic than PVC. A mixture of chalk and
titanium dioxide have an effect on PVC films as inactive fillers. The increase of their con-
centration contributes to the decrease of the breaking strength of these films, their relative
elongation and internal stresses as the result of weak interaction of polymer with filler par-
ticles. Filled films are characterized by an inhomogeneous globular structure, owing to a
poor compatibility with the filler. The contact angle of wetting of polymer films is much
larger than that of the filler. The character of the supramolecular structure of modified poly-
vinyl chloride is preserved at the introduction of a larger amount of filler into the compo-
sition up to 150200 weight fractions.
Formation of a homogeneous fine-globular structure is observed at the introduction of
the magnesium salt of the series C17 C20 into the composition. Formation of films with
this structure increases elasticity from 40 up to 70%, reduces rigidity from 3.48 down to
3.11 g, increases the breaking stress from 3.2 up to 4.0 MPa, decreases internal stresses from
1.3 down to 0.6 MPa, as well as the yield temperature of the compositions, which enables
the processing of filled polyvinyl chloride compositions on the existing equipment.

9.6 Ways of protecting metallized packaging materials


One of the ways of protection is formation of a metal layer between film materials. The
properties of combined materials are determined by various physicochemical factors. They
include the nature of polymer and nonpolymer layers, molecular mass, molecular-mass
294 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

distribution, extent of polydispersity, composition and concentration of modifiers; inter-


layer adhesion strength; supramolecular structure of polymer layers, which also depends on
their production process; surface phenomena determined by their small thickness, large
specific surface and extent of orientation of the structural elements in the layer. Individual
layers of a combined material can perform reinforcing functions with respect to the material
as a whole. It is commonly recognized that at precritical loads two main conditions are ob-
served: the additivity of partial forces and the simultaneous deformation of layers.
Using model systems as an example, the tensile forces of multilayer materials were
determined, for instance, of low-density polyethylene and polyethylene terephthalate wet-
ted with water and joined. Their tensile forces proved to be strictly equal to the sum of par-
tial tensile forces determined from the stressstrain curves for particular layers. At the same
time, the breaking stress proved to be higher than the calculated value as the result of a larg-
er elongation of the system at the moment of rupture than that of the component, which de-
termines the strength of all the specimen.
Of great importance is the order of the layers. The largest strengthening factor is
achieved using the sequence of elastic rigid elastic material. The elastic polymer layer
protects the rigid layer from the rapid formation of cracks in it. The rigid layer impedes the
deformation of elastic layers. More elastic layers, in turn, affect the deformation of rigid
layers. Two films from the same material, joined by an adhesion layer, have a higher rela-
tive breaking elongation than the single film of the same total thickness, and the
stressstrain curve does not depend on whether the layer functions independently or as part
of the composition. The cause of this phenomenon is associated with the features of struc-
ture formation at the interface of the layers. The layer of an adhesion-promoting agent has
an effect on the magnitude and concentration of internal stresses in the system and the prop-
erties of materials on the whole.

9.7 Effect of modification on the properties of protective coatings from


epoxy compositions
The anticorrosion properties of epoxy coatings and their chemical endurance in various ag-
gressive media depend on the nature of hardener. To increase the protective properties of
epoxy coatings, use is made of acidic type hardeners, in particular, anhydrides of carboxylic
acids (aromatic, alicyclic and linear aliphatic), as well as complexes with catalysts based
on aromatic amines and hardeners of acidic type, derivatives of dicyandiamide
HN=C(NH2)NHCN and tertiary amines. The most widely used aromatic amines are m-phe-
nylene diamine and 4,4-diamino diphenyl methane. Coatings produced from epoxy oligo-
mers hardened by these hardeners are distinguished by an increased resistance to organic
acids, for instance, to acetic acid. However, a significant drawback of epoxy compositions
with these hardeners are the high temperature of hardening (150C and higher), as well as
significant internal stresses commensurable with the adhesion and cohesion strengths of
coatings. In this connection, of great practical importance is the development of methods
for increasing the durability of such coatings on the basis of a decrease of internal stresses
in them and an improvement of their adhesion properties by means of special additives. We
proposed A-2 as such an additive. Introduction of additives in the amount of 23 wt. % to
epoxy oligomer ED-20 makes it possible to improve significantly the properties of coatings
(Tables 9.3 and 9.4).
CHAPTER 9 295

Table 9.3 Effect of structural additive on the properties of epoxy coatings with acid-type
hardeners.

Properties Concentration of additive, wt. %

0 2 3 4

Bending strength, MPa:


after heat cycling from 60C up to +80C 86 128 120 90
initial 69 125 120
Adhesion strength, MPa:
initial 5.0 10.0 9.6 5.7
after heat cycling in 20 days 4.8 10.0 9.6
at high relative humidity 2.8 8.3 7.3
after heat ageing at 180C (1000 h) 4.5 10.0 9.5
Internal stresses, MPa 8.0 3.0 2.5 8.0
Preservation of initial adhesion strength, %:
after heat cycling 9.0 100 100
after fog room 56 83 78
after heat ageing 91 100 100

Table 9.4 Effect of structural additive on the properties of epoxy coatings with cyanamine-type
hardener.

Parameters Concentration of additive

0 10 20 30

Bending strength, MPa:


initial 120 123 145 150
after heat cycling 97 134 140
Adhesion strength, MPa:
initial 7.4 7.4 9.4 10.5
after heat cycling 6.7 9.3 10.5
after heat ageing at 180C (1000 h) 5.8 9.6 10.9
Internal stresses, MPa 9.0 8.0 3.5 4.9
Hardening time at 85C, h 6 6 3 4
Preservation of initial adhesion strength, %:
after heat cycling 90 99 100
after heat ageing 78 102 104

From the analysis of the results given in the tables, it follows that introduction of an
optimal amount of a structural additive to epoxy compositions with hardeners of different
nature makes it possible to significantly improve the physicomechanical and adhesion pro-
perties of coatings, especially under conditions of the performance at increased humidity.
Formation of a more homogeneous and ordered structure in epoxy compositions and
coatings on their basis by small additions enables a significant (23-fold) decrease of in-
ternal stresses and an increased resistance of coatings to ageing under various conditions.
The properties of modified coatings in various aggressive media depend on the con-
centration of A-2.
296 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Equipment and shipping containers of meat and dairy industries are operated under
conditions characterized by the diversity of aggressive media. They include acids (lactic
etc.), water, steam, blood; besides, the equipment is subjected to regular washing by special
alkaline compositions.
Of great importance for protection of equipment from corrosion are polymer coatings.
The following requirements are imposed on protective coatings:
resistance to the impact of the manufactured product and to the operation of the
equipment;
high physicomechanical properties;
good decorative appearance;
harmlessness for the human organism and the environment;
possibility of using energy- and resource-saving processes in application and forma-
tion of coatings.
Container and packaging materials, equipment of meat-and-dairy industry have been
painted up to the present mainly by alkyd, pentaerythritol-modified phthalic coating com-
positions or nitrocellulose and other compositions, which do not provide for high-quality
coatings resistant to aggressive media. Therefore, the problem of developing long-lasting
protective coatings for meat-and-dairy industry is topical and of great practical significance.
Based on earlier studies of various classes of film formers for developing chemically
resistant anticorrosion coatings for protection and decorative finish of components and
equipment of meat-and-dairy industry and other branches of the agroindustrial complex, we
chose epoxy enamels. However, coatings from these enamels, formed at room temperature,
are also characterized by comparatively low properties.
The further increase of the durability of anticorrosion coatings was achieved by intro-
duction of special modifying additives. The protective properties of the coatings developed
were investigated in interaction with various aggressive media characteristic of these indus-
tries.
Objects of studies were lacquer-and-paint coating based on commercially used enamel
EP and enamel EP modified by addition A-2 at a mass ratio of 100:2.
Compositions were applied to respective primers (EP-0010) by spraying. Coatings
were formed at a temperature of 1820C on steel plates.
Tests were carried out in model media characteristic of meat-and-dairy industry and
food industry: 3% solution of lactic acid and 1.5% solution of NaOH by immersing a spec-
imen into solutions at a temperature of 202C. During the tests, we registered the changes
in the appearance of coatings, adhesion and impact strengths by the respective State Stan-
dards GOST 9.403-80 and GOST 9.407-84.
We obtained comparative data on the effect of the alkoxysilane additive on the phys-
icomechanical and protective properties of epoxy enamel EP during the impact of aggres-
sive media at a temperature of 20C.
As the result of studies, it was found that the coating based on enamel EP applied over
the primer EP-0010 does not change its protective properties at the impact of a 3% solution
of lactic acid for 14 days, points of corrosion appear in 20 days; at the impact of a 1.5%
solution of alkali, the coatings do not change their properties for 60 days, and points of cor-
rosion appear in 150 days.
To increase the chemical resistance of coatings, the alkoxysilane additive A-2 was in-
troduced into enamel EP before the application to plates.
Coatings based on enamel EP with a 2% modifying additive A-2 with primer EP-0180
thoroughly applied to the plates at the action of a 3% lactic acid solution do not change their
CHAPTER 9 297

properties for 300 days, and points of corrosion appear in 500 days in a medium of 1.5%
alkali liquor; the loss of decorative properties begins in 300 days, and points of corrosion
appear in 360 days.
The improvement of the physicomechanical and protective properties of coatings
based on enamel EP modified by the oligomer alkoxysilane additive A-2 is due to a
57-fold decrease of internal stresses of coatings; adhesion to metal supports increases two
times after the ageing in a 3% solution of lactic acid and 1.5% alkali liquor.
The studies showed that alkoxysilane additive A-2 in small amount plays the role of
an inhibitor of corrosion in coatings and is a modifier providing for the required set of per-
formance properties of lacquer-and-paint coatings intended for protection of components
and equipment in meat-and-dairy industry and food industry, which have no immediate
contact with food products.
In accordance with the recommendations, the durability of coatings based on enamel
EP modified by alkoxysilane additive A-2 is 10 years.
The effect of alkoxysilane additive A-2 on the resistance of coatings from epoxy enam-
el EP at the impact of aggressive media of mineral fertilizers was studied by immersing
specimens, 15075 cm steel plates, with the coating into solutions and suspensions of min-
eral fertilizers at a temperature of 202C.
Coatings based on enamel EP with the 2% modifying additive of cold-drying additive
A-2 were tested as compared with specimens of coatings without the additive, hardened at
a temperature of 1202C.
As mineral fertilizers, we used 10% solutions of potassium chloride, ammonium ni-
trate; a suspension of ammonium sulfate. Tests were continued for 120 days.
During the tests, we registered the change of the appearance of coatings in accordance
with State Standard GOST 9,407-84.
It has been found that the change of the protective properties of EP coatings with ad-
dition of cold-hardened A-2 is similar to that of coatings and EP enamel of hot hardening
in all media studied at 1202C for 2 h.
For the second layer of enamel, the composition is prepared according to the same
principle as for the first layer. The thickness of the overall lacquer-and-paint coating should
be 100120 m.
The second layer is dried at room temperature for 24 h or at 1202C for 2 h.
The complex system of coatings should be held for no less than 7 days before its
operation.
Green enamel EP-525 can also be used in the complex system as the coating layer.
Enamel EP-525 is a suspension of pigments in solution of resin E-41. The enamel should
be applied in 23 layers over the primed surface at a working viscosity of 1215 s accord-
ing to VZ-4.
Before the application, a hardener is added to enamel; the contents are thoroughly
mixed, held for 1530 min, then a corrosion inhibitor is added in terms of 2 g per 100 g
enamel. The contents are mixed again and brought to the working viscosity by solvent R-5.
The prepared enamel can be used for no more than 8 h.
The enamel is dried at 1202C for 2 h, in repair painting it could be dried at a tem-
perature of 1023C for 24 h.
The process sheet of painting external surfaces of the equipment and metal structures
from ferrous metals was worked out based on recommended systems of complex anticor-
rosion lacquer-and-paint coatings for use in meat-and-dairy industry and other food indus-
tries.
298 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The quality of painting works is controlled visually. The service life of lacquer-and-
paint coatings and their appearance depend on the correct choice of the coating system, the
observance of the surface preparation process before painting, on the application and drying
of lacquer-and-paint coatings.
The quality of prepared and painted surface is controlled by a visual examination of
100% articles by naked eye.
The quality of surface preparation before painting is controlled in accordance with
GOST 9.402-80, Section 5.
The extent of drying of the coating is guaranteed by the observance of the drying
regimes, and if necessary is controlled on witness specimens according to GOST 19007-73.

9.8 Technology of producing protective coatings with improved


performance properties
The process of anticorrosion coatings production is traditional and consists of the succes-
sive execution of the following operations: preparation and control of lacquer-and-paint
materials, preparation of the surface, priming and drying, application of a required number
of layers of coating lacquer-and-paint materials with intermediate and final drying.
Preparation of the surface. The surface preparation process includes all or part of the
following technological operations: removal of old coatings, corrosion products and foreign
impurities, cleaning of hot-sealed seams and degreasing. The surface is treated using one
of the methods of abrasive preparation: shot-blasting, shot-throwing, hydroabrasive; or a
mechanical method using a hand tool.
The extent of purification of black-metal surfaces from corrosion products should be
no less than 2 according to GOST 9.402-80, i.e., examination by naked eye should find no
scale and rust.
Degreasing of metal surfaces is performed using brushes or cleaning cloth wetted with
white spirit. Brushes and cleaning cloth should leave no traces on the treated surface (par-
ticles of material, fluff etc.).
The extent of surface degreasing should correspond to grade 1 as per GOST 9.402-80.
The interval between the abrasive cleaning of the surface and the painting should not
exceed 7 hours; it is admissible to exceed this interval up to 24 h in the absence of visible
changes on the prepared surface.
Duration of the interval between the end of degreasing and priming should be no more
than 1 hour.
In the cases when the use of abrasive treatment of metal surfaces is impossible, it is
recommended to use primers rust modifiers EP-0199.
One of the ways to prepare the surface of articles is metallization with aluminium or
nickel. To determine the protective properties of coatings, specimens of plates with the met-
allized coating from Al and Zn, as well as specimens with the combined coating from enam-
el and EP and modified anticorrosion additive were immersed into distilled water, 3% and
30% NaCl solutions, 1.5% NaOH solution and 3% solution of lactic acid; the change of the
appearance in time was registered. The results of the tests showed (Table 9.5) that metal-
lized coatings possess a low chemical endurance in food media; application of a combined
coating leads to an increase of the protective properties. Modification of EP enamel in an
optimal amount (2%) by additive A-2 makes it possible to increase the corrosion resistance
of metal several times, except the coating with a zinc sublayer in a 3% solution of lactic
acid.
CHAPTER 9 299

Preparation of the surface of equipment and metal structures prior to painting works
is of great importance for producing a lacquer-and-paint coating with high protective prop-
erties, which possesses a good adhesion to metal and provides for a highly efficient protec-
tion from corrosion.
Studies were carried out to reveal the effect of an aqueous solution of product A-2, as
well as aqueous extracts from coatings based on epoxy resins containing 2 wt. % of product
A-2, on the electrochemical characteristics of the system, the value of steady-state potential,
pH of the medium and current density. From Table 9.5, it follows that product A-2 provides
for the efficient inhibition of electrochemical processes, which cause corrosion of metal,
i.e., reduce the value of steady-state electrode potential by shifting it to the positive side, as
well as decrease the current density and increase pH of the medium (Table 9.6).
Table 9.5 Results of tests of metallized and combined coatings in media.

System Time before bubbles appear, days

H2O 3% solution 30% solution 1.5% 3% solution of


of NaCl of NaCl solution of lactic acid
NaOH

Metallization by aluminium 15 30 10 1 60
Metallization by EP 60 380 380 60 230
Metallization by EP + A-2 380 380 380 380 380
Metallization by zinc 1 15 90 1 1
Metallization by EP 30 60 90 60 1
Metallization by EP + A-2 60 90 380 90 60

Table 9.6 Effect of corrosion inhibitor on the steady-state electrochemical potential of steel,
current density and pH of the medium measured using an KhSO-1 chlorine-silver reference
electrode.

Test object Testing Steady-state Current pH


time electrochemical density,
potential, mV mA/cm2

Water 5 hours 700 50.00 5.1


Aqueous solution of A-2 product 5 hours 200 18.00 6.5
Aqueous extract from an E-40-based coating 10 days 570 2.40 5.3
Aqueous extract from a coating based on E-40 10 days 390 2.07 6.0
+ 2% A-2

9.9 Ways of thixotropic decrease of internal stresses in the formation of


coatings from polymer dispersions for finishing of packaging materials
Polymer dispersions are widely used for production of coatings, glue layers, sealants,
industrial-rubber articles, nonwoven and laminated materials of various purposes. The de-
velopment of the physicochemical bases of producing materials from such systems related
to the studies of the structure of dispersion particles, its effect on the specific features of
structural transformations and changes of the properties at various stages of the film forma-
tion process. When conducting such studies, which are aimed at establishing a relationship
300 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

1
20

10, MPa
2
10 3

2 4 96 192 288 , h

Figure 9.1 Kinetics of internal stresses in the formation of coatings from solutions of SKS-50 (1),
SKN-40 (2), SKD-1M (3).

between the structure of particles of dispersions and the kinetics of the change of properties
and structure at various stages of film formation, special attention was paid to studies of the
kinetics of increment and relaxation of internal stresses, which characterize the incomple-
tion of the relaxation processes and cause a spontaneous curling, warping and breakdown
of materials both in the process of their formation and in operation.
This made it possible to develop the physicochemical ways of decreasing internal
stresses in the formation of various-purpose coatings and to obtain materials with a given
set of properties. The object of study were various types of dispersions latexes, emulsions
of polymers and oligomers, powdered compositions from oligomer and polymer systems.
A peculiarity of forming films from polymer dispersions is related to the complex and in-
homogeneous structure of their particles. Using the method of electron-microscopy, parti-
cles of dispersions were shown to represent supramolecular formations consisting of
structural elements, which are characteristic of amorphous and crystalline polymers. For
most polymer dispersions, the structure of particles is globular. The size of globules, their
number and packing density depend on the molecular structure of polymer (its chemical
composition, nature of functional groups and character of their distribution in the chain, of
conformations and flexibility of macromolecules), as well as on the colloidal-chemical
properties of dispersions. Studies of the structure of particles of dispersions based on syn-
thetic rubbers and elastomers showed that, given rigid aromatic fragments in the chain,
globules 510 nm in diameter are formed from individual folded macromolecules; the
structure of part of butadiene nitrile latex SKN-40 was presented. The particles are seen to
reveal a globular inhomogeneous structure with a more dense packing of structural ele-
ments in the boundary layers. The structure of various types of particles of dispersions was
given: of suspension polyvinyl chloride used for fabrication of plastisols, dispersions of
polyurethane based on polyester and diphenyl methane diisocyanate obtained by mechan-
ical dispersion of granules in an aqueous medium in the presence of surfactants, fluoroplas-
tic dispersions. It was revealed that globules in polyvinyl chloride particles 100150 nm in
size represent complex secondary structures. They are not broken down during the swelling
of dispersion particles in plasticizer. This results in the formation of an inhomogeneous de-
fect structure in coatings; the structure does not match well with fillers. Particles of poly-
urethane and fluoroplastic dispersions consist of finer structural elements 5100 nm in di-
ameter, which are commensurable with the size of individual macromolecules. For
dispersions from polar polymers containing a significant number of functional groups ca-
pable of participating in specific intermolecular interaction, particles of dispersions consist
CHAPTER 9 301

U, % 10, MPa
80 8

60 6

40 4
1

2
20 2 4
5
6

3
1 2 3 48 240 , h

Figure 9.2 Kinetics of internal stresses (13) and of moisture content changes (46) in the forma-
tion of coatings from dispersions of SKS-50 (1, 4), SKN-40 (2, 5), SKD-1M (3, 6).

of unfolded macromolecules. This takes place, for instance, for dispersions based on alkyl
acrylates with a large concentration of carboxyl groups. When obtaining dispersions from
oligomers with the regular alternation of active groups, for instance, from oligourethane
methacrylates with aromatic and aliphatic oligomer blocks, particles of dispersions are
characterized by a plate- or flake-like crystalline structure.
Inhomogeneity of the structure of dispersion particles, as well as the presence of spe-
cial protective layers on their surface in some cases stipulates the incompleteness of the re-
laxation processes in the formation of films from such systems and the complex character
of the occurring structural transformations. This is especially pronounced in studies of the
kinetics of increment and relaxation of internal stresses in the process of film formation
from dispersions. Such investigations are rather important not only for studying the specific
formation of films from dispersions, but also for developing the physicochemical ways of
decreasing internal stresses. Figures 9.1 and 9.2 present the data on the kinetics of increment
and relaxation of internal stresses in the formation of coatings from dispersions and solu-
tions of synthetic rubbers of various chemical compositions. These curves are typical in the
formation of coatings from dispersions of polymers of various chemical compositions. In
contrast with solutions of polymers, formation of films from dispersions is seen to be
multi-stage and not to be competed after the removal of the liquid phase. Formation of local
links between particles of dispersions as the consequence of the removal of the medium at
the initial stage of film formation is accompanied by a sharp increment of internal stresses.
The subsequent relaxation of internal stresses indicates the incompleteness of relaxation
processes, instability of the properties of coatings and occurrence of complex structural
transformations in the system. Depending on the structure of dispersion particles, the relax-
ation processes can proceed very slowly, more than 30 days. The structure of coatings from
latex SKS-50 was presented, which corresponds to the maximal and equilibrium value of
internal stresses in 30 days of formation at 20C. It is seen that after the liquid phase is re-
moved, the structure of individual particles of dispersion and the interfaces between them
are clearly revealed. A homogeneous structure emerges after the regrouping of structural
elements and the completion of relaxation processes in the system. This character of
302 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

structural transformations is typical in the formation of coatings not only from latexes, but
also from dispersions of various types of polymers; the structure of coatings from a poly-
vinyl acetate emulsion at various stages of their formation was given; structure formation
in production of coatings from acrylic powders in their melting at 200C was presented. It
is seen that, irrespective of the type of dispersion and its chemical composition the structure
of dispersion particles and the interfaces between them are revealed. In subsequent forma-
tion, structural elements are regrouped and a homogeneous structure is formed.
It follows from these data that the breakup of dispersion particles into initial structural
elements and their regrouping in the process of film formation are typical of many polymer
dispersions obtained by different methods. However, each of them imposes its own specific
features on the rate of these processes and the character of the kinetic curves of the change
of internal stresses. In the formation of coatings from powdered materials, the kinetics of
the change of internal stresses is observed to have an induction period associated with the
inhomogeneity of the structure of particles and a broad molecular-mass distribution. This
leads to a weak intermolecular interaction at the initial stage of film formation due to the
melting of, apparently, the most low-molecular-mass fractions and the presence of a defect
structure with air bubbles. The subsequent warming-up of coatings at a temperature signif-
icantly exceeding the melting temperature of the oligomer is accompanied with the total de-
struction of particles and the emergence of local links between their constituent structural
elements. Regulation of the film formation process from such powdered systems is rather
complicated, as it proceeds at temperatures close to the decomposition of the polymer and
is accompanied with the formation of craters and other defects.
Thus, these data sugest that the complex structure of dispersion particles, the presence
of protective layers from more fine and densely packed structural elements and surfactants
on their surface significantly extend the period of film formation, determine the instability
of the properties of materials and the occurrence of significant internal stresses. The de-
velopment of the physicochemical ways of forming coatings with stable and high perfor-
mance properties can be done by introducing modifiers, which facilitate the breakup of dis-
persion particles into initial structural elements and provide for a stronger interaction
between them, as well as by synthesizing dispersions with a homogeneous structure of par-
ticles, increased concentration of polar groups on their surface and an optimal flexibility of
the chains.
It was shown that in the formation of coatings from latexes based on alkyl acrylates
with a large concentration of carboxyl groups on the surface of dispersion particles and their
homogeneous structure, the coating formation time decreases to several minutes instead of
tens of days; coatings are characterized by high and stable physicomechanical properties
and low internal stresses. In the formation of coatings from powdered materials with the
regular distribution of functional groups in the chain, the homogeneous structure emerges
very rapidly at the oligomer melting temperature of 6070C.
To decrease internal stresses and improve the properties of coatings from dispersions
with an inhomogeneous structure of particles, we used various modifications of methods
based on the creation of a thixotropic structure by preliminarilyy dispersing the particles
and crosslinking them by means of special additives. This enables a significant improve-
ment of the adhesion and stress strain properties of coatings and an increased durability
of materials. The choice of modifiers depends on the type of dispersion, structure of parti-
cles, chemical composition of polymer. For dispersions based on butadiene and its deriva-
tives, it is achieved by modification with water-soluble oligomers and polymers; for those
of polyurethanes, by introduction of various surfactants; for emulsions of epoxy resin-based
CHAPTER 9 303

oligomers, by a correct combination of dispersing and stabilizing surfactants in the system;


for dispersions based on alkyl acrylates, by introduction of bifunctional compounds and or-
ganosilicon oligomers contributing to the crosslinking of particles of dispersions.
Depending on the type of modifier introduced, the development of a thixotropic struc-
ture can be performed as the result of dispersing particles and increasing the intermolecular
interaction between their constituent structural elements contributing not only to the dis-
persing of particles but also to the orientation of the structural elements to form a sparse
three-dimensional network from ordered anisodiametric structures.
Modification of polymer dispersions is based on the formation of an ordered structure
with a certain distribution of the physical and chemical bonds in the systems by using var-
ious additives or by changing the colloidal chemical properties of the dispersions. De-
pending on the character of this structure, materials with a certain set of properties can be
created. A significant change of the properties of elastomers can be done by regulating their
colloidal chemical properties (pH of the medium, molecular mass of polymer, nature and
concentration of emulsifier). The action of these factors leads to the change of information
of macromolecules, size and morphology of supramolecular structures present in the parti-
cles of the dispersions. For butadiene styrene latexes and their derivatives, for dispersions
based on alkyl acrylates, an ordered supramolecular structure of structural elements of ani-
sodiametric type was found to be formed at a certain optimal pH of the medium owing to
the unfolding of macromolecules; this structure is characterized by higher adhesion and
strength properties and low internal stresses, which makes it possible to eliminate coiling
and warping of backed materials in the production process. It was shown that the structure
of coatings from butadiene styrene latexes with pH 11.7 is globular. It is known that the
globular conformation of macromolecules does not make it possible to realize the properties
of polymers associated with peculiar structural features of the polymer chain. With pH de-
creasing to 8.7, a pronounced anisodiametric structure is formed in coatings under the same
conditions. The change of the ultimate shearing stress and viscosity of latexes depending
on pH of the medium is associated with the possibility of unfolding macromolecules of car-
boxylated latexes. The mechanism of this process is explained by the electrostatic repulsion
as the result of the neutralization of carboxyl groups in an alkaline medium and their con-
version to COO ions. It is possible that the unfolding of macromolecules in this case is due
to the increased intermolecular interaction as the result of the hydrolysis of anion-active
emulsifiers of the type of soaps, which is enhanced at a decrease of pH. The further decrease
of pH leads to the emergence of an inhomogeneous globular structure, which consists of
densely packed latex particles 0.1 m in diameter and finer structural elements in between
them. Etching of specimens by active oxygen revealed that latex particles under these con-
ditions consisted of larger globules than particles in the initial latex with pH 11.7. The cause
of this phenomenon is due to the fact that, as pH is decreased, the purely coagulating action
of hydrogen ion is of importance besides the shift of the hydrolytic equilibrium. This char-
acter of structure formation in dispersions of polymers depending on pH of the medium
leads to a nonmonotonic change of the thermophysical adhesion and mechanical parameters
of films and coatings. The best properties were found to exist at an optimal pH 8.7.
A significant improvement of the physicomechanical properties by regulating pH of
the medium was also done for coatings from acrylic dispersions. At an optimal pH of the
medium, a thixotropic structure from ordered structural elements is formed in acrylic dis-
persions; this structure contributes to the acceleration of the relaxation processes, a decrease
of internal stresses and a significant improvement of the stress strain properties of films
(Table 9.7).
304 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 9.7 Effect of PAA on the properties of coatings from acrylic dispersions.

Amount of Gloss Agglutination, Adhesion, Relative Breaking


PAA, % value, % MN/m2 MN/m2 elongation, % strength, MN/m2

0 30 45 0.11 0.13 5.5 200 7.8


0.6 20 35 0.08 0.10 4.4 250 8.0
1.2 40 55 0.10 0.12 9.0 300 8.5
3.6 15 25 0.16 0.17 6.6 120 8.5

An especially efficient factor for the regulation of the properties of dispersions is their
modification by surfactants containing polar groups, which specifically interact with poly-
mer to form hydrogen bonds. Surfactants of this type not only contribute to the dispersal of
the dispersion particles, but also cause the orientation of structural elements in the presence
of aromatic groups in the chain. Surfactants with polar groups are efficient for dispersions
based on polar polymers, for instance, polyurethanes based on polyesters, acrylic polymers
with a greater concentration of polar groups, polyester amidourethanes.
The use of surfactants of this type in dispersions of polymers makes it possible to re-
duce the size of structural elements, to create an ordered structure, to increase the intermo-
lecular interaction during the formation of films. Along with a decrease of internal stresses,
this is accompanied by an improvement of the stress strain properties.
A significant improvement of the adhesion and physicomechanical properties of coat-
ings from dispersions of polymers is observed in their modification by bifunctional com-
pounds with various chain flexibilities, which crosslink the structural elements of the
dispersion and provide for a sufficient elasticity of the system. However, with the concen-
tration of polar groups in polymers decreasing, these compounds act as plasticizers, which
contribute to an increase of the elasticity of coatings and a decrease of their strength.
For dispersions based on nonpolar polymers the development of a thixotropic ordered
structure can be done by introduction of sodium salts of some surfactants, which contribute
to the increase of the local bonds between the structural elements. This is explained by the
interaction of sodium ions with polar groups of surfactants adsorbed by dispersion particles.
This makes it possible to sharply decrease internal stresses in the formation of coatings, to
improve the strength properties of coatings based on butyl rubber dispersions.
However, in some cases the choice of modifiers is stipulated by the need to impart the
coatings with special properties. For instance, a rather important characteristic of coatings
and films based on butyl rubber dispersions, along with the above properties, is their high
tearing strength. In this connection, of great practical significance are methods of modifying
dispersions by oligomer systems polymerized in an aqueous medium to form the three-
dimensional network formed by chemical bonds, as well as the use of water-soluble poly-
mers as modifiers. For these purposes, use is usually made of phenol-formaldehyde and re-
sorcinol-formaldehyde resins and their initial components (resorcinol, urotropine etc.). The
improvement of the physicomechanical properties is observed at the direct introduction of
oligomer modifiers into the polymer dispersion. Introduction of water-soluble polymers can
have different effects on polymer dispersions depending on the chemical composition and
concentration of additives.
Small additions of polyvinyl alcohol, gelatin, sodium carboxymethyl cellulose in the
amount of 1 up to 5% accelerate the first stage of coagulation of diluted latexes. With the
concentration of polymer additives increasing, the duration of the first stage of coagulation
increases, and at concentrations higher than 20% additions of polymers have no effect on
CHAPTER 9 305

coagulation. Coagulation at the introduction of small additions of the given polymers is ex-
plained by the formation of bridge bonds between individual latex particles. With the con-
centration of polymer increasing, the saturation of the surface of latex particles and their
stability increase. The effect of polymer additions is manifested the stronger, the greater the
molecular mass of polymer is and the less saturated the surface of latex particles is.
Slightly different regularities are observed in studies of the effect of the same additives
on the coagulation of nondiluted latexes based on butadiene and its derivatives. It proved
that at a small concentration of polyvinyl alcohol (up to 5%) the stability of latexes to the
action of electrolytes increases. At a further increase of the concentration of polymer up to
10% the rate of coagulation increases. The stability of latexes to the action of small addi-
tions of polymers is explained by the structuring of the adsorption layer. The further in-
crease of the concentration of polymer above 10% leads to the stabilization of the system
as the result of the total coating of the surface of latex particles by polymer.
Thus, at small concentrations of polymer additives the stability of dispersions can be
increased as the result of the formation of envelopes with high structural-mechanical prop-
erties around particles. With the increase of the concentration of polymer in the dispersion,
the intermolecular interaction between particles can increase to form a three-dimensional
network. This effect is observed not only in the modification of polymer dispersions by lin-
ear polymers with a high molecular mass, but also during the introduction of oligomer sys-
tems of the type of resol, phenol- and urea-formaldehyde resins capable of condensation in
an aqueous medium to form a three-dimensional network. Such additives are usually intro-
duced to improve the strength properties of films, as well as to fix porous structures formed
under certain conditions. Of especially great practical significance is the introduction of
such additives in production of films from dispersions of polymers by the ionic deposition
method, when the action of electrolytes in some cases leads to a considerable decrease of
their strength.

9.10 Modification of finishing dispersions for paper and offprints by


polymer systems
Studies of the effect of resorcinol-formaldehyde resin on coagulation of diluted latexes
showed that in small amounts it reduces the time of the first stage of coagulation. With the
concentration increasing, its stabilizing effect is manifested, similar to the case of linear
polymers. Unlike linear polymers, small additions of this resin are not observed to lead to
the growth of aggregates. Resins condensed before being introduced into latex do not con-
tribute to the improvement of the properties of materials. Introduction of partially con-
densed resins leads to an increase of the strength of films from dispersions of rubbers.
Introduction of these additives considerably improves the adhesion properties of films from
dispersions of butyl rubber.
The possibility of using phenol-polyamide-formaldehyde resin as a modifier of chlo-
roprene latex L-7 was studied. Mixtures of the latex with the resin are distinguished by a
good stability. The greatest strength of films is achieved at a small content of the resin
(about 1%).
The effect of the character of interaction between butadiene styrene rubber and resor-
cinol-formaldehyde resin on the reinforcement of rubbers was studied. The latexresin sys-
tem was coagulated by solutions of aluminium and potassium salts. Isolated rubber,
modified by the resin, was dried and treated on rolls at 70C. The absence of chemical bonds
between molecules of rubber and resin was shown. Formation of a network structure is ob-
306 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

served during the storage of the system, as the result of which the rigidity of the system in-
creases and the mechanical and process properties become worse. In the presence of only
the physical interaction between the modifier and rubber the reinforcing effect from the in-
troduction of the modifier and the stability of the process properties are preserved in
long-term storage of specimens.
Application of modifying additives and surfactants renders a significant effect on the
vulcanization of rubbers; the effect of several surfactants on the kinetics of sulfur vulcani-
zation of films from an aqueous dispersion of polyisoprene synthetic rubber SKI-23 and
rubber mixtures on its basis was studied. Anion-active potassium resinate and cation-active
cetyl pyridinium chloride were used as emulsifiers of aqueous dispersions. It was shown
that the rate and extent of sulfur vulcanization of films from aqueous dispersions of rubbers
is considerably higher than using respective rubber mixtures containing no surfactants.
The possibility of using unsaturated urethane rubbers of alkyl-phenol-formaldehyde
resins as texturing agents was studied, as well as the use of phenol and n-tert-butyl phenol
disulfides as the curing agent of general-purpose rubbers. Resin vulcanizates are inferior
than sulfur vulcanizates with respect to a number of physicomechanical characteristics
(resistance to rupture and tearing strength, elasticity, wear resistance) and exceed them by
other properties (residual elongation, hardness, endurance). Resin rubber mixtures also
have much better process properties. When comparing the texturing activity of various
n-tert-butyl phenol sulfides, it was found that an increase of the number of sulfur atoms be-
tween phenol rings and an increase of the extent of condensation of alkyl pnenol sulfides
contributes to the increase of their curing capacity; what is more, with the increase of the
content of methyl groups in the resin the physicomechanical characteristics of vulcanizates
increase.
The distribution and texturing action of modifiers in rubber mixtures based on
polychloroprenenairine for creating a stable bond in the rubbertextile system were stud-
ied. For better compatibility and more uniform distribution of modifiers of the type of re-
sorcinol and resotropin in the mixture, they were treated with surfactant Alkamon.
Introduction of such modifiers contributes to the structuring of the system.
Thus, introduction of modifiers from oligomer and polymer systems in an aqueous dis-
persion of polymers makes it possible to significantly improve the physicomechanical and
adhesion properties of films and coatings as the result of creating a more homogeneous and
ordered structure. However, the mechanism of action of these additives on the structural
transformations in dispersions of polymers and coatings on their basis has been little stud-
ied, the cause of reinforcement of rubbers by oligomer systems is associated with the con-
densation of resin as thin films on the surface of particles of dispersions to form a
continuous chain structure. Based on electron-microscopy studies of vulcanizates contain-
ing phenol-formaldehyde resin, a conclusion was made on the possibility of hardening of
phenol-formaldehyde resin particles in latexes. More fine particles of the resin are covered
in this case by a rubber envelope, which can be coupled with the surface of resin particles
by chemical or intermolecular bonds. Rubberresin particles have a uniform dense packing
with a specific chained distribution, which provides for higher strength parameters; here-
with, the vulcanizate has a greater elasticity and lower hardness. In a number of cases, the
interaction of oligomers with latexes is explained by electrostatic forces, as well as by
crosslinking rubber macromolecules by a phenol-formaldehyde resin of the resol type as
the result of the interaction of methylol groups of the resin with -methylene hydrogen of
isopentene groupings of rubber. Formation of chemical bonds is assumed in many works.
Considering the strong dilution of the resin in latex, the possibility of its condensation in
CHAPTER 9 307

latex is excluded, and the increase of the strength of films is related to the effect of the resin
as a fine-dispersed filler.
A significant thing for elucidating the mechanism of action of such additives is to study
the kinetics of increment and relaxation of internal stresses in such systems; studies of the
formation of coatings from dispersions of butadiene rubbers showed that introduction of
phenol-formaldehyde resins renders an effect not only on the value of internal stresses but
also on the character of their change in the coating formation process. In latex coatings not
modified by oligomers, relaxation of internal stresses is observed after drying. In coatings
from modified latexes internal stresses remain constant after achieving an ultimate value
(see Figs. 9.1 and 9.2) and in prolonged storage of specimens under conditions of their for-
mation. The value of internal stresses sharply changes depending on the time of preliminary
holding of the modified dispersion prior to its application to the support. If the dispersion
is applied to the support immediately after modification, comparatively small internal
stresses are observed. With the holding time of the mixture of the dispersion and resin in-
creased up to 30 min, a sharp increment of internal stresses is observed; their values signif-
icantly exceed those of the stresses in coatings from the initial components and from the
freshly prepared mixture. At a further increase of the holding time of the mixture up to 60
min prior to its application to the support, internal stresses sharply decrease. At the same
time, the value of internal stresses depends significantly not only on the holding time of the
resinlatex mixture, but also on the maturation time of the resin itself prior to its introduc-
tion to latex. For coatings from a freshly prepared mixture the dependence of internal stress-
es on maturation time of the resin is nonmonotonic. At an increase of the maturation time
of the resin, internal stresses first go up and then sharply drop down. These data suggest
that the character of the change of internal stresses is determined by the extent of completion
of the polycondensation process in the resin itself. In the absence of latex, this process is
much faster, which is due to the strong dilution of the resin at its introduction into latex. A
sharp increment of internal stresses is observed only at a certain extent of condensation of
the resin. A significant condensation of the resin prior to its introduction to latex contributes
to a decrease of internal stresses down to the values smaller than internal stresses in coatings
from nonmodified latexes.
Conditions for the destruction of latex particles in the dispersion and for the formation
of a thixotropic structure were found; as well as the effect of structural transformations on
the physicomechanical properties of dispersions and coatings on their basis was studied
with the view of developing the physicochemical ways of reducing internal stresses. The
object of study was divinyl styrene latex SKS-50. The structure of dispersions and coatings
was regulated by introduction of polyacrylamide (PAA) of various molecular masses and
urea-formaldehyde resin (UFR). Modifying additives render a significant effect on the
rheological properties of dispersions.
The flow curves for the initial latex modified by UFR and polyacrylamide or their mix-
ture were presented. It is seen that the initial latex is a semistructured system with a rela-
tively low viscosity. Introduction of resin does not have a significant effect on the character
of the flow curve, and only in the presence of polyacrylamide or its mixture with the resin
a considerable structuring of the system is observed, which is accompanied with an increase
of the ultimate shearing stress and a 23-fold increment of viscosity. Introduction of addi-
tives also has an effect on the kinetics of increment of viscosity. The viscosity of the initial
latex does not change in long-term holding under room conditions, whereas in the presence
of texturing agents, especially of a mixture of polyacrylamide and UFR, an increment of
viscosity in time is observed.
308 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Studies of the properties of coatings obtained from modified and nonmodified disper-
sions found that the rate of increment and relaxation of internal stresses in the formation of
coatings also depends on the nature of additives and time of preliminary structuring of a
modified dispersion prior to its application to the support. Coatings modified by resin are
characterized by an increase of internal stresses without any significant change of the char-
acter of the kinetic curves. In the presence of low-molecular-mass polyacrylamide with a
molecular mass of 0.25106, a sharp increment of internal stresses is observed. As the mo-
lecular mass of polyacrylamide increases, internal stresses go down at a simultaneous in-
crease of the rate of their increment and relaxation.
Modification of latex by a mixture of UFR polyacrylamide contributes to a decrease
of internal stresses and an increase of the rate of the relaxation processes. Herewith, a sig-
nificant decrease of internal stresses as compared with coatings from the initial latex is ob-
served to occur at a preliminary holding of the mixture for 20 min up to 24 hours prior to
the application to the support. During the formation of coatings from structured dispersions,
the period of formation of coatings with more stable properties is considerably reduced.
Modifying additives render an effect on the value and kinetics of the change of the thermo-
physical parameters of latex coatings. During the formation of coatings, the thermophysical
characteristics change antibately to internal stresses. UFR has a lesser influence on the value
and rate of change of the thermophysical parameters of coatings as compared with other
modifying additives, whereas polyacrylamide sharply slows down the rate of the relaxation
processes and decreases the thermophysical parameters. Modification of latex by a mixture
of polyacrylamide and UFR is observed to lead to an increase of the thermophysical char-
acteristics up to the values observed for coatings from initial latex, and the increase of the
rate of the relaxation processes.
Introduction of modifying additives in latex has an effect on the adhesion and strength
properties of coatings (Table 9.8). In the presence of polyacrylamide and its mixture with
UFR, the strength of films sharply increases, along with good deformation properties and
elasticity. From comparison of the structural-mechanical properties of dispersions modified
by texturing agents, and coatings obtained on their basis, it follows that the high strength in
Table 9.8 Effect of the nature and molecular mass of modifying additives on the properties of
laminated materials.
Composition Molecular mass Breaking Elasticity Resistance to Rigidity, Vapour
of PAA, strength, modulus, delamination, G proofness,
106 MN/m2 GPa MN/cm mg/(cm2 h)

SKS-50 0.8 4.2 0.39 40 3.00


MFS 2.7 8.5 0.83 92 4.97
PAA 0.25 0.6 6.0 0.52 52 5.60
0.55 1.3 5.0 0.11 47 4.62
0.75 1.8 9.0 0.14 42 5.10
1.45 0.28 44 4.49
1.75 2.3 9.0 0.73 38 4.70
PAA + MFS 0.25 1.8 8.0 0.75 55 5.30
0.55 2.3 7.8 0.87 51 5.50
0.75 2.5 8.8 0.83 39 5.35
1.45 0.70 54 5.30
1.75 1.10 65 5.50
CHAPTER 9 309

combination with elasticity and high rate of relaxation processes is observed only for coat-
ings produced from thixotropic dispersions characterized by an ordered structure.
To elucidate the role of introduced additives in the formation of the structure of latex
coatings, we studied their supramolecular structure at various stages of structure formation
by means of an electron microscope, using the method of oxygen etching of specimens,
which makes it possible to reveal the structure of latex particles. We obtained replicas from
the surface of coatings from initial latex SKS-50 and modified PAA, as well as UFR. It was
shown that at the introduction of PAA the initial structure of dispersion particles breaks
down into finer structural elements observed for coatings obtained from solutions of the
same polymers. Simultaneously with the destruction of the structure of latex particles we
observed aggregation of newly formed structural elements. The rates of destruction and
subsequent aggregation depend on the molecular mass of PAA. With the molecular mass
of PAA decreasing, structural transformations proceed slower, which is indicated by the
data on the kinetics of increment and relaxation of internal stresses, as well as the data on
the change of the thermophysical parameters of coatings.
In the presence of modifying additives, structural transformations are much faster in
the dispersion itself before the film formation process as the result of a preliminary holding
of the mixture of latex with additives prior to the application to the support.
In coatings obtained from latex modified by PAA prestructured for 30 min, a globular
structure is observed, similar to the structure of coatings from nonmodified latex and having
a higher strength and elasticity due to the binding of individual structural elements by PAA
molecules. Destruction of dispersion particles and crosslinking of structural elements of la-
tex particles occur the fastest during the formation of coatings from latexes modified by
UFR. However, in the presence of only UFR the destruction process is, apparently, not to-
tally completed, as the result of which an inhomogeneous structure is observed in coatings,
which consists of various-size particles bound by molecules of the resin. Along with this,
such coatings are found to have structural elements not observed earlier in latex coatings
and formed as the result of polymerization of the resin in the latex medium. Coatings with
this structure, despite a high strength, are distinguished by an increased rigidity (see Table
9.8). Coatings obtained from latexes modified by a mixture of UFR and low molecular mass
PAA are characterized by optimal properties. Along with high strength and adhesion, they
are distinguished by a small value of internal stresses as the result of relaxation processes
at two different levels: in the formation of a thixotropic structure in the liquid phase and in
the formation of coatings. In coatings with optimal properties, a band- and network-type
structure is observed.
Phenol-formaldehyde resins were also used for modifying dispersions of butyl rubber.
The physicomechanical properties of coatings depend on the modification method. In ex-
periment I, resorcinol-formaldehyde resin (RFR) precondensed for 18 hours under room
conditions was added to the dispersion; in experiment II, the resin was added to the disper-
sion after a condensation for 1 hour ((Table 9.9). Films were formed by the method of ionic
deposition. It is seen from the table that modification of a butyl rubber dispersion by 10%
RFR under optimal conditions according to method I makes it possible to increase the
breaking strength of films more than twofold and the tearing strength more than threefold
with the elasticity of films preserved. To elucidate the mechanism of strengthening butyl
rubber by resin, we investigated the effect of additives on the properties of films obtained
from dispersions unfilled and filled with carbon black. Films were hardened under the same
conditions (Table 9.10). From the data of the table it follows that for films from unfilled
dispersions of butyl rubber the breaking strength and tearing strength are increased by more
310 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

than an order of magnitude in the presence of modifying additives. From the comparison
of the data of Tables 9.9 and 9.10, it follows that at an optimal concentration of the modi-
fying additive the tearing strength of films from carbon black-filled and unfilled butyl rub-
ber dispersions is the same. This indicates that the tearing strength of films from butyl
rubber dispersions modified by resin is determined by the density of the three-dimensional
network formed by the resin in the dispersion.
Table 9.9 Physicomechanical properties of films from compositions based on RFR-modified butyl
rubber dispersions.

Test Content of Breaking Tearing Elasticity Shrinkage, Relative


RFR, % strength, strength, modulus, % elongation,
MN/m2 MN/m2 GPa %

I 0 11.0 1.8 5.0 16 520


5 18.9 5.5 7.4 6 750
10 24.5 6.3 1.0 8 500
30 17.1 3.7 3.2 6 620
II 5 9.0 4.6 12 800
10 18.2 5.4 11 650
30 22.0 5.7 6 500

Table 9.10 Physicomechanical properties of films from RFR-modified butyl rubber dispersions.

Content of RFR, % Breaking strength, Tearing strength, Elasticity modulus, Shrinkage,


MN/m2 MN/m2 GPa %

0 0.7 0.10 12.5 0


5 10.5 2.00 11.2 8
10 13.3 6.44 18.5 5
30 16.2 7.50 12.6 5

The concentration of an additive has a significant effect on the value of internal stress-
es in the formation of coatings (Table 9.11). At an optimal concentration of a modifying
additive, internal stresses are sharply reduced. Thus, it has been shown that modification of
polymer dispersions by oligomer and polymer systems soluble in the liquid phase makes it
possible under certain conditions to create a thixotropic structure in the initial film former
and in coatings on their basis. This was achieved by introduction of modifiers with an op-
timal flexibility and extent of branching of the chain into the dispersion; the modifiers had
a reduced solubility in the liquid phase and formed a three-dimensional network in cells of
which dispersion particles or the supramolecular structure of the main polymer are located.
In dispersions with a broad distribution of polymer particles by size, the skeleton of
the network structure is formed from finer particles, whose surface is not completely ex-
posed to surfactants owing to dissimilar adsorption of emulsifier by particles of different
size. The use of surfactants of a polymer type with active polar groups for producing such
dispersions enables a stronger bond of larger dispersion particles with the network structure.
Regulating the nature of polymer or oligomer, which forms the network structure, by
introduction of various types of modifiers, it became possible to increase significantly the
adhesion strength of coatings, to change within broad limits their stress strain character-
istics. Creation of a thixotropic structure enables a sharp reduction of internal stresses in the
CHAPTER 9 311

formation of coatings and an increase of the rate of relaxation processes, which made it pos-
sible to produce coatings with stable physicomechanical properties and sharply reduce their
formation time.
Table 9.11 Effect of the concentration of RFR on internal stresses in coatings from
butyl rubber dispersions.

Concentration of RFR, % Internal stresses, MN/m2

0 0.6
5 0.6
10 0.3
30 0.6

Formation of the thixotropic structure was performed also without destruction of dis-
persion particles. The object of study were latexes of acrylic copolymers based on butyl
acrylate and butyl methacrylate taken at a ratio of 30:70 with monomers containing polar
groups of different nature (methacrylic acid, nitrile of acrylic acid). Polyacrylamide of the
molecular mass 0.25106 (PAA) and low-molecular-mass bifunctional compounds (ethyl-
ene glycol, propylene glycol) were used as modifiers changing the structure and properties
of the three-dimensional network. This problem was solved by comparing the structure of
the network using the method of electron microscopy and by studying the rheological prop-
erties and comparing them with the stress strain, relaxation and adhesion properties of
coatings. Films and coatings were formed on glass supports, papers, fibrous bases at 20 and
70C. The structure was studied by taking carbonplatinum replicas from the surface of
coatings. The stress strain characteristics were studied at a deformation rate of 10
mm/min. The kinetics of increment and relaxation of internal stresses and adhesion of coat-
ings to the glass support was studied by the photoelastic method; adhesion to fibrous sup-
ports, by the delamination method.
Studies of structure formation in films from latexes of acrylic copolymers showed that
the network from latex particles is formed at a large concentration of polar groups in the
system and on their surface, which takes place at the introduction of more than 12% mono-
mers with functional groups into acrylic latexes in the process of their emulsion polymer-
ization. Data on the structure of films from acrylic copolymer with 12% methacrylic acid
(BMM) and 12% nitrilacrylic acid (BMN), obtained under the same conditions were pre-
sented. It was shown that coatings from BMM have a structure consisting of latex particles,
which have no dense packing; in gaps between particles, this structure is not revealed. The
fine structure of latex particles is not revealed by oxygen etching of specimens, either. This
is, probably, due to the fact that at a large concentration of carboxyl groups in the macro-
molecule system the polymer is characterized by an unfolded conformation of macromol-
ecules, and the connection between individual latex particles is performed as the result of
the formation of a network from a finer structural elements 1020 nm in diameter, found
in studies of the initial latex structure. This network structure is strong and is preserved at
a prolonged heating of films at 70C. Formation of a network from such structures is, prob-
ably, due to the fact that their surface is not coated with an emulsifier, unlike latex particles.
Similar regularities in the formation of the network from latex particles are observed at a
large concentration of nitrile groups. Owing to a greater flexibility of macromolecules and
a smaller intermolecular interaction, the skeleton of the three-dimensional network in films
from copolymer BMN consists of globular structures similar by their size to the globules
312 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

that form latex particles. In cells of such a network, latex particles are characterized by a
hexagonal packing.
The specific features of the formation of the three-dimensional network in copolymers
distinguished by the nature of functional groups have a great influence on their physicome-
chanical properties. From the analysis of the stress strain properties of films from latexes
BMM and BMN, it is seen that films from BMM have a high modulus, breaking strength
and comparatively low relative elongation in contrast with films from BMN, which are
characterized by a larger strain, low elasticity modulus and strength. Studies of the kinetics
of increment and relaxation of internal stresses in the formation of coatings from these sys-
tems showed that the relaxation processes in coatings from BMM are slower. At the initial
stage of formation, comparatively high internal stresses emerge in them; these stresses can
cause a spontaneous disruption of materials in operation.
To accelerate the relaxation processes, latex BMM was modified by polyacrylamide.
Introduction of polyacrylamide does not change the size and shape of latex particles and
leads to an increase of the distance between them. Probably, polyacrylamide interacts with
finer structural elements located in between latex particles, and contributes to an increase
of strength and elasticity of the network, as well as adhesion of coatings. This is accompa-
nied with a decrease of internal stresses in the system and an increase of the rate of the re-
laxation processes. We obtained data on the kinetics of increment and relaxation of internal
stresses in the formation of coatings from BMM, modified by an optimal amount of poly-
acrylamide at 20C. Introduction of a thixotropic additive significantly decreases internal
stresses and reduces the formation period of coatings on different-type papers and offprints.
This regularity is manifested under different conditions of formation of coatings, both at
20C and at 70C; the rheological properties of latex modified by polyacrylamide were pre-
sented. Introduction of modifier was shown to contribute to an additional structuring of the
system.
Data on the effect of polyacrylamide on the properties of latex coating were obtained.
It was shown that introduction of an optimal amount of PAA improves the decorative and
physicomechanical properties of coatings.
A different character of structure formation is observed in modification of latexes by
low-molecular-mass additives.
In the presence of these additives, the size of latex particles does not change, and the
coupling between them is performed by means of the network formed by fine globular
structures. At the introduction of propylene glycol, hexagonal packing of the structural el-
ements of the network are observed. In the formation of coatings at 70C, the ordering of
the structure of the network skeleton is disturbed; herewith, fine globular structures are dis-
tributed unevenly in the gaps in between latex particles; the data on the dependence of the
physicomechanical properties of films on the concentration of modifier involved in the for-
mation of the network structure were presented. It is seen that introduction of an optimal
amount of modifiers significantly increases adhesion of coatings to the tissue, increases the
strength and relative breaking elongation, decreases internal stresses in the system.
From these data, it is seen that formation of the network in disperse systems without
disrupting latex particles from finer structural elements and regulation of its structure using
various modifiers makes it possible to significantly increase the rate of coatings formation
and improve their physicomechanical properties.
CHAPTER 9 313

9.11 Combined packaging materials with increased protective properties


The use of polymer packaging materials is of great importance for the economy, as it makes
it possible to intensify foodstuff production processes, reduce the losses of foods, improve
quality, extend service life, decrease transportation expenses and in some cases to refrain
from the use of deficit tinplate containers.
A process for producing a number of novel combined materials was developed; the
materials are intended for packaging various foodstuffs: those subjected to heat treatment;
of a high degree of preparedness, including freeze-dried; second-course meals warmed be-
fore use; various conserves and preserves (fish, fruit-and-vegetable, milk etc.), granular
products.
Developed materials make it possible to perform sterilization of packages at a temper-
ature of 120C for 1 hour in an aqueous medium, to perform packaging and long-term stor-
age in an inert gas medium and under vacuum. They can be successfully processed on
high-speed packaging equipment, have an attractive appearance owing to the possibility of
multicolour printing. Their production technology makes it possible to apply colour images
both on the external layer and in between layers.
Combined sterilized materials are obtained by modification of batch-produced poly-
urethane glues. This provided for the stability of the performance characteristics of films at
the autoclave sterilization and chemical endurance in media modelling food products.
Works on the modification of glues were carried out with the aim to accelerate their
hardening. Preliminary results assume the development of a new process for production of
sterilized films using glues without solvents.
The characteristics of materials are given in Table 9.12.
Materials developed were thoroughly tested under performance conditions in contact
with media, which model food products: water, solutions of organic acids (acetic, lactic,
tartaric), solutions of cooking salt, crude vegetable oil.
Tests of pilot batches of materials for packaging and storage of various fruit-and-veg-
etable were carried out. Based on the data obtained, materials are recommended for pack-
aging and storage of the following types of products: second-course meals (storage time,
1230 months); meat and vegetable conserves (storage time, 2430 months); vegetable
conserves (storage time, 1218 months); juices and beverages (storage time, 9 months); to-
mato hot-spices (storage time, 6 months).
Within the specified storage times, the quality of conserves corresponds to the require-
ments of normative and technical documentation for these products.
By the results of studies of containers and ready-prepared products, changes were in-
troduced into the acting normative and technical documentation relative to packaging of
products into bags from polymer combined materials based on aluminium foil.
Tests of combined film materials PET + F + PEcm, PET + F + PP for packaging and
storage of bacterial preparations for cheese-making were conducted. The preparations were
packaged into investigated materials under vacuum, in a nitrogen and carbon dioxide me-
dium. Six batches of biopreparations were tested. Preparations in these packagings were
tested in the process of storage in a combined regime, which reflected the regime of trans-
porting the preparation to plants and its storage before use for the first 10 days at non-reg-
ulated (room) temperature, and then for up to 4 months at a subzero temperature (in the
freezing chamber of a refrigerator). The content of microflora (total amount) and aro-
ma-forming compounds were determined, as well as the acid-forming activity, the mass
fraction of moisture, and the amount of inoculum prepared from the bacterial preparation
314 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

in the initial medium without replanting, in 10 days and at the end of storage. The control
was the preparation packaged into sealed glass vials.

Table 9.12 Characteristics of materials.

Parameter PETP PETP PA PA OPP PETP PA+Al PETP PA OPP


+ + + + + + + + + +
PEcm PP PEcm PP PEcm Al+PP PEcm A1+PE Al+PP Al+PE

Resistance to 290 290 290 290 196 290 290 290 290 196
delamination,
N/m
Breaking 39.0 39.0 49.0 49.0 34.0 39.0 49.0 39.0 49.0 34.0
strength, MPa
Ultimate 30 30 30 30 30 10 10 10 10 10
elongation, %
Puncture 9.8 14.7 9.8 9.8 9.8 14.7 9.8 14.7 9.8 9.8
resistance,
MPa
Weld seam 1200 1500 1200 1500 1200 1500 1200 1200 1500 1200
strength, N/m
Resistance to 118 147 118 147 118 147 147 147 147 147
delamination
after steriliza-
tion in aqueous
medium, N/m
Weld seam 840 1050 840 1050 840 1050 840 840 1050 840
strength after
sterilization in
aqueous
medium, N/m

Note: 1. PETP, polyethylene terephthalate; PEcm, polyethylene; PP, polypropylene; PA, polyamide;
OPP, oriented polypropylene; A1, aluminium foil. 2. The width and admissible deviations for the
width are (60 750) 1 mm.

Table 9.13 Results of studies of preparations.

Parameter Vials Packets from film 1 Packets from film 2


without
vacuum under in N2 in CO2 under in N2 in CO2
vacuum atmo- atmo- vacuum atmo- atmo-
sphere sphere sphere sphere

Bacterial numbers,
billion cfu/g
initial total 380
initial aroma-forming 360
in four months
total 330 370 340 360 330 280 350
aroma-forming 230 240 260 250 270 240 230
Acid-forming activity
CHAPTER 9 315

Table 9.13 Results of studies of preparations.


(continued)
Parameter Vials Packets from film 1 Packets from film 2
without
vacuum under in N2 in CO2 under in N2 in CO2
vacuum atmo- atmo- vacuum atmo- atmo-
sphere sphere sphere sphere

initial 39
in 10 days 35 35 36 36 35 36 34
in 4 months 32 31 32 31 31 32 32
Mass fraction of
moisture, %
initial 4.50
in 10 days 4.35 5.0 4.50 4.75 5.25 5.00
in 4 months 5.37 5.0 5.25 5.12 4.87 5.50 5.12

As the result, the materials (PET + F +PEcm and PET + F + PP, Table 9.13) were found
to be suitable for packaging and storage of dry bacterial preparations. These materials pro-
vide for a sufficiently good preservation of the preparation within the investigated period
of time. Storage of the preparation in packages under a vacuum, in a nitrogen or carbon di-
oxide atmosphere at a temperature regime required for the preparations showed (as com-
pared with the control) a tendency to an increased survivability of microflora. In packaging
into packages without vacuum, the parameters after storage were identical to those of the
control specimen.
Thus, a series of promising combined materials with high protective properties and im-
proved hygienic parameters were developed.

9.12 Effect of pH of the medium on the specific features of structure


formation and the properties of coatings from polymer dispersions
Studies of film formation from latexes of polyalkyl acrylates found that at a certain chem-
ical composition they form coatings with a homogeneous ordered structure on fibrous bases
and on paper with good decorative properties, high physicomechanical and adhesion char-
acteristics. However, at a low pH value of acrylic latexes they can cause the yellowing of
the fibrous bases and paper, the corrosion of process equipment.
The properties of dispersions and the process of film formation from these systems de-
pend on the structure and composition of dispersion particles and interphase layers, the
composition of the dispersion medium. A significant effect on the properties of the disper-
sion and coatings from polyalkyl acrylates is rendered by pH of the medium. During the
titration of carboxyl groups of copolymers in the latex by alkali, the system exhibits the
properties of a weak acid with dissociation constants of 10 8 10 10 depending on the hy-
drophilicity of the dispersed phase, the glass-transition temperature, length and extent of
crosslinking of copolymer chains in particles and other factors, determining the accessibil-
ity of carboxyl groups in the titration by alkali. These effects are associated with the change
of entropy of neutralized latexes as the result of conformation changes of macromolecules
and the release of particles of hydrophilic groups to the surface.
The conductometric curves for acrylic copolymers, besides the main points of equiv-
alency, corresponding to the complete neutralization of all carboxyl groups, were found to
316 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

have intermediate points of inflection corresponding to the neutralization of carboxyl


groups located near the interphase surface. The pH value of the medium has a significant
effect on the structure of the surface protective layers of dispersion particles. Salt groups
formed in the neutralization of acidic links of the polymer are concentrated on the surface
of the particles, which is accompanied by an increase of the saturation of interphase layers
and a redistribution of emulsifier, i.e., a decrease of the surface tension of the system. The
surface tension was found to be the lower, the larger the amount of bound methacrylic acid
(MAA) in the copolymer was; what is more, its dependence on pH passes through a mini-
mum. The increase of the surface tension at large pH is explained by the increase of the in-
terphase surface as the result of the swelling of dispersion particles in the neutralization of
inner carboxyl groups, which do not get to the surface of particles even in hydrated state
owing to steric hindrances. The ability of latexes of acrylic copolymers to become denser
under the action of alkali is associated with these phenomena. By the character of viscosity
change depending on pH, latexes of various copolymers are divided into three groups. For
systems of the first group, the viscosity of latexes does not change or changes slightly de-
pending on pH; for systems of the second group, it increases significantly at the introduction
of alkali and then slightly decreases at high values of pH; for systems of the third group,
viscosity changes nonmonotonically and exhibits a maximum. It is assumed that the small
effect of pH on the viscosity of dispersions is characteristic of latexes from nonpolar copol-
ymers, for polymer chains with a high glass-transition temperature, which do not in practice
swell in water alkali.
An increase of viscosity with the pH rise of second-group latexes is explained by the
total or partial dissolution of carboxylated copolymer owing to the fact that the energy of
hydration of salt groups formed in neutralization is higher than the energy of intermolecular
interaction, for instance, for styrene-carboxylated latexes with 20% MAA. However, even
at a MAA content of 2025%, the viscosity may not change depending on pH. An incre-
ment of viscosity with pH increasing was also found for hydrophilic carboxylated latexes
with a certain amount of crosslinking agents, which strongly swell in alkaline water but are
incapable of forming molecular solutions.
The nonmonotonic change of viscosity on pH was only found for copolymers of acryl-
ic ethers. A sharp increment of viscosity at a certain pH and its subsequent decrease are ex-
plained by the successive processes (occurring with the neutralization developing) of
swelling and subsequent dissolution of swollen particles. It is believed that the thickening
of latexes occurs at the stage of true solutions as the result of the formation of intermolecular
hydrogen bonds between carboxyl and ester groups. Studies were carried out for strongly
diluted latexes to rule out the effect of protective interphase layers on the process of local
thickening and dissolution of particles. By the example of latex of the copolymer of ethy-
lacrylate with methyl methacrylate and acrylic acid with the dry substance content of 50%,
it was shown that the extent of alkaline thickening can change from 1 up to 29 units at other
conditions equal, depending on the ratio of ionic and nonionogenic emulsifiers. The data
on the effect of colloidal chemical factors are rather contradictory, which indicates that
the mechanism of structural transformations and properties of dispersions at a change of pH
of the medium has not been studied sufficiently.
The effect of pH on the properties of dispersions and coatings from acrylic latexes
based on butyl acrylate, methyl methacrylate and methacrylic acid at a constant ratio of the
first two components and various contents of MAA, as well as at a constant content of MAA
and various contents of the first two components was studied. Latexes were obtained under
the same conditions using sulfanol S-10 as emulsifier and ammonium persulfate as initiator.
CHAPTER 9 317

The content of dry residue was 50%; size of particles, 0.09 m; the content of residual
monomer, 0.05%, pH 2.5; surface tension, 38 mN/m. For comparison, butadiene nitrile la-
tex SKN-40 1GP was studied. The size of particles was determined by the method of sed-
imentation analysis in a centrifugal force field. Structural transformations in dispersions
were studied using the method of electron microscopy, potentiometric and conductometric
titration, rheological methods.
To study the conformational transitions of macromolecules depending on various
physicochemical factors, use was made of the concentration dependence of the reduced vis-
cosity of the solutions of copolymers of latexes, as well as the curves of their turbimetric
titration. The process of film formation was studied by the kinetics of change of internal
stresses at various formation stages, stipulated by the incompletion of the relaxation pro-
cesses. The physicochemical properties of films were studied by standard methods by es-
tablishing their thermomechanical curves, kinetics of swelling in organic solvents,
determination of tensile strength and relative elongation.
Studies of the properties of latex SKN-40 depending on colloidal chemical parame-
ters of dispersions found that its viscosity does not practically depend on pH within a broad
range of values, from 3 up to 11. Similar regularities in the change of rheological properties
depending on pH were found for latexes of copolymer of styrene with a minor amount of
MAA. This effect is associated with the high glass-transition temperature of copolymers
and with the predominance of hydrophobic links in macromolecules, as the result of which
particles of dispersions do not in practice swell in water alkali. However, the investigated
butadiene nitrile latex is not hydrophobic, its particles swell in a dispersion medium and
change their sizes in the process of film formation. The change of pH in this case, too, has
a comparatively small effect not only on the rheological properties of dispersions, but also
on the physicomechanical characteristics of films, increasing them within the range of 15
to 30%. Studies of the structure of dispersion particles by the method of electron-micros-
copy found them to consist of more fine globular-type structural elements of up to 2025
nm in diameter, formed as the result of folding of individual macromolecules.
From the data on the kinetics of formation of coatings from these dispersions, it fol-
lows that, irrespective of pH, a sharp increment of internal stresses is observed after the re-
moval of the liquid base; the increment indicates the emergence of local bonds between
dispersion particles, which clearly preserve their interfaces after the removal of moisture.
At a subsequent formation of coatings under the same conditions, one observes a regrouping
of structural elements present in the dispersion particles; the regrouping is completed in 15
days at 20C to form a homogeneous globular structure. At this stage of formation, one ob-
serves a decrease of internal stresses owing to the relaxation processes.
Other regularities are observed in the change of properties of dispersions and coatings
for latexes of acrylic copolymers. Studies of the dependence of the relative viscosity on pH
of acrylic latexes found that at a content of MAA up to 3% the change of pH has no influ-
ence on the value of relative viscosity.
At a MAA content of more than 3% in the copolymer, the curves for the dependence
of relative viscosity on pH are found to have two characteristic regions. Up to pH 8.5, the
viscosity is practically constant, and then a maximum is observed at pH 1011. Similar reg-
ularities are observed in the change of colloidal chemical properties of dispersions de-
pending on pH. As is seen in Table 9.14, within the pH range of 3.4 up to 8.2, the size of
particles, optical density, structural viscosity remain constant.
At a further increase of pH, they change nonmonotonously, exhibiting a maximum, the
same way as the relative viscosity.
318 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

At a constant chemical composition of copolymers and the invariability of the other


colloidal chemical properties, within the pH range of 3 up to 8.5, it could have been ex-
pected that the change of pH in this region would not have rendered a significant effect on
the process of film formation and the properties of coatings. However, the character of the
change of the physicomechanical characteristics films depending on pH does not correlate
with the regularities in the change of the colloidal chemical properties of latex up to

Table 9.14 Colloidalchemical properties of latex of acrylic copolymers at different pH.

pH of latex Most probable radius Optical density Structural viscosity at


of particles, nm shear stress of 103 N/m2, Pas

3.4 45 2.42 3.1


5.4 45 2.42 3.1
6.7 45 2.43 3.2
7.5 45 2.62 3.3
8.2 166 2.84 10.5
9.2 204 2.70 12.4
10.2 290 2.20 127.2
10.5 100 1.38 99.7
12.5 140 1.24 90.3

pH 8.5. While the colloidal chemical properties of dispersions in this pH range do not
practically change, the tensile strength of films increases, and relative elongation drops
down. At a further increase of pH, the character of the change of the physicomechanical
characteristics of films and the colloidal chemical properties of latexes correlate. The ef-
fect of pH on the film formation processes is manifested differently depending on the range
of its change. At pH smaller than 8.5, internal stresses change nonmonotonously in the pro-
cess of film formation: first they increase and then relax. This character of their change, as
is shown by the method of electron microscopy, is related to the features of structure for-
mation at various stages of film formation. Internal stresses reach a maximum after the re-
moval of the liquid phase and the emergence of local bonds between dispersion particles.
Then internal stresses relax to a constant value, which is due to the regrouping of structural
elements in the latex particles.
The extent of incompletion of the relaxation processes, which determines the value of
internal stresses and the character of their change in the process of film formation for latexes
from acrylic copolymers depends on pH. With pH increasing from 8.5 up to 1011, internal
stresses decrease 34 times and are observed to increase monotonically in the process of
film formation up to an ultimate maximum value, which remains constant at a subsequent
storage of specimens under the same conditions. It was found by the method of electron mi-
croscopy that the loosening of the structure of latex particles and their decomposition into
initial structural elements occurs in the dispersion at pH greater than 8.5. These regularities
are well consistent with the data of the rheological studies of copolymer solutions at various
pH values and with the results of their turbidimetric titration. It was shown that with pH
increasing the Huggins constant increases and the quality of the solvent worsens.
The solubility of copolymer with the change of pH depends on the content of MAA in
the chain. Copolymers with the content of MAA greater than 3% did not dissolve in dioxane
at pH 1012, and at pH 88.5 swelled within several days to dissolution. The change of
CHAPTER 9 319

the quality of the solvent with respect to copolymer from latexes with different pH affects
the dependence of the optical density of solutions on the share of the precipitation agent.
It is seen from the turbidimetric titration curves that, at pH greater than 2, inflections
or additional peaks are observed, which are determined by the formation of associates from
different-composition components. The result of this is that additional transitions are also
observed in the thermomechanical curves for films from dispersions with high pH. The de-
composition mechanism of dispersions in pH range from 8.5 up to 12 was studied, as well
as the causes for the absence of correlation in the change of colloidal chemical properties
of dispersions and films in the pH range from 3 up to 8.5. The properties of coatings depend
on the size and structure of associates entering into the composition of latex particles.
To study the conformational transitions of macromolecules in associates depending on
pH, use was made of various physicochemical methods. Irrespective of the method of pro-
ducing latex (the order of introducing components, time, dosage, other factors), an increase
of pH contributes to a monotonic increment of the surface tension from 4748 up to 5256
MN/m. This indicates that alkali as a surface-inactive substance diffuses depthward into the
latex particles. To study the mechanism of the processes occurring in the introduction of
alkali, the potentiometric titration curves of polymethacrylic acid (PMAA), synthesized un-
der the same conditions in the presence of an emulsifier and initiator used in the synthesis
of latexes from copolymers, were recorded. From the analysis of these results, it follows
that the potentiometric titration curve of PMAA is typical of polyelectrolytes containing
secondary associated structures. The initial increment of pH is due to the ionization of the
functional groups of macromolecules. In transition from a weakly dissociated acidic form
to a strongly dissociated salt form in the associated state, an inflection on the curve and a
sharp slowdown of the rate of pH rise are observed. This part of the curve corresponds to a
conformational transition of macromolecules from a compact ball into a more unfolded
shape. The transition is accompanied by the mutual repulsion of macromolecules as the re-
sult of the accumulation of like-charged groups, which can lead to the loosening or destruc-
tion of associates. A weak change of pH in this region is stipulated by a possible
compensation of its increment with the chain charge increase, by unfolding of macromol-
ecules and by the decrease of the linear density of the charge. Then an increase of pH in the
nonstructured system is observed. For latex of the copolymer, a significant increment of pH
is observed at the initial stage as compared with PMAA, which is, probably, due to a weaker
intermolecular interaction of associated macromolecules owing to a smaller number of po-
lar groups in the copolymer. Further on, a point of inflection and a sharp slowdown of the
dissociation process are observed, which can be due to the loosening of associates owing
to the weakening of intermolecular interaction. The absence of a region of the subsequent
significant increment of dissociation indicates that, unlike PMAA, in the case of copolymer
the conformation changes of macromolecules are not completed by the destruction of asso-
ciates. The higher the concentration of PMAA in the copolymer, the nearer the character of
potentiometric curves of copolymers approaches the similar curves for PMAA. The com-
monality of conformation changes in macromolecules of PMAA and PMAA-containing co-
polymers is confirmed by the results of studies of the dependence of reduced viscosity on
concentration. It is known that for solutions of uncharged polymers the dependence of re-
duced viscosity on concentration obeys the Huggins equation, according to which the vis-
cosity increases by a linear law as the concentration is increased. In the case of polyelec-
trolytes, an anomalous dependence of viscosity on concentration of the solution is observed.
This is related to the increase of the linear sizes of macromolecular balls due to the electro-
static repulsion of like-charged links of the chain owing to the swelling of macromolecules
320 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

at a decrease of the ionic strength of the solution with its concentration decreased. The con-
formational transitions determining the character of the dependence of reduced viscosity on
concentration for PMAA and for copolymers are the same. The dependence of reduced vis-
cosity on pH for diluted dispersions of copolymers is similar to the regularities in the change
of relative viscosity on pH for dispersions of the same composition. This is, probably, due
to the fact that conformational transitions in associated macromolecules are responsible for
structural transformations during the change of pH for solutions and dispersions of copol-
ymers.
From the presented data, it follows that a significant effect on the film formation mech-
anism and properties of latex coatings is rendered by the structure of latex particles and as-
sociates that form them. A change of pH from 3 up to 8.5 has no influence on the
colloidal chemical properties of dispersions, but does significantly affect the film forma-
tion process and properties of films as the result of conformational transitions of macromol-
ecules in associates and of the change of intermolecular interaction of the system. At a
further increase of pH, the conformational transitions in associated macromolecules lead to
the breakdown of particles of dispersions into initial structural elements. This is accompa-
nied by an acceleration of the relaxation processes in the system, a sharp decrease of internal
stresses and an increment of the strength parameters owing to an increase of the intermo-
lecular interaction.
The effect of pH of the medium on the formation and properties of properties of coat-
ings from latex BM-12 based on acrylic monomers of methacrylic acid was studied with
the view of developing compositions with optimal process properties. Dispersions with pH
from 2.5 up to 8.4 were obtained by the method of hot neutralization by introducing various
amounts of ammonia into the latex. The kinetics of increment and relaxation of internal
stresses in the formation of coatings at 20C was studied. The character of the kinetic curves
and value of internal stresses were shown to depend on pH of the medium. At pH from 2.5
up to 5, coatings are formed very quickly, in 1530 min. At a subsequent prolonged holding
of coatings under formation conditions for 810 days, internal stresses do not change in
practice. With pH increasing above 5, internal stresses in the formation of latex coatings
were observed to change nonmonotonically. First internal stresses rise up to a maximal ul-
timate value, and then relax. The coating formation period up to the extreme and equilibri-
um values of internal stresses increases with pH of the medium increasing. The formation
process is the most quick for coatings from dispersions with pH of the medium from 2.5 up
to 5. However, internal stresses in this case are significant, from 0.4 up to 1.0 MPa. With
pH increased up to 7.7, the coatings formation time increases up to 34 hours at a signifi-
cantly lower value of internal stresses about 0.2 MPa. At a further increase of pH up to
8.28.4 the equilibrium values of internal stresses are achieved in 5070 hours at a simul-
taneous increment of their magnitude.
The effect of pH on the rheological properties of latex was studied to elucidate the
causes of the different character of the change of internal stresses in the formation of coat-
ings from latexes differing by pH of the medium.
From the results of the study of the dependence of viscosity on shearing stress for la-
texes BM-12 at different pH values, it follows that dispersions are structured systems. With
pH increasing from 2.5 up to 7.7, the ultimate shearing stress and viscosity of the disrupted
structure increases. At a subsequent increase of pH, the ultimate shearing stress decreases
and the character of the rheological curves changes. At pH 8.2, a sharp difference between
the upper and lower levels of viscosity is observed, which is indicative of the occurrence of
a small number of contacts between structural elements, weak intermolecular interaction
CHAPTER 9 321

between them. Latex with pH 7.7 is the most structured dispersion. Coatings produced from
this dispersion exhibit the lowest internal stresses (Table 9.15).
Table 9.15 Effect of pH on the properties of coatings from latex BM-12.

pH Gloss, % Adhesiveness, a, MPa b, MPa p, MPa , %


MPa

3.0 35 40 0.10 4.0 0.8 6.8 210


5.3 35 40 0.15 7.8 0.5 9.0 250
7.7 40 45 0.07 14.5 0.3 9.3 310
7.9 25 30 0.15 12.0 0.5 7.0 250
8.2 23 228 0.10 11.0 0.7 6.7 200

The data on the rheological properties were compared with the size of latex particles
determined by electron microscopy. The size of latex particles was shown to change non-
monotonically with respect to pH. With pH increasing from 3 up to 7.7, it decreases from
0.15 to 0.06 m, and then at the subsequent increase of pH up to 8.4, increases up to 0.2
m. The peculiar feature of these dispersions is that, starting from pH 7.7, the polydispersity
of latex significantly increases, and, along with large particles of up to 0.060.2 m, glob-
ules of 1520 nm in diameter are found, which correspond to the size of separate folded
macromolecules. This character of structure formation at higher pH values indicates the in-
teraction of ammonium ions with carboxyl groups of macromolecules in the polymer, a de-
crease of intermolecular interaction and dispersal of latex particles at an optimal pH. At the
subsequent increase of pH, ammonia acts as an astabilizing agent contributing to the ag-
glomeration of latex particles.
The structure of coatings, corresponding to the equilibrium value of internal stresses,
was studied using the method of oxygen etching to elucidate the peculiar features of struc-
ture formation in dispersions depending on pH of the medium. It was shown that at pH from
2.5 up to 7 latex particles are characterized by a very fine structure formed by unfolded
densely packed macromolecules. With pH decreasing, the ability of latex particles to coa-
lesce worsens. At pH 7.7, a network structure from anisodiametric structural elements is
observed. At a subsequent increase of pH, an inhomogeneous globular structure from ag-
gregated structural elements is formed.
Formation of a set of supramolecular structures of various sizes in dispersions with an
alkaline medium extends the formation time of coatings as the consequence of incomplete
relaxation processes and contributes to the nonmonotonic change of internal stresses in the
coating formation process. Formation of coatings from a dispersion with pH 7.7 makes it
possible to produce materials with optimal properties: low internal stresses, good physico-
mechanical characteristics and adhesion strength, high gloss and the absence of tack. Sim-
ilar regularities in the change of the properties of coatings on the value of pH are observed
in their formation at higher temperatures, for instance, at 60C.

9.13 Polyurethane chemically resistant coatings for protection of container


and packaging materials
The main requirements imposed on modern polymer materials are economic feasibility,
ecological safety and high quality. It is not easy to provide for the combination of all these
properties in one product. As a rule, each of them has both advantages and drawbacks. Poly-
322 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

urethane polymers satisfy these requirements the most. They are widely used for protection
of airplanes, automobiles, bridges, chemical equipment, furniture, household electrical ap-
pliances, etc.
Over the past thirty years, the range of polyurethane materials has been significantly
expanded, and to date there are a larger number of formulations, beginning with traditional
lacquers and enamels and ending with modern ecologically favourable systems. By the vol-
umes of production and consumption, they give way to other types of products. In Western
Europe, for instance, the share of polyurethane film formers on the market of resins is 15%,
whereas for alkides this parameter reaches 40%. However, by the consumption increment
rates polyurethanes are almost two times ahead of all other types of polymer materials. Ac-
cording to predictions by specialists, in the near future, demand for them would grow 46%
a year on average. At present, polyurethanes are produced by a large number of big and me-
dium-size firms all over the world. Among the most known are ICP (England), Bayer (Ger-
many), Akzo Nobel (Holland), Monsanto (USA), King Ind (USA), Reichhold (Germany),
BASF (Germany), Kemira (Finland), Cray Valley (England), DSM (Holland), Rhone-Pou-
lenc (France) etc.
The rise of popularity of polyurethanes is explained by that coatings on their basis are
distinguished by a high quality. They dry fast, are resistant to the action of the atmosphere,
water, abrasion, low temperature and heat. Polyurethanes possess a high adhesion to various
supports, including metal, wood, plastic, concrete, as well as have good decorative proper-
ties.
Along with the unique performance properties, it is not difficult to fabricate ecologi-
cally friendly materials on their basis, which would totally satisfy the current sanitary
norms. They find ever increasing use in production of materials with a decreased content
of solvents, aqueous dispersions, ink powders and systems of traditional drying. As for the
economic feasibility of polyurethane materials, there is no common opinion in this issue.
This parameter is determined by the cost of initial raw materials: hydroxyl-containing oli-
gomer and isocyanates. Polyols and hydroxylated acrylates, polyesters, epoxides, alkides,
vinyl compounds etc. are used as the former. For crosslinking of these oligomers, use is
made of aliphatic, aromatic, cycloaliphatic and other kinds of diisocyanates and polyisocy-
anates. The most widespread are 2,4- and 2,6-toluylene diisocyanates, 1,6-hexamethylene
diisocyanate, polyisocyanate biuret, isophorone diisocyanate and adducts based on the list-
ed compounds.
Polyurethanes are more expensive than most known polymer materials. However, with
account for the durability of coatings and their performance properties they can be consid-
ered competitive.
Polyurethanes can be one- and two-pot systems. According to the international classi-
fication, they can be divided into several groups. The first are two-pot systems hardened at
usual or elevated temperature. The second group unites materials, which harden at usual
temperature by the air moisture. The third group are polyurethane materials of hot drying,
which form coatings at high temperature (up to 150C). The fourth group are polyurethanes,
which harden under room conditions, in particular, aqueous dispersions. The last group also
includes lacquer-and-paint materials based on modified polyurethanes uralkides of oxi-
dative drying.
Polyurethane coatings of organic solvent-base type, as well as ecologically friendly
materials on an aqueous base, with a high dry residue, powdered and of radiation drying
have specific spheres of application; some of them are only suitable to be used in rather
narrow areas, whereas others are universal.
CHAPTER 9 323

Among organic solvent-base polyurethanes, the most popular are two-pot lacquers and
enamels, one of whose components is a solution of polyol with pigments and additives, and
the other is a solution of isocyanate hardener. Components are mixed directly before use,
because their spreadable time is restricted by an interval of 6 up to 72 hours. Many poly-
urethanes of this class harden at usual temperature, others require heating or introduction
of additional catalysts. However, in all cases they form coatings of high quality, which are
distinguished by abrasion, chemical, low-temperature and water resistance properties, have
good decorative properties.
Owing to their high corrosion resistance, two-pot polyurethanes are successfully used
as a component of multilayer coatings of various metal engineering structures operated un-
der atmospheric conditions. As a rule, they serve as a material for the upper layers of coat-
ings and to a large extent provide for their durability. In combination with epoxides or other
anticorrosion primers, polyurethane lacquers and enamels are used for protection of bridg-
es, reservoirs, pipelines, airplanes, excavators, railway cars, combines.
In recent years, two-pot materials started to be actively used in automobile industry
for formation of priming, intermediate and top coatings. For instance, five production lines
for painting of automotive bodies operate at present in the USA. As the drying temperature
of such materials is not higher than 80C, it is very convenient to use them for the joint
painting of plastic and metal components of the body. To produce colourless finishing coat-
ings of the bodies, use is made of acryl urethane lacquers based on aliphatic isocyanates.
Coatings from such lacquers do not exhibit the aptitude for gradual yellowing, as it happens
with lacquers containing aromatic isocyanates. Despite the fact that two-pot polyurethanes
quite satisfy the requirements imposed on their performance properties, they have a number
of drawbacks, which include the inconformity with modern ecological norms. One of the
possible ways to overcome this drawback is to reduce the content of volatile organic com-
pounds by increasing the amount of the dry residue. This approach assumes the use of re-
active thinners instead of volatile solvents.
When preparing formulations of two-pot polyurethanes with high dry residue, it is nec-
essary to thoroughly choose the components in order to provide for the required balance of
the spreadable life, viscosity and drying rate of materials. The observance of these param-
eters makes it possible to produce compositions with the content of volatile solvents not
higher than 280 g/l. Polyurethanes with a high dry residue are used in the same fields as
traditional lacquers and enamels.
Of great interest are two-pot polyurethanes with 100% dry residue, which are widely
used for anticorrosion coatings. They are fabricated using low-viscous isocyanates and spe-
cial polyols. Owing to high heat resistance, low-temperature resistance, wear resistance and
shock resistance, polyurethanes containing no solvents are used for protection of petroleum
and gas pipelines, metal constructions, sewage collectors and other facilities operated under
conditions of cold or hot climate. Polyurethanes of this class are also suitable coatings on
flexible supports (canvas, tents, rainwear).
Two-pot polyurethane materials are used, which are based on urethane prepolymers
hardened by air moisture. In this case, the composition consists of solutions of prepolymer
with free isocyanate groups and hardening catalyst, which are mixed before use. Mois-
ture-hardened polyurethanes are also manufactured as one-pot systems, which are more
convenient to use. They preserve their resistance in storage, and rapidly harden in the pres-
ence of moisture to form water- and abrasion-resistant coatings. A promising application
of moisture-hardened polyurethanes is protection of metal, concrete and reinforced-con-
crete constructions operated under atmospheric conditions. These materials provide for
324 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

high-quality coatings with service life of 1520 years, resistant to the action of UV radia-
tion and exceeding epoxy coatings by elasticity. A promising approach is to use mois-
ture-hardened polyurethanes for thick-walled coatings of floors over the concrete base in
industrial, municipal and sports buildings. Such coatings impart the surface with vibration
resistance, elasticity, sound-absorbing properties and wear resistance.
Among one-pot polyurethanes, special mention should be made of hot-hardening sys-
tems, which are solutions of hydroxyl-containing oligomers and blocked isocyanates. They
are stable at usual temperature and, when heated above 100C, split to release free isocy-
anates, which play the role of hardeners proper. Owing to the achievements of polymer
physics and chemistry in the use of catalysts and the modification of film formers, thermo-
setting polyurethanes with a reduced drying temperature of up to 100C were developed,
which form high-quality long-lasting coatings.
The largest developer of two-pot aqueous dispersions of polyurethanes is the company
Bayer. They are distinguished by ecological safety, good spreadable life, the possibility
of producing thick-layer coatings up to 80 m, as well as strength, water resistance, chem-
ical resistance and weatherability.
Despite the high quality, unique durability and ecological merits, water-base two-pot
polyurethanes have significant drawbacks, associated with restricted pot life and relative
toxicity of the isocyanate component. One-pot analogs based on prepolymers of physical
drying or self-crosslinking film formers are much more processible and safe. Polyurethane
dispersions find use for painting wood, concrete, plastics, leather and are manufactured by
the largest Western companies. A promising field of application is protection of metal
items: rolled metal, aerotechnics, nuclear facilities, finish hardware, as well as metal con-
structions operated in very contaminated atmosphere. Production of water-borne polyure-
thanes for coatings of wood parquet flooring expands at a high rate. In the last five years,
production of aqueous polyurethanes for these purposes increased 2.5-fold in the industrial
sector and 10-fold in retail sales. They are also used for finishing offices, furniture, interior
design. The systems most widely used for wood finishing are polyurethane dispersions in
a mixture with acrylic latexes, acryl urethane dispersions and compositions on their base
with particles of the nucleusshell type. They are intended for finishing not only wood but
also metal and concrete.
The most important sphere of use of polyurethanes is production of powdered compo-
sitions. These materials are most popular in the USA and Japan, where their share is up to
35% of the total marker of powders consumption. In Western Europe, this parameter is only
4%. Powdered compositions are widely used for protection of household appliances due to
their high hardness and shock resistance, resistance to yellowing in the process of hot dry-
ing. Acryl- and polyester-urethane powders are widely used for high-quality finishing of
electrical appliances.
Powdered polyurethanes are produced using polyester polyols as well as epoxy and
acrylate polyols.
Powdered compositions are characterized by a rather high hardening temperature,
which leads to a significant consumption of energy. To reduce the drying temperature, use
is made of tin-containing catalysts; in this case, the drying temperature decreases down to
140160C, which makes possible a 25% reduction of energy consumed for hardening. To
produce polyurethanes with a reduced drying temperature, use is made of powders based
on polyester polyols crosslinked using the toluylene diisocyanate trimer. These composi-
tions occupy the third place by the volume of production in Western Europe after epoxy
and epoxy-polyester materials. Coatings based on powdered compositions are character-
CHAPTER 9 325

ized by a low water absorbance, good thermal resistance and light permanence. They are
widely used for protection of garden metal furniture, window frames, doors, electrical
household appliances and metal constructions operated under atmospheric conditions. On
their base, powders with decreased hardening temperature were developed; this factor is es-
pecially important for painting of metal profiles with plastic elements.
Polyester urethane materials based on isocyanate-modified alkyd resins harden due to
oxidative polymerization by the double bonds. They are used for packaging compositions
of solvent- or water-soluble types, are cheap and accessible among various polyurethane
materials. Coatings from them rapidly harden in the air and are distinguished with good pro-
tective properties. By the atmospheric and wear resistance, they exceed considerably coat-
ings from alkyd materials, are resistant to air moisture due to the absence of free isocyanate
groups, which makes unnecessary introduction of additives for absorbing moisture from
raw-material components. The great diversity of polyurethanes makes it possible to produce
highly competitive long-lasting and high-quality coatings for various purposes. Among the
reasons impeding the introduction of polyurethanes into practice are complexity of work
with two-pot systems, toxicity of isocyanates, relatively high cost of raw materials and final
product. These reasons and the deficit of raw materials explain the unsatisfactory condition
of the market of polyurethane materials. The volume of domestic production can not satisfy
the requirements of their use. Unfortunately, production of Russian-made environmentally
benign polyurethane materials (aqueous and powdered) is insignificant.
When developing polyurethane materials, it is necessary to take into account the effect
of the structure of polyurethane blocks on internal stresses in coatings, causing a spontane-
ous delamination and destruction of coatings in operation, and being a criterion of their du-
rability.
The developed polyurethane compositions are of great interest for protection of con-
tainer and packaging materials.

9.14 Protective polyurethane coatings and adhesive compounds


Coatings based on polyurethanes are characterized by a valuable set of properties: high
chemical endurance, adhesion strength, good decorative and protective properties.
A great number of formulations have been developed, including traditional lacquers
and enamels, which are distinguished by modern ecologically friendly properties. However,
by the volumes of production and consumption polyurethane compositions give way to oth-
er kinds of polymer products. In spite of the comparatively small volume of their production
as compared with other film formers, the rates of consumption growth of polyurethane ma-
terials are two times higher than those of all the other film formers.
A valuable set of the performance properties of polyurethanes is determined by their
mesomorphic ordered structure, associated with the regular alteration of flexible and rigid
blocks in their structure.
The aim of our work is to compare the formation process and properties of polyure-
thane coatings of two different classes, distinguished by the chemical composition and coat-
ing-formation method.
Polyurethane (No 1) developed in Germany (grade Morefree 402A + C79) was ob-
tained based on diphenyl methane diisocyanate and polyester, taken at a ratio of 2:1. The
composition contains no solvents. Formation of coatings is performed as the result of fusion
of particles of the powdered system. Hardening of films and coatings is performed by the
stepwise regime: at 60C, 20 min; at 165C, from 1 up to 5 min.
326 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

60 C 90 C 20 C

Dynamic viscosity, Pa s
200

150

100

50

5 10 15 20 Time, h

Figure 9.3 Dependence of viscosity on structuring time at various temperatures of composition 1.

200
Dynamic viscosity, Pa s

90 C 20 C
150 60 C

100

50

10 20 30 40 Time, h

Figure 9.4 Dependence of viscosity on structuring time at various temperatures of composition 2.

Coatings from composition No 2 of domestic production were held preliminarily for


24 hours at 20C to remove the solvent, then were hardened according to a regime similar
for films from composition No 1.
Viscosity of film formers was determined by the falling-ball method. The adhesion
strength was assessed by the effort of delaminating the splicings held in touch with the ad-
hesion-promoting agent for 10 min under a load of 200 g. The physicomechanical charac-
teristics were studied at a loading rate of 50 mm/min. Internal stresses were determined by
the photoelastic method on an instrument with the automatic registration of path dif-
fereence.
Figure 9.3 presents the dependence of viscosity of composition No 1 on time at various
temperatures. Preliminarily, the viscosity enabling quality films of materials with a homo-
geneous structure was determined. It is seen in the figure that, as temperature increases, vis-
cosity rises, apparently, owing to the interaction of the systems components. At 20C, a
significant increment is observed in 5 h. The structurizing of the film former, associated
with the loss of yield at 20C, begins in 18 hours.
Figure 9.4 presents a dependence of viscosity on time at various temperatures for com-
position No 2. It is seen that, as compared with composition No 1, the same value of vis-
cosity can be obtained at a temperature increase for a smaller time of the significant
increment of viscosity at 20C and is observed after 8 hours. The loss of yield by compo-
sition No 2 at 20C is observed in 3540 h.
CHAPTER 9 327

3500

Resistance to lamination, N/m


3000 1
2500
2
2000
1500
1000
500
0
0 50 100 150 200 250 300 350 400 450
Hardening time, h

Figure 9.5 Dependence of delamination resistance on hardening time of bonded joints from com-
position 1 (1) and composition 2 (2).

Optimal regimes were assessed by the delamination strength of compositions from


polypropylene with polyethylene bonded by bonding adhesives No 1 and No 2 (Fig. 9.5).
It is seen in the figure that the dependence of the delamination force on hardening time is
of a nonmonotonic character. For bonding adhesive No 1, the optimal hardening time is
from 50 up to 130 hours and is characterized by the maximal delamination load. For film
former No 2, this parameter is from 5 up to 50 h.
Due to the presence of a solvent in the film former, its hardening and an increment of
the resistance to peeling occur faster than in bonding adhesive No 1 to make 2700 N/m in-
stead of 3200 N/m for system No 1.
Figure 9.6 presents the physicomechanical properties of films from systems No 1 and
No 2. It is seen that the character of the curves for films from system No 2 is typical of amor-
phous materials. They are also distinguished by a greater elasticity. The breaking stress for
them is 2.1 MPa, and strain is 460%. For films from composition No 1, these parameters
are, respectively, 6 MPa and 268%.
Studies of the kinetics of increment and relaxation of internal stresses found that (Fig.
9.7) they change nonmonotonically for coatings from composition No 1. Such regularities
in the change of internal stresses are characteristic of coatings adsorbing the moisture from
the air owing to their high porosity and imperfection of the structure.
Internal stresses in the formation of coatings from composition No 2 in similar condi-
tions reach an ultimate constant value in 3 hours of hardening at 20C and remain stable
even after a heating of coatings at 165C.
From the analysis of the results of the studies, it follows that materials from polyure-
thane of domestic manufacture are characterized by stable and high performance properties.
They are used as glue compositions in production of packaging combined materials.
The CJSC Scientific-and-Technical Company Korona-Lak developed and orga-
nized commercial production of polyurethane lacquer-and-paint materials and the system
of coatings on their basis.
The main distinctive feature of polyurethane coatings is the high level of protective
properties due to the reactivity of the isocyanate group (N=C=O), the heterogeneous na-
ture of its double bonds. This makes it possible to produce most diverse polyurethane lac-
quer-and-paint materials based on polyester, alkyd, acryl and epoxy resins containing active
hydrogen, which provides for the formation of urethane bonds.
328 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

6
a
5

Stress, MPa
4

0
0 10 50 90 130 170 210 250 268
Deformation, %

2.5
b
2.0
Stress, MPa

1.5

1.0

0.5

0
0 20 60 100 140 180 220 260 300 340 380 420 460
Deformation, %

Figure 9.6 Dependence of stress on strain for system 1 (a) and system 2 (b).

Polyurethane coatings are distinguished by light permanence and stability of the dec-
orative properties in long-term operation of articles from ferrous and nonferrous metals,
plastics, wood and other materials in various climatic conditions. Coatings are stable to the
action of subzero temperatures, mineral and organic oils; possess water, petrol and abrasion
resistance.
Reliability and durability of polyurethane coatings depend on:
the properties of initial raw material components, chosen based on the technical re-
quirements for the operation of coatings;
the system of a coating; conditions and regimes of its formation;
ways of preliminary preparation of the surface to be painted.
Due to the relatively high cost, polyurethane lacquer-and-paint materials should be
used in cases when expenses for their use are paid off by either durability (no less than 10
years), or by the necessity to restrict the volume of use of traditional lacquer-and-paint ma-
terials.
The feasibility calculations showed that in painting one railway car the replacement of
enamel PF-115 by polyurethane lacquer-and-paint materials leads to a 3-fold increase of
the service life, as the result of which not only the consumption of lacquer-and-paint mate-
rials decreases from 100 down to 30 kg and painting expenses by 25%, but, respectively,
the ecological load in painting works is reduced.
CHAPTER 9 329

1.2
a

Internal stress, MPa


1.0
0.8
0.6
0.4
0.2
0
0 1 2 3 4 1 3 5
Time, h Time, min
0.50
0.45 b
Internal stress, MPa

0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0
0 1 2 3 1 3 5
Time, days Time, min at 165 C

Figure 9.7 Kinetics of internal stresses for system 1 (a) and system 2 (b).

The world production of polyurethane lacquer-and-paint materials is approximately


700 tons/year. In Russia, polyurethanes are only 5% of the total range of produced lacquer-
and-paint materials. In the USSR, the development of polyurethane lacquer-and-paint ma-
terials was hindered by the insufficient means for importing raw materials, but the modern
economic situation significantly simplifies the solution of this problem. Starting from 1998,
in connection with the increasing demand for new domestic types of lacquer-and-paint ma-
terials, such enterprises as Yaroslavl Lacquer-and-Paint Plant Pobeda Rabochikh, Joint
Stock Company Ekolpol, Close Joint Stock Company Korona-Lak, conduct research
into development of polyurethane lacquer-and-paint materials. The company Korona-
Lak in a comparatively small period of time developed and phased in a number of new
polyurethane materials for painting airplanes, gliders, hydroplanes, petrol trucks, railway
cars, plastics and art objects (Table 9.16).
Introduction and phasing-in of new lacquer-and-paint materials is accompanied with
consumer technical service. Together with the Testing Center Kortest, accelerated cli-
mate tests, stardardization and certification of lacquer-and-paint materials are carried out.
Among the developed materials, of interest is primarily the polyester acryl urethane enamel
KPU-1, which by the properties of coatings is not inferior than aviation-grade enamels of
the company Akzo Nobel, and costs 1015% less.
Gliders painted with the systems of coatings based on epoxyurethane primer KPU-02
330 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

and urethane enamel KPU-14 are exported to Great Britain and the USA.
There is already a three-year-long positive experience of painting gas tank trucks with
the coating based on red-orange enamel KPU-12.

Table 9.16

Application Lacquers / paints / system Film former


of coatings

Painting of passenger Primer EP-0215 (light- Epoxy resin hardened with amino siloxane resin
aircraft yellow)
Lacquer AK-113 Acrylic resin
Primer EP-028 (light- Epoxy resin hardened with polyisocyanate
yellow) biuret
Enamel KPU-1 (various
colours)
Painting of gliders and Primer KPU-02 (white) Epoxy resin hardened with polyisocyanate
water aircraft biuret
Enamel KPU-14 (white) Epoxy urethane resin hardened with polyiso-
cyanate biuret
Painting of fuel tank Phosphating primer VL-02 Polyvinyl butyral resin with addition of acid
trucks catalyst
Primer KPF-01 (russet) Quick-drying alkyd resin
Enamel KPU-12 (orange- Alkyd urethane resin hardened with polyiso-
red) cyanate biuret
Painting of passenger Primer KPU-02 (yellow) Epoxy resin hardened with polyisocyanate
rolling equipment biuret
Enamel KPU-14 (various Ditto
colours)
Painting of elastomeric Mat lacquer KPU-25 Oligourethane elastomer hardened with
plastics isocyanate-containing adduct
Painting of wooden con- Lacquer KAU-1 Alkyd urethane resin
structions and artwork
Painting of metallized Lacquer KPU-15 Biuret-hardened epoxy urethane resin
plastics

The results of accelerated climatic tests of the coating system primer KPU-02 and
epoxyurethane enamel KPU-14 made it possible to recommend this system for painting
railway cars. These coatings provide operation for 10 years under conditions of cold and
moderate climate.
The most interesting developments include matte elastomer lacquer KPU-25 for dec-
orative finish of rubberlike polyurethane films.
A 15-m-thick coating hardened at 80C has a matte silky surface and withstands the
tensile elongation up to the complete rupture of the support.
In the nearest future, it is planned to develop a broad range of two-pot epoxyurethane
lacquer-and-paint materials, coatings based on which have a high rate of hardening,
chemical endurance and resistance to scratches. Application of additives of the company
Byk Chemie made it possible to develop thixotropic lacquer-and-paint materials for paint-
ing furniture fittings, lacquers for finishing metallized plastics and articles from ebony with
a highly sliding surface, which excludes scratches. Operational tests of red transparent
CHAPTER 9 331

epoxyurethane lacquer are being carried at present; the lacquer is intended for painting
retroreflective road signs of the type of cats eye.
332 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY
10 Methods of Developing
Polymer Gas-selective
Systems for Storage of
Fruits and Vegetables

10.1 Problems of storage of agricultural raw materials and foodstuffs


In the processing chain of foodstuff production from the field to the consumer, an important
place is occupied by the storage of raw materials and end products. The use of cold in trans-
portation, storage and processing of products in the agroindustrual complex makes it pos-
sible to avoid considerable losses. By estimates of specialists, the energy expenses for
refrigeration and storage of a unit product is nine times lower than for its production.
At the same time, cold-storage facilities available in the country provide for one-time
storage of less than 12% of perishable products of agriculture and food industry. This makes
necessary the development of storage infrastructure. Special attention is paid to the devel-
opment of storage parameters for various types of products, such as temperature, relative
humidity, composition of the gas medium, special protective properties of coatings. Indus-
tries manufacture insufficient amounts of modern equipment and instruments for the con-
trol and regulation of a microclimate in storage chambers, as well as mechanical appliances
for handling operations. Specially acute is the issue of the development of modern facilities
for storing fruit-and-vegetable products and potatoes in the country. Russia is the largest
producer of these products. At the same time, supply of domestic vegetables and potatoes
to the population in the course of the year does not exceed 5060%; and fruits, 25%. At all
stages of promotion of these products, the losses are up to 4050%; and the quality is sharp-
ly reduced.
Application of technologies using artificial cold and regulated gas medium (RGM)
makes it possible to decrease 57-fold the losses of fruit-and-vegetable products; 23-fold,
of animal-origin products. R&D on the development of technologies for production of
quick-frozen vegetables, berries and fruits is promising. The high level of the preservation
of vitamins and other nutritive substances, prolonged storage life, exclusion of the use of
aseptic means and sugar make these products indispensable infants food, dietary food,
health food and prophylactic food. Consumption of quick-frozen products per capita is in
Russia 0.5 kg per year; in Western countries, up to 50 kg per year.
334 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

10.2 Selectively permeable polymer materials


One of the most efficient inexpensive and simple methods of storage is the use of cooling
under conditions of a modified gas medium (MGM). Containers from polymer materials
with gas selective membranes are the least material- and energy-intensive devices for stor-
ing fruits and vegetables in MGM.
Storage of fruits and vegetables under these conditions is based on creating the atmo-
sphere with an increased content of carbon dioxide and a decreased content of oxygen inside
a container. Such an atmosphere is established as the result of interaction of two processes
respiration of fruits and diffusion of gases through membranes. An increased content of
carbon dioxide and a decreased oxygen content inhibit respiration of fruits and contribute
to their larger storage life.
To create a modified gas medium, two methods are used the most the method of
forming the required gas medium (active method), given the name of the regulated gas me-
dium (RGM), and the creation of a modified gas medium due to the vital activities of
fruit-and-vegetable products in a closed volume (passive method) given the name of the
modified gas medium (MGM).
During the storage in RGM, special gas generators and absorbents remove excess gas-
es and maintain their preset concentration. This method is rather efficient; however, it has
not found wide use for all its positive merits due to the complexity and high cost of equip-
ment.
The method of storing fruit-and-vegetable products in MGM is the least material-
intensive, does not require special devices and installations. It assumes the use of various
membranes possessing a selective ability to pass gases, which contributes to the creation of
a medium with a decreased content of oxygen and an increased content of carbon dioxide
in closed tanks. To enable a required storage regime, it is necessary to know, besides the
parameters of the membrane, the characteristics of stored products and, first and foremost,
the respiration intensity. If this parameter is known, the calculation of the gas regime can
be done by, for instance, setting the concentration of oxygen. Then the concentration of car-
bon dioxide will be the function of this parameter.
The consumer properties were studied and containers for storing fruits and vegetables
were developed. For solving this problem:
processes occurring in storage were analyzed to develop an optimal gas regime,
the effect of various factors on the kinetics of attainment of the steady state regime
with consideration of the parameters of products was studied, as well as the method of pack-
aging, selectivity and vapour permeability of the membranes for monitoring the gas com-
position,
the inhomogeneity of membranes with respect to their permeability and selectivity
was determined, as well as the admissible boundaries of scatter,
the method of calculating the parameters of containers with two different-type mem-
branes was developed with the view of attaining an optimal regime of storage,
the method of and device for removing excess moisture from containers was devel-
oped, using capillary porous textile materials, for instance, nonwoven materials from syn-
thetic fibres.
Broad industrial introduction of the MGM method throughout the country is impeded
by the labour intensity of assembling and operating gas selective devices, insufficient avail-
ability of tissue-base membranes. The absence of a systematic analysis of gas selective ma-
terials and systems from the point of view of a unified methodological approach prevents
CHAPTER 10 335

prediction of the composition of the gas medium as a function of the performance charac-
teristics of these systems.
Quantitative dependences were established, which make it possible to regulate the gas
composition in containers and packagings from polymer materials by combining the per-
formance characteristics of gas-selective polymer materials and developing novel gas se-
lective systems. A relationship was found to exist between the contents of oxygen and
carbon dioxide in polymer gas selective systems and their diffusion and geometric charac-
teristics. This enabled the development of optimal conditions for prolonged storage for each
concrete type of fruit-and-vegetable products.
For this purpose, gas-selective paper-polymer material was developed, which is a com-
bination of two layers of paper or paperboard with reduced adsorbability and a polyethylene
layer in between them, 2060 m in thickness, as well as membrane material consisting of
the paper support with a hydrophobic layer and a layer of an organosilicon substance ap-
plied to it. The use of these materials made it possible to reduce natural losses of apples
after 6.5 months of storage 58-fold and to increase the yield of standard products by 30%.

10.3 Effect of diffusion characteristics of polymer materials on the formation


of a gas medium
Experimental works conducted in various climatic zones of the country dealt with the de-
termination of optimal gas compositions for various types of fruits and vegetables, temper-
ature regimes of storage, trade analysis of the results of long-term storage, experimental
selection of the area of membranes and development of various container/packaging de-
signs using selectively permeable membranes. For industrial storage of fruits in MGM, use
is made of containers with polyethylene inserts 150200 m in thickness in combination
with gas selective membranes, which can be fixed directly in the wall of the polyethylene
insert or be mounted into the internal cavity of the gas selective device from shock-proof
polystyrene. Perforated walls of the body do not prevent the gas exchange through the mem-
brane and protect it from the mechanical impact of the surrounding fruits.
As the sizes of containers are constant, approaches to the choice of diffusion charac-
teristics of polymer materials for gas-selective containers were developed for creating
optimal regimes of storing fruit-and-vegetable products in gas media. According to the
modern views, the limiting stage of gas transfer through polymer material is diffusion, and
the main characteristic of polymer materials for these purposes are their diffusion coeffi-
cient for oxygen and carbon dioxide. The effect of diffusion characteristics of a wide range
of domestic materials on the composition of the modified gas medium in storage of apples
was studied. For this, packagings from gas-impermeable material cellophanefoilpoly-
ethylene and packagings from the same material with inserted membranes from various
polymer materials were fabricated.
Coefficients of diffusion and permeability of materials with respect to oxygen or car-
bon dioxide at apple storage temperature were determined with consideration of the area of
the polymer membrane, diffusion coefficients of oxygen and carbon dioxide, difference of
their concentrations on both sides of the membrane, respiration intensity of fruits and veg-
etables, weight of products (Table 10.1).
For membranes, the chosen polymer materials differ by their productivity by several
orders of magnitude.To obtain comparable data on the formation of the gas medium, pack-
agings were fabricated with membranes of different area. For polyamide, polyimide,
polypropylene and LDPE the area was 0.150.15 m2; for HDPE, LDPE+GKZh-94,
336 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

HDPE+LDPE, 0.100.10 m2; for PLP (Sigma), membranes based on PVTMS paper,
0.0304 m2.
In storage of fruits in a sealed tank without membranes the gas composition constantly
changed without reaching an equilibrium value. In packagings with membranes from polya-
mide and polyimide the gas medium changed in a similar way. This indicates that flows of
gases through membranes from these materials are insufficient to form gas regimes accept-
able for maintaining the vital activity of fruits.

Table 10.1 Diffusion characteristics of polymer materials at 4C.

Polymer material Thickness, Diffusion coefficient, Permeability, Q10 12,


x10 5, m D10 12, m2/s m3/(sN)

O2 CO2 O2 CO2

Polyamide 2.5 0.20 0.032 0.0079 0.017


Polyimide 4.0 0.39 0.069 0.014 0.071
Polypropylene 2.0 1.14 0.71 0.11 0.36
LDPE 6.0 7.89 5.76 0.089 0.35
HDPE+LDPE (70:30) 3.0 9.78 8.71 0.15 1.01
HDPE+GKZh-94 5.5 16.23 12.05 0.22 0.71
HDPE 4.0 16.61 11.50 0.36 1.41
Cambric-based PDMS 15.0 56.31 238.05
Polycaprolactam-based 12.3 91.20 224.15
PDMS
Paper-based PDMS 13.3 147.20 537.10
PVTMS 14.5 5623.00 2818.00

When using other types of polymer materials, the process of gas exchange of packag-
ings with the environment has two characteristic stages: non-steady state and steady state.
The first period was characterized by a decrease in the content of oxygen and an accumu-
lation of carbon dioxide. The intensity of change of the concentration and the duration of
the non-steady state period depend on the polymer materials used and variety features of
fruits. In storage of packagings with little-permeable membranes, the time of attainment of
the steady state was usually larger. For apples, a more intensive change of the gas compo-
sition was characteristic of carbon dioxide, which is due to the rates of transfer of these gas-
es in polymers. The greatest absorption of oxygen and the accumulation of carbon dioxide
occur in packagings from polypropylene and low-density polyethylene. The use of mem-
branes from PDMS on various bases and from PVTMS modified the gas medium insignif-
icantly; despite the fact that their area is much smaller, the gas composition in packagings
with such membranes is close to the atmospheric composition.
Simultaneously, the kinetics of change of the gas composition in storage of apples in
packagings with membranes from various polymer materials was studied; the respiration
intensity of fruits, i.e., the amount of gas evolved or absorbed by a unit weight of fruits per
unit of time, was measured. This characteristic in the postharvest period depends on the
storage temperature and composition of the gas medium. For correct calculation of the con-
tainer parameters, one should know the respiration intensity of fruits in the gas medium,
which formed in polymer containers as the result of the vital activities of fruits and selective
permeability of polymer materials. The method for determining the respiration intensity of
CHAPTER 10 337

fruits during their storage in polymer containers without violating the storage conditions
and air-tightness of containers was worked out.
Analysis of experimental data on the effect of diffusion, area of polymer material,
weight of products and respiration intensity of fruits with respect to oxygen and carbon di-
oxide on the composition of the modified gas medium indicates that the reduced perfor-
mance of membranes should be used as the main process parameter determining the gas
composition. Methods of predicting the composition in storage of fruit-and-vegetable prod-
ucts, having the respiration intensity close to that parameter at the beginning of storage,
were proposed.
Prediction of the characteristics of gas selective polymer materials is carried out with
consideration for the composition of the gas medium, area and thickness of membranes, as
well as the ratio of the concentration of oxygen and carbon dioxide. Selective permeability
of polymer materials is determined by many factors, including by the molecular interaction
of the polymer matrix and a diffusing substance.
The required gas composition can be obtained in various ways using little-permeable
materials, for instance, polyethylene of 150200 m in thickness with high-performance
membranes, or using solid packaging material with the optimal ratio of the diffusion coef-
ficient, area, thickness. Membranes from a paper support with the consecutively applied hy-
drophilic layer (of the composition containing polyvinyl alcohol and low-molecular-mass
additive) and the surface layer (from an organosilicon substance) were developed. Intro-
duction of a low-molecular-mass additive makes it possible to obtain a layer of hydrophilic
polymer with the defect-free silicon film.
Despite the large economic and social effect of the use of polyethylene inserts with
gas selective membranes, they have not found wide commercial use, which is due to the
high labour intensity of assembling and operating such systems.
A multilayer fibrous material consisting of paper or paperboard with absorbability of
535 g/m and a polyethylene layer of 2060 m in thickness in between them was devel-
oped. The weight of the coating was 50 g/m2, which provided for a permeability of
4.6210 12 and 11.6810 12 m3/(sN) with respect to oxygen and carbon dioxide, respec-
tively, at 25C. The material is used for fabricating bags 11.5 kg in capacity.
Block copolymers based on vinyl trimethylsilane, which are distinguished by the suc-
cession of arrangement of the blocks, molecular mass, chemical composition were used for
fabrication of gas selective membranes with high parameters. Using the methods of electron
microscopy and diffusion measurements, it was shown that siloxane block copolymers
manifest the phase inversion at a concentration of polymethyl siloxane blocks from 20 up
to 45%. The properties of these membranes depend on the morphology of supramolecular
structures. It was shown that membranes from block copolymers are characterized by a high
selectivity of gas separation.
Modified polydimethylsiloxane block copolymers. were developed for fabrication of
membranes. It was found that at a small molecular mass of polydimethylsiloxane about 350
the copolymer is a single-phase system with the glass-transition temperature of 125C. The
phase separation is observed at an increase of its molecular mass.
By varying the composition of block copolymers, the mechanical properties can be
changed within a broad range from rigid material with small elongation of up to several
percent to elastic material with high elongation.
Even in the absence of crosslinks, they behave as crosslinked silicon rubbers, which
is explained by their two-phase morphology; herewith, polysulfonyl blocks render a rein-
forcing action.
338 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Gas permeability of block copolymers through the membrane increases 3.4 times as
the mass fraction of polydimethylsiloxane is increased from 30 up to 80%. Block copoly-
mers can be used to produce membranes with selective properties in storage of agricultural
products, when their losses can exceed 60%. They can be used for creating an atmosphere
with a decreased concentration of oxygen and an increased content of carbon dioxide.
The method of storing fruits and vegetables in a regulated gas medium is based on the
use of membrane gas exchangers installed in sealed refrigeration chambers, and film poly-
mer packagings equipped with gas-selective membranes.
It was found that polymer membranes in the shape of hollow fibres are the most ratio-
nal and promising technical solution as compared with plane and asymmetric membranes.
Hollow gas-separating fibres based on block copolymers were produced; they differ
from the plane ones by a larger surface per unit volume.
The intensity of physiologo-biochemical processes in fruit-and-vegetable products,
quality and duration of storage depend on temperature-moisture regimes; to create and
monitor these regimes, various systems of maintaining a microclimate are used. Such sys-
tems differ by the methods of air exchange organization.
In Russian and Western practice, two types of ventilation are used: general mechanical
ventilation (circumfluent systems) its main drawback is the unevenness of the tempera-
ture-moisture field inside the stack and the system of active ventilation. These systems
are expensive and require significant operational expenses.
A system of flow ventilation of stacks and standard rack-mounted trays was proposed;
it is devoid of the main drawbacks of the circumfluent systems and active-ventilation sys-
tems. The cost of the construction part of such a system does not exceed that of circumfluent
devices; however, it enables a higher uniformity of air distribution in the entire volume of
the stored products.
The system provides for different temperature levels, drying of products, supply of air
in input ventilation of the stack. Such systems include the equipment for heat-moisture
treatment of the air, including the means for heating, cooling and drying. The ventilation
system contains the vertical main air duct, located in the butt-end part of the stacks with
regulated fittings connected with air ducts formed by trays of containers, air flow limiters,
installed in the opposite butt-end part of the stacks. In the main air duct, there are horizontal
partitions arranged to form alternating air supply and -exhaust sections, and the air flow lim-
iter is made in the shape of a wall along the entire height of the stacks.
It is recommended to use to system of maintaining a microclimate, in which the mix-
ture of incoming and recirculating air is processed in heat-exchanging devices to be fed to
the air-supply sections of the vertical main air duct. The alternating air-supply and -exhaust
sections operate as regenerative heat exchangers. Two-side ribs on the partitions make it
possible to increase the heat removal between the sections. The direction and consumption
of the air is regulated by fittings, which can be rotated inside the air duct. To prevent the
flow-over of the air into the stack, with a small number of containers along the length (up
to 1015), it is recommended to cover the sections with air-impermeable material in the
butt-end part.
The existing technologies of storing food products are characterized by a compromise
between the scientifically grounded and experimentally verified requirements to storage
conditions, on the one hand, and the possibilities for their realization, on the other hand.
Technologies can possibly be refined both by increasing the requirements to the quality of
products to be stored and by expanding the technical potential of storage facilities, improve-
ment of containers, packagings and other technical means. To optimize the heat and mass
CHAPTER 10 339

exchange processes in the productstorage system, which determine the change of quality
of products in storage, use was made of the fundamental principles of irreversible thermo-
dynamics. This makes it possible to establish relations between particular elements of the
system and consolidate them with account for the changeability of the parameters.
We studied the behaviour of the system with account for the structure, temperature lev-
el of storage, moisture content, intensity of the chemical processes, which determine a re-
duction of the parameters of quality, with the view to define the concept of the stability of
the system as the ability to maintain a certain state and return to it after admissible devia-
tions of some parameters.
The change of entropy is considered as the parameter of change of the properties of a
stored product, in particular, the change of entropys components: entropy emerging inside
the system (product) and entropy brought from (released to) the external medium. Entropy
inside a product is minimal at an increase of the requirements to the quality of products to
be stored. A decrease of intensity of change of external entropy in the productstorage sys-
tem is achieved by the localization of external effects in the storage subsystem.
Of prevalent significance was found to be the temperature level of storage, which re-
flects the intensity of heat exchange processes and, respectively, associated processes of
change of the quality of food products. Important factors are also a decrease of the ampli-
tude of temperature variations in storage of food products, as well as the way the energy is
supplied to stored goods, provision of an even temperature field along the volume of the
storage facilities, i.e., the thermal inertia of the productstorage system.
An important role in storage of food products is played by mass (moisture) exchange;
what is more, for hygroscopic products, this is directly related to the change of their mois-
ture content; for products in a packaging, its intensity largely determines its storageability.
For calculations and prediction of the mass exchange process, it is proposed to deter-
mine the zones of optimal temperature-moisture states of the air in the storage based on ther-
mophysical and mass exchange characteristics of stored products.
With consideration of these parameters, an optimal temperature-moisture regime of
storage in a criterion form is provided for. Based on the theoretical and experimental stud-
ies, the following criteria providing for the optimal storage conditions were established: for
underground storage facilities with climatization systems, K is 0.960.98; for ground-based
heated storage facilities with conditioning and cooling systems, 0.940.96; for heated stor-
ages without forced ventilation systems, 0.900.92; for non-heated storages, 0.700.75.
One of the types of storage of food products is the use of antioxidants in the form of
biologically active additives to food. They are used for the correction of nutrition of modern
man, improvement of the quality and safety of food products. Introduction of biologically
active additives provides for the inhibition of oxidative processes in foodstuffs and increas-
es their storage life. The most widespread antioxidants are ascorbic acid, tocopherols, beta
carotene, selenium. Formulations and technologies were developed to produce products en-
riched in the given biologically active additives, as well as iodine and iron. Iodine-treated
salt and beta carotene are added to vegetable oils. The content of biologically active addi-
tives in the end product provides for 1/32/3 of the daily requirement of an adult in essential
nutrients. It was shown that the use of antioxidants in biologically active additives prevents
oxidative spoilage, provides for an increase of the guarantee storage life. The use of these
compounds was found to render no negative effect on the organoleptic characteristics of
products.
A project of normative documents was worked out and hygienic certification tests
were performed with the aim to start manufacturing of products.
340 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

10.4 Methods of developing an optimal gas medium and the technology of


storage
The polyvinyl trimethylsilane (PVTMS) membrane manufactured by Kuskovo Chemical
Plant found use for storage of agricultural products. Depending on volumes of storage, the
membrane can be used in polyethylene bags with inserted gas-exchange devices (GED) for
8100 kg of fruits or vegetables, or in throw-overs from polyethylene with GEDs for
1,00030,000 kg of agricultural products.
A further increase of the storage volume requires the use of membrane units for creat-
ing a regulated gas medium in airproof refrigerating chambers. The units include a mem-
brane module from the PVTMS membrane, a compressor and/or vacuum pump and the
control system for monitoring the composition of the gas medium. A relatively inexpensive
membrane gas-separating unit manufactured by the firm Klimbi contains one or more mem-
brane module(s) of disk type 160 mm in diameter, 800 mm in length and 15 kg weight. The
size of the module can be reduced to 230 mm; it incorporates 30 membrane elements. A
compressor with the air flow of 50 m3/h at a pressure of 1.0 MPa requires 10 modules,
which provide for the oxygen content regulation limits of 38% and produce 1020 m3/h
of the required gasair mixture. The size of such a membrane device containing 10 modules
does not exceed 1 m3; the weight is 200 kg. The time of start and attainment of the regime
is 25 min; the operation period, no less than 5 years.
Klimbi membrane modules are characterized by the following parameters. At an air
pressure before the membrane 0.4 MPa; after the membrane, 0.1 MPa for a module includ-
ing 30 elements (area, 1 m2) the feeding air flow is 1.0 m3/h; the target air flow, 0.5 m3/h
at an O2 content of 10%; at an O2 content of 3% for a module including 60 elements (area,
2 m2), 1.1 and 0.1 m3/h, respectively; at an O2 content of 10%, 1.8 and 0.7 m3/h; for a mod-
ule including 90 elements (area, 3 m2), at an O2 content of 3%, 1.7 and 0.2 m3/h; at an O2
content of 10%, 2.6 and 1.0 m3/h; for a module including 110 elements (area, 3.8 m2), 2.2
and 0.3 m3/h, 3.3 and 1.3 m3/h, respectively. At an air pressure before the membrane
1.0 MPa and after the membrane 0.1 MPa for a module including 30 elements (area, 1 m2),
at an O2 content of 3% the feeding air flow is 2.0 m3/h, the target air flow, 0.4 m3/h, at an
O2 content of 10%, 3.4 and 1.7 m3/h, respectively; for a module including 60 elements (ar-
ea, 2 m2), at an O2 content of 3%, 3.9 and 0.8 m3/h, at an O2 content of 10%, 6.7 and 3.4
m3/h; for a module including 90 elements (area, 3 m2), 5.8 and 1.2 m3/h, 10.1 and 5.1 m3/h;
for a module including 110 elements (area, 3.8 m2), 7.5 and 1.6 m3/h, 12.8 and 6.3 m3/h,
respectively. Performance of the PVTMS membrane for oxygen is 4600 l/m2 h MPa; for
nitrogen, 1400 l/m2 h MPa.

10.5 Efficiency of using polymer materials and protective coatings in


long-time storage of fruits
The problem of reducing the losses in long-term storage of fruits is very topical, as losses
due to microbial and physiological diseases in some years can reach 2030% (annual loss-
es, 817% on average).
One of the most accessible methods of increasing the preservation of fruits is the use
of polyethylene throw-overs with gas selective membranes in refrigerated storages for cre-
ation and regulation of a modified atmosphere. The gas composition in polyethylene
throw-overs of 10 tons capacity is regulated using a gas selective membrane, grade
PA-160-S-3,1.
CHAPTER 10 341

The efficiency of this method of storage was tested on apples of Jonathan and Golden
Delicious varieties. The results obtained showed that both varieties are better preserved in
a modified gas medium than in usual atmosphere; herewith, Jonathan fruits had higher qual-
ity characteristics by the end of storage (Table 10.5.1).

Table 10.5.1 Quality produce yield and losses in storage of apples in common atmosphere and in
modified gas medium (MGM) (in brackets).

Variety Storage time, Standard Losses, % Physiological


days produce diseases
yield, % natural caused
losses by rot

Jonathan 209 (209) 63.2 (88.7) 5.4 (1.2) 31.4 (10.1) Spot disease ()
Golden Delicious 141 (209) 54.5 (83.2) 9.0 (1.4) 36.5 (15.4) Withering ()

In storage in common atmosphere: temperature, (0 + 1)C; humidity, 85%; in storage in MGM:


temperature, (0 + 1)C; humidity, 90 95%; composition of MGM: CO2, 3.5%; O2, 10 16%; N,
79 83%.

When stored in the usual atmosphere, Jonathan fruits acquire spots, which increase
with time and merge. The spot disease leads to a significant decrease of the quality of pro-
duce and inflicts a considerable economic damage. During the tests, by the end of storage
the losses from this disease reached 40% under usual conditions, whereas no spot disease
was observed in MGM storage.
Apples of the Golden Delicious variety in storage under usual conditions strongly
wither, which is due to the biological features of the variety; these fruits have a thin skin
and weak wax coating. It is difficult to maintain an optimal moisture content required for
this variety. The use of polyethylene throw-overs with gas selective membranes made it
possible to increase the storage time of fruits by 68 days. Apples by the end of storage has
a fresh appearance and good taste qualities.
Studies of the biochemical composition of apples at the and of storage found that fruits
stored in MGM preserved their nutritive and taste qualities better (Table 10.5.2).

Table 10.5.2 Biochemical composition changes of apples in storage in common atmosphere and in
MGM (in brackets).

Variety Dry Sugar, Total Vita- Tanning pH Pectins, %


matter, % acidity, min and
% % C, colouring proto- soluble total
mg % substances, pectin
mg %

Jonathan 12.8 10.0 0.34 6.16 0.40 3.37 0.30 0.33 0.63
(13.0) (10.5) (0.48) (8.80) (0.60) (3.64) (0.44) (0.33) (0.77)
Golden 14.2 10.9 0.23 7.20 0.26 3.64 0.34 0.39 0.73
Delicious (14.6) (11.0) (0.26) (9.20) (0.30) (4.41) (0.32) (0.43) (0.75)

Thus, the results of tests confirm the efficiency of storing fruits of Jonathan and Golden
Delicious varieties using polyethylene throw-overs with gas selective membranes. As
342 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

compared with the existing technology their storage life increases (up to 2 months), losses
from rot and natural losses decrease, high vendibility qualities of fruits are preserved.
Fruits of most varieties of pears as compared with apples are characterized by a lower
preservation, which is due to postharvest ripening processes. For their preservation, it was
proposed to use polyethylene containers of up to 500 kg in capacity, where the gas compo-
sition is regulated using a Sigma gas selective membrane. The tested varieties of pears in-
clude Vilyame, Krasny Kavkaz, Vere Vosk, Konferentsiya, Talgarskaya Krasavitsa, Nart,
Fevralskaya and Kyure (first and highest commercial varieties). By the example of the va-
rieties Krasny Kavkaz, Konferentsiya, Nart and Kyure (Table 10.5.3), it is seen that using
MGM the duration of storage is increased by 1.52 months, natural losses are reduced 23
times, the yield of standard products (first commercial variety) in the first inspection
(1516 February) was 8498%. Fruits of the varieties Vilyame, Vere Vosk and Konferen-
tsiya, when stored in MGM had no signs of physiological diseases; in the varieties Krasny
Kavkaz, Nart and Kyure the browning of the skin did not exceed 3.4%.
Table 10.5.3 Yield of quality produce and losses in storage of pears in common atmosphere and in
MGM (in brackets).

Variety Storage time, Yield of Losses, %


days standard
produce, % natural caused by rot due to
losses physiological
diseases

Krasny Kavkaz 81 (159) 81.7 (98.0) 3.5 (1.3) 10.8 (2.0) 14.3 ( )
(summer variety)
Konferentsiya 138 (220) 70.9 (94.9) 4.7 (1.5) 26.8 (5.1) 2.3 ( )
(autumn variety)
Nart 95 (151) 49.3 (83.7) 2.5 (1.0) 25.9 (16.3) 24.8 (3.2)
Kyure 143 (196) 81.9 (92.5) 4.4 (1.5) 14.8 (6.2) 3.3 ( )

Note: In storage in common atmosphere: temperature, (0 + 1)C; humidity, 85%; in storage in MGM:
temperature, (0 + 1)C; humidity, 90 95%; composition of MGM: CO2, 3.5%; O2, 8 10%.

When storing the fruits under usual conditions, damage from rot was from 10 up to
42%, withering losses reached 40% for the variety Fevralskaya, browning losses in the va-
riety Nart were 25%.
Studies of the biochemical composition of fruits showed that, when stored in MGM,
fruits preserved higher taste and nutritive qualities.
The technology of storing pears using polyethylene containers gives a profit of 160 up
to 360 roubles per ton depending on variety.
With the view of further increasing the storage times and reducing losses in storage of
fruits in MGM, the possibility of using natural ceolytes and those saturated with prepara-
tions with fungicidal properties was studied. According to preliminary data, losses of fruits
from microbial and physiological diseases in storage in MGM in combination with ceolytes,
natural and saturated with sulfur dioxide, is by 0.68,3% lower than in storage in MGM
only.
Film forming coatings are being developed, which protect fruits from microbial and
physiological diseases. Polymer compositions based on polyvinyl alcohol and starch with
addition of a 4% CaC12 solution were tested. Fruits picked up from a tree were immersed
CHAPTER 10 343

into a solution for 1 min. Within 510 min, a thin film was formed on the surface of the
fruit. Air-dried fruits were put into boxes and placed into a refrigeration chamber. Fruits
were stored at a temperature of 0 + 1C and relative air humidity of 85%. The postharvest
treatment of pear fruits with water-soluble polymer made it possible to reduce the losses
from 1832% to 56% (Table 10.5.4). The biochemical composition of treated fruits indi-
cates that film-forming coatings inhibit the maturation processes and preserve better the
structure of the fruits meat. Besides, the content of vitamin C and acidity are maintained
at a required level.
Table 10.5.4 Storage of pears treated with water-soluble polymer and not treated (in brackets).

Variety Storage Standard Losses, % Change of biochemical


time, produce composition of fruits
days yield,
% caused due to natural dry total vitamin C,
by rot skin losses matter, acidity, mg/100 g
browning % %

Nart 125 94.3 5 0.5 0.2 12.0 0.27 4.49 (4.49)


(125) (66.2) (20) (10) (3.8) (10.4) (0.27)
Konferentsiya 125 95.5 3 1.5 14.7 0.14 7.13 (6.79)
(125) (81.9) (10) () (8.1) (12.1) (0.13)

Thus, the use of polyethylene throw-overs, containers, protective coatings is at present


an accessible and efficient way to increase the time of storage of fruits and reduce losses.
344 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY
11 Structure and Properties of
Oligomer Compositions for
Protection of Transport
Containers

11.1 Corrosion resistance of coatings for transport containers


Polymer coatings are the main means of protecting metals from corrosion. However, the
mechanism of their protective action has been studied insufficiently, especially in biologi-
cally active media containing organic acids, enzymes, microorganisms and other compo-
nents. This is due to the complexity of physicochemical processes occurring in the
formation and performance of coatings, as well as to the influence of various factors on the
protective properties: adhesion strength, internal stresses, barrier properties, nature of the
support and method of its surface preparation, composition of the aggressive medium etc.
These properties of coatings are determined not only by the chemical composition of poly-
mer, but also by the specifics of structure formation in coatings, which determines the de-
gree of inhomogeneity of coatings along the thickness of the film, level of its ordering,
character of distribution of the chemical bonds and polar groups, and therefore the swelling
capacity of coatings, rate of transfer of water and ions, direction of their movement, charge,
rate of destructive processes.
The set of properties of biochemically resistant anticorrosion coatings is determined
by their purpose and operating conditions. High requirements to the toxicology, as well as
to the effect on organoleptic characteristics and quality of food products are imposed on
manufactured Western and Russian coatings recommended for protection of equipment,
constructions and industrial facilities of food enterprises, as well as large-size tanks for pro-
cessing, storage and transportation of food media.
Food media are biologically active compositions containing a set of various enzymes,
amino acids and other active biocomponents.
It was found that under the action of bioactivators the rate of decomposition processes
of polymer systems increases three and more times as compared with the rate of develop-
ment of electrochemical processes under the action of heat and moisture. The cause of this
phenomenon is due to the fact that microflora uses polymer materials as food products, and
biodegradants formed in their vital activities, in particular, organic and inorganic acids, are
activators of corrosion.
346 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Polymer coatings are the main means of protecting various materials from biodegra-
dation under the action of microflora, photo- and thermooxidative destruction in the fabri-
cation and operation of articles. However, manufactured polymers, owing to the heterounit
character of chains, broad molecular-mass distribution, conformational and configurational
set of macromolecules are characterized by an inhomogeneous imperfect supramolecular
structure caused by the existing methods of their synthesis.
A significant share of chemical and physical bonds, which determines the protective
properties and durability of polymer coating, is consumed on the formation of supramolec-
ular structures and is not involved in the formation of their protective properties.
The studies of Russian and Western coatings we conducted using the method of mass
chromatospectroscopy, making it possible to determine the content of polymer coatings
components in food media, are indicative of a comparatively small service life of such coat-
ings. Components present in coatings are found, depending on the chemical composition,
in several months. Herewith, there occurs a spontaneous local decomposition of coatings
to form micropores and microcracks under the action of internal stresses. Restoration of
coatings is associated with significant expenses. Studies by Western investigators have
found that expenses for the works on surface preparation, application processes and forma-
tion of coatings exceed more than threefold the costs of polymer compositions used.
In this connection, of great scientific and applied significance is the development of
the scientific bases of the formation and ageing of polymer coatings with account for the
effect of various physicochemical factors, such as the nature, concentration and character
of distribution of the functional groups in the polymer chain, the morphology of the su-
pramolecular structure and its dependence on the formation conditions, the kinetics of in-
crement of internal stresses affecting the durability of coatings.
The aim of the studies was to work out scientific principles of developing regular-
structure composite materials based on oligomer and polymer systems, providing for the
biochemical resistance of polymer protective coatings and a high durability, more than
510 years depending on the operational conditions.

11.2 Structural conversions in hardening of thermosetting oligomers


At present, there are no generally recognized views of structural transformations that occur
during the hardening of thermosetting resins. The specific properties of these systems, in
accordance with various models of the structure of spatially crosslinked polymers are usu-
ally attributed to the formation of a continuous three-dimensional network by both covalent
and van-der-Waals bonds. Conversion of such products to a soluble state or making them
fluid at elevated temperatures and pressures is achieved by intensive mechanical impacts,
which stipulate the decomposition of chemical bonds.
Many theories pertaining to the structure of thermosetting resins assume the existence
of infinitely large three-dimensional molecules, whose size is limited only by the size of the
reaction vessel. This view of the structure of three-dimensional polymers is given, for in-
stance, in works by Flory, who considered the static conditions of forming large molecules
in a multifunctional system. Views of the presence of a homogeneous network structure,
formed as the result of a chemical interaction of monomer or oligomer molecules, are in
contradiction with their mechanical properties.
Calculations of the strength properties of network polymers, based on such a model of
a gigantic three-dimensional molecule, differ greatly from real measurements. De Boer cal-
culated the tensile strength of polymers from phenol-formaldehyde resins, accepting the
CHAPTER 11 347

hypothesis that only chemical bonds are involved in the formation of the three-dimensional
structure, and obtained magnitudes, which are 550 times as large as the real strength of poly-
mers. Then, with consideration of steric factors, the calculation was carried out proceeding
from the fact that secondary bonds of the type of van-der-Waals ones emerge between in-
dividual structural elements. In this case, the tensile strength was only 5 times as large as
the experimental value. Howink assumes that, with the crucial role of physical bonds in the
formation of a three-dimensional structure, the discrepancy between the theoretical and ex-
perimental values of strength is due to the defects of the type of irregularity of the shape of
resin macromolecules. Other authors, who represent hardened thermosetting resins as a ball
of tangled macromolecules, arrive at similar conclusions.
The change of physicomechanical properties in the formation of coatings from oligo-
mer systems is associated with the emergence of a continuous three-dimensional network.
Studies of the effect of the type of bonds on the character of thermomechanical prop-
erties, the elasticity modulus and equilibrium rubberlike deformation of three-dimensional
polymers based on phenol-formaldehyde resins, epoxy and other thermosetting film form-
ers showed that a significant role in the formation of a three-dimensional structure in these
systems belongs to physical bonds. It follows from the thermomechanical curves of poly-
mers with different contents of crosslinks that they are characterized by a significant rub-
berlike deformation, but do not pass into a viscoelastic state due to the presence of the
three-dimensional structure. The glass-transition temperature of three-dimensional poly-
mers increases with the rise of the extent of hardening, which depends on the formation tem-
perature. However, even at a high temperature (140C) the hardening is not complete, and
the three-dimensional network is thermally labile. This is expressed by the fact that, as
three-dimensional polymers are heated and a load is applied, part of the bonds forming the
network are destroyed, and new bonds are formed, whose number increases with the tem-
perature increasing. The re-recording of thermomechanical curves for the same specimen
shows that the rubberlike deformation is preserved, though the glass-transition temperature
shifts to the region of higher temperatures, and the elasticity modulus increases. Experi-
mental studies of structure formation in hardening of phenol-formaldehyde resins, conduct-
ed by V.A. Kargin and G.I. Slonimsky et al., indicate that at a given stress and temperature
not exceeding 220C, the destruction and repeated formation of intermolecular bonds is
possible. Hardened phenol-formaldehyde resin did not exhibit a capability of the emergence
and development of plastic deformations; at the same time, the change of its properties in
the repeated heating and deformation is indicative of the formation of a large number of
crosslinks. The calculation of the energy of bonds responsible for the formation of a
three-dimensional structure showed that these bonds do not exceed 25.1 kJ/mol and corre-
spond to the energy of the hydrogen bond. The essential role of physical bonds in the for-
mation of the three-dimensional network in thermosetting resins is indicated by the data on
the sharp decrease of their strength and elasticity modulus (more than 24-fold) during the
heating to higher than the glass-transition temperature. During the cooling of specimens to
the initial temperature, their strength is again restored. This is also accompanied by the re-
versible change of internal stresses at the repeated heating and cooling of specimens based
on thermosetting resins. The thermomechanical curves of epoxy polymers with various
contents of epoxy groups, hardened by polyethylene polyamine at 200C for 10 h, indicate
a high elasticity of three-dimensional polymers, which increases with the content of epoxy
groups decreasing.
These data suggest that the spatial structure of network polymers is formed by bonds
of both chemical and physical nature, in particular, hydrogen and dispersion ones. The
348 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

occurrence of chemical bonds stipulates the distinctive feature of network polymers their
infusibility and insolubility in organic solvents. However, the ratio of these bonds is such
that the structure of network polymers is thermally labile.
The rubberlike properties have also been found for other network polymers. A.A. Ber-
lin and O.G. Selskaya have shown that the elasticity of polyester acrylates depends on the
flexibility of the ester block, which forms crosslinks in the three-dimensional network. An
increase of the length of the crosslink block in the three-dimensional polymer structure
leads to an increase of the segmental mobility of the chains, an increase of rubberlike de-
formation and a decrease of the glass-transition temperature. An increase of the rubberlike
deformation can be also achieved by a substitution in the ester block of phthalic acid by se-
bacinic acid; at the same time, the replacement of diethylene glycol by butylene glycol leads
to an increase of the rigidity of polymer and an increase of its destruction temperature.
Taking into account the discrepancy between the experimental and calculated data on
the physicomechanical properties of network polymers, A.A. Berlin with coworkers sug-
gest that a real network polymer is a set of limited-size network aggregates, in which the
links of macromolecules are sterically linked by chemical bonds, and the aggregates them-
selves can be connected by both chemical and van-der-Waals or hydrogen bonds. Such a
model of an imperfect and inhomogeneous network structure was proposed by the authors
as the result of the studies of the polymerization kinetics of various-structure polyester acry-
lates using chemical methods of analysis, infrared spectroscopy and electron paramagnetic
resonance. From these data, it follows that in the hardening of oligoester acrylates in the
block even at very small degrees of conversion, when one would expect the formation of a
non-branched product, the entire product of polymerization consists of the three-dimen-
sional polymer. In the initial stages of the process, such aggregates consist of branched mac-
romolecules linked by scarce bridges and represent microregions of local immobilization
of liquid monomer or oligomer. The mobility of free radicals in such aggregates is extreme-
ly small as compared with the mobility of radicals outside these aggregates, so the chain
termination constant during the polymerization in the microregion would be lower than in
the bulk. This leads to a much larger rate of polymerization inside microregions than outside
them. These results suggest that, from the very beginning of the conversion, simultaneously
two processes occur in these systems, with different rate constants: one in the free liquid
phase to form a nonbranched product, and the other at a much larger rate on microregions
to form a network polymer. The ratio between the rates of these two processes can change
depending on polymerization conditions. With the length of molecules decreasing (less re-
active end allyl groups), as well as in the presence of a chain propagation agent the ability
of the chains to form aggregates with a three-dimensional structure decreases, and the yield
of nonbranched products increases.
These regularities, and the mechanism of formation of a network structure proposed
based on them, are the most physically substantiated. The data supporting such a mecha-
nism of structure formation in hardening of thermosetting film formers are presented in a
work, which discusses the presence of colloidal-size aggregates, separated by a structure
from lower-molecular-mass fractions easily removed by solvents, in hardened blocks from
epoxy, phenol-formaldehyde and other resins. Such structures do not represent one single
molecule, but consist of fine particles bound stronger owing to the high polarity of resins.
Leaching with solvents succeeded in revealing isolated structures of globular shape, of
8090 nm in size, in epoxy, phenol and other thermosetting resins. The existence of struc-
tures of such size was confirmed also by the method of small-angle X-ray scattering. The
number of particles and their size determine the properties of materials, because
CHAPTER 11 349

van-der-Waals forces are efficient at distances of no more than 0.5 nm between globules.
However, the methods used in those works did not make it possible to reveal the fine struc-
ture of particles and the character of their distribution in films.
Thus, already the first electron-microscopy studies have shown that all models of net-
work polymers based on the emergence of a continuous molecular three-dimensional net-
work are not substantiated physically. Neither a skeletal network nor large formations of
tangled macromolecules were found.
A systematic study was carried out of supramolecular structure of network polymers
with consideration of the effect of the chemical composition of film former, the nature of
the support and fillers and conditions of application and formation. For this purpose, use
was made of indirect methods based on studies of the kinetics of change of physicomechan-
ical and thermophysical properties in the formation of coatings and films from monomer
and oligomer systems, and their supramolecular structure and thickness of the three-dimen-
sional network depending on various physicochemical factors were studied directly.
Associates in oligomer systems were investigated by taking replicas from the surface
of fractures of oligomers instantaneously frozen from +20 down to 180C, as well as by
studying the structures of fine oligomer films applied by blowing a bubble or obtained on
the surface of mercury.
Studies of associates in model monomolecular oligomer systems by taking replicas
from a fracture of oligomers instantaneously frozen from +20 down to 100C found their
morphology to depend significantly on the flexibility of the oligomer block. Oligocarbonate
methacrylate with rigid blocks of grade OCEM is characterized by the occurrence of asso-
ciates of anisodiametric type, apparently formed from unfolded molecules. For OCDM oli-
gocarbonate methacrylate with flexible blocks, globular structures are observed, whose
emergence is related to the folding of clusters of molecules. The morphology and size of
these structural elements are preserved at their rapid heating from 20 up to 90C as the result
of polymerization. The effect of the structure of the oligomer block on the mechanism of
formation of associates was studied by comparing the data on the molecular mobility of
skeleton and end groups of the block depending on temperature. The data were obtained by
the method of 1H NMR, with the temperature dependence of oligomers heat conductivity
and the character of their structure.
The high-resolution NMR spectra within the temperature range of 20 up to +20C
were recorded on a RYa-2303 spectrometer with the proton stabilizer. The working fre-
quency for 1H nuclei was 60 MHz. In the region of lower temperatures, the spectra were
recorded on a broad-line spectrometer with the working frequency of 22 MHz. A specimen
in an ampule 5 mm in diameter was placed into a thermostatted sensor. The mechanism of
structure formation in oligomer systems was studied by investigating the molecular mobil-
ity of the main constituents of the oligomer block by the NMR method.
The high-resolution NMR spectrum of OCEM oligomer at 22C had four lines, which
were rapidly broadened with the temperature decreasing. The assignment of the lines is giv-
en in Table11.1.
The line width in the spectra of investigated oligomers can be said to be determined
mainly by the type and speed of molecular motion (ppm). This is also confirmed by the ob-
vious temperature dependence of the width of individual lines, which is determined by the
increasing role of dipole interactions during the cooling of specimens.
The motion of methyl groups is inhibited slower than that of groups -CH2 CH2-. This
is quite probable, as the rotation of the CH2 group relative to the single CC bond de-
pends to a lower extent on the steric factors than the motion of the oligomer block on the
350 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

whole. Two lines from nonequivalent protons of the end vinyl groups are broadened in an
almost the same way as the line of the CH2 CH2 group of the block. As the intensity of
these lines is small, it is difficult to determine their width at a decreased temperature. At a
temperature lower than 5C, the NMR spectrum of OCEM does not resolve due to the
strong broadening of the lines. At this temperature, individual lines merge into one line with
a width of 1103 Hz. Presumably, here the oligomer block completely loses a possibility of
translational mobility. Herewith, the vibrational and rotational movements of individual el-
ements are preserved.
Table 11.1 Assignment of high-resolution NMR spectra of oligomer OCEM.

Proton-containing group Chemical shift, ppm Possible area of shifts,


of polymer ppm
relative to relative to
water signal TMS signal

C CH 3.46 8.26 8.0 8.5


CH2 0.67 5.47 5.2 5.8
0.58 4.22 3.7 4.7
CH2 C 1.15 3.65 3.7 4.7

For the range of 5 to 196C, we recorded the first derivatives of the NMR absorp-
tion lines and plotted a dependence of the 2H second moment on temperature. It follows
from the said that the molecular motion in OCEM is totally inhibited at a temperature of
60C. At a further decrease of temperature (down to 196C) the NMR spectrum of
OCEM did not change.
The spectra of OCDM differ from those of OCEM by only the line with a chemical
shift of 6.3 ppm from TMS. This line, which is in immediate vicinity to the line of the
CH2 CH2 group is assigned to ethylene groups linked by an oxygen bridge. Thus, the
NMR spectrum quite corresponds to the chemical formula of OCDM. The mid part of the
oligomer block CH2 OCH2 has a smaller mobility as compared with the peripheral
part CH2 CH2. However, with the temperature decreasing to 5C the widths of the lines
of the groups CH2 CH2 and CH2 OCH2 coincide and change further in a similar
way. For OCDM the mobility of the main groups differs noticeably from that of the main
groups of the link. Here, probably, an increase of the length and of the general flexibility
of the oligomer block have their effects. At a temperature lower than 15C the spectrum
of OCDM does not resolve owing to the strong broadening of the lines. In OCDM, the mo-
lecular motion is totally inhibited at a temperature of 70 to 80C, i.e., 1012C lower
than for OCEM.
The mobility of molecules of oligomer at 20C is higher than that of OCDM and de-
creases with the decrease of length and flexibility of the oligomer block. Along with this,
at a temperature decrease the molecular motion is inhibited the slowest in the system with
the most flexible molecular chain. The difference of the temperature of transition to the rig-
id lattice is 1520C for OCDM and OCEM. The differences in the intensity of molecular
motion of these oligomers are observed both in the region of predominant translational mo-
bility (down to 10 to 15C) and in the region of vibrational and rotational movement of
the oligomer chain.
When explaining the observed dependences, it is necessary to take into account the po-
tential of associative structuring of oligomers.
CHAPTER 11 351

In the systems studied the width of the NMR lines can be determined not so by the
structural viscosity of the system as by the local viscosity of associated molecules, which
is determined by the instantaneous mobility of the chains. In turn, the local viscosity de-
pends on the interaction of molecules. In the formation of associates from OCEM mole-
cules, the preferable conformation is the unfolded conformation owing to a larger rigidity
of the oligomer block. On the contrary, the significant flexibility of OCDM admits a more
free globular shape of associates. In the former case, the adjacent molecules of the oligomer,
which form anisodiametric structures from parallel-stacked blocks, create larger hindrances
for the mutual mobility of molecules than in associates from folded clusters of molecules.
Indeed, the mobility of the CH2 CH2 links is higher in OCDM, and the general mobil-
ity of this system is preserved at lower temperatures.
A proof of two types of associates in these oligomers can be the comparative behaviour
of the end and skeleton CH2 groups. In OCEM, the end groups lose their mobility simulta-
neously with the skeleton groups. In OCDM, the end groups of CH2 preserve their mobility
longer than the skeleton ones. This is indicative of a more free packing of molecules and of
differences in the spatial barriers for the movement of the entire block and its end groups.
The folded conformation of OCDM molecules in associates should hinder the motion rel-
ative to the oxygen bridge in CH2 OCH2 groups.

11.3 Formation kinetics of coatings from polymerization oligomers


The specifics of polymer coatings formed from oligomer systems is that the process of hard-
ening is associated with polymerization on the support; the polymerization is completed
with the formation of supramolecular structures, which make up a three-dimensional net-
work. In this connection, the nature of the support has a significant effect on the formation
of coatings. In spite of the fact that the effect of the nature of the support on the properties
and durability of polymer and lacquer coatings has been known since long ago, in many
works the structure and properties of polymer coatings are not altogether correctly identi-
fied with the structure and properties of films and block materials, while the role of the sup-
port in the formation of the properties of polymer coatings has been studied insufficiently.
A widely used technique in studies of the formation of polymer coatings is the method
of studying the kinetics of increment and relaxation of internal stresses. The effect of vari-
ous physicochemical factors on the formation of coatings, such as the chemical composition
of oligomers, nature of the support, strength of interaction at the filmsupport and
polymerfiller interfaces, application and formation conditions, was studied using this
method.
Studies of the formation of coatings from oligoester maleinate phthalates hardened by
styrene showed that at 20C internal stresses reach an ultimate value in 2030 days and do
not exceed 1.0 MPa for coatings 300 up to 1000 m thick. Internal stresses reach an ultimate
value much faster in hardening at 80C. Stresses emerging in hardening of polyester coat-
ings are small. A sharp increment of internal stresses is observed in cooling of coatings sub-
jected to thermal hardening. Similar regularities in the change of internal stresses were
found in the formation of coatings from other oligomer systems.
The most significant increment of internal stresses and a sharp decrease of the duration
of gelation are observed with the increase of the formation temperature up to the glass-
transition temperature of polymers; at the subsequent increase of formation temperature, the
stresses change insignificantly. This is, apparently, due to an increase of segmental mobility
of molecules in this temperature range, which contributes to the formation of the largest
352 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

number of bonds between structural elements, to a slowdown of the relaxation processes


and an increment of internal stresses.
It is also noteworthy that there is no unambiguous dependence between the kinetics of
/shrinkage and the kinetics of increment of internal stresses. More than 7080% of the en-
tire shrinkage is exhibited at the time of transition of the system to the gelated state, which
corresponds to the use of the largest number of functional groups involved in polymeriza-
tion, and to the appearance of a temperature maximum on the thermometric curves.
Studies of the kinetics of hardening of unsaturated oligoesters by the method of IR
spectroscopy showed that polymerization in such systems at 20C is completed in 45 h
involving 5060% double bonds, and at 80C in 4060 min involving 8090% double
bonds. It would seem that at a significant use of double bonds at the initial stage of harden-
ing the formation of a three-dimensional network structure is at the stage of completion,
and coatings and films should have the highest physicomechanical characteristics.
Based on the rheological, physicomechanical, thermophysical and structural data, it
was shown that in production of coatings from oligomers at the first stage of their formation,
local bonds are formed within a small number of molecules, which is accompanied with
physicochemical processes mainly in supramolecular structures; and at the second stage,
links between these structures emerge and a three-dimensional network is formed. At the
last stage, owing to the inhibition of the relaxation processes, a sharp increment of internal
stresses is observed.
Studies of the rheological properties of oligoester maleinate phthalates at various stag-
es of hardening indicate that initial oligomers are Newton-type systems. In a certain period
of formation, not only an increment of viscosity is observed, but also a change of the char-
acter of the rheological curves, which is due to the transition of the system to a structured
state determined by the formation of a network structure. From the data on the kinetics of
consumption of the double bonds, on the increment of internal stresses, breaking strength,
elasticity modulus and viscosity in the formation of coatings from these systems, it is seen
that, despite the involvement of a significant number of functional groups in polymerization
at the initial stage, coatings are characterized by low internal stresses and other physicome-
chanical properties. A sharp increment of the latter is observed at the second stage, when
7080% of functional groups in the system is consumed.
The presence of the induction period in the formation of a three-dimensional network
is detected in studies of oligomer hardening by the NMR method. The use of NMR in such
studies is based on the difference (by several orders of magnitude) of the proton correlation
frequency of the nonhardened phase. This makes it possible to separate the absorption line
obtained at any time of hardening into two regions and, based on them, make a judgement
on the course of the reaction. From the data on the change of the first derivative of the ab-
sorption line and the proton spin relaxation time depending on the duration of hardening, it
follows that there is an induction period in the change of proton correlation frequency in
the formation of the three-dimensional network.
This character of structural transformations was observed in studies of the formation
of coatings from unsaturated polyesters in polymerization under an electron microscope
and in other conditions, in studies of the supramolecular structure at various stages of hard-
ening of coatings from oligoester urethanes of different chemical composition, alkyd resins,
epoxides, as well as organosilicon oligomers. Thus, a peculiar feature of the formation of
coatings from monomer and oligomer systems is an induction period in the kinetic curves
of increment of internal stresses and mechanical properties. This period is observed in the
formation of coatings from film formers with prepared supramolecular structures, for in-
CHAPTER 11 353

stance, from dispersions of polymers. From the kinetic curves, it also follows that the rate
of increment of stresses increases with the decrease of thickness of coatings. This character
of change in the formation of coatings from oligomers could not be explained proceeding
from the views of a continuous three-dimensional structure from separate molecules in such
systems.
Inhibition of the relaxation processes at a certain stage of hardening of oligomers has
an effect on the kinetics of change of other properties, in particular, thermophysical prop-
erties. A relationship between the kinetics of change of the thermophysical parameters and
of internal stresses both in the formation and during the ageing of polymer coatings was
established.
The microstructure of polyester coatings from 25% oligoester maleinate solutions in
acetone was studied. Individual globular associates were revealed in such systems by the
fast freezing method. The action of an electron beam for 5 min has no effect in practice. A
15-min action of an electron beam reveals a fine globular structure, similar to that found in
hardened coatings by the method of slices. Subsequent irradiation reveals aggregation of
structural elements to form larger supramolecular structures. In 2025 min of formation,
streaked structures are observed along with globular structures. In 30 min of irradiation, the
film is observed to crack. Herewith, one layer of the coating is displaced relative to the oth-
er, which is due to the different structure of layers along the thickness of the film.
In a film 4050 nm thick, four layers with different structures are revealed. The de-
composition process begins from the surface. The first stage of decomposition is the for-
mation of streaked structures, which emerge as the result of a re-grouping of structural
elements in the rupture of links between individual globular formations. The structural el-
ements are packed the most densely in the layer adjacent to the support. The structure of
this layer is revealed not clearly enough, only in some places. Nearer to the interface with
the air, the size of the structural elements increases, and their packing density decreases.
The number of layers with different structure along the thickness of the film depends on the
thickness and nature of the support. Subsequent irradiation and thermal hardening of these
preparations at 80C for 24 h revealed no additional changes in the structure of coatings.
Structural transformations in polymerization of coatings and free films, which were pre-
pared according to the known method, were compared. A drop of oligomer was applied to
the surface of water; after its spreading and stabilization of the film, a net was put onto the
film and it was extracted by means of a microscope slide. Polymerization in this case pro-
ceeds unevenly along the area of the film. First, after 3 h of heating at 80C, there arise more
dense zones in the shape of bands, the fine structure of which is not revealed. In subsequent
irradiation by an electron beam, the process of structure formation begins inside these band
structures and near them. In 5 hours of hardening, the number of band formations increases;
herewith, globular structures emerge in the surface layer, which is accompanied with its si-
multaneous breakdown. In subsequent heating of films, the globular structure is revealed
more clearly as the result of the aggregation of structural elements. Heating of films for over
8 h and subsequent irradiation do not lead to the change of their structure. From comparison
of the structural data, it follows that primary structural elements in polymerization of coat-
ings and free films are similar by their morphology and size. The character of secondary
supramolecular structures formed in subsequent polymerization is different. In films, the
globular structure is preserved, and in coatings chain-type structures are formed.
A structure from elements of anisodiametric shape is found in the formation of coat-
ings from the same lacquer on wood. As in thin films, it was also inhomogeneous along the
thickness.
354 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

An important point for understanding the mechanism of formation of the three-dimen-


sional network is the study of the kinetics of three-dimensional polymerization. In process
of the latter, the size of macrochains is given, their molecular-mass distribution, conforma-
tion of structural elements forming the supramolecular structure, packing density of mac-
rochains and structural elements, and other characteristics. Knowledge of the complex of
these factors, which have a crucial effect on the properties of formed three-dimensional
polymers, is imperative. In the case of polyfunctional monomers and oligomers, singling-
out of formed macromolecules appears possible first of all at the stages preceding the ge-
lation of the system. The structural characteristics of diallyl isophthalate (DAIP) at different
stages of polymerization preceding the gelation were studied. The chosen object is conve-
nient for studies of the initial stage of polymerization, as the extent of its conversion Pcr is
2025%, and polymerization proceeds via the stage of soluble polymer formation.
Polymerization of DAIP (boiling point 156158C at 133 Pa, Pd 293 = 1,5260) was
carried out in sealed ampules at 353 K in the presence of benzene peroxide (0.5 wt. %). Af-
ter holding for a certain time, the ampules were opened and the forming polymer was iso-
lated by addition of acetone followed by precipitation with methanol from 2530%
solutions. The completeness of sedimentation was controlled by adding distilled water into
the mother liquor. The precipitated polymer was filtered, washed again with methanol and
dried in a vacuum cabinet at 25C and 260500 Pa to a constant weight. The extent of
monomer-to-polymer conversion was calculated by the weight of the product obtained. For
qualitative characterization of molecular-mass distribution, use was made of gel-penetrat-
ing chromatography. Chromatography was performed on columns filled with polystyrene
gel; the permeability of the columns was 3103, 1104 and 1105, the solvent was tetrahy-
drofuran. The residual saturation in obtained specimens was controlled by the method of
ozonation and IR spectroscopy. Ozonation was performed on an ADS-2 instrument. The
concentration of solutions in benzene was 0.1%. When recording the IR spectra, the absorp-
tion band at 1610 cm 1, characteristic of valent vibrations in the phenyl nucleus, was used
as an internal standard; the change of the double bond in the allyl grouping was followed
by the decrease of intensity of the absorption band at 935 cm 1 (deformation vibrations of
CH in RCH=CH2) and 1645 cm 1 (valent vibrations of C=C). The viscosimetric studies
were performed in a Ubbelohde capillary viscosimeter at 203C. The initial concentrations
of solutions in benzene were 10 g/dl. The molecular mass of specimens at various stages of
polymerization were determined by the method of ebullioscopy and light scattering. Ebul-
lioscopic measurements were carried out on an EP-68 precision ebulliograph; light scatter-
ing, on a Sofica photogoniodiffusiometer. The molecular and structural parameters were
calculated by the method of double extrapolation, intensity of scattering was measured
within the interval of angles 30150.
The high-resolution NMR spectra in specimens deuterated in chloroform and acetone
(concentration, 15% at 35C) were recorded on a Tesla D-487C spectrophotometer; the
working frequency for 1H nuclei was 80 MHz. The magnitudes of chemical shifts in -scale
were recalculated relative to the signal of hexamethylene disiloxane. The structure of films
from the sol fraction of the polymer was studied by the method of electron microscopy by
taking replicas from the surface of films subjected to oxygen etching. Internal stresses were
studied by the photoelastic method.
The result of studies of the parameters characterizing the sol fraction of DAIP polymer
and obtained at different stages of polymerization are presented in Table 11.2.
High-resolution NMR spectra contained the following signals (ppm): 5, DAIP; 4.61,
CH2O; 5.04, =CH2, trans); 5.25, =CH2, cis); 5.8, = CH2; 7.79, aroma. These data confirm
CHAPTER 11 355

the chemical formula ascribed to DAIP. The NMR spectra recorded from the sol fraction
of the polymer, besides the above signals, were found to have signals 4.25 and 1.75, as-
signed to protons of methylene groups formed in the process of polymerization, respective-
ly, in the groupings CH CH O and CH CH2 CH .

Table 11.2 Molecular structural parameters of the sol fraction of DAIP polymers.

Parameters Polymerization time, h

0.5 1 2 3 4

Yield, % 1.7 3.5 7.5 11.5 15.0


[], 102 dl/g 3.7 4.0 4.5 4.8 5.4
Kn 2.4 1.3 1.1 1.2 1.1
Residual unsaturation, % 40 35 30 25 10
MW 103 19.5 26.9 53.5 135.0 143.0
M 103 7.3 6.2 9.0 8.4 11.0
MW /M 2.6 4.3 6.0 16.0 13.0
A2, 105 cm3mol/g 195.0 65.0 8.0 70.0 19.0
(P) 1/2, nm 154.0 169.0 177.0 224.0 220.0

The obtained NMR spectra were used to calculate the extent of residual unsaturation
of the polymers sol fraction at different stages of polymerization as a ratio of the areas of
the peaks corresponding to protons of nonreacting allyl groups to the total area of the peaks
characteristic of protons of nonreacting allyl groups and groups, which entered into the re-
action CH CH2 O .
The extent of residual unsaturation was determined as the ratio of nonreacting groups
to their total content (see Table 7.2). With the increase of the extent of conversion, it de-
creases from 40 to 10%. A similar dependence of the residual unsaturation was obtained
for the sol fraction of the polymer using the method of IR spectroscopy, as well as ozona-
tion. This result is in contradiction with the data presented in one work, but coincides with
the results of other works.
The characteristic viscosity of solutions of the sol fraction of DAIP polymer increases
in good solvents (benzene, methyl ethyl ketone) with the advance of polymerization; the
observed nonlinear character of the dependence of characteristic viscosity on molecular
mass in logarithmic coordinates is, probably, due to the presence of nonbranched molecules
in the system. The values of the Huggins constant Kn calculated from the viscosimetric data
decrease starting with the specimen with the low molecular mass and then do not practically
change for all specimens of the polymer at a change of the duration of polymerization and
are equal to 11.3. This dependence of Kn on the duration of polymerization indicates the
worsening of the interaction of the forming polymer with the solvent, and the order of mag-
nitude of Kn suggests a ball-like shape of macromolecules in polymer sol fraction in these
solvents. A decrease of the value of the second virial coefficient A2 at an increase of the
duration of polymerization is also indicative of the worsening interaction of macromole-
cules with the solvent with the extent of conversion increasing. From the data of Table 11.3,
it follows that for the number-average Mp and weight-average molecular mass, as well as
for the root-mean-square radius of inertia (R)1/2 the tendency of an increase is observed with
356 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

the increase in the duration of polymerization. The same applies to polydispersity (the ratio
Mw /Mn); the order of magnitude of the latter indicates the significant polydispersity of the
sol fraction of DAIP polymer. It should be noted that at an increase of the duration of po-
lymerization up to 4 h, in some experiments the molecular mass was found to decrease,
which is, apparently, due to the fact that near the gelation point a partial crosslinking of mac-
romolecules and their aggregation is possible to form the three-dimensional network. Here-
with, the system becomes not completely soluble in benzene, there occurs a partial
delamination of the system, and the found molecular mass and other parameters coincide
with the parameters of specimens taken at earlier stages of polymerization.

Table 11.3 Properties of coatings from various film formers.

Binding Formation Glass E, p, b, Linear extension


agent-based temperature, transition GPa MPa MPa coefficient, C 1
polymer C temperature,
C

Polyimide PM 320 515 3.0 3.5 170 2.0 0.510 4


Polystyrene 80 81 2.8 3.4 30 1.5 0.710 4
Polyethylene:
LDPE 200 100* 0.52 0.79 22 29 7.5 (2.1 5.5)10 4
HDPE 200 80* 0.15 0.25 0.8 16 4.0 (2.2 5.5)10 4
PVC 80 80 39 59 2.0 2.010 4
Polymethyl
methacrylate: 80 45 2.8 76.5 8.0 0.710 4
FL-50 180 50 2.5 21 28 3.0 0.410 4
NP-1 80 45 3.0 30 3.5 3.5 (0.7 2)10 4
ED-20 100 60 80 2.3 3.5 40 90 12 20 (0.4 0.6)10 4
Polyvinyl alcohol 60 85 5.3 63 120 2.0 (0.7 1.2)10 4
Phenol formaldehyde 80 60 2.5 40 50 15.0 (0.1 0.9)10 4
resin
Natural rubber 60 68 0.0013 10 0.4 2.1610 4
SKS-50 60 50 8 1.0 2.1610 4
SKN-40 60 32 7 0.8 1.510 4
SKD-1-3 60 60... 95 1 0.5 1.810 4
Butyl rubber 200 67... 75 20 1.5 1.9410 4

*Brittleness temperature.

From these data, it follows that the sol fraction of the polymer at each time moment of
polymerization includes a set of molecules of different molecular masses and different com-
plexity, i.e., there are both linear molecules and branched molecules, with branches of dif-
ferent length. If the average residual unsaturation is distinct from 50%, this means that on
average macromolecules are branched, though in this case a partial consumption of double
bonds is possible as the result of the cyclization reaction, which has a negative effect on the
development of the extent of branching of DAIP macromolecules.
The change of the character of structural transformations of polymers sol fraction de-
pending on the duration of polymerization was studied by the method of electron micros-
copy to elucidate the specifics of structure formation in polymerization of DAIP. The work
CHAPTER 11 357

adduces the data on the structure of DAIP films in polymerization at different stages. It was
found that after 0.51 h of polymerization against the background of the homogeneous
structure individual globular formations from 20 up to 200 nm in size are revealed. In sub-
sequent polymerization, the poorly resolved structure of the polymer matrix, which in-
cludes larger structural elements, becomes sufficiently well resolved, and the predominant
type becomes a globular-type structure with globules 2030 nm in size; herewith, larger
structural formations, owing to their aggregation, acquire the shape of anisodiametric struc-
tures. The emergence of anisodiametric-type structures can be due to the fact that the extent
of branching and polydispersity of the system increase with the advance of polymerization.
Recorded electron diffraction patterns and data of differential thermal analysis indicate
that specimens have an amorphous structure. Studies of internal stresses in the formation
of coatings under room conditions from systems chosen at different stages of polymeriza-
tion found that, with the polymerization time increased up to 4 h, internal stresses decrease
1.5 times. This is due to the change of the character of relaxation processes depending on
molecular mass and extent of branching of macromolecules.
Thus, sol fractions of polymers are characterized by a broad molecular-mass and struc-
tural distribution and contain molecules of various complexities. The higher-molecular-
mass fractions occurring in polymerization form supramolecular structures of different size
and structure. In the subsequent polymerization, a three-dimensional polymer with an ir-
regular network is formed as the result of their crosslinking.
The incompleteness of the relaxation processes in the formation of polymer coatings
from oligomer systems greatly affects their properties. A significant feature of polymer
coatings is that phenomena occurring at the interface render a significant effect not only on
the character of structural transformations, but also on the rate of relaxation processes and
the properties of coatings. The restrained character of relaxation processes in the formation
of coatings, which is due to the emergence of local bonds between structural elements and
the adsorptional interaction of the film former with the surface of the support, is accompa-
nied with a sharp increase of internal stresses. In this connection, we put forward internal
stresses as a criterion of incompleteness of the relaxation processes, which largely depends
on the specific features of structural transformations in the formation and ageing of polymer
coatings.

11.4 Causes of internal stresses in formation of coatings


Internal stresses emerging in the formation of polymer coatings are usually considered as
the mechanical characteristics, are calculated as a product of the elasticity modulus of poly-
mer by the value of shrinkage or the difference of linear expansion coefficients in thermal
hardening.
Shrinkage of the polymer is implied to be a reduction of linear or volume sizes of spec-
imens as the result of the removal of solvent, dispersion medium or advancement of the po-
lymerization process. When determining internal stresses in the process of thermal
hardening of coatings, one considers the difference of linear expansion coefficients of the
polymer and the support (when using supports, which absorb the liquid phase), the differ-
ence of shrinkage of the coating and the support.
The incorrectness of this treatment of the causes of internal stresses in the formation
of polymer coatings was first indicated in the works by V.A. Kargin and A.V. Lykov with
coworkers. They had shown that internal stresses emerging in the formation of polymer
coatings depend significantly on the rate of relaxation processes and are determined not by
358 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

the entire shrinkage of the system, but only by the incompleted shrinkage, exhibited after
the solution passes into a gelated state. Our works showed that internal stresses depend on
the number, nature and distribution of local bonds and can be used as the main characteristic
in studies of the kinetics of formation and ageing of polymer coatings.
Shrinkage is a physical property of a material and, by itself, does not lead to the emer-
gence of internal stresses. A uniform shrinkage along the thickness and area of the film is
not accompanied by the appearance of internal stresses. This takes place in the formation
of very thin films on non-adhesive supports. As the thickness of free films increases, they
begin to experience internal stresses as the result of nonuniform hardening determined by
the dissimilar solvent removal rate along the thickness of the specimen or a nonuniform ad-
vancement of polymerization. The value of internal stresses increases significantly in the
formation of films on adhesive supports, and it is the greater, the higher the strength of ad-
hesion interaction is. The cause of this phenomenon is associated with the incompleteness
of the relaxation processes.
To reveal the role of shrinkage in determining the value of internal stresses, the phys-
ical nature of the phenomenon of shrinkage was studied and the way it is closely related to
and determined by the main regularities of the film formation process. Shrinkage of films,
as internal stresses emerging in them, does not depend on density, specific weight of poly-
mer and final volume, but is determined by the factors affecting the rate of gel formation
of the solution or the rate of increment of viscosity in the process of film formation. In this
connection, internal stresses emerging in film formation are of a relaxation character, are
proportional to the volume of the solvent evaporated from gel, and will be the higher, the
more solvent the film contains at its transition to gel.
Using these regularities, changing the concentration of the initial solution or the
amount of solvent by the moment of gel formation in the system and formation of an adhe-
sion bond, we developed the physicochemical routes of a sharp reduction of internal stresses
in polymer coatings.
Thus, not any change of linear size and volume of the film formed from polymer so-
lutions leads to the emergence of internal stresses. Internal stresses are determined by
shrinkage of gels formed in the formation of coating, and begin to be exhibited after their
formation owing to the inhibition of relaxation processes. In this connection, internal stress-
es in coatings are affected by factors, which determine the rate of gel formation. Besides
the concentration of the initial solution, these factors include the effect of the nature of sol-
vent and various structurizing additives.
Formation of coatings from monomer or oligomer systems, performed as the result of
their polymerization directly on the support, is also accompanied by the shrinkage of the
film. In this case, as in the formation of coatings from solutions of polymers, the values of
internal stresses are affected by only an insignificant part of the general shrinkage exhibit-
ing after gel formation in the system. The rate of structure formation in such systems is de-
termined by the number of functional groups involved in polymerization and the rate of
their use and, because of this, depends on the chemical composition of the film former and
accelerators of polymerization, on formation conditions.
Shrinkage of polymers also changes depending on the physical factors polymeriza-
tion temperature, heating and cooling rates and nature of fillers. Internal stresses emerge
both in coatings formed on supports and in free films and block materials. The cause of the
emergence of internal stresses is the slowdown of relaxation processes in the system due to
the nonuniform hardening of individual layers owing to the dissimilar rates of polymeriza-
tion, the temperature gradient or moisture content or the interaction of polymer with the
CHAPTER 11 359

surface of solids the support, fillers, reinforcing materials. For polymer coatings, the cru-
cial effect on the incompleteness of relaxation processes is rendered by the interaction of
the polymer with the support. In the absence of such an interaction, internal stresses emerg-
ing in the coatings are insignificant. As the strength of interaction at the polymersupport
or polymerfiller interface rises, internal stresses sharply increase.
Internal stresses emerging in the formation of coatings render a significant effect on
the mechanical, adhesion, electrophysical and other properties of coatings and are a crite-
rion determining their durability.
In this connection, for working out the physicochemical bases of forming polymer
coatings and developing the ways of reducing internal stresses, it is necessary to study the
effects of various physicochemical and technological factors on the value of internal stress-
es and the kinetics of their increment in the formation and ageing of polymer coatings.
Internal stresses as a criterion of incompleteness of relaxation processes depend sig-
nificantly on the physical state of polymers. The effect of the physical state on internal
stresses is revealed the most vividly during the heating of polymers of the same chemical
composition up to a temperature lower and higher than the glass-transition temperature. We
present the data on the change of internal stresses during the heating of coatings with a
three-dimensional structure produced based on epoxy, phenol-formaldehyde resins and un-
saturated oligoesters. Internal stresses were measured by the photoelastic method. It is seen
that at a temperature of 20C, i.e., lower than the glass-transition temperature, which for
coating studied is 4080C depending on their chemical composition, internal stresses are
315 MPa. When heating them up to 80C, i.e, higher than the glass-transition temperature,
we observed a gradual decrease of internal stresses down to 0.10.5 MN/m2.
Table 11.3 presents the data on the effect of the chemical composition and physical
condition of polymers on internal stresses in coatings, measured at 20C. It is seen that the
largest internal stresses emerge in coatings from polymers, which are in a glassy state at the
operation temperature, and especially in coatings with a spatially crosslinked polymer
structure. Comparative data for coatings from oligomers formed by thermal hardening of a
spatially crosslinked structure indicate that the largest internal stresses emerge in the for-
mation of coatings from epoxy resins as compared, for instance, with polyester oligomers.
A sharp increment of internal stresses in the formation of epoxy coatings could not be ex-
plained by the differences in shrinkage or different linear expansion coefficients of the film
or support. The linear expansion coefficient of epoxy coatings of various chemical compo-
sitions, as is seen in Table 7.3, changes within the limits of (4565)10 6 C1, and shrink-
age does not exceed 2%. For coatings based on unsaturated polyesters depending on their
chemical composition, the linear expansion coefficient is greater than (70200)10 6 C 1
(dimension, 1/C), and shrinkage in hardening is 1012%. The linear expansion coefficient
of coatings from elastomers, for instance, butadiene and its derivatives, is much greater and
changes within the limits of (130216)106. Internal stresses emerging in thermal hard-
ening of coatings based on elastomers differ little from stresses emerging in their formation
at 20C.
All these indicate that the crucial role in determining the value of internal stresses is
played by the specifics of structural transformations in the formation of polymer coatings,
which determines the rate of relaxation processes. The character of structure formation in
a very general form is determined, first and foremost, by the molecular structure of film
formers and their conformation, specific features of supramolecular structures they form,
the number, nature and distribution of links in the formation of coatings.
A significant effect on the value of internal stresses is rendered by the molecular mass
360 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

of film former molecules, which affects their flexibility and conformation and structural-
mechanical properties of the system.
Table 11.4 presents the composition and characteristics of dianic epoxy resins, widely
used in production of coatings, and the physicomechanical properties of coatings on their
basis, obtained in thermal hardening.
It is seen from the table that internal stresses decrease as the molecular mass increases.
It could be assumed that a decrease of internal stresses with the molecular mass of ep-
oxides increasing is related to the decrease of the number of epoxy groups involved in po-
lymerization, and to the formation of a less dense three-dimensional network. However, the
weak effect of the concentration of epoxy groups on the other physicomechanical properties
(elasticity modulus, breaking strength) indicate that the number of functional groups in the
molecule, which are capable of participating in polymerization, does not always determine
the density of the three-dimensional network in the formation of coatings.
The density of the three-dimensional network in epoxy coatings depends on the nature
of hardener and significantly affects the value of internal stresses. In coatings from epoxy
resins, hardened by isocyanates, the emerging internal stresses are 1.52 times greater than
using amine-type hardeners. The cause of this phenomenon is stipulated by the formation
of a denser three-dimensional network between the structural elements when using isocy-
anate hardeners.
Table 11.4 Physicomechanical properties of coatings based on epoxy diane resins.

Molecular Content of epoxy Content of hydroxyl E, GPa b, p,


mass groups, % groups, % MPa MPa

300 400 24.8 21.5 0.1 0.8 2.7 10 20 30 40


400 600 21.5 14.5 0.8 2.5 2.7 8 15 30 40
600 800 14.5 10.10 2.5 4.6 2.5 5 10 25 30
800 1000 10.0 8.0 4.6 5.1 1.8 2.5 24 20 25
1000 1400 8.0 6.0 5.1 6.0 2.5 24 30 34
1400 1800 6.0 4.0 6.0 6.5 3.0 13 30 34
1800 3500 4.0 2.0 6.5 6.8 3.2 12 30 35

It is known that in hardening of epoxy resin by isocyanates the hydroxyl groups of the
resin interact with isocyanate groups to form the urethane bond:

CH OH + N C OR CH N COOR

The epoxy group is also capable of interacting with isocyanate to form five-membered
cycles of 2-oxazolidones:
CH2 CH2
CH2 CH + N C O N O

O C
O
It is also not to rule out the possibility of interaction of the amide group formed by re-
action I with epoxy groups of the resin. With this in mind, it can be assumed that, as the
CHAPTER 11 361

result of hardening of epoxy resin by isocyanates, a polymer with a greater density of the
three-dimensional network is formed, which contains no free functional groups. In the case
of using amine hardeners, the hydroxyl groups are not involved in the chemical interaction.
Hardening is performed as the result of the interaction of epoxy groups with primary and
secondary amines; epoxy resin hardened by amines has the structure represented by the fol-
lowing scheme:
O

NH2 + 2CH2 CH CH2 [R ]n CH2 CH CH2

CH2 CH CH2 [R]n CH2 CH CH2

OH O
R'N

CH2 CH CH2 [R]n CH2 CH CH2

OH O

where R is alkyl or aryl radical of amine


CH3
R group O C OCH2 CH CH2

CH3 OH

For this reason, epoxy coatings hardened by isocyanates are more stable to the action
of various aggressive media and swell in solvents less. At the same time, the number of
chemical bonds does not determine unequivocally the swelling ability of films and coatings
in solvents; the character of their distribution is important. Using amine hardeners, coatings
formed in 1 h at 20C and 2 h at 160C swell in alcohols less with the increase of the mo-
lecular mass of the resin. For coatings hardened by isocyanates under the same conditions
an inverse dependence of swelling on molecular mass is observed: the swelling decreases
with the decrease of the molecular mass. Thus, there is no one-to-one dependence between
the swelling and density of the three-dimensional network.
These data are also indicative of the significant effect of not only the number and
nature of bonds on the value of internal stresses, but also the character of their distribution
in the system. The absence of correlation between the density of the three-dimensional net-
work, determined by the swelling method, and the value of internal stresses was also
observed for other oligomers.
Coatings have a characteristic inhomogeneous structure along the thickness of the
film. The structure of epoxy coatings of about 300 m in thickness, hardened on a glass
support at 80C, was studied. After hardening for 5 h, the coatings peeled off the support.
The character of delamination was controlled by the structure of the support and coating
layers bordering with the support. The structure was studied by the method of electron
microscopy by taking carbonplatinum replicas, as well as by layer-by-layer slices on an
ultratome.
362 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

A sharp change of the structure of epoxy coatings was observed in layers bordering
with the support and the air. Away from the border by 100200 nm, the structure of the
middle layers is stabilized and does not change significantly in passing from one layer to
another. At the interface with the support, a homogeneous globular structure was observed
owing to the adsorption interaction of oligomers with its surface. The size of globules is
1020 nm and coincides with the size of associates in epoxy oligomers. Away from the in-
terface, the mobility of structural elements increases, they aggregate to form more complex
supramolecular structures.
In layers bordering with the air, secondary supramolecular formations significantly
worsen the protective and decorative properties of coatings. The architecture of secondary
supramolecular structures, their number, size and character of their distribution on the sur-
face depend on the heterounit character of chains, molecular-mass distribution. In coatings
from epoxy dianic oligomers, for instance, E-41, with a broad molecular-mass distribution
from 600 up to 20,000 complex supramolecular formations are crater origination centres.
Studies of the mechanism of structure formation in solutions of epoxy oligomers found that
the cause of this phenomenon is due to the dissimilar solubility of various-molecular-mass
fractions in complex solvents, for instance, R-5, and the emergence of secondary supramo-
lecular formations in oligomer solutions.
It was shown that in the centre of a crater there is a nucleus from more ordered and
densely packed structural elements. By the radii of the craters, spheres with various struc-
tures and clear-cut interfaces are observed. The architecture and structure of secondary su-
pramolecular formations depend significantly on the nature of the support; data were
presented on the layer-by-layer inhomogeneity of the structure of epoxy coatings from oli-
gomers with molecular masses of 400600, filled with titanium dioxide and formed at
80C. Along with the globular structure characteristic of epoxides, a fibrillar structure is
formed in layers bordering with the support, near the surface of particles of the filler. For
layers bordering with the air, owing to a larger mobility of structural elements, an ordered
structure from densely packed structural elements is found near particles of active filler. The
oriented layers of polymer, which enclose the filler particles, are joined by structural ele-
ments of the fibrillar type. The inhomogeneity of the structure along the thickness of the
film is also observed at the introduction of other active fillers in various concentrations. Ori-
ented supramolecular structures of surface layers of coatings form a network. Formation of
an imperfect layer-by-layer inhomogeneous structure is observed in fabrication of protec-
tive coatings from epoxy oligomers with a higher molecular mass from 1200 up to 2000,
widely used for protection of equipment and production facilities in food industry. The
structure of an epoxy coating from oligomer E-41, hardened at 80C, of about 150 m in
thickness, was given.
The most chemically resistant cold-hardened epoxy polyamine coatings possess low
protective properties in biochemically active media even at short-term exposure. The cause
of this phenomenon is associated with the fact that formation of a three-dimensional struc-
ture is accompanied with the emergence of an inhomogeneous imperfect network with the
nonuniform distribution of chemical bonds in the system, of internal stresses commensura-
ble with adhesion strength and stipulated by the incompleteness of the relaxation processes.
The use of special modifiers we developed makes it possible to reduce considerably
from 2 up to 10 times internal stresses, to increase adhesion of coatings, to increase their
durability, including in hardening under conditions of natural drying. It was found that the
use of epoxy compositions of nitrogen-containing surfactants as modifiers makes it possible
to significantly reduce internal stresses as the result of a decrease of adhesion strength at
CHAPTER 11 363

the polymersupport, polymerfiller interface. At an optimal concentration of surfactants,


as the result of forming a more ordered structure in coatings, an increase of the tensile
strength of films is observed. However, the worsening of adhesion is accompanied with a
decrease of the resistance of coatings to aggressive media. The use for modification of
epoxides of compounds with functional groups capable of interacting chemically with the
support and film former, causes, along with an increase of adhesion strength, a sharp incre-
ment of internal stresses.
With consideration of these regularities, modifiers based on nitrogen-containing oli-
gomers with active functional groups with respect to the support and to oligomer with an
optimal degrees of branching of macromolecules were developed. The effect of the modi-
fiers on the structure, physicomechanical and protective properties of coatings was studied.
The object of study were epoxy oligomers E-40 and E-41, as well as mass produced enamels
on their basis. A modifier was introduced into solutions of oligomers and enamel prior to
their application to metal. Hexamethylene diamine was used as hardener. The concentration
of modifier was varied within the range of 0.114%. Coatings were formed on steel de-
greased with white spirit; a layer of 80120 m in thickness was applied by pneumatic
spraying. The protective properties of coatings were assessed by the capacitanceresistance
method; the capacitance and resistance of painted metal in electrolyte were measured using
an a.c. bridge. As working electrolyte, use was made of a 1% solution of sodium chloride.
A 3% solution of lactic acid was used as a model medium due to the insufficient resistance
of epoxy coatings in organic acids. The protective properties of coatings were assessed by
the capacitance and resistance coefficients calculated as a ratio of respective electrophysical
parameters at frequencies of 20,000 and 2,000 Hz. The physicomechanical properties of
coatings (hardness, adhesion, impact strength) were determined by the standard methods.
Internal stresses were measured by the photoelastic method. The structure of coatings was
studied by electron microscopy.
It was found that good protective and physicomechanical characteristics are observed
at a modifier concentration of about 2%. The properties of coatings at an optimal concen-
tration of the modifier are given in Table 11.5.
It is seen in the table that introduction of a modifier significantly improves the physi-
comechanical and protective properties of coatings, decreases internal stresses at a simul-
taneous increase of adhesion and durability.
Table 11.5 Effect of the modifying additive on the properties of epoxy coatings.

Properties E-40 E-41 Enamel


of coating
Initial Modifying Initial Modifying Initial Modifying

Relative hardness, arb. 0.81 0.86 0.85 0.85 0.47 0.51


units
Impact strength, J 3.0 5.0 3.0 5.0 4.0 5.0
Adhesion on Erichsen 2.0 9.0 2.2 9.5 4.5 9.6
tester, mm
Internal stresses, MPa 5.0 2.5 3.0 1.5 4.5 1.8
KC 0.37 0.53 1.30 0.90 0.96 0.99
KR 2.42 5.40 12.50 17.30 7.20 9.30
G, Sm 4.5 3.0 4.9 3.3 3.2 1.1
Longevity, days 40 520 30 550 63 500
364 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The effect of the concentration of modifier on the structure of coatings formed at 20


and 120C was studied. Coatings hardened at 20C were shown to have an inhomogeneous
globular structure with the size of globules 2540 nm; the globules formed aggregates and
anisodiametric structures 65250 nm in size with a loose packing of the structural elements.
With the coating formation temperature increased up to 120C, the diameter of globular ag-
gregates is observed to decrease to 80 nm. Introduction of an optimal amount of modifier
contributes to a decrease of the globules size to 1020 nm and their aggregates size to
5080 nm, respectively, under conditions of hardening at 20 and 120C; the packing den-
sity of structural elements is also increased.
Formation of an ordered structure in coatings from modified compositions contributes
to a more uniform distribution of chemical bonds in the system, to a decrease of internal
stresses, improvement of the adhesion and protective properties of coatings. Introduction
of a modifier stabilizes the frequency dependence of the electrophysical characteristics of
coatings under conditions of their performance in a lactic acid solution.
The chemical interaction of modifier with epoxy oligomer was confirmed by the meth-
od of IR spectroscopy. This is expressed in a decrease of intensity of the absorption band
of epoxy groups in the region of 920 cm 1 and the emergence of an arm on the side of low
frequencies, as well as in a decrease of absorption intensity of nitrogen-containing func-
tional groups in the region of 33003450 cm 1. Introduction of a modifier also contributes
to the acceleration of hardening after the stage of gelation.
A network of secondary supramolecular structures was shown to be formed in coat-
ings layers bordering with the air. Using the method of oxygen etching and at a large mag-
nification, the secondary structures forming craters were studied. The effect of coatings
formation conditions on the defect-formation mechanism, structure and properties was
studied. Studies of the kinetics of increment of internal stresses found that a specific feature
of coatings formation from epoxy oligomers with broad molecular-mass distribution con-
sists in a jump-like change of properties and the occurrence of induction periods at partic-
ular stages of formation. In formation of coatings at 20C, minor internal stresses emerge
at the initial stage, and only in 5 h they begin to increase to an ultimate value, which is ob-
served in 10 days. With the formation temperature increasing up to 90C, the stresses
change jump-like, in three stages, which are characterized by different rates. The same num-
ber of periods is observed in hardening of coatings at 120C. They differ by the value of
initial and final stresses. The kinetics of changes of internal stresses in the formation of coat-
ings is correlated with the polymerization kinetics at various hardening conditions.
Studies of the defects by the optical method with magnification from 70 up to 500
found that their size changes from 0.1 up to 1.5 mm. Craters have an oval, oblong or round
shape. When changing from smaller to larger magnifications, it is seen that a defect is in-
homogeneous and consists of various regions in the shape of spheres assembled around a
centre and having clear-cut boundaries. In the centre, there is the most dense part the nu-
cleus whose shape can be different and whose size is from 0.1 up to 0.25 diameter of a
crater. The nucleus is transparent for light beams and occupies a certain volume. To be able
to see its particular parts, it is necessary to change the focal distance. At a larger magnifi-
cation, it is easy to see the structuredness of the centre of a defect and the differences in the
structure of its individual parts. The defects nucleus is not a particle of dust or other foreign
body getting inside in application of the coating. The latter form defects in the coating,
which are essentially different by their structure.
Thus, the specifics of structure formation in coatings from epoxides with a compara-
tively high molecular mass is that complex supramolecular formations emerge in the
CHAPTER 11 365

surface layer of the film at the boundary with the air. The formations consist of radial rings
with different morphologies of the structural elements, size and density of packing.
To study the crater formation mechanism, epoxides were fractionated into individual
monomolecular fractions by the method of liquid adsorption chromatography. Silica gel
KSK-2 was used as adsorbent; the fractions were dissolved in acetone. The molecular mass
of the fractions was determined by the method of light scattering. The molecular mass of
the fractions increases, as their number rises from 150 up to 2,000.
Coatings obtained from the monomolecular fractions of epoxy oligomer are observed
to have a homogeneous globular structure. The size of structural elements increases with
the molecular mass of the fractions increasing; herewith, coatings are observed to have no
defects.
To prevent aggregation of structural elements and emergence of crater-formation cen-
tres, we developed methods of modifying epoxy oligomers by compounds with the meso-
morphic structure of the type of PCOA (P, aromatic radical; A, aliphatic radical). The
proposed modifiers with the regular arrangement of aromatic and aliphatic radicals with ac-
tive functional groups, in accordance with the StewartBrigleb model provide for the local
interaction of modifier with film former and the surface of solid bodies. The scientific prin-
ciples of developing a regular structure using structure-forming modifiers made it possible
to produce coatings with high performance properties and durability.
As the result, it was found that:
protective and decorative polymer coatings are distinguished with a diversity of prop-
erties depending on their purpose and operating conditions;
requirements to the increase of protective properties and durability of materials con-
stantly rise in connection with the necessity to provide for the ecological safety of the pop-
ulation; in connection with increased technogenic emissions, which pollute the atmosphere,
soil and water and contribute to the development of pathogenic microflora.
Degradation of polymer materials under the action of microflora is three times faster
than due to other factors accelerating the corrosion processes. The cause of this phenome-
non is due to the consumption of components of polymer compositions by microorganisms,
which excrete enzymes, organic and inorganic acids strong activators of the decomposi-
tion of practically all materials: metals, concretes, wood, polymers, etc.
The development of the scientific principles of increasing the durability of polymer
coatings is inseparably related to the studies of the specific features of the structure forma-
tion mechanism and the development of scientifically substantiated methods of normalizing
the supramolecular structure.
The normalizing is meant to be the development of scientific approaches, which make
possible the use of the largest number of active functional groups in macromolecular film
formers in the formation of the three-dimensional network.
A major part of functional groups (more than 50%) are consumed in hardening of poly-
mer systems for the formation of complex supramolecular structures practically not in-
volved in the formation of the three-dimensional network, which determines the
performance properties of coatings.
A criterion of homogeneity and imperfection of the network in the formation of coat-
ings are internal stresses, which depend on the rate of the relaxation processes at various
stages of structure formation.
The effect of various physicochemical factors (nature of the film former, regimes of
formation, molecular mass) on the value of internal stresses in the formation of coatings
was studied.
366 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The scientific principles of creating a homogeneous regular ordered structure were de-
veloped, which make it possible to considerably increase the protective properties and du-
rability of coatings. Methods of modification based on the use of compounds with the
mesomorphic structure and regular arrangement of aromatic and aliphatic radicals with ac-
tive functional groups were proposed. In accordance with the StewardBrigleb model,
compounds with the mesomorphic structure provide for the local interaction of modifier
with film former and the surface of solid bodies. Scientific principles of developing a reg-
ular structure using a structure-forming modifier make it possible to obtain coatings with
high performance properties.

11.5 Effect of the nature of hardener and initiator on the formation and
properties of coatings for transport containers
The change of the concentration and nature of the polymerization hardener and initiator
makes it possible to regulate the hardening kinetics of coatings and their properties.
It is known that the dependence of internal stresses and other physicomechanical prop-
erties of films on the amount of hardener in the system is nonmonotonic and exhibits a max-
imum corresponding to the formation of the largest number of crosslinks. In this
connection, a decrease of internal stresses by changing the amount of hardener is accompa-
nied with the worsening of other physicomechanical properties of films. For instance, the
strength of specimens from polyester resins is greatly affected by the amount of added ini-
tiator and accelerator of polymerization, which is related to the different degree of harden-
ing. At the same time, the larger the rate of hardening, the greater the initial strength is (but
the smaller the strength after ageing is). It follows from these data that the extent of hard-
ening is not the only factor determining the strength and durability of coatings and films.
From the experimental data presented further, it follows that the strength properties of net-
work polymers correlate with the change of internal stresses emerging in the formation and
ageing of specimens. The effect of the concentrations of initiator and accelerator on internal
stresses and physicomechanical properties of specimens from polyester resin elasticity
modulus, breaking strength and bending strength was studied. To prepare specimens,
polyester resin with various concentrations of initiator and accelerator was poured into
molds 5, 50 and 120 mm in size. The specimens were hardened for 3 days at 18C. Cumene
hydroperoxide was used as a polymerization initiator. The reaction was accelerated by ad-
dition of a 8% styrene solution of cobalt naphthenate. Internal stresses were measured by
the photoelastic method. The ultimate value of internal stresses essentially depends on the

Table 11.6 Dependence of internal stresses in polyester resin specimens on material of the molds.

Amount of Amount of initiator, Internal stresses, MPa Hardening time,


accelerator, % % days
Steel Glass Fluoroplastic

8 3 6.24 3.84 0.76 1.5


6 3 10.5 5.04 0.56 1.5
8 1 3.60 1.80 3.0
8 2 7.60 3.90 3.0
8 3 4.00 2.80 3.0
8 4 1.61 2.01 3.0
CHAPTER 11 367

material of the mold (Table 11.6). The lowest internal stresses emerge in hardening of the
resin in molds lined with fluoroplastic. With consideration for this, the further results were
obtained for specimens hardened in such forms.
From the concentration dependence of internal stresses on the content of polymeriza-
tion accelerator, it follows that internal stresses are maximal in the presence of 1012%
accelerator in the system.
For various batches of the resin, differing by the content of styrene, the maximum
shifted to the side of the lower content of accelerator. A similar nonmonotonic dependence
of the concentration of accelerator was also observed for the elasticity modulus, which was
studied by the dynamic method on an impulse-excitation unit. The frequency of oscillations
was 800 kHz; the division value of scan, 0.2 s.
The elasticity modulus was calculated according to the equation

2 1 ( 1 + ) ( 1 2 )
E = C p ----------------------------------------------- ,
1

where C is the speed of sound; p is density; is the Poisson coefficient. From the analysis
of the data, it follows that internal stresses correlate with the change of the elasticity mod-
ulus depending on the content of the polymerization accelerator. In the concentration de-
pendence of internal stresses on the content of polymerization initiator, a maximum is
observed at its 3% concentration in the system. The amount of accelerator in these experi-
ments was 8%. At this concentration of initiator, the maximal values of other physicome-
chanical characteristics are observed: elasticity modulus, hardness, tensile strength and
bending strength of coatings. These parameters correlate with the change of internal stress-
es, which is stipulated by the most complete use of functional groups under these conditions
of polymerization and the formation of the largest number of chemical crosslinks.
The optimal amount of polymerization initiator and accelerator depends on the chem-
ical composition of polyester lacquers, as is seen from the data on the dependence of inter-
nal stresses on initiator and accelerator concentrations in the formation of coatings at 80C
from oligomaleinate phthalate lacquer PN, which contains triethylene glycol diester of
methacrylic acid as the polymerizing solvent. Specimens were hardened in the presence of
initiator (mixtures of cumene hydroperoxide and cyclohexanone) and accelerator (a styrene
solution of cobalt naphthenate); the dependence of internal stresses on initiator and accel-
erator concentrations in the system is nonmonotonic, as for coatings from oligoester PN.
The maximal rate of hardening is at 2% initiator and 4% accelerator.
However, more stressed specimens are distinguished by a lower resistance to ageing.
The presence of high internal stresses, reaching 2535% of the breaking and bending
strengths, leads to spontaneous breakdown of specimens. A decrease of internal stresses by
regulating the content of initiator and accelerator of polymerization is accompanied by a
considerable worsening of other physicomechanical properties.
With consideration for this, of great interest for regulating the properties of coatings
are studies of the effect of hardeners nature on the properties of coatings. The effect of var-
ious hardeners on the properties of coatings from epoxy oligomers was studied the most.
Epoxy resins are oligomer systems with a low molecular mass, characterized by the pres-
ence of epoxy (ethylene oxy) groups with a molecular mass 43, having the shape of three-
membered oxygen-containing cycles. In ring opening, this group is capable of interacting
with the labile atom of hydrogen in amines, amides, acids, alcohols or phenols to form a
hydroxyl group.
368 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Polyamines with the molecular mass of 3701000 are used for hardening dianic epoxy
resins. Di- and polyamines interact with epoxides to form network polymers:
H2C N CH2

R'

H2C N CH2
CH2CH R CHCH2N R' NCH2CH R CHCH2 N CH2
OH OH CH2 OH OH R'

H2C N CH2
Aliphatic polyamines diethylene triamine (H2N(CH,)2NH(CH2)2NH2), triethylene
triamine (H2N(CH2)2NH(CH2)2NH(CH2)2NH2), hexamethylene diamine (H2N (CH2)f
NH2) are widely used as hardeners.
Along with polyamines, oligoamides with molecular masses of 2,000 up to 5,000 are
widely used for hardening epoxides.
Oligoamides are obtained by interaction of dimerized fatty acids of drying oils with
polyethylene polyamines. Along with secondary free amino groups, they contain more
Table 11.7 Effect of the nature and concentration of hardener on the physicomechanical
parameters of films from ED-20.

Content of Strength of glueing, MPa b, E, GPa , % Tg, C


hardener, % MPa
Steel Copper Titanium

TEPA Hardening (150C, 4 h)


5 68 C 71 C 59 C 38
6 77 C 74 C 70 C 52 1.66 2.4 60
8 82 C 77 A 86 C 56 2.40 5.1 74
10 68 C 36 A 59 C 46 1.43 80
15 56 C 28 A 52 M 38 1.43 4.0 88
20 26 A 18 A 49 A 46 1.60 4.6 83
25 28 A 2A 48 A 38 1.44 3.5 80
50 29 A 5A 44 A 58 2.01 7.4 60

PO-300 Hardening (120C, 2 h)


10 5C
15 24 C
20 37 C 51 2.84 4.3 55
25 26 C 52 2.70 4.8 75
30 22 A 53 2.48 5.9 97
40 27 A 47 1.96 5.0 87
45 39 1.26 4.3 75
50 23 A 46 1.76 5.0 62
60 21 C 15 0.75 42.0 34

Note: A, adhesion breakdown; M, mixed breakdown; C, cohesion breakdown.


CHAPTER 11 369

reactive primary amino groups arranged by the ends of the chain. Reactive oligoamides are
prepared with excess amine with respect to dimers of fatty acids to increase the content of
amino groups in the chain. Owing to their larger molecular mass as compared with amines,
polyamides are nonvolatile and nontoxic.
The nature of hardener renders a significant effect on the physicomechanical and ad-
hesion properties of epoxy coatings. As seen in Table 11.7, a combination of high adhesion
strength and cohesion strength is observed at an optimal content of the hardener. Epoxy
coatings hardened by tetraethylene pentamine (TEPA) exhibit higher physicomechanical
and adhesion properties as compared with coatings hardened by polyamide resin PO-300
a production of the interaction of polyamides with di- and trimerized acids of plant oils.
IR spectroscopic studies of the consumption of epoxy groups depending on the con-
centration of PO-300 indicate a nonmonotonic character of this dependence. The maximal
consumption of epoxy groups was observed at a concentration of 35% and corresponds to
the highest physicomechanical characteristics of coatings. Herewith, the consumption of
epoxy groups is greater than that calculated from the reaction of maximal addition of epoxy
groups to amine groups. This is, probably, due to the catalytic polymerization of epoxides
in the presence of tertiary atoms of nitrogen present in polyamide resin.
The regularities of increment and relaxation of internal stresses depending on the tem-
perature of hardening of films and the nature of hardener were studied.
The object of study was epoxy resin ED-20. Hexamethylene diamine and phe-
nol-formaldehyde resin were mixed with epoxy resin as solutions; the former, in ethyl al-
cohol; the latter, in acetone. After formation of coatings for 14 h at 110C and, respectively,
2025 h at 70C internal stresses reach ultimate values in all cases. The measurement of
internal stresses was performed by the photoelastic method. At room temperature the stress-
es relax in accordance with the Shvedov equation (Fig. 11.1). The relaxation time depends
on the nature of a hardener. The highest value of the relaxation time (81 h) is observed in
the formation of coatings in the presence of polyethylene polyamine; the lowest (50 h), in
the presence of hexamethylene diamine. In films hardened by phenol-formaldehyde resin
the relaxation time was about 76 h.
Figure 11.2 presents a concentration dependence of internal stresses on the content of
polyethylene polyamine for epoxy coatings formed at 110C for 15 h. It is seen in the figure
that stresses change nonmonotonically. The maximal values of internal stresses were found
at a hardener concentration of 68%. This indicates that the formation of a maximal amount
of chemical bonds is prevented not only by the deficiency of hardener but also by its excess.
This is also confirmed by the data on the change of the hardness of coatings depending on
the concentration of hardener.
During the formation of coatings in the presence of phenol-formaldehyde resin, inter-
nal stresses are observed to increase monotonically with the concentration of hardener in-
creasing (Fig. 11.3).
The critical thickness, at which a spontaneous delamination of coatings under the ac-
tion of internal stresses is observed, also depends on the nature of hardener. Figure 11.4 pre-
sents the data on the change of internal stresses depending on the thickness of formed epoxy
films. It is seen in the figure that films hardened by polyethylene polyamine peel off at a
significantly smaller thickness than in hardening by hexamethylene diamine. Herewith, in
all cases delamination was accompanied with the breakdown of the surface layers of the
glass support.
The effect of the concentration and the nature of hardener on internal stresses in coat-
ings from various epoxy resins was studied. The objects of study were epoxy resins ED-20,
370 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

logG
1.4

1.0

0.6
3
2
1

0.2

48 144 240 Time, h

Figure 11.1 Kinetics of relaxation of internal stresses in epoxy coatings from ED-20 formed with
hexamethylene diamine (1), phenol-formaldehyde resin (2) and polyethylene polyamine (3).

N, GPa b, MN/m2
0.20 7
1
6
2
0.15 5

5 10 15 20
Polyethylene polyamine, %

Figure 11.2 Effect of the concentration of polyethylene polyamine in ED-20 on hardness (1) and
internal stresses (2).

ED-16, ED-casting and E-33 with epoxy numbers, respectively, 25.75, 18.3, 8.15, 10.22%.
Phthalic anhydride, metaphenylene diamine, polyamide with amine number 216 were used
as hardeners. The film-forming mixtures were prepared by introducing the hardener into the
resin heated up to 100110C or dissolved in mixed solvents (acetone, xylol, cellosolve).
The data on the kinetics of increment of internal stresses in the formation of coatings
at 130C from epoxy resins ED-20 and ED-casting, mixed with various amounts of phthalic
anhydride, and their relaxation during the storage of specimens under standard conditions
were given. It is seen that the rate of increment and the maximal value of internal stresses
depend on the composition of the film former. The largest magnitudes of these values are
observed at a 67% content of hardener in terms of the initial ratio. The relaxation periods
CHAPTER 11 371

b, MN/m2
4

20 60 100
Phenol formaldehyde resin, %

Figure 11.3 Effect of the concentration of phenol-formaldehyde resin in ED-20 on internal stresses.

14

3 2
1
10
b, MN/m2

0 200 400 600 800


Film thickness, m

Figure 11.4 Dependence of internal stresses on the thickness of coatings from ED-20 hardened by
hexamethylene diamine (1), phenol-formaldehyde resin (2), polyethylene polyamine (3).

also depend on the composition of the film former. The sharpest decrease of internal stress-
es is observed at a lowest content of anhydride.
During the change of the ratio between resin and hardener, the ultimate internal stress-
es emerging after the formation of films, change nonmonotonically. During the formation
of coatings from ED-20 with metaphenylene diamine, ED-16 and ED-casting with phthalic
anhydride, the largest value of internal stresses is observed at equivalent ratios between ep-
oxy groups of the resin and functional groups of the hardener. In the hardening of films by
phthalic anhydride, the losses of this hardener as the consequence of the lyophilization were
taken into account.
Figure 11.5 presents the data on the effect of the content of metaphenylene diamine on
the extent of swelling of films from resin ED-20. The minimal extent of swelling is ob-
served at an equivalent ratio between the epoxy groups of the resin and the functional
372 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

30

Degree of swelling, %
20

10

0 10 20 %

Figure 11.5 Effect of metaphenyl diamine on the swelling of coatings from ED-20.

groups of the hardener. From the comparison of the data of Figs. 11.4 and 11.5, it is seen
that coatings with the greatest degree of hardening correspond to systems with maximal in-
ternal stresses.
To produce epoxy coatings resistant to the action of alkali, water, acids and high tem-
peratures up to 250300C, resol phenol-formaldehyde, urea- and melamine-formaldehyde
resins are used as hardeners. They are added in the amount from 20 to 30 weight fractions.
Coatings are hardened at high temperatures (150200C) as the result of interaction of me-
thylol groups of resol phenol-formaldehyde resin with epoxy groups. In the case of using
butanolized phenol resins, butoxyl groups react with hydroxyl groups of the resin at a tem-
perature greater than 180C. Table 11.8 presents data on the effect of the nature of hardeners
on the value of internal stresses in 10200 m-thick epoxy coatings hardened at 120C.
Table 11.8 Effect of the nature of hardener on internal stresses in 120 m-thick coatings from
ED-20 formed at 120C.

Hardener Ultimate b, Quasi-equilibrium b,


MPa MPa

Polyethylene polyamine 6% 10.0 6.0


Polyamide PO-300 30% 7.0 5.0
Hexamethylene diamine in equivalent ratio 4.0 3.0
Phenol formaldehyde resin at a ratio 1:1 6.0 4.0
Phenol formaldehyde resin at a ratio 1:0.3 4.0 3.0
Butanized phenol formaldehyde resin 1:0.3 2.5 2.0
Phthalic anhydride 67% 4.0 3.0
Metaphenylene diamine 15% 5.0 2.3

Polyethylene polyamine, hexamethylene diamine, phenol-formaldehyde resin, phthal-


ic anhydride, metaphenylene diamine, butanized phenol resin were used as hardeners. The
greatest internal stresses emerge in hardening of epoxy coatings by polyethylene poly-
amine. A considerable decrease of internal stresses is observed in hardening of coatings by
butanolized phenol resin.
CHAPTER 11 373

By example of coatings from higher-molecular-mass epoxy resins, the most resistant


to aggressive media were shown to be coatings hardened by diisocyanates to form a ure-
thane bond owing to the interaction of hydroxyl groups and isocyanate groups:

O H
H C OH + O C N R H C O C N R

Besides this main reaction, which proceeds at room conditions, at high temperatures
(180200C) epoxy groups interact with isocyanates to form additional chemical bonds.
As hardeners of epoxy resins, use is usually made of 2,4-toluylene diisocyanate (prod-
uct 102T) and its mixture with 2,6-toluylene diisocyanate at a ratio 65:35 (product 65T), as
well as hexamethylene diisocyanate.
CH3 CH3 CH3
NCO NCO OCN NCO

NCO NCO NCO


102T 65T
Coatings hardened by isocyanates are characterized by a denser three-dimensional net-
work as compared with epoxy coatings hardened by polyamines. This provides for their
greater stability to aggressive media.
Anhydrides of organic acids are used as hardeners to produce heat-resistant coatings.
Methyl tetrahydrophthalic anhydride is applicable for increasing the acid resistance and
thermal resistance of coatings:
CH2 O
HC CH C
O
C CH C
H3C O
CH2
In the process of hardening, the anhydride interacts not only with epoxy groups of the
resin but at a higher temperature also with hydroxyl groups. The structure of hardened resin
can be represented by the following scheme:
CH3
CH2 CH CH2 O C O CH2 CH CH2
n
O O CH3 O
C OC O C O
R R R
C OC O C O
O O CH3 O
CH2 CH CH2 O C O CH2 CH CH2
n
CH3
374 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

16
1
2
12
3

b, MN/m2
8

4
4

1 2 4 6 8 10 , h

Figure 11.6 Kinetics of internal stresses in hardening of epoxy coatings from EDT (1, 4) and EKhD
(2, 3) phthalic anhydride (1), methyl tetrahydrophthalic anhydride (2), diamet X (3), triethylene tetra-
amine (4).

It is seen in Fig. 11.6 that hardening of epoxy resin ED-20 modified by glycidyl ester
of diethylene glycol (DEG-1) of the following structure is accompanied with a significant
increment of internal stresses.
O

[CH2 CH CH2 [ O (CH2)2 O (CH2)2 O CH2CH CH2

O (CH2)2 O(CH2)2 O CH2 CH CH2]n

O
A significant decrease of internal stresses takes place when using primary and second-
ary di- and polyamines, in particular, triethylene tetramine, as hardeners in coatings from
dianic resins modified by DEG-1. Interaction of amines with the resin proceeds via epoxy
groups to form coatings with the network structure:
R'
N CH2 CH R' CH CH2 N CH2CH R' CH CH2 N
R OH OH OH OH R'

N CH2 CH R' CH CH2 N CH2 CH R' CH CH2 N ...


OH OH R' OH OH
R is the hydrocarbon residue of amine

R' CH2 O C(CH3)2 O CH2 O

The presence of ether bonds, in contrast with compounds with ester groups provides
for a high stability of coatings to the action of alkalis, and the significant number of
CHAPTER 11 375

hydroxyl groups in the chain creates a high adhesion of coating. A relationship was found
to exist between the nature of hardener used in production of coatings from epoxy resin
ED-8 with 810% of epoxy groups and the density of the three-dimensional network af-
fecting the internal stresses and other properties of coatings (Table 11.9). The data of the
table indicate that the density of the three-dimensional network, calculated by the equilib-
rium rubber-like elasticity, increases in hardening of oligomer ED-8 by cycloaliphatic and
especially aromatic anhydrides. This is accompanied by a slowdown of the relaxation pro-
cesses and an increment of internal stresses.

Table 11.9 Effect of the nature of hardener on internal stresses (b), subchain between
3-dimensional network nodes (Mc), glass transition temperature (Tg) and ultimate elongation () of
coatings based on epoxy resin ED-8.

Hardener b, MPa Mc Tg, C , %

Phthalic anhydride 4.6 523 110 3


Methyl tetrahydro phthalic anhydride 3.2 720 75 10
Hexahydro phthalic anhydride 4.2 813 90 4
Succinic anhydride 2.1 1310 70 21
Adipic acid polyanhydride 1.2 1980 46 38
Sebacic acid polyanhydride 0.6 2410 38 42
Paraphenylene diamine 5.0 621 104 4.9
Metaphenylene diamine 4.8 780 99 5.3
Benzidine 3.9 838 96 5.8
3,3-Diamino diphenyl sulfone 3.6 1010 92 6.2
Dicyane diamine 2.9 1410 89 1.3

Internal stresses decrease using aliphatic polyanhydrides. Their magnitude is the


smaller, the longer the aliphatic chain in the structure of the hardener is. During the hard-
ening by both anhydrides and amines, one reveals a regularity in the decrease of internal
stresses at an increase of particular functionality, molecular mass of the hardener and the
extent of branching of its structure.
Regularities in the change of internal stresses depending on the nature of hardener cor-
relate with other properties of coatings the glass-transition temperature, relative breaking
elongation.
The nature of hardener also renders a significant effect on the properties of coatings
from chlorine-containing epoxy resins EKhD, which represent a product of the interaction
of epichlorohydrin with 3,3-dichloro-4,4-diamino diphenyl methane Diamet X.

O O
Cl Cl
CH2 CH CH2 CH2 CH CH2
N CH2 N
CH2 CH CH2 CH2 CH CH2

O O
Figure 11.7 presents the data on the kinetics of increment of internal stresses in the for-
mation of coatings by the stepwise regime (100C, 3 h; 120C, 3 h; 150C, 3 h; 170C, 3 h)
from epoxy resin EKhD in the presence of the hardener Diamet-X
376 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

16
1

12 2

b, MN/m2 8
3

2 4 6 8 10 12 , h

Figure 11.7 Kinetics of internal stresses in the formation of coatings from cyclic epoxides UP (1),
UP-632 (2), UP-639 (3).

NH2 CH2 NH2

and iso-methyl tetrahydrophthalic anhydride I-MTHPA


CH2 O
CH CH C
O
C CH C
H2C O
CH2
It is seen that in the presence of Diamet-X the coating hardens at lower temperatures
with lower internal stresses than in the introduction of the hardener MTGFA.
A sharp increment of internal stresses is observed using aromatic hardeners to produce
coatings from alicyclic epoxy resins (Table 11.10).
Table 11.10 Characteristics of alicyclic epoxides.
Oligomer Structural formula Mole- Content
cular of epoxy
mass groups, %

3,4-Epoxy hexahydro- CH2 CH O CH2 324 28 30


2
benzal-3,4- epoxy-1,1- CH
bis-hydroxymethyl O CH2 O O
cyclohexane (UP-612) CH2

3,4-Epoxy cyclohexyl CH2 CH2 306 28 32


methyl-3,4-epoxy cyclo- CH2 C O
hexane carboxylate O O
CH2 HC2
(UP-632)
CH2 CH2
bis-3,4-Epoxy cyclo- O O 436 19 21
hexyl methyl adipinate
CH2 C (CH2 )4C H2C
(UP-639) O O
CHAPTER 11 377

As seen in Table 11.11, the value of internal stresses in coatings from these resins also
depends on the thickness of the three-dimensional network.
Table 11.11 Structural mechanical properties of coatings based on alicyclic epoxides.
Oligomer b, MPa Mc Tg, C , %
UP-612 12.0 310 230 1.5
UP-632 9.8 631 250 2.0
UP-639 6.8 797 150 5.0
Characteristics of hardeners

Name Structural formula Molecular Melting


mass temperature, C

Phthalic anhydride (PA) O


C
O 148.11 130.5
C
O
Methyl tetrahydro phthalic O
anhydride (MTHPA) C
O 166.09 64.0
H3C C
O
Hexahydro phthalic anhydride (HHPA) 154.00 32.0
Succinic anhydride O
CH2 C
O 90.00
CH2 C
O
Adipic acid polyanhydride O O
C (CH2 )4 C n 43.0 85.0
O
Sebacic acid polyanhydride O O
C (CH2)8 C n 47.0 91.0
O
Metaphenylene diamine (MPDA) NH2

H2N 108.00 63.0

Paraphenylene diamine (PPDA)


H2N NH2 108.00 64.0

Benzidine
H2N NH2 188.00 123.0

3,3-Diamino diphenyl sulfone H2N NH2

SO4 236.00 169.0

Dicyane diamine NH
H2N C 84.60 207.0
NHCN
378 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

However, the use of anhydrides of organic acids in common epoxy resins is made dif-
ficult due to their low solubility under room conditions. To decrease internal stresses in the
formation of coatings, ester acids with different chain structure were used as hardeners. De-
pending on the nature of trifunctional ester acid used for hardening epoxides, the properties
of coatings changed. With the length of branchings increasing, elasticity went up. However,
if the hardening of films based on glycerol tricebacinate was performed not at 120C but at
200C, their elasticity was smaller than for triadipinate-based films formed at 120C. This
is due to the fact that at a higher temperature, along with the reaction between carboxyl and
epoxy groups, a side reaction probably proceeds between carboxyl and hydroxyl groups
formed as the result of the first reaction. This, in turn, leads to an additional crosslinking.
Coatings were formed from compositions consisting of equal volumes of 6085%
alcoholacetone solutions of ED-20 and, respectively, 70% acetone solutions of glycerol
trisuccinate, triadipinate and tricebacinate at a ratio of 1:1.
From the data on the kinetics of increment and relaxation of internal stresses, and
change of hardness in the formation of coatings from these compositions under conditions
of heating at 120C followed by holding at 20C, it follows that compositions based on
glycerol trisuccinate and triadipinate harden well under these conditions, and compositions
with glycerol tricebacinate very slowly; therefore the formation of coatings from them
was performed at 200C.
Table 11.12 Physicomechanical properties of films and coatings from copolymers of various
molecular compositions and epoxy resin.

Composition P, MPa E, GPa , % A, MPa Strength margin

Copolymer 1 25.2 1.5 1.4 15 18


Copolymer 2 34.3 2.4 0.7 15 49
Copolymer 3 21.5 1.2 2.2 9
ED-20 60.0 2.4 7.0 13 8

The largest internal stresses emerge in coatings hardened by glycerol trisuccinate. The
results of these studies suggest that, as the length of branchings of ester acids hardening ep-
oxy resin increases, internal stresses decrease, and the elasticity of coatings increases. If the
length of branchings is larger than the optimal value, which takes place in the presence of
glycerol tricebacinate, there is no hardening of the resin at 120C. With the formation tem-
perature increased up to 200C, coatings based on this composition exhibit the highest
physicomechanical properties. This is indicated by the data presented in Table 11.12. Coat-
ings from the first two compositions spontaneously break down at 200C in the process of
formation due to their high brittleness.
Coatings based on glycerol trisuccinate and tricebacinate hardened under optimal con-
ditions can be used within a broad range of thicknesses without spontaneous decomposition
and delamination.
A specific feature of coatings based on glycerol tricebacinate is that, with the high ad-
hesion, breaking strength and hardness preserved, they exhibit comparatively small internal
stresses.
The further decrease of internal stresses at the preservation of their high adhesion and
strength properties can be performed by ordering the structure of polyester epoxide mole-
cules. To elucidate the effect of the structure regularity of the molecules on the properties
of coatings, studies were carried out to investigate polyester epoxy and silicon-containing
CHAPTER 11 379

polyester aminoepoxy film formers of regular and irregular structure. Synthesis of the poly-
ester epoxy systems was performed according to the scheme:
C[CH2OC(CH2)nCOOH]4 + 2CH2 CHCH2OROCH CH2
O O
O

C CH2OC(CH2)nCOCH2CHCH2OROCH2CHCH2OC(CH2)nCOCH2 C
O O OH OH O O
Hydroquinone diglycidyl and diphenylol propane diglycidyl were used as the digly-
cidyl component.
Organosilicon polyester amidoepoxy compositions were obtained in two stages. At the
first state, tetraadipine pentaerythrite was condensed with bis-(phenyl aminomethyl)-tetra-
methyl disiloxane according to the scheme:

O
H2O
C[CH2OC(CH2)4COOH]4 + 2 HNCH2 Si(CH3)2OSi(CH3 )2CH2NH

C CH2OC(CH2)4C NCH2Si(CH3)2 OSi(CH3)2CH2N C(CH2)4COCH2 C


O O O O

The obtained polymers containing phenylamino methylsilyl, carboxyl groups were


converted by interaction with diglycidyl esters to copolymers with regular distribution of
carbon atoms in the network. The physicomechanical properties of copolymers of the fol-
lowing chemical composition were studied:
1 CH3
C CH2OC(CH2)4COCH2CHCH2O C
O O OH CH3

OCH2CHCH2OC(CH2)4CO CH2 C
OH O

2 CH3 CH3
C CH2OC(CH2)4C NCH2SiOSiCH2NCH2CHCH2OROCH2CHCH2C(CH2)4COCH2 C
O O CH3 CH3 OH OH O O

Copolymer 3 is a product obtained by condensation of pentaerythrite with adipic acid


and diglycidyl ester of diphenylol propane at a simultaneous charging of the components
and was distinguished by the irregularity of the structure.
To elucidate the effect of the composition and structure of molecules of copolymers
on the properties of coating, the kinetics of increment of internal stresses and other
380 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

13
10
8
1

b, MN/m2
6

4
2

2 3
4

6 12 18 24 48 72 , h

Figure 11.8 Kinetics of internal stresses in the formation of coatings from ED-20 (1) with poly-
ethylene polyamine, copolymer 1 (3), 2 (4) and 3 (2) at 160C.

E, GPa
0.6 2.4 4
1
0.5 5
0.4 1.6 6
Hardness

2
0.3
0.2 3
0.8
0.1
0
5 10 15 20 25 30 Time, h

Figure 11.9 Kinetics of change of the elasticity modulus (1 3) and hardness (4 6) in the forma-
tion of coatings at 160C from copolymer 1 (2, 4), 2 (1, 5) and 3 (3, 6).

parameters (Figs. 11.8 and 11.9). From these data, it follows that the ordering of the struc-
ture of molecules contributes to a 23-fold decrease of internal stresses as the result of re-
laxation processes during the structuring of the system. Coatings from regular-structure
copolymers are also distinguished by the stability of the properties. They feature a minor
relaxation of stresses in storage of specimens under room conditions (Table 11.13).
From the data on the change of the elasticity modulus in the formation of coatings from
the same copolymers, it follows that the elasticity modulus reaches a constant ultimate
value in 1015 h.
Table 11.13 Effect of the composition of hardeners on the physicomechanical properties of
coatings.
Hardener T, C , % E, GPa P, MPa A, MPa

Glycerol trisuccinate 120 6.0 0.9 15 13


Glycerol triadipinate 120 1.5 0.4 5 10
Glycerol trisebacinate 120 2.5 1.2 35 15
CHAPTER 11 381

Coatings from copolymer 2 harden the most rapidly at 160C. The character of the de-
pendence of internal stresses on film thickness for copolymers of different chemical com-
position is linear.
Coatings from regular-structure copolymers, along with small internal stresses, are
distinguished by a high adhesion strength. From the comparison of the properties of coat-
ings produced from different copolymers and resin ED-20, it follows that internal stresses
in coatings from compositions 1 and 2 are 410 times smaller than in coatings from epoxy
resin hardened by polyethylene polyamine. Herewith, epoxy coatings break down at a com-
paratively small thickness of about 400 m, whereas for films based on copolymers this
value of internal stresses is achieved at a thickness of 2500 m. This is indicative of a much
greater margin of their strength.

11.6 Biodeterioration of container/packaging materials


The storability of protective coatings depends on the efficiency of measures on protection
of constructions from corrosion, ageing and biodeterioration. It is known that most process-
es of metal corrosion and polymer ageing are associated with the impact of microorganisms.
According to the data by foreign investigators, damage from direct biodeterioration exceeds
3% of the volume of industrial products. More than 50% of all corrosion processes are re-
lated to the action of microorganisms. According to expert estimates, the cost of damage at
present exceeds 40 billion dollars.
In this connection, protection of lacquer-and-paint materials and coatings from prema-
ture degradation as the result of microbial and fungal action is an important economic prob-
lem.
Such materials as polymers, lacquer-and-paint materials and coatings, cements, con-
cretes, metals etc. find wide use at agroindustrial complex enterprises. Practically all of
them are subject to biodeterioration caused by bacteria and microscopic fungi. The most
aggressive biodegraders of agroindustrial materials are molds.
Molds are widespread in all over the world. They are present in soil, water and air.
Most molds possess the propagation energy. Owing to their microscopic size, spores can
penetrate into invisible cracks and pores in the material. Spores of molds are capable of ad-
sorption on the smooth surface. At the initial stages, they can use components of various
pollutants (dust, residues of fats, oils, greases etc.) available on the surface of materials as
sources of nutrition. Then, in the absence of elements of nutrition, the enzymic apparatus
of the mold rearranges to enable it to use new substrates as sources of nutrition.
Development of molds requires organic carbon and nitrogen, as well as mineral sub-
stances (biogenic elements P, Md, Ca, S, Fe and others), though their requirement is so
small that even particles available in the dust are sufficient. Many sources of carbon can be
assimilated by molds. Practically any carbon-containing compound (including those that
are poisonous for some molds) can be a source of nutrition.
The optimal temperature for the propagation of all species of molds is within the range
of 24 to 30C; molds in the vegetative stage die at a temperature higher than 80C and lower
than 10C.
The mold growth rate depends on the water absorption ability of a coating and the
moisture of the ambient air. Water is the main constituent part of the cell body of molds.
Nutrients arrive to the cell in a dissolved form, so for the mold to normally develop the en-
vironment should contain a large percentage of water. Fouling of the most diverse materials
by molds is due to the excess of moisture and high air temperature in the environment. An
382 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

optimal medium for the development of molds has pH 48. Strongly acidic and strongly
alkaline media are fatal for the bacteria.
Mold formation in a material is also affected by air flows and aeration. If materials are
moist, the air flow dries them and inhibits or stops the growth and development of molds.
Molds are typical agents of oxidative fermentation. It can occur only in the case when
microorganisms have special enzymes reductases promoting the incomplete degrada-
tion of hydrocarbons in the presence of oxygen of the air. As intermediate products of this
biochemical process, organic acids are formed (gluconic, fumaric, tartaric, malic, oxalic,
succinic and citric), which cause corrosion of metals and organic materials, erosion, reduc-
tion of weight, change of coloration, loss of strength etc.
Biochemical reactions caused by molds together with bacteria can be divided into two
groups:
1) anabolic (energy-consuming) processes, which lead to the formation of living mat-
ter and cell material and to the assimilation of nutrition;
2) catabolic (splitting) processes, which proceed with the evolution of energy.
In anabolic processes, molds (bacteria) make use of the components of material; name-
ly these biochemical processes contribute to deterioration (microbial corrosion).
Catabolic processes form aggressive metabolites, whose action is called the secondary
corrosive process.
One of the most widespread materials used by various enterprises are lacquer-
and-paint materials and coatings. Lacquer-and-paint materials and lacquer-and-paint coat-
ings used under conditions favourable for the growth and development of molds and bac-
teria (high temperature and air moisture) can be subject to microbial deterioration. Its
characteristic features are gray-green, brown and other colour spots and blooms of molds
and bacterial mucus on painted surfaces in places with increased humidity; cracking, exfo-
liation and delamination of coatings; formation of lumps and holes and other kinds of de-
terioration.
Biodeterioration of lacquer-and-paint coatings is usually combined with the damaging
action of other external factors atmospheric moisture with dissolved chemical substances,
sun light, elevated temperatures, etc., causing the ageing of materials. Processes of ageing
and biodeterioration can occur simultaneously or not coincide in time, but in most cases
they are complementary to one another, accelerating and aggravating the degradation of
materials and deteriorating their performance and decorative properties.
The main agents of microbial deterioration of lacquer-and-paint coatings are molds.
Bacterial damage is more rare and manifests itself in the form of colourless or coloured mu-
cous deposition. Microorganisms, deteriorating lacquer-and-paint coatings, are often rep-
resented by fungi of the genera Aspergillus, Penicillium, Fusarium, Trichoderma,
Alternaria, Cephalosporium, Pullularia; bacteria of the genera Pseudomonas and Fla-
vobacterium. The species composition of the molds deteriorating lacquer-and-paint coat-
ings is specific for each particular soil and climate zone. It is made up by the species, which
make the community characteristic of soils of this or that zone.
Molds develop on lacquer-and-paint coatings by either consuming the components of
coatings or substances polluting the surface of lacquer-and-paint coatings. Deterioration of
lacquer-and-paint coatings occurs as the result of the mechanical impact of mold mycelium
on the coating and under the action of metabolites excreted by micromycetes in their vital
activities (organic acids, amino acids, enzymes etc.). The latter were also found to cause a
decrease of the physicomechanical characteristics in lacquer-and-paint coatings, such as the
elasticity modulus, tensile strain and relative breaking elongation.
CHAPTER 11 383

Biodeterioration of lacquer-and-paint coatings occurs more often under conditions of


moist tropical and subtropical climate, as well as in constructions and premises with in-
creased humidity and temperature (enterprises of meat-and-dairy industry and canning in-
dustry, live-stock farms, pools, baths, etc.) Here they can inflict the greatest amount of
damage. However, even under conditions of a moderate climate, especially when the oper-
ating rules are violated, microbial decay can inflict a considerable amount of damage. In
regions with dry climate, such kind of deterioration is very rare.
One should distinguish between deterioration of lacquer-and-paint materials (especial-
ly of water-emulsion paints) by microorganisms at the stage of production (storage) and
biodeterioration of hardened lacquer-and-paint protective and decorative coatings applied
to supports. In the former case, microorganisms get into semifinished lacquers and paints
in the process of their production (with raw materials, water from the air of production pre-
mises, etc.); in the latter, spores of molds and bacteria precipitate on the surface of fabricat-
ed coatings from the environment, which is largely contributed to by various pollutions.
Characteristic features of biodeterioration of some water-soluble emulsion paints can
be the change of colour, gas formation (bulging of containers), appearance of foreign smell,
liquefaction and finally gelation.
Biostability of ready-prepared lacquer-and-paint coatings largely depends on their
composition, chemical nature of the polymer bonding adhesive and pigments. Biostability
is also affected by other components of lacquers and paints (solvents, thinners, stabilizers,
hardeners etc.), as well as by material to which the coating is applied, by the support. Thus,
coatings on wood are preserved better than on metal or silicate construction materials. On
ferrous metals, they are often less biostable than on nonferrous metals.
Biostability of lacquer-and-paint coatings also depends on the hydrophobicity of the
coating and the distribution of moisture condensate on the surface of material. The higher
the hydrophobicity of the coating, the greater its mold resistance is.
One should distinguish between the mold resistance of lacquer-and-paint materials and
that of lacquer-and-paint coatings. Cases are known when a lacquer-and-paint material re-
sistant to the action of micromycetes was deteriorated by molds in the system of lac-
quer-and-paint coatings; and the other way round, a mold-nonresistant lacquer-and-paint
material exhibited biostable properties. This is, probably, due to the fact that the mold re-
sistance of the system of lacquer-and-paint coatings depends on the composition of all its
components the support, the primer, the coating. Therefore, to be able to give recommen-
dations on the performance of lacquer-and-paint coatings from the point of view of their
mold resistance, it is necessary to study the biostability of not only individual components
of the system of lacquer-and-paint coatings, but of all the system as the whole.
The peculiar features of mold corrosion of lacquer-and-paint coatings on metals was
studied. As supports, use was made of aluminium alloys D16, AMg, AMts and A1-9 cov-
ered with primers EF-0137, VL-02 and AK-070. The supports were coated with enamel:
ML-12 (grey), ML-165 (silver), KhV-518, PF-115 (black), EF-1118M, FP-5246, PF-178.
As the result of the studies, it was found that systems of lacquer-and-paint coatings, where
the supports were alloys D16 and AMts, were more subject to damage by molds irrespective
of the variant of the experiment. An exception was the specimen of AMts with enamel
PF-178, on which the growth of molds did not exceed 1 point. The least damaged were spec-
imens of the alloy A1-9 at the application of primer EF-0137. The authors of that work note
that the difference in the mold fouling of metal specimens coated with lacquer-and-paint
coatings is rather difficult to explain, because the molds are not in direct contact with metal
and are on the surface of the protective coating. However, there are data on the high
384 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

vulnerability of aluminium alloys D16.


Studies of micromycete deterioration of lacquer-and-paint coatings on metals found
that enamels applied to aluminium and titanium alloys were affected by micromycetes to
various degrees. Such systems of lacquer-and-paint coatings as A1-9 + primer EF-0137 +
enamel ML-12 (grey), T-5 (titanium alloy) + primer VL-02 + enamel EF-1 I 8 and VT-10
+ primer VL-02 + enamel EF-1118 exhibited the highest resistance to molds.
Film-forming substances mainly determine the biostability of lacquer-and-paint mate-
rials and protective coatings on their basis. A crucial factor here is, on the one hand, the
chemical structure of a polymer film former and, on the other, its physical properties both
in nonhardened and hardened state (swelling capacity, moisture-holding capacity, hardness,
smoothness of the surface, porosity etc.).
A relationship between the chemical structure of film formers used and the growth rate
of a number of widespread strains of molds was established.
Out of the number of investigated film-forming substances, synthetic film-forming
polymers (thermoplastic and thermosetting) possess the best biostability. The mold biosta-
bility of these coatings decreases in the following sequence: epoxy, polyurethane,
melamine alkyd, organosilicon, pentaerythritol-modified phthalic. An increased rate of
hardening of the film-forming substance, decrease of the water absorption ability, rough-
ness and porosity of the film contribute to the increase of mold resistance. Smooth glossy
uniform films are more stable because they are less contaminated, and spores of molds ad-
sorb on them less.
Among natural film formers, the most widespread are drying oils oils of plant origin
(flax, cotton, hemp-seed, sunflower, tallow etc.). All of them possess a relatively low mold
resistance, because they are a good nutritive substrate for microorganisms. Considering the
relation between the drying rate and the mold resistance, the quick-drying Chinese wood
oil, which contains glycerides of fatty acids with several conjugated double bonds, is attrib-
uted to the best oils. Slowly drying oils, such as flax, soybean, cotton-seed etc., which rep-
resent glycerides of fatty acids with double nonconjugated bonds, are considered to be less
biostable.
Organic impurities decrease the biostability of oils; for this reason, oils used in fabri-
cation of lacquer-and-paint materials are refined. The characteristic consequences of the de-
terioration of vegetable oils by molds are a significant decrease of their viscosity, an
increase of acidity and, as the result, a worsening of the polarization capability, i.e., the rate
of forming the film and its protective properties.
Of natural resins used as film formers in lacquer-and-paint materials, shellack varnish,
wood rosin and copal possess an increased resistance to microbial deterioration. The resis-
tance of wood rosin to the action of micromycetes is associated with the presence of terpe-
nes, which possess fungicidal properties, as well as with the formation of acidic products
in the film during the production of the protective coating.
Bitumens used as film formers have insufficient biostability. To increase the biosta-
bility, the composition of bitumen lacquers and bitumen protective coatings is supplement-
ed by phenolic, maleic and other synthetic resins.
Thermoplastic synthetic resins used for production of quick-drying lacquers form solid
coatings, as a rule, with high biostability. Biostable resins include indene and cumarone res-
ins, chlorinated rubber, polystyrene and its copolymers with butadiene, copolymer of vinyl
chloride with vinyl acetate etc.
A widespread polymer bonding adhesive is the polyvinyl acetate dispersion. Paints,
coatings, mastics, primers and other materials on its base are mold-nonresistant.
CHAPTER 11 385

Noplasticized dispersions are affected by molds stronger than plasticized ones. Not only
coatings from polyvinyl acetate paints are mold-nonresistant, but also the liquid paints
themselves, which in the process of storage are affected by molds and bacteria. Herewith,
their viscosity decreases, gaseous products are formed, etc.
Thermosetting synthetic resins (glyptal, pentaerythritol-modified phthalic, epoxy, sil-
icon, urea-formaldehyde etc.) used in hot- and cold-hardened lacquers and enamels possess
a high biostability; what is more, some of them even exhibit fungicidal properties. Coatings
from them are distinguished with a high hardness, smoothness and low permeability, which
contributes to the increase of biostability.
Water-soluble film-forming substances (represented by cellulose derivatives and pro-
tein compounds: dextrin, gum, gelatin, albumin, casein, etc.) are deteriorated by molds.
Their decreased biostability is associated with inherent hygroscopicity and capability of
swelling. Under humid conditions, microscopic fungi often deteriorate casein, dextrin and
other water-emulsion glue colours.
In contrast with organic water-soluble film formers, inorganic film formers possess a
high biostability. An example of such film formers is liquid glass used in production of sil-
icate paints.
Another important component, which determines the biostability of lacquer-and-paint
coatings, is pigment. Pigments confer the required colour and covering capacity to the paint,
regulate viscosity, improve the resistance to solar radiation and water resistance of the coat-
ing. Owing to the increased hardness, pigment particles mechanically hinder the growth and
development of mycelium. They can also have a toxic effect on molds and other microor-
ganisms.
Zinc oxide, copper oxide, barium metaborate and some other pigments possess fungi-
cidal properties and, therefore, increase the biostability of lacquer-and-paint coatings. At
the same time, such pigments as chalk, chrome yellow, titanium dioxide, aluminium pow-
der, chromium oxide, carbon black do not possess biocidal properties by themselves; how-
ever, oil paints on their base possess an increased fungal resistance. Oil paints with
pigments of antimony and lead oxides, lithopone (a mixture of ZnS and BaSO4 in the form
of fine powder) are distinguished by a lower mold resistance. Titanium dioxide and lead
titanate, introduced into lacquer-and-paint materials, produce coatings yielding to deterio-
ration by molds. Zinc oxide mixed with lead oxide communicate a better biostability to a
protective film of lacquer-and-paint coatings than zinc oxide mixed with lead carbonate.
A number of inorganic pigments and fillers, for instance, talcum, graphite, muscovite
mica reduce the resistance of lacquer-and-paint coatings to microbial deterioration.
One of the factors causing the corrosion of metals and alloys in the atmosphere, in con-
tact with water and soil is microbial action. Biodeterioration of metals and metal construc-
tions is commonly called biocorrosion.
It was found that during the growth on materials directly contacting with metals (tis-
sue, lacquer-and-paint materials, fuel), microscopic fungi can enhance the corrosion of met-
al constructions. The action of microorganisms on metals can be different. First of all,
corrosion of metals can be caused by aggressive microbial exometabolites mineral and
organic acids and bases, enzymes etc. They create a corrosion-active medium, in which, in
the presence of water, corrosion proceeds according to the usual laws of electrochemistry.
Colonies of microorganisms can create overgrowths and films of mycelium or mucus,
under which corrosion pits can develop as the result of the electrical potential difference at
various regions of the metal surface and assimilation of metal ions by microorganisms
themselves.
386 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Metal corrosion caused by bacteria can proceed under aerobic and anaerobic condu-
tions.
Active aerobic corrosion agents are iron bacteria, thionic bacteria, nitrifying bacteria
and some others, which form corrosion metabolites.
Under anaerobic conditions, metal corrosion is accelerated in the presence of dinitri-
fying and especially sulfate-reducing bacteria. The basis of microbial action on metals is an
electrochemical process.
It was found that the mechanism of the corrosion process of iron, which involves
sulfate-reducing bacteria, is related to cathodic depolarization. In the process of metabo-
lism, sulfate-reducing bacteria consume hydrogen atoms formed on the surface of corroding
metal and, thus, perform cathodic depolarization in the absence of oxygen.
The mechanism of anaerobic corrosion involving sulfate-reducing bacteria can be pre-
sented in the form of the following reactions:
Anode reaction

4Fe 4Fe2+ + 8e;


8H2O 8H+ + 8OH;

Cathode reaction

8H + + 8e 8H.

Cathode depolarization involves the participation of bacteria:

SO42 + 8H S2 + 4H2O.
Corrosion products

Fe2+ + S2 FeS;
3Fe2+ + 6OH 3Fe(OH)2.
The general reaction:

4Fe + SO42 + 4H2O FeS + 3Fe(OH)2 + 2OH


The action of fungi on metals often leads to the deterioration of electrical and physico-
mechanical parameters of articles, in which these metals are used. A decrease of strength
in various grades of steel, aluminium, titanium and copper alloys is observed at the action
of fungi on them.
Efficient biocides, their peculiar features and the mechanism of their action in polymer
coatings of various chemical composition were reviewed.
Among the basic methods of protecting materials from biodeterioration by micro-
organisms, the following can be singled out:
1. Mechanical elimination of pollution.
2. Maintenance of the correct sanitary-hygienic and temperature-moisture regime
(20 > t C > 60; humidity no less than 80%, aeration).
3. Physical methods (bacterial filters, electromagnetic and radioactive irradiation, UV,
ultrasound, electrochemical protection, etc.).
4. Hydrophobization of the surface.
5. Prevention of the penetration of microorganisms to the object of biodeterioration
(sealing, air purification, vacuum, biocide gas medium).
CHAPTER 11 387

6. Removal of one of the elements required for microbial growth (use of chelate com-
pounds of iron and magnesium, binding one of the metals required for microbial growth).
7. Biological protection (antagonism, competition of microorganisms, negative
homeostasis of fungi and bacteria).
8. Development of materials with preset properties by their biostability (for one or
several components of material to possess biocide properties).
9. Chemical means of protection (biocides). The use of biocide compounds is one of
the most efficient and widespread methods of protection.
Biocides used for eradication of microorganisms should not worsen the performance
properties and toxicological safety of coatings.

11.7 Effect of the polymerization initiation method on the formation and


properties of coatings for transport containers
Along with chemical initiation of polymerization, a great effect on the formation and prop-
erties of coatings is rendered by the method of power supply in hardening of the systems.
The most widely used methods for this purpose are convection heating, radiant heating and
ultraviolet radiation.
Effects of various ways of power supply on the formation and properties of polyester
coatings were studied to choose optimal conditions of hardening. Convection heating was
carried out using two regimes, usually used in the industry: at 60C for 8 h and stepwise
40 min at 60C and 40 min at 80C. Radiant-heat infrared drying of polyester coating
applied to glass supports was done under ZS lamps (power 500 Wt). The averaged results
of the studies are given in Table 11.14.
Table 11.14 Dependence of internal stresses on the method of hardening of coatings
from lacquer PE-220.

Hardening technique Internal stresses, MPa

Convection 1.3
Stepwise convection 2.0
Radiant heating 3.0

The largest internal stresses emerge in hardening of coatings by infrared beams. The
simultaneous impact of heat and infrared radiation accelerates the polymerization process
and contributes to the nonuniform hardening of coatings, probably, due to the low perme-
ability of infrared radiation.
With the thickness of coatings increased, the influence of the method of power supply
on the value of internal stresses decreases (Fig. 11.10).
The observed regularities in the change of internal stresses depending on the method
of hardening do not depend on the nature of the support and were also observed for polyester
coatings formed on various kinds of wood. In the formation of coatings on wood, radiant
heat was carried out stepwise: first at a heating-surface temperature of 100C and the dis-
tance of 100 mm from the heater; heating time, 30 min. At the second stage, the heating
was performed at a heating-surface temperature of 180C for 5 min at the same distance
from the heater. In all methods of hardening, the coatings were formed to the same hardness.
The breaking strength of films was determined at the loading rate of 14 mm/min. With
consideration of these data, a conditional reserve of the cohesion strength was calculated,
388 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

b, MN/m2
1
7 2
3
6

5
4
4

3 6 9 12 15 , h

Figure 11.10 Kinetics of internal stresses in hardening of polyester coatings by infrared illumina-
tion (1, 3) and by the convective method (2, 4) at a film thickness of 200 m (1, 2) and 100 m (3, 4).

and the accelerated test of the durability of coatings hardened by various methods was car-
ried out.
The reserve of strength determined in this way is a conditional characteristic and
makes it possible to obtain relative data on the efficiency of using this or that method of
hardening, as the value of strength depends on the loading rate.
Accelerated tests for durability consisted in alternation of low temperature 40C for
1 h and 60C also for 1 h in repeating cycles (Table 11.15). Coatings with the highest in-
ternal stresses were the least durable. Based on these data, the convection method of drying
Table 11.15 Dependence of internal stresses (b), breaking strength (p) and longevity () of
coatings, formed on nuts, on the hardening method.

Hardening technique p, MPa b, MPa Strength margin Longevity, cycles

Convection 13.3 1.8 7 14


Stepwise convection 11.2 3.0 4 2
Convection at increased moisture 16.6 2.6 8 10
content (50 min at 90C)
Radiant heating 10.3 11.0 1 1

can be recommended. The most efficient method is hardening under the action of ultraviolet
radiation. The specific feature of this radiation is that it easily penetrates through the lacquer
coatings and causes their uniform hardening in the bulk. PRK-2 lamps were used as a source
of radiation. In this method of formation, hardening of coatings from various polyester lac-
quers occurs in 1015 min at a small value of internal stresses, by an order of magnitude
smaller than in the convection method. This method is especially efficient in the formation
of coatings from cold-hardened lacquers characterized by a relatively low adhesion.
CHAPTER 11 389

CO,%
4 1
100
3

60 2 5

20

10 30 50 , h

Figure 11.11 Change of the number of CO groups of the polyester in ultraviolet radiation of non-
filled coatings (1); filled with aerosil (2); with aerosil modified with 2% (3), 10% (4) and 39% (5)
octadecyl amine (ODA).

Hardening under the action of ultraviolet radiation is observed to improve the adhesion
and physicomechanical properties of coatings.
Using the method of IR spectroscopy, it was found that in this method of formation
the time of utilizing double bonds of unsaturated polyester and styrene is reduced to 1015
min. The cause of this phenomenon was determined by an additional initiation of polymer-
ization under the action of ultraviolet radiation as the result of the increase of the number
of free radicals. Polyester coatings are characterized by a high degree of permeability for
ultraviolet radiation, up to 8 mm.
The mechanism of formation of polyester coatings under the action of ultraviolet ra-
diation in the presence of photostabilizer was studied. Octadecyl amine (ODA) was used as
a photostabilizer; its NH groups interact with hydroxyl groups of the surface and under def-
inite conditions can enter into interaction with CO groups of the polyester.
The rate of formation and decomposition was assessed by the change of the intensity
of the absorption band of polyesters CO groups in the process of irradiation and the change
of internal stresses, which were determined by the photoelastic method.
Studies of the structural transformations in ultraviolet irradiation of coatings filled
with aerosil showed that in filled systems particles of aerosil are sites of forming more or-
dered secondary supramolecular structures, which emerge as the result of the interaction of
polyesters CO groups with OH groups of the surface of the filler to form hydrogen bonds.
In the presence of the filler, the structure of polyester coatings is more resistant to the action
of ultraviolet radiation.
In modification of the fillers surface by 2% ODA, the rate of decomposition sharply
increases as the result of interaction at the polymerfiller interface (Fig. 11.11).
In the complete substitution of NH groups of the modifier for OH groups of the surface
of aerosil as the result of adsorption of ODA by the surface of the filler in the amount greater
than the monomolecular layer, part of the modifier at the treatment of specimens with a so-
lution of polyester resin, probably, leaves the surface of the filler and can interact with poly-
ester to form a hydrogen bond between NH groups of the modifier and CO groups of the
resin. This is indicated by a sharp increase of the arm on the side of the low frequencies at
the absorption band of CO groups, observed earlier for systems containing aerosil modified
by 10% ODA.
390 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Introduction of excess modifier with respect to OH groups of the surface of aerosil


leads to the further, even sharper, decrease of the rate of decomposition under the action of
ultraviolet radiation.
The effect of ODA on the molecular processes in ultraviolet radiation of nonfilled
coatings was studied to elucidate the role of ODA in structural transformations during the
formation and ageing of polyester coatings. Table 11.16 presents the data on the change of
the number of CO groups in polyester coatings containing 110% ODA at various stages
of ultraviolet radiation. With the irradiation time increasing, the intensity and halfwidth of
the absorption band of valent vibrations of polyesters carbonyl groups change. A decrease
of intensity of the absorption band of CO groups in the process of ultraviolet radiation in-
dicates complex oxidative conversions in coatings, probably due to, as in the case of thermal
decomposition, the formation of volatile oxidation products evolving in the bulk.

Table 11.16 Change of optical density of the absorption band of polyester CO group depending on
the radiation time and concentration of ODA.

Content of ODA in Radiation time, h


polyester, %

0 5 6.5 13 26 31 46
1 1.382 1.151 0.570 0.477 0.316
2 1.329 0.558 0.419 0.088 0.028
3 1.054 0.403 0.396 0.277 0.083

The rate of these processes and the change of the number of interacting functional
groups were assessed as the ratio of the differences of optical densities in the maximum of
the initial absorption band and the absorption band after irradiation to the initial optical den-
sity. Data on the change in the amount of carbonyl groups in the process of ultraviolet ra-
diation of the polyester coating are presented. In the first 5 h of irradiation more than 50%
of all CO groups of the polyester are degraded. Further on, the rate of the process sharply
slows down, and it is totally completed in 100 h of irradiation. At the introduction of 1%
ODA into polyester coatings, the rate of oxidative processes in ultraviolet radiation sharply
slows down and makes only 10% in 10 h of decomposition.
At a further irradiation, the rate of decomposition increases, remaining much lower
than the rate of oxidative processes in nonmodified polyester coatings.
With the content of the modifier increased up to 2%, the rate of decomposition of poly-
ester molecules increases as compared with nonmodified coatings; in 10 h of irradiation, it
is 90%. At a significant content of the modifier in the system, the transparency of specimens
decreases, and the rate of decomposition of polyesters CO groups slows down insignifi-
cantly as compared with coatings from nonmodified oligoester. This character of change of
the decomposition rate is associated with the fact that particles of ODA at an optimal con-
tent of modifier under the action of ultraviolet radiation interact with polyester to form a
hydrogen bond between CO groups of the resin and NH groups of the modifier. This is in-
dicated by a sharp increase of the halfwidth of the absorption band of the carbonyl groups
in the process of ultraviolet radiation of coatings as compared with an increment of the half-
width of the absorption band of the same groups in the absence of ODA. At a further in-
crease of the content of ODA, the absorption halfwidth of polyesters CO groups slightly
decreases, which is, probably, due to the restricted amount of NH groups of the modifier,
the same way as with OH groups of aerosil. Therefore, the further increase of the content
CHAPTER 11 391

of ODA contributes to the aggregation of modifiers particles and a worsening of its inter-
action with the polyester.
The greatest increase of the halfwidth of the absorption band of CO groups in the pres-
ence of 1% ODA is observed in the induction period. A slight decrease of the rate of de-
composition at a large content of ODA in the system (in the amount of 10%) is, probably,
due to a decrease of the transparency of coatings with respect to ultraviolet radiation.
The interaction of the polyester with the modifier added in an optimal amount contrib-
utes to an increase of the durability of coatings under conditions of ultraviolet radiation.
Along with the intensity of the absorption bands of carbonyl groups in the process of ultra-
violet radiation of polyester, one also observes a change in the intensity of the absorption
bands of ethers and esters. The rate of conversion of these groups is much greater than of
CO groups and depends on the content of ODA in the system (Table 11.17). These groups

Table 11.17 Change of optical density of the absorption bands of ester groups depending on the
radiation time and concentration of ODA.

Content of ODA Irradiation time, h


in polyester, %
0 5 6.5 9 13 21 26

Ether bond 1140 cm


0 0.328 0.070 0.055
1 0.502 0.202 0.224 0.170 0.130
2 0.466 0.100 0.060 0.054
10 0.462 0.149 0.130 0.114 0.048
Ester bond 1300 cm
0 0.415 0.122 0.092
1 1.048 0.403 0.434 0.355 0.269 0.109
2 0.852 0.156 0.090 0.065
10 0.852 0.255 0.209 0.193 0.066 0.045 0.0057

are, apparently, involved in the formation of hydroperoxides, which are degraded in the pro-
cess of irradiation. We failed to record the emergence of hydroperoxides by the method of
IR spectroscopy, probably, due to the high rate of their degradation.
Figure 11.12 presents the data on the kinetics of change of internal stresses in polyester
coatings. In the presence of ODA, the rate of increment of internal stresses is greater than
in nonmodified coatings, both in thermal hardening and in ultraviolet radiation, which is
indicative of faster polymerization processes. Herewith, the value of internal stresses in
hardening under the action of ultraviolet radiation is 1.52 times smaller than in thermal
hardening (Fig. 11.12). The formation process under the action of ultraviolet radiation pro-
ceeds much faster and is practically complete in 3060 min after the onset of irradiation,
whereas in coatings hardened at 80C it is complete in 4 h. In irradiation for more than 20
h, internal stresses are increased but to a significantly lower degree than in coatings ob-
tained in thermal hardening.
It is seen from the data adduced that a sharp increment of internal stresses at a content
of 2% ODA in the system, as well as of the halfwidth of absorption of carbonyl groups and
the rate of their conversion, are observed only at the action of ultraviolet radiation and are
not found in thermal hardening of the coatings.
392 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

a 2
4

b, MN/m2
3

2 1
3
1
4

8 50 100 200 600 , h

2 2
b 3
1
b, MN/m2

1
4

2 4 40 80 , h

Figure 11.12 Kinetics of internal stresses in polyester coatings non-modified (1) and modified with
1% (2), 2% (3) and 10% (4) ODA: a, hardening at 80C in the presence of an initiator and an accel-
erator followed by UV irradiation; b, without catalysts under the action of UV irradiation.

The second feature of the processes proceeding in polyester coatings in the presence
of a modifier is that they are exhibited most efficiently at a strictly definite content of the
modifier in the system (in the amount of 2%) irrespective of the method of its introduction
(whether the modifier is introduced directly into the solution of polyester or together with
the filler). This is, probably, due to the fact that formation of coatings, the same way as their
ageing, is the most efficient at a certain content of hydroperoxide in the system, which in
the given case is regulated by the content of ODA in the polyester. At its direct introduction
into the polyester, the rate of increment and relaxation of internal stresses in the process of
ultraviolet radiation is much greater than in coatings filled with aerosil codified by ODA.
An increase of the rate of chemical conversions in modified nonfilled coatings as compared
with filled ones is, probably, due to the more uniform oxidative processes along the thick-
ness of filled coatings as the result of their greater permeability for ultraviolet radiation, be-
cause in more thin films used for recording IR spectra of filled and nonfilled systems these
differences in the rate of oxidative processes are less essential.
From the adduced data, it follows that ODA is a regulator of the rate of hydroperoxide
formation in the system under the action of ultraviolet radiation; at a definite content in the
system, it can on the one hand harden polyester coatings without introducing usually
used initiators and accelerators of polymerization and on the other hand sharply de-
crease the rate of ageing of polyesters as the result of the interaction of NH groups of the
modifier and CO groups of the polyester to form a hydrogen bond.
From the data on the structure of polyester coatings hardened as the result of initiation
of polymerization by various methods, it is seen that the most ordered homogeneous struc-
ture is obtained at the initiation of polymerization by ultraviolet radiation.
CHAPTER 11 393

Taking into account these regularities, methods of modifying epoxy resins by acrylic
monomers were proposed, which also make it possible to produce rapidly hardened coat-
ings with ordered structure providing for a sharp reduction of internal stresses and high per-
formance properties. The statement of this problem is due to the fact that epoxy resins are
widely used in industry for production of coatings, glueing layers of sealants, bonding ad-
hesives in production of materials and articles for various purposes owing to high adhesion
and physicomechanical characteristics.
However, coatings produced based on epoxy oligomers also have a number of essen-
tial drawbacks. The process of hardening of epoxides is comparatively slow and even at
high temperatures is completed in several hours. The high adhesion of epoxides to the sur-
face of solid bodies is accompanied by a sharp inhibition of the relaxation processes in the
formation of coatings and the emergence of significant internal stresses, in some cases com-
mensurable with the value of adhesion.
A decrease of internal stresses in the formation of epoxy coatings by introducing plas-
ticizers and regulating the temperature regime of hardening leads to the simultaneous wors-
ening of adhesion and strength properties of coatings.
A characteristic feature of epoxides is also that they form coatings with a globular
structure inhomogeneous along the thickness and area of the film and significantly depen-
dent on the nature of the support.
With consideration for this, of great practical importance is the development of meth-
ods of modifying epoxides and the physicochemical routes of their hardening providing for
the formation of a homogeneous structure and a decrease of internal stresses in coatings.
Modification of epoxy resin ED-16 was carried out by etherification of methacrylic acid in
the medium of butyl methacrylate and methyl methacrylate taken at a ratio of 1:1 and mak-
ing 50% of the weight of etherifying components. Dimethylalanine was used as a catalyst.
The results of the kinetic studies indicate that the etherification of epoxy resin under these
conditions is a second order reaction. Hardening of coatings was carried out by the method
of photopolymerization under the action of ultraviolet radiation.
The coating formation process was studied by the yield of the gel fraction using the
method of IR spectroscopy by the change of intensity of the characteristic band of vibrations
of the group CH2=C in the region of 16001640 cm 1, as well as by studying the kinetics
of increment and relaxation of internal stresses and by the change of the physicomechanical
properties. The change of the properties in photopolymerization was compared with the
character of structural transformations at various stages of hardening of the coatings, which
were investigated by the method of electron microscopy using oxygen etching of speci-
mens.
The adduced data on the dependence of the yield of the gel fraction on irradiation time
for an epoxyacrylic composition with 60 and 75% etherification indicate that the character
of the curves is identical, and the major part of chemical bonds involved in the formation
of the three-dimensional network emerge after 1 min of irradiation. The polymerization pro-
cess is totally completed in 3 min of irradiation, after which decomposition of the polymer
begins. The yield of the gel fraction in films from epoxyacrylic oligomers is 9798.5%.
The extent of etherification of epoxy esters has an insignificant effect on the rate of
polymerization and the yield of the gel fraction. This conclusion is also supported by the
data on the studies of the coating formation kinetics by the method of IR spectroscopy.
Data on the kinetics of photopolymerization of epoxy acrylic oligomers in the produc-
tion of coatings of various thicknesses were presented. It is seen that at a thickness of 10
m the formation of coatings studied by the change of intensity of the absorption bands of
394 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

1
2
5.0
3
Internal stresses, MPa, MPa

Impact strength, Nm
2.0 2.0 4.0

Adhesion, MPa 4
3.0
5

1.0 1.0 6 2.0

1.0

0 0
1 2 3 4
Irradiation time, min

Figure 11.13 Dependence of adhesion strength (1, 2), impact strength (3, 4), internal stresses (5, 6)
for epoxy coatings with the etherification degree of 60% (1, 3, 5) and 75% (2, 4, 6).

the double bonds in the region of 16401660 cm 1 is completed in 30 s of irradiation. With


the thickness of the film increased up to 40 m, the formation of the three-dimensional net-
work is completed in 2 min.
Figure 11.13 presents the data on the kinetics of change of the physicomechanical pa-
rameters in photopolymerization of epoxyacrylic oligomers. It follows from the figure that
most parameters for all systems reach a maximum in 3 min of irradiation.
Comparison of the regularities of change of the physicomechanical characteristics
with the kinetics of polymerization indicates the absence of correlation between the rate of
polymerization and the rate of formation of chemical bonds in the formation of the three-
dimensional network responsible for the mechanical properties of coatings. The absence of
such a correlation was also observed in studies of the mechanism of formation of the three-
dimensional network in thermal hardening of coatings.
It is also noteworthy that, with the extent of etherification of epoxy esters increasing,
the physicomechanical characteristics and the rate of their increment in the process of hard-
ening are decreased.
To understand the mechanism of formation of the three-dimensional network in pho-
topolymerization, the supramolecular structure of coatings at various stages of hardening
was studied. The structure of coatings from epoxyacrylic oligomers at various stages of
their photopolymerization on metal and glass supports was presented. An inhomogeneous
structure was found to emerge in coatings on metal in 2 min of irradiation. Along with glob-
ules of about 10 nm in diameter, larger structures of anisodiametric type emerge, and also
separate areas are observed, the structure of which is not revealed. A homogeneous network
structure from densely packed anisodiametric structural elements was observed after irra-
diation for 3 min. An increase of the photopolymerization time leads to the breakdown of
anisodiametric structures.
CHAPTER 11 395

The process of structure formation proceeds slower for coatings on a glass support,
which is distinguished by a smaller adhesion to epoxyacrylic oligomers. After 2 min of ir-
radiation, the structure of coatings under these conditions is revealed not clearly; only in-
dividual supramolecular formations of about 5 nm in diameter are observed. In irradiation
for 3 min, an inhomogeneous structure from globules of 1520 nm in diameter and their
aggregates are revealed. A further increase of irradiation time causes the structure to de-
compose.
Under deep-conversion conditions of thermal hardening of coatings at 100C for 2 h,
a globular-type structure of about 3040 nm is formed; herewith, the surface layers of coat-
ings are found to have secondary supramolecular formations, which deteriorate the decora-
tive and protective properties of coatings and are characteristic of coatings from oligomer
systems with the statistical distribution of functional groups, obtained in thermal hardening
of oligomers, in the oligomer block. Formation of this structure is accompanied with a sharp
increment of internal stresses.
From the adduced data, it follows that the process of photopolymerization, the same
way as that of thermal polymerization, is multistage and proceeds via the stage of supramo-
lecular structures formation at the initial stage of hardening. From the analysis of the ki-
netic data, it follows that at the onset of irradiation the polymerization proceeds within a
small number of molecules and is accompanied with the formation of supramolecular struc-
tures. At a further irradiation, in the formation of coatings on supports with high adhesion,
structural elements get oriented and a homogeneous network structure from anisodiametric
structural elements is formed.
A sharp increment of the physicomechanical parameters is observed at the second
stage and corresponds to the formation of chemical bonds between supramolecular struc-
tures.
An increase of the extent of reetherification of epoxy esters to higher than the optimal
value (60%) leads to the worsening of intermolecular interaction in the system and to the
formation of an inhomogeneous imperfect structure, consisting of globules and their aggre-
gates, in the process of irradiation. This is indicated by the data for coatings from epoxy-
acrylic compositions with a 75% reetherification of epoxy ester.
Comparison of the specific features of structural transformations in the formation of
coatings using various physicochemical methods of hardening is indicative of the signifi-
cant advantages of photopolymerization. Unlike thermal hardening and along with the con-
siderable rate of hardening up to a high extent of conversion, it enables production of
coating with a homogeneous structure and higher physicomechanical characteristics.

11.8 Studies of the possibility of using stabilized radicals in protective


coatings
Works on chemical reactions have since long ago mention free radicals, i.e., molecular frag-
ments with very small lifetime and high reactivity, characterized by the presence of an un-
paired electron.
However, due to a high activity of radicals, their concentration in reacting chemical
systems is extremely small, and their lifetime is, as a rule, 10 3 10 10 s. Chemists have
always tried to obtain stable radicals, resistant under usual conditions, which would exist
as individual substances. Organic stable radical paramagnetics of various chemical classes
have been synthesized, including the most known of them diphenyl picryl hydrazyl. Un-
fortunately, all of them decomposed comparatively rapidly, were poorly soluble and
396 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

unstable to oxygen; what is more, many of them could be obtained by complex and not eas-
ily accessible syntheses. Those radicals found no use in practice.
In 1970s, researchers at the Institute of Chemical Physics, USSR Academy of Sciences
developed a new class of organic paramagnetic substances nitroxyl radicals of the follow-
ing structure:
X X
X X

N N N N
O O O O
where X are the substituents of a very diverse structure, for instance,
CH2 CH2 CH2 CN
H, Cl, Br, CN, OH, COOH; NH2; NH3+ ; O ; N etc.
CH2 CH2 CH2 CN

To date, several hundred of this class of substances have been synthesized; all of them
are paramagnetics in solution, in the gas phase, crystals and in the melt. Nitroxyl radicals
have a simple chemical structure, are stable within a broad temperature range from 270
up to +250C, are resistant to oxygen, alkali and acids, soluble in most liquids and organic
solids (the solubility can be easily regulated by changing the substituent X). The lifetimes
of these radicals under usual conditions are many years and decades.
The first nitroxyl radical was synthesized and isolated by O.L. Lebedev and
S.N. Kazarnovsky. The significance and prospects of the new class of radicals was ap-
praised by M.B. Neiman, who initiated these works at the Institute of Chemical Physics,
USSR Academy of Sciences.
New and simple methods for the synthesis of radicals have been proposed; they were
found to possess a unique property the ability to react without affecting the unpaired elec-
tron, i.e., preserving the paramagnetism.
The ability of radicals to preserve the paramagnetic centre enables the synthesis of new
paramagnetic materials polymers, antibiotics and other drugs, in particular, anticancer
preparations. The same ability opened an exceptional possibility of introducing the already
prepared radicals into other molecules, which in this case become radicals and acquire para-
magnetic properties. The potential of assembling paramagnetic molecules of any structure
is practically unlimited.
An exceptional contribution to the chemistry of nitroxyl radicals was made by
M.B. Neiman and E.G. Rozantsev; reactions without affecting unpaired electron
(NeimanRozantsev reactions) are broadly used by chemists and biochemists all over the
world. Dozens of NeimanRozantsev reactions have been developed; organometal radicals
containing thallium, mercury, iron and other substances have been synthesized; paramag-
netic polymers have been obtained. Individual polyradicals of the type of R and , in which
paramagnetic fragments R are joined by bridges into a united molecular system, have been
developed; the number of unpaired electrons in such systems n = 2, 3, 4 and more.
Along with reactions without affecting the paramagnetic centre, nitroxyl radicals par-
ticipate in typical radical reactions: at elevated temperatures they break loose atoms of H,
Cl and other elements and attach themselves to multiple bonds; attach many active radicals
CHAPTER 11 397

leading chemical reactions; the latter property of accepting active radicals is of special in-
terest. It is essential that even if chemical reactions affect unpaired electron and are accom-
panied with the loss of paramagnetism, the paramagnetic centre is easily regenerated and
paramagnetism is restored by simple chemical actions.
The causes of unusual stability of nitroxyl radicals consist in, first, the sharing of un-
paired -electron between atoms of N and O and a reduction of its energy level; second, in
a strong spatial screening of the paramagnetic centre by four bulky methyl groups.
The ability of nitroxyl radicals to trap other active particles opened large vistas for us-
ing radicals in chemical technology as inhibitors and regulators of the processes of poly-
merization, oxidation, epoxidation etc.
Nitroxyl radicals and their molecular precursors sterically hindered amines (SHA)
are used as nontarnishing light-protective additives, which protect polymers from degrada-
tion and extend the service life of polymer articles (especially films and fibres). By their
quality, new light stabilizers significantly exceed the best Western specimens; processes of
their production have been developed.
Generalizing the works on the use of nitroxyl radicals and SHA as stabilizers of poly-
mer, the following basic directions of research can be singled out:
1. Development of methods for the synthesis of multifunctional stabilizers, which con-
tain in one molecule a fragment of both SHA or nitroxyl radical and a UV adsorber, organic
phosphite, sterically hindered amine, thioester, derivatives of metals, especially nickel, etc.
Introduction of UV adsorber fragments is usually expressed in an enhanced efficiency
of photoprotective action owing to the different synergic mechanism between the UV ab-
sorber and antioxidant, and fragments of UV adsorber can quench the excited state of ni-
troxyl responsible for the photochemical change. Introduction of an additional group of
antioxidant is mainly associated with the necessity to increase the stability of material in
the process of its use.
2. Works to obtain compounds including several sterically hindered amines or nitroxyl
fragments. The mechanism by means of which the efficiency of photostabilizers with two
or more sterically hindered fragments increases has not been established. Empirically, the
efficiency of nitroxyl in the inhibition of thermal oxidation of polypropylene was observed
to increase with the rise of the number of paramagnetic centres in the molecule. The effi-
ciency of thermal stabilizers of biradical type increases when the distance between the para-
magnetic centres decreases.
This phenomenon is observed, probably, owing to the reaction of alkyl radical, which
is formed in the interaction of polymer with nitroxyl of another nitroxyl group. This reaction
sterically hinders the initiation of oxidation by nitroxyl radical. There is no satisfactory ex-
planation to the increase of the efficiency of photostabilizer with the rise of the number of
NH groups, because polyradicals are formed in the photooxidation of sterically hindered
amines.
3. Stabilizers of high compatibility with polymers were synthesized; several fragments
were introduced into the stabilizer, for instance, alkyl substituents provide for a high effi-
ciency of photostabilizers for polyolefins. Some characteristics of the structure of stabiliz-
ers, apparently, contribute to their accumulation in the sites of photooxidation. This is
especially applicable for polypropylene, which is oxidized inhomogeneously.
4. Methods for the synthesis of stabilizers from sterically hindered amines were being
developed with the aim to reduce the costs and use accessible raw materials.
The mechanism of action of photostabilizers of polymers from sterically hindered
amines evoked a great interest after numerous reports of their high efficiency.
398 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

At present, the following methods are used for protection of polymers against photo-
oxidation:
1. Use of substances to be added to the polymer composition, which first adsorb UV
radiation and then release adsorbed energy in the form not destructive for the polymer.
These components called UV adsorbers protect the polymer against UV radiation by direct
adsorption.
2. Incorporation of substances, which can catalyze non-radical degradations of hydro-
peroxides, into the polymer.
3. Incorporation of substances, which can deactivate the photoexcited state, into the
polymer.
4. Use of substances (antioxidants) capable of trapping free radicals propagating as the
result of oxidation, by means of which oxidized chains are disrupted.
Sterically hindered amines, nitroxyl radicals and products of their conversion can not
act according to the mechanism of screening UV beams or quenching photoexcited states.
Their action is mainly due to their involvement into the oxidation processes, which take
place in photooxidation of polymer. Thus, they act as radical-trapping antioxidants. But a
number of important features distinguishes them from usual aromatic antioxidants (phenols
or amines), which are weak polymer photostabilizers.
Several reactions can be involved in providing protection for the polymer against pho-
todegradation. The contribution of each of the processes depends on the nature of polymer
and oxidation conditions. The time within which sterically hindered amine is converted into
nitroxyl in polypropylene is small as compared with the induction period. At the same time,
piperidines and respective nitroxyl radicals are almost equal by the efficiency of stabiliza-
tion of polymers. In rubber, which is oxidized more readily than polypropylene, nitroxyl
radicals are much more efficient than sterically hindered amines. The reaction of the sub-
sequent conversions of nitroxyl radicals is given below:

> N.O + P. > OP (1)

OH
. .
> N O + OH
OH N (2)
O

> N.O + PH >NOH + P. (3)

> N.O + POOH >NOH + PO.2 (4)

hV
> N.O + PH >NOH + P. (5)

The antioxidative action of nitroxyl radicals is due to their ability to react to alkyl rad-
icals as in reaction (4). Owing to their reactivity to alkyl radicals, nitroxyls are the best pho-
tooxidative inhibitors than inhibitors of other classes.
In view of the above said, of great scientific interest is the problem of increasing the
durability of lacquer-and-paint coatings by introduction of nitroxyl radicals and their pre-
cursors sterically hindered amines into the anticorrosion composition.
The first stage of the work was to study the possibility of introducing the nitroxyl
CHAPTER 11 399

radical tanol of the formula (6) and SHA the diammonium salt of methylene disalicilic
acid (7) and DTG-5 (8).
The best solvent from those studied (acetone, toluene, ethyl alcohol, butyl acetate, eth-
yl cellosolve, butyl alcohol) for substances (6), (7) and (8) was found to be ethyl cellosolve.
Modifying additives were added to EP enamel in the amount of 0.5, 1.0, 1.5, 2.0 weight
fractions per 100 weight fractions of enamel.
The anticorrosion coating was formed on plates at room temperature for 24 h and at
80C for 2 h. Modifying additives without hardener were found not to promote the forma-
tion of coatings.
OH
O O
H4NO C CH2 C ONH4 (6)

OH

OH
O O
H4NO C CH2 C ONH4 (7)

OH

S C S

S
CH3
H3C CH3 (8)
N
H
In application of coatings, an incomplete moistening of plates was observed. The re-
sults of preliminary tests showed that introduction of additives (6) and (7) contributes to a
1.52-fold decrease of internal stresses in formation of coatings at 80C and an improve-
ment of their protective properties.
400 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY
12 Biochemically Stable
Coatings for Protection of
Transport Containers

12.1 Coatings based on Ftorlon copolymers


An increase of adhesion of ftorlon coatings to metals is, as a rule, related to the growing
sophistication of their production process: high-temperature treatment or use of intermedi-
ate primers based on other polymers, which affects adversely the properties of the systems
of coatings separately and as a whole.
One of the ways of increasing the adhesion of coatings based on various fluorine-
containing copolymers to metal supports is chemical modification of the metal surface prior
to the application of coatings. Three types of polyfunctional silanes, the molecular structure
of which contains ethoxyl and amine groups, were studied as such modifiers. Modifiers
AGM-9, AGM-3, ASOT-2 are silanes containing, respectively, three ethoxyl groups and
one amine group; at the same number of ethoxyl groups two amine groups (primary and
secondary); the molecular structure of ASOT-2 includes nine ethoxyl and seven amine
groups.
Ftorlons of grades F-42L, F-32L were used as polymers. Coatings were hardened on
carbon steel and aluminium.
Chemical modification of the surface of the support leads to a significant increase of
the adhesion strength of coatings. The disruption forces of films exceed 30004000 N/m,
i.e., are commensurable with their mechanical strength, which is 3040 MPa; herewith,
delamination is of a cohesion character. Coatings applied to a nonmodified metal surface
peel off at 1015 N/m.
Adhesion of coatings to steel in corrosion-aggressive media was studied at different
temperatures. The results of the studies indicate a high stability of adhesion of coatings ap-
plied to the modified metal surface. In the absence of chemical modification of the metal
surface, the stability of adhesion of the same coatings does not exceed 2 h in cold media
(293 K) and 15 min at 363 K; in a 3% HCl solution the stability of adhesion was 12 min.
An increase of the stability of adhesion by 23 orders of magnitude and more not only
in pure water but also in electrolytes indicates the formation of a chemosorption adhesion
bond. The stability of adhesion of ftorlon coatings is maximal in the case when the modifier
contains the largest amount of functional groups.
The smaller the number of functional groups, especially ethoxyl groups, in the modi-
fier is, the faster adhesion of coatings to steel decreases, and also the smaller its stability is.
402 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

At the maximal functionality of the modifier, the dependence of adhesion on temperature


is observed to be extreme.
Polyfunctional siloxanes containing ethoxyl and amine groups in the molecule are ad-
sorbed on the metal surface from solutions in accordance with the Langmuir adsorption iso-
therm. This character of adsorption indicates the chemical nature of the interaction of amino
alkoxysilanes with the surface of metals.
The practical realization of the proposed method consists in the following. The metal
surface prepared predominantly by shot blasting is treated with a solution of modifier at a
concentration of 520 wt. % in toluene, acetone or another solvent, active with respect to
the modifier. The solution can be applied to the surface by dipping, spraying or by a brush
after drying for 2040 min. Excess modifier is removed by the solvent, and the surface is
again dried for 2040 at 291296 K. To the prepared metal surface, the solution is applied
by spraying, by a brush or by dipping the coating, and the surface is dried for 1 h under the
same conditions.
Using the above modifiers, adhesion is increased 2030-fold. With respect to the de-
pletion of the efficiency of increasing adhesion, amino alkoxysilanes can be arranged in the
following sequence: ASOT-2 > AGM-3 > AGM-9. In this sequence, the functionality of
amino alkoxysilanes decreases, i.e., the content of ethoxyl and amine groups in the molec-
ular structure goes down.
We developed structure-forming modifiers, which make it possible to increase the ad-
hesion strength of ftorlon coatings to metal several tens of times. Their peculiar feature is
that they provide for a significant improvement of the performance properties of coatings
when introduced in small amounts (up to 2%) directly into the composition. These com-
pounds belong to the class of polyfunctional structure formers. In their presence, a homo-
geneous supramolecular structure is formed in coatings along the thickness of the film with
regular alternation chequerwise at the interface of structural elements with chemical and
physical bonds. Modifiers structure formers sharply reduce internal stresses and in-
crease durability of coatings operated under various conditions.

12.2 Structure of modified Ftorlon coatings


Modification of thermoplastics by reactive oligomers is a promising method of obtaining
novel materials possessing the properties of thermoplastic and thermosetting polymers. De-
velopers of such materials should primarily take into account the process compatibility of
the component on condition that oligomer plays the role of a temporary plasticizer. How-
ever, at more advanced stages of conversion owing to the hardening of oligomer, the inter-
action between the polymer and oligomer components becomes more complicated.
A cold-hardened lacquer ftorlon epoxy composition of grade LFE-42K based on ftor-
lon F-42L and chlorine-containing epoxy resin EKhD in combination with amine-type
hardener AF-2 was studied.
It was found that films from a solution of EKhD have one temperature jump-like tran-
sition between 58 and 73C in the region of devitrification of hardened resin. The film from
lacquer LF-42L has two transitions in the region between 77 and 94C in the form of an
endothermal peak at 142C assigned to the melting temperature of copolymers crystalline
structure.
Introduction of resin with hardener into lacquer LF-42L has a significant effect on the
temperature and thermophysical values of transitions. At a maximum content of oligomer
in the composition, the glass-transition temperature of films increases by 13C, and the
CHAPTER 12 403

melting temperature decreases by 6C. With the rise in the content of hardened oligomer,
a decrease of the melting heat from the heat capacity in the devitrification region is ob-
served. In compositions with nonhardened resin, similar structural changes are not ob-
served. Therefore, in polymerization of the resin the segmental mobility of copolymers
macromolecules decreases, and various defects, including stresses in crystals, are formed.
Based on the structure studies, ftorlon and the epoxy composition, irrespective of the
aggregate state, were found to be a microheterogeneous system, with the resin localized as
individual particles, which represent microaggregates, and unevenly distributed in ftorlon.
This conclusion made based on the results of electron-microscopy and X-ray studies
enables considering this composition as a filled polymer, where the filler is rigid oligomer
EKh resin, and the matrix is copolymer of tetrafluoroethylene with vinylidene fluoride.
A higher strength of composite materials at a temperature increase as compared with
initial ftorlon can be explained by the ordering of their structure, as the result of increased
crystallinity, observed in heating of specimens to a temperature higher than the glass-
transition temperature of hardened EKhD.

12.3 Coatings based on modified and ladder polyphenyl sesquioxanes


Ladder polyphenyl silsesquioxane polymers possess a number of valuable properties. By
thermal resistance, chemical resistance and elasticity they exceed polymers of the similar
composition, having no regular ladder structure. The composition and structure of mono-
mer molecules, from which organosilicon polymers are obtained, predetermine the charac-
teristic features of their properties.
The cohydrolysis reaction of various organochlorosilanes makes it possible to change
within a wide range the ratio between radicals framing the silicon atom and to obtain cohy-
drolysis products with a large diversity of properties. The formation of coatings based on
rigid-chain ladder polymers, aimed at the development of compositions for heat-resistant
coatings with a given set of physicomechanical properties, was studied.
To increase the adhesion of ladder polymers, various amounts of vinyl groups from
1.5 up to 8% were introduced into the cycle. With their number increasing, adhesion in-
creases monotonically and at a concentration of 8% is three times larger. Along with this,
to increase adhesion of coatings to the support, it was treated with organosilicon fluoropoly-
mers containing various active groups. The best results were obtained using organosilicon
compounds with labile hydrogen atom as a sublayer; herewith, along with an increase of
adhesion, internal stresses were observed to decrease and durability of coatings to increase.
Formation and ageing of coatings from polyphenyl silsesquioxanes with the molecular
mass of 500,000 with different concentrations of vinyl groups in the main chain, which were
introduced to increase adhesion of coatings, was studied. Coatings were obtained from so-
lutions of polymers in toluene. The formation of coatings was investigated with account for
the kinetics of increment and relaxation of internal stresses, adhesion and supramolecular
structure. Thermal ageing of coatings was performed at temperatures from 200 up to 600C.
For the electron-microscopy study of the structure of organosilicon compounds, used was
made of the method of ion bombardment of the preparations. The object of study were non-
modified and modified polymers filled with 50% aluminium powder (Table 12.1).
The content of dimethylsiloxane links in polymer was regulated by changing the ratio
of components entering into hydrolytic co-condensation. An increase of the concentration
of dimethylsiloxane links in the polymer leads to an increase of its elasticity and to a simul-
taneous decrease of the thermal stability of materials.
404 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 12.1 Effect of the concentration of vinyl groups of the sublayer on adhesion and ultimate
internal stresses.

System No Concentration Internal stresses, MPa Adhesion, MPa


of vinyl groups
Nonfilled Filled Nonfilled Filled
coatings coatings coatings coatings

1 0.5 0.8 0.7 1.7


2 2 0.7 1.0 1.1 2.1
3 5 1.1 1.5 1.7 4.5
4 8 1.7 2.1 2.1 5.8
5 8 + sublayer 1.5 7.0

A number of polymers with an average building block was obtained. Parameter n


changed within the limits of 1.5, 1.0, 0.5, 0.25.
C6H5 C6H5 CH3
Si O Si O SiO
O O CH3
n

It was found that the formation of coatings based on polyphenyl siloxanes with n from
0.25 up to 1.0 is accompanied with the spontaneous cracking and delamination of coatings.
It was shown that, with the concentrations of methylsiloxane links increasing, adhesion and
strength of coatings also increases 2.53 times. The lowest internal stress, not exceeding
0.5 MPa, was found to emerge in coatings from oligomer with n = 1.5. With the concentra-
tions of methylsiloxane links decreasing, internal stresses increase and so does the coating
formation time to more than 2 h. Using rheological methods, it was shown that introduction
of dimethylsiloxane links into the copolymer contributes to the structuring of the composi-
tion. Deterioration of coatings from polymer with a small concentration of methylsiloxane
links is determined by the slowdown of the relaxation processes as the result of a sharp in-
crement of viscosity of the composition; herewith, the rate of gel formation slows down.
The different character of structural transformations in the formation of coatings from
copolymers with n from 0.25 up to 1.5 renders a significant effect on their supramolecular
structure. A globular structure with globules 1012 nm in diameter was observed in coat-
ings with n = 1.5, whose formation is accompanied by a a small rate of increment of vis-
cosity. With the concentration of methyl groups decreasing, at n = 0.5 the size of globules
increases up to 3050 nm; herewith, their number per unit of surface increases significant-
ly. Formation of coatings from copolymers with small n is accompanied with their cracking.
To improve the physicomechanical properties, they were filled with aluminium pow-
der. At the introduction of 10% pigment, the adhesion strength of coatings from copolymers
with a small concentration of methylsiloxane links (up to 0.5) increases up to 1.5 MPa.
However, this value of adhesion is insufficient and coatings peeled off spontaneously in the
process of formation under the action of internal stresses. In coatings with a concentration
of methylsiloxane links up to 1.0 and 1.5 internal stresses were smaller respectively, 1.0
and 15 MPa, which, owing to a larger adhesion, evoke no spontaneous delamination of coat-
ings. A significant increase of adhesion is observed in coatings with 50% aluminium
powder.
CHAPTER 12 405

Unlike nonfilled coatings, the critical thickness, at which coatings spontaneously peel
off, is observed for pigmented materials to be shifted to a value of 500 m.
In contrast to nonpigmented coatings, which exhibit the largest adhesion when using
copolymers with the maximal concentration of methylsiloxane links (1.5), when aluminium
powder is added, adhesion increases with the decrease of the concentration of methylsilox-
ane links in the homologous series of copolymers. The greatest adhesion strength of about
12 MPa is observed for coatings from copolymer with a small concentration of methylsi-
loxane links equal to 0.25. With their content increasing from 0.5 up to 1.5, the adhesion
strength of coatings changes insignificantly from 8 to 7 MPa.
In the presence of pigment, unlike nonfilled coatings, the effect of concentrations of
methylsiloxane links changing from 0.5 up to 1.5 is insignificant; herewith, internal stresses
change within the limits of 3 to 2.5 MPa. A sharp increment of stresses, more than two
times, is observed with the decrease of the concentrations of methylsiloxane links to 0.25.
Thus, in the presence of aluminium powder the adhesion and cohesion strengths of
coatings increase significantly at various concentrations.
The effect of the filler on the supramolecular structure of films with different param-
eters n was studied to elucidate the role of aluminium in the formation of the properties of
coatings. It was found that initial particles of aluminium powder have a plate-like structure
of various thicknesses along the area of the particle. In nonfilled coatings, the structure of
polymer is not exhibited. However, in coatings from polymer with n = 1.5 the distribution
of the filler is more uniform than in coatings with small n, lower than 0.5. Structural trans-
formations leading to the emergence of a globular structure 1015 nm in diameter, with the
size of the globules approaching that of the structural elements of the support, contribute to
a better interaction at the interface to form a larger number of chemical bonds responsible
for the adhesion strength.
The further increase of adhesion was performed by modification by compounds with
hydroxyl groupings. The cause of this phenomenon is due to the crucial role of active
groups Si O , involved in the chemical interaction of particles of filler and the support
in the formation of adhesion/cohesion bonds. This effect is also achieved by using pigments
with the regular distribution of active functional groups on the surface of particles.

12.4 Photohardenable epoxy acrylates for protection of transport containers


Experience of investigating polarized oligomer systems has shown that coatings formed by
polymerization directly on the support are distinguished with higher physicomechanical
characteristics and resistance to aggressive impacts than coatings obtained from polymer
solutions. The efficiency of using these coatings from oligomer-monomer systems without
solvents increases using accelerated methods of drying: accelerated electrons (AE), ultra-
violet (UV), infrared (IR) radiation. Their use not only contributes to the increased quality
of a coating, the decrease of labour and energy expenses for drying, the reduction of the
drying to seconds, but for the most part also partially solves the problem of protection of
the environment. According to the literature data, in the UV method of hardening no more
than 2% of applied material gets to the atmosphere, whereas usual methods release up to
60% of applied substances and solvents to the atmosphere.
It should be noted that, of all radiative methods of hardening, the method of UV drying
is the most promising owing to the simplicity and low cost of equipment. A UV unit does
not need large production facilities. All these advantages contributed to the development of
406 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

the chemistry of photopolymerized oligomers. To date, a very large number of photopoly-


merized compositions have been proposed and found application in furniture trade, printing
industry, paper industry, radioelectronics industry, metal working industry.

12.5 Physicochemical bases of developing photohardenable coatings


Polyfunctional oligomers with -bonds are usually used as bonding adhesive of photo-
polymerized compositions capable of forming coatings with high adhesion to the support
and large density of the three-dimensional network.
When modelling photopolymerized compositions for coatings, the functionality of oli-
gomers is determined by the need to provide for, on the one hand, a high rate of polymer-
ization by the radical or ion mechanism and, on the other, adhesion of the coating to the
substrate and formation of the three-dimensional network.
The photopolymerization rate depends on the kind of crosslinking groups and their ac-
tivation energy.
The efficient value of activation energy of any polymerization process is determined
by the equation:

E = 1/2 Ein + Eg 1/2Et,

where Ein is initiation energy of the process, Eg is energy of the polymer chain growth, Et
is polymer chain termination energy.
In photopolymerization, Ein = 0. Therefore, the photopolymerization energy is deter-
mined by the relation:

E = Eg 1/2Et .

According to the data by Bagdasaryan, the chain growth energy of most alkenes is
within the limits of 49 kcal/mol. Herewith, vinyl monomers of the type of methyl acrylate
and methyl methacrylate have the minimal energies of activation and chain growth
4.24.5 kcal/mol.
The use of low-molecular-mass monomers of the type of methyl methacrylate for pro-
duction of photohardened coatings is associated with significant problems. On the one
hand, acrylic monomers, though are low volatile (boiling temperature, 100150C), evap-
orate in photopolymerization on the open surface. On the other hand, in polymerization of
acrylic monomers the structure is consolidated and the specific volume decreases by
2021%. However, in one application protective coatings are known to be produced on
metal and wire by photopolymerization of low molecular mass acrylates in the gas phase at
a rarefaction of 10 3 10 5 mm vapours. But the presence of a short-wave region (200 nm)
in the spectrum of ultraviolet radiation often leads to adsorption of low-molecular-mass
dimers and trimers from the gas phase to the support, which deteriorates the quality of the
polymer coating. The use of a system of filters, which rule out the short-wave part of the
spectrum, is not always efficient for preventing polymerization in vapours prior to the sed-
imentation of monomer on the support. For this reason, films obtained in irradiation are of-
ten rather soft and have a linear structure. Studies of polymethyl methacrylate films
produced by photopolymerization showed that the mean chain length L = 10 nm, which
makes 15 monomer units. The use of non-polyfunctional oligomers leads to the formation
of polymers of the three-dimensional structure, possessing the stability at increased
CHAPTER 12 407

temperatures, a larger hardness in combination with elasticity, resistance to corrosion and


atmospheric effects. Herewith, for polyfunctional oligomers the rate of photopolymeriza-
tion is much higher, the polymerization rate of oligocarbonate acrylates and oligoester acry-
lates noticeably increases with the increase of the content of the methacrylic groups. What
is more, acrylic monomers are polymerized at a much larger rate than methacrylic mono-
mers, and, as the length of the molecular chain increases, the polymerization rate does
down.
At the same time, an increase of the molecular mass of polyfunctional oligomers is ef-
ficient from the point of view of forming coatings with the largest rate of relaxation pro-
cesses, which leads to a decrease of internal stresses.
From the theoretical point of view, a positive effect of reducing stresses can be
achieved by internal plastification by comonomers or copolymers. When choosing comono-
mers, one should take into account Mayer theory, according to which the elasticity of poly-
mer is determined by the multivariance of macromolecular conformations, the ultimate
magnitude of which, according to the laws by Gut, Mark and Kun, is directly proportional
to the square root from the number of bonds between carbon atoms. The literature mentions
the use for these purposes of esters of -, -ethylene-unsaturated acid and mono- or poly-
basic alcohol with the number of carbon atoms from 1 up to 18 of normal or iso structure,
for instance, 2-oxyethylene methacrylate, mono-2-hydroxyethyl(methacrylate), mono-
(2-hydroxyethyl)itaconate, methyl-2-hydroxyethyl itaconate, methyl-2-hydroxypropyl
maleate, octyl-2-hydroxypropyl maleate, trimethacrylate neopentyl glycol etc.
To produce polymerized systems forming coatings with small internal stresses,
Nechols and Flowers recommend to dissolve polymer in monomer.
The use of a 1030% solution of polymethyl methacrylate in monomer considerably
reduces the shrinkage by decreasing the exothermic effect of polymerization. Using this
modification grafting at a respective choice of ready polymers (acryl/vinyl series or rub-
bers), it is possible to succeed in obtaining a product, which gives a coating with reduced
shrinkage stresses at ultraviolet radiation of the coating. The literature describes photopo-
lymerized compositions based on saturated polymer in a solution of acrylic monomer, po-
lybutylene and copolymer of polybutadiene in a solution of styrene, polyvinyl butyral in
ethylene-unsaturated solutions, in which the polymerization process is performed by the
method of modification grafting.
When considering a theoretical model for photohardened coatings, the major require-
ment to any coating is its high adhesion to substrate. In adhesion of polymer to metal, the
role of the chemical nature of adhesion proves to be instrumental. This dependence is de-
termined by the type of active polar groups, their number and donoracceptor properties of
the functional groups. Depending on the character of the functional groups, the interaction
of oligomer with the metal support in photopolymerization can proceed by the type of a co-
valent bond between electrons of labile hydrogen atoms (hydroxyl, carboxyl, amine group)
and d-orbit electrons of metal or by the type of an ionic bond.
Formation of an ionic bond is characteristic of metals with oxide layer. Most often,
this type of bond is realized in contact of metals with carboxyl-containing and hydroxyl-
containing polymers. Various chemical bonds can emerge between the metal surface coated
by a hydrated oxide layer and functional groups of polymers.
For instance, epoxy resins can react with the metal surface according to the scheme
>Me OH + CH2 CH Me O CH2 CH

O OH
408 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Carboxyl-containing polymers can interact with the metal surface by forming bonds
of the type:

MeO + RCOOH Me OCOR


as well as iondipole type bonds

MeO H OCOR
Isocyanates, by reacting with surface films of oxides and hydroxides on the surface of
metal, can form bonds of the type:
MeOH + O C NR Me O C NHR
O

MeO MeO
+
MeO + O C NR O C N R or O C N R

Coordination-type bonds can also occur in the polyamidemetal system:

MeO

CH2 C N CH2
O H
The existence of such bonds is possible at the polymermetal interface in the cases,
when adhesion is determined by trivalent nitrogen. A rather widespread type of interaction
at the polymermetal interface should be considered to be iondipole interaction and hy-
drogen bonds.
Depending on the purpose of coatings and the nature of the support, a great diversity
of photopolymerized bonding adhesives with various types of reactive functional groups
are manufactured at present. Known Western photopolymerized compositions are usually
solutions of polyester unsaturated resins in readily copolymerized ethylene monomers in a
mixture with photoinitiator. The content of polar (carboxyl, hydroxyl, amino, isocyanate)
groups in the bonding adhesive depending on the purpose of the coating is regulated in the
process of formation in the polycondensation reaction by changing the concentration and
chemical composition of the components.
Thus, bonding adhesives for printing plates are known to be produced using light-
sensitive compositions based on polyamides, mixtures of polyacrylates and polyesters with
isocyanate groups in a solution of copolymerized acrylic monomers, sometimes containing
products of partial etherification of polyester polyols of acrylic or methacrylic acid, N-(oxy-
methyl)acrylamide or N-(oxymethyl)methacrylamide. For production of letterpress print-
ing plates, use is made of compositions based on mixtures of block copolymers in solutions
of unsaturated polyol esters. Blocks of copolymers are monovinyl acrylene polymers and
dienic polymers, for instance, styrenebutadienestyrene. For the same purposes, as well
as for polygraphic lacquers, inks and coating, use is made of mixtures of polycondensation
products of unsaturated polybasic acids, and polybasic alcohols and copolymerized mono-
mers of a mixture of haloid-containing polymers with end carboxyl groups and double
CHAPTER 12 409

bond-substituted nitrile and nitro groups; mixtures of products of interaction of epoxy resins
with -, -unsaturated mono- or dicarboxylic acids with acrylates of mono- or polybasic
alcohols.
Earlier, printing plates were fabricated using photopolymerized compositions based
on acidic and mixed cellulose esters of oligoester acrylates and oligocarbonate acrylates and
copolymerized monomers with ethylene bonds.
The number of patented photopolymerized compositions for protective coatings in the
recent 5 years increased significantly. There is a UK application for the composition and
process of producing photopolymerized compositions for protection of aluminium surface.
The basis of the composition is unsaturated polyester, which is produced by a two-stage
etherification of copolymer of ethylene oxymonomers, first with -, -unsaturated carbox-
ylic acid, and then part of carboxyl groups is epoxidized by monoepoxyvinyl monomer. The
coating mixture contains about 50% of organic solvents, which requires a preliminary dry-
ing of the coating with hot air. The coating hardened by ultraviolet light for 3 min does not
dissolve in acetone for 92%. To produce protective coatings with rubberlike properties, use
can be made of a photohardened liquid polymer composition based on polyene polythiol
and an accelerator of photohardening. The presence of several side and end functional car-
boxyl and mercato groups provide for adhesion to metal.
Based on the polyenepolythiocol system, aqueous protective and decorative paints
were developed, which can be applied to metal without a primer. The coatings harden and
dry under the action of ultraviolet rays for 130 min. There are polyene-polythiocol com-
positions, which contain diallyl maleinate and toluylene diisocyanate and harden under the
light of an ultraviolet lamp (power, 5 kWt) in the presence of benzophenone and phosphoric
acid. The viscosity of the compositions is 120180 poise, pH 4.55.5. Coatings on tinplate
10 m thick irradiated for 35 s are characterized by gloss and high abrasion resistance.
There is an application of aqueous dispersions of polymers produced by emulsion po-
lymerization of vinyl esters, acrylates, methacrylates, styrene, acrylonitrile and their mix-
tures with other unsaturated monomers to be used as aqueous protective paints crosslinking
under the action of light.
Coatings based on compositions from light-sensitive N-containing synthetic resin are
characterized by a high mechanical strength and water resistance. The resin includes a poly-
mer, which contains nitrogen in the form of quaternary ammonium salt.
The recommended composition is well soluble in water. For protective coating of met-
al foil and sheets, it is proposed to use lacquers based on polyester dissolved in unsaturated
aliphatic monomer, compositions based on saturated polymer in a solution of acrylic mono-
mer. Coatings based on epoxy materials are characterized by high adhesion, thermal stabil-
ity and weatherability; such coatings are products of modification of epoxy resins of
ethylene-unsaturated acids. In the automatic line, the moist coating is hardened in one run
under a quartz lamp of 200 Wt, placed at a distance of 5 cm; the passage speed, 7 m/min.
For coatings of metal, there is a composition of vinyl resin hardened by photoirradia-
tion. The composition contains (A) 260% wt. % of the salt of 2- or 3-valent metal of un-
saturated mono- or dicarboxylic acid and (B) 9840 wt. % of an unsaturated compound
with 0.512 polymerized unsaturated bonds per unit with molecular mass 1000. Coatings
based on this composition are distinguished with high chemical and mechanical properties.
Photohardened coatings based on vinyl resins are known to be produced using a solution
(in vinyl monomer) of unsaturated acrylic resin obtained by a 3070% polymerization of
unsaturated monomers with anhydride groups with vinyl monomers. There are patents for
polyester compositions modified by fatty acid and isocyanate, compositions based on
410 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

copolymers of unsaturated methacrylic acid, its alkyl ether and polyester, polysiloxane
compositions containing polysiloxane with haloid phenyl and haloid alkylene radicals and
end ethylene-unsaturated bonds and crosslinking solvents.
A patent was applied for a composition based on the polycondensation product of
-,-dioxydimethyl polysiloxane (molecular mass 758) and methacryloyl oxypropyl tri-
methoxysilane. Polysiloxane compositions are characterized by high protective properties
and are used for protection of aluminium sheets.

12.6 Photochemical processes and structural transformations in formation


of coatings under the action of ultraviolet light
Formation of coatings from oligomer systems is related to the polymerization reaction im-
mediately on the support, therefore, the thickness of the film and the nature of the support
have a significant effect on the polymerization kinetics, structure and properties of coatings.
The effect of the nature of the support is evident from the adsorption interaction of the oli-
gomer with the support to form supramolecular structures in the boundary layer of the liquid
phase prior to the onset of the polymerization process.
It was shown that these structures perform the role of blocks and blanks in the forma-
tion of coatings. Data of studies suggest that formation of coatings from oligomer systems
proceeds stepwise via the stage of the formation of supramolecular structures followed by
the establishment of stronger bonds between these structures. Depending on the nature of
oligomer, of the support and structure-forming conditions, the number of bonds and the
character of supramolecular structures change in polymerization; in turn, they are respon-
sible for the physicomechanical properties and durability of coatings.
Formation of coatings under the action of ultraviolet radiation is a specific process,
characterized by the primary photochemical act. Absorption of a light quantum by oligomer
causes the initiation of polymer chain growth.
The rate of photochemical initiation (Vin) is directly proportional to the intensity of ab-
sorbed light and equals to

Vin = 2Ja,

where is the quantum yield of initiation, determined by the number of pairs of radicals
formed during the absorption of one light quantum and Ja is the number of light quanta (ein-
steins) absorbed per unit of time (second) in unit volume (litre);

J0 = J0 [M],

where J0 is the intensity of the light quantum incident to the monomer, is the coefficient
of extinction for a certain wavelength of absorbed light, [M] is the concentration of
monomer.
In the case of using photoinitiators, which under the action of the light quantum split
to radicals initiating the photopolymerization of monomers with -multiple bonds, the ini-
tiation rate is determined by the equation:

Vin = 2 J0 [],

where [] is the concentration of the initiator.


The rate of the entire photopolymerization process Vg is then equal to
CHAPTER 12 411

Vg = kg [M](Vin /2kt)1/2,

where kg and kt are the chain growth and termination constants.


Substituting the values of the photopolymerization initiation velocity Vin and taking
into account the LambertBuger law, we obtain the equation for the photopolymerization
rate:

[ ]b 1/2
J 0 ( 1 e )
V p = k p [ M ] ----------------------------------------- .
kt

As the last equation shows, the rate of photopolymerization is proportional to the con-
centration of the photoinitiator. However, one observes here not only the quantitative de-
pendence. Studies showed the efficiency of photopolymerization to depend on the
photoactivity of the initiator.
A high activity of photolytic homolysis is characteristic of carbonyl compounds, for
instance, ketones:
O O
h
R C R' R C + R'
benzoin and its esters:
h
C6H5 C CH C6H5 C6H5 C + CHC6H5
O OH O OH

h
C6H5 C CH C6H5 C6H5 C + CHC6H5
O OCH3 O OCH3

disulfides, sulfochlorides, derivatives of naphthalene and xanthone, organometal and other


compounds absorbing in the near ultraviolet region.
The reaction of photopolymerization can be initiated by photosensitizers. In contrast
with initiators, they are only carriers of electron excitation energy.
The most active photosensitizers are benzophenone and its derivatives, anthraquinone
and its haloid- and nitrosubstituted derivatives, fluorescein, eosine and other dyes.
The photopolymerization sensitization process consists of a number of successive el-
ementary acts.
I. Under the action of photons of light due to the transition of valence electrons from
n orbitals to antibinding p* orbitals, the photosensitizer molecule z passes into an excited
state:
z + h z*.

The direction of the spin of paired electrons changes, and the molecule passes from
the stable singlet state (complete spin S = 0 and the spin quantum number J = 1) to the triplet
state (complete spin at the parallel direction of spin vectors S = 1 and J = (2S) + 1 = 3).
II. The electron excitation energy of the photosensitizer is spent by nonradiative
412 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

triplettriplet transition for the excitation of polymerized monomers M.


z* + M z + M*.
In this way, the triplet state of the sensitizer is quenched, and the unpaired electron is
transferred to the antibinding orbital of the monomer.
III. The formed monomer radical initiates polymerization according to the scheme:
M* + M M M*;

M M* + M M M M* etc.
This process will continue up to the establishment of an equilibrium in the system,
when the chain will simultaneously grow and be terminated due to recombination and dis-
proportionation.
IV. Owing to the increase of viscosity in the system at the final stages, the chain growth
rate drops down and the probability of termination increases.
Herewith, a dead polymer is formed according to the scheme:
Mn1 M* + M Mn + M* or Mn1 M* + Mn1 M* M2n
At the primary stage of initiation by benzophenone and its derivatives with the absorp-
tion band in the region of 360 mm of the photopolymerization of vinyl monomers, there
occurs the photoreduction of the light-sensitive substance to form a respective semipinacol
radical. Studies by Granchik et al. showed that the monomer inhibits the yield of semipi-
nacol radical. Using the method of pulse photolysis, the authors recorded the decay signals
of semipinacol radical in methyl methacrylate solution. By means of laser methods, vinyl
monomers were found to be efficient quenchers of the triplet state of benzophenone. The
authors believe that this explains the decrease of the yield of semipinacol radical in the pres-
ence of methyl methacrylate. Herewith, the deactivation of the triplet state is assumed to be
performed by way of donoracceptor interaction of the excited benzophenone molecule
with the molecule of methyl methacrylate.
The effect of the donoracceptor interaction of the excited benzophenone molecule
with the molecule of vinyl monomer is enhanced in the presence of amines, which play the
role of a photoreducer.
Herewith, the rate of polymerization of vinyl oligomers increases significantly, espe-
cially in the presence of tertiary amines.
When studying the hardening processes of unsaturated polyester resin based on fumar-
ic and maleic acids and polyols in a solution of styryl with a viscosity of 1545 poise at 20C
and acid number of 32 mg KOH/g on a film 24 mm in thickness, E. Mleziva and
V. Chermak found the following substances to possess the greatest photoinitiating activity
(in the order of the rate of decrease): benzoin isopropyl ester, benzoin n-amyl ester, 2-chlo-
ride of 1,4-dibutyl naphthalene sulfonic acid, benzoin isobutyl ester, benzoin n-butyl ester
and benzoin methyl ester.
Benzoin itself is characterized by a low capability of photoinitiation. For the class of
sulfochlorides, excluding naphthalene derivatives of sulfides and ketones, the time of pho-
topolymerization with the power source a high-pressure mercury lamp with the voltage
of 125 V at a distance of 30 cm (from the film) was of the order of 10003000 s. Works
by Western scientists showed that the mechanism of photoinitiation using benzoin and its
derivatives consists in the formation of radicals, differing in their energy state, as the result
of photolysis under the action of light quanta. Using NMR and IR spectroscopy methods,
CHAPTER 12 413

an intramolecular hydrogen bond in the benzoin molecule was found; this is assumed to in-
crease the activation energy of benzoin photolysis:

O OH O HO
h
C C C + CH

O
C H
O OH
C + CH

Radicals formed from benzoin under the action of light quanta should, in the opinion
of the authors, overcome the energy of the hydrogen bond to be able to exit the cell, and
only those that exited the radical cell are capable of initiating polymerization.
The high photolytic activity of benzoin derivatives was established by the company
E9 du Pont de Nemours, but the firm Bayer AG was issued a patent for benzoin esters of
secondary alcohols, which, besides the high photopolymerization initiation rate, provide for
the stability of polyester resin compositions in storage.
Studies of the photopolymerization rate of trimethacrylic ester of pentaerythrite adip-
inate and triacrylic ester of pentaerythrite (PETA) under the action of irradiation by a DRSh
high pressure mercuryquartz lamp at a film thickness of 3 m by the method of gel frac-
tion also showed that benzoin esters have the highest activity (Table 12.2). Using trietha-
nolamine as a reducer and the photoinitiator trigonal, we succeeded in reducing the rate of
PETA polymerization to 1 s. Tests of the coatings obtained showed them to be elastic, me-
chanically strong and resistant to the action of acidic and alkaline media.

Table 12.2 Activity of photoinitiators.

Photoinitiator Formula Polymerization rate, sec

7 20 PETA

Benzoin C6H5 C CH C6H5 300 89

O OH
Benzoin methyl ester C6H5 C CH C6H5 77 34

O OCH3

Trigonal 10 3
C6H5 C CH C6H5
O OR

Benzophenone C6H5COC6H5 900 600


Michlers ketone [(CH3)2NC6H5]2CO 480 180
Mixture of benzophenone 8 5
and Michlers ketone (1:2)
414 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

(continued)
Table 12.2 Activity of photoinitiators.

Photoinitiator Formula Polymerization rate, sec

7 20 PETA
Anthraquinone C6H4(CO2)C6H4 420 115
-Chloroanthraquinone C6H4(CO2)CH3Cl 49 6
-Chloroanthraquinone 49 17
Butyl anthraquinone C6H4(CO2)CH3C4H9 126 63
Androne C6H4COCH2C6H4 1600 1800
Dibenzyl ketone C6H5CHCOCHC6H5 50 75
Benzyl chloride C6H5CHCl 77 34
2-Nitrophenanthrene C6H5 C CH C6H5
600 365
NO2 NO2

Toluene sulfochloride C6H5CH2SO2Cl 23 8


Dinitrodiphenyl C6H5NO2C6H5NO2 600 2000
Diazo diethyl aniline C6H5N NC2H4C6H5NH2 2000 55

The efficiency of photopolymerization is also determined by the nature of oligomer


and its structure (Table 12.3). Studies of the reactivity of oligoester acrylates also showed
that trimethacrylic ester of pentaerythrite adipinate is the most polymerized oligomer.
Table 12.3 Photopolymerization rate of acrylic monomers.

Monomer, oligomer and its commercial grade Structural formula* Polymeriza-


tion rate, s

Oligoester acrylates

Methacrylic ester of diethylene glycol phthalate


MFF-2 M D P D P D M 70
Methacrylic ester of triethylene glycol phthalate
MGF-9 M T P T M 70
Dimethacrylic ester of glycerol phthalate M
TMGF-11 25
M G P G M
M
Trimethacrylic ester of pentaerythrite adipinate M M M 10
7 20
M P Ad P Ad P M
M M M
Dimethacrylic ester of
triethylene glycol TGM-3 M T M 40
Dimethacrylic ester of
tetraethylene glycol TGM-4 M Te M 42
Dimethacrylic ester of
polyethylene glycol M-6600, TGM-13 M PeE M 15
Methacrylic ester of ethylene glycol carbonate
OKM-1 M E C E M 15
CHAPTER 12 415

Table 12.3 Photopolymerization


(continued) rate of acrylic monomers.
Monomer, oligomer and its commercial grade Structural formula* Polymeriza-
tion rate, s

Methacrylic ester of diethylene glycol carbonate


OKM-2 M D C D M 20
Methacrylic ester of triethylene glycol carbonate
OKM-3 M T C T M 35
Methacrylic ester of tetraethylene glycol 35
carbonate
TGM-4 M Te C Te M
Chloroacrylate 15
M T M
Cl3C CCl3

Monoacrylic ester of diethylene glycol carbonate


OKA-2 A D C D A 1
Monoacrylic ester of triethylene glycol carbonate
OKA-3 A T C T M 4
Triacrylic ester of pentaerythrite 3
Tetramethacrylic ester of pentaerythrite 11
Trimethylol propane triacrylate 26
Urethane acrylates
PDI-4AK 13
PPG-4AK 13
OUA-2000T 10
Aminated acrylates
Diethylamino ethyl methacrylate Et 35
M Et N
Et
Chloroethyl methacrylate 68
M Et
Cl
Dimethylamino ethyl methacrylate 55
Me
M Et N
Me
Cyano-ethyl methacrylate M E CN 40

Trimethacrylic ester of triethanolamine (M ET)3N 45

Glycidyl methacrylate M CH2 CH CH2 45


O

Note: Photopolymerization rate was determined by the time of irradiating films 3 m thick by
DPSh-500 lamp radiation, during which time a coating achieved a maximum extent of hardening as
determined by the gel fraction method. Designations: M, methyl acrylate; P, phthalate; E, ethylene
glycol; D, diethylene glycol; T, triethylene glycol; Te, tetraethylene glycol; G, glycerol; Pe,
pentaerythrite; Ad, adipinate; C, carbonate; A, acrylate; Et, ethyl; Me, methyl.
416 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Using the kinetic methods, the activity of phenylene diacrylates (PDA), phenylene
dimethacrylates (PDMA) and isomers of amino esters acryloyl aminophenyl acrylate
(ACAPA) and methacryloyl aminophenyl acrylate (McAPMA) of the general formula was
assessed:
O O
CH2 CR C O NH C CR CH2,

R H (ACAPA) or CH3 (McAPMA).


The photopolymerization reaction was initiated by 5 wt.% of benzoin isoamyl ester un-
der a DPSh-500 mercury lamp in dimethylformamide solution. Using the EPR and IR spec-
troscopy and dilatometry methods, it was shown that derivatives of acrylic acid are the most
active in photocrosslinking reactions; what is more, for phenylene diacrylates the activity
is higher than for amino ester. Of amino esters, the m-isomer is the most active, then o- and
n-isomers. The spectroscopy data (the change of intensity of the absorption band in the re-
gion of 990910 cm 1 conforming to the deformation vibrations of hydrogen atoms at the
double bond) showed that n-phenylene diacrylate reaches the maximal extent of conversion
of the double bonds (73%) in 200 s. The kinetic changes of the intensity of the band at the
wave number of 990910 cm 1 obey the second-order equation

1/(a x) = K2ef t + C or l/D = K2ef t + C,

where a is the concentration of monomer; x is the amount of monomer, which reacted for
time t; K2ef is the second-order age constant; C is a constant; D is optical density.
The following values were obtained:
n-PDMA 3.410 5
n-PDA 1.710 4
n-McAPMA 1.510 5
m-McAPMA 610 5
o-McAPMA 7.510 5.
The rate of photocrosslinking of epoxyacrylates of the following structure was studied
using the method of IR spectroscopy by the vanishing of the absorption band of C=C vibra-
tions in the region of 1640 cm 1:
CH3
IA. CH2 CHCOO CH2 CH CH2 O C O CH2 CH
OH CH3 OH

CH2 OCOCH CH2


Molecular mass: calc. 809, found 871; 25C = 12,400 poise.

IIA. CH3 CH3


CH2 CHCOO CH2 CH CH2 (O CH2 CH)n O CH2 CH O CH2 CH
OH OH

CH2 OCOCH CH2


CHAPTER 12 417

Molecular mass: calc. 692, found 749; = 13 poise.


IIIA. CH2 CHCOO CH2 CH CH2 (OCO COO CH2
OH

CH CH2)n OCO COO CH2 CH CH2 OCOCH CH2


OH OH

Molecular mass: calc. 662, found 573; = 1367 poise.

It was shown that at the stage of initiation (photoinitiator, 1 wt. % benzoin ethyl ester)
the rate of photocrosslinking is controlled by molecular mobility. The rate of photopoly-
merization for epoxyacrylates with low viscosity is higher than the same rates of photo-
crosslinking for epoxyacrylates with high viscosity. The rates of photocrosslinking for
epoxyacrylates at the last stage are more dependent on the glass transition of epoxyacry-
lates. Epoxyacrylate IIA, which has a lower viscosity, in 40 s of irradiation is characterized
by an almost 100% degree of conversion; epoxyacrylate IIIA, 9293% conversion; epoxy-
acrylate IA, 70% conversion. The molecular mobility of epoxyacrylates at the stage of ini-
tiation and the stage of glass transition is determined by the structure of epoxyacrylates. A
decrease of the viscosity of epoxyacrylate IA by dilution with styrene at a styrene to epoxy-
acrylate IA ratio of 10:90 decreased the rate of photocrosslinking at the stage of initiation,
but increased at the glass-transition stage. The maximal conversion (95%) is achieved by
the system in 90 s of irradiation by a 500-Wt high-pressure mercuryquartz lamp (model
USH-500D) at a distance of 30 cm from the source of the light.
The effect of the structure on the rate of photopolymerization of epoxyacrylates in a
solution of methyl methacrylate and butyl methacrylate, and the extent of conversion of the
double bonds was determined by the method of IR spectroscopy by the disappearance of
the absorption band of CH2=C valence vibrations in the region of 16601640 cm 1.
The data obtained are well consistent with the results of the gel fraction studies. It was
shown that the process of photocrosslinking is extremal, depends on the thickness of coat-
ings and is limited by the etherification of free epoxy groups in the catalytic effect of the
photoreducer benzophenone-2-diethylaminoethanol. Kinetic studies of the joint photopo-
lymerization of OUA-200 OT with tri-(oxyethylene)-,-dimethacrylate (TGM-3) and
methacrylic acid (MAA) by the method of dilatometry, during the irradiation by a
LUF-80-04 lamp with an illumination intensity of 0.410 3 Wt/(cm2 C) showed that, ir-
respective of the type of photosensitizer [benzophenone (BP), benzaldehyde (BA)], or pho-
toinitiator [benzoin (BN), benzoin methyl ester (BME)], the maximal extent of conversion
does not exceed 7076%.
The dependences of consumption of monomeroligomer mass per unit of irradiated
surface / on the irradiation time t show that, using initiating compounds of various nature
and concentration in this system, the reaction in all cases is of accelerated autocatalytic
character. The process proceeds with auto-acceleration at the early stages ( = 3555%)
followed by the auto-slowdown at the more advanced stages of conversion ( = 7076%).
The authors explain this character of polymerization by an increment of the structural
viscosity of the system, which is accompanied by the gel effect. A particular feature of the
three-dimensional structuring of the system in photopolymerization is the layer-by-layer
418 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

advancement of the process, which is characterized by a constant frontal (relative to the


light flux) displacement of the polymerized three-dimensional layer (solid phase) and the
oligomer layer (liquid phase). As the result of this heterogeneity of the system, as well as
the redistribution between the chain termination constant and chain growth constant, the
photopolymerization of the systems studied is of auto-catalytic character. Based on the re-
sults of the kinetic studies, the authors arranged all initiating compounds by the photoac-
tivity in the sequence: BA, BP < BN < BME. Printing plates produced based on the systems
studied, owing to the low extent of conversion of photopolymerized compositions, were
characterized by insufficiently high physicomechanical characteristics, an increased swell-
ing in solvents and aged rapidly. Using the heat treatment at 75C after photoinitiation of
the BME system, the degree of conversion was increased up to 9092%, which, in all prob-
ability, is due to the increase of the mobility of reaction groups and a further structuring of
polymer material.
Additional introduction of the initiator azo-,bis-isobutyric acid dinitryl (ADN) in-
creases the extent of conversion up to 9698%. In the opinion of the authors, this is due to
the formation of a complex between the carbonyl group of BME in a triplet state and azo
groups of ADN, which accelerates the photopolymerization process, under the action of UV
irradiation.
D.S. Phillips with coworkers, studying the photopolymerization of N,N-4,4-sulfonyl
diphenylene dimaleimide, found using electron spectra that the mechanism of photopoly-
merization proceeds via the formation of a donoracceptor complex of the sensitizer with
monomer.
Processes in photohardening of oligodienes of copolymer of divinyl with isoprene, oli-
gobutadiene SKD-0 and oligobutadiene diol ORD were studied. Using the method of infra-
red spectroscopy, it was shown that in irradiation with UV light there occurs first
photooxidation and decomposition of carbon chains at single CC bonds and then
crosslinking of macromolecules via oxygen-containing bridges.
The studies showed that the rate and mechanism of photopolymerization and structural
transformations in irradiation has a crucial effect on the formation of the structure of coat-
ings, whose character determines their physicomechanical properties durability.
The mechanism of photohardening of a composition based on hydroxyl-containing
methacrylates and products of interaction of oligodiethylene glycol adipinates with
2,6-toluylene diisocyanate in solutions of methyl methacrylate, methyl methacrylate in a
mixture with methacrylic acid, as well as in a solution of oligoester acrylate TGM-3 (20%),
was investigated.
Using the method of IR spectroscopy, it was shown that in irradiation of films on her-
metically sealed glasses from KBr by ultraviolet light of a DRT-220 mercuryquartz lamp
for 1520 min practically all unsaturated compounds are copolymerized. The absorption
band in the region of 1630 cm 1, which characterizes the CH2=C valence vibrations, dis-
appears. The authors found that the physicomechanical properties of coatings are also con-
trolled by the reaction of isocyanate groups with hydroxides, which continues after
irradiation. The greatest breaking strength (15.030.0 MPa) of coatings is obtained at a ra-
tio NCO/OH = 2.5. Using macrodiisocyanates with a smaller molecular mass (800), the de-
pendence of strength on the NCO/OH ratio is of extremal character, and films with
NCO/OH = 1.5 achieve the highest strength of 370 kg/cm2. In the opinion of the authors,
additional hardening of the film due to the condensation by isocyanate groups and hydroxyl
groups makes it possible to obtain coatings with high elasticity (bending strength, 1 mm by
the ShG scale) and impact resistance (50 kgf/cm). A disadvantage of these coatings is their
CHAPTER 12 419

small hardness 0.20.4 (pendulum M-5) and tackiness, which disappears during the hold-
ing of the coating in the air for 12 h after irradiation. To eliminate the inhibitory effect of
oxygen of the air, moist coatings were covered by a polypropylene film and irradiated
through it.
Due to the inhibitory effect of oxygen of the air, without introduction of a paraffin
floating additive it is impossible to achieve the photohardening of oligoester maleinates.
Modification of oligoester maleinates by polyisocyanates makes it possible to avoid the in-
hibitory effect of oxygen.
Using infrared spectroscopy, it was found that the structuring of unsaturated oligoester
maleinate urethanes in styrene under the influence of UV irradiation includes three
processes:
copolymerization of unsaturated oligoester maleinate urethanes with styrene via C=C
bonds (disappearance of the absorption band in the region of 1645 cm 1);
copolymerization of monomer with isocyanate groups via vinyl bonds (disappear-
ance of the absorption band of valence vibrations ofN=C=O groups at 2270 cm 1);
addition polymerization due to side reactions of free isocyanate groups.
The authors revealed the effect of the chemical structure, its regularity, density of
crosslinks and concentration of polar groups (the ratio NCO/OH) on the physicomechanical
properties of the polymer coating. The use of aromatic isocyanate 2,4-toluylene diisocyan-
ate in the synthesis of oligoester maleinate urethane yielded a coating with larger values of
hardness (0.45 using M-5) and tensile strength (22 MPa) than for coatings based on oli-
goester maleinate and hexamethylene diisocyanate. With increased excess of the diisocy-
anate component, the tensile strength increases to reach the maximal values at a molar ratio
of NCO/OH = 1.51.75. At an increase of the molecular mass of macrodiisocyanate, the
hardness and strength of coatings decrease. All coatings are characterized by a high yield
of the gel fraction, 9296%.
Our works showed that an increase of the formation rate of the polyester coating under
the action of ultraviolet radiation increases the rate of relaxation processes, which provides
for a higher strength (15 MPa) and decreases internal stresses in the coating down to 0.6
MPa. Internal stresses in the same coatings at the radiant-heat hardening are 3.3 MPa, and
the strength of coating is 10.3 MPa. In the opinion of the authors, the efficiency of UV ir-
radiation is stipulated by uniform initiation of copolymerization in the entire bulk, which
provides for the formation of a more homogeneous and ordered structure. Kinetic electron-
microscopy and IR-spectroscopy studies of the structure of photohardened coatings based
on epoxyacrylic oligomers showed that the coating formation process is multistage. At the
first stage, we observe the formation of chemical bonds within the limits of a small number
of molecules and initial adsorption blanks; at the second stage, formation of the three-
dimensional network by forming local bonds between supramolecular structures, which is
accompanied by a sharp increment of the physicomechanical properties. As the result of the
high rate of the relaxation processes, the formation of the three-dimensional network ho-
mogeneous ordered structure is observed in photopolymerization. At a 60-m thickness of
the coating, optimal physicomechanical properties could be obtained by UV irradiation by
a PRK-7 mercuryquartz lamp 1000 Wt power from a distance of 10 cm for 3 min. The
coatings obtained are characterized by high adhesion (2.83.2 MPa) and insignificant in-
ternal stresses (1.21.6 MPa).
Depending on the number of conjugated and unsaturated bonds formed in ultraviolet
radiation and treatment with an acetylenenitrogen mixture in an alkaline medium of
oil AS-8 based on hydrocarbon and naphthene fractions, the forces of adhesion of photo-
420 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

hardened coatings were observed to be different. It was shown that the adhesion force of
coatings is proportional to the intensity and duration of irradiation.
It was found that a bonding adhesive containing more than two conjugated bonds, for
instance, CH2=CHOOCRCH2 COOCH=CH2, is capable of hardening under the ac-
tion of UV irradiation in 0.53.0 min to form a glossy coating. With the amount of unsat-
urated bonds in the product decreasing to 1%, there was practically no polymerization and
the value of the force of adhesion was zero.
The effect of the nature of crosslinking monomers on the content of the three-dimen-
sional polymer and the resistance to breaking loads in photohardening of oligodiethyl ma-
leinate adipinate have been shown in a number of works. The authors found that during the
introduction of styrene and methyl methacrylate at a ratio of 2:1 with respect to the bonding
adhesive, the photopolymerization rate is optimal, and the coatings thus obtained (in irra-
diation by LUF-80 for 7 min) are characterized by a high resistance to swelling in cyclo-
hexanone and a resistance to stretching and abrasion.
Thus, analysis of the literature data shows that, despite a great diversity of studies and
commercial designs of photohardened coatings, formation of coatings from oligomer sys-
tems under the action of ultraviolet light has been studied insufficiently. The data of patents
on the physicomechanical and anticorrosion properties mainly represent the results of vi-
sual studies. The issues of photohardening of coatings from oligomer systems have been
studied insufficiently both on the molecular and supramolecular level. Experiments did not
always show the dependence of the rate of photocrosslinking on intensity of irradiation,
thickness of the coating, concentration of sensitizers and photoreducer. The mechanism of
sensitization in the presence of photoreducers and oligomers has not been sufficiently stud-
ied. Such parameters as the density of the three-dimensional network and interaction with
solvents have not been investigated, and their dependence on the structure of oligomer and
their effect on the physicomechanical, stress strain and relaxation characteristics of coat-
ings has not been revealed. The relationship between the corrosion resistance of photohard-
ened coatings and the density of the three-dimensional network and structural
transformations in the process of photocrosslinking has not been studied.
Studies of these characteristics and dependences is not only of scientific interest, but
is a must in practice for finding optimal variants of photocrosslinking coatings.
Analysis of Western and domestic experience of protecting metal from corrosion
showed that one of the promising directions for producing quick-drying primers for rolled
steel on production lines is the method ultraviolet hardening.
As the result of theoretical discussion and experimental studies, it was found that the
system based on unsaturated epoxyesters in a solution of esters of unsaturated acids and
monobasic and polybasic alcohols quickly hardens under the action of ultraviolet radiation
at a wavelength from 250 up to 400 nm; from the radical polymerization mechanism, con-
ditions of etherification of epoxy resins ED-16 and EIS-1 by methacrylic acid were deter-
mined; the constants of the etherification rates at various temperatures (70, 80, 9394C)
were calculated and the etherification activation energies were found (EED-16 = 1.745109,
EEIS-1 = 1.604106).
Using the method of extraction, the optimal amount of photosensitizer benzophenone
in the systems studied was found to be 2% of the weight of polymerized components.
The inverse dependence of the time of photohardening on the extent of etherification
of the bonding adhesive was determined using the methods of IR spectroscopy and extrac-
tion. It was found that the optimal time of photohardening (i) for compositions based on
epoxyester ED-16 with etherification of 6075% at the thickness of a coating of 40 m is
CHAPTER 12 421

2.50.5 min; (ii) for compositions based on epoxyester EIS-1 with the same extent of ether-
ification at a thickness of 40 m, 30.5 min. These data correspond to the results of studies
of adhesion, internal stresses and impact strength of coatings depending on the time of pho-
tohardening and the extent of etherification of the bonding adhesive. At an optimal time of
photohardening, coatings are characterized by the highest adhesion, optimal internal stress-
es and impact strength.
Higher values of the physicomechanical characteristics correspond to compositions
with a 60% etherification of the bonding adhesive. This is a consequence of the formation
of additional adhesion bonds due to the interaction of free epoxy groups with the metal sub-
strate. It was found that for high-adhesion coatings to be produced it is sufficient to perform
etherification up to 75% at a bonding adhesive to solvent ratio of 70:30 and up to 60% at a
bonding adhesive to solvent ratio of 50:50.
As the result of studies of the physicomechanical and protective properties of coatings
based on the developed photopolymerized compositions, it was determined that coatings
based on epoxyester of resin ED-16 possess the best parameters.
It was found that introduction of oligoester acrylate MGF-9 -,-bis-methacrylate
triethylene glycol phthalate into photopolymerized epoxyester compositions increases
the elastodeformation properties of coatings and their resistance to atmospheric action, wa-
ter, acids and salt fog.
As the result of a series of studies, we revealed the optimal compositions of photopo-
lymerized compositions (conditionally designated as foton-4 and foton-1) and their process
parameters. Photohardening primers foton-4 and foton-1 are recommended for protection
of rolled steel and rolled metal on conveyor production lines.
Using the method of IR spectroscopy, it was confirmed that photopolymerized com-
positions based on unsaturated epoxyesters and oligoester acrylates do not practically
evolve volatile components into the environment in photohardening.
Technical-and-economic calculations of the efficiency of proposed photopolymerized
coatings for protection of rolled steel were performed.
The economic effect in the introduction of foton-1 and foton-4 in terms of 1 m2 pro-
tection with respect to reduced expenditures as compared with primer KhO-068 is much
larger as the result of better protective properties.
The cost of the loss of metal from corrosion in six months in the absence of protection
of rolled steel was determined. With consideration of this cost, it was found that, depending
on the thickness of rolled metal (15 mm), there is an additional economic effect at the
phasing-in of photopolymerized primers foton-1 and foton-4.

12.7 Properties of epoxy acrylate coatings for transport containers


An optimal time of irradiation is 23 min for all compositions. The characteristics studied
are maximal for this time. Compositions based on bonding adhesives with 60% etherifica-
tion are characterized by slightly higher parameters of adhesion and of internal stresses,
which can, apparently, be explained by the formation of additional bonds of free epoxy
groups with metal of the support. Therefore, it is expedient to perform the etherification of
the bonding adhesive only for 60%. An increase of the adhesion bond with metal can also
be done by increasing the content of free epoxy groups in the composition by changing the
ratio of the bonding adhesive and solvent to 70:30. Herewith, the optimal time of hardening
(3 min) remains the same.
Based on the kinetic studies, it can be concluded that the best composition with
422 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

1.5

Resistance coefficient, k
1.0
4

1
0.5 5
2
3
0
0 30 60 90
Time of effect of the medium on primer coatings, days

Figure 12.1 Dependence of the resistance coefficient of primer coatings on the impact time of an
aggressive medium (water) (1, foton-1; 2, foton-2; 3, KhS-068; 4, foton-4; 5, foton-5).

consideration of the physicomechanical properties and photohardening rate is the compo-


sition based on epoxyester ED-16 with the etherification of 60% at a bonding adhesive to
solvent ratio of (7050%): (3050%) and the amount of photoinitiator of 2% (of the total
mass of polymerized components).
Studies of the photopolymerization kinetics of unsaturated epoxyesters in a medium
of unsaturated solvents showed that the main process of photohardening occurs due to the
opening of double bonds and polymerization by the free radical mechanism. The disappear-
ance of the absorption band of CH2=C valence vibrations in the region of 16601640 cm 1
in the infrared spectra of photohardened coatings is an indicator of completion of the poly-
merization process.
Studies of adhesion of photohardened coatings after the impact of aggressive media
on them showed that they significantly exceed KhS-068 by their resistance to water, 20%
NaOH solution, 1 and 0.1 n HCl solutions (Fig. 12.1). It should be noted that coatings based
on primer foton-4 are the most resistant to the action of water and acidic solutions; and coat-
ings on foton-1, to the action of alkali. Coatings based on foton-2 proved close to KhS-068
by their resistance. But introduction of MGF-9 had a positive effect. The resistance of the
coating foton-5 is much higher than that of foton-2.
The results of studies of the resistance of foton coating to the action of aggressive me-
dia were supported by tests in a salt-fog cabinet at a temperature of 40C for 150 h.
The resistance coefficients of coatings were calculated by the formula:

k = A1/A0,

where A0 and A1 are the average adhesion values determined, respectively, before and after
the impact of an aggressive medium.
Figure 12.2 presents the curves of the change of the resistance coefficient of foton and
KhS-068 primers depending on the impact time of an aggressive medium.
As the studies showed, coatings based on epoxyesters with addition of MGF-9 are
more elastic, shock-resistant and resistant to the action of water, though the yield of the gel
fraction is slightly lower than in compositions without oligoester acrylate. Herewith, it
should be noted that the composition based on epoxyester ED-16 is distinguished with high-
er parameters. To enable the final conclusion on the comparison of compositions based on
epoxyesters ED-16 (No 38) and EIS (No 39) and with addition of MGF-9 (Nos 41 and 45),
we studied the protective properties of coatings.
CHAPTER 12 423

1.5

Resistance coefficient, k
1.0

3 1
0.5 4
5
0 2
0 30 60 90
Time of effect of the medium on primer coatings, days

Figure 12.2 Dependence of the resistance coefficient of primer coatings on the impact time of an
aggressive medium (1 n solution of HCl) (1, foton-1; 2, foton-2; 3, KhS-068; 4, foton-4; 5, foton-5).

1.5
Resistance coefficient, k

1.0
4
0.5 1
5
2
0 3
0 30 60 90
Time of effect of the medium on primer coatings, days

Figure 12.3 Dependence of the resistance coefficient of primer coatings on the impact time of an
aggressive medium (1 n solution of HCl) (1, foton-1; 2, foton-2; 3, KhS-068; 4, foton-4; 5, foton-5).

The protective properties of coatings based on photopolymerized compositions Nos


38, 39, 41 and 45, which were conditionally designated as foton-1, 2, 4 and 5, were assessed
by the results of tests of the coatings in the atmosphere, in a salt-fog cabinet and under lab-
oratory conditions. The laboratory studies provided for the determination of the resistance
to aggressive media using local elements. Adhesion of coatings to metals was determined
after the impact of aggressive media: 1 n solution of HCl, 0.1 n solution of HCl, 20% solu-
tion of NaOH and water for three months (Figs. 12.3 and 12.4). The results obtained were
processed by the statistical method of least squares at a confidence coefficient P = 0.95 and
the number of degrees of freedom f = 6. Table 12.4 presents the data of the statistical treat-
ment of the results of determining the adhesion of photopolymerized compositions and
primer KhS-068 after the impact of aggressive media for 7, 14, 28, 60 and 90 days.
Coatings based on KhS-068 were intumescent, cracked, often completely destroyed;
active corrosion of metal was observed. Coatings on foton-2 proved to be permeable, and
underfilm corrosion was observed over a 20% area of the coating; the film was disrupted
in places. Specimens based on foton-5 looked much better after the tests. Underfilm point
corrosion is observed only on an area of 25% of the total surface; herewith, the continuity
of the film is preserved. Coatings based on foton-4 totally preserved their initial form. Coat-
ings based on foton-1 slightly changed. For them, we observed the appearance of underfilm
point corrosion on an area of 0.10.4% of the total surface.
424 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

1.5

Resistance coefficient, k
1.0

0.5 1
4
2
5
0 3
0 30 60 90
Time of effect of the medium on primer coatings, days

Figure 12.4 Dependence of the resistance coefficient of primer coatings on the impact time of an
aggressive medium (20% solution of NaOH) (1, foton-1; 2, foton-2; 3, KhS-068; 4, foton-4; 5,
foton-5).

Thus, the results of tests of primers protective properties enabled their arrangement
in the following sequence by their resistance: foton-4 > foton-1 > foton-5 > foton-2 >
KhS-068.

Table 12.4 Atmospheric constancy of coatings based on primers Foton and KhS-068 (according to
State Standard GOST 6992 68).

Primer Test duration, months

1 2 3 6

Assessment of properties, points

decorative protective decorative protective decorative protective decorative protective

Foton-4 5 8 5 8 5 8 5 8
Foton-1 5 8 5 8 5 8 5 8
Foton-5 5 8 5 8 4* 8 4* 8
Foton-2 4 8 3 7 2 4 2 4
KhS-068 3 6 3 4 2 3 2 3

*Browning in some points of the surface.

Studies of the weatherability of coatings based on photopolymerized primers support-


ed this conclusion. The physicomechanical properties of coatings are in Figs. 12.5 and 12.6.
A reduced resistance of coatings based on foton-5 and foton-2 is explained by the in-
homogeneity of resin EIS-1, containing free phenols. Introduction of MGF-9 into this com-
position significantly increased the chemical endurance and weatherability of the coating;
so for coatings based on foton-5 the parameters were observed to be higher.
Analysis of the obtained results shows that foton-4 and foton-1 are the best primers
with high protective properties. Advantages of the latter are their insignificant volatility un-
der the action of UV irradiation. This is supported by the data of IR spectroscopy.
As the main volatile components of compositions are -,-unsaturated acid and esters
(methacrylic acid, methyl methacrylate, butyl methacrylate, MGF-9), the occurrence of
CHAPTER 12 425

Ib
2.0 5.0
Internal stresses, MPa

Impact strength, Nm
2.0

Adhesion, MPa
4.0
IIb
II
3.0
1.0
I
1.0 2.0
Ia

IIa 1.0

0 0
1 2 3 4
Irradiation time, min

Figure 12.5 Dependences of the physicomechanical properties of coatings foton-1 and foton-2 (I,
II, adhesion; Ia, IIa, internal stresses; Ib, IIb, dynamic strength) on irradiation time and extent of ether-
ification of the bonding adhesive.

2.0 5.0
Ib
Internal stresses, MPa

Impact strength, Nm
2.0 4.0
Adhesion, MPa

Ia
II
I 3.0
1.0 IIa
1.0 2.0
IIb
1.0

0 0
0 1 2 3 4
Irradiation time, min

Figure 12.6 Dependences of the physicomechanical properties of coating foton-4, foton-5 (I, adhe-
sion; Ia, internal stresses; Ib, dynamic strength; II, adhesion; IIa, internal stresses; IIb, dynamic
strength) on irradiation time and extent of etherification of the bonding adhesive.

these compounds in a hardened coating can be determined from the characteristic frequency
of vibrations of the carbonyl group in IR spectra.

12.8 Biocidal coatings based on styromal


Synthesis and the physicomechanical properties of organic and organotin styromal deriva-
tives and coatings on their basis were described. The peculiar feature of these coatings is
426 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

that, along with the high physicomechanical properties, they possess bactericidal, antimi-
crobial and antifouling activities.
Styromal exhibits characteristic reactions peculiar of organic anhydrides and readily
enters into etherification reactions with organic hydroxyl-containing compounds.
Copolymers based on styromal were obtained at the interaction of trialkyl stannanols
or hexaalkyl distannoxanes with styromal or copolymerization of maleic anhydride, styrene
and organic or organotin maleates:

1. R3MOH
CH CH CH CH2 CH CH CH CH2
CO CO CO COOH
O O
x
MR3 x

CH CH CH CH2
CO CO
O O
SnR3 SnR 3 x

2. CH CH + CH CH2 + CH CH
CO CO CO CO
O O O
SnR3 SnR3

CH CH CH CH2 CH CH CH CH2
CO CO COOSnR3 COOSnR3
O
x

where M = C1Sn, R = H1CH3, C2H5.


The physicomechanical properties of coatings based on organic and organotin styro-
mal derivatives (SMA) were studied. The study of the thermomechanical properties of or-
ganic and organotin styromal derivatives was done on a Tsetlin instrument at a load of 100 g
on a punch of 4 mm in diameter.
At the introduction of organotin groups into styromal, we observed a sharp shift of the
softening temperature to the region of higher values, by approximately 100C. The thermo-
mechanical properties of tert-butyl styromal esters with varying degrees of etherification*
and triethyl stannyl styromal derivatives were studied.
At the same extent of conversion of carboxyl groups to ester groups in the case of

*The percentage of etherified carboxyl groups in copolymer was calculated based on the data of
elemental analysis and potentiometric titration.
CHAPTER 12 427

butanol or triethyl stannol as etherifying agents, the properties of copolymer are observed
to change sharply.
The emergence of a significant deformation of the copolymer containing a di-triethyl-
stannyl substituent in the anhydride group
CH CH
COOSnR 3 COOSnR3
is, probably, due to the weakening of intermolecular interaction owing to the absence of free
carboxyl groups.
The composition of produced copolymers was determined from the results of the ele-
mental analysis and potentiometric titration. Table 12.5 presents some physicochemical
characteristics of produced copolymers.
Table 12.5 Physicochemical constants of synthesized copolymers.

Copolymer Tsoft, Capacity of In Elemental analysis, %


C COOH groups DMF
in mgeq/h C H O

found calc. found calc. found calc.

SMA 1:1 205 71.26 71.28 5.15 4.95


217 8.50 0.52 71.34 5.12
SMA with tert-butyl 201 70.25 70.03 6.35 6.27
ester 215 2.50 2.65 70.10 6.17
SMA with triethyl 300 2.42 2.80 57.95 57.47 5.53 5.74 18.11 18.9
stannanol 57.03 5.76 18.66
SMA with hexaethyl 300 1.87 64.25 64.13 5.64 4.34 11.01 10.50
distannanol 63.90 5.15 10.95

Film formers based on styromal modified by organotin compounds form brittle coat-
ings, which break down and peel off in the formation process at a comparatively low value
of internal stresses.
A dependence of internal stresses on the content of triethyl stannanol in the copolymer
was given. It is seen that with the increase of the extent of etherification of anhydride groups
by triethyl stannanol the internal stresses sharply drop down. This is, probably, due to the
weakening of intermolecular interaction of copolymer chains with the decrease of the con-
tent of free hydroxyl groups. At a styromal/triethyl stannanol molar ratio smaller than 1:0.04
we observed a spontaneous destruction of coatings in the process of formation and ageing.
Modification of styromal by butanol improves the physicomechanical properties of
coatings.
Table 12.6 presents the data on the effect of the percentage of tert-butanol and triethyl
stannanol on internal stresses and strength properties of coatings. It is seen that modification
of styromal by R3COH and R3SnOH (where R = CH3, C2H5) affects the physicomechanical
properties of coatings in different ways.
A sharp increment of internal stresses is observed in the system at a small content of
etherifying agents; herewith, the breaking strength of coatings changes insignificantly as
compared with the strength of the copolymer.
428 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 12.6 Dependence of internal stresses (in) and strength (p) (in kgs/cm2) on the ratio of
initial components for coatings based on styromal modified by butanol and triethyl stannanol.

Molar ratio of components (CH3)3COH (C2H5)3SnOH

b p b p

1:0 1.5 18.0 1.5 18.0


1:7.02 3.5 21.6 3.6 16.4
1:0.04 3.0 22.8 3.0 16.8
1:0.06 2.6 27.4 2.5 15.5
1:0.1 2.2 30.7 2.3 11.5
1:0.2 1.9 21.9 2.3 10.8

As the content of these components in the system increases, internal stresses go down,
and the strength of coatings increases in the modification by tert-butanol and drops down
in the modification by triethyl stannanol. A sharp increase of internal stresses in coatings
formed from the mentioned systems is probably due to the reaction of tert-butanol or tri-
ethyl stannanol with anhydride groups of copolymer in the process of film formation.
Coatings based on triethylstannyl styromal ester spontaneously break down in the pro-
cess of formation.
To improve the physicomechanical properties of coatings based on styromal and its
organic and organotin derivatives, their copolycondensation with glycols at 80100C in
an organic solvent was carried out.
Data on the effect of the content of triethyl stannanol or diethylene glycol on internal
stresses and strength properties of coatings based on styromal and diethylene glycol or sty-
romal and triethyl stannanol were given. It is seen that this dependence is nonmonotonic.
Introduction of triethyl stannanol into the styromal diethylene glycol system within the
limits of 0.10.15 wt. % induces an increment of internal stresses, herewith, the strength
of the coating drops down. The further increase of the content of triethyl stannanol leads to
a decrease of internal stresses and a considerable increment of strength.
A significant increment of internal stresses at a certain ratio of the initial components
is, probably, due to the formation of a three-dimensional structure by crosslinking styromal
by diethylene glycol, as well as to the coordinating effect of electron-deficient organotin
groups of the type of R3Sn.
The largest effect of the increase of strength and of the decrease of internal stresses is
observed in modification of the styromal diethylene glycol system by triethyl stannanol
as compared with the styromal triethyl stannanol system modified by diethylene glycol.
Coatings from three-component systems based on styromal diethylene glycol and tri-
ethyl stannanol are more resistant to ultraviolet ageing as compared with coatings from one-
and two-component systems; data on the change of internal stresses in ageing of coatings
based on styromal and its derivatives under the action of ultraviolet irradiation by a PRK-2
lamp were given. It is seen that the sharpest decrease of internal stresses indicative of the
decomposition of polymer is observed in coatings from styromal. Modification of styromal
by organotin compounds increases the resistance of coatings to ageing.
Preliminary copolycondensation of these components by heating at 80100C for 30
min prior to the application of the solution to the support makes it possible to improve the
physicomechanical properties of coatings as the result of decreasing internal stresses in
them more than threefold (Table 12.7).
CHAPTER 12 429

Table 12.7 Dependence of internal stresses (b) of coatings based on the triethyl stannyl derivative
of styromal modified by diethylene glycol (DEG) on the ratios of the initial components and
formation conditions.

SMA: :DEG molar ratio* b, MPa

with preheating without preheating

1:0:1 0.30 1.2


1:0:5 0.50 1.5
1:0.08:5 0.70 1.7
1:0.13:5 0.48 1.8
1:0.2:5 0.30 1.3
1:0.44:5 0.21 1.0
1:0.1:0 0.28 1.3
1:0.1:1 0.42 1.5
1:0.1:3 0.35 1.6
1:0.1:5 0.30 1.2
1:0.1:10 0.28 1.0

*Percentage of diethylene glycol.

The low-molecular-mass copolymer of styrene and maleic anhydride (styromal) and


its organic and organotin derivatives were synthesized and characterized.
The thermomechanical, adhesion and strength properties of copolymers were studied.
It was found that introduction of organotin groups R3Sn into the copolymer by ether-
ification or copolymerization leads to a sharp shift of the softening temperature to the region
of higher values by about 100C.
Modification of organic or organotin styromal esters by diethylene glycol makes it
possible to produce new film formers with higher physicomechanical properties.
Copolymers containing organotin groups R3Sn possess a resistance to ultraviolet light
and good bactericidal properties. They were found to have a high bactericidal activity with
respect to the aurococcus; coliform, hay and brucella bacteria and some others, as well as
to plankton organisms, which inhabit the water of industrial reservoirs. Copolymers con-
taining groups (CH3)Sn, (C2H5)3Sn, (n-C4H9)3Sn and (C6H5CH2)3Sn possess high-
er bactericidal properties.
430 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY
13 Technology of the
Protection of Large-tonnage
Foodstuff Containers

13.1.1 Methods of protecting storage tanks for potable 96% ethyl alcohol
The basic task of storage tank facilities in storage of a product is to provide for its qualitative
and quantitative preservation in long-term storage.
Most enterprises store products in cylindrical steel tanks made from steel grade 3.
Examination of the corrosion state of the internal surface of tanks for storage of ethyl
alcohol showed metal of these tanks to be in satisfactory state fissures on the bottom are
no more than 0.5 mm deep after a one-year operation.
According to reference data [Vorobyeva, G.Ya., Corrosion Resistance of Materials to
Aggressive Media of Chemical Productions, Moscow: Khimiya Publishers, 1975 (in Rus-
sian)] alcohol is a weak corrosion medium, characterized by an average rate of corrosion
no more than 0.001 mm/year at its action on steel grade 3.
Nevertheless, the quality of alcohol after its contact with rust, which catalyzes oxida-
tive processes, changes to a certain extent towards the formation of such products as acetic
acid (Table 13.1).
Thus, the storage of alcohol in steel tanks renders an unsatisfactory effect on the qual-
ity of the product.
Studies of the issue revealed that steel grade 3 is not in the list of metals allowed for
contact with alcohol, and in the world practice it is stored in tanks from stainless steel.
Therefore, for tanks from steel grade 3, in which alcohol is stored, it is obligatory to use
protection of the product from metal of the tanks.
Two methods of protection are usually used for protection of the inner surface of steel
tanks from steel grade 3:
inhibition of the protective surface under the action of the medium;
polymer coatings based on lacquers and paints.
The first method of protection from corrosion is applicable mainly for airtight volumes
(pipelines, pressure vessels, etc.). For RVS-3000 intended for storage of food products this
method is difficult to use for a number of reasons:
volatile inhibitors contain amines, which are poisonous and for this reason are not
used in food industry in pure form;
solutions of inhibitory substances should be only aqueous, so their use is impossible
in winter time.
432 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 13.1 Results of chromato-mass-spectrometric analysis of alcohol after accelerated tests in


contact with polymer coatings.

Compound Concentration, mg/l

Initial specimen After contact with After contact with


Baryer-1P rust

Methyl acetate 4.32 4.75 4.68


Ethyl acetate 0.36 0.57 0.55
Diethoxy ethane 0.15 0.20 0.20
Methanol 75.0 74.0 75.0
Toluene 0.04 0.05 0.04
Ethyl butyrate 0.20 0.23 0.24
Propanol-1 3.82 4.78 4.75
Butyl acetate 0.01 0.03 0.01
2-Methyl propanol-1 0.56 0.62 0.60
Butanol-1 0.08 0.04 0.05
Xylol 0.02 0.01 0.01
1,3-Dimethoxy propanol-2 0.25 0.16 0.22
3-Methyl butanol-1 0.14 0.15 0.14
1,2,4-Trimethyl benzene 0.03 0.01
Cyclohexanone 0.15
Acetic acid 0.06 0.06 0.29
Propylene glycol 0.02 0.01 0.01
Ethyl ester of hexanoic acid 0.01 0.01 0.01

Besides, if the inhibitor would be totally removed which, in fact, is not real in prac-
tice the stored product would be in contact with metal of the tank, thus leading to the de-
terioration of its quality in long-term storage.
In this situation, protection should be of the barrier type to exclude the contact of the
product with metal. In full measure, this requirement is satisfied by lacquer-and-paint pro-
tective systems.

13.1.2 Objects and methods of studies


The total of 30 grades of coatings based on water-borne and organic epoxy resins, polyure-
thane and latex elastomers, chlorosulfonated polyethylene, copolymer epoxy organosilicon
and inorganic compositions were studied.
Standard free films of 30 grades of coatings were prepared and tested in contact with
alcohol by the gravimetric method.
The following methods were used in the work.

Study of the resistance of the coating by the gravimetric method


Free films of 30 grades of coatings were placed into a solution of alcohol at a ratio of
1:1 as compared with the ratio of the inner surface to the volume of the product (0.214 ml
to 1 cm2 coating). The film of the coating was weighed on a daily basis till a dynamic equi-
librium was established in the product with respect to the leachability of the components of
the coating and the swelling of the film in the product, which is reflected in the stability of
CHAPTER 13 433

the weight of the tested coating. Usually, the dynamic equilibrium of such a system is es-
tablished over the period of 7 to 14 days.
If the leachability of the coatings components predominates, the weight of the film
decreases daily. In this case, the coating is unsuitable for use in the tested medium.
If the swelling of the film of the coating predominates, then the film of the coating is
considered to be resistant in the tested medium in the case, when the increase of the weight
does not exceed 3%.
Method of accelerated tests
Accelerated oxidation of the product was performed in an ST-80M-2 thermostat for 4
months at a temperature of 45C in airtight glass vessels without access of oxygen of the
air in contact with chosen coatings.
Quality of the coating after accelerated tests was checked by the following parame-
ters: weight of the specimen film, adhesion to the support, appearance.
Quality of the product was determined by the following parameters: physicochemical
and organoleptic characteristics of quality; chromato-mass-spectrometric analysis of the
depletion of the coatings components; safety parameter of alcohol.

13.1.3 Results of studies


Preliminary tests of 30 grades of coatings in contact with alcohol indicated that most of the
recommended coatings used in food industry did not endure a prolonged contact (up to 14
days) with ethyl alcohol of 96% concentration.
Characteristics of the leachability of epoxy, urethane and copolymer coatings are giv-
en in Table 13.2.
Table 13.2 Leachability of components of coatings in medium.

Group of coatings Leachability. wt. %

Epoxide from 4.66 to 31.93


Urethane from 10.45 to 16.99
Copolymer from 0.11 to 11.64

Out of 30 grades of coatings, 5 specimens passed preliminary tests. They include:


1. Epoxy organosilicon lacquer
2. Fluoroplastic coating
3. Inorganic coating
4. Copolymer modified coating
5. Epoxy coating for food containers.
These grades of coatings were recommended for accelerated tests in contact with
alcohol.
After accelerated tests, specimens of coatings were analysed to assess their appear-
ance, adhesion and change of weight.
The appearance of all five specimens remained without visible changes as compared
with the initial specimens without contact with alcohol.
Adhesion increased from 1 point up to 2 points, except for the inorganic coating.
The change of weight of the coating specimens towards the decrease was characteristic
of four grades of coatings. An exception was the inorganic coating, in which the weight of
specimens remained unchanged after the accelerated tests in the medium.
434 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Analysis of the quality of alcohol


Five types of coating were tested in contact with alcohol. After contact with the prod-
uct, a satisfactory result was shown by one composition, whose characteristics are presented
in Table 13.3.
Table 13.3 Quality indices of alcohol-resistant coating.

Index Value

Base
Colour and appearance Clear liquid with yellowish tint
Density, g/cm3 1.18 1.19
Silica modulus 3.6 4.5
Composition
Appearance and colour Even mat coating of gray colour without
drips or inclusions
Mass fraction of nonvolatiles, %, no less than 80
Time of drying to degree 3 at 20C, hours, no more than 2
Viability at 20C, hours, no less than 10
Relative viscosity by VZ-246 (nozzle 4), s, no more than 21 30
Coating
Impact strength of film on a U-1 instrument, J (kgf/cm2), 1.0 (10)
no more than
Adhesion of film, points, no more than 2
Bending elasticity, mm, no more than 20
Pendulum hardness, arb. units, no less than 0.6

The inorganic alcohol-resistant coating is a two-component system. The base is high-


modulus liquid glass; the filler, zinc powder.
The parameters of quality of the base and of the ready-to-use coating are presented in
Table 13.3.
We tested initial alcohol, alcohol after contact with polymer coatings and alcohol after
contact with rust of the inner surface of the tank.
The results of the tests are represented by the following characteristics of the objects
of study.
1. Ethyl alcohol:
physicochemical and organoleptic characteristics of quality,
chromato-mass-spectrometric analysis of the leachability of coatings components,
safety parameters correspond to the norm.
2. Polymer coatings: the list of component parts of the formulations.
physicochemical and organoleptic parameters are given in Table 13.4.
Organoleptic parameters
the appearance: colourless liquid without foreign inclusions and residue,
colour: colourless liquid,
taste and aroma: characteristic of food-grade first-quality rectified alcohol without
taste and smell of foreign substances.
Analysis of the content of trace elements
Elemental analysis was performed on a Liberty-200 inductively coupled plasma
emission spectrometer (Varian).
CHAPTER 13 435

The chosen analytical lines, nm:

Cu 324.754 Cd 214.438 Pb 220.353 As 188.979


Hg 184.950 Zn 2206.200 Fe 259.940 Si 251.611

Table 13.4 Physicomechanical and organoleptic parameters of quality of alcohol.

Parameter Unit Quality indices


measure
Regulatory Real value
norm
initial after
specimen contact

Volume fraction of ethyl alcohol, no less than % 96 96.0 96.0


Purity test with sulfuric acid ml passed passed passed
Oxidizability test at 20C, no less than min 10.0 12.0 11.0
Mass concentration of aldehydes in terms of acetic mg 10.0 6.8 8.2
aldehyde per 1 dm3 of anhydrous alcohol, no more than
Mass concentration of fuel oil in terms of isoamyl and mg 10.0 7.3 9.0
isobutyl alcohols (1:3) per 1 dm3 of anhydrous alcohol,
no more than
Mass concentration of esters in terms of acetic ethyl mg 50.0 46.0 45.0
ester per 1 dm3 of anhydrous alcohol, no more than
Volume fraction of methyl alcohol in terms of % 0.05 0.009 0.009
anhydrous alcohol, no more than
Mass concentration of free acids (without carbonic mg 15.0 0.07 0.07
acid) in anhydrous alcohol per 1 dm3, no more than
Content of furfurol nd nd nd

nd, not determined

The content of silicon was determined because it is present in the components of the
coatings:
Conditions of recording the spectra:
power 1.5 kWt,
consumption of argon in plasma 15.0 l/min,
consumption of argon for blowing off the burner 2.25 l/min,
consumption of analyzed solution 1.5 ml/min,
pressure on the atomizer 100 kPa,
viewpoint optimized by the signal/noise ratio,
integration time 5 s,
replication number 5.
The calibration was carried out using Merck standards.
The results are presented in Table 13.5.
From the data presented in the table, it follows that:
1. By the content of toxic metals Cu, Zn, Pb, Cd, As, Hg, Fe all investigated ethyl
alcohol specimens correspond to the safety criteria of the medico-biological requirements
MBT 5061-89 of the Ministry of Health of the Russian Federation.
2. The concentration of Si and Zn present in the component of anticorrosion coatings
does not increase in specimens of ethyl alcohol.
436 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 13.5 Content of trace elements in alcohol.

Index Unit Regulatory Initial Specimen after


measure norm specimen contact with coating

Mass concentration of lead mg/kg 0.10 <0.01 <0.01


Mass concentration of cadmium mg/kg 0.05 <0.01 <0.01
Mass concentration of arsenic mg/kg 0.10 0.02 0.02
Mass concentration of mercury mg/kg 0.03 <0.001 <0.001
Mass concentration of copper mg/kg 0.50 0.23 0.24
Mass concentration of zinc mg/kg 5.00 0.48 0.46
Mass concentration of iron mg/kg 5.00 0.06 0.05
Mass concentration of silicon mg/kg nd 5.3 5.3

Study of ethyl alcohol specimens by the method of chromato-mass-spectrometry


Chromatographic parameters:
quartz capillary column DBWAX (analogue of Carhowax), length 30 m, inner diam-
eter 0.25 mm, film thickness of immobile phase 0.25 m;
temperature regime: stage 1, 2.5 min at 35C; stage 2, temperature increase up to
180C at a rate of 5C/min;
injector with flow divider (1:10), temperature 220C;
linear rate of carrier gas 5 ml/min.
Mass-spectrometric parameters:
range of masses 41450;
type of ionization by electron impact;
scanning rate 1 spectrum/s;
ionization time setting automatic.
The results are presented in Table 13.5.
From the data presented in the table, it follows that the investigated specimens are to-
tally identical, which indicates that there is no leaching of volatile organic components from
anticorrosion coatings in their contact with ethyl alcohol.
Thus, the inorganic coating rendered no negative effect on the product and itself did
not undergo significant changes under the influence of alcohol.

13.1.4 Technology of anticorrosion protection of the inner surface of ethyl alcohol


storage tanks

The technology of protecting the internal surface of VRS-3000 from corrosion includes the
following operations:
quality check of lacquer-and-paint material
preparation of the surface of metal
sealing of welded seams of the internal surface
application of the protective layers of the coating
post-operation process control
commissioning of the protected surface for operation.
1. Quality check of lacquer-and-paint material
The supplied materials should satisfy the requirements of respective technical specifi-
cations:
CHAPTER 13 437

the composition of the coating. In this case, for food purposes the composition is sup-
plied without the hardener. The applied coating is not subjected to the carbon dioxide treat-
ment,
the solvent in the recommended process is a mixture of ethyl alcohol and acetone at
a ratio of the weight fractions 1:1.
The characteristics of the composition and coating on its basis are presented in Table
13.6.

Table 13.6 Quality indices of composition and coating on its basis.

Quality indices of material Norm per


technical specifications

Appearance and colour Upon drying, the film is even, of


matte gray colour, without drips or
mechanical inclusions
Drying time at 202C up to degree 3, hours, no more than 2
Viability at 202C, hours, no less than 10
Relative viscosity by VZ-246 with nozzle 4 at 202C, hours,
no more than 36
Mass fraction of volatiles, % no less than 80
Coating
Impact strength by U-1A instrument, J (kgf/cm2), no less than 1(10)
Bending elasticity, mm, no more than 20
Initial equilibrium potential, mV 980
Adhesion, points, no more than 2
Pendulum hardness, arb. units, no less than 0.6

2. Preparation of the surface of metal


Preparation of the metal surface of the tank consists in its purification from rust, scale,
dust, grease and other contamination.
Purification should be done by pneumatic metal brushes, whose characteristics are pre-
sented in Appendix.
An industrial vacuum cleaner is used for dusting the purified surface.
In cases of grease pollution, the surface is cleaned by wiping cloth soaked in a solvent.
An alcohol-acetone mixture prepared at a component ratio (w/w) of 1:1 is used as the sol-
vent. Degreasing of the prepared surface is also carried out by this solvent. Consumption
of the solvent is 0.15 g/m2.
After degreasing, the surface is held for no less than 1 h in a premise with exhaust ven-
tilation.
The prepared surface should be clean, even; the presence of a dense residual rust of no
more than 40 m thick is allowed.
3. Sealing of welded seams of the internal surface
Welded seams should be thoroughly dusted and degreased in accordance with the pro-
cess as per p. 2 above.
The prepared surface of welded seams is wiped by wiping cloth soaked in the base of
the composition.
In 1 h, one layer of the composition is applied to the surface of treated welded seams
and in the weld proximity of 10 cm on both sides of the seam.
438 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The composition is diluted to working viscosity of 2325 s according to VZ-246 with


nozzle 4 with distilled water.
Application of the ready-to-use composition is done by any of the traditional methods:
by a brush, roll or spraying.
4. Application of the protective layers of the coating
Prior to the application of the coating, all the surface is treated with the base of the
composition. In 24 h after the application of the coating to the welded seams, the treated
internal surface is protected by two layers of the coating. The formulation of the first and
second layer is the same as in p. 3. The consumption of the composition for one layer of the
coating is 250 g/m2. The interlayer drying of the coating is 3 h at the application temperature
of no less than 5C. The composition is not used at negative temperatures of the surface, as
the solvent for it is water.
Painting workers move from top to bottom: roofage upper parts lower parts bot-
tom.
In three days after the last layer of the coating is applied, it should be treated with car-
bon dioxide to finalize the formation of a strong film of the coating. For this purpose, use
is made of pressure vessels with carbon dioxide, dry ice or carbon-dioxide fire extinguish-
ers.
The thickness of the ready coating on seams is no less than 350 m; and on the other
surface of the tank, no less than 300 m.
5. Post-operation quality control
When performing the work on the application of the composition, the quality control
is provided for at all stages of its execution; this is be reflected in the documents for the
preparation of the surface and application of the composition.
The quality of the coating is assessed by its appearance, extent of drying and adhesion.
The appearance of the coating is assessed according to the State Standards.
The extent of drying of the coating is controlled in accordance with the State Stan-
dards.
Adhesion of the coatings is checked by the method of lattice notches.
The thickness of the coating is controlled by any thickness gauge.
6. Commissioning of the protected surface for operation
After all process operations, the coating is ready for performance in contact with a food
product in 5 days of holding at a temperature of the environment no less than 5C. The coat-
ing is not electrically conductive, which solves the problem of the electrostatic sparking
safety inside a filled tank. At a prolonged holding of the empty tank, the coating performs
the protective functions and withholds temperatures from minus 30C to plus 50C of the
ambient air. The service life of the coating is no less than 15 years.

Requirements to the safety of works, industrial sanitary and fire safety


Works on the protection of tanks from corrosion should be performed with the obser-
vation of safety rules in accordance with the State Standards and preventive fire-fighting
rules for industrial enterprises, as well as sanitary rules approved by the Ministry of Health.
Anticorrosion works should be maximally mechanized; means should be provided to
ensure the elimination of hazardous factors and the reduction of harmful industrial factors
for the workers. The level of hazardous and harmful industrial factors should not exceed
admissible values.
Anticorrosion works should be carried out in accordance with the requirements of the
State Standards.
CHAPTER 13 439

When performing works on open sites or in facilities equipped with forced (local and
general induced draft) ventilation, it is necessary to have fire-fighting means. Ventilation
should satisfy the requirements of the State Standards. Work with faulty ventilation is for-
bidden.
The content of harmful substances in the air should not exceed the maximally permis-
sible concentrations.
Organization of production premises, utility rooms and work places should correspond
to the requirements of the construction and sanitary norms and design regulations approved
by the Russian Federation Construction Committee and the Ministry of Health.
The level of noise and vibration on work places should not exceed the norms.
Work places should be organized with consideration for the ergonomic requirements
and convenience of workers movements and actions.
Anticorrosion works are allowed to be carried out by persons not younger than 18
years, who passed a medical examination, received training and instructions. Workers
should be regularly checked for their knowledge of instructions and pass regular medical
examinations.
Production personnel should not be allowed to perform anticorrosion works without
personal protective equipment. Kinds of personal protective means are determined by nor-
mative documents for the technological process, for materials and equipment used. The
working order of the personal protective means should be checked before work.
Workers should have knowledge of:
hazardous, harmful production factors associated with works performed; harmful
substances occurring in applied materials and present in the air of the working area; the
character of their action on the human organism;
instruction for the sequence of work and the maintenance of the workbench;
instruction on the safety rules, fire-fighting regulations and industrial sanitary;
first-aid techniques to casualties;
rules of personal hygiene;
rules of using personal protective means.
Personnel working with fire- and explosion-dangerous harmful substances and their
mixtures should be granted periodic 10-min work breaks each hour during the working
shift.
Personnel working at a height of more than 3 metres should use safety belts.
When preparing and painting the surfaces of tanks, no less than two technicians should
be on permanent duty at the entrance. Personnel working inside the tank and those on duty
should always communicate (by means of sound or light signals or by means of a rope, one
end of which should be taken outside and tied to a support and the other to the safety belt
of the painting worker). Personnel on duty should be equipped with the same means as the
painting workers.
Electrical equipment for painting works should correspond to classes of fire and ex-
plosion safety for premises, as determined by the rules for electrical equipment installation
approved by Gosenergonadzor (State Power Supply Inspectorate). Electrical equipment
should be installed and operated in accordance with the rules for technical maintenance of
electrical installations. Equipment and articles to be painted should be grounded.
Rules for the Design and Safe Operation of Vessels Working under Pressure
approved by Gosenergonadzor bodies should be observed when using equipment operated
under pressure (spraying compressors, shotblasting units, etc.)
Placement of the equipment should take into account the convenience of its
440 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

maintenance and safe evacuation of workers in emergency. Equipment used for anticorro-
sion works should correspond to the requirements of the State Standards.
At working sites, it is forbidden to smoke, keep and take food, use sources of open fire
and tools causing spark formation.
Before the start and after the end of works, the production area and protected objects
should be ventilated.
Metal components or assembly units in places of possible spark formation upon impact
or shift should be isolated one from another.
Polymer material, solvents, thinners and hardeners should be kept in storage facilities
equipped with a forced air supply and fire-fighting means in accordance with the require-
ments of the State Standards (GOST) and in intact sealed containers with appropriate iden-
tification information.
Dirty wiping cloths, working cans, painting tools and production wastes should be put
to specially allotted places and degreased.

13.2 Bactericidal wear-resistant coatings for storage and processing of grain


and grain products
The development of highly efficient preserving technologies for storage of grain and its
products using bactericidal coatings, which provide for a significant decrease of contami-
nation of grain and its products by spore bacteria (B. subtilis, B. mesentericus), fungi and
molds, causing the microbial damage of grain fibrin and potato disease of grain, is a top-
ical scientific and applied problem.
Its solution is associated with the development of ecologically pure technologies for
production and processing of agricultural raw materials and functional polymer materials
with special properties. The so called bread diseases, which are caused by the fact that up
to 80% of harvested grain in some regions are affected by pests, pose a serious problem for
bread-baking industry. Even if the food-making technology provides for the subsequent
high-temperature processing of raw materials, it is preceded by low- and mid-temperature
stages, where in the absence of bactericidal protective materials biodeterioration processes
of raw materials with increased autolytic activity (of especially valuable part of grain, glu-
ten) can develop further. This leads to a decrease of safety and native value of grain and its
products, as well as initiates and intensifies the biodegradability of basic stock.
Microorganisms get to flour mainly from the surface of grain during its growth and
grinding, as well in transportation within a flour-grinding plants. For this reason, both the
species composition and amount of microorganisms depend on the conditions and time of
grain storage and pretreatment before grinding, as well as on the content of hull particles
(i.e., on the grade of flour).
The actual contamination of flour by various bacterial species varies within very wide
limits and depends on the content of hull particles in the product and on the thorough prep-
aration of grain for grinding. Examination of various flour samples showed that the general
content of bacteria in them can vary from 1,300 up to 20,000 per 1 g. The bacterial content
in high-grade flour is, as a rule, 23 times lower than in first- or second-grade flour.
Bread-baking plants receive up to 6065% of the general volume of flour with reduced
bread-baking properties. Usually, the reduced quality of flour, especially from injured
grain, is accompanied by an increased contamination with spore bacteria (B. subtilis, B. me-
sentericus), which cause the potato disease of bread. Bread with signs of potato disease
causes acute gastrointestinal disorders.
CHAPTER 13 441

Various measures are worked out to reduce the negative consequences of this phenom-
enon, including the processes of producing safe baked goods from flour contaminated with
spore-forming bacteria.
The most topical and efficient solution of the problem is the active (but safe for the
human organism) inhibition of pathogenic microflora using bactericidal coatings at the ear-
ly stages of the grainflourbread chain. The proposed approach enabled storage, treat-
ment and processing of grain with the lowest losses of its most valuable part gluten, made
it possible to prevent the significant damage to health, as well as to increase the cost effi-
ciency of elevator, flour-grinding and bread-baking plants. The known developments in this
field are based on the use of coatings with low-molecular-mass bactericidal additives. In
operation, the latter easily migrate from the coating, which leads to the rapid loss of bacte-
ricidal properties and contamination of food raw materials. With this in mind, technologies
were worked out for storage of grain and its products using bactericidal coatings containing
high-molecular-mass (oligomer and polymer) additives, chemically bound to the polymer
base of the coating and not subject to migration. These bactericidal coatings will provide
for a stable bactericidal effect, microbial preservation and safety of food products through-
out the entire service life of the coating.
The obligatory stage of the process of producing high-quality baked goods is matura-
tion of flour in special bunkers for several months. This biochemical process proceeds much
faster, for 4560 days, if the flour is constantly aerated. In this connection, along with bac-
tericidal properties coatings should possess a high wear resistance to granular products.
Maturation is the process of improving bread-baking properties of freshly baked flour
in its storage. Such a flour from new-harvest grain is characterized by a low water-absorb-
ing capability, increased enzyme activity, relatively weak gluten. Bread from immature
flour has the dense and sticky crumb, insufficient volume and porosity. The essence of flour
maturation is to increase its strength as the result of the oxidative action of oxygen of the
air and peroxides on protein substances and enzymes.
Together with the Joint Stock Company Krasky BEP, we developed and introduced
enamel of grade BEP for coatings with high bactericidal properties and abrasion resistance.
Enamel is produced in cream and light-gray colours. Other colours are possible on re-
quest (using nontoxic iron-oxide pigments).
Parameters of quality of the enamel base, hardener and ready-to-use enamel should
correspond to the requirements given in Table 13.2.1.
Table 13.2.1

Parameter Value Testing method

BASE
Extent of grind, m, no 40 According to GOST and
more than per p. 2 of these technical
specifications
HARDENER
Colour and appearance Homogeneous liquid of yellow-brown Per p. 3 of these technical
colour without foreign inclusions. Tint is specifications
not rated.
ENAMEL
Colour and appearance Upon drying, enamel should form an even According to GOST and
of film semi-glossy film of respective colour per pp. 4 and 5 of these
442 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 13.2.1 (continued)

Parameter Value Testing method

without foreign inclusions. Brush marks technical specifications


are admissible. Tint is not rated.
Mass fraction of volatiles, 5 According to GOST and
%, no more than per p. 6 of these technical
specifications
Thickness of non-dripping 0.5 Per pp. 4 and 7 of these
wet layer, mm, no less technical specifications
than
Time of drying t up to 24 According to GOST and
degree 3 at 20 2C, per p. 4 of these technical
hours, no more than specifications
Impact strength of film by 40 According to GOST and
U-1 instrument, cm, per p. 4 of these technical
no less than specifications
Bending elasticity of film, 3 According to GOST and
mm, no more than per p. 5 of these technical
specifications
Adhesion of film, points, 1 According to GOST,
no more than Section 2 and per p. 4 of
these technical
specifications
Resistance of film to static 2 According to GOST,
action of water at Method A and per pp. 4
(1002)C, hours, and 8 of these technical
no less than specifications
Abrasion resistance, 10.5 GOST, international
kgf/m standard ISO 77 84

Note: Resistance of film to static action of water is checked by samplings, no less than twice a year.

Methods of tests
1. Taking samples according to the State Standard.
Before conducting tests, samples of hardener and enamel base are held for not less than
24 h at a temperature of 202C, and then are thoroughly mixed. It is admissible to warm
or cool the sample to this temperature on a water bath during the mixing.
2. The degree of grinding of the enamel base is determined in accordance with the State
Standard (GOST) by the boundary of the beginning of the lines, by the place of the appear-
ance of the third uninterrupted line, with its depth reaching the metal. A separate uninter-
rupted line, beginning at a distance of more than 15 mm from the other lines, is not taken
into account.
3. Determination of the colour and appearance of the hardener are performed visually.
The hardener is poured into a test tube and viewed in transmitted light. The absence of in-
clusions is checked by pouring onto a glass, which is viewed in reflected and transmitted
light.
4. Preparation of enamel for the test.
4.1. Before conducting the test, the enamel base is thoroughly mixed with the hardener
for 35 min.
4.2. To determine the colour and appearance of the film, it drying time, impact
CHAPTER 13 443

strength, adhesion and resistance to the static effect of liquids, enamel is applied to plates
from steel, grades 08 kp or 08 ps, 7050 mm in size and 0.81.0 mm thick, prepared ac-
cording to GOST. To determine the bending elasticity of the film, the primer and enamel
are applied to tin plates 20100 mm in size and 0.2528 mm thick, prepared according to
GOST.
4.3. To determine the colour and appearance, drying time, impact strength and adhe-
sion of the film, enamel is applied to the plates in one layer on one side. To determine the
resistance to the static effect of water, enamel is applied to the plates in one layer on both
sides, protecting the edges by the tested material. Enamel is applied by a brush. The thick-
ness of the one-layer enamel film after drying should be 150200 m. The thickness of the
film is measured by any thickness gauge, which provides for the measurement within the
given range with an error margin of no more than 8 m.
4.4. To determine the thickness of the nondrip wet layer, enamel is applied to steel
plates not less than 150150 mm in size by means of an applicator.
4.5. To determine the abrasion resistance, enamel is applied in one layer on one side
of glass plates made from special-purpose glass 9060 mm in size and 1.2 mm thick. Enam-
el is applied by an applicator with the height of the slit 200 m.
4.6. Before the determination of the colour and appearance, impact strength, bending
strength and adhesion of the film, specimens are dried at a temperature of 202C for 24 h.
4.7. Before determining the resistance to water and abrasion resistance, specimens
dried at a temperature of 202C for 24 h are held for complete hardening at a temperature
of 802C for 1 h or at a temperature of 202C for 6 days. Prior to the test, the specimens
hardened at the increased temperature are held at room temperature for no less than 1 h.
5. The colour and appearance of the enamel film are determined visually at natural
light or artificial diffuse daylight.
6. The weight fraction of volatiles is determined in ready-to-use enamel according to
GOST at a temperature of 802C for 2 h.
7. Determination of the thickness of the nondrip wet layer.
7.1. Devices and materials:
applicator as per GOST with the slit height of 0.5 mm; 0.3 mm;
spatula or glass rod.
7.2. Carrying out the test.
Ready-to-use enamel is applied by an applicator from the centre to the edge of the plate
such that the length of the trail of paint be no less than 100 mm. Then the plate is installed
vertically, the painted part up, and the dripping is observed for 1 h. The temperature of the
air during the test should be within the limits of 202C. The thickness of the nondrip wet
layer is no less than the value set by the applicator, if the dripping is not observed during
the examination. A displacement of the layer of material relative to the support is consid-
ered to be a dripping. A sag (of up to 1 mm) on the lower boundary of the layer of the ma-
terial is admissible.
8. The resistance of the film to the static effect of water is determined according to
GOST.
Tested specimens are held in distilled water at a temperature of 1002C.
After holding in liquid media, specimens are wiped with a soft wiping cloth, held at a
temperature of 202C for 1 h and examined visually.
Regularities of grain contamination with toxins secreted by fungi at various stages of
grain growth and processing, as well as the effect of mycotoxins on the ecological safety of
food for man and animals, have been established based on the works performed at the
444 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

All-Russian Institute of Grain Research (VNIIZerna) and its branches for over 30 years on
problems of microbial pollution of grain and it its products.
Domestic grain is subject most often to accumulation of aflatoxins B1 and G1. The
most hazardous regions from the ecological point of view are the southern regions of Eu-
ropean part of Russia, Ukraine, Moldova and Kazakhstan.
An increased-risk crop is maize. In some regions, aflatoxin B1 was found to affect up
to 40% of maize lots; in Southern Caucasus, 14%.
Small-grain cereals (rye, wheat) are more resistant to the damage by the fungi As-
pergillus flavus and contamination by aflatoxins.
The routes of pollution by mycotoxins were fount to be as follows:
Unfavourable conditions of storing grain mass due to the violation of the tempera-
ture-moisture regime. This leads to mold development and spontaneous heating. The local-
ization zone of mycotoxins is the surface layer of the grain;
Mycotoxins affect the head and grain in ripening in the field. In some years, products
of their vital activities affect wheat grain batches of up to 4 million tons;
The degree of contamination of grain depends on the anatomic features of a crop, the
character of development of producing fungi, the chemical properties of mycotoxins, as
well as on the technology of storage and processing.
Mycotoxins concentrate mainly in bran and feed wastes, which is predominantly
caused by the surface growth of saprophyte species of fungi.
The content of aflatoxins B1 in bran exceeds that in initial grain 34-fold, whereas in
flour it was 14 times smaller.
As the fungus and mycotoxins penetrate deep into the grain kernel, processing of af-
fected wheat only leads to a weak decontamination of the product. All sorts of flour
(4954% of the grain content) are contaminated uniformly.
The same high concentrations of mycotoxins are observed in bread, which makes af-
fected grain hazardous.
In chaffy crops (rice, barley), considerable part of mycotoxins is removed with husk;
an insignificant part of mycotoxins get into grits.

13.3.1 Modified coatings of tanks for storage of vegetable oil


Storage of vegetable oils is accompanied with changes, which affect their food value and
biological value.
The quality of vegetable oil is determined to a large extent by its stability with respect
to spontaneous oxidation by atmospheric air.
Oxidized oil has a reduced biological value of fats and decreased organoleptic prop-
erties (taste, smell, colour, consistence), the most characteristic of which is rancidification.
In storage, all oils are subject to oxidative and autooxidative rancidification, i.e., the
emergence of specific unpleasant flavour and smells.
The mechanism of oxidation and major processes, occurring in vegetable oil and other
fats in storage, have been fundamentally studied.
The extent of oxidative changes of oil in long-time storage depends on a number of
factors: particular features of the chemical composition of raw materials; production pro-
cess, catalytic action of transition metals and secondary oxidation products on oxidation,
storage temperature, packaging materials or materials of the storage tank, etc.
The authors have shown that one of the factors initiating the autooxidation processes
of vegetable oil are ions of heavy transition metals (Me), such as Ni, Co, Fe, Mn etc.
CHAPTER 13 445

During the storage of vegetable oil in vertical steel unprotected tanks made from steel
grade 3, the initial content of iron ions increases in 1218 months more than 2 times, which
is seen in Table 13.7.

Table 13.7 Content of iron ions in vegetable oil samples.

Iron content in an average sample, mg/kg

Initial data in an average After 12 months After 18 20 months


sample of storage of storage

0.210 0.310 0.405 0.557 0.565


0.295 0.443 0.487 0.578 0.500
0.488 0.570 0.586 0.785 0.785
0.500 0.665 0.700 0.850 0.975
0.700 0.765 0.800 1.050
0.507 0.818 0.825 1.107 1.130
0.450 0.665 0.700 0.945 0.990
0.550 0.825 0.885 0.887 0.995
0.500 0.742 0.825 1.200 1.230
0.620 0.882 1.107 1.100 1.150

Iron present in oil in the amount of 0.250.28 mg/kg increases the intensity of forming
peroxides of organic compounds of oil 1.52-fold. An even greater oxidation intensity
should be expected from the presence of iron in an average oil sample in the amount of
0.8821.100 mg/kg.
At the same time, iron was noted to concentrate in the lower layer of oil in the residue,
which is explained by the interaction of metal with proteins and phospholipids sedimenting
to the bottom of the tank. The increase of iron content in oil is noted to directly depend on
the amount of free fatty acids in it.
Earlier studies have shown that the mineral part of vegetable oil is represented by al-
kaline and alkaline-earth metals, as well as variable-valence metals.
The unprotected inner metal surface made from steel grade 3 is leached under the in-
fluence of vegetable oil. This leads to an increase of the content of iron compounds in oil,
which is seen in Table 13.8 presenting the dynamics of change of the iron content along the
height of oil during its storage in a tank (average climatic zone).
Table 13.8 Dynamics of the change of iron content in vegetable oil during storage.

Storage time, Mass fraction of iron, mg/kg


months
Upper layer Mid layer Lower layer

0 2.39 2.42 2.44


6 1.47 2.56 3.68
12
18 0.68 1.75 5.26
24 0.39 0.88 7.13
30 0.44 0.76 7.07
36 0.36 0.47 7.39
446 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

From the data presented, it follows that the initial period of oil storage is characterized
a rather uniform distribution of iron ions in the bulk of oil. Further on, the content of iron
in the upper and mid layers was gradually observed to decrease (by 75%) at a simultaneous
increase (2.5 times) in the bottom layers.
This indicates the migration of iron from top to bottom, probably, in the form of orga-
nomineral compounds (salts, complexes) formed as the result of interaction with free fatty
acids of oil. Unfortunately, the form of organomineral compounds in oil is not yet clear.
The classical scheme of hydrocarbon oxidation requires the presence of Me in its high-
est valence:
Me + RH --- Me + R + H propagation of the chain reaction
Me + O --- Me + O
The high catalytic activity of transition metals can be seen by example of Fe+3, which
accelerates the oxidation of linolic acid C17H29COOH or its methyl esters at the addition
of 1 part of ironporphyrin complexes per 100 mln parts of acid. The similar catalytic prop-
erties are exhibited by solutions of iron salts in oxidation of fats.
It is commonly recognized that copper and iron are the most efficient catalysts of the
oxidation of edible fats.
It was shown that if Me occurs in fats in small concentrations (1 mg/g fat), then by
their catalytic activity they are arranged in the sequence:

Cu > Fe > Ni > Zn > Co > Mn,

and at large concentrations of Me in fats (10 mg/g) this sequence looks as follows:

Fe > Cu > Co > Mn > Ni > Zn.

Metal catalysts can have various effects on the rancidification process of vegetable oil:
affect the initiation rate of the autooxidation chain process by a direct reaction be-
tween the catalyst and the oxidized vegetable oil molecule;
at the stage of development of the oxidation chain reaction, they can catalyze the deg-
radation of hydroperoxides to free radicals and accelerate the autooxidation reaction:

Me + ROOH - - - Me + RO +

Me + ROOH - - - Me +RO +
can stipulate the termination of the oxidation chain reaction, for instance, for an aque-
ous solution of hydrogen peroxide:

Fe + - - - Fe + +

Fe + - - - F +

Fe + - - - Fe +

Analysis of the already published works on long-term storage of vegetable oil and the
classical views of the oxidation of organic compounds in the presence of variable-valence
metals indicate that a required measure for stabilization of the quality of oil in its storage
in tanks is protection from oxidation initiators, i.e., from the direct contact of metal with the
food product.
CHAPTER 13 447

The most convenient method of protection is the anticorrosion coating based on oil-
resistant lacquer-and-paint material, which should conform the following requirements:
the coating should not contain toxic impurities and additives, which impart vegetable
oil with off-flavour and taste;
the coating should be resistant to oil within a certain temperature range;
the coating should have satisfactory adhesion and physicomechanical properties
(elasticity, hardness, impact strength etc.).
Companies in the West widely use epoxy coatings for palm oil storage tanks, as well
as reinforced polyester coatings, lining with thin stainless-steel sheets, deposition of a thin
layer of titanium.
The aim of the study was to issue recommendations on the anticorrosion protection of
the internal surface of steel tanks intended for long-term storage of oil. The tasks of the work
were as follows:
choice of protective coating;
accelerated tests of chosen materials in contact with oil;
analysis of the quality of oil after the accelerated tests;
by the results of the test, preparation of technical documents for the Moscow City
Centre of the Russian Sanitary Epidemiological Control Committee;
procurement of the hygienic certificate for the recommended coating.
Food-grade compositions were chosen for contact with vegetable oil. A total of 12
types of coatings were tested; after contact with vegetable oil, satisfactory results were
shown by three compositions, whose characteristics are presented below.
1. Food-grade epoxy composition EP-1M.
Quality parameters of the base and ready-to-use enamel are given in Table 13.9.

Table 13.9

Index Value

BASE
Colour White, brown, rose
Appearance Homogeneous viscous mass without foreign
inclusions
Degree of grind, m, no more than 40
ENAMEL
Appearance and colour of film Upon drying, film is smooth and
homogeneous
Mass fraction of volatiles, %, no more than 5
Thickness of non-dripping wet layer, mm, no more 0.5
than
Time of drying to degree 3 at 20C, hours, no more 24
than
Impact strength of film by U-1 instrument, cm (g), 30 (0.3)
no more than
Adhesion of film, points 1
Solvent Alcohol acetone mixture

The composition is permitted to be used in contact with many food products: sugar
molasses, wheat, 20% ethyl alcohol, meat products, etc.
448 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

2. Food-grade polyurethane, permitted for contact with potable water.


The physicomechanical properties are given in Table 13.10 (certificate No 000412 of
12/04/1995 for contact with food products).
Table 13.10

Index Value

Colour Milky white without inclusions


Relative elongation, % 400 500
Breaking strength, MPa 18 22
Shore hardness A, arb. units 65 75
Impact resilience, % 25 30
Tearing strength, kN/m 60 65
Brittleness temperature, C minus 65
Shrinkage, % not available

3. Food-grade epoxy enamel EP-2M. The physicomechanical properties are given in


Table 13.11.
Table 13.11

Index Value

Appearance and colour Homogeneous viscous mass of gray colour


Viscosity by VZ-246, sec, no less than 30
Content of nonvolatiles, wt. %, no less than 90
Impact strength, N/m, no less than 5
Adhesion, points 1
Viability at 20C, no less than 6
Solvent Alcohol acetone mixture

Crude sunflower oil, quality category 2, was chosen as the object of study in contact
with polymer coatings.
Sunflower oil has parameters of quality, presented in the quality certificate.

Method of accelerated tests of vegetable oil in contact with polymer coatings


Accelerated oxidation of vegetable oil with specimens of coatings and a control with-
out a coating was carried out in a ST-80-2 thermostat for 60 h (6 h per day) at a temperature
of 40C in sealed glass vessels without access of oxygen of the air, which corresponds to
18 months of the storage of this product in a steel tank.
Vegetable oil was taken in terms of one litre per one sample in contact with 5 cm2 of
each type of coating, which corresponds to the stringency of the test with respect to full-
scale investigations as 1.5:1 for RVS-700 and 2:1 for RVS-400.

13.3.2 Results of tests


The results of the tests are represented by the following characteristics of the objects of
study.
CHAPTER 13 449

1. Vegetable oil:
physicochemical and organoleptic characteristics of quality,
composition of the volatile part of oil,
parameters of safety of oil in accordance with safety regulations MVT 506189.
2. Polymer coatings: the list of component parts of formulations.
The physicochemical and organoleptic characteristics of quality after accelerated tests
in contact with polymer coatings are given in Table 13.12.
Table 13.12 Characteristics of quality after accelerated tests.

Quality index Norm Initial After accelerated tests


specimen
Specimen Specimen Specimen Control
6 7 8

Moisture and volatiles, %, 0.30 0.15 0.075 0.080 0.084 0.078


no more than
Content of phosphatides, 0.070 0.021 0.021 0.022 0.020 0.020
wt. % in terms of
phosphorus pentoxide, no
more than
Acid number, mg KOH, no 6.0 3.52 2.97 3.03 3.00 3.05
more than
Organoleptic indices
Transparency: specimens are transparent without residue.
Smell and taste: peculiar of sunflower oil without foreign smell, off-flavour and bitter taste.

Analysis of the content of trace elements


Weights of specimens of vegetable oil Nos 6, 7, 8, 10 (control sample) were subjected
to wet cineration according to the standard method in an MSD-2000 microwave oven. Three
parallel samples of each specimen were taken for the analysis.
Elemental analysis was carried out on a Liberty-200 inductively coupled plasma-
emission spectrometer (Varian).
The chosen analytical lines, nm:
Cu 324.754 Cd 214.438 Pb 220.353 As 188.979
Hg 184.950 Zn 206.200 Fe 259.940 P 178.284
Ca 317.933 Ba 493.409 Sr 421.552 Si 251.611
Ti 334.941
The contents of calcium, barium, strontium, silicon and titanium were determined
because they are present in the components of the coatings.
Conditions of recording the spectra:
power 1.5 kWt,
consumption of argon in plasma 15.0 l/min,
consumption of argon for blowing off the burner 2.25 l/min,
consumption of analyzed solution 1.5 ml/min,
pressure on the atomizer 100 kPa,
viewpoint optimized by the signal/noise ratio,
integration time 5 s,
replication number 5.
The calibration was carried out by the Merck standards.
450 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The results are presented in Table 13.13.


Table 13.13 Elemental analysis of specimens after accelerated tests.

Index Unit Norm Specimen


measure
6 7 8 10

Mass concentration of lead mg/kg 0.10 <0.01 <0.01 <0.01 <0.01


Mass concentration of cadmium mg/kg 0.05 <0.01 <0.01 <0.01 <0.01
Mass concentration of arsenic mg/kg 0.10 0.02 0.02 0.015 0.02
Mass concentration of mercury mg/kg 0.03 <0.001 <0.001 <0.001 <0.001
Mass concentration of copper mg/kg 0.50 <0.10 <0.10 <0.10 <0.10
Mass concentration of zinc mg/kg 5.00 3.20 2.90 3.20 3.10
Mass concentration of iron mg/kg 5.00 1.90 1.80 1.70 1.80
Mass concentration of calcium mg/kg below norm 48.0 51.0 46.0 51.3
Mass concentration of barium mg/kg below norm 0.63 0.57 0.54 0.62
Mass concentration of strontium mg/kg below norm 0.26 0.26 0.24 0.25
Mass concentration of titanium mg/kg below norm absent absent absent absent
Mass concentration of silicon mg/kg below norm absent absent absent absent
Mass concentration of mg/kg 350 205 216 196 203
phosphorus in terms of
phosphorus pentoxide

From the data presented in the table, it follows that:


by the content of toxic metals Cu, Zn, Pb, Cd, As, Hg, Fe all investigated sam-
ples of vegetable oil correspond to the safety criteria,
the concentration of Ca, Ba, Sr, Ti and Si, present in anticorrosion coatings compo-
nents, is not increased in samples of vegetable oil,
the concentration of phosphorus-containing substances is within admissible limits.

Study of specimens of vegetable oil by the method of chromato-mass-spectrometry


Volatile components occurring in vegetable oil were isolated using a Kuznetsov con-
centrator by transferring them into the phase of normal hexane.
The concentrates obtained were analyzed by the method of chromato-mass-spectrom-
etry on a Saturn-3 instrument (Varian).
Chromatographic parameters:
DB-5 quartz capillary column (analogue of SE-54), length 30 m, internal diameter
0.25 mm, thickness of the film of the immobile phase 1 m;
temperature regime: stage 1, 0.1 min at 40C; stage 2, temperature increase up to
100C at a rate of 20C/min and holding for 3 min at 100C; stage 3, temperature increase
up to 200C at a rate of 5C/min and holding for 20 min at 200C;
SPI-type injector (direct input) with temperature programming: initial temperature
60C, then heating at a rate of 225C/min up to 250C;
input pressure: 0.6 atm.
Mass-spectrometric parameters:
range of masses: 41450,
type of ionization: by electron impact,
scanning rate: 1 spectrum/s,
CHAPTER 13 451

ionization time setting: automatic.


Investigated samples are totally identical, which indicates the absence of the leaching
of volatile organic components of anticorrosion coatings in their contact with vegetable oil.

Analysis of the content of chloroorganic pesticides


Vegetable oil (12 ml) was placed into a 200-ml conical flask, 1015 ml of n-hexane
was added, and the contents were subjected to extraction for 1520 min on a shaker. The
extracts were purified in flat-bottomed flasks on a slide by shaking for 57 min with 510
ml saturated solution of anhydrous sodium sulfate in concentrated sulfuric acid. After set-
tling, the extract was decanted into another flask. The contents of the flask with acid after
the primary purification was rinsed with 12 ml hexane, which was added to the main ex-
tract. Purification was done several times until the layer of acid after mixing was colourless.
The purified extract was transferred into a separating funnel, 25 ml of 0.5 n sodium
bicarbonate solution was added, the contents were shaken for 12 min, the aqueous part
was discarded, then the extract was washed with distilled water to the neutral reaction of
the washing waters. The final extract was filtered through anhydrous sodium sulfate into a
flask for distillation of the solvent.
The solvent was evaporated on a rotary unit to a small volume (57 ml), then in a
nitrogen flow to a volume of 0.51.0 ml and was analysed by the method of gas-liquid chro-
matography on a Star 3400 CX instrument (Varian).
Two samples were arbitrarily chosen and analysed: No 10 (control) and No 6.
Chromatographic conditions:
DEZ electron capture detector;
DB-5 quartz capillary column, length 30 m, internal diameter 0.25 mm, thickness of
the film of the immobile phase 1 m;
temperature regime: stage 1, 1 min at 90C; stage 2, heating up to 180C at a rate of
25C/min and holding for 10 min at 180C; stage 3, heating up to 240C at a rate of 2C/min
and holding for 20 min at 240C;
SPI-type injector (direct input) with temperature programming.
Qualitative analysis was performed by the retention times of standard compounds;
quantitative analysis, by the internal standard.
The results are presented in Table 13.14.
Table 13.14 Assay of the content of chloroorganic pesticides.

Index Unit Regulatory Specimen 6 Specimen 10


measure norm

Mass concentration of GHCG, sum of mg/kg 0.05 0.012 0.013


isomers
Mass concentration of heptachlor mg/kg not admissible absent absent
Mass conc. of DDT and its metabolites mg/kg 0.10 0.005 0.0042
Mass concentration of epoxy heptachlor mg/kg below norm absent absent
Mass concentration of endosulfon 1 mg/kg below norm 0.006 0.008
Mass concentration of dieldrin mg/kg below norm absent absent
Mass concentration of endrin mg/kg below norm absent absent
Mass concentration of endosulfan 2 mg/kg below norm absent absent
Mass concentration of endrin aldehyde mg/kg below norm absent absent
Mass concentration of endosulfan sulfate mg/kg below norm absent absent
452 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

From the data presented, it follows that by the content of chloroorganic pesticides the
investigated samples of vegetable oil correspond to the safety requirements.
The constituent parts of the formulations of coatings: enamel EP-1M, food-grade poly-
urethane, enamel EP-2M.

Conclusion
The results of the tests of quality and the technical documents for the coating EP-1M
were handed over to the Moscow City Centre of the Russian Sanitary Epidemiological Con-
trol Committee. Based on this, we received a certificate for the safety of use of the coating
EP-2M in contact with oil, and developed the process of its application to the internal sur-
faces of steel tanks with the guarantee period of 15 years.

13.4 Food-grade coatings resistant to the action of sign-variable


temperatures
We developed compositions for food- and technical-purpose coatings, resistant to the action
of various reagents and sign-variable temperatures, as well as process documents for their
production and applications.
Enamel is intended for protection of the inner surfaces of steel and concrete tanks for
storage and processing of 96% alcohol, alcohol-containing products, including beer, malt,
cognac, vodka, wine; cold potable water, juices, lemonades, other cold drinks, oil-contain-
ing products, including vegetable oil. It is admissible to be used for protection of high-
capacity reservoirs operated in contact with granular food products (sugar, flour, grits,
grain, etc.). The operation temperature range, from 25 up to +40C. It is permitted to be
used for protection of sewage systems, as well as for painting of walls and ceilings in public
baths and pools.
Peculiar features of coatings:
the coating possesses high anticorrosion properties, resistance to organic media,
fresh and sea water, oils, petrol, detergents; admits steaming. The durability of the coating:
57 years;
thixotropic materials; enable application of a required thickness of coatings in two
layers;
low content of volatile substances, 5%.
Main characteristics:
two-package materials based on epoxy resins and amine-type hardeners; hardener :
base ratio, 20 g / 100 g;
colour: creme, brown; tints not rated;
appearance of the coating: homogeneous semiglossy;
methods of application: by airless spraying, brush or roller;
spreadable life of materials at temperatures from 5 up to 30C: from 2 to 0.5 hours;
a layer of coating dries at a temperature of 20C for 24 hours;
consumption of materials per layer: 250350 g/m2;
recommended number of layers, 2; total thickness of coating, 400 mm;
guaranteed storage time of the base, 12 months; of the hardener, 6 months.
Recommendations on use:
Preparatory work
The metal surface should be cleared of rust, scale, metal oxides etc. to grade 2 accord-
ing to GOST (the surface should have a uniform roughness, metal gloss; a darker hue of
CHAPTER 13 453

metal is admitted on areas cleared of scales) and degreased to grade 1 according to GOST
(no traces of grease on filter paper after wiping the surface). Cleaning should be done by
sand-blasting or shot-blasting treatment; it is permitted to use cord brushes. For degreasing,
the surface of metal is cleaned by wiping cloth soaked in white spirit and by dry wiping
cloth; use of easily volatile solvents is not permitted. If painting is to be done immediately
after the sand-blasting (shot-blasting) treatment, degreasing could be not carried out; here-
with, it is recommended to degrease too dirty areas preliminarily. If it is necessary to paint
components of vessels fabricated from alloy steels, aluminium, titanium or copper alloys,
the metal surface should be painted with a very thin (not more than 20 m) layer of phos-
phatized primer VL-02 or VL-023 to provide for adhesion.
The surface of concrete should be completely cleared of dirt and the old coating. The
fresh concrete surface should be matured for no less than 1 month before application of
enamel, slightly scraped to open pores in concrete and dust should be removed.
The test for the determination of the completeness of water removal from concrete: a
segment of the tank of no less than 1 m2 area is covered with a rubber mat or closely fitting
piece of polyethylene film and left for 24 hours. If the covered segment did not become dark
and there are no drops of condensed water, the concrete is ready for application of the
coating.
The maximal interval of time between the preparation of the surface and the applica-
tion of the coating is 24 hours.
Painting
The temperature of the base and hardener before the application should be within the
range of 1530C. Prior to the beginning of work, the base and hardener are well mixed to
homogeneity over all the volume of the can; dry films should be preliminarily removed
from the surface of the hardener, if they were formed.
Enamel is applied by airless spraying units, by a roller or a brush.
In application by airless spraying units with separate supply of the components, the
base to hardener volume ratio of 3.5:1 is maintained; it is admissible to warm the compo-
nents up to a temperature of 4060C.
For application by a brush, roller or an airless spraying unit with the supply of the pre-
pared mixture, the material is prepared by adding 20 g of hardener for 100 g of the base and
thoroughly mixing. It is admissible to add ethyl alcohol, a mixture of ethyl alcohol with ac-
etone at a ratio of 1:1 or another solvent in the amount of no more than 10% of the weight
of the ready-to-use material. The composition of the solvent is chosen with consideration
of the sanitary requirements to the coating. The material is prepared by portions of no more
than 20 litres (taking into account the spreadable life). It is recommended to prepare por-
tions for 2030 min of work.
Enamel is applied to metal in two layers. The drying between layers should be up to
grade 3 according to GOST (to the disappearance of tackiness;24 hours at 20C). When pre-
paring enamel for the first (priming) layer for concrete, it is to be diluted with ethyl alcohol,
a mixture of ethyl alcohol with acetone at a ratio of 1:1 or another solvent suitable for di-
lution of epoxy materials in the amount of about 50% of the mass of enamel. The compo-
sition of the solvent is chosen with account for the sanitary requirements to the coating.
The first (priming) layer of diluted enamel on concrete is dried for no less than 24
hours, then two layers of enamel are applied, with intermediate drying up to grade 3 accord-
ing to the State Standard (GOST). The enamel for application of the subsequent layers is
prepared without dilution or with dilution of no more than 10%.
The maximal interval between the painting of the layers is 3 days after the last layer
454 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

has dried. If the interval is larger, it is recommended to sandpaper the surface to a matte
finish and to remove dust.
The number of layers is chosen such that the total thickness of the hardened coating
be 350400 m.
Material is applied at an ambient temperature of 10 up to 30C and relative humidity
no more than 80%; the temperature of the painted surface should be higher than the dew
point.
Before operation begins, the tank painted with enamel should be washed according
to the tank-washing instruction in force at the enterprise.
It is preferable to use neutral or alkaline detergents.
The duration of holding a coating after drying the last layer before the washing:
at a temperature of 20C and higher, no less than 10 days,
at a temperature of 1519C, no less than 15 days,
at a temperature of 515C, no less than 30 days.
After washing, the painted tank is filled with tap water, held for 24 h and a sample is
taken to determine the weight fraction of migrating chemical substances, smell and taste. If
the weight fraction of migrating substances, smell and taste do not correspond to the norm,
the washing is repeated.
Safety precautions
Material is highly inflammable! Harmful if inhaled or swallowed. Do not work near
open fires. Work should be done in rubber gloves with good ventilation in the working area.
If material gets onto the skin, wash the skin with warm water and soap. Keep material in-
doors, excluding direct sunlight and moisture.
14 Ecology and Safety
of Utilization of
Container/Packaging
Materials

14.1 Methods of utilization of packaging materials


Since the time the first polymer materials appeared, much effort has been used to solve the
problem of their stabilization and extension of their service life. This problem has not been
completely solved until now. However, as production and consumption of polymers in-
creased, it became clear that many polymer materials, in particular, those for packaging,
have excessive lifetimes. The most heavy-duty polymers polyolefins, polyvinyl chlo-
ride and polystyrene are not subjected to biodegradation and are preserved under natural
conditions for many years.
In countries with developed polymer industry, plastic containers, films and packaging
materials have become one of the major sources of pollution of forests, fields, rivers and
sea coasts.
According to the available data, wastes are and will be in the near future about 30% of
the total output of plastics. A significant part of wastes of polymer materials are films and
packaging materials. These are just the sort of wastes, which are most difficult to collect.
It should be noted that wastes of polymer materials are valuable resources, which can
be recycled and used again both as polymer materials and as raw materials for production
of monomers, oligomers, lubricants, construction materials, and as fuels.
Issues of regulating the degradation rates of polymer material wastes, which do not get
into the collection system and become a source of pollution, have been considered.
Wastes of polymer materials were analyzed in the USA. It turned out that 90% of all
wastes are three polymers: polyethylene, polyvinyl chloride and polystyrene (21%). Ac-
cording to Swiss data, wastes of polyolefins are 55%; polystyrene, 15; and polyvinyl chlo-
ride, 13%,; i.e., these polymers make 83% of all wastes. Therefore, it is necessary to
develop methods of increasing the rates of decomposition of namely these polymers.
Polymers degrading under natural conditions at a growing rate are used in the West to
produce not only packaging materials, but also agricultural films for mulching, which de-
grade over one season. Thus, for instance, the output of such films in Japan is at present
25,000 tons per year.
It is desirable that polymer wastes getting into the environment degrade under the
action of natural conditions: light, oxygen, air, water, microorganisms, fungi. However,
456 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

studies have shown that polyolefins, polystyrene and polyvinyl chloride are preserved un-
der natural conditions for an extremely long time, for many years. Measures are, therefore,
required to accelerate the degradation processes. Polymers rapidly degrading under natural
conditions should satisfy a number of requirements dictated by the conditions of its appli-
cations:
polymers should degrade rapidly, but only after they are discarded, not in processing,
storage and performance of a respective article,
time to degradation should be known beforehand and should be variable,
the consumer should be aware of the time when rapid degradation of polymer begins,
modification of polymer, which leads to an increase of the rate of decomposition un-
der natural conditions, should not significantly change its performance characteristics.
Only polymers degradable under the action of light and biodegradable to a lesser ex-
tent satisfy these requirements. Therefore, we shall consider the works on the development
of photodegradable polymers. It is those works that led to the creation of polymer materials,
degradable sufficiently rapidly under natural conditions.

14.2 Accelerated degradation of polymers by biocides


Experiments with aliphatic low-molecular-mass direct-chain hydrocarbons modelling
polyethylene showed that biodegradation proceeds to a molecular mass M < 450 (C32).
Chain branchings prevent the assimilation of hydrocarbons by bacteria. If polyethylene is
subjected to pyrolysis, biodegradation proceeds when the average molecular mass of poly-
ethylene reaches 3,0001,000. For biodegradation of polystyrene to become possible, its
molecular mass should be less than 4,000 (by the number of links, equivalent to polyethyl-
ene with a molecular mass of 1,000). Thus, for the biodegradation of these polymers to be-
gin, they should be preliminarily decomposed to low-molecular-mass products.

14.3 Photodegradable polymers


Photodegradable polymers have no drawbacks mentioned above. A given polymer resistant
to the action of light can be converted to a photodegradable polymer either by using addi-
tives or by introducing light-sensitive groups or groups with weak bonds into the macro-
molecule. Only variations of these two principles are discussed and are used in practice. It
should be noted that it is sufficient to bring decomposition of macromolecules under the
action of light to a molecular mass of 5001000, because hydrocarbons with such a molec-
ular mass, as we noted above, can be assimilated by microorganisms and, thus, be included
into the natural biological cycle.
Ketone groups are usually introduced into macromolecules to produce photodegrad-
able polymers. This is due to the fact that these groups are rather resistant to processing con-
ditions, whereas under natural conditions under the action of light they degrade. The light
with the wavelength of more than 350 nm is not absorbed by ketones, especially aliphatic
ones. Therefore, polymers with ketone groups are stable indoors.
Polymers are produced by copolymerization of common monomers styrene, ethyl-
ene, vinyl chloride with monomers of the structure
R C CH2
R1C O
CHAPTER 14 457

or carbon oxide. In the former case, polymers with the ketone group in the side chain are
obtained; in the latter, in the main chain. By varying the nature of R and R, as well as the
concentration of the chromophore groups, we can obtain, e.g., based on ethylene, polymer
degradable under natural conditions in the time from several hours up to several months.
Ketone groups can be also introduced into ready-prepared polymer. Thus, interaction
of copolymer of ethylene and vinyl alcohol with diazo acetophenones yields a polymer con-
taining aryl ketone groups in the side chain. The rate of decomposition of this polymer de-
pends on the structure of the substituent in the aromatic nucleus of ketone.
Using the method of copolymerization, it is possible to introduce not only ketone
groups but also aldehyde groups. Thus, for instance, copolymerization of methyl methacry-
late or styrene with propiol aldehyde yields a polymer degradable under the action of light
much faster than corresponding homopolymers. However, the decomposition rate of copol-
ymers of styrene or methyl methacrylate with methyl vinyl ketone is much larger under
these conditions.
Studies of polyolefins showed that the processing conditions of polymers render a sig-
nificant effect on the light permanence of articles. Thus, the heating of high-density poly-
ethylene at 200C decreases the time to cracking of the film prepared from this polymer
with the extent of oxidation increasing under the action of light. Thermooxidation of the
polymer was shown to occur under these conditions. The main oxidation products are poly-
mer carbonyl-containing compounds. Thus, heat treatment leads to the formation of chro-
mophore groups, mainly carbonyl ones, and can be considered as one of the ways of
chemical modification of the polymer.
Chromophore groups can be also introduced by way of a special treatment of a com-
pleted article. For instance, a completed polyethylene film can be converted into a photo-
degradable one under the action of UV radiation in the presence of carbon oxide or a
mixture of methyl acetylene and tetrafluoroethylene. Products of grafted polymerization of
these monomers are degraded in the light and induce the conversion of polyethylene film.
Not only the method of copolymerization but also the method of polycondensation is
applicable for production of photodegradable polymers. Thus, for instance, Japanese
authors obtained from dioximes and diisocyanates polyoxime urethane film-forming poly-
mers of the general formula:
( ON R NO C NH R' NH C )n (I)
O O
As monomers, they used dimethylglyoxime (II), cyclohexandione dioxime (III) and
benzoquinoglyoxime (IV):
HON C C NOH (II)
CH3 CH3

HON NOH (III) HON NOH (IV)

These monomers were polymerized with hexamethylene diisocyanate (V) or diisocy-


anate of diphenyl ester (VI):

O C N O O O N C O (V)
458 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

O C N (CH2)6 N C O (VI)

A study of the light permanence of polyoxime urethane polymers showed their molec-
ular mass rapidly drop down in irradiation. This is primarily due to the rupture of the weak-
est NO bond, whose energy is about 53 kcal/mol. The ester group breaks down slightly
slower.
It is known that polyolefins containing side aliphatic groups are oxidized under the ac-
tion of light much easier than polyethylene. This feature of polymer photodecomposition is
used in production of photodegradable polymers. A method of producing polybutene-1 and
copolymers of butene-1 with ethylene and propylene or cis-butadiene was developed in the
USA. The polybutene-1 film of about 25 m thick decays in 2575 days depending on the
concentration of antioxidants, UV absorbers and other additives.
Double-bond polymers possessing a low light permanence are also used to produce
materials degrading under the action of the sunlight. Japanese investigators developed a
novel process for production of polybutadiene containing more than 90% of 1,2-structures.
Polybutadiene used in production of films possesses a syndiotactic structure and has a crys-
tallinity of 1030%. A packaging from this polybutadiene degrades during the summer
time under the action of light in one week. Light stabilizers can extend the service life up
to several months.

14.4 Modified photodegradable polymers


Production of photodegradable polymers by synthesis of new polymers containing chro-
mophore or reactive groups, as well as by modifying mass-produced polymers, requires the
existing polymer-producing technology to be changed or new processes to be developed.
Apparently, for this reason a major part of works seek to find efficiently acting additives;
what is more, mainly their action on polyolefins and polystyrene is investigated.
By their action, the additives used can be divided into the following groups:
photosensitizers,
additives preventing the crosslinking of macromolecules;
polymer oxidation catalysts;
complex metal compounds, which are stabilizers of polymers, but in the process of
recycling or photochemical decomposition of polymers are converted to oxidation cata-
lysts. As photosensitizers of decomposition of polyolefins, it is proposed to use aromatic
hydrocarbons, aliphatic and aromatic ketones and diketones, quinones and other com-
pounds; in particular, compounds mentioned in patents are aldol-2-naphthyl (VII), aldol-2-
(VIII) and aldol-1-naphthylamine chromone (IX), flavone (X) and xanthone (XI), 1,4-di-
alkyl-substituted benzene (XII), benzophenone (XIII) derivatives, p-benzoyl benzophe-
none (XIV); derivatives of acetophenone (XV), anthraquinone (XVI), benzathrone (XVII),
cumene (XVIII), mercaptobenzothiazole (XIX), acridine (XX), chlorinated aromatic com-
pounds, aliphatic ketones (XXI) and diketones (XXII).

CH2CH(OH)CH2CHO

N CHCH2CH(OH)CH3
(VII) (VIII)
CHAPTER 14 459

O O

(IX) (X)

(XI) R R' (XII)

C (XIII) C C (XIV)

O O O

C CH3 (XV)
(XVI)

O
O

CH3
(XVII) CH (XVIII)

CH3
O

N
XSC (XIX) (XX)

S N

R C R' R C C R
(XXI) (XXII)
O O O
To accelerate photodegradation of polystyrene, additives were proposed, which are
close by their properties to those used for polyolefins, for instance, 1,4-naphthoquinone
(XXIII), 1-nitronaphthalene (XXIV), aromatic ketones (XXV)

O NO2 O

(XXIII) (XXIV) (XXV)

O O
460 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

and high-molecular-mass additives, for instance, halogenated polystyrene produced by the


action of chlorine or bromine on polystyrene.
The efficiency of sensitizers depends not only on the class they belong to but also on
the nature of substituents. Thus, quinones containing methyl groups or haloid atoms as sub-
stituents are more efficient, and amino and oxy groups less efficient, sensitizers of the ox-
idation of polystyrene than unsubstituted quinones.
Usually sensitizers are proposed to be used at concentrations from 0.01 up to 10%
(most often about 1%). As experience shows, at these concentrations they are consumed
much faster than the required polymer decomposition rate is achieved. However, photode-
composition of polymer does not stop after conversion of sensitizer, because by this time a
sufficient amount of photooxidation products of polymers are formed, which are also sen-
sitizers.
The use of ketones and some derivatives of aromatic compounds as sensitizers is as-
sociated primarily with the fact that they initiate the conversion of polymer only under nat-
ural conditions, as such compounds are stable under conditions of polymer processing and
in storage of articles indoors, where the light gets through the window glass, which absorbs
a shorter wave component of the sunlight.
The mechanism of action of sensitizers in polymers has been studied insufficiently yet.
The action of compounds containing carboxyl groups, especially ketones, was studied the
most completely. Probably, this is due because the mechanism of photochemical reactions
of ketones in solutions has been studied the most completely. Compounds, containing car-
bonyl groups, are able in an electron-excited state to break loose H atoms from macromol-
ecules or fall into radicals. Low-molecular-mass radicals formed react with macro-
molecules, thus initiating the oxidative decomposition of polymer. By analogy with the
known photochemical reactions of compounds containing CHal bonds in liquid and fro-
zen solutions, it could be assumed that chlorinated aromatic compounds and halogenated
polystyrene fall under the action of light into radicals via the CHal bond. This process can
be sensitized, using compounds with sufficiently high levels of electron-excited states.
Probably, for this reason some works, to accelerate the decomposition of polymers under
the action of light, recommend to use mixtures of compounds with CHal bonds with
ketones.
The decomposition mechanisms of polymers sensitized by aromatic hydrocarbons or
heterocyclic compounds has been studied to a lesser extent.
The decomposition rate of polymers can be also increased by introducing substances,
which are photochemically inactive. Thus, additions of small amounts of paraffin or oleic
acid significantly increase the decomposition rate of polyethylene. It was shown that the
presence of these additive reduces the crosslinking of polyethylene, because additives are
added to macromolecules. Formation of the branched polymer in this process, in turn, ac-
celerates decomposition.
Other photochemically active compounds, which can accelerate decomposition of
polymers, are oxidation catalysts. Usually, compounds of transition metals are used as cat-
alysts: iron, copper, manganese, as well as metals in free state. Catalysts are used mainly in
a mixture with sensitizers. They accelerate oxidation of polymer during the action of sen-
sitizer, and when the sensitizer is consumed, they complete the decomposition of polymer.
Sometimes, use is made of metal compounds, for instance, of iron naphthenate, which can
serve simultaneously as sensitizer and catalyst of polymer decomposition. The role of cat-
alysts in polymers filled with carbon black or other pigments is less clear. Probably, films
from such polymers, owing to their opacity, are warmed significantly under the action of
CHAPTER 14 461

the sunlight, and the catalysts strongly accelerate the thermooxidation of the polymer. How-
ever, it is possible that the role of catalysts in these compositions is to accelerate the ther-
modecomposition of polymer mainly in processing, which is known to lead to a strong
decrease of the light permanence of articles. The latter hypothesis seems to be the most suit-
able to explain the increase of the decomposition rate of double-bond polyolefins and poly-
mers in the presence of metal salts.
One of the most interesting classes of substances used as additives for accelerating the
decomposition of polymers are complex metal compounds, which stabilize polymers
but under the action of light or in the processing are converted to oxidation catalysts. An
example of such compounds are, for instance, dialkyl dithiocarbamates of metals (XXVI):

Alk S
N C Me(n) (XXVI)
Alk S n

Compounds of iron are the most efficient. The use of such compounds enables issues
important for practical purposes to be solved. The proposed additives protect the polymer
in processing. An additive can be chosen and adjusted in such a way that the polymer will
be also protected under natural conditions for a certain time. In practice, it is exhibited in
the occurrence of the onset of the polymer decomposition process in the presence of the ad-
ditive. After the decomposition of the complex to form the catalyst, the decomposition rate
increases and the polymer is decomposed faster than the control specimen of the additives.
During the induction period, the coloration of the complex compound vanishes. By the
change of coloration, the consumer can determine the onset of the decomposition of the giv-
en article.
Using metal dialkyl dithiocarbamates, it is not possible to produce compositions with
a sufficiently high degradation rate under natural conditions, so the introduction of a pho-
toactivator is proposed, for instance, iron acetyl acetonate. The value of the induction time
of photooxidation of polymer in this case will also depend on the concentration of photo-
activator.
Besides the above said, another method of delaying the degradation of polymers is also
proposed. A water-soluble film containing a light stabilizer is applied to the surface of poly-
mer, for instance, polypropylene. The film protects the polymer, but after it is removed the
article is rapidly decomposed.
The effect of additives on the rate of photodecomposition of polyvinyl chloride has
been studied much less. It is only known that polymethyl vinyl ketone does not affect the
rate of decomposition. Stearate and oxide of trivalent iron significantly accelerate the de-
composition. Photodecomposition of polyvinyl chloride, in contrast with polyolefins, is lit-
tle affected by iron dialkyl dithiocarbamates.
The main requirements to which polymer materials rapidly degrading under the action
of light under natural conditions should satisfy were noted above. We should add to them
three more uses of such polymers dictated by the practice:
polymers should be nontoxic, because their major applications are packaging mate-
rials;
costs of photodegradable polymers should not significantly exceed those for com-
mon polymers;
and finally, it is desirable that conversion of polymer to a photodegradable form does
not exclude the possibility of its recycling.
462 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

At present, there is no polymer or method of converting known polymers to photode-


gradable form(s), which would completely satisfy all these requirements.
The main advantage of the methods based on the introduction of chromophore groups,
or groups readily oxidized under natural conditions, into macromolecules is complete non-
toxicity. However, if high-molecular-mass compounds are used as additives as, for in-
stance, in the method of converting polystyrene into a photodegradable form at the addition
of halogenated polystyrene, or iron compounds are used, then it is also possible to obtain
photodegradable polymers, which are in practice nontoxic.
A disadvantage of the method of modification is, first of all, the need to change the
existing polymer production process, which would inevitably lead to an increase of the cost
of a polymer. Besides, the signal mechanism, which would indicate the fast degradation of
polymer, has not yet been developed for modified polymers.
Disadvantages of the methods of converting a polymer into a photodegradable form
by introducing additives are, first of all, the slow rate of degradation in the presence of small
concentrations of additives (of the order of several percent). Introduction of large concen-
trations of additives can lead to a significant change of the mechanical properties of poly-
mer. Introduction of catalysts or substances, which change into oxidation catalysts, hampers
the reprocessing of the polymer.
Probably, for this reason some works make use of both the modification of polymers
and introduction of additives. Thus, organometal compounds salts of mono- and polycar-
boxylic acids; acetyl acetonates of copper, iron, manganese, chromium and some other
complex compounds of transition metals; also additives of light stabilizers are proposed
to be additionally introduced into copolymer of ethylene and carbon oxide (the content of
CO, 612 wt. %) as a degradation accelerator to produce articles with a preset lifetime from
polybutene-1 and 1,2-polybutadiene, because without stabilizers they degrade under natural
conditions too rapidly.
The extent of photodegradability of packagings largely depends on the place of their
disposal. Time to decomposition of a given article under natural conditions would depend
on the colour, thickness and shape of the article and not only on the properties of the initial
material.
Owing to great interest in photodegradable polymers, the most successful develop-
ments are introduced into industry.
Thus, polybutene-1 used for production of mulching films and photodegradable poly-
styrene are commercially available. Other photodegradable polymers being launched in-
clude copolymer of styrene with methyl vinyl ketone (Ecolight S), 1,2-polybutadiene, as
well as polyethylene and polystyrene, which contain additives accelerating their decompo-
sition.
Mainly industrial production of films for agriculture is being developed, because the
requirements to them are more mild as compared with packaging materials, and they are
used within one season only. In the West, the use of such films is considered to be econom-
ically advantageous for the consumer. In the future, photodegradable packaging materials
would, probably, be also widely produced. Though it would require some additional ex-
penses, their use would prove profitable for the society as a whole.

14.5 Principles of developing modifiers for biodegradable materials


1. Biodegradation of latex envelopes. Packaging materials are a means of protecting and
decreasing the losses of foodstuff production from the impact of the environmental factors.
CHAPTER 14 463

By protecting a product, the packaging contributes to the contamination of the environment.


To solve the problem of the polymer matrix, it is proposed to introduce polyfunctional
natural substances capable of simultaneously unifying the set of the performance properties
of polymers and to provide for its biodegradation after use.
The effect of a set of dietary supplements on the biodegradability of active latex enve-
lopes was studied. Systems based on vinyl acetate modified by an activated mixture of lactic
bacteria (dietary supplement), rennin, were studied. A combination of polymer matrix and
dietary supplements affects the kinetics of the biodegradation process. Introduction of ad-
ditives activating the growth of bacteria providing for the biodegradability under natural
conditions accelerates the fragmentary decomposition of the polymer matrix.
The increase of biodegradability of films in time is related to the structure of coatings;
dietary supplements are distributed in the bulk of the film between globules of polymers to
form the fragmentary structure of the film an aggregate of components united on the
supramolecular level.
As biodegradation (utilization) of the dietary-supplement additive by microorganisms
proceeds from the surface layers to deeper layers, the access to dietary supplements of the
deeper layers is facilitated, and biodegradation of the coating continues. The change of
character of the process at the initial stage of biodegradation using the enzyme as a dietary
supplement is related to the structural changes of the coating and the character of distribu-
tion of the enzyme in the polymer matrix.
2. Prospects of developing a biodegradable packaging from natural polymers. Eco-
logically safe containers and packagings can be rapidly degraded under natural conditions
or recycled to enable their use as feed additives.
For this purpose, an advanced method is to use accessible, cheap and rapidly repro-
duced natural raw materials for packaging materials. High-molecular-mass compounds of
animal and plant origin have a broad range of process and performance compositions for
coatings, film materials and consumer containers.
Thermoplastic compositions based on plasticized triple systems starchcellulose
derivativescollagen partial decomposition product were developed; also, the technolo-
gy of their processing into container-and-packaging materials with polyfunctional proper-
ties conforming with modern requirements was worked out.
3. Promising self-degrading polymers. Coatings based on polyvinyl alcohol and
polysaccharides for protection of meat and fish products. Self-degrading polymers are de-
graded under the action of the environment much faster than traditional polymers. Their
degradation can occur under the action of bacteria, sunlight or chemically.
In world practice, much attention is given to biodegradable packaging materials, es-
pecially to polyolefins with addition of starch from cereal crops.
Biodegradable films based on polyvinyl alcohol with the contents of maize starch as
a biodegradable additive from 30 up to 150% were produced. The effect of the amount of
additive on the technological, thermophysical and stress strain parameters of films was
studied; the biodegradability indices were determined by the method of Shturm. Addition
of up to 30% of starch has no significant effect on all packaging characteristics of films; at
a concentration of starch over 50%, the stress strain properties of films decrease and the
biodegradation index drops down from 80 to 1.
The process parameters of producing biodegradable coatings based on polyvinyl alco-
hol modified by an optimal amount of starch were developed.
4. Use of reproducible plant raw materials for production of biologically degradable
polymer packaging materials. The use of polymers from natural raw materials or their
464 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

combination with traditional plastics makes it possible to solve some problems associated
with pollution of the environment, reduction of reserves, energy resources and global war-
mup of climate owing to the disturbance of the CO2 balance.
A rational approach from the technological point of view is to use natural polysaccha-
rides starch and cellulose, which possess a set of valuable properties.
A method of producing biodegradable polymer materials with a wide range of plastic-
ity and the required set of performance properties was worked out.
The regularities of the rheological behaviour of melts of thermoplastic starches plas-
ticized with water, glycerol and their mixtures were studied.
It was found that tribasic alcohol in the plasticizing system increases the temperature
of the onset of gelatinization; studies of the transitions of the starchplasticizer system by
thermomechanical methods indicate that water and glycerol possess a selective effect on
polysaccharides.
They endow materials with a set of rational properties, such as elasticity, in the case
of plasticizing with water, and rubberlike properties when using glycerol.
Optimal thermoplastic properties are observed at a concentration of the plasticizing
waterglycerol mixture at a ratio of 25:25.
Thermoplastic starch is recommended to be used as a concentrate to endow synthetic
polymers with biodegradable properties.

14.6 Industrial and domestic plastics wastes

14.6.1 Secondary plastic raw materials in the public reproduction process


The raw materials base of the country is the sum total of raw materials available for a certain
period of time from its own stocks and from imports. The raw materials base includes pri-
mary and secondary raw materials. Primary raw materials are mineral resources and all min-
eral and biochemical raw materials mined in nature. Secondary raw materials are
production and consumption wastes, which can be returned into the public production pro-
cess as a subject of labour, because they still preserved their value to a significant extent.
Industrial wastes are substances which in the process of social reproduction lost totally
or partially their initial consumer properties as a subject of labour or a subject of consump-
tion. In the available form they are useless for a given or any other industrial process, i.e.,
are not consumed in processes of fabrication, conversion or refinement of a material.
Wastes emerging in the consumption sphere are previously used materials and articles.
They are assigned to potential secondary raw materials. As soon as wastes are transferred
by various methods into the form suitable for use, they immediately occupy their place in
the raw materials base of the country.
Primary plastic raw materials are understood to be materials, which are presented in a
suitable form for production of final or semifinished products from them. This, as a rule, is
associated with the formation or conversion of a substance. Secondary plastics raw materi-
als are reprocessed into finished articles (once or many times).
Plastics are used in all branches of the economy, because this saves materials and in-
creases the productivity of labour. Despite the finite resources of the majority of raw mate-
rials and increasing costs of their recovery, the consumption of raw materials constantly
increases. Polymer materials are characterized by higher rates of increase as compared with
other groups of materials. The state and volume of modern industrial production, the
CHAPTER 14 465

general exchange of industrial products with the environment has reached such a scale that
nature can not do without the conscientious activity of man to protect it. Costly works are
required to be carried out to prevent (or eliminate) the damage inflicted to the environment,
including that due to pollution by chemically resistant polymer materials.
On the other hand, major part of the countrys national income is spent due to the ab-
sence of our own sufficient raw materials base for purchasing polymer raw materials, whose
costs are constantly rising owing to the rise of energy expenses for their recovery and pro-
cessing.
The existing macroeconomic situation makes it necessary to solve two main problems:
the efficient thrifty use of materials by reducing production wastes or using waste-free tech-
nologies and economy constructions; the economical efficient preparation of wastes for
processing and using as secondary raw materials.
Approximately 1011% of the demand in plastics should be covered by secondary
plastics raw materials. This necessitates investments into studies and developments in this
field, long-term plans for solving the problems associated with the reduction of the amount
of wastes and their rational use. Scientific research is to be carried out, new technologies
developed, industrial installations worked out, principles of decreasing the materials con-
sumption in designing new plastic articles developed, drawbacks in this field eliminated.
In Germany, for instance, more than 400 various types of industrial wastes are pro-
duced at present; about 25% of them are used again. Simultaneously with the commitment
to reduce the amount of production wastes, it is necessary to increase the volumes of their
use, which leads to the decrease of the demand in primary raw materials, the decrease of
the costs of primary and secondary polymer raw materials.
A significant economic effect also arises due to the lower cost of secondary raw ma-
terials. The amount of plastics scrap in production and consumption constantly increases
despite the numerous measures to reduce the intensity of use of materials. When performing
scientific and technical measures for the development of small- or no-waste technologies
and respective equipment, it is necessary to take into account the issues of economic effi-
ciency both within the framework of a particular enterprise and the countrys economy.
The complex character of the problem renders its solution difficult, as, for instance, in
the case of using household plastics wastes.

14.6.2 Sources and turnarounds of secondary polymer raw materials


Plastic wastes emerge in industry in production of materials, their processing, fabrication
of semi-finished products and articles, as well as in the consumption sphere as overage
articles.
Production wastes are used in the same production process (this is a closed turnover
of material, it is characterized by the lowest losses of material resources); in another pro-
duction process after a respective preparation (this is a branched flow of materials); are not
used at all (the turnover of the material flow is theoretically closed via the environment).
One should always aim for closed turnovers, which save the material and yield the greatest
economic effect. The modern level of scientific-and-technical development makes it possi-
ble to create closed material turnovers.
Plastics are characterized by all these three forms of material turnovers. If a regenerate
of a thermoplastic is introduced into primary raw materials, and a mixture is produced for
the fabrication of the same articles as previously, we have a closed material turnover rela-
tive to production wastes.
466 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Material I Material II
Mining

Extraction
Production Preparation
wastes Processing (stage 1)
Preparation of wastes

Processing (stage 1, Processing (stage 2)


semifinished / finished
products)

Use
Processing (stage 2,
finished products)

Consumption Preparaition
Use
wastes of wastes

Harmless disposal

Scheme 14.6.2 Closed and branching turnarounds in plastics technology.

As multiple processing leads to a change of the structure and properties of material,


the deterioration of the properties being largely uncontrollable, regenerates are as rule used
for fabrication of articles with lower consumer properties. Here we have the case of a
branching material flow, because the regenerate is used in another process. When the re-
generate of a thermoplastic is prepared from consumption wastes, prediction of the extent
of deterioration of the properties is the most difficult.
The third variant, i.e., the non-use of wastes, occurs especially frequently in production
of articles from thermosetting materials. Their wastes are subjected to long-time storage and
even disposal (incineration).
Secondary plastics raw materials are classified using various, mainly technological,
criteria, which enable conclusions on their possible applications. The criteria include the
place and sphere of origin (production or consumption wastes), as well as specific features
of appearance: contamination, type and shape. Using these criteria, one can characterize the
turnarounds of secondary plastics raw materials, singling out five different situations,
which require various economic, organizational and specifically technological measures for
their realization (Scheme 14.6.2, Table 14.6.1).
Turnaround I of the secondary plastics raw materials occurs in plastics-producing in-
dustry. Wastes include crusts formed on the walls of reactors and filters, off-standard poly-
mers (decreased or increased molecular mass, undesirable isometry, non-standard size of
particles), as well as specimens of materials after physicomechanical tests. About 40% of
such wastes can still be sold as marketable products, and the other 60% are wastes proper.
In copolymerization of vinyl chloride, these are mainly deposits on the walls of reactors; in
production of polypropylene, atactic isomers; in production of polyethylene, low-molecu-
lar-mass products; and in production of styrene, too small or excessively large granules, etc.
CHAPTER 14 467

Partially, such wastes are used by producers of plastics themselves (by means of depoly-
merization, for instance, using the method of low-temperature pyrolysis or oxidative deg-
radation). According to some estimates, in production of polyolefins the share of wastes is
about 1.2%, and on average in the plastics-manufacturing industry lower than 1% in differ-
ent countries.

Table 14.6.1 Characteristics of turnarounds of secondary plastic materials.

Turnaround Sources of secondary Type of raw Extent of Appearance and shape


of secondary raw materials materials pollution
plastic raw
materials

I Industries producing Single-type Not polluted Powder, granulate,


plastics agglomerate
II Industries reprocessing Single-type Not polluted Pieces of different size
plastics
III Industries processing Single-type Not polluted Pieces of different size,
articles from plastics and combined film, canvas, bands, fibres,
pieces of foamed materials
IV Used plastics from Damaged Polluted Articles, films, pieces of
production and consu- single-type foamed materials
mer spheres and combined
V Plastics from the sphere Damaged Polluted Articles, films
of individual and public mixed and
consumption combined

Turnaround II of secondary plastics raw materials is attributed to plastics-processing


industry (wastes are used at the same plants where they emerge). The procedures of using
wastes strongly differ from plant to plant. At present, the predominant method is collection
of same-type cast-gate wastes, rejects, other wastes emerging at the start-up of the process-
ing machine. These wastes are usually comminuted in the cutting mill and then passed
through the single-screw extruder for homogenization, stabilization, dyeing and granula-
tion. There are examples of automatic separation of manufactured articles and cast gates,
their automatic preparation and return to the same process. This method provides for the
highest purity and uniformity of type of material. There are no data on in-plant recovery of
wastes; the number varies from 3.1 up to 3.6%. According to German experts, the share of
turnover plastics material is about 5%.
The estimate of the total wastes of plastics-processing industries is 8.3%. In the USA,
the share of wastes in primary processing of plastics is assessed to be within the limits of
5.66.9%; from 1.9 up to 2.5% is not used subsequently. However, with introduction of
new processing technologies these estimates are constantly decreasing. Also, the share of
plastics scrap strongly depends on the type of material and method of processing. It is es-
pecially high in processing of polytetrafluoroethylene, polyurethane and epoxy resins, and
also foamed polymer materials.
Turnaround III of secondary plastics raw materials embraces thermoplastic produc-
tion wastes occurring in the subsequent processing of semifinished products and articles.
Thermoplastic semifinished products pass further treatment (vacuforming, pressing, cut-
ting, shaping) at a large number of plants, often very small (and even in craft workshops),
so the storage, preparation and re-use of emerging wastes requires the solution of many
468 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

problems. Selection of one-type secondary raw materials is also complicated by the fact that
wastes mix with other materials, and in sites where they emerge personnel often has no suf-
ficient knowledge of the processed materials to be able to collect them in a correct way.
Some important industries in Germany, oriented on the consumption of thermoplastic
secondary raw materials inside the country, were analyzed. The minimal calculated share
of thermoplastic wastes was 1.4% without the data for plants manufacturing packaging
means and fancy goods from artificial leather. With account for these plants, where the
amount of wastes is 9,000 tons, the total minimal share of wastes increases up to 1.6%.
In industry processing plastic semifinished products and components, the share of
wastes is 360 thousand tons a year or 6.55%. The use of these wastes is even more compli-
cated, as their preparation and use can only in rare cases be done at the same plants where
they emerged.
Many technical problems also occur in connection with wastes of combined materials,
for instance, combinations of plastics with textiles. In Germany, such wastes make 17.6%
of thermoplastic wastes.
Turnaround IV of secondary plastics raw materials involves thermoplastic wastes,
which emerge in the production and consumption spheres as used products. These, for in-
stance, are film materials in agriculture and packaging materials in trade. Such wastes are
usually strongly soiled, contain foreign bodies, are distinguished by increased moisture
content. Often over the years of operation the structure of materials has strongly deteriorat-
ed, as the result of which they should be subjected to additional preparatory operations on
special process equipment before being used as wastes. Of this group of wastes, the most
important are films from low density polyethylene, polypropylene bands and containers
from high density polyethylene. Available literature data on plastic packaging for chemical
industry are rather contradictory.
Turnaround V of secondary plastics raw materials covers plastics wastes of individual
and partially public consumption. A major part of such wastes is from households. They
are not of one type, are as a rule soiled and contain foreign bodies. Until recently, these ther-
moplastic wastes were considered unsuitable for use; however, interest in them constantly
increases in many countries. Special installations for their preparation and processing are
now being developed and phased in on the pilot scale. Due to the problems associated with
the control of the extent of deterioration, because of the variation of composition, wastes
are not separated by the type of plastics. Secondary plastics raw materials are produced with
relatively low mechanical properties.
Significant expenses for the collection of these wastes, as well as for their sorting and
cleaning are the main obstacles for their wide use.

14.6.3 Economic assessment of secondary plastic raw materials


The economic effect in the procurement, preparation and use of secondary plastics second-
ary raw materials should be calculated in the national aspect. This also concerns the tech-
nical solutions on the level of enterprises, which should be acted upon only taking into
account the interests of the economy.
The national economic effect is a complex value affected by a multitude of economic
and non-economic factors. The quantitative assessment of the economic effect of using sec-
ondary raw materials requires a system of absolute and relative characteristics, which re-
flect as closely as possible all expenses and positive results received by the economy.
Herewith, the criteria should be specified with respect to expenses and results:
CHAPTER 14 469

With respect to expenses:


One-time expenses
capital investment
training
Current expenses
prime cost
intensity of use of material
purchase prices
consumption of energy
Expenses for import
requirement in work force
pollution of the environment
With respect to results:
Profit, production volume, payback time
Economy of labour time, productivity of work, less work force is required
Economy of material
Quality of products, export potential
Economy of energy
Reduction of imports
Ecological characteristics, economy on the storage of wastes, less facilities are re-
quired, lower expenses for environment protection measures.
The purchase price for thermoplastic wastes should be stimulating and cover the ex-
penses. It is known from experience that plants where wastes emerge do not want to give
them away free of charge or at a price just covering the expenses, if it becomes known that
secondary raw materials would be used further. Logically, this contradicts the fact that in-
significant expenses for the harmless disposal of these wastes are compensated for by the
state.
There are various opinions on the collection of used plastics, and a certain experience
was accumulated in this field, based on which in Germany collection of household thermo-
plastic wastes was decided to be expedient.
The active use of secondary plastics secondary raw materials naturally requires signif-
icant capital investment. Available capacities are insufficient, and the required technolog-
ical level has not been achieved to enable using previously used combined plastic materials.
Special production facilities are required, as well as transport means, packaging materials,
installations for compaction or grinding, additional personnel, which should be specially
trained.
Criteria with respect to the results can only partially be expressed quantitatively. One
of the possible characteristics is the ratio of the costs of secondary and primary raw mate-
rials; one should also take into account the level of properties of the regenerate. Material
and energy values present in wastes and relatively small expenses for recycling predeter-
mine a significant economic effect, which is even greater due to the economy of primary
resources. It is known that production of 1 ton of polyethylene and 1 ton of PVC requires
the processing of, respectively, 32 and 16 tons of petroleum (the initial product can be spe-
cific petrol fractions of petroleum). Together with petroleum required for production of en-
ergy for processing of raw materials and for synthesis, it is required to use 1.9 tons of
petroleum to produce 1 ton of ethylene the monomer for polyethylene synthesis. With the
most advanced methods of synthesis, if we exclude the energy expenses, the petroleum
equivalent would be:
470 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

1.6 ton of petroleum 1 ton of PE and 1.2 ton of petroleum 1 ton of PVC.
Production of primary plastic raw materials is extremely energy-intensive. The data of
Table 14.6.3 can give an idea of the total energy consumed and separately of the energy
used for polymerization for some widespread bulk plastics. These data form grounds in de-
ciding upon the preparation of plastic wastes for use as secondary raw materials.
Table 14.6.3 Consumption of energy in production of plastics.

Plastics Total energy, Energy for Energy Enthalpy of


kWh/t polymerization, equivalent*, combustion**,
kWh/t kWh/t kWh/t

HDPE 13.670 8.840 10.100 20.850 12.010


LDPE 8.187 6.830 4.600 18.900 12.070
PP 8.240 8.070 4.700 20.020 11.950
PVC 9.490 9.180 2.300 14.180 5.000
PS 18.905 10.840 10.500 21.960 11.120
Polyamide P-6 38.170 46.150 7.980
Polymethylene oxide 28.410 4.390

*Energy equivalent also includes the energy consumed for the cracking of raw petroleum, auxiliary
technological processes and additional substances, transport expenses and the energy required for
polymerization.
**Enthalpy of combustion expresses the content of energy in a substance.

The difference between the values of the energy equivalent and enthalpy of combus-
tion can be understood as materialized labour, which is expressed in the use value of prod-
ucts (this is approximately equal to the total consumption of energy). If plastic materials are
subjected to further processing to obtain semifinished products or articles, the energy equiv-
alent increases from 800 up to 3,500 kWth/t depending on the processing method.
When thermoplastic wastes are used, the earlier materialized labour is used again to a sig-
nificant extent. Preparation of secondary raw materials from these wastes requires an insig-
nificant consumption of energy for many process methods. If, however, the energy of
plastic wastes as well as pyrolysis products is used for production of heavy-duty plastics,
then we can obtain only 35 to 65% of the energy equivalent. On the other hand, a significant
economy can also give a decrease of the cost of storing wastes and freeing storage facilities
(for instance, about 4000 m3 of storage space is required for storing 100 tons of plastic bot-
tles); what is more, it is altogether impossible to express the effect from the point of view
of protection of the environment. Thus, a big problem in storage of phenol-containing plas-
tic wastes is pollution of ground waters.
On the whole, the use of thermoplastic secondary raw materials, including plastic re-
generates with the low level of properties, which replace better-quality regenerates and ma-
terials, improves the provision of polymer materials; in turn, this makes it possible to reduce
primary raw material imports, and to increase exports of domestic thermoplastics.

14.6.4 Collection and use of thermoplastic wastes from domestic consumption sphere
Wastes of this category are characterized by inhomogeneity and considerable extent of
damage. This determines two major methods of their preparation: selective collection of
CHAPTER 14 471

plastic wastes via procurement organizations and isolation of plastic wastes from domestic
wastes. The latter approach requires large investment expenses and has a number of draw-
backs, though makes it possible to isolate and use other valuable components (iron, nonfer-
rous metals, glass, paper).
For territories with a large concentration of industries, it could be expedient to have
the selective collection. Herewith, (as for all the other kinds of secondary raw materials oc-
curring in the consumption sphere), the share of plastics returned to production depends on
the limitations (for technical and hygienic reasons) on the procured kinds of wastes, on the
range of coverage, method of actions and reliability of the procurement system, as well on
the preparedness of the general public to cooperate. Proceeding from the experience of pro-
curing other types of secondary raw materials from the public, the return rate of 20% could
be taken at the initial phase of procurement. This enables an estimate of the reserves of this
kind of raw materials in Germany of approximately 10,000 tons a year (which is about 1.5%
per capita). The accepted low rate of return makes it possible to account for the complex
conditions of procurement. With the improvement of the arrangement, the rate of return can
be made higher.
Rational organization of the procurement of municipal thermoplastic wastes should
satisfy the following requirements: clear-cut limitations on the range of procured wastes (at
a simultaneous provision of small soiling, low amount of inclusions of foreign bodies and
observance of health, occupational safety and fire-fighting requirements), a strict regulation
of amenability, rights and responsibilities of all participants of the procurement process
organization where wastes emerge, collectors, procurement bodies, enterprises preparing
and processing plastic wastes; regulation of the required economic parameters minimal
economic and material expenses of enterprises where wastes emerge, and the procurement
process itself; the stable and valid organization of procurement intended for work under var-
ious conditions and making it possible to reach a high rate of return of wastes.
At present, there are various variants of procurement systems. For instance, in Funas-
abi (Japan) (400,000 population and about 30,00 households) household plastic wastes are
collected from domestic garbage. About 300 workers are involved. Preparation for procure-
ments was done by way of a written appeal to the public. Plastic wastes are collected into
weekly issued light plastic bags, which are collected once a week. This system of collection
is expensive, but its advantage is that the share of plastics is 90% on average [foreign sub-
stances include metals (up to 5%), as well as glass, textiles, paper and other materials].
Most diverse one-time experiments are known. Thus, in one of the districts in the USA
28 thousand polyethylene bottles were collected and recycled to drainage pumps. A similar
experiment was carried out in Halle-Neustadt. Information is available on broad experi-
ments on the collection of plastic wastes in Great Britain, Austria and Germany. However,
they can not be a substitute for procurement systems on a permanent basis.
In France, manufacturers of PVC established a special society with the view of recy-
cling bottles, because more than one quarter of all drinks and liquid food products there are
sold in PVC bottles, which makes 20% (or 130 thousand tons per year) of the total con-
sumption of PVC. The aim of the society is to provide for the return and regeneration of
40 thousand tons of material per year. In collection sites, bottles are pressed into packs of
about 90 kg, which makes expedient the transportation of material to distances of up to 500
km. In Havre and Lyons, two installations for preparation of polymer raw materials for use
were operated; the regenerate is used mainly for fabrication of drainage and cable pipes. It
is known that individual procurements are carried out in France and Belgium also for other
kinds of used plastic materials.
472 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

In agricultural regions of Austria, procurements of used polyethylene (LDPE) bags for


fertilizers, films for hothouses etc. are dealt with by volunteer fire brigades (an insignificant
money reward makes it possible to stimulate this activity).
Of special significance is the storage of procured raw materials under conditions pre-
venting it from pollution and moisture. This requires large storage facilities and sites. Films
are pressed and processed predominantly in special enterprises. Water after washing bags
for fertilizers is used for watering plants, which simultaneously makes unnecessary the con-
struction of expensive waste disposal facilities. The regenerate is used for fabrication of
thick films, construction pipes and components.
The most favourable variant from the point of view of the considered criteria is pro-
curement via the system of trade for secondary raw materials. Its disadvantage are high pur-
chase prices, which are set due to the necessity of approaching the conditions of purchase
of the other kinds of household secondary raw materials. At a purchase price of plastic bot-
tles (predominant articles) equal to 0.05 DM per piece, the purchase cost of 1 ton is 1500
DM. The lowest limit rendering a stimulating effect on the procurement process is the pur-
chase price of 1.00 DM per 1 kg for mixed plastic wastes. At such conditions of purchase,
an economically advantageous use of secondary raw materials is possible only in special
cases. The advantage of procurement via the secondary raw materials trade is the obser-
vance of the stringent requirements to the purity of procured plastic wastes, the absence of
inclusions of foreign materials.
Another acceptable variant of procuring secondary raw materials, similar to that ac-
cepted in Funabasi (Japan) is collection into polyethylene bags. In new building areas, it
should be combined with the installation of special containers for collection of only plastic
household wastes in allocated places. The purpose of the containers should be identified by
the signs on them. From hygienic considerations, such containers should have self-closing
covers. Collection of these containers could be done by municipal bodies, organizations
dealing with purchase of secondary raw materials, enterprises processing the collected
wastes into the regenerate.
This variant has two drawbacks. The first is the absence of material incentives. How-
ever, the experience of Japan shows that this approach can be realized by raising public
awareness, but with a relatively low return rate (for instance, due to the availability of gar-
bage disposers in multistorey block of flats). The second drawback is that other municipal
wastes would also get into these bags, so the contamination of secondary plastics raw ma-
terials would be higher and, respectively, expenses for its sorting and cleaning would rise.
Other presented variants require a number of additional organizational measures to be
taken: expansion of the network of trade by secondary raw materials for purchasing plastic
wastes for fixed prices with account for the quality of raw materials, charge-free procure-
ment of raw materials by processing enterprises etc.
The success in the organization of procuring household thermoplastic wastes depends
on the conscientious support by the general public. Though most citizens are in principle
prepared to participate in procurements, it is necessary to constantly and purposefully raise
the public awareness and provide information on this subject, using radio, TV, newspapers,
posters and postcards. It is necessary to attract public organisations, which already had an
experience of procuring other kinds of secondary raw materials. Economic stimulation,
though playing a supporting role, can not become the dominating motif of procurements.
Procurement of plastic wastes can be done in two stages. First, it is expedient to
procure plastic bottles: in Germany they make about 30% of the total amount of household
wastes; material of bottles is of relatively one type, the risk of foreign inclusions not high.
CHAPTER 14 473

From the point of view of hygiene, it is necessary to demand the thorough cleaning and rins-
ing of submitted bottles. The same-type composition of procured wasters significantly fa-
cilitates their regeneration. Subsequently, with the development of processing facilities and
and the increased demand for the regenerate, procurements should change to mixtures of
plastic articles, but still excluding combined articles (for instance, plastics with metals), as
well as, if possible, articles from thermosetting materials.
When accepting household wastes in a trade of secondary raw materials, the purity of
the accepted material is controlled visually, it is weighed. Soiled packagings of food prod-
ucts are returned, foreign bodies and thermosetting materials are separated. The procured
plastic raw materials are kept in special vessels (boxes, bags, mesh containers etc.), which
could be used not only for storage but also for transportation. Transportation from procure-
ment centres to places of intermediate storage is carried out by traders of secondary raw
materials. Intermediate storage, as a rule, is required to accumulate the amount of secondary
raw materials, expedient to be supplied to processing plants. The rational use of transport
is a serious problem. Secondary raw materials should be compacted in intermediate storage.
Processing enterprises can be at distances of several hundred kilometres from procurement
centres. To efficiently use transport means, it is necessary to comminute thermoplastic
wastes or press them into rolls. For this purpose, procurement enterprises should be
equipped with special devices (impeller breaker mills, presses, etc.).
Collection and delivery of plastic wastes in polymer bags does not make possible the
control of wastes contents. It could be expected that in delivery of bags once a week only
preliminarily washed plastic wastes would be submitted. The demand in work force for the
organization of such a variant of procurement is smaller than in equipping special pick-up
centres. Issue and collection of bags for plastic wastes can be done by local communal en-
terprises. Before transportation, the collected raw materials in this case should also be com-
pacted (comminuted or pressed) and well as liberated from non-plastic component parts.
Wastes collected in containers placed in allocated sites can be soiled very much. De-
livery of containers can be performed by communal enterprises and processing plants. Sep-
aration of non-plastic component parts, considering the high degree of contamination of the
wastes collected, requires additional work force.

14.6.5 Separation of plastic wastes from domestic garbage


This variant can be economical only when all components of garbage are subsequently used
as secondary raw materials. Earlier developments on garbage separation focused primarily
on scrap metal and waste paper. Utilization of old glass, nonferrous metals and plastics sig-
nificantly increases the economic efficiency of the separation method. The composition of
domestic wastes varies depending on the season and locality. Below we present the com-
position of domestic wastes collected in Holland and Sweden and separated in RRR-type
installations, %:

Paper, paperboard 23 50 Glass 8 12


Iron 2.5 5 Plastics 5.5 8
Nonferrous metals 0.3 0.5 Wood, textiles, leather up to 5
Organic products 20 37 Sand, ceramics up to 20

To separate garbage, it is necessary to perform processes of comminution and separa-


tion. Separation can be wet and dry.
474 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The wet method is characterized by a high consumption of water and energy (especial-
ly for the subsequent drying), significant expenses for the purification of water, and sepa-
rated products are of relatively low quality. If garbage is supplied in polymer bags, the
process of its preparation begins with the cutting of bags. For coarse comminution of gar-
bage, hammer swing mills and one- and two-roll impeller breaker mills are used; and for
fine comminution, impeller mills. For inorganic components of garbage (stones, bricks,
etc.) use is also made of grooved rolls. Fractionation is performed using drum and vibrations
sieves.
Separation of wastes by the wet method can be carried out in flotation chambers or
counterflow separators. The operation of flotation chambers is based on the flotation of
some and sedimentation of other components of the separated mixture. In counterflow sep-
arators, the separation into the floating and sedimenting fractions is performed in accor-
dance with the set flow rate. To separate ferromagnetic component parts of garbage, use is
made of electromagnetic drum or band separators. In the wet method, heavy nonmagnetic
fractions are separated using liquid media of high density. Especially great technical prob-
lems occur in separation of paper, polymer films and combined polymer textile films. A
high-voltage separator was designed for separation of paper and polymer films. In the wet
method, paper is dissolved and is thus separated from insoluble plastic and textile compo-
nent parts. A known variant of the wet method is the BlackClawson method. An installa-
tion in Franklin (Ohio, USA; capacity 150 thousand per year) operates according to this
method.
Separation units for automobile scrap, operated by the wet method, were designed by
the firm Bureau of Mines. In flotation chambers, plastics of various types are separated; and
in aqueous counterflow separators, floating (for instance, porous materials), precipitated
(heavy metals) and flotated (light metal, glass, rubber, heavy plastics) fractions. The further
separation of nonferrous metals is performed in separators with heavy media (for instance,
with barite).
The wet method of separation should be used when the component parts of garbage
are presented in an already enriched form; purification and fine separation occur in the pro-
cess of preparation. Thus, the process developed by the firm Bureau of Mines makes it pos-
sible to obtain the paper fraction of 99.8% purity. The firms Recycling B.V. and Esmil B.V.
(Holland) make use of the wet method only to separate the light fraction; the yield of poly-
mer films is from 70 to 80% at a purity of 99%.
Most processes developed for separation of domestic wastes use the dry method at the
first stage. The equipment used are air separators and classifiers; classifiers are predomi-
nantly with the zigzag air ducts. In the process developed by the firm Kraus-Maffei (Ger-
many) the dry method predominates. Only for separation of paper and plastic fractions a
hydroseparator is used, in which the component parts are comminuted even more, and the
paper fraction is turbulized and isolated by means of water. Plastics together with textiles
form an easily removed upper layer. The method is intended for recovery of paper, but can
be also used for utilization of plastics.
A combined method of processing domestic wastes was developed in Aachen (Ger-
many). After the magnetic separation of iron and sieving of fine garbage, large components
are comminuted and separated. The light fraction, which consists predominantly of paper
and plastics, is separated by the wet method; moreover, the paper fraction, in water. The
further processing of the heavy fraction is performed in a counterflow classifier or a sepa-
rator with heavy media. This method can prove to be economically advantageous at an an-
nual volume of recycled material of 250 thousand tons.
CHAPTER 14 475

A significant advantage of the last three processes is that comminution is carried out
after the separation of the larger part of the metal fraction (mainly preserve cans).
In Rome, a completely automated unit for separation of garbage is operated. Garbage
is first roughly sorted, then, after magnetic separation, comminution, air separation and
sieving, light fractions containing paper and polymer films are isolated. Separation of poly-
mer films and cardboard, as well as heavy paper, is performed by means of compressed air.
Light paper is separated from polymer films by means of mechanical clamp shells. Due to
the high content of polyethylene (LDPE) film in garbage, the unit is intended to yield just
these plastic raw materials. Then PVC and polystyrene are isolated by the wet method, as
well as glued paperaluminium films. Polyethylene films are washed, dried, subjected to a
special treatment to eliminate the smell and are pressed into rolls 25 kg each. They also con-
tain 5% of other plastics, 4% paper and paperboard, 2% inorganic components and 0.12%
wood, rags, feathers and porous materials. Using various methods of purification and sep-
aration, it is possible to reduce the content of foreign materials to 0.12%, so that in the end
a high-quality regenerate is obtained, which can be used for production of films by the blow
method. The yield of the regenerate reaches 3040%. Two such installations in Rome an-
nually process 1.8 thousand tons of garbage. The efficiency of these installations is higher
than that of garbage incineration units.
The process developed at the Franklin Institute (USA) makes use of exceptionally dry
separation. Garbage is comminuted in a hammer swing mill, then separated using air and
magnetic separators and air classifiers. Additional comminution is provided for certain in-
termediate fractions. Separation of paper and plastics is carried out in a high-voltage trap.
The RRR process is similar. The plastic fraction is pressed into a roll. In Stockholm, a unit
of 120 thousand tons per year capacity is operated, which supplies 6 thousand tons of sep-
arated plastics per year. The Holland units have a lower productivity.
The recovery of secondary plastics from domestic wastes is considered differently.
Foaming agents, as well as other auxiliary substances, change the density so strongly that
the floatingsedimentation processes do not make it possible to obtain pure fractions. A
significant role in the separation process is played by the geometric shape of wastes and the
soiling of the surfaces with fats, oils and surfactants. As the result, the separation of only
97 to 99% can be achieved, and impurities can have a significant effect on the process prop-
erties of material. Therefore, methods of separating plastic wastes from domestic wastes re-
alized in practice are mainly restricted to the recovery of used LDPE films.

14.6.6 Application of plastic wastes as fillers and additives


Wastes of thermosetting materials after comminution can in certain amounts be added to
formation masses without any significant change of properties of the latter. This approach
is justified if the cost of preparing the material does not exceed 50% of its new cost.
Installations for preparing and mixing thermosetting plastic wastes, developed by the
companies Hull (USA) and Meiki (Japan) do not differ in principle. The installations are
mobile, their output is about 50 kg/h.
Ground wastes of thermosetting materials are used as inert fillers whose particles
should be of the same size as particles of the filler in the new material. Before the formation,
the primary material and the used secondary raw material should be well mixed. Mixtures
with wastes of thermosetting materials are reprocessed by pressure die casting and injection
molding; these methods make possible a good homogenization of the melt.
Addition of wastes as a filler slightly reduces the yield of the mass. Thus, introduction
476 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

of up to 15% filler insignificantly changes impact viscosity, tensile strength and bending
strength, electric and chemical properties, thermal resistance under load also increases. Ad-
dition of such a filler in the amount of higher than 20% is used only for nonessential articles.
An efficient method is comminution of thermosetting material wastes at low temper-
atures the size of almost 95% of particles becomes less than 0.4 mm. Addition of 1520%
of this powder to the formation masses does not worsen the properties of the material.
Comminuted wastes of thermosetting materials can be also added to thermoplastics as
fillers. The filler often has to be dried before use. No technological problems arise in pro-
cessing of powders of filler and thermoplastic. Chips of synthetic-resin bonded paper lam-
inate and fabric-based laminate, formed in machining of pressed laminated materials, can
be added to polyamide. Materials containing up to 30% fillers from wastes of thermosetting
materials can be processed by injection molding. The surface of articles produced is of sat-
isfactory quality. With the content of the filler increased, an insignificant decrease of the
strength of articles at a simultaneous increase of their rigidity is observed.
Addition of industrial wastes of LDPE to concrete the major construction material
yields concrete with increased thermal insulation properties. Milled packaging articles
from foam polystyrene are used as sound absorbents under the seamless floor. Addition of
flocs to concrete yields foam concrete, which is distinguished with good sound and heat in-
sulation properties.
Additions of comminuted rubber wastes in the amount of 0.51 wt. % improve the
performance properties of hollow concrete blocks. Large additions of rubber wastes are not
used, which is due to the problems with comminution of wastes. This approach can be also
used for filling gypsum walls. Household plastic wastes were used in production of body
brick 16 wt. % of comminuted plastic wastes was added to the brick mass. After burning,
the density of bricks decreases by approximately the same value (16 wt. %); the thermal
insulation properties of the brick are significantly improved.
In road construction, thermoplastic wastes are used for modification of bitumens, the
requirements to which are sufficiently high softening temperature and small brittleness at
low temperatures. These contradictory requirements are partially fulfilled for bitumens
based on petroleum with a large content of paraffins. Studies were carried out with the view
of achieving required structural changes in the complex colloidal system of bitumen by its
modification by wastes of LDPE, HDPE and SEVA. These polymers were introduced as
granulates into liquid bitumen at a temperature of 160180C. This process requires about
2 hours, which restricts its use for production of casting asphalt. Additions of polymers
(57%) lead to the formation of typical casting asphalt mixtures with increased strength in
compression and bending within the temperature range of 040C. Herewith, the yield does
not change significantly as compared with nonmodified material, and in tests for long-term
strength under dynamic loads the material exhibits itself as a stronger substance. The ma-
terial passed long-term tests on the roads. A similar use of wastes of polyethylene as addi-
tives to bitumen is known to be used also in Austria. Polypropylene and ABS resins match
with bitumen much worse. Addition of 7 up to 8% polypropylene considerably widens the
temperature region of applications of bitumen asphalt. It is expedient to introduce commi-
nuted wastes of PVC to asphalt mixtures in repairs of road pavement, as this contributes to
the increase of its low-temperature and heat resistance. A positive experience of using PVC
as an additive is known to exist in Japan. Wastes of polystyrene are also applicable for this
purpose.
Plastic wastes granulates are used in underground excavations for pipeline placement;
flocs of foamed polystyrene, as an intermediate layer to increase water impermeability.
CHAPTER 14 477

In agriculture, wastes of foamed polystyrene (flocs) are used for soil amelioration.
This increases the air and water permeability of loamy soils in the long term, because these
wastes are not degradable. Flocs of wastes are mixed with soil, and this mixture replaces
peat or pine needles. For better drainage, they are placed into a package. This approach fa-
cilitates the treatment of soil and saves on other materials used for soil reclamation, heating
of soil is faster (in comparison with pine needles, the temperature of soil is 2C higher); the
soil structure becomes better and the capillary effect smaller, which is important for sensi-
tive seed buds. In Germany, over 100 thousand m3 of wastes was used for this purpose.

14.6.7 Mechanism of degradation


Photochemical degradation is a manifestation of the ageing of polymer materials under the
action of UV radiation with the wavelength of 330 nm. At the action of common lighting
equipment, a material placed behind the glass should preserve its properties for a time cor-
responding to the requirements, with account for the climatic conditions and season in the
degradation period. A special indicator, for instance, a stained substance added into the ma-
terial, indicates the acceleration of the degradation process. To perform both photolytic and
accelerated photooxidative degradation, the following can be used: introduction of photo-
sensitizing links into the polymer chains (destruction of chains occurs predominantly at
these sites); introduction of photosensitizing catalysts, which enhance the natural process
of ageing; new specially synthesized sensitizing polymers. Photodegradable polymers are
obtained by introduction of ketocarbonyl groups, which under the action of UV radiation
cause the degradation of organic compounds. Vinyl ketones are introduced into polymer-
ization polymers; bifunctional monomers, into polycondensation polymers. For mixed
polymers, use can be made of dibasic acids, diamines or glycols:
R'
HOOC (CH2)n C (CH2)n COOH,
R C O

R'
H2N (CH2)m C (CH2)n NH2,
R C O

R'
HO (CH2)m C (CH2)n OH.
R C O

where R is alkyl, aryl, alkaryl or alkenyl C1VC2; R is H or alkyl C1 C6; m, n = 2, 4.


Degradation is faster if the ketone group is not part of the main chain but is directly
adjacent to it. Sensitization assumes the mobility of segments, so that polymers should have
the glass-transition temperature not higher than 30C.
The method is used in production of packaging films and films for agriculture from
polystyrene. Sensitized copolymers are added to usual commercial materials, so that, for
instance, for polystyrene the content of carbonyl groups is from 1.4 up to 0.08%. Decom-
478 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

position time in this case is from 6 up to 60 sunny days. A significant advantage of the meth-
od is that materials are in the end decomposed to give H2O and CO2. Materials pose no
hazard for ground waters and are quite suitable for packaging food products. As additives,
a large number of aromatic carbonyl-containing unsaturated ketones and dienic monomers
are proposed to be used.
A method developed by Scott is an example of using photooxidative catalysts. Organic
complex compounds, for instance, iron diethyl dithiocarbamate, serve as additives. Under
the action of UV radiation, these compounds form a radical possessing a catalytic action.
If, after a certain induction period, radicals are formed, the further decomposition of poly-
mers occurs without the action of light. The induction period depends on the amount of
compounds added. The decomposition products are then degraded by microorganisms. In
recycling, additives act as heat stabilizers.
Organic salts of polyvalent transition metals are recommended to be used as degrada-
tion catalysts, predominantly of Fe, Mn, Zn or Co, as well as chelates with these metals of
the general formula CH3COCH2COOR. A combination of both these mechanisms are of-
fered. Similar organic ferrous compounds were developed by the Swedish company Aker-
lund and Rausing.
Peroxides and hydroperoxides are also light adsorption centres in polymers and induce
chain growth reactions.
Initiation reactions are caused by multivalent transition metals under the action of
light:
h
Fe3+OH Fe3+OH ,

Fe2+OH Fe2++ OH ,

OH + RH H2O + R .
To perform this function, compounds of heavy metals should be soluble in polymers.
Compounds of the form X Fe Y have a good solubility in polyethylene; besides, X can
be a hydroxyl group, and Y are stearates or oleates, which contribute to the solubility. Many
derivatives of ferrocene have been proposed.
Polyisobutylene oxide belongs to polymers, which have a relatively weak photostabil-
ity. It is recycled mainly to produce packaging films. To provide for a certain degradation
time, it is also necessary to introduce photosensitizers into polyisobutylene oxide, though
at lower concentrations than in the case of heavy-duty plastics.
After a certain time, the mechanical properties of the material change owing to decom-
position. This is especially manifested in a decrease of relative breaking elongation. Films
become rigid and brittle, first break into pieces and then finally turn to powder.
An example of biodegradable polymers is bioplastic filled with 1040% starch, de-
veloped by Coloroll (UK). A special treatment can enhance adhesion between polymer and
particles of starch. This enables producing films by the method of blown extrusion. These
films are used as a packaging material.
During the storage of old films starch is an ideal object for the attack of a multitude of
microorganisms, which, by excreting enzymes, transfer it into soluble amylase. These pro-
cesses also proceed in sea water. Only the sunlight without the involvement of microorgan-
isms does not cause accelerated decomposition. Products of decomposition are absolutely
harmless.
CHAPTER 14 479

Separation of water-soluble films, for instance, from hydroxypropyl cellulose or poly-


vinyl alcohol, combined with oiled paper, aluminium foil, polyvinyl chloride or polyethyl-
ene, causes no problems, because cellulose is easily and harmlessly degraded by means of
microorganisms. Naturally, the potential for the introduction of such films is limited.

14.6.8 Energy efficiency of incineration of plastic wastes


Plastics and elastomers are high-quality combustible materials, which yield a high combus-
tion temperature. Combustion of polyolefins, for instance, makes it possible to save an ap-
proximately equal amount of black-oil fuel. Combustion of wastes produces energy
converted to steam, which can be used for heating, or to electricity. If wastes of elastomers
and plastics are burned together with domestic wastes, they are energetically the most en-
ergy-rich part of this fuel. According to estimates of British experts, about 2% of energy
requirements in Europe can be met if a significant part of municipal wastes are burned in
centralized installations and the energy carrier is produced in the form of steam.
In contrast with goal-oriented production of energy, the aim of common incineration
of garbage is to produce a hygienically admissible residue in the form of slag, whose vol-
ume is much smaller than that of incinerated garbage. The produced heat can be used for
maintaining the incineration process or for heating purposes.
The heat of combustion of common domestic wastes is 29008400 kJ/kg; the com-
bustion heat of plastics is more than twice higher. In incineration of garbage, it is expedient
to separate it or enrich with particular components. Higher combustion temperatures are
achieved in the presence of plastic components in garbage. For the content of plastics of
5% in garbage, its incineration presents no problems; at a more than 10% of plastics, it is
recommended to separate them and perform incineration in special furnaces.
Characteristics of production units for garbage incineration were compared. The pro-
ductivity of the units reaches 27 tons/day. Material should be loaded in a ground state. Fur-
naces with the travelling-chain grate and fire feeding by means of black-oil fuel or gas are
used. The technological problems in connection with the lining of furnaces occur at high
temperatures from 900 up to 1200C and the presence of aggressive gases. Excessive for-
mation of soot occurs. Combustible waste gases via the air blower are supplied for inciner-
ation; herewith, waste gases with a temperature of about 1000C are formed, which are used
for heating the air supplied to the incineration furnace.
According to the environment protection requirements, glue gases, which may contain
toxic components (ammonia, chlorine, hydrogen chloride, hydrogen cyanide, nitrous gases,
sulfur dioxide), should be purified before being discharged into the atmosphere. There are
a wet and dry methods of purifying flue gases. In the wet method, alkali liquors or suspen-
sions are injected into the evaporative reactor; in the dry method, alkaline dust, for instance,
NaOH. Both methods need tissue and electric filters for dust separation to be installed.
A unit for incineration of wastes of plastics and elastomers has been developed in
Czech Republic; the installation incinerates 1 m3 of wastes per hour with addition of 20 kg
of diesel fuel, light petroleum product or heating gas. There is no pollution of the environ-
ment in this case.
A pilot plant in Germany recycles 400 kg/h of plastic wastes (rubber, plastic films and
articles, packaging materials, nonwoven materials). In the first stage, wastes pass a thermal
preparation; in the second, they are incinerated. Modern production methods of pyrolysis
and gasification of plastic wastes give significant results. For instance, their incineration in
the deficit of oxygen yields heating gases with the heat value of up to 12,600 kJ/kg.
480 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

14.7 Secondary raw materials based on packaging material wastes


Of all raw materials used for economic activities, only 12% become products, the rest goes
for wastes, the great bulk of which cause harm to nature. Enterprises of meat-and-dairy in-
dustry massively use polyethylene, polypropylene, saran films; cellophane, aluminium foil,
multilayer films, paper with paraffin and polymer backing.
Many of them can last for several hundred years. However, when unsuitable for useful
applications, they are converted to wastes, which are incinerated or utilized.
An ecologically efficient method of protecting the environment from pollution with
wastes of polymer packaging materials is to develop polymers with the regulated service
life. These are biodegradable polymers capable of being degraded to low-molecular-mass
products under the action of heat, light, air oxygen and soil microorganisms. An efficient
approach is the development of edible packagings for food products.
Many materials can be used as secondary raw materials in fabrication of light sand-
wich-type materials. They include large-size tilt-up layered wall sections, whose mass is 50
kg per 1 m2 with foam-plastic filler.
Such constructions are suitable for small enterprises, as well as in constructing auxil-
iary building and refrigeration storages of 250100 ton capacity.

14.8 Use of secondary energy resources


Food industry enterprises are large consumers of heat energy resources. The problem of fuel
economy in food industry is especially acute. The most energy-intensive is sugar produc-
tion, where about 40% of the total fuel is consumed; the next in the range are fat-and-oil,
distillary, vegetable-dehydration productions etc.
Of great importance in the solution of these tasks is the use of secondary energy re-
sources, which are up to 10% in the fuel-and-energy balance of the country. The issue of
using secondary energy resources is also important because the discharge of thermal wastes
into the environment, especially into natural reservoirs, leads to thermal pollution and the
disturbance of ecological equilibrium.
Theoretical calculations and experience of operating thermal schemes testify to the
significant potential of fuel economy by using secondary energy resources. Systematic
measures on the use of secondary energy resources require certain efforts on the develop-
ment of special devices and energy technology combination.
There are considerable losses of thermal energy in food industry owing to the improper
organization of heat economy, so it is necessary to introduce measures to decrease unpro-
ductive losses of energy and the most complete use of secondary energy resources. Second-
ary energy resources represent a potential of a certain kind of energy (thermal, chemical,
mechanical, electric) contained in wastes, intermediate or ready-prepared products.
The secondary energy resources of food industry enterprises can be divided into four
main groups:
the heat of waste gases and liquids (flue gases from boilers and furnaces, as well as
the heat contained in barometric water, distillary stillage, etc.);
the heat of waste steam of steam-power units and secondary steam, heat-consuming
units (evaporation units, rectification apparatuses, driers, self-evaporating vapours);
the heat of combustible wastes (for instance, the husk in oil-extracting plants is used
as fuel in steam boilers);
the heat contained in products and production wastes (this group includes the heat
CHAPTER 14 481

contained in slags of boilers, bagasse of sugar plants, hot bread, sugar, etc.; and also the
heated air of hot production shops).
Of the groups listed, the role of the first two groups is the most significant; that of the
fourth group is less significant. The heat of the secondary energy resources is used in three
directions: for processes proceeding in the main process installations inside the shop or en-
terprise (closed schemes); for external purposes not related to processes proceeding in the
main process units, which are the sources of the secondary energy resources, for instance,
the use of secondary energy resources for district heat supply and hot water supply of res-
idential buildings (open schemes); for internal and external purposes with respect to the pro-
cess in a technological unit (combined schemes).
Each branch of food industry has its own sources of secondary energy resources. Var-
ious principles of the technology determine their qualitative composition (temperature level
and properties of the heat carrier) and quantitative composition. Consider the most ener-
gy-intensive branches.
Sugar industry. By its volume, complexity and the costs of the heat energy facilities,
by the inseparability of links between the heat energy processes, as well by the possibility
of using secondary energy resources, sugar production occupies a leading position among
the food industry branches.
The main constituent parts of secondary energy resources are the heat of steam from
vacuum apparatuses, self-evaporating vapours (boiler deaerator, saturators and sulfiters,
collectors of condensates and process solutions), waste gases from boilers, condensates,
barometric water, blowdown water of boilers, pulp press water, enthalpy of pulp, heated air
of production facilities.
Distillation industry. As secondary energy resources, the heat of stillage from the dis-
tillation column is used; of secondary stillage; production products (alcohol, fusel oil,
yeasts, ether-aldehyde fraction, etc.); the heat of condensers, distillation water, secondary
steam from yeast driers, cooling water from condensers and refrigerators, heated air of pro-
duction facilities, waste gases from blowdown-water boilers.
Distilleries equipped with installations for evaporation of secondary stillage, addition-
ally as secondary energy resources have the heat of secondary steam, condensate of evap-
oration apparatuses, barometric water from the condenser.
Brewing industry. Secondary energy resources include the heat of secondary steam of
boiling vessels, condensates, cooling water, effluent gases of driers and boilers.
Baking, confectionary and starch industries. Elements of secondary energy resources
are the heat of condensates, secondary steam of vacuum apparatuses, coiled columns, baro-
metric water, secondary steam of evaporation units, production products, waste gases of
furnaces, driers and boilers.
Fat-and-oil industry. As secondary energy resources, use is made of condensates and
cooling water, production products, heat of incineration of wastes, heat of waste gases of
driers and boilers.
Canning industry. Secondary energy resources of canning production include the heat
of secondary steam of evaporation units and vacuum apparatuses, barometric and cooling
waters, condensates, semifinished products and ready-prepared products, the heat of waste
gases of dryers and boilers. Consumption of thermal energy for the main products by the
fields of food industry are (in mln GJ/year):
Sugar industry 127 Brewing industry 16.5 Distillation industry 50
Baking and confectionary industry 60 Fat-and-oil industry 15 Starch industry 8
Canning industry 1.05
482 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Estimates of experts relative to the possibilities of using secondary energy resources


vary, which can be explained by the absence of a unified method of determining and ac-
counting for the secondary energy resources.
Analyzing the heat balance of an enterprise, one should pay attention to large heat loss-
es with production wastes (cooling or recirculating water, unused process products, excess
condensors, heated air, hot gases, blowdown water, etc.), accompanied with the tapping of
the heat carrier (liquid, solid, gaseous). A simple and widespread way of decreasing heat
losses is to return the tapped heat carrier to the process flow again; in this case, the returned
working medium and heat are saved.
The problem of using secondary energy resources and protection of the environment
in food industry are closely connected. Many enterprises are forced to put out of operation
a significant amount of wastes, including those that have elevated temperature, which leads
to large heat losses, pollution of the environment and disruption of the ecological balance.
The wastes that have a sufficiently high temperature are sources of secondary energy
resources (unexpended heated waters, flue gases, exhaust from drying installations,
self-evaporating vapours, hot air, etc.). To date, sufficient experience of using low-potential
heat has been accumulated:
development of heat exchangers (recuperative and contact-type, operated at a small
temperature difference);
return of heated waste waters to the process cycle;
use of flue gases for drying processes;
maximum use of condensates for feeding steam boilers;
use of excess condensate for process purposes;
introduction of surface condensers;
use of secondary steams of vacuum apparatuses and vacuum evaporators;
use of self-evaporating vapours for heating liquids;
use of heated air for heating production facilities;
use of secondary steam for district heat supply;
recovery of cooling water to the process cycle;
elaboration of condensate traps and condensate schemes;
replacement of steam heating by water heating;
multivariant calculation of heat schemes and search for optimal solutions with the
view of saving fuel, electric energy, materials;
recirculation of the drying agent;
improvement of heat application schemes with the maximal use of secondary energy
resources;
compression of secondary steam in jet and mechanical compressors;
use of thermal wastes for cold production, etc.

14.9 Economic and ecological aspects of utilization of secondary raw


materials
High growth rates of production and consumption of plastics, characteristic of industrially
developed countries, stipulated the emergence of a relatively new problem disposal and
utilization of plastic scrap. This problem is of special significance both because the pack-
aging industry is one of the largest consumers of polymer materials and due to short service
life of containers and packagings.
On the whole, the content of plastics in solid wastes is at present in the Western Euro-
CHAPTER 14 483

pean countries 34%, in Japan, 8%; in the USA, 5% and increases up to 68, 1215 and
710%, respectively.
The growing volume of plastic scrap leads to the necessity of preventing the pollution
of the environment, which is associated with considerable expenses. Expenses for control-
ling the pollution of the environment in chemical industry of industrially developed coun-
tries reach 610% of all capital investment. A significant part of expenses (up to 25%) is
related to the prevention of the pollution with solid wastes.
According to the data available, the costs of processing and disposing plastic scrap ex-
ceed approximately eightfold the expenses for processing most industrial wastes and almost
threefold for disposal of household wastes. As plastics do not decay and do not decompose,
their wastes could not be compacted during the disposal; as the result, plots of land required
for the disposal should be four times as large as those for the disposal of household wastes.
In incineration, plastics usually evolve toxic and corroding substances; the required in-
cineration temperature is approximately 600700C higher, and the volume of evolved in-
cineration products 35 times larger than in incineration of household wastes; all these
factors make the process more expensive.
One of the waste disposal methods developed specially for polymer containers is in-
troduction (during the synthesis or recycling) of additives, which initiate bio-, photo- or
water degradation of containers used. Containers from decomposing plastics are produced
mainly in Japan, Germany, the UK and the USA.
The practice of using decomposable plastics revealed a restricted potential of this
method for solving the pollution problem: wastes of containers, when getting into the gen-
eral mass of household or industrial wastes, cease to be subjected to the action of factors
that cause their decomposition. If decomposition does occur, its products can also cause the
secondary pollution of soil and water. Besides, there is a possibility of contaminating a
packaged product with substances formed in decomposition.
Recent studies by the sanitary services of Germany, Great Britain and the USA indi-
cate a negative effect of decomposing plastics also on the environment. All these make one
to assess the prospects of using decomposing materials with caution, though does not rule
out the possibility of their use in a number of fields, for instance, in agriculture.
Thus, a brief consideration of the main waste-disposal methods for polymer containers
shows that they require considerable expenses and in many cases can not efficiently solve
the problem of pollution of the environment.
In the recent years, methods of utilizing wastes of polymer containers have been de-
veloped, primarily the following: recycling of plastics based on wastes of structural mate-
rials, thermal and catalytic cracking, pyrolysis of wastes of polymer containers.
Recycling is the most expedient method of utilizing wastes formed in production of
containers. Economy of the expenses for processing packaging wastes can reach 70% of
the cots of fresh raw materials.
Wastes of polyethylene film widely used for packaging various products can be recy-
cled to produce either secondary granulate or be mixed with fresh raw material to produce
films.
In connection with the rapid development of producing multilayer packaging films and
combined materials with layers of foil, paper and tissue, much attention is given to the meth-
ods for the regeneration of these materials.
Consumption of containers from plastic foam high expands at a high rate. Wastes the
weight of which reaches 30% of the weight of produced containers can either be used again
in production of foamed articles, or be recycled into granulate after their degassing. Wastes
484 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

of foam plastics are also used as one of the layers in production of combined packaging ma-
terials, where base layers (paper, tissue, foil, polymer films) are alternated with layers of
comminuted plastic foam. Containers from thermosetting materials are used on a much
smaller scale than containers from thermoplastics; however, their absolute volume of con-
sumption are still high. An important condition of increasing the efficiency of these con-
tainers is recycling of wastes produced. Installations for the fine comminution of wastes of
thermosetting materials are operated in the USA and Japan. Regenerate is used an additive
(up to 20%) to fresh raw materials; herewith, the properties of the initial composition are
not worsened considerably.
Reprocessing of used polymer containers is more complex as it is associated with the
need to collect, sort and clean them. Nevertheless, this problem is successfully solved in a
number of countries. Thus, the experience of work of German firms for reprocessing of
packaging wastes indicates the economic feasibility of these measures and shows that the
rational organization of the collection of packaging wastes makes it possible to reduce the
amount of household and industrial wastes by no less than 40%.
In the USA, a number of large dairy enterprises perform recycling of polymer contain-
ers for milk products; a specialized enterprise Seajay Plastic Bottles Center provides ser-
vice to companies producing polymer containers. Used containers are recycled into
secondary granulate, which is then used for fabrication of agricultural-purpose articles. The
cost of granulate is 2.53 times as low as that of the initial raw material. Recycling of pack-
aging wastes for food products is, as a rule, preceded by the stage of purification from the
residues of the product.
In Japan, household plastics wastes, which are mainly various kinds of packagings, are
collected. Collected wastes in the form of a mixture are processed on units of various ca-
pacity (50 up to 700 kg/h) into secondary granulate. The cost of obtained material does not
exceed 25% of the cost of the cheapest primary polymer. The secondary material obtained
is mainly used as heat and sound insulation in construction and agriculture. However, it can
also be used for packaging purposes. Thus, in Japan, cups and other containers from poly-
styrene are recycled to fabricate packaging materials used to produce, for instance, packag-
ing boxes. In Germany, polyethylene bags used for packaging chemical fertilizers and peat
are recycled. The secondary granulate obtained is again used for fabrication of bags, which
meet the requirements and, besides, as compared with bags from primary raw materials, are
less slippery when stacked.
One of the economic methods of utilization of polymer packaging wastes is production
on their basis of structural materials, in which the wastes play the role of a polymer bonding
adhesive. In this case, there is no need to purify and screen wastes; it is also possible to uti-
lize packaging wastes together with other components of household and industrial wastes.
The properties of such materials are largely determined by the properties of the filler; they
can be used in municipal and road construction, in production of furniture, as heat and sound
insulation materials. Their cost is 23 times lower than that of replaced traditional materials
and articles. This method is especially widely used in Japan, where it is realized in a number
of semi-industrial installations. It is envisaged to expand the existing facilities and to con-
struct new installations of 46 tons per hour capacity.
A promising method of utilizing polymer material wastes is their depolymerization to
oligomer or initial monomer products. Of the depolymerization techniques, of greatest sig-
nificance are pyrolysis, thermal and catalytic cracking. The conditions of the process and
the nature of reprocessed wastes are determined from the ratio of the products obtained: hy-
drocarbons for the synthesis of plastics, gas oil, kerosene, fuel oils, activated carbon etc.
CHAPTER 14 485

The energy crisis due to the deficit of oil-and-gas raw materials, created prerequisites
for the development of this method of utilization.
Works are underway to include pyrolysis installations into production of plastics fro
oil-and-gas raw materials. There is experience of using obtained gases for production of
electrical energy.
Below, we present a technical-and-economic comparison of the methods of thermal
treatment of wastes: incineration as the main method of disposal, on the one hand, and py-
polysis, cracking, on the other hand. Capital operational expenses for installations operated
by the thermal cracking method are, respectively, 5 and 1.52 times as low as similar pa-
rameters for units of comparable capacity (3 tons/h), operated by the incineration method.
One should also take into account an additional economy from the use of products obtained.
Thus, fuel oils whose yield in the pyrolysis of discarded polyethylene containers is 94.7%,
contain no sulfur, which is an advantage with respect to raw petroleum products and com-
mon types of fuel.
On the whole, the technical-and-economic parameters of the methods of utilization of
polymer packaging wastes do not exceed the expenses for their disposal, and in some cases
are even lower. Besides, wastes utilization methods, in contrast with disposal methods pro-
vide for the rational use of raw material resources. They are also the most efficient from the
point of view of preventing the pollution of the environment by production wastes and con-
tainer consumption wastes.
The development of photo-, bio- and water-degradable plastics is caused by environ-
ment protection requirements. Overage articles from such plastics are degraded harmlessly.
Degradation of plastics occurs due to photolytic, photooxidative and biological reactions.
The use of these plastics contributes to the decrease of environmental pollution and
labour costs, especially in agriculture, where polymer films reach such an extent of degra-
dation after the vegetation period of agricultural crops, that they do not prevent soil treat-
ment; to a sharp reduction in the amount of plastics scrap in refuse dumps. On the other
hand, degradable plastics are not involved further in material and energy turnarounds. It
should also be noted that there is still no clear understanding as to the action of plastic deg-
radation products on soil and on ground waters.
The effect of decomposition is achieved mainly due to the introduction of additives or
addition of initiating groups to polymer chains. In any variant, this makes the material more
expensive. Herewith, the exact economic assessment is impossible due to the complexity
of accounting for the expenses for protection of the environment. If plastic wastes are kept
unexposed in storage facilities, their degradation can be only biochemical. There is also
some negative psychological effect of using articles from degradable plastics due to the
awareness that self-degradation of plastic articles probably contributes to the contamination
of the environment.

14.10 Self-degrading polymer materials


Most polymer materials manufactured at present are distinguished by an exceptionally high
resistance to microbial action. This is one of the major reasons of their wide use. However,
this advantage turns to be a serious drawback for waste polymers. Under natural conditions,
polymer wastes are degraded extremely slowly, are practically not subjected to the action
of soil and air microorganisms, and are, thus, a source of environmental pollution. In recent
years, great attention has been given to the development of self-degrading polymer materi-
als. These materials are divided into three major groups: biodegradable, degradable under
486 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

the action of light and chemically degradable.


Biodegradable materials. Biodegradable polymers are photodegradable composi-
tions, which, being for a certain time under atmospheric conditions, are degraded so strong-
ly that are easily assimilated by microorganisms present in the soil and in the atmosphere.
Therefore, photodegradable polymers are called biodegradable.
The company ICI (Great Britain) developed a technology of producing a new packag-
ing material in bioreactors biopol the use of which for packaging food, pharmaceutical
and cosmetic products would make it possible to solve problems associated with utilization
of traditional plastic packagings.
Biopol is the first biodegradable thermoplast in the world. It is produced by fermenta-
tion of such agricultural raw materials as sugar and starch. Used packagings from biopol
can be freely dumped on acting waste disposal sites without disturbing the ecological bal-
ance. Biopol completely degrades in soil under the action of fungi and bacteria. The degra-
dation rate of used packagings depends on their thickness and type of surface treatment.
Rough films degrade faster than bottles with smooth surface fabricated from the same ma-
terial.
Biopol is a thermoplastic aliphatic polyester (polyhydroxybutylate). The physical
properties of this material (melting point, crystallinity, etc.) are the same as in prolypropy-
lene, though its rigidity and brittleness parameters are slightly higher. Biopol is processed
as traditional thermoplastics. Technical and economic prerequisites for the re-use of biopol
in industry were established.
In the opinion of ICI specialists, the use of sugar or starch for production of biopol is
justified from the economic and ecological point of view. Economic forecasts suggest that
in the foreseeable future costs for sugar in the Commonwealth countries would go down to
the level of the world market. Besides, the general reduction of costs on agricultural produce
due to the intensification of agriculture is expected. Production and application of biopol in
sugar supplying countries which have no stocks of oil of their own for production of plastics
is economically justified already today.
At present, biopol is produced at a pilot plant at the ICI Biotechnological Centre in the
UK. Its costs are still relatively high, as the process developed by the company enables the
production of the final product with a diverse range of the physical properties. By the esti-
mates of specialists, the mass production of biopol is economically justified at an annual
output of no less than 1,000 tons.
The company Weisstech Edward Weiss (UK) developed three biodegradable polymer
materials having different degradation rates, costs and application areas. One of the mate-
rials is based on polyethylene with addition of polyamide links and several other chemical
substances. Depending on the content of stabilizers, its life time can vary within a rather
wide limits from 30 days up to 4 6 months. Another material can be degraded at a tem-
perature of 25C in water for 45 sec. The third material (25 m thick) possesses a light trans-
mission value of 4% and surface smoothness of 78%. The latter material has high protective
properties at the action of alkali and most known solvents, is heat impermeable and
low-temperature-resistant. Apparently, it would find use in packaging chemical additives
of agrotechnical application and aggressive pesticides. Placing a packaging with these sub-
stances into slightly warmed water, one immediately obtains a solution of the substance.
The packaging dissolves completely and has no effect on the properties of the fertilizer.
One of the ways of creating polymers degrading under the influence of microorgan-
isms present in the soil and atmosphere is addition of substances, which easily degrade
themselves and are assimilated by microorganisms, into the polymer matrix.
CHAPTER 14 487

They include carboxymethyl cellulose, various kinds of starch (rice, potato, wheat,
etc.), mannitol, lactose, casein, yeasts, urea and many other compounds of natural origin.
Material based on grain starch compares favourably to polymers, whose basis are com-
paratively hard-to-degrade macromolecules. Experts claim that the starch basis can be used
for series production of materials degradable under the action of one of the three degrada-
tion factors or their combined effect.
Specialists of Warner-Lampert Co (USA) succeeded in developing a technology of
producing polymer materials capable of complete degradation under the action of the envi-
ronment conditions. New polymer materials are fabricated based on starch. Until now,
self-degrading polymers were obtained based on compounds isolated from petroleum.
According to reports by specialists of the company, the cost of the new polymers is
quite comparable with known self-degrading materials, because their production will be
based on renewable raw materials potatoes, grain and rice. At present, material known
under the name of biopolymer starch (trade name Novon) started to be used for fabrication
of pharmaceutical capsules, which before then had been produced from gelatin.
The possibility of series production of small self-degrading polymer packagings from
Novon was demonstrated by Warner-Lampert Co. It is expected that in the near future
self-degrading film packagings based on this material will be available.
The company Capsugel AC (Switzerland) together with the Institute of Polymers
(Zurich) also developed a process for production of packaging material from starch. Pro-
duced material is absolutely harmless for the environment, its physicochemical properties
are similar to those of traditional thermoplastic materials (polyethylene, polypropylene,
polystyrene), discarded packagings are degraded in the soil without disturbing the ecolog-
ical balance. It was found experimentally that biopolymers (starch, cellulose, gelatin etc.)
could be subjected to thermal treatment by pressure without changing their properties. The
crucial role in this case is played by the correct choice of temperature and pressure. Exper-
imental studies made use of a machine for casting under pressure, which traditionally is
used for fabrication of disposable cups and tableware. Common powder starch was fed into
the charging funnel to yield in the end a solid shape of required configuration. The company
has begun series production of this material. The first serial product were capsules for med-
icines.
In agriculture, this material could be used to fabricate long plastic tunnels for protec-
tion of vegetable crops from atmospheric forcing. After being used under field conditions
for one or two months, these tunnels are subjected to simple biological degradation in soil.
Besides materials obtained on the basis of grain starch, a polymer based on potato peels
started to be developed; potato peels are first converted to glucose and then to lactic acid
introduced into polymers and copolymers.
At present, when the reprocessing of domestic wastes is oriented not to incineration
but composting, the use of novel packaging material from starch has some advantages; in
particular, there is no need for preliminary sorting of domestic wastes. For instance, carrot
tops or potato peels are composted together with containers (bags from starch film).
Grain starch can be used to produce thermoshrink and stretch film materials widely
applied in packaging, disposable cups for cold drinks, wrapping materials for confections.
Auxiliary components for packaging (for instance, connective rings, clips, etc.) can be also
fabricated from polymers with the degradation time of 3 months up to 2 years.
Materials degraded under the action of light. The main action on light-degradable ma-
terial is rendered by ultraviolet rays present in the solar spectrum. Usually, to impart poly-
mers with an ability to be degraded under the action of light, use is made of special additives
488 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

or special light-sensitive groups introduced into the polymer. For such polymers to find
practical application, they should satisfy the following requirements:
as the result of modification, the performance characteristics of the polymer should
not change significantly;
additives introduced should not be toxic, because polymers are primarily intended for
fabrication of containers and packagings;
polymers should be reprocessible by a traditional method and be non-degradable by
the process;
polymer breakdown time should be known and vary within a wide range;
items fabricated from these polymers should be stored and operated for a long time
in the absence of direct ultraviolet radiation;
polymer degradation products should not be toxic.
One of the most known methods of creating photodegradable polymers is introduction
of carbonyl-containing groupings into the polymer chain. Under the action of ultraviolet ra-
diation in natural or artificial conditions, such photodegradable polymers fist crack, then
are covered with a continuous network of cracks, and, finally, break up to pieces of various
sizes, which subsequently turn to powder.
In the USA, a technology was developed for production of ketone-series polymers.
The process is used in the synthesis of polystyrene powders. Ketone branchings from the
main polystyrene chain create favourable conditions for photodestruction under the action
of ultraviolet rays of the solar spectrum. The rate of destruction is directly proportional to
the content of ketone-based copolymer.
Chemically degradable materials. In chemical decomposition, there occur oxidative,
hydrolytic and other reactions with macromolecules of polymer compounds. In Switzer-
land, a process was developed, which admits both reprocessing of polymer materials, and
their self-degradation. The new technology consists of using polymers based on acrylates,
which totally dissolve in alkaline solutions. Film material, the micromolecular chains of
which have acidic groups, dissolves in solutions with acidity of 9 up to 12. The solubility
of polymer material can be changed by varying the number of acidic groups. Material with
high solubility can be totally degraded in sea water in 4 days.
One of the areas of using new polymer materials is fabrication of labels for returnable
glass containers. The use of such labels was calculated to reduce the duration of washing
containers in caustic soda by one-third. It is also possible to use this material for labelling
dairy packs from high-density polyethylene. After a simple flush, the packaging is com-
pletely suitable for reprocessing. Herewith, the possibility of polluting the polymer mass
with other undesirable chemical compounds is excluded.
Increased production of self-degrading polymer materials in the USA is associated
with increased demand for disposable packagings, which should be utilized or destroyed.
American experts on environment protection believe that self-degrading polymer materials
should play in the future the main role in reduction of the amount of solid wastes. Many
packaging materials (paper, cardboard, etc.), getting to waste deposits, degrade very slowly
(no less than 10 years), which presents certain problems in protection of the environment
and makes the authorities to expand waste disposal sites. The use of biodegradable pack-
agings could help to solve this problem, because polymers degrade rapidly under the action
of heat, moisture and light and decompose to form water and carbon dioxide, which do not
disturb the biospheric equilibrium of the ecological system on the planet.
Complete transition to production of bags from self-degrading polymers is an issue un-
der consideration in the USA; these bags would be given to customers in shops. However,
CHAPTER 14 489

manufacturers of plastics regard mass production of such packaging materials with great
care. The main reason for this is the non-coordination of actions by manufacturers and con-
sumers. In the opinion of a number of organization, self-degrading polymer materials could
not totally replace the existing polymers, especially in packaging business. Besides, the de-
velopment and setting-up of series production of such materials requires large capital in-
vestment. Opponents of the use of such materials also believe that landfarming of
self-degrading films creates the danger of polluting neighbouring plots of land. Besides, the
film biodegradation rate, depending on the amount of active microorganisms in soil and
photodegradation determined by the intensity of solar radiation, is different for different
areas.
A number of public organizations in the USA argue against the uncontrollable release
of self-degrading polymers, as, in their opinion, aesthetic problems associated with film
degradation products still remain unresolved and the possibility of polluting the environ-
ment has not been ruled out. In the near future, research is to be carried out to elucidate the
possible side effects caused by the degradation of polymer packaging materials. In the opin-
ion of specialists, standards for self-degrading packagings and packaging materials should
be worked out. Simple and reliable methods for separation of self-degrading and common
polymers should be developed. The viability of self-degrading polymers in common dis-
posal sites should be assessed in full measure.
490 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY
15 Packaging of Meat and
Meat Products

Manufacture of meat and meat products has always been and remains the most labour-
intensive and expensive industry. Meat goods, especially specialty foods, are high-nutritive
value products, which provide for the requirements of man in animal proteins, vitamins,
mineral substances.
Preservation of the quality of meat and specialty meat products, as well as increase of
their shelf life is a very topical problem. In storage, complex biochemical and microbio-
logical processes occur in meat and meat products. They not only decrease the quality of
products and deteriorate their appearance, but can also produce food poisoning, dysbacte-
riosis, allergic reactions, metabolic disorders and often make products unsuitable to be used
for food.
The aim in this field is to develop high-quality packagings, capable of not only pre-
serving their properties in transportation, storage and sale of a product, but also of protect-
ing it for the time required.
However, lack of knowledge of packaging materials properties, packaging techniques
and requirements imposed by food products, when the sole criterion of choosing a packag-
ing material is its cost, can not only make achieving the desired result impossible, but also
lead to an adverse effect of the packaging on the quality of the product.
When choosing a packaging for meat and meat products, of great importance are
microbiological and biochemical processes occurring during the storage of fresh meat and
meat products, which can additionally be subjected to culinary and heat treatment. There-
fore, the main requirement for packaging of meat products is that polymer material should
not interact with the product, change its quality and create hazardous media. The expiry
date, conditions of storage and transportation of the product should also be taken into
account.
The packaging should ensure, first and foremost, protection from the environment,
namely, should possess the set of optimal properties, which would enable preserving the
original quality of the product. Packaging material should have a sufficient mechanical
strength, air tightness, chemical endurance; should possess optimal barrier properties:
aroma permeability, permeability for gases, water, vapours and fats. Almost all meat
products are fat-containing, so polymer materials intended for their packaging should be
grease-resistant and simultaneously provide for protection from oxygen, which initiates
oxidation of fats.
A broad range of polymer film materials is used at present for packaging meat and
meat products.
492 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Cellophane, polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene


and other films are used as single-layer films. Besides single-layer monofilms, combined
multilayer film materials are widespread. Of special attention are thermoformed combined
materials, including deep draw films, which are characterized by a high strength of heat seal
and a high rupture strength.
Use of materials with a given set of physicomechanical properties for packaging a con-
crete type of product by a definite method ensures optimal preservation of the product.

15.1 Range of single-layer packaging materials in meat packaging


Cellophane both common and waterproof is produced from regenerated cellulose. The
specific features of cellophane are its low air permeability, resistance to sunlight, fats, oils
and aromatic substances. The film preserves its properties at a change of temperature within
the range of 40C up to +150C. In dry state, cellophane has a high mechanical strength.
Drawbacks of this film include moisture permeability and the dependence of its prop-
erties on humidity. The mass of products containing a significant amount of moisture and
packaged into common cellophane film decreases in storage; that of dry products stored in
facilities with increased humidity, increases. Common cellophane is not heat sealable but
can be pasted by dextrine adhesive.
To increase its water resistance, cellophane is lacquered on one or both sides with
various lacquers based on copolymers of vinyl and vinylidene chloride, epoxy resins, nitro-
cellulose. The lacquer coatings 0.00450.006 mm thick reduce water and vapour perme-
ability of cellophane. Lacquered cellophane yields to heat sealing, which makes it possible
to use it in packaging machines.
The international system of designating individual brands of cellophane:
A and M resistant to atmospheric action, lacquered
H flexible
S heat sealable
T uncoloured
P common nonlacquered.
Widespread materials used for packaging meat products are films from polyolefins:
polyethylene (PE) and polypropylene (PP), which possess valuable physicomechanical and
physicochemical characteristics. Proceeding from the polyethylene production process,
three kinds of polyethylene film are distinguished: low pressure (high density), high pres-
sure (low density) and medium pressure.
High-pressure polyethylene (HPPE) films have no smell, taste, are chemically inert
and nontoxic. Polyethylene belongs to thermoplastic polymers: the film is readily sealable
at a temperature of 110150C by contact and thermopulsed methods. Its high gas perme-
ability for oxygen and carbon dioxide in combination with moisture impermeability and
low hydrophilicity make this film suitable for packaging chilled meat, meat semifinished
products and other products. However, in prolonged contact with fat and oils it swells, its
strength decreases, and fats and oils acquire a specific smell. High-pressure polyethylene
films are insufficiently transparent and have a low heat resistance (90100C).
Low-pressure polyethylene (LPPE) films, as compared with high-pressure films, are
more heat resistant (up to 125C). Besides, they are characterized by a lower moisture per-
meability and permeability for volatile aromatic substances, a greater resistance to fats and
oils, a higher rupture and puncture strength.
CHAPTER 15 493

Low-density linear polyethylene (LDLPE) is structurally similar to HDPE, i.e., it is


based on linear macromolecules, which have longer side chains. This product has excellent
performance properties at high and low temperatures, a good chemical endurance and is
used for production of impermeable stretch films and shrink films.
Thermoshrinkable (oriented) PE films, whose shrinkage under the action of heat is
from 15 up to 65% are used for packaging food products.
The most promising and widespread material for packaging fresh meat on trays is
HDPE (LPPE) the mono- and biaxial oriented thermoshrinkable film. The advantage of
this polymer is an ideal combination of oxygen permeability, because fresh meat needs
oxygen for its colour to be preserved.
Polyethylene films are manufactured under various trade marks: Germany, Suproten,
V-56; USA, Cryovac-U, Irraten, Diotex, Conolex; UK, Rijitex; Japan, Estron-s; etc.
A particular feature of Irraten, along with its enhanced heat resistance (up to 130C)
is its capability of heat setting (about 50%).
V-56 films (Germany) yield to deep drawing, endure high temperatures (120140C),
the action of oxidizers and chemical reagents excluding aromatic and haloid-substituted
hydrocarbons.
Colonex (USA) possesses an increased strength, is stable within the temperature range
from +120C to 70C.
UK-manufactured Rijitex films of up to 0.025 m in thickness have a high gas and wa-
ter impermeability, low vapour permeability, high chemical endurance, and heat resistance
up to 120C.
In Germany, food products are packaged using new types of polyethylene films. Thus,
low-pressure linear polyethylene (HDPE) has the unbranched molecular structure, which
provides for the required strength at the simultaneous increase of transparency and impact
strength and a decrease of gas permeability.
To protect food products from various undesirable impacts (e.g., ultraviolet radiation)
and to increase the quality of PE films further, copolymerization of ethylene with other ole-
fins is broadly introduced. The known film materials are Marlex-500 based on copolymers
of ethylene with butene; Dutral and Norden, with acrylate; Zetafin, with ethylacrylate;
Elvax, EVA, with vinyl acetate; etc.
Films based on copolymers of ethylene with vinyl acetate (CEVA) became the most
widespread. By their properties, they are close to materials from high-pressure PE, but dif-
fer from them by a lower melting temperature, greater transparency, elasticity, high
low-temperature resistance and satisfactory sanitary-hygienic properties. At present, main-
ly two types of such films are used in packaging practice: deep drawn to 55 mm and
thermoshrinkable oriented.
Formable films, e.g., EVA (USA) have a high strength (20002500 MPa) and rigidity,
as well as increased elasticity at a temperature of minus 3035C, which provides for the
formation of disposable packagings of various sizes.
Thermoshrinkable films from these copolymers are capable of up to a 50% shrinkage
at a temperature of 90100C. The film is strong, possesses an increased grease resistance,
is well heat sealable.
Along with CEVA, products of its saponification are used copolymers of ethylene
with vinyl alcohol (trade mark EVOH), which possess a high transparency, glossy surface
and low gas permeability, in particular, with respect to oxygen and carbon dioxide. These
copolymers are suitable for packaging meat and finished goods.
Ionomers (offered most often under the trade mark of SURLYN-A of the Swiss
494 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

company Du Pont) are based on polyethylene with carboxyl groups arranged along the
polymer chain, which provides for stable ionic bonding. The cationic bonding is provided
for by metal ions (sodium, potassium, magnesium, zinc). The polymers are processable by
all methods known for thermoplastics. The high strength of the melt enables their use for
extrusion coatings and in skin packagings. Films from ionomers are distinguished by a high
transparency, puncture resistance, grease resistance, tight adhesion to the support, increased
strength of the heat seal in contamination of the film surface with fats, powders, etc.
At present, research is underway to develop films from polyolefins with special prop-
eerties. The film from transparent AFFINITY polyolefin plastomers (POPs) for packag-
ing meat possesses the properties similar to those of surlyn ionomers but costs one third less.
Manufactured according to the INSITE technology developed by Dow Chemical Company,
it is easily heat sealable, is characterized by the strong heat seal for rupture and high barrier
properties. Transparency and gloss of this film promote efficient exposure of packaged
products.
After PE, the most widespread films for packaging meat products are polypropylene
(PP) films. This is a material with good performance properties and relatively established
consumption structure. They are not toxic, are chemically inert, have no taste or smell, are
not subject to mold development. Their vapour impermeability approaches the similar value
for PE films; their moisture and gas impermeability is much higher than these parameters
for PE; their light permeability approaches that of glass.
By their basic properties (inertia to most chemical agents, to acids and alkali), PP and
PE films are similar.
PP films possess a higher heat resistance (120C) and have an increased resistance to
oils and fats, but their heat sealability is inferior to that of PE films. However, the low-
temperature resistance of PP film is only about 20C. It is readily oxidized, as the result
of which its mechanical characteristics deteriorate. The ultimate tensile strength of PP films
is higher than that of polyethylene films, the drawbacks of the film are eliminated by its
orientation in extrusion in two mutually perpendicular directions. Orientation increases the
rigidity of PP film, its resistance to solvents, as well as water and vapour impermeability.
The low water-absorbing value and good resistance of PP films to fats and oils stipu-
lates their use for packaging fat-containing and culinary articles, edible rendered fats etc.,
and the high heat resistance enables sterilization of products in these films at a temperature
of 120130C.
Polypropylene films, as well as polyethylene films, are manufactured under various
trade marks: in the USA, Moplefan-TQ and Moplefan-Q, Profax, Proplin, Cryovac-U; in
Italy, Moplen, Marlen; etc.
According to several estimates, about 10% of the total production of polymer packag-
ing throughout the world is biaxially oriented polypropylene (BOPP).
In Russia, the market for this product is yet at the development stage; nevertheless, the
estimated market potential of this packaging film can reach 100,000 tons. Experts call
BOPP the queen of polymer films. Owing to its crystal-clear transparency, shock resistance,
absence of smell and flavour, high protective properties and pronounced gloss, this film is
used for manufacturing various packagings mainly for food products.
It should be noted that the cost of PP films is higher than that of similar items from
LDPE, so they are used in applications, which require higher barrier properties, transpar-
ency and gloss than those provided by LDPE. Besides, PP finds wide use as sheets in form-
ing disposable plastic containers and as blown material to produce various plastic bottles
and cans.
CHAPTER 15 495

A new type of PP, Pro-fax SC-204 (Montell North America) is especially suitable for
packaging frozen products. Although this material becomes rigid, it possesses a mechanical
strength to damage and replaces the bilayer composite materials used until now.
Recently, the market of polyolefin-based packaging materials was supplemented by
an advanced development of the Swedish company Ecolean, lean material, a 21st century
packaging product. Manufactured from calcium carbonate in combination with polyolefins,
which are produced from natural gas, it is capable of replacing many materials used now-
adays. This is a universal packaging material recommended for a broad range of food
products. Its increased barrier properties to ultraviolet radiation make it possible to use this
film for automatic or manual packaging of chopped meat patties.
Lean materials possess evident advantages over a number of currently used packaging
materials. The technological merits of lean materials demonstrate a considerable economy
at all stages of packaging production. The economy is present already at the stage of pro-
duction of these materials. This is achieved, first of all, by using generally available resourc-
es as raw materials. Besides, the production process requires less energy consumption as
compared with traditional packaging materials with paper, foil and plactics as their compo-
nents. As lean materials consist of calcium carbonate by 50%, they require no energy for
utilization and completely dissolve in soil in several months. Thus, these materials have
excellent ecological parameters and do not contaminate soils. Lean materials can be
formed, made soft as silk or hard as glass.
Along with polyolefins, film materials from polyvinyl chloride (PVC) are used for
packaging food products.
They can be conditionally divided into two groups: the first group, rigid films based
on nonplasticized PVC and rigid shock-resistant films based on modified PVC; the second,
plasticized films with plasticizer content of over 30%.
Nonplasticized PVC films are rigid films possessing a high mechanical strength and
high chemical endurance; they are characterized by low vapour, water and aroma perme-
ability, resistance to fats, oils, acids, alkali and a number of solvents; are practically devoid
of smell and taste; are resistant to mold development, are physiologically harmless.
One of the valuable properties of rigid PVC films is their capability of molding, which
stipulates their widespread use as consumer containers (tubes, cups, bottles, etc.) for a broad
range of food products, including meat products and fats. A disadvantage of these films is
their low heat resistance, light resistance and poor heat sealability.
Plasticized PVC films are soft packaging films. Application of a plasticizer (diethyl
phthalate, dioctyl phthalate, dibutyl cebacinate, butyl stearate etc.) increases their low tem-
perature resistance, tearing strength, imparts them with elasticity, but decreases heat resis-
tance even more. The strength and chemical endurance of plasticized PVC films are lower
than those of nonplasticized films; and vapour, water and gas permeability are higher.
At an increased temperature and high humidity, the vapour permeability of plasticized
(soft) PVC films increases severalfold. Under these conditions, it is subject to microbial ac-
tion, which is due to the presence of plasticizers in the film. Plasticized PVC films have high
strength parameters but poor slide.
Soft PVC films have advantages over PE films with respect to resistance to puncture,
but are more permeable for water vapours and change their properties stronger under the
action of temperature.
Plasticized PVC films are used the most for packaging food products. They possess an
increased low temperature resistance (minus 3050C), preserve their elasticity at these
temperatures, are heat sealable on common packaging machines. A characteristic property
496 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

of such type of films is their capability of heat setting (about 60%). These valuable proper-
ties determine their wide use for packaging various food products (meat, fish, vegetable,
fruit etc.).
The most known trade marks of PVC films are as follows: in Italy, Cryovac-XL,
Cryovac-HS; in Germany, Resinit-PC, Vinol, Elaston, Miraplast; in the USA, Vitafilm; in
the UK, Vestolit, Suproterm etc.
Polyvinylidene chloride (PVDC) films are films from copolymers of vinyl chloride
and vinylidene chloride. They are manufactured as hoses and plane-oriented films
0.010.07 mm thick. The films are strong, elastic, transparent; have a low vapour, water,
gas and aroma permeability; are resistant to fats, oils, chemical reagents; are wear-resistant.
The thinnest PVDC film exceeds by its vapour impermeability the thickest films from other
polymers. Thus, the gas permeability of a PVDC film for oxygen and carbon dioxide is
500-fold, and for nitrogen 320-fold lower than that of a twice thicker film from other poly-
mers.
At a temperature below 0C, PVDC films lose their elasticity, become more rigid,
reaching a maximum rigidity at 18C. Therefore, they are not recommended to be used
for packaging long-storage products.
The most known and competitive brands of PVDC films are as follows: the USA and
Italy, Saran, Cryovac-S and S-204; Japan, Kurehalon CA, CB, SB, F; Russia, Poviden.
They are manufactured as strongly oriented films (up to 80%). In orientation, polymer crys-
tallizes, which significantly increases the strength characteristics of film material; besides,
the oriented film is more transparent than the non-oriented one.
Orientation imparts the film with a capability of heat setting, which depends on the fab-
rication conditions, extent of orientation, temperature and composition of polymer and
varies within the range of 3080%. Setting of the film begins at 5060C, and at heating
up to 95100C it reaches 6080%. At 8090C, the setting stress reaches a maximum
(12.715.6 MPa).
A characteristic property of these films is their ability to carry an electric charge, which
provides for electrostatic adhesion; owing to a combination of these two properties (heat
setting and electrostatic adhesion), a packaging from the film overwraps the product very
well, prevents the development of molds on it, improves the appearance of the packaged
product, etc.
PVDC films are heat sealed at a temperature of 155165C. The most efficient method
of heat sealing is by high frequency.
Russian chemical industry manufactures the Poviden film of grade U (thickness,
0.030.04 mm) and grade VU (thickness, 0.030.051 mm). Along with the main basic
properties characteristic of such type of films, these grades have their own features. Thus,
the extent of heat setting of the film of grade U is 1525%; and of grade VU, 3540%.
The Japanese company Kureha Chemical Industry Co. Ltd manufactures Krehalon
films of grades CA, CB, S8 and F; the Italian company Grace Italiana S.P.A., the film Cry-
ovac of grades S, S-204, O-300, etc.
The Krehalon film of grade CA is characterized by a low vapour and gas permeability;
a good stickiness of the film makes it suitable for manual packaging. The film of grade CB
has an even lower permeability for vapours and gases. Grade CB films are characterized by
a high transparency and increased tearing strength; grade F films have an increased setting
value in heating.
Owing to their physical and protective properties, PVDC films are widely used for
packaging food products. Their gas, water and vapour permeability enables their use for
CHAPTER 15 497

packaging products under vacuum or in a modified gas atmosphere (carbon dioxide, nitro-
gen or a mixture of gases). This kind of packaging increases the shelf life of products.
Another widespread method of packaging food products is called Cryovac (with
second skin appeal), based on the capability of the film for heat setting. It is applied, as a
rule, simultaneously with vacuumizing the product and makes possible long-term storage
of products, because the film adheres to the product as tightly as the skin leaving almost no
air in the packaging, and thus preventing the development of aerobic microorganisms. Low
temperature storage at minus 1820C of products packaged by the Cryovac method pro-
vides for the preservation of their high quality for 610 months.
Polyamides are obtained by condensation of dibasic acids with diamines and are
characterized by the number of carbon atoms in each of the monomers. Of commercial
significance for production of films are polyamides PA-12, PA-6 and PA-66. Besides
monofilms obtained by blow extrusion, a great number of laminates with them are manu-
factured (e.g., polyamidepolyethylene) and coextrusion films (e.g., PAadhesivePO,
POadhesivePAadhesivePO).
Polyamides are a rigid material with a high breaking strength and high abrasion hard-
ness. They withstand sterilization up to 140C by steam and up to 180C by dry air. PA
films possess a high vapour permeability and low gas permeability. Nonoriented and little-
oriented PA films in combination with heat sealable layers are widely used for thermo-
vacuum packaging by automatic machines. They are aroma-impermeable, require no addi-
tional treatment for overprinting. These films are resistant to organic solvents, oils, fats. The
transparency and gloss of PA films are not too high, but are improved by addition of mod-
ifiers and by biaxial orientation, which improves their mechanical properties, rigidity;
vapour and gas permeability.
Nonoriented PA films preserve their strength properties within the temperature range
from 20 up to +150C; and oriented films, from 60 up to +150200C. The films are
resistant to alkali, organic solvents and oils. However, they are little resistant to oxidants.
The vapour permeability of these films depends on temperature; e.g., at 205C, this param-
eter increases 2.5-fold as compared with usual temperature (2022C).
The currently used PA films for packaging food products in the West are Rilsan
(France) based on polyamide 11; Silon Nylon-film (USA); Supronyl, Suprotex (Germany),
etc.
PA films are used for packaging meat articles, semifinished products, ready-to-eat
meals under vacuum or in an inert gas medium. They are used when oil resistance is
required, as well as if products are subjected to low temperatures, because films remain
flexible even under these conditions.
Polyester films are mainly polyethylene terephthalate (PET) films.
The structure of PET imparts material with truly unique properties: a high transparen-
cy in amorphous state, low gas permeability, and, therefore, excellent barrier properties;
resistance to fats and mineral acids; high shock resistance (90 kJ/m2) within a wide temper-
ature range; low moisture absorption coefficient; easy coloration in the bulk; excellent
colour overprinting; good processibility by extrusion, injection casting, thermoforming.
This set of properties stipulates a wide use of PET in packaging industry.
These films are distinguished by an increased rupture and impact strength. Possessing
a high endurance to surface inflections, they withhold over 20,000 deformations before fail-
ure. The films have a high heat resistance; herewith, the strength properties are preserved
within the temperature range from 60 up to +150C. However, prolonged heating for
1.52 h at a temperature of 150C insignificantly decreases the mechanical characteristics.
498 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

PET films are grease-impenetrable, chemically inert, resistant to organic solvents and acids.
Fats were found not to penetrate a 0.025 mm thick film after two months of storage at a
temperature of 20C. PET films are moisture permeable; the gas permeability of these films
is low, they are considered to be gas-impermeable in practice.
PET films are used for packaging frozen meat, ready-to-eat meat meals, spices.
The known trade marks of PET films are Filmon-C5 (Italy), Melinex and Terilen
(UK), Mylar and Liminen (USA), Terphan-12F (France), Hostaphan and Nalophan (Ger-
many). The (oriented) PET film manufactured in Russian is lavsan.
The disadvantage of PA and PET films is their poor heat sealability.
In the recent years, polyamide and polyethylene terephthalate films have found wide
use in manufacturing of combined packaging materials (polyamidepolyethylene, poly-
ethylene terephthalatepolyethylene, polyethylene terephthalatefoilpolyethylene etc.).
Polystyrene (PS) is a transparent thermoplastic polymer, hard, rigid, brittle; has no
smell or taste; is physiologically inert. The strength characteristics of polystyrene deterio-
rate with temperature increasing. In practice, it can be used at a temperature no higher than
80C. At the same time, the strength and constant size of polystyrene films do not depend
on humidity of the environment, which is a positive property of this material.
In the recent 1015 years, new types of PS plastics were developed and are used for
packaging food products. They are produced by combining PS with synthetic rubbers. They
possess improved thermal and chemical properties and impact strength (hence the name
impact-resistant polystyrene).
Impact-resistant polystyrene is characterized by a high strength, resistance to alkali,
oils; is well processed into articles by various methods: injection casting, press molding,
extrusion. Russian industries manufacture impact-resistant polystyrene of several grades to
be used for packaging dairy products (cups, trays, etc.) and meat products (trays for pack-
aging meat and meat products).
In Western literature, there are many reports of the use of various containers from PS
and its copolymers for packaging dairy and meat products. At present, two-fold and
multi-fold impact-resistant PS films are successfully introduced into the market. By their
physicotechnical properties, two-fold PS films are in practice analogous to single-fold
films.
Trays for packaging meat and meat semifinished products are also produced from
polystyrene foam with the uniform fine-pore structure (styrofoam). The company Applied
Research (UK) manufactures the polystyrene foam film of 0.873.1 mm in thickness,
which is used not only for fabrication of polymer trays for meat packaging, but also con-
sumer containers for meat products, including after culinary treatment; it can be used to
warm up products in a microwave oven.
Polystyrene foam Styropor (Germany) is used for packaging frozen food products.

15.2 Combined film materials


Each of the above polymer materials possesses a set of valuable properties; however, none
of them is capable of satisfying absolutely all requirements imposed on film materials. If
we take only one industry manufacture of packaging materials for food products even
here the requirements to packaging films are diverse and often contradictory. Films should
satisfy the following requirements:
eye-catching appearance, gloss, transparency
protective barrier properties against the action of oxygen of the air, moisture, aromas,
CHAPTER 15 499

light (especially ultraviolet), fats, microorganisms


resistance to stretching, punctures, cuts, bends
sufficiently low friction coefficient to ensure the sliding of the film in the packaging
machine, but not too low so that packagings could be put one on another, stack up etc.
rigidity low enough for the packaging to be flexible, but sufficient to ensure the pas-
sage of the film through the packaging machine and provide for the attractive packaging
ability to endure high temperatures, boiling, warmup in a microwave oven and at
the same time to be formable at sufficiently low temperatures.
When choosing a packaging, one of the most important questions asked by food man-
ufacturers is shelf life. Most often food products manufacturing companies, considering
their production processes, decide in favour of this or that type of packaging, being guided
by the recommendations of packaging manufacturers. However, to make a correct choice,
it is necessary to know the features of various materials used for packaging.
For better preservation of products, usually polymer materials are used, which possess
the greatest barrier properties, i.e., are capable of preventing the penetration of gases (such
as oxygen, carbon dioxide) water vapour and off-flavours. The stable atmosphere inside the
packaging is capable of preventing the development of harmful microorganisms and of pre-
serving the product for further safe use. Especially in the case when a packaging from a
multi-fold barrier film, hermetically sealed under vacuum, is used. Besides, if this packag-
ing would subsequently be pasteurized or sterilized, the shelf life of the product would be
significantly increased.
Thus, the permeability of polymer materials for gases, first and foremost for oxygen,
and for water vapour is the main factor affecting the shelf life, and should be taken into ac-
count when choosing the material for packaging.
Taken separately, polymer materials do not possess universal properties to be able to
provide for the entire range of consumer properties. Thus, some of them have excellent bar-
rier properties for oxygen, but at the same time are well permeable for water vapour.
Besides, far from all of them can be used as material well sealable to the material of the
packaging support. Therefore, usually multilayer films are used as packaging material with
good barrier properties.
If we consider various types of widely used polymer materials from the point of view
of their ability to prevent penetration of gases and water vapour and arrange them in a de-
creasing sequence of the barrier properties with respect to oxygen, we will have the follow-
ing sequence:
EVOH (copolymer of ethylene and vinyl alcohol)
PVDC (polyvinyl dichloride)
PA (polyamide)
PET (polyethylene terephthalatelavsan)
The column of polymer materials with depleting barrier properties with respect to
water vapour is as follows:
HDPE (high-density polyethylene)
PP (polypropylene)
LDPE (low-density polyethylene).
Table 15.1 presents the values of permeability coefficients for oxygen and water
vapour for various polymer materials (according to the data by Exxon Mobil).
Of the factors affecting the barrier properties of polymer films, we would first note the
temperature of the environment as well as the thickness of polymer material. As is known,
ooo
500 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 15.1

Type of material Vapour permeability coefficient Oxygen permeability coefficient


(g/m2 for 24 h at 90% relative humidity (cm3/m2 for 24 h at 23C)
and temperature of 38C)

LDPE 1520 300013000


HDPE 312 5003000
Nonoriented PP 810 10006000
Oriented PP 5 2400
PVDC 15 13
EVOH 1550 0.22.5
Polystyrene 120 25007700
PA >150 30100
PET 1530 50150

a decrease of temperature of the environment and an increase of thickness of polymer ma-


terial increases the barrier properties of film material. It is seen in the table that material of
EVOH has the greatest barrier properties with respect to oxygen. However, its use is some-
what restricted due to its high cost. The undoubted leader in both parameters of the barrier
properties is PVDC; however, this material does not yield to reprocessing, is not in practice
utilizable and its incineration produces poisonous gases.
When choosing a polymer capable of preventing the penetration of water vapour into
the packaging, the most frequently used films are those, which include HDPE. The most
widespread type of barrier films intended for storage of meat and fish products are films,
which have LDPE and PA in their composition. This type of packaging is, in fact, the very
optimal variant from the point of view of cost versus effect.
With the view to ensure the high protective properties of the polymer packaging for
food products, combined films were developed. A combined film consists of the base film
and an applied film. The composition of the combined film can also have other additional
layers with special properties.
The base film is most often characterized by mechanical strength and is, to a greater
or lesser extent, gas-impermeable for oxygen or aromatic substances. The most frequently
used base films are cellophane, PET (biaxially oriented), PA, PP (biaxially oriented).
As packaging materials should be heat sealable, one of the layers of combined film ma-
terial should be a heat sealable film, as a rule, polyolefin.
The properties of individual layers of the combined film are manifested the most only
if they are strongly joined.
At present, the following multilayer polymer materials are mainly used for packaging
meat products:
PET (lavsan) / PE (polyethylene) for vacuum prepackaging of chilled and frozen
meat products with shelf life from 14 up to 30 days
OPA (oriented polyamide) / PE for vacuum prepackaging of chilled and frozen
meat products with shelf life from 30 up to 180 days and more
PA (nonoriented polyamide) / PE for vacuum prepackaging of meat products fol-
lowed by heat setting.
Packaging materials can also contain a larger number of layers. Thus, for instance,
portioned sausage articles, ham and other specialty products are, as a rule, with the aim to
CHAPTER 15 501

increase their shelf life, also packaged under vacuum into multilayer films with high barrier
properties, e.g., PE/PA/PE or PE/PET/PE. For products with an increased fat content
(bacon, lard), it is recommended to use films from grease-resistant polymers, such as, e.g.,
saran (PVDC), polyamide. The films based on nonoriented PA and PE are often used for
slicings.
The assortment of packaging combined films is broad. They are conditionally divided
into three groups: flexible films (including those for packaging products under vacuum or
in a modified gas atmosphere); thermoformable films for packaging products under vacuum
or in a modified gas medium; films sterilized or subjected to boiling, including aluminium
foil-based multilayer films.
At present, thermoformable materials are paid special attention in the packaging tech-
nique. This is due to the fact that they enable packaging a product into a formable package,
thus providing for the reliable air tightness of the seal, unlike the packaging into a flat bag,
e.g., from C/PE, when creases or folds are possible. Formable polymer materials (PA/PE,
PET/PE, PP/PE) are used in meat industry for packaging meat, meat semifinished products,
sausage articles, frozen meals, etc.
In the recent years, a broad assortment of multilayer combined materials are produced
in Germany, Finland, Italy, the USA and Japan; these materials are distinguished by a high
puncture and impact strength, etc.
Thus, the Finnish company Wihuri OY Wipak developed a special type of multilayer
film based on PA and PE; the film is suitable for reprocessing on thermoformation ma-
chines. It is flexible and elastic, possesses a high strength, is readily formed on traditional
thermoformation equipment. The multilayer film is gas-, vapour- and aroma-impermeable;
it has a considerable deep drawing value, is recommended for a broad assortment of food
products, including meat (cuts, large slabs, semifinished products, ham and other items).
The Holland company Krehalon Synclair Packaging manufactures a wide assortment
of high-barrier thermoformed films consisting of 5, 7 and 14 layers. PA, PE and EVOH in
various combinations, joined by an adhesive, are used as the main layers. Thus, for instance,
14-layer films of the following composition: PE/Tie Layer/PA/EVOH/PA/Tie Layer/
/PE/PE/Tie Layer/PA/EVOH/PA/ Tie Layer/PE possess very high barrier properties with
respect to gases, are resistant to punctures, have an increased protection from ultraviolet ra-
diation, which makes them indispensible for packaging diverse meat products, intended for
long-term storage, including large bone-in meat cuts.
A special group of multilayer combined films are Cryovac thermoshrink films based
on PVDC and polyolefins. These films are manufactured in Italy and the USA and are in-
tended for packaging products under vacuum by the Cryovac method. The films are char-
acterized by a high strength and elasticity; vapour, gas and aroma impermeability; grease
resistance. Their distinctive feature is the capability of heat setting and easy heat sealability.
These are a kind of combined materials based on saran in combination with low- and me-
dium-pressure PE. They were developed by Grace Italiana S.P.A. (Italy) and at present are
the most widespread item for packaging dairy and meat products.
In the USA, Standard Packaging Corporation developed a new type of polymer pack-
agings for portioned meat for trading networks. The packaging is a rigid formed bag (e.g.,
from PVC or PS) sealed with the double lid. The outer part of the lid is impermeable and
the inner part is well permeable for oxygen. According to the data by the company, this
packaging enables storage of meat at a temperature of 01C for three weeks. During the
sales, before meat is put into cooled counters, the outer lid is removed and the natural colour
of meat is restored in 510 min.
502 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 15.2 presents some variants of multilayer films and their application areas.
Table 15.2 Films for vacuum thermoforming packaging machines.

Lower film, Upper film, Properties Application Note


m m of packaging

PA/PE 100250 OPA/PE 75100 Average barrier Vacuum Vacuum


properties; packaging of forming of the
mechanical fresh meat, support; if high
strength, lower slices, setting is used,
support layer sets cheeses, etc. mechanical
extrusion is
added; forms
p a c k a g i n g

are cut by
blades
Cellulose For sterilization Packaging of
medical
preparations
PA/EVOH/PE OPA/EVON/PE High barrier Vacuum
100250 75100 properties; packaging of
mechanical foods
F l e x i b l e

strength; more
expensive than
PA/PE
PET saran/PE
75100
PA/PP 100250 OPA/PP 75100 Average barrier Vacuum
properties; gloss; packaging of
sterilization medical
allowed preparations
and foods for
subsequent
sterilization
PVC/PE 300600 PET saran/PE or Average Packaging of Preheating of
OPA/PE 75 hermeticity; high any foods on film required;
strength; high rigid support forms are cut by
capability of press tools
p a c k a g i n g

thermoforming
PVC/C/PE 300600 PET saran/PE 75 The same but high The same but
hermeticity in a modified
atmosphere
PS 4001000 Lacquered foil No hermeticity; Yoghurts; Two stages of
good water desserts film preheating
permeability recommended;
forms are cut by
R i g i d

press tools
PS/PET 4001000 Lacquered foil The same but fat Margarine,
resistance butter, creams
PS/PE 4001000 PET/PE 75 Hermeticity, water Smoked and
permeability, frozen
aroma/fat foodstuffs
resistance
Foil/PE
CHAPTER 15 503

Table 15.2 Films for vacuum thermoforming packaging machines.


(continued)
Lower film, Upper film, Properties Application Note
m m of packaging

PS/EVOH/PE PET saran/PE 75 Low gas Packaging in


4001000 permeability; modified
barrier; aroma atmosphere;
resistance; replaces
hermeticity PVC/C/PE
and PVC/PE
PS Low gas Packaging of Special
modified/EVOH/PE permeability; can pasteurized requirements to
4001000 be heated up to foodstuffs in film preheating
8590C modified stage
atmosphere
PP/EVOH/PP The same but up to Packaging in
4001000 120C modified
atmosphere;
warming up in
microwave
oven; can be
sterilized
PS exp./ EVOH/PE Low permeability, Packaging of
4001000 hermeticity foodstuffs for
long-term
storage in
modified
atmosphere
PP exp./ EVOH/PE The same but with High warmup
warming up in temperatures
microwave oven
PET/EVOH/PE Gloss, Packaging in Special
300600 transparency, low modified equipment for
permeability, atmosphere for form-cutting
hermeticity station
PVC 200400 Lacquered PVC, Very good Non-food use Positive
cellophane or thermoformability of the type of forming, heat
paperboard blister sealing
packaging
PVC 100 The same plus gloss Special
high-frequency
sealing-off
equipment
PETP 200400 PETP 100 The same but
welding is stronger

This is just an insignificant part of multilayer materials in the arsenal of packaging


manufacturers.

15.3 Modern trends in the development of chilled meat packaging technology


Packaging of fresh meat is a special topic. When packaging fresh meat, it is necessary to be
aware that in the living organism it is sterile, because blood leucocytes leave no chances to
504 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

foreign bacteria to survive. However, after the product was separated, bacteria getting on
the surface of meat from the air or from items with which it is in contact, immediately begin
propagating in geometrical progression. Therefore, when packaging meat, the crucial issue
is the time that passed from the moment of separation and the conditions of product storage.
Investigators pay great attention to the development of the most rational and efficient
technology of packaging chilled meat, because its production in dressed and packaged
shape is one of the ways to increase endurance and to reduce shrinkage in storage.
It is known that the quality of chilled meat changes in the process of storage. The taste
and flavour, tenderness, digestibility and assimilability improve, but the colour of the mus-
cle and fatty tissue deteriorates; there occur shrinkage, oxidation of fat, etc. Packaging into
film materials along with cooling, the main preservation method enables preserving the
quality of chilled meat to a greater extent and increasing its shelf life. However, this term
largely depends on the technology of the refrigeration treatment of meat, gas permeability
of packaging material, method and parameters of packaging and storage conditions.
The main requirements imposed on polymer materials used for packaging chilled meat
are as follows: physiological harmlessness, chemical inertness, high mechanical strength
(especially for punctures and notches), elasticity; vapour, water and grease impermeability;
transparency, impermeability for microorganisms.
Polymer materials used for short-time storage of meat up to one kilogram in weight
and natural semifinished products mainly have a high oxygen permeability and low vapour
permeability. This provides for the preservation of bright red colour and insignificant losses
due to evaporation of chilled meat. Such materials include lacquered viscose films (cello-
phane), polyethylene, plasticized polyvinyl chloride, plyofilm, etc.
Changes of heme pigments can depend to a significant extent on conditions of meat
storage, in particular, on the gas permeability of packaging material. Oxygen-permeable
films contribute to the preservation of the colour of muscle tissue for 23 days at a temper-
ature of 04C. The quality of chilled meat (bone-in and boneless beef and pork cuts), pack-
aged into oxygen-permeable films, remains sufficiently high for 34 days of storage at a
temperature of 02C.
In further storage, the absorption spectrum characteristic of meat pigments changes,
because oxymyoglobin is reduced to myoglobin and is subsequently oxidized to metmyo-
globin. By the same time of storage (35 days), microorganisms on the surface of meat ac-
tively develop.
Packaging of chilled meat into film materials with a low gas permeability makes it pos-
sible to decrease the oxidative changes of pigments and lipids, shrinkage of meat and in-
hibits microbial growth to some extent. Herewith, of special interest is the process of
packaging chilled meat under vacuum and in a modified atmosphere (MAP).
Studies carried out in this direction showed that the duration of storage of chilled beef
and pork cuts, packaged under vacuum into a polyethylenecellophane film or saran, at a
temperature of 04C is 23 weeks. Herewith, the quality of beef cuts stored in packages
at a degree of vacuumizing of 98% was noticeably higher than at 8085%.
Studies of the effect of the extent of vacuumizing and storage temperature on changes
of heme pigments of meat showed that the higher the extent of vacuumizing and the lower
the storage temperature are, the smaller the rate of the oxidative changes of muscle tissue
pigments is. The coloration of packaged meat is preserved for 2835 days at the vacuumiz-
ing of 9598% and storage temperature of 13C. The predominant colour in the colora-
tion of chilled meat packaged under vacuum at an oxygen partial pressure in the package
0.81.0 mm Hg (1.01.33 kPa) is purple-red colour of reduced myoglobin.
CHAPTER 15 505

A MAP system consists in the replacement of the air in the packaging with a mixture
of gases of an appropriately chosen composition, depending on the type of packaged
product. The appropriate composition of gases chosen for the packaged product inhibits the
degradation processes occurring in the product. Owing to this, it is possible to preserve the
natural properties of the product, which are associated or identified with its freshness.
The composition of gases introduced into the packaging are subject to some changes
during the storage of the product, owing to either the permeability through the material of
the packaging or as the result of processes occurring in the product, such as, e.g., dissolution
of this gas in fresh meat. An obligatory condition of using the MAP system is the use of
packaging materials with the high barrier properties with respect to gases.
The use of MAP contributes to:
an increased safety of products for health, owing to the limited development of
microorganisms
preservation of the nutritive properties by preventing oxidation of fats, biologically
active compounds, vitamins
inhibition of undesirable physicochemical processes
significant extension of the stability period of the product.
The current significance of MAP is indicated by the number of packagings in which
it is used. For instance, in 1997 the British market for it was estimated to be 2.7 billion, and
a growth up to 3.7 billion is envisaged in the next 10 years.
The main gases used in MAP are carbon dioxide, oxygen and nitrogen. Carbon dioxide
(usually used at a concentration higher than 20%, and only in a few cases lower than this)
is distinguished by strong inhibitory properties, which inhibit the development of bacteria
and molds. The mechanism of the inhibitory action has not yet been completely studied;
however, the impact on some anaerobic microorganisms shows that some other factors ap-
pear here besides the factor of oxygen removal. The presence of CO2, especially in food
products containing a large amount of moisture, decreases pH of the product as the result
of the formation of acetic acid. Solubility of CO2 decreases the molecular pressure of this
gas in the mixture, leading in extreme cases to a shrinkage of the packaging on the prod-
uct, which is an effect similar to vacuum packaging. This effect can be balanced by intro-
ducing another gas, usually nitrogen, into the packaging. Nitrogen, having no inhibitory
effect on microbial development, has no direct impact on the stability of the packaged prod-
uct. However, the use of this gas for bathing the products in the packaging prior to filling
it with the gas mixture provides for the maximally possible elimination of the remaining
oxygen, thus countering the development of anaerobic bacteria and also preventing oxida-
tion of fats. At a higher content of N2 in the packaging (Table 15.3), it is easier to maintain
a constant concentration of the gas mixture owing to the fact that the molecular pressure of
N2 is closer to the equilibrium condition. In the cases when it is possible to use a higher
content of N2, one should bear in mind the economic factor due to the lower cost of N2 as
compared with other gases used.
When packaging many products, it is possible to avoid the presence of oxygen respon-
sible for oxidation and rancidity of fats and spoilage of products as the result of anaerobic
bacterial growth. However, there are cases when it is recommended that the content of
oxygen involved, e.g., in the enzymatic oxidation of fresh meat is respectively greater. Pres-
ervation of the bright-red colour of beef, which is associated with its freshness, requires the
content of oxygen in the packaging to be even up to 80%. The oxygen entering the reaction
is consumed, its amount in the packaging decreases, but the content of CO2 dissolved in the
506 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

product increases. In MAP, it is required especially thoroughly to set the content of oxygen
in the packaging.
Introduction of carbon dioxide into the gas mixture is estimated to be positive. Forma-
tion of carboxymyoglobin provides for the stability of meat coloration. The presence of car-
bon dioxide not only has an inhibitory action on microorganisms but is also cytocidal. This
effect is achieved at 210% of CO2. It is also promising to use ethylene oxide in MAP, as
it provides for a bactericidal action.
Application of ozone. The antimicrobial action of ozone is associated with the distur-
bance of the physiological function of cytoplasmic membranes as the result of involving
the lipid fraction in the ozonolysis, as well as with the oxidation of thiol groups of enzymes.
To increase the storage life of chilled beef, it is suggested to perform ozonolysis by main-
taining the concentration of ozone for 4 h at a level of 1020 mg/m3 daily for the first four
days, and then on the level of 46 mg/m3 by 3 h with an interval of two days. Taking into
account the specific features of the reactions occurring in ozonolysis, the issue of using
ozone for increasing the storage times of chilled meat can be solved positively on condition
of a direct proof of preserving the biological value of the product and the absence of the
development of toxic substances in it.
At present, there is a sufficiently large experience of choosing the composition of gas
mixtures depending on the type of product. As it follows from information by various sourc-
es, this composition can, however, vary for the same products (Table 15.3). The data pre-
sented in the table can be considered as general recommendations, which are to be
confirmed in concrete applications.

Table 15.3 Composition of the gas mixture in packaging of various groups of foodstuffs in a
modified atmosphere.

Foodstuff Gas mixture composition, %

O2 CO2 N2

Meat and meat products


Raw meat 6085 4015
Fresh beef or pork 70 20 10
Fresh meat and sausage from raw meat 80 20
Beef, pork, veal steaks 70 30
Fresh minced meat (not frozen) 70 30
80 20
Raw chicken gobbets 20 30 50
Boiled ham 40 60
Smoked sausage and ham 30 70
Roast sausage 25 70
Lunchmeat 100
Pelmeni with minced meat filling 30 70
Boiled meat 2530 7570
Poultry 75 25
50 25 25

Packaging of chilled meat in a medium of carbon dioxide or nitrogen significantly


extends its shelf life at a temperature of 04C. Packaging of portioned meat in a gas
CHAPTER 15 507

medium with an increased content of oxygen (7080%) and a relatively high concentration
of carbon dioxide (2030%) increases the shelf life at a temperature of 2C up to eight days.
Of special interest is the technology of packaging boneless cuts of 23.5 kg in gas me-
dia. Exudation of meat fluid from boneless beef cuts stored for 1520 days in packagings
with carbon dioxide or nitrogen is 12.2%, which is 1.5 times lower than from cuts pack-
aged under vacuum.
Packaging of meat into gas-impermeable materials under vacuum and in a modified
atmosphere can contribute to a great extent to the preservation of the colour of chilled meat
and a decrease of oxidative changes of lipids, makes it possible to slow down microbial
spoilage of meat and increase its shelf life. Herewith, the parameters of packaging, as well
as the qualitative characteristics of packaged meat have a significant effect on the duration
of its storage.
For packaging meat, of interest is the use of heat-sealed combined materials
(polyesterpolyethylene, polyamidepolyethylene, polyamidesaranpolyethylene, mul-
tilayered polyester). These materials are the most cost-efficient and can be used on mech-
anized processing lines, where the processes of fabricating containers, packaging of the
product, weighing and labelling of packagings makes one whole. The productive capacity
of such mechanized lines is 1525 and more packagings per minute.
The most classical materials used as packagings for vacuumizing were considered for
many years to be:
cellophanepolyethylene laminate
PTE/PE laminate
films from VDC copolymers
PET and PA films as hoses, the air from which is removed by heat setting of the pack-
aged article
PA/PE laminate.
The appearance of PA/PE laminates suitable for deep-draw forming initiated the in-
troduction of a process, in which vacuum packaging and later MAP packaging was united
with preliminary thermal forming of a complex-shape article, whose size, the depth includ-
ing, corresponded to the size of the packaged product. At present, the assortment of pack-
aging materials, which can be used for vacuum packaging and are mainly intended for
MAP, is much broader. There is no drastic difference between materials used in both sys-
tems, though MAP packaging requires higher barrier properties.
In both cases, there is a possibility of using ready-made packages from laminates,
though much frequently used systems are those of thermoforming, filling with or introduc-
tion of a mixture of gases, as well as heat sealing. Part of thermoformed packagings can be
made from flexible or rigid material. Rigidity in this case, as increased strength, is the result
of not only using thicker materials, but also due to using higher elasticity-modulus poly-
mers, such as PS, PP, PEHD, PVC. Packaging in a mixture of gases also makes use of the
horizontal system of forming, filling and heat sealing. Table 15.4 compares multilayer ma-
terials used in MAP as well as in vacuum packaging. The table covers both rigid materials
and flexible materials intended for the thermoformed layer, as well as flexible materials in-
tended for heat sealing of thermoformed packagings and for package production.
Thus, the currently available methods of packaging chilled meat can be conditionally
divided into three types: packaging into gas-permeable films for short-term storage of meat;
packaging into gas-impermeable films under vacuum; packaging in a modified gas atmo-
sphere; which provide for an increase of the shelf life of meat products.
508 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 15.4 Laminates used as thermoformed packaging layers in the MAP system.

Rigid and semirigid laminates Flexible laminates Comments

PVC/PELD PA/PELD
PS/E\VAL/PTLD PA/PP
PP/E\VAL/PP OPA/PELD Very small trays
PS/PVDC/PELD OPAmet/PELD
PS/E\VAL/PS/PELD PET/PELD Very small trays
PETmet/PELD Very small trays
PET/A1/PELD Very small trays
PA/E\VAL/PELD
PA/E\VAL/surlyn
PET/PVDC/PELD Very small trays
PET/AI/PP Very small trays

15.4 Methods and equipment for packaging of meat and meat products
One of the methods of packaging portioned meat and meat semifinished products is their
wrapping on the tray with a transparent polymer material.
The most widespread material for this packaging is the PE thermoshrink film of
0.0250.035 mm in thickness and lacquered cellophane (4045 g/m). Support trays can be
fabricated from paperboard or polymer materials. Of greatest interest are trays from
impact-resistant polystyrene 0.0400.055 mm thick. They are fabricated on thermoforming
equipment by the method of deep draw formation.
The method of packaging meat on support trays is at present widely used in the USA,
Italy, France, Germany and other countries. High-production packaging equipment has
been developed for this purpose.
Packaging machines Automac 22 and Automac 44 developed in Germany pro-
duce, respectively, 28 and 50 packagings per minute, to provide packaging of meat and
meat products into support trays with wrapping them with a thermoshrink PE film.
Delford Div. (UK) together with its German branch Sanpack GmbH developed the
horizontal packaging machine Delford SF-600, which wraps polymer trays with the prod-
uct (fresh-killed and chilled meat, meat semifinished products) into PE or plasticized PVC
films. The performance of the machine is 65100 packagings per minute.
Hayssen Europa Ltd (UK) manufactures automatic machines of T7 series for packag-
ing chilled meat into PE and PVC thermoshrink films. The high performance of the machine
is combined with the possibility of using packagings of different sizes, quick adjustment
and tuning. The product intended for packaging is supplied directly into the drum with the
film, is wrapped into the film (with its margins overlapped), after which the longitudinal
and transverse heat sealing of the seam is performed. The packaged product is weighed. The
productivity of the machine, models PT-414 and PT-110, is respectively 80 and 120 pack-
agings per minute.
Taking into account that the shelf life of meat and meat products packaged into oxy-
gen-permeable film materials is rather limited and makes 4872 h at a temperature of 24C,
research is under way in this country and abroad to increase the shelf life of meat in such
materials.
In Germany, a method was developed to enable increasing twofold the storage time of
CHAPTER 15 509

meat in oxygen-permeable films. The new method is known under the name of a conserv-
ing packaging, i.e., the packaging providing the preservation of freshness of the product.
The conserving packaging is a package from an oxygen-permeable film with an inserted
SMS filter (limestone subjected to calcination at a temperature of 1500C) with a high mois-
ture-absorbing capacity. The SMS filter, absorbing moisture (meat fluid) deprives micro-
organisms of the nutrient medium, which in turn contributes to the decrease of the rate of
microbial growth in the package. Using this method of packaging, the amount of microor-
ganisms per 1 g of product after 46 days of storage at a temperature of 24C is 20,000
microbial cells, which corresponds to the sanitary requirements and food regulations. The
new method was recognized as an invention and was protected by a patent.
The use of modern instrumental equipment enabled Russian and Western researchers
to prove that in packaging meat under vacuum its purple-red colour is due to the presence
of myoglobin on the surface. The content of this pigment at a partial oxygen pressure of
about 1.9 GPa is 7080%; under these conditions, formation of metmyoglobin on the sur-
face of meat practically does not occur, as the concentration of oxygen is very low.
When meat is removed from the packaging and kept for 2025 min in the air, its colour
changes to bright red as the result of interaction with oxygen of the air and formation of
oxymyoglobin. As the concentration of oxygen in the packaging goes up, the possibility of
restoring the original (natural) coloration decreases.
The technology of vacuum packaging of meat products into combined film materials
(polyethylenecellophane, polyethylenepolyamide, polyethylene terephthlatepolyethy-
lene) is assimilated by meat-processing enterprises in 1970s. Portioned meat (0.51.0 kg)
was first packaged on semiautomatic vacuum packaging machines operated according to
the chamber principle, of the type of Negro, Darvac (Italy); Eurovac TV, Multivac B-6
(Switzerland); Supervac (Germany). The mass of the product to be packaged was limited
by the size of the vacuum chamber, whose height (depth) was 100150 mm.
In subsequent years, vacuum packaging equipment was modernized and the above ma-
chines were replaced by two-chamber vacuum packaging machines of the type of Autovac
variant (Kramer+Grebe, Germany); Supervac GK and Multivac (Austria), etc., and then the
vacuum packaging machines Autovac X4 and Compack (Kramer+Grebe), Multivac B-7
(Multivac R) and others equipped with conveyors for the automatic supply of packagings
with the product to the vacuum chamber and the removal of ready packagings. Taking into
account that the depth of the vacuum chamber of such machines is about 150280 mm, they
can pack products of 3.55.0 kg in weight.
A number of enterprises in Germany, Great Britain, the USA tested and use the method
of vacuum packaging into thermocaked packages from the combined polyamidesurlyn
film.
Surlyn is a heat sealed ionomeric film developed by Du Pont. At present, it is widely
used in manufacturing combined materials. By its protective properties, surlyn consider-
ably exceeds films from polyethylene compositions.
A characteristic property of packaging into polyamidesurlyn packagings is that after
vacuumizing the package with the product comes into the thermotunnel, where the seam of
the package is caked but not heat sealed as in PVDC films. This additional treatment of
packagings makes it possible to guarantee their air tightness in long-term storage of prod-
ucts.
According to the specialists of the Federal Scientific and Research Center for Nutrition
and Food (Kulmbach, Germany), packaging into a caked package makes it possible
to preserve the high quality of the product. For instance, meat for steaks is stored at a
510 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

temperature of 02C for three weeks, and at a temperature from 1C up to +1C for four
weeks. According to the available data, about 10% of steak meat supplied to the Western
European market and about 25% to the US market is packaged at present into packages from
the polyamidesurlyn film.
One of the later methods of packaging meat products under vacuum into combined ma-
terials is packaging into the thermoformed film of the type of polyamidepolyethylene.
This method of packaging is widespread in the meat industry of the USA, Germany, Italy,
France, Finland, Sweden and other countries, which is due first and foremost to the fact that
it is performed on high-performance equipment, into a formed package fabricated directly
in the packaging machine. This equipment enables combining the entire complex of pack-
aging operations: fabrication of the package, filling it with the product, vacuumizing,
weighing, labelling.
The principle of operation of the vacuum thermoforming line is as follows:
the rolls of packaging material, usually two multilayer films upper and lower are
loaded; the films can be of different thickness and different composition
the lower film is heated and stretched by compressed air (or simultaneously using
additional mechanical pressure, if the film is sufficiently rigid) to take the given shape of
the support
the supports pulled out of the film are moved to the loading section, where the product
is placed
then the supports are sealed by the upper film; vacuum or an inert gas medium is cre-
ated if it is necessary
packaged products are separated one from another and come to the outlet conveyor;
wastes of film are collected.
This is a continuous process.
Packaging of products in thermoforming lines gives the following advantages:
low prime cost of packaging materials (sometimes two times as low) due to the use
of film rolls, which in the previous case are only a semifinished product for package prep-
aration
the possibility of labelling on the upper film to save on self-adhesive labels
the appearance of the package is by an order of magnitude higher, because the prod-
uct is placed into the prepared container and sealed uniformly on all sides
this is a continuous process, where the rate of work is set by the machine but not by
man
the automatic machines are equipped with replaceable formation units for fabricating
packages of different sizes.
The widespread use of the method of packaging into a combined thermoformed film
was contributed to by the reliable air tightness of the heat seal in contrast with packaging
into flat packages from combined materials, where folds and wrinkles are possible in the
heat sealing region and, therefore, air tightness of the package can be disturbed.
The main group of thermoformed combined materials (0.0110.013 mm) have the for-
mation depth of up to 60 mm. The most widespread thermoforming machines manufactured
abroad are Multivac, models R67, F70, R70, M72; Tiromat VT (Germany) and others.
As we reported above, a new group of multilayer combined materials manufactured in
the USA, Finland, Japan and other countries appeared on the world market in the 1980s.
These materials are characterized by the low gas permeability with respect to oxygen and
have the formation depth of up to 180 mm. The use of these materials on thermoforming
CHAPTER 15 511

machines makes possible the packaging of cuts (or group packaging of boneless meat), as
well as large slabs of semifinished products of 2.58 kg in weight.
The most known brands of packaging equipment for deep draw formation of packag-
ing (up to 380 mm) are Multivac, models R 5100, M 8551, R 7000; Hammer, models
VT-50, VT-55, VT-100 (Austria); Tiromat VA, models 430T, 560T and Tiromat, models
CS 430, CS 430SLT (Germany) and many others.
In the recent years, the technological properties of multilayer materials were improved
by introducing an additional layer an ionomer surlyn. Besides the properties characteristic
of traditional thermoformed materials based on polyamide, multilayer materials with surlyn
possess not only an increased strength, which is required for deep draw formation (up to
380 mm) of packagings, but are also capable of heat setting (1030%) at a temperature of
8095C and, which is no less important, are heat sealable within a broad temperature
range.
It should be noted that such type of multilayer film is sealed even with the sealing seam
contaminated (by meat, fat, salt), which provides for an increased performance of packag-
ing machines.
In new packaging automatic machines (e.g., Tiromat VA, Germany) operated by the
principle of deep draw and making use of multilayer films with ionomer surlyn, heat setting
is performed without using the setting tunnel, but using a special device, which works as
follows: after vacuumizing and heat sealing, ready-to-use packages are irrigated with water,
whose temperature is 8595C (depending on the thickness of the film). Irrigation with wa-
ter is done by a turbulently sprayed flow, as the result of which the film is rapidly and evenly
heated. Heat setting occurs without forming folds, the films closely adheres to the product,
taking its shape; therefore, the shelf life of the product increases and its vendibility im-
proves. Despite the relatively high temperature of water, the product is not warmed up, as
the time of contact of water with the film is 25 seconds, and the film itself possesses good
isolation properties.
In the West, the main machines used for packaging meat products in a gas medium are
Multivac, models R 7000, R 5100; Tiromat VT, Swissvac and others.
In Denmark, the method Atmas-pak was introduced for packaging portioned meat; the
method provides for the use of a gas mixture consisting of 7580% O2 and 2025% CO2.
When introducing the method, the multilayer films used were improved by applying
an outer coating, which adsorbs the condensate formed in storage of meat to improve the
vendibility of the product.
Thus, based on available information on the equipment and technology for packaging
meat and meat products, it can be concluded that packaging under vacuum and in a gas me-
dium provides for the preservation of a high quality of meat in long-time storage. Herewith,
the parameters of the packaging process, as well as the qualitative characteristics of meat,
have an effect on its shelf life.
In most meat-processing enterprises, packaging of products in a modified atmosphere
is performed at the same thermoforming machines as packaging under vacuum, as almost
all of their types and models are equipped with gas-filling devices. No adjustment of equip-
ment is required. The packaging process is regulated, which provides for the complete con-
trol of the level (pressure) of gas in the package.
Current developments in the field of packaging technology for meat products and
equipment used for this are aimed at the broader use of polymer film materials with high
barrier properties, assimilation and series production of the most advanced packaging ma-
terials, as well as development of new efficient equipment and polymer materials with a
512 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

given set of physicotechnical characteristics.


Analysis of Russian and Western data made it possible to reveal the main directions
of studies in the field of chilled meat packaging technology. All of them have certain ad-
vantages; however, it should be admitted that of special interest is meat packaging into
gas-impermeable film materials under conditions of a minimal oxygen content under vac-
uum and in a modified atmosphere, in particular, carbon dioxide or nitrogen, proceeding
from the possibility of preserving high consumer qualities of meat (colour, taste, consis-
tence, etc.) and an increase of its shelf life.

15.5 Active packaging technology


Systems associated with the use of active packaging are a new field of development of pack-
aging equipment. They are a refutal of the existing tendencies to exclude all interactions
between the packaging and its contents. The purpose of active packaging is a directed im-
pact on the product to provide for its higher quality, as well as to extend the period of sta-
bility and usability for consumption.
The technologies related to active packaging broadened the functions of packagings
from a passive barrier with respect to external effects to the active protection of the product.
Only part of the emerging solutions, in view of the applied chemical means, was recognized
to be suitable for contact with food products; however, already at present it is envisaged
that technologies in this field will have a significant effect on the further development of
food industry.
The packaging technologies using active packaging can embrace:
introduction of chemical or enzymatic substances into the package or into packaging
materials to adsorb and eliminate atmospheric oxygen inside the packaging
introduction of substances, which create or adsorb carbon dioxide
monitoring the content of ethylene in the package, by means of adsorption to oxidiz-
ing substances or organometal compounds, application of ethanol as a vapour inside the
package as a factor inhibiting the development of microflora
use of preservatives, bactericidal substances and antioxidants to be oozing from the
packaging material
application of moisture regulators
application of a technology enabling the control of taste and smell
use of light adsorbants
application of films releasing a mineral substance to preserve the colour of the prod-
uct
refinement of the surface of the film to change its permeability
use of susceptors, i.e., films controlling the warming-up of the product in a micro-
wave oven.
It is impossible to describe all the listed technologies; therefore, taking their impor-
tance into consideration, below we shall characterize systems of active packaging associat-
ed with the elimination of remaining oxygen from the packaging.
Complete elimination of oxygen, even in the case of vacuum packaging, as well as
flushing with inert gas, is impossible in practice. In many cases, even a minor amount of
oxygen remaining in the packaging renders a harmful effect on the quality of the product.
Prior to injection of a chemical substance reacting with oxygen, its content in the pack-
aging should be decreased to a minimum. This is done, e.g., using iron compounds, such as
CHAPTER 15 513

iron oxide and iron carbonate together with catalytic systems, which initiate the reaction.
Nonmetal and organometal substances are also used. Depending on the type of substance
and method of introducing it into the packaging, a decrease of the oxygen content in the
package could be even up to several tens of ppb.
There are also many commercially available preparations intended for these applica-
tions. An example could be Mitsubishis Agelles and Freshinax. Agelles used in the form
of a sachet is introduced into packages with a higher barrier properties and makes it possible
already in several hours to decrease the content of oxygen to a level of less than 0.1%, pre-
serving this content for several months. Freshinax can be, e.g., in the coating layer, in the
inner wall of the packaging or in a piece of paperboard saturated with this substance and
introduced into the packaging. Its application makes it possible to decrease the content of
oxygen in the packaging to a level of 0.01%.
An interesting solution is the preparation Freshhiiztr C of the Japanese company Top-
pan Printing. Eliminating oxygen, it simultaneously creates carbon dioxide, which prevents
the collapse of the wall of the flexible packaging owing to the vacuum emerging as the result
of a decrease of oxygen concentration.
The packaging with an antimicrobial coating is a promising form of active packaging
for food products, in particular, meat products. As microbial contamination emerges pre-
dominantly on the surface as the result of transportation after technological treatment, it has
been attempted to increase the safety and delayed spoilage development by using antimi-
crobial sprays or impregnation solutions. The direct application of antimicrobial substances
on the surface of food products yielded a limited advantage, as during the contact the active
substances were neutralized or quickly absorbed from the surface deeper into the product.
On the other hand, addition of bactericidal or bacteriostatic substances to the formulation
of a product can lead to a partial inactivation of active substances by components of the
product and, therefore, expectedly, only a limited effect on the surface microflora will be
obtained.
Therefore, the use of packaging films with antimicrobial substances can be more ef-
fective owing to the slow transfer of the substances from the packaging material onto the
surface of the product; thus, it helps to preserve a high concentration on required sites. If
the antimicrobial substance can be released from the packaging at the time of a more pro-
longed shelf life, the activity can also propagate to the stage of transportation and storage
during the delivery of the food products.
Antimicrobial substances introduced into packaging materials are capable of control-
ling microbial contamination, decreasing the growth coefficient and the maximal growth of
the population and/or increasing the lag phase of the sought-for microorganism, or else in-
activating microorganisms during the contact.
Introduction of an antimicrobial substance into the packaging system for food products
is carried out by a number of methods. One of them is application of the active substance
by placing it into the extruder during the fabrication of the film or the film subjected to co-
extrusion. A disadvantage of this method is its economic inefficiency, because the antimi-
crobial substance not deposited onto the surface of the film does not completely exhibit its
antimicrobial properties. An alternative is introduction of an antimicrobial additive into the
controlled material; e.g., it can be introduced into the layer contacting with the foodstuff
(usually serving as the inner heat sealing layer) of the multilayer packaging material.
According to Han, when developing or modelling a film or packaging with antimicro-
bial properties, the following factors should be taken into account.
The chemical nature of films/coatings, conditions of the casting process and residual
514 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

antimicrobial activity.
The choice of an antimicrobial substance is often limited by the instability of the com-
ponent to the action of heat or by the incompatibility of the substance with packaging ma-
terial. For instance, 1% potassium sorbate in an LDPE film inhibited the growth of yeasts
on agar plates. The LDPE resin and potassium sorbate can be mixed, subjected to extrusion
and used to press granules for production of the mother batch. These granules can be added
into LDPE resin. The mother batch should be produced at a low temperature to avoid the
decomposition of potassium sorbate under the action of heat. But in the course of another
study (Weng and Hotchkiss) it became clear that relatively polar sorbate, benzoate and pro-
pionate are incompatible with nonpolar LDPE. It had been believed that acid anhydrides
are more compatible than free acids and their salts, due to their lower degree of polarity.
The residual antimicrobial activity is the efficient activity of an antimicrobial sub-
stance used after press molding (extrusion) and reprocessing (lamination, labelling, drying).
The qualitative analysis of the effect of adhesives and solvents is also required.
The characteristics of antimicrobial substances and food products.
Components of food products seriously affect the efficiency of antimicrobial substanc-
es and their release. The physicochemical characteristics of food products can change the
activity of antimicrobial substances. For instance, the level of pH can affect ionization (dis-
sociation/association) of most active chemical substances and is capable of changing the
antimicrobial activity of organic acids and their salts. The antimicrobial activity and chem-
ical stability of introduced active substances can also be affected by the activity of water.
Besides, each food product has its own characteristic microflora. The kinetics of releasing
antimicrobial substances should be developed in such a way so that to preserve the concen-
tration at a level exceeding the critical inhibitory concentration, with account for the possi-
ble presence of infecting microorganisms.
Storage temperature.
The storage temperature is capable of affecting the antimicrobial activity of chemical
preservatives. In general, an increased storage temperature can accelerate migration of ac-
tive substances in the film / layers with a coating, whereas cooling slows it down.
It is necessary to predict the temperature regime in production and delivery and to de-
termine its effect on the residual antimicrobial activity of active substances.
The physical properties of packaging materials.
During the introduction of substances with an antimicrobial activity into packaging
materials to decrease microbial growth, these substances may affect the general physical
properties of packaging materials. Han and Floras, performing their study, found out that
transparency of the film decreased in the introduction of an active substance. The charac-
teristics of packaging material should be preserved after the introduction of active substanc-
es even despite an inhomogeneity of the composition.
As we mentioned above, approaches to the development of packagings with an anti-
microbial coating can be attributed to one of two types. The first consists in a substance
binding to the surface of the packaging; this requires the sufficiently large molecular struc-
ture to be capable of maintaining its activity on the surface of the microbial cell, even bound
to the plastic. Probably, these substances are reduced to enzymes or other proteins with an-
timicrobial properties. The second approach consists in releasing active substances and
their contacting with the surface of the food product.
Packaging materials of inedible packaging systems can contain any types of food-cat-
egory additives. Some chemical substances naturally occur in plants or fermented food
products. But mainly they are obtained by chemical synthesis and are attributed to the cat-
CHAPTER 15 515

egory of chemical additives; in some cases, rules for restricting the use of these additives
are required.
In Japan, silver-substituted zeolite was developed, silver being the most widespread
antimicrobial substance imbedded into a plastic. Silver ions inhibiting the activity of quite
a number of metabolic enzymes is a broad-range potent antimicrobial factor. Ceolite, on the
surface of which a number of atoms are substituted for silver, is imbedded as a thin layer
(36 nm) into the surface of the polymer contacting with the food product and, as it appears,
silver ions are (gradually) released as fluid from the surface of the food product penetrates
unprotected depressions of the porous structure. The coating layer itself contains less than
0.001% of silver.
A rather promising approach is also to use these active shells as edible coatings. Edible
films based on natural polymers possess a high sorptivity, which predetermines their posi-
tive physiological effect. Thus, when getting into the organism, these substances adsorb and
excrete metal ions, radionuclides (products of radioactive decay) and other harmful com-
pounds, thus playing the role of a detoxicant. Addition of flavouring and coloring agents
into the polymer shell can adjust the taste and flavour of the meat product in the edible film,
thus changing the sensory perception of the product by the consumer, which is especially
important during the intake of dietary products, e.g., foods with reduced content of fat, sac-
charose, with addition of plant (e.g., soybean) protein. Besides, the ability of edible film to
retain various compounds makes it possible to enrich food products with minerals, vita-
mins, trace elements etc., thus compensating the deficit of required food components.
In spite of its evident advantages, active packaging has not yet found wide use in Rus-
sia. The problem is that the demand for this kind of packaging is yet hidden, potential con-
sumers either know little of home technologies or are not aware of the advantages of
investing into this field. Having a possibility to compare imported and domestic meat prod-
ucts, one can see for oneself that Russian products are not inferior to imported stuff in qual-
ity, and in many cases exceed it. Evidently, using advantages of active packaging, home
food products would find its consumer not only in Russia but also beyond its borders. Pos-
sibly, this is one of the ways for Russian products to the world market.
516 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY
Conclusion

Modern packaging materials are developed using eco-friendly resource-conserving tech-


nologies. Their characteristic feature is that, at minimal practicably justified consumption
rates of polymer film materials, they can be developed only using scientific principles and
physicochemical bases of forming an ordered regular structure in polymer systems.
In the works by Academician V.V. Korshak, it has been shown that in Russia and
abroad chemical production of polymer materials of various compositions is at present
based on methods of synthesis, which enable producing polymers only with the heterounit
structure of macromolecules. Under these conditions of the chemical reaction, produced
polymers of one brand differ by their molecular mass, chemical composition; number, char-
acter of distribution and alternation of the functional groups in the chain; conformation and
configuration of macromolecules, and, therefore, morphology and architecture of supramo-
lecular structure they form.
Taking these regularities into account, for imparting packaging materials with the re-
quired set of performance properties we proposed methods of regulating the structure of
polymers, based on introduction of small amounts of modifying structure formers into com-
positions.
In accordance with the phenomenon of the thixotropic decrease of internal stresses in
polymer systems, discovered by us, their mechanism of action is based on creating a su-
pramolecular structure in coatings, with uniform distribution of chemical and physical
bonds within the volume between the structural elements of the polymer matrix. These
bonds determine the impermeability of films for various reagents, structure imperfection,
biochemical endurance in food media, protective and physicomechanical properties of
films and coatings.
It has been shown that internal stresses emerging during the formation and use of poly-
mer materials are a criterion of homogeneity and imperfection of their structure and deter-
mine the set of performance properties of articles.
The scientific principles of decreasing internal stresses in various polymer systems
have been worked out.
A method has been proposed for the determination of internal stresses in various poly-
mer composite materials under conditions of their formation and use. An instrument for the
automatic registration of internal stresses has been designed and fabricated.
Based on the analysis of the regularities establishing the relationship between the
structural transformations in polymer systems with the set of performance properties, the
scientific bases for modification of compositions have been worked out. These scientific
bases were used in developing packaging materials for production and storage of food
products.
518 POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Special attention has been given to consideration of advanced compositions based on


polymerized oligomers, whose solvents are involved in the formation of the three-dimen-
sional network during the buildup of coatings. They also include modified powder systems,
which make it possible to produce coatings with high performance characteristics at a tran-
sient impact of a short-wavelength radiation.
Of great practical significance in production of packaging materials are modified
self-crosslinking dispersions of polymers with a polyfunctional set of properties.
The above compositions are the most ecologically safe and enable production of pack-
aging polymer materials with the lowest consumption of heat, electrical energy, labour in-
put and high performance characteristics.
Advanced methods have been developed for recycling and reuse of wastes of packag-
ing materials as secondary raw materials for production of industrial packaging for trans-
portation, prepackaging of products in the trading network and in agricultural enterprises.
Biodegradable packaging materials have been created, whose composition includes
biodegradants as packagings service-life regulators. The purpose of bioregulators is to pre-
vent the formation of molds in packaged food products and contribute to the biodegradation
of utilized packagings in soil.
References

Krivoshey, V.N. et al., Handbook of Polymer Packaging, 232 pp., Kiev, Tekhnika (1982)
(in Russian).
Briston, J.H. and Catan L.L., Polymer Films, 382 pp., Moscow, Khimiya (1993)
(translated from English).
Handbook on Modern Packaging, issue 4, Moscow, Information-Analytical Centre
Avgust Borg (2001) (in Russian).
Gul, V.E., Polymers for Food-production Packaging, Tara i Upakovka, No 3 (1993) (in
Russian).
Leonova, O.G. et al., Combined Packaging Materials with Enhanced Protective
Properties, Plast. Massy, No 4 (1993) (in Russian).
Modern Packaging Materials, Pakindustriya, December (1998) (in Russian).
Novelties on the Market of Shrink Films, Pakindustriya, August (2001) (in Russian).
Thermosetting and Shrink PVC Films, Pakindustriya, August (2001) (in Russian).
Meat Packaging Methods, Pakindustriya, May (2001) (in Russian).

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