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Rapra Industry Analysis Report Series

Polymer Foams

Trends in Use and Technology

David Eaves

Europes leading plastics and rubber consultancy


with over 80 years of experience providing
industry with technology, information
and products
Polymer Foams
Trends in Use and Technology

A Rapra Industry Analysis Report

by

David Eaves

February 2001

Rapra Technology Limited


Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
Tel: +44 (0)1939 250383 Fax: +44 (0)1939 251118 http://www.rapra.net
The right of David Eaves to be identified as the author of this work has been asserted by
him in accordance with Sections 77 and 78 of the Copyright, Designs and Patents Act
1988.

2001, Rapra Technology Limited

ISBN: 1-85957-240-5

All rights reserved. No part of this publication may be reproduced, stored in a retrieval
system, or transmitted in any form or by any meanselectronic, mechanical,
photocopying, recording or otherwisewithout the prior permission of the publisher,
Rapra Technology Limited, Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK.
Polymer FoamsTrends in Use and Technology

Contents
1 INTRODUCTION............................................................................................................ 1
1.1 Background ............................................................................................................. 1
1.2 Scope ......................................................................................................................1
1.3 Methodology ............................................................................................................ 2
2 EXECUTIVE SUMMARY................................................................................................ 3
2.1 Introduction.............................................................................................................. 3
2.2 Blowing Agents ........................................................................................................ 4
2.3 Flexible Polyurethane Foam .................................................................................... 5
2.4 Rigid Polyurethane Foam......................................................................................... 5
2.5 Polyolefin Foam ....................................................................................................... 6
2.6 Polystyrene Foam.................................................................................................... 7
2.7 Polyvinyl Chloride Foam .......................................................................................... 8
2.8 Phenolic Foam......................................................................................................... 8
2.9 Latex Foam.............................................................................................................. 9
2.10 Microcellular Foam................................................................................................. 9
2.11 Environmental Influences on the Foam Industry .................................................. 10
References .................................................................................................................. 10
3 BLOWING AGENTS..................................................................................................... 11
3.1 Introduction............................................................................................................ 11
3.2 The Montreal Protocol............................................................................................ 11
3.3 Alternative Physical Blowing Agents to Meet the Montreal Protocol ....................... 16
3.3.1 HCFCs ............................................................................................................ 16
3.3.2 Hydrocarbons.................................................................................................. 17
3.3.3 HFCs............................................................................................................... 18
3.3.4 CO2 ................................................................................................................. 20
3.4 Chemical Blowing Agents ...................................................................................... 21
References .................................................................................................................. 23
4 FLEXIBLE POLYURETHANE FOAM ........................................................................... 25
4.1 Introduction............................................................................................................ 25
4.2 Materials ................................................................................................................ 25
4.2.1 Isocyanates ..................................................................................................... 25
4.2.2 Polyols ............................................................................................................ 26
4.2.2.1 Polyether Polyols ...................................................................................... 26
4.2.2.2 Polyester Polyols ...................................................................................... 27
4.2.2.3 Other Polyols ............................................................................................ 27
4.2.3 Blowing Agents................................................................................................ 27
4.2.4 Catalysts ......................................................................................................... 28
4.2.5 Surfactants ...................................................................................................... 29
4.2.6 Scorch Inhibitors.............................................................................................. 30
4.2.7 Flame Retardants............................................................................................ 32
4.2.8 Mould Release Agents .................................................................................... 33
4.3 Processes.............................................................................................................. 33
4.3.1 Basic Foam Processes.................................................................................... 33
4.3.2 Slabstock Production....................................................................................... 34
Polymer FoamsTrends in Use and Technology

4.3.3 Use of Liquid Carbon Dioxide in Slabstock Foam Processes .......................... 36


4.3.4 Variable Pressure Foaming............................................................................. 37
4.3.5 Moulding Processes........................................................................................ 37
4.4 Recycling of Polyurethane Foam........................................................................... 41
4.4.1 Rebonding ...................................................................................................... 41
4.4.2 Regrinding ...................................................................................................... 42
4.4.3 Solvolysis........................................................................................................ 42
4.5 Properties of Flexible Polyurethane Foam ............................................................. 43
4.6 Markets and Applications ...................................................................................... 47
4.6.1 Flexible Slabstock Foam ................................................................................. 49
4.6.2 Flexible Moulded Foam................................................................................... 50
References.................................................................................................................. 53
5 RIGID POLYURETHANE FOAM.................................................................................. 55
5.1 Introduction ........................................................................................................... 55
5.2 Materials................................................................................................................ 55
5.2.1 Polyols ............................................................................................................ 55
5.2.2 Blowing Agents ............................................................................................... 58
5.2.3 Additives ......................................................................................................... 63
5.2.3.1 Catalysts .................................................................................................. 63
5.2.3.2 Surfactants ............................................................................................... 64
5.2.3.3 Cell Openers ............................................................................................ 65
5.2.3.4 Blend Compatibilisers............................................................................... 66
5.3 Processes ............................................................................................................. 66
5.4 Recycling............................................................................................................... 67
5.5 Properties.............................................................................................................. 68
5.6 Markets and Applications ...................................................................................... 69
5.6.1 Construction.................................................................................................... 69
5.6.2 Appliances ...................................................................................................... 71
References.................................................................................................................. 73
6 POLYOLEFIN FOAM ................................................................................................... 75
6.1 Introduction ........................................................................................................... 75
6.2 Materials................................................................................................................ 75
6.3 Processes ............................................................................................................. 79
6.3.1 Extruded, Non-Crosslinked Foam ................................................................... 79
6.3.2 Extruded Crosslinked Foam............................................................................ 81
6.3.2.1 The Irradiation Crosslinking Process ........................................................ 81
6.3.2.2 The Chemical Crosslinking Process ......................................................... 81
6.3.3 Press Moulded Foam ...................................................................................... 83
6.3.3.1 Single-Stage Process ............................................................................... 83
6.3.3.2 Two-Stage Process .................................................................................. 84
6.3.3.3 Injection Moulding Foam Process............................................................. 84
6.3.4 The Nitrogen Autoclave Process..................................................................... 85
6.3.5 Bead Processes.............................................................................................. 86
6.3.6 Post-Manufacturing Operations....................................................................... 87
6.4 Recycling............................................................................................................... 88
6.5 Properties.............................................................................................................. 89
Polymer FoamsTrends in Use and Technology

6.6 Markets and Applications ....................................................................................... 91


6.6.1 Packaging ....................................................................................................... 91
6.6.2 Automotive ...................................................................................................... 92
6.6.3 Other Applications ........................................................................................... 93
References .................................................................................................................. 94
7 POLYSTYRENE FOAM................................................................................................ 95
7.1 Introduction............................................................................................................ 95
7.2 Processes.............................................................................................................. 95
7.2.1 Expandable Polystyrene (EPS) ....................................................................... 95
7.2.2 Extruded Expanded Polystyrene (XPS) ........................................................... 97
7.2.3 Other Extrusion Processes .............................................................................. 97
7.2.4 Finishing Operations........................................................................................ 98
7.3 Recycling ............................................................................................................... 98
7.4 Properties ............................................................................................................ 100
7.5 Markets and Applications ..................................................................................... 102
7.5.1 Building and Construction.............................................................................. 104
7.5.1.1 Roof Insulation........................................................................................ 105
7.5.1.2 Wall Insulation ........................................................................................ 106
7.5.1.3 Sound Insulation ..................................................................................... 108
7.5.1.4 Other Construction Applications.............................................................. 108
7.5.2 Packaging ..................................................................................................... 109
7.5.3 Other Applications ......................................................................................... 110
References ................................................................................................................ 110
8 POLYVINYL CHLORIDE FOAM................................................................................. 111
8.1 Introduction.......................................................................................................... 111
8.2 Materials .............................................................................................................. 111
8.2.1 Polymer ......................................................................................................... 111
8.2.2 Blowing Agents.............................................................................................. 111
8.2.2.1 Chemical Blowing Agents ....................................................................... 111
8.2.2.2 Physical Blowing Agents ......................................................................... 113
8.2.2.3 Stabilisers ............................................................................................... 114
8.2.2.4 Processing Aids ...................................................................................... 114
8.2.2.5 Lubricants ............................................................................................... 114
8.3 Processes............................................................................................................ 115
8.3.1 Extrusion Foaming ........................................................................................ 115
8.3.2 Crosslinked Rigid PVC Foam ........................................................................ 116
8.3.2 Flexible PVC Foam ....................................................................................... 117
8.4 Properties ............................................................................................................ 117
8.5 Markets and Applications ..................................................................................... 118
8.5.1 Rigid PVC Foam............................................................................................ 118
8.5.2 Flexible PVC Foam ....................................................................................... 119
References ................................................................................................................ 119
9 PHENOLIC FOAM...................................................................................................... 121
9.1 Introduction.......................................................................................................... 121
9.2 Materials .............................................................................................................. 121
9.2.1 Phenols ......................................................................................................... 121
Polymer FoamsTrends in Use and Technology

9.2.2 Aldehydes ..................................................................................................... 122


9.2.3 Novolac Foam............................................................................................... 122
9.2.4 Resol Foam .................................................................................................. 122
9.3 Processes ........................................................................................................... 123
9.4 Recycling............................................................................................................. 124
9.5 Properties............................................................................................................ 124
9.6 Markets and Applications .................................................................................... 126
References................................................................................................................ 127
10 LATEX FOAM .......................................................................................................... 129
10.1 Introduction ....................................................................................................... 129
10.2 Materials............................................................................................................ 129
10.3 Processes ......................................................................................................... 129
10.3.1 The Dunlop Process ................................................................................... 129
10.3.2 Talalay Process .......................................................................................... 130
10.3.3 The Heat Sensitive Process........................................................................ 130
10.4 Recycling........................................................................................................... 131
10.5 Properties.......................................................................................................... 131
10.6 Markets and Applications .................................................................................. 131
References................................................................................................................ 132
11 MICROCELLULAR FOAM ....................................................................................... 133
11.1 Introduction ....................................................................................................... 133
11.2 Processes ......................................................................................................... 133
11.3 Properties.......................................................................................................... 137
11.4 Markets and Applications .................................................................................. 137
References................................................................................................................ 138
12 ENVIRONMENTAL INFLUENCES ON THE FOAM INDUSTRY .............................. 139
12.1 Introduction ....................................................................................................... 139
12.2 Emissions.......................................................................................................... 139
12.3 Blowing Agents and the Montreal Protocol ........................................................ 140
12.4 Waste Recovery ................................................................................................ 141
12.4.1 The Packaging Waste Directive .................................................................. 141
12.4.2 The Draft Landfill Directive .......................................................................... 142
12.4.3 The Draft Directive on Recycling End-of-Life Vehicles ................................ 143
12.5 Biodegradable Foam ......................................................................................... 144
12.6 Environmental Standards .................................................................................. 144
12.7 Positive Environmental Contributions ................................................................ 145
References................................................................................................................ 145
Polymer FoamsTrends in Use and Technology

1 INTRODUCTION

1.1 Background

It is hard to think of any area of application where polymer foams do not have a significant
market. The lighter weight and lower cost compared with solid polymer, and the wide
range of properties and fabrication methods available, make expanded materials the first
choice for a wide variety of uses, and market growth in many segments continues to be
higher than that of gross domestic product (GDP). Polymer foams may be flexible and
elastomeric as typified by latex, ethylene copolymers and flexible polyurethane (PU)
foams, or rigid materials of low extensibility such as phenolic, polystyrene (PS) and
polyisocyanurate (PIR) foams. Foams based on polyethylene (PE) or polypropylene (PP)
have intermediate properties, showing extensibility without full recovery, making these
materials good energy absorbers with applications for packaging and impact protection.
The ability of some foams to undergo thermoforming processes subsequent to initial foam
manufacture (crosslinked polyethylene foam is a good example) adds further to
application possibilities.

A major feature of polymer foams is their ability to be tailored to meet particular


application requirements. Properties depend not only on the particular polymer used but
also on the degree of expansion (characterised by the foam density) and the foam
structure (principally the extent of open cell versus closed cell content). These
characteristics are under the control of the manufacturer and enable user needs to be
closely matched.

Essentially all polymers are capable of being produced in an expanded form. The
processes used and the degree of expansion possible vary considerably, depending
principally on the particular polymer characteristics and the required final form of the foam,
e.g., thin continuous sheet or thick block. Processes used depend also on the producers
preferences and, particularly for polyolefins, no single method dominates. Most processes
have been around for many years with only minor changes. However, all processes
dependent on the use of a chlorofluorocarbon (CFC)-type physical blowing agent have
had to be adapted to the requirements of the Montreal Protocol which calls for use of
these materials (and also, on a more extended timescale, hydrochlorofluorocarbons
(HCFCs)) to be phased out.

Although polymer foams are in general less costly per unit volume than the original solid
polymer, foams are not generally produced with cost reduction as the main objective.
They are valued more for the special properties they possess. Such properties can
include thermal and acoustic insulation, energy absorption, cushioning, flexibility, and, of
course, lightness. Cost reduction of foams is generally achieved by production at lower
density since the usual approach of filler addition leads to density increase with little or no
benefit to properties. Development work aiming for cost reduction has to find a route to
maintain properties at an acceptable level as the foam density decreases.

1.2 Scope

Foams derived from the most commonly available polymers are considered in this report:
PU (flexible and rigid, including polyisocyanurate), polyolefins (PP, PE and ethylene
copolymers), PS, phenolics, polyvinyl chloride (PVC) and latex. The production of foams
using the recently developed microcellular process is discussed (Section 11), as are
physical and chemical blowing agents (Section 3). Density of the foams considered is

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Polymer FoamsTrends in Use and Technology

generally in the range 15300 kg/m3. High density materials with low degrees of
expansion are not included in any significant detail. Environmental issues are also
reviewed (Section 12).

1.3 Methodology

The information reported has been acquired mainly through desk research making use of
the Rapra Abstracts database and library. This technical literature has been
supplemented by visits to and discussions with foam producers, and by information
available from company brochures and publications. Technical and company/product
information has also been obtained from the internet. Most foam producers and
fabricators have now set up informative web sites and the internet will undoubtedly be
used increasingly as a source of technical and commercial information.

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Polymer FoamsTrends in Use and Technology

2 EXECUTIVE SUMMARY

2.1 Introduction

Although most of the processes used for the manufacture of polymer foams are well
established, many producers have had to carry out development work over the last few
years to adapt to new blowing agents which meet the requirements of the Montreal
Protocol. This agreement has had repercussions worldwide and will continue to influence
technical development for some time to come as the producers fine tune formulations to
try to match or exceed the material and process advantages provided by the original CFC
blowing agents. These are still in use in developing countries which have a more relaxed
timescale for CFC elimination, but adoption of non-CFC technology will take place in
these areas in due course.

Whilst the replacement of CFC blowing agents has been one common factor influencing
many parts of the foam industry, another has been the growing influence of environmental
concerns to conserve energy and to dispose of waste responsibly. The former has led
many foam producers to promote strongly the thermal insulation characteristics of their
products whilst the latter has led to the development of waste recovery processes for all
the major foam types.

Many of the applications for foam products have been established for some time, e.g.,
thermal insulation for buildings, protective packaging, cushioning for bedding and
furniture. Nevertheless, in most countries, market growth for all foam materials tends to be
somewhat above that of GDP as customers increasingly recognise and demand the
comfort and other benefits that foams can provide. For instance, demand for polymer
foams in the USA increased by an average of nearly 6% per year from 1993 to 1998 with
GDP at around 3% annual growth. Projections indicate somewhat lower figures in the
future for both foam demand and GDP.

Foam production is dominated by polyurethane (rigid and flexible) followed by polystyrene


and PVC. Production levels of the main types of polymer foam compared with total
polymer production levels are shown in Table 2.1.

Table 2.1 Production of Foams vs Total Polymer Production in Europe, 1998


Polymer Type Foam Production Polymer Production % of Polymer
(000 tonnes) (000 tonnes) Production
Polyurethane 685 (rigid) 2,500 77
1,500 (flexible)
Polystyrene 730 (EPS and XPS) 2,852 26
Polyolefins 55 (PE and PP) 15,833 0.3
PVC 290 5,621 5.1
Others 50 (estimate) 6,428 0.8
Total 3,310 33,234 10
Source: see data in later chapters, and 1998 thermoplastic polymer data from APME web site
(www.apme.org/europe)

Overall, foam production is around 10% of total polymer production, but variations in the
percentages of individual polymers converted to foam are large ranging from 0.3% for
polyolefins, to over 70% for polyurethane.

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Polymer FoamsTrends in Use and Technology

A useful overview of the main foam applications is given in a report [1] by Arthur D. Little,
Inc., for the Alliance For Responsible Atmospheric Policy and this is summarised in Table
2.2.

Table 2.2 Main Applications for Polymer Foams


Insulation Construction PS board
Polyolefin pipe
Rigid PU and PIR board, panels, pipes
Rigid PU spray-in-place roofing
Phenolic board and pipe
Appliance Rigid PU refrigerator and box lining
Transport Rigid PU panels
PS panels
Packaging Sheet PS single service
PS food and miscellaneous packaging
Polyolefin cushion packaging
Flexible and rigid PU packaging
Moulded Polyolefin cushion packaging
Block Polyolefin cushion packaging
Cushioning Slabstock Flexible PU seating, bedding, underlay
Moulded Flexible PU seating and auto bumpers
Safety Moulded Polyolefin auto bumpers
PU steering wheels and headrests
Sheet Polyolefin flotation, life vests
Board Polyolefin flotation
PS flotation
Source: [1]

2.2 Blowing Agents

The major development target with regards to physical blowing agents over the last few
years has been the identification of acceptable replacements for CFCs, in line with the
Montreal Protocol. In the USA, HCFC-141b has been widely adopted as a drop-in
substitute for CFC-11 in rigid PU and PIR foams, whilst for expanded polystyrene (EPS)
HCFC-142b has been adopted to replace CFC-12. However, the HCFCs are also
scheduled to be phased out, reductions being required in developed countries after 2003,
and hydrofluorocarbons (HFCs) are receiving more attention despite additional costs. In
Europe, substitution of CFCs by hydrocarbons is widespread despite the process and
machine modifications necessary to cope with the flammable and (in mixtures with air)
explosive nature of these substances. The advantages of carbon dioxide (CO2) as a
secondary or primary physical blowing agent (zero ozone depletion potential and low cost)
are resulting in substantial technical development. However, the use of CO2 requires
significant modifications to equipment in order to deal with technical problems associated
with the pressures generated by CO2 injection systems.

Chemical blowing agent systems have changed little over the last few years with
azodicarbonamide (AZDC) and sodium bicarbonate systems the most used. Reported
developments have been mainly in the endothermic sodium bicarbonate systems to
improve aspects such as nucleating potential. Some recent applications for the
endothermic systems have been in foamed blow moulded and rotational moulded parts to
reduce weight and increase wall thickness and stiffness.

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Polymer FoamsTrends in Use and Technology

2.3 Flexible Polyurethane Foam

In slabstock PU foam, the replacement of CFC-11 as a secondary (or auxiliary) blowing


agent (which increases expansion without additional isocyanate, reduces viscosity and
lessens the foam exotherm) has been the main area of development. Initially, the usual
approach involved omitting a secondary blowing agent altogether, relying on additional
water to generate more CO2 by chemical reaction with isocyanate. This requires careful
control and monitoring of the reaction exotherm to avoid scorch and to minimise fire risk
during production. More recently, direct injection of CO2 is being used following the
development of suitable process equipment. Other related developments include
improved surfactants to ensure good nucleation so as to provide a fine cell structure.

Formulations which meet various flammability specifications are now widely available,
generally incorporating melamine and other flame retardant additives.

Whilst toluene diisocyanate (TDI) is the conventional isocyanate used for slabstock foam,
diphenylmethane diisocyanate (MDI) systems have recently been developed by ICI and
BASF. These are claimed to have advantages such as lower emissions of isocyanate and
other volatiles, a lower exotherm, fewer additives and novel recycling possibilities. The
systems can be run on existing production facilities.

In moulded foams, CO2 systems have been introduced (by Hennecke and Cannon) to
enable the elimination of CFC-11. The CO2 is either metered directly to the mixing head or
premixed in either the polyol or the isocyanate reservoir. Mixing heads optimised for CO 2
have been developed. The other main area of research has been density reduction whilst
maintaining properties, resulting for instance in the introduction by Bayer of a new family
of isocyanates based on TDI. These are claimed to give the advantageous properties of
MDI foams (such as good green strength and high hardness) but with lower foam density
and improved processing characteristics.

The rebond process continues as an important method of recycling slabstock production


scrap but other processes are being developed aimed particularly at recycling PU foam
recovered from automotive use. Grinding equipment has been used to provide a
particulate which can be incorporated as a filler in virgin systems. Solvolysis processes (to
recover reactive components) have also been developed, e.g., by BASF, Elastogran and
ICI, but these are not suitable for the mixed quality material generally recovered from
automotive use.

Consolidation of production and marketing operations is evident in the global scene with
just five companies (BASF/Elastogran, Bayer, Dow Chemical, Huntsman Polyurethanes
and Lyondell Chemical Co.) serving some two-thirds of the market. Global consumption of
all PU products reached some 7.5 million tonnes in 1998 and is expected to increase to
some 9.5 million tonnes in 2003 with an annual growth rate of 4.7%, somewhat less than
the 6.1% over the period 19931998. Approximately 70% of global consumption is
accounted for by four sectors: automotive (15%), construction (17%), technical insulation
(10%), and furniture and mattresses (28%). There is a tendency to transfer price-sensitive
industries such as furniture and automotive to countries having lower production costs.

2.4 Rigid Polyurethane Foam

Since rigid PU foams are expanded by use of a physical blowing agent, not by release of
CO2 from water/isocyanate reactions, development work to find alternatives to the CFC
blowing agents has been pursued even more extensively than for flexible PU foams. Rigid

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Polymer FoamsTrends in Use and Technology

PU foams are substantially closed cell and the blowing agent remains in the cells to
contribute to insulation efficiency. CFCs have good thermal insulation characteristics and
this is an additional desirable requirement for CFC substitutes in these systems.

Worldwide, no single blowing agent technology has been universally adopted and there is
a broad diversification of rigid PU foam processes using HCFC-142b, HCFC-22 with 142b,
HCFC-134a, pentane isomers and CO2. The latter has inferior insulation properties,
particularly in the longer term as it diffuses out of the foam faster than alternatives.
Pentane isomers require special fire precautions during the manufacturing process and
also result in lower fire resistance of the foam unless additional flame retardant additives
are used. The HCFC materials are only an interim solution as they still have an adverse
environmental effect and are to be phased out in developed countries starting in 2004.
Various HFC substances are being looked at as the best longer term solutions for CFC
substitution and the likely scenario over the next few years is the continuation of, in
Europe, pentane-based technology and, in the USA, the replacement of HCFC-141b by
HFC-365mfc or blends thereof. In Asia, there will be a mix of technologies with some
(developing) countries still using CFC processes.

Formulation development has shown a move to polyisocyanurate foams using aromatic


polyester polyols due to the better fire performance of such foams. This is particularly
beneficial where the blowing agent has an adverse effect on flame resistance.

Increasing attention is being paid to the problems of disposal of waste. Glycolysis has
been in use for some time as a method for the recovery of polyols from waste rigid PU
foam. The recovered polyols can be used for the manufacture of new foam. Granulation
processes are also in use, the granules being mixed with MDI and pressed to produce
rigid boards for construction applications.

The main application for rigid PU foam is in the construction industry for insulation. The
market leader in this sector is mineral wool with a 63% share in Europe followed by PS
foam with 17.5%, whilst rigid PU foam has a 14% share. The total used worldwide in
construction applications was 1050 kt in 1996. This is expected to increase to 1380 kt by
2001. The other significant application is in appliance insulation with a worldwide market
of 464 kt (1997), some 40% of which was used in construction.

Developments over the next few years are likely to concentrate on optimisation and cost
reduction of the new CFC- and HCFC-free systems.

2.5 Polyolefin Foam

Several processes are in use for the production of polyolefin foams including extrusion of
continuous sheet using either chemical or physical blowing agents, production of thick
block by press moulding and thin block by the nitrogen autoclave route. Foams are
available in either crosslinked or non-crosslinked form depending on the process, with
better properties achieved with crosslinked foam.

The use of CFCs for extruded non-crosslinked foam has been discontinued in developed
countries, and hydrocarbons such as pentane or isobutane appear to be the most
favoured replacement blowing agents. Precautions against the flammable and, in mixtures
with air, explosive nature of the substances are necessary during foam production and
there is some concern regarding the effect of any residual volatile hydrocarbons in the
foam.

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Polymer FoamsTrends in Use and Technology

Low density polyethylene (LDPE) is the most common polymer foamed producing a semi-
rigid material, but other polymers in use range from flexible ethylene copolymers, such as
ethylene vinyl acetate copolymer (EVA), to stiff polymers with better high temperature
performance, such as high density polyethylene (HDPE, foamed commercially only with
the autoclave process) and PP. This range has been extended recently by the availability
of polyolefins produced using metallocene catalysis technology and several producers
have marketed foams based on these new materials. Foam properties are claimed to
show significant improvement over those of foams from conventional polymers although
there are some processing disadvantages, such as extrusion problems.

Non-crosslinked polyolefin foams can be recycled by granulation and subsequent


moulding or extrusion. Crosslinked foams are tougher and stronger and are best recycled
by reuse. Where this is not appropriate the comparatively low level of crosslinks allows
melt reprocessing.

The wide range of properties available from polyolefin foams by variation of polymer
density and additive components, and the ability of crosslinked foams to be post-formed
by heat moulding makes these materials very versatile. There are applications in
essentially all market sectors with new uses continually appearing. Significant application
areas include packaging, automotive, building and construction, aerospace, marine,
health care, sports and leisure, electronics and military. The estimated total European
market in 1997 was 55 kt, and the worldwide market was 252 kt with a growth rate of
4.8%.

2.6 Polystyrene Foam

Foamed PS materials are produced as expandable beads (EPS) incorporating


hydrocarbon blowing agents introduced at the polymerisation stage and also in expanded
sheet form (XPS) by extrusion of PS with a physical blowing agent, originally CFC-12.
CFC-12 has been replaced in the USA by HCFC-142b, used with a small amount of a co-
agent such as ethyl chloride. In Europe, most manufacturers use a non-flammable blend
of HCFC-142b and HCFC-22. More recently, processes using HFCs or carbon dioxide
have been developed. Production of EPS is some ten times that of XPS.

Recycling of PS foam is relatively straightforward as the material can readily be recovered


by melt processing. The main difficulty is the logistics of separating foam from other waste
material and transporting it to the recycling unit. Solution processes have been developed
to facilitate separation of foam from contaminants. At the production stage, this is not a
significant problem and a proportion of scrap can be incorporated with virgin polymer.

The market for PS foam is mature, the material having been developed some 50 years
ago. Even so, demand for the product continues to slowly grow. Global demand in 1997
was 2120 kt with expected growth of 2.5% in Western Europe and between 3% and 6% in
Asia and Eastern Europe.

The main applications for PS foam are in building and construction and in packaging
which account for 55% and 38% of production, respectively. In building and construction,
the good thermal and sound insulation characteristics are the main attraction and PS foam
(EPS and XPS) is second only to low-cost mineral wool in market share (17.5% versus
63%) whilst being recognised as a technically superior product. A recent report [2] by
Freedonia Group of the USA forecast that worldwide demand for thermal insulation
materials will rise by 3.7% per year up to 2002. Whilst glass fibre and mineral wool will

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Polymer FoamsTrends in Use and Technology

continue to dominate the market, the growth rate of foamed plastics is projected to be
somewhat higher than that for fibre-based insulation.

In packaging, use is made of the ability of PS foam to absorb impact to protect delicate
items during transport. The main foam competitor in this application is PE (crosslinked
and non-crosslinked) which is used in smaller quantities for special and more demanding
packaging. PE foam is more costly than PS foam but is tougher and has a better multi-
impact performance.

Foams from blends of PS with other polymers have been developed for use where
property enhancement or improved processing is needed.

2.7 Polyvinyl Chloride Foam

PVC rigid foam profiles are made by extrusion of PVC with a chemical blowing agent such
as azodicarbonamide or sodium bicarbonate. There are two main variations: the free
foaming process where the extrudate is allowed to expand freely on exit from the die, and
the Celuka or inward foaming process where the expansion is directed towards the core
by the presence of a mandrel within the die. Co-extrusion of solid PVC and foam PVC can
be used to provide a solid skin over a foam core.

Development work has found that a combination of blowing agents (azodicarbonamide


(exothermic) and sodium bicarbonate (endothermic)) is capable of producing the lowest
foam density. Work on physically blown systems, most recently using direct injection of
carbon dioxide, has shown that CO 2 is capable of giving similar foam densities to the
conventional systems but it is proving difficult to achieve a fine cell size. Further
development of direct gas injection technology can be expected.

Incorporation of a plasticiser into the PVC formulation enables the production of flexible
foams. The blowing agent is normally azodicarbonamide and the common process is to
coat the foamable plastisol onto a substrate (fabric, carpet, flooring) which is passed
through an oven to enable expansion.

Although no reference has been found to recycling PVC foam, there should be no difficulty
in recovery of usable material by melt processes. It is reported that recycled PVC can be
used to produce foam products.

There are three main markets for rigid PVC foam: profile, sheet, and pipe. The total
European market in 1998 was 165 kt with an annual growth rate of 5% to 10% during the
previous decade. The majority of applications (85%) are in building and construction.

Flexible PVC foam can be processed by thermoforming and this fabrication method is
used in many of its applications, for example, in the automotive industry to produce sun
visors and trimming.

2.8 Phenolic Foam

Phenolic foams are rigid, often brittle materials formed by complex catalysed reactions
between phenols and formaldehyde in the presence of a blowing agent. A novolac foam is
produced using an acid catalyst whilst resol foam synthesis uses a basic catalyst. Blowing
agents are normally of the physical type, originally CFCs but more recently HCFCs or low
boiling hydrocarbons. Manufacturing equipment is similar to that used for production of
rigid PU foam.

8
Polymer FoamsTrends in Use and Technology

Recycling is by granulation due to the friable nature of phenolic foams. Granulate may be
reused in phenolic or other compositions.

Phenolic foams have good thermal insulation properties and outstanding fire resistance,
making them competitors for rigid PU foam in building and construction applications. The
material is available as blocks, sandwich panels and continuous laminated board for
insulation in buildings and other applications such as shipbuilding where fire resistance is
at a premium. However, the insulation market is dominated by mineral wool and PS foam
with phenolic foam taking only around 1% share of the total.

2.9 Latex Foam

Latex foam has been available for some 70 years. Although it was originally produced
from natural rubber latex, less expensive synthetic latices were introduced in the 1960s
and currently most latex foams are produced either from styrene butadiene rubber (SBR)
latex or a mixture of SBR and natural rubber latex. Natural rubber latex is easier to
process and gives a stronger foam whilst SBR latex gives higher foam compression
properties and can therefore be used at lower (less costly) foam density to support an
equivalent load. The manufacturing process incorporates air as the foaming gas so the
replacement of blowing agent is therefore not an issue with latex foam. Recycling of latex
foam products has not received great attention as there is little waste in the process and
the product does not have a major market in developed countries compared with other
foam materials.

The main application for latex foam is in mattresses, pillows and cushions. The majority of
this market is taken by lower cost flexible PU foam which has replaced latex foam in most
of its traditional applications in developed countries. However, there remains a niche
market where the generally superior comfort properties of latex foam are appreciated.

Production of latex foam has consolidated to just a few companies in Europe and the USA
but these remaining producers continue to operate successfully, and it appears the market
has now stabilised. Indeed, Latex Foam Products (the only latex foam producer in the
USA) has reported a 25% annual increase in sales over the period 1993 to 1998 and is
planning to expand. In developing countries, the production of latex foam is more
widespread but is likely to decrease as PU technology is introduced.

2.10 Microcellular Foam

Microcellular foams, defined as foams having cell diameters of the order of 0.01 mm or
less, are produced by processes where gas (usually CO2) dissolved in a polymer is
released by a thermal or pressure induced phase separation. The processes were
originally studied (and patented) by Professor Nam Suh and colleagues at the
Massachusetts Institute of Technology. The foams are generally of high density (over 500
kg/m3). The original aim was to provide greater toughness (and lower cost) by producing a
material having a lower density than the original solid polymer with a multiplicity of cells
having sizes less than those of the micro-inclusions and inhomogeneities which are
considered to be the sites for stress failure.

Whilst much of the work has been of an academic nature, commercial scale extrusion of
microcellular PS foam sheet at rates up to some 450 kg/h has recently been
demonstrated; the technology is licensed by Trexel under the trademark MuCell.

9
Polymer FoamsTrends in Use and Technology

A further development has been demonstrated by Engel, extending the process to


injection moulding. Weight reduction is the main advantage but there are other benefits,
such as lower moulding pressures and faster demould times. The process has been
operated with several other polymers besides PS.

It is reported that a licence has been taken up by some 20 companies but as yet no
markets have been established for microcellular foam products. Those suggested include
food trays, packaging, automotive, building and construction, toys, aerospace, prostheses
and telecommunications.

2.11 Environmental Influences on the Foam Industry

The Montreal Protocol and resulting legislation has had a considerable influence on those
parts of the foam industry which have in the past used CFC blowing agents. These
substances have been phased out in developed countries although they continue in use
pro tem in many developing countries such as India and China. Use of HCFCs, which
some manufacturers used as interim alternatives to CFCs, will be phased out in
developed countries at the end of 2003. Hydrocarbons, CO2 and HFCs are the main
blowing agents acceptable in the long term.

Another environmental issue requiring attention from some foam manufacturers is growing
legislation in both North America and Europe to regulate emissions of volatile organic
compounds (VOCs). These substances include hydrocarbon and methylene chloride
blowing agents.

Waste recovery processes exist for most types of foam and are being used increasingly
both to improve manufacturing economics and to meet new regulations such as those
resulting from the EU Packaging Waste Directive and the Draft Directive on Recycling
End-of-Life Vehicles.

Whilst such issues frequently require foam manufacturers to carry out product and
process development work to meet environmental requirements, foams have considerable
environmental benefits (energy saving, reduced fuel consumption) when used for
applications such as thermal insulation in buildings and weight reduction in vehicles.

References

1. http://www.arap.org/adlittle/9.html, Global Comparative Analysis of HFC and


Alternative Technologies for Refrigeration, Air Conditioning, Foam, Solvent, Aerosol
Propellant and Fire Protection Applications. Final report to the Alliance for
Responsible Atmosphere Policy, Arthur D. Little, Inc., August 1999.

2. Study #1063 World Insulation, Freedonia Group, December 1998.

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Polymer FoamsTrends in Use and Technology

3 BLOWING AGENTS

3.1 Introduction

The production of a polymer foam almost always involves the use of a blowing agent to
generate a gas within the polymer whilst the latter is in a fluid state. Whilst other methods
exist for foam production, e.g., use of hollow microspheres incorporated within a polymer
mix to produce syntactic foams or frothing with air to produce latex foams, these are (with
the exception of latex foams) used only for production of speciality materials. The choice
of blowing agent is important not only for the process but also in determining some of the
properties of the final product, such as the microstructure of the foam and its insulation
characteristics.

There are two broad categories of blowing agents: physical and chemical. Physical
blowing agents change from liquid to gas (or are liberated as gas from solution in the
polymer) as the temperature changes or the pressure falls. Chemical blowing agents
decompose above a certain temperature to liberate a gas (or usually a mixture of gases).
Chemical and physical blowing agents may be used together in the same process; for
instance, CO2 may be generated chemically at an early stage and a physical blowing
agent may be used subsequently to enable a higher degree of expansion.

Physical blowing agents are generally of low cost and leave no solid residue. They are
unreactive in the foam system and are compressed gases (such as CO2 or nitrogen),
volatile liquids (such as water or low molecular weight hydrocarbons) or members of the
CFC/HCFC family of substances. They influence the process through their vapour
pressure/temperature relationship (which determines blowing temperature and degree of
expansion) and their ability to reduce the viscosity of the polymer mix.

There is no doubt that the major development target for physical blowing agents over the
last few years, and which will continue for some years to come, is the identification of
acceptable replacements for CFCs within the timescale defined by the Montreal Protocol.
The Montreal Protocol resulted from the realisation that depletion of the earths protective
ozone layer was primarily due to the presence of CFCs and related chemicals in the upper
atmosphere. These chemicals were defined and categorised by the Montreal Protocol and
phase-out dates for cessation of production of each class of substance were agreed for
developed and developing countries; later phase-out dates apply to the developing
countries. As it has heavily influenced trends in the development of physical blowing
agents, the current status of the Montreal Protocol is outlined in the next section.

3.2 The Montreal Protocol

The Montreal Protocol [1] is regarded by many as a landmark environmental treaty, which
could serve as a model for future multilateral treaties dealing with vital global issues. It has
its origins in the Vienna Convention for the Protection of the Ozone Layer, which was
adopted by governments in 1985 following widespread concern that certain man-made
chemicals were acting to deplete the ozone layer. This layer is located in the stratosphere
between 10 km and 50 km above ground level. By absorbing harmful ultraviolet (UV)
radiation the ozone layer gives protection against the effects of UV radiation, such as the
suppression of the immune system, the production of skin cancers and eye disorders such
as cataracts, and effects on the ecosystem and climate. Excess UV radiation adversely
affects all plants and animals and causes the deterioration of many plastics. The ozone
layer is constantly being destroyed and regenerated by photochemical processes. Some

11
Polymer FoamsTrends in Use and Technology

compounds, and in particular those which contain chlorine and bromine, are sufficiently
stable (long atmospheric half-life) to reach the ozone layer and interfere with these
processes resulting in ozone depletion. Compounds which are known to have this effect
include CFCs, halons and a broad range of industrial chemicals used as refrigerants,
foaming agents, aerosol propellants, fire retardants, solvents and fumigants.

At the 1985 Vienna Convention, governments committed themselves to protect the ozone
layer and to co-operate in research to improve understanding. The consequent Montreal
Protocol on Substances that Deplete the Ozone Layer was agreed by governments in
1987 and has since been amended four times, mostly to tighten restrictions in the light of
evidence that ozone depletion was occurring more rapidly than anticipated:

Initial Montreal Protocol 1987


First Amendment, London 1990
Second Amendment, Copenhagen 1992
Third Amendment, Vienna 1995
Fourth Amendment, Montreal 1997

As of 28 January 2000, the Vienna Convention had been ratified by 173 countries, the
Montreal Protocol by 172, the London Amendment by 138, the Copenhagen Amendment
by 104 and the most recent Montreal Amendment by 33 countries.

The Montreal Protocol (and its Amendments) provides a schedule for the phase-out of
consumption of ozone depleting substances (ODSs). Consumption is defined as
production plus imports less exports. Trade sanctions can be imposed against states
which do not comply with the Montreal Protocol (although such retaliation would in
practice conflict with the General Agreement on Tariffs and Trade (GATT) and the actual
position regarding sanctions is not clear).

Developing nations, including China and India, have expanding markets for appliances,
such as refrigerators and air conditioners, which traditionally use CFCs. They have argued
that they are not (so far) responsible for the ozone damage and have a right to enjoy the
benefits of CFC use that developed nations have enjoyed for many years, This debate
resulted in Article 5 of the Protocol which allows the signatory developing nations an
additional 10 years to implement the regulations.

In June 1990, a $100 million World Bank fund was set up to aid developing nations in their
work to reduce CFC usage. However, there is concern that the gains resulting from the
Montreal Protocol will be eroded by concessions made to developing countries regarding
implementation dates. It is also likely that, as the allowed quotas of ODS approach zero
and the 10-year delay for developing countries comes to an end, some nations will
present arguments to GATT administrators to water down the consequent trade sanctions.
A GATT ruling against the sanctions would result in substantial environmental damage
that many nations have agreed requires urgent action to remedy.

The Protocol differentiates ODSs into eight different classes. Specific substances in each
class and their ozone depletion potential (ODP) are shown in Tables 3.1.13.1.5. ODP is
a measure or estimate of a compounds potential rate of ozone depletion taking account of
its atmospheric half-life and with CFC-11 taken as 1.0. Hence, a substance with an ODP
greater than 1.0 is more damaging than CFC-11. Where a range is estimated, the higher
figure is used for comparison purposes. Single value ODPs have been determined from
calculations based on laboratory measurements whilst those listed as a range are based
on estimates and hence are less certain. The figures are subject to revision in the light of
further data.

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Polymer FoamsTrends in Use and Technology

Table 3.1.1 Montreal Protocol ODS Classification Annex A


Classification Name Chemical name ODP
Group I CFC-11 Trichlorofluoromethane 1.0
CFC-12 Dichlorodifluoromethane 1.0
CFC-113 1,1,1-Trichlorotrifluoroethane 0.8
CFC-114 Dichlorotetrafluoroethane 1.0
CFC-115 Monochloropentafluoroethane 0.6
Group II Halon-1211 Bromochlorodifluoromethane 3.0
Halon-1301 Bromotrifluoromethane 10.0
Halon-2402 Dibromotetrafluoroethane 6.0

Table 3.1.2 Montreal Protocol ODS Classification Annex B


Classification Name Chemical name ODP
Group I CFC-13 Chlorotrifluoromethane 1.0
CFC-111 Pentachlorofluoroethane 1.0
CFC-112 Tetrachlorodifluoroethane 1.0
CFC-211 Heptachlorofluoropropane 1.0
CFC-212 Hexachlorodifluoropropane 1.0
CFC-213 Pentachlorotrifluoropropane 1.0
CFC-214 Tetrachlorotetrafluoropropane 1.0
CFC-215 Trichloropentafluoropropane 1.0
CFC-216 Dichlorohexafluoropropane 1.0
CFC-217 Chloroheptafluoropropane 1.0
Group II CCl4 Carbon tetrachloride 1.1
Group III C2H3Cl3 1,1,1-Trichloroethane 0.1

Table 3.1.3 Montreal Protocol ODS Classification Annex C Group 1


Name Formula ODP
HCFC-21 CHFCl2 0.04
HCFC-22 CHF2Cl 0.055
HCFC-31 CH2FCl 0.02
HCFC-121 C2HFCl4 0.010.04
HCFC-122 C2HF2Cl3 0.020.08
HCFC-123 C2HF3Cl2 0.020.06
HCFC-123 CHCl2CF3 0.02
HCFC-124 C2HF4Cl 0.020.04
HCFC-124 CHFClCF3 0.022
HCFC-131 C2H2FCl3 0.0070.05
HCFC-132 C2H2F2CI2 0.0080.05
HCFC-133 C2H2F3Cl 0.020.06
HCFC-141 C2H3FCl2 0.0050.07
HCFC-141b CH3CFCl2 0.11
HCFC-142 C2H3F2Cl 0.0080.07
HCFC-142b CH3CF2Cl 0.065
HCFC-151 C2H4FCl 0.0030.005
HCFC-221 C3HFCl6 0.0150.07
HCFC-222 C3HF2Cl5 0.010.09
HCFC-223 C3HF3Cl4 0.010.08
HCFC-224 C3HF4Cl3 0.010.09
HCFC-225 C3HF5Cl2 0.020.07
HCFC-225ca CF3CF2CHCl2 0.025

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Polymer FoamsTrends in Use and Technology

Table 3.1.3 Continued


Name Formula ODP
HCFC-225cb CF2CICF2CHCIF 0.033
HCFC-226 C3HF6Cl 0.020.10
HCFC-231 C3H2Cl5 0.050.09
HCFC-232 C3H2F2Cl4 0.0080.10
HCFC-233 C3H2F3Cl3 0.0070.23
HCFC-234 C3H2F4Cl2 0.010.28
HCFC-235 C3H2F5Cl 0.030.52
HCFC-241 C3H3FCl4 0.0040.09
HCFC-242 C3H3F2Cl3 0.0050.13
HCFC-243 C3H3F3Cl2 0.0070.12
HCFC-244 C3H3F4Cl 0.0090.14
HCFC-251 C3H4FCl3 0.0010.01
HCFC-252 C3H4F2CI2 0.0050.04
HCFC-253 C3H4F3CI 0.0030.03
HCFC-261 C3H5FCI2 0.0020.02
HCFC-262 C3H5F2CI 0.0020.02
HCFC-271 C3H6FCI 0.0010.003

Table 3.1.4 Montreal Protocol ODS Classification Annex C Group 2


Formula ODP Formula ODP
CHFBr2 1.0 C3HF4Br3 0.52.2
CHF2Br (HBFC-22b) 0.74 C3HF5Br2 0.92.0
C3HF6Br 0.73.3
CH2FBr 0.73 C3H2FBr5 0.11.9
C2HFBr4 0.30.8 C3H2F3Br 30.25.6
C2HF2Br3 0.51.8 C3H2F4Br2 0.37.5
C2HF3Br2 0.41.6 C3H2F5Br 0.91.4
C2HF4Br 0.71.2 C3H3FBr4 0.081.9
C2H2FBr3 0.11.1 C3H3F2Br3 0.13.1
C2H2F2Br2 0.21.5 C3H3F3Br2 0.12.5
C2H2F3Br 0.71.6 C3H3F4Br 0.34.4
C2H3FBr2 0.11.7 C3H4FBr3 0.030.3
C2H3F2Br 0.21.1 C3H4F2Br2 0.11.0
C2H4Br 0.070.1 C3H4F3Br 0.070.8
C3HFBr6 0.31.5 C3H5FBr2 0.040.4
C3HF2Br5 0.21.9 C3H5F2Br 0.070.8
C3HF3Br4 0.31.8 C3H6FBr 0.020.7

Table 3.1.5 Montreal Protocol ODS


Classification Annex E Group 1
Name ODP
Methyl bromide (CH3Br) 0.6

The source for Tables 3.1.13.1.5 is the United Nations Environment Programme (UNEP)
Division of Technology, Industry and Economics, OzonAction Programme under the
Multilateral Fund for the Implementation of the Montreal Protocol,
www.unepie.org/ozat/protocol/ods.html.

14
Polymer FoamsTrends in Use and Technology

The latest phase-out schedule agreed at the Montreal meeting of September 1997 is
shown in Table 3.2 (developed countries) and Table 3.3 (developing countries). Within the
timetable there are some exemptions for essential use [2] but these do not, in general,
include use for blowing agents.

Table 3.2 Consumption Phase-out of ODSDeveloped Countries


Date Central Measure
July 1989 Freeze of Annex A CFCs
January 1992 Freeze of halons
January 1993 Annex B CFCs reduced by 20% from 1989 levels
Freeze of 1,1,1-trichloroethane
January 1994 Annex B CFCs reduced by 75% from 1989 levels
Annex A CFCs reduced by 75% from 1986 levels
Halons phased out
Methyl chloroform reduced by 50%
January 1995 Methyl bromide frozen at 1991 levels
Carbon tetrachloride reduced by 85% from 1989 levels
January 1996 HBFCs (hydrobromofluorocarbons) phased out
Carbon tetrachloride phased out
Annex A and B CFCs phased out
1,1,1-trichloroethane phased out
HCFCs frozen at 1989 level + 2.8% of 1989 consumption of CFCs
(base level)
January 1999 Methyl bromide reduced by 25% from 1991 levels
January 2001 Methyl bromide reduced by 50% from 1991 levels
January 2003 Methyl bromide reduced by 70% from 1991 levels
January 2004 HCFCs reduced by 35% below base levels
January 2005 Methyl bromide phased out
January 2010 HCFCs reduced by 65%
January 2015 HCFCs reduced by 90%
January 2020 HCFCs phased out, allowing for a service tail of 0.5% until 2030 for
existing refrigerators and air conditioning equipment
Source: United Nations Environment Programme (UNEP) Division of Technology, Industry and
Economics, OzonAction Programme under the Multilateral Fund for the Implementation of the
Montreal Protocol, www.unepie.org/ozat/protocol/countdow.html

There were 46 original signatories to the 1987 Protocol, which included the United States,
Canada, Australia, Japan, Russia, the UK and all other EU countries. There are at present
113 countries (with a further 11 temporarily categorised) operating under Article 5 of the
Protocol which allows them additional time to achieve phase-out and which also makes
them eligible for financial assistance and technical co-operation, including the transfer of
technologies to enable compliance. Up to December 1998, $233.9 million had been
approved for work in 64 countries to support such projects, with $103.8 million
disbursements. Countries in this category (the developing countries) include several with
sizeable populations such as China, India, Pakistan, Korea and South Africa.

Whilst the Protocol has had significant effect in the original major ODS producing
countries, with world CFC production falling by about 60% between 1986 and 1993 (from
about 0.9 to 0.4 million tonnes), production in developing countries exploded, rising 87%
over this period with exports rising 17-fold. Additionally, it has been said that a large black
market exists, with estimates that 20% of sales are illegal and originate in developed
countries.

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Polymer FoamsTrends in Use and Technology

Table 3.3 Consumption Phase-out of ODSDeveloping Countries


Date Central Measure
1 July 1999 Freeze of Annex A CFCs at 19951997 average levels
1 January 2002 Freeze of halons at 19951997 average levels
Freeze of methyl bromide at 19951998 average levels
1 January 2003 Annex B CFCs reduced by 20% from 19982000 average
levels
Freeze of 1,1,1-trichloroethane at 19982000 average levels
1 January 2005 Annex A CFCs reduced by 50% from 19951997 average
levels
Halons reduced by 50%
Carbon tetrachloride reduced by 85% from 19982000
average levels
1,1,1-Trichloroethane reduced by 30% from 19982000
average levels
1 January 2007 Annex A CFCs reduced by 85% from 19951997 average
levels
Annex B CFCs reduced by 85% from 19982000 average
levels
1 January 2010 CFCs, halons and carbon tetrachloride phased out
1,1,1-Trichloroethane reduced by 75% from 19982000
average levels
1 January 2015 1,1,1-Trichloroethane phased out
1 January 2016 Freeze of CFCs at base line figure of year 2015 average levels
1 January 2040 HCFCs phased out
Source: United Nations Environment Programme (UNEP) Division of Technology, Industry and
Economics, OzonAction Programme under the Multilateral Fund for the Implementation of the
Montreal Protocol, www.unepie.org/ozat/protocol/countdow.html

3.3 Alternative Physical Blowing Agents to Meet the Montreal Protocol

Although use for foam expansion is only one of a number of applications for CFCs, it is
one of the more demanding in terms of the properties required. Ideally, substitution with a
CFC alternative results in little or no change to the production process, causes no
deterioration of physical properties in the final product, is safe to use (non-toxic, non-
flammable and, of course, zero ODP and global warming potential (GWP)), and has
acceptable process economics. Global warming potential is a measure or estimate of the
potential of a substance to contribute to global warming with CO2 taken as 1.0. In practice,
there are no environmentally acceptable substances which precisely match the
performance of CFCs. Hence there is a reluctance to change as this involves costs
associated with materials and modifications to processes with a possible deterioration in
product properties.

3.3.1 HCFCs

In the USA, the phase-out of CFCs has been made possible by the availability of HCFC
substitutes. In rigid PU and PIR foams (see Section 5), where CFC-11 was the usual
blowing agent, HCFC-141b has become the accepted alternative. It is essentially a drop-
in substitute with acceptable safety and toxicity, and the foam produced closely matches
the insulating properties of the CFC-11 blown products, both in the short term and long
term. In the case of expanded polystyrene (XPS, see Section 7), CFC-12 has been

16
Polymer FoamsTrends in Use and Technology

substituted with HCFC-142b with a small amount of ethyl chloride. Again, there is little
change in process or products with these systems. In Europe, XPS foam is generally now
produced using a blend of HCFC-142b and HCFC-22. This blend is non-flammable and
process modifications to take account of the flammability of pure HCFC-142b are avoided.
HCFCs are also used (HCFC-141b, HCFC-142b blends with HCFC-22, or HCFC-22 with
CO2) in some flexible PU manufacture, such as integral skin, but are not technically
necessary for flexible slabstock since CO2 is generated in any case as an expansion
agent during the foaming reaction (although greater expansion and more formulation
flexibility is possible if an additional physical blowing agent is used). Other polymer foams
now being produced using HCFCs are phenolics (HCFC-141b) and polyolefins (HCFC-22,
HCFC-142b). A comparison of the properties of these substances with those of CFCs is
given in Table 3.4.

Table 3.4 Properties of some CFCs and HCFCs


Property Blowing Agent
CFC-11 CFC-12 HCFC-141b HCFC-142b HCFC-22
Molecular weight (g/mol) 137.4 120.9 116.9 100.5 86.5
Boiling point (C) 23.8 -29.7 32.2 -9.8 -40.6
Thermal conductivity 9.2 9.8 10.7 9.7 10.7
(mW/m K)
Vapour flame limits none none 7.617.7 6.714.9 none
(% vol)
ODP 1.0 1.0 0.11 0.065 0.055
GWP* 4,000 3,800 630 1,800 1,500
Atmospheric lifetime 50 102 9.4 18.4 12.1
(years)
* i.e., 4,000 kg of CFC-11 have the same global warming effect as 1 kg of CO2 over a time period
of 100 years
Source: [3]

The HCFCs are interim substances, as they still have significant ODP and their phase out
is scheduled in the Montreal Protocol.

3.3.2 Hydrocarbons

Whilst HCFCs have been developed as interim CFC alternatives in the USA, in Europe,
CFC substitution by hydrocarbons is widespread despite the process modifications
needed to deal satisfactorily with the flammable and (in mixtures with air) explosive nature
of these substances. Systems for the production of rigid PU and PIR foam have been
developed, and extruded PS foam (EPS), polyolefin foam, phenolic foam and integral skin
flexible PU foam have all been produced using hydrocarbon blowing agent technology.
Hydrocarbons (n-pentane, i-pentane and cyclopentane), alone or in blends, have the
advantage of zero ODP and are acceptable under the Montreal Protocol. Their main
disadvantages are flammability, lower product insulation and fire resistance
characteristics, and the necessity for significant formulation modification. Nevertheless,
the technology widely operated in Europe is now being introduced in the USA where the
deadline for HCFC phase-out is approaching. In 1998, the Exxon Chemical Co.
announced a decision to make cyclopentane-based blowing agents in the USA to meet
expected demand. The materials are offered under the trade name Exxsol and are said to
offer foam properties similar to HCFC-141b. Also in 1998, Atlas Roofing Corporation,
Atlanta, announced conversion from HCFC-141b to a pentane-based system for rigid PU
boardstock and sandwich panels and claims that developments in technology allow these

17
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foams to match HCFC blown foams in all key characteristics. Similar claims have been
made by ICI Polyurethanes regarding both the fire performance and insulating
characteristics of hydrocarbon blown polyisocyanurate foams. It remains to be seen
whether the inherent property deficiencies of hydrocarbon blown foams will be totally
remedied by formulation development so that company claims are realised. Some
properties of hydrocarbon blowing agents are compared to those of CFC-11 and CFC-12
in Table 3.5.

Table 3.5 Properties of Hydrocarbon Blowing Agents Compared with


CFC-11 and CFC-12
Property Blowing Agent
CFC-11 CFC-12 n-pentane i-pentane cyclopentane
Molecular weight (g/mol) 137.5 121 72 72 70
Boiling point (C) 23.8 -29.7 36 27.8 49.3
Vapour thermal 9.2 9.8 13.7 13.3 11.2
conductivity (mW/m K)
Flash point (C) none none -40 < -51 -37
Vapour flame limits none none 1.38.0 1.47.6 1.49.4
(% vol)
ODP 1 1 0 0 0
GWP 4000 3800 11 11 11
Source: [3]

Although pentane hydrocarbons have zero ODP and very low GWP, they are not totally
free from environmental concern. Unlike most fluorocarbons (including CFC-11, CFC-12,
HCFC-141b, HCFC-142b), hydrocarbons, including all the isomers of pentane, are
classified in the USA as VOCs and are subject to strict emission controls necessitating
expensive emission capture technology to meet regulations. It is anticipated that VOC
regulations will be introduced in other countries including Europe and Japan; in Europe,
the VOC Solvent Emissions Directive, adopted by the European Commission in 1999,
aims to reduce VOC emissions by 67% from 1990 base levels by 2007.

3.3.3 HFCs

Whilst hydrocarbons are regarded by some as the final solution, needing only formulation
refinement to improve foam thermal insulation, work has also proceeded on the
development of HFCs to eliminate the process disadvantages of hydrocarbons and to
improve insulation values. These substances are at present more expensive and less
widely available than HCFCs or hydrocarbons, but are likely to be used more in the future
as so called third-generation blowing agents. The two leading candidates are HFC-245fa
and HFC-365mfc. Properties of these candidates are given in Table 3.6.

Allied Signal, USA, intends to supply HFC-245fa, whilst Solvay, Belgium, is developing
plant for HFC-365mfc production. HFC-245fa, with its lower boiling point, appears to be a
good option for rigid PU in appliance applications, whilst HFC-365mfc looks the better
option for rigid PU in building and construction. Whilst HFC-245fa would be 21% more
expensive to use in appliances than HCFC-141b (and cyclopentane 19% more costly),
benefits arising from the better insulation obtained with the HFC foam more than
compensate in the longer term for the higher initial expense. There will be a greater
incentive to move to foams with the best insulation when the new US energy regulations
(calling for a 30% energy consumption improvement of refrigerator-freezers and
refrigerators) come into force in July 2001.

18
Polymer FoamsTrends in Use and Technology

Table 3.6 Properties of HFC Blowing Agents


Properties HFC-245fa HFC-365mfc
Structure CF3CH2CHF2 CF3CH2CF2CH3
Molecular weight 134 148
Vapour thermal conductivity (mW/m K) 12.2 10.6
Vapour flame limits (% vol) none 3.59.0
ODP 0 0
GWP 820 840
VOC no no
Source: [3]

A comparison of the cost of physical blowing agents is given in Table 3.7.

Table 3.7 Comparison of Blowing Agent Costs


Blowing agent Cost $/lb
n-pentane 0.25
iso-pentane 0.40
c-pentane 0.85
HCFC-141b 1.00
HCFC-22 1.00
HFC-245fa 3.00
HFC-134a 2.00
Water negligible
Liquid CO2 low
Source: [4]

Solvay [5] has studied the use of blends of HFCs (HFC-365mfc/HFC-245fa, and HFC-
365mfc with various pentane isomers) for the production of PU foam. Azeotropic blends of
HFC-365mfc with pentane remain flammable but have boiling points close to that of the
traditional CFC-11 and give foams with better thermal insulation properties than pentane.
Such combinations allow a choice of blowing agent to be made based on flammability
characteristics, desired boiling point, effect on thermal insulation, and cost, to suit
particular requirements.

Historically, CFC-12 has been used to manufacture PS but production has generally
moved to HCFC-142b, alone or in blends with HCFC-22 or ethyl chloride. This may not
yet be the case in developing countries such as China and India where a 10-year
extension to the Montreal Protocol schedule applies. However, these countries have an
additional incentive to change if they wish to export expanded foam products to developed
countries. Elf Atochem [6] reported the HFCs best suited to EPS as HFC-134a and HFC-
152a. Properties of these blowing agents are given in Table 3.8.

These HFCs have been used in Germany and Northern Europe where there are stringent
local regulations (e.g., the phase-out of HCFC-142b in Sweden from 1 January 1997).

A recent report [7] commented that HFCs are most likely to be adopted as alternative
blowing agents for insulating foams. In these products, the additional cost of HFCs can be
mitigated by the beneficial effect such foams have on energy consumption. Worldwide
consumption of HFC blowing agents is forecast to be 75,000 tonnes in 2004 (following the
HCFC phase out in 2003), increasing to 115,000 tonnes in 2010. After 2010, growth rates

19
Polymer FoamsTrends in Use and Technology

are predicted to be in line with overall growth rates of foam consumption with HFCs used
in some 20% of all rigid foam.

Table 3.8 Properties of HFC Blowing Agents and CO2


Property Blowing Agent
HFC-134a HFC-152a CO2
Formula CF3CFH2 CH3CF2H CO2
Molecular weight 102 66 44
Boiling point (C) -26.4 -24.7
Vapour thermal conductivity (mW/m K) 13.6 13.4 16.6
Vapour flame limits (% vol) none 3.718.0 none
ODP 0 0 0
GWP 1300 140 1
Source: [6]

3.3.4 CO2

CO2 has many attractions as an alternative blowing agent to CFCs. It is abundant in


nature, is very low in cost, expands some three times more than available alternatives, is
nonflammable and has no effect on workers health or factory safety. As it is produced as
a by-product from other industrial processes, no additional gas is added to the
atmosphere through its use as a blowing agent. With zero ODP, it is acceptable
environmentally although it does have a significant global warming effect.

Most development work with CO2 has been targeted at the flexible PU foam industry for
both slabstock and moulded integral skin processes (see Section 4), where CFCs have
traditionally been used as auxiliary blowing agents. CO2 is generated in any case by
reaction between water and isocyanates, and the first thought might be to increase water
levels in formulations to produce additional CO2. This is not a good option as it requires
additional expensive isocyanate and also increases the heat generated by the reaction
exotherm. Although rapid cooling methods are widely used in the production of slabstock
foam to control the exotherm, this general procedure is not without risk.

The use of injected liquid carbon dioxide in PU foam has been studied for some time and
a number of systems and formulations have been developed. Account must be taken of
the low bubble stability in a carbon dioxide system and special silicone-based stabilisers
have been developed for this application.

The technologies for production of polyurethane slabstock foam provide for the metering
of natural liquid carbon dioxide into the high pressure polyol stream where it is
subsequently dissolved by passing through a static mixer. Cannons CarDio system has
been in commercial use since May 1994; other equipment manufacturers have since
offered CO2 technology. The Novaflex process developed by Bayer and Hennecke has
been adopted by British Vita for flexible slabstock foam production. Gusmer-Admiral Inc.,
USA, has developed a process which involves introducing a stream of liquid CO2 directly
into the mixing head rather than pre-blending it with polyol. This technology is being
adopted in Japan. Beamech Group Ltd., has developed liquid CO 2 blowing agent
technology for its Maxfoam and Vertifoam processes. It is possible to retrofit this
technology to existing equipment.

Hennecke has developed a related technology for moulded polyurethane foamthe


Novaform processand some data on PU foam formulations for moulding applications

20
Polymer FoamsTrends in Use and Technology

using CO2 blowing agent have been published [8]. This data shows that a density
reduction of 15% can be achieved whilst maintaining good processability.

An alternative possibility is variable pressure foaming such that the CO2 generated in the
reaction causes additional expansion in a lower pressure environment, reducing or
eliminating the necessity for any additional gaseous blowing agents. However, due to the
high investment costs for the provision of the necessary large volume foam containment
vessel for pressure control, this technology does not seem to be an ideal alternative.
Nevertheless, it is reported that it has been adopted by Foamex International in North
America.

A more complete discussion on the use of CO2 as a blowing agent in flexible polyurethane
foams is given in Section 4.

N2 like CO2 is abundant in nature and low in cost, but its low solubility in polymer systems
has generally precluded its use as a physical blowing agent with the exception of the
nitrogen autoclave process used by Zotefoams, UK (see Section 6) and some
microcellular foam processes under development (see Section 11).

3.4 Chemical Blowing Agents

Chemical blowing agents are substances which are sufficiently stable to be incorporated
into a polymer under normal process mixing conditions, but which subsequently, at higher
temperatures, decompose to produce a gas which expands the polymer. Chemical
blowing agents are receiving additional attention as alternatives to CFC physical blowing
agents, although in 1998 the market was estimated as still only some 10% of that of
physical blowing agents. In North America, sales are estimated as $3040 million [9].

Chemical blowing agents can also be used as nucleating agents in physically blown
systems to produce a more homogeneous cell structure with fewer defects. Such
materials are known as active nucleators (as opposed to non-active nucleators such as
talc or other silicates). Chemical blowing agents used for this purpose are generally based
on endothermic citric acid/sodium bicarbonate blends, as opposed to substances such as
azodicarbonamide (AZDC) which decomposes exothermically. A list of chemical blowing
agents with some of their properties is given in Table 3.9.

Table 3.9 Chemical Blowing Agents and Typical Properties


Blowing agent Processing Gas yield Gas yielded
temperature cm3/g
C
Azodicarbonamide (AZDC) mainly N2,
150215 155230
CO, NH3, CO2
Azoisobutyronitrile (AZDN) 70 125 N2
p-Toluene sulphonylhydrazide 105110 115 N2, H2O
4,4oxybis(benzenesulphonylhydrazide)
155165 120125 N2, H2O
(OBSH)
Dinitrosopentamethylenetetramine N2, NH3,
195 240
(DPNT) HCHO
5-Phenyltetrazole 232288 200 mainly N2
Citric acid/sodium bicarbonate 150230 100150 CO2, H2O
Source: [10]

21
Polymer FoamsTrends in Use and Technology

Choice of blowing agent is determined by the process temperature, the required amount
of gas evolution, the decomposition rate and the influence on the process of the
exotherm/endotherm of decomposition.

The azo compounds are the most important class being the most widely used, and the
organic systems in general offer better control than inorganic ones. AZDC, for instance, is
available in a range of particle sizes, physical form (pellets, powder) and modified
chemistry which allow control over blending, particle distribution and precise
decomposition temperature, all of which are tailored to a particular foam process.
Decomposition temperature has been shown to depend on heating rate, being lowest at
lower rates and is modified by the addition of kickers (a variety of materials based on
group II and group IV metal salts, primarily lead acetate, lead oxide, zinc oxide, zinc
stearate and zinc acetate which accelerate the decomposition of the blowing agent and
allow lower blowing temperatures to be used). The mechanism of the catalytic
decomposition of AZDC in the presence of metal salts is not clear, but the effect allows
the decomposition temperature to be adjusted to suit almost any expansion process in the
160 C to 210 C range.

Exothermic chemical blowing agents commonly generate more gas and hence a higher
pressure than endothermic ones and are used where high yield and pressure are
important, such as crosslinked polyolefin foams, PVC foams and many extruded foam
products. Endothermic chemical blowing agents produce foams with a smaller cell
structure and enhanced appearance and physical properties.

A recent development is a combination product from Boehringer Ingelheim Pharma KG


containing both exothermic and endothermic blowing agents. The exothermic compound
provides the gas volume and pressure required for low density foam production whilst the
endothermic component produces a fine homogeneous cell structure. A general
comparison of exothermic and endothermic chemical blowing agents is given in Table
3.10.

Table 3.10 General Comparison of Chemical Blowing Agents


Properties Exothermic Exothermic plus Endothermic
Endothermic
Density reduction Excellent Very good Good
Cell structure Coarse Medium Fine
Colour Yellow Pale yellow White
Discolouration Yes Small amount None
Odour Pungent (NH3) Fair Little
Gas N2 (plus others) Mainly N2/CO2 CO2
Environmental impact Low Low Little or none
Source: [11]

Research at the University of Manchester, UK, [12] concluded that whilst the magnitude of
the decomposition exotherm can be controlled by use of blends of azodicarbonamide and
sodium bicarbonate in a crosslinked polyethylene foam formulation (see Section 6), the
blends are unsuitable for foaming processes where the expansion is carried out at
atmospheric pressure. Under these conditions, CO2 and NH3 gaseous decomposition
products can be liberated prior to a sufficient build up of crosslinking and contribute less
effectively to expansion since they can rapidly diffuse out of the polymer melt. Conversely,
advantages were found in processing such systems by compression moulding since the
gases are retained and the reduction in exotherm (compared with pure
azodicarbonamide) is helpful in mitigating thermal degradation. It is suggested there

22
Polymer FoamsTrends in Use and Technology

would be applications for production of PVC foams where there is an even more stringent
requirement to minimise heat build up, and which with a lower gas permeability should
show better retention of gases.

Blowing agent development tends to be small improvements rather than completely new
systems.

Boehringer Ingelheim has introduced Hydrocerol CF 40T which both foams and nucleates
PS, acrylonitrile butadiene styrene (ABS) and other styrenes used in blow moulding and
extrusion. Storage stability is said to be improved by use of a new carrier which also aids
incorporation of the blowing agent into the melt. It has also announced the introduction of
Hydrocerol CT1110 (for PE) and CT1111 (for PS). These are 40% talc-filled for improved
dispersion and cell consistency.

Kycerol 91 and 92 are available from Rit-Chem and are sodium bicarbonate type
endothermal blowing agents designed for polyolefins and styrenics in extrusion and
injection moulding. These are based on blends of organic acids and carbonates, and have
the FDAs generally accepted as safe status for use in contact with food. These blowing
agents are said to provide fine celled foams and smooth surfaces in extruded film, sheet,
profiles and moulded toys and furniture.

Also from Rit-Chem, Extend-7 comprises endothermic sodium bicarbonate blended with a
modified exothermic azodicarbonamide. This blowing agent is aimed at markets requiring
good colour retention, even in the presence of flame retardants.

Uniroyal offers Celogen 754-A, an azodicarbonamide with applications in moulded and


extruded flexible PVC and TPEs. This agent is based on azodicarbonamide activated with
an innovative system rather than the conventional zinc and zinc stearates. The agent
activates over a broad temperature range quoted as 170205 C yet remains efficient in
gas generation (180200 cm3/g).

Other applications for blowing agents are in rotational moulded parts and, more recently,
foamed blow moulding has been used to achieve weight reduction, increase wall
thickness, increase stiffness (at the same amount of resin), improve mould filling and to
provide insulation. Endothermal systems give good results in foam blow moulding due to
the production of fine cell structure (good nucleation) and slow gas release during the
process. In rotational moulding, a variety of blowing agents have been used. The
traditional blowing agent for rotational moulding is p,p-oxybis(benzenesulphonyl
hydrazide) (OBSH), but the endothermic or mixed systems are said to be good substitutes
due to the decomposition kinetics and their approval in many instances for use in contact
with food.

References

1. Protecting the Global Ozone Layer, Montreal Protocol Unit (New York), 1998,
available on the Internet at http://www.undp.org/seed/eap/montreal/index.htm#six.

2. Handbook on Essential Use Nominations, Technology and Economic Assessment


Panel, UNEP, 1994.

3. D.J. Williams, L. Chin, M.C. Bogdan and P.B. Logsdon, Proceedings of Utech Asia
99, Singapore, Appliance Paper 4.

4. Urethanes Technology, 1998, 15, 5, 38.

23
Polymer FoamsTrends in Use and Technology

5. L. Zipfel, P. Dournel and W. Kruecke, Proceedings of Utech Asia 99, Singapore,


Building and Construction Paper 7.

6. A. Albouy, J-D. Roux, D. Mouton and J. Wu, Cellular Polymers, 1998, 17, 3, 163.

7. Global Comparative Analysis of HFC and Alternative Technologies for Refrigeration,


Air Conditioning, Foam, Solvent, Aerosol Propellant and Fire Protection Applications,
Final report to the Alliance for Responsible Atmosphere Policy, Arthur D. Little, Inc.,
August 1999, http://www.arap.org/adlittle/9.html.

8. E. Occhiello, L. Fedili and O. Grillot, Proceedings of Utech Asia 99, Singapore,


Automotive Paper 8.

9. W. Santos, Chemical Marketing Reporter, 1995, 24, SR14.

10. Modern Plastics 1998, Mid-November, Foaming Agents, C-78.

11. D. Scholz, Proceedings of Blowing Agent Systems: Formulations and Processing,


Rapra Technology Limited, Shawbury, UK, 1998, Paper 10.

12. G.L.A. Sims and W. Sirithongtaworn, Cellular Polymers 1997, 16, 4, 271.

24
Polymer FoamsTrends in Use and Technology

4 FLEXIBLE POLYURETHANE FOAM

4.1 Introduction

The term polyurethane is used to designate the many polymers resulting from the
polyaddition reaction of polyfunctional isocyanates with compounds containing at least two
hydroxyl groups. The predominant group resulting from this reaction is a urethane:

- NH - CO - O -

However, other groups may be formed (e.g., urea, amide, biuret, allophanate, ether and
ester linkages), and there is considerable scope for choosing the isocyanate and polyol
compounds used for the reaction. Hence, polyurethane is a generic term used to describe
a wide range of polymers with different structures and properties.

Polyurethane foam divides readily into two categories: flexible (including semi-rigid) and
rigid. Rigid foams result from the reaction of polyfunctional isocyanates with low molecular
weight polyols having three or more reactive hydroxyl groups. This leads to close-meshed,
crosslinked, polymer structures with mainly closed-cell morphology. The crosslinked
structure is usually further enhanced by using excess isocyanate, leading to additional
crosslinking points through allophanate, biuret or isocyanurate groups (see Section 5).
Flexible polyurethane foams have open-cell morphology and result from the reaction of
long chain triols and water with isocyanates, producing a wide meshed elastic network.
Crosslinking takes place both chemically (triols reacting with polyfunctional isocyanates)
and physically (by phase separation into generally amorphous rigid urea segments and
flexible polyol segments).

Processes for the production of flexible polyurethane foam are essentially slabstock
foaming and moulding. Slabstock foaming produces large blocks of foam by a continuous
process in which the reaction mixture is dispensed onto a conveyor, allowed to foam, and
then cut into blocks up to 60 m in length. These are stored for at least 24 hours and then
cut to the required shape. Moulded foams are produced by dispensing the reactive mix
from a metered dispenser into a mould which may be open or closed. The final desired
shape is produced during foaming and no further cutting is necessary.

4.2 Materials

4.2.1 Isocyanates

The two most widely used isocyanates are diphenylmethane diisocyanate (MDI) and
toluene diisocyanate (TDI).

Monomeric MDI (MMDI) exists in two isomeric forms: 2,4-MDI, and 4,4 -MDI. Both are

solid at room temperature, the latter with a tendency to dimerise.

Prepolymers with terminal -NCO groups are made by reaction of a polyol with excess
isocyanate. By this process, part of the addition reaction is carried out in advance. This
gives two advantages: a lower vapour pressure of isocyanate to improve the working
environment and better control of processing.

The more important form of MDI in terms of volume is polymeric MDI (PMDI), a mixture of
isocyanates with two or more aromatic rings remaining in the distillation residue. PMDI is

25
Polymer FoamsTrends in Use and Technology

a yellow to brown liquid with a higher functionality than MMDI but, owing to the lower NCO
content, of lower reactivity.

TDI is a colourless liquid and is commercially available as a mixture of the 2,4- and 2,6-
isomers in a ratio of 80:20 (TDI T-80) or 65:35 (TDI T-65).

Other isocyanates are available, such as, 1,6-hexamethylene diisocyanate, isophorone


diisocyanate and tetra methyl xylene diisocyanate. These are used for special applications
such as light, weather and heat resistant coatings, but have little application in flexible
foams.

Isocyanates may be modified by including linkages such as allophanate, carbodiimide and


isocyanate to control reactivity and lower vapour pressure. They may also be blocked by
reaction with compounds containing labile hydrogen atoms, e.g., phenols and
nitrophenols. Blocked isocyanates have the advantage of being inert at room temperature
but liberate free isocyanate groups for reaction when the temperature is raised. This
technology has application in heat activated coatings, but again, is not commonly used for
foam production.

4.2.2 Polyols

There are two main classes of polyol used in the manufacture of flexible polyurethane
foam: polyethers and polyesters. Polyester-based foams have good mechanical
properties but only moderate hydrolytic stability. Polyether-based foams are more
hydrolytically stable but are prone to oxidation.

4.2.2.1 Polyether Polyols

Polyether polyols are produced by the alkali-catalysed polymerisation of ethylene and


propylene oxide using low molecular weight di- and polyfunctional alcohols or amines as
initiators. The structure of the polyol, and hence the processing and properties of the PU
products, can be controlled by selecting the length (molecular weight) and composition of
the polymer chains and by the functionality of the initiator molecule. For flexible foams,
polyether polyols based on trifunctional initiators such as glycerol or trimethylol propane,
and with molecular weights around 6,000 g/mol, are generally used.

Potassium hydroxide (KOH) is commonly used as a catalyst for the production of


polyalkylene oxide, but there are side reactions which result in the formation of vinyl-
terminated monols. This causes difficulties in the production of polyols with molecular
weight greater than 5,000 g/mol (which give greater flexibility and softness), and there has
been work in the past to find alternative catalysts which can produce higher molecular
weights. Asahi Glass offers its new generation Preminol polyols with a narrow molecular
weight distribution and low monol content which are claimed to give products with
excellent properties with MDI or TDI. These polyols are aimed at the automotive market
for seat cushions.

Polyether polyols are also available in various modified forms, e.g., graft polyether polyols
(polymer polyols, copolymer polyols) first developed by Union Carbide, and polyurea
dispersion polyols (PHD polyols) developed by Mobay Corp.

Graft polyether polyols include acrylonitrile-grafted and styrene/acrylonitrile-grafted


materials. When first introduced, graft levels were about 20%, but polyols with graft levels
up to some 50% are now commercially available. Dow Chemical offers its Specflex range

26
Polymer FoamsTrends in Use and Technology

of such polyols for automotive seating applications. Shell Chemicals has developed new
polymer polyols using its POSTech process technology. These polyols (e.g., Caradol
MD30-02 and more recently, Caradol SCF 50-03) are said to be suitable for the
production of the complete range of high load-bearing slabstock foams. Asahi Glass has
introduced a polymer-dispersed polyol, UC-801, for use in automotive seat cushions.
Acclaim polyols, from Arco Chemical, are said to improve toughness and other properties
in polyether slabstock and moulded foam systems.

4.2.2.2 Polyester Polyols

Polyester polyols are the reaction products of adipic acid or phthalic anhydride with
aliphatic diols containing up to 6 carbon atoms or with oligo ether diols or triols (e.g.,
glycerol or trimethylol propane). Although they have good mechanical and oxidative
stability, they are less hydrolytically stable than polyether polyols and also more costly.
They are used in smaller quantities for specialised foam applications, e.g., shoulder pads
for clothing to provide resistance to dry cleaning.

4.2.2.3 Other Polyols

Polyols are available from certain vegetable oils containing hydroxyl groups such as
castor oil. These were used originally for the production of semi-rigid foams (now replaced
by polyether polyols). As these polyols come from a renewable source, there is some
recent research interest from an environmental standpoint. A partnership of BASF, Hobum
Harburger Fettchemie and Empe Werke, in a research project sponsored by the German
federal agricultural ministry, has developed plant-based polyols and associated
technology to produce PU. The moulded parts produced are claimed to be competitive in
price and quality with petrochemical-based products. However, there is some way to go
before properties are acceptable for demanding applications and use of these materials is
limited.

Shell Chemical has a range of saturated, linear hydrocarbon-based diols consisting of


ethylene/butylene copolymers with narrow molecular weight distribution and terminated by
primary hydroxyl groups, termed Kraton Liquid Polymers. The polyols have been
evaluated in production of both solid and foam PU. Materials are said to have good
hydrolytic stability and a broad service temperature range.

4.2.3 Blowing Agents

The main blowing agent in flexible polyurethane foam production is CO 2 produced by


reaction of the isocyanate groups with water.

Other gas producing reactions have been described, for example, the reaction of
carboxyl-terminated polyether oligomers with isocyanate groups to liberate CO2 and the
reaction of formic acid with isocyanate to produce CO and CO2. However, these are not in
commercial use for reasons of cost and performance.

The addition of physical blowing agents in the form of low molecular weight liquids with
low boiling points is advantageous in foam production; for instance, the system viscosity is
lowered facilitating pour-in-place moulding and the reaction exotherm is mitigated by
evaporation of the blowing agent reducing discolouration and the risk of fire. Also, in rigid
closed-cell foams, physical blowing agents remain in the foam for long periods up to the

27
Polymer FoamsTrends in Use and Technology

end of the products useful life to confer enhanced thermal insulation, but this is not the
case in open cell flexible foams.

In Section 3, physical blowing agents are listed and described in some detail. Essentially,
CFCs were the substances first used to aid the production of flexible polyurethanes,
specifically CFC-11. However, CFCs have been phased out in developed countries in
compliance with the Montreal Protocol. Methylene chloride has also been used for a long
time and since it has no ozone depleting characteristics, it is acceptable under the
Montreal Convention. However, in some countries there are occupational and
environmental concerns, and its use is being increasingly restricted. In the USA, in 1997,
workplace exposure levels for methylene chloride were reduced 20-fold (to 25 ppm) by the
US Occupational Safety and Health Administration and an air pollution ruling by the US
Environmental Protection Agency is intended to reduce emissions from foam plants (such
emissions are estimated to comprise 98% methylene chloride) by 70%. Whilst existing
plants have until October 2001 to comply, new foam plants must comply from the moment
they come on stream. Hence, substantial work has been done to identify satisfactory
alternatives to CFCs and methylene chloride. These have focused on:

HCFCs, such as HCFC-141b, which are generally regarded as an interim measure as


they still have an (albeit small) ozone depletion potential and are due for phase-out
over a defined period. HCFCs are more expensive than CFCs or methylene chloride.

HFCs (e.g., HFC-134a or HFC-356), which have zero ozone depletion potential but
are even more expensive than HCFCs.

hydrocarbon mixtures, which can be selected to have appropriate volatility


characteristics but are flammable and explosive in mixtures with air. Although in
theory there should be no residue in the flexible foam (as it is open cell and the
blowing agent should rapidly diffuse out), in practice it appears that FR-performance
of the foam deteriorates if hydrocarbon blowing agents are used and the FR
requirements of furniture, for example, can no longer be met.

liquefied CO2, which requires modified dispensing equipment to handle the


pressurised gas and formulation changes to ensure adequate cell nucleation.

In rigid polyurethane foam, the use of HCFCs and, in the future, HFCs, seems to be the
route producers are taking to retain insulating properties whilst complying with the
CFC/HCFC phase-out requirements. In flexible polyurethane foam, where insulation is not
a significant requirement, the initial response was the omission of the CFC physical
blowing agent and reliance on the reaction of water with isocyanate (chemical CO2
generation) alone. This requires careful control and monitoring of the reaction exotherm to
avoid scorch and to minimise fire risk during production. More recently, direct injection of
liquid CO2 has been increasingly used (see Section 4.3). Methylene chloride remains in
use in countries including the UK.

4.2.4 Catalysts

Two types of catalyst are commonly used in formulations for the production of flexible
polyurethane foams:

tin catalysts, such as dibutyltin dilaurate, which promote the reaction between
isocyanate and hydroxyl groups, i.e., the formation of the urethane linkage, and

28
Polymer FoamsTrends in Use and Technology

tertiary amine catalysts, which catalyse mainly the water-isocyanate reaction, i.e., the
gas generating reaction, but also catalyse the hydroxyl-isocyanate reaction to some
extent.

The two catalyst types show some synergetic effects and are combined to control the
degree of blow versus growth. The most commonly used combination is triethylene
diamine and tin octoate.

Delayed action catalysts were introduced to enable adjustment of the reactivity profiles in
both rigid and flexible moulded foam and catalyst development continues so as to provide
the ideal balance of isocyanate reactions.

Nitroil Europe GmbH has developed two amine catalysts which are claimed to increase
significantly the blowing power of conventional flexible foam formulations, resulting in
lower foam density and higher foam hardness without significant negative effects on other
foam properties. One of these catalysts also reduces the odour of the end product. A new
delayed action catalyst from Air Products and Chemicals, Dabco BL-93, is reported to give
improved properties in flexible moulded PU foams. The same company offers stabilising
additives, such as Dabco 33LV, for use with conventional tertiary amine gelling catalysts.
These additives are said to give dramatic improvements to dimensional stability and
processibility as well as improving physical properties.

Another recent area of development has been non-fugitive gelling and blowing catalysts
which chemically bind into the foam matrix and cannot migrate out of the foam after the
reaction is complete. Such materials meet an emerging automotive need for lower and
ultimately zero emissions of PU foam additives into the atmosphere. Such emissions can
lead to odour and fogging (deposition of volatile components on interior surfaces of
vehicles, particularly windscreens), as well as being environmentally undesirable. Work on
this type of catalyst has been reported by Air Products and Chemicals Inc. [1]. A similar
study has been reported by Nitroil Performance Chemicals [2], where replacement of
traditional catalysts such as triethylene diamine with a reactive product (PC CAT HP1, N-
aminopropylimidazole) resulted in a 20% reduction in VOCs. In combination with a
reactive blowing catalyst (PC CAT BDP, bis(dimethylamino)-2-propanol), VOCs were
reduced by 50% although at the expense of ageing properties under conditions of high
humidity.

4.2.5 Surfactants

Surfactants for polyurethane foams have a major influence on cell morphology and control
the cell size and degree of open structure. They also act as emulsifiers and foam
stabilisers and are normally based on copolymers of dimethylsiloxane and alkylene
oxides. The copolymers may have a linear, branched, or pendant structure, with their
function controlled principally by the ratio of ethylene oxide, propylene oxide and silicone
groups.

An important area of surfactant influence is cell opening. In flexible polyurethane foams,


the cells are required to be closed during expansion so as to retain the blowing agent, but
to open when expansion is complete and gelification has taken place (i.e., when the
polymeric crosslinked network has formed). At this stage, the foam structure is stable, but
if CO2 is held in a closed-cell structure, the faster diffusion rate of CO2 out of the cells
compared with the diffusion rate of air into the cells, will result in a partial vacuum which is
incapable of being sustained by the flexible network and the foam will shrink and collapse.
By opening the cells, foam shrinkage and collapse is prevented. This contrasts with rigid

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Polymer FoamsTrends in Use and Technology

polyurethane foam where the stiffness of the foam resists collapse and it is important to
retain auxiliary blowing agents in closed cells to enhance thermal insulation.

There is a wide range of surfactants available to suit various foam requirements, and
development continues to expand the range and enhance performance. For instance,
Nitroil offers several silicone surfactants: PC STAB SN81 yields very high air permeability
in conventional slabstock foam production and PC STAB SN82 is particularly suitable for
use in climatic conditions of high humidity and can be used with a wide range of
formulations including chalk-filled systems and systems using methylene chloride as an
auxiliary blowing agent.

The advent of liquid CO2 as a blowing agent has required surfactant development to
ensure initial nucleation to obtain a fine cell structure and thereafter to regulate the
expansion of the foaming mix during the evaporation of the CO2. Large bubbles and a
rapid uncontrolled gas release have to be avoided, otherwise there may be pin holes and
splits in the final product. In slabstock foam produced with injected CO2, it has been
pointed out that the rapid pressure drop between the mixing head and the laydown device
requires all the gas bubbles (which produce the final foam cells) to be generated in a very
short space of timeparts of a second.

PC STAB SN74 and PC STAB SN76 were developed by Nitroil to meet the special
requirements of the liquid carbon dioxide method. Witco Organosilicones recommends its
Niax L-703, SC-154 and SC-155 surfactants for use in liquid CO2 systems, giving good
nucleation and fine cell structure. OSi Specialities SA has also reported silicone stabilisers
for CO2 blown systems. Th. Goldschmidt offers silicone polyether stabilisers suitable for
CO2 blown PU foams: Tegostab B8232 for FR systems, the universal surfactants
Tegostab B8220, which combines very high activity with good nucleation, and Tegostab
B8240 which has lower activity but higher nucleation. These have all been tested both in
the laboratory and in commercial machines. Silicone stabilisers suitable for CO2 systems
are also available from other manufacturers, e.g., Nitroil.

4.2.6 Scorch Inhibitors

Both the polymerisation and the decarboxylation (blowing) reaction in polyurethane foam
production are strongly exothermic and thermo-oxidation can occur as a result. This is
usually manifested by discolouration, known as scorch, although it is not unknown for
temperatures to reach the foam ignition point, resulting in fire, if conditions are abnormal.
For this reason, large blocks of foam (slabstock) are normally monitored immediately after
manufacture until the exotherm is complete.

The environmental concerns which have led to the elimination of CFCs have exacerbated
the scorch problem, since the evaporation of the CFC auxiliary blowing agent is a useful
way of absorbing the heat and reducing the maximum temperature reached during
manufacture. Replacement of CFC by additional CO2 from the water-isocyanate reaction
adds to the exotherm and further increases the scorch problem.

The usual method of controlling scorch involves the addition of one or more antioxidants
of which butylated hydroxytoluene (BHT) is the one most commonly used. However, the
volatility of BHT is becoming an increasing problem in its use, particularly for
manufacturers of low density, high water foam where exotherms are greatest. Migration of
BHT occurs from the centre of the bun where temperatures are highest (and the need for
scorch inhibition is greatest). The material can evaporate from the foam and deposit on
equipment, causing build-up problems requiring periodic maintenance. In the USA, there

30
Polymer FoamsTrends in Use and Technology

is also concern that BHT could be a sensory irritant when used in carpet cushioning in the
home and polyol producers are reported to be replacing BHT with other antioxidants.

Improved performance is seen [3] with phenolic antioxidants of lower volatility than BHT.
The lower volatility is achieved by increasing molecular weight through the addition of long
hydrocarbon chains or by coupling four phenolic moieties. Lowinox DBNP and Anox BF
are liquids leading to easier handling and metering in polyurethane systems. The
materials studied (products of Great Lakes Chemical Corporation except where noted)
were:

Lowinox DBNP (dibutyl nonyl phenol),


Anox BF (phenol, with alkyl and long chain ester substituents),
Anox PP18, Irganox 1076 (Ciba Speciality Chemicals) (as Anox BF, with longer chain
ester), and
Anox 20, Irganox 1010 (Ciba Speciality Chemcials) (tetra phenolic ester).

Lowinox DBNP and Anox BF combine low volatility and good anti-scorch with the
advantages of a liquid product form. Anox PP18, Irganox 1076, Anox 20 and Irganox 1010
have lower volatility than BHT and better scorch performance.

Dow Polyurethanes has introduced BHT-free polyols for use in slabstock foam,
commenting that BHT can cause foam to yellow and discolour fabrics, a problem
significantly reduced with its new antioxidant package. Bayer has introduced BHT-free
polyols for slabstock polyurethane foam. Mutranol 7059 is a polyoxypropylene whilst
Mutranol 7100 is a long-chain version of 7059 aimed at automotive foams. As with the
Dow polyols, these BHT-free materials are said to reduce the fabric yellowing caused by
contact. Shell has described its BHT-lean polymer polyol, produced by its POSTech
technology. This product, designated MD32-04, is said to offer good properties in TDI
formulations for automotive seating.

Further scorch protection can be achieved by the addition of preventative or secondary


antioxidants which act at the initiation stage of degradation through a radical chain
mechanism. These prevent the formation of radical products by reacting with
hydroperoxide to form non-radical products, and are commonly based on thioesters or
phosphites.

Ciba Speciality Chemicals has developed a new lactone-based stabiliser, HP-136, which
can be used in flexible PU slabstock manufacture, and offers scorch inhibitors developed
specifically as BHT replacements in PU slabstock foam:

for polyether polyol foams, a combination of liquid Irganox 1135 hindered phenol and
liquid Irganox 5057 aromatic amine in a ratio of 4:1 or 2:1, and
for polyester polyol foams, a mixture of Irganox 1135 hindered phenol and Irgafos
DDPP phosphite.

Th. Goldschmidt has recently added two new anti-scorch agents to its portfolio: Ortegol
AO 1 and Ortegol AO 2.

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Polymer FoamsTrends in Use and Technology

4.2.7 Flame Retardants

Polyurethane foams are inherently flammable, and substantial work has been done to
enable flexible foams to meet the strict flammability regulations which now exist in the
areas of foam furniture and public transportation. Rigid polyurethane foam for use in
building insulation also has to meet strict flammability regulations.

In characterising the flammability of polyurethane foam, the important factors are:

ease of ignition,
rate of surface flame spread,
amount and rate of heat release,
amount and rate of smoke evolved,
burning time, and
toxicity of combustion gases.

Whereas rigid polyurethane foam can be formulated to have substantial fire resistance
without the addition of flame retardants, flexible polyurethane foam requires additives to
control fire behaviour. Such additives may be halogenated compounds, such as
brominated polyethers, dibromopropanol and dibromoneopentyl glycol, often used in
conjunction with antimony trioxide as a synergistic additive. Antimony/halogen systems
operate by quenching radical reactions in the gas phase after release from the foam by
the heat of the fire. An alternative additive is alumina trihydrate (ATH) which operates by
the endothermic release of water which reduces the exotherm and dilutes the flammable
decomposition gases. Residual ATH may also offer some surface layer protection. These
additives affect the foam properties, and an ideal flame retardant which eliminates
significant flammability with little or no effect on foam properties remains to be found.

Combustion modified high resilience (CMHR) foam was introduced by Mobay Chemical in
1983 and is based on a polymer polyol with TDI. It originally contained substantial
amounts of ATH together with other flame retardant additives. The use of melamine as a
flame retardant for CMHR foam was proposed by BASF, and other types of nitrogen-
containing compounds such as cyanamid, guanidine, melamine-formaldehyde condensate
and aminoplast resins have appeared in patents, but are not known to be in use.

In the UK, regulations for furniture flammability are governed by BS 5852, Part 2, Source
5. Various formulations have been listed [4] which will meet this test, which is satisfied by
CMHR foams. Generally, some 2830 pphr of melamine, together with 814 pphr of flame
retardant (a phosphohalogenated compound in the disclosed formulation) are required,
depending on the formulation. However, by using modified isocyanates developed by
Enichem, it was possible to reduce melamine levels to around 15 pphr and omit the flame
retardant. British Vita has a foam development, Reflex, that is claimed to meet the UK fire
regulations without the use of melamine or other flame retardant fillers. The technology,
which is undisclosed, accounts for a significant part of British Vitas furniture foams
business.

The superior thermal and hydrolytic stability of brominated diphenyl oxide flame
retardants, compared with halogenated phosphates, has made the former a commonly
used additive in flexible polyurethane foams. Nevertheless, there are concerns regarding
toxicity and effects on the environment, although there is little hard evidence to support
such fears and a 1995 European Union initiative to ban brominated diphenyl oxide flame
retardants has been withdrawn. A new (non-diphenyl oxide) aromatic, bromine, flame
retardant additive, CN-2065, from Great Lakes Chemical Corp., is claimed to give
excellent scorch resistance and no centre softening in high resilience (HR) foam. The CN-

32
Polymer FoamsTrends in Use and Technology

2065 additive has also been found to enable flame lamination of polyether-based foams,
which is difficult in foams containing brominated diphenyl oxide. Clariant has its Exolit
range of non-halogenated additives for flexible polyether slabstock and moulded foams,
mentioning specifically applications in the automotive industry. Exolit OP 550 is a low
fogging additive for polyether slabstock foams where discolouration is critical; Exolit OP
560 has emission characteristics to comply with the latest VOC and fog requirements
according to DaimlerChryslers test procedure PB VWT 709; Exolit AP 422 is aimed at
polyester foams and is claimed by the manufacturer to have a low scorch effect and good
ageing resistance and emission performance. Exolit OP flame retardants are non-
halogenated liquid phosphorus polyols.

4.2.8 Mould Release Agents

Release agents for moulded foam products are in common use. As many are based on
hydrocarbon carriers, they contribute to the amount of VOCs released during processing.
Water-based release agents are much more environmentally acceptable and are currently
being used by both Ford and BMW. They have been found to be suitable for MDI, hot cure
and TDI T-80 formulations. Some recent advances have been reported by Klueber
Chemie. The Klueber Aqua release agent T-80 is said to perform well with cold cure
moulded PU foam with no VOC emissions and with lower build up/longer cleaning cycles
than are typical of solvent-based systems.

4.3 Processes

4.3.1 Basic Foam Processes

Urethane foams can be made by the one-shot, semi-prepolymer (quasi-prepolymer), and


prepolymer processes.

In the one-shot process, which is commonly used for both flexible and rigid foams, the
reaction components are supplied separately to the mixing head or, in order to achieve
greater viscosity control and mixing accuracy, some of the components such as polyol,
catalyst, auxiliary blowing agent (if any) and water may be premixed. All reaction takes
place after mixing, which is done at ambient temperature.

In the semi-prepolymer or quasi-prepolymer process, polyol is pre-reacted with excess


isocyanate to provide a low molecular weight, isocyanate-tipped prepolymer. This is fed
as one stream to the mixing head with the second stream comprising further polyol and
other components, as in the one-shot process. The semi-prepolymer method has the
advantages of easy processing, stabilised foam rise and lower exotherm, and is
sometimes preferred for these reasons despite the additional cost of semi-prepolymer
preparation.

In the prepolymer process, polyol and isocyanate are reacted in the final required ratio to
give a high molecular weight, isocyanate-tipped prepolymer. This is mixed with water,
catalyst, surfactant and any auxiliary blowing agent to produce the foam. Since the
prepolymer is of high viscosity, with poor flow characteristics, and the isocyanate available
for reaction with water is limited, this method has not until recently been used significantly
for foam manufacture. However, ICI and BASF have MDI prepolymer systems for
slabstock production.

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Polymer FoamsTrends in Use and Technology

4.3.2 Slabstock Production

There are basically three processes currently used for the production of slabstock foam.
These are the Vertifoam process, the Maxfoam process and the conventional (inclined)
conveyor process.

The conventional conveyor process is the method originally developed for slabstock
production from polyester polyols, later modified for use with polyether polyols. The
reaction components are dispensed from a mixing head onto a moving conveyor which is
inclined downwards at an angle of 0.5 to 4.5 degrees. The rising foam is contained by
sidewalls or side conveyors which are continuously lined with paper or polyethylene film.
The angle of inclination and the conveyor speed are controlled with respect to the foam
reaction profile, foam density and output from the mixing head, so that the top surface of
the foam remains essentially level. Nevertheless, a disadvantage of the conventional
process is that the block shape is domed, although this can be improved using a flat top
system (e.g., the Draka and Petzetakis process). Block sizes are typically 2.2 x 1.2 m and
2 to 60 m, in length. An annual output of some 700 tonnes from one line can be achieved
with single shift working. Similar processes allowing flat top bun production are the
Hennecke, Planiblock and Econofoam systems.

Foam properties are generally good, with absence of pin holes and acceptable property
distribution throughout the foam. Both polyester and polyether foams can be processed.
Disadvantages, in addition to the dome shape which can result in high levels of waste
when cutting, include high machine cost and losses at grade change due to high running
speeds. Longer runs are required in order to minimise start, stop and grade change
losses.

The Maxfoam process was developed in the early 1970s to produce flat top slabstock
foam, and is probably the most used rectangular bun process. The reactive components
are fed from the mixing head into the bottom of a trough where the mix is evenly
distributed across the machine width and the initial reaction takes place. The expanding
foam flows from the top of the trough onto a fall plate which is continuously covered with
paper at a rate matching that of the subsequent conveyor. The slope profile of the fall
plate is adjusted to match the expansion of the foam and final block height. Vertical
papers line the sidewalls, moving at conveyor speed. The fall plate is set at some 70% of
final block height so that only 30% upwards expansion is required, reducing vertical
downward friction and resulting in a good block shape. Block sizes are similar to those of
the conventional process with conveyor speeds 35 m/min, giving similar annual
production rates to the conventional process.

The Maxfoam process gives good quality foam with even property distribution, though cell
structure (pin holes) is generally somewhat inferior to that of foam from the conventional
process. Blocks have a good shape, and hence there is less cutting waste. Equipment
costs and factory space are less, and there is less waste at grade changes. A
disadvantage is that polyester foams cannot be produced, and long production runs are
still necessary to minimise losses at start and stop.

The Vertifoam process was developed in the 1980s for the production of rectangular and
round foam blocks, and is licenced worldwide by Hyman International, UK. It is essentially
a continuous, vertically oriented, moulding process, producing blocks of well-controlled
shape. Hence, there is minimum subsequent cutting waste. Output rates are substantially
lower than those of the conventional and Maxfoam processes (some 60 kg/min at a
conveyor speed of 1.0 m/min). Reaction components are fed from a mixing head to a
bottom feed trough where the reaction starts. The expanding foam rises into a chamber of

34
Polymer FoamsTrends in Use and Technology

either circular or rectangular cross section which is continuously lined with paper or
polyethylene film. After passing through a heated cure section, the foam block is picked
up by vertically driven pin rollers which transport the foam through a cut-off machine
where blocks up to 3 m long are cut. The blocks are conveyed to ground level for
subsequent storage and processing.

Good quality foam is produced by the Vertifoam process, although cell structure is
generally inferior to that of foam from the conventional process. Property distribution
within the foam is excellent and the good block shape minimises cutting waste. Factory
space requirements are low provided there is adequate heightsome 11 m is necessary
around the machine. The low conveyor speeds and machine output result in minimal
losses at grade changes. Disadvantages include the greater control required for
operation, e.g., good temperature control of the expansion chamber is necessary, and
experienced operators are required. Polyester PU foams cannot be processed using this
process.

A recent development has been the Ultima process, developed by Beamech in 1994. This
combines the advantages of the Maxfoam and conventional processes by use of a
specially designed fall plate which permits both a Maxfoam profile and a continuous slope
between 0.53.5 degrees. A variable angle, variable height pour plate is also provided
prior to the fall plate, to allow an increased length primary expansion zone. The Ultima
machine, therefore, offers substantial scope for configuring to suit a wide variety of foam
formulations. Both polyether and polyester polyol systems can be processed using this
system.

Whilst TDI is the isocyanate mostly used for the production of slabstock foam, MDI-based
systems have been developed by ICI Polyurethanes and BASF. MDI-based systems have
a number of significant advantages over TDI systems including:

better working conditions due to lower isocyanate emissions and lower foam
exotherm,
fewer additives at only low levels, and
novel chemical recycling possibilities.

Problems in producing low density flexible foams with MDI arise from its low isocyanate
and high aromatic content. ICI claims to have overcome these problems with its new
technology which utilises two new (undisclosed) chemical intermediates.

The ICI technology, producing Waterlily water-blown MDI-based foams for applications in
mattresses and furniture, is said to produce very low VOC levels (<5 ppm) and especially
low levels of free isocyanate (<1 ppb). Only a small amount of surfactant is required, only
one catalyst (no tin salts required) and no auxiliary blowing agents. Exotherms are
reduced due to the use of prepolymer technology and to the presence of excess water
producing steam during foaming, so the maximum temperature at the centre of a typical
1.2 x 2.2 m bun is approximately 120 C. No special antioxidant packages are necessary
to prevent scorch/autoignition. The current grade range is from 30 to 80 kg/m3, and the
system has been proven with various conventional and Maxfoam production processes.
Such foams are claimed to have significant flame retardant properties, meeting the
Cigarette test (EN 1022-1), the Simulated Match test (EN 1021-2) and the German B2 test
(DIN 4102 part 1) without any added flame retardants. Foams have begun to appear on
the market in furniture and mattress applications and (in the USA) as prime carpet
underlay.

35
Polymer FoamsTrends in Use and Technology

It is claimed that BASFs MDI slabstock process, like ICIs, is capable of being run on
existing production facilities. It is based on the special prepolymer Lupranol VP9237,
which can be used either alone or in combination with polymeric MDI. Three classes of
foam can be produced:

HR foams in different density ranges,


polyester foams, and
viscoelastic or controlled recovery foams (CRF).

Formulations have been published [5] for all these classes based on BASF proprietary
components. The MDI-based foams are claimed to have faster cure rate, better
crushability, more open cells, improved slab geometry and lower hardness gradient
through the slab compared with their TDI-based counterparts although TDI-based foams
had some physical property advantages at low foam densities. The MDI technology is
seen as offering the possibility of expanding the foam product range by providing
additional variations in foam properties. Sales may be at the expense of TDI foams.

4.3.3 Use of Liquid Carbon Dioxide in Slabstock Foam Processes

The use of liquid CO2 as an auxiliary foaming agent in slabstock foams presents problems
in dispensing and mixing, and requires formulation changes for optimum results. However,
in recent years, machine developments have increasingly enabled foam manufacturers to
take this route to eliminate the use of CFC blowing agents. The three main processes are
the CarDio process, the Novaflex process and the Beamech CO2 process.

The processes involve:

in-line mixing of a precise amount of CO2,


thorough mixing of the components and good bubble nucleation, and
laydown of the frothed mixture on the conveyor with elimination of unmixed bubbles of
CO2 which can result in pin holes or chimneys.

In the CarDio process, metering of liquid CO2 is carried out with a specifically designed
pump. A CO2/polyol stream is subsequently passed to a CarDio mixing head where TDI
and water are added. Nucleation is assured by a mechanical nucleation device with in-line
addition of nitrogen; pin holes and chimneys are eliminated using proprietary laydown
equipment which provides for a progressive pressure drop in the laydown phase. This
critical laydown device controls the expansion of the liquid froth when the mix is exposed
to atmospheric pressure. The system is supplied in various configurations either as a new
foam machine or as a retrofit installation where the technology is grafted onto an existing
machine. In a retrofit installation, there is the possibility of using the Direct System where
the CarDio activator streams are supplied by high pressure pumps metering directly into
the high pressure zone of the system. Alternatively (and less preferably), an Indirect
System may be used if existing activator metering pumps are utilised.

It is claimed by Cannon that throughput of a CarDio plant is much lower than that of a
conventional or Maxfoam system, being typically 40 to 60 kg/minute, with conveyor
speeds of 1 m/minute to produce normal block sizes, (e.g., 1.2 x 2 m). This is similar to
the Vertifoam process, giving the advantages of Vertifoam, (e.g., reduced waste at grade
changes) without the height requirement. Plant length can be as little as 20 m compared
to 100 m and 75 m for a conventional and Maxfoam process, respectively. Cannon

36
Polymer FoamsTrends in Use and Technology

indicates that a full range of hard and soft foams, down to a foam density of 14 kg/m3, can
be produced with less manpower and with good plant economics compared with other
processes. The smaller plant size also gives benefits in that smaller volumes of exhaust
need to be removed and scrubbed and smaller volumes of factory air need to be
conditioned.

The Novaflex process, developed by Hennecke, is reported as the currently most widely
used CO2 system for slabstock foam [6].

Whilst the original development of CO2 processes was in response to environmental


pressures, it has been reported that properties can also be improved [7]. At comparable
hardness and density, CO2 blown foams have been found to have finer (average 500 m)
and more open cells with better strut formation than foams made using methylene chloride
as a blowing agent. The cell structures are less oriented and physical properties more
isotropic. Other tests found better compression set and greater resiliency, ascribed to
better phase separation of the hard segments in the polyurethane polymer.

There seem to be no problems in process operation, and in some respects the process is
less demanding than conventional ones. Much lower levels of tin catalyst are needed, and
there is less variation of catalyst levels between different grades giving greater stability in
operation during grade changes. The solvating power of CFC-11 and particularly
methylene chloride on the PU polymer is eliminated and there is also a significant cost
saving. Taking account of the lower expansion efficiency of methylene chloride, and (in
some countries and certain states in the USA) the environmental tax imposed on its
consumption, the net blowing agent cost of CO2 is said to be only 10% that of methylene
chloride.

4.3.4 Variable Pressure Foaming

Another route to the elimination of auxiliary blowing agents is use of variable pressure
foaming (VPF) in which the CO2 generated in the reaction causes additional expansion in
a lower pressure environment, reducing or eliminating the necessity for any additional
gaseous blowing agents. However, due to the high investment costs for the provision of
the necessary large volume foam containment vessel for pressure control, this technology
does not seem to be an ideal alternative. Nevertheless, it is reported to have been
adopted by Foamex International in North America which announced a $25 million
investment to more than double its VPF capacity. A comparison [8] of the systems
developed for environmentally friendly slabstock foam manufacture has concluded that
the VPF process shows advantages over the use of liquid CO2.

4.3.5 Moulding Processes

In the production of moulded polyurethane foam two main processes can be


distinguishedthe older, hot cure process and the more recent cold cure process.

In the hot cure process, the reaction mixture is dispensed from the mixing head into a
mould which may be open or closed. The moulds are then heated to temperatures of 160
C to 200 C to cure the foam, and then cooled to between 35 C and 55 C before
demoulding.

In the cold cure process, the mould temperature is held constant at a particular
temperature, between 35 C and 55 C, depending on the formulation. This necessitates
the use of more highly reactive polyether polyols, with hydroxyl numbers of 28 to 35

37
Polymer FoamsTrends in Use and Technology

(molecular weights 4,000 to 6,000 g/mol). The higher reactivity not only allows lower
mould temperatures but also permits use of the less reactive MDI, or MDI prepolymers, or
MDI/TDI mixtures, whereas in the hot cure process only TDI can be used.

Advantages of the cold cure process include lower energy consumption owing to the
absence of any need to heat and cool moulds, shorter cycle times, reduced mould wear,
the option of incorporating foam inserts and the possibility of using technologies such as
dual hardness foaming and back foaming. The hot cure process enables production of
foams with lower densities and better physical properties (higher elongation and tensile
strength), but the level of properties achievable with cold cure moulded foam is sufficient
for many applications.

Dual hardness foaming is frequently used for applications such as car seats in order to
provide a different (higher) foam hardness specification at the base and sides of the seat.
This is achieved in one operation by first dispensing the reaction mix for the softer seat
area into the mould. The mixing ratio is then automatically adjusted so that the later
portion of the mix which goes to form the base and sides of the seat is of a harder
formulation. Alternatively, a second mixing head is used to discharge a polyol component
yielding a harder foam which bonds seamlessly to the softer component.

Back foaming, or foaming in place, allows the production of cushioning which is combined
with a covering material during the moulding process. Formable covering material is
drawn by vacuum to conform to the mould profile. The reaction mixture is introduced into
the mould and expands to bond with the covering material. The product has the
appearance of a tailored fit cover without the time consuming and costly process of cutting
and sewing a covering material for subsequent fitting in a multi stage operation.

Cannon has introduced technology which provides a thermoplastic or polyurethane film on


one or both halves of a mould. A vacuum is used to hold the film securely without creases
or wrinkles whilst the polyurethane foam is dispensed and cured. The film may adhere to
the foam, becoming an integral part of the final product, or may act as a release layer. In
both cases, the foaming system makes no contact with the mould and mould cleaning is
minimised or eliminated. Adherent films may be thermoplastic polyurethane (good
properties but high cost), polyurethane film (low cost, cold cure only, poorer properties,
and requires corona treatment for adhesion), or a thermoplastic film developed by Cannon
which is claimed to combine good properties with low cost. This film is suitable for the hot
cure process only. No corona treatment is necessary for adhesion. If a release film
technology is to be used, polyethylene (no corona treatment) or a Cannon-developed
thermoplastic film can be used. Cannon offers advice on the most suitable film types.

The technology offers full automation (and hence low operating cost) for the production of
polyurethane moulded parts, and plants are in operation for the production of automotive
sound insulation parts, carpet back foaming and seat cushions. (In the production of
carpets or other products having a functional layer on one side, film is applied on the
opposite side of the mould to that contacting the functional layer.)

Hennecke has introduced two processes which are claimed to provide flexible foam
mouldings up to 20% lighter than those from conventional systems (and hence offering a
substantial cost saving if reasonable properties can be maintained):

The NovaForm process introduces carbon dioxide either continuously in liquid form
just before the mixing head by an in-line method or as a gas in solution with one of
the reaction components. Applications include any foam-in-cover process as the foam
will not penetrate the coverstock even at the delivery point to the mould.

38
Polymer FoamsTrends in Use and Technology

The VakuForm process, which uses no additional carbon dioxide but requires the
expansion of the reaction mix to be controlled by careful regulation of the internal
mould pressure. This process results in little foam waste, from escape through parting
lines or by overfilling. Applications are envisaged for automotive seating, headrests,
armrests and carpet backing in addition to sound absorbing foam for the recreational
and sporting goods industries.

The NovaForm process tends to produce an open-cell foam with good elastic and
recovery properties but with some pin holes, whilst VakuForm foams have a very fine
uniform cell structure giving high strength.

Formulations for moulded polyurethane foams vary substantially worldwide. They are
developed by foam producers, generally using a specific foam chemistry, to suit the type
of dispensing equipment available, the mould design, the desired processing conditions,
and the properties needed to meet the customers specification:

hot curebased on TDI and requiring elevated cure temperatures,


TM20-HRhigh resiliency foam based on an 80/20 blend of TDI isomers (2,4 and
2,6), together with polymeric MDI
TDI-HRfoams made using the 80/20 blend of TDI isomers, and
MDI-HRfoams made with blends of pure and polymeric MDI and/or prepolymers of
MDI.

There is also a minor class of formulations using crosslinker or modified forms of TDI. A
breakdown of global usage of these various chemistries is shown in Table 4.1.

Table 4.1 Global Usage of Alternative


Flexible Moulded Foam Chemistries
Chemistry %
MDI-HR 22
TDI-HR 37
TM-20 HR 16
Hot cure 22
Other 3
Source: [9]

These systems provide soft flexible foams for applications such as automotive seating.
Systems based on TDI or TDI/MDI blends generally have the advantage of low foam
density (giving weight and cost savings) and low viscosity (allowing easy flow to fill
complex mould shapes). MDI-based foams have short cycle times (giving enhanced
productivity), rapid post cure (allowing rapid handling and post production operations such
as trimming), high green strength (resulting in low demould defects), good hardness, and
the ability to change foam hardness within the formulation possibilities of a single basic
system by changing component ratios.

Reduction in weight by reduction in foam density is the most obvious route to lower costs.
However, it is clearly necessary to do this whilst maintaining an adequate level of
properties for the application; for automotive seating, foam hardness is of particular
importance. Using TDI T-80 as the isocyanate, a considerable increase in the copolymer-
polyol content is needed to compensate for the loss of hardness resulting from density
reduction. Production of foams having different hardness levels normally requires the use

39
Polymer FoamsTrends in Use and Technology

of two polyol formulations with different solids content (i.e., different levels of graft
polymer). Conversely, the hardness of MDI cold cure foams can be adjusted simply by
varying the proportion of polyol to isocyanate. In addition, the intrinsic hardness of MDI-
based foams is high enough to meet automotive specifications without adding a polymer
polyol. Density reduction with MDI-based systems however, is limited, with better physical
properties being available at low foam density from TDI systems.

Bayer offers a family of isocyanates known as TDI-HP (High Performance), produced by


TDI modification. It is claimed these isocyanates allow the production of moulded foams of
the TDI-HR type with the advantageous property profile of MDI foams but with lower
densities and improved flow. Compared with conventional TDI foams, these new
isocyanates are claimed to have much greater reactivity, higher intrinsic hardness and
dual hardness capability. Hardness adjustment requires much lower levels of copolymer
polyol. The materials are currently aimed at cold cure automotive seat mouldings.

As with slabstock foams, alternatives to CFC auxiliary blowing agents have been sought
in recent years. Cannon has developed two systems utilising liquid CO2:

The Cannoxide system for medium-high levels of CO2 (generally above 1%). The CO2
is metered and injected directly to the mixing head, and the level can be varied shot
to shot.

The EasyFroth system for medium-low levels of CO 2 (generally less than 1%). In this
case, the CO2 is premixed in either the isocyanate or the polyol reservoir and the
level is fixed.

In both systems, mixing heads optimised for CO2 have been developed.

Gusmer Admiral has introduced new technology using liquid CO2 injected directly into the
mixing head. The technology is being used commercially in Japan and is reported to be
both reliable and affordable. Moulders are able to stop and start injections of short
duration without altering the concentration of CO2 in the reacting mixture and without the
need for recirculation of the gas.

Ipianti OMS has developed CO2 systems for moulded polyurethane foam and concludes
that a gaseous CO2 system has advantages particularly in the ease and cost of retrofitting
with a premixing device independent of the high pressure foaming machine.

Formulations incorporating CO2 have been developed by EniChem for carpet backing,
automotive front seats and moulded furniture. Property changes within several product
groupings affected by the use of CO2 have been described [10]:

In carpet backing, use of CO2 resulted in a reduction in density allowing a decrease of


about 20% in the weight of material injected, lower hardness (but this is not critical in
carpet foam), and enhanced compression setexplained by the nucleating effect of
CO2 bubbles leading to more homogeneous cell structure

In the production of an automotive front seat, use of CO2 did not affect the skin of
cushion, and demould time was kept constant at 4 minutes. At 1.5% CO2 addition, a
reduction in density of 10% was achieved. Hardness was kept constant by adjustment
of isocyanate index (i.e., by increasing isocyanate levels to maintain hardness at the
lower density). Compression set was found to worsen (from 6.4% to 7.4%) or remain
unchanged, depending on formulation. Dynamic fatigue was not found to be affected
by density reduction, continuing to meet automotive requirements.

40
Polymer FoamsTrends in Use and Technology

A density reduction of 10%15% was found to be possible when using CO2 to


produce moulded furniture, depending on index. Hardness was found to decrease,
and could not be compensated for by use of higher index. Compression set and
dynamic fatigue remained essentially unchanged.

In these systems, the addition of CO2 not only resulted in a density reduction but, with the
right choice of formulation, it was also possible to maintain or even improve physical
properties.

Flexible polyurethane foam can also be produced by one-shot aerosol dispensing for
small-scale applications such as sealing. Baxenden has announced a material of this type
designated DP2009.

4.4 Recycling of Polyurethane Foam

Waste foam arises from two main sources: production waste from grade changes and
post-production trimming, and foam waste from the final product after completion of its
lifecycle. The amount of PU foam scrap produced in Europe each year is estimated at
100,000 tonnes [11]. The pressure to recycle materials has increased substantially over
the last decade and several processes are now available. Since polyurethane foam is
made from a wide variety of starting chemicals giving foams having widely different
structures, the chemical composition of scrap foam is not usually known, and recycling
technology has to take this into account. The technologies in use are rebonding,
regrinding and solvolysis.

4.4.1 Rebonding

This process has been in use for a considerable time. Scrap foam is shredded and mixed
with a PU-based binder to yield rebond foam. Scrap foam is said to be separated
relatively easily from automotive shredder residue (ASR) as it has a much lower specific
gravity than other components, but it is likely to be contaminated by air, dirt and water. It
has been reported [12] that some 9% of raw ASR is recoverable PU foam; this reduces to
about 6% after cleaning by solvent and detergent washing. Post-production operations in
slabstock foam production can result in as much as 25% waste. This source is much
cleaner than ASR foam. Moulding processes produce less scrap, but such foam presents
special problems as it is often mixed with other components such as textiles, glass fibre
and steel. As with ASR scrap, separation of the foam component has only recently being
given attention.

A major application for rebonded foam is in carpet underlay, particularly in North America.
Polyurethane foam scrap has been baled and shipped to North America in quantities
estimated variously as 70,000 tonnes per year [13] and 79,000 tonnes per year [14]. The
earnings from this are substantial, the economics apparently justifying shipping around the
world. However, it is predicted [14] that this trade will steadily decline due to a decrease in
the USA needs and the cost of long distance transport and other methods of recycling
have been or are being developed. Data [14] from the US Alliance for the Polyurethane
Industry indicates, in the USA, a total PU carpet underlay market in 1996 of 416 kt, of
which 383 kt is bonded foam waste (the remainder being virgin material). The bonded
waste comprises 345 kt of scrap and 38 kt of binder adhesive. The make up of the scrap
is:

non foam scrap, 6%


regrind scrap, 4%

41
Polymer FoamsTrends in Use and Technology

post-manufacturing moulded scrap, 10%


post-manufacturing slabstock scrap, 42%
post-consumer scrap, 23%, and
imported scrap (estimated), 23%.

4.4.2 Regrinding

Polyurethane foam scrap can be pulverised into fine particles with modern grinding
equipment. The regrind powder can be used as a filler in virgin systems at levels up to
10% although in a recycling process described by Leoben, Austria [15], levels up to 20%
are claimed to be achievable whilst maintaining a good level of foam properties.

Research at the Tennessee Technological University has shown [16] that powder of
average particle size 200 microns can be produced using a pressure shear pulverisation
process from cold-cured flexible polyurethane foam scrap derived from used automotive
seats and cushions. Compression moulding was used to produce samples from 100%
recycled powder with no binders or additives. Mechanical properties (elastic modules,
tensile strength and elongation) depended on particle size (being greatest at the lower
particle sizes) and were comparable to the properties of virgin solid elastomers based on
the same polyol/isocyanate system.

A study by Martel and Associates [17], of equipment for the reclamation of polyurethane
foam from automotive seats, concluded that a ring mill is the best option for accomplishing
the initial size reduction of automotive waste allowing for subsequent separation of the
foam.

4.4.3 Solvolysis

Waste polyurethane foam recovered from, e.g., automotive use, is of mixed quality and
variable properties and is not suitable for chemical recycling methods. Production waste,
however, is much more homogeneous, and solvolysis using glycols has been used with
rigid PU foam (see Section 5) to provide polyols for subsequent reuse. However, the high
levels of glycol necessary prevents reuse for most flexible polyurethane foam products
and polyurethane elastomers. BASF and Philip Services have opened a facility in Detroit,
Michigan, designed to recycle chemically moulded polyurethane products, including semi-
rigid materials, using BASFs patented glycolysis technology. Philip Services collects and
processes the polyurethane waste whilst BASF reprocesses the recovered polyols for
formulation into polyurethane systems.

Work by Regra Recycling GmbH and Elastogran GmbH has suggested that solvolysis of
flexible polyurethane foam using carboxylic acids could be an alternative method [18]. The
molecular weight of the main reaction products (esters, amides and imides), and hence
whether they are liquids or solids, depends on the temperature (the reaction temperature
required for completion at sufficiently high a rate is 180 C). The products are immiscible
in the polyether polyol reaction medium and are formed as a stable dispersion by the
incorporation of a grafting reaction into the process. Tests incorporating the products into
flexible foam formulations showed that even at 50% recyclate levels the effect on
processing (cream times, slab temperatures and foam volume) were only moderate and
good foam properties were obtained. At incorporation levels up to 30%, little change in
physical properties was found, whilst at the 50% level, tensile strength, elongation,
compression resistance and compression set were found to deteriorate by 5% to 10%.
The process has been operated on scales up to production levels, and a recycling plant is

42
Polymer FoamsTrends in Use and Technology

on stream to handle the production wastes of a flexible foam manufacturer. Plant


economics appear attractive.

ICI has developed a split-phase glycolysis process which operates on flexible MDI-based
foams. The technology produces two product streams. The main phase is a polyol
suitable for flexible foam production whilst the second phase contains the isocyanate
moieties which, after further processing, can be used in rigid PU foam manufacture. Trials
are in progress. If successful, it is planned to build a 5,000 t/y plant with ICIs partner in
this development, du Vergier Ltd.

A 10-year strategic review of the impact on the polyurethane foam industry of various
environmental and health issues has concluded [19] that recycling is necessary for sales
of polyurethane products to continue growing in an environmentally more conscious
society and that whilst initially there may be a reduced demand for sales of virgin material,
in the longer term demand for foam products should increase.

4.5 Properties of Flexible Polyurethane Foam

In many types of polymer foam, properties depend mainly on density. In polyurethane


foam, properties depend on many other factors, most of which are formulation variables.
Hence, this section includes examples of properties of some of the various types of
flexible polyurethane foam including some of the more recently developed systems.

Density is an important property for applications where weight must be minimised (e.g.,
the automotive market to improve vehicle performance and reduce fuel consumption). It
is, of course, necessary to maintain other appropriate properties at any reduced density.
Cost is very density dependent.

Hardness, resilience, and compression properties are important in mattresses,


furnishings, automotive seats, headrests, etc., since they affect the perceived comfort of
the product. These applications require properties to be maintained after multiple
compressions, and fatigue and set are used as measures of performance after extended
use. Compression and set properties are important not only for comfort applications but
also for packaging, energy and sound absorption, carpet underlay and shoe soling.
Automotive consoles is a further application where appropriate compression and good
recovery properties are needed. Most applications will look for a minimum level of strength
properties including tensile, tear and high elongation at break to ensure physical
deterioration during normal use is minimised.

Applications in furniture and mattresses require an assessment of foam comfort. Shell


Chemicals has suggested [20] that comfort requires both a soft initial feel and a high
degree of support and has defined a

foam comfort factor (ability of the foam to compress with only small forces) = Force at
20% compression/Force at 5% compression, and

foam support factor (ability of the foam to sustain and distribute the forces imposed by
significant loads) = Force at 65% compression/Force at 25% compression.

General purpose flexible foams have comfort factors around 1.1 with support factors of
around 2.2. Comfort factors of HR foams are in the region 1.3 to 1.9 with support factors
2.3 to 2.1 depending on density, cell structure, solids content and type. Shells CARATech
foams, formulated to provide a more linear stress-strain profile, and using a specially

43
Polymer FoamsTrends in Use and Technology

developed polymer polyol (Caradol SCF50-03), are claimed to have comfort factors
around 2.5 with support factors about 3.5. Properties are compared for TDI T-80 slabstock
foams in Table 4.2.

Table 4.2 Comparison of TDI Slabstock Foams


Property Foam Type
Conventional HR CARATech
Isocyanate index 107 95 100
3
Density (kg/m ) 39.3 38.2 40.7
Hardness CLD40 (kPa) 3.8 1.7 1.8
Hardness ILD40 (N) 156 63 74
Resilience (%) 51 55 61
Hysteresis (%) 20.5 18.8 22
Comfort factor 1.25 1.31 2.85
Support factor 2.09 2.89 3.55
Tensile strength (kPa) 100 102 98
Elongation (%) 190 182 156
90% Compression set (%) 4 6 6
Dynamic fatigue*
Thickness loss (%) 1 1 2
Hardness loss (%) 19 13 12
* Loss of thickness and hardness after constant load pounding
CLD = compression load deflection
ILD = indent load deflection
Source: [20]

High comfort and support are demonstrated by the CARATech foams, with a lower
elongation relative to conventional and HR foams.

Similar comparisons have been given [21] by Lyondell Chemical Worldwide Inc., for
slabstock foams formulated to give foam densities of 29 kg/m3 and the resulting properties
are compared in Table 4.3. In this case, the comparison is of conventional and HR foams
with foam made using Lyondells second-generation high performance, high resilience
(HPHR) system based on Ultracel Polyol 2000 which allows production of foam over a
wide density and firmness range without the use of auxiliary blowing agent.

Table 4.3 Comparison of Properties of 29 kg/m3 Slabstock Foams


Property Foam Type
Conventional HR HPHR
Resilience (%) 50 55 59
65% IFD (N) 240 280 311
Support factor 2.0 2.3 2.58
Tensile strength (kPa) 110 103 103
Elongation at break (%) 190 130 135
Tear strength (N/cm) 3.3 2.5 2.5
90% Compression set (%) 4.5 10 5
IFD = indentation force deflection
Source: [21]

The higher support factor and resilience of the HPHR foams is apparent from this data.

44
Polymer FoamsTrends in Use and Technology

The effect of TDI index on physical properties has been studied at Polytechnic Institute
and State University of Virginia [22]. Using a formulation with TDI T-80, a 2,700 molecular
weight triol with 6 pph water and no auxiliary blowing agent, it was found that as TDI index
increased the following trends in physical properties resulted:

hardness at 65% compression increases with TDI index,


tensile strength increases with TDI index,
elongation increases, except at the highest TDI index,
compression set is independent of TDI index, and
recovery from set is better (i.e., less permanent set) at high TDI index.

Examination of foam morphology indicated that the lowest index foam had better phase
separation than the highest index foam, supporting a view that the increased covalent
crosslinking resulting from high isocyanate indices causes imperfections in the hard
segment domains.

Data for MDI-based flexible slabstock foams [5] show the effect in these foams of
increasing water content (from 2% to 4.4%). As water content increases, so density
decreases (from 53 to 26.5 kg/m3) and physical properties deteriorate:

tensile strength decreases from 113 to 77 kPa,


elongation at break increases from 177% to 215%, and
compression set increases from 5.9% to 9.4%.

(Formulations were based on Lupranol 2040/4100 polyols).

Lower density can be achieved in the ICI Waterlily MDI foams by using liquid carbon
dioxide as an auxiliary blowing agent. Some properties are shown in Table 4.4 comparing
formulations using no CO2 and two different levels of CO2.

Table 4.4 Properties of MDI Slabstock Foams using Liquid CO2


as Auxiliary Blowing Agent
Property CO2 level (%)
0 2 3
3)
Density (kg/m 36 28.5 25.0
Hardness (CLD 40%) (kPa) 5.2 3.5 3.1
Resilience (%) 53 53 53
Tear strength (N/m) 161 137 122
90% Compression set (%) 7.2 7.2 7.0
Source: [23]

As can be seen in Table 4.4, resilience and set properties are maintained well at the lower
density resulting from higher CO2 levels, but tear strength and hardness are reduced.

General purpose flexible slabstock foams can also benefit from use of liquid CO2 as an
auxiliary blowing agent, and some published properties are shown in Table 4.5,
comparing foam produced using different auxiliary blowing agents.

The lower density foam produced using CO2 shows inferior set and elongation to that from
R-11, but hardness and resilience are well maintained.

45
Polymer FoamsTrends in Use and Technology

Table 4.5 Properties of General Purpose Polyurethane Foam


using Auxiliary Blowing Agents
Property Auxiliary blowing agent
None CO2 (1.3 phr) R-11 (7 phr)
Density (kg/m3) 43.5 32.5 34
Tensile strength (kPa) 85 70 70
Elongation at break (%) 135 165 220
Hardness (40%) (kPa) 4.4 2.5 2.1
Resilience (%) 55 53 48
90% Compression set (%) 2.2 3.1 2.8
Formulation - 2 phr water, 105 index
Source: [24]

Physical properties of flexible moulded polyurethane foams are affected by factors such
as skin thickness and degree of overfilling the mould in addition to formulation variables.

ICI Polyurethanes claims to have made advances in reducing foam density for automotive
seating applications. Some typical properties of low density all-MDI moulded automotive
foams are summarised in Table 4.6.

Table 4.6 Physical Properties of all-MDI Moulded Foams for Automotive Seating
Property Application
Front seat Trim Seat back
cushion
Core density (kg/m3) 60 32 35
Hardness 40% CLD (core) (kPa) 7.8 3.7 5.4
Tear strength (N/m) 300 190 210
Tensile strength (kPa) 155 105 127
Elongation (%) 125 90 92
50% Compression set (core) (%) 5.6 11.0 9.0
Fatigue test (BMW)
Height loss (%) 4.2 - -
Hardness loss (%) 11.4 - -
Corrected hardness loss (%) 21.2 - -
Source: [25]

An interesting comparison of some properties of moulded foam manufactured by the four


main chemistries has been made by Dow Chemical [9]. Using an isocyanate index of 100%
and foam chemistry to give a density of 45 kg/m3, fatigue properties (load loss, height loss
and relative retention of hardness) were measured under normal and tropical conditions for
hot cure, MDI-HR, TDI-HR and TM 20-HR systems. Results are summarised in Table 4.7.

Table 4.7 Comparison of Dynamic Fatigue Properties of Moulded Foam Systems


Property Formulation
MDI-HR Hot Cure TM 20-HR TDI-HR
A B A B A B A B
Height loss (%) 3.6 4.0 3.7 4.3 3.7 6.1 2.5 4.4
Load loss (%) 22 23 18 23 22 30 20 26
Retention of hardness 96 82 90 90 100 86 90 82
(% of original 50% IFD)
A = normal conditions, B = tropical conditions
Source: [9]

46
Polymer FoamsTrends in Use and Technology

The MDI-HR and TDI hot cure systems show better retention of properties in tropical
conditions than the other foams.

4.6 Markets and Applications

There is a continuous global trend towards concentration in the supply of raw materials
(i.e., polyols and isocyanates) with just five companies serving roughly two-thirds of the
market. These are BASF/Elastogran, Bayer (which recently acquired Lyondells polyols
business), Dow Chemical, Huntsman Polyurethanes (which has recently bought ICIs PU
business) and Lyondell Chemical Company. Consolidation of production and marketing
operations is the main priority for these producers in order to take advantage of size and
organisational efficiencies. However, where there are growth areas which are difficult to
supply from existing facilities, e.g., China and Korea, new plants are still being built.

It is worth noting that demand for isocyanates, which is representative of the demand for
polyurethane and polyurethane foam as a whole, is strong. In 1998, global demand for
MDI was 1.8 m tonnes with manufacturers running at 90%100% capacity [26]. In Europe
and the Middle East, demand was 760,000 tonnes accounting for some 42% of the total.
In Europe, Dow Chemical has forecasted an average growth rate for MDI of 6%7% over
the period 19972007 with TDI growing at 4%5% [27].

In Asia, growth of TDI demand has been estimated [28] at 15%20% annually and this
has resulted in several manufacturers moving to install plants in the area. These include
BASF with ICI and Nippon Polyurethane Industry (160,000 t/y MDI plant in China), BASF
with four Chinese partners (130,000 t/y TDI plant in China), Huntsman Polyurethanes with
BASF in a multiway joint venture in China, and Enichem with Qatar General Petroleum
(100,000 t/y TDI plant in Qatar). Mitsui in Japan plans to double its production of both MDI
and TDI by 2007 and also has planned increases at its plant in South Korea. Bayer has
bid for a second MDI and TDI plant in China. Korea Fine Chemical plan to double TDI
capacity to 66,000 t/y. However, the new plants will not be on stream for several years
and there is likely to be a shortfall of both MDI and TDI raw materials in the interim. China
is the biggest polyurethane market in Asia consuming some 80,000 t/y of MDI and 90,000
t/y of TDI in 1997 [29].

In 1998, global consumption of polyurethane, estimated to account for some 5% of the


total polymer market [30], reached 7.5 million tonnes, an increase of 8.6% over the 6.9
million tonnes consumed in 1996 [31]. There are, however, significant regional differences
as shown in Table 4.8.

Table 4.8 Consumption of Polyurethane by Region (kt)


Area Year
1993 1998 2003
NAFTA 1,866 2,413 2,999
Europe 1,732 2,461 2,958
Japan 450 522 601
Latin America 300 432 557
Asia Pacific (excluding Japan) 835 1,181 1,706
Rest of World 372 456 593
Total 5,555 7,465 9,414
Source: [31]
NAFTA = North American Free Trade Alliance Area

47
Polymer FoamsTrends in Use and Technology

Average annual growth rate was 6.1% during 19931998, but is expected to reduce to
4.7% up to 2003, with the greatest growth expected in Asia Pacific (8.9% growth during
the period 19982003).

In the NAFTA region, the USA accounts for 90% of consumption with an expected annual
growth rate of 4% over the next five years. The total foam market in the USA is expected
to grow at a rate of 1.3% annually with polyolefins, polyurethanes and PVC foams
increasing but polystyrene foams declining [32].

Some 70% of global polyurethane consumption is accounted for by four main sectors:
automotive, construction, furniture/mattress and technical insulation (i.e., thermal
insulation of refrigerators, containers, tanks and pipes). The remaining 30% is distributed
amongst a large number of specialist applications such as shoe soles, encapsulation
compounds, clutch elements and others. A breakdown by sector for 1998 is given in Table
4.9.

Table 4.9 Global Polyurethane Consumption by


Sector, 1998
Sector kt
Automotive 1,125
Construction 1,300
Technical insulation 40
Furniture and mattress 2,100
Speciality 2,200
Source [31]

A study released by the Alliance for the Polyurethane Industry indicated a growth rate of
3.1% for polyurethanes in North America (USA and Canada) during the year 2000 [33].
Total consumption in 1998 was 2641.8 kt, an increase of over 8% per year during 1996
1998. A breakdown by sector is shown in Table 4.10.

Table 4.10 North American Consumption of


Polyurethane by Sector, 1998 (%)
Sector %
Construction 26
Transportation 23
Furniture 10
Carpet cushioning 9
Appliances 5
Packaging 4
Bedding 4
Textiles and fibres 3
Tanks and pipes 3
Machinery 3
Foundry 2
Marine 1
Footwear 1
Wheels and tyres 1
Electronics 1
Other 6
Source: [33]

48
Polymer FoamsTrends in Use and Technology

Flexible polyurethane slabstock foam was the largest product type, accounting for 844 kt
(32%) in 1998. Flexible moulded foam amounted to some 265 kt (10%). In the USA, rigid
foam accounts for some 27% of the total market for polyurethane and hence total PU
foam production comprises around 70% of polyurethane production.

The other major sector for flexible polyurethane foam is in the furniture and mattress
industry. Although there is a niche market for latex foam and there is still widespread use
of sprung mattresses, it seems unlikely that polyurethane foam will be replaced by these
alternatives in present application areas. There is, however, substantial pressure on
prices which is exacerbated by the recent changes imposed on polyurethane foam
producers to meet environmental and flammability requirements resulting from the
Montreal Protocol and fire and flammability regulations. There is also a significant
dependence on fashion trends in the furnishings industry, e.g., use of low cost futon beds
and wooden lath support for mattresses.

An analysis of the (mainly Asia-Pacific) market [34] compared growth rates of flexible
polyurethane foam in furnishing and mattresses with GDP growth in various countries. In
countries with high GDP economies, the growth rate is low or zero. This is particularly so
in Japan where traditional sitting and sleeping habits are still preferred. However, in
rapidly developing economies (e.g., Indonesia), furniture and bedding foam consumption
is growing faster than GDP. An overall growth rate of 8% has been projected for the Asia-
Pacific area. In India, demand could double over the next few years to 78,600 tonnes per
year (from 0.03 to 0.062 kg per capita) [35]. A tendency to transfer price-sensitive
industries such as furniture and automotive to areas having more competitive production
costs is likely to enhance growth in these countries.

In Europe, the polyurethane market is expected to show a steady growth of around 2.8%
over the next five years [36]. Flexible foam is the largest market accounting for 33% of
demand but with a growth rate of only 1.5% (compared with 3% for rigid PU foam).
Declining demand in the furniture and bedding sector is being offset by growth in the
automotive industry [37]. In Central Europe, growth of polyurethane products has been
forecast [38] as 5.9% with foam production increasing to some 228,000 tonnes by 2002.

4.6.1 Flexible Slabstock Foam

The main applications for slabstock foam (with a normal density range of 15 to 50 kg/m3)
are mattresses, upholstered furniture parts and textile laminates (particularly polyester
polyol based slabstock foam). Some new products have appeared, for instance, an air
bed which inflates automatically by virtue of a highly elastic foam core, and foam
development continues to introduce new specialities into the grade range. Examples of
these are latex-like, hydrophylic and soft foams, and there is a trend towards these,
particularly in Europe.

It has been suggested [23] that the more recently developed MDI-based slabstock foam
systems could have applications in markets including discontinuous block foam
production, prime carpet underlay and packaging, particularly for packaging under
conditions of low static stress which requires the foam to absorb energy under prescribed
dynamic conditions. MDI-based flexible slabstock foams are claimed by ICI to provide
packaging systems capable of cushioning a wider load range than TDI systems. (A more
detailed account of cushion packaging requirements is given in Section 6).

For the US carpet underlay market, ICI has compared the performance of a current 46
kg/m3 TDI product and an industry standard 95 kg/m3 rebonded foam product with an MDI

49
Polymer FoamsTrends in Use and Technology

foam produced from a Maxfoam slabstock line [23]. At a foam density of 46 kg/m3,
physical properties of the MDI foam were comparable to the TDI product but with superior
fatigue properties to both the TDI and rebond foams.

An interesting development has been viscoelastic foam, produced using speciality


polymer polyols which give foams having very low resilience [21]. Density can be varied
over a wide range, with rebound resilience around 5%8% compared with conventional
non-viscoelastic foams which have a resilience of 40%65%. The foams also exhibit long
recovery times after compression, ranging from two to ten seconds. Applications which
have been developed for these foams in the USA, Europe and more recently, Asia,
include medical devices, sports equipment, mattress toppers, packaging and laminates for
ski-boots. These applications all make use of the ability of these speciality foams to
reduce the stress on pressure points. In a medical mattress for use with patients with
long-term limited mobility, the incidence of bed sores is reduced. A speciality polyol
R2215, introduced by Lyondell for viscoelastic foam, is claimed to reduce the temperature
sensitivity of damping characteristics which is important in applications such as ski-boots
where exposure to a wide range of temperatures is likely.

A viscoelastic MDI slabstock foam has been developed by Nippon Polyurethane


Industries for applications in hospital bedding and pillows. This foam has excellent load
distribution and support properties so minimising the risk of bedsores. It is of interest to
note that this foam is the only flexible slabstock foam to show any significant growth in
Japan in the last decade [39].

Thermoformable foams made by slab manufacture, using polyether polyols (hydroxyl


numbers 200500 mg KOH/g) and PMDI find application in large area, lightweight, easily
installed components in automotive interiors. The components are built up as sandwich
structures, comprising, for instance, a non-woven backing, woven glass mat,
thermoformable polyurethane foam (in the density range 2050 kg/m3) and a decorative
layer. The layers are bonded using a hot melt adhesive. The decorative layer may
comprise non-woven textiles, leather or thermoplastic films. The polyurethane is
preheated to 180 C and thermoforming/bonding is carried out in an 80 C press. The
mouldings are said to be heat resistant to 130 C and are used as headliners, package
trays and under-bonnet insulation. These foams have good sound absorbing properties.

4.6.2 Flexible Moulded Foam

The main applications for moulded foams are upholstered furniture and, in the automotive
sector, seats, seat backs, arm and back rests, head rests and a variety of other car
components.

The average passenger car currently contains some 89 kg of moulded TDI (density 30
45 kg/m3) and cold moulded MDI (density 3855 kg/m3) products. Trends in both the USA
and Europe are towards cold moulded foams. In the USA, TDI-based systems are
favoured (though MDI systems are now generating some interest) whilst in Europe, both
systems are in use with MDI slightly favoured [31]. BMW, whose market is growing at a
rate of 7% per year, uses MDI seating for both front and rear seats of its Series 5 models,
the first car thus equipped.

Some two-thirds of the total quantity of raw materials used for automotive foam
applications goes into the production of seat cushioning, with a total volume in 1997
estimated as close to 400 kt per year [40]. Seat cushions are frequently produced using
dual hardness systems with the sides harder than the base to ensure a secure seating

50
Polymer FoamsTrends in Use and Technology

position. Automated systems have been developed to cope with the volume and quality
requirements of production. Since May 1998, a Krauss-Maffei system has been used by
BMW in Munich to produce dual hardness car seat squabs at a rate of two every 18
seconds on double mould carriers. The equipment incorporates a runner system moving
at 6 m/min with 28 double mould carriers and two industrial robots, each manipulating a 4
component mixing head to dispense the reaction components into the moulds. Other
system components are also automated, including the application of mould release agents
and a vacuum crusher to open the cell walls so as to ensure good stability and elasticity.
Seat backs and rear cushions can also be produced by this technology.

Trends in the area of seat cushioning are towards cost reduction (e.g., by density
reduction using liquid CO2 technology) whilst maintaining the exacting property
specification required by automotive manufacturers. Huntsman Polyurethanes has a
range of technologies based on MDI systems which will reduce seating foam thickness by
up to 50% and material usage up to 25%. The technology, still in development, should
allow greater scope for solving automotive design problems associated with space, as
well as being economically attractive.

Another automotive application for moulded foam is centre consoles/instrument panels,


long available as ready-to-mount prefabricated units produced using semi-rigid foam with
a vinyl backing. This provides an attractive appearance with possibilities for colour co-
ordination with the vinyl skin, with a soft touch and some impact protection in the event of
collision. Similar commercial applications are door panels, knee bolsters, covers for glove
compartments, armrests and airbag covers. The typical production method is back
foaming of vacuum formed, rotationally moulded or blow moulded vinyl skins. Foam
density in these components is about twice the free rise density, i.e., from 60120 kg/m3.
Formulations avoid the use of low boiling auxiliary blowing agents and certain amine
catalysts. The latter can cause discolouration and embrittlement of the vinyl sheet.

Various Federal Motor Vehicle Safety Standards (FMVSS) suggest the application of
energy absorbent materials, for instance:

FMVSS 201 Head impact


FMVSS 208 Head and thorax
FMVSS 213 Child seats
FMVSS 214 Side-impact
FMVSS 581 Bumpers

Energy absorbent polyurethane foams are semi-flexible, and are characterised by their
viscoelastic deformation behaviour. Application of an impact load results in deformation
with absorption of energy. After deformation, the foams recover over periods of 2 to 3
minutes and a high level of recovery is attained even after repeated loadings. Application
of these materials in the automotive industry is for protective internal paddings and
external bumpers. These can be manufactured either by foam filling a pre-moulded
casing, which gives an intimate bond between filling and skin, or by pre-moulding a foam
for subsequent insertion into a casing. Foam densities are in the range 60100 kg/m3.

An alternative energy absorbing foam can be produced using rigid polyurethane


technology. These foams have lower density (in the range 4060 kg/m3), but do not
recover after impact, reducing to a powder. The component must then be replaced.

The Arco Chemical Company has introduced Flexure polyurethane systems which are
claimed to span the range of energy absorption performance requirements from head
impact to bumpers. Ranging in density from 35250 kg/m3, the foams compressive

51
Polymer FoamsTrends in Use and Technology

strength extends from 504,500 kPa, with 24 hour recovery from compression between
50% and 99%. Dynamic impact performance is claimed to be superior to that of expanded
polypropylene at equivalent density.

Integral skin foams, which have the characteristics of a cellular core and a compacted
high density surface, are used for the production of items such as steering wheels and
gearshift knobs. Currently, these products comprise a metal core covered by a flexible,
integral skin, moulded polyurethane which provides good grip and a degree of impact
protection. Larger parts, such as bellows for articulated buses can also be made by this
technology. Foam density ranges from 150800 kg/m3, and foam hardness can be
controlled in the range 2090 Shore A to suit the application.

Non-automotive applications for integral skin foam include armrests for office chairs and
beer barrel jackets.

Laminate structures using foam as a backing for comfort and/or sound deadening are
widely used in automotive applications. For sound deadening, foams with high density and
low resilience are the most effective, and for this application, semi-rigid foams filled with
barytes may be used. Back-foamed carpets can be designed to meet specific sound
proofing requirements, and offer excellent fit together with ease of installation. The foam
formulation may be tailored to attenuate specific unwanted frequencies.

A significant application for injection moulded flexible polyurethane integral skin foams is
shoe soles. Foam density in this application is very high, in the range 450700 kg/m3, but,
nevertheless, polyurethane shoe soles are lighter than many conventional materials.
Other advantages include flexibility (some types maintaining flexibility down to 30 C),
high abrasion resistance, resistance to oil and hydrocarbons (for safety boot application),
good thermal insulation and good impact absorption to provide a high degree of comfort.
Production may use separate polyurethane foam inserts as insoles and liners or, by
injection of polyurethane around a shoe upper placed in a mould, provide an accurately
fitted moulded sole. Alternatively, the outsole can be manufactured separately and
polyurethane flexible foam injected between outsole and upper to provide a comfort layer
which bonds the two together.

Shoe sole formulations are generally based on MDI prepolymer systems. For applications
such as walking boots and shoes, polyether polyols are used to give good hydrolysis
resistance. Polyester polyols have superior mechanical properties and, being more
resistant to oils and hydrocarbons, are suited to safety shoes. Bayer has developed a new
generation of MDI prepolymers, primarily aimed at footwear applications, based on a
hybrid polyether/polyester approach. These systems are claimed to have several
advantages over conventional materials including easier storage, handling and processing
and greater latitude in formulating.

Shoe soling utilises a variety of materials, including leather, natural rubber, vulcanised
rubber, PVC, polyurethane, EVA and latex rubber, with polyolefin elastomers (from
metallocene catalysts) as future contenders. The total global soling market in 1998 was
estimated [41] as 5,177 kt, with polyurethane taking some 6% (303 kt). By far the largest
market for shoe soling is Asia Pacific (3,544 kt, 68%), but usage of polyurethane is low at
78 kt (2%) compared with, for instance, 97 kt in Western Europe. Polyurethane comprises
20% of a total Western Europe soling market of 486 kt. Although overall global growth is
forecast at around 2.7% per year, this is dependent on further introduction into the Asia-
Pacific area. One hindrance is the unique nature of polyurethane soling technology, where
the liquid reaction process involves special manufacturing equipment and significant entry
costs.

52
Polymer FoamsTrends in Use and Technology

A novel application for flexible moulded PU foam is for electrically heated carpets laid on a
house floor and used as direct or indirect heating. The demand in Japan is said to be
some 2.5 million units per year. Matsushita Electric and Nippon Polyurethane have jointly
developed an electric carpet using PU flexible foam pour-in-place technology with an all
MDI water blown system.

References

1. L.A. Mercando, J.G. Kneiss, J.D. Tobias, A. Plana, M.L. Listeman and S. Wendle,
Proceedings of Polyurethanes Expo 99, Lancaster, Pennsylvania, USA, 103.

2. S. Keimling and M. Sikorski, Kunststoffe Plast Europe, 2000, 90, 2, 34.

3. R.L. Gray and R.E. Lee, Plastics Additives: An A-Z Reference, ed. G. Pritchard, 1998,
Chapman and Hall, 567.

4. F.O. Sam, B. Cellarosi, M. Checchin and A. Petrone, Proceedings of Polyurethanes


World Congress 97, Amsterdam, The Netherlands, 69.

5. H.D. Lutter and D.C. Mente, Proceedings of Polyurethanes World Congress 97,
Amsterdam, The Netherlands, 63.

6. K.W. Fries, H. Klahre, E. Kurt and J. Ferrand, Proceedings of Polyurethanes Expo


99, Lancaster, Pennsylvania, USA, 289.

7. M. Taverna, H. Meloth and T. Griffiths, Proceedings of Utech Asia 97, Singapore,


Paper 45.

8. J.B. Blackwell, G. Bickley and S.W. Blackwell, Proceedings of Utech 96, The Hague,
The Netherlands, Paper 32.

9. F.M. Casati, R. Broos, H. Phan Thanh, R.M. Herrington, Y. Miyasaki and D. Cadolle,
Proceedings of Polyurethanes Expo 98, Dallas, Texas, USA, 417.

10. E. Occhiello, L. Fedeli and D. Grillot, Proceedings of Utech Asia 99, Singapore,
Automotive Paper 8.

11. W. Macdonald, European Chemical and Polymer Engineer, 1998, December, 8.

12. P.V. Bosigmore, B.J. Jody and E. Daniels, SAE Paper 910854, Separation
Techniques for Automotive Shredder Residue.

13. D. Reed, Urethanes Technology, 1998, 15, 6, 26.

14. Alliance for the Polyurethane Industry website, www.polyurethane.org.

15. E. Pilz and R.W. Lang, Kunststoffe Plast Europe, 1998, 88, 4, 24.

16. W.K. Law, T. Patel and F. Shutov, Proceedings of Utech Asia 99, Singapore, Science
and Testing Paper 4.

17. B. Martel, Proceedings of Polyurethanes World Congress 97, Amsterdam, The


Netherlands, 588.

18. G. Bauer, M. Kugler and R.S. Chakrabarti, Kunststoffe Plast Europe, 1999, 89, 2, 25.

53
Polymer FoamsTrends in Use and Technology

19. J.L. Fosnaugh, Proceedings of Polyurethanes Expo 96, Las Vegas, Nevada, USA,
266.

20. C. Banner, H. Sakamoto and J. Tan, Proceedings of Utech Asia 99, Singapore,
Slabstock Paper 7.

21. F.K.S. Wong, O. Sloan and S.L. Hager, Proceedings of Utech Asia 99, Singapore,
Slabstock Paper 5.

22. D.V. Dounis and G.L. Wilkes, Journal of Applied Polymer Science, 1997, 66, 13,
2395.

23. E. Cassidy, P. Chaffanjon and R. Lockwood, Proceedings of Polyurethanes World


Congress 97, Amsterdam, The Netherlands, 55.

24. H. Klahre and G. Jacobs, Kunststoffe Plast Europe, 1997, 87, 6, 13.

25. H. Nakamura and Y.J. Lee, Proceedings of Utech Asia 97, Singapore, Paper 9.

26. European Chemical News, 1998, 69, 1839, 20.

27. S. Milmo, Chemical Marketing Reporter, 1997, 252, 18, 8.

28. T. Brand, Chemical Marketing Reporter, 1997, 251, 11, 1.

29. Plastics and Rubber Asia, 1997, 12, 70, 33.

30. R. Clausius, Kunststoffe Plast Europe, 1998, 88, 10, 42.

31. R. Clausius, Marketing Director, Polyurethanes Business Group, Bayer AG,


Leverkusen, Germany, personal communication.

32. Polymer News, 1997, 4, 144.

33. M. McNulty, Urethanes Technology, 1999, 16, 5, 20.

34. R. Sandham, Proceedings of Utech Asia 97, Singapore, Paper 46.

35. V.K. Sood and J. Desai, Proceedings of Utech Asia 99, Singapore, Plenary Paper 5.

36. S. Robertson, European Chemical News, 1999, 71, 1870, 169.

37. Coatings and Composite Materials, 1997, 19, 5, 15.

38. Popular Plastics and Packaging, 1998, 43, 12, 33.

39. K. Saiki, T. Taguchi and T. Satou, Proceedings of Polyurethanes Expo 98, Dallas,
Texas, USA, 161.

40. P. Berthevas, H. Phan Thanh and S. Hamada, Proceedings of Utech Asia 97,
Singapore, Paper 7.

41. S. Lee, Proceedings of Utech Asia 99, Singapore, Footwear Paper 1.

54
Polymer FoamsTrends in Use and Technology

5 RIGID POLYURETHANE FOAM

5.1 Introduction

Isocyanate-based rigid cellular plastics for insulation use were first introduced in the early
1950s, and are generally regarded as of two types: rigid urethane (PUR) and rigid
polyisocyanurate (PIR) foams.

PUR foams derive from the exothermic reaction of a polyol and an isocyanate, usually
MDI. In a closed-cell foam, expansion results largely from the concurrent evaporation of a
liquid blowing agent dissolved in one of the components. Alternatively, a gas with a boiling
point well below room temperature may be used, which is dissolved under pressure in one
of the components. This comes out of solution when the mixed components are
depressurised. The overall reaction is affected by various factors including the presence
of additives such as catalysts, surfactants and fire retardants. These additives regulate the
rate of reaction, the type of chemical structure formed, the cell structure and, ultimately,
the physical properties of the foam.

PIR foams are formed using special polyol/catalyst blends and a substantial excess of
MDI (typically 50%). This excess MDI is the real key to the production of isocyanurate
foams as it reacts with itself in the presence of certain metal salt catalysts to form cyclic
trimeric isocyanurates. The final structure actually contains both urethane and
isocyanurate groups and such materials are more correctly described as polyurethane-
modified polyisocyanurate foams.

The rapid increase in the use of rigid polyurethane foams, following their introduction in
the 1950s, was due mainly to their enhanced water resistance (both liquid and vapour)
and low thermal conductivity. Hitherto, isocyanate foams had a generally open-cell
structure through which water or water vapour could easily penetrate, and thermal
conductivity of around 32 mW/m K at 10 C. The new, rigid, closed-cell, isocyanate-based
foams were essentially impervious to water and, using low thermal conductivity expansion
gases such as CFC-11 or CFC-12, thermal conductivity was reduced to typically 17
mW/m K. Hence, insulation thicknesses could be reduced to half that of the old products
which depended on the presence of air trapped in cells and foam interstices for insulation
performance. It was soon realised, however, that the insulation performance of the new
closed-cell products decreased with time as the CFC gas diffused out of the cells, but
even so a superior thermal performance was maintained.

The basic chemistry involved in the manufacture of PUR and PIR foams has been
discussed at length elsewhere but some trends which have been reported recently include
the move towards the use of polyisocyanurate foams incorporating aromatic polyester
polyols [1], new additives for rigid PU foams and the move away from CFC-11 and CFC-
12 to blowing agents having greater environmental acceptability to meet Montreal Protocol
requirements.

5.2 Materials

5.2.1 Polyols

The combustibility of all materials is related to the release of volatile flammable products
during the early stages of thermal decomposition. An improvement in thermal stability can
be expected to lead to improvement in fire resistance. Polyurethane linkages decompose

55
Polymer FoamsTrends in Use and Technology

at around 200 C with a char yield of less than 20%. The isocyanurate ring decomposes
at substantially higher temperatures (above 300 C) and char yield is typically 50%. The
char, particularly if it is foamed to some extent, has a low thermal conductivity and
insulates the underlying foam from the source of ignition. It has a high degree of oxidative
stability and hence is slow to be consumed by fire, and the block surface reradiates a
significant proportion of the heat load further enhancing insulation characteristics in a fire
situation. Thus, PIR foams provide a superior fire performance to PUR foams.

The beneficial char forming characteristics of PIR foams can be further enhanced by
appropriate choice of polyol. It has been found that char yield is directly related to the
number of aromatic ring structures incorporated into the polymer backbone. Use of
aromatic polyester polyols (APPs) can therefore increase char formation and further
enhance fire performance.

APPs are produced by the reaction of alcohols with carboxylic acids derived from dimethyl
terephthalate (DMT), polyethylene terephthalate (PET) or phthalic acid or anhydride (PA).

DMT is an intermediate in the production of PET, arising as a residue. Plant economics


are improved if such residues can be treated at the same site and the usual process is
production of polyesters by glycolysis. The functionality of APPs based on DMT residues
is around 2.2 to 2.3 through the incorporation of methyl and benzyl esters of biphenyl and
triphenyl di- and tri-carboxylic acids. This gives an advantage over the PET- and PA-
based polyesters which have functionality close to 2.0. Other advantages of DMT-based
APPs are the improved viscosity stability (due to the heterogeneous, polydisperse nature
of the composition) and higher fire resistance (due to the higher aromatic functionality).

APPs based on PET are produced from waste sourced from consumer scrap, such as
bottles, packaging, fibres and film backings. The increasing impact of the European
Packaging Waste legislation and the ever greater use of polyester film in packaging will
lead to increasing pressure for recycling of such waste. As a result, PET-based APPs are
likely to become increasingly and widely available. Currently, some 500 million PET
bottles require recycling each year in Europe, and PET recycling is a substantial business.
Recyclers have their own proprietary methods for processing the scrap which have to take
account of the contaminated nature and varied source of most scrap, and the necessity of
refining the APP product, e.g., by removal of catalyst residues.

In Europe, so-called second-generation PET-based APPs are now available, produced by


a patented process which allows improved control over molecular structure. Materials are
more consistent and have a lower viscosity which leads to improved processing.

The fire performance of PIRs improves with the use of APPs, and best fire resistance is
found using APPs based on PET or DMT. This can be attributed to the higher softening
temperature/heat stability of polymers based on terephthalic acid (see Table 5.1). Foams
based on DMT/PET derived APPs also have greater thermal stability.

Table 5.1 Melting Points of Polyesters


from Phthalic Acid (PA) Isomers (C)
Glycol Ortho-PA Iso-PA Tere-PA
Ethylene (EG) 6365 103108 256
Diethylene (DEG) 1011 5560 6570
Source: [1]

56
Polymer FoamsTrends in Use and Technology

The degree to which APPs contribute to fire performance depends to some extent on the
isocyanate index of the modified PIR foam formulation. Above an index of 300, the
isocyanurate cyclic trimers provide the bulk of the fire retardancy but as the index is
lowered to 200 (to reduce MDI costs) the proportional contribution of the APPs increases,
and differences between them can be distinguished.

Polyols made from PA, a material used widely for the production of phthalate plasticisers
for PVC, are pure, clearly defined materials which are used in formulations where precise
functionality and fixed mix ratios are needed. However, for many applications this level of
purity is not needed.

Rigid polyether foams are based on polyols derived from propylene oxide (PO) or
ethylene oxide (EO) reacted with polyfunctional initiators such as glycerol, sucrose,
sorbitol or ethanolamines. Flammability is high due to the aliphatic backbone and
(generally) high PO content. As with the rigid polyester foams, flammability performance
can be enhanced by the introduction of aromatic groups into the polymer structure. This
may be done by using aromatic initiators (such as toluene diamine). Flammability
behaviour can be further enhanced by reducing the PO content. Novel aromatic polyols
sold under the Charkol tradename and manufactured by PUR (Products) Ltd.contain no
PO and require less than half the level of fire retardant additive to achieve the same fire
resistivity. Such materials have good crosslinking ability and are well suited for use as
copolyols with APPs.

In Japan, Asahi Glass has developed novel polyols which are a blend of aromatic and
aliphatic compounds. These are designated the AG series and are said to be useful in
formulations for refrigerator and building insulation. AG-1001 is designed to give good
nucleation with HFC-245fa as a blowing agent, whilst AG-1750 and AG1755 are designed
to give good solubiluty and reactivity. The new systems require no modification to current
foaming machines.

In the USA, there has been an almost total acceptance of APPs in rigid foams for
construction, initially owing to an economic advantage since polyesters are typically 20%
cheaper than polyethers. However, also of significance is the lower hydroxyl value which
results (if MDI levels are kept constant) in excess MDI which is available for the formation
of cyclic isocyanurate groups. A cost comparison of polyether and polyester systems [1]
has shown a cost saving of around 7% for an HCFC-141b polyester system using pentane
as blowing agent.

APPs were used initially in the USA as low cost extenders, replacing only a part of the
polyether polyol. The enhanced fire performancelow flammability and low smoke
formationwas soon recognised and APP-based foams now constitute almost 100% of
US board stock. APPs are often used in blends with copolyols, since the polyesters are
not fully compatible with blowing agents such as HCFC-141b or pentane. The copolyols
may be added to the foam mix during foam production, or may be incorporated into the
polyol backbone by transesterification.

Whilst PIR foams have been widely adopted in the USA, acceptance in Europe is slower.
The use of pentane as a blowing agent has intensified the need for good flame resistance
and is a potent factor in driving the change. A further factor is the move in many European
countries to reduce or eliminate the use of fire retardants from products on grounds of
concern for the environment or health and safety. This results in a need for greater
intrinsic fire resistance of the foam itself.

57
Polymer FoamsTrends in Use and Technology

The slower acceptance of PIR foams in Europe appears to be due to two main factors. It
is not straightforward to replace a PUR system with a PIR system. European
manufacturers of rigid board (about 40 to 50) mostly use low speed machines as opposed
to the high speed machines used by US manufacturers. A change to PIR would require
machinery to be modified or changed, with consequent investment costs. PIR formulations
also run at higher temperatures and generally need greater process control. The higher
temperatures can lead to short-term dimensional stability problems after processing.
Product requirements must still be met with new formulations. Formulation development to
meet precise application requirements is necessary.

The complicated fire performance scene in Europe is also holding back the wider adoption
of modified PIR technology. Each country has its own fire test system and requirements
and manufacturers struggle to meet all the relevant tests. However, the situation should
now improve with European Union member countries changing to a harmonised Reaction
to Fire classification system in line with the Construction Products Directive. Under this
scheme, products will be tested using procedures aiming to replicate end-use situations.
The main test for polyurethane-based building products will be the so-called Single
Burning Item (SBI) test and a small-scale Kleinbrenner test (similar to the German DIN
4102 B2 test). The performance of PU products will need to be established, but once
done, the test certification should allow acceptance in all EU countries. Doubtless, it will
take some time before such test results are taken as the sole criteria for acceptance.

5.2.2 Blowing Agents

The replacement of CFCs has been the main development target of the rigid PU foam
industry since 1986, and the repercussions of this, in optimising the performance of
alternative non CFC formulations and moving away from transitional substances,
continue.

The success of work to replace CFCs can be judged from Table 5.2, which shows the use
of ozone depleting substances by the European foam industry since 1986.

Table 5.2 Use of Ozone Depleting Substances


by the European Foam Industry
Year ODP (1000 weighted
tonnes*)
1986 63
1987 67
1988 70
1989 70
1990 69
1991 51
1992 39
1993 22
1994 4
1995 4
1996 4
1997 4
1998 4
1999 4
* normalised to CFC-11/CFC-12
Source: [2]

58
Polymer FoamsTrends in Use and Technology

The desirable characteristics of blowing agents for rigid PU foams are well understood,
and essentially are:

A boiling point in the range 20 C to +30 C,


good solubility in the foam precursors,
poor solubility in the foam polymer,
low thermal conductivity of gas/vapour,
low diffusion rate of gas/vapour through the polymer (for long-term retention in the
cells),
zero ODP,
low flammability both as liquid and gas, and
chemically inertness.

Development to meet the longer term requirements of the Montreal Protocol have resulted
essentially in two types of blowing agent: the HCFCs such as HCFC-141b and
hydrocarbons such as n-pentane. Some characteristics of these substances are shown in
Table 5.3.

Table 5.3 Characteristics of Some Alternative Blowing Agents


Property CFC-11 HCFC- HFC- CO2 n- Cyclopentane
141b 134a Pentane
Formula CCl3F CH3CCl2F CH2FCF3 CO2 C5H12 C5H10
Molecular weight 137 117 102 44 72 70
Boiling point (C) 24 32 -26.5 - 36 49
Vapour pressure at
- 0.8 - - 0.82 0.53
30 C (bar)
Vapour thermal
conductivity at 20 8 9 14 15 13 11
C (mW/m K)
Flash point (C) none none none none < -50 -42
Explosion limits in
none 7.415.5 none none 1.47.8 1.48.0
air (% by volume)
Threshold limit
1,000 500 1,000 - 1,000 600
value (ppm)
ODP (cf., CFC-11) 1.0 0.11 0 0 0 0
Permanency in
good good good poor good good
cells
Source: [2]

From Table 5.3, it may be recognised that there is no ideal replacement for CFC-11.
HCFC-141b, whilst giving a very substantial reduction in ODP, does not have a zero ODP
factor and the Montreal Protocol requires its eventual phase-out. In addition, thermal
conductivity is slightly worse and mixtures with air are explosive (within defined limits).
HFCs, such as HFC-134a, do have zero ODP and are acceptable under the Montreal
Protocol (although they do have some potential for global warming). They are non-
flammable and non-explosive, but thermal conductivity is significantly worse than CFC-11.
Carbon dioxide is a very safe gas to work with but again has worse thermal properties
which are exacerbated by the impermanence of the gas in the cells, leading to a gradual
deterioration in insulation and some dimensional stability problems. It also contributes to
global warming, so is not totally environmentally acceptable (though it may be argued that
environmental deterioration due to the use of CO2 as a blowing agent is vastly outweighed
by contributions of CO2 to the atmosphere from transport and energy production).

59
Polymer FoamsTrends in Use and Technology

Hydrocarbons have zero ODP (and negligible global warming potential) and hence offer a
permanent solution to Montreal Protocol requirements, but they are flammable and form
explosive mixtures with air. Compared with CFC-11, there is also a significant worsening
of insulation performance.

In addition to the intrinsic properties of alternative blowing agents and the properties
consequently imparted to the foam, the effect on processing is also very important.
Whereas HCFC-141b is essentially a drop-in agent which can be run with relatively minor
adjustments on conventional machines, engineering solutions have had to be found to
introduce gases and flammable blowing agents.

Worldwide, no single blowing agent technology has been universally adopted. The phase-
out of CFCs has resulted in a broad diversification of rigid PU foam processes using
HCFC-141b, HCFC-22 with HCFC-142b, HFC-134a, pentane isomers and CO2.

HFC-141b is currently used largely in the manufacture of metal-faced sandwich boards.


Whilst it is drop-in technology, greater control of processing is needed and some
dimensional stability problems require higher foam density. This technology has been in
place for some 5 years producing foams of density 3843 kg/m3 by a continuous process
and 4143 kg/m3 by a discontinuous process. This is the main technology adopted in the
USA owing to the large emphasis placed on energy conservation and the environmental
penalties exacted for units with large energy demands.

HCFC-22/142b has been used particularly in Germany and offers advantages of good
dimensional stability but with some worsening of thermal conductivity.

HFC-134a, has been used industrially to a small extent in both the continuous and
discontinuous processes. The substance is dosed into the high pressure polyol stream in
continuous operations, or used in a fully saturated polyol component in discontinuous
operations.

Foams blown with CO2 produced from the water/isocyanate reaction are also made
successfully by panel manufacturers, with density ranging from 43 kg/m3 to 48 kg/m3. The
inferior long-term ageing (loss of insulation) due to diffusion of CO2 from the cells can be
mitigated by use of an impervious facing. It is claimed by Dow that with such composites,
thermal conductivity remains practically unchanged for a long time in the largest part of
the panel (i.e., the foam insulation). A recent variant is the use of liquid CO2 to partially
replace water. The CO2 is metered and fed in the high pressure polyol stream at a level of
some 3 parts by weight. Some process advantages have been described, but engineering
modifications are necessary to handle and meter the gas and the technology has not so
far found use industrially for sandwich panels due to unclear economics in comparison
with all water blown technology.

The use of pentane (n-pentane or cyclopentane) is now widespread in the European


industry for the production of metal-faced rigid PU panels. Technology has been
developed to deal with the problems imposed by flammability, including membrane pumps
for dosing and static mixers for blending with the polyol stream. Strict precautions are
taken to ensure there is no build-up of explosive vapours, and continuous monitoring
ensures levels are maintained below 10% of the lower explosion limit. Ignition sources
must be eliminated. With these precautions, pentane can be used safely and the first
equipment for production of pentane-blown rigid PU was introduced in 1990 (the Contimat
from Hennecke, now widely used in Europe). Pentane may be partially emulsified (and not
solubilised) in the polyol stream depending on the amount used and its solubility in the
polyol.

60
Polymer FoamsTrends in Use and Technology

Pentane has some advantages:

zero ODP,
poor solubility and low permeability in the PU matrix,
acceptable foam insulation values (though inferior to those of CFC foams), and
low price.

The obvious disadvantage is its flammability. In addition to the necessity of introducing


new equipment to provide adequate operating safety there is an adverse contribution of
the hydrocarbons to the foam combustion behaviour, and an inferior fire performance is
normal. This may be combated by the introduction of additional fire retardants, or by use
of polyisocyanurate foam chemistry, but this results in a cost penalty. Thus, the
economics of pentane blown foam compared to other technologies (see Table 5.4)
depend on the fire classification requirements.

Table 5.4 Economics of Rigid PU Foam Production


Blowing agent Comparative cost of 1 m3 of foam to meet
DIN 4102 B3 DIN 4102 B2
HCFC-141b 100 107
CO2 - water 111 114
Pentane 96 126
Source: [3]

Cyclopentane and n-pentane (or n/i-pentane blends) are sufficiently different in properties
to give rise to significant differences in processing and foam properties. Where a
homogeneous blend is preferable (discontinuous processes), cyclopentane is preferred,
and this also provides optimum thermal properties. n-Pentane costs less and gives a
lower foam density, resulting in better foam economics.

There is significant work still ongoing in the polyurethane industry to replace fully HCFC-
141b in developed countries during the year 2002. Whilst pentane and CO2 technologies
are already in place, neither provides the advantageous process and product
characteristics given by CFC-11. For a few years now, HFC-245fa and HFC-365mfc have
been identified as the leading candidates. Whilst neither of these substances entirely
matches CFC-11, a blend of HFC-365mfc with either HFC-134a or HFC-245fa provides a
non-flammable blowing agent with good thermal insulation performance and a convenient
boiling point in the range 2025 C. Such a blend would provide a drop-in replacement for
HCFC-141b (and CFC-11), but is the most expensive option of those under examination.

A further possibility for the future is an azeotropic blend of HFC-365mfc with any of the
three pentane isomers (n, i, or cyclo). Although these azeotropes are flammable, they do
provide a more cost effective solution than use of HFC-365mfc alone, and results show
good foam thermal insulation values. Some characteristics of these third-generation
blowing agents are shown in Tables 5.55.7.

These recent developments, which have included foaming trials, have focused attention
on the possibilities afforded by HFC-365mfc, and Solvay has taken a decision to develop
production at pilot scale level (on stream mid-1999) with a view to making this substance
available as an HCFC-141b substitute at the end of 2002.

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Polymer FoamsTrends in Use and Technology

Table 5.5 Main Characteristics of HFC Blowing Agents


Property HFC-245fa HFC-365mfc
Boiling point (C) 15.3 40.2
Vapour pressure (bar at 20 C) 1.24 0.47
Vapour thermal conductivity at 25 C (mW/m K) 12.2 10.6
Flash point none none
Flame limits (% by volume) none 3.59.0
GWP (relative to CO2 = 1) 820 840
Source: [4]

Table 5.6 Main Characteristics of HFC-365mfc/HFC-245fa Blends


Property Blend ratio
100/0 50/50 95/5 93/7 0/100
Boiling point (C) 40.2 24 37 20 15.3
Flash point none none none none none
Vapour thermal conductivity 10.6 11.4 10.7 10.8 12.2
at 25 C (mW/m K)
Source: [4]

Table 5.7 Main Characteristics of HFC-365 mfc/Pentane Azeotropes


Property HFC cyclopentane isopentane n-pentane
HFC/Pentane ratio 100/0 73/27 46/54 58/42
Boiling point (C) 40.2 32 22.5 27
Flash point none yes yes yes
Vapour thermal conductivity 10.6 11.1 (calc.) 13 (calc.) 13 (calc.)
at 25 C (mW/m K)
Source: [4]

The scenario for blowing agents over the next few years is likely to be the replacement in
the USA of HCFC-141b by HFC-365mfc, or a blend thereof, with pentane technology
continuing to dominate in Europe. In Asia, a mixture of technologies will be utilised, with
some countries (such as China and Korea) still relying on CFC-11. Money is being made
available by the World Bank and the United Nations Development Program to subsidise
the considerable capital costs involved in changing to flammable blowing agents. Whilst
some manufacturers in the Asia-Pacific region have made the (relatively easy) change to
HCFC-141b, as in the USA, most are now looking at pentane technology to comply with
the Montreal Protocol and to achieve cost reductions which are important in view of the
economic turmoil in Asia. In Japan, conversion to pentane technology is well advanced.

Formulation development to optimise manufacture with alternative blowing agents has


been necessary. For instance, Asahi Glass Co has reported new rigid foam systems for
pour in place and refrigerator systems which use HCFC-141b, HFC-245fa, or
cyclopentane instead of CFCs. Polyols AG-3600 and AG-3610 are for pour in place and
polyols FD-2001, FD-3001, FD-4001, FD-5001 and FD-6001 are intended for
refrigerators.

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Polymer FoamsTrends in Use and Technology

5.2.3 Additives

The main technical development in rigid PU foams has been the move away from CFC
blowing agents, but there has been substantial formulation development to mitigate
property changes resulting from use of CFC alternatives.

5.2.3.1 Catalysts

Foam catalysts have a very substantial influence on process rheology, process latitude,
dimensional stability and physical properties. They comprise:

tertiary amines,
quaternary ammonium salts, and
potassium salts.

Huntsman Corp has introduced a low-cost catalyst system for refrigeration and pour-in-
place foams aiming to optimise the performance and processing issues arising particularly
with HCFC, HFC and hydrocarbon blowing agents. The best single catalyst was found to
be Jeffcat ZF-10 (N,N,N-trimethyl-N-hydroxyethyl-bisaminoethylether) but catalyst
blends are likely to give a superior performance.

A new proprietary catalyst from Air Products and Chemicals is Polycat 48, developed from
work on HCFC-141b rigid polyurethane appliance foam but of use in rigid foam with a
variety of blowing agents. It is a balanced blow, gel and trimerisation catalyst and can be
used as the sole catalyst in rigid PUR and PIR foam formulations. It is claimed to provide
high catalytic activity, improved dimensional stability without cell opening, low thermal
conductivity factors (particularly for HCFC-141b foam) and excellent masterbatch stability.

The improvement in dimensional stability has been attributed to the relatively complete
formation of secondary products (isocyanurates and allophanates) before the foam cools,
which strengthens the struts and lamellae, allowing the foam better to withstand the
internal vacuum resulting on cooling.

Catalyst systems from Nitroil Europe GmbH for rigid polyurethane foam systems include:

PC CAT NP 33 R widely used but narrow production window.

PC CAT NP 10 improved flowability and faster final cure.

PC CAT R 137 as NP 10 above, but with even faster final cure.

PC CAT NP 72 NT a catalyst blend of low odour which can lower foam density,
recommended for spray foam.

PC CAT NP 15 gives best results for physical properties and variability in


reaction profile, also nearly odourless. Especially useful in block
foam.

PC CAT NP 135 faster reaction than NP 15 above at the same catalyst level,
recommended for thinner boards or panels.

PC CAT RL series developed for polyisocyanurate foams.

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Polymer FoamsTrends in Use and Technology

5.2.3.2 Surfactants

By reducing the surface tension of polyol, surfactants can perform several useful functions
in foam manufacture. They can stabilise the initial liquid-air dispersion (controlling the
number of cells); they can emulsify and stabilise a blend of incompatible reagents; they
can stabilise the rising foam. Appliance foam generally incorporates highly functional
polyols and isocyanates which results in a relatively high liquid phase viscosity and good
foam stability. The surfactant is used mainly to control cell size and to enable blend
miscibility of incompatible reagents. Surfactants commonly used are copolymers of
polydimethyl siloxane and polyalkylene oxide.

Dabco 5700 has been developed by Air Products and Chemicals and is claimed to give
improved foam process and property characteristics in rigid PU HCFC-141b formulations
using higher water levels. Higher water levels allow a reduction in HCFC with consequent
cost saving but normally with reduced dimensional stability, lower thermal conductivity
values and increased foam density which negate the cost savings from reduced levels of
blowing agent. The new surfactant is claimed to allow water levels up to 2.6% to be used,
with a 36% reduction in use of HCFC-141b. Minimum fill density increases to a small
extent (from 29.8 to 31.9 kg/m3) but dimensional stability and thermal conductivity values
are maintained.

Another new surfactant is Dabco DC5580, designed for cyclopentane-blown PU rigid


foam. This surfactant is claimed to improve pentane emulsification during the
polymerisation process, and maintains system clarity where many surfactants experience
serious problems with phase separation. Although specifically developed for
cyclopentane, it is claimed to be effective with other pentane systems.

Development work on surfactants has been carried out by Th. Goldschmidt AG, Germany.
For HCFC-141b blown refrigerator foams, Tegostab B8465 has been found to perform
well in European polyether systems, but less well in US systems which usually contain a
mixture of ether and ester polyols and a greater quantity of HCFC-141b. Some new
surfactants, designated EP1406 and EP1418, were found to give improvements both in
processibility and in physical properties (fewer foam defects and better density
distribution). There was also better retention of thermal conductivity after long-term
ageing.

For PUR/PIR continuous foams (panel production), Th. Goldschmidts surfactant


development has aimed to improve nucleation (to obtain finer cell size, more regular cell
structure and lower thermal conductivity factors), increase stabilisation (to counter the
solvating effects of HCFC-141b), improve horizontal flow (to achieve maximum foam yield
and good adhesion at the upper laminate interface) and to minimise any effect of
surfactant on flame retardancy performance. Requirements of a silicone surfactant to
achieve this are to some extent contradictory, and Goldschmidts work has resulted in
development and trial of some polyether cosurfactants. Superior results have been
reported for materials designated OS5 and OS6 [5].

For foams with high flame retardancy requirements, Th. Goldschmidts silicone surfactant
development aimed to provide systems which minimised the generation of SiO2. This is a
decomposition product which is thought to catalyse the pyrolytic process. The critical
structural parameters of the silicone surfactant were found to be the degree of branching
of the silicone backbone and the type of polyether attached. Above a certain polyether
molecular weight, the solubility of the surfactants in reaction components increases
resulting in a decrease in burning rate. Unfortunately, there is also a large increase in
thermal conductivity. This work resulted in the development of Tegostab B8455, which

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Polymer FoamsTrends in Use and Technology

eliminates the negative influence of the surfactant on the combustion process, and
Tegostab B8454, which maintains an almost optimal k factor without sacrificing flame
retardancy properties.

A summary of Th. Goldschmidts recent surfactant developments is given in Table 5.8.

Table 5.8 Developments in Rigid PU Foam Surfactants from Th. Goldschmidt


Application System/blowing agent Surfactant
Refrigerators and Cyclopentane (Europe) Tegostab 8467
Linings HCFC-141b (USA) EP 1406 and
EO 1418
Continuous panel Low index, n-pentane Tegostab B8466
Low index, high pentane level Tegostab B8469
Low index, HCFC-141b Tegostab B8465
PUR/PIR, HCFC-141b (polyol side) Tegostab B8457
PUR/PIR, HCFC-141b (isocyanate side) Tegostab B8471
High FR requirement n-pentane Tegostab B8455
HCFC-141b Tegostab B8454
Source: [5]
FR = flame retardant

5.2.3.3 Cell Openers

It is normal practice to obtain adequate dimensional stability by increasing foam density,


but it has recently been suggested that this can be achieved more cost effectively by
increasing the ratio of open to closed cells, which is normally in the range 10 to 20%. This
would increase the rate of gas permeation out of the cells and its replacement by air, thus
reducing the time to reach internal/external pressure equilibrium, so enhancing foam
stability. The downside of this is a reduction in insulation performance, as air has a higher
thermal conductivity than most blowing agents. This approach is, therefore, only
appropriate for applications where insulation properties are of low importance.

Whereas cell opening of flexible foams can be achieved by mechanical crushing, with rigid
foams this would result in permanent compressive deformation. Hence, a chemical
method is necessary.

Dabco DC5000 (Air Products and Chemicals) is a new cell opener for rigid foams. It is
designed as a separate additive for use with traditional silicone-polyether surfactants to
allow good formulation flexibility. The additive is incorporated in small amounts up to 0.25
parts per hundred polyol to promote cell window rupture immediately prior to the rapid
viscosity build up as the polymeric crosslinked network is formed. It acts by replacing the
foam-producing surface film with an alternative film with little or no surface elasticity which
rapidly thins and breaks as the foam expands. Alternative mechanisms considered but not
investigated were use of silica particles to absorb and remove surface active material from
the cell surface, or promotion of lamellae drainage by reduction of surface viscosity.

Physical properties given for the resulting foams showed the expected improvements in
dimensional stability, but with a substantial loss in insulative properties. Thermal
conductivity (24h, mW/m K) increased from 18.7 to 39.9 for an HCFC-141b system with
0.20 pph Dabco 5000. Open cell content increased from 20% to 88% with Dabco 5000.

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Polymer FoamsTrends in Use and Technology

Tegostab B8919 was introduced by Th. Goldschmidt AG in 1995, and is recommended for
use in foams blown with CO2 for applications in packaging, agriculture and core material
for vacuum insulation panels. In all these applications, dimensional stability and
compression strength is more important than insulation. However, Tegostab B8919 is an
emulsion and not a homogeneous solution. Therefore, it can show a tendency to
separate. A more recent development is Ortegol 501, which has the same cell opening
characteristics but gives a clear and homogeneous system with no tendency to separate.
However, it does need to be used at twice the addition level to achieve similar results.

5.2.3.4 Blend Compatibilisers

One of the major limitations of hydrocarbons as blowing agents is their poor solubility in
polyol. Use of higher amounts is desirable, particularly in PIR applications, as it would
allow an improvement in reaction kinetics by the reduction or elimination of water. Higher
levels of hydrocarbon above the solubility limits can result in phase separation during and
before the foam reaction leading to foam inhomogeneity.

Air Products and Chemicals has developed Dabco Kitane 20AS which can solubilise or
emulsify hydrocarbons in polyether and polyester polyols, respectively. Use level is
formulation dependent, but it is suggested that a similar level be used to that of the
hydrocarbon. The additive is claimed to be effective with all pentane isomers and it is
reported that good physical properties are maintained in the foam.

Ortegol 410, a compatibiliser from Th. Goldschmidt AG, helps to solubilise pentane in rigid
foam polyols. Using technical cyclopentane (70% cyclopentane and mainly n- and i-
isomers) in a European appliance polyol system, clarity up to 11 pph pentane was
achieved without additive. With 5.0 pph of Ortegol 410, clarity was maintained up to 15.0
pph pentane. At 10 pph Ortegol 410, clarity was maintained up to 18.0 pph pentane.

5.3 Processes

The original method for production of PUR and PIR foam was simply to pour the foam mix
into a box mould. The product was subsequently cut to form boards, pipe shells and other
complex shapes. This method is essentially that now used for pour-in-place applications
such as insulative linings for refrigerators. Increasing product volumes required more
economic production methods, and a continuous process for block foam was developed,
followed later by continuous lamination technology for panel production. The latter allows
efficient production of rigid PU board with different facing materials like bituminous paper,
glass fibre reinforced bitumen sheets, multi-layer papers or metal sheets.

Currently, both discontinuous and continuous processes operate for production of


laminated rigid PU panels, although the continuous process is dominant. In a typical
continuous process (Henneckes Contimat), galvanised steel sheets (0.50.8 mm) are
wound off large coils and fed through a profiling unit to provide edge and surface profiles.
Lower and upper facings pass through simultaneously and are then preheated to the
process temperature required. The reactive PU mix is dispensed onto the lower facing
using a linear application method whereby the mix head oscillates across the entire plate
width. Sophisticated control ensures uniform distribution giving expansion only in the
vertical direction, resulting in uniform density through the sheet and optimum production
output. An adjustable gap between upper and lower conveyors controls panel thickness.
Conveyor lengths are typically 20 m to 30 m. Panels are cut to length around 10 m after
leaving the conveyor. Output rates of a double conveyor plant with a 30 m length pressure

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Polymer FoamsTrends in Use and Technology

zone and 1.2 m width are typically 860 m2/h (50 mm thickness) and 390 m2/h (150 mm
thickness). Output rate is directly dependent on conveyor length.

The discontinuous process comprises a series of steps linked to provide a manufacturing


operation:

Preparation and positioning of metal sheets, either from a coil of metal or by use of
stacked sheets.

Profiling of edge and surfaces of the sheets.

Feeding of the sheets to a double daylight press characterised by a central pressing


plate. The pressing plate moves to close an upper mould in preparation for
dispensing the PU foam mix whilst releasing the lower mould for removal of the
finished panel and insertion of further facing sheets. Such presses may be configured
as 1+1, 2+2, 3+3 or 4+4 (e.g., a 2+2 configuration would be 2 moulds in the upper
section and 2 moulds in the lower section of the press).

Optimum output of a discontinuous process is achieved when curing time and operating
time are of equal duration and when the platen area of the presses is fully utilised. Typical
output rate of a 4+4 daylight press, 6 m long, 1.2 m wide, maximum platen area utilised, is
150170 m2/h (50 mm thickness) and 4050 m2/h (150 mm thickness).

A joint co-operation between Hennecke GmbH and Bayer AG has resulted in the
VarioCast process which is claimed to not only reduce the cycle time for discontinuous
panel foaming operations but also to improve cell structure, to increase dimensional
stability and to reduce raw material costs by 5%. The equipment is modular, is said to give
cycle time savings up to 30% and is compatible with various blowing agents including
pentane.

The continuous process has higher output rates and there is no technical limitation on
panel length (in Europe, currently up to 18 m). Foam density is generally lower than that of
foam produced by the discontinuous process (4045 kg/m3 compared to 4555 kg/m3). In
the discontinuous process, panel length is limited by press dimensions, but there is
greater flexibility in the use of facing materials (these may include chipboard, plywood, or
light building board, in addition to the usual steel or aluminium sheet). Cell structure and
uniformity is inferior in the discontinuous process since the distribution of reaction mixture
is not uniform and expansion occurs sideways as well as vertically. Dimensional stability
of the foam is adequate but inferior to that from the continuous process. There is,
however, more scope for sheet profiling, including the ends as well as the sides, which is
not feasible in the continuous system.

It is also possible to spray foam in place for insulative or sealing applications.


Formulations are required with high reactivity and low odour. A new isocyanate having a
high reactivity suitable for rigid spray foam has been introduced by Nippon Polyurethane
Industry.

5.4 Recycling

Whilst rigid PU foam is a stable product with a long lifetime, material for disposal can arise
when, for instance, appliances are scrapped or when underground insulated pipes are
replaced. It also naturally arises from within a process, from trimming and from out-of-
specification foam during process start up and change over. Companies are giving

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Polymer FoamsTrends in Use and Technology

increasing attention to the problems of waste due to environmental concerns and the cost
of disposal.

Two German companies, Aprithan Schaumstoff GmbH and Puren Schaumstoff GmbH,
are both using glycolysis to process their relatively pure PU scrap whilst other wastes,
comprising rigid PU foam mixed with covering layers of paper, mineral wool, glass fibre
and aluminium, are dealt with by a mechanical process. Glycolysis turns the PU waste
back into polyols for new rigid PU slabstock production and is a process which has been
used for many years.

Puren Schaumstoff has, in addition, developed a variant whereby the PU waste is mixed
with scrap PET from, e.g., soft drink bottles. This has the advantage of reducing
methylene diphenylamine (MDA) levels in the polyol produced, arising from MDI-based
PUs. MDA content can reach undesirable levels if only PU waste is used, resulting in
unwanted reactions in subsequent use.

Contaminated waste, i.e., waste containing PU foam mixed with covering paper, etc., is
first separated and pressed into briquettes which are then granulated and transported to a
mixing system. An MDI-based binder is added and the mixture pressed at 140160 C at
a pressure of 13 MPa for about 3060 seconds to form boards which are subsequently
cut to size. The product is said to have good mechanical properties, low heat conduction
and to be moisture resistant. Board thickness ranges from 5 to 60 mm with density from
250 to 850 kg/m3. Various construction applications are envisaged, including floor
insulation and sandwich elements. The process was sufficiently successful for Puren to
decide in 1997 to build a second plant to increase capacity.

BASF has developed a second-generation chemistry using glycolysis to recover polyols


from a variety of PU systems including rigid PU foam. Residual amine is claimed to be
less than 1%. The polyols are said to be reusable in polyisocyanurate foam, insulation
non-critical foam, structural foam, friable energy absorbing foam, low density void filling
foam, elastomeric coatings, rigid non-cellular PU and moulded semi-rigid foam.

Logstor Ror A/S, Denmark, has made a substantial investment (DM 2.5 million) in a
recycling operation to handle rigid PU foams recovered from underground pipe insulation.
The investment has been made under a licence agreement with BASF AG and its
Elastogran subsidiary, and initially involves a mechanical recovery operation to separate
the PU insulation layer together with the outer PE protective layer. After granulation, the
PE is removed by sieving (and is reused separately). The PU granulate is fed to a
glycolysis unit for recovery of polyol. Amines generated from the isocyanate moieties are
removed in a separate process. It is claimed the polyols can be reused in rigid foam
formulations without any fundamental formulation modification.

5.5 Properties

Some of the properties of rigid PU foam important in its applications are:

high insulating capacity with low thickness,


lightweight, with high mechanical strength,
chemically and biologically resistant,
durable,
satisfies fire regulations for particular applications,
quickly and easily processed on site, and
can be sprayed in place.

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Polymer FoamsTrends in Use and Technology

In many applications, insulation is the characteristic of most importance, and considerable


work has been done to investigate the performance of rigid foams with the newer blowing
agents, and in particular the long-term performance. Predicting long-term performance
from short-term accelerated ageing tests has also received recent attention.

Some published data is shown in Table 5.9.

Table 5.9 Thermal Conductivity of Rigid PU Foam Boards After Ageing (W/m K)
Blowing Product Time at 23 C Time at 70 C
agent thickness 6 2 5 25 39
weeks years years weeks weeks
Pentane 40 mm 0.0237 0.0267 0.0272 0.0266 0.0266
Pentane 80 mm 0.0230 0.0252 0.0263 0.0255 0.0257
HCFC-141b 50 mm 0.0203 0.0243 0.0252 0.0229 0.0231
HCFC-141b 60 mm 0.0192 0.0247 0.0257 0.0229 0.0231
Source: [6]

The data show that (at 23 C) the loss in thermal conductivity due to gas exchange occurs
mainly in the first two years but is not fully complete after five years. After 39 weeks at 70
C, conductivity loss was still less than 5 years at 23 C.

Analysis of gas in the cells showed the loss of blowing agent and its replacement by air
associated with the deterioration in insulation performance. Thicker foams show a slower
loss, as expected.

A method for predicting long-term (25-year) ageing values based on measuring the
increase in thermal conductivity after 25 weeks at 70 C has been described [2]. It is
claimed that the method is satisfactory irrespective of rate of ageing and the presence of
facings. This work indicates that HCFC-141b and n-pentane blowing agents are similar to
CFC-11 and CFC-12 in that a stable thermal conductivity value is reached in less than 25
years, and this value is likely to be maintained well beyond 50 years. The predictive
formulae given for 25-year values (25) are:

CFC-blown 25 = (1 - 6.5) mW/m K


Pentane-blown 25 = (1 - 5.4) mW/m K
HCFC-141b-blown 25 = (1 - 6.7) mW/m K

where 1 is the initial value (measured after less than two days ageing for thin samples).

5.6 Markets and Applications

The two major application sectors for rigid PU foam are construction and appliances.

5.6.1 Construction

In the construction industry, rigid PU foam is used for insulating boards and panels, as an
in-situ material for sprayed-in-place insulation and as a one-component bonding foam.
Boards are used in pitched and flat roofs, in suspended ceilings, in floor slabs with or
without underfloor heating, in walls for external, internal or cavity insulation (with rendering
if required) and in a wide range of buildings from multistorey car parks to farms. Load
bearing rigid sandwich panels formed by combining the rigid PU foam with rigid wood or

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Polymer FoamsTrends in Use and Technology

metal sheet facings are used for insulating roof and wall cladding. In thicknesses greater
than 100 mm, PUR sandwich panels are used for cold storage facilities and for
refrigerated storage and transport. Roofs and industrial components such as tanks or
pipes may be insulated by using polyurethane spray to produce an in-situ foam. Doors
and window frames can be fixed and joints sealed using one-component bonding foams.

In roof, wall, floor and ceiling applications, rigid PU foam has much in common with
polystyrene foam which is used for similar insulation applications (see Section 7). The
insulation market, however, is dominated by mineral or glass fibre wool which, whilst less
technically attractive, costs less as a material and more easily meets fire resistance
requirements. Data on the market share of various materials for insulation applications are
given in Table 5.10.

Table 5.10 Market Share of Thermal Insulation Products in Europe, 1998


Material kt % % 1995 Growth Rate
19982003 (%)
Mineral wool/glass fibre wool 2,400 63 60.5 1.9
EPS 530 14 27.7 2.1
XPS 130 3.5 3.4 2.4
Rigid PU 530 14 7.4 3
Others 210 5.5 1.0
Total 3,800 100 2.0
Source: [7] (1995 data [8])

The demand within the construction industry has been growing (see Table 5.11) and this
growth is expected to continue at a rate greater than that of the construction industry itself,
in line with increasing demands for the improved comfort provided by insulation, and the
energy savings available when insulation is used. Environmental as well as economic
pressures are driving this with building regulations being introduced in many countries to
increase insulation levels to reduce energy usage, although some cautions have been
voiced regarding risks from condensation and increased moisture levels. The
environmental benefits of rigid PU insulation have been examined by an eco-balance
calculation for pitched roof insulation and floor insulation [9]. Savings in energy used for
heating during use far outweigh the environmental costs of production and eventual
recovery, and the idea of allocating an eco-label to insulating materials that boast a lower
energy of production than competitive materials is questioned, since the latter may give a
greater long-term energy saving.

Table 5.11 Market Growth Data for Rigid PU Foam in the Construction Industry (kt)
Country 1992 1996 2001 (est)
North America 380 470 580
Europe 310 360 450
South-East Asia 30 90 170
Japan 80 90 110
South America 5 10 20
Rest of World 15 30 50
Total 820 1,050 1,380
Source: [8]

A breakdown of rigid PU foam usage by construction application is given in Table 5.12.

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Polymer FoamsTrends in Use and Technology

Table 5.12 Applications for Rigid PU Foam in Construction, 1996


Application Quantity (kt) Share (%)
Insulation boards/Insulation blocks 451 43
Panels 283 27
Binders 158 15
Miscellaneous 158 15
Total 1,050 100
Source: [8]

A report by the Freedonia group [10] predicts that USA demand for polyurethane in
construction products will rise by nearly 4% annually to reach 684,400 tonnes in 2001 and
816,480 tonnes by 2006. These figures include both rigid and flexible foams. The demand
for rigid polyurethane foam in insulation applications is predicted to rise by 4% annually to
reach 408,000 tonnes in 2001 and 499,000 by 2006.

5.6.2 Appliances

Refrigerator insulation is the other main application for rigid PU foam. In 1997, the
consumption of PU worldwide in refrigerators and freezers was 464 tonnes, some 40% of
the amount used in construction. A breakdown of consumption by region is given in Table
5.13.

Table 5.13 Shipments and PU Consumption in Refrigerators by Region, 1997


Region Shipment Consumption Share
(millions of (kt) (%)
units)
Europe 18.9 155 33
USA 11.5 98 21
Japan 4.8 28 6
South America and Mexico 10.7 54 12
China 13.2 78 17
Far East and India 12 51 11
World Total 71.1 464 100
Source: [11]

The larger markets in Europe, North America and Japan are well developed and although
there is a trend towards larger and more sophisticated models to meet customer demand,
the growth of the market in these countries is small or nil. These countries account for
60% of the total worldwide consumption of rigid PU foam in refrigeration. The market in
less developed countries, however, is not yet saturated and still shows significant growth.

Between 1993 and 1995, European refrigerator manufacturers moved away from CFC
blowing agents, mostly to cyclopentane, although HCFC-141b, HCFC-141b/HCFC-22
blends, and hydrocarbon blends have also been used. In the USA, as with rigid PU foams
for construction, HCFC-141b was the preferred blowing agent.

Whilst initially in Europe the resulting poorer performance (higher density and hence
higher shot weight, lower insulation value) of the non-CFC foams was accepted,
subsequent development work has aimed to meet the overall properties of the original
CFC foams. Legislation has been one of the driving forces, not only the Montreal Protocol

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Polymer FoamsTrends in Use and Technology

but also regulations on the reduction of appliance energy consumption introduced by the
EU and the voluntary Eco-Label of the EU. The key requirements for the Eco-Label are:

Sufficient insulation for the refrigerator to be rated A or B according to the 94/2/EC


Energy Efficiency Index regulation. For an A rating, energy consumption must be
below 55% of the standard value defined by the EU directive, whilst for a B rating
energy consumption must be between 55% and 75% of this value.

Foam blowing agent must have an ODP of zero and a GWP of no more than 15 CO2
equivalents.

The blowing agent requirements rule out both HCFCs and HFCs, limiting candidates to
hydrocarbons or CO2.

The appliance energy consumption regulations and the Eco-Label arrangements came
into force in 1999 (96/57/EC).

In the USA, HCFC-141b use is allowed by the US Environmental Protection Agency


(EPA) as a transition measure until energy efficient, zero ODP replacements become
available. Formulation development has essentially enabled such foams to match the
insulation performance of the CFC foams they replace, enabling refrigerator and freezer
manufacturers to remain in compliance with US Department of Energy (DOE)
consumption regulations.

The deadline for replacing HCFC-141b in the USA has been set by the US EPA as 1
January 2003. Additionally, the US DOE has issued an energy consumption regulation for
refrigerators and freezers sold from 1 July 2001. This calls for up to 30% reduction in
energy consumption from the levels permitted under the 1993 regulations. The US DOE
has estimated that this will result in significant savings in primary energy consumption and
a consequent reduction in CO2 emissions amounting to some 465 million tonnes over 30
years.

In Japan, a variety of CFC alternatives are in use with a ban on HCFCs planned for 2004.
There are no regulations for energy consumption for appliances although the importance
of energy saving is well recognised in the industry and strongly supported by the
government. The saturation of the market in Japan is illustrated by the figure of 1.2
refrigerators, on average, for each Japanese household.

The growth regions of South America and South-East Asia are less advanced in both CFC
replacement and energy reduction regulations, but the technologies now available are
being put in place and Brazil, for instance, has a regulation to eliminate CFCs in
household refrigerators by 1 January 2001.

China and India are areas where the relatively low market saturation offers good market
growth potential. The change over from CFCs is happeningalbeit slowly as use of CFCs
is still permitted under the Montreal Protocolthe trend being to use the drop-in HCFC
systems with hydrocarbons being used in some joint venture foam plants involving
European companies.

Development trends in the industrial countries are targeted at cost reduction whilst
continuing to meet environmental legislation for blowing agents and energy consumption.
In Europe and Japan, this focuses on improving hydrocarbon-blown foams either by
improving existing pentane-based systems or by development of systems based on
cyclopentane blends with various butane and/or pentane isomers. The latest systems are

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Polymer FoamsTrends in Use and Technology

claimed to match the properties of CFC-11 foams with lower cabinet fill weights, shorter
demould times and improved thermal conductivity factors. This has been achieved by
tailoring the basic polyol and isocyanate materials to the requirements of the new blowing
agents rather than continuing to use the original materials formulated for use with CFCs.

In the USA, HFC-245fa has been identified as the most suitable replacement for HCFC-
141b. Work done by Appliance Research Council and Bayer has shown that appliance
insulation made using this blowing agent has an energy consumption matching that of
HCFC-141b systems. Vacuum-based insulation panels are also receiving attention as this
technology is able to provide low thermal conduction properties. However, manufacturing
and installation costs are high and only a few manufacturers in the USA, Europe and
Japan offer appliances with such insulation. This may change with further tightening of
energy consumption regulations.

Process developments have also been implemented to achieve cost reductions and
improved insulation performance. TopFlow Technology, developed by Hennecke and
Bayer, injects the PU foam mix through the optimum filling point in the centre of the back
of the cabinet (rather than at the compressor end as is conventional). A Flowter serves
as both a mixing chamber and distribution valve and allows the fast injection of highly
reactive systems. This results in a good distribution of the PU mix with the shortest
possible flow length. The advantages claimed are:

finer cell size with lower conductivity factors,


improved density distribution,
shorter demould times,
lower cabinet fill weights, and
reduced maintenance of process equipment.

It can be expected that development will continue so as to satisfy customer and legislative
requirements, and it will be some time before formulations focus on one or a few systems
recognised as economically and environmentally optimal.

References

1. R. Brooks, Urethanes Technology, 1999, 16, 1, 34.


2. G.W. Ball, Cellular Polymers, 1997, 16, 2, 110.
3. L. Bertucelli, M. Vreys, F. Pignagnoli, A. Ottens and P. Keller, Proceedings of Utech
Asia 99, Singapore, Building and Construction Paper 6.
4. L. Zipfel, P. Dournal and W. Kruecke, Proceedings of Utech Asia 99, Singapore,
Building and Construction Paper 7.
5. G. Burkhart and M. Klincke, Proceedings of Utech Asia 97, Singapore, Paper 27.
6. W. Albrecht and H. Zehender, Cellular Polymers, 1997, 16, 1, 35.
7. C. Galbraith, Materials Technology, 2000, 15, 1, 103.
8. R. Kaufung, Proceedings of Polyurethanes World Congress 97, Amsterdam, The
Netherlands, 1997, 2.
9. E. Weigand, Insulation Journal, 1999, March/April, 11.
10. Report #928 Plastics in Construction to 2001, Freedonia Group Inc., 1998.
11. Bayer AG, Urethanes Technology, 1997, 14, 4, 42.

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Polymer FoamsTrends in Use and Technology

6 POLYOLEFIN FOAM

6.1 Introduction

Polyolefin foams are a relatively recent development in comparison with other foams such
as polyurethane and polystyrene. The main processes were introduced in the 1960s, with
significant commercial production beginning in the 1970s. Several processes are currently
operated: extrusion, moulding, bead and autoclave. The foams may be crosslinked or
non-crosslinked. Polymers foamed include polyethylene, polypropylene and copolymers
such as ethylene vinyl acetate (EVA). Properties, as with all foams, depend on the
properties of the starting material and the degree of foam expansion, and are modified by
the presence of any crosslinking. The base polymers vary substantially in stiffness and
flexibility, e.g., from stiff polymers such as high density polyethylene (HDPE) and
polypropylene homopolymer (PP), to relatively elastic materials such as ethylene
copolymers. The foam properties reflect this, and so foams can be rigid with good impact
resistance and high load support ability, or soft and flexible with good resilience and a
high comfort factor.

The morphology of most polyolefin foams is closed-cell, and the air or other gas trapped
within the foam structure contributes significantly to properties, especially with the softer
foams. Open-cell foam can be produced as a speciality by crushing a low strength
expanded polymer.

The range of foam properties has been expanded further recently by the availability of
metallocene-catalysed polyolefins. This new catalyst technology provides a high degree of
control over polymer structure, including extent and type of chain branching and
comonomer placement. Several manufacturers have developed new foams with
enhanced properties based on metallocene-catalysed polyethylene, polypropylene and
copolymers, and as further new polyolefins become available it is likely that they will be
considered for foam manufacture at an early stage of commercialisation.

6.2 Materials

The main polymer used for polyolefin foam production is low density polyethylene (LDPE)
made by high pressure polymerisation. This polymer is readily crosslinked using
peroxides, and even in the uncrosslinked state has sufficient melt strength to allow foam
production by extrusion processes using physical blowing agents. LDPE foams are semi-
rigid, with maximum use temperatures in the range 90110 C, depending on foam
density.

To achieve higher foam operating temperatures, a higher melting grade of polymer is


needed. Two materials have been used to achieve this: HDPE and PP.

HDPE (typically 0.958 g/cm3 compared to 0.920 g/cm3 for LDPE) is more highly crystalline
than LDPE with a significantly higher and sharper melting point. The higher processing
temperature required makes it difficult to incorporate crosslinking agents or blowing
agents (either chemical or physical) and Zotefoams is the only manufacturer producing
crosslinked HDPE block foam. This is possible because the autoclave process allows
production of extruded slabs with no addition of crosslinking agent or blowing agent.
Crosslinking is done later (by irradiation) and nitrogen blowing agent is incorporated at the
autoclave stage. The resulting foam is exceptionally tough and strong, with a service

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Polymer FoamsTrends in Use and Technology

temperature some 2030 C higher than the equivalent LDPE foams. HDPE foams are
rigid rather than semi-rigid.

Polypropylene has a higher melting point than polyethylene and offers another route to
improved high temperature performance. Its sharp melting point and low melt strength
have until recently given problems in the production of extruded non-crosslinked foams,
but the higher melt strength materials developed by, e.g., Montell and Borealis have
overcome these problems.

Production of crosslinked polypropylene foams has to overcome a further difficulty, that of


achieving sufficient crosslinking without undue polymer degradation which occurs if
peroxide crosslinking is attempted. A number of patents have appeared covering additives
which are claimed to enhance crosslinking of polypropylene with peroxides, and
manufacturers of polypropylene foam use proprietary crosslinkable formulations. The
formulations are normally blends including propylene copolymers and can produce semi-
rigid foams with temperature stability up to some 130 C.

Over the last few years the production of polyolefins using metallocene catalysts has
received wide attention. Since the commercialisation of metallocene polyethylene (mPE)
by Exxon Chemical, Dow Chemical and BASF, mPE has become well established with
consumption in 1997 of 120 kt in Europe and 535 kt worldwide. An estimate [1] of
consumption for the year 2001 is 450 kt in Europe and 2,030 kt worldwide. Similar growth
rates are expected for polypropylene and ethylene propylene copolymer (EPDM). Several
foam producers have launched products incorporating metallocene-catalysed polymers.

A summary of the 1999 availability of these materials in Europe is given in Table 6.1.

Table 6.1 Commercial Availability of mPE (Europe)


Producer Product Co-monomer Density range (g/cm3)
Borealis Borecone 1-hexane 0.9340.940
Dow Chemical Elite 1-octane 0.9160.935
Dow Chemical Affinity 1-octane 0.8680.915
Dex Plastomers Exact 1-octane 0.902
DuPont Dow Elastomers Engage 1-octene 0.88630.910
Exxon Exceed 1-hexane 0.918
Elenac Luflexen 1-hexane 0.918
Elenac Luflexen 1-butene 0.9030.917
Phillips mPact 1-hexane 0.9160.933
Source: [2]

It can be seen that the density range for mPE covers the range of conventional
polyethylenes, except for HDPE:

medium density polyethylene (MDPE), 0.930.94 g/cm3


low density polyethylene (LDPE), 0.9150.935 g/cm 3
linear low density polyethylene (LLDPE) and very low density polyethylene (VLDPE),
0.900.93 g/cm3

In the mPE area, a differentiation may be made between polyolefin plastomers (POP) and
polyolefin elastomers (POE), the former having density above 0.91 g/cm3 and the latter
0.91 g/cm3 or lower.

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Polymer FoamsTrends in Use and Technology

The two factors of most relevance to foam applications are the greater toughness which is
achieved with some POPs, and the commercial availability of POEs as alternatives to, for
example, EVA for production of flexible foams.

A significant disadvantage of mPEs is inferior processing behaviour due to the generally


narrow molecular weight distribution. This can lead to lower extrusion rates to avoid
excessive heat generation and premature blowing or crosslinking. This is hindering wider
use of mPEs in all application areas, and is being addressed by the polymer producers
whose aim is to eventually provide mPEs which can be processed like LDPE whilst
retaining the advantageous properties. This is already being tackled by widening the
molecular weight distribution (e.g., Finacene from Fina, pilot plant stage), and/or by
introducing long chain branching (e.g., Evolve from Mitsui, not yet commercially available
in Europe). Both of these approaches make the polymer structure more like that of LDPE
and it remains to be seen whether the advantageous properties of mPEs can be fully
maintained in modified versions having better processibility.

Foams based on mPE of density 0.910.92 g/cm3 (designated MP grades) and density
0.870.89 g/cm3 (designated MV grades) have been described by Zotefoams, with MP
foams having density ranging from 15 kg/m3 (only achievable with the autoclave process)
to 45 kg/m3 commercially available. A flame retardant 15 kg/m3 grade is also produced.
The MP foams have tensile strength some 60% greater and tear strength more than twice
that of LDPE foams of similar density. Exceptionally good thermoforming properties have
also been found for these materials, attributed to good hot melt strength.

It is claimed by Sentinel that all its foams incorporate metallocene resins. H-cell, Microcell,
T-Cell, Opcell and SSP-NE are based on POPs and are said to be stronger than
conventional polyethylene foams. POEs are used for EMR, CMR and T-Cell MPO
elastomeric grades. These latter foams are seen as competing with cellular elastomers
such as EPDM blends or PVC-nitrile blends with the advantage of lower foam density
whilst matching properties. The enhanced properties of these materials are claimed to
arise from the use of mPE resins combined with silane crosslinking systems which
overcomes the processing problems imposed by the narrow molecular weight distribution
present in mPEs. Silane groups are grafted onto the polymer chain during processing and
crosslinking is effected later by exposure to water vapour. A combination of peroxide and
silane crosslinking can give enhanced physical properties in these materials, notably
improved compression set.

An interesting addition to the widening range of metallocene-catalysed polyolefins is Dow


Chemicals range of Index Interpolymers. These are based on the copolymerisation of
ethylene and styrene using Insite technology. The new polymers have already been
commercialised in foams.

For instance, Synergy Soft Touch Foams from Dow Performance Foams, USA, are
produced from a blend of LDPE and the new ethylene styrene Index copolymer. These
foams are claimed to offer strength and low abrasion combined with resilience and a soft
touch. They also have shock absorbing and vibration damping qualities. Other products
include QUASH dBI Sound Management Foam, claimed to offer outstanding sound
absorption properties, and ENVISION Custom Foam Laminate, incorporating foams
based on Index Interpolymer. The new foams are made with Dow Chemicals Rapid
Release technology, using a hydrocarbon blowing agent and an accelerated curing
system reducing the emissions of blowing agent.

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Polymer FoamsTrends in Use and Technology

Senflex, from Sentinel, is said to be an ultraflexible foam with density as low as 16 kg/m3
with low compression set and superior shock absorption characteristics. This material is
produced using a physical blowing agent with Sentinels metallocene foam technology.

Sekisui Chemical has introduced a new honeycomb polyolefin foam said to be recyclable
and much stronger than polystyrene foam for application as sound proofing and impact
energy absorption in cars. Materials under development include a family of polyethylene
and polypropylene foams with compression stiffness optimised in the vertical direction.

Other polymers which are in general use are ethylene copolymers, mainly EVA
copolymer. These are flexible materials which provide soft resilient foams, generally of
higher strength than an equivalent density LDPE foam. A recent introduction by
Zotefoams is a foam based on EMA copolymer. This foam is characterised by exceptional
softness and fine cell size.

All copolymer foams have a lower maximum service temperature compared with LDPE
foams owing to the lower melting point of the polymer. Comonomer levels are normally in
the range 9% to 18%.

Additives are used to confer special properties:

Pigments: No additives are needed for a white foam since reflections from the cell
walls normally give foams an opaque white appearance. Colouring pigments may be
added to the mix directly or in masterbatch form, the latter being cleaner and more
accurate, but at extra cost.

Flame retardants: Antimony trioxide with an organic halogenated compound is


normally used, with brominated compounds being preferred. Foams with suitable
additives can be made self-extinguishing, meeting various furniture, aircraft and other
fire and flammability standards.

Antistatic agents: These additives diffuse to the foam surface where they absorb
moisture and enable the surface to become sufficiently conductive to dissipate any
build up of static electrical charges. Whilst in common use for the manufacture of
foam for packaging sensitive electronic components, they do have some general
problems: a dependence on humidity levels for proper performance, an absence of
antistatic agent on freshly cut surfaces and a tendency for effectiveness to reduce on
ageing.

Conductive additives: Polyolefin foams can be made electrically conducting (e.g., with
a volume resistivity of less than 10 4 FP FRPSDUHG ZLWK QRUPDO LQVXODWLYH YDOXHV RI
about 1014 FP E\ FRPSRXQGLQJ ZLWK KLJK VWUXFWXUH carbon black. Such foams are
also used for packaging and assembling sensitive electronic components, and tend to
be more stable and reliable in their properties than the antistatic foams, albeit at
extra cost.

Fillers: Whilst it is technically possible to incorporate fillers in polyolefin foams this is


not normally done because there is no reinforcement effect; the filler essentially
increases foam density without contributing to properties. Cost reduction of foams is
best pursued by density reduction.

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Polymer FoamsTrends in Use and Technology

6.3 Processes

6.3.1 Extruded, Non-Crosslinked Foam

The traditional process still used for production of polyethylene foam by extrusion uses a
physical blowing agent which originally was CFC-11. In a single step extrusion line, a
homogeneous melt is established in the first section of the barrel where all the additives
such as nucleating agents, pigments and process aids are incorporated. The blowing
agent is metered in at a second section where it is mixed and dispersed at high pressure,
typically 1520 MPa. The melt viscosity falls after addition of the blowing agent, allowing
effective cooling of the mix down to temperatures close to the polymer melting point. At
the die there is a rapid pressure drop and the polymer expands directly from the die.
Adiabatic cooling effects help to reduce the extrudate temperature to stabilise dimensions
and allow post production operations. A maturing period is necessary to allow air to
diffuse into the foam and blowing agent to escape, and equipment is necessary to collect
and exhaust the vapours so produced.

A preferred, technically superior, process is a tandem extrusion system which, whilst more
capital intensive, allows separation of the initial melt homogenisation and blowing agent
mixing from subsequent melt cooling. This becomes necessary at high output rates (250
500 kg/h) or if a wide range of formulations is to be processed. The primary extruder may
be a co-rotating twin screw type, which allows considerable flexibility in setting up to
obtain optimum mixing conditions. Attention must be paid to the provision of adequate
sealing at the rear of the second extruder.

The use of CFC-11 has been discontinued in developed countries and alternative blowing
agents are now used (see Section 3). HCFCs or HFCs would be possible replacements
but hydrocarbons such as pentane and isobutane appear to be the most widely adopted,
since HCFCs have only a limited period before they too are phased out under the
Montreal Protocol, and HFCs are relatively costly. It is necessary to take precautions in
production to accommodate the flammable and (in mixtures with air) explosive nature of
the hydrocarbons. There has also been concern regarding the possible presence of
residual hydrocarbon blowing agents in the foam. The main danger is from a build up of
vapour in the atmosphere surrounding foam stored in a closed container, for instance
during transportation, or in a packaging application. Controlled maturing is required to
allow the vapours to diffuse out of the finished foam before the product is dispatched.

Other non-CFC blowing agents which have been examined for polyolefin foams include
CO2. As with other CO2 blown foam systems, this has the advantages of low cost and
zero ozone depletion potential, but the operating process is more sensitive and requires
higher operating pressure with some problems which have to be overcome to ensure
adequate sealing. The resulting foams tend to have poor cell structures with large cell
dimensions and some dimensional instability due to the rapid diffusion rate of CO2 out of
the foam compared with the slower rate of air into the foam. CO2 is best used for higher
density foams.

Extrusion technology for production of non-CFC blown extruded polyolefin foams is


available from, e.g., Reifenhauser GmbH, Germany (REI cell lines) and Berstorff GmbH,
Germany (Shaumex and Schaumtandex lines). Reifenhauser offers a direct gas injection
technology which allows foamed polypropylene and polystyrene to be made on the same
extrusion line. The manufacturer claims that foam density is lower than that available from
use of chemical blowing agents, and that there is an opportunity to produce multilayer
sheets by co-extrusion.

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Polymer FoamsTrends in Use and Technology

The MuCell extrusion process (see Section 11) is claimed to be able to produce
microcellular polypropylene by extrusion using CO2 as the expansion gas. This new
technology is available for license from Trexel.

The usual polymer used for non-crosslinked extruded polyolefin foam is LDPE produced
by high pressure reactor technology; this has very suitable processing characteristics
resulting in smooth flow at relatively high extrusion rates. More recently, PP variants have
been introduced, notably by Montell (Higran) and Borealis (Daploy HMS130D), which
overcome the problems generally experienced in foaming this polymer. PP produced by
conventional catalysts has a linear chain structure and is characterised by a sharp melting
transition and low melt strength (i.e., low resistance to melt elongation). Cell stabilisation
is insufficient with these polymers to produce good quality foam. In the 1980s, Montell
developed technology which introduced long chain branches into polypropylene, and
these materials exhibit good melt strength and strain hardening. Cell stabilisation is
substantially improved and these polymers, known as HMS (High Melt Strength) PP and
available commercially from Montell as Higran, can be used in non-crosslinked extrusion
foam processes to produce PP foam with densities ranging from as low as 20 kg/m3 up to
600 kg/m3.

Montell has adapted this process for the formation of PP foam beads. In this technology,
which is a recent alternative to the batch bead process (see Section 6.3.5), the extrudate
is cut directly at the die plate by means of a rotary knife. The pellets expand immediately
due to the pressure drop and are cooled by passing into a water flow, followed by drying
and bagging. The process, which can also be used for polyethylene, produces spherical
beads with densities down to 18 kg/m3, suitable for steam chest moulding. Montell
produces expanded PP (EPP) beads commercially at its Bayreuth site under the trade
name Higran F. Production started in 1996.

Grand Polymer Co., (Japan) has developed a new polypropylene claimed to have
extremely high foaming properties that can replace polystyrene in expanded sheet
applications.

A variant of the extrusion foaming process was introduced by Berstoff which enables the
extrusion of thermoplastic elastomers (TPEs) to produce foam. The development, which
resulted from co-operation between AES Corporation and Berstorff, uses water as the
blowing agent and gives a fine cell structure. Using Santoprene, best results were
obtained with 1% water giving a foam with a density of 300 kg/m3. The process can
provide high density foam profiles for use as alternatives to EPDM foam in automotive
applications. It is of interest to note that no additional nucleating agent is necessary to
obtain fine cell size since the dispersed rubber phase of the TPE acts in this capacity. A
single stage extruder is used of 30 length:diameter ratio (L/D) with a mid-point injection for
the blowing agent. Special mixing sections are used to ensure adequate dispersion of the
blowing agent, and cooling of the polymer is from 220 C at the injection point to 195 C at
the die. The extruded foam profile is quenched by water spray and taken away on a belt
conveyor.

Compared with the traditional EPDM batch process, the TPE extruded foam process is
claimed to give a more consistent product, has no harmful emissions, and enables waste
to be recycled with virgin TPE to produce foam or other products.

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Polymer FoamsTrends in Use and Technology

6.3.2 Extruded Crosslinked Foam

The processes for manufacturing extruded crosslinked foam were developed in Japan in
the 1960s and have subsequently been commercialised through subsidiary companies
worldwide. Essentially, there are two process variants, one using irradiation crosslinking
and the other chemical crosslinking. Both processes use a chemical blowing agent for
expansion.

6.3.2.1 The Irradiation Crosslinking Process

This process was developed by Sekisui Electrical Co. (Japan). Although generally
considered a continuous process, it is actually carried out in two separate stages:
extrusion and crosslinking followed by expansion.

Powder grades of LDPE homopolymers or EVA copolymers blended with pigments,


lubricants, activators and the blowing agent (which is normally azodicarbonamide (AZDC))
are suitable for extrusion. Powder grades are necessary to allow addition of the blowing
agent system at levels of 1020 phr and to ensure a homogeneous feed to the extruder
screw. Melt temperatures are reduced by the presence of lubricants and are typically 130
145 C, significantly below the activation temperature of the blowing agent. A sheet die is
used to provide a thin uniform extrudate of width 1.01.5 m and thickness 34 mm which
is then exposed to radiation. The radiation source may be electron beam or cobalt 60
(gamma ray), but shielding problems generally preclude the use of radioactive isotopes in
a normal factory environment. Crosslinking is achieved by a dose of 0.120 Mrad.

For thin sheets, irradiation gives an essentially uniform level of crosslinking through the
sheet profile, but there are problems of non-uniformity if sheet thickness is too great.
Increasing the radiation dose can result in surface damage. Better crosslinking uniformity
in thick sheet can be achieved by irradiating both sides of the extrudates, but sheet
thickness remains a limitation.

In the stage following radiation crosslinking, expansion is carried out in an infrared (IR)/hot
air oven, often arranged vertically. Arrangements have to be made to handle the sheet in
its hot state as it rapidly expands up to 30-fold in all three dimensions. Temperatures up to
250 C are typical.

Whilst in theory the extrusion and expansion stages could be linked, in practice,
differences in extrusion speed, crosslinking and final expansion preclude the development
of a fully continuous operation.

6.3.2.2 The Chemical Crosslinking Process

There are two slightly different processes used for the production of chemically
crosslinked polyolefin foam, differing mainly in the expansion stage.

The Furukawa process utilises a separate initial compounding stage to incorporate both
the blowing agent and the chemical crosslinking agent, and the other additives such as
pigments and lubricants. Adequate dispersion of blowing agent and crosslinker is
essential for the production of foam with fine uniform cell structure, but compounding
problems are imposed by the time/temperature decomposition dependence of these
ingredients.

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Organic peroxides with short half-lives and low activation temperatures are necessary to
ensure, in the post extrusion step, that crosslinking is essentially complete before
significant expansion takes place. Dicumyl peroxide (DCP, decomposition half-life of 1
minute at 170 C) is usually employed, normally with a carrier to improve dispersion and
to eliminate slipping effects when the compound melts (5560 C). Another peroxide
sometimes used is 1,2-bis (t-butyl peroxy isopropyl) benzene which decomposes at a
somewhat higher temperature giving greater latitude in processing as regards onset of
crosslinking.

Use of AZDC blowing agent, activated by metal compounds such as zinc oxide or an
organo zinc complex, does not normally pose problems provided temperature during
compounding is held to 120130 C. However, problems can arise from residual material
in the mixer, resulting in excessive dwell times.

Important characteristics of the blowing agent are gas yield, decomposition temperature,
and rate of decomposition/gas evolution. As well as the presence of chemical activators,
the particle size and distribution are factors in determining these characteristics. Coarse
grades of AZDC with a minimum of fine particles are normally used with average particle
size up to 35 microns.

Compounding techniques include both Banbury type batch mixers and twin screw
compounding extruders, in both cases followed by a pelletiser.

In the next stage, an extruder is used to produce a non-crosslinked, unexpanded sheet.


Melt temperatures in the extruder are maintained around 110115 C. Single screw
extruders are used with a screw design aimed to provide good mixing but with controlled
shear for minimum heat generation. Sheet from the die is passed through a cooling unit
and normally stored for at least 24 hours before progression to the expansion stage. This
maturing period helps to provide a good fine cell structure in the expanded product.

In the final (expansion) stage, the unexpanded sheet is passed through a three-zone
horizontal high velocity hot air oven. Air jets are used not only for heating purposes but to
ensure the hot expanding sheet does not adhere to the transport mechanism, which is a
continuous wire mesh conveyor. At the exit, the expanded sheet is released from the
conveyor by air jets and wound onto a take off reel.

The Hitachi process is very similar to the Furukawa process until the final expansion stage
where there are significant differences in oven design. Specifically, an initial IR oven is
used in the Hitachi process to effect rapid crosslinking prior to expansion. This enables
the expanding foam to be transported through the main three-zone oven without the use
of a wire conveyor, its hot strength being sufficient to allow free expansion supported only
by air jets. This results in a fine cell structure and a smooth surface finish.

The higher level of crosslinking achieved in the Hitachi process by use of the separate
crosslinking zone enables lower densities to be achieved with a smooth skin owing to the
absence of a wire conveyor. However, more critical control over crosslinking levels is
necessary. A high crosslink level will cause excessive shrinkage on exit from the
expansion oven, whilst too low a level can result in low melt strength and tearing/breaking
of the sheet whilst unsupported in the expansion oven.

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Typical formulations for extruded crosslinked polyolefin foam are (per 100 parts of LDPE
polymer):

5 parts AZDC and 0.5 parts DCP to give foam density 100 kg/m3
10 parts AZDC and 0.7 parts DCP to give foam density 60 kg/m3
17 parts AZDC and 0.9 parts DCP to give foam density 30 kg/m3

Formulations are adjusted to give the correct balance between crosslinking and gas
release. Early decomposition of AZDC at low crosslink levels results in gas loss from the
polymer melt which at that stage has insufficient melt strength to contain the gas. Late
decomposition results in restricted expansion. By separating the crosslinking and
expansion steps, the irradiation process eliminates the possibility of overlap between
crosslinking and gas evolution and allows greater latitude in the selection of blowing agent
grades.

6.3.3 Press Moulded Foam

Extrusion processes for crosslinked foam have limitations in the sheet thickness which
can be produced, particularly the irradiation process whereby non-uniform crosslinking
may result for thicker extrusions. In the chemically crosslinked processes, heat transfer is
the limiting factor. Whilst lamination can be used to build up thicker sheets from the initial
1020 mm maximum of primary foam, non-laminated foam in the 80100 mm thickness
range can only be produced by press moulding methods. See, however, the nitrogen
autoclave process, Section 6.3.4, which can produce foam blocks up to some 50 mm in
thickness.

6.3.3.1 Single-Stage Process

In this process, which is similar to that used for expanding other polymers such as flexible
PVC and various elastomers, a compound of polymer, crosslinker (usually DCP) and
blowing agent (activated AZDC), and any required additives, is produced using mixing
conditions which preclude any significant crosslinking or blowing agent decomposition.
The compound is placed in a mould and heated under pressure, typically for 45 minutes at
150170 C. After completion of the curing cycle, the press is opened which allows
extremely rapid expansionthe product jumps out of the mould.

Whilst having the advantage of simplicity, the single-stage process has several
disadvantages:

high mould pressures can be generated, requiring high clamping forces and heavy
duty presses,
high press opening speeds (>10 cm/s) are needed to accommodate the rapid
expansion,
only a part of the platen area can be used (to avoid contact of the expanding foam
with guide pillars),
mould design is critical to avoid excessive internal stresses (resulting in splitting
during expansion),
density of less than some 70 kg/m 3 cannot be achieved since the rapid rate and high
degree of expansion causes foam splitting and failure.

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6.3.3.2 Two-Stage Process

The two-stage process, which has a number of variants, overcomes the disadvantages
inherent in the single-stage method. Essentially, in the first stage, crosslinking is effected
under conditions resulting in no, or only partial, expansion when the mould is opened.
Expansion is carried out separately at the second stage. Variants include:

Press curing for some 40 minutes at 130150 C, which is followed by partial


expansion when the mould is opened. The intermediate product is immediately
transferred to a hot air oven for second stage expansion, typically 170 C for 50
minutes.

Press curing for some 20 minutes at 130 C. This provides partial crosslinking but no
expansion, the latter being carried out subsequently in a hot air oven, 130165 C for
60 minutes.

Press curing at 170 C followed by chilling. The blowing agent is essentially all
decomposed but since the product is chilled before the mould is opened, no
significant expansion occurs as it is restricted by the higher strength and stiffness of
the polymer at ambient temperatures. Expansion is carried out in a hot air oven,
although immediate transfer from the first stage is not necessary.

Intermediate products may be placed in moulds for the second stage expansion, which
allows better control of density and dimensions. Heating in this case can be by steam.

In both the single- and two-stage processes, the interdependence of formulation


components (crosslinking versus gas release) is not so critical as in the extrusion
processes. Formulations are generally based on blends of LDPE with EVA copolymer, the
latter giving higher crosslinking rates and increased melt strength during expansion.
Levels of 8% to 20% EVA are typical, with even greater amounts used if flexible elastic
foams are required. A level of 6 phr AZDC for a 70 kg/m3 density foam is typical.

Evolution Foam Moulding has developed a process for the manufacture of crosslinked
polyethylene foam blocks in the range 30 to 100 kg/m 3. The process involves use of a
chemical blowing agent and expansion is in two stages. Two prototype plants have been
built. The investment and running costs are said to be low and the process may be
attractive to entry-level manufacturers.

6.3.3.3 Injection Moulding Foam Process

For injection moulded polyolefin foam, polymers are selected to give high melt fluidity in
the range 100120 C to permit compounding without pre-decomposition. Screws with
L/D ratios of 2530:1 are used to achieve good mixing prior to injection. EVA copolymers
or blends are used to achieve adequate crosslinking rates, and the blowing agent is
normally a highly activated form of AZDN. It is usual to precompound prior to injection as
this gives a greater degree of control over the formulation accuracy and the dispersion of
its components. Mould design is important to avoid internal stresses on expansion which
occurs immediately after mould opening. Similar considerations apply as with the single-
stage process as regards press requirements, and density is generally limited to a
minimum of 100 kg/m3 ranging typically up to 300 kg/m3. Mould temperatures are normally
about 200 C and must be maintained by insulation, particularly at the parting line. Small
decreases in temperature here result in lower surface crosslink levels, giving a line of

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weakness leading to possible splitting of the skin during expansion/ejection from the
mould.

6.3.4 The Nitrogen Autoclave Process

The autoclave process is a unique foam production method carried out only by one
company worldwideZotefoams plc, UK.

The process has three stages:

extrusion and crosslinking,


gassing, and
expansion.

At the first stage, a polyolefin (e.g., LDPE), with any additives required, is extruded to give
a sheet up to some 12 mm in thickness. A peroxide crosslinking agent may be
incorporated at this step, in which case the sheets pass through an oven to effect
crosslinking. The sheets are carried on a conveyor using a textile belt with a fluorinated
polymer coating to enable release of the sheets from the belt after curing. At the end of
the extrusion line, sheets are cut to precise sizes and stored for the second stage.

If no chemical crosslinker has been used, crosslinking either by electron beam or cobalt
60 (gamma) radiation is used. Since the irradiation treatment is carried out off line (and off
site), there is no factory problem with shielding during production. If high intensity electron
beam treatment is used, appropriate exposure regimes ensure crosslinking uniformity
through the sheets.

At the second stage, the blowing agent is incorporated by exposing the crosslinked
extruded slabs to nitrogen under pressure in an autoclave. Temperature is raised above
the melting point of the polymer to, e.g., 150 C, and nitrogen is pumped in to reach
pressures up to 6070 MPa. Nitrogen dissolves in the polymer to an extent which is
determined by the precise pressure and temperature in the autoclave. The high
pressures, which are required to ensure significant amounts of nitrogen are incorporated,
make considerable demands on the design of the autoclave and ancillary equipment, and
this part of the plant has a high capital cost. After a period of several hours to ensure
complete and uniform dissolution of nitrogen in the polymer slabs, the pressure is reduced
and the slabs cooled to a temperature near to ambient. As the pressure is reduced, the
nitrogen comes out of solution to form the nuclei of cells, but conditions are controlled
such that significant expansion is prevented by the high modulus and strength of the cold
polymer. The slabs, now containing the required amount of blowing agent, and with the
cells fully nucleated, are removed from the autoclave and transferred to the final stage.

Nucleated slabs are expanded in a heated low pressure autoclave. Application of


pressure, typically some 1.5 MPa, prevents expansion whilst the slabs are heated above
the polymer softening point. When this is reached, the pressure is released to allow
expansion of the slabs to their final dimensions. This method eliminates the possibility of
foam distortion which would result from the initial expansion of edges and surfaces as
they are the first points to reach the polymer softening temperature.

The process has a number of advantages over other methods for the production of
poylolefins:

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the blowing agent is pure nitrogen gas, leaving no solid residues in the foam, which
is, therefore, very pure,
crosslinking and expansion are separated making it easy to control these processes
and allowing considerable latitude in the choice of polymers,
the foam cell structure is excellent showing good uniformity and integrity leading to
good physical properties, and
cell size is readily controlled at the nucleation phase of the high pressure autoclave
cycle to allow production of foams with cell sizes in the range 0.20.8 mm.

The main disadvantage is the high capital cost of the equipment compared with other
processes, and, with the demanding design and operating parameters which have not
been disclosed by Zotefoams, has prevented more widespread adoption of this
technology. Although this is a batch process, Zotefoams has done considerable
development work using larger autoclaves at both gassing and expansion stages and
production economics are good, especially for low density foam which has the highest
loading in the (costly) high pressure autoclave.

It is of interest to note that foam density is determined by the temperature and pressure at
the gassing stagethe same formulation can be used to provide a range of foam density.

Developments in the autoclave process, apart from those to improve production


economics, have been aimed at expanding the range of foams available. Until recently
thickness was limited to 3035 mm by the long cycles required for thicker slabs to allow
adequate time for nitrogen to saturate but now thicker foam sheets, up to 52 mm, can be
produced. Foam density reduction to 15 kg/m3 is another recent development, making
these materials the lightest crosslinked polyethylene foams in production worldwide. The
lower density is made possible by modifications of the second stage gassing conditions
which increase the amount of nitrogen taken up by the polymer slabs. Experimental work
carried out by Zotefoams has demonstrated the possibility of producing foams with
densities as low as 10 kg/m3 and the technical limit for density reduction in this process
has not yet been realised. Other processes using chemical blowing agents are mostly
limited to 2025 kg/m3 at the lower end of the density range due to the cost of increased
levels of blowing agent, the difficulties of compounding and the higher levels of blowing
agent residues.

6.3.5 Bead Processes

An alternative method for the production of foam mouldings, first developed for
polystyrene by BASF in the 1950s, is the use of foam particles or beads. During the
1970s, mouldable polyethylene particle foams were introduced in Europe and Japan, and,
in the 1980s, polypropylene particle foams were developed.

In the bead production process, the polymer is converted to micropellets and loaded into a
large tank as an aqueous slurry. The pellets are impregnated with a hydrocarbon blowing
agent such as propane at elevated temperature and pressure and are subsequently
expanded to spherical foam particles of diameter 45 mm. The volatile blowing agent is
recovered and recycled. Residual blowing agent in the particles is low. In contrast to
polystyrene beads, which may be transported in the partially expanded state since the
blowing agent is retained for weeks or months after manufacture (depending on storage
conditions), polyethylene or polypropylene beads do not retain the blowing agent for any
significant length of time and are, therefore, fully expanded at the time of manufacture and
transported in this form.

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Expanded polyolefin beads are available from several manufacturers, e.g., BASF
(Neopolen), Arco, Gefinex (Vestocel), Fagerdala (FAWO CEL), Kaneka.

The processing of expanded polyolefin beads uses equipment similar to that used for
polystyrene beads (see Section 7). Essentially, the foamed particles are fused together by
means of steam at an appropriate pressure in metal moulds.

An important control parameter is the back pressure used when the beads are blown into
the mould. Higher back pressures result in greater compression of the beads and hence,
since the beads are blown into the mould until it is volumetrically full, a greater loading
and so a higher density for the final product. Back pressure controls moulding weight and
product density.

The low bulk density of EPP particles (down to 11 kg/m3) leads to relatively high transport
costs, and techniques for moulding lower density products from higher bulk density beads
have been developed. For instance, by subjecting the particles to a stepwise increase of
air pressure (0.30.4 MPa) at room temperature additional blowing gas can be introduced.
The beads are transferred to a moulding machine for immediate use. This pre-
pressurisation technique allows a moulded part of 30 kg/m 3 to be produced from foam raw
material of bulk density 28 kg/m3 compared with 17 kg/m3 with no pre-pressurisation,
giving a substantial reduction in raw material freight and storage costs. Disadvantages of
the technique include the large pressure vessels and long treatment times (~ 24 hours)
needed.

BASF developed a method whereby the pre-pressurisation is carried out at elevated


temperature (7080 C). This technique, designated the Pressure and Temperature (PAT)
system, reduces the treatment time from 24 hours to 46 hours, and can be operated
quasi-continuously.

6.3.6 Post-Manufacturing Operations

Polyolefin foams can be processed by a variety of methods to form the final products:

sawing, adhesive bonding,


splitting, routing,
die stamping, sanding,
hot wire cutting, drilling,
laminating, flocking, and
butt welding, printing.

The non-polar nature of the substrate must be taken into account when choosing
adhesives, and this is also the case for flocking and printing. Pre-treatment of the surface
by, for instance, corona discharge improves results. Bonding, printing and flocking of
copolymer foams, such as EVA, is generally easier than with PE foams, owing to the more
polar surface characteristics of the EVA.

Lamination of sheets to build up thick products requires no adhesive as both crosslinked


and non-crosslinked foams are capable of self bonding if heated above the softening
point. This can be done by hot air blowers or by passing the foam sheets over a heated
blade. The bond is at least as strong as the foam.

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Polymer FoamsTrends in Use and Technology

The ability of crosslinked foam to remain stable at temperatures above the polymer
softening point is made use of in thermoforming processes. This is not generally possible
with non-crosslinked foams as the polymer matrix has little strength above the softening
point and the foam collapses unless the moulding temperature is kept within impractically
narrow limits. Crosslinked foams have a much wider latitude in moulding temperature.

The moulding processes used are:

Heat mouldingAn unheated piece of foam, usually precut to appropriate


dimensions, is placed in a cold two-part mould with an overload of some 10%. The
mould is closed and then heated to an appropriate temperature. At the end of the
cycle the mould is allowed to cool and the part removed.

Heat impression mouldingIn this process the foam is preheated by infrared or hot
air oven (the latter is preferable as it gives better temperature control) and transferred
to a cold mould. The mould is closed and then, after an appropriate time, opened to
remove the moulded foam. Manufacturers of foam give recommendations concerning
heating and moulding times for their various foam grades at different thicknesses.
Typically, for LDPE foam of 45 kg/m3 density, heating time in a hot air oven is 10
seconds at 140 C per 1 mm of foam thickness. Moulding times are similar to heating
times.

Heat impression moulding has obvious advantages over heat moulding in giving
faster moulding times and less costly moulds but makes more demands of the foam
regarding stability in the heated softened state, and affects the ability of the hot foam
to deform rapidly to the mould dimensions without tearing or splitting. Mould design,
avoiding high draw ratios and sharp corners, is important. Improved thermoforming
performance is seen as foam density increases, although if the foam has a good cell
structure and high intrinsic melt strength, foams with density of 24 kg/m3 and below
can be processed in this way.

Vacuum formingThis is a variant of heat impression moulding whereby the heated


sheet of foam is placed in a one-piece mould and vacuum is applied to draw the
sheet to the mould shape.

An interesting thermoforming variant is used for medical applications to make perfectly


fitting, removable splints and supports. This technique uses the human body as the
mould. Heated foam is applied directly to the body, e.g., an arm, leg or neck, and allowed
to cool to give an exact match to the body shape. Although the foam is preheated to some
140 C, no discomfort is experienced by the subject as the low heat capacity and thermal
conductivity of the foam prevents the skin reaching an uncomfortably high temperature.

6.4 Recycling

Polyolefins are thermoplastic materials and can readily be recycled by granulation for
remoulding or extruding. In the case of non-crosslinked foams, the foam structure is
destroyed and moulded products are solid unless the granulated recyclate is passed
through the foaming process again, which is feasible at addition rates of 10 to 20%. As
with all recycling processes, there can be problems in collection and transport which are
exacerbated in the case of foams by the low density of the product. There is also the
usual problem of separating material from possible contaminants. Recycling within a foam
manufacturing operation is not too difficult where control can be exerted over the

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collection of waste materials and transport is not an issue, but collection and recycling of
products after use is more difficult although systems have been set up to enable this.

Crosslinked foam is more difficult to recover by melt reprocessing as even the


comparatively low crosslink level present (compared with crosslinked elastomers) is a
substantial hindrance to melt flow. However, the presence of the crosslinks gives the
foams improved physical properties which enables applications such as reusable
packaging, e.g., in-factory transit packs for automotive plants. Reuse may be considered
the best form of recycling.

Where reuse is not applicable, the low crosslink levels still allow a degree of melt
reprocessing, and several recovery processes are operated:

Foam is coarsely chopped (to 1020 cm pieces) and passed on a conveyor through a
heating chamber, followed by light consolidation using shaped rollers or in a press.
The pressed product can be used as, e.g., drainage liners in roof-top gardens, since
water can pass through the voids between the consolidated foam pieces.

Foam is granulated (to 0.51.0 cm pieces) and the granules are passed to a machine
for consolidation by shear between a rotating and stationary plate. This heats the
granules above their melting point and breaks down the foam structure. The granules
are collected and may be used as a coarse moulding powder, although the original
objective of the treatment was density reduction to facilitate waste disposal. Bulk
density of the consolidated granules is in the region of 300400 kg/m3 compared with
a foam density of, for example, 50 kg/m3.

Energy recovery by burning is often considered the best option for recycling plastics,
although this is not encouraged by the European Packaging Regulations. Polyolefin foam
can be combusted to produce heat and in this respect is some three times more effective
than paper or wood (on a weight basis). Domestic waste can be difficult to incinerate
effectively without the presence of waste polyethylene.

6.5 Properties

As with all foams, properties of expanded polyolefins depend primarily on foam density
and the nature of the base polymer used. However, almost all polyolefin foams are closed
cell, and the enclosed gas also contributes to properties. As the base polymer increases
in flexibility so the contribution of the enclosed gas becomes more important, particularly
for compression properties. Foam structure (the perfection of the cellular network) and
polymer structure (presence or absence of crosslinking) make a significant contribution to
properties such as tensile strength, tear strength, compression set, and impact
performance.

Published data [3] show that Zotefoams autoclave process gives foams with good cell
structure compared with foams produced by other processes. Strength properties in
particular are at the top end of the range for these materials compared with those of
extruded chemically or physically blown foams, chemically blown moulded foams or bead
foams.

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Table 6.2 Properties of LDPE Foams (Autoclave Process)


Grade LD24 LD33 LD45
Nominal density (kg/m3) 24 33 45
Compression strength (25%)(kPa) 35 40 50
Compression set (72 h, 50% RH) (%) 32 27 22
Tear strength (N/m) 410 690 1,130
Tensile strength (kPa) 340 455 600
RH = relative humidity
Source: Zotefoams technical data sheets

A comparison of properties of foams made from various ethylene polymers is shown in


Table 6.3. At a nominal density around 30 kg/m3, the exceptionally high tear strength of
the HDPE foam (HD30) and mPE foam (MP33) may be noted. The polypropylene foam
(PP30) has similar compression characteristics to the HDPE foam but with the higher use
temperature characteristic of polypropylene foams.

Table 6.3 Property Comparison of Polyethylene Foams (Autoclave Process)


Grade LD33 HD30 MP33 PP30
Nominal density (kg/m3) 33 30 33 30
Compression set (25%) (kPa) 40 60 40 60
Tear strength (N/m) 690 1,320 1,000 875
Source: Zotefoams technical data sheets

Some data for EVA copolymer foam is shown in Table 6.4.

Table 6.4 Properties of EVA Foams (Autoclave Process)


Grade EV30 EV50
Nominal density (kg/m3) 30 50
Compression strength (25%) (kPa) 35 40
Compression set (72 h, 50% RH) (%) 38 28
Tear strength (N/m) 800 1,300
Tensile strength (kPa) 740 930
RH = relative humidity
Source: Zotefoams technical data sheets

The greater flexibility of the EVA foams is not readily shown by compression strength data
due to greater hysteresis in the LDPE stress strain curves (compression data is taken on
the fourth compression). Note the high tear strength of these materials.

An important application for polyethylene foam, reviewed in Section 6.6, is packaging,


where the impact absorption properties are significant. The mechanism of impact
absorption of foams is well understood and so-called cushion curves showing the relation
between static stress and peak deceleration over a range of heights and foam thicknesses
are available from foam manufacturers for their packaging grades.

A development in recent years has been to make the data available to users in the form of
computer software which allows the customer to calculate the optimum foam grade and
dimensions (and cost!) to give the required impact performance for a packaged
component of specified fragility over a defined drop height. Such software is available
from both Dow Performance Foams and Zotefoams.

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Polymer FoamsTrends in Use and Technology

Zotefoams offers its HL grade which incorporates an ethylene polymer of stiffness


intermediate between LDPE and HDPE. These foams are aimed at packaging
applications and have been shown to have an impact absorption effectiveness twice that
of non-crosslinked LDPE foam (on a foam weight basis).

6.6 Markets and Applications

The market for thermoplastic foams (essentially applications for polystyrene (EPS and
XPS), PVC and polyolefins) is dominated by EPS (more than 900,000 tonnes per year in
Europe in 1997). The European market for polyolefin foam has been given [4] as 55,000
tonnes in 1997, about 5% of the total thermoplastic foam market (see Table 6.5).

Table 6.5 Market Data for Polyolefin Foam, 1997


Area Demand (kt) Percentage (%)
North America 124 49
Japan 73 29
Western Europe 55 22
Total 252 100
Source: [4]

During 1997, growth was estimated as 4.8%, with significant growth of new applications
particularly in the automotive area; this level of growth may be expected to continue.
Compared with the mature polystyrene foam industry, polyolefin foam is a relatively young
product with significant developments in both materials and products still taking place.

Markets differ somewhat according to area. In North America, protective packaging


accounts for almost half the total usage (47%, 58 kt) whilst automotive applications
account for about one-fifth (18%, 22 kt), leaving 35%, 43 kt in a wide variety of
applications such as sports and leisure, footwear and medical.

In Japan, packaging is again the largest market, consuming nearly one-third of the total,
followed by construction, footwear, and automotive. In Europe, packaging accounts for
some 30% of the market (16.5 kt) followed by construction and transportation (26%, 14 kt)
and automotive (21%, 11.5 kt).

Five companies (Alveo, Armstrong Insulation Products, HT Troplast, NMC, Thermaflex


Industries) have joined forces to form the European Polyethylene Foam Organisation
(EUPEFA). The organisation is non-profit making and has the goal of developing a
positive image of European polyolefin foam producers and fabricators as well as
promoting cross-fertilisation without affecting competitiveness.

6.6.1 Packaging

The use of foam inserts for the protection of fragile articles during transit is the largest
market for polyolefin foams, and many types and grades are used for this application,
including non-crosslinked physically blown foam, non-crosslinked bead foam and
crosslinked autoclave foam.

The mechanism of shock protection is energy absorption by the deformation of cell walls
when the foam is subject to rapid compression. The more rigid foams, or foams with poor

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cell structure, can take on a significant permanent set and may not perform as well on
multiple impacts, but in semi-rigid foams the restoring effect of the gas in the closed cells
generally gives sufficient recovery for the foams to be reasonably effective in multiple
impacts. Multiple impact performance is best with crosslinked foams.

The design of cushion packaging is carried out making use of cushion curves which show
the behaviour of foams of different thicknesses when subject to impact over a range of
drop heights and with different weights of impactor. A plot of static stress against peak
deceleration produces a cushion curve showing a minimum deceleration under defined
conditions. Packaging is designed so that the expected use conditions match the
minimum of the curve so as to make the most effective use of the material.

Other properties affecting impact performance are creep resistance and the effect of
temperature on properties. The creep resistance of a foam defines the highest load which
can be packaged without deterioration due to dimensional changes caused by
compressive creep. A maximum of 10% creep is the usual design criterion. Changes in
flexibility (increased flexibility at high temperatures, reduced flexibility at low temperatures)
affect impact performance if transport temperatures are unduly high or low. By selecting
design data at the high or low end of the static stress range, acceptable operating
conditions may be from 40 C to 20 C (maximum static stress) or 2050 C (minimum
static stress).

Cushion stability (i.e., foam compression rather than buckling) can be assured provided
that thickness is no greater than twice the width or length.

Zotefoams, Dow and other foam producers offer foam optimised for packaging
applications. Sealed Air Corporation has recently introduced Stratocell laminated
polyethylene foam and CelluPlank polyethylene foam. Stratocell is a multlayer plank 15
inches (2.513 cm) in thickness, and the materials are aimed to provide high performance
cushioning over a wide range of applications.

6.6.2 Automotive

The particular benefits offered by polyolefin foams in automotive applications are:

weight saving, hence reducing fuel consumption,


comfort, by use of soft touch materials in interior areas,
low fogging potential (particularly foams produced without chemical blowing agent,
e.g., autoclave foams), and
wide conversion possibilities (lamination, vacuum forming, press forming, low
pressure moulding).

Applications for crosslinked foams include:

gaskets, cavity fillers and spacersto seal against dust, moisture, water and noise,
water shieldssealing against water, moisture and noise,
pressure sensitive adhesive tapesfor fixing of badges and trim,
dashboards and door panelsfor interior comfort,
interior trim using foam laminates foils or textilesfor comfort and appearance,

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carpet underlayfor comfort and sound deadening,


headlinersfor comfort and impact protection, and
knee bolsters and pillars.

Where a soft touch is needed, ethylene copolymer foams are used whilst propylene
copolymer foams are used where the highest temperature stability is needed. For many
applications, however, LDPE foams of appropriate density are the most usual candidates.

An interesting development is a dashboard module based on a monomaterial conceptall


components are made from polyolefin:

an outer material produced from a polyolefin film moulded to give an aesthetically


pleasing grained surface,
foam backing of EPP (bead foam), and
a reinforcing inner crossbeam produced by injection moulding fibre reinforced
polypropylene.

The use of a single material type ensures good compatibility and interfacial bonding of the
components and facilitates component recycling at the end of the vehicles useful life. This
contrasts with dashboards produced from, e.g., polyolefin outer, polyurethane foam
backing and ABS inner reinforcement. Here, the incompatibility of the components makes
recycling difficult. The use of polypropylene in automotive interior panels is growing at the
expense of PVC and polyurethane.

The most significant application for EPP bead foams in the automotive sector is for energy
absorbing bumper cores. At a density of 60 kg/m3 it offers a similar energy absorbing
capacity to polyurethane with a density of 100 kg/m 3, and hence offers a weight-saving
method for automotive manufacturers to meet legislative requirements for impact
protection. A good level of performance is maintained over multiple impacts. Bead foam
can also be used to assist side impact protection.

Other automotive applications for bead foam include visors (injection moulded PP with an
EPP foam core), childrens seats and, recently from BASF, thermal insulation for an
automotive battery.

6.6.3 Other Applications

Applications for polyolefin foams in other areas are extremely varied. Some are listed
below:

Building and construction


Sealing Impact/sound absorption
Expansion joints Pipe insulation
Glazing seals Eaves fillers

Aerospace
Seating Sound insulation
Flotation cushions Ducting lining and gasketing

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Polymer FoamsTrends in Use and Technology

Marine
Life jackets Oil booms
Lifebuoys Floating hoses
Fenders Boat formers

Health care
Splinting Exercise mats
Cervical collars Implement handles
Orthopaedic shoe insoles Orthotic supports

Sports and leisure


Buoyancy aids Sports shoe insoles
Swim vests Body protection
Kickboards Canoe seats
Pool games Toys and games
Camping mats Gym mats
Waterslide mats Helmet liners
Backpack packing Surf boards

Electronics (using conductive or static dissipative foams)


Packaging Workstation mats
Pin insertion Tote box liners
Shielding Shoe insoles (conductive)

Military
Cold weather sleeping mats Helmet liners
Missile packaging Trauma padding
Weapons packaging Riot shields

References

1. J.R. Cousins and F. Domas, Proceedings of Cellular Polymers, London, UK, 1991,
Paper 34.

2. R.D. Maier, Kunststoffe Plast Europe, 1999, 89, 3, 45.

3. D.E. Eaves, Cellular Polymers, 1988, 7, 4, 297.

4. Rubber World, 1998, 217, 6, 17.

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7 POLYSTYRENE FOAM

7.1 Introduction

Polystyrene was one of the first synthetic polymers available for commercial use, being
made on an industrial scale by BASF in 1930. A process to produce expandable
polystyrene beads (EPS) followed some 20 years later and has hardly changed since that
time. The beads are used in post-production processes to manufacture a wide range of
products of which packaging is probably the most familiar. The other main manufacturing
process is extrusion to form extruded expanded polystyrene (XPS).

7.2 Processes

7.2.1 Expandable Polystyrene (EPS)

The process principles for EPS comprise an initial polymerisation of monomeric styrene
incorporating 6% to 7% of one or more low boiling point hydrocarbon blowing agents,
such as pentane or butane, to produce beads (0.23.0 mm diameter) for subsequent
expansion. Bead size is a parameter which is controlled in the production process. Small
bead sizes are best for thin-walled products such as drinking cups; medium size beads
are used for moulding larger shapes with thicker walls; large size beads are used for block
moulding.

The first expansion stage, or pre-expansion, may be carried out using hot water, but is
virtually always carried out with steam at about 100 C, which increases the bead
temperature well above the glass transition temperature of the polystyrene hydrocarbon
blend, hence softening the raw material and increasing the internal vapour pressure of the
blowing agent above the external pressure, causing the beads to expand. Expansion at
this stage is to some 50 times the original volume. Bulk density, reflecting the degree of
foaming, is usually between 10 and 30 kg/m3.

The pre-expansion stage may be carried out continuously or batchwise, with each method
having advantages depending on subsequent production processing.

Waste products at this stage (steam and blowing agents) may be released to atmosphere
but are better collected by extraction equipment. This is appropriate both for
environmental reasons and because the blowing agent produces flammable vapours
(pentane and butane are classed as A1 flammable substances with flash points below 20
C).

The second expansion stage requires the pre-expanded beads to be cooled and stored
whilst they stabilise. They are initially fragile and require care in handling. As the beads
cool, blowing agent and steam collect in the cells resulting in a partial vacuum. Air diffuses
in to compensate and mechanical stability is not achieved until this process is complete.
At this stage the beads typically contain some 4%5% blowing agent.

The third stage involves a further expansion of the pre-expanded beads. In block
moulding the beads are conveyed pneumatically from the ageing store to the mould feed
silo. They enter the mould either through gravity or using blowers. Steam is utilised to
soften the beads and to vapourise remaining blowing agents causing expansion and
cohesion of the beads to form a rigid block. Such blocks are currently moulded up to 0.9
m high, 1.3 m wide and 5.5 m in length. Length is limited only by physical handling

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considerations. A maturing time of a minimum of 2 days is required to stabilise block foam


during which time air can diffuse in and water vapour and hydrocarbon blowing agents
can diffuse out. The thickest blocks can require up to 30 days maturing before a
reasonable level of stability is achieved.

Continuous production methods have been developed for EPS foam blocks which involve
the feeding of pre-expanded beads onto perforated steel conveyor belts (perforations are
smaller than bead sizes). The separation of the belts determines the block thickness
which can be up to 0.25 m, whilst bulk density can be controlled in the range 10160
kg/m3. At start up, a moulded expanded polystyrene block is positioned within the belt
system to form a dam. Separate non-perforated steel belts seal the system at the sides.
Bead stock is fed to the conveyor belt at a rate sufficient to ensure complete fill between
the belts which then carry the expandable beads through a steam zone followed by a
vacuum zone and then a cooling zone. The final section provides for automated cutting
and trimming operations to form the required block sizes.

For shaped mouldings, steam chests on open mount frames are used. Pre-expanded
beads are blown into closed moulds to fill them completely. Steam enters through small
holes to expand the beads so as to fill the interstices between them and bond them
together. Prior to removal, a vacuum is applied which results in the expanded beads
forming to the precise mould shape and which also increases the rate of diffusion of
residual steam and blowing agent out of the product. The product is ejected from the
mould after chilling with water and transferred to a storage and maturing area.

EPS production processes must take into account the ignition and flammability properties
of the materials and blowing agent. In the semi-finished state (i.e., as pre-expanded
beads) the product contains 4%5% by weight of flammable hydrocarbon blowing agent
than in the original formulation. The blowing agent escapes slowly by diffusion and in a
sealed container vapour concentrations could build up to unacceptable levels. In air, the
explosive limits are between 1.3% and 7.8% of blowing agent by volume. Hence, shipping
and storage containers are not absolutely airtight (so as to allow egress of vapours), and
ventilated storage areas are normally provided with gas alarms to check that hydrocarbon
vapours remain well below hazardous concentration levels.

The flammability of pre-expanded material is influenced by the foam structure and


moisture content as well as by the intrinsic flaming properties of the polymer and blowing
agent. No single precise flash point can be specified because the blowing agent is soluble
in the polymer, but determinations in accord with DIN 51755 give values in the region of
2530 C, well above the flash point of the hydrocarbon blowing agent. The high moisture
content of freshly pre-expanded material gives effective protection against ignition.
However, as drying progresses, flammability increases until when dry the material is more
flammable than the original polymer.

After moulding, the hydrocarbon content of EPS foam drops to about 50% of that originally
present, i.e., about 3%4% by weight. This quickly falls as the material is stored and the
blowing agent diffuses out through the cell walls and interstices, reaching a residual level
after some two weeks of 10%15% of the original level, i.e., about 1% by weight.
Standard precautions at the moulding stage comprise avoidance of flame and other
ignition sources (sparks from grinding or welding work, lighted cigarettes, electrostatic
discharges, etc.). Such sources do not normally affect the final matured foam product.

EPS process developments are enhanced by co-operation between bead producers, such
as BASF, and machine manufacturers. Some recent developments include:

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Polymer FoamsTrends in Use and Technology

use of continuous pre-expanders,


use of sophisticated control instrumentation,
use of fluidised beds for rapid heat transfer during initial handling of pre-expanded
beads, and
automation at the moulding stage.

7.2.2 Extruded Expanded Polystyrene (XPS)

The production of XPS has been heavily influenced by the changes necessary to comply
with the Montreal Protocol (see Section 3). CFC-12 has long been the blowing agent of
choice due to a combination of unique properties including non-flammability, low toxicity
and good processibility. The main application of XPS, thermal insulating boards, is greatly
enhanced by the particularly low thermal conductivity of this blowing agent which is
retained within the closed cells of the final foam product and substantially contributes to
the product performance.

The rapid phase-out of CFC-12 in developed countries in recent years has been made
possible by the availability of HCFCs. In XPS insulating boards, HCFC-142b, either alone
or blended, has been recognised as the best alternative. In the USA, HCFC-142b with a
small amount of a co-agent such as ethyl chloride has been the chosen alternative. In
Europe, most manufacturers use a non-flammable blend of HCFC-142b and HCFC-22
(60/40 by weight), although products using pure HCFC-142b with a low molecular weight
alcohol such as ethanol can also be found. More recently, the use of liquid CO2 or HFCs
(HFC-134a and HFC-152a) has been developed by some XPS board producers in
response to stringent local regulations (such as the phase-out of HCFC-142b in Sweden
from 1 January 1997). A report for the Alliance for Responsible Atmospheric Policy by the
Arthur D. Little organisation [1] suggests that HFC-134a and CO 2 will become the
preferred blowing agents for XPS after the phase out of HCFCs in 2003, and that
applications for thermal insulation are able to stand the additional costs of HFCs owing to
their energy saving benefits. The reference provides details of energy saving calculations.

HFCs are recognised as having zero ODP but are not a wholly satisfactory final solution to
the environmental problems of the CFC blowing agents since they retain a significant
GWP (Global Warming Potential) and, like HCFCs, have a higher thermal conductivity
than CFC-12. The thermal insulation of expanded board products is hence reduced, which
is a negative factor from both the economic and environmental point of view.

7.2.3 Other Extrusion Processes

A recent development has been Reifenhausers REIcell direct gas injection process which
enables the production of foamed XPS sheet in a single step directly from thermoplastic
raw materials, including polystyrene. The core of this process is a Reifenhauser twin-
screw co-rotating extruder which provides the necessary high mixing and dispersing
efficiency whilst at the same time giving good melt temperature control. The process is
said to be capable of using both gaseous (CO2, N2) and volatile hydrocarbon (pentane,
butane) blowing agents which are injected into the extruder barrel under pressure. A
circular foaming dye allows production of a cylindrical sheet of foam, which is extruded
over a sizing mandrel where both surfaces of the foam are cooled. The cylindrical sheet is
then split and wound onto a roller take off unit.

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An advantage of the REIcell process is the ability to co-extrude solid layers in combination
with the foam in-line rather than by separate post-extrusion lamination, e.g., a solid layer
of polystyrene with EPS.

Other polymeric materials, such as polypropylene, can also be expanded by the REIcell
process. Minimal equipment change is required when changing between polystyrene and
polypropylene.

One of the problems which has to be solved in foam produced by extrusion is reliable
sealing of the extruder barrel at the gearbox end. Direct gas injection processes can
generate pressures up to several hundred bar (20 MPa). In a system similar to the REIcell
process, Berstorff has equipped its Schaumex and Schaumtandex lines with a patented
active melt seal which is claimed to be particularly effective in retaining the pressurised
blowing agent. The lines are designed to meet specific foam requirements and may be
single screw or (for Schaumtandex lines) two single screws in tandem or a twin screw
followed by a single screw in tandem. Berstorff includes polystyrene as one of several
thermoplastic polymers which can be foamed on a Schaumex line. Blowing agents are
CO2 or butane, and (interestingly) water. Battenfield Gloucester Engineering Co., offer
tandem extrusion lines suitable for a range of polymers including polystyrene.

Although such lines can produce quite wide expanded sheets (e.g., Berstorff flat extrusion
dies up to 1.2 m width), thickness is limited to about 5 mm by the need to control the
temperature of the extruded profile.

7.2.4 Finishing Operations

Blocks of foam may be cut or trimmed to provide boards. This is normally carried out
using oscillating heated wires or band saws, taking care to avoid overheating and
subsequent fire risk. Dust production needs to be controlled to avoid combustion risks due
to the large surface area and susceptibility to electrostatic charging.

Other finishing operations which have been developed include lamination (e.g., with
aluminium foil), surface flocking or printing, and elastification (for noise insulation board).

Elastification is carried out by pressing the foam inside the mould or by increasing the
volume during the moulding process. Finished sheets can be treated by pressing or
rolling. The process increases the perceived elasticity of the product by introducing
greater flexibility into the cell walls.

7.3 Recycling

Environmental pressures, the beneficial economics of scrap reduction and the increasing
cost of waste disposal have focused attention on methods of recovering scrap material at
all stages of manufacture and use. Polystyrene foam, since it is not crosslinked, can be
recovered and used more easily than some other types of foam (e.g., crosslinked
polyethylene foam and foamed elastomers where crosslinks limit the possible recovery
processes). Polystyrene foam was one of the first plastics for which practicable closed-
loop recycling and scrap recovery systems became available.

At the production stage, it is possible to recycle a proportion of production scrap by mixing


with virgin material. Scrap must be clean, dust-free and of controlled particle size. As with
all polymers recovered in this way, there is a small deterioration in physical properties, but
the basic polymer is fairly stable (significant decomposition to produce gaseous products

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does not start until about 200 C) and in many applications the customer specification can
still be met.

Ground production waste has been sold for many years as a soil additive for applications
such as fruit growing, viticulture, landscape gardening, construction of sports pitches and
pipe and slot drainage, (e.g., BASFs Styromull, classified in Germany as a soil additive).

Simple injection moulded parts can be produced from scrap by sintering and melting to
provide consolidated pellets for moulding operations.

A major problem in most foam recycling operations is the collection and transportation of
scrap product due to the low density (and hence high volume) of the expanded material.
Two American companies have developed processes to transform polystyrene foam into a
gel state, hence greatly reducing the volume of collected material and making
transportation more economical.

Styro Solve, a citrus-based biodegradable solvent, has been developed by International


Foam Solutions Inc. (IFS), USA. Different solvent blends are available depending on the
desired solution rate. The process is claimed to work for both foam and other polystyrene
products, and comprises a shredding operation followed by application of a solvent spray
to dissolve or gelify the granulated foam. This is carried out using the IFS Solution
Machine which may be bought or leased from IFS. The dense polygel so produced is
stored in drums and then shipped to IFS for further processing. IFS reliquifies the gel by
addition of more solvent which then allows removal of contaminants by passing through a
proprietary filtration stage. No heat is used and hence polymer degradation is minimised
or eliminated. Contaminant levels are claimed to be less than one part per million.

A similar process has been developed by Resource Recovery Technologies (RRT), USA.
A solvent is used to dissolve the polystyrene. Contaminants either sink or float and are
then removed. The solvent is non-flammable and is claimed to be easily separated from
the resin with a recovery of 99.9% and with no atmospheric emissions. The recycled
material is produced as a continuous sheet about 1.8 m wide, which is granulated to
provide the end product. Maximum temperature in the process is 93 C, hence
degradation is nil or minimal and the product is of high quality. It is claimed that injection
moulding of the product can be carried out at temperatures some 55 C lower than is
typical for virgin material, and operating pressures are also lower than is normal (possibly
due to plastification by small amounts of retained solvent).

Both the IFS and RRT processes are at an early stage of commercial development.
Currently, for instance, customers are shipping foam to the RRT plant rather than carrying
out the solution operation themselves, which negates the main advantage of reduction of
transport costs. However, both companies aim to eventually locate the reclamation
processes in or near to the foam producers or users.

A further outlet for scrap EPS foam has been developed by Colorado Building
Technologies Inc., USA. It produces Poly/Lite, an innovative lightweight concrete made
from fly ash and discarded EPS foam. This material is claimed to have three times the
insulation value of regular concretes whilst being stronger and lighter than standard
lightweight concretes. Applications are envisaged for roof tiles, bricks, foundation walls,
cinder blocks, pavers, mortar, flooring, roofs and similar products. Poly/Lite is claimed to
be fire resistant despite the loading of polystyrene and is also freeze-thaw and wear
resistant. Application for shingles appears to be an initial target where the product has the
advantages of lightness with the absence of cracking when sawed, drilled or screwed.

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Polymer FoamsTrends in Use and Technology

Poly/Lite is patented, and the company is currently looking for affiliates to take up
manufacture.

Waste disposal by uncontrolled burning is not possible owing to the dense black smoke
emissions caused by incomplete combustion and charring. However, energy recovery
from granulated waste by steam generation using incinerators is possible although
measures need to be taken to ensure flue gas emissions are within legal limits. A body of
opinion holds that this is the most cost-effective method of waste disposal for all polymeric
scrap including foam and, in view of transport costs, also the most environmentally
acceptable. However, the European Packaging Regulations place a limit on this recovery
process for packaging products.

It has been reported that EPS recycling organisations in the USA, Europe and Asia have
co-operated to form the International EPS Alliance to distribute uniform information
concerning EPS on a worldwide scale. The Alliance includes the US-based Alliance of
Foam Packaging Associations (AFPA), European Manufacturers of Expanded
Polystyrene, and Asian Manufacturers of Expanded Polystyrene. The AFPA is acting as
the executive office.

7.4 Properties

Expanded polystyrene is a closed-cell foam and its properties are determined by the
characteristics of the polymer and the compression of gas in the cells together with the
bulk density. Properties are modified by the presence of any additives such as fire
retardants.

It may be noted that properties associated with the amount of polymer present (as
reflected by the density) increase as density increases. Such properties include
compressive strength, flexural strength, tensile strength and elastic modulus. The latter,
for polystyrene foam, is controlled more by the stiff cell walls than by the compression of
air in the cells. Transmission of water vapour is also essentially a function of foam density.
Thermal conductivity, however, is relatively independent of foam density at a density
below 30 kg/m3.

The wide range of values quoted for all strength properties is associated with the bead
nature of the moulded foam. Failure generally occurs at bead interfaces, and the integrity
of these depends on factors such as bead size and precise moulding conditions.

Temperature stability, i.e., the ability to withstand compression forces at elevated


temperatures, is mainly determined in foams by the heat distortion characteristics of the
polymer. Polystyrene passes through a glass transition at some 85 C and the maximum
temperature at which significant compressive stress can be maintained is given as 80 C.
However, BASF has developed Styrotherm which provides mouldings with very
significantly higher heat distortion temperatures, up to 135 C. Mechanical strength and
energy absorption on compression are also improved, hence increasing cushioning
performance for packaging applications. Some properties of Styrotherm are compared to
Styropor (foam density = 30 g/cm3) in Table 7.1.

Expanded polystyrene reacts to chemicals and solvents essentially in the same way as
the base polymer. Hence, polystyrene foam is resistant to attack by water, alkalis and
most strong acids. Substances such as aromatic solvents which soften or dissolve
polystyrene will affect polystyrene foam similarly. However, since the cell walls are thin
and foam densities are generally very low, the rate of attack is much faster in foams,
increasing as the foam density decreases.

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Table 7.1 Physical Properties of Styrotherm EPS Compared to Styropor EPS


(High Heat Distortion Temperature)
Property Styrotherm Styropor
Thermal conductivity at 10 C (mW/m K) DIN 52612 3235 3135
Stress for 10% compression strain (kPa) DIN 53421 160260 200250
Flexural strength (kPa) DIN 53423 410510 330570
Shear strength (kPa) DIN 53427 200300 210260
Tensile strength (kPa) DIN 53430 370470 300480
Source: BASF Data Sheet HSR 9500 e

In practice, organic solvents and plasticisers are the substances most likely to cause foam
deterioration. Adhesives and paints containing such substances should not be used in
contact with expanded polystyrene. Similarly, contact with plasticised PVC should be
avoided.

Exposure to UV light will also cause a slow deterioration in foam properties (which could
be countered by addition of UV stabiliser) but this is not a problem in most applications
since the foam is not normally exposed to direct sunlight.

Like most organic materials, expanded polystyrene is combustible and ignition


characteristics are exacerbated by the cellular nature of the material. According to DIN
4102 (Fire Behaviour of Building Materials and Building Components), EPS board is
highly flammable. DIN 4102 is a vertical flame test using a small flame as the ignition
source at the base of a vertically held foam sheet. Under these conditions, the foam
exhibits a flame spread of more than 15 cm per 20 seconds. Such behaviour is
comparable with that of cellulosic materials such as paper, cardboard and wood veneer.

Fire resistant grades of polystyrene foam are available, e.g., BASFs Styropur F, generally
incorporating brominated fire retardants such as hexabromocyclo dodecane (HBCD). In
the early 1990s, considerable efforts were made to find alternatives to the brominated
materials due to the perception that they could liberate toxic brominated dibenzodioxins.
However, alternative non-brominated or non-halogenated fire retardants giving a
comparable level of fire resistance whilst maintaining physical properties have not been
developed and the drive to replace the brominated additives has diminished.

Some data for the fire gas emissions from expanded polystyrene of both normal and fire
retardant type (Styropor P and Styropor F BASF) are shown in Table 7.2.

The burning behaviour of fire retardant grades of EPS is sufficiently improved to allow
such materials to be classified as flame retardant according to DIN 4102. Styropor F
grades are rated as HF1 according to the UL94 horizontal burning test for classifying
foamed materials.

For automotive applications, the horizontal rate of spread of flame according to the
FMVSS 302 standard is the normal criteria and this cannot be met by non fire-retarded
polystyrene foam.

However, the FMVSS 302 requirement is met by BASFs heat resistant grade Styrotherm
at densities of 60 kg/m3 and more. As is normal with organic foams, the rate of spread of
flame in a horizontal test depends, amongst other things, on the amount of polymer
present per unit volume, and hence increases as the density decreases.

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Table 7.2 Fire Gas Emissions from EPS (Styropor P and Styropor F) Foams
Material Gas constituents Gas composition (ppm)
300 C 400 C 500 C 600 C
Styropor P Carbon monoxide 10 200 400 1,000
Styrene monomer 200 300 500 50
Other aromatics traces 10 30 10
Hydrogen bromide 0 0 0 0
Styropor F Carbon monoxide 10 50 500 1,000
Styrene monomer 50 100 500 50
Other aromatics traces 20 20 10
Hydrogen bromide 10 15 13 11
Pine wood Carbon monoxide 400 6,000 12,000 15,000
Aromatics - - - 300
Wood fibre board Carbon monoxide 14,000 24,000 59,000 69,000
Aromatics traces 300 300 1,000
Expanded cork Carbon monoxide 1,000 3,000 15,000 29,000
Aromatics traces 200 1,000 1,000
Source: BASF Data Sheet HSR 8708 e

Polystyrene foam is electrically non-conducting with low dielectric constant and dissipation
factor, and has high specific dielectric strength. The high resistivity can result in the
surface of the foam acquiring and retaining an electrostatic charge. This can cause an
unpleasant shock but is not regarded as intrinsically dangerous except in situations where
there is a possibility of igniting flammable vapours. The effects can be mitigated by
treating the surfaces of moulded parts with antistatic agents.

Polystyrene foams are not hydroscopic, but the structure will absorb water by percolation
through bead interstices and diffusion through cell walls if the foam is brought into direct
contact with water. The rate of diffusion is controlled by water vapour concentration and is
increased if there is a temperature gradient.

As temperature increases, polystyrene foam remains relatively intact until the polymer
reaches its glass transition temperature, above which the foam softens and shrinks (100
110 C) and, at higher temperatures, melts. At temperatures below 100 C, the foam
shows an inverse relationship of stiffness with temperature.

7.5 Markets and Applications

Polystyrene foam was originally developed in 1950, and the markets developed for this
product over the last 50 years are now relatively mature, particularly in Western Europe.
Even so, the requirement for the product continues to grow. Applications, at least in
Europe, are dominated by thermal insulation in buildings (71%) and packaging (27%)
which together account for 98% of production [2]. Worldwide, the average annual growth
rate for EPS has averaged 5% over the last 10 years, and in 1997, global demand was
2,120 million tonnes (see Tables 7.3 and 7.4).

Table 7.3 Global Demand for EPS Foam (kt)


1960 35
1970 410
1980 950
1990 1,550
1997 2,120
Source: [3]

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Table 7.4 Average Growth in Demand for EPS (%/y)


World Europe
1960-1970 28 27
1970-1980 9 9
1980-1990 5 3.5
1990-1997 4.6 3.5
Source: [3]

As may be seen from Table 7.4, growth rate has been decreasing in recent years, but it is
expected to remain positive at some 2.5% per year in Western Europe and somewhat
higher, 3%6% per year in Asia and Eastern Europe. Indeed, since Eastern European
markets opened up to the West, an average annual growth in demand in this area of 7%
has been observed, which is expected to continue. Manufacturing capacity in Western
Europe is expected to be able to cope with demand growth over the next few years.
Market leaders are shown in Table 7.5

Table 7.5 Annual Capacity of Leading EPS Bead


Manufacturers (kt)
BASF 228
Shell 170
BP 155
Enichem 105
Huntsman 84
Styrochem 40
BSL 40
Sunpor 40
Kaucuk 38
Source: [3]
Note: BP has strengthened its market position by the
acquisition of Styrenix (formerly Hls), whilst Nestes EPS
activities have been sold to Styrochem (Radnor/USA).

The maturity of the market in Western Europe compared with that elsewhere is illustrated
by the per capita EPS consumption shown in Table 7.6.

Table 7.6 Per Capita Consumption of EPS, 1997 (kg)


Western Europe 1.9
USA 1.5
Japan 1.7
Asia 0.2
Latin America 0.2
Source: [3]

Globally, the main applications for expanded polystyrene are building and construction,
which accounts for 55% of consumption, and packaging (38%). A further 6% of global
production goes into the manufacture of products for handling and presenting food such
as disposable beakers and trays. These figures differ greatly according to region owing to
differing climates and culture, as shown in Table 7.7. The considerably greater per capita
consumption of EPS for beakers, etc., in the USA is of note.

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Table 7.7 Breakdown per Capita of EPS Consumption, 1997 (kg)


Country Construction Packaging Beakers, etc.
Western Europe 1.33 0.55 0.02
Japan 0.12 1.55 0.03
USA 0.63 0.39 0.48
Source: [3]

In Western Europe, Germany is by far the largest user of EPS. Distribution by region is
shown in Table 7.8.

Table 7.8 Distribution of EPS Consumption by European Country, 1997


Country Consumption (kt) Share (%)
Germany 235 32
Switzerland/Austria 40 6
Belgium/Netherlands 80 11
Italy 95 13
France 90 12
Great Britain 50 7
Scandinavia 70 9
Spain/Portugal 40 6
Others 30 4
Source: [3]

Most of the data quoted refers to EPS. XPS is used in substantially smaller quantities; for
instance, XPS has one-tenth of the EPS market in Western Europe for insulation in the
building and construction industries [2].

7.5.1 Building and Construction

In Western Europe and USA, building and construction provides the largest market for
polystyrene foam. In this application, the ability of the material to provide excellent noise
absorption, thermal insulation and environmental protection is paramount.

It is now common in all industrial countries for building regulations to specify minimum
requirements for the thermal insulation of both heated and air conditioned buildings. Even
in countries with moderate tropical climates, thermal insulation is often a regulated
building requirement. The benefits of thermal insulation in countries with relatively low
winter temperatures are clear. Less obvious are the benefits in hot climates, but in fact the
energy lost through use of air conditioning in summer is often greater than the energy
used for heating buildings during cold winter periods.

The main competitor (and market leader) of expanded polystyrene for thermal insulation is
mineral wool (MW). Use of MW is very cost-effective but it does not have the technical
advantages of EPS and XPS. MW has less satisfactory heat insulating properties, can
absorb water and moisture and is less convenient in application. EPS and XPS products
can be tailor-made to enable easy application with no toxicological safety hazard.

Some European market data with estimated growth rates are shown in Tables 7.9 and
7.10.

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Table 7.9 Demand for Insulation Material by Region (million m2)


Region 1987 1997 %/y 2002 %/y
North America 3,253 4,460 3.7 5,040 2.6
Europe 2,886 3,543 2.2 4,230 3.8
Japan 418 575 3.7 665 3.1
China 222 527 13.7 740 8.1
Rest of World 860 1,426 6.6 1,810 5.4
Total 7,909 10,531 3.3 12,485 3.7
Source: [4]

Table 7.10 Demand for Insulation Materials by Material (million US$)


1987 1997 %/y 2002 %/y
Foamed Plastics 3,263 5,099 5.6 6,750 6.4
Glass Fibre 3,399 4,206 2.3 5,222 4.8
Mineral Wool 2,120 2,869 3.5 3,603 2.5
Other 391 443 13.3 530 3.9
Total 9,173 12,617 3.7 16,105 5.5
Source: [4]

Total demand for thermal insulation products is expected to reach 4.3 million tonnes by
the year 2003 [5].

The property profile of polystyrene foam (and rigid PU foam) compared with MW is clearly
sufficient to justify the higher cost in many instances. EPS is used mainly for domestic and
commercial building insulation. XPS is more expensive with applications in cold storage
and refrigerated transport. In Europe, Germany is the largest consumer of both EPS (41%
of market) and XPS (31% of market) [5].

The market for insulation products in roofs and walls, whilst being tied to the fluctuations
of the building and construction industry, is expected to continue to increase. Factors
influencing the demand include consumers increasing call for improved comfort in their
living spaces (reflected in the Building Regulation requirements which call for a minimum
thermal conductivity value of 0.45 W/m2 K for exposed walls and which are currently
under review). A further factor is an environmental concern to reduce the demand for
fossil fuels and the generation of CO2. The government has set a target of 20% reduction
in CO2 emissions by the year 2010, and this is considered unachievable without
significant reductions in the energy expended in heating and air conditioning buildings.
Heat loss in an uninsulated building is estimated to be typically 35% through the walls and
25% through the roof. CO2 emissions from the fuel used for heating/air conditioning
buildings is estimated to be some 30% of the total generated, second only to that
generated by transport. Increased use of insulation to reduce energy consumption is
considered essential if the governments target is to be achieved. The energy and CO2
emissions saved by insulation vastly outweigh those used in its manufacture.

7.5.1.1 Roof Insulation

In designing expanded polystyrene products for application in roof construction, it is


necessary to take account of the considerable stresses present in this area. These include
heat and cold, dryness and wetness, wind and driven snow on the outside with generally
higher relative humidity on the inside. Ingress and retention of moisture in contact with
wooden roof beams can lead to eventual rotting and failure. Plastics of various kinds, both

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foamed and solid, are widely used to eliminate harmful effects, e.g., as insulating layers,
waterproofing membranes, vapour barriers, gutters and down pipes, etc.

Flat roof insulation may be carried out with loose-laid EPS fixed by adhesives or
mechanically to the roof surface.

Insulation of a non-ventilated flat roof may be achieved by laying down insulation units of
EPS which have been precoated with roofing felt. The felt lamination protects the
insulating layers when the roof seal is made by the application of hot bitumen.

Unlaminated EPS boards are used in tarpaulin roofs where the boards and plastic sheet
sealing are loosely laid and subsequently held in place using gravel ballast or special
fixing dowels.

In many countries where pitched roofs are common, there is an increasing trend to
incorporate the roof space into the living area, hence increasing the utilisation of total
building space. In both existing houses (by loft conversion) and in original designs, roof
space is being utilised for guest rooms, play rooms, hobby rooms and as general
additional living areas. Adequate thermal insulation of the roof surface as the boundary
between inside and outside, is essential, not only in winter for warmth, but also in summer
to minimise excessive heating from the effects of sunlight.

For insulation of pitched roofs, EPS may be used as rigid insulating boards laid either on
or between the rafters. Such boards can also be in the form of composite units, and make
for fast and economical construction with lasting thermal protection.

EPS is also used for insulating existing pitched roofs. Tiles are removed and overlapping
mould foam boards with an underlying vapour barrier are laid onto the existing rafters. The
tiles are then relaid on the profiled insulating units.

7.5.1.2 Wall Insulation

Wall insulation functions so as to protect rooms against weather, excessive temperatures


and high noise levels. The optimum type of construction from the technical standpoint is to
apply insulation to the exterior of the load bearing masonry and then to face this with a
suitable layer for weather protection and aesthetics, for instance, by use of a special
external layer of reinforced plaster. Such panels can be preconstructed and lightweight,
large-panel wall units have become established particularly in the USA. The units give the
impression of a solid external wall. A method widely used in Europe is that of external
insulation with EPS boards which are fixed to the masonry by bonding mortar and are
subsequently covered with a fabric-reinforced plaster. The fabric reinforcement comprises
alkali resistant glass fibre sheets and is necessary to absorb the stresses in the plaster
layer due to temperature fluctuations.

Another system of thermal insulation in widespread use is the placing of EPS mouldings
dry which are then filled with concrete.

Insulation of cavity walls can be achieved by placing an EPS layer inbetween the load
bearing wall and external facing masonry. The closed-cell boards, which fit together
precisely at fully rebated edges, make it possible to dispense with the normal air gap
between insulation and facing masonry. Existing cavity walls can be insulated by blowing
expanded particles into the cavity. Holes are drilled in the skin and then closed after the
operation. Foamed beads are delivered in special silo vehicles.

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A further technique is to introduce EPS into the hollow cross section of specially made
bricks, either by pushing it in, moulding it in during production, or filling the cavities with
loose pre-expanded beads and expanding in situ with steam.

EPS formwork elements (used for temporary support) can be used to produce reinforced
concrete ribbed floors, the underside of which is insulating and which may be
subsequently finished by plastering or other lining.

The variety of expanded polystyrene wall units is considerable and is continually


increasing through design innovations. Units can be made on continuous moulding
machines and may include stainless connection elements. A precoating may be provided
to enhance plaster bonding.

Heat loss through joints is usually reduced by use of a light masonry mortar.

Although the optimum location for thermal insulation is on the exterior of walls, and this is
done as far as possible, thermal insulation meeting current requirements can also be
provided in existing buildings by use of EPS/plasterboard composite units on the internal
surfaces of walls.

It has been recognised, particularly in North America, that prefabricated units make more
cost-effective construction methods possible. The good mechanical load bearing and
dimensional stability of polystyrene foam enables the material to be used successfully in
prefabricated building construction. Lightweight, large-panel units covered with sheeting
such as wood or chipboard are used to provide thermally insulating wall or roof units.
Sandwich units covered with fibrated concrete slabs are used for thermal insulating
facade units. Large format wall and roof units with metal coating are used particularly for
industrial construction. These units are also used for cold rooms and cold storage
installations in countries such as South America and Australia.

The ease of transportation of such lightweight composite units enables cost-effective


transport over large distances. They are, therefore, of particular value where
accommodation has to be provided under difficult and inhospitable conditions. Such
constructions have been used to provide economic pleasant living conditions in both cold
Antarctic areas and hot dry deserts. The Australian Antarctic research station utilises 100
mm to 150 mm thick EPS (Styropor) sandwich units and is required to withstand
temperatures down to 40 C and wind speeds up to 280 km/h (174 mph). Other Antarctic
stations also use this construction system. Hearson village in Western Australia suffers
from cyclones and temperatures up to 45 C. All the buildings of this settlementbuilt for
1,800 people engaged in the development of a natural gas deposituse an EPS
(Styropor) sandwich unit construction method. These examples demonstrate the
transportability of the material and its ability to withstand temperature extremes and
adverse weather conditions.

The use of EPS beads for the production of lightweight and thermally insulating plaster,
concrete and porous bricks has been investigated by BASF and formulations for various
density ranges with different properties developed. Fine particles of EPS added to plaster
mortar substantially reduce the apparent density. The product can be sprayed onto
external walls as a coating to improve thermal insulation. Of particular interest is the
development of EPS concrete in the very light density range; this product can be used for
the production of houses where the concrete/foam mix is sprayed onto an expandable
shell former and left to set. A further application of this lightweight concrete is as a
prefabricated wall unit system in which tubular cavities are later filled with normal concrete

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which undertakes load bearing and reinforcing functions. Recesses or openings can be
cut out simply by using a saw.

7.5.1.3 Sound Insulation

Noise, which has been defined as sound unwanted by the recipient, can be extremely
disturbing and is an increasing problem. Some four million people in the UK are estimated
to suffer from noisy neighbours! In industry, safety legislation requires sound levels to be
held below 90 decibels unless ear defenders are worn. The cost in terms of accidents at
work, working days lost and hearing loss is difficult to estimate, but in France a figure of
25 million Francs has been published [6] for health costs, whilst social cost is estimated as
hundreds of millions of Francs.

The two materials normally used in construction for sound insulation are mineral wool and
foams. Mineral wool, or another porous absorber, works by allowing the sound to
penetrate the material where it is dissipated within the flexible open structure. Rigid,
closed-cell foams such as EPS do not function well in comparison, since the sound waves
cannot penetrate the closed-cell structure and the foam is too rigid to dampen the sound
vibrations which are transmitted through the material. However, an application for impact
sound insulation has been developed for polystyrene foam where the foam is elasticated
by precompression to reduce dynamic rigidity to a level which can still sustain the
compressive stress of an overlaid cement screed (mineral wool has too low a
compressive strength for this application). This is known as the floating floor system,
common in Germany and a number of other European countries. The screed/elasticated
foam together form a spring-mass system which substantially prevents the penetration of
structure-borne sound through the floor structure.

Impact sound insulation is often combined with underfloor heating where, to avoid
downward heat loss, a layer of EPS is laid between the underfloor heating and the impact
sound insulation. Boards with moulded-in grooves or elevations on the upper side are
used to permit easy laying of flexible polyethylene hot water pipes.

7.5.1.4 Other Construction Applications

A number of other construction applications have been developed:

Drainage boards. These are EPS beads foamed so as to provide a large continuous
pore volume. As a vertical filter layer in front of cellar walls or retaining walls, drainage
boards prevent seepage water accumulating in the ground until it exerts hydrostatic
pressure. The boards form a path of seepage from the overlying tile to a drain tile at
the foundation of the wall. A further use is for the drainage of roof girders where
thermal insulation combined with low weight offers advantages in comparison with a
drainage layer of gravel.

Permanent formwork. To reduce the weight per unit area of large concrete
floors/ceilings, EPS elements cut from large blocks or moulded as special units are
used. Large format wall formwork is produced by pushing board sections into a
suitably designed mesh of galvanised steel wires. After assembly, concrete is cast in
the cavity, and the formwork is subsequently plastered or lined, the outer steel mesh
forming a good anchorage. Textured formwork may be used for fascias where an
image relief is cut into the foam (for instance, by using a hot wire) and the foam is
then used as a former for concrete.

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Foundation engineering. In countries with severe winters and deep ground frost,
thermal insulation is necessary to protect foundations and buried pipelines. The long-
term stability of EPS and its immunity to moisture and ground bacteria, together with
its good insulating properties, have resulted in use for road and railway construction.
In areas where poor load bearing soil is present, EPS foam has been used as a load
distributive substructure for road and bridge approach ramps. Rigid foam blocks with
apparent densities over 20 kg/m3 are necessary to support the compressive forces.
These applications were originally developed in Scandinavia, but are now being
extended to the Netherlands and North America.

There is essentially no lower temperature limit for polystyrene foam in construction


applications. The upper temperature limit depends on the duration of exposure and the
mechanical loading. Brief exposure to high temperatures (e.g., fixing with hot bitumen) is
possible, but above 100 C the foam will soften and melt. Non fire retardant polystyrene
foam is classified as B3 when tested to DIN 4102 and is inadmissible as a construction
material. Fire retardant grades, however, meet B1 requirements, and are also non
dripping when they burn. In most cases, therefore, the use of polystyrene foam in fire
retardant grades for constructional purposes is permitted.

7.5.2 Packaging

The use of polystyrene foam in packaging is widespread, and familiar to most people.
Some of the important properties which polystyrene foam offers for packaging applications
include:

lightweight,
shock absorbent,
does not absorb moisture,
easily moulded to special shapes,
good compressive strength (hence stackable),
approved for food contact,
chemically resistant, and
easily recyclable.

Although the widespread use of packaging has come under some environmental
pressure, there is little doubt that without packaging, product loss due to deterioration and
damage during transit and storage would be substantial, outweighing the environmental
and economic cost of packaging production and use. The European Packaging
Regulations call for significant levels of recycling and reuse of packaging. Polystyrene
foam is particularly amenable, being readily recyclable by melt reprocessing.

The density of EPS used in packaging is typically in the range 2030 kg/m 3, though higher
density can be used if loads require this. Deformation at loads up to 11 daN/cm2 are only
slight. At higher (shock) loadings the foam deforms and acts as a cushion, preventing
product damage by lowering the deceleration forces experienced by the protected article.
The behaviour of foam grades under shock impact conditions is well established and such
data is commonly used to calculate dimensions for an appropriate cushion packaging
design. Calculations take account of factors such as product mass, anticipated drop
height and product fragility, and allow dimensions such as cushion thickness to be defined
for optimum protection. Shock absorption of polystyrene foam is excellent on first impact
but deteriorates significantly on subsequent impacts. For multiple impacts, foams such as
crosslinked expanded polyethylene give more sustained protection (see Section 6).

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Packaging requirements include presentation, ease of handling and good economics as


well as shock protection. Presentation can be enhanced by moulding effects followed by
subsequent printing or painting. Inks and paints must avoid the use of solvents which can
damage the foam.

Coatings are also possible using solvent-free epoxy resins or polyurethanes, or by


lamination with plastic films or paper. Such operations can be carried out either
immediately after the completion of foam moulding, or in a separate operation in a special
coating unit.

Packaging of some products, e.g., fresh fish, requires thermal insulation. Packaging for
these applications makes use of the good insulation properties of EPS foam; design
calculations provide the necessary thickness of insulation to maintain adequately low
temperatures during transit. The use of ice as a cooling accumulator is normal.

For large-scale production, automatically formed moulded packing is unrivalled. Mouldings


for smaller scale production can be manufactured from large foam blocks by simple
mechanical and thermal methods. For consignments involving only a few, or one-off
items, foamed EPS chips are frequently used as a loose pourable cushioning material. By
completely surrounding the article, an excellent degree of protection is achieved.

7.5.3 Other Applications

Although polystyrene foam is not generally used for appliance thermal insulation, a
product from Dow Chemical, Instill open-cell polystyrene foam, is claimed to offer the best
insulation value of any core material yet introduced.

References

1. www.arap.org/adlittle/9.html. Global Comparative Analysis of HFC and Alternative


Technologies for Refrigeration, Air Conditioning, Foam, Solvent, Aerosol Propellant
and Fire Protection Applications. Final report to the Alliance for Responsible
Atmosphere Policy, Arthur D. Little, Inc., August 1999.

2. Macplas, 1998, E4, 30.

3. W. Phillip, Kunststoffe Plast Europe, 1998, 88, 10, 20.

4. Study #1063 World Insulation, Freedonia Group, December 1998.

5. C. Galbraith, Materials Technology, 2000, 15, 1, 103.

6. P. Destang, Insulation Journal, 1998, January/February, 16.

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8 POLYVINYL CHLORIDE FOAM

8.1 Introduction

The basic extrusion process for the production of PVC foams was developed in the 1960s,
with the first products appearing on the market in the early 1970s. Extrusion is the
principal method used for the manufacture of foam profiles, foam sheet, and foam pipe.
As with other foams, the cellular structure can be formed either by physical or chemical
blowing agents. However, physical blowing agents are infrequently used for PVC foam
manufacture and hence the environmental pressures, which have resulted in substantial
work to replace ozone depleting physical blowing agents in other foaming processes,
have had few repercussions within the PVC foam industry.

8.2 Materials

Foamed PVC formulations are a complex mixture of thermal stabilisers, processing aids
and lubricants, pigments and fillers, nucleating agents and blowing agents, and (for soft
flexible foams) a plasticiser. All these components affect both the processing behaviour
(melt flow, melt strength, melt viscosity, gelation, thermal stability, blowing temperature)
and the final product density, surface finish and overall properties. There can be
interactions between components of the mix.

8.2.1 Polymer

All the basic types of PVC (emulsion, suspension and mass polymerised PVC, as well as
copolymers and PVC/ABS blends) are used for PVC foam extrusion, although it is
generally accepted that the best PVC for rigid foam production is suspension or mass
polymerised material.

The most important characteristic of the PVC polymer for foam application is the
molecular weight, characterised by the K-value (a measure of its solution viscosity). At low
K-value (and low molecular weight) the polymer has a low melt strength increasing the
propensity for cell rupture and leading to high foam density. A high K-value results in high
melt viscosity which restricts cell expansion and again leads to high foam density.
Materials with a K-value of 55 to 58 are reported to process well, and, unlike crystalline
materials (polyethylene and polypropylene), have a fairly broad processing range. Higher
K-values however, are sometimes used (with the addition of processing aid) for the
production of foam core pipe.

Polymer rheology affects cell size and density. A high polymer viscosity restricts
expansion resulting in fine cell size but high foam density, whereas a low viscosity and
melt strength can result in cell rupture and foam collapse. Melt strength is dependent on
the molecular weight of the polymer and by the presence of any acrylic processing aids.

8.2.2 Blowing Agents

8.2.2.1 Chemical Blowing Agents

The processing window for rigid PVC foam is around 160 C to 190 C. An ideal chemical
blowing agent for PVC foam should decompose within this temperature range with a high
gas yield delivered over an appropriate time scale. Decomposition products should be

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non-toxic, environmentally acceptable and compatible with PVC with no adverse effects
on either polymer stability or processing characteristics. Other desirable characteristics
are good storage stability, good incorporation and dispersion characteristics, and low cost.

The blowing agents coming closest to these ideal characteristics are AZDC and sodium
bicarbonate. These are often used together as they have complementary characteristics,
AZDC being exothermic and sodium bicarbonate endothermic in decomposition
behaviour.

AZDC decomposes at about 215 C with a gas yield of some 220 cm3/g to produce
nitrogen, carbon dioxide, carbon monoxide and ammonia. It is the presence of ammonia
which gives AZDC-blown foams their characteristic odour following manufacture. This
odour gradually disperses as the expansion gases diffuse out of the foam and are
replaced by air. The time period for this depends on storage temperature and product
thickness. Since the AZDC decomposition temperature lies outside the processing
temperature range for PVC, it is normal to use an activator to lower the decomposition
temperature to within the required range. Examples of activators are zinc and lead salts
which also act as thermal stabilisers for PVC.

Oxy bis-benzenesulphonyl hydrazide (OBSH) is sometimes mixed with AZDC as an


activator, decomposing in the temperature range 150160 C to release nitrogen and
water vapour. Decomposition characteristics of the AZDC/OBSH mix depend on the blend
ratio.

Sodium bicarbonate decomposes over a wide temperature range (150230 C), the lower
end of which is within the processing requirements of PVC. Gaseous decomposition
products are carbon dioxide and water vapour, and the gas yield is 100150 cm3/g.

To produce a foam of density 500 kg/m3, some 0.5 phr AZDC suffices compared with over
2 phr sodium bicarbonate. Foams produced using sodium bicarbonate have a coarse,
irregular cell structure whilst AZDC gives a fine uniform cell structure. This may be
associated with the narrower temperature range and faster rate for decomposition of
AZDC, together with the lower solubility in PVC of nitrogen (from AZDC) compared with
carbon dioxide (from sodium bicarbonate). The overall effect is to create a higher
nucleation rate in AZDC-blown PVC foam, giving a greater cell density and hence a finer,
more uniform cell size.

An advantage of the endothermic sodium bicarbonate systems is the absence of


discolouring (yellowing) so that pure white foams can be readily obtained. The
endothermic systems are reported to behave better in coextrusion processes in which
they tend to remain more within the foam layers. The liberated carbon dioxide readily
diffuses from the foam product, reducing or eliminating the need for ageing before any
subsequent paint process. In the moulding of rigid PVC foam, up to 20% faster cycle
times are claimed. Disadvantages include the release of water during decomposition
which can lead to mould corrosion, and the higher cost due to the lower efficiency. The
slower expansion however, makes it possible to achieve a compact, smooth outer skin
which is particularly advantageous in the Celuka process.

Developments in chemical blowing agents for rigid PVC are mostly confined to
improvements of currently used systems, or blends of systems, rather than radically new
agents. For instance, the dispersion problems and variable gas yields of sodium
bicarbonate can be attributed to the hygroscopic nature of this substance, and these
problems have been largely overcome with current products by coating with oil or wax.

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Environmental Products Inc., USA, has endothermic blowing agents which do not release
water and hence eliminate corrosion problems.

Considerable work has been done on exothermic/endothermic blends of AZDC and


sodium bicarbonate, and these are reported to give better control of extrudate density,
product colour and processibility. The lowest foam densities are achieved by using a
combination of the two blowing agents. Commercial systems are available from Boeringer
Ingelheim Pharma KG (Exocerol 232), Environmental Products Inc. (Polycor 50), Rit-
Chem (Bio Foam Extend-7) and Lehman and Voss (Luvopor systems). Such systems
were originally introduced in the 1970s and were targeted at PVC foam moulding where
the endothermic components act to control the exotherm and to mitigate thermal
degradation. More recently, these blends are being used in extrusion processes, for
instance, in the manufacture of PVC foam core pipe. The synergy between AZDC and
sodium bicarbonate has been attributed to the nucleating effectiveness of nitrogen which
stabilises the bubbles of CO2, and the endothermic effect of the sodium bicarbonate,
which reduces melt temperature and the tendency for cell collapse.

In the production of PVC foam profiles by the Celuka process, expansion occurs from a
solid skin to the centre achieved by the use of a fixed torpedo in the extruder die.
AZDC/bicarbonate blends are found to give the best results.

In the production of PVC sheets by free foaming, the expanded sheet is guided through a
series of temperature-controlled calibrators. High content bicarbonate systems have been
found to give a poor sheet surface, hence blowing agent mixtures with no or small
amounts of bicarbonate give best results.

PVC foam core pipes are formed in a co-extrusion process. As with the free-foaming
process, blowing agent systems with no or little bicarbonate are recommended.

The optimum ratio of AZDC to sodium bicarbonate depends on the application and the
manufacturing process. For rigid PVC profiles, which are normally made by the Celuka
process, a high level of sodium bicarbonate is used with a low level of AZDC. The latter
essentially provides for nucleation and hence fine cell structure whilst the slower gas
release from the former leads to a thicker smoother skin. Foam sheet is normally made by
the free-foaming process, and in this application it has been found that high levels of
sodium bicarbonate lead to a poor surface finish. Hence, the best systems for foam sheet
are said to be mixtures of exothermic blowing agents with little or no sodium bicarbonate.

8.2.2.2 Physical Blowing Agents

Physical blowing agents are not generally used for the extrusion of foamed PVC, although
injection of physical blowing agents into twin-screw extruders with screw lengths 1822 D
has been used for the production of foamed PVC sheet [1].

An apparently attractive alternative is to use direct gassing with carbon dioxide or


nitrogen, and significant effort is being made to develop such processes. However, there
are substantial problems to overcome:

sealing the extruder against the gas pressure,


achieving sufficient pressure in the extruder to reach significant levels of gas in
solution,
gas distribution and mixing, and
cooling the extrudate.

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Owing to its lower solubility in PVC (and other polymers), these problems are greater with
nitrogen than with carbon dioxide and most work is being done with the latter. Using
carbon dioxide injected into a single screw extruder with L/D ratio of 40, rigid PVC foam
with density similar to those achieved with conventional technology has been produced
[2]. However, it proved difficult to get a fine foam structure although there was an
improvement when talc was added as a nucleating agent.

There is little doubt that further work will be done on direct injection of carbon dioxide, and
this may be the way forward in the longer term for physically blown foam.

8.2.2.3 Stabilisers

PVC is susceptible to thermal degradation, characterised by evolution of hydrogen


chloride (which catalyses further degradation) and the formation of conjugated chain
sequences which results in coloration. Other chemical changes take place at chain ends
and branch points. PVC stabilisers work by reacting with hydrogen chloride, displacing
labile chlorine atoms, disrupting double bonds and deactivating free radicals.

In PVC foams, stabilisers usually have a dual role: prevention of thermal decomposition of
PVC and activation of the decomposition of AZDC. Lead and zinc stabilisers are
particularly effective for AZDC activation, but organotin stabilisers, which are widely used
in PVC by reason of their good heat stability, excellent stabilising effect and low toxicity
compared with lead based systems, are not good activators for AZDC. Use of an
organotin stabiliser in a PVC foam formulation normally requires the addition of other
components to achieve adequate gas yield.

8.2.2.4 Processing Aids

Processing aids are widely used in PVC extrusion to increase melt extensibility and
strength, promote fusion and improve surface characteristics. They are normally based on
high molecular weight acrylic copolymers. It is customary to include a processing aid in
PVC foam formulations to enhance melt strength and elasticity, so inhibiting collapse of
the cellular structure at lower foam densities.

As the molecular weight of the processing aid increases, progressively lower foam density
can be achieved before cell collapse sets in. Foam surface appearance is also improved.
Increasing the level of processing aid (up to 8 phr) also leads to progressive reduction in
achievable foam density.

8.2.2.5 Lubricants

In PVC formulations, lubricants are important to control gelation, melt viscosity, flow and
surface finish. Lubricants are generally classed as internal (compatible) and external (non-
compatible). In PVC foam formulations, a balance of internal and external lubricants is
used to ensure that the PVC particles gel sufficiently early in the extruder to allow sealing
and dissolution of the gaseous decomposition products from the blowing agent, and that
sufficient shear heating is generated to reach the necessary temperature range for
decomposition of the blowing agent without causing cell collapse or thermal degradation
of the PVC.

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8.3 Processes

8.3.1 Extrusion Foaming

In extrusion foaming of PVC, gas is introduced into the molten polymer in the extruder
barrel by thermal decomposition of the blowing agent (or, infrequently, by direct injection
of a physical blowing agent). The gaseous decomposition products essentially dissolve in
the polymer under the temperature and pressure conditions existing within the extruder.
Some of the blowing agent is left unreacted and acts as a nucleator for subsequent
bubble formation. As the mix exits the die, the now supersaturated melt releases gas
within the PVC matrix as discrete bubbles which cause the extrudate to expand. The
external surfaces of the extrudate cool, resulting in termination of bubble growth and
formation of a high density skin layer enclosing a low density foam core.

It is necessary to cool the extrudate very quickly to avoid foam collapse as bubble growth
is retarded. This is done by passing the foam through a chilled calibration unit which
freezes the cellular structure. The surface quality, density and thickness of the skin are
substantially controlled by the distance between the die and the calibration unit and by the
intensity of cooling. Cell size and morphology are influenced by the formulation used, and
particularly by the type and amount of chemical blowing agent used. For most
applications, a closed, fine-cell structure is desirable.

Within the basic PVC extrusion foaming process, there are two main variations: the free-
foaming process and the Celuka process. In the free-foaming process, which is more
commonly used, the extrudate is allowed to expand freely from the die before entering a
calibration system situated a short distance away. The foam has a relatively even density
profile with a thin, high density skin, and is typically used for pipe, sheet and simple
profiles. In the Celuka, or inward-foaming process, the foaming is directed towards the
core by the presence of a mandrel in the die. There is no gap between the die and the
calibration unit. This technique results in a harder, smoother surface with a substantially
lower density core. The overall density of free-foamed PVC is typically 700 kg/m3, whilst
that of a Celuka-foamed PVC is typically 500 kg/m3. The Celuka process essentially gives
an outer surface similar to solid extrusions, whereas free-foamed products have a
rougher, textured surface. The Celuka process is used for making pipes, sheets and
profiles of more complex geometries.

A third option is possible whereby co-extrusion is used to give a solid PVC skin over a
foam core. This technique offers the best control over skin thickness, core density, foam
structure and skin/core ratio. The skin layer may be a different colour than the core. The
co-extruder may be single or twin screw, and feeds an outer die having the desired profile.
Only the outer surface may be coated, or both external and internal surfaces may be
coated. Coating is carried out either by using two co-extruders or by feeding the skin
extrudate into a die where it is divided into two concentric layers. The core material is fed
in between the two skin layers.

Lines have been developed which allow switching between pipe types and which also
ensure close control over skin thickness. Reifenhauser has developed lines using three
extruders which allow precise control over skin thickness. Modular lines are available
which allow switching between two and three extruder systems.

A useful summary of PVC foam extrusion processes [3] also gives data on the economics
of rigid PVC foam. The overall cost of coextruded foam sheet ($1.78 per linear foot for
sheet 4 feet wide and 1/4 inch thick) was reported as slightly lower than Celuka sheet

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($1.79 per linear foot) which in turn was lower than free-foam sheet ($1.86 per linear foot).
Physical properties of the coextruded sheet were somewhat better than the other two
types.

As may be expected, processing conditions play an important part in controlling the foam
density and structure which determines foam properties.

Foam density generally decreases with increasing extrusion temperature up to a certain


optimum temperature and then begins to rise. This has been attributed [1] to low foaming
efficiency at low temperature due to high polymer melt viscosity and surface tension,
together with low gas pressure. As the temperature rises, foaming efficiency increases up
to the optimum, after which lower viscosity and polymer destabilisation result in cell
collapse and density increase.

It has also been found that increased extrusion rates generally lead to decreased foam
density due to better mixing and reduced viscosity, although very high rates can lead to
cell collapse due to shear heating.

8.3.2 Crosslinked Rigid PVC Foam

The incorporation of difunctional isocyanates in a PVC mix allows the production of so-
called crosslinked foam which comprises an interpenetrating network of PVC and
polyurethane. The components include one or more diisocyanates (normally TDI or MDI),
one or more chemical blowing agents and a thermal stabiliser for the PVC. In addition,
there are a number of optional components including solvents, plasticisers, polymerisable
monomers and acid anhydrides based on phthalic or maleic acid.

In the first stage of the manufacturing process, components are mixed to form a viscous
plastisol, usually under vacuum to eliminate air bubbles. The mix is poured into a mould
and placed in a heavy duty press (usually multi daylight to accommodate several moulds
simultaneously). The press is heated to between 160 C and 180 C at which temperature
the PVC plastisol mix gels and the blowing agent decomposes to release the expansion
gas(es). As the mould is kept under pressure, no expansion takes place, with the gases
being held, either dissolved or in small microcells, in the polymer mix. The press is then
cooled and the embryo foam removed from the mould. At room temperature, the
mechanical strength of the moulded PVC is sufficient to retain the released gases and
prevent expansion. This first stage takes about two hours, depending on the thickness of
the moulded product.

In the second stage, the embryo foam slab is either transferred to a new mould or placed
on a plate for free expansion. Use of a mould provides for accurate final product
dimensions, whilst free expansion allows for a simpler less costly process. The
temperature is raised to 100 C in a water or steam bath to soften the polymer and
release the trapped and dissolved gases to expand the product. At the same time, water
vapour begins to permeate the foaming materials to initiate the curing process by reaction
with isocyanate. The reaction also produces carbon dioxide which contributes to the
expansion gases. This stage of the process is lengthy, typically taking some ten hours; the
duration of this stage is defined not by the time to heat the material to expansion
temperatures (this is relatively short as water and steam have good heat transfer
characteristics) but by the diffusion rate of water into the material to initiate sufficient cure.

The third stage provides for curing which, except for thin, low density products, is only
initiated during expansion and is usually far from complete. Cure conditions are typically
5060 C at 100% relative humidity, with cure times up to 400 hours.

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The process is capable of giving products with density as low as 35 kg/m3 with a high
level of mechanical strength and good insulation properties. However, the process is
lengthy and expensive, and it is difficult to make thick products except by post-lamination
of thinner low density sheets.

A modified process for production of crosslinked rigid PVC foam [4, 5] which substantially
reduces the production time for thick section heavy density products is being commercially
exploited by Dynoplast. The requirement is to release water to enable the cure reaction,
but only after the higher temperature expansion stage has been completed. Earlier
release of water (e.g., by incorporation of substances such as aluminium trihydrate,
zeolites or amorphous silica which evolve water at elevated temperatures) results in
premature crosslinking which hinders expansion and leads to foam splitting. The
Dynoplast method makes use of the acid produced by mild degradation of the PVC to
react with a tertiary alcohol (for instance, t-butyl alcohol) to release water uniformly
throughout the foam late in the process. The curing process is initiated throughout the
foam without depending on diffusion of water from the outer surface. This technology is
being exploited for the production of (thick) buoyancy elements for use in the North Sea.

8.3.2 Flexible PVC Foam

Incorporation of a plasticiser into a PVC composition produces an initially viscous fluid


plastisol which becomes homogeneous on heating and cools to produce a flexible
polymer composition. Incorporation of a blowing agent (normally AZDC with a catalyst to
promote decomposition at an appropriate temperature) enables flexible foam production
with these systems. The most common processes coat the foamable plastisol onto a
substrate, (e.g., fabric, carpet, flooring), which is then passed as a continuous sheet
through an oven where free expansion occurs. After cooling, the expanded product is
wound onto take-up spools.

The introduction of crosslinks in flexible PVC foam is of interest mainly to enable foam
density reduction (with inherent savings in raw material) whilst maintaining an acceptable
level of physical properties. Approaches reported include crosslinking using:

silanes,
peroxides, and
radiation.

8.4 Properties

As with most foams, the single most important factor determining the physical properties
of PVC foams is relative density, i.e., the ratio of average foam density to the density of
solid PVC. Further important factors are the skin integrity, texture, and thickness, and the
cell morphology (cell size, uniformity and open cell content).

Mechanical properties of rigid PVC foam profile compared with solid PVC are given in
Table 8.1.

The reduction in impact and tensile properties compared with solid PVC is seen in Table
8.1. The influence of the skin in improving impact strength is shown in the data for the
Celuka profile; the solid surface eliminates crack-initiation caused by bubbles acting as
stress raisers. Impact performance, an important property in applications for rigid PVC
foam, is improved by a uniform, fine cell structure, whilst coarse bubbles in the surface in
crease the chance of crack initiation and reduce impact properties.

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Table 8.1 Mechanical Properties of Rigid PVC Profile


Property Test Values
Method Free foam Celuka Solid PVC
profile* profile**
Density @23 C (kg/m3) DIN 53420 600 550 1,400
Impact strength @23 C (kJ/m 2) DIN 53453 12 25 no failure
Tensile stress at yield (MPa) DIN 53455 17.5 17 58
Tensile stress at break (MPa) Speed V 16 15 35
Elongation at break (%) 40 30 27.5
Shore D hardness DIN 53505 50 80 80
Modulus of elasticity (MPa) ISO/R178 1,200 1,200 3,050
Vicat softening temperature (C) DIN 53460 63 67 78
* 120 x 3 mm
** 140 x 10 mm, 0.5 mm skin
Source: [1]

8.5 Markets and Applications

8.5.1 Rigid PVC Foam

The three main markets for rigid PVC foam are profile, sheet and pipe, with a total
European tonnage in 1998 of some 165 kt (UK market = 50 kt) [1]. Growth rate in the
1990s has generally been 5%10%, with a worldwide average growth rate of 12% quoted
for 19951998 [6]. Most applications (some 85%) are in the building and construction
industry, with considerable regional variations due to preferences in building design and
differences in building regulations. Within Europe, the UK offers the largest market for
foam profiles whilst in Germany, foam sheet is the major product. Foam pipe is the most
important market in France, and also dominates the market in the USA.

In the UK, foam profile for wood replacement is a major application. PVC foam has
characteristics matching wood in its ability to be fabricated and machined. It can be sawn,
nailed or screwed without splitting or cracking, and can be extruded to resemble wood in
colour, appearance and feel. The product is more expensive than wood on the basis of
cost per unit volume, but costs become more comparable taking into account the lower
scrap resulting and the fewer finishing operations needed. There is also some
environmental pressure to preserve forest resources, although conversely wood can be
regarded as a renewable resource if harvested in an environmentally responsible manner.

Examples of the use of foam profiles in building to replace wood products are skirting
boards, cornices, wall and ceiling panels, window sills, door frames, roofing products,
cladding, soffit boards, coving and rails for curtains and shutters. PVC properties which
lend themselves to these applications are chemical resistance, good weatherability
(absence of rotting), good fire retardancy (Class B1 according to DIN 4102) and
resistance to attack by rodents or other vermin. It can be used for both interior and
exterior applications, giving a virtually maintenance-free product requiring no painting. Its
main disadvantage over wood, apart from cost, is a reduced toughness which needs to be
taken into account at the design stage.

PVC foam sheet, which can have its surface enhanced or decorated by printing, painting
or silk screen processes, is used for display boards, signs and advertising boards. Foam
sheets are used in building for partitions, garage door panels, table tops, shelves, etc. Its

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rigid, lightweight characteristics are advantageous in use as the core material for
sandwich structures in boat building, and its insulation characteristics for tanks and
refrigerated vehicles. The foam structure is essentially retained after thermoforming, which
widens further the range of possible applications.

PVC foam pipe is used only in applications where there is no internal pressure. Its
advantage over solid PVC is higher stiffness for the equivalent weight of pipe, leading to
applications for drain pipes, sewer pipes, effluent pipes, ventilation and cable ducts and
cores for winding textile or paper. The major market is in France.

Crosslinked PVC foams have a higher mechanical strength and may be produced at a
lower density than standard PVC rigid foam. These products have applications in
sandwich construction for boats, aircraft, and road transport of liquefied gases where the
combination of good mechanical properties and high insulation value with low weight is
utilised.

8.5.2 Flexible PVC Foam

Flexible PVC foam, in addition to its attractive cushioning properties, has the ability to be
thermoformed whilst essentially retaining its cellular structure. It is highly suitable for high
frequency (HF) welding by dielectric heating. The process of HF welding essentially
involves placing a material with high dielectric heat absorption or loss factor between two
electrodes across which a high frequency alternating voltage is passed. This produces
molecular oscillations which generate uniform heating in the section of material between
the electrodes. PVC has a high loss factor and heats readily in a high frequency field to
temperatures which allow thermoplastic flow and fusing.

Flexible PVC foam gives a particularly clean edge when tear sealing. An electrode with a
sharp edge sinks under pressure through the material which fuses, leaving the surplus
material outside the weld line to be stripped away. Typical weld times are around 5
seconds using a power level of some 0.1 kW/cm 2, and machines are set to control various
factors affecting weld performance: tool pressure, depth of sink, HF power, welding times,
cooling time and platen temperature. Examples of tear-sealed applications include:

automotivesun visors, door trims, panels,


stationerybinders, wallets, diaries, holders,
appliquelogos and images for sports and leisure,
medicalneck collars, wheelchair padding, mattresses, seat padding, and
otherpadding for prams and pushchairs, electric blankets, kneeling mats, shoe
insoles.

References

1. N.L. Thomas, Progress in Rubber and Plastics Technology, 1998, 14, 3, 129.

2. S.K. Dey, C. Jacob and M. Xanthos, Journal of Vinyl and Additive Technology, 1996,
2, 1, 48.

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3. J. Patterson and R. Hughes, Proceedings of Vinyl Retec 97, Atlanta, Georgia, USA,
91.

4. K. Redford, L.T. Hoydal, A. Stori, K.H. Holm, A. Jorgenson and J. Groudal, Cellular
Polymers, 1995, 14, 6, 429.

5. K. Redford, L. Hoydal, A. Stori, K.H. Holm, A. Jorgenson and J. Groudal, PCT


application, No/94/00034 to Dynoplast AS., Norway 1993.

6. J. Patterson, in Plastics Additives, An A-Z Reference, Ed., G. Pritchard, Chapman &


Hall, London, 1998, 526.

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9 PHENOLIC FOAM

9.1 Introduction

Phenolic resins are condensation polymers formed by reaction of phenols and aldehydes
and were amongst the first polymers to be developed and utilised almost one hundred
years ago. Phenolic foams were a later development, but were apparently in use in
Germany in 1940, where use was made of their low density and weight as substitutes for
balsa wood in aircraft manufacture. More recently, applications take advantage of the
good insulation characteristics and an intrinsic resistance to fire which enables flame
retardant standards in the construction industry to be met easily, often without the addition
of any flame retardants.

Phenolic foams have similarities to rigid polyurethane foams in the manufacturing


process, properties and applications.

9.2 Materials

There are two broad classes of phenolic foam:

novolac, produced by the reaction of excess phenol with formaldehyde in the


presence of an acid catalyst to give a linear condensation product. A crosslinking
agent, such as hexamethylene tetramine, and a chemical blowing agent are added to
the linear polymer and the foam is produced by moulding at elevated temperature and
high pressure.

resol, produced by reaction of phenol and formaldehyde in the presence of a basic


catalyst to form a liquid, low molecular weight polymer. An acid catalyst and a
physical blowing agent are then added and the foam is produced by moulding. A
benzylic ether-type liquid precursor can also be obtained by this route through the
reaction of phenol and formaldehyde in a non-aqueous phase.

9.2.1 Phenols

The choice of phenol is important in controlling the chemistry of the condensation reaction
which can take place at the 2-, 4- or 6-position on the aromatic ring. If any of these
positions is blocked by alkyl or other substituent groups, the polymerisation reaction is
constrained to occur at the remaining positions.

Table 9.1 Functionality of Phenols


Type Functionality Melting Point (C)
Phenol 3 41
o-cresol 2 30
m-cresol 3 10
p-cresol 2 35
2,4-xylenol 1 26
2,3-xylenol 2 75
3,5-xylenol 3 64
2,5-xylenol 2 75
2,6-xylenol 1 45
3,6-xylenol 2 65

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If formaldehyde (which is difunctional) is used, linear polymers are formed with


difunctional phenols whilst crosslinked structures are formed if trifunctional phenols are
used. A monofunctional phenol will terminate the reaction. Functionalities of phenols
(phenol, cresol and xylenol isomers are generally used in phenolic foam manufacture) are
shown in Table 9.1.

9.2.2 Aldehydes

Although various alkyl and aryl aldehydes can be used, formaldehyde is the one applied
most generally to foam manufacture. In aqueous solution, formaldehyde is known as
formalin and this is the usual material commercially available. It contains methylene glycol
(or trimethylene glycol), which is produced from formaldehyde by hydrolysis, and
methanol at a level of around 10% to prevent the formation of a precipitate of
polymethylene glycol. Formaldehyde content is some 37%40%.

9.2.3 Novolac Foam

A typical recipe for production of a novolac resin is phenol (1 mole), formalin (0.8 mole)
and acid catalyst (0.02 mole). Reaction time is 12 hours at a temperature of 90130 C.
Water is removed from the resin by dehydration at 150 C under vacuum.

For subsequent crosslinking, hexamethylene tetramine is normally used in amounts of


5%20% of the resin. The crosslinker decomposes into formaldehyde and ammonia
during the reaction.

Novolac foams utilise a chemical blowing agent for expansion of the composition during
curing. Di-nitroso compounds, such as di-N-nitroso pentamethylene tetramine, are
commonly used.

It is possible to use fibre reinforcing agents such as glass fibre or polypropylene fibre.
These additives can be incorporated into novolac foams in order to improve mechanical
properties and heat stability, but it is more difficult to use them in resol foams as these
have a higher viscosity during manufacture and uniform fibre distribution is not easy to
achieve.

9.2.4 Resol Foam

A typical recipe for the production of a resol resin is phenol (1 mole), formalin (1.2 to 2.0
moles) and alkaline catalyst (0.010.05 mole). Reaction temperature is less than 100 C
(e.g., 90 C) and reaction time is about 3 hours. After reaction, a neutralising acid is
added, and water removed by dehydration at 4050 C under vacuum.

Basic reaction catalysts can be hydroxides (e.g., barium, sodium, potassium or


ammonium hydroxide), or carbonates, (e.g., sodium or potassium carbonate).

After production of the liquid resol, curing may be effected by heating to a high
temperature. However, curing at room temperature can be achieved by addition of an
acidic curing catalyst which may be inorganic (hydrochloric acid, sulphuric acid,
phosphoric acid), organic (benzene sulphonic acid, toluene sulphonic acid, phenol
sulphonc acid) or mixtures of acids. An organic acid is preferred in order to minimise the
possibility of subsequent metal contact corrosion caused by residual catalyst residues in
the foam.

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Acid neutralising agents can also be added to minimise possible corrosion caused by the
foam. These may be metal powders (zinc or aluminium) or carbonates (calcium carbonate
or magnesium carbonate).

Surfactants are commonly incorporated in recipes for foam production. These may be
either silicone or non-ionic alkylene oxide type, and act to aid initial blending of the foam
ingredients and later control cell formation and growth and hence cell size and
morphology (closed-cell versus open-cell).

Blowing agents for resol foams are normally of the physical type, i.e., low boiling liquids
which volatilise under the exothermic reaction conditions. CFC-11 and CFC-113 have
been used in the past but alternatives are now required to meet the Montreal Protocol
phase-out schedule (see Section 3). Other materials used are hydrocarbons (n-hexane, n-
heptane and pentane) and methylene chloride (although use of the latter has recently
raised some environmental concerns). Cape Insulation, for instance, have developed
Capaphen, a phenolic foam insulation product using neither CFCs nor HCFCs as blowing
agents.

Since phenolic foams, like the basic phenolic polymers, are very rigid with low
extensibility, they are generally friable with poor abrasion resistance. Modifiers are
frequently added to formulations to reduce friability by increasing flexibility and toughness.
These modifiers can be reactive components incorporated into the chemical structure
such as polyvinyl alcohol, copolymers of vinyl alcohol and vinyl chloride or low molecular
weight additives such as o-cresol (functionality 2). Alternatively, non-reactive polymeric
modifiers can be used such as urea-formaldehyde or epoxy resins.

Use of flame retardants is not necessary in phenolic foams to provide non-igniting


properties, but may be added to improve flame retardancy further in order to meet specific
tests. Useful fire retardant additives for phenolic foam are ammonium polyphosphate and
aluminium trihydrate. These are added in powder form and good mixing is necessary to
achieve uniform dispersion and optimum effectiveness.

9.3 Processes

Manufacturing equipment for phenolic foam is similar to that used for rigid polyurethane
foam, and may be continuous or batch. Resol foams are produced by metering resol
resin, blowing agent and catalyst to a three-component mixing head designed to give
good mixing of liquids having large viscosity differences (high viscosity resol resin, low
viscosity blowing agent). Corrosion resistant materials must be used to afford protection
against acid catalysts. As a consequence, phenolic foam producing equipment is
significantly more costly than polyurethane foam machinery.

For the production of continuous laminate, the mix is dispensed between two sheets of
facing material on a double conveyor (as for the production of rigid polyurethane foam
laminate, see Section 5). Provision is made for even distribution of the dispensed mix
across the sheet conveyor, and for heating to ensure proper cure is achieved over an
appropriate time. Water is removed at the end of the production stage.

A cream time of 20 seconds, a gel time of 150 seconds and a rise time of 200 seconds
(somewhat longer than is typical of polyurethane foams) are normal.

Facing materials may be metal, flexible plastic, glass fibre or a combination of these. As
with rigid polyurethane foam, profiled laminates with edge covering as well as top and
bottom facings can be produced by feeding preshaped metal strip to the conveyor. Large

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laminated phenolic foam blocks can be made in this way, and the process is in use in
Japan, Europe and North America.

An alternative process is used for production of sandwich panels, in which the mix is
dispensed into a mould containing a lower facing material. The top facing is inserted after
the mix has been dispensed and the panels foamed and cured in a multi-daylight press.
This is an open-mould method, to be distinguished from the closed-mould method used
for batch manufacture of rigid polyurethane block, although a (patented) method of
producing phenolic foam block batchwise, exactly as for rigid polyurethane has been
described [1].

Spray-in-place production of phenolic foam is also possible. American Foam


Technologies, for instance, has developed a two-component flame retardant system, in
this case formulated with a chemical blowing agent to avoid any problems from ozone
depleting, or flammable, blowing agents. This technology allows users to fill spaces
around, e.g., fire doors, engine bulkheads and aircraft compartments, with a thermal and
acoustically insulating material. The foam density can be varied from 8 to over 700 kg/m3.
An integral skin is formed which enhances toughness and good resistance to water
penetration is claimed. The material is called Thermo-Cor 2.

The manufacturing process of novolac foam comprises an initial mix of formulation


ingredients followed by grinding and then addition of fillers, as required, to produce a
moulding compound. The compound is placed in a mould and heated in a press to
decompose the blowing agent and cure the foam.

Post-manufacture operations for phenolic foams are similar to those for rigid polyurethane
foams (see Section 5).

9.4 Recycling

No references have been found regarding recycling processes for phenolic foam. The
stable character of the polymer would make it difficult to develop a chemical recovery
process, as is operated for polyurethanes, and the crosslinked structure precludes
recycling by melt processes. However, the generally friable nature of the material should
make it a candidate for regrinding and incorporation as a filler in phenolic or other
products.

9.5 Properties

The properties of a phenolic foam, as typified by Cape Insulations Phenofoam, are shown
in Table 9.2.

Foams of this type are closed cell, giving good insulation and have been formulated to
provide a high degree of fire resistance. Data quoted by Cape Insulation are:

Ignitability BS476 Part 5 Class P


Surface spread of flame BS476 Part 7 Class 1
Building regulations 1985 Class 0
Smoke generation BS5111 Part 1
ASTM D2843 mean max. obscuration 1.8%
Punking behaviour BS5946 39%

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Punking is a phenomenon whereby the surface of a closed-cell phenolic foam pops and
breaks when subjected to flame and can be a cause of failure in fire testing. Formulations
have been developed to minimise this phenomenon.

Table 9.2 Properties of Phenolic Foam


Property Foam density (kg/m3)
35 60
Compressive strength
perpendicular to face (kN/m2) 120 200
2
parallel to face (kN/m ) 170 300
Cross breaking strength (kN/m2) 150200 300500
Shear strength (kN/m2) 100 -
Tensile strength
perpendicular to face (kN/m2) 150 250
parallel to face (kN/m2) 250 430
Thermal conductivity at 10 C (W/m K) 0.020 0.020
Dimensional stability - linear change after
2.0 2.0
7 days at 130 C (%)
Maximum continuous service
120 120
temperature (C)
Source: Cape Insulation data sheet

The self-adhesive properties of phenolic (resol) foam are adequate for the production of
composites with water-absorbing facing materials such as plywood, non-woven cloth,
paper and plaster board (although not so good as that of polyurethane foam). Adhesion to
steel and aluminium plate, however, is poor.

Other good inherent properties of phenolic foams are:

moisture resistivity (of closed-cell foams), including low water vapour transmission,
low absorption and good dimensional stability,
chemical resistivity, being virtually unaffected by all solvents and weak acids/alkalis,
and
biological resistivity, non-nourishing to fungal growth.

Taken together, these properties lead to long life expectancy in applications such as
building and construction.

The combination of outstanding intrinsic fire resistance (even without non-combustible


facings) and excellent thermal insulation properties make phenolic foam a competitor for
rigid polyurethane foam and other insulating materials in building and construction. A
significant difference is the low smoke production from phenolic foams. This is due to the
behaviour of the foam in fire conditions, where an insulating char is formed on the foam
surface. This burns only slowly, without flaming or melting, thus avoiding the production
and volatilisation of low molecular weight organic species which contribute to smoke
production. The effect is similar to that of protective intumescent coatings. Tests carried
out by the TNO Institute for Building Materials and Structure on behalf of the phenolic
foam resin manufacturers of the Association of Plastics Manufacturers in Europe (APME)
have given optical density data comparing phenolic foam with polystyrene foam. Results
indicated polystyrene emits 150 times as much smoke as phenolic foam.

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The slow burning behaviour of phenolic foam results in the composition of the combustion
gas being principally carbon monoxide, carbon dioxide and water vapour with only trace
amounts of other compounds arising from breakdown of the catalyst system. The ratio of
oxides of carbon depends on oxygen availability.

The combination of slow burning rates with low smoke and toxic gas emissions is an
advantageous property of phenolic foams, although commercial advantage is to some
extent hindered by the absence of any uniform standard for assessing and regulating
these properties. In Europe, some member states regulate directly for fire and smoke,
whilst others regulate for smoke for a limited number of end uses; in the UK, there is no
smoke regulation. European harmonisation of fire testing should go some way to rectifying
this and there is an expectation that smoke production will be incorporated in a European
classification system.

9.6 Markets and Applications

Use of phenolic foam in relation to competing materials is governed by its property


advantages and disadvantages. In summary, high friability and low strength need to be
compensated in the application by good thermal insulation and outstanding fire
resistance.

The main application is, therefore, insulation, particularly in areas where fire resistance is
a primary concern. Example applications are:

block foam (resol type)cut to size and shape for applications as thermal insulation
in buildings and pipe covering,

sandwich panels (resol type)thermal insulation in building and construction for


ceilings, partitions, walls, doors, etc.,

continuous laminated board (resol type)with the facing often an integral part of the
initial design and left visible. Profiled sheets are also used with both edges and
top/bottom surfaces covered.

An example of the use of phenolic foam in demanding environments can be found in


shipbuilding. Permali has supplied its LST2 fire safe phenolic foam as the core material for
composite panels and other structural elements in three Type 23 frigates built at Yarrow
Shipbuilders, Glasgow.

Meirion Insulations, UK, and Advanced Insulation Products, UK, jointly offer Greenphen
phenolic foam, claimed to offer an advance over existing insulation materials in terms of
fire behaviour and corrosive effects. This product is said to be capable of production in the
form of complex shapes with integral skin for applications such as valve covers and pipe
lagging. The key to this development appears to be use of an alternative catalyst which
facilitates elimination of corrosive acid catalyst residues in the finished product.
Applications for foam filling of building panels, plastic extrusions and metal structures are
also envisaged. The technology is available for license.

Detailed figures for the phenolic foam share of the insulation market are not readily
available but an estimate [2] indicated a figure of 0.9 x 106 m3 of phenolic foam in Western
Europe in 1995. This is about 1% of the total market. The market is dominated by mineral
and glass fibre wool (60.5%), followed by polystyrene foam (31.1% EPS plus XPS) and
rigid PU foam (7.4%). The relatively poor market share for phenolic foam reflects its

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disadvantages which are not compensated by a superior fire performance in most


insulation applications.

A minor but well-known application for open-cell resol phenolic foam is as a flower support
in flower arranging. The open-cell structure allows penetration of water to reach and
sustain the flowers, whilst the comparatively weak friable nature of the foam allows the
flowers to be pushed into position without stem damage.

Novolac foam is moulded at the manufacturing stage and its use is generally restricted to
applications where its freedom from acid catalyst residues, and hence low potential for
metal corrosion, is an advantage. Applications include thermal insulation for pipes,
chemical plants and storage vessels for liquefied gas.

References

1. K. Iwasaki, Handbook of Plastic Foams, Ed., A.H. Landrock, Noyes Publications, New
Jersey, USA, 1995, 183.

2. R. Kaufung, Proceedings of Polyurethanes World Congress 97, Amsterdam, the


Netherlands, 2.

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10 LATEX FOAM

10.1 Introduction

Latex foam was one of the earliest polymeric foam materials with production beginning in
about 1930. In the 1950s, latex foam was the major outlet for rubber latex with some 70%
of world production being used to produce foam. More recently, the versatility and
production economics of flexible polyurethane foam have led to this material replacing
latex foam in many of its furnishing and bedding markets. However, latex foam remains a
preferred product for a part of the mattress, pillow and related market, and for some
specialist applications where its soft feel and high degree of comfort cannot generally be
matched by polyurethane foams.

10.2 Materials

Whilst the original processes were developed using natural rubber (NR) latex, synthetic
rubber (SR) latices are less expensive and have been introduced progressively since the
1960s. The Dunlopillo Co., (Pannal, UK) uses a blend of NR and SR latices. Latex Foam
Products Inc., USA, uses styrene-butadiene rubber (SBR) and acrylonitrile butadiene
rubber (NBR) latices. NR latex gives the foam good properties, and in the manufacturing
process mould stripping is easier owing to the high hot tear strength. Improvements to
synthetic latices have, however, largely overcome the problems that they originally
imposed on foam manufacture. Mould shrinkage of SR latex foams is somewhat less than
that of foams based on NR latex, and this prevents easy substitution of materials in foam
manufacture as this could require a change in mould dimensions.

10.3 Processes

10.3.1 The Dunlop Process

The Dunlop process, originally developed in 1929, involves making an initially liquid foam
by aerating a rubber latex. A planetary whisk was used for this, and is still used today for
short runs or single mouldings. More usually, a continuous foaming machine is used from
which latex is passed to a blending unit where the other formulation components are
added, of which the important ones are zinc oxide (35 phr) and sodium silico fluoride,
Na2SiF6 (11.5 phr). The mix is passed to a mould where gelation occurs. Natural rubber
latex contains ammonia and stabilising soaps. Hydrolysis of the sodium silico fluoride
results in release of hydrofluoric acid which lowers pH and destabilises the latex by
reducing the surface activity of the stabilisers, resulting in gelation when the pH drops
below about 8. Unfortunately, the air bubbles can also destabilise and good process
control is necessary to avoid problems at this stage. Following gelation, the latex is cured
by passing the moulds through a steam oven, after which the foam is stripped from the
moulds, washed and dried.

The main advantage of the Dunlop process is that gelation takes place throughout the
foam by an internal process which makes it possible to produce mouldings of virtually any
shape and size with good physical properties. Sheet foam 2050 mm thick can be made
by spreading the foamed latex onto a continuous conveyor. A disadvantage is the close
process control needed owing to the sensitive nature of the gelling process in relation to
foam stability. The foam has limited stability at ambient temperature in the early stages of
the process. Some mould scrap is normal.

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For these reasons, the Dunlop process has generally been superceded by the Talalay
process.

10.3.2 Talalay Process

The Talalay process was invented in 1935 with further developments taking place over the
next 25 years. It overcomes the main disadvantage of the Dunlop process (the necessity
of destabilising the rubber/water interface whilst maintaining the air/water interface) by
freezing the foam before gelling. Formulations, therefore, contain no initial gelling agent,
the main additive being zinc oxide curative at 35 phr.

In a typical Talalay process, a relatively high density liquid foam (~ 200 kg/m3), produced
by aeration and blending as in the Dunlop process, is poured into a mould. The mould is
only partially filled, vacuum being applied through a semi-permeable gasket to expand the
liquid foam to fill the mould. It is then necessary to freeze the foam rapidly, which is
carried out by passing coolant (ethylene glycol/water at 30 C) through the mould.
Talalay moulds have a pin core structure which enables good heat exchange and also
gives the foam its characteristic cored appearance. After freezing, CO2 is passed into the
mould to destabilise and gel the rubber after which the frozen foam is thawed (ethylene
glycol/water at 25 C) and then cured (ethylene glycol/water at 110 C). The process
takes about 30 minutes. The product is stripped from the mould, washed and dried as for
the Dunlop process.

The key to the process is the mould design which has to facilitate all these process
operations. The complexity of the mould and ancillary equipment means that moulds are
permanently fixed and cannot be incorporated in a continuous conveyor system as with
the Dunlop process. Where several moulds are in use, dispensers are required to move to
the mould positions for filling.

The Talalay process is readily automated and there is no mould scrap. The foam stability
at ambient temperature is good and process sensitivity is low. Disadvantages are the
relative inflexibility of the moulds compared with the Dunlop process and their high capital
cost. The process is not suited for one-off products or products with complex shapes.
Where high-volume production of a single product is required, the process has good
economics. An advantage of the pin core mould is that it provides products which, whilst
having a cored structure for softness and feel, can nevertheless be cut to provide smaller
products without having to take account of the core structure. This lends the process to
the manufacture of mattresses and pillows which is its major application.

10.3.3 The Heat Sensitive Process

This process involves frothing the latex to expand to a desired density after which
ammonium acetate and zinc oxide are mixed in. The zinc oxide is solubilised to some
extent by amine complexes formed by the ammonia in the latex, predominantly the zinc
tetramine complex. In the presence of these complexes, the latex shows heat sensitive
gelation behaviour. The mix is poured into a heated mould (6070 C) where gelling takes
place after some 510 minutes. After gelation, the mould is heated to 100 C to cure the
foam, and this is followed by the usual washing and drying step.

The process is limited by heat transfer. In large mouldings, the rate of heat transfer to the
centre of the foam is slow resulting in poor foam structure, and the process is generally
applied only to thin-section products with thickness up to 12 cm, e.g., carpet underlay
and backings. Physical properties are poor in relation to the other processes.

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A typical formulation for the heat sensitive process would contain 4 phr zinc oxide and 1
phr ammonium acetate, with latex ammonia levels greater than 0.5%.

10.4 Recycling

A method has been suggested for the conversion of process wastes from latex foam (and
some other products) by crumbing and subsequently using as a filler in natural
rubber/high styrene rubber microcellular sheets [1]. However, there is little published
information suggesting this or any other recovery method is currently in use.

10.5 Properties

Some typical properties of NR and SBR latex foams of similar compression modulus are
shown in Table 10.1

Table 10.1 Latex Foam Properties


Property NR SBR
Tensile strength (MPa) 0.12 0.06
Elongation at break (%) 300 150
Compression modulus (kPa) 6.3 7.3
Rebound resilience (%) 75 69
Modulus loss after flexing (%) 14 10
(2.5 x 105 cycles)
Compression set (%) 10 20
(22 h at 70 C)
Source: [2]

Essentially, NR latex foam has the greater strength and is easier to process for this
reason. SBR latex foam has a somewhat higher compression modulus and hence can be
produced at a lower density to support an equivalent load. Since it is also a less
expensive raw material, SBR latex foam presents the better production economics
provided the foam properties are adequate for the application.

10.6 Markets and Applications

The main application of latex foam is in mattresses, pillows and cushions. For these
applications, good recovery from compression (and low creep in compression) are
required and these properties are readily available from latex foam, particularly if it
includes a proportion of NR latex. It is not surprising that the major producers of latex
foam have entered into associations with bedding manufacturers; e.g., Dunlopillo Co., UK,
with Auping, a Dutch manufacturer of bed bases; and Latex Foam Products, USA, with
the French company, Pirelli-Sapsa Bedding (this joint venture is named Delviel).

In 1997, BTR sold its Dunlopillo foam bedding and seating business and its automotive
components units in the UK to a management buy out group and in Germany to SP
Reifenwerke GmbH.

Whilst the latex foam mattress industry has substantially decreased through competition
from lower cost polyurethane products, there is still a significant market for what is seen
as a quality product. Manufacture has generally consolidated to a few companies, e.g.,
Latex Foam Products is the only manufacturer of latex foam mattresses in North America.

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However, the market does seem to have stabilised, and Latex Foam Products reported a
25% increase each year in sales during the period 19931998. This company is planning
another factory in the USA, possibly as a joint project, and has nearly tripled the size of its
French joint venture facility with Pirelli-Sapsa Bedding. New products in the mattress area
have been introduced by this company, for example, (in May 1998) its RaceTrack
mattress core. This comprises an inner latex foam with an outer surround of polyurethane,
and is aimed at customers unwilling to pay the cost of a full latex mattress.

Latex Foam Products is also reported to be targeting UK markets with a flame retardant
latex foam pillow meeting UK fire retardancy regulations. This product was developed
after a year of research and is said to offer better properties at lower cost than competitive
products.

Dunlopillo Co., introduced its Millenium collection, a new range of beds said to have a
sumptuous feel and superior quality and appearance.

Another significant application for latex foam is cosmetics, where latex foam pieces for
application of make-up are cut by slitting/die stamping and shaped, if required, by buffing.
The softness of the foam makes it particularly attractive where contact with delicate skin is
involved.

Other minor applications include foam toys, models and puppets (e.g., the Muppets,
Spitting Image). NR latex foam is preferred as the combination of softness and flexibility is
a close approximation to the characteristics of human flesh. Sheet foam produced by the
Dunlop process, either in solid or cavitied form, is used for various padding applications.

In summary, in developed countries polyurethane foam has replaced latex foam to a large
extent in its traditional market of mattresses and cushions, and latex foam manufacture
has been consolidated with a few manufacturers. As polyurethane foam manufacture
increases in less developed countries, latex foam manufacture is likely to follow the same
route in these areas. Niche markets where the unique characteristics of latex foam are
valued are likely to remain. Whilst polyurethane research and development has latex foam
properties as an objective, it is unlikely that these will ever be so closely matched as to
make latex foam obsolete.

References

1. R. Stiathukutty, R. Joseph and K.E. George, Polymer Recycling, 1997/1998, 3, 4,


303.

2. T.D. Pendle, Cellular Polymers, 1989, 8, 1, 1.

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11 MICROCELLULAR FOAM

11.1 Introduction

Microcellular foams may be defined as those having cell diameters of the order of 0.01
mm or less, whereas conventional foams normally have cell sizes of 0.1 mm and above.
The original concept in developing these foams in the 1980s was to reduce the cell size to
less than that of the micro-inclusions and inhomogeneities which are the sites for stress
failure (the so-called critical flaw size). If this could be achieved, then it was anticipated
that as apparent foam density fell, strength properties would be maintained to a
substantially greater extent than is found with conventional foams. The work was aimed to
meet a general commercial objective: to reduce the amount of material used in plastic
products without sacrificing physical properties, particularly toughness.

Work at the Massachusetts Institute of Technology (MIT) resulted in a laboratory process


for the production of microcellular polystyrene, which was the subject of a 1984 patent [1].
The method, which has been widely studied since, utilised a thermally induced phase
separation in which an amorphous material such as polystyrene is saturated at moderate
temperatures with a gas such as CO2. The material is subsequently removed from the
vessel and heated above the glass transition of the polymer. Under these conditions, the
solubility of the gas in the polymer is reduced and the gas is released to produce a
microcellular foam. Although other gases have been studied, most work has been done
with CO2 owing to its relatively high solubility in many polymers and the reduction in gas
solubility as temperature is raised. Polymers which have been foamed in this way [28]
include polymethyl methacrylate, PVC, polystyrene, polycarbonate and polyethylene
terephthalate.

A related process has been subsequently developed in which a polymer is saturated with
CO2 (or nitrogen) at relatively high temperatures and pressures in the supercritical regime,
followed by rapid depressurisation to atmospheric pressure at (relatively) constant
temperature [2]. This method makes use of the depression of the glass transition by gases
such as CO2, often to temperatures approaching ambient, resulting in swelling and
significant plasticisation of many amorphous polymers. Soaking with the carbon dioxide is
carried out above the depressed glass transition. Again, most work has been carried out
with CO2 owing to its relatively high solubility, and the polymer most studied is
polystyrene.

11.2 Processes

In work carried out at Massachusetts University, microcellular polystyrene was produced


using CO2 under pressure with a typical soaking temperature of 100 C [910]. At the end
of this period, the material is foamed by venting the carbon dioxide (over a period of 3 to 5
seconds) and the material then removed from the vessel and allowed to cool.

It was found that foam structures could be controlled by manipulating process conditions.
Experiments varying the foaming temperature whilst holding other parameters constant
showed that higher temperatures reduce density and produce larger cell sizes provided
that free expansion is permitted. Under these conditions, samples retain their original
geometry during expansion and cells are isotropic. If expansion is restricted by the vessel,
expansion occurs along the vessel axis and cells are anisotropic, as are subsequent
polymer properties. Lower depressurisation rates decrease the rate of gas dissolution and
lengthen the period of cell growth, leading to larger cell sizes. Foams with a bimodal

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distribution of cell sizes have been produced by reducing the pressure in two stages.
Higher saturation pressures reduce foam density if the foam expands freely. If expansion
is restricted to achieve constant apparent density, higher saturation pressures result in
smaller cell sizes. Values for cell size given for polystyrene expanded with CO2 to a
(restricted) density of 300 kg/m3 are in the range 0.005 to 0.034 mm (dimensions of minor
cell axis) [9]. Foam strengths of these materials were significantly higher than would be
expected for conventional foams of the same density, and such higher strengths have
been demonstrated by others working with microcellular foams.

The microcellular process using supercritical gases to expand polymers by pressure


release at temperatures above their glass transition point is related to the nitrogen
autoclave process, developed in the late 1950s for polyethylene and progressed to its
present state by Zotefoams plc, UK (see Section 6). In the autoclave process, nitrogen
gas is dissolved in polyethylene slabs at high temperatures (above the polymer melting
point) and pressures (up to 100 MPa is possible in Zotefoams laboratory). Nitrogen has a
negative heat of solution in polyethylene and, unlike CO2 in polystyrene, comes out of
solution if the temperature is lowered. However, rather than by lowering the temperature,
phase separation is achieved by rapid pressure reduction, temperature reduction being
only that due to adiabatic cooling effects. The released gas initiates cell formation and
subsequently expands the material.

Whilst CO2 is the favoured gas utilised in the microcellular foam process, it is not currently
used commercially in the autoclave process. The apparent advantage of high solubility
(and therefore low pressures to achieve high saturation levels and high expansion) is
negated by the low rate of pressure reduction from large vessels, which results in
unacceptably large cell sizes. A further disadvantage of CO2 in foaming polymers like
polyethylene, which are substantially above their glass transition at room temperature, is
the high diffusion rate of gas out of the cells. This is much greater than the diffusion rate of
air into the cells resulting in a partial vacuum and cell collapse (i.e., foam shrinkage)
unless the cell walls are stiff enough to withstand the resulting stress. Whilst polystyrene
below its glass transition can withstand the collapse pressures at apparent foam density
above about 15 kg/m3, polyethylene cannot. However, if nitrogen is used as the expansion
agent, the diffusion rates (nitrogen out and air (which contains some 78% nitrogen) in) are
similar and, in practice, nitrogen autoclave foams are quite stable immediately following
production, needing no maturing period.

Much of the work reported on microcellular foams refers to small-scale non-commercial


experimentation. However, commercial-scale extrusion of microcellular polystyrene foam
sheet has been demonstrated [11]. This technology is licensed by Trexel under the
trademark MuCell. MuCell foams are defined by Trexel as foamed thermoplastic materials
having cell size less than 50100 microns and nucleation density (i.e., number of cells per
cm3 of foam) greater than 108 cells/cm3.

The MuCell continuous foam extrusion process was initially demonstrated at MIT in the
early 1990s. Development of the process on a commercial scale began in 1994 and has
been taken to a point where extrusion rates of up to some 450 kg/h are claimed to be
possible with tandem extruders, and somewhat less with single extruders.

The MuCell process extends the concept of cell nucleation and growth using supercritical
fluids by carrying out mixing and saturation in an extruder. The expansion gas (generally
CO2) is injected as bubbles directly into the polymer melt where the bubbles are stretched
and broken apart by shearing within the extruder. The mixing accelerates the diffusion of
gas into the polymer so that saturation levels can be reached within acceptable residence
times. Once the saturation level has been reached, the optimum rheology for cell

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nucleation is achieved by close control of melt temperature. It is also important to control


melt pressure within the extruder. Conditions are arranged such that cell nucleation
occurs through a massive pressure drop which begins in the die. Nucleation is
homogeneous, driven by the thermodynamic changes bringing the dissolved gas out of
solution. The homogeneous nucleation rate is much greater than that from heterogeneous
nucleation sites (the inclusions and flaws which are always present) and this results in the
creation of large numbers of cells with consequent high cell density and small cell size in
the expanded foam. Control at the nucleation stage is essentially effected by attention to
both die design and the pressure profile in the die. Die design appears to be a key aspect
of the process.

As the nucleated polymer melt exits from the die and equalises with atmospheric
pressure, further gas comes out of solution and causes the cells to expand. Little further
nucleation takes place at this stage. The final extrudate cell growth is controlled by post
die cooling conditions.

Flat or annular dies are used as in conventional processes, and the normal take-off
facilities are used (such as chill roll stocks or cooling mandrels) for dimensional control of
the final product.

For both pilot- and commercial-scale development work, Trexel has used a tandem
extrusion system. The first extruder melts the polymer which is then passed through a
melt pipe to the second extruder dedicated to melt cooling and mixing. With the cooling
screw of the second extruder turning at a different speed (generally much slower) than the
primary extruder, cooling is optimised and a much broader range of process temperatures
can be controlled with varying flow rates.

Extrusion rates quoted by Trexel are 45 to 63 kg/h for a pilot system using a 50.8 mm
primary and a 63.5 mm secondary extruder. For its commercial-scale system, Trexel has
achieved 68 to 105 kg/h using a 63.5 mm primary and a 76.2 mm secondary extruder. A
larger scale system using a 114 mm primary and a 152 mm secondary extruder has also
been described and output rates over 400 kg/h claimed.

Conversion of a traditional line to allow MuCell production would require:

addition of (or modification to an existing) gas/supercritical fluid injection system,


addition of injection ports and injectors,
modified screw according to MuCell design specification, and
die meeting MuCell design specification.

A larger L/D ratio extruder may be necessary in order to provide sufficient residence time
for adequate mixing.

It is claimed that the process is quite robust and allows considerable flexibility in polymer
characteristics. Expanded sheet has been produced using polystyrene with melt flow
indices ranging from 1.5 to 9.0. Other gases and gas blends can be used, and
development is in progress on other polymers such as polypropylene. MuCell
polypropylene sheet has been produced on both single screw and tandem extrusion
systems at production rates up to 80 kg/h. Cell sizes are in the range 10 to 60 microns.
Some product data are shown in Table 11.1.

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Table 11.1 Product Data for MuCell Polypropylene


Form Density Dimensions Die
(kg/m3) (mm)
Sheet 130800 0.21.0 (thickness) Annular/Flat
300 (width)
Rod 30720 9 (diameter) Orifice
Coatings 400700 0.120.37 Crosshead
Source: [12]

Sheet production with annular dies has been demonstrated in the thickness range of 16
mm. Profiles have been produced up to 25 mm cross section. Although development aims
to increase this range, the process does not currently seem amenable to the production of
thick extruded block.

Application of the MuCell technology to products currently not foamed owing to the
limitations imposed on materials by the normal dimensions of the cells (for instance,
foamed thin films) can allow significant increases in volumetric output, since mass
throughput can be held essentially constant whilst the lower density provides a higher
volume. In a tubing application described by Trexel, with a 30% density reduction, a 22%
increase in production was observed. Provided properties are maintained at an adequate
level, this can be regarded as a real advantage.

A further development of the MuCell process has been demonstrated by Engel. This
extends the principle to injection moulding, where the foamed melt is injected into a mould
where it is shaped and cooled. Modifications to extruder barrel and screw are necessary
to allow a single phase system to be developed from the polymer/injected gas, and some
machine software modifications are also required to maintain melt uniformity. Engel can
supply either a complete production machine, or can retrofit existing units. The system
allows application to a much wider range of mouldings than hitherto possible with
conventional foam systems. Engel claims it can be used effectively in parts as thin as
1mm.

The production of an automatic air conditioning unit was demonstrated by Engel at


Interplas in 1999, using 20% talc-filled polypropylene running on a 900-tonne Duo
machine with an 80 mm MuCell barrier-type screw. Density reduction was small, but
nevertheless a 12% weight saving was claimed.

Whilst weight saving is the key attraction, there are other benefits claimed from the MuCell
process for injection moulding. For instance, melt viscosity is substantially reduced by the
presence of gas in the polymer, and so moulding pressures may also be reduced. Parts
can be run with a smaller clamp unit than normally requiredas much as 50% lower
pressure is claimed. The viscosity effect can also allow the use of lower melt temperatures
with consequent shorter cooling times and requirements, and more rapid demould. Other
benefits include a reduction in sink marking and the ability to obtain a good surface finish,
particularly where complex mould geometries are used. Many of the benefits of gas
assisted moulding are claimed in components where cored out gas channels are difficult
to introduce. Engel has commented that the process is well suited to its Tecomelt system
where a molten plastic backing is injected onto textiles or films in a mould.

Engel has carried out development work on the application of the MuCell process to
injection moulding with several other polymers, including polycarbonate/ABS blends and
thermoplastic elastomers, as well as polypropylene. Development centres have been set
up by Engel in Schwertberg, Austria, and Guelph, Canada.

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Whilst the original development involved MTI, DuPont Co., Boeing, Eastman Kodak,
Lockheed and Kraft Inc., the exclusive licence for this material, including both the original
batch production process and the more recently developed continuous extrusion process,
is currently held by Trexel. The technology has generated considerable interest and a
licence has been taken up by some 20 companies, mostly in the USA but also in Europe,
Japan and Korea. Some of those identified are Alusuisse-Lonza Group (extrusion), Engel
(injection moulding and supply of injection moulding equipment), Battenfeld (injection
moulding), Injectronics (injection moulding), Dumaplast (PVC extrusion), Milacron
(injection moulding), Arburg (supply of injection moulding equipment) and Ferromatik
Milacron (supply of injection moulding equipment including retrofitting).

11.3 Properties

Microcellular technology has been demonstrated on a commercial scale both as


continuous film extrusion and as injection moulding. However, major commercial
application is yet to come, and there are no widely available data sheets showing
properties. Properties of development material have been given in technical papers and
some data are shown in Table 11.2.

Table 11.2 Properties of MuCell Foam Compared to Conventional PS Foam


Density Average tensile Average toughness** Average
(lb/ft3) strength* (psi in/in) compressive
(psi) strength***
(psi)
MuCell PS foam MuCell PS foam MuCell PS foam
2 80 80 10 3 20 20
4 270 190 30 17 60 18
6 460 310 40 23 110 15
* Testing according to ASTM D638
** Measured by total area under the stress strain curve
*** Testing according to ASTM D695
Source: [12]

Whilst there appears to be data to support the thesis that microcellular foams have
improved properties (owing to cell diameters less than the critical flaw size), further data
are required on commercial-scale products using a variety of test methods to establish an
adequate basis for comparison. The real advantages of the microcellular process may be
the ability to dispense with costly and still environmentally undesirable blowing agents,
such as the various HCFCs, and the ability to extrude good quality expanded film at
thicknesses substantially less than 1 mm where normally cell diameters would result in
surface irregularities as the cells are comparable to or greater than film thickness.

11.4 Markets and Applications

At the time of writing, the status of microcellular foam development is such that whilst
commercial-scale foam production by both extrusion and injection moulding has been
successfully demonstrated, and it is known that several companies have licensed the
process from Trexel and are involved in process and product development, few
commercial applications have been publicised.

Applications originally suggested are those which would be anticipated for thin polystyrene
foam sheet, namely food trays and packaging, but other areas mentioned are automotive

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mouldings, toys, aerospace, medical prostheses, telecommunications and extrusions for


building and construction.

Injectronics has commented that the productivity improvements offered by the process
(reduced part weight, reduced injection pressure and clamp tonnage, shorter cycle time)
will help to meet the increasingly tight price pressures facing automotive moulders.

Dumaplast, Belgium, is reported to be using the technology for full-scale production of


PVC extrusion profiles for interior applications such as ceilings and hollow-wall claddings.
Dumaplast are able to produce thin product cross sections of less than 0.5 mm whilst
maintaining desireable surface qualities and physical properties.

Commercial applications are taking longer to evaluate than was anticipated in the early
stages of microcellular process development, but can be expected to accelerate in the
near future.

References

1. J.E. Martini-Vvedensky, N.P. Suh and F.A. Waldman, US Patent No. 4,473,665,
1984.

2. S.K. Goel and E.J. Beckman, Polymer Engineering and Science, 1994, 34, 1137 and
Polymer Engineering and Science, 1994, 34, 1148.

3. V. Kumar and J.E. Weller, Proceedings of Antec 91, Montreal, Canada, 1401.

4. V. Kumar and M.M. Van der Wel, Proceedings of Antec 91, Montreal, Canada, 1406.

5. D.F. Baldwin, C.B. Park and N.P. Suh, Polymer Engineering and Science, 1996, 36,
1437 and Polymer Engineering and Science, 1996, 36, 1446.

6. S.W. Cha, N.P. Suh, D.F. Baldwin and C.B. Park, US Patent No. 5,158, 986, 1992.

7. V. Kumar, Cellular Polymers, 1993, 12, 3, 207.

8. M.R. Hall, M. Ma, V. Kumar and R.R. Kwapisz, Cellular Polymers, 1998, 17, 4, 271.

9. K.A. Arora, A.J. Lesser and T.J. McCarthy, Polymer Engineering and Science, 1998,
38, 12, 2055.

10. K.A. Arora, A.J. Lesser and T.J. McCarthy, Macromolecules, 1998, 31, 14, 4614.

11. S. Tupil, K. Buchner and M. Pallaver, Proceedings of Foamplas 97, Mainz, Germany,
163.

12. K. Blizard and M. Pallaver, Proceedings of New Plastics 98, London, UK, Paper 11.

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12 ENVIRONMENTAL INFLUENCES ON THE FOAM INDUSTRY

12.1 Introduction

Particularly in developed countries, there has been an increasing realisation of the


adverse environmental effects of many industrial activities. The recognition of such effects
and a better knowledge of environment interactions, stimulated by action groups such as
Greenpeace, have resulted in a steady growth of environmental legislation aiming to
reduce or eliminate such adverse effects for the benefit of both present and future
generations. This legislation, together with a heightened consciousness of environmental
effects and consequent pressure from customers, has impacted on the foam industry in
several ways which are briefly reviewed in this section. Actions to reduce or eliminate
such adverse effects have been ongoing for some time and are likely to continue for some
while before environmentally optimum production and use is achieved. This will occur
sooner in developed countries where environmental and legislative pressures are
greatest.

12.2 Emissions

It is generally recognised that some chemical emissions from industrial processes have a
significant effect on the global environment. Emissions include:

gases such as carbon dioxide and methane which add to the natural greenhouse
effect contributing to global warming,

gases such as sulphur dioxide and oxides of nitrogen which, being acidic, can have
a deleterious effect on vegetation, buildings, etc., and

volatile organic compounds (VOCs), which can contribute to photochemical pollution


including smog and ground level ozone.

It is estimated [1] that, on an annual basis, some 24% of Europes VOCs come from
industrial use of solvents. Other major sources are natural vegetation, transport, and
combustion processes for power generation. There is both a geographical and a seasonal
variation due mainly to the contribution from natural sources. Production of solvents in
Western Europe amounts to over four million tonnes annually, over half of which is used in
paints and coatings manufacture.

Legislation has been enacted in many countries aiming to reduce VOC emissions. In
Europe, this takes the form of the VOC Solvent Emissions Directive which was adopted by
the European Commission in 1999. The Directive targets a reduction in VOC emissions of
67% by 2007 compared with 1990 base levels. Members of the EU are expected to put in
place legislation to achieve the Directives requirements either as set out or more
stringently. Emission limits will be set which are required to be met immediately for new
plants and after a specified time limit for existing plants. Compliance in the industry
sectors involved is likely to be challenging and costly.

Foam manufacturers do not make a large contribution to VOC production, but blowing
agents such as pentane, isobutane and methylene dichloride are classed as VOCs and
are included in the legislation. It is ironic that some of these substances have been
introduced as satisfactory alternatives to CFCs to comply with Montreal Protocol
requirements and that CFCs, HCFCs and HFCs are not classed as VOCs. In the USA,

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where VOC control is incorporated in standards set by the US Environmental Protection


Agency under the Clean Air Act Amendments, the problems of collection and destruction
of hydrocarbon emissions from foam production using hydrocarbon (VOC) blowing agents
have been successfully dealt with by installation of extraction facilities.

A number of foam processes generate obnoxious or toxic vapours, which can cause
problems if such vapours are allowed to escape into the factory atmosphere or are
released in an uncontrolled manner from the factory. For instance, polyurethane foam
manufacture can produce isocyanate vapours, and foam production using azo blowing
agents can release ammonia. Additional attention to emission control has been necessary
in recent years, both to ensure a demonstrably safe working environment and to comply
with local factory emission regulations. Whilst there has been no significant difficulty for
companies to comply with tighter emission control requirements, there is an additional
cost in providing such control, and there is a greater interest in the development of
foaming systems which have an intrinsically low or zero level of obnoxious emissions. ICI
is promoting its MDI-based Waterlily foams for applications in mattresses and furniture.
These systems are claimed to produce very low levels of volatiles (<5 ppm) and free
isocyanate (<1 ppb) during manufacture. BASF has developed an MDI PU slabstock
system, and both the BASF and ICI systems are said to be capable of running on existing
production facilities.

In polyolefin foam production, Zotefoams has for many years operated a process using
pure nitrogen as the expansion agent, free from the emission problems resulting from
processes using azodicarbonamide. The ammonia released by this blowing agent can
cause environmental problems not only in production but during fabrication and use,
through slow release of ammonia trapped in the closed cells. The high capital cost of
manufacturing equipment is allowing only relatively slow spread of the nitrogen technology
which is currently operated only by the one company, but environmental concerns could
enhance the appeal of this process and its products.

12.3 Blowing Agents and the Montreal Protocol

The action of chlorofluorocarbons (CFCs) on depletion of the ozone layer is well


documented and resulted in the Montreal Protocol which was initiated in 1987 and
modified several times since, most recently in 1997. The production of CFCs has now
ceased in developed countries and alternative substances with reduced environmental
impact have had to be developed for foam expansion and other uses. The current status
of such alternatives is reviewed in Section 3. Transition to HFCs has been the first stage
for many companies, but, as these substances still have an ozone depleting effect, a
further change will eventually be required to use of compounds such as HFCs (zero ozone
depletion but significant global warming effect, and more costly), hydrocarbons (zero
ozone depletion, significant global warming effect, flammable and classified as VOCs with
emission controls), or CO2 (zero ozone depletion but the main contributor to global
warming and requires substantial process modification). Additionally, foam properties can
deteriorate using CFC alternatives although foam manufacturers claim that recent
developments essentially overcome this problem. There is little doubt that the area of CFC
alternatives will continue to be an important development topic for many foam
manufacturers over the next few years.

The effect of these changes on foam markets has so far not been too significant. Foam
manufacturers have endeavoured to absorb additional process and material costs, and
users have accepted that any small deterioration in foam properties is part of the price to
pay for compliance with Montreal Protocol requirements, at least in the short term. There

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is an expectation that properties of the original CFC-based foams will eventually be


matched. If this proves in practice to be unrealistic, the use of foams to replace other
materials (e.g., polymer foam insulation in place of mineral wool insulation) could slow
down.

12.4 Waste Recovery

There has always been a cost incentive for the elimination and/or recovery of waste from
the manufacturing process, and the reduction of waste and elimination of scrap is an
important part of the quality system adopted by most manufacturers (and required by their
customers). Legislation is now having an impact in this area, not only for foam producers
but for foam users and indeed for all those involved in the chain from raw material to used
foam product. The main relevant legislation in Europe is the European Union Packaging
Waste Directive (94/62/EC) which has been introduced to deal with generally increasing
problems of waste disposal. Other relevant legislation proposed includes the European
Draft Landfill Directive and the European Draft Directive on Recycling End-of-Life
Vehicles.

12.4.1 The Packaging Waste Directive

Packaging accounts for some 42% of plastics consumption in Europe, and the Packaging
Directive is seen as having a significant impact on the reduction of plastics waste. It is
worth noting, however, that plastics waste accounts for less than 0.7% of the total waste
produced in Western Europe and plastics waste recovery can have only a relatively small
impact on total waste production.

The Directive is not legislationeach Member State is required to introduce appropriate


national legislation to meet the Directive. Essentially, the Directive established a target of
50% recovery (i.e., diverted from landfill) of all packaging materials with a material
recycling rate of 2545% and a minimum allowable recycling rate for any particular
material (such as plastics) of 15%. Recovery includes production of heat for energy by
direct incineration, but the targets preclude burning all (packaging) waste for this purpose;
some recycling is necessary.

Implementation of the Directive varies across Europe and is fully reviewed in [2]. Most
countries have introduced levies on packaging at a single point in the packaging chain (at
the packer/filler stage). In the UK, however, under legislation (The Packaging Waste
Regulations) which became law on 6 March 1997, there is a shared responsibility system
which imposes a varied percentage throughout the chain:

raw materials 6%,


converters 11%,
packer/fillers 36%, and
retailers/distributors 47%.

UK companies handling more than 50 tonnes of packaging (excluding exports but


including imports) and with a turnover of more than 2 million are currently obligated
under modified legislation effective from 1 January 2000. UK recovery and recycling
targets will be phased in as shown in Table 12.1.

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Table 12.1 UK Recovery and Recycling Targets


Year Minimum recycled of Minimum
each material (%) recovered (%)
1999 10 43
2000 13 45
2001 16 52*
* of which a minimum of 26% must be recycled

Some minor changes were made public in November 1999, including an amendment of
the minimum turnover from 1 million to 2 million.

In the UK, obligated companies can comply with legislation either by their own efforts (by
arranging for used packaging to be collected and recycled) or by joining a collective
compliance scheme that (for a fee) undertakes recycling obligation on behalf of its
members. All individually registered businesses have to submit an annual compliance
plan to the relevant agency and the individual route is likely to be subject to greater
checks in future to ensure compliance.

Whilst recycling processes have been developed for most types of polymer foam
(described in the appropriate sections in this report), there remain problems in the
collection and sorting of foam waste and in developing realistic outlets for the recycled
product. These problems apply to all plastics, not just foams. However, since foams are
by their nature of low density, the volume of foam waste is correspondingly high and the
cost of collection and transport to a recycling facility can be uneconomic as well as
environmentally undesirable in view of the fuel used for transport. Plastics packaging in
the form of film is easier to deal with and receives priority from companies seeking to meet
their obligations.

Nevertheless, some foam manufacturers (e.g., Dow) have taken the step of offering to
collect packaging from waste arising from the use of their materials to recycle it to produce
new foam. Other companies (e.g., Zotefoams) emphasise the durability of their particular
type of foam which can be reused for multiple journeys and hence, unlike some packaging
foams, does not become waste after the first journey. Whilst this minimises foam waste at
the user stage, such packaging enters the normal waste stream when it is no longer fit for
use.

Foams particularly used for packaging applications include flexible polyurethane,


polystyrene (EPS) and polyolefin (polyethylene sheet and block) foam. Recycling
processes have been developed for all these materials.

12.4.2 The Draft Landfill Directive

In addition to the packaging waste regulations, there is pressure to reduce the amount of
waste going to landfill. The majority of municipal waste in Europe is still sent to landfill
and, according to figures from the APME, the amount of plastics waste going to landfill
increased between 1995 and 1997 despite the growth of recycling facilities [2]. The
European Council of Ministers have reached agreement on the form of a draft Landfill
Directive which sets out rules aiming to prevent or reduce adverse environmental effects
resulting from landfill waste. These include classification of waste (as hazardous, non-
hazardous and inert) and targets for the volume reduction of biodegradable waste. There
does not appear to be any direct legislation for plastics. However, the European Recycling
and Recovery Association (ERRA) has proposed that a quantitative restriction of landfill

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should replace the current recycling and recovery targets of the Packaging Waste
Directive, with the amount of packaging waste going to landfill stabilised and Member
States free to reuse, recycle or incinerate to deal with the rest of the waste. This proposal
has the merit of being easier to apply and monitor than current legislation, but there is no
sign of adoption at least in the short term.

In the UK, the landfill tax introduced in October 1996 has aimed to discourage waste
disposal by landfill. From 1 April 1999, the standard rate is 10 per tonne, escalating at 1
per year for the next five years. There has been little sign that this has had any great
effect (except to increase Government income to a sum estimated as 100 million per
year!), and cases of illegal dumping are said to have doubled. Since plastics, and
particularly foam waste, are of low density, the impact of the tax is quite small.

12.4.3 The Draft Directive on Recycling End-of-Life Vehicles

In July 1997, the European Commission accepted a Proposal for a Directive on


Recycling End-of-Life Vehicles which would require each Member State by the year 2005
to reuse and/or recover 85% of the vehicles weight, with 80% of the vehicle weight
reused or recycled; these figures rise to 95% and 85%, respectively, by 2015.

The motor industry, whilst accepting the need for action in this area, has lobbied hard to
obtain amendments on some Articles to make them, in its view, more practical and
acceptable. Nevertheless, to some protest, the Directive was approved in February 2000.
Some areas of concern are:

the requirement for vehicle manufacturers to finance a significant part of take back
costs from 2006,
onerous recycling targets,
recycling problems with new lightweight materials which could help fuel economy and
lower emissions, and
a reluctance of the European Commission to accept the recycling definition in the
Packaging Waste Directive which allows chemical recycling.

Current status concerning automotive plastics waste is discussed in some detail in [2].

The foams used in vehicles are mainly flexible polyurethane (seat cushions), semi-rigid
polyurethane (bumpers, surface padding) and polyolefin (polypropylene bumpers,
polyethylene or polypropylene sheet for door liners, mirror backings, boot liners, tool
containers, etc.). Recycling of these materials is not a technical problem; the main
difficulties are separation of the foams (which may be bonded to other components),
identification, and the cost of collection and transport to a recycler. Collection and
transport is a major problem for all plastics waste, but is particularly so for foam waste due
to the low density of the product. Consolidation (i.e., density reduction) at the point of
collection is helpful, but, nevertheless, the cost of recycled plastics from foam (or even
non-foam) sources is currently greater than the cost of new virgin material.

There is currently considerable design and development work associated with end-of-life
vehicle disposal. Trends affecting foam manufacturers and supplies to the automotive
industry include:

vehicle weight minimisation, to reduce the amount of waste eventually produced,


and

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minimisation of the number of types of material used, to simplify eventual separation


and identification of components.

The development of one-material dashboards is an example of the latter, using


polyolefins, styrenics, or PU compatible systems. Another example is DuPonts proposal
for automotive seats produced entirely of polyester, with Ecofil fibre cushioning, Dacron
textile cover and a glass-reinforced polyester shell. This, if it achieves commercial
success, could impact on use of flexible PU cushioning.

Further developments impacting on foam recovery and recycling in the automotive


industry can be expected as the European Directive begins to take effect.

12.5 Biodegradable Foam

The Packaging Waste Directive allows for organic recycling to provide organic residues or
methane, and there has been interest in the development of polymers which, after their
useful life, could be composted for use as a top dressing or soil conditioner. Whilst early
work examined the use of UV sensitisers to provide photo-degradable polymers, more
recently polymers based on polyhydroxybutyrate have been developed. The best known is
Biopol, produced initially by ICI and subsequently sold to Monsanto (production ceased in
1998). More recently, Symphony Environmental launched a totally degradable polymer
Spi-Tek, comprising polyethylene with around 3% additive which allows controlled
degradation by heat, light or stress. The product is being used for items such as dustbin
liners and sandwich bags.

Whilst many foam manufacturers will have considered developing this type of foam to
promote as an environmentally friendly product, and in packaging applications to help
meet legislative regulations, there has been no significant development and production of
a biodegradable polymer foam. Most foam applications, including cushion packaging,
require good resistance to environmental factors such as UV light, heat and microbial
attack, and a biodegradable foam would almost invariably not be fit for its original intended
purpose. Applications for biodegradable polymers are currently in areas where short life is
acceptable, e.g., compost bags and single-use food packaging.

12.6 Environmental Standards

The quality standard BS 5750, now ISO 9000-1, has for many customers become an
essential supplier requirement, demonstrating that a company has in place a quality
system which ensures that customers specifications are always met. Compliance requires
independent verification. More recently, an environmental standard has been defined,
originally BS 7750 (and related in many ways to the quality standard) and now published
as ISO 14001. This standard sets out the requirements of a system which ensures that a
company is aware of, and meets, its environmental responsibilities. It differs from the
quality standard in that it requires demonstration of continual improvement of
environmental performance (e.g., reduced levels of waste disposal and emissions). It also
requires complete awareness of, and compliance with, all relevant environmental
legislation.

Whilst this standard is not as well known as the quality standard, and not yet required by
customers as an essential prerequisite to do business, it is likely that recognition of its
relevance will increase and it will take its place alongside the quality standard as a
business essential. Some foam companies have already achieved the qualification.

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Polymer FoamsTrends in Use and Technology

12.7 Positive Environmental Contributions

Whilst industrial activities which contribute adversely to the environment generate the
most publicityglobal warming, noxious emissions, ozone depletionthere is scope for
foam manufacturers to ensure that positive contributions are better known, and some
manufacturers already address this in their product literature. The most obvious is use of
foam for thermal insulation which conserves energy otherwise needed for heating and
consequently reduces carbon dioxide emissions from energy production. Calculations
carried out for rigid PU insulating foam have demonstrated that the savings on heating
energy far outweigh the environmental costs involved in production (see Section 5).

Another environmental benefit of foams is use in protective transport packaging to ensure


fragile products arrive intact and undamaged at their destination. Damaged products have
to be repaired or replaced, involving extra energy in both production and transport. Foams
(polystyrene, polyurethane, polyolefin) have a proven record of effectiveness in this
application and, because they are made to a reproducibly defined specification, foam
packaging can be designed to provide the required impact protection with the minimum
amount of foam.

It can be expected that foam manufacturers will increasingly emphasise these positive
attributes of their products.

References

1. I. Dobson, Pigment and Resin Technology, 1999, 28, 2, 89.

2. S. Hulse, Plastic Products Recycling, Rapra Technology Limited, Shrewsbury, UK,


2000.

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146
Rapra Technology Limited
Rapra Technology Limited is the leading international
organisation with over 80 years of experience providing
technology, information and consultancy on all aspects of
plastics and rubber.

The company has extensive processing, analytical and testing


laboratory facilities and expertise, and produces a range of
engineering and data management software products, and
computerised knowledge-based systems.

Rapra also publishes books, technical journals, reports,


technological and business surveys, conference proceedings and
trade directories. These publishing activities are supported by an
Information Centre which maintains and develops the worlds
most comprehensive database of commercial and technical
information on plastics and rubber.

ISBN: 1-85957-240-5

Shawbury, Shrewsbury, Shropshire SY4 4NR, United Kingdom


Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118
http://www.rapra.net

Cover photographs reproduced with permission from Cannon Group, Italy (top), and Zotefoams plc, UK (middle and bottom)