Assessing Food Safety of Polymer Packaging PDF

ISBN: 1-85957-527-7
Jean-Maurice Vernaud and Iosif-Daniel Rosca

Assessing Food Safety of Polymer Packaging
Rapra Technology Assessing
Rapra Technology is a leading international
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Food Safety Cover 2.indd 1 17/5/06 1:58:22 pm

Assessing Food Safety of
Polymer Packaging
Jean-Maurice Vergnaud
Iosif-Daniel Rosca
Smithers Rapra Limited

A wholly owned subsidiary of The Smithers Group
Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom

Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118
http://www.rapra.net
First Published in 2006 by
Smithers Rapra Limited

Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
2006, Smithers Rapra Limited
All rights reserved. Except as permitted under current legislation no part

of this publication may be photocopied, reproduced or distributed in any
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reproduced within the text and the authors and publishers apologise if
any have been overlooked.
ISBN-13: 098-1-84735-026-8
Typeset by Smithers Rapra Limited

Cover printed by Livesey Limited, Shrewsbury, UK
Printed and bound by Smithers Rapra Limited
Contents
Preface ......................................................................................................................... 1
1. A Theoretical Approach to Experimental Data...................................................... 7
1.1 Mass Transfer by Diffusion or Convection: Basic Equations ........................ 7

1.1.1 Diffusion ......................................................................................... 7
1.1.2 Convection...................................................................................... 7
1.1.3 Analogy With Heat Transfer ........................................................... 7
1.1.4 Basic Equations ............................................................................... 8
1.1.5 Solid-Liquid Interface...................................................................... 8
1.1.6 Properties of Convection ................................................................. 9
1.1.7 Applications of the boundary conditions......................................... 9
1.1.8 Note on the Innite Value of the Coefcient of Convection .......... 10
1.1.9 Partition Factor ............................................................................. 10
1.2 Differential Equation of Diffusion ............................................................. 10
1.3 Methods of Solution with the Separation of Variables ............................... 12
1.4 Solution of the Equation of Diffusion: Sheet of Thickness 2L

Immersed in a Liquid of Innite Volume and Innite Value of
the Coefcient of Convection .................................................................... 13
1.4.1 Applications of the Equations of Transfer of Substance
Into or Out of a Sheet of Thickness 2L with: -L < x < +L .............. 17
1.5 Other Solutions for the Problem of Diffusion: Sheet of Thickness
2L Immersed in a Liquid of Innite Volume and Innite Value of

Immersed in a Liquid of Finite Volume and Innite Value of the
Coefcient of Convection .......................................................................... 20
i
Assessing Food Safety of Polymer Packages
1.6.1 The Diffusing Substance Enters the Sheet ...................................... 21

1.6.2 The Diffusing Substance Leaves the Sheet ..................................... 23
1.6.3 Note on Equation (1.41) with an Innite Volume of Liquid .......... 25
Immersed in a Liquid of Innite Volume and a Finite Value of
1.7.1 Notes on the Case Described in Section 1.7 .................................. 28
1.8 Ratio Volume/Area of the Food Package.................................................... 28
1.9 Determination of the Parameters of Diffusion ........................................... 29

1.9.1 Simple Ways of Evaluating the Parameters of Diffusion
(Diffusivity)................................................................................... 29
1.9.2 Using a Numerical Model ............................................................. 30
1.9.3 Using the Appropriate Numerical Model ...................................... 31
1.10 Diffusion through Isotropic Rectangular Parallelepipeds ........................... 38
1.10.1 Diffusion with an Innite Value of the Coefcient of Convection .... 39
1.10.2 Diffusion with a Finite Value of the Coefcient of Convection ........ 40
1.10.3 Approximate Value of the Diffusivity for Small Times and
Innite h ........................................................................................... 41
1.10.4 Approximate Value of the Diffusivity for Long Times and
Innite h ........................................................................................... 41
1.11 Case of a Membrane of Thickness L .......................................................... 41
1.11.1 Transport of the Substance through the Membrane for Innite h .... 42
1.11.2 Results for the Membrane with Innite Value of h on Both Sides .... 43
1.11.3 Results for a Membrane with a Finite Value of h on the Right Side .. 45
1.11.4 Results for a Membrane with Finite Value of h on Both its Sides ..... 47
1.12 Evaluation of the Parameters of Diffusion from the Proles
of Concentration ....................................................................................... 49
1.12.1 Experimental................................................................................. 50
1.12.2 Theoretical .................................................................................... 50
1.12.3 Results Obtained with the Gradients of Concentration ................. 51
1.13 Conclusions on the Diffusion Process ........................................................ 54
ii
Contents
2. Mass Transfer Through Multi-layer Packages Alone ........................................... 57
2.1 Recycling Waste Polymers and Need of a Functional Barrier ..................... 57

2.1.1 Role of the Functional Barrier ....................................................... 57
2.1.2 Mass Transfer Occurring During the Co-extrusion Stage .............. 58
2.1.3 General Problem of Diffusion Through the Layers of the
Packaging Alone ........................................................................... 58
2.2 Bi-layer Package: Recycled Polymer-Functional Barrier ............................. 58
2.2.1 Mathematical Treatment of the Process ....................................... 59
2.2.2 Results Obtained with Two Layers of Equal Thicknesses .............. 61
2.3 Bi-layer Package with Various Relative Thicknesses................................... 67
2.3.1 Mathematical Treatment of the Process ....................................... 67
2.3.2 Results with Two Layers of Different Relative Thicknesses ........... 68
2.4 Three-Layer Packages ................................................................................ 73
2.4.1 Mathematical Treatment of the Process of Matter Transfer........... 73
2.4.2 Results with Three Layers of Equal and Different Thicknesses ...... 76
2.5 Bi-layer Package with Complex Situations: Different Diffusivities and
Factor Coefcient Different from One ....................................................... 85
2.5.1 Mathematical Treatment of the Process of Matter Transfer .......... 85
2.5.2 Results with Bi-layer Films in Complex Situations ........................ 87
2.6 Conclusions on Multi-layer Packages ........................................................ 94
3. Process of Co-Extrusion of Multi-Layer Films ..................................................... 99
3.1 Scheme of the Process of Co-Extrusion ...................................................... 99
3.2 Principles of Unidirectional Heat Transfer ............................................... 101

3.2.1 Basic Equations of Heat Transfer by Heat Conduction ............... 101
3.2.2 Heat Convection ......................................................................... 103
3.3 Coupled Heat and Mass Transfer in Bi-Layer Films ................................. 105
3.3.1 Theoretical Treatment of the Transfer of Heat ........................... 105
3.3.2 Theoretical Treatment of the Mass Transfer Coupled
with the Heat Transfer ................................................................ 107
3.4 Evaluation of Heat and Mass Transfers in Bi-Layer Films ....................... 108
iii
3.4.1 Consideration of the Process of Heat Transfer ............................ 108

3.4.2 Effect of the Value Given to the Coefcient of Heat Convection ... 109
3.4.3 Effect of the Thickness of the Film on the Transport of Heat
and Matter .................................................................................. 114
3.4.4 Simultaneous Effect of the Thickness of the Film and the
Coefcient of Convective Heat Transfer ...................................... 118
3.5 Evaluation of Heat and Mass Transfers in Tri-Layer Film........................ 120
3.5.1 Theoretical Study of Heat and Mass Transfers ............................ 122
3.5.2 Heat and Mass Transfers in a Tri-Layer Film .............................. 122
3.6 Heat and Mass Transfers in Tri-Layer Bottles with a Mould at
Constant Temperature on the External Surface ........................................ 123
3.6.1 Theoretical Treatment of the Process .......................................... 123
3.6.2 Heat and Mass Transfers with Heat Conduction through
the Mould and Polyethylene Terephthalate (PET) and
Heat Convection on the External Surfaces .................................. 125
3.6.3 Results Obtained with the 0.03 cm Thick PET Bottle ................. 126
3.6.4 Results Obtained with a 0.06 cm Thick PET Bottle .................... 130
3.7 Heat and Mass Transfers in Tri-Layer Bottles with a Mould Initially
at the Temperature of the Surrounding Atmosphere ................................ 133
3.7.1 Theoretical Treatment of the Process .......................................... 133
3.7.2 Selection of the Values for the Parameters Used for Calculation .. 135
3.7.3 Results Obtained with the Surrounding Atmosphere at
20 C or 40 C ............................................................................ 136
3.8 Coupled Mass and Heat Transfers - Conclusions ..................................... 142
4. Mass Transfers Between Food and Packages ..................................................... 145
4.1 General Introduction to the Various Problems ......................................... 145
4.2 Theoretical Treatment ............................................................................. 147

4.2.1 Revision of the Main Parameters and Principles of Diffusion ...... 147
4.2.2 Differential Equation of Diffusion............................................... 150
4.2.3 The Case of a Sheet of Thickness 2L Immersed in a Liquid of
Finite Volume and Innite Value of the Coefcient of Convection . 150
4.2.4 Case of a Sheet of Thickness 2L Immersed in a Liquid of
iv
Contents
Infinite (or Finite) Volume and a Finite Value of the

Coefficient of Convection............................................................ 153
4.2.5 General Conclusions on the Mathematical Treatment ................. 156
4.3 Mass Transfer in Liquid Food from a Single Layer Package ..................... 157
4.3.1 Theoretical for a Single Layer Package in Contact with
Liquid Food ................................................................................ 157
4.3.2 Effect of the Coefficient of Convective Transfer .......................... 159
4.3.3 Effect of the Ratio of the Volumes of Liquid and Package ..........163
4.4 Bi-layer Packages Made of a Recycled and a Virgin Polymer Layer,

by Neglecting the Co-extrusion Potential Effect ....................................... 165
4.4.1 Theoretical Treatment with a Bi-layer Package ........................... 165
4.4.2 Results with the Bi-layer Package ................................................ 166
4.5 Mass Transfer from Tri-layer Packages (Recycled Polymer Inserted

Between Two Virgin Layers) in Liquid Food ............................................ 171
4.5.1 Theory of the Mass Transfer in Food with the Tri-layer Package... 171
4.5.2 Results Obtained with the Tri-layer Package in Contact with
a Liquid Food ............................................................................. 172
4.6 Effect of the Co-extrusion on the Mass Transfer in Food ......................... 174
4.6.1 Mass Transfer in Food with a Co-extruded Bi-layer Package ...... 174
4.6.2 Mass Transfer in Food with Tri-layer Bottles Co-injected
in the Mould whose External Surface is Kept at 8 C .................. 177
4.6.3 Mass Transfer in Food with Tri-layer Bottles Co-injected in
Normal Mould ........................................................................... 181
4.7 Conclusions on the Functional Barrier ..................................................... 183

4.7.1 Interest of a Functional Barrier ................................................... 183
4.7.2 Effect of the Co-extrusion and Co-moulding on the Mass Transfer . 185
4.8 Conclusions on the Diffusion-Convection Process ................................... 185
4.9 Problems Encountered with a Solid Food ................................................ 186

4.9.1 Theoretical Part of the Problem .................................................. 187
4.9.2 Results for the Transfer in the Solid Food ................................... 188
v
5. Active Packages for Food Protection ................................................................. 201
5.1 Process of Transfer with Active Packages ................................................. 201

5.1.1 Passive Packages ......................................................................... 201
5.1.2 Modified Atmosphere Packages for Perception of Freshness ....... 202
5.1.3 Active Packages with Antimicrobial Properties ........................... 203
5.1.4 Applications of Antimicrobial Package in Foods ......................... 205
5.1.5 Testing the Effectiveness of Antimicrobial Packages and
Regulatory Issues ........................................................................ 205
5.1.6 Detection Systems ....................................................................... 206
5.2 Active Packages Theoretical Considerations ......................................... 206
5.2.1 Process of Release and Consumption, and Assumptions ............. 206
5.2.2 Mathematical and Numerical Treatment ..................................... 207
5.3 Results Obtained by Calculation ............................................................. 208
5.3.1 Results Obtained for High Values of R ....................................... 209
5.3.2 Results Obtained with Low Values of R ...................................... 213
5.3.3 Establishment of the Dimensionless Numbers ............................. 217
5.4 Conclusions about the Active Agents ....................................................... 218
6. A Few Common Misconceptions Worth Avoiding ............................................. 221
6.1 Using Equations Based on Infinite Convective Transfer ........................... 222

6.1.1 The Problem Presented................................................................ 222
6.1.2 Theoretical Survey ...................................................................... 223
6.1.3 Conclusions Drawn from the Problem ........................................ 224
6.2 Infinite Thickness of the Film and Infinite Convective Transfer ................ 229
6.2.1 Description of the Experimental Part .......................................... 229
6.2.2 Theoretical Consideration by the Authors ................................... 230
6.2.3 Conclusions About the Ideas Presented ....................................... 232
6.3 Combination of Semi-infinite Media and Finite Volume of Liquid ........... 233
6.3.1 Description of the Experimental Part .......................................... 233
6.3.2 Theoretical Part .......................................................................... 234
6.3.2 Tentative Conclusions on the Ideas that have Emerged ............... 234
vi
Contents
6.4 Innite Rate of Convection in a Finite Volume of Liquid ......................... 235

6.4.1 Principle of the Process ............................................................... 235
6.4.2 Theoretical Development ............................................................ 235
6.4.3 Tentative Conclusions on the Ideas that Emerged........................ 236
6.5 Double Transfer Process and the Membrane System ................................ 238
6.5.1 Principle of the Double Transfer in Plasticised PVC Immersed
in a Liquid .................................................................................. 238
6.5.2 Process of Mass Transfer through a Membrane .......................... 239
6.5.3 Observations on the Assumption of the Membrane .................... 242
6.6 Heat Transfer: Conduction or Convection ............................................... 245
6.6.1 The Problem Considered in the Literature ................................... 245
6.6.2 Recall of the Theory of Mass and Heat Transfers ....................... 246
6.6.3 Conclusions on Convection-Conduction Heat Transfers ............. 248
6.7 Proles of Concentration in Two Semi-innite Media .............................. 250
6.7.1 Description and Study of the Moisans Method .......................... 250
6.7.2 Study of the Technique ................................................................ 250
6.7.3 Conclusions on Moisans Method ............................................... 251
6.8 Double Transfer of Substances in a Sheet ................................................. 252
6.8.1 Study Carried Out in a First Paper .............................................. 252
6.8.2 Analysis of a Somewhat Similar Study ........................................ 255
6.9 Methodology for Measuring the Reference Diffusivity ............................ 256
6.9.1 Presentation of the Ideas and the Methods .................................. 256
6.9.2 Analysis of the study ................................................................... 257
6.9.3 Conclusions ................................................................................ 258
6.10 Conclusions on the Remarks Made in Chapter 6 ..................................... 259
7. Conclusions ....................................................................................................... 267
Appendix: The First Six Roots n of tan = R ....................................................... 271
vii
viii
Preface
Even if the subject of mass transport controlled by diffusion has been considered in various
situations by these two authors over a long period of time, it has been a fascinating but
also a ticklish task to write a book with the title: Assessing Food Safety of Polymer
Packaging. The main problems which have arisen come from various sources:
i) Describing the problems of diffusion is highly complex, because various equations

are used, which are obtained by a mathematical treatment based on very precise
requirements, such as the initial and the boundary conditions, as well as the shape of
the material through which the substance diffuses, and still more, without forgetting
the fact that this substance enters into the surrounding atmosphere through the process
of convection.
ii) The majority of the people using these equations are in general, competent researchers,
who are able to manage pretty well, sophisticated apparatus by applying the
appropriate techniques. But as a result of this previous competence, and the time
necessary to acquire it, little time remains to get the pertinent knowledge on the
theoretical treatment of diffusion.
iii) It should be noted that if a few excellent books devoted to the subject of diffusion
have been launched on the market since 1975, these books are addressed to either
theoreticians or at least well-informed researchers about these difcult problems of
mass transfer.
iv) The problems concerned with diffusion are widely spread over various subjects:
the release of a permanent gas or the evaporation of a vapour from a solid with
the process of drying;
the release of a drug from diffusion-controlled release dosage forms in

pharmacy;
the diffusion of a liquid into and through various solids such as wood (an
anisotropic medium) or rubber (provoking eventually a change in dimension);
and last but not least;
1
the release of some additives from the polymer package into the food, with the
possibility of inserting some recycled polymer packages through multi-layer systems
(that last problem of recycling including a possible inter-diffusion of potential additives
through the layers during the stage of co-extrusion, which is mainly controlled by the
heat transfer process; this heat transfer process being itself controlled by conduction,
for which the laws are similar to those of diffusion through the solid, as well as by
convection on the surfaces).
Amongst the books devoted to the process of diffusion the most well-known is The
Mathematics of Diffusion [1], largely cited everywhere and especially in this present
book. This book covers almost all the cases which could exist, theoretically speaking at
least. So, they appear in succession and following this order: the innite or semi-innite
medium, the sheet of nite thickness, and other shapes such as the cylinder and sphere.
It should be noted that the trivial cases of a cube or a parallelepiped are not discussed, as
they were considered more obvious by the author than perhaps by all the readers. In the
same way, the bi- or tri-layer packages made of virgin and recycled polymer layers have
not been considered, whether the initial concentration of diffusing substance in the recycled
layer is uniform or not. While developing the diffusion through a sheet, the idea of taking
2L for its thickness, with L<x<+L is of interest, leading to general applications, but it is
assumed that the reader would understand that in this case a symmetry exists with the
mid-plane at x = 0 playing the role of a plane of symmetry. For the sheet - which is the
important topic in the present book - the rst equations which appear in Cranks book
are determined in the hypothetical case where the concentration of the diffusing substance
on its surfaces attains instantaneously its value at equilibrium with the concentration
maintained at constant in the innite surrounding medium. These equations expressed
either in terms of trigonometric and exponential series or in terms of error function, are
easy to determine, mathematically speaking, by the students who have to nd them at
the beginning of their studies on the partial derivative equations. Thus these exercises
are excellent examples of mathematical treatments, but it is necessary to state that the
coefcient of convection at the package surface as well as the volume of liquid are both
innite. But the readers generally do not appreciate exactly the signicant extent of this
boundary condition which is not very precisely displayed, e.g., the sheet is immersed in a
medium of innite medium, and more, in addition, the coefcient of convective transfer
at the solid-liquid interface is innite. It is obvious that these two conditions are totally
unrealistic, especially the second with the innite rate of convection which necessitates an
innite rate of stirring. Following this rst treatment with the sheet, the solutions of two
important cases are given in succession: 1) when the volume of the surrounding atmosphere
is nite, the ratio of the volume of this atmosphere by that of the sheet, per unit area,
plays the main role, but one must remember to state that the coefcient of convection at
the solid surface is innite; 2) when the coefcient of convection on the sheet surface is
nite, with an innite volume of the surrounding atmosphere, by considering in this nal
case that a convective effect should play a role at these surfaces.
2
Preface
The other books, not so widely known, are written with an engineering bias [2, 3]. Thus
the role of this coefcient of convective transfer is denitively examined, by placing
more emphasis upon the importance of the convective factor in considering the process
of evaporation [3]. When a permanent gas evaporates from a solid following the stage of
diffusion through the thickness of the solid, it can be seen that the rate of evaporation of
this gas is innite and that the concentration on the surface of the solid falls to zero as
soon as the process starts. However, the boundary conditions are quite different when the
diffusing substance gives off a vapour at the surface, as there is a nite rate of evaporation
for any vapour, and in this general case, the process of matter transfer is controlled by
both the stages of diffusion through the thickness of the sheet and of evaporation at the
solid-air interface. Furthermore, when the surrounding atmosphere is a liquid, the same
experimental process appears, as the diffusing substance has to overcome a resistance
in penetrating into this liquid; and the liquid not being so permeable as the air is, it is
understandable that it will take some time for this matter to disseminate in it, this fact
leading to the nite rate of convective transfer from the solid surface into the liquid. The
stage of convection has been widely studied in the process of heat transfer, in a whole
theoretical way [4] as well as in an applied and engineering way [5].
More generally, the two processes of heat transfer (except for the radiant-heat transmission)
and mass transfer controlled by diffusion are somewhat similar. Two stages can be
distinguished in these two processes: heat conduction (or mass diffusion) through the
solid, followed by heat convection (or mass convection) at the surface in contact with
the surrounding atmosphere. It is not surprising that the book describing the theory of
heat transfer [4] was used as a kind of model for the following book on diffusion [1]. In
the case of heat transfer, the interesting book for engineers [5] is worth citing because
of its practical applications. This last book describes, very precisely, the processes of
heat convection from a heated surface into the surroundings, with the free (or natural)
convection in a motionless uid or with the forced convection when the surrounding
atmosphere is stirred, without forgetting that in both cases the process may be either in
laminar or in turbulent conditions.
Thus from this recall of heat transfer, with the similarity between the two processes of
heat transfer and mass transfer controlled by diffusion, the necessity of admitting without
ambiguity that the course for the mass transfer should emerge as follows: diffusion
through the thickness of the sheet associated with the convection into the liquid. Finally,
the parameters of main importance for a polymer package in contact with a liquid food
are the diffusivity and the coefcient of convection. The diffusivity is concentration-
dependent, as for example the case of highly plasticised polyvinylchloride where the
plasticiser concentration may reach up to 50% of the polymer, but in the present case
of the low concentration of the additives distributed in the polymer of the packaging -
which are necessary to provide its qualities - the diffusivity can be considered as constant.
3
On the other hand, the value of the coefcient of convection largely depends on the rate
of stirring of the liquid. Both these parameters, e.g., the diffusivity and coefcient of
convection, increase with temperature. The solubility of the diffusing substance in the
liquid may appear of interest, in spite of the fact that the concentration of the additives
in the polymer package is very low. When the solubility of this substance in the food is
much lower than its initial concentration in the polymer, a partition factor intervenes,
as its concentration in the food is limited by the solubility.
Dimensionless numbers are introduced as much as possible, in order to build master

curves which can be used by any worker, whatever the values of the parameters.
This book is divided into six chapters, which are independent, in order to make
reading easier.
Chapter 1 is devoted to the theoretical part concerned with the process of diffusion
through a sheet. The mathematical treatment is made, as it is usually shown in many
books, in the case of an innite coefcient of convection on its surface with an innite
volume of liquid. The other two cases are following in succession: when the volume
of liquid is nite and the coefcient of convection on the surfaces is innite; when the
volume of liquid is innite and the coefcient of convection is nite on the sheet surface.
And nally, the more general case is considered, when the volume of liquid and the
coefcient of convection are both nite. Special emphasis is placed upon this general
and common case. The ratio of the volume of the food by the surface of the package in
contact with the food, which is connected with the ratio of the volumes of food and
package, is examined. The methods of evaluating the values of the two parameters of
diffusion, namely, the diffusivity and the coefcient of convection, are considered in
succession to yield to this objective, by considering that the best way for the researcher
who is not aware of the mathematical treatment is to use a numerical model capable
of providing the value of these two parameters. The problem of the membrane has also
been considered, not only when the concentrations are kept constant on both sides of the
sheet as usual, needing an innite coefcient of convective transfer on the two surfaces,
but also in the more general and realistic case when the concentration of the diffusing
substance is constant in the uid on each surface with a nite coefcient of convective
transfer. Finally, the method of calculation based on the proles of concentration
developed through the solid is described in depth. As the technique of spectrometry
coupled with a microscope is very efcient this method provides the user with all the
parameters of diffusion, e.g., the diffusivity, the coefcient of convection at the surface
as well as the amount at equilibrium, in the shortest time possible.
Chapter 2 is concerned with the transfer of the contaminant taking place in packages before
being in contact with a food. The diffusion of this contaminant is thus dened through the
4
Preface
layers of the package (bi- or tri-layer) made of recycled polymer layer in perfect contact
with a virgin polymer layer playing the role of a functional barrier. In all these cases, the
mathematical treatment is feasible when the diffusivity is the same in the layers, leading
to either trigonometrical series for the proles or exponential series for the kinetics.
Chapter 3 is devoted to the problems set up by the process of co-extrusion or co-moulding

of the lms or of the packages. Thus the matter of heat transfer is examined as clearly
as possible, recalling the analogy with the diffusion, by introducing the notion of heat
conduction through a solid (diffusion) and that of heat convection at the solid-uid
interface (matter convection). Applications are made in resolving some problems of heat
transfer which play a role either in co-extrusion of lms or in co-moulding of bottles, and
in evaluating the diffusion of matter associated with the heat transfer.
Chapter 4 is the main chapter in which some applications of the theoretical considerations
established in the previous Chapters 1 to 3 are developed. The process of release of additives
or contaminants in food is extensively studied by considering the diffusion-convection
couple, when the food is either in liquid or in solid state.
Chapter 5 is of interest for people thinking of the future, when the active packages will
be considered and wide spread in the market place.
Chapter 6 is devoted to the most striking misconceptions of the processes or misuses of

equations. It appears that along the way of determining the diffusion parameters from the
experimental data, the misconception about the process is described rst, followed by the
misuse of equations or numerical models. An explanation should be given on this subject.
The authors of the book had two choices: i) try to collect all the papers concerned more
or less with the subject of food packaging, or ii) to pick up some of these papers either
drawn from important laboratories or typical in the sense that the misuse of the equation
is worth pointing out. We are sure that building an extensive bibliography covering all the
facts with their authors is not possible if we consider the number of papers appearing in
the literature: one hundred a year in research managed by Rapra over the last six years,
but perhaps twice or even three times this amount if another attempt is made in the various
journals or conferences. We have not tried to achieve a complete bibliography in this present
book, thinking that a work of this type would be of little use. We have preferred to make
a in depth analysis of the concepts that were proposed and developed in a few relevant
papers coming from the most important laboratories dealing with the food package. In
fact, the history is as follows: with his book, Crank came rst at a time when the authors
were silent on the subject [1]. Afterwards, from the late 1970s, more and more researchers
found that they had a lot of experimental results, and when trying to evaluate the diffusion
parameters from these data, they preferred to select simpler equations instead of the
correct equation for the problem. The task of a theoretician coming at that time is huge,
5
as he has to face many mistakes. The theoretician should be neither a mathematician, as

the mathematical treatment was already achieved, nor a researcher, but located between
these two domains, the specialist in chemical engineering. The chemical engineer starts
working with the process in determining its nature, following with the assumptions to
build, and nally concluding his work with the theoretical treatment (either based on the
mathematical treatment leading to equations, or on a numerical treatment with numerical
analysis and computerisation).
References
1. J. Crank, The Mathematics of Diffusion, 2nd Edition, Clarendon Press, Oxford,

UK, 1975.
2. J-M. Vergnaud, Liquid Transport Processes in Polymeric Materials: Modelling

and Industrial Applications, Prentice Hall, Englewood Cliffs, NJ, USA, 1991.
3. J-M. Vergnaud, Drying of Polymeric and Solid Materials: Modelling and

Industrial Applications, Springer-Verlag, London, UK, 1992.
4. H.S. Carslaw and J.C. Jaeger, Conduction of Heat in Solids, Clarendon Press,
Oxford, UK, 1959.
5. W. McAdams, Heat Transmission, 3rd Edition, McGraw-Hill, London, UK 1954.
Jean-Maurice Vergnaud
Iosif-Daniel Rosca
April 2006
6
1
A Theoretical Approach to Experimental Data
1.1 Mass Transfer by Diffusion or Convection: Basic Equations
The matter transfers taking place between polymer packaging and a liquid are
controlled either by convection at the liquid-solid interface or by diffusion through
the polymer.
1.1.1 Diffusion
Diffusion is the process by which matter is transported from one part of a polymer
to another, as a result of random molecular motions. Diffusion is observed essentially
in solid materials such as polymers, under the inuence of a concentration gradient
of diffusing substance, without appreciable displacement of the macromolecules
of polymer.
1.1.2 Convection
This phenomenon takes place in liquids - it involves the transfer of matter by mixing
one part of uid with another. The motion of the uid may be entirely the result of
differences of density or of concentration as in natural convection, or the motion may
be produced by mechanical means, as in forced convection.
1.1.3 Analogy With Heat Transfer
Heat conduction occurs when heat passes through the solid under the inuence of a
gradient of temperature, and there is an analogy between the processes of heat conduction
and the matter transfer controlled by diffusion. This was recognised by Fick in 1855,
who put diffusion on a quantitative basis by adopting the mathematical equation of
heat conduction established some years earlier by Fourier in 1822.
7
1.1.4 Basic Equations
The mathematical theory of diffusion in isotropic materials is thus based on the hypothesis
that the rate of transfer of diffusing substance through unit area of a section of the material
is proportional to the concentration gradient measured normal to the section, as shown
in Equation (1.1)
C
F = D (1.1)
x
where:
F is the rate of the diffusing substance transferred per unit area of section,
C is the concentration of the diffusing substance,
x is the space coordinate normal to the section along which the diffusion takes place, and
D is the diffusion coefcient, also called diffusivity.
The negative sign arises because diffusion occurs in the direction opposite to that of
increasing concentration.
By expressing F, the amount of diffusing substance, and C, the concentration, in terms of

the same unit of quantity, e.g. grams, D is independent of the mass. In the CGS system,
very often used in diffusion, the dimensional equation of D becomes:
(length)2/(time) or cm2/s (1.2)
1.1.5 Solid-Liquid Interface
At the packaging-liquid interface, the rate at which the substance is transferred into the
liquid is constantly equal to the rate at which this substance is brought to the surface by
internal diffusion through the polymer packaging, leading to the relationship:
C
(
D = h CL , t Ceq
x
) (1.3)
where:
h is the coefcient of transfer by convection in the liquid next to the surface,
CL,t is the concentration of the diffusing substance on the surface of the solid, and
Ceq is the concentration of the diffusing substance on this surface required to maintain
equilibrium with the concentration of this substance in the liquid, at time t.
8
1.1.6 Properties of Convection
The coefcient of convection has the dimensional cm/s.
As the transfer by convection into the liquid is much faster than the transfer by diffusion
through the polymeric solid, the concentration in the liquid of the diffusing substance is
considered to be constantly uniform.
As previously noted, two kinds of convection exist:
Natural convection, when the liquid is motionless, and

Forced convection when the liquid is strongly stirred.
The value of the coefcient of convection, h, largely depends on the type of convection:
being rather low in motionless liquid, it increases notably with the rate of stirring of the
liquid up to a very large value when the liquid is strongly stirred.
1.1.7 Applications of the boundary conditions
Two important applications of the boundary conditions expressed by Equation (1.3) are
obvious and relevant:
1 - When the coefcient of convection, h, is innite, the following facts appear:
The concentration of the diffusing substance on the surface of the solid instantaneously
reaches its corresponding value at equilibrium with that in the liquid as soon as the
process starts; this fact is expressed by the relationship:
t =0 CL ,0 = Ceq h (1.4)
The value of the ux is very high, if not innite, explaining the vertical tangent at the
origin of time of the kinetics of transfer of diffusing substance:
t =0 FL ,0 (1.5)
2 - Process of absorption or of release. Equation (1.3) is of value either for the release
of additives out of the polymer in the liquid or for the absorption of the liquid into the
polymer. Only the relative values of the two concentrations intervene on the process, by
the following relationships:
CL , t > Ceq release of additives in the liquid (1.6)
CL , t < Ceq absorption of liquid by the polymer (1.6)
9
1.1.8 Note on the Infinite Value of the Coefficient of Convection
It should be said that it is too often found in scientic papers, without any relevant
proofs, an innite value of the coefcient of convection, h. This assumption would be
responsible for the following abnormal process taking place over a short time, e.g., when
the polymer sheet is immersed into a liquid of nite volume, at time 0, the concentration
of the diffusing substance on the solid surface, being equal to that in the liquid when the
partition factor is 1, decreases abruptly down to 0, and afterwards increases slightly with
the concentration of the substance in the liquid.
1.1.9 Partition Factor
For various reasons, chemical essentially, due to the fact that the solubility of the additives
is much larger in one of the two polymer-liquid media, the concentration of an additive
is not the same in the polymer and the liquid, at equilibrium. This fact can be written in
the form of the ratio of concentrations:
CL ,
K= (1.7)
Cliquid,
where:
K is the partition factor,
CL, is the concentration of the diffusing substance on the polymer surface at equilibrium,
attained after innite time,
Cliquid, is the concentration of the diffusing substance in the liquid at equilibrium.
Let us note that generally, and fortunately for the consumers, the concentration of the
additives in the polymer used as a packaging is very low, so that their concentrations in
the liquid do not exceed their solubility in the food liquid. The same fact occurs when the
packaging consists of two layers: one made of a recycled polymer and the other of a virgin
polymer. It is obvious that the partition factor K is equal to 1 when these two layers are
in perfect contact in the packaging and are made of the same polymer.
1.2 Differential Equation of Diffusion
The differential equation of diffusion in a thin isotropic sheet is built as follows:
Let us consider (Figure 1.1) an element of volume in the form of a thin sheet of thickness,
x, whose sides are perpendicular to the axis of diffusion. The rate of increase (or decrease)
10
Figure 1.1 Scheme of the transport of the diffusing substance through a sheet of
thickness, dx, while the concentration, Cx,t, is a function of the position x and time t,
and Fx is the ux of substance at position x and time t.
of diffusing substance in the element of volume S x is calculated by considering the rates

of transfer of substance entering through the area S of the plane x and leaving the same
area of the plane x + x, during the time t, the increments of time t and of space x
being as small as possible:
F
S ( Fx Fx +x ) = S x (1.8)
x
The rate at which the amount of diffusing substance increases is also given by:
C
S dx (1.9)
t
And from the equality of these two expressions of the rate, by using the value of the ux
F given in Equation (1.1), we have:
C C
= D (1.10)
t x x
When the diffusivity, D, is constant, and independent of the concentration, this equation
reduces to:
C 2C
=D 2 (1.11)
t x
11
Finally, Equation (1.1) expressing the ux of diffusing substance and Equations (1.10)
or (1.11), expressing the variation of the concentrations with time and space, are the
fundamental equations of diffusion through a sheet of an isotropic material. Equations
(1.10) and (1.11) are partial derivative equations, in the sense that the concentration C
depends on the two parameters of time and space.
1.3 Methods of Solution with the Separation of Variables
By making the assumption that the variables of space x and of time t are separable, an
attempt can be made to nd a solution for the partial differential equations of diffusion,
when the diffusivity is constant.
Upon putting in Equation (1.11) of a one-dimensional diffusion through a sheet:
C x , t = C x .C t (1.12)
where Cx and Ct are functions of only space x and time t, respectively, the general equation
of diffusion (1.11) becomes:
C t 2C x
C x = DC t (1.13)
t x 2
This ordinary differential equation can be rewritten after separation of the variables:
1 C t D 2C x
= (1.14)
C t t C x x 2
where the left-hand side depends on time only, and the right-hand side depends on x only.
Both sides therefore must be equal to the same negative constant, which is convenient to
take as: 2D
Thus the two ordinary equations are obtained:
1 dC t
= 2D (1.15)
C t dt
D d2C x
and = 2D (1.16)
C x dx 2
12
The solutions of these two equations are either obvious for (1.15):
(
C t = ( constant ) exp 2Dt ) (1.17)
or known for (1.16):
C x = A.sin x + B. cos x (1.18)
And nally a particular solution of the equation of diffusion for a sheet with constant
diffusivity D is of the form:
C x ,t = C x C t = A sin x + B cos x exp( 2Dt) (1.19)
where the constants A and B are to be found for each particular problem.
This equation (1.19) being a linear equation, the general solution is obtained by summation
in terms of a series these particular equations, as follows:
(
C x ,t = A n sin n x + B n cos n x.exp 2n Dt ) (1.20)
n=0
where the constants An, Bn and n are unknowns which should be determined for each
particular problem, by considering the boundary and initial conditions of this problem.

Immersed in a Liquid of Infinite Volume and Infinite Value of the
Coefficient of Convection
The sheet in the region -L < x < +L is initially at the uniform initial concentration Cin, and
the surfaces are maintained at a constant concentration C.
This fact corresponds with the problem of a sheet of thickness 2L immersed in an innite
volume of liquid strongly stirred.
The initial and boundary conditions shown in Figure 1.2 are:
t=0 L < x < +L C = Cin sheet (1.21)

t>0 x = L C = C surfaces (1.22)
13
Figure 1.2 Scheme of the sheet of thickness 2L, with -L < x < +L. Cin is the uniform
concentration of diffusing substance initially in the sheet, and C is the concentration
of this substance in the exterior of the sheet as soon as the process starts, with h
As the mid-plane x = 0 of the sheet is a plane of symmetry, there is also the condition at
any time:
C
t 0 at x = 0 mid-plane (1.23)
x
The solution of this problem is given by the general Equation (1.20), obtained by using the
method of separation of variables, where the constants are to be determined. It becomes:

(
C x ,t C = A n sin n x + B n cos n x.exp 2n Dt ) (1.24)
n=0
The condition at the mid-plane, is written as follows:
C x , t
=0 (1.23?)
x
and necessitates that the terms in cosines in the derived Equation (1.23) are equal to 0,
leading to:
An = 0 (1.25)
The boundary condition (1.22), for example x = L and CL,t C = 0, for t > 0, is fullled
when:
cos nL = 0 = cos (2n + 1)

and n =
(2n + 1) (1.26)
2 2L
14
The initial condition (1.21) becomes:

(2n + 1)x
Cin C = B n cos for -L < x < L (1.27)
n =0 2L
The coefcient Bn is obtained as follows, by multiplying both sides of Equation (1.27) by
cos
(2n + 1) x x , and integrating between -L and +L. Then it becomes:
2L
(2n + 1) xx =
(C C )
+L
in L
cos
2L
+L (2n + 1)x +L (2n + 1)x (2p + 1)x

Bn cos2 x + $ + B p cos cos x $ (1.28)
L L
2L 2L 2L
1 1
As cos n cos p = cos ( n + p) + cos ( n p) and cos2 n = 1 + cos 2n
2 2
and applying it to Equation (1.28), all the terms in Bp where p is different from n are equal
to 0, while the rst term in the right side of Equation (1.28) becomes equal to BnL.
Moreover, the integral in the left-hand side of the Equation (1.28) gives:
4L
sin
(2n + 1) which can be written as 4L 1n
(2n + 1) 2 (2n + 1)
The coefcient Bn is thus equal to:
4 1
n
Bn = (1.29)
(2n + 1)
Finally, the prole of concentration of diffusing substance developed within the sheet of
thickness 2L, with -L < x < +L, can be expressed in terms of space x and of time t by the
following series:
2n + 1 2 2
( 2n + 1) x ( )
n
4 1
C x , t C
= cos
exp D t (1.30)
Cin C n =0 2n + 1 2L 4 L2

15
The amount of diffusing substance which is transferred into or out of the sheet at time t,
Mt, is obtained by integration of the ux of substance through the surface with respect
to time:
C

t
Mt = 2 D t for x = L (1.31)
0
x x =L
C
As the gradient of concentration becomes equal to:
x
2n + 1 2 2
C 2 (Cin C ) ( ) D t

x x =L
=
L
exp
4L2
n =0
n
since 1 sin
( 2n + 1) 2n
= 1 = 1
2
nally, the amount of diffusing substance transferred at time t, Mt, is given by:
2n + 1 2 2
4 (Cin C ) D
( ) D t t
0
t
Mt = exp (1.32)
L 4L2
n =0

1 2
As the series =
(2n + 1)
2
n =0 8
and the amount of diffusing substance which has left or entered the sheet after innite
time, M, is given by:
M = 2 (Cin C ) L (1.33)
the kinetics of transport of the substance into or out of the sheet of thickness 2L is expressed
by the following relationship:
2n + 1 2 2
Mt 8
= 1 2
1
exp ( ) D t (1.34)
M n =0 (2n + 1)2 4L2

16
1.4.1 Applications of the Equations of Transfer of Substance Into or Out of a

Sheet of Thickness 2L with: -L < x < +L
1. Both the equations for the proles of concentration (1.30) and for the kinetics of
transfer (1.34) can be applied for a sheet of thickness L, with: 0 < x <L, when it
is in contact on one side only with the liquid (at x = L), while there is no transfer
on the other side (at x = 0). This fact results from the direct application of the
symmetry of the sheet with regards to the plane of symmetry at x = 0, as shown
in Figure 1.3.
2. For a sheet of thickness called L in contact with a liquid on the two sides, both
Equations (1.30) and (1.34) can be applied. Obviously, only the actual thickness L
of the sheet has to be equal to 2L in these equations: L = 2 L
Figure 1.3 Scheme of half the sheet of thickness 2L with -L < x < +L, showing the
symmetry with respect to the mid-plane of abscissa x = 0. Because of this symmetry,
there is no matter transfer through this mid-plane.
3. The value of the concentration on the surface(s) at innite time, or at equilibrium with
the liquid is zero for a liquid of innite volume with an innite value of the coefcient
of convection of the surface(s), when this liquid is free from diffusing substance:
C = 0 innite volume of pure liquid with h
In fact, this concentration of C is the initial and constant concentration of the diffusing
substance in the liquid.
4. Of course, as has already been stated, both these equations (1.30 and 1.34) can be applied
either in the case of the release of the diffusing substance in the liquid or in the opposite
17
case, when this diffusing substance is absorbed by the sheet, depending on the respective
values of the concentrations of the diffusing substance in the sheet and in the liquid:
CL, t > release of additives in the liquid (1.6)
CL, t < absorption of additives by the sheet (1.6)
5. A dimensionless number appears in both these equations (1.30 and 1.34), either for
the proles of concentration developed through the thickness of the sheet or for the
kinetics of transfer of diffusing substance:
Dt Dt
= with a thickness: 2L = L (1.35)
4L2 L '2
6. The problem of release of the additives from a plastic packaging into a liquid of nite
volume is of great interest. In this case, the term Ceq is surely better than C in both
Equations (1.30) and (1.34) for dening the concentration of the diffusing substance
at equilibrium with the liquid. As a matter of fact, whatever the value of the partition
factor K, the concentration of the diffusing substance on the surface of the packaging
CL,t is in equilibrium at any time with its corresponding value in the liquid; and because
of the nite volume of liquid, the concentration in the liquid increases with time up
to its nal value attained at innite time (at least theoretically speaking). As described
more precisely in Chapter 4, a numerical model is necessary to resolve this interesting
and important problem.
7. In fact, it could be said that the only reason to put C in Equation (1.30) is for expressing
the value of the concentration on the surface CL,t as well as of the concentration Cx,t,
both at innite time.
8. Equations (1.30) and (1.34) can be applied at any time, and more precisely for any value
of the amount of diffusing substance transferred between the sheet and the liquid.
Mt
0< <1 Equations (1.30) and (1.34) of value (1.36)
M
9. When the value of the ratio shown in Equation (1.36) is larger than 0.5-0.6, the series in
Equation (1.34) strongly converges and can be reduced to the rst term. Thus it becomes:
Mt 8 2D t Mt
= 1 2 exp 2
0.6 < <1 L < x < +L (1.37)
M 4L M
18
Figure 1.4 Proles of concentration of the diffusion developed through the thickness of
the sheet at various times. Time is expressed in terms of the dimensionless time
Dt
, with h and an innite volume of liquid.
L2
Some proles of concentration of the diffusing substance developed through the thickness
of the sheet of thickness 2L, with -L < x < +L, are shown in Figure 1.4 with an innite
volume of liquid and an innite value of the coefcient of convection h, showing also the
symmetry with regard to the plane x = 0.
1.5 Other Solutions for the Problem of Diffusion: Sheet of Thickness

2L Immersed in a Liquid of Infinite Volume and Infinite Value of the
Another solution is known [1-3] for this problem, by using the error function.
Thus, the kinetics of transfer of a diffusing substance between the sheet of thickness 2L
and the liquid of an innite volume so strongly stirred that the coefcient of convection
is innite, is:
Mt D t
0.5

nL
0.5 + 2 (1) ierfc
n
= 2 2 (1.38)
M L n =1 Dt
where ierfc(x) is the integral of the error function complementary, with:
erfc(x) = 1erf(x)
ierfc(x) = 0.5exp(x2)xerfc(x)
19
The following remarks are of interest in determining the diffusivity D:
1. The interesting thing about Equation (1.38) is that is stands for small times, for which
the series is negligible. Thus, for small times expressed by the ratio of the amounts of
substance transferred, there is:
0.5
Mt Mt 2 D t
< 0.5 = L < x < +L (1.39)
M M L
Equation (1.39) shows that a straight line is obtained when plotting the ratio Mt/
M versus the square root of time. But, one has to pay great attention, because this
relationship is of value only when the coefcient of convection is innite, with a
strongly stirred liquid; thus, this fact reduces the use of this equation in calculating
the diffusivity.
2. As already stated in Section 1.4.9, Equation (1.37) is very useful for determining the
diffusivity D for long times, expressed in terms of the ratio of the amounts of diffusing
substance transferred.

Immersed in a Liquid of Finite Volume and Infinite Value of the
As shown in Section 1.4 where the volume of liquid is very large, if not innite, the
concentration of the diffusing substance in this liquid always remains equal to 0. In sharp
contrast to this case (the problem of diffusion considered in Section 1.6), the volume of
liquid is nite. This case of nite volume is very common, while the case of innite volume
is obtained only when the sheet is washed by a running liquid, constantly kept pure. On
the other hand, the assumption made with the innite coefcient of convection is not
exactly easy to comply with.
When the liquid of nite volume is strongly stirred, the solution of the problem of diffusion
depends only on time, and the essential condition is that the total amount of diffusing
substance in the sheet and the liquid remains constant when diffusion proceeds. Two
opposite cases appear, the one with the absorption of the substance by the sheet, the other
when the substance leaves the sheet. Let us note that in these two cases, the problem is
created by diffusion through the sheet.
20
1.6.1 The Diffusing Substance Enters the Sheet
Suppose that an innite sheet of uniform material of thickness 2L is immersed in the liquid
and that the diffusing substance is allowed to enter the sheet and to diffuse through it.
As shown in Figure 1.5, the sheet occupies the space L x +L
while the liquid of limited volume is extended as follows:
L A x L as well as L x L + A
where A is the relative thickness of the liquid, equal to its volume V per unit area.
The solution of the equation of diffusion (1.11):
C 2C
=D 2 (1.11)
t x
with a constant diffusivity is required, with the initial condition:
t=0 -L < x < +L C=0 (1.40)
and the boundary condition expressing the fact that the rate at which the diffusing substance
leaves the liquid is constantly equal to the rate at which it enters the sheet on its two sides:
C C
t >0 x = L A = D (1.40)
t x
Figure 1.5 Scheme of the sheet of thickness 2L placed in a volume of liquid, the total
volume being represented by the thickness 2A. 2(A-L) is the volume of liquid per unit
area in contact with the sheet.
21
When the partition factor K is 1, the concentration on the sheet surfaces are constantly
equal to the concentration of the diffusing substance in the liquid.
When the partition is not equal to 1, the concentration of diffusing substance on both
surfaces of the sheet is constantly K times that in the liquid. In this case, the thickness of
the liquid is modied, becoming A/K instead of A.
The solution of the problem, whatever the partition factor, is given as follows [1-3]:
Mt
2 (1 + ) q2 D t
= 1 exp n 2 (1.41)
M n =1 1 + + 2
q s
n L
where the qns are the non-zero positive roots of:
tan qn = qn (1.42)
and the ratio of the volumes of liquid and sheet are given either by Equations (1.43) or
by (1.44), depending on the value of the partition factor K:
A
when K = 1 = (1.43)
L
A
when K 1 = (1.43)
KL
Some roots of Equation (1.42) are given in various books [1-3] for the values of
corresponding to a few values of the nal fractional uptake of the diffusing substance by
the sheet.
At equilibrium, since the total amount of diffusing substance in the sheet and liquid is the
same as that initially in the liquid, the matter balance written for this substance gives:
A C
+ L C = A Cin (1.44)
K
by calling C the uniform concentration in the sheet at equilibrium, and C /K

the corresponding value in the liquid, when the partition factor is K.
Obviously when K = 1, the concentrations at equilibrium are similar in the liquid and in
the sheet.
22
The amount of diffusing substance at equilibrium in the sheet is given by:
2 A Cin
M = 2 L C = (1.45)
1+
and the fractional uptake of the sheet is obtained as follows:
M 1
= (1.46)
2 A Cin 1 +
The prole of concentration developed through the thickness of the sheet is given by:
Cx,t
cos(q n x / L) 2 (1 + ) D t
= 1+ exp qsn 2 (1.47)
C n =1 cos q n 1 + + qn
2 s
L
1.6.2 The Diffusing Substance Leaves the Sheet
The solution of Equation (1.11) with the boundary condition (1.40) requires the new
initial conditions:
t =0 L < x < +L C x ,0 = Cin (1.48)
On writing C = Cin Cx,t in Equation (1.47), the proles of concentration are also
calculated by this equation, when the corresponding value Cxt replaces Cx,t, and C
replaces C.
The kinetics of the diffusing substance released from the sheet is still expressed by Equation
(1.41), by considering that Mt and M represent the amount of substance transferred into
the liquid either at time t or at an innite time, respectively.
The fractional uptake of the diffusing substance is given by the ratio:
M
= (1.46)
2L Cin 1 +
The kinetics of release (or of absorption) of the diffusing substance out of the sheet of
thickness 2L is drawn in Figure 1.6 for various values of the ratio of volumes ; it is
expressed in terms of dimensionless numbers, either for the amount of substance transferred
Mt/M or for the time (Dt/L2)0.5.
23
Figure 1.6 Kinetics of transfer of the diffusing substance into (or out from) the sheet
with a sheet of thickness 2L, and an innite value of h, with various values of the ratio
of volumes dened by . The values of are shown in the gure. These master curves
are drawn by using the dimensionless numbers Mt/M and Dt/L2 for the co-ordinates.
It clearly appears from the curves that the kinetics obtained with values of larger than,
say, 100 or even 50, are similar to the kinetics determined with an innite volume of
liquid, depending on the accuracy desired. A straight line passing through the origin is
observed with the large values of the ratio of the volumes .
It is also of interest to draw the kinetics of matter transfer in terms of Mt/Min instead of
Mt/M for the ordinate, as shown in Figure 1.7. From the rst view, some essential differences
appear between these two (Figures 1.6 and 1.7), resulting from the following facts:
The ratio Mt/M is independent of the ratio of the volumes of liquid and polymer, as
whatever the value of the volume of the liquid, the amount of additives transferred tends
to its limit M after innite time, leading to Mt/M = 1.
The ratio Mt/Min largely depends on the value of the ratio of the volumes of liquid
and of polymer, as the amount of the additives initially located in the polymer sheet is
simultaneously distributed in the liquid and the polymer.
24
with a sheet of thickness 2 L, and an innite value of h, and various values of the ratio
of volumes dened by . The values of are shown in the gure. These master curves
are drawn by using the dimensionless numbers Mt/Min and Dt/L2 for the co-ordinates.
Thus for a very large volume of liquid, with , the ratio Mt/Min tends to 1 in Figure 1.7,
in the same way as Mt/M) in Figure 1.6. By contrast, the amount of substance is distributed
at equilibrium between the polymer and the liquid in relation to their respective volumes.
For example, for = 5, the amount of diffusing substance in the liquid is 83% of its initial
amount in the polymer.
1.6.3 Note on Equation (1.41) with an Infinite Volume of Liquid
When the volume of liquid is innite, = , and the roots of Equation (1.42) relative
to the value of qn, are in the form: qn = (n + 0.5), and thus Equation (1.41) reduces to
Equation (1.34):
2n + 1 2 2
Mt 8
= 1 2
1
exp ( ) D t (1.34)
M n =0 (2n + 1)2 4L2

25

Immersed in a Liquid of Infinite Volume and a Finite Value of the
This case corresponds with the process of diffusion of the diffusing substance through the
sheet coupled with evaporation of this substance from (or condensation onto) the surfaces
of the sheet. But it should be said that it also represents the process of a sheet immersed
in a liquid when the coefcient of convection is nite. In fact, the solution of the problem
when the coefcient of convection h, is innite and expressed by the equations (1.30) and
(1.34) in Section 1.4 is very often, if not always, unrealistic.
With a nite coefcient of convection h, the basic equations are as follows:
The one shown already in Equation (1.11), expressing the diffusion through the thickness
of the sheet:
C C 2C
F = D =D 2 (1.11)
x x x
and the other representing the boundary condition when h is nite:
C
(
D = h CL , t Ceq
x
) (1.3)
When the initial condition is given by a uniform concentration of the diffusing substance,
expressed by Equation 1.21, there is a solution for the problem:
t =0 L < x < +L C = Cin (1.21)
The solution of Equation (1.11) with the initial and boundary conditions is given for the
proles of concentration developed through the thickness of the sheet as follows:
x
2R cos n
C C x , t
L Dt
= 2 exp 2n 2 (1.49)
C Cin n =1 (n + R + R) cos n
2
L
where the n are the positive roots of:
tan = R (1.50)
26
and the dimensionless number R is given by:
hL
R= (1.51)
D
The kinetics of transfer of diffusing substance by using the dimensionless number Mt/M
is expressed in terms of the dimensionless number Dt/L2 by the following equation:
M M t 2 R2 Dt
= 2 2 exp 2n 2 (1.52)
n =1 n (n + R + R) L
2
M
The kinetics of substance transferred is drawn in Figure 1.8 for various values of the
dimensionless number R, by using the dimensionless numbers Mt/M for the amount of
substance and (Dt/L2)0.5 for the time. It clearly appears that a straight line is obtained
for the innite value of R (and of the coefcient of convection h) as well as for R values
larger than 50.
Figure 1.8 Kinetics of transfer of the diffusing substance into (or out from) the sheet with
a sheet of thickness 2L and a nite value of h, and an innite value of the ratio of volumes
dened by . The values of R = hL/D are shown in the gure. These master curves are
drawn by using the dimensionless numbers Mt/M and Dt/L2 for the co-ordinates.
27
Of course, the total amount of substance enters or leaves the sheet, depending on the relative
values of the concentrations C and Cin, as shown previously in equations 1.6 and 1.6:
C > Cin absorption of diffusing substance by the sheet (1.6)

C < Cin release of diffusing substance by the sheet (1.6)
1.7.1 Notes on the Case Described in Section 1.7
1 This method of calculation is of great interest to describe the process of drying, but
only when the diffusivity is constant and does not depend on the concentration of the
diffusing substance in the sheet.
2 In the same way, the surroundings can be considered as innite provided that the
sheet is not conned in a closed volume, because in this case, the concentration of the
evaporated substance in the atmosphere, far from remaining constant, would increase
regularly as the evaporation proceeds.
3 It should be noted that the rate of convection h is related to the rate of evaporation
of the diffusing substance per unit area Ft, by the relationship:
Ft = h CL,t (1.53)
showing that the rate of evaporation of substance evaporated is proportional to the

actual concentration of liquid on the surface of the solid. This concentration of liquid
in the polymer, expressed in terms of volume of liquid per total volume of polymer
and liquid is lower than 1, while in the pure liquid, the concentration is 1.
Of course, when the concentration of the liquid is expressed in terms of mass per
volume, the rate of evaporation is also expressed in terms of mass of substance
evaporated per unit time and per unit surface of the solid.
1.8 Ratio Volume/Area of the Food Package

The most common case encountered in food packages occurs when the volume of food
located in the plastic package is nite, and the liquid is not so strongly stirred that the
coefcient of convection h would be innite.
It is usual to dene the volume of liquid as a fraction of the surface of the package when
this food package has the shape of a cube. It gives for a cube of side a:
volume a3 a
= = (1.54)
area 6a 6
2
28
Let us note that this assumption made for a cube is also of reasonable value for a cylindrical
bottle, as the area of the packaging for 1 litre (1 dm3) is 5.75 dm2 (instead of 6 for the
cubic form).
As the volume of the package is proportional to its thickness, with a thickness of 100
m, for a volume of 1 litre (1 dm3) and the associated area of 6 dm2, the volume of the
package is 6 cm3. Thus, the ratio of the volumes and thicknesses shown in Equation (1.43)
is either 166 for the cubic form or around 174 for the bottle.
1.9 Determination of the Parameters of Diffusion
The parameters of diffusion for a sheet are as follows: mainly the diffusivity (also called
coefcient of diffusion), the coefcient of convection at the liquid-solid interface, without
forgetting the thickness of the sheet.
Surely, the best way to test the accuracy of the values obtained for these parameters is to have
the experimental data tted on the theoretical curve drawn by using these parameters.
Two methods can be used for the determination of these parameters:
Drawing various curves which enable one to determine the values of these parameters.
Using a numerical model, taking into account not only the diffusivity but also the
coefcient of convection.
1.9.1 Simple Ways of Evaluating the Parameters of Diffusion (Diffusivity)
1.9.1.1 Diffusivity
The rst way used for evaluating the value of the diffusivity is to express the kinetics of
release of the additive in terms of the square root of time. As shown with the Equation
(1.39), the value of the slope of the straight line obtained is proportional to 2/L(D/)0.5 for
a sheet of thickness 2L. Only when this curve is a straight line passing through the origin
of time (that is obtained when the coefcient of convection h is innite), does the slope of
this straight line give the value of the diffusivity. Theoretically speaking it should be said
that the experimental conditions have to meet the following three requirements:
The ratio of the volume of liquid and of the sheet is very large, e.g., larger than 20;
The rate of stirring is so strong that the coefcient of convection is so large that the
dimensionless number R is larger than 50 (Figure 1.8);
29
The amount of diffusing substance released as a fraction of the corresponding value

at innite time (at equilibrium) is lower than 0.5.
Generally, an S-shaped curve similar to those drawn in Figure 1.8, is obtained, proving
that the coefcient of convection h is nite. And under these conditions, the value of this
parameter h has to be evaluated.
1.9.1.2 Coefficient of convection h
An innite value of the coefcient of convection h can be obtained from the kinetics of
release of the additive expressed in terms of time, at the beginning of the process, from
the shape of the curve, but a vertical tangent is far from being easy to determine precisely,
even by expanding the scale of time.
Another easier way consists of expressing the kinetics of additive release in terms of the
square root of time and using Equation (1.39). Curves like those shown in Figure 1.8 are
helpful in giving a rough idea of the value of this coefcient of convection h.
1.9.1.3 Thickness of the sheet
The measure of the thickness should be made accurately, as the time necessary for a given
transport controlled by diffusion is proportional to the square of this thickness.
Calculations have been carried out for using a sheet in the previous sub-chapters, but
nevertheless, the equations and conclusions as well as the curves drawn in the various
gures can be used for a cylindrical bottle, for the main and reasonable reason that the
radius of this cylinder is far larger than the thickness of the package.
1.9.2 Using a Numerical Model
This way of working is surely the easiest one, but only when the model is perfectly built.
It is necessary when reading the instructions of the model to nd the equation upon which
it is based. For example, a model built only by using Equation 1.34 obtained with an
innite value of the coefcient of convection is a very poor model; the accuracy of the
value determined for the diffusivity can be appreciated by comparing the kinetics curves
obtained either by calculation with the model or by plotting the experimental data.
Moreover, the kinetics curves would be expressed preferably either in terms of time or by
using the square root of time, and be drawn with an expanded scale of time.
30
Thus, in the valuable model, the kinetics of release of the additives is expressed by Equation
(1.52), while the amount of the additive in the liquid is obtained from the value of the
concentration measured at any time t in the liquid, by the obvious relationship:
Mt
Cliquid, t = (1.55)
Vliquid
where the volume of liquid is noted in the denominator, and Mt is the amount of additive
released at time t.
So, the kinetics of release of the additives should be determined by following the increase
in the concentration of this additive in the liquid.
The method consists of tting theoretical kinetics with the experimental data, the best
theoretical kinetics being obtained with the right value of the dimensionless number R.
Of course, the values of the coefcient n shown in the Equation (1.52) for the theoretical
kinetics are necessary, and generally some tables are provided [1-3], but the number of
these values is limited, generally to 10 values for the dimensionless number R. While the
best way consists of calculating the n values by using Equation (1.50) associated with
some hypothetical values of the dimensionless number R, selected not by the rule of thumb
but by using an iterative method, a table is given with a wide range of the R values.
1.9.3 Using the Appropriate Numerical Model
The numerical model should take into account the following assumptions:
the ratio, , of the volumes of the liquid and of the sheet, is obtained experimentally;
the coefcient of convection h is nite;
the other experimental data, such as the kinetics and the thickness of the sheet.
In response, the model should be able to draw the theoretical curve which ts the
experimental data better, and give the diffusion parameters obtained for this tting, the
diffusivity and the coefcient of convection, as well as the error coefcient evaluating the
accuracy of these values as high as possible.
The simultaneous effect of the parameters R and is depicted in Figure 1.9. The curves
obtained with the value of R = 100 and either = 50 (curve 1) or = 200 (curve 2) are
perfectly superimposed, proving that the effect of the ratio of the volumes of liquid and
package is negligible when it is larger than 50, as already stated in Section 1.6. On the other
hand, the curves 3 and 4 obtained with the same values of 50 (curve 3) or 200 (curve 4)
for , and for the lower value of R = 20, are also superimposed together. However, this
31
with a sheet of thickness 2L and a nite value of h, and a nite value of the ratio of
volumes dened by . These master curves are drawn by using the dimensionless
numbers Mt/M and Dt/L2 for the co-ordinates. With R = 100 and = 50 (curve 1),
and = 50 (curve 2); With R = 20 and = 50 (curve 3), and = 200 (curve 4)
curve (curve 3 and 4) notably differs from the other one (curves 1 and 2), because of the
change in the value of R as well as of h.
In order to stress the importance of the effect of the coefcient of convection h and
subsequently, that of the dimensionless number R, the following Figures 1.10-1.13 are drawn
under the following conditions, while the volume of the liquid is so large that :
Figure 1.10 Obtained when R is innite, either for the full line and circles.
Figure 1.11 S-shaped experimental curve (full line) drawn with D = 10-7 cm2/s and R = 10;
curve (dotted line) tting best the experimental curve, obtained with R innite, leading
to D = 0.73 x 10-7 cm2/s; straight line (full line) tangent to the experimental curve along
its linear part, (thus drawn with R innite) leading to D = 0.92 x 10-7 cm2/s.
its linear part (thus drawn with R innite), leading to D = 0.61 x 10-7 cm2/s.
32
with a sheet of thickness 2L and innite value of h, and innite value of the ratio
of volumes dened by . These master curves are drawn by using the dimensionless
numbers Mt/M and Dt/L2 for the co-ordinates.
its linear part (thus drawn with R innite), leading to D = 0.44 x 10-7 cm2/s.
These Figures 1.10 to 1.13 lead to some interesting conclusions:
i) Of course, in the hypothetical case when the coefcient h and the dimensionless number
R are innite, or at least very large, the experimental (circles) and the theoretical (full
line) are perfectly superimposed, as shown in Figure 1.10.
ii) In the Figures 1.11 to 1.13, when the coefcient h is nite, as well as the dimensionless
number R, the experimental S-shaped curve (full line) differs notably from the
theoretical curve (dotted line) passing through the coordinates origin. Let us recall
that these two curves are calculated and drawn by using the same thickness for the
lm but different values for the parameters (diffusivity and dimensionless number R).
Moreover, the tangent (full line) to the experimental curve along its linear part does
not pass through the coordinates origin.
33
with a sheet of thickness 2L and a nite value of h, and innite value of the ratio of
numbers Mt/M and the square root of time for the co-ordinates.
Full line: experimental S-shaped curve with R = 10 ; D = 10-7 cm2/s; L = 0.1 cm. Dotted
line: curve, with innite R ; L = 0.1 cm ; D = 0.73 x 10-7 cm2/s. Straight line (full line),
tangent to the experimental curve with D = 0.92 x 10-7 cm2/s.
iii) Furthermore, the effect of the value given to the parameter h and the dimensionless
number R clearly appears by comparing the curves drawn in Figures 1.11 to 1.13.
Thus the following statement holds: the lower the coefcient of convection h, as well
as the value of the dimensionless number R, the more different the experimental curve
is from its theoretical counterpart.
iv) Quantitatively, the conclusion given in iii) appears with the values obtained for the
diffusivity D when they are calculated by using the equation 1.39:
when R = 10, D is lower than the correct value by around 9%,

when R = 2, D is lower than the correct value by around 40%, and
when R = 1, D is lower than the correct value by around 60%.
v) It is necessary to compare the value of the diffusivity obtained by drawing the

theoretical curve which gives a closer t with the experimental curve, in each Figure.
34
Full line: experimental S-shaped curve with R = 2; D = 10-7 cm2/s; L = 0.1 cm. Dotted
line: curve, with innite R; L = 0.1 cm; D = 0.39 x 10-7 cm2/s. Straight line (full line),
tangent to the experimental curve with D = 0.61 x 10-7 cm2/s.
They should be lower than the correct value by 27% in Figure 1.11, 62% in Figure
1.12, and it is only one-quarter of the correct value in Figure 1.13.
vi) Thus, there is a dramatic decrease in the value of the diffusivity obtained by calculation
from the experimental curves, when using Equation (1.39) instead of Equation (1.52)
taking into account the nite values of the dimensionless number R.
vii) It is true that in Figure 1.11 with R = 10, drawn with the full scale of the amount
of diffusing substance transferred, the three curves do not look very different. But
this difference appears more apparent in Figure 1.14 when the scale is reduced for
the coordinates. Obviously, this difference between the three curves largely increases
from Figures 1.14 to 1.16 where R is 10, 2, or 1, respectively. Let us note that very
often, when the amount of the diffusion to be released after innite time is known,
the experimetal curves obtained are those shown in Figures 1.14 to 1.16.
35
Full line: experimental S-shaped curve with R = 1; D = 10-7 cm2/s; L = 0.1 cm. Dotted
line: curve, with innite R; L = 0.1 cm; D = 0.25 x 10-7 cm2/s. Straight line (full line),
tangent to the experimental curve with D = 0.44 x 10-7 cm2/s
1.9.3.1 Note: Quick Approach to the Value of the Diffusivity
When the process of additive release from the sheet into the liquid complies with the
following requirements:
the volume of the liquid is much larger than that of the sheet, with > 20;
the system is so strongly stirred that the coefcient of convection is innite, or R > 100;
the whole kinetics of release is obtained, or at least the amount of additive released at
equilibrium is known; in fact it could be the amount which was initially in the sheet,
these two facts leading to the value of M.
In these cases, and only when these three assumptions are satised, can the two equations
1.37 and 1.39 be applied to the time t0.5 at which half the amount of the additive is released,
36
with a sheet of thickness 2 L and a nite value of h, and innite value of the ratio
of volumes dened by . These master curves are drawn by using the dimensionless
numbers Mt /M and the square root of time for the co-ordinates.
Full line: experimental S-shaped curve with R = 10; D = 10-7 cm2/s; L = 0.1 cm.
Dotted line: curve, with innite R; L = 0.1 cm; D = 0.73 x 10-7 cm2/s. Straight line
(full line), tangent to the experimental curve with D = 0.92 x 10-7 cm2/s.
Mt/M = 1/2 is thus obtained, L being half the thickness of the sheet:
0.5
Mt 1 2 D t Mt
= = for < 0.5 (1.37)
M 2 L M
Mt 8 2 D t Mt
= 1 2 exp for > 0.5 (1.39)
M 4L2 M
From the relationship Equation (1.37), it is found:
L2
D = 0.196 (1.56)
t0.5
37
numbers Mt/M and the square root of time for the co-ordinates. Full line: experimental
S-shaped curve with R = 2; D = 10-7 cm2/s; L = 0.1 cm. Dotted line: curve, with innite
R; L = 0.1 cm; D = 0.39 x 10-7 cm2/s. Straight line (full line), tangent to the experimental
curve with D = 0.61 x 10-7 cm2/s
and from the relationship (1.39), we get:
L2
D = 0.192 (1.57)
t0.5
It clearly appears that the value of the diffusivity D is nearly the same in these two
equations, varying only by 2%.
1.10 Diffusion through Isotropic Rectangular Parallelepipeds
Rectangular parallelepipeds (a polyhedron with six faces all of which are parallelograms)
are sometimes used instead of sheets, making this sub-chapter of practical interest. The
sheet has been considered as a rectangular parallelepiped whose one side, the thickness,
38
numbers Mt/M and the square root of time for the co-ordinates. Full line: experimental
S-shaped curve with R = 1; D = 10-7 cm2/s; L = 0.1 cm. Dotted line: curve, with innite
R; L = 0.1 cm; D = 0.25 x 10-7 cm2/s. Straight line (full line), tangent to the experimental
curve with D = 0.44 x 10-7 cm2/s
is very thin as compared with the other two sides, and the effect of the edges on the total
matter transfer can be neglected.
Some materials are anisotropic, e.g., wood [3] or stretched polymers. In fact, the
following equations can also be used for those materials, provided that the right
diffusivity associated with each direction is put in the corresponding function. The
problem with three axes of diffusion is resolved whatever the value of the coefcient
of convection h, nite or innite.
1.10.1 Diffusion with an Infinite Value of the Coefficient of Convection
The amount of diffusing substance transferred through the surface of the parallelepiped after
time t, as a fraction of the corresponding amount after innite time, is expressed in terms of
time by the product of the three series obtained for a one-dimensional transport.
39
Thus, the following equation is obtained for an innite coefcient of convection h:
M M t
= f (x, a) f (y, b) f (z, c) (1.58)
M
where each function f is given by Equation (1.34) applied to the corresponding axis and
length, the three lengths of the parallelepiped being a, b, c, respectively, and x, y, z being
the perpendicular axes of diffusion.
For example, there is more precisely for f(x, a):
8 1 (2n + 1)2 2
f (x, a) =
n =0 (2n + 1)
2 2
exp 2
D t (1.59)
4a
the other functions of f being obtained by substituting a for b in f(y, b) and for c in f(z, c).
1.10.2 Diffusion with a Finite Value of the Coefficient of Convection
For the nite coefcient of convection on each surface, the equation becomes:
M M t
= g(x, h, a) g(y, h, b) g(z, h, c) (1.60)
M
where the function g(x, h, a) is drawn from the Equation (1.52) by replacing the parameters
as follows:

2 X2 D t
g(x, h, a) = exp 2n 2 (1.52)
n =1 n (n + X + X) a
2 2 2
ha
with X = (1.51)
D
while the n are now the positive roots of
tan = X (1.50)
The other functions g(y, h, b) and g(z, h, c) are obtained from the three previous relationships
(1.50) to (1.52) by substituting the parameters: (a, X, n) for (b, Y, n) in g(y, h, b), and for
(c, Z, n) in g(z, h, c), respectively. Of course, the new values of n in the three functions
should be recalculated by using the relationship similar to (1.50).
40
1.10.3 Approximate Value of the Diffusivity for Small Times and Infinite h
For an innite value of the coefcient of convection and low values of time expressed by
the ratio Mt/M < 4, the series in Equation (1.38) vanishes, leading to a simple relationship,
as shown already in (1.39), applied to the length a instead of L:
0.5
Mt 2 D t
= for a < x < +a and h (1.39)
M a
Thus, for the rectangular parallelepiped of sides 2a, 2b and 2c, the following equation
is obtained:
0.5
Mt 2 2 2 D t
= + + (1.61)
M a b c
1.10.4 Approximate Value of the Diffusivity for Long Times and Infinite h
For long times, e.g., for Mt/M > 0.5, the rst term of the series in Equation (1.59) is
preponderant compared to the others. And by applying the way of calculation shown
in Equation (1.58) to a rectangular parallelepiped of sides 2a, 2b and 2c, the amount of
diffusing substance transferred after time t, is expressed by the relationship:
M M t 512 1 1 1 2D t
= 6 exp 2 + 2 + 2 (1.62)
M a b c 4
1.11 Case of a Membrane of Thickness L
In spite of the fact that the food package never plays the role of a membrane, this case is
still considered in this general chapter. The membrane is widely used as a patch for the
transdermal drug delivery because of its advantages [4]. Only the theory of the process
is developed, leading to the main equations. The results are expressed in terms of either
the kinetics of matter transport or of proles of concentration of the diffusing substance
developed through the thickness of the membrane. Nevertheless, the effect of the value of
the coefcient of convection on the surfaces of the membrane is considered (Figure 1.17).
41
Figure 1.17 Scheme of the membrane of thickness L. The concentration of the liquid
in contact with each side is Cin on the left and C = on the right. At each liquid-
membrane interface, the coefcient of convection is either innite or nite.
1.11.1 Transport of the Substance through the Membrane for Infinite h
The membrane is a sheet of thickness L whose sides are maintained at constant

concentrations, while the substance is transported from the higher to the lower
concentration by diffusion. Thus, the process is controlled by the one-directional transient
equation of diffusion through the sheet, as already shown:
C 2C
=D 2 (1.11)
t x
where: C is the concentration of the substance at time t and position x,

D is the diffusivity of the substance.
When the coefcient of convection is innite on both sides of the membrane, the
concentration on each surface of the membrane is equal to that in the liquid in contact
with it, as soon as the process starts.
The initial and boundary conditions for a sheet of thickness L playing the role of a
membrane are as follows:
t=0 0<x<L C=0 (1.63)
t>0 x=0 C = C0 = Cin (1.64)
t>0 x=L CL =
42
Under these conditions, when the coefcient of convection on the surfaces of the sheet is
very large, the concentration of the diffusing substance developed through the thickness
of the membrane, obtained by using the method of separation of variables, is expressed
in terms of time through the following series:
Cx,t x 2 1 nx D t
= 1 sin exp n2 2 2 (1.65)
C0 L n =1 n L L
The amount of substance, which emerges from the side with the lower concentration, at
position L, is expressed by the series:
M t D t L 2L (1)n D t
= 2 2 exp n2 2 2 (1.66)
C0 L 6 n =1 n L
Equation (1.65) shows that the concentration of diffusing substance in the membrane increases
with time, and the proles of this substance tend to be linear when the series vanishes.
In the same way, from Equation (1.66), the amount of substance emerging from the side of
the membrane kept at the lower concentration increases with time as the series vanishes.
Thus, after a given period of time the kinetics of the substance leaving the membrane
tends to become linear, and the expression of the asymptote is given by:
DC0 L2
Mt = t (1.67)
L 6D
the slope of which is:
M t DC0
Slope = = (1.68)
t L
and the intercept on the time-axis is:
L2
ti = (1.69)
6D
1.11.2 Results for the Membrane with Infinite Value of h on Both Sides
When the coefcient of convection on the two sides of the membrane is innite, the Equations
(1.65) to (1.69) hold. Calculation is made by using the following values for the parameters:
L = 0.05 cm D = 10-8 cm2/s C0 = 50 mg/cm3 h
43
The results are expressed in terms of the kinetics of diffusing substance transferred out of
the membrane (Figure 1.18) and of the proles of concentration developed through the
thickness of the sheet (Figure 1.19). They lead to a few conclusions:
i) A typical pattern is shown in Figure 1.18 for the kinetics of transport. Starting at the
origin of the two coordinates, the curve increases slowly before tending asymptotically
to an asymptote at a time larger than 50 hours.
ii) The proles of concentration developed through the thickness of the sheet also tend
to be linear, and for times greater than 3000 minutes (50 hours) it can be said that
the stationary part of the curve is nearly reached. However, it is difcult to dene
experimentally at which time the proles of concentration become linear.
iii) In the same way, it is not easy to determine with good accuracy the intercept on the
time-axis, and the curve needs to be expanded on a larger scale, as shown in Figure 1.18.
Thus, from the measurement made on the curve this time seems to be 11.6 hours, while
calculation made by using Equation (1.69) and the parameters gives 11.55 hours. The
accuracy is quite perfect, but for a rather large value of this time. Let us note that good
knowledge of this time is of interest for evaluating an accurate value of the diffusivity.
Figure 1.18 Kinetics of matter leaving the right side of the membrane, when the
coefcient of convection is innite on both sides. L = 0.05 cm; Cin= 50 mg/cm3;
D = 10-8 cm2/s; h innite on both sides.
44
Figure 1.19 Proles of concentration developed through the thickness of the membrane
when the coefcient of convection is innite on both sides. L = 0.05 cm; Cin = 50 mg/cm;
D = 10-8 cm2/s; R innite on both sides.
1.11.3 Results for a Membrane with a Finite Value of h on the Right Side
By using a numerical model, the same calculation is made for a nite value of the coefcient
of convection h on the right side and innite value of h on the left side of the membrane,
by keeping the other parameters equal to those given in Section 1.11.2: L = 0.05 cm;
D = 10-8 cm2/s; C0 = 50 mg/cm3; h = 10-6 cm/s on the right side and R = 5.
The results are also expressed in terms of the kinetics of mass transferred out of the
membrane (Figure 1.20) and of the proles of diffusing substance developed through the
thickness of the sheet (Figure 1.21).
Some conclusions of interest are obtained, especially by comparing the kinetic curves
and proles of concentration with their counterparts obtained with the innite value of
h and R:
i) The kinetics of the diffusing substance transferred out of the membrane in Figure 1.20
look similar, at a rough estimate, to that drawn in Figure 1.18. However, the intercept
on the time-axis is much larger, at 15.36 hours. Of course, this greater time results
from the fact that the nite convection coefcient on the right side decreases the rate
45
coefcient of convection is innite on the left side and nite on the right side.
L = 0.05 cm; Cin= 50 mg/cm3; D = 10-8 cm2/s; h = 10-6 cm/s on the right side;
h innite on the left side.
Figure 1.21 Proles of concentration developed through the thickness of the membrane,
when the coefcient of convection is innite on the left side and nite on the right side.
L = 0.05 cm; Cin = 50 mg/cm3; D = 10-8 cm2/s; h = 10-6 cm/s on the right side;
h innite on the left side.
46
of transfer. This fact is also responsible for a lower value of the diffusivity by using
Equation (1.69). Thus, neglecting the presence of a nite convection coefcient on the
right side gives a shorter wrong value of the diffusivity, as already shown in Section
1.9.3 under other conditions.
ii) The proles of concentration drawn in Figure 1.21 are quite different from those
shown in Figure 1.19. This is especially true for times greater than 300 minutes
when the diffusing substance emerges out of the right side of the membrane. The
concentration on the surface is not 0, but increases constantly up to a limit attained
when the stationary state is nearly reached. This fact results from the condition on the
right side established by considering that the rate at which the substance leaves the
sheet is constantly equal to the rate at which the substance is brought to the surface
by internal diffusion; this condition is written with the nite value of the coefcient
of convection as follows, which is quite different from Equation (1.3).
C
D = h (CL 0) = h CL right side (1.70)
x L
iii) The proles of concentration drawn in Figure 1.21 also show that the concentration on
the left side of the membrane is kept at the constant value Cin of the liquid. As soon as
the process starts, because of the innite value of the coefcient of convection h on the
left side, the concentration of the diffusing substance on the left surface of the membrane
reaches the constant value maintained in the liquid with which it is in contact.
1.11.4 Results for a Membrane with Finite Value of h on Both its Sides
The results are obtained by using a numerical model, with the same nite value of the
coefcient of convection on both sides, and keeping the other parameters taken in
Section 1.11.2: L = 0.05 cm; D = 10-8 cm2/s; Cin = 50 mg/cm3 on the left side; Cout = on
the right side; h = 10-6 cm/s on both sides and R = 5.
In addition to the case Section 1.11.3, the nite coefcient of convection on the left side
of the membrane appears, written in a form slightly different from Equation (1.3):
C
D = h (Cin C0, t ) (1.71)
x 0
These results are also expressed in terms of the kinetics of mass transferred out of the
membrane (Figure 1.22) and of the proles of diffusing substance developed through the
thickness of the sheet (Figure 1.23).
47
coefcient of convection is nite on both sides. L = 0.05 cm; Cin = 50 mg/cm3;
D = 10-8 cm2/s; h = 10-6 cm/s on both sides.
Figure 1.23 Proles of concentration developed through the thickness of the membrane,
when the coefcient of convection is nite on both sides. L = 0.05 cm; Cin = 50 mg/cm3;
D = 10-8 cm2/s; h = 10-6 cm/s on both sides.
48
Some interesting conclusions are obtained, especially by comparing the kinetic curves
and proles of concentration with their counterparts obtained with the innite value of
h and R:
i) The kinetics of the diffusing substance leaving the membrane in Figure 1.22 is slightly
different from the other two kinetics obtained either with an innite value of h on
both sides (Figure 1.18) or with innite value of h only on the left side (Figure 1.20).
The time at which the asymptote of the curve intercepts the time-axis is longer than
for the previous cases, at around 20 hours, resulting from the presence of the low
value of h on both sides.
ii) The proles of concentration drawn in Figure 1.23 are quite different from those shown
either in Figure 1.19 with innite value of h on both sides or in Figure 1.21 with innite
value of h on the left side only. The main difference between the Figures 1.21 and 1.23
results from the presence of the nite value of h on the left side of the membrane
in Figure 1.23. In addition to the case shown in Figure 1.21, it takes some time for
the concentration of the substance on the left surface to increase up to the value at
equilibrium which is maintained at a constant under the stationary condition. This
time is around 50 hours, in the same way as in Figure 1.21 when the coefcient of
convection is nite only on the right side of the membrane or as in Figure 1.19 when
the coefcient of convection is innite on both sides.
iii) It is worth noting that, not only do the proles of concentration developed through
the thickness of the membrane give a fuller insight into the nature of the process
of diffusion-convection, but they also enable one to evaluate better the time at
which the stationary conditions are attained with the asymptotical tendency of the
kinetics curve.
1.12 Evaluation of the Parameters of Diffusion from the Profiles

of Concentration
A constant drawback with the problems of diffusion comes from the long, time-consuming
experiments. The dramatic dilemma arises from the difculty of approaching the value
of the amount of the diffusing substance released after innite time. In fact, experiments
associated with the safety of the consumers can take not only months but years. Of
course, a solution exists, not well known by the majority of the workers, which consists
of reducing the thickness of the lm, according to the dimensionless number Dt/L2
which stands in all the equations of diffusion describing either the kinetics or the proles
of concentration, the time necessary for a given percentage release is proportional to the
square of the thickness of the material in contact with the liquid. Nevertheless, if it is not
49
difcult to make experiments to follow the kinetics of release of a substance, the time of
the operation is often too long.
A new method consists of evaluating the proles of concentration of the diffusing substance
developed through the thickness of the sheet during the process of release [5]. Modern
equipment has considerably improved the technique rst proposed by Moisan [6] a few
decades ago.
1.12.1 Experimental
In the present case [5], the polymer is a 0.2 cm thick polypropylene (PP) with olive oil as
the liquid considered as the diffusing substance. Disks of 3 cm diameter are immersed in the
liquid kept at 40 C for a period not less than 64 days. At intervals, a disk is removed for
analysis by using the IR absorbance of oil. The PP disk is put in the analytical beam of an
FTIR spectrometer and a virgin PP is used as a reference. After calibration of the olive oil, by
drawing the absorbance versus the concentration, quantitative analysis of the olive oil in the
PP is made possible. Moreover, greater accuracy is obtained for the position taken through
the thickness of the polymer sheet by using a microscope connected with the spectrometer.
1.12.2 Theoretical
The equation of one-dimensional diffusion with constant diffusivity is:
C 2C
=D 2 (1.11)
t x
With the initial condition expressing that the polymer sheet is free from olive oil:
C = 0 for -L < x < L and t = 0 (1.40)
and the boundary condition expressing that the rate at which the liquid enters the polymer
by diffusion is constantly equal to the rate at which the liquid is brought or rather put
into contact with the polymer surface by convection and inserted into the polymer:
C
(
D = h CL , t Ceq
x
) (1.3)
the general solution for the gradient of concentration of the diffusing substance developed
through the thickness of the sheet is given by Equation (1.49), whatever the value of the
initial concentration in the polymer sheet, which is 0 in the present case:
50
x
2R cos n
C C x , t
L Dt
= 2 exp 2n 2 (1.49)
2
L
where the n are the positive roots of:
tan = R (1.50)
hL
R= (1.51)
D
On the other hand, the kinetics of transfer of diffusing substance are expressed in terms
of the dimensionless number Dt/L2 by using the dimensionless number Mt/M:
M M t 2 R2 Dt
= 2 2 exp 2n 2 (1.52)
n =1 n (n + R + R) L
2
M
Moreover, the obvious relationship should be added for the value attained at innite time:
M = 2L C (1.72)
Thus, the values of the three parameters of diffusion, namely, the diffusivity and the
coefcient of convection, as well as the amount of liquid absorbed after innite time,
should be determined. Additionally, the value of the concentration C0,t on the surface of the
polymer sheet should also be calculated, as it is not possible to determine it experimentally
with this apparatus.
1.12.3 Results Obtained with the Gradients of Concentration
The proles of concentration of the diffusing substance developed through half the thickness
of the sheet are plotted in Figure 1.24, as they are calculated at different times: 1, 7, 14, 28,
56 and 112 days. Two other results, also evaluated by calculation, are shown in the other
Figures. Figure 1.25 shows the kinetics of the increase in the concentration of the diffusing
substance on the polymer surface in contact with the liquid, expressed by using dimensionless
numbers; the process being symmetrical, only half the sheet is considered.
Figure 1.26 represents the kinetics of increase of the amount of the liquid absorbed,
expressed by using dimensionless numbers.
51
Figure 1.24 Proles of concentration of olive oil developed through the thickness of
a 0.2 cm thick PP sheet after various times of contact: 1, 7, 14, 28, 56 and 112 days,
as they are calculated with the following parameters: L = 0.1 cm; D = 7 1011cm2/s;
h = 108cm/s. Only a half of the PP sheet of thickness 0.2 cm is shown in the gure,
because of the symmetry. Dimensionless numbers are used for the coordinates.
Figure 1.25 Kinetics of increase in the concentration of olive oil on the surface of the 0.2
cm thick PP sheet calculated at various times with the same parameters as in Figure 1.24.
52
Figure 1.26 Kinetics of absorption of olive oil by the 0.2 cm thick PP sheet, calculated
at the same times and with the same parameters as in Figure 1.24.
From the curves depicted in Figures 1.24-1.26, with the parameters of diffusion
D = 71011cm2/s and h = 108cm/s, some relevant conclusions are worth mentioning:
i) A relatively good correlation is obtained [5] between the experimental and calculated
proles of concentration developed through the polymer sheet, in spite of the disadvantage
of not having the experimental concentration on the surface. Thus, this value C0,t should
be extrapolated by calculation from the proles by using Equation (1.49).
ii) Figure 1.24 clearly shows that the concentration on the surface of the polymer in contact
with the liquid increases with time rather slowly, as after 112 days the value is far from
reaching equilibrium. This is an obvious and denitive proof for the presence of a
convective mass transfer at the liquid-polymer interface. The process is thus denitively
controlled either by diffusion through the thickness of the polymer sheet or by convection
onto its surface. The value of the dimensionless number R is around 14.
iii) The coefcient of convective transfer h plays an important role, considerably reducing
the rate of the process of transfer. Moreover, the curve drawn in Figure 1.25, expressing
the kinetics of increase in the concentration on the surface with time, is of great interest.
It clearly appears that after 112 days, the concentration on the surface C0,t is very
close to the value at equilibrium, as the ratio of the concentrations C0,t/C0, reaches
a little more than 0.8, making the extrapolation easy to do for innite time.
53
iv) The curve expressing the kinetics of the liquid absorbed in Figure 1.26 is also of great
interest, especially on the purpose of didactics. As the amount of liquid absorbed at
equilibrium M can be evaluated by using the Equation 1.72 and the corresponding
value of the concentration on the surface, C, is easily obtained by extrapolation (Figure
1.25), it is possible to draw the kinetic curve of absorption shown in Figure 1.26.
v) As shown in Figure 1.26, the amount of liquid absorbed after 112 days as a fraction of
the corresponding amount at innite time, Mt/M, is less than 0.25. Thus, for such a
low value, it is impossible to extrapolate the value at innite time, M. The advantage
of the method based on the proles of concentration over the usual method consisting
of measuring the amount absorbed can clearly be seen. The problem arises because
a rather complex apparatus is necessary to do the experiments for measuring these
gradients of concentration.
1.13 Conclusions on the Diffusion Process
After considering the various parts of the process of the matter transport controlled
by diffusion, it seems necessary to recall the most important facts, in the form of a
conclusion.
Various parameters intervene in the process of diffusion when a lm is in contact with a

liquid food. First, those concerned with the lm itself, with its thickness and the diffusivity
of the substance, secondly, the volume of the food. The diffusing substance intervenes
through the diffusivity which depends on the diffusing substance-polymer couple, as
well as its solubility either in the polymer or in the food; the partition factor results
from the presence of the solubility in both these media which limits the concentration of
this substance. The rate of stirring plays the major role, because of the presence of the
convection stage at the liquid-package interface.
The ratio of the volume and package, denoted , is only of concern when it is lower than
20; it is clear that for a 1 litre bottle, whatever its shape, this ratio being around 166,
its effect becomes negligible except when a very high accuracy is needed.
By contrast, the rate of stirring always plays the most important role in the process of
transport of the diffusing substance, because of the presence of the convection at the
liquid-lm interface. This coefcient of convection h is of such great concern that it should
always be considered. In fact, it is clear that when h is innite, the concentration on the
lm surface reaches the value at equilibrium instantaneously as soon as the process starts.
This fact makes the equations expressing either the kinetics (1.34 and 1.39) or the proles
of concentration through the lm thickness (1.31) quite oversimplied.
54
A strong difference also appears between the lm playing the role of a package or used as a
membrane. On the one hand, a package contains a nite amount of diffusing substance, which
decreases during the process; on the other hand, the concentration of the diffusing substance
is kept constant on both sides of this membrane, whatever the convection on each side.
When it comes to considering the main fact, e.g., the convection, associated with the
diffusivity, it should be said that the convection is very important for the food protection
as it acts upon the polluting transport as an additional resistance to the diffusion stage.
A relevant proof for the presence of this convective transfer at the liquid-package interface
is demonstrated by considering the case of diffusion of a liquid such as olive oil through
a PP sheet when this polymer sheet is immersed in the liquid.
Finally, a numerical model is of interest, if not necessary, to solve the diffusion problems
because of the values of the n, which should be determined through Equation (1.50) for
calculating the kinetics of the substance transferred by using Equation (1.52).
Some emphasis is put upon the dimensionless numbers Dt/L2 and hL/D, as well as Mt/M
or Mt/Min and Ct/Cin. By using them, the kinetics or the proles of concentration obtained in
typical cases are transformed into master curves which can be used whatever the nature of
the diffusing substance-polymer couple and the other parameters, e.g., the dimension of the
lm and the time, as well as the initial concentration of the substance bound to diffuse.
References
1 J. Crank, The Mathematics of Diffusion, 2nd Edition, Clarendon Press, Oxford,

UK, 1975, Chapter 4.
2 J-M. Vergnaud, Controlled Drug Release of Oral Dosage Forms, Ellis Horwood,
New York, NY, USA, 1993, Chapters 1, 2 and 3.
3 J-M. Vergnaud, Liquid Transport Processes in Polymeric Materials: Modelling and

Industrial Applications, Prentice Hall, Englewood Cliffs, NJ, USA, 1991, Chapters
1 and 13.
4 J-M. Vergnaud and I-D. Rosca, Assessing Bioavailability of Drug Delivery

Systems: Mathematical and Numerical Treatment, CRC Press, Boca Raton, FL,
USA, 2005, Chapter 4, section 4.1 and Chapter 10.
5 A.M. Riquet, N. Wolff, S. Laoubi, J.M. Vergnaud and A. Feigenbaum, Food

Additives & Contaminants, 1998, 15, 6, 690.
6 J.Y. Moisan, European Polymer Journal, 1980, 16, 10, 979.
55
Abbreviations
A half the thickness of the liquid (volume per unit area) in case of nite
volume of liquid
a length of the edge of a cube, considered as a model for the volume/area ratio
ratio of the volumes of the liquid and of the sheet, per unit area, in
Equation (1.43)
An, Bn, n constants used in Equation (1.15)
n positive roots of Equation (1.50)
Cx,t, CL,t concentration of diffusing substance at position x or at position L, at time t.
Cin, C, Ceq concentration of diffusing substance, initially, after innite time, and at
equilibrium with that in the surrounding, liquid or gas respectively
CGS Centimetre, gram, second system
D diffusivity (coefcient of diffusion) expressed in cm2/s (square length)/

unit time
Fx,t ux of matter at position x and time t (mass per unit area and per unit time)
h coefcient of convection expressed in cm/s
K partition factor shown in Equation (1.7), dimensionless number
L half the thickness of the sheet (of thickness 2L)
Mt, M amount of matter transferred by diffusion after time t, innite time,

respectively
PP polypropylene
qn non-zero positive roots of Equation (1.42)
S area of the sheet in contact with the liquid
x, t coordinate along which the diffusion occurs, and time, respectively
Dt/L2 dimensionless number, expressing time
hL/D dimensionless number, expressing the quality of stirring of the liquid
56
2
Mass Transfer Through Multi-layer
Packages Alone
2.1 Recycling Waste Polymers and Need of a Functional Barrier
Accumulation of waste in the environment has recently stimulated investigations of

processes, which can reuse discarded plastics. Since plastics for food packages represent
more than 50% of the overall consumption of plastics in Europe, an efcient approach
consists of making new packaging materials from recycled plastic packaging. Several
techniques are now available. The main difculty in this eld is that discarded plastics
may be contaminated by various substances, which may migrate into the food [1]. A
solution to this problem could be the incorporation of recycled plastics into multilayer
structures, where a layer of virgin polymer is placed between the recycled polymer and
the liquid food. The layer of virgin polymer then behaves as a functional barrier, which
protects the food from migration of contaminant, at least over a given period of time,
which should be known.
2.1.1 Role of the Functional Barrier
Of course, the role of this virgin polymer placed between the food and the recycled
polymer is of prime importance. As a matter of fact, the contaminant located in the
recycled plastics cannot reach the food before a lag time resulting from its diffusion
through the functional barrier. This functional barrier is efcient if this lag time is larger,
or at least equal, to the intended shelf life of the food. Various parameters determine
the efciency of the functional barrier, such as the level of contaminant originally in
the recycled layer, the nature of the polymer-contaminant couple, the presence of a
food transfer through the functional barrier, and the thicknesses of the recycled lm
and of the functional barrier [2-4]. This problem can be very complex, both from a
practical and from a theoretical point of view. The functional barrier and the recycled
layer can be made of different polymers, so that the diffusivity of contaminants may
change in the two layers; moreover, if a layer is made of glassy polymer, the diffusion
may be non-Fickian, modifying the mathematical treatment. The concentration of these
contaminants is also a relevant factor, as its solubility in these two polymers could be
so different that a partition factor could intervene at their interface. Finally, and this
57
is not the least stage in the process, if the food enters the polymer with which it is in
contact, as proved in studies concerned with plasticised PVC, the concentration of this
liquid will also increase the diffusivity of the contaminant [4, 5].
2.1.2 Mass Transfer Occurring During the Co-extrusion Stage
During the stage of co-extrusion, both the polymers made of either recycled or virgin
materials are melted and put rmly in contact so as to form a bi-layer or a three-
layer lm, before being cooled down. It is clear that during this stage a fast transfer
of contaminant would take place, resulting from a high diffusivity and perhaps some
convection effect, but fortunately this strong transfer takes place over a short period of
time, as the thin sheet is cooling down rapidly, and this factor may be a counterbalance
to the high diffusivity.
2.1.3 General Problem of Diffusion Through the Layers of the

Packaging Alone
To face the complexity of these problems and resolve them, the various stages will be
considered separately in different chapters. In Chapter 2, the diffusion of a contaminant
through the polymer layers alone, without liquid is studied. From a practical point of
view, this part concerns the behaviour of the packaging before its use as a food container.
From the theoretical point of view, the problems of diffusion through the polymers will be
examined in depth, and this knowledge should be useful in the following chapters when
the packaging is in contact with a food either in liquid or in viscous state.
The general conditions of concern which are covered in Chapter 2, are:
As there is no liquid, both surfaces are in contact with air;
As the contaminant is not volatile, the rate of evaporation of this contaminant is

assumed to be negligible.
2.2 Bi-layer Package: Recycled Polymer-Functional Barrier
The scheme of the bi-layer package is shown in Figure 2.1, which consists of a virgin layer
and of a layer made of recycled polymer.
58
Mass Transfer Through Multi-layer Packages Alone
Figure 2.1 Scheme of the bi-layer system with recycled polymer layer on the left and
the virgin polymer layer on the right, playing the role of a functional barrier.
Cin is the uniform concentration of diffusing substance which is initially in the
recycled polymer layer.
2.2.1 Mathematical Treatment of the Process [1, 6]
Assumptions
The following assumptions are made in order to describe the process precisely:
i) The packaging is a laminate made of two lms of the same polymer in perfect contact;
there is no resistance to mass transfer at the interface between the two lms.
ii) At the beginning of the process, the concentration of contaminant is uniform in the
recycled lm, while the virgin lm is free from contaminant.
iii) The transfer of contaminant is controlled by Fickian diffusion.
iv) The diffusivity of the contaminant is constant, and it is the same in both lms, since
they are made of the same polymer.
v) The contaminant does not evaporate out of the external surfaces of the packaging.
vi) The concentration of contaminant is so low that there is no change in the thickness
of each layer resulting from the transfer.
vii) There is no contact between the package and food.
59
Mathematical Treatment
Following assumptions (iii) and (iv), the transport of contaminant through the two layers
is governed by the unidirectional equation of diffusion with a constant of diffusivity:
C x , t 2C x , t
= D (2.1)
t x 2
where Cx,t is the concentration of contaminant at abscissa x and time t, while D is the
constant diffusivity.
Following assumptions (ii) and (v), the initial and boundary conditions are expressed by:
t=0 0<x<H C = Cin (2.2)
H<x<L C=0 (2.2)
C C
t>0 = =0 (2.3)
x x =0 x x =L
The analytical solution of the problem is obtained by using the method of separation of
variables (shown in Chapter 1.3).
The concentration of pollutant Cx,t at position x is thus expressed as a function of time:
Cx,t H 2 1 nH nx n2 2
= + sin cos exp 2 D t (2.4)
Cin L n =1 n L L L
The amount of contaminant transferred into the functional barrier at time t is obtained
by integrating the concentration Cx,t with respect to the space between the abscissa H and
L. This amount is expressed as a fraction of the amount of contaminant initially found
in the recycled polymer layer:
M t L H 2L 1 nH
2
n2 2
= 2 2 sin p 2 D t
exp (2.5)
M in L H n =1 n L L
It is of interest to know the concentration of contaminant at position L where the virgin

layer is in contact with air - this concentration is obtained by putting x = L in Equation
(2.4), leading to Equation (2.6).
60
CL , t H 2 (1)n nH n2 2
= + sin exp 2 D t (2.6)
Cin L n =1 n L L
When H << L, a simplication can be made. The ratio of thicknesses H and L being very
small, as sin x/x 1 when x 0, Equations (2.4) and (2.5) are reduced to:
Cx,t H
nx n2 2
= 1 + 2 cos exp 2 D t (2.7)
Cin L n =1 L L
CL , t H n2 2
= 1 + 2 (1)n exp 2 D t (2.8)
Cin L n =1 L
Mt L H H n2 2
= 2 exp 2 D t (2.9)
M L L L
For longer times, the series in Equation (2.7) reduces to:
Cx,t H x 2
= 1 + 2 cos exp 2 D t (2.10)
Cin L L L
2.2.2 Results Obtained with Two Layers of Equal Thicknesses
The following three results are of interest to understand the process:
the proles of concentration of the contaminant developed through the two layers;
the kinetics of transfer of contaminant; and
the variation with time of the contaminant concentration on the external surfaces.
2.2.2.1 Profiles of Concentration
The proles of concentration of contaminant are calculated by using Equation (2.4) in the
case where the two layers have the same thickness (L = 2 H). The following dimensionless
numbers are used:
Cx,t/Cin for the concentration, the ratio x/L for the position, and Dt/L2 for the time.
61
Figure 2.2 Proles of concentration of the diffusing substance developed through the
bi-layer system for various values of the dimensionless time Dt/L2, when H = L/2. Other
dimensionless values are used for the concentration Cx,t/Cin and for the abscissa x/L.
Thus, the curves thus drawn in Figure 2.2 can be used whatever the values of the diffusivity,
the initial concentration of contaminant, and the thickness of the packaging, provided
that L = 2H.
Thus, they behave like master curves. These master curves show noteworthy features:
i) Of course, the contaminant diffuses through the two layers, with the same diffusivity.
ii) Steep gradients are developed at the beginning of the process at the interface between
the two lms. In fact, for very low times, the concentration of contaminant falls
abruptly on the surface of the recycled layer, exhibiting a vertical curve at time 0.
iii) At any time, the concentration of contaminant at abscissa H is half the initial
concentration, when L = 2H.
iv) After innite time at equilibrium, the concentration would be uniform throughout
the two lms. Practically, when Dt/L2 = 0.6, the ratio of the concentrations Cx,0.6/Cin
reaches 99.7% of the value at equilibrium.
62
v) The concentration of the contaminant at any place through the functional barrier up
to the surface which would be in contact with the food increases in an exponential
way, as shown in Equation (2.4).
vi) The proles of concentration developed through the two layers are symmetrical with
respect to the point of coordinates both equal to 1/2 and 1/2.
2.2.2.2 Kinetics of Matter Transfer Through the Interface
The kinetics of the contaminant transferred from the recycled layer into the virgin layer
through the interface at position H located at the mid-plane of the packaging are shown
in Figure 2.3. They are calculated by using Equation (2.5) by making L = 2H.
Figure 2.3 Kinetics of the amount of diffusing substance transferred from the recycled
polymer layer into the virgin polymer layer, expressed in terms of dimensionless
values: Dt/L2 for time, and Mt/Min for the amount, with two different scales of
the dimensionless time.
63
The following two dimensionless numbers are used for the coordinates:
the amount of contaminant transferred in the virgin layer at time t as a fraction of

the amount of contaminant initially located in the recycled layer, e.g., Mt/Min;
and the time which is expressed by the other dimensionless number already
shown Dt/L2.
The following conclusions are worth noting:
i) The rate of transfer is very high at the beginning of the process, corresponding to
the vertical tangent of the curve at time 0. This fact results from the perfect contact
between the two lms of the packaging. Two different scales for the time are used in
the same Figure 2.3 in order to gain a fuller insight of this fact.
ii) The rate of the contaminant transfer decreases exponentially with time.
iii) It should be noted that after innite time, the ratio Mt/M tends to 1, and that of
Mt/Min tends to 0.5, as M = Min/2, when L = 2H.
2.2.2.3 Contaminant Concentration versus Time, at the Surface in Contact

with the Food
As the functional barrier will be in contact with the food, it is of interest to get good
knowledge of the concentration of contaminant on its external surface dened by x = L.
This concentration CL,t as a fraction of the initial concentration Cin in the recycled layer
is expressed in terms of time (or rather the dimensionless time) in Figures 2.4 and 2.5 for
various scales of the time, as they are obtained by using Equation (2.6).
Some conclusions can be drawn from Figures 2.4 and 2.5:
i) The contaminant concentration increases very slowly on this surface;
ii) Moreover, a lag time is observed over which the concentration is nearly 0; this fact
results from the time needed for the contaminant to diffuse through the virgin layer;
in that sense, this virgin layer plays the role of a functional barrier.
iii) As shown in Figure 2.4 and more precisely in Figure 2.5, this lag time could be
dened by the value Dt/L2 = 0.01 or 0.012, depending on the accuracy needed for
the contaminant concentration that is acceptable on the surface.
64
Figure 2.4 Increase in concentration of the diffusing substance with time on the
external surface, at position L, which will be in contact with the food, with the
dimensionless time Dt/L2 and the concentration CL,t/Cin, with a large scale of time.
Figure 2.5 Increase in concentration of the diffusing substance with time on the external
surface, at position L, which will be in contact with the food, with the dimensionless time
Dt/L2 and the concentration CL,t/Cin, with a short scale of the dimensionless time, up to 0.1.
65
iv) Some values of the relative contaminant concentration at the surface are given in
Table 2.1 for various dimensionless times.
These values are of great interest as they can be used whatever the parameters of
diffusion, for example, the nature of the contaminant and of the polymer, and thus the
diffusivity of this contaminant, as well as the thickness of the packaging L, provided
that the thicknesses of the layers are equal.
v) Of course, it is obvious from the dimensionless numbers that the time necessary for the
same concentration to be reached on the surface is proportional to the square of the
thickness: in other words, for a given polymer-contaminant system, when the thickness
of the functional barrier is doubled, the corresponding lag time is quadrupled.
vi) From the dimensionless number expressing the time, it is also clear that the time of
protection is also inversely proportional to the diffusivity of the contaminant. And
some values of the dimensionless times are shown in Table 2.2 for various values of
the diffusivity of contaminants in the same polymer (polypropylene).
vii) In order to show how to get the ordinary times, e.g., expressed in hours, the time at
which the concentration of contaminant reaches given values on the surface which will
be in contact with the food, are given in Table 2.2 for various contaminants whose
diffusivity is provided in the literature [6, 7]
As shown in Table 2.2, the transport is expressed in terms of the relative concentration
CL,t/Cin on the surface of abscissa L which will be in contact with the food.
Table 2.1 Relative contaminant concentration on the surface versus time

Dt/L2 8.3 x 10-3 1.16 x 10-2 1.89 x 10-2 0.1
-4 -3 -2
CL/Cin 10 10 10 0.267
Table 2.2 Time necessary for given transport of contaminants in a polypropylene

packaging of thickness L = 100 m with L = H (time in hours)
D x 1011, CL/Cin
Contaminant 2
(cm /s) 10 -2
10-3 10-4
Limonene 0.65 80.8 49.3 35.3
Ethyl acetate 15 3.48 2.15 1.55
Methane 300 0.17 0.107 0.076
Methanol 420 0.12 0.077 0.055
66
2.2.2.4 Conclusions for the Functional Barrier of Thickness Equal to That of

the Recycled Layer
Some temporary conclusions can be drawn concerning the role of the virgin layer located
between the recycled layer and the food:
i) The mathematical treatment is possible for the transfer of contaminant through the
two layers of the package when it lies alone without contact with the food. In this
case, analytical solutions expressed in terms of series are obtained.
ii) The case of the two layers of same thickness has been studied, which is reasonable, but
it seems interesting to dene the effect of the relative thickness of the two layers.
iii) The two layers being made of the same material, the diffusivity is the same in these
layers, and the partition coefcient is 1.
iv) The results have been expressed in terms of dimensionless numbers, leading to master
curves, which are of use whatever the contaminant-polymer couple and the thickness
of the packaging, provided that the two layers are made of the same material with
the same diffusivity of the contaminant, and have the same thickness.
v) The curves of interest are not only the kinetics of contaminant transfer, but also those
showing the change in the concentration of the contaminant, either at the mid-plane
or on the surface, which will be in contact with the food.
vi) Thus, it clearly appears that the virgin layer plays the role of a functional barrier,
as it is able to retard the progression of the contaminant up to the surface of the
package, which will be in contact with the food. This fact is especially true when the
dimensionless number DT/L2 expressing the time is lower than 0.01.
2.3 Bi-layer Package with Various Relative Thicknesses
2.3.1 Mathematical Treatment of the Process [1, 8]
The mathematical treatment made in Section 2.1.1, leading to the Equations (2.1) to (2.6)
can be used for any bi-layer package with various thicknesses.
All the assumptions are right, except the one concerning the relative thicknesses.
Thus, the total thickness of the packaging is always L, but the ratio H/L varies within a
rather large range.
67
2.3.2 Results with Two Layers of Different Relative Thicknesses
The results of interest for determining the efciency of the functional barrier on the transfer
of contaminant include the following:
The proles of concentration developed through the two layers;
The kinetics of transfer of contaminant from the recycled layer to the virgin layer;
The increase in the contaminant concentration on the external surface which will be
in contact with the food.
2.3.2.1 Profiles of Concentration Through the Thickness of the Package
These are calculated through the two lms which are maintained rmly in contact, so
that there is no matter resistance at their interface.
Equation (2.4) is used for this calculation, and the curves are drawn with the same dimensionless
coordinates, Cx,t/Cin for the concentration at abscissa x, and Dt/L2 for the time.
The effect of the relative thicknesses of these two layers L and H, while the total thickness
L is kept constant, can be appreciated in the following gures:
Figure 2.2 when H/L =1/2; Figure 2.6 when H/L = 1/3; Figure 2.7 when H/L = 1/4
Some conclusions can be drawn from these gures:
i) The curves drawn in these three gures are master curves, as the coordinates are
dimensionless numbers;
ii) As already stated, in Figure 2.2, with 2H = L, the curves are symmetrical with respect
to the point of coordinates both equal to 1/2 and 1/2;
iii) When the ratio of the thicknesses H/L is not 1/2, there is the same point of symmetry,
but only for short times, when the contaminant has not yet diffused up to the
external surface;
iv) Equilibrium is nearly reached when the dimensionless time Dt/L2 is 0.6 in Figure 2.2,
and 0.8 in the Figures 2.6 and 2.7;
v) The values of the concentrations at equilibrium are given by Equation (2.4) when the
series tends to 0, e.g., Cx,/Cin = H/L;
vi) The gradient of concentration of contaminant is at at the external surfaces, x = 0 and

x = L, at any time, since there is no mass transfer through these surfaces.
68
bi-layer system for various values of the dimensionless time Dt/L2 when H = L/3.
Other dimensionless values are used: for the concentration Cx,t/Cin and for abscissa x/L.
bi-layer system for various values of the dimensionless time Dt/L2 when H = L/4.
69
2.3.2.2 Kinetics of contaminant transfer through the interface
The kinetics of transfer of contaminant into the virgin layer are calculated by using the
Equation (2.5), and the curves are drawn in Figure 2.8 for the various relative thicknesses
of the two layers of the package.
The following comments can be made:
i) A vertical tangent appears at the beginning of the process, associated with a very high
value of the rate of mass transfer. This fact results from the perfect contact between
the two layers of the package.
ii) The rate of transfer of contaminant into the virgin layer decreases exponentially with
time, as shown in Equation 2.5.
iii) For a value of the dimensionless time around 0.6, the rate of transfer becomes
very low.
Figure 2.8 Kinetics of diffusing substance transferred from the recycled polymer layer
into the functional barrier, expressed in terms of dimensionless values: Dt/L2 for
time, and Mt/Min for the amount, with different values of the relative thickness H/Lof
the bi-layer system.
70
2.3.2.3 Increase in the Contaminant Concentration with Time on the External

Surface x = L
The increase in concentration of the contaminant with time at the external surface which
will be in contact with the food, at position x = L, is calculated by using Equation (2.6)
for the various values of the relative thicknesses of the two layers. The curves expressing
these variations of CL,t/Cin with the dimensionless time Dt/L2 are shown in Figure 2.9 for
times between 0 and 0.8, and in Figure 2.10 for times between 0 and 0.05.
Studying the curves can lead to the following observations:
i) The virgin layer plays the role of a functional barrier in the sense that a time exists
over which there is no contaminant on the external surface.
ii) This time of protection largely varies with the relative thicknesses of the two layers, with
the obvious statement: the larger the virgin layer, the longer the time of protection.
iii) After this time of protection, the concentration of the contaminant on the external
surface increases by following a S-shape.
dimensionless time Dt/L2 and the concentration CL,t/Cin, , for various values of the
relative thickness H/L of the bi-layer system with a large scale of time up to 0.8.
71
dimensionless time Dt/L2 and the concentration CL,t/Cin, for various values of the
relative thickness H/L of the bi-layer system with a short scale of time lower than 0.05.
iv) The concentration at equilibrium on the external surface is given by the ratio of H/L
in Equation (2.6), when the time is long enough so that the series vanishes.
v) Some values of the relative concentration of the contaminant are given in Table 2.3
by considering the unit dimensionless time of Dt/L2 = 102.
Table 2.3 Effect of the relative thickness of the two layers on the concentration
on the surface for various values of the dimensionless time Dt/L2
Unit time Dt/L2 = 102
H/L
0.1 0.2 0.5 1
-8 -5 -2
3/4 2 x 10 7 x 10 1.2 x 10 7.7 x 10-2
2/3 10-13 10-7 8.5 x 10-4 1.8 x 10-2
1/2 10-28 10-15 6 x 10-7 4.1 x 10-4
72
2.3.2.4 Conclusions on the Effect of the Relative Thicknesses of the Two

Layers in the Package
Some additional temporary conclusions are drawn on the role played by the virgin layer
in the package, and especially on the relative thicknesses of the two layers, when the total
thickness of the packaging is kept constant.
i) The same mathematical treatment can be made whatever the relative thicknesses of the two
layers, and the same Equations (2.4) to (2.6) represent the phenomenon of transfer.
ii) According to the following statement: the larger the relative thickness of the virgin
layer, the longer the time of protection, it would be of interest, initially at least, to use a
thicker virgin layer to the detriment of the thickness of the recycled layer. However, this
idea is counterbalanced by the need to recycle a large quantity of recycled polymer.
iii) Master curves are obtained by using dimensionless numbers in these gures. By reading
them, it would be possible to predict the time necessary for a given transport in terms
of the diffusivity associated with various polymer-contaminant couples, and of the total
thickness of the package as well as of the relative thicknesses of the two layers.
2.4 Three-Layer Packages
The three-layer package consists of three layers, the one made of recycled polymer being
located between the other two layers of virgin polymer, as shown in Figure 2.11.
2.4.1 Mathematical Treatment of the Process of Matter Transfer [9]
2.4.1.1 Assumptions
The following assumptions are made in order to describe the process precisely:
i) The packaging is a laminate made of three lms of the same polymer in perfect contact;
there is no resistance to mass transfer at the interface between the three lms.
ii) At the beginning of the process, the concentration of contaminant is uniform in the
recycled lm, while the virgin lms are free from contaminant.
iii) The transfer of contaminant is controlled by Fickian diffusion.
iv) The diffusivity of the contaminant is constant, and it is the same in the three lms,
since they are made of the same polymer.
73
Figure 2.11 Scheme of the three-layer film, when the recycled polymer layer is between
two virgin polymer layers, in a sandwich form. Cin is the uniform concentration of
diffusing substance initially in the recycled polymer layer. The relative abscissae are noted.
v) The contaminant does not evaporate out of the external surfaces of the package.
vi) The concentration of contaminant is so low that there is no change in the thickness
of each layer resulting from the transfer.
vii) There is no contact between the package and food.
2.4.1.2 Mathematical Treatment

Following assumptions (iii) and (iv), the transport of contaminant through the two layers
is governed by the unidirectional equation of diffusion with a constant of diffusivity:
C x , t 2C x , t
= D (2.1)
t x 2
As shown in Figure 2.11, the initial conditions are:
t=0 L1 < x < L2 Cin (2.11)

0 < x < L1 C=0
L2 < x < L C=0
74
The boundary conditions express the fact that there is no transfer of matter through the
external surface of the three-layer package:
C C
t>0 = =0 (2.12)
x 0 x L
The solution of the problem is obtained by using the method of separation of variables.
Thus, the concentration of the diffusing substance (pollutant), at time t, through the
three-layer lm is expressed by Equation (2.13):
Cx,t L 2 L1 4 1 n(L 2 L1) n(L1 + L 2 ) nx n2 2

= + sin cos cos exp 2 D t (2.13)
Cin L n =1 n 2L 2L L L
The amount of the diffusing substance (pollutant) at time t within each layer is obtained
by integrating the concentration at time t with respect to space, as follows:
Lj
M j, t = C x,t
x (2.14)
0
Thus the Equations (2.15), (2.16) and (2.17) are obtained for each layer, respectively:
M1, t L1 2L
1 nL 2 nL1 nL1 n2 2
= + 2 2 sin sin sin exp 2 D t (2.15)
M in L (L 2 L1) n =1 n L L L L
M 2, t L 2 L1 2L
1 nL 2 nL1
2
n2 2
= 2 2 sin sin exp 2 D t (2.16)
M in L (L 2 L1) n =1 n L L L
M3, t L L2 2L
1 nL 2 nL1 nL 2 n2 2
= 2 2 sin sin sin exp 2 D t (2.17)
M in L (L 2 L1) n =1 n L L L L
More important than the amount of diffusing substance located in each layer at time
t, are the concentrations obtained on each external surface. They are obtained from
Equation (2.13). By putting x = 0, the surface concentration on the surface on the left of
the Figure 2.11 is:
C0 , t L 2 L1 4 1 n(L 2 L1) n(L 2 + L1) n2 2

= + sin cos exp 2 D t (2.18)
Cin L n =1 n 2L 2L L
75
By putting x = L, the surface concentration on the surface on the right of the Figure 2.11 is:
CL , t L 2 L1 4 (1)n n(L 2 L1) n(L 2 + L1) n2 2

= + sin cos exp 2 D t (2.19)
Cin L n =1 n 2L 2L L
2.4.1.3 Note for the Sandwich with Three Layers of Equal Thickness
In this particular case, the problem looks similar to that studied in Section 2.1, by
considering the symmetry with respect to the mid-plane, at abscissa L/2. Thus the same
equations are obtained, only by making H/L = 1/3, H being the thickness of the recycled
polymer layer and L that of the three-layer lm.
The proles of concentration of the diffusing substance through the lm are given by:
Cx,t1 2 1 n nx n2 2
= + sin cos exp 2 D t (2.4)
Cin 3 n =1 n 3 L L
The kinetics of diffusing substance released from the recycled polymer layer becomes:
Mt 2 6 1 n n2 2
= 2 2 sin2 exp 2 D t (2.5)
M in 3 n =1 n 3 L
The concentration-time history on each external surface is expressed by:
CL , t 1 2 (1)n
C0, t n n2 2
= = + sin exp 2 D t (2.6)
Cin Cin 3 n =1 n 3 L
2.4.2 Results with Three Layers of Equal and Different Thicknesses
The following three results are of interest to understand the process:
The proles of concentration of the contaminant developed through the three layers.
The kinetics of transfer of the diffusing substance (contaminant).
The variation with time of the contaminant concentration on the external surfaces.
76
2.4.2.1 Profiles of Concentration Developed Through the Three-layer Film
The proles of concentration of contaminant are calculated by using Equation (2.13) in

the case where the three layers have the thickness L1, L2 L1 and L L2.
The following dimensionless numbers are used for this purpose:
Cx,t/Cin for the concentration, the relative abscissa for position, and Dt/L2 for the time.
These proles are drawn for the following various thicknesses:
In Figure 2.12 when the three layers have the same thickness;
In Figure 2.13 when L1 = 0.1; L2 L1 = 0.5; and L L2 = 0.4
In Figure 2.14 when L1 = 0.2; L2 L1 = 0.4; and L L2 = 0.4
Figure 2.12 Proles of concentration of the diffusing substance developed through

the three-layer system, for various values of the dimensionless time Dt/L2 when the
three layers have the same thicknesses. Other dimensionless values are used: for the
concentration Cx,t/Cin and for abscissa x/L.
77
three-layer system, for various values of the dimensionless time Dt/L2 when the three
layers have different thicknesses: L1 = 0.1; L2 L1 = 0.5; and L L2 = 0.4.
These proles are used to give a fuller insight into the nature of the process, leading to
the following conclusions:
i) The concentration of the diffusing substance in the recycled polymer falls abruptly
at the beginning of the process. For very short times, associated with dimensionless
times (Dt/L2) lower than 5 x 10-3, the concentration at each interface between the
recycled polymer and the functional barriers is about half the initial concentration of
the diffusing substance in the recycled polymer.
ii) Of course, these proles are symmetrical with respect to the mid-plane of the
lm, at abscissa L/2 for the case shown in Figure 2.12, when the three thicknesses
are equal.
iii) As the matter transfer proceeds, the proles of concentration become more and more
complex in Figures 2.13 and 2.14. A typical fact is worth noting: over a period of time,
the concentration of the pollutant is higher in the thinner functional barrier than in the
recycled layer, e.g., at the dimensionless times between 0.05 and 0.6 in Figure 2.13, and
78
three-layer system, for various values of the dimensionless time Dt/L2 when the three
between 0.08 and 0.5 in Figure 2.14. It is also clear from the curves shown in these
two gures that the paradoxical situation largely depends on the relative thicknesses
of the functional barrier on the left with the following statement: the lower the ratio
L1/L, the higher the maximum concentration in the thin functional barrier.
iv) In fact, this paradoxical situation shown in iii) can be easily explained by considering
the various proles of concentration developed through the thinner layer on the left
and the recycled layer in Figure 2.13. For a value of the dimensionless time Dt/L2
lower than 0.05 the matter transfer is carried out from the recycled layer into the
thinner layer, in the direction of the decreasing concentration, and as a result, a higher
concentration appears in the thinner layer. For times longer than 0.05 the matter
transfer takes place in the other direction towards the recycled layer and the thicker
functional barrier where the concentration is lower.
v) For the values around 0.2, 0.5 or 0.6 of the dimensionless time in Figures 2.12 to
2.14, the prole becomes rather at, close to equilibrium, with a uniform value equal
to L2 L1/L for the relative concentrations Cx,t/Cin.
79
2.4.2.2 Kinetics of Matter Transfer
The kinetics of the amount of diffusing substance transferred from the recycled layer into
the two functional barriers is determined by Equations (2.15) to (2.17).
These kinetics are drawn:
In Figure 2.15 when the three layers are equal;

In Figure 2.16 when L1 = 0.1; L2 L1 = 0.5; and L L2 = 0.4, and
In Figure 2.17 when L1 = 0.2; L2 L1 = 0.4; and L L2 = 0.4.
i) All the kinetics exhibit a vertical tangent at the beginning of the process. This fact
results from the perfect contact between the three layers and thus the innite coefcient
of mass transport through the two interfaces.
polymer layer into the two virgin polymer layers, expressed in terms of dimensionless
values: Dt/L2 for time, and Mt/Min for the amount, when the thicknesses of the three
layers are the same. Curve 2: kinetics of release from the recycled polymer layer;
Curves 1 and 3: kinetics of substance transferred into each virgin polymer layer.
80
Figure 2.16 Kinetics of the amount of diffusing substance transferred from the
recycled polymer layer into the two virgin polymer layers, expressed in terms of
dimensionless values: Dt/L2 for time, and Mt/Min for the amount, when the three
Curve 1: substance transferred into the virgin polymer layer of relative
thickness L1 = 0.1;
Curve 2: release from the recycled polymer layer of relative thickness L2 L1 = 0.5;
Curve 3: substance transferred into the virgin polymer layer of relative thickness
L L2 = 0.4.
ii) A typical pattern is observed for the kinetics of matter transfer in the thinner
functional barrier, as the kinetics pass through a maximum value. This paradoxical
fact corresponds with the increase in concentration of matter in the thinner functional
barrier up to higher values than the value reached at equilibrium, as already shown
in Figures 2.13 and 2.14.
iii) At equilibrium, the amount of matter located in each layer is proportional to its
relative thickness. This clearly appears in Figures 2.15 to 2.17 when the dimensionless
time Dt/L2 becomes very large, e.g., up to 0.6, and up to 0.2 in Figure 2.15.
81
polymer layer into the two virgin polymer layers, expressed in terms of dimensionless
values: Dt/L2 for time, and Mt/Min for the amount, when the three layers have different
thicknesses: L1 = 0.2; L2 L1 = 0.4; and L L2 = 0.4
Curve 1: substance transferred into the virgin polymer layer of relative thickness L1 = 0.2;
Curve 2: release from the recycled polymer layer of relative thickness L2 L1 = 0.4;
Curve 3: substance transferred into the virgin polymer layer of relative thickness
L L2 = 0.4.
2.4.2.3 Kinetics of Increase in Concentration on the External Surfaces
It is of great interest to learn more about the concentration-time histories of the diffusing
substance on the external surfaces, either from the theoretical point of view or from
a practical point of view. In fact, each functional barrier plays an important role in
protecting either the food from pollution with the barrier on the right in Figure 2.11 or
the consumers hand with the barrier on the left. It is thus of great concern to know the
concentration-time histories of the diffusing substance on the surface which will be put
in contact with the food, as well as on the other external surface. This information is
certainly useful for evaluation of the efcacy of the functional barriers and the decrease
of this efcacy with time.
82
The kinetics of the increase in concentration of the diffusing substance on the external
surfaces are shown:
In Figure 2.18 when the three layers are equal to 0.33,
In Figure 2.19 when L1 = 0.1; L2 L1 = 0.5; and L L2 = 0.4,
In Figure 2.20 when L1 = 0.2; L2 L1 = 0.4; and L L2 = 0.4.
The following conclusions are of interest:
i) The concentration-time histories for the diffusing substance are quite different for
each external surface, except in Figure 2.18 where a symmetry is shown, resulting
from the fact that the three layers have the same thickness. This difference in
the other two gures results from the different thicknesses of the two functional
barriers.
external surfaces, at position L which will be in contact with the food (curve 2), and
on the other surface at position 0 (curve 1), with the dimensionless time Dt/L2 and the
relative concentration CL,t/Cin, when the thicknesses of the three layers are the same.
83
Figure 2.19 - Increase in concentration of the diffusing substance with time on the external
surfaces, at position L which will be in contact with the food (curve 2), and on the
other surface at position 0 (curve 1), with the dimensionless time Dt/L2 and the relative
concentration CL,t/Cin, when the relative thicknesses of the three layers are as follows:
L1 = 0.1; L2 L1 = 0.5; and L L2 = 0.4.
ii) On the external surface of the thinner functional barrier, the concentration of the
diffusing substance increases slowly at the beginning of the process, and after a short
time passes through a maximum which is higher than the concentration at equilibrium.
This feature is associated with the so-called paradoxical event already noticed for the
proles of concentration and the kinetics of diffusing substance transferred.
iii) Comparison between curve 1 in Figures 2.19 and curve 1 in Figure 2.20 shows the
effect of the relative thickness of the thinner functional barrier on the concentration-
time histories, with the obvious statement: the thinner the functional barrier, the higher
the maximum.
iv) On the external surface which will be in contact with the food, which is also in contact
with the thicker functional barrier in Figures 2.19 and 2.20, the concentration of the
diffusing substance increases continuously with time up to the equilibrium value. It
is worth noticing that a short time delay can be observed in Figures 2.18-2.20, at the
very beginning of the process. This period of time of full protection results from the
84
Figure 2.20 Increase in concentration of the diffusing substance with time on the external
surfaces, at position L which will be in contact with the food (curve 2), and on the
other surface at position 0 (curve 1), with the dimensionless time Dt/L2 and the relative
concentration CL,t/Cin, when the relative thicknesses of the three layers are as follows:
L1 = 0.2; L2 L1 = 0.4; and L L2 = 0.4.
time necessary for the polluting substance to diffuse through the functional barrier; as
this time of diffusion is proportional to the square of the thickness of the functional
barrier, the time of protection is obviously larger in Figure 2.20 where there is also a
thinner recycled layer.
2.5 Bi-layer Package with Complex Situations: Different Diffusivities

and Factor Coefficient Different from One
2.5.1 Mathematical Treatment of the Process of Matter Transfer [10]
2.5.1.1 Assumptions
As shown in Figure 2.1, for a bi-layer package, the following assumptions are made in
order to clarify the process of mass transfer:
85
i) One layer contains the diffusing substance (pollutant or contaminant) while the other
is free from this substance.
ii) The initial concentration of the diffusing substance may be uniform or not.
iii) The transfer by diffusion is perpendicular to the plane surfaces of the lm.
iv) This transfer is controlled by transient diffusion, with constant diffusivities.
v) The diffusivities may be different in the two layers, resulting from the fact, for example,
that thee two polymers are different.
vi) Perfect contact is maintained at the interface separating the two layers.
vii) No evaporation of the diffusing substance occurs on the external surfaces of the lm.
viii) A partition factor may exist at the interface separating the two layers.
2.5.1.2 Mathematical and numerical treatment
The general equation of one-directional diffusion with constant diffusivity in each layer is:
C x , t 2C x , t
= D (2.1)
t x 2
Following the assumptions (i), (v) and (viii) in the previous section, the initial and boundary
conditions are expressed by:
t=0 0<x<H C = Cin (2.2)
H<x<L C=0 (2.2)
C C
t>0 D1 = D2 (2.20)
x 1 x 2
Equation (2.20) means that the rate of transfer is the same on each face of the interface,
proving also that in each layer of the lm, the value of the gradient of concentration is
inversely proportional to the diffusivity. At each interface, the partition factor is the ratio
of the concentrations of diffusing substance on each face of the interface:
86
C1
t>0 K= (2.21)
C2
In all cases, whether an analytical solution exists or not, the numerical treatment is feasible.
The thickness of the layer is divided into nite increments of space x and the increment
of time t is considered [3, 4]. The Crank-Nicolson method is used for calculation [10].
2.5.2 Results with Bi-layer Films in Complex Situations
The following results are considered and analysed in succession: the proles of concentration
of the diffusing substance developed through the two layers of the lm, the kinetics of
transfer of the diffusing substance from one layer to the other, the concentration of diffusing
substance - time histories on the external surface of the functional barrier which will be
in contact with the food.
2.5.2.1 Profiles of Concentration of the Diffusing Substance
The proles of concentration are drawn as they are obtained by a numerical treatment in:
Figure 2.21 with D1/D2 = 2 and K = 1; Figure 2.22 with D1/D2 = 10 and K = 1;
Figure 2.23 with D1/D2 = 2 and K = 2; Figure 2.24 with D1/D2 = 10 and K = 2;
In all of these Figures 2.21 to 2.24, the recycled polymer layer on the left is denoted 1,
while the virgin polymer layer on the right is denoted 2.
The following conclusions can be drawn from these curves:
i) The proles of concentration are symmetrical with respect to the mid-plane and half
the value of the concentration, only when the diffusivity is the same in the two layers,
as shown in Figure 2.2. In all the Figures 2.21 to 2.24, there is no symmetry.
ii) Based on Equation (2.20), in each layer of the lm, the gradient of concentration
is inversely proportional to the value of the diffusivity. Thus, the gradient of
concentration is steeper in the functional barrier (on the right) than in the recycled
polymer layer (on the left) where the diffusivity is higher. In the same way, the
gradient of concentration is steeper still in Figures 2.22 and 2.24 when the values
of the diffusivity are more different.
87
Figure 2.21 Proles of concentration of diffusing substance Cx,t/Cin developed through

the bi-layer system with layers of the same thickness at different times (expressed in
terms of dimensionless times Dt/L2), with different diffusivities in each layer: D1/D2
= 2, and the coefcient factor K = 1. The medium 1 (on the left) initially contains the
diffusing substance, while the medium 2 (on the right) is free from this substance.
iii) There is no discontinuity in the proles of concentration of the diffusing substance

at the interface between the two layers, as shown in Figures 2.21 and 2.22, when the
partition factor is 1. On the contrary, the concentration of the diffusing substance at
the interface between the two layers falls abruptly in the virgin layer. The partition
factor K = 2 means that at the interface, the concentration in the recycled layer is K
times that in the virgin layer, K being equal to 2 in both Figures 2.23 and 2.24.
iv) A question arises about the reason why the value of the partition factor is different
from 1. The simple answer comes from the solubility which can be different from one
polymer to another. For example, in Figures 2.23 and 2.24, it clearly appears that the
solubility of the pollutant in the virgin polymer (on the right) is two times lower than
the concentration of the pollutant in the recycled polymer layer (on the left).
v) The effect of the values of the diffusivity in each layer of the lm can be appreciated
by comparing the values of the gradient of concentration either in Figures 2.21 and
2.22 when K = 1 or in Figures 2.23 and 2.24 when K = 2.
88

the bi-layer system with layers of the same thickness at different times (expressed in
terms of dimensionless times Dt/L2), with different diffusivities in each layer: D1/D2 =
10, and the coefcient factor K = 1. The medium 1 (on the left) initially contains the
diffusing substance, while the medium 2 (on the right) is free from this substance.
vi) The diffusivity D1 in the recycled polymer layer (on the left) being much larger than
the diffusivity D2, in the virgin polymer layer (on the right), as D1 is kept the same in
Figures 2.21 (or 2.23) or in the Figures 2.22 (or 2.24), the diffusivity in the functional
barrier becomes lower and lower. As a result, the time necessary for the concentration
of pollutant to reach a given value is longer when the diffusivity in the functional
barrier is lower. That fact clearly appears by comparing the time at which equilibrium
is nearly attained, e.g., 4 for the dimensionless time Dt/L2 in Figures 2.22 and 2.24
while this time is 1 in Figures 2.21 and 2.23, and only 0.6 in Figure 2.2.
2.5.2.2 Kinetics of Transfer of the Diffusing Substance
The kinetics of transfer of the diffusing substance (pollutant or contaminant) from the
recycled polymer layer into the functional barrier are drawn in Figure 2.25, by using
dimensionless numbers for the amount of substance transferred Mt/Min and for the
time Dt/L2.
89

the bi-layer system with layers of the same thickness at different times (expressed
in terms of dimensionless times Dt/L2), with different diffusivities in each layer:
D1/D2 = 2, and the coefcient factor K = 2. The medium 1 (on the left) initially contains
the diffusing substance, while the medium 2 (on the right) is free from this substance.
The four cases considered in Figure 2.25 are:
Curve 1 with D1/D2 = 2 and K = 1;

Curve 3 with D1/D2 =2 and K = 2;
Curve 4 with D1/D2 =10 and K = 2.
The following conclusions can be drawn from these curves:
i) A vertical tangent is observed at the beginning of the process, associated with the
perfect contact between the two layers.
ii) The kinetics of transfer is faster when the value of the diffusivity is larger, for example,
with D1/D2 = 2, either when K = 1 (curve 1) or K = 2 (curve 3).
iii) Half the amount of diffusing substance initially in the recycled polymer layer can be
transferred into the functional barrier at equilibrium, when K = 1 (curves 1 and 2).
90

the bi-layer system with layers of the same thickness at different times (expressed in terms
of dimensionless times Dt/L2), with different diffusivities in each layer: D1/D2 = 10, and
the coefcient factor K = 2. The medium 1 (on the left) initially contains the diffusing
substance, while the medium 2 (on the right) is free from this substance.
One-third of this amount initially in the recycled polymer layer can be transferred into
the functional barrier under the same conditions, when K = 2 (curves 3 and 4), resulting
from the mass balance.
2.5.2.3 Concentration-time Histories of the External Surface
As already shown, the increase in concentration of the diffusing substance on the external
surface of the virgin polymer layer, playing the role of a functional barrier, which will be
in contact with the food, is of great interest.
Two gures express these results in all the four cases considered in Section 2.4:
Figure 2.26 for dimensionless times Dt/L2 as long as 2.5,
Figure 2.27 for dimensionless times Dt/L2 shorter than 0.5.
91
Figure 2.25 - Kinetics of matter transferred with the various bi-layer systems of the
same thicknesses with dimensionless time Dt/L2 and relative amount of matter Mt/Min:
Curve 1: the ratio of the diffusivities D1/D2 = 2, and K = 1; Curve 2: the ratio of the
diffusivities D1/D2 = 10, and K = 1; Curve 3: the ratio of the diffusivities D1/D2 = 2,
and K = 2; Curve 4: the ratio of the diffusivities D1/D2 = 10, and K = 2.
The four curves are noted in the same way as for the kinetics of mass transfer:

Curve 4 with D1/D2 = 10 and K = 2.
i) From the rst approach, the curves in Figure 2.26 expressing the concentration-
time histories on the external surface of the virgin polymer layer look like those in
Figure 2.25 expressing the kinetics of mass transfer.
ii) However, while a vertical tangent exists at the origin of time in the kinetics drawn in
Figure 2.25, a lag time appears for the concentration-time histories on the external
surface of the virgin polymer layer, proving then its role of functional barrier. Of
92
Figure 2.26. Concentration-time histories on the external surface of abscissa x = L, in

various cases of the bi-layer system, when the thicknesses of the layers are equal, with
dimensionless concentration CL,t/Cinand for dimensionless time Dt/L2 up to 2.5.
course, this time of full protection of the food results from the time necessary for the
pollutant to diffuse through the virgin polymer layer.
iii) As shown more precisely in Figure 2.27, the time of full protection of the food largely
depends on the following two factors: the diffusivity and the partition factor.
iv) The effect of the diffusivity clearly appears in Figure 2.26 and more precisely in Figure
2.27. For the lower value of the diffusivity D2 in the functional barrier, both the curve
2 with K = 1 and curve 4 with K = 2, depict a much lower increase in the concentration
on the external surface.
v) The effect of the value of the partition factor K on the increase in the concentration
on the external surface also appears in Figure 2.26 and 2.27. The increase in the
concentration-time histories being lower when K = 2 than for K = 1, moreover the
time of full protection is much larger.
93
Figure 2.27. Concentration-time histories on the external surface of abscissa x = L, in

various cases of the bi-layer system, when the thicknesses of the layers are equal, with
dimensionless concentration CL,t/Cinand for dimensionless time D1t/L2 lower than 0.5.
2.6 Conclusions on Multi-layer Packages
In this chapter, calculations are made for evaluating the transfer of a diffusing substance
through the two or three layers of the package, when this package is empty, without food
contact. The diffusing substance being non volatile, no transfer of this substance takes
place from the two external surfaces of the package.
This calculation is possible by using a mathematical treatment in simple cases when the
diffusivity is the same in the layers of the package. It is made by considering the method of
separation of the variables of space and time. In other more complex cases when the values of
the diffusivity are different from one layer to the other, a numerical method is employed.
The results are expressed through three ways:
The proles of concentration of diffusing substance developed through the thickness

of the package at various times, as these proles are able to provide a fuller insight
into the nature of the process.
94
The kinetics of transfer of the diffusing substance out of the recycled polymer layer.
The increase in concentration of the diffusing substance versus time on the external
surfaces, and especially on the surface which will be in contact with the food.
Various pieces of information are thus delivered:
i) When the package is kept empty over a long period of time, a transfer of diffusing
substance already takes place. This fact will be considered in the Chapters devoted
to the transfer of diffusing substance into the food.
ii) Following this previous conclusion, the calculation of the transfer of diffusing
substances into the food will be more complex, as the initial proles of concentration
in the package will not be uniform, making a numerical treatment the only possible
way to resolve the problem.
iii) The gures are drawn by using the dimensionless parameters: Dt/L2 for time, Mt/Min
for the amount of diffusing substance transferred, and CL,t/Cin for the concentration on
the external surfaces. It should be said that this fact is of great concern, as the curves
in all the gures play the role of master curves which can be used whatever the values
of all the parameters.
iv) When the polymers used in the layers of the package are similar, the diffusivity could
have the same value, and thus, the only parameters of interest are the value of the
diffusivity and the relative thicknesses of the layers.
v) When the polymers considered in the layers of the package are different, the values
of the diffusivity differ from one layer to the others. In the same way, the value of the
partition factor between the surfaces may be different from unity.
vi) Basically, the partition factor results from the difference in the solubility of the
diffusing substance in the two polymers in contact, and essentially it intervenes when
the concentration of this substance in the recycled layer is larger than its solubility
in the virgin layer.
vii) Finally, in order to reduce the transfer of the diffusing substance, there are three
parameters upon which we can act: the relative thickness of the recycled polymer layer
with respect to that of the virgin polymer layer, the values of the diffusivity in each
layer, and the value of the partition factor. Obviously, as far as possible, using for the
functional barrier a polymer having a low diffusivity for the diffusing substance, as
well as a low solubility for this substance, is the best solution.
95
References
1. S. Laoubi, A. Feigenbaum and J-M. Vergnaud, Packaging Technology and Science,

1995, 8, 5, 249.
2. Food and Drug Administration, Points to Consider for the Use of Recycled
Plastics: Food Packaging, Chemistry Considerations, FDA Division of Food
Chemistry and Technology publication HP 410, Washington, DC, USA, 1992.

UK, 1975.
4. J-M. Vergnaud, Liquid Transport Processes in Polymeric Materials, Prentice Hall,

Englewood Cliffs, NJ, USA, 1991.
5. D. Messadi, J.L. Taverdet and J-M. Vergnaud, Industrial and Engineering

Chemistry Product Research and Development, 1983, 22, 1, 142.

1995, 8, 1, 17.
7. M.R.G. Zobel, Polymer Testing, 1985, 5, 2, 153.
8. A. Feigenbaum, S. Laoubi and J-M. Vergnaud, Journal of Applied Polymer

Science, 1997, 66, 3, 597.
9. S.Laoubi and J-M.Vergnaud, Polymer Testing, 1996, 15, 3, 269.
10. I.D. Rosca, J-M. Vergnaud and J. Ben Abdelouahab, Polymer Testing, 2001, 20,
1, 59.
96
Abbreviations
C concentration of the diffusing substance
Cx,t concentration of the diffusing substance at position x and time t
Cin concentration of the diffusing substance initially in the recycled polymer

layer
CL,t concentration of the diffusing substance at position L and time t
(C/x)x,t gradient of concentration of the diffusing substance at position x and

time t
D diffusivity expressed in cm2/s
D1, D2 diffusivity of the substance in medium 1 and in medium 2, respectively
K = C1/C2 partition factor at the interface (Section 2.4)
H thickness of the recycled polymer layer in bi-layer lm
L thickness of the layer, of the lm
L1, L2 abscissa for position of the three-layer package (in Section 2.3)
M amount of diffusing substance
Min amount of diffusing substance initially in the recycled polymer layer
Mi,t amount of diffusing substance transferred at time t in the medium i
Mt/Min dimensionless term: amount transferred at time t in any medium as a

fraction of the initial amount of substance located in the recycled polymer
layer
x, abscissa taken through the thickness of the lm
t time
97
98
3
Process of Co-Extrusion of Multi-Layer Films
3.1 Scheme of the Process of Co-Extrusion

As shown in Figure 3.1, the two polymer sheets made of the recycled polymer and the virgin
polymer, previously heated separately to a temperature at which they turn out to be melted
in a highly viscous state, are put together in contact so that they can be co-extruded into
a bi-layer lm. A somewhat similar process is used for a tri-layer lm (Figure 3.2). After
co-extrusion under a very high pressure through a circular device, the bi-layer (or tri-layer)
lm shaped into a circular sheath is blown in order to stretch the lm and thus decrease its
thickness down to the desired value. Then, the tube-like sheath is drawn vertically along a
given distance necessary for the lm to cool down to a temperature at which it does not stick.
Finally, the lm can be folded up and rolled up, and bags are prepared from the sheath.
For a bottle, the process is somewhat similar, except for the machinery which should be
different, since the melted polymer is injected into a cold mould shaping the bottle. Thus
the two polymers (or the three) are injected into the mould, in succession. The second
polymer is injected while the surface of the previous one is still melted.
However, whatever the system of injection, the process of heat transfer, as well as that of
mass transfer, is shown in Figures 3.1, 3.2 and 3.3.
Figure 3.1. Scheme of the bi-layer lm showing the process of heat and mass transfers.
99
Figure 3.2. Scheme of the tri-layer lm in sandwich form showing the process of heat
and mass transfers.
Figure 3.3 (a) Scheme of heat and mass transfers through the thickness of the tri-layer
bottle, with conduction heat transfer through the polymer and mould, and convective
heat transfer on the internal surface of the bottle and on the external face of the mould.
(b) Scheme of heat and mass transfers through the thickness of the tri-layer bottle, with
convective heat transfer on the two surfaces of the bottle.
100
Of course, as soon as the two melted polymers are put into contact, mass transfer may
take place, rstly by convection when the materials are melted even if they are in a highly
viscous state, and then by diffusion through the solid afterwards. As the diffusivity is
temperature-dependent, the transfer of the diffusing substance through the layers of the
lm occurs over a short time but at a high rate.
From this fact, it is clear that a good knowledge of the process of heat transfer coupled
with the subsequent mass transfer of the diffusing substance acting as a pollutant is of
great interest. In Section 3.2, the principles of heat transfer are summarised, by considering
the heat conduction and the heat convection.
3.2 Principles of Unidirectional Heat Transfer
In spite of the fact that the lm is circular in shape, the process of heat transfer can be
taken as unidirectional through its thickness, because the thickness of the lm is much
smaller than the radius of the cross-section (circular in shape), either for the sheath or
for the bottle.
The following modes of heat transmission are considered: conduction and convection,
since radiation does not seem to play an important role.
3.2.1 Basic Equations of Heat Transfer by Heat Conduction [1-3]
Fouriers law for unidirectional conduction of heat states that the instantaneous rate of
heat ow dQ/dt is equal to the product of three factors: the area of the section A taken
at right angles to the direction of heat ow; the temperature gradient dT/dx which is
the rate of change of temperature with respect to the length of path x; and the factor of
proportionality , called the thermal conductivity, which is a physical property of the
material. Mathematically, Fouriers law is written as:
dQ dT
= A (3.1)
dt dx
Transfer of heat by conduction is due to random molecular motions, and thus there is
an analogy between the heat conduction and the matter diffusion processes. Historically,
Fourier rst established the mathematical theory of heat conduction in 1822, putting it
on a quantitative basis; and a few decades later (1855), Fick recognised the analogy and
adopted a similar mathematical theory for the diffusion of a substance.
101
By considering that the temperature is a function of time and space, Equation (3.1) can
be rewritten in the same form as Equation (1.1) written for the diffusion of matter:
T
Fx , t = (3.2)
x
where Fx,t is the rate of heat transfer per unit area of section at position x and time t.
The negative sign arises because the heat flux occurs in the direction opposite to that of
increasing temperature.
Q being expressed in calories and T in degrees Celsius, the dimensional equation of the
thermal conductivity is: cal/cm/s/deg.
The same calculation as made in Chapter 1 for the mass transport by diffusion through a
thin sheet of thickness dx leads to the main equation of heat conduction under transient
conditions:
T T
c = (3.3)
t x x
which can be reduced when does not vary with temperature and space:
T 2T
= (3.4)
t c x 2
3.2.1.1 Values of the Thermal Conductivity of a Few Materials
The thermal conductivity of a material is measured by putting a sheet of it between

the slabs made of highly conductive material kept at constant temperatures, either by
measuring the heat flux under stationary conditions, or by measuring the temperature
history at various places under transient conditions.
The order of magnitude of some polymeric materials and others, as compared with
metals, is listed in Table 3.1. These values expressed in cal/cm/s/deg are multiplied by
104 in Table 3.1.
102
Table 3.1 Values of the thermal conductivity of materials (to be divided by 104),
cal/cm/s/deg
Silicone rubber 4.2
Natural rubber 3.5
PVC 3-4
Polyamides 6 or 6,6 5-6
Asbestos-board 2.7
Copper 9 103
Low-density polyethylene 8-10
High-density polyethylene 11-12
EVA 6
Polyamide 11 7
Air 0.5
Steel alloy 18/8 500
Remarks on the sets of units: 1 cal/cm/s/deg = 360 kcal/m/h/deg = 418 W/m/deg
PVC: polyvinyl chloride; EVA: ethylene vinyl acetate
3.2.2 Heat Convection [1-3]
At the surface of the solid in contact with a uid, the heat transfer which takes place
is called heat convection. When the ux of heat transfer across the surface of the solid
is proportional to the temperature difference between the surface and the surrounding
medium (gas or liquid), the surface condition expressing the fact that the rate of heat by
conduction through the surface of the solid is continually equal to the rate of heat by
convection in the surrounding medium at the surface of the solid, is written as follows:
T
= h h (Ts Tsurrounding ) (3.5)
x
where hh is the coefcient of heat convection at the solid-uid interface, Ts is the

temperature of the solid surface, and Tsurrounding the temperature of the surrounding uid
far away from the surface.
In the same way as for the transport of matter in the surrounding uid, depending on
whether the uid is stirred or not, heat convection is called either forced or natural.
103
When the uid is forced rapidly past the surface of the solid, Equation (3.5) holds, while
the value of hh, the coefcient of heat convection at the solid-uid interface largely depends
on the rate of stirring of the uid.
When the uid is motionless, the heat convection at the surface is called natural and the
coefcient of free convection (or natural convection) is expressed in terms of the difference
of temperature (Ts Tsurrounding).
3.2.2.1 Method of Evaluation of the Coefficient of Heat Convection
To pave the way for people interested in evaluating the coefcient of convection, the
methods are briey described in the following sections, when the process is driven either
under forced or under natural convection.
3.2.2.2 Evaluation Under Forced Convection
Various studies have been made to resolve experimentally the problem of a uid circulating
in a tube. The problem of heat convection between the external surface of a cylinder and
the uid is quite different. An equation can be used expressing two dimensionless numbers,
the Nsselt (Nu) number in terms of the Reynolds (Re) number:
Nu = a (Re)n (3.6)
where the Nsselt number and the Reynolds number are given by:
hh L
Nu = (3.7)

L u
Re = (3.8)

Where L represents the main dimension of the system, e.g., diameter of a tube,
u is the velocity of the gas, a is a constant depending on the operational conditions,
and are the density and the viscosity of the gas, respectively.
Some values of the coefcients a and n are listed, as a function of the values of Re:
1< Re< 4 n = 0.33 a = 0.89

4< Re< 40 n = 0.38 a = 0.82
40< Re< 4000 n = 0.47 a = 0.61
104
3.2.2.3 Natural (Free) Heat Convection
With free convection, when the gas is motionless, three dimensionless numbers are
considered, the Nsselt number, the Grashof (Gr) number and the Prandtl (Pr) number:
g 2 L3
Gr = T (3.9)
2
c
Pr = (3.10)

where g is the acceleration due to the gravity,

and are the cubic expansion and the density of the gas, respectively,
c is the specic heat of the gas,
L is the representative dimension of the system, plane height or cylinder diameter, and
T = Ts Tsur
The Nsselt number is expressed in terms of the other two dimensionless numbers:
Nu = a (Gr Pr)n (3.11)
The values of a and n depend on the nature of the convection, as follows:
Laminar state, with 104 < Gr Pr < 109 n = 0.25

Turbulent state with Gr Pr > 109 n = 0.33
Vertical plane or cylinder laminar: a = 0.56 turbulent: a = 0.12
Horizontal cylinder laminar: a = 0.47 turbulent: a = 0.10
Horizontal plane facing upward laminar: a = 0.54 turbulent: a = 0.14
Horizontal plane facing downward laminar: a = 0.24 turbulent: a = 0.14
3.3 Coupled Heat and Mass Transfer in Bi-Layer Films
3.3.1 Theoretical Treatment of the Transfer of Heat
It is assumed that as soon as the two layers are in contact, this time being considered as
the origin of time, the temperature is uniform through the bi-layer system of thickness L,
leading to the initial condition:
t=0 L < x < +L
T = Tin (3.12)
105
On each surface of the lm, heat is transferred from the solid into the surrounding
atmosphere by convection, and the boundary conditions express the fact that the rate at
which heat is transferred by convection is constantly equal to the rate of the heat which
is brought to the surface by internal conduction:
t>0 x = L and x = +L (3.13)
T
x
where hh is the coefcient of heat convection at the solid-uid interface,

Ts is the temperature of the solid surface, and Tsurrounding the temperature of the surrounding
uid far away from the surface which is kept constant.
Unidirectional heat transfer by conduction takes place through the lm, by assuming that
the heat conductivity is independent of the temperature:
t>0 L < x < +L
T 2T 2T
= 2 = 2 (3.14)
t c x x
with the thermal diffusivity dened by:

= (3.15)
c
Finally, the solution of the problem of heat transfer through the solid lm in contact with
the surrounding uid is obtained by resolving Equations (3.5) and (3.14), with the initial
temperature uniform through the solid.
3.3.1.1 Case of Constant Thermal Parameters
When all the thermal parameters are independent of temperature, an analytical solution
exists. This solution is expressed in the similar form as that shown for the transfer of
matter in Equation (1.52) in Chapter 1 [1-3]:
x
2R h cos n
Tx , t Tsur
t
= L exp 2n 2 (3.16)
Tin Tsur n =1 cos n (n + R h + R h )
2 2
L
106
where:
hh L
Rh = (3.17)

while the n are obtained from the relationship:
tan = R h (3.18)
3.3.1.2 Case of Temperature-Dependent Thermal Parameters
In this more general case, no analytical solution exists, and the problem should be resolved
by using a numerical treatment, as shown in various papers [4-10].
3.3.2 Theoretical Treatment of the Mass Transfer Coupled with the Heat Transfer
As shown in Figure 3.1 with the bi-layer lm, the initial conditions for the diffusing
substance are expressed by:
t=0 L < x < 0 C = Cin recycled layer (3.19)

0 < x < +L C=0 virgin layer
The boundary condition expresses the fact that the diffusing substance does not evaporate
out of the surfaces of the lm. In fact, the lm remains at a high temperature over a short
time. Let us note that this assumption is not mandatory as shown in [5].
C C
t>0 = =0 (3.20)
x L x +L
The proles of concentration of the diffusing substance are expressed in terms of space
and time by the relationship:
C C
= DT (3.21)
t x x
where DT is the temperature-dependent diffusivity of the substance, which is dened as:
E
DT = D0 exp (3.22)
RT
107
D0 being a constant characterising the polymer-diffusing couple, E the energy of activation,

expressing the temperature dependency of the diffusivity, R is the ideal gas constant, and
T the local temperature which varies with time and space.
3.4 Evaluation of Heat and Mass Transfers in Bi-Layer Films
Two kinds of results are given separately: those concerned with the heat transfer, expressed
in terms of the temperature-time histories in various parts of the lm and of the proles
of temperature developed through the thickness of the bi-layer lm; the other related
to the transport of the contaminant by diffusion, expressed in terms of the proles of
concentration of this diffusing substance developed through the thickness of the lm.
Two bi-layer lms whose layers have the same thickness are considered, with the total
thickness for the lm of 0.01 and 0.03 cm, respectively.
Polyethylene terephthalate is chosen for the polymer - its thermal properties are found in
the literature [11]. The values of the diffusivity at high temperature are not known yet, and
some assumptions are made from the value at room temperature [12, 13] (Table 3.2).
Table 3.2 Characteristics of the polymer for heat and mass transfers
Heat transfer = 10-3 + 10-7 T cal/cm/s/deg Temperature, C
through the
polymer = 10-3 + 7 10-7 T cm2/s Temperature, C
Heat transfer
hh = 0.5 and 0.05 cal/cm2/s/deg
by convection
D300 = 10-6 D250 = 10-7 D30 = 10-12 cm2/s
Diffusion of
the matter 8655
D = 2.42 exp cm2/s Temperature, K
T
3.4.1 Consideration of the Process of Heat Transfer
For a lm, the polymer sheath is moving with a rather high speed, leading to a forced heat
convection between the sheath surface and the surrounding air. Thus heat is transferred
either by forced convection at the lm-air interface or by conduction through the thickness
108
of the lm. It is assumed that the process of heat convection is similar on each surface of
the lm. In the case considered here, the coefcient of convective heat transfer should be
evaluated by using Equations (3.6) to (3.8). From these equations, it clearly appears that
the value of hh largely depends on the value of the diameter of the sheath which stands
in both Equations (3.7) and (3.8), with the Nsselt number (where L, the representative
dimension, plays the role of the diameter) and the Reynolds number. It should be noticed
that the velocity of air u usually used in the Reynolds number is in the present case the
velocity of the sheath in motionless air.
As the diameter of the polymer sheath varies within a wide range, depending on the nal
use of the lm, the values of the Nsselt and of the Reynolds numbers also vary largely.
This is the reason why, as examples, two very different values are selected for the coefcient
of heat convection: hh = 0.5 and 0.05, expressed in cal/cm2/s/deg.
The two layers being made of the same polymer and with the same thickness, the interface
between the recycled and virgin layers at abscissa 0 plays the role of a plane of symmetry,
since the effect of the contaminant must be of very low effect.
Thus the effect of the two main parameters of interest, e.g., the thickness of the lm and the
value of the coefcient of convective heat transfer, is examined intensively for the process of
heat transfer and consequently for the process of mass transfer of the diffusing substance.
Because of the temperature-dependency of the thermal parameters, Equation (3.16)

dening the proles of temperature developed though the thickness of the lm cannot be
used. Thus only a numerical treatment is feasible, as shown in previous papers [4-10]. In
fact, the same numerical model is used for evaluating either the proles of temperature
or the proles of concentration of the diffusing substance. In this numerical model, the
thickness of the lm is divided into N equal sections of same thicknesses, and the time
is divided into increments of time. Thus at each time, the proles of temperature and of
concentration are evaluated.
It should be noticed that at that time it is difcult to measure the value of the diffusivity
at high temperature, and the values shown in Table 3.2 are estimated.
3.4.2 Effect of the Value Given to the Coefficient of Heat Convection
In order to determine the effect of the heat convection at the lm-air interface, the following
gures are drawn, by keeping the thickness of the lm constant at 0.03 cm, and varying
the coefcient of heat convection within a wide range, from 0.5 to 0.05 cal/cm2/s/deg.
Figure 3.4: Temperature-time histories in various places of the 0.03 cm thick bi-layer lm.
109
Figure 3.5: Proles of temperature developed through the thickness of the 0.03 cm thick
lm at various times (in seconds) with hh = 0.5 cal/cm2/s/deg.
Figure 3.7: Proles of concentration of the diffusing substance developed through the
thickness of the 0.03 cm thick lm, with hh = 0.5 cal/cm2/s/deg.
From the curves drawn in Figures 3.4 3.8 obtained with a 0.03 cm thick lm, and the
two values of the coefcient of forced convection hh of 0.5 and 0.05 cal/cm2/s/deg, the
following conclusions are worth noting:
i) The temperature decreases rather quickly from its initial value down to room
temperature, as shown in Figure 3.4. The temperature-time histories decline in a
continuous manner, as no physical transformation of the polymer, e.g., solidication
or crystallisation, is considered in the present calculation. Of course, the temperature
of the surface falls almost as quickly, but not exactly abruptly because of the presence
of the nite coefcient of convective heat transfer at these surfaces. The temperature
decreases more slowly in the middle of the sheet than on the surface. Moreover, the
temperature seems to be kept constant in the mid-plane for a very short period of
time of nearly 0.01-0.015 s, as it takes some time for heat to be transferred from
the middle to the surface of the lm by conduction.
ii) The effect of the value given to the coefcient of convection ht on the cooling process
is very large, precisely as shown in Figure 3.4 in all places of the lm.
iii) The proles of temperature developed through the thickness of the lm provide a
fuller insight into the nature of the process of heat transfer. As already said, there
is a plane of symmetry at the middle of the lm, depicted in Figures 3.5 and 3.6.
The effect of the values given to the coefcient of convection ht also appears on the
proles of temperature by comparing the curves drawn in the Figures 3.5 and 3.6.
On the one hand, the higher value of hh at 0.5 is responsible for steeper proles; on
the other hand, while 0.4 seconds is necessary for the temperature within the lm
to reach the room temperature, a time much longer than 0.6 seconds is mandatory
to attain the same result when hh is 0.05.
110
Figure 3.4. Temperature-time histories in various places of the 0.03 cm thick bi-layer
lm initially at 300 C cooled in air at 20 C. (1) surface; (2) mid-plane with
hh = 0.5 cal/cm2/s/deg. (1) surface; (2) mid-plane with hh = 0.05 cal/cm2/s/deg.
Figure 3.5. Proles of temperature developed at various times (seconds) through the
thickness of the bi-layer lm of total thickness 0.03 cm; hh = 0.5 cal/cm2/s/deg.
111
thickness of the bi-layer lm of total thickness 0.03 cm; hh = 0.05 cal/cm2/s/deg.
Figure 3.7. Proles of concentration of the diffusing substance (contaminant) developed

at various times (seconds) through the thickness of the bi-layer lm of total thickness
0.03 cm whose layers are equal; hh = 0.5 cal/cm2/s/deg. Concentration as a fraction of
the uniform concentration of the contaminant initially in the recycled layer Cx,t/Cin.
112
Figure 3.8. Proles of concentration of the diffusing substance (contaminant) developed

at various times (seconds) through the thickness of the bi-layer lm of total thickness
0.03 cm whose layers are equal; hh = 0.05 cal/cm2/s/deg. Concentration as a fraction of
the uniform concentration of the contaminant initially in the recycled layer Cx,t/Cin.
iv) As shown in Figures 3.7 and 3.8 which depict the proles of concentration of
the diffusing substance developed through the thickness of the lm, a signicant
transfer of matter is observed. At the beginning of the process of heat and mass
transfer, the concentration of the substance falls abruptly, resulting from the perfect
contact between the two layers of the lm. It should be noticed that these curves
are symmetrical with respect to the value Ct/Cin = 0.5 and the abscissa 0 which
denes the mid-plane of the lm.
v) The effect of the value given to hh on the proles of concentration clearly appears
by comparing the curves drawn in Figures 3.7 and 3.8. Thus, at very short
times, e.g., lower than 0.01 s, the proles are similar, whatever the value given
to this coefcient of heat convection. However, for longer times, the proles of
concentration become quite different in these two gures. When hh = 0.5 in Figure
3.7, the proles of concentration remain nearly the same for times longer than
0.05 s. When hh = 0.05 in Figure 3.8, the proles of matter concentration expand
up to 0.2 s.
113
3.4.3 Effect of the Thickness of the Film on the Transport of Heat and Matter
The effect of the thickness of the lm on the process of heat transfer and on the subsequent
mass transfer is acquired by making the same calculation for a 0.01 cm thick lm as that
made for the thicker lm. The other conditions are kept the same, for the coefcient of
convective transfer as well as for the heat and mass transfer. The results obtained are
expressed in terms of the following gures presented in a similar way as those drawn for
a lm with a thickness of 0.03 cm.
Figure 3.9: Temperature-time histories in various places of the 0.01 cm thick bi-layer lm.
Some conclusions of interest can be drawn from these curves:
i) In Figure 3.9, the temperature-time histories look like those drawn in Figure 3.4, except
for the values of time. In fact, about the same decrease in temperature is obtained
after 0.05 s for the 0.01 thick lm, while 0.4 s is necessary for the 0.03 cm thick lm.
By considering the dimensionless number t/L2 which appears in Equation (3.16),
it seems clear that the time necessary for a given heat transfer is proportional to the
square of the thickness of the lm. But this conclusion is only true when the values of
Rh and of the ns are the same in both cases. However, the coefcient of heat transfer
by convection hh depends on the operational conditions of the sheath production,
essentially characterised by the Reynolds number, with the diameter of the sheath
and the speed of circulation of this sheath. This is the reason why it is not possible
to express the results for the temperature decrease obtained for the lms of different
thicknesses on the same gure by putting t/L2 instead of time in abscissa.
ii) Similar conclusions can be traced by comparing the proles of temperature obtained
with the same value of hh = 0.5 and different thicknesses in Figures 3.5 and 3.10, and
the other value of ht = 0.05 in Figures 3.6 and 3.11. Finally, it can be said that these two
parameters, e.g., thickness and coefcient of convective heat transfer hh independently
play an important role in the process, while the statement holds true that the larger
the value of hh, the better t is attained by plotting t/L2 instead of time.
114
Figure 3.9. Temperature-time histories in various places of the 0.01 cm thick bi-layer
lm: (1) surface; (2) mid-plane with hh = 0.5 cal/cm2/s/deg . (1) surface; (2) mid-plane,
with hh = 0.05 cal/cm2/s/deg.
thickness of the bi-layer lm of total thickness 0.01 cm and hh = 0.5 cal/cm2/s/deg.
115
Figure3.11. Proles of temperature developed at various times (seconds) through the

thickness of the bi-layer lm of total thickness 0.01 cm and hh = 0.05 cal/cm2/s/deg.
Figure 3.12. Proles of concentration of the diffusing substance developed at various

times (seconds) through the thickness of the bi-layer lm of total thickness 0.01 cm
whose layers are equal and hh = 0.5 cal/cm2/s/deg. Concentration as a fraction of the
uniform concentration of the contaminant initially in the recycled layer Cx,t/Cin.
116
Figure 3.13 Proles of concentration of the diffusing substance developed at various

times through the thickness of the bi-layer lm of total thickness 0.01 cm whose layers
are equal, and hh = 0.05 cal/cm2/s/deg. Concentration as a fraction of the uniform
concentration of the contaminant initially in the recycled layer Cx,t/Cin.
iii) From the rst approach only, the proles of concentration of the diffusing substance
developed through the thickness of the lm look similar to each other by comparing either
Figures 3.7 and 3.12 obtained with hh = 0.5 or Figures 3.8 and 3.13 drawn with hh = 0.05.
Of course the time is different, being roughly proportional to the square of the respective
thickness of the lms. If this conclusion is only true for the larger value of hh = 0.5 (Figures
3.7 and 3.12), it is far from being exact for the lower value of hh = 0.05.
iv) Finally, as a matter of conclusion, it should be said that no simple law or gure is
able to dene exactly either the proles of temperature or the subsequent proles of
concentration obtained under these operational conditions, by using master curves with
dimensionless numbers. The reason is the presence of the coefcient of convective heat
transfer which does not depend on the thickness of the lm, leading to different values
of the dimensionless number Rh (dened by Equation (3.17)) when the thickness of
the lms is varied from 0.01 to 0.03 cm. In other words, only when the number Rh is
kept constant whatever the thickness of the lm (meaning that the value of hh should
be inversely proportional to the thickness L), could the process of heat and of mass
transfer could be expressed through single curves by plotting t/L2 in the abscissa.
117
v) Let us mention that all the curves in Figures 3.7, 3.8 and 3.12 and 3.13 are drawn by
using dimensionless numbers, either for the concentration Ct/Cinor for the space x/L.
vi) It is easy, but not highly informative, to predict that a lower value of the coefcient of
convective heat transfer hh during the cooling process of the sheath associated with a lower
thickness of the lm is responsible for a larger transport of the diffusing substance.
3.4.4 Simultaneous Effect of the Thickness of the Film and the Coefficient of
Convective Heat Transfer
As shown in Equation (3.17), the thickness of the lm L and the coefcient of convective
heat transfer hh are connected to each other. As a conclusion, when the product of the
values of these two parameters are kept constant, the resulting constant value of the
dimensionless number Rh leads to similar values of n and thus is responsible for similar
proles of temperature developed through the thickness of the lm at any time along the
cooling process. This fact can be observed in Figures 3.14 and 3.15 where the proles of
temperature (Figure 3.14) and of the subsequent proles of concentration of the diffusing
substance (Figure 3.15) are shown with the following data:
Figure 3.14 curve 1: L = 0.01 cm hh = 0.15 cal/cm2/s/deg

Figure 3.15 curve 2: L = 0.03 cm hh= 0.05 cal/cm2/s/deg
Some conclusions are worth noting:
i) In Figure 3.14, the proles of temperature are very similar at the beginning of the
process of decrease in temperature, when the time is lower or equal to 0.01 s. However
for times larger than 0.1 s, a small but signicant difference is observed for these
proles. This difference results from the fact that the other thermal parameters and
vary with time.
ii) In spite of the small difference in the proles of temperature appearing for the lower
values of the temperature, the proles of concentration of the diffusing substance
developed through the thickness of the lm expand in the same way, whatever the
value of the thickness of the lm, as shown in Figure 3.15.
iii) Master curves are obtained in these Figures 3.14 and 3.15, which can be used whatever
the value of the thermal and diffusion parameters.
iv) However, maintaining Rh as constant, means that the following statement should hold:
the lower the thickness of the lm, the larger the value of the coefcient of convective
heat transfer, which is not easy to follow, at least in a quantitative manner.
118
Figure 3.14 Proles of temperature developed through the thickness of the two
lms during the cooling process from 300 C in air at 20 C: Curve 1: L = 0.01 cm,
hh = 0.15 cal/cm2/s/deg; Curve 2: L = 0.03 cm, hh = 0.05 cal/cm2/s/deg
Figure 3.15 Proles on concentration of the diffusing substance expanded through

the thickness of the two lms, resulting from the cooling process shown in
Figure 3.12. Curve 1: L = 0.01 cm, hh = 0.15 cal/cm2/s/deg; Curve 2: L = 0.03 cm,
hh = 0.05 cal/cm2/s/deg
119
3.5 Evaluation of Heat and Mass Transfers in Tri-Layer Film
The process of heat and mass transfers in a tri-layer lm, when the recycled polymer layer
is surrounded by two virgin polymer layers, is shown in Figure 3.2.
In this section, the thermal and diffusion parameters, described in Table 3.3 are somewhat
similar to those shown in Table 3.2, except for the number of layers.
Thermal
= 10-3 + 10-7 T cal/cm/s/deg Temperature, C
conductivity
Thermal
= 10-3 + 7 10-7 T cm2/s Temperature, C
diffusivity
Heat transfer
hh = 0.5 and 0.05 cal/cm2/s/deg
by convection
D300 = 10-6 D250 = 10-7 D30 = 10-12 cm2/s
Diffusion of
8655
the matter D = 2.42 exp cm2/s Temperature, K
T
The temperature-time histories in various planes of interest are shown in Figure 3.16,
and the proles of temperature developed through the thickness of the lm are shown in
Figure 3.17; the subsequent proles of concentration of diffusing substance are evaluated
in Figure 3.18.
120
Figure 3.16. Temperature-time histories in various places of the 0.03 cm thick tri-layer
lm with layers of same thicknesses: (1) surface; (2) mid-plane with hh = 0.5 cal/cm2/s/deg.
thickness of the tri-layer lm of total thickness 0.03 cm with layers of same thickness
and hh = 0.5 cal/cm2/s/deg.
121
Figure 3.18. Proles of concentration of the diffusing substance developed at various

times (seconds) through the thickness of the tri-layer lm of total thickness 0.03 cm
whose layers are equal and hh = 0.5 cal/cm2/s/deg. Concentration as a fraction of the
uniform concentration of the contaminant initially in the recycled layer Cx,t/Cin.
3.5.1 Theoretical Study of Heat and Mass Transfers

The process of heat and mass transfers through the tri-layer lms is similar to that in bi-
layer lms. Thus the theoretical treatment described in Section 3.3.1 is of value for the
heat transfer, and the theoretical treatment described in Section 3.3.2 can be used for the
mass transfer controlled by diffusion.
When the thermal parameters are constant, Equation (3.16) can be used in the case of
forced convection on both surfaces with the same coefcient of convective convection hh
which appears in Equation (3.17) expressing the dimensionless number Rh.
However, a numerical treatment is made, based on nite differences, for the following
two reasons: the thermal parameters are temperature-dependent, and the diffusivity of
the coupled mass transfer controlled by diffusion is also temperature-dependent.
3.5.2 Heat and Mass Transfers in a Tri-Layer Film

The results are expressed in terms of temperature-time histories selected in various planes
of interest (Figure 3.16), of proles of temperature developed through the thickness of
122
the lm at various times (Figure 3.17) and of proles of concentration of the diffusing
substance expanded through the thickness of the lm (Figure 3.18).
From Figures 3.16 to 3.18, the following conclusions are worth noting:
i) As the coefcient of heat transfer is the same on both sides of the lm, the proles of
temperature developed through the thickness of the lm are symmetrical, the plane
of symmetry being the mid-plane of the lm at the relative abscissa x/L of 1.5, in
Figure 3.17.
As already stated, these proles of temperature developed through the thickness of

the lm in the case of forced heat convection can be dened by Equation (3.16) when
the thermal parameters are constant.
ii) The temperature-histories shown in Figure 3.16, because of the symmetry with respect
to the mid-plane x/L = 1.5, are similar at the two interfaces between the recycled layer
and the two virgin polymer layers, at the relative abscissa 1 and 2, respectively.
iii) For times longer than 0.2 s, the proles of temperature become nearly at, the
temperature through the lm reaching that of the surrounding air.
iv) The results concerned with the proles of concentration follow the results obtained
for the heat transfer. Thus the proles of concentration of the diffusing substance
developed through the lm are symmetrical with the plane of symmetry at the mid-
plane x/L = 1.5. This symmetry results from two facts: the proles of temperature
developed through the lm are symmetrical, and the thicknesses of the two virgin
polymer layers surrounding the recycled polymer layer are equal.
v) Under the cooling conditions with forced convection on both sides of the lm with the same
coefcient of forced convection hh = 0.5 cal/cm2/s/deg, the nal prole of concentration is
attained at around a time of 0.1 s. In fact, at that time, the temperature through the lm
is low enough for the diffusivity of the diffusing substance to become very low.
3.6 Heat and Mass Transfers in Tri-Layer Bottles with a Mould at

Constant Temperature on the External Surface
3.6.1 Theoretical Treatment of the Process
This important problem has been already studied a few years earlier [7], by considering
the following operational conditions:
i) After injection of the polymeric materials in the cold mould, heat is transferred by
conduction either through the polymer or through the mould (Equation (3.3)). The
123
rate of heat transfer on each side of the polymer-mould interface is the same, leading
to Equation (3.23), where the thermal conductivity in the polymer and the mould
as well as the gradients of temperature next to the surfaces appear on each side of
this equation.
ii) After extraction of the bottle out of the mould, heat is transferred by conduction
through the three polymer layers and by free convection on both sides.
iii) The temperature of the surrounding air is constant far away from the external surface,
while it varies with time inside the bottle.
The rst condition at the polymer-mould interface is expressed by:
T T
p = m (3.23)
x p x m
The heat transfer by conduction in each medium (mould, PET) is expressed by:
T T
c = (3.3)
t x x
The condition on the external surface of the mould when the polymer is in it, as well as
on the external and the internal surfaces of the bottle when it has been removed from
the mould is written by using Equation (3.5), where the temperature (Tsurrounding) is kept
constant far away from the mould and from the bottle.
T
x
The condition on the internal surface of the bottle, leads to the following equation
expressing the fact that the volume of air (V) enclosed in the bottle is heated - the
variation of the temperature of the air located inside the bottle with time is obtained
from this relationship:
dQ = V ( c)air dT (3.24)
These assumptions made on both surfaces of the package are true, but the heat capacity
of the enclosed air depends on the volume V of the bottle.
124
3.6.2 Heat and Mass Transfers with Heat Conduction through the Mould
and Polyethylene Terephthalate (PET) and Heat Convection on the
External Surfaces
The values of the parameters of the thermal and mass transfers are collected in Table 3.4.
Thermal PET = 103 + 107 T cal/cm/s/deg
Temperature, C
conductivity Steel = 0.038 cal/cm/s/deg
Thermal PET = 103 + 7 107 T

cm2/s Temperature, C
diffusivity Steel = 0.04
Air density = 1.298 0.005 T g/l Temperature, C
Air specic
Cp = 0.24 1.4 105 T cal/g/K Temperature, K
heat
Steel specic
Cp = 0.12 cal/g/K
heat
Heat transfer
H = 7 104 (T0 Tsurrounding)0.25 cal/cm2/s/deg
by convection
D300 = 106 D250 = 107 D30 = 1012 cm2/s
Diffusion of
the matter 8655
D = 2.42 exp cm2/s Temperature, K
T
Operational conditions
PET Initial temperature = 280 C
Initial temperature = 8 C
Mould
External surface kept at 8 C
Thickness of the PET bottle 0.03 cm, also 0.06 cm
Thickness of the mould 1.5 cm
External temperature of air 20 C
Initial temperature of air in the bottle 20 C
Time of residence of the bottle in the mould 1 second
125
3.6.3 Results Obtained with the 0.03 cm Thick PET Bottle
The results are expressed either in terms of the proles of temperature developed through
the thickness of the PET bottle and of the mould or in terms of mass transfer of the additive
through the thickness of the bottle. The following gures are drawn, as they are obtained
from calculation using a numerical model:
Figure 3.19 describing the temperature-time histories obtained in various places selected
through the thickness of the PET bottle.
Figure 3.19A showing the variation of the uniform temperature of the volume of air
(1 litre) located inside the bottle.
Figure 3.20 picturing the proles of temperature developed through the thickness of the
PET bottle at various times.
Figure 3.20A depicting the proles of temperature developed through the thickness of
the mould at various times.
Figure 3.21 representing the proles of concentration of the diffusing substance expanded
through the thickness of the bottle at various times.
From these Figures 3.19-3.21, the following conclusions are worth noting:
i) As shown in Figure 3.19, the temperature on the surface of the PET bottle in contact
with the mould falls abruptly to a temperature around 60 C, and afterwards decreases
slowly with time to around 50 C when the bottle is removed from the mould.
During the same time (1 second in the mould), the temperature decreases slowly with
time, up to around 60 C on the internal surface that is in contact with air.
ii) During this 1 second, the temperature of the air located inside the bottle increases
from the room temperature (20 C) up to 100 C and then decreases continuously
with time down to 82 C after 1.25 second (Figure 3.19A).
iii) The proles of temperature expanded through the thickness of the PET bottle shown
in Figure 3.20 at various times bring a fuller insight into the nature of the process
of cooling. The temperature falls abruptly on the surface in contact with the mould,
while the temperature decreases rather slowly on the internal surface of the bottle
(at the abscissa x = 3L). Nevertheless, after 1 second in the mould, the temperature
throughout the thickness of the PET bottle is nearly uniform at around 50 C.
126
Figure 3.19. Temperature-time histories in various places when the bottle is cooled down
by conduction heat transfer through the polymer and mould, and convective heat transfer
on the internal surface. L = 0.03 cm. Initial temperature of the PET: 280 C; external
temperature of the mould kept at 8 C. 0: PET surface in contact with the mould; other
places noted L, 2L; 3L: internal PET surface in contact with air.
Figure 3.19A. Temperaturetime histories of the air located in the 1 litre bottle, under
the same conditions as shown in Figure 3.19.
127
Figure 3.20. Proles of temperature developed at various times (seconds) through

the thickness of the bottle when it is cooled down with a free convective heat
transfer on the internal surface and conduction heat transfer on the external surface.
PET thickness = 0.03 cm. Initial temperature of PET = 280 C. External temperature of
the mould kept at 8 C. Mould thickness = 1.5 cm.
Figure 3.20A. Proles of temperature developed at various times (seconds) through

the thickness of the mould whose temperature is kept at 8 C on the external surface.
Mould thickness = 1.5 cm; PET thickness = 0.03 cm. Initial PET temperature 280 C.
128
Figure 3.21. Proles of concentration of the diffusing substance developed through the
thickness of the bottle when it is cooled down under the conditions of Figure 3.20. PET
thickness = 0.03 cm. Initial temperature of PET = 280 C. External temperature of the
mould kept at 8 C. Mould thickness = 1.5 cm.
iv) The proles of temperature developed through the thickness of the mould (Figure
3.20A) bring complementary information on the cooling process. The surface of the
mould in contact with the polymer quickly increases up to around 60 C. At 1 second,
the prole of temperature through the thickness of the mould tends to be linear from
8 C to 43 C.
v) The proles of concentration of the diffusing substance expanded through the

thickness of the PET bottle (Figure 3.21) are able to provide the following relevant
information:
the proles of concentration are far from being symmetrical, this fact resulting from
the difference in the cooling processes applied on the two sides of the PET bottle.
the contaminant has diffused much more in the direction of the surface in contact with
the air located in the bottle; this fact will be a drawback for the food protection.
after around 0.2 second, the rate of diffusion of the contaminant becomes so low that
it can be neglected.
129
vi) In conclusion, the cooling process is far more efcient on the side of the bottle in contact
with the mould than on the other side in contact with air. Moreover, the injection of
cold air at temperatures lower than 20 C should not bring a signicant improvement.
Only injection of air with ne droplets of liquid in it that can be vaporised could be
a solution.
vii) As precisely shown with Equation (3.23), heat transfer taking place through two solid
media is driven by conduction. This is in contradiction with the assumption made
by some authors [14] considering that the cooling process of the PET lm would be
handled by forced convection, the metal mould playing the role of surrounding air
strongly stirred.
3.6.4 Results Obtained with a 0.06 cm Thick PET Bottle
The same calculation made with a much thicker PET bottle (0.06 cm) leads to some
relevant results, expressed by the following gures:
Figure 3.22 with the temperature-time histories at various places selected through the PET
thickness, as well as on the mould surface in contact with the bottle.
Figure 3.22A showing the variation of the uniform temperature of the volume of air (1
litre) located inside the bottle.
Figure 3.23 picturing the proles of temperature developed through the thickness of the
PET bottle at various times when the bottle is in the mould up to 1 second.
Figure 3.24 representing the proles of concentration of the diffusing substance expanded
through the thickness of the bottle at various times.
From Figures 3.22 3.24 the following comments of interest are noted:
i) As shown in Figure 3.22 the temperature on the surface of the PET bottle in contact
with the mould falls abruptly to a value around 60 C, in the same way as for the
thinner thickness of 0.03 cm. Comparison between Figures 3.19 and 3.23 is of
interest, as it shows precisely the effect of the thickness of the bottle. The temperature
in various places within the thickness of the bottle decreases more slowly with the
larger thickness. For example, after 2 seconds, the temperature on the PET surface in
contact with the air still remains at around 130 C.
ii) During the time of 1 second, the temperature of the volume of air located in the 0.06
cm thick bottle reaches the high value of 180 C (Figure 3.22A), instead of a little
more than 100 C attained when the thickness is 0.03 cm (Figure 3.19A).
130
Figure 3.22. Temperature-time histories in various places when the bottle is cooled
down by conduction heat transfer through the polymer and mould, and convective heat
transfer on the internal surface. PET thickness = 0.06 cm. Initial temperature of the
PET: 280 C; external temperature of the mould kept at 8 C. 0: PET surface in contact
with the mould; other places noted L, 2L; 3L: internal PET surface in contact with air.
Figure 3.22A. Temperaturetime histories of the air located in the 1 litre bottle, under
the same conditions as shown in Figure 3.22.
131

PET thickness = 0.06 cm. Initial temperature of PET = 280 C. External temperature of
the mould kept at 8 C. Mould thickness = 1.5 cm.
thickness of the bottle when it is cooled down under the conditions of Figure 3.22. PET
thickness = 0.06 cm. Initial temperature of PET = 280 C. External temperature of the
mould kept at 8 C. Mould thickness = 1.5 cm.
132
iii) The proles of temperature developed through the thickness of the PET bottle are
of great interest (Figure 3.23). Thus a thickness of 0.06 cm is responsible for higher
values of the temperature within the bottle, since after 1 second, the temperature on the
surface in contact with the air is not less than 180 C, and the prole of temperature
is far from being at.
iv) The proles of concentration of the diffusing substance developed through the thickness
of the PET bottle shown in Figure 3.24 provide information not only on the cooling and
diffusion processes but also on the effect of the thickness given to the PET bottle:
in the same way as for the thickness of 0.03 cm, the proles of concentration of the
diffusing substance are not symmetrical.
the contaminant diffuses much more towards the side of the PET bottle in contact
with the air located in it.
after a time of not less than 0.6 second, the rate of diffusion of the contaminant
becomes negligible.
the nal prole of concentration expressed in terms of relative abscissa look similar,
whatever the value given to the thickness of these two PET bottles.
v) Finally, the same general conclusions hold for the two PET bottles with different
thicknesses, by taking care of considering the relative abscissa for the nal prole of
concentration of the contaminant.
3.7 Heat and Mass Transfers in Tri-Layer Bottles with a Mould Initially
at the Temperature of the Surrounding Atmosphere
3.7.1 Theoretical Treatment of the Process
This question is concerned with the actual problem, which appears in industry: generally,
the polymer is injected into a mould initially at the temperature of the surrounding
atmosphere. In the same way, the temperature of the air injected into the bottle is also
equal to that of this surrounding atmosphere.
Thus, from certain aspects, this problem looks like the problem considered in the previous
sub-section 3.6, with the only difference being that the initial temperature of either the mould
or the air injected into the bottle is the same as that of the surrounding atmosphere.
The temperature of this surrounding atmosphere is 20 C in the rst case, as well as

40 C in another extreme case, which can be found in summer time or in hot countries.
133
The main assumptions are as follows:
i) The polymer material, initially at 280 C for the PET, is injected into the mould initially
at room temperature (either 20 C or 40 C). The rate of heat transfer by conduction
at the mould-polymer interface is the same on each side.
ii) The air injected into the bottle, almost simultaneously with the polymer injection, is
initially at room temperature.
iii) After 1 second in the mould, the bottle is extracted and kept in contact with the
surrounding atmosphere.
iv) Heat is transferred by conduction at the mould-polymer interface, and by free

convection either at the external surface of the mould or inside the bottle.
v) During the process, the pollutant diffuses through the thickness of the three layers
of the bottle. The recycled layer is injected so as to be inserted within the two virgin
layers. The thickness of each layer is 0.01 cm leading to a total thickness of 0.03 cm
for the sheet.
The equations shown in the Section 3.6 are also relevant to describe the process.
At the polymer-mould interface, the rate of conduction heat transfer is equal on each side:
T T
p = m (3.23)
x p x m
Through each medium (mould, polymer) heat is transferred by conduction:
T T
c = (3.3)
t x x
On the external surface of the mould, as well as on the internal surface of the bottle, heat
is transferred by free convection:
T
x
where the temperature Tsurrounding is constant far from the mould and from the bottle
surface.
134
The condition on the internal surface of the bottle, leads to the following equation
expressing the fact that the volume of air V enclosed in the bottle is heated; the variation
of the temperature of the air located inside the bottle with time is obtained from this
relationship:
dQ = V ( c)air dT (3.24)
3.7.2 Selection of the Values for the Parameters Used for Calculation
The values of the parameters are shown in Table 3.5.
Thermal PET = 103 + 107 T cal/cm/s/deg Temperature C
conductivity Steel = 0.038 cal/cm/s/deg
3 7
Thermal PET = 10 + 7 10 T cm2/s Temperature C
diffusivity Steel = 0.04 cm2/s
Air density = 1.298 0.005 T g/litre Temperature g/L C
Specic heat Cp = 0.241.4105T cal/g/K
Steel Specic heat Cp = 0.12 cal/g/K
Heat transfer
h = 7 104 (T0 Tsurrounding)0.25 cal/cm/s/deg
by convection
D300 = 106 D250 = 107 D30 = 1012 cm2/s
Diffusion of
the matter 8655
D = 2.42 exp cm2/s Temperature K
T
Operational conditions:
PET initial temperature = 280 C
Mould: initial temperature = temperature of the surrounding atmosphere
Thickness of the PET bottle: 0.03 cm
Thickness of the mould: 1.5 cm
External temperature of air: 20 C = Initial temperature of air in the bottle: 20 C
External temperature of air: 40 C = Initial temperature of air in the bottle: 40 C
Time of residence of the bottle in the mould = 1 s
135
3.7.3 Results Obtained with the Surrounding Atmosphere at 20 C or 40 C
The results are expressed in terms of proles of temperature developed through the
thickness of the polymer bottle and of the mould, and in terms of proles of concentration
of the diffusing substance (pollutant) obtained through the thickness of the polymer.
The following gures are obtained from calculation using a numerical model taking all
the above facts into account:
Figure 3.25 describes the proles of temperature developed through the thickness of
the polymer and a part of the mould, over a time of 1 second when the polymer is in
the mould, when the temperature of the surroundings is 20 C.
Figure 3.26 depicts the proles of temperature developed through the thickness of
the mould, over a time of 1 second when the polymer is in the mould, and when the
temperature of the surroundings is 20 C.

PET thickness = 0.03 cm. Initial temperature of PET = 280 C. Initial temperature
of the mould = 20 C. Mould thickness = 1.5 cm. Temperature of the surrounding
atmosphere and of the air injected in the bottle = 20 C.
136

the thickness of the mould whose initial temperature is 20 C. Temperature of the
surrounding atmosphere = 20 C; Mould thickness = 1.5 cm; PET thickness = 0.03 cm;
Initial PET temperature 280 C.
Figure 3.27 represents the proles of concentration of the diffusing substance (pollutant)
developed through the process, when the temperature of the surroundings is 20 C.
Figure 3.28 describes the proles of temperature developed through the thickness of
the polymer and a part of the mould, over a time of 1 second when the polymer is in
the mould, when the temperature of the surroundings is 40 C.
Figure 3.29 depicts the proles of temperature developed through the thickness of
the mould, over a time of 1 second when the polymer is in the mould, and when the
temperature of the surroundings is 40 C.
Figure 3.30 represents the proles of concentration of the diffusing substance (pollutant)
developed through the process, when the temperature of the surroundings is 40 C.
From Figures 3.25 to 3.30, the following relevant conclusions appear:
i) As shown in Figures 3.25 and 3.28, the temperature on the surface of the PET bottle in
contact with the mould falls abruptly to a value which depends on the temperature of
the surrounding atmosphere: it is around 65 C for the temperature of the surrounding
atmosphere of 20 C and around 80 C when it is 40 C.
137
Figure 3.27. Proles of concentration of the diffusing substance developed through

the thickness of the bottle when it is cooled down under the conditions of Figure 3.25.
of the mould = 20 C. Mould thickness = 1.5 cm. Temperature of the surrounding
atmosphere = 20 C.
ii) As proved in Figure 3.25 and 3.28, where the proles of temperature are developed
through the thickness of the bottle, a residence time of 1 second is enough for
these proles to become nearly at at a low value. However, there is an effect of
the temperature of the surrounding atmosphere: when it is 20 C, after 1 second
in the mould, the temperature through the thickness is between 50 and 75 C,
whereas when it is 40 C, the temperature through the thickness is between 70
and 90 C.
iii) Comparison between either both Figures 3.25 and 3.26 or both Figures 3.28 and 3.29
shows the effect of the value of the thermal conductivity of the mould and of the
polymer. Steeper gradients of temperature are developed through the polymer than
through the thickness of the mould.
iv) The proles of concentration of the diffusing substance drawn in Figures 3.27 and
3.30, show that these proles developed through the thickness of the polymer up to
a time around 0.2 second. After this time, no signicant matter transfer is observed.
138
v) A relevant result is obtained for the effect of the temperature of the surrounding
atmosphere. Whatever its value, ranging from 20 to 40 C, the proles of concentration
of the diffusing substance (pollutant) look similar.
vi) Of course, the proles of concentration of the diffusing substance is more advanced
on the side of the bottle in contact with the air (this side will be in contact with the
food) than on the other side which was in contact with the mould.

of the mould: 40 C. Mould thickness = 1.5 cm. Temperature of the surrounding
atmosphere and of the air injected in the bottle = 40 C.
139

the thickness of the mould whose initial temperature is 40 C. Temperature of the
surrounding atmosphere: 40 C. Mould thickness = 1.5 cm. PET thickness = 0.03 cm.
Initial PET temperature 280 C.
140
Figure 3.30. Proles of concentration of the diffusing substance developed

through the thickness of the bottle when it is cooled down under the conditions
of Figure 3.28. PET thickness = 0.03 cm. Initial temperature of PET = 280 C.
Initial temperature of the mould = 40 C. Mould thickness = 1.5 cm. Temperature of
the surrounding atmosphere = 40 C
141
3.8 Coupled Mass and Heat Transfers - Conclusions
Some general conclusions about heat transfer applied to the co-extruded lms or to the
injected bottles are worth noting:
i) The process of heat transfer is controlled by conduction through a solid, as well as at

the interface between two solids.
ii) The process of heat transfer is controlled by convection at the surface of a solid in
contact with a surrounding atmosphere, such as a liquid or a gas.
iii) Heat transfer is controlled either by forced convection when the uid is stirred or by
free (natural) convection when the uid is motionless. In both these cases, depending
on the value of the parameters expressing the convection, it is run under laminar or
turbulent conditions.
iv) In the general case of a bottle, the polymer is injected into a mould initially at room
temperature, while air is pushed into the internal surface of the bottle. The surrounding
atmosphere (air either on the external surface of the mould or inside the bottle) is at
room temperature (taken in section 6.7 at 20 and 40 C, respectively).
v) Thus, gradients of temperature are developed through the thickness of the lm or of

the bottle during the cooling period.
vi) The high temperature of the melted polymer and the time necessary for the polymer
layers to cool down are responsible for a signicant mass transfer of the additives
through the thickness of these layers. This problem becomes relevant either for
multi-layer lms or for the layers of the bottles, when these layers contain a recycled
polymer. At the end of production, the pollutant initially in the recycled polymer layer
has diffused into and through the virgin polymer layer. Thus the effect of this mass
transfer on the consumers safety is evaluated in Chapter 4.
142
References
1. H.S. Carslaw and J.C. Jaeger, Conduction of Heat in Solids, Clarendon Press,
Oxford, UK, 1959.
2. W.H. McAdams, Heat Transmission, 3rd Edition, McGraw-Hill, London, UK, 1954.
3. J-M. Vergnaud and J. Bouzon, Cure of Thermosetting Resins, Springer-Verlag

Publishers, London, 1992.
4. A.L. Perou and J-M. Vergnaud, Computational and Theoretical Polymer Science,
1997, 7, 1, 1.
5. A.L. Perou and J-M. Vergnaud, Plastics, Rubber and Composites, 1999, 28, 2, 74.
6. A.L. Perou and J-M. Vergnaud, International Journal of Numerical Methods for
Heat and Fluid Flow, 1998, 8, 7, 841.
7. I-D. Rosca and J-M. Vergnaud, Polymers and Polymer Composites, 1999, 7, 2, 89.
8. A.L. Perou, S. Laoubi and J-M. Vergnaud, Journal of Applied Polymer Science,
1999, 73, 10, 1939.
9. A.L. Perou, S. Laoubi and J-M. Vergnaud, Advances in Colloid and Interface
Science, 1999, 81, 1, 19.
10. A.L. Perou, S. Laoubi and J-M. Vergnaud, Computational and Theoretical
Polymer Science, 1998, 8, 3/4, 331.
11. ICI, Melinar Polyethylene Terephthalate, G5: Physical properties.
12. M.M. Nir, A. Ram and J. Miltz, Journal of Polymer Engineering Science, 1996,
36, 6, 862
13. R. Franz, M. Huber, O-G. Piringer, A.P. Damant, S.M. Jickells and L.J. Castle,
Journal of Agriculture and Food Chemistry, 1996, 44, 3, 892.
14. P.Y. Pennarun, Y. Ngono, P. Dole and A. Feigenbaum, Journal of Applied Polymer
Science, 2004, 92, 5, 2859.
143
Abbreviations
A area through which heat is transferred in Equation (3.1)

thermal diffusivity (cm2/s), dened by Equation (3.15)
n term in Equation (3.9) obtained by using Equation (3.18)
c heat capacity of the polymer (cal/g/deg)
Cx,t concentration of contaminant at position x and time t
D, DT diffusivity of the substance (cm2/s), diffusivity at temperature T
D0 constant for the diffusivity versus temperature
dT/dx gradient of temperature through the lm
dC/dx gradient of concentration of the diffusing substance
E activation energy expressing the temperature dependency of the diffusivity
EVA ethylene vinyl acetate
thermal conductivity (cal/cm/s/deg)
Gr Grashof number
hh coefcient of heat convection at the solid-uid interface(cal/cm2/s/deg)
hm coefcient of mass transfer at the solid-uid interface (cm/s)
density of the polymer (g/cm3)
L half the thickness of the lm
Nu Nsselt number
PET polyethylene terephthalate
Pr Prandtl number
PVC Polyvinyl chloride
Q heat (calorie)
R ideal gas constant
Re Reynolds number
Rh term in Equation (3.16) dened by the Equation (3.17)
Tx,t temperature at position x and time t (Celsius or Kelvin)
Tair constant temperature of the surrounding air
t time
x space abscissa
144
4
Mass Transfers Between Food and Packages
4.1 General Introduction to the Various Problems
A few decades ago, food was sold mainly from bulk containers, the packaging being done
by the retailer after selling. Thus milk was taken from a large milk can by a soup-ladle to
be dropped in the milk jug of the consumer. No need to say that the milk should have been
boiled very quickly. In the same way, butter was cut by a large knife, and put on a grease-
proof paper to be weighed and packed, ignoring the fact that sometimes it was wrapped
up in an old newspaper, which at that time was a common way to reuse these paper
materials. Pre-packaging was developed in the mid 1900s with the production of sealable
glass bottles and airtight metal cans. Later on, exible materials, such as cellophane, were
introduced instead of greaseproof paper. Today, since they exhibit outstanding usage
properties, plastics are used preferentially for packaging foodstuffs.
Plastic packages are capable of retarding and sometimes preventing detrimental changes in
the packed material due to external inuences such as oxygen, light, and microorganisms.
Plastics are also able to reduce to a great extent, the loss of components such as water or
avour in the packed material. Resulting from this protection, plastic packages enable the
consumer to use foodstuffs in perfectly hygienic conditions, and to store them without
loss in quality over an extended period of time.
But plastics contain low molecular compounds such as oligomers and sometimes
monomers, and additives such as plasticisers, lubricants, stabilisers and antioxidants, which
are absolutely necessary either for the processing or the stability of the nal polymeric
materials. The drawback of using these is the potential migration of these additives from
the package into the packed material. This is a problem of major interest where food or
drugs are concerned.
Moreover, as the use of plastic packages is now widespread in all countries, a large amount
of old packages are discarded in the garbage heaps, if not anywhere. Thus a few solutions
are given in order to answer the question: what to do with various kinds of old plastics?
A few ways have already been explored, if not widely used:
i) One consists of burning them in the same way as crude oil; it is true that polyolens
and even polystyrene, in spite of the smoke evolved from the poor combustion of
145
aromatics, produce energy in burning. It does not work for polyvinyl chloride (PVC)
because of the hydrogen chloride produced by its decomposition, this fact making
this polymer re-proof.
ii) The other way lies in reusing them as new packages. But it should not be forgotten that
very often the old cans or bottles made of plastics are commonly used to keep other
liquids such as weed-killers and other chemicals potentially dangerous for health. And
in the same way that the additives initially in the virgin polymer may migrate into the
food, these chemicals may also deeply diffuse into the old polymeric package, and a
simple washing even with boiling water is not able to extract them. Thus we have to deal
with a potentially polluted material. And nally, the only way to resolve the problem
is to build new packages consisting of two layers, one made of the recycled polymer,
while the other is made of virgin polymer which will be put in contact with the food.
The process of contaminant transfer from the package into the food can be generally
described by transient Fickian diffusion through the package, and either convection in the
food in a liquid state or diffusion in the food when it is highly viscous or solid.
The theoretical treatment of the process of mass transfer controlled by diffusion-convection

with liquid food or even by diffusion-diffusion when the food is solid is described
precisely. Emphasis is placed on the fact that an innite rate of convection cannot exist
at the package-liquid interface in our nite world, and consequently we have to deal with
more complex equations. The question of the volume of the package as a fraction of the
volume of the liquid is also considered. In fact, the problems of diffusion are not simple
to resolve, either by considering the experiments or by making calculations.
Some results are given for the case of a single layer package by studying the effect of the
thickness of the package as well as that of the rate of stirring of the liquid which acts
upon the coefcient of convective transfer. In all cases, the results are expressed in terms
of proles of concentration of the diffusing substance developed through the thickness of
the package and of the kinetics of transfer of this substance in the liquid. Dimensionless
numbers are used, as often as possible, so as to build general curves called master curves,
which can be used in various different cases.
The problem of bi-layer systems is also examined, when the package consists of the layer
made of the recycled polymer bound to the virgin polymer layer. As this virgin layer is
placed in contact with the food, it plays the role of a functional barrier. The effect of the
various parameters is determined, without forgetting the effect of the mass transfer taking
place between these two layers during the stage of co-extrusion.
The problem of tri-layer packages seems, to some extent, to be somewhat similar to that
appearing with the two-layer packages.
146
Finally, a section is devoted to the difcult problem of solid or highly viscous food in
bottles. In this case, the diffusion acts as the driving force either through the thickness
of the package or within the solid food. But the problem should be resolved using three-
dimensional transport, leading to a non uniform concentration of the contaminant in
the food.
4.2 Theoretical Treatment
4.2.1 Revision of the Main Parameters and Principles of Diffusion
As already stated in Chapter 1, the matter transfers taking place between a polymer package
and a liquid are controlled either by diffusion through the polymer or by convection at
the liquid-solid interface.
4.2.1.1 Basic Equations of Diffusion Through the Solid
The mathematical theory of diffusion in isotropic materials is thus based on the hypothesis
that the rate of transfer of diffusing substance through unit area of a section of the material
is proportional to the concentration gradient measured normal to the section, as shown
in Equation (4.1):
C
F = D (4.1)
x
F being the rate of diffusing substance transferred per unit area of section,
C is the concentration of the diffusing substance,
x is the space coordinate normal to the section along which the diffusion takes place, and
D is the diffusion coefcient, also called diffusivity.
The negative sign arises because diffusion occurs in the direction opposite to that of
increasing concentration.
4.2.1.2 Basic Equation at the Solid-Liquid Interface
At the packaging-liquid interface, the rate at which the substance is transferred into the
liquid is constantly equal to the rate at which this substance is brought to the surface by
internal diffusion through the polymer packaging, leading to the following relationship:
147
C
D
x
(
= h CL , t Ceq ) (4.2)
where: h is the coefcient of transfer by convection in the liquid next to the surface,
CL,t is the concentration of the diffusing substance on the surface of the solid,
Ceq is the concentration of the diffusing substance on this surface required to maintain
equilibrium with the concentration of this substance in the liquid, at time t.
The value of the coefcient of convection, h, largely depends on the type of convection;
being rather low in motionless liquid, it increases with the rate of stirring of the liquid up
to a very large value when the liquid is strongly stirred.
4.2.1.3 Units Employed for the Parameters of Diffusion
By expressing F, the amount of diffusing substance, and C, the concentration, in terms of

the same unit of quantity, e.g., gram, D is independent of the mass. In the CGS system,
very often used in diffusion, the dimension equation of D becomes:
length2/time or cm2/s (4.3)
The coefcient of convection has the dimensions: cm/s (4.3)
As the rate of transfer by convection into the liquid is much faster than the rate of transfer
by diffusion through the polymeric solid, the concentration in the liquid of the diffusing
substance is considered as constantly uniform.
4.2.1.4 Applications of the Boundary Conditions
Two important applications of the boundary conditions expressed by Equation (4.2) are
as obvious as they are relevant:
1. When the coefcient of convection, h, is said to be innite, the following facts appear:
The concentration of diffusing substance on the surface of the solid instantaneously

reaches its corresponding value at equilibrium with that in the liquid as soon as
the process starts, this fact being expressed by the relationship:
t=0 CL,0 = Ceq h FL,0 (4.4)
148
This innite value of the ux is associated with the vertical tangent at the origin
of time of the kinetics of transfer of the diffusing substance.
2. Process of absorption or of release. Equation (4.2) is of value either for the release of
additives from the polymer in the liquid or for the absorption of the liquid into the
polymer. Thus, only the relative values of the two concentrations intervene on the
process, by following the relationship:
CL,t > Ceq release of the diffusing substance in the liquid (4.5)
CL,t < Ceq absorption of the diffusing substance by the polymer (4.6)
4.2.1.5 Note on the Infinite Value of the Coefficient of Convection
It should be stated that it is too often found in scientic papers, without any relevant
proofs, an innite value of the coefcient of convection, h. This assumption would be
responsible for the following abnormal process over a short time, e.g., when the polymer
sheet is immersed into a pure liquid of nite volume in a ask: at time 0, the concentration
of the diffusing substance on the solid surface, being equal to that in the liquid when the
partition factor is 1, decreases abruptly down to 0, and afterwards increases slightly with
the concentration of the substance in the liquid.
4.2.1.6 Partition Factor
For various reasons, but essentially chemical, due to the fact that the solubility of the
additives is much larger in one of the two polymer-liquid media, the concentration of an
additive is not the same in the polymer and the liquid, at equilibrium. This fact can be
written in the form of the ratio of concentrations:
C L ,
K= (4.7)
Cliquid,
where: K is the partition factor,
CL, is the concentration of the diffusing substance on the polymer surface at

equilibrium, attained after innite time, and
Cliquid, is the concentration of the diffusing substance in the liquid at equilibrium.
149
Let us notice that generally, and fortunately for the consumers, the concentration of the
additives in the polymer used as a package is very low, so that their concentration in the
liquid do not exceed their solubility in the food liquid. The same fact occurs at the interface
of the two layers of a package, the one made of a recycled polymer and the other of a
virgin polymer; in the bi-layer system, it is obvious that the partition factor K is equal to 1
when these two layers in perfect contact in the package are made of the same polymer.
4.2.2 Differential Equation of Diffusion
The basic differential equation of one-dimensional diffusion in a thin isotropic sheet, shown
in Chapter 1, when the diffusivity is concentration-dependent or not constant, is:
C C
= D (4.8)
t x x
When the diffusivity D is constant, independent of the concentration, this equation

reduces to:
C 2C
=D 2 (4.9)
t x
Finally, the Equations (4.8) or (4.9), expressing the variation of the concentrations with time
and space in the polymer and Equation (4.2) dening the so-called boundary condition,
are the fundamental equations of diffusion through a sheet of an isotropic material, and
thus of mass transfer between the polymer and the liquid. Equations (4.8) and (4.9) are
partial derivative equations, in the sense that the concentration C depends on the two
parameters of time and space. When the diffusivity is constant, Equations (4.9) and (4.2)
should be considered, as well as the initial prole of concentration in the sheet.
4.2.3 The Case of a Sheet of Thickness 2L Immersed in a Liquid of Finite

Volume and Infinite Value of the Coefficient of Convection
When the liquid of nite volume is strongly stirred, the solution of the problem of diffusion
depends only on time, and the essential condition is that the total amount of diffusing
substance in the sheet and the liquid remains constant when diffusion proceeds.
Two opposite cases appear, the one with the absorption of the substance by the sheet, the
other when the substance leaves the sheet. Let us note that in these two cases, the problem
is concerned with the diffusion through the sheet.
150
Suppose that an innite sheet of uniform material of thickness 2L is immersed in the liquid
and that the diffusing substance is allowed to leave the sheet and to diffuse through it.
As shown in Figure 1.5, the sheet occupies the space:
L x +L
while the liquid of limited volume is extended as follows:
LA x L as well as L x L + A
where A is the relative thickness of the liquid, equal to its volume V per unit area.
The solution of the equation of diffusion, Equation (4.9):
C 2C
=D 2 (4.9)
t x
with a constant diffusivity and with the initial condition of a uniform concentration of the
diffusion in the package, as well as with the boundary condition expressing the fact that
the rate at which the diffusing substance leaves the liquid is constantly equal to the rate
at which it enters the sheet on its two sides (meaning that the coefcient of convection
is innite):
C C
t>0 x = L A = D (4.10)
t x
is given as follows, whatever the partition factor [1-3]:
Cx,t
cos(q n x / L) 2 (1 + ) D t
= 1+ exp q2n 2 (4.11)
C n =1 cos q n 1 + + qn
2 2
L
Mt
2 (1 + ) q2 D t
= 1 exp n 2 (4.12)
n =1 1 + + q n
2 2
M L
where qn is the non-zero positive root of:
tan qn = qn (4.13)
and the ratio of the volumes of liquid and sheet are given either by Equations (4.14) or
by (4.15), depending on the value of the partition factor K.
151
When the partition factor K is 1, the concentration on the sheet surfaces is constantly
equal to the concentration of the diffusing substance in the liquid.
When the partition is not equal to 1, the concentration of diffusing substance on both
surfaces of the sheet is constantly K times that in the liquid. In this case, the thickness of
the liquid is modied, becoming A/K instead of A.
A
when K = 1 = (4.14)
L
A
when K 1 = (4.15)
KL
Some roots of Equation (4.13) are given in various books [1-3] for the values of corresponding
to a few values of the nal fractional uptake of the diffusing substance by the sheet.
4.2.3.1 Case of the Diffusing Substance Entering the Sheet
At equilibrium, since the total amount of diffusing substance in the sheet and liquid is the
same as that initially in the liquid, the matter balance written for this substance gives:
A C
+ L C = A Cin (4.16)
K
by calling C the uniform concentration in the sheet at equilibrium, and C/K the
corresponding value in the liquid, when the partition factor is K. Obviously when K = 1,
the concentrations at equilibrium are similar in the liquid and in the sheet.
The amount of diffusing substance at equilibrium in the sheet is given by:
2 A Cin
M = 2 L C = (4.17)
1+
and the fractional uptake of the sheet is obtained as follows:
M 1
= (4.18)
2 A Cin 1 +
152
4.2.3.2 The Diffusing Substance Leaves the Sheet
The fractional uptake of the diffusing substance is given by the ratio:
M (4.19)
=
2L Cin 1 +
4.2.4 Case of a Sheet of Thickness 2L Immersed in a Liquid of Infinite (or

Finite) Volume and a Finite Value of the Coefficient of Convection
This case corresponds with the process of diffusion of the diffusing substance through
the sheet coupled with evaporation of this substance from the surfaces of the sheet. But
it should be said that it also represents the process of a sheet immersed in a liquid when
the coefcient of convection is nite. In fact, assuming that the coefcient of convection
h is innite is in all cases totally unreal and unreasonable.
With a nite coefcient of convection h, the basic equations are as follows:
The one shown already in Equation 1.11, expressing the diffusion through the thickness of
the sheet:
C 2C
=D 2 (4.9)
t x
and the other representing the boundary condition with a nite h:
C
D
x
(
= h CL , t Ceq ) (4.2)
When the initial condition is given by a uniform concentration of the diffusing substance,
expressed by Equation (4.20), there is a solution for the problem:
t=0 L < x < +L C = Cin sheet (4.20)
The solution of this problem with the above initial and boundary conditions is given for
the proles of concentration developed through the thickness of the sheet as follows:
x
2R cos n
C C x , t
L Dt
= 2 exp 2n 2 (4.21)
2
L
153
where n is the positive root of:
tan = R (4.22)
hL
R= (4.23)
D
The kinetics of transfer of diffusing substance by using the dimensionless number Mt/M
is expressed in terms of the dimensionless number Dt/L2 by the following equation:
M M t 2 R2 Dt
= 2 2 exp 2n 2 (4.24)
n =1 n (n + R + R) L
2
M
Of course, the total amount of substance enters or leaves the sheet, depending on the relative
values of the concentrations C and Cin, as shown previously in Equations (1.6) and (1.6):
C > Cin absorption of diffusing substance by the sheet (4.25)
C < Cin release of diffusing substance by the sheet (4.26)
4.2.4.1 Notes on the Example Described in Section 4.2.4
(1) Process of drying
This method of calculation is of great interest in describing the process of drying, but
only when the diffusivity is constant and does not depend on the concentration of the
diffusing substance in the sheet.
In the same way, the surroundings can be considered as innite provided that the sheet is
not conned in a closed volume, because in this case, the concentration of the evaporated
substance in the atmosphere, far from remaining constant, would increase regularly as
the evaporation proceeds.
It should be noticed that the rate of convection, h is related to the rate of evaporation of
the diffusing substance per unit area Ft, by the relationship:
Ft = h CL,t (4.27)
showing that the rate of evaporation of the substance evaporated is proportional to the
actual concentration of liquid on the surface of the solid. This concentration of liquid
154
in the polymer, expressed in terms of volume of liquid per total volume of polymer and
liquid is lower than 1, while in the pure liquid, the concentration is 1.
(2) Release of the additives from the polymer in the liquid
Both Equation (4.21) for the proles of concentration of the additive developed through
the thickness of the polymer sheet and Equation (4.24) for the kinetics of transfer of this
additive should be widely used. In fact, they stand for any cases given as follows:
When drying a polymer sheet (or when a vapour is absorbed by the polymer);
When the additives are released from the package into the liquid.
The question of the innite volume is of great concern, and the answer is as follows:
When the ratio of the volumes of liquid and polymer expressed by in Equation (4.14)
is larger than a value, which depends on the accuracy required, the volume of the liquid
can be considered as innite. As already shown in Chapter 1 with Figure 1.6, and more
precisely in Figure 1.9, it could be said that a value of of either 50 or 20 gives similar
results with the same kinetics of release. Let us recall that for a package of 1 litre and a
thickness of 0.01 cm (100 m) of the container, the value of is 166 for a cubic form and
174 for a bottle. Of course, for a thicker bottle, e.g., 0.03 cm, this ratio is 58.
4.2.4.2 Notes on Equations (4.12) and (4.24) with an Infinite Volume of Liquid
and Infinite Value of the Coefficient of Convection
When the volume of liquid is innite, = , the roots of Equation (4.13) relative to the value
of qn, are in the form: qn = (n + 0.5), and thus Equation (4.12) reduces to Equation (4.28):
2n + 1 2 2
Mt 8
= 1 2
1
exp ( ) D t (4.28)
M n =0 (2n + 1)2 4L2

In the same way, by considering the hypothetical case of the innite value of the coefcient
of convection, the dimensionless number R is innite, and the n values are given by
n = (n + 0.5)
so that Equation (4.24) also reduces to Equation (4.28).
Let us recall that in the hypothetical case of the innite value given to the coefcient of
convection at the polymer sheet-liquid interface, Equation (4.29) is also of interest.
155
D t 0.5 nL
0.5
Mt
= 2 2 + 2 (1) ierfc
n
(4.29)
M L n =1 Dt
where: ierfc(x) is the integral of the error function complementary to the following:
erfc(x) = 1 erf(x)
ierfc(x) = 0.5 exp(x2) x erfc(x)
The interesting thing about Equation (4.29) is that it stands for small times. As the
series becomes negligible, the kinetics expressed by the ratio of the amounts of substance
transferred versus time reduces to:
0.5
Mt Mt 2 D t
< 0.5 = L < x < +L (4.30)
M M L
This equation (4.30) shows that a straight line is obtained when plotting the ratio Mt/M
versus the square root of time. But, as already stated in Chapter 1, this relationship is of
value only when the coefcient of convection is innite, with a liquid strongly stirred, thus,
this fact reduces the interest of this equation in calculating the diffusivity. In fact, Equation
(4.30) can be used only as a rst approach to obtain an approximate value of the diffusivity.
With the same approximation, Equation (4.28) can be useful for determining an approximate
value of the diffusivity for long times, as it reduces to the simple Equation (4.31):
Mt 8 2 D t Mt
= 1 2 exp for > 0.5
5 (4.31)
M 4L 2
M
4.2.5 General Conclusions on the Mathematical Treatment
As already stated in Chapter 1, devoted to the mathematical treatment of the mass transport
from a polymer package into a liquid, when this transfer is controlled by diffusion, the
following conclusions can be drawn:
1. The best and unique equation to be used for evaluating the value of the diffusivity
from the kinetics of transfer is Equation (4.24), as the rate of stirring is generally not
so strong that the coefcient of convective transfer, h could be assumed to be innite.
Moreover, this Equation (4.24) can be used only when the ratio of the volumes of
liquid and of the polymer package is larger than a given value, this value depending
on the accuracy required. It has been seen that this value expressed by should be
larger than 50 for the results to be obtained precisely. When the ratio of the volumes
is very low, e.g., lower than 20, a numerical model with nite differences should
156
be used, by taking care that all the facts are accounted for, and especially the ratio of
the volumes and the nite coefcient of convection.
2. Equation (4.28), or rather the more simple Equation (4.30), which is mostly appreciated
by the users, perhaps because it looks simpler, can be used only from the rst approach
in order to get an approximative value of the diffusivity.
3. Then, the approximate value of the diffusivity obtained with this simple method shown
previously in case 2 with Equation (4.30) can be introduced into Equation (4.24) through
the dimensionless number R expressed by the relationship (4.23). Of course, various
values of the coefcient h should be tested, by following a trial and error method, and
by determining the corresponding values of the n in Equation (4.22).
4. Finally, when the operations required in the previous sections seems too tedious, the
convenient numerical model could be used.
4.3 Mass Transfer in Liquid Food from a Single Layer Package
This is the most common case of release of some additives taking place from the polymer
package into a liquid food. The process, controlled either by diffusion through the
thickness of the package or by convection at the solid-liquid interface, has been described
in Chapter 1, as well as in Section 4.2.
4.3.1 Theoretical for a Single Layer Package in Contact with Liquid Food
The principle of the process is depicted in Figure 4.1 where the scheme is drawn.
Figure 4.1 Scheme of the package, with the thickness 0 < x < L, showing the symmetry
for the diffusion process with respect to x = 0.
157
4.3.1.1 Assumptions
i) The thickness of the package is L, with: 0 < x < + L, and there is no mass transfer on
its external surface x = 0;
ii) The process is controlled either by diffusion through the thickness of the package or
by convection into the liquid food;
iii) When the diffusivity is constant and the initial concentration of the diffusing substance
is uniform, the mathematical treatment is feasible, leading to an analytical solution.
When one of these two requirements is not complied with, a numerical analysis should
be made leading to a numerical model with nite differences;
iv) When the volume of liquid is larger than that of the package, with >20, the
mathematical treatment is feasible, otherwise, the numerical model should be used.
vi) As shown already, because of the convection in the liquid, the concentration of the
additive is uniform in the liquid at any time. Thus, the one-dimensional transfer can
be considered, per unit area.
4.3.1.2 Mathematical or Numerical Treatment
The equation of diffusion through the package is:
C 2C
=D 2 (4.9)
t x
The boundary conditions are written as:
C
=0 on the external surface of the package, and as (4.32)
x
C
D
x
(
= h CL , t Ceq ) at the package-liquid interface (4.2)
Depending on the volume of the liquid food, and especially on the ratio of the volumes
of the liquid and of the package, , two ways of calculation are possible.
When >20-50, depending on the accuracy required, the mathematical treatment is

feasible, leading to the equation for the kinetics of release of the additive:
158
M M t 2 R2 Dt
= 2 2 exp 2n 2 (4.24)
n =1 n (n + R + R) L
2
M
tan = R (4.22)
hL
R= (4.23)
D
On the other hand, when < 20, the numerical treatment with nite differences should
be applied for determining either the kinetics of release or the proles of concentration, in
order to take into account all the facts, e.g., the nite volume of the liquid and the nite
coefcient of convection.
It is clear that, because of the symmetry to the plane located at the abscissa x = 0, all the
equations written for a thickness 2L of the package with -L < x < +L and a mass transfer
on both sides, can be used, and especially Equation 4.24, in spite of the fact that the actual
thickness of the package shown in Figure 4.1 is only L.
Various studies have been made by considering either the diffusion of the contaminant
through the polymer package or its release into the liquid food. The basic question has also
been considered with the two possibilities of the transport into the food which can be driven
either by diffusion through the solid food or by convection into the liquid food [4].
4.3.2 Effect of the Coefficient of Convective Transfer
The results obtained in this case have already been established in Chapter 1. They are
expressed in terms of the proles of concentration of the diffusing substance developed
through the thickness of the package (Figure 4.2 and Figure 4.3), and of the kinetics of
release of the substance in the liquid food (Figure 4.4 and Figure 4.5).
Some emphasis is placed on the value given to the coefcient of convective transfer h, and
thus to the dimensionless number R, either for the proles of concentration or for the kinetics
of release. Dimensionless numbers are used for the coordinates, and the curves obtained are
master curves which can be used whatever the characteristics of the problems.
The proles of concentration of the diffusing substance expanded through the thickness
of the package are drawn in Figure 4.2 with the hypothetical innite value for the number
R, and in Figure 4.3 with the realistic value of R = 5.
159
thickness of the package at different times, for R innite and innite volume of food.
Time is expressed in terms of the dimensionless time Dt/L2.
thickness L of the package at different times, for R = 5, and a large volume of food
with >20-50. Time is expressed in terms of the dimensionless time Dt/L2.
160
Figure 4.4. Kinetics of transfer of diffusing substance with the package of thickness L, for
different values of the dimensionless number R and a large value of the volume of liquid
with >20-50. Dimensionless numbers are used for the co-ordinates: Mt/M and (Dt)0.5/L.
Figure 4.5. Kinetics of transfer of diffusing substance with the package of thickness L,
for different values of the dimensionless number R and a nite value of the volume of
liquid such as >20-50. Dimensionless numbers are used for the co-ordinates: Mt/M
and (Dt)0.5/L. The curves are drawn with an expanded scale.
161
The kinetics of release of the diffusing substance are drawn in Figure 4.4 for various values
of the dimensionless number R, while these same curves are also drawn in Figure 4.5 by
using more expanded scales for the coordinates.
i) As already stated in Chapter 1, the innite value given to the coefcient of convection
h and to the dimensionless number R is responsible for the following two facts: the
concentration of the diffusing substance on the surface in contact with the liquid (x =
+L) falls abruptly to 0 instantaneously as the process starts, as shown in Figure 4.2.
On the other hand, when the dimensionless number R is nite, the concentration of
the diffusing substance on the surface in contact with the liquid falls rather slowly,
without reaching the 0 value, even after the dimensionless time Dt/L2 is equal to
1. In fact the 0 value can be attained after innite time only when the volume of the
liquid is innite. For a nite volume of the liquid and the partition factor K of 1, the
concentration is the same in the liquid and the polymer, given by:
C Vp
=
Cin Vl + Vp
when the concentration is expressed per unit volume of material, and where Vp and V1
are the volumes of the polymer and liquid, respectively.
ii) The kinetics of release expressed in terms of the square root of time (Figures 4.4 and
4.5) drawn for various values of the dimensionless number R show precisely the effect
of the coefcient of convective transfer at the package-liquid interface. All the curves
pass through the origin, but the value of the slope at the beginning of the process
increases largely when the value given to the dimensionless number is increased. A
straight line is obtained when R is innite, this fact resulting from the application of
the equation 4.30 for short times associated with Mt/M < 0.5. On the other hand, the
rate of transfer at the very beginning of the process is innite with a vertical tangent
when time is used on the abscissa.
iii) It should be said that the results for the proles of concentration and for the kinetics,
calculated for a volume of liquid innite, are also of value for a nite volume of the
liquid, provided that the ratio of the volumes of liquid and polymer, , would be larger
than, for example, 20 as previously shown [5].
iv) Figures 4.2-4.5 are drawn by using dimensionless numbers, so that they are playing
the role of master curves. Thus these curves can be used whatever the values of the
various parameters of diffusion intervening in the process, such as the concentration
162
initially located in the polymer (Figures 4.2 and 4.3), the thickness of the package, the
diffusivity of the additive, and the time through the dimensionless time.
The kinetics of release of the additive in the liquid can also be used (Figures 4.4 and 4.5)
whatever the values of the parameters: the amount of the additive initially located in the
package, the thickness of the package L, the diffusivity of the additive and the amount
of the diffusing substance initially located in the package which is equal to M when the
volume of liquid is innite. This method of calculation enables the user to get a value
of the concentration in the liquid when all the parameters are known, for > 20.
v) The effect of the coefcient of convection h, as well as of the dimensionless number

R, is so important that it should be necessary to control it, or at least to evaluate its
value in any experiments concerned with food packages. Let us recall that the same
problem appeared in the pharmaceutical industry in 1984-1988 with the determination
of the kinetics of the drug liberation from controlled release dosage forms [6]. Typical
apparatus were built and tested, and nally normalised, by dening the dimensions
of the ask, the way of stirring and the shape of the paddles so as to ensure the same
rate of stirring [7].
4.3.3 Effect of the Ratio of the Volumes of Liquid and Package
The effect of the ratio of the volumes of the liquid and of the polymer package, , as
well as that of the coefcient of convection, are considered simultaneously in Figures 4.6
and 4.7.
Figure 4.6 shows the proles of concentration developed through the thickness of the
package, with R = 5 and two values of = 20 and innite. Figure 4.7 depicts the kinetics
of release of the additive in the liquid in the following three cases: 1 with = innite,
2 with = 20, and 3 with = 50, and for all them R = 5.
Some conclusions are worth noting from these two gures:
i) By comparing the curves drawn in the Figures 4.4 or 4.5 with the curves in Figure 4.7,
it clearly appears that the effect of the parameter R on the kinetics is much effective
than that of the ratio of the volumes , even when this last parameter is varied within
a wide range:
= 166, for a cube of 1 dm3 (1 litre) and a package thickness of 100 m.

= 16.6, for a cube of 1 cm3, and a package thickness of 100 m.
= 50, for a cube of 27 cm3, and a package thickness of 100 m.
163
thickness L of the package at different times, for R = 5, and two values of the ratio of
the volumes of the food and package : (full line), = innite: (dotted line), = 20.
Time is expressed in terms of the dimensionless time Dt/L2.
Figure 4.7 Kinetics of transfer of diffusing substance with the package of thickness L,
for different values of , and with R = 5. Curve 1 with innite; curve 2 with = 20;
curve 3 with = 50. Dimensionless numbers are used for the co-ordinates.
164
ii) The proles of concentration developed through the thickness of the package (Figure
4.6) are exactly similar for = innite and = 20, with R = 5, when the dimensionless
time is lower than 0.4. This time of 0.4 is associated with a value of Mt/M of around
0.5, as shown in Figure 4.7 whatever the value of , for R = 5.
iii) The kinetics of release of the additive drawn for these two values of = 20 and of
= innite for R = 5 are nearly similar, and it is necessary to extend the scales of the
co-ordinates so as to be able to appreciate the difference.
iv) After innite time, the concentration of the additive remaining in the package as
well as the amount of additive released in the liquid are different when = 20 and
= innite:
For = 20, there is C/Cin = 1/21 when K = 1 and M/Min = 20/21
For = innite, there is C/Cin = 0 and M/Min = 1 whatever the value of K.
v) This is a conrmation of a previous study concerned with the effect of the volume of
liquid as a fraction of the volume of a plasticised PVC [5] on the kinetics of release of
the plasticiser in the liquid. It was shown that the ratio of these two volumes, denoted
as , plays a role in the transfer of the plasticiser only when is lower than 20.
4.4 Bi-layer Packages Made of a Recycled and a Virgin Polymer Layer,

by Neglecting the Co-extrusion Potential Effect
Because of the interest in recycling old polymer packages into new packages, the
consumers safety has to be considered and so bi-layer packages must be tested before
use. As shown in Figure 4.8, the bi-layer package consists of a recycled polymer layer
co-extruded with a virgin polymer layer, while the virgin polymer layer is in contact
with the food. As it takes some time for the contaminant potentially located into the
recycled polymer to diffuse through both these layers, and especially through the virgin
polymer layer, this virgin polymer layer plays the role of a functional barrier. The main
problem which stands out is the evaluation of the time of protection of the food offered
by this functional barrier.
4.4.1 Theoretical Treatment with a Bi-layer Package
The problem is different from the case shown with the single layer package.
165
Figure 4.8 Scheme of the bi-layer system with recycled polymer layer on the left and
the virgin polymer layer on the right, playing the role of a functional barrier. Cin is the
uniform concentration of the diffusing substance initially in the recycled layer.
4.4.1.1 Assumptions
As no analytical solution is obtained from the mathematical treatment, only a numerical

method should be used. Thus there are no limitations concerned with the assumptions.
Nevertheless, calculations have been made by using a constant diffusivity, and a uniform
concentration of the diffusing substance, considered as the contaminant, is assumed to
stand initially in the recycled polymer layer. In fact, these assumptions are not necessary,
provided that the data are known beforehand. In the same way, one-dimensional diffusion
is considered, leading to an easier problem.
4.4.2 Results with the Bi-layer Package
The results are expressed in terms of the following gures:
Figure 4.9 showing the proles of concentration of the diffusing substance developed
through the thickness of the two layers of the package, when there is no food, and no
transfer on both sides of the package.
Figure 4.10 showing the proles of concentration of the diffusing substance developed
through the thickness of the two layers of the package of equal thickness, when the food is
on the right, at the relative abscissa 1, with the value of the dimensionless number R = 5.
166
Figure 4.9 Proles of concentration of diffusing substance developed through the

package at various times, expressed in terms of the dimensionless time Dt/L2, when
there is no contact with the food, and with H = L/2.

package at various times, expressed in terms of the dimensionless time Dt/L2, when the
package is in contact with the food, with R = 5, and = 166, and with H = L/2.
167
Figure 4.11 depicting the kinetics of release in the food of the diffusing substance initially
located in the recycled layer, with a package made of two layers of equal thickness, with
various values of dimensionless number R, and a volume of liquid of 1 litre stored in a
0.01 cm thick package, leading to a very large value of equal to 166.
Figure 4.12, describing the proles of concentration of the diffusing substance developed
through the thickness of the two layers of the package, when the thickness of the recycled
layer is one-third that of the package, the food being on the right, at the relative abscissa 1,
with the value of the dimensionless number R = 5; the volume of liquid is 1 litre, leading
to a very large value of equal to 166.
Figure 4.13, depicting the kinetics of release in the food of the diffusing substance initially
located in the recycled layer, when the package is made of two layers of different thickness,
(the thickness of the recycled layer is only one-third of that of the package), with various
values of the dimensionless number R, and a volume of liquid of 1 litre, leading to a very
large value of equal to 166.
The Figures 4.9 to 4.13 lead to the following comments:
i) Typical proles of concentration are drawn in Figures 4.9 and 4.10, as well as in
Figure 4.12. Comparison between Figures 4.9 and 4.10 shows the main difference
which exists between them. When there is no transfer of substance into the liquid, the
gradient on the surfaces is at, according to Equation (4.32) indicating that there is
no transfer. On the other hand, in Figure 4.10, the gradient on the surface is negative,
indicating the fact that there is a transfer of substance into the food.
Another difference is shown in Figures 4.9, 4.10 and 4.12: when there is no transfer
of substance into the food, as shown in Figure 4.9, the proles are symmetrical from
the beginning to the end of the process; the proles are symmetrical only for short
times, when the diffusing substance has not reached the surface in contact with the
food (Figure 4.10) or a distance longer than that of the recycled layer (Figure 4.12).
ii) The kinetics of release of the substance in the food drawn in the Figures 4.11 and
4.13 show the important effect of the dimensionless number on the rate of release. A
faster release is obtained with the innite value of R (which corresponds to an innite
value of the coefcient of convection h).
iii) The effect of the thickness given to the recycled polymer layer is also of importance
on the rate of release in the food. However, it appears obvious that the economic
interest should be to have a larger relative thickness than that shown in Figures 4.12
and 4.13.
168
Figure 4.11 Kinetics of transfer of diffusing substance in the liquid food with = 166,
with the bi-layer system with H = L/2 and different values of the dimensionless number R.

package at various times, expressed in terms of the dimensionless time Dt/L2, when the
package is in contact with the food, with R = 5, and = 166, and with H = L/3.
169
Figure 4.13 Kinetics of transfer of diffusing substance in the food with = 166, with
the bi-layer system with H = L/3 and different values of the dimensionless number R.
iv) The effect of the parameters which interfere in this process has been extensively studied
in previous papers such as:
the value of the ratio of the volumes of liquid and of the package [8],
the relative thickness given to the recycled layer as a fraction of the total thickness
of the package [9],
the value of the coefcient of convection and thus of the dimensionless number
R [10].
Moreover, general theoretical results [11-13] have been published in order to pave
the way to the further studies to be carried out by researchers.
v) As dimensionless numbers are used either for the time with Dt/L2 or for the
concentration in the package Ct/Cin, as well as for the amount of substance released
in the food Mt/M, master curves are obtained, which can be employed whatever the
values of the parameters, provided that they are known.
170
4.5 Mass Transfer from Tri-layer Packages (Recycled Polymer Inserted

Between Two Virgin Layers) in Liquid Food
This case is of great interest in the sense that the recycled polymer layer being inserted
between two virgin polymer layers, the protection against contamination is ensured on
both sides of the lm, or inside and outside of the bottle.
The problem is considered in this section by neglecting the effect of the mass transfer
taking place during the stage of co-extrusion. The scheme of the process is shown in
Figure 4.14.
4.5.1 Theory of the Mass Transfer in Food with the Tri-layer Package
The process of transfer of the diffusing substance, initially located in the recycled layer,
is controlled either by diffusion through the thickness of the three layers of the package
or by convection at the polymer-liquid interface.
In the present case, as shown in Figure 4.14, the initial concentration of the contaminant in
the recycled polymer layer is uniform. However, this assumption is not mandatory, as the
model can take into account any shape for this initial prole. As already stated, when the
food is in a liquid state, the convection of the contaminant is so strong and so fast compared
Figure 4.14 Scheme of the package made of a tri-layer system where the recycled layer
is inserted between two virgin layers. Cin is the uniform concentration of the diffusing
substance initially in the recycled layer.
171
to the slow rate of diffusion through the polymer, that the concentration in the liquid is taken
as uniform at any time. Moreover, the radius of the bottles is much larger than the thickness
of the package. For these two reasons, a one-dimensional diffusion can be considered.
In the same way as for the bi-layer lm in contact with the liquid food, there is no
analytical solution for the problem. It should be resolved by using a numerical treatment
with nite differences.
4.5.2 Results Obtained with the Tri-layer Package in Contact with a Liquid Food
The results obtained either for a lm or for a bottle are expressed in terms of proles of
concentration of the diffusing substance developed through the thickness of the package,
and of the kinetics of transfer into the liquid food.
Figure 4.15 shows the proles of concentration of the contaminant initially located in the
recycled layer, as they develop through the tri-layer package when it is in contact with the liquid
food. The total thickness of the package is 0.03 cm and the volume of liquid is 1 litre.
Figure 4.16 shows the kinetics of release of the contaminant in the food, for various values
of the dimensionless number R which characterises the convection in the food. The volume
of liquid is 1 litre and the thickness of the package is 0.03 cm.
Some comments of interest are drawn from these two gures:
i) As there is no transfer at the external surface of the bottle, the gradients of

concentration of the contaminant in Figure 4.15 are at next to this surface, according
to the relationship (4.32):
C
= 0 external surface at x = 0 (4.32)
x
On the contrary, the gradients of concentration on the internal surface of the package in
contact with the liquid food, exhibit a negative slope, according to Equation (4.2):
C
D
x
(
= h CL , t Ceq ) (4.2)
ii) As it takes some time for the contaminant initially located in the recycled layer to
diffuse through the virgin polymer layer in contact with the food (at the abscissa L in
Figure 4.14), the virgin layer in contact with the food plays the role of a functional
barrier. In the present case, the time expressed in terms of the dimensionless number
Dt/L2 is around 0.012.
172
Figure 4.15 Proles of concentration of the diffusing substance developed at various times
(dimensionless time Dt/L2) when the three layers have the relative thicknesses shown in
the gure. The package is in contact with a liquid food with = 55.3 and R = 5.
Figure 4.16 Kinetics of transfer of diffusing substance in the food of large volume with
= 55.3, associated with the case shown in Figure 4.15 with various values of R.
173
iii) The virgin layer located on the external surface of the bottle (between 0 and L1) is
acting in two ways: First, it protects the consumers hand from contamination when
the contaminant does not evaporate. Secondly, this layer acts as a reservoir in which a
part of the contaminant penetrates and thus is stored. Resulting from this fact, as there
is no transfer on the external surface, the concentration of the contaminant increases
in this layer, and becomes larger than that in the recycled layer, at a time between 0.03
and 0.05. Thus, nally, this external layer could be also considered as the external part
of the functional barrier.
iv) The kinetics of release of the contaminant in the food shown in Figure 4.16 for various
values of the dimensionless number R, are typical. They look like those obtained for the
bi-layer system in Figure 4.13. In the same way, the effect of the coefcient of convection
at the package-liquid interface is of prime importance. As dimensionless numbers are
used either for time and the amount of contaminant transferred, these curves are master
curves which can be used in any case, provided that the parameters are known.
v) The effect of the relative thicknesses of the three layers has been deeply studied intensively
in various papers [14-18], while an overview of these results was given [19]
4.6 Effect of the Co-extrusion on the Mass Transfer in Food
4.6.1 Mass Transfer in Food with a Co-extruded Bi-layer Package
4.6.1.1 Heat Transfer and Mass Transfer During the Stage of Co-extrusion
The scheme of the process of co-extrusion is shown in Figure 3.1, where the two layers after
their co-extrusion into a single package at 300 C are cooled down by heat convection in the
surrounding atmosphere at room temperature. According to the temperature-time histories
(Figure 3.2) drawn when the heat convection is either high (ht = 0.5 cal/cm2s) or low (ht =
0.05 cal/cm2s), the temperature through the 0.03 cm thick package falls rapidly during this
cooling period to room temperature after 0.4 s in the rst case and after 0.6 s in the second
case. The proles of concentration of the diffusing substance developed during the same
cooling stage shows that they are slightly different in the two following cases: when h = 0.5
with L = 0.03 cm (Figure 3.5) and when h = 0.05 with L = 0.03 cm (Figure 3.6).
From these gures, the main results are:
i) A prole of concentration of the contaminant is developed during the process of co-

extrusion, up to the short time of 0.1 s, whatever the value of the coefcient of heat
transfer h.
ii) The prole of concentration shows that the diffusing substance reaches the relative
abscissa 0.04 with h = 0.5, and around 0.05 with h = 0.05.
174
4.6.1.2 Mass Transfer from the Co-extruded Bi-layer into the Liquid Food
The scheme of the process is shown in Figure 4.17, where the mass transfer is controlled
either by diffusion through the thickness of the bi-layer package or by convection into
the liquid, while there is no transfer on the external surface of the package.
In Figure 4.18, are drawn the proles of concentration of the contaminant developed
through the thickness of the package (0.03 cm) when it is in contact with the liquid
food (1 litre, expressed by the thickness of 1.66 cm), with the dimensionless number
R = 5. The times are expressed in terms of the dimensionless number DT/L2.
Figure 4.19 shows the kinetics of transfer of the contaminant in the food, under the
same conditions as shown in Figure 4.18 (L = 0.03 cm; 1 litre liquid), for various
values of the coefcient of convection dened by the dimensionless number R.
Some conclusions of interest can be drawn from these two gures:
i) As shown in Figure 4.18, at time 0 when the package is put in contact with the
liquid food, the prole of concentration is not uniform in the recycled layer, and
the virgin layer is not free from contaminant. However, this prole of concentration
at time 0 differs slightly from the prole taken when the effect of the co-extrusion
is neglected.
Figure 4.17. Scheme of the bi-layer package made of a recycled layer and a virgin
layer in contact with liquid food, by taking into account the transfer of the diffusing
substance during the co-extrusion stage.
175

the bi-layer package in contact with the liquid food of nite volume with = 55.3, for
various values of the dimensionless time Dt/L2, with R = 5. The initial concentration at
time 0 is that attained at the end of the co-extrusion stage.
Figure 4.19 Kinetics of transfer of diffusing substance in the liquid food of volume such
as = 55.3, in the case of the bi-layer package shown in Figure 4.18, with various values
of the dimensionless number R. Dimensionless numbers are used in the co-ordinates.
176
ii) From this time 0, the contaminant diffuses through the thickness of the package, leading to
the proles of concentration shown in Figure 4.18. The slope of these gradients is equal to
0 on the external surface where there is no transfer, on the contrary, this slope is negative
on the internal surface in contact with the liquid food, this last fact being associated with
a transfer of the contaminant into the food. As the dimensionless number R = 5, is nite,
the concentration of the contaminant on the internal surface does not fall to 0.
iii) There is an axis of symmetry (x/L = 0.5, and Ct/Cin = 0.5) until the diffusing substance
has not reached the external surface.
iv) The kinetics of release of the contaminant into the liquid food drawn in Figure 4.19
shows the importance of the effect of the coefcient of convection at the package-
liquid interface, through the dimensionless number R.
v) The virgin layer (0.015 cm thick) plays the role of a functional barrier, the food being
fully protected over a time around 0.125, expressed in terms of the dimensionless
number Dt/L2.
In fact, the following main results appear as highly relevant:
1. The effect of the mass transfer which has taken place during the stage of co-
extrusion is not signicant;
2. The effect of the coefcient of heat transfer during the co-extrusion stage is
negligible.
3. Of course, these results are of value only if the temperature-dependent diffusivity

follows the law selected in Chapter 3.
vi) As dimensionless numbers are used in both Figures 4.18 and 4.19, master curves are
obtained which can be used whatever the operational conditions.
4.6.2 Mass Transfer in Food with Tri-layer Bottles Co-injected in the Mould
whose External Surface is Kept at 8 C
After their preparation, the tri-layer bottles, made of three layers co-injected in the mould,
are put in contact with the liquid food, according to the scheme in Figure 4.20. As shown
in this Figure, at time 0, the contaminant is located not only in the recycled polymer layer
but also in the borders of the two virgin polymer layers. This prole of concentration has
been developed during the cooling stage of the bottle in the mould.
The thickness of the bottle is 0.03 cm, each layer having the same thickness of 0.01 cm.
177
Figure 4.20. Scheme of the tri-layer package, in contact with the liquid food, obtained
after the stage of co-extrusion.
There is no transfer of the contaminant on the external surface of the bottle, at x = 0,

while a mass transfer takes place into the food on the internal surface at x = 3L.
The operational conditions described in Chapter 3 as shown in Figure 3.21, are

summarised:
Figure 3.21 shows the proles of concentration of the contaminant developed through
the thickness of the bottle cooled in the mould whose external surface is kept at 8 C.
Thickness of the polyethylene terephthalate (PET) bottle = 0.03 cm; thickness of the
mould = 1.5 cm; temperature of the PET at injection = 280 C; time of residence of the
PET bottle in the mould = 1 s.
Figure 4.21 shows the proles of concentration of the contaminant when the bottle is put
in contact with the liquid food. The thickness of the bottle being 0.03 cm and the volume
of the liquid 1 litre (thickness of 1.66 cm with one-dimensional transport), = 55.3.
Figure 4.22 shows the kinetics of release of the contaminant into the liquid food, for
various values of the dimensionless number R (which characterises the convection).
Figure 4.23, where the kinetics of release of the contaminant into the liquid food shown
in Figure 4.22, are represented with a larger scale.
Some results of concern are worth noting from Figures 4.21-4.23:
i) The proles drawn in Figure 4.21 give a fuller insight into the nature of the process
either during the stage of moulding or the stage over which the bottle is in contact
with the food.
178
thickness of the tri-layer package when it is in contact with a liquid food of volume such
as = 55.3, with the dimensionless number R = 5. At time 0 for the dimensionless time
Dt/L2, the prole of concentration is that attained at the end of the stage of co-extrusion.
Figure 4.22. Kinetics of transfer of diffusing substance in the liquid food of nite
volume, such as = 55.3, with various values of the dimensionless number R.
The kinetic curves correspond with the case shown in Figure 4.21.
179
Figure 4.23. Kinetics of transfer of diffusing substance in the liquid food of nite
volume such as = 55.3, with various values of the dimensionless number R.
The kinetic curves correspond to the case shown in Figure 4.21, with a larger scale
than in Figure 4.22.
The main point appears here. When the bottle is extracted from the mould, a prole
of concentration has been developed for the contaminant. This prole is taken
at time 0 when the bottle is put in contact with the food, at the beginning of the
stage of release into the food. It is clear that the prole of concentration at time 0
slightly differs from the prole dened when the stage of heating and co-extrusion
is neglected (with square angles).
ii) The process of release of the contaminant is thus controlled either by diffusion through
the three layers of the bottle or by convection into the liquid (on the right at abscissa
x = L).
iii) As there is no mass transfer through the external surface, as shown in Figure 4.20, the slope
of the gradients of concentration is equal to 0 in Figure 4.21. On the contrary, resulting
from a contaminant transfer into the food, the slope of the gradients of concentration is
negative on the internal surface of the bottle in contact with the food.
iv) As it takes some time (around 0.01 for the dimensionless time Dt/L2) for the contaminant
to diffuse through the virgin polymer layer in contact with the food, this layer acts upon
180
the pollution process as a functional barrier. Nevertheless, as a signicant part of the

contaminant is stored in the other virgin layer in contact with the external surface of
the bottle, this layer plays the role of a reservoir, very efcient at the beginning of the
process, for dimensionless times between 0.04 and 0.1. For this reason, it can be said
that the external layer contributes to the protection, not only for the consumers hand
but also for the food as it takes part to the time of food protection.
v) The kinetics of release of the contaminant into the liquid food shown in Figure 4.22
exhibit the effect of the value of the rate of convection at the polymer-liquid interface,
characterised by the dimensionless number R. These kinetics of release shown in Figure
4.23 by using an extended scale for the co-ordinates, allows the determination of the
time of full protection.
4.6.3 Mass Transfer in Food with Tri-layer Bottles Co-injected in Normal Mould
This is the case where the mould is initially at room temperature, in the surrounding air
at 40 C, with a convection heat transfer on the external surface of the mould.
The PET layers are injected in the mould, by following the operational conditions described
in Figure 3.30. The bottle components, initially at 280 C have been previously injected in the
mould, where they are cooled down for 1 second. The thickness of the mould is 1.5 cm.
In Figure 4.24, the kinetics of release of the contaminant into the food are shown for
various values of the dimensionless number R.
In Figure 4.25, the kinetics of release of the contaminant in the food shown in Figure
4.24, are extended with a large scale.
Some interesting results appear from these curves:
i) An important fact is shown in Figure 4.26, where the proles of concentration of the
contaminant are drawn at the end of the stage of cooling, associated with the various
cases of co-extrusion and of co-moulding calculated in Chapter 3.
In Figure 4.26 all the proles of concentration of the contaminant obtained at the
end of the stage of cooling collected in the various cases shown in Figures 3.21, 3.24,
3.27 and 3.30, are altogether nearly similar.
ii) Thus it is obvious that the proles of concentration developed by the contaminant in
Figure 4.21 are of value in the present case.
181
Figure 4.24. Kinetics of transfer of a diffusing substance in the liquid food of nite
volume such as = 55.3, with various values of the dimensionless number R.
The initial prole of concentration of the diffusing substance is that attained at the
end of the co-moulding stage described in Figure 3.30 for the three-layer bottle.
Dimensionless numbers are used for the co-ordinates.
Figure 4.25. Kinetics of transfer of a diffusing substance in the liquid food of nite
volume such as = 55.3, with various values of the dimensionless number R, with
expanded scale. The initial prole of concentration of the diffusing substance is that
attained at the end of the co-moulding stage described in Figure 3.30 for the three-layer
bottle. Dimensionless numbers are used for the co-ordinates.
182
Figure 4.26. Proles of concentration attained by the diffusing substance at the end
of the stage of co-moulding with three-layer bottles in various cases: 1: Figure 3.21;
2: Figure 3.24; 3: Figure 3.27; 4: Figure 3.30.
iii) Finally, the kinetics of release of the contaminant into the food for various values of
the dimensionless numbers drawn in Figures 4.24 and 4.25 are similar to those drawn
in Figures 4.22 and 4.23.
4.7 Conclusions on the Functional Barrier
In terms of conclusions about the effect of the functional barrier, two facts of importance
can be looked upon, either by estimating the time of protection provided by the presence of
this virgin polymer layer or by considering the decrease in this time of protection resulting
from the advancement of the proles of concentration of the contaminant which takes
place during the process of co-extrusion or co-moulding.
4.7.1 Interest of a Functional Barrier
The interest of the functional barrier is obvious, as it appears in the various gures depicting
the kinetics of release of the contaminant in the liquid food. In each case, there is a time
183
of full protection. Moreover, after this time, the amount of contaminant in the liquid food
(as well as the concentration) increases rather slowly, bringing another partial protection.
On the contrary, without a functional barrier, the kinetics of release of the contaminant
into the liquid food exhibits a high rate, especially at the beginning of the process.
Quantitative results are given in the following three Tables (Tables 4.1, 4.2 and 4.3).
Table 4.1 Contamination versus dimensionless times for various values of R

Mono-layer Mt/Min
R 0.0001 0.001 0.01 0.1
-4 -3 -2
1 1.00 10 1.02 10 1.08 10 0.1281
-5 -4 -3
5 2.01 10 2.11 10 2.37 10 3.50 10-2
10 1.00 10-5 1.08 10-4 1.28 10-3 2.22 10-2
50 2.00 10-6 2.35 10-5 3.49 10-4 1.10 10-2
- 7.50 10-7 7.86 10-5 7.93 10-3

Bi-layer Mt/Min
R 0.0001 0.001 0.01 0.1
-2 -2 -2
1 2.04 10 3.48 10 7.49 10 0.2458
-2 -2 -2
5 1.57 10 2.47 10 4.72 10 0.1325
-2 -2 -2
10 1.44 10 2.22 10 4.13 10 0.1135
-2 -2 -2
50 1.27 10 1.92 10 3.50 10 9.59 10-2
1.19 10-2 1.80 10-2 3.30 10-2 9.10 10-2

Tri-layer Mt/Min
R 0.0001 0.001 0.01 0.1
-3 -2 -2
1 9.79 10 1.72 10 3.92 10 0.1656
-3 -2 -2
5 7.40 10 1.18 10 2.32 10 7.18 10-2
10 6.72 10-3 1.05 10-2 1.98 10-2 5.80 10-2
50 5.76 10-3 8.74 10-2 1.60 10-2 4.53 10-2
5.31 10-3 8.02 10-3 1.47 10-2 4.18 10-2
184
They provide information on the time (expressed in terms of the dimensionless time
Dt/L2, L being the total thickness of the package or bottle) necessary for given values
of the amount of contaminant (expressed in terms of the amount of contaminant in the
liquid food as a fraction of the amount initially in the recycled polymer layer, Mt/Min) to
be released in the food, with various values of the dimensionless number R dening the
convective effect at the package-liquid interface.
The Tables 4.1, 4.2 and 4.3 show the results obtained:
With the mono-layer, and = 166, as shown in Figures 4.4 and 4.5
With the bi-layer, and =166, as shown in Figure 4.11
With the tri-layer, and = 55.3, as shown in Figures 4.22 and 4.24
From these tables, the effect of the convective transfer at the package-liquid food denitely
appears in a quantitative manner.
4.7.2 Effect of the Co-extrusion and Co-moulding on the Mass Transfer
From the calculations made by using a law of temperature-dependency of the diffusivity,

as far as this law was representative of the fact, the following results clearly appear:
The time of residence of the bottle in the mould is short, at around 1 second, but the
heat transfer is strong. This fact results from the high thermal conductivity of the
metal with respect to the lower one of the polymer.
Even if the diffusivity of a contaminant in PET is high at a temperature of 280 C, the

temperature decreases rather quickly, so that the transfer of the contaminant is small.
It is not necessary to cool down the mould, moreover, the effect of the value of the
temperature in the surrounding atmosphere ranging from 20 to 40 C is negligible.
4.8 Conclusions on the Diffusion-Convection Process
Finally, in terms of conclusions on the process of pollution in a liquid food, the striking
points can be noted:
i) Because of the convective transfer through the liquid, the concentration of any
contaminant at any time is uniform.
185
ii) And thus, the contaminant transfer from the package into the liquid food can be
considered as a one-dimensional transfer, taking place per unit area, the volumes
being reduced to lengths, whatever the shape of the ask or bottle.
iii) The process of transfer is controlled either by one-dimensional transient diffusion

through the thickness of the polymer package or convective transfer at the polymer-
liquid interface.
iv) The ratio of the volumes of liquid and package, , on the transfer is negligible, when
this number is larger than 20-40, depending on the desired accuracy. The value of
is equal to 166 for a litre bottle in cubic form with a thickness of 100 m.
v) The effect of the convective transfer is of great importance. The dimensionless number
R dened by the ratio hL/D, where L is the total thickness of the polymer package in
contact with the liquid food on one side, expresses the effect of the convective transfer.
As the rate of convective transfer h plays such an important role in the contaminant
transfer, it should be necessary for the food package problems which concern the
public health, to follow the process which was dened for pharmaceutical applications.
The pharmacists are obliged to control precisely the conditions of stirring when they
evaluate the kinetics of drug release from controlled release dosage forms by using
standardised tests [6, 7].
vi) The gures drawn by using dimensionless numbers are master curves which can be
used, whatever the data. They are: Mt/M, Ct/Cin, Dt/L2, hL/D.
vii) Recycling polymer packages in new packages is made possible by using a virgin polymer
layer in contact with the food, which acts upon the process as a functional barrier.
viii) The decrease in temperature during the process of co-extrusion for a lm or co-
moulding for a bottle is fast, whatever the technique used. Thus the effect on the
change in the proles, of concentration of the contaminant at the interface between
the layers is so low that it becomes negligible, as far as the law expressing the
temperature-dependency of the diffusivity is correct.
ix) The data shown either in the tables of Section 4.7 as well as in Figures 4.5, 4.11 and
4.22 can be of help for selecting the type of package, which is necessary to comply
with the requirements desired for food protection.
4.9 Problems Encountered with a Solid Food
There are two different cases when the food is in a solid state: the one when the solid
food is made of grains separated from each other by a gas; the other when the solid is
186
homogeneous as, for example, yoghurts or butter. Only the second case is considered here,
the food being in a gel state, however homogeneous and isotropic. Thus the transfer of
any additive through the solid food is controlled by diffusion.
The problem of diffusion through a solid food stored into a bottle has already been studied
and resolved through various papers. The first when the bottle is made of a virgin layer
[20], the second by considering a bottle made of a bi-layer system with a recycled polymer
layer and a virgin polymer layer in contact with the food [21], while the third is devoted
to the effect of the relative thicknesses of the two layers of the bi-layer bottle [22].
4.9.1 Theoretical Part of the Problem
4.9.1.1 Assumptions
The following assumptions are made to define the process:
i) The food is either in a solid state or in a gel state, however isotropic and homogeneous.
ii) The process of transfer into, and through, the solid food is controlled by transient
diffusion.
iii) Because of the bottle shape, the diffusion is both radial and longitudinal either through
the solid food or through the thickness of the bottle.
iv) A perfect contact is obtained at the bottle-food interface.
v) The diffusivity is constant either in the bottle or in the solid food.
vi) The partition factor is 1 at the food-bottle interface.
4.9.1.2 Mathematical Treatment
The equation of diffusion taking into account the radial and the longitudinal transport is:
C 2C 2C 1 C
= D 2 + 2 + (4.33)
t z r r r
where z represents the longitudinal axis and r the radial axis, C is the local concentration
of the diffusing substance which is a function of time and of position defined by the two
co-ordinates r and z, and D is the constant diffusivity.
187
An analytical solution is found when the values of the diffusivity are the same in the
polymer and in the food [3, 4], but it seems that no solution exists when the diffusivity
of a diffusing substance in the food is different from that in the polymer.
The initial conditions in the polymer bottle and in the solid food are:
t=0 C = Cin in the polymer of the bottle (4.34)

C = 0 in the food
The boundary conditions are:
At the external surface of the bottle:
C C
t>0 = 0 and = 0 (4.35)
h r
meaning that the contaminant does not diffuse out of the bottle.
At the food-bottle interface, where the concentrations are equal in the polymer and the food:
C C
Dp = Df (4.36)
r p r f
C C
Dp = Df (4.36)
h p h f
meaning that the rate of transfer of the diffusing substance is the same on both sides of
the food-bottle interface.
Moreover, Equation (4.33) holds either for the polymer bottle or for the food located in it.
As the diffusivity of the contaminant (diffusing substance) is generally much larger in the food
than in the polymer of the bottle, no simple analytical solution is obtained. Thus, the problem
is resolved by using a numerical method based on nite differences. It takes into account the
radial and longitudinal diffusion, leading to an axis of symmetry along the Z-axis.
4.9.2 Results for the Transfer in the Solid Food
The results are expressed in terms of kinetics of release of diffusing substance in the solid
food and of proles of concentration of this diffusing substance developed in various
188
places of the food. These proles of concentration are calculated and drawn in two
sections of the food and polymer: the one which is a cross section perpendicular to the
Z-axis of the bottle at position A1A3, the other which is a radial section of radius 2 cm
(D1D3) in Figure 4.27.
The scheme of the process is depicted in Figure 4.27, with a quarter of the bottle. The
scheme is not drawn to scale. The radial and longitudinal diffusion are shown.
The following other gures are considered:
Figure 4.28 represents the kinetics of release of the diffusing substance into the solid
food, for three values of the diffusivity in the food selected within a large range, while
the diffusivity is kept constant in the polymer of the bottle.
Figure 4.27. Scheme of the one-layer bottle in contact with a solid food.
189
Figure 4.28. Kinetics of transfer of the diffusing substance into the solid food, for
various values of the diffusivity in the solid food expressed in cm2/s. The diffusivity
in the bottle is 108 cm2/s. The dimensions of the bottle are: radius = 4 cm and
height = 20 cm, with a thickness of the bottle of 0.03 cm.

the plane section perpendicular to the Z-axis at position A1A3, and especially in the
polymer thickness denoted A2A3 with Dp = 108 cm2/s and Df =10-6 cm2/s.
190
Figure 4.29 represents the proles of concentration of the diffusing substance developed
through the plane section perpendicular to the Z-axis at the position A1A3, and especially
in the polymer thickness noted A2A3 when the diffusivity is 108 cm2/s in the polymer and
10-6 cm2/s in the food.
in the food thickness noted A1A2 when the diffusivity is 108 cm2/s in the polymer and
106 cm2/s in the food.
through the cylindrical section parallel with the Z-axis of radius 2 cm, taken at position
D1D3, and especially in the polymer thickness denoted D2D3 when the diffusivity is 108
cm2/s in the polymer and 106 cm2/s in the food.
D1D3, and especially in the food thickness noted D1D2, when the diffusivity is 108 cm2/s
in the polymer and 106 cm2/s in the food.
plane section perpendicular to the Z-axis at the position A1A3, and especially in the
food thickness noted A1A2 when Dp = 108 cm2/s and Df = 106 cm2/s.
191

the cylindrical section parallel with the Z-axis of radius 2 cm, taken at position
D1D3, and especially in the polymer thickness denoted D2D3 when Dp = 108 cm2/s
and Df = 106 cm2/s.
cylindrical section parallel with the Z-axis of radius 2 cm, taken at position D1D3, and
especially in the food thickness denoted D1D2, when Dp = 108 cm2/s and Df = 106 cm2/s.
192
in the polymer thickness denoted A2A3, when the diffusivity is 108 cm2/s in the polymer
and 104 cm2/s in the food.
in the food thickness noted A1A2 when the diffusivity is 108 cm2/s in the polymer and
104 cm2/s in the food.
D1D3, and especially in the polymer thickness noted D2D3 when the diffusivity is 108
cm2/s in the polymer and 104 cm2/s in the food.
D1D3, and especially in the food thickness denoted D1D2, when the diffusivity is 108 cm2/s
in the polymer and 104 cm2/s in the food.
polymer thickness denoted A2A3, when Dp = 108 cm2/s and Df = 104 cm2/s.
193
food thickness denoted A1A2 when Dp = 108 cm2/s and Df = 104 cm2/s.
cylindrical section parallel with the Z-axis of radius 2 cm, taken at position D1D3, in
the polymer thickness denoted D2D3 when Dp = 108 cm2/s and Df = 104 cm2/s.
194
Figure 4.36. Profiles of concentration of the diffusing substance developed through the
cylindrical section parallel with the Z-axis of radius 2 cm, taken at position D1D3, and
especially in the food thickness denoted D1D2, when Dp = 108 cm2/s and Df = 104 cm2/s.
The characteristics are shown in Table 4.4
Table 4.4 Characteristics of the problem used for calculation

Bottle Internal radius = 4 cm; height = 20 cm,
thickness = 0.03 cm, = 61.35
Diffusivity in the polymer Dp = 108 cm2/s
Diffusivity in the food Df = 106 cm2/s and Df = 104 cm2/s
C/Cin = 0.0163 D2C2 = 2 cm A1B2 = 4 cm
From Figures 4.28 to 4.30, the following comments are worth noting:
i) As shown in Figure 4.28, the effect of the rate of transfer of the diffusing substance
through the food, expressed by the diffusivity, is of importance. The obvious statement
holds: the larger the diffusivity of the substance in the food, the faster the kinetics of
release. Nevertheless, the transfer is controlled either by diffusion through the polymer
195
or through the food. In the present case, the diffusivity of the substance through the
polymer plays the role of a limiting factor.
ii) The kinetics of release of the diffusing substance in the food is also expressed in terms
of change in the concentration of this substance in various places in the polymer
and in the food. Because of the perfect contact between the food and the bottle, the
concentration of the diffusing substance is the same on both sides of the food-bottle
interface. Obviously, the concentration of the diffusing substance decreases in the
polymer as it increases in the food.
iii) After a long time, innity, theoretically speaking, the concentration in the food tends
to a uniform value, which is inversely proportional to the ratio of the volumes of
food and polymer. In the present case, this concentration, expressed in terms of the
ratio Cf,/Cin being equal to 1/1 + is 0.0163 as the partition factor K is taken as 1.
iv) The effect of the value of the diffusivity of the substance in the food is of importance,
as shown by comparing the curves in the Figure 4.28 for the kinetics, and the proles
of concentration developed at various times either in Figures 4.29-4.32 when the
diffusivity in the food is Df = 106 cm2/s or in Figures 4.33-4.36 obtained with Df =
104 cm2/s.
v) From the rst approach, the proles of concentration of the diffusing substance
developed through the thickness of the bottle look similar, but a closer study enables one
to appreciate the differences. For example, after the short dimensionless time of 0.01,
the relative concentration at the radial polymer-food interface A2 is lower than 0.1,
while it is larger than 0.1 at the same interface taken at position D2 between the food
and the bottom of the bottle. In the same way, the proles developed through either the
radial or the at cross-section in Figures 4.29 and 4.31 exhibit other differences.
vi) Of course, because of Equation (4.36) and (4.36), expressing the equality of the rate
of transfer through the polymer and the food, especially at their interface, the slope
of the proles of concentration being inversely proportional to the corresponding
diffusivity, is considerably higher in the polymer than in the food (without considering
the change in scale taken in these gures for the food and polymer).
vii) The proles of concentration developed in the food either through the at cross-
section A1A2 or through the radial section D1D2 are quite different. For example, at
the dimensionless time of 5, the substance has diffused across about 3 cm, reaching
the position 1 (Figure 4.30) and about the same position along the Z-axis (Figure
4.32). However, the strong difference appears, as the concentration after this time
of 5 remains the same along the Z-axis. Thus at a distance of nearly 4-5 cm from
196
the bottom of the bottle, the effect of the transfer from the bottom becomes of low
significance. In other words, at this distance from the bottom, the radial diffusion is
becoming more and more important compared to the longitudinal diffusion as the
distance at which it is taken away from the bottom is larger.
viii) The effect of the value of the diffusivity in the food appears with the Figures 4.33-
4.36, by comparing them with the corresponding Figures 4.29-4.32. At first glance,
these figures look similar, two at a time when evaluated and drawn at the same places.
However, the profiles are quite different, depending on the value of the diffusivity of
the food. For example, a dimensionless time of 2 is enough for the profiles to become
flat with Df = 104 cm2/s while it is more than 20, with Df = 106 cm2/s. Another strong
difference is worth noting, with the profiles of concentration developed through the
food. For example, the profiles obtained with Df = 104 cm2/s (Figure 4.34) are not
so steep as the corresponding ones shown in Figure 4.30 obtained with Df = 106
cm2/s.
ix) The effect of the longitudinal transfer from the bottom of the bottle on the profiles of
concentration is nearly the same, whatever the diffusivity in the food. Thus, as shown
in Figure 4.36 and Figure 4.32, at a distance between 3 and 4 cm from the bottom, the
transfer seems to be radial only, leading to the same concentration along the Z-axis.
References

UK, 1975, Chapter 4.
2. J-M. Vergnaud, Controlled Drug Release of Oral Dosage Forms, Ellis Horwood,
New York, USA, 1993, Chapters 1, 2, and 3.
3. J-M. Vergnaud, Liquid Transport Processes in Polymeric Materials: Modelling and

Industrial Applications, Prentice Hall, Englewood Cliffs, NJ, USA, 1991, Chapters
1, and 13.
4. S. Laoubi and J-M.Vergnaud, Polymers and Polymer Composites, 1996, 4, 6, 397.
5. D. Messadi and J-M. Vergnaud, Journal of Applied Polymer Science, 1981, 26,
7, 2315.
6. J-M. Vergnaud and I-D. Rosca, Assessing Bioavailability of Drug Delivery

USA, 2005, Chapter 4, section 4.1, and Chapter 10.
197
7. M. Siewert, European Journal of Drug Metabolism and Pharmacokinetics, 1993,

18, 1, 7.
8. S. Laoubi and J-M. Vergnaud, Food Additives and Contaminants, 1996, 13,
3, 293.

1995, 8, 5, 249.
10. S. Laoubi and J-M. Vergnaud, Packaging Technology and Science, 1995, 8, 2, 97.
1995, 8, 1, 17.

Science, 1997, 66, 3, 597.
13. S. Laoubi and J-M.Vergnaud, Food Additives and Contaminants, 1997, 14, 641.
14. S. Laoubi and J-M. Vergnaud, Journal of Polymer Engineering, 1996-1997, 16,
1-2, 25.
15. A.L. Perou, S. Laoubi and J-M. Vergnaud, Computational and Theoretical
Polymer Science, 1998, 8, 3-4, 331.
16. A.L. Perou, S. Laoubi and J-M. Vergnaud, Journal of Applied Polymer Science,
1999, 73, 10, 1939.
17. A.L. Perou, S. Laoubi and J-M. Vergnaud, Advances in Colloid and Interface
Science, 1999, 81, 1, 19.
18. A.L. Perou and J-M. Vergnaud, Journal of Polymer Engineering, 1997, 17, 5, 349.
19. J-M. Vergnaud, Advances in Colloid and Interface Science, 1998, 78, 3, 267.
20. I-D. Rosca and J-M. Vergnaud, Plastics, Rubber, and Composites Processing and
Applications, 1997, 26, 235.
21. I-D. Rosca and J-M. Vergnaud, Polymer Recycling, 1999, 3, 2, 131.
22. I-D. Rosca and J-M. Vergnaud, Journal of Applied Polymer Science, 1997, 66,
7, 1291.
198
Abbreviations
A half the thickness of the liquid (volume per unit area) in case of finite
volume of liquid
a length of the edge of a cube, considered as a model for the

volume/area ratio
ratio of the volumes of the liquid and of the sheet, per unit area, in
Equation (4.14)
n positive roots of the Equation (4.22). Table is given in the Appendix
Cx,t, CL,t concentration of diffusing substance at position x, on the side at position

L, at time t, respectively
Cin, C, Ceq concentration of diffusing substance, initially, and after infinite time,
respectively, and at equilibrium with that in the surrounding, liquid or gas
CGS Centimetre, gram, second system of physical units
D diffusivity (coefficient of diffusion) expressed in: cm2/s, square length/

unit time
Fx,t flux of matter at position x and time t (mass per unit area and per
unit time)
h coefficient of convection expressed in cm/s
K partition factor shown in Equation (4.15), dimensionless number
L half the thickness of the sheet (of thickness 2L); thickness of the package
Mt, M amount of matter transferred by diffusion after time t, infinite time,

respectively
n integer
PET polyethylene terephthalate
PVC polyvinyl chloride
qn non-zero positive roots of Equation (4.13)
199
S area of the sheet in contact with the liquid
x, t coordinate along which the diffusion occurs, and time, respectively
Dt/L2 dimensionless number, expressing time
hL/D dimensionless number, expressing the quality of stirring of the liquid
200
5
Active Packages for Food Protection
5.1 Process of Transfer with Active Packages
5.1.1 Passive Packages
Red wines and some aged cheeses are just about the only packaged foods that get better
as they get older. Beyond this well known fact, virtually all food products deteriorate
over time. As a result, packaging researchers are developing technology to slow that
deterioration and, in some cases, to use the package in actively improving food quality.
Semi-rigid plastic and exible packages are taking over an increasing share of the packaging
market from glass, jars and metal cans; demand for glass, cans, and paper-board is stalled,
while plastic and exible package use is growing. This trend is driven both by cost and
functionality. Using ketchup, as an example: it is very oxygen-sensitive, and therefore it
must have a very high oxygen barrier material in order for it not to darken and solidify.
Unfortunately although glass ts the bill, for oxygen permeability, people like ketchup in
a squeezable bottle, a function which cannot be obtained with glass. Oxygen permeability
is an issue with plastic bottles, too. Oxygen gets in and makes the product go bad with
common plastics, whereas this does not happen with glass. On the other hand, plastic takes
up less room, weighs less, and does not break, this quality being particularly attractive for
beer sales at sporting events and concerts, where plastic bottles are often thrown away.
The can also suffers from consumers impressions about canned food, including that the
interior coating does not look good, and also thinking that, that fact affects the avour,
of course, it is not true, but the perception is there [1].
Another disadvantage of the can is the customers perception of it they compare cans
with exible, polyethylene terephthalate (PET) containers, and the can does not seem to
be very modern. In other words, new packages spark new interest.
Consumers reap benets from all these package developments in terms of user-friendly
containers, such as longer product shelf life, and convenient ready-to-eat foods. Everybody
keeps looking for the elusive perfect material.
Until recently, the emphasis has been on passive barriers, which just sit there and act as
a barrier between the environment and the product. Such materials are often mixed so
201
as to take advantage of the nal desired properties - if a lm looks like it is one layer, in
fact it might be ve to nine layers of different plastics. An example is exible high-barrier
materials that greatly reduce the rate of oxygen transfer to the food, such as squeezable
ketchup bottles, the rst breakthrough type consisting of two layers of polypropylene
attached by tie layers to an inner barrier polymer layer of ethylene vinyl alcohol. Other
passive materials, such as plasticised PVC, slow moisture loss while letting oxygen pass
through - this property is useful for products like red meat, which needs oxygen to maintain
a bright colour generally associated with quality by consumers - at the same time, the
moisture barrier prevents the meat from drying out.
Oxygen and moisture are not the only substances that must be kept on the appropriate
side of a package, since avour and aroma barriers become more necessary. So packages
are being developed to make sure that the good avours are kept in and the bad avours
out. These materials can be polyester or oriented polypropylene metallised with a thin
coat of aluminium.
There are numerous other possible packaging combinations. Materials such as PET,
polyamides and polypropylene are coated with silicon or aluminium oxide to create
barriers for oxygen and organics. Clay-polyimide nanocomposites have been evaluated
as barrier materials for oxygen, carbon dioxide and water vapour.
Other food packages include polyethylene naphthalate (PEN) and PEN-PET blends as
high-barrier lms or rigid containers.
As a matter of conclusion, there are a large number of materials as well as the ability to
combine them in a lot of different ways to produce passive barriers of all kinds, but the
next step is bound to be the active packages.
5.1.2 Modified Atmosphere Packages for Perception of Freshness
People want to consume more products that are perceived as fresh, and in answer to this
desire, perhaps, some active packages may go to far in terms of what they imply about
the nature of their contents.
Oxygen and carbon dioxide levels in modied atmosphere packages (MAP) change as a
function of the respiration rate of the produce, temperature, the characteristics of the lm
and especially the O2 and CO2 permeability coefcients of the package materials [2].
High moisture content pasta placed in a carbon dioxide-nitrogen atmosphere within a

moisture-barrier package has an extended shelf life to about six weeks - such packages
include packets containing iron-based compounds, which rust and thus absorb oxygen
out of the package.
202
The modied atmosphere packages, with high oxygen and carbon dioxide permeability,
give salads or other sorts of vegetables two weeks of shelf life.
The package also has to be breathable, because the product continues to respire, emitting
gases, and when these gases build up inside, they would spoil the produce, so they have
to permeate through the package.
On the other hand, the packages may contain potassium permanganate adsorbed onto
silica to absorb ethylene and retard ripening.
In conclusion, as food products become more complex, so must their packages [1].
5.1.3 Active Packages with Antimicrobial Properties
On the whole, an active package works in concert with the food product and its
environment to produce a desired effect. While the passive package simply provides a
barrier able to protect the product, the active package plays an active role in maintaining
or even improving the quality of the enclosed food. The possible permutations on this
theme are to some extent endless. In fact, one option of using active packaging has been
to provide an increased margin of safety and quality. The following generation of food
packaging includes materials with antimicrobial properties. These package technologies
can play a role in extending the shelf-life of foods and reducing the risk from pathogens.
Antimicrobial polymers may be useful in other contact applications as well.
An antimicrobial package is a form of active package, as it interacts with the product or the
headspace between the package and the food system, to obtain a desired outcome [3]. Likewise,
antimicrobial food packaging acts to reduce, inhibit or retard the growth of microorganisms
that may be present in the packed food or the packaging material itself [4].
5.1.3.1 Types of Antimicrobial Packages
These packages can take several forms including [4]:
i) addition of sachets or pads containing volatile antimicrobial agents into packages;

ii) incorporation of volatile and non-volatile antimicrobial agents directly into polymers;
iii) coating or adsorbing antimicrobials onto polymer surfaces;
iv) immobilisation of antimicrobials to polymers by ion or covalent linkages;
v) use of polymers that are inherently antimicrobial.
203
5.1.3.2 Addition of Pads Containing Antimicrobial Agents to Packages
The most successful commercial application of this type of package has been sachets
that are either enclosed loose or attached to the interior of a package. The following
three forms have predominated: oxygen absorbers, moisture absorbers and ethanol
vapour generators.
Oxygen and moisture absorbers have been used in bakery, pasta, and meat packaging
to prevent oxidation and water condensation. If oxygen absorbers are not exactly
antimicrobial, reduction in oxygen inhibits the growth of aerobes and moulds, in the
same way as moisture absorbers [5].
Ethanol vapour generators consist of ethanol absorbed or encapsulated in carrier

materials, enclosed in polymer packets which let the ethanol permeate the selective barrier
and thus be released into the headspace within the package.
5.1.3.3 Incorporation of Antimicrobial Agents Directly into the Polymers
Incorporation of antimicrobials into polymers has been commercially applied in drug

and pesticide delivery, surgical implants and other biomedical devices. Few food-related
applications have been commercialised, but the number of articles and patents indicate
that research on this subject has more than doubled in the last ve years.
Numerous potential antimicrobials have been considered. Allyl isothiocyanate, an

antimicrobial extracted from plants, has been approved as an additive in Japan - diffusing
as a vapour it can extend the shelf life of meat, sh and cheese.
Derived agents such as benzoic acid, sodium benzoate, sorbic acid, and propionic
acid, some of them having been used in edible coatings. Zeolites have also been
incorporated in packages to release ions, or enzymes able to release antimicrobials as
hydrogen peroxide.
5.1.3.4 Coating or Adsorbing Antimicrobials to the Polymer Surface
Antimicrobials that cannot tolerate the temperature used in the processing of packaging
are often coated onto the material after forming or are added to cast lms. Examples
include nisin, an antibiotic, coated onto low-density polyethylene lm in a methyl-
cellulose carrier [4].
204
5.1.3.5 Immobilisation of Antimicrobials by Ionic or Covalent Linkages

to Polymers
This type of immobilisation requires the presence of functional groups on both the
antimicrobial and the polymer, these groups being spacer molecules linking the polymer
surface to the bioactive agent.
The enzyme naringinase has been immobilised in a polymer that could be potentially be used
as a liner inside a grapefruit carton, and the avonones responsible for bitterness in citrus
products are broken down. When the juice is stored in contact with the lm, the enzyme
hydrolyses the bitter compounds, making the beverage taste sweeter over time [1, 4].
5.1.3.6 Use of Polymers that are Inherently Antimicrobial
Antimicrobial packages have also been developed. As surface growth of microorganisms

is one of the leading causes of food spoilage, a package system that allows for slow release
of an antimicrobial agent into the food could signicantly increase the shelf life and so
improve the quality of a large variety of food [1, 4].
5.1.4 Applications of Antimicrobial Package in Foods
Antimicrobial polymers can be used in several food applications, including packaging. The
rst use is to promote safety and thus extend the shelf-life by reducing the rate of growth
of specic microorganisms by direct contact of the package with the surface of solid foods,
such as meat, or in the bulk of liquids as milk. Secondly, these antimicrobial packages
could be self-sterilising, reducing the potential for recontamination of the products and
simplify the treatment required to eliminate the product contamination.
5.1.5 Testing the Effectiveness of Antimicrobial Packages and Regulatory Issues
There are a variety of ofcial test methods to determine the resistance of plastic materials to
microbial degradation, but there is no agreement upon standard methods to determine their
effectiveness [4]. Food packaging is highly regulated around the world and development
projects on antimicrobial packages must take these regulations into consideration. At
this time, antimicrobials in food packaging that may migrate to food are considered to
be food additives and must meet the food additives standards.
205
5.1.6 Detection Systems
Despite all these efforts, microorganisms continue to be found in food. Researchers are
working on a detection system for bacterial toxins and pathogens in food. The idea being
that this system using cells engineered to react with their surroundings, would promote
colour changes in the presence of pathogens in food. Also used to alert consumers to
problems are time-temperature indicators, which can show whether the enclosed frozen
food product has been mishandled during shipping or storage.
5.2 Active Packages Theoretical Considerations
5.2.1 Process of Release and Consumption, and Assumptions
The process of release and consumption of the agent is described by considering the three
stages in succession:
1. The package consists of two main parts: the usual polymer package, which is
impermeable to the agent, and a polymer sheet called linen which contains the active
agent with a uniform concentration.
2. The agent diffuses through the linen and is released into the food.
3. The agent reacts with the microorganisms, and a part of this agent is consumed.
The following assumptions are made in order to simplify the problem:
i) In spite of the fact that the package is a bottle, or is bottle-shaped, there is a mono-
directional transfer of the agent through the linen and into the food. This assumption
can be made as the thickness of the polymer is very low as compared with the radius
of the bottle. Moreover the ratio of the volume of the food and the surface of the
package V/S = a/6 for a cube, and thus for a litre of food, the thickness of the food
is 1.66 cm.
ii) The kinetics of release of the agent is controlled either by diffusion through the polymer
linen or by convection into the food.
iii) The kinetics of consumption of the agent by the microorganisms located in the
food is described by a rst-order reaction with respect to the concentration of the
agent [6].
206
5.2.2 Mathematical and Numerical Treatment
The transfer of the agent through the polymer linen is expressed by the one-dimensional
equation of diffusion with constant diffusivity:
C 2C
= D 2 (5.1)
t x
and at the linen-food interface, the boundary conditions apply:
C
D = h (CL , t C f , t ) (5.2)
x
meaning that the rate at which the agent enters the food is constantly equal to that at which
it is brought to the linen surface by diffusion, where h is the coefcient of convection into
the food and D is the diffusivity of the agent through the linen.
On the other surface of the linen, there is no transfer of the agent:
C
=0 (5.3)
x
The rate of consumption of the agent by the microorganisms in the food is given by:
C
= K Cf ,t (5.4)
t
in the homogeneous food phase, where the concentration Cf,t is uniform.
When a reaction takes place, the amount of the agent located in the food Y is given by
the relationship:
dY dM
= K Yt (5.5)
dt dt
where M is the amount of the agent delivered in the food by the linen at time t.
The kinetics of release of the agent out of the linen, controlled either by diffusion through
the thickness of the linen or by the convection at the linen-food interface, is expressed by
the following relationship:
207
M M t 2R 2 2 D t
= 2 2 exp n 2 (5.6)
n =1 n (n + R + R)
2
M L
tan = R (5.7)
and R is given by:
hL
R= (5.8)
D
The letters given for the various parameters are dened at the end of Chapter 5.
5.3 Results Obtained by Calculation
The scheme of the system, representing the process, is shown in Figure 5.1, with the
impermeable layer, the linen of thickness L1 = X2 X1 containing the active agent
with the initial concentration Cin, and the food. As already proved in Chapter 1,
resulting from the fact that the internal convective transfer through the liquid is fast
enough, and at least much larger than the rate of release of the agent into the food, the
concentration of this active agent as well as that of the microorganisms in the liquid
food is constantly uniform.
Figure 5.1 Scheme of the system: impermeable polymer (1); linen (2); liquid food (3).
208
Figure 5.2 Kinetics of release of the agent in the food when there is no consumption of
the agent (expressed through the dimensionless number Dt/L2), with various values of
R = hL/D = 1; 2; 20; 100; K = 0; L = 0.1 cm and Lf = 1.66 cm (1 litre food)
The kinetics of release of the active agent into the liquid free from any microorganisms
is shown in Figure 5.2 for a wide range of values of the dimensionless numbers R. Other
dimensionless numbers are also used: Dt/L2 for time, and the ratio Cf/Cin of the concentration
of the agent in the food at any time as a fraction of the initial concentration in the linen.
The problem is similar to that of the release of a drug from a dosage form whose release
is controlled by diffusion [7]. No analytical solution exists, and the problem should be
resolved by a numerical treatment. Time is expressed in terms of nite increments t,
with the integer j such that t = jt. Starting with j = 0, which corresponds with the initial
conditions, calculation is made at j = 1 for either the amount of active agent released out
of the linen at that time or for the proportion which is consumed by the microorganisms,
by following the Equations (5.4) to (5.6), and so on, for the following values of j.
5.3.1 Results Obtained for High Values of R
The dimensionless number, sometimes called the Sherwood number, is taken at R = 100,
by considering two values of the components of R, e.g., the thickness of the linen and the
coefcient of convection h. With R = 100, the process of release is controlled by diffusion
through the thickness of the linen, as the coefcient of convection is rather high.
209
Two ways are followed to obtain this value of R = 100, by varying simultaneously the thickness
of the linen and the value of the coefcient of convection, as shown in Table 5.1.
Table 5.1 Values of the parameters used for calculation

K (/s) 0 108 107 106 105 104 103
Figures 5.3
SN 0 0.01 0.1 1 10 100 1000
and 5.5
Figures 5.4
SN 0 0.0025 0.025 0.25 2.5 25 250
and 5.6
The following gures are considered:
Figure 5.3 depicting the kinetics of the active agent remaining free in the liquid, with the
process controlled by diffusion and the values: L = 0.1 cm; D = 108 cm2/s; h = 105 cm/s,
for various values of the killing rate constant K and of the Savoie number (SN).
Figure 5.4 showing the kinetics of the active agent remaining free in the liquid, with the
diffusion-controlled process and the values: L = 0.05 cm; D = 108 cm2/s; h = 2105 cm/s,
for various values of the killing rate constant K and of the SN.
Figure 5.5 representing the kinetics of the agent consumed by the microorganisms in food
with the diffusion-controlled process for various values of K and SN, with L = 0.1 cm;
D = 108 cm2/s; h = 105 cm/s.
Figure 5.6 Kinetics of the agent consumed in food with the process controlled by
diffusion, with Sherwood number 100, for various values of K and SN, with L = 0.05 cm;
D = 108 cm2/s; h = 2105 cm/s.
From these gures, some comments are worth considering:
i) The effect of the value of the SN, (KL2)/D, which is proportional to the rate constant
of the kinetics of consumption of the agent is of considerable importance. Curve 1 in
the Figures 5.3-5.6 is obtained with no consumption reaction (K = 0). It can also be
seen that for low values of K, e.g., less than 108/s, the kinetics of the agent consumed
and thus the complementary kinetics of the agent remaining free in the food are
nearly similar (curve 2) to those obtained with K = 0, over a time of 1,000 hours. The
corresponding values of the SN are 0.01 with the conditions of the Figures 5.3 and
5.5 and 0.0025 with the conditions of the Figures 5.4 and 5.6. In both these cases,
the active agent can be considered entirely free, since a small amount is consumed.
210
Figure 5.3. Kinetics of the agent remaining free in food with the process controlled by
diffusion, with a Sherwood number of 100, for various values of K and SN: KL2/D.
L = 0.1 cm; D = 108 cm2/s; h = 105 cm/s; Lf = 1.66 cm (1 litre food). 1: K = 0;
2: K = 108; 3: K = 107; 4: K = 106; 5: K = 105; 6: K = 104; 7: K = 103/s
Figure 5.4. Kinetics of the agent remaining free in food with the process controlled by
2: K = 108; 3: K = 107; 4: K = 106; 5: K = 105; 6: K = 104; 7: K = 103/s
211
Figure 5.5. Kinetics of the agent consumed in food with the process controlled by
2: K = 108; 3: K = 107; 4: K = 106; 5: K = 105; 6: K = 104; 7: K = 103/s
diffusion, with a Sherwood number of 100, for various values of K and Savoie number:
KL2/D. L = 0.05 cm; D = 108 cm2/s; h = 2105 cm/s; Lf = 1.66 cm (1 litre food).
1: K = 0; 2: K = 108; 3: K = 107; 4: K = 106; 5: K = 105; 6: K = 104; 7: K = 103/s
212
ii) For larger values of the consumption rate constant and of the SN, the shape of the
kinetics is quite modied. Thus, the statement holds: that the higher the value of K, the
faster the kinetics of consumption and the lower the amount of the agent remaining
free in the liquid food. For high values of K, e.g., larger than104/s, the active agent is
quickly consumed after a time which does not exceed 200-400 hours depending on
the thickness of the linen.
iii) For intermediate values of the rate constant K, typical curves are obtained. On the
one hand, the curves expressing the kinetics of the drug remaining free, pass through
a maximum whose position (time and height) depends on the value of K. On the
other hand, the kinetics of consumption exhibit a S-shape which is clearly shown as
curve 4 obtained with K = 106/s and SN = 1 under the conditions of Figure 5.5 and
SN = 0.25 with those of Figure 5.6.
iv) The relative effect of the thickness of the linen is also of interest. Whatever the value
of the coefcient of convection, a thicker linen is responsible for faster kinetics of the
agent release in the liquid, as well as for the agent consumed.
5.3.2 Results Obtained with Low Values of R
The values of the dimensionless number R is taken at 1, by considering the two values
of the components of R, the thickness of the linen and the coefcient of convection h.
With such a low value, the process of the agent release from the linen is controlled by
convection at the linen-liquid food interface. The values of the Motiers number (MN)
are shown in Table 5.2.
Table 5.2 Values of the parameters used for calculation

K (/s) 0 108 107 106 105 104 103
Figures 5.7
MN 0 0.01 0.1 1 10 100 1000
and 5.9
Figures 5.8
MN 0 0.0025 0.025 0.25 2.5 25 250
and 5.10
The following gures are considered:
Figure 5.7 depicting the kinetics of the active agent remaining free in the liquid, with the
process controlled by diffusion and the values: L = 0.1 cm; D = 108 cm2/s; h =107 cm/s,
for various values of the killing rate constant K and of the MN.
213
Figure 5.8 showing the kinetics of the active agent remaining free in the liquid, with the
diffusion-controlled process and the values: L = 0.05 cm; D =108 cm2/s; h = 2107 cm/s,
for various values of the killing rate constant K and of the MN.
Figure 5.9 representing the kinetics of the agent consumed by the microorganisms in
food with the diffusion-controlled process for various values of K and of the MN, with
L = 0.1 cm; D = 108 cm2/s; h =107 cm/s.
Figure 5.10 Kinetics of the agent consumed in food with the process controlled by diffusion,
with Sherwood number 1, for various values of K and of the MN, with L = 0.05 cm;
D = 108 cm2/s; h = 2107 cm/s.
The following conclusions can be drawn from Figures 5.7-5.10:
i) For low values of the rate constant of the reaction K (equal or lower than 108/s) and
MN lower than either 0.01 in Figures 5.7 and 5.9 (curve 1 and 2) or 0.0025 in Figures
5.8 and 5.10, the active agent remains almost free in the liquid food. Obviously, there
is no consumption of this active agent when K = 0.
ii) For large values of the rate constant of the reaction K (larger than 104/s), with the
corresponding values of the MN of either 100 in the case of the Figures 5.7 and 5.9
(curves 6 and 7) or 25 in the case of the Figures 5.8 and 5.10 (curves 6 and 7), the
active agent reacts and thus disappears as soon as it is released in the food.
iii) For the intermediate values of the rate constant of the reaction K, and with the
corresponding values of the MN located between 0.0025 and 25, the curves expressing
the kinetics of the concentration of the active agent remaining free in the food pass
through a maximum, as shown in Figures 5.7 and 5.8. The position of this maximum
varies with the value of the MN, the time at which it is obtained, as well as its height
decreases as the rate constant K is increased. On the other hand, in a complementary
way, the kinetics of consumption of the active agent increases with the value of the
rate constant K, exhibiting a kind of S-shaped curve.
iv) The thickness of the linen plays an important role on the process of release of the
active agent in the food. Obviously, the kinetics of release of the active agent in the
food increases with the thickness of the linen, as shown by comparing the curves in
Figures 5.7 and 5.8.
In the same way, the kinetics of consumption of the active agent also increases with the
thickness of the linen.
214
Figure 5.7. Kinetics of the agent remaining free in food with the process controlled
by diffusion, with a Sherwood number of 1, for various values of K and SN: KL2/D.
L = 0.1 cm; D = 108 cm2/s; h = 107 cm/s; Lf = 1.66 cm (1 litre food). 1: K = 0; 2: K = 108;
3: K = 107; 4: K = 106; 5: K = 105; 6: K = 104; 7: K = 103/s
Figure 5.8. Kinetics of the agent remaining free in food with the process controlled
2: K = 108; 3: K = 107; 4: K = 106; 5: K = 105; 6: K = 104; 7: K = 103/s
215
2: K = 108; 3: K = 107; 4: K = 106; 5: K = 105; 6: K = 104; 7: K = 103/s
Figure 5.10. Kinetics of the agent consumed in food with the process controlled
2: K = 108; 3: K = 107; 4: K = 106; 5: K = 105; 6: K = 104; 7: K = 103/s
216
5.3.3 Establishment of the Dimensionless Numbers
On the whole, there are two ways to establish a dimensionless number [8]. The one, which
is very simple but also hazardous, consists of building a fraction where the numerator
has the same dimension as the denominator. The other, which is more consistent, is
obtained by equilibrating the two opposite acting forces which are facing each other, and
simplifying afterwards.
According to the second method [9, 10] selected, let us recall that the dimensionless
number R is obtained as follows:
Equation (5.2) can be rewritten in the form:
D Cp
= h (C p C f ) (5.9)
Lp
leading to the well-known relationship expressing the dimensionless number R:
h Lp Cp
= =R (5.10)
D Cp Cf
where the right side-member is dimensionless, being the ratio of two concentrations of
the active agent.
In the same way, the other new dimensionless numbers are established in the following way:
When the process is controlled by diffusion:
M C
= D p = K M = K C f L f (5.11)
t x
which can be rewritten in the simple manner:
D Cp
= K Cf L f (5.12)
Lp
This equation leads to the dimensionless number, the SN:
K L2p
= SN (5.13)
D
217
since the ratio of the concentrations is inversely proportional to the volumes:
Cf L p
= (5.14)
Cp L f
When the process is controlled by convection at the polymer-liquid interface, with a low
value of the coefcient of convection, the limiting relationship is obtained by writing
that the rate of the agent released in the food is equal to its rate of consumption by the
microorganisms:
h (C p C f ) = K C f L f (5.15)
which leads to the dimensionless number, the MN:
K Lp
= MN (5.16)
h
by taking into account relationship (5.14).
5.4 Conclusions about the Active Agents
It is difcult to predict what the future for the development of the active agents will be.
By considering what was declared by very well informed authors [1], there are potential
applications for the active agents to achieve long-term food protection. Certainly, it is true
that protecting food for a few days is one thing, but there is a quite another objective,
more attractive, to be able to keep the same food under safety conditions over a period
of time exceeding one or two weeks.
However, a problem appears with the various qualications of the specialists necessitated
by the work. There should be the specialists in polymers and polymer additives, the
people responsible for the food, the experts in packaging, but also the bacteriologists as
well as the analysts, but fortunately, the experts in chemical engineering could unite all
those people, and the rst step is the introduction of the dimensionless numbers. The
dimensionless number allows those people to work independently, nevertheless having
in mind the same objective.
218
References
1. S.L. Wilkinson, Chemical and Engineering News, 1998, 76, 24, 26.
2. T. Al-Ati and J.H. Hotchkiss, The Role of Film Permeselectivity in MAP (private
review paper).
3. A.L. Brody, E.R. Strupinsky and L.R. Kline, Active Packaging for Food
Applications, Lancaster, PA, Technomic Publishing Co, 2001.
4. P. Appendini and J.H. Hotchkiss, Review of Antimicrobial Food Packaging

(Private review paper).
5. Active Food Packaging, Ed., M. Rooney, Blackie Academic & Professional,

Glasgow, UK, 1995.
6. I-D. Rosca and J-M. Vergnaud, Pharmaceutical Sciences, 1995, 1, 391.

USA, 2005.
8. W.H. McAdams, Heat Transmission, 3rd Edition, McGraw-Hill, New York, NY,
USA, 1954.
9. M. El Kouali, M. Salouhi, F. Labidi, M. El Brouzi and J-M.Vergnaud, Plastics,

Rubber and Composites, 2003, 32, 3, 127.
10. M. El Kouali, M. Salouhi, F. Labidi, M. El Brouzi and J-M. Vergnaud, Polymers

and Polymer Composites, 2003, 11, 4, 301.
219
Abbreviations
a side of a reference cube of volume V and area S
ns positive roots of the Equation (5.7)
C concentration of the active agent
Cin initial concentration of the active agent in the linen
Cf concentration of the active agent in the food at any time
Cf/Cin dimensionless number, for the concentration of the agent in the food
D diffusivity (cm2/s)
Dt/L2 dimensionless number, for time
h coefcient of convective transfer at the linen-liquid interface (cm/s)
K rate constant of the rst-order bactericidal reaction (/s)
L thickness of the linen (cm)
Lf thickness of the liquid food, with one-dimensional transfer (10/6 cm for 1 litre)
MAP Modied atmosphere packages
Mt, M amount of active agent released at time t, innite time, from the linen
(Equation (5.6))
MN Motiers number, dimensionless number KL/h
PEN Polyethylene napthalate
PET Polyethylene terephthalate
R Sherwood number, dimensionless number hL/D
S area of the reference cube of side a
SN Savoie number, dimensionless number KL2/D
V volume of the reference cube of side a
x position
Y amount of active agent in the bottle
t time
220
6
A Few Common Misconceptions
Worth Avoiding
It has been written in June 2005 [1] that from a recent survey, one-third of scientists
admitted to questionable practices. Okay, so the games up - scientists, it turns out, are
neither perfect nor perfectly ethical. Scientists aws include engaging in a wide range
of questionable practices. Without looking at the cases of gross scientic misconducts,
such as fabricating or plagiarising results, that can end up in the headlines, they are many
other behaviours that can compromise the integrity of research and the interest of the
results nally obtained. Among the top 10 behaviours and the percentage of respondents
admitting to them are the following:
Failing to present data that contradict ones own previous research (6%)
Overlooking others use of awed data or questionable interpretation of data (12.5%)
Changing the design, methodology, or results of a study in response to pressure from

a funding source (15.5%)
Inappropriately assigning authorship credit (10%)
Dropping data points from an analysis based on a gut feeling that they were
inaccurate (15.3%)
Keeping inadequate records related to research projects (27.5%)
Refusing to give ones own data to other people who might interpret them differently,
in order to avoid any discussion on this interpretation.
It was also said that the modern scientist faces intense competition, and is further burdened
by difcult, sometimes unreasonable regulatory, social, and managerial demands. This
mix of pressures creates many possibilities for the compromise of scientic integrity that
extends well beyond the ofcial denition of research misconduct, which is fabrication,
falsication, or plagiarism in proposing, performing, or reviewing research results. It
was also added that chemistry journal editors are seeing a growing number of cases in
which authors are trying to publish essentially the same manuscript in different journals,
a practice known as duplicate submission, or self-plagiarism.
221
Another reason stands out, especially when the analysis of the data needs some difcult
theoretical treatment. It is easy to understand that as science is spreading out on quite
different sides, people in research have to become specialised. Thus, there are people able
to obtain good data by using either costly or new apparatus, as well as other people who
will be able only to treat these results theoretically. The researcher is necessary because he
gets the data, but the theoretician can improve these data by evaluating accurate values
of the parameters and perhaps nding a general scheme for the process. In fact, in a few
words, this conclusion can be seen to hold true: we cannot have the researcher without
the theoretician.
A few misinterpretations are thus considered in this chapter, which are made either by
using an inadequate equation resulting from a wrong or poor theoretical approach, or
by building an inaccurate model for describing the process.
6.1 Using Equations Based on Infinite Convective Transfer
6.1.1 The Problem Presented
This is the most common case when the researcher uses an equation, or some mathematical
model found in the literature, which is based on the rough assumption that the coefcient
of convective transfer at the interface between the polymer lm and the liquid is innite.
Of course, as already stated in this book, and not only in Chapter 1 (the mathematical
treatment of the diffusion), the assumption of the innite coefcient of convection
corresponds with the extreme case of evaporation of the diffusing substance behaving
like a permanent gas; and in this case the rate of evaporation of the gas, not a vapour, is
so high that it may be considered as innite. In all the other cases, in the surrounding air,
the rate of evaporation of the vapour is nite, and furthermore, the same thing happens
in a liquid where the diffusing substance has not the same ability to escape as rapidly as
in the surounding air.
A typical example is found in a recent paper [2], concerned with the kinetics of sorption
of various alcohols in a variety of polyethylene terephthalates (PET). Not only is the
programme utilised in the work, based on the innite coefcient of convection at the
liquid-polymer interface, but the kinetics provided by the software [3] were drawn by
way of nearly two straight lines, the one diverting slightly from the ordinate axis and
remaining very close to it, and the other parallel with the abscissa axis, being practically
recorded at right angle. No reader is able to use the data resulting from these gures, so
as either to conrm the result provided by the software or to try to discuss them.
222
A Few Common Misconceptions Worth Avoiding
6.1.2 Theoretical Survey
Recalling the equations shown in Chapter 1 devoted to the theoretical basis of the diffusion
process, there are the following equations to consider:
The case of a nite value of the coefcient of convection at the sheet-liquid interface.
The main equations for a sheet of thickness 2L in contact on both sides with the liquid
are as follows, with: -L < x < +L
The solution of the problem, whatever the partition factor, is given as follows:
The kinetics of transfer of diffusing substance, by using the dimensionless number

Mt/M, is expressed in terms of the dimensionless number Dt/L2 by the following
Equation (1.52):
M M t 2 R2 Dt
= 2 2 exp 2n 2 (6.1)
n =1 n (n + R + R) L
2
M
where the n are the positive roots of Equation (1.50):
tan = R (6.2)
while the dimensionless number R is given by the relationship (1.51):
hL
R= (6.3)
D
The case of the highly optimistic hypothetical assumption of an innite value of the
coefcient of convection. It has been shown that for the innite value of the coefcient
of convection h and of the dimensionless number R, Equation (6.1) reduces to
Equation (6.4):
2n + 1 2 2
Mt 8
= 1 2
1
exp ( ) D t (6.4)
M n =0 (2n + 1)2 4L2

In order to point out the error from using such a software based on the innite value of
the coefcient of convective transfer of the substance at the polymer-liquid interface, the
kinetics of the absorption (or desorption) of the same substance are calculated by using
the same operational conditions, except for the value of the dimensionless number R
which is taken either as nite or innite. Moreover, the curves are expressed in different
ways by selecting two different scales for the time put in the abscissa.
223
The kinetics are shown in the following six gures for different values of R selected within
the 10-2 range, and for R innite, as well as for different values of the thickness of the lm,
so as to compare them. These sheets are in contact with the liquid on both sides.
Figure 6.1 Kinetics calculated with R = 10, L = 0.01 cm, D = 10-7 cm2/s, and drawn, the one
up to 500 minutes, the other only up to 25 minutes, for the scale of time (full line). Kinetics
calculated with the same parameters, except for R which is innite (dotted line).
Figure 6.4 Kinetics calculated with R = 10, L = 0.03 cm, D = 10-7 cm2/s, drawn, the one up
to 4000 minutes, the other only up to 100 minutes, for the scale of time (full line). Kinetics
Figure 6.5 Kinetics calculated with R = 5, L = 0.03 cm, D = 10-7 cm2/s, and drawn, the one up
Figure 6.6 Kinetics calculated with R = 2, L = 0.03 cm, D = 10-7 cm2/s, and drawn, the one up
6.1.3 Conclusions Drawn from the Problem
From Figures 6.1 to 6.6, by considering either the effect of the value given to the
dimensionless number R or the effect of the scale of time selected in the drawing, the
following comments are worth noting:
i) On the whole, the effect of the scale of time selected in the curves expressing the kinetics
of transfer of the diffusing substance appears clearly on these six gures. With the
thickness of 0.01 cm, when this scale of time is very large, up to 500 minutes, the two
curves obtained with the two different values of the dimensionless number, e.g., R nite
or R innite, are quite well superimposed, as shown in Figures 6.1-6.3. By contrast, these
224
Figure 6.1. Kinetics of transfer of the diffusing substance calculated with D = 10-7 cm2/s
and L = 0.01 cm either with R = 10 (full line) or innite R (dotted line). Two scales of
time are used, one with 500 minutes, the other with 25 minutes.
225
226
227
same kinetic curves drawn with the other scale of 25 minutes, are expressed through two
curves, which are distinctly separated. Thus, the following statement holds true: using
a too large a scale of time can lead to deceptive information and wrong results. This
consequence remains whatever the value of the dimensionless number R. Similar results
are obtained when the thickness is 0.03 cm (Figures 6.4-6.6) with a longer time.
ii) The effect of the rate of stirring is shown in the six gures, by comparing the kinetics
shown as the value of R and subsequently of the coefcient of convective transfer at
the polymer-liquid interface which can measure the effect of this rate of stirring.
iii) Of course, resulting from the dimensionless number Dt/L2, by keeping the value of the
diffusivity constant, the time necessary for a given transfer is proportional to the square
of the thickness of the sheet. Thus, for a thickness of 0.03 cm, the times are almost ten
times larger than for the thinner thickness of 0.01 cm, for the same value of R. This
fact explains the larger time scale, nearly ten times longer, used in Figures 6.4-6.6.
iv) An important fact also appears, resulting from the value given to R, either innite
or nite. In each of the Figures 6.1-6.6, the kinetics obtained with these two values
of R (nite or innite) are superimposed on each other, by taking the larger scale of
500 minutes when L = 0.01 cm, and of 4000 minutes when L = 0.03 cm. But, if the
kinetics drawn with R nite are obtained by taking D = 10-7 cm2/s, the other kinetics
drawn with R innite should be obtained with a much lower value of the diffusivity
expressed by the essential relationship:
D (with innite R) = aD (with nite R)
this coefcient a being lower than 1.
Moreover, the value of a largely depends on the values given to the other two
parameters, e.g., R, and the thickness of the sheet L, as shown in Table 6.1.
Table 6.1 Values of a with the values given to R and L

L, cm R a R a R a
0.01 10 0.73 5 0.59 2 0.38
0.03 10 0.73 5 0.59 2 0.38
v) In other words, to conclude, two successive stages take place in the process of transfer of
the diffusing substance from the polymer into the liquid: the diffusion of the substance
through the thickness of the sheet, followed by the convection of the substance through
the polymer sheet-liquid interface. Thus, assuming that R is innite means that the
228
second stage is eliminated, which leads to a faster rate of transfer than in the case of
a nite value of R. Finally, the same kinetics curves obtained with either an innite or
a nite value of R implies that the value of the diffusivity should be larger when the
value of R is nite. But the worst is coming with the fact that from one experiment to
another, it is probable, that the conditions for stirring are different, and nally that the
values of the dimensionless number R are kept constant. The process of stirring is highly
complex, and the coefcient of convection h, and in the same way R, largely depends on
various factors, and amongst them are: the nature of the liquid with this viscosity and
wettability, the volume and form of the ask (the apparent viscosity of a liquid varies
with the dimensions of the ask in which it is stirred), and the nature of the rotating
paddle. It is worth noting that the systems of ask and rotating paddle have been
extensively studied in pharmaceutical applications in order to evaluate the capability of
the in vitro dissolution tests which are strictly standardised [4, 5]. So, what has been true
for pharmaceutical applications (for the purpose of comparing precisely the kinetics of
dissolution of various dosage forms) would also be true in food safety applications (for
determining the time of food safety allowed by a package as precisely as possible).
6.2 Infinite Thickness of the Film and Infinite Convective Transfer [6]
6.2.1 Description of the Experimental Part
The materials and methods used for evaluating the matter transfer are presented next.
Three-layer lms made of high-impact polystyrene (HIPS) are co-extruded in such a way
that the contaminated layer is inserted between the two virgin layers. The contaminant
is either toluene or chlorobenzene, which is previously inserted into the contaminated
layer by absorption.
The lms are cut and sealed to pouches of 2 dm2 inner surface, and the pouches are lled
with 20 ml food simulant made of 50% ethanol in water at 40 C. The concentration
of the contaminant in this liquid is determined by gas chromatography at various times
over 76 days, for different values of the thickness of the barrier B varying between 0
and 0.02 cm and keeping the thickness of the contaminated layer constant at 0.015 cm.
From these dimensions, it appears that the thickness of the liquid is very low, and that
no stirring is possible in it.
The values of the diffusivity for each simulant are given at 40 C as well as 200 C:
Toluene D = 1.25 x 1012 cm2/s D = 1 x 10-6 cm2/s

Chlorobenzene D = 1.72 x 1012 cm2/s D = 8.1 x 10-6 cm2/s
229
6.2.2 Theoretical Consideration by the Authors [6]
In this paper [6], a physico-mathematical model describing the migration across functional
barrier layers into foodstuffs is described.
The system appears as follows: a polymer barrier B of thickness b initially free from
contaminant is surrounded by a semi-innite matrix 1, with a concentration C1 of diffusing
substance, considered as a contaminant and by another semi-innite matrix 2, whose
potential pollutant concentration is C2, while the diffusivity of the diffusing substance is
called in these three media: D1, D2, DB, respectively.
The diffusion being mono-directional, and perpendicular to the planes separating the
media, the equation of diffusion is:
C 2C
= D 2 (6.5)
t x
where C, the concentration of the diffusing substance, varies with time and space.
By following, these assumptions, the initial condition may be written as:
t= 0 x>0 C=0 (6.6)
while the boundary condition is:
t>0 x=0 C = Cin (6.7)
The solution of the problem of diffusion from a semi-innite medium into another semi-
innite medium, is generally expressed in terms of the error-function complement [7]:
x
C x , t = Cin erfc (6.8)
2(D t)0.5
and the kinetics of the matter transfer through the two semi-innite media is obtained,
by evaluating the derivative with respect to space x of the concentration of the substance
at position 0 where the two media are separated, and by integrating this derivative with
respect to time. The following equations are obtained.
For the derivative with respect to space at position 0:
C Cin
= (6.9)
x x =0 ( D t)0.5
230
and for the kinetics of the matter transferred through the two semi-innite media:
0.5
D t
M t = 2 Cin (6.10)

Equation 6.10 is the basis of the model used in the paper [6].
At that time, the mathematical treatment is correct, provided that the assumption
of an innite thickness for the recycled layer and for a volume of liquid innity is
accepted.
By applying to the barrier polymer B, of thickness b, the equation expressing the amount
of substance transferred through a membrane under stationary state, it appears:
DB C1 b2
Mt = t (6.11)
b 6.DB
by assuming that the concentration C1 is kept constant and the concentration C2 is

maintained very low, if not equal to 0.
But Equation (6.11) is transformed in such a way by the authors [6] that the
amount transferred into the matrix 2 (food of semi-innite medium) becomes at the
time t = :
M = 0.039 b C1/ B (6.12)
where b is the thickness of the polymer barrier B,
and C1/B is the concentration at the matrix 1-barrier B interface.
After this transformation, the kinetics of the diffusing substance released in the food
(medium 2 semi-innite) is thus expressed as follows by the authors [6]:
D
M t = C1 0.039 b + 2 P (t0.5 0.5) (6.13)

in which Dp is not specied, but which could be assumed to be that of the barrier B.
The comments about this method are given, as much as possible, in Section 6.2.3.
231
6.2.3 Conclusions About the Ideas Presented [6]
There is more than one idea in the paper, although all of them are not followed by a clear
development and application in terms of proles of concentration or of kinetics:
i) The rst idea is concerned with the possible values of the diffusivity in the three media,
with the following: D1>>DB<<D2. It means that the polymer barrier B is in contact
with a kind of liquid on both sides.
ii) This rst assumption is an argument for the second idea which is concerned with the
polymer barrier B playing the role of a membrane.
iii) This membrane B is surrounded by two semi-innite media. It means that the
thickness of the recycled layer 1 is innite the same assumption holds for the food
in medium 2.
iv) The assumption of a semi-innite medium in iii) allows the authors to make a treatment
leading to equation 1 (in the paper) and noted [Equation (6.12)] for the mass of
contaminant transferred at time . This equation is thus applied to the transfer of
contaminant through the system in the following equations, e.g., Equation (6.13). It is
difcult to understand how this relationship as well as the value of 0.039 is obtained.
v) To meet the real-life situation a hypothesis is made [6]: during the diffusion process
from matrix 1 until concentration equilibration with the barrier layer B, the technical
barrier thickness b can be theoretically subdivided into an impure and a clean part.
The clean part can be considered as the still effective barrier with a corresponding
relative layer thickness of thickness br characterisable by its lag time r, which, however,
is a priori unknown. It is difcult to know what the term equilibrium means, as
the process goes on continuously with time, moreover, the concept of an impure and
clean part in the barrier is vague.
vi) The square-root relationship x/(2(Dt)0.5) appears, showing that the idea of diffusion
into a semi-innite medium is in mind, but simultaneously, the idea concerned with
the diffusion through the membrane is maintained with the time = b2/6D. Let us
recall that this time dened by Equation (1.69) in Section 1.11.2, is the intercept on
the time-axis of the kinetics curve of the matter transferred through the membrane of
thickness b, and it does not mean exactly that it is the time necessary for the diffusing
substance to cross the membrane.
vii) Finally, it would have been fair to draw the proles of concentration developed through
the system, but the following question arises: is it possible with equations which
contain only the time? There is also mention that the diffusivity has been calculated
232
from the experiments by using Equation (6.10). The increase in concentration

with time at the barrier B-liquid interface has also been drawn, but it is difcult to
understand how it has been calculated.
viii) The increase in concentration with time at the surface of the barrier lm B in contact
with the liquid, which represents the efcacy of this functional barrier, is drawn for
various values of the ratio of the thicknesses of the barrier B and recycled layer. But it
is not known which equation was used for doing this estimation. It should be assumed
that this calculation was made by using Equation (6.8) which is the only equation
expressed in terms of x and time.
ix) To come to an end, whichever equations are used, either Equation (6.10) based on
the principle of the innite medium 1 or the membrane separating two media with
a constant concentration on each side, in both cases the coefcient of convective
transfer into the liquid is innite. Let us also note that the diffusivity was estimated
for a contaminant diffusing through the polystyrene at 200 C.
6.3 Combination of Semi-infinite Media and Finite Volume of Liquid [8]
6.3.1 Description of the Experimental Part
The package has a three-layer structure made of PET where the contaminated layer is
surrounded by two layers free from contaminant. These packages prepared by co-extrusion
have different thicknesses for the two virgin layers: as the total thickness of the package
is 0.04 cm, these thicknesses for each virgin layer are 0, 0.002, 0.004, and 0.006 cm.
Two migration tests are considered:
One is called migration tests using compression type cells for single-sided contact. The
sheets are held in the cells with 45 g water in contact with 95.4 cm2 area, leading to
a value of = 25, and the partition coefcient is assumed to be 1. The experiment of
diffusion is made at 60 C and samples are taken and analysed at intervals.
The other is called migration tests with the pouch method. The lms are cut and
formed into pouches of 2 dm2 inner surface. The pouches are lled with 20 cm3 of
liquid, sealed and stored at 20, 40, or 50 C. In this case, the ratio of the volumes is
= 5. The liquid consists of 3% acetic acid in water and isooctane. The amount of
the contaminant is measured in the liquid at intervals.
233
6.3.2 Theoretical Part
Starting with the idea that the concentration of the contaminant is already uniform in the
package at the beginning of the process of migration in the liquid, Equation (6.14) is used:
Mt
2 (1 + ) q2 D t
= 1 exp n 2 (6.14)
M n =1 1 + + 2
q 2
n L
where qn is the non-zero positive root of:
tan q n = q n (6.15)
and the ratio of the volumes of liquid and sheet are given by Equation (6.16), as the
partition factor K is taken as 1:
A
when K = 1 = (6.16)
L
The concentration of diffusing substance is Cin throughout the semi-innite medium,

initially, while the surface, x = 0, is maintained at a constant concentration 0. In this case,
the coefcient of convection at the package-liquid interface is innite.
But, at that time a second case appears where the package and liquid are considered as
two semi-innite media, allowing Equation (6.10) to be shown:
0.5
D t
M t = 2 Cin (6.10)

6.3.2 Tentative Conclusions on the Ideas that have Emerged [8]
In this paper [8], two ideas are mixed even if they contradict each other.
i) On the one hand, the concentration of the contaminant is uniform in the whole
package, so that there is no functional barrier.
ii) Equation (6.14) used for evaluating the kinetics of release of the contaminant into
the liquid stands for the case of an innite coefcient of transfer at the package-liquid
interface. This means that the liquid should be strongly stirred, but it is difcult, if
not impossible to stir such a small volume of liquid.
234
iii) After this assumption leading to Equation (6.14), another quite different assumption
is made, since the package-liquid system is considered as two semi-innite media
through which diffusion takes place, leading to Equation (6.10).
iv) Finally, these two assumptions, in contradiction with the actual package-food system
lead to mathematical models which are irrelevant to the problem.
6.4 Infinite Rate of Convection in a Finite Volume of Liquid [9]
6.4.1 Principle of the Process
After collecting from the literature a large quantity of data concerned with the diffusivity
of various diffusing substances in different polymers, it has been possible for the authors
[9-11] to rene an equation relying on the experimental values of the diffusivity of
polyolen material. The rened equation thus obtained is worth citing:
10454
DP = D0 exp A P 0.1351 M 2i / 3 + 0.003 M i (6.17)
T
where D0 is equal to 104 cm2/s, the term Ap has the role of a conductance of the polymer
matrix towards the diffusion of the migrant substance, Mi is the molecular mass of
the diffusing substance and the last term expresses the temperature dependence of the
diffusivity, in Kelvin.
Moreover, various values of these parameters are listed for the following polymers: low-
density polyethylene (LDPE), high-density polyethylene, and polypropylene (PP) [9].
Finally, the principle of an innite coefcient of convection in a nite volume of liquid

was presented.
6.4.2 Theoretical Development
Assuming that there is no boundary resistance at the package-liquid interface, and that
the concentration of the diffusing substance in the package is initially uniform, Equation
(6.14) is obtained and probably used for calculating the diffusivity:
Mt
2 (1 + ) q2 D t
= 1 exp n 2 (6.14)
M n =1 1 + + 2
q 2
n L
235
6.4.3 Tentative Conclusions on the Ideas that Emerged [9]
The following conclusions are obvious to draw:
i) At last, the idea of semi-innite media previously introduced [6, 8] is abandoned in

this paper [9].
ii) Only the assumption of the innite coefcient of convection at the package-liquid
interface is maintained. But the example given in the gure 2 of the paper [9] clearly
shows that this assumption is not valid. By taking as correct, the tting calculated in
this paper, it appears that the slope at the beginning of the process obtained by the
authors is very low, e.g., 140 mg/h/dm2, which is far from the innite slope associated
with Equation (6.14) used in the paper for calculation. This contradiction between
the experimental and theoretical results proves that the idea of basing the model on
Equation (6.14) is inaccurate if not wrong. This gure 2 [9] is not reprinted, but only
a draft of this gure is shown in Figure 6.7, allowing the author to point out the
drawback of the method. Concerning the calculated kinetics curve, by using Equation
(6.14) (as there is no other equation in the paper), based on the principle that the
coefcient of convection is innite, it is highly surprising that the tangent at the origin
is not vertical as it should be.
iii) It should be stated that it is not easy to evaluate the diffusivity and redraw the kinetics
curve shown in Figure 6.7 for the following reasons: the value at equilibrium (or rather
that which is obtained after a long time) is not given; there are no measurements made
at lower times, e.g., 1 hour if not 0.5 hour, which are very useful in order to get an
accurate value of the diffusivity and of the coefcient of convection.
iv) The values of the diffusivity predicted by Equation (6.17) have been drawn from
experiments made by various authors whose operational conditions were different and
sometimes not clearly dened. This fact explains the wide range through which the data
initially collected were lying. As shown in Figure 6.8 (Figure 4 in [9]), the values of the
diffusivity obtained for the additives in LDPE, expressed by decimal logarithms, are
lying between a large range of around 100; as the time necessary for a given transport
is inversely proportional to the diffusivity, it means that the time for contamination also
varies by 100 times, e.g., from 10 days to 3 years. The curve expressed by Equation 5 in
this Figure 6.8 [9] which, ts the data better is the basis on which Equation (6.17) has
been obtained. Equation (6.17) obtained from a renement of these data perhaps does
not show a better accuracy for these mean values. However, this equation is useful, in
the sense that it provides the user with a rst tentative value of diffusivity, which can
be introduced in the numerical model, enabling the right values of either the diffusivity
or the convective coefcient to be obtained by a trial and error.
236
Figure 6.7. Draft representing the example of tting calculated and

experimental results.
Figure 6.8. Logarithm of the diffusivity of a variety of additives in LDPE at 23 C

as a function of their relative molecular weight. (Reprinted from J. Brandsch,
P. Mercea and O. Piringer in Food Packaging, Ed., S.J. Risch, ACS Symposium
Series No.753, 1999, Chapter 4, p.27-36, Figure 4 [10], with permission from
the American Chemical Society).
237
v) It can be added that the idea developed in this paper, based on the nite volume of the
packaging and of the liquid, leading to Equation (6.14), as well as to Equation (6.17)
predicting the diffusivity, has not only been maintained but also published again more
recently [12].
vi) It should not be forgotten that a dilemma exists about the method described to estimate
the maximum initial concentration (MIC) of migrant in the food-contact material or
article based on specic migration limits for compliance checks [12]. In evaluating the
value of the diffusivity from the experimental data, by using the Equation (6.14) (or
[Equation (6.4)] which neglects the effect of the convection, this value is lower than
the actual value which should be obtained when taking into account the convective
effect with Equation (6.1). On the other hand, Equation (6.14) with a given diffusivity
leads to faster kinetics than Equation (6.1) does. Then, which value is to be used for
the diffusivity? Remember that there is a strong uncertainty about the values of the
diffusivity, as shown in v) which depends on many factors, such as the author, the
method followed for the experimental work and calculation. Thus, as a conclusion,
using Equation (6.14) leads to a vicious circle where little is known.
6.5 Double Transfer Process and the Membrane System
6.5.1 Principle of the Double Transfer in Plasticised PVC Immersed in a Liquid
When a sheet made of plasticised polyvinyl chloride (PVC) is immersed into a liquid, a
double mass transfer may take place, with the liquid into, and the plasticiser out of the
PVC [13-15]. This process is highly complex for the following reasons [16]:
i) The presence of the double mass transfer which are connected with each other (the
transfer of plasticiser takes place only when the solid is immersed into the liquid
through which the plasticiser is soluble; the liquid enters the polymer through the
plasticiser with a rate that increases strongly with the percentage of plasticiser, this
rate becoming negligible when there is no plasticiser).
ii) Being controlled by a diffusion process, the diffusivity of each diffusing substance is
concentration-dependent; it means that the diffusivity of the liquid increases with the
concentration of both the liquid and plasticiser, with a slight adjustment between them.
Thus it took a long time for studying this process, and two methods were developed:
1. The short test method, in order to get a rst value of the diffusivity, by using various
percentages of plasticisers. The short tests enable one to determine the values of
the diffusivity and their concentration-dependency either for the liquid or for the
plasticiser [17].
238
2. A method coupling experiments and modelling the process [18, 19].
3. The long tests. These tests are run over several days and are able to test the
accuracy of the data obtained with the short test method and possibly to adjust
them more precisely.
As a result of this double mass transfer, when a plasticised PVC sheet is immersed into a
liquid, two gradients of concentration are developed through the thickness of the sheet, with
a high concentration of liquid and a low concentration of plasticiser on both sides [20].
When this sheet is removed from the liquid and exposed to the surrounding atmosphere, the
liquid can evaporate through a complex process, resulting from these two facts [21]:
i) The diffusivity is concentration-dependent, and the proles of concentration of both

the liquid and plasticiser are not initially uniform.
ii) When the concentrations of the plasticiser and of the liquid on the surfaces are very low,
the diffusivity of the liquid is so low that the rate of evaporation becomes negligible,
this fact being responsible for the difculty in drying the polymer completely [21, 22].
Then, after a convenient stage of drying, the plasticised PVC sheet exhibits a typical
pattern, with a symmetrical gradient of concentration of plasticiser next to its sides with
a very low concentration on the surfaces. Of course, when the stage of drying is properly
achieved, only a very small amount of liquid remains in the sheet [21, 23].
Thus, at that time with the knowledge gained previously, it is understandable that when
re-immersing this new PVC sheet prepared as previously discussed into a liquid, no mass
transfer would take place in, or out, of the sheet. That fact was not only predicted but also
experimentally observed many times, by using various liquids and different percentages
of plasticiser [24, 25].
6.5.2 Process of Mass Transfer through a Membrane
According to the principle of the transfer of matter through a membrane, the substance
diffuses through the thickness of the sheet from one side to the other, while a concentration
of matter is maintained on both sides.
The one-dimensional diffusion of the diffusing substance is expressed by Equation (6.5):
C 2C
= D 2 (6.5)
t x
239
With the initial conditions expressing that the membrane is initially free from
substance:
t=0 0<x<L C=0 (6.18)
and with the boundary conditions meaning that there is no resistance to the transfer on
both surfaces, written as follows:
t>0 x=0 C = C0 (6.19)

x=L C=0
the amount of substance which emerges from the side with the lower concentration, at
position L, is expressed by the series:
M t D t L 2L (1)n D t
= 2 2 exp n2 2 2 (6.20)
C0 L 6 n =1 n L
while the proles of concentration of the substance developed through the thickness of
the membrane at various times are given by:
Cx,t x 2 1 nx D t
= 1 sin exp n2 2 2 (6.21)
C0 L n =1 n L L
Equation (6.21) shows that the concentration of the diffusing substance in the membrane
increases with time, and the proles of this substance tend to be linear when the series
vanishes, theoretically after innite time.
In the same way, from Equation (6.20), the amount of substance emerging from the side
of the membrane kept at the lower concentration increases with time as the series in
Equation (6.20) vanishes. Thus after a given period of time (innite time, mathematically
speaking) the kinetics of substance leaving the membrane tends to become linear, and the
expression of the asymptote is given by:
DC0 L2
Mt = t (6.22)
L 6D
the slope of which being:
M t DC0
Slope = = (6.23)
t L
240
while the intercept on the time-axis is:
L2
ti = (6.24)
6D
Thus the time ti dened by Equation (6.24) represents an extrapolated time which has
no physical signicance. As shown in Figure 6.9, where this time ti is 11.57 hours, the
diffusing substance emerges out of the membrane largely before this time. Moreover,
the proles of concentration developed in Figure 6.10 clearly show that at a time
around ve hours the diffusing substance appears at the outlet of the membrane.
The slope in Equation (6.23) expresses the value of the ux of matter which emerges
from the membrane - this ux increases with time up to the constant asymptotic
value theoretically attained after innite time, and at least for times longer than 50
hours when the prole of concentration through the thickness of the sheet tends to
be linear.
Figure 6.9. Kinetics of the matter emerging out of the membrane, with L = 0.05 cm;
Cin = 50 mg/cm3; D = 10-8 cm2/s; coefcient of convection is innite on both sides.
241
Figure 6.10. Proles of concentration developed through the thickness of the membrane
at various times, with L = 0.05 cm; Cin = 50 mg/cm3; D = 10-8 cm2/s; coefcient of
convection is innite on both sides.
6.5.3 Observations on the Assumption of the Membrane
Simplifying a process is often of great interest, especially when this process is highly
complex. However, the new simplied process should be representative of the process
itself, by keeping the main facts of the actual process, and it should provide results which
are in substantial agreement with the experimental data.
From the papers [26-29] concerned with the representation by a membrane of the double
transfer of liquid into, and plasticiser out of the plasticised PVC sheet immersed in a
liquid, the following observations emerge:
i) The main characteristics of the membrane should be dened as precisely as possible.

But how is its thickness evaluated? At the end of the two stages necessary for the
preparation of the plasticised PVC exhibiting low matter transports, e.g., the immersion
over a short time in a liquid, evaporation of the liquid, a gradient of concentration of
the plasticiser is obtained. Some proles of concentration are shown in Figure 6.11 [17]
obtained after various long times at 30 C with the initial 50% plasticiser, previously
immersed in n-heptane. Other proles of concentration have been calculated for very
short times, either for the liquid (n-hexane) or for the plasticiser in Figure 6.12 [23].
242
ii) Another main characteristic of the membrane is concerned with the concentration of
the diffusing substance. Initially, by using Equations (6.20) and (6.21) as it was done by
other authors [26-29], the membrane is free from liquid and plasticiser. Equations (6.20)
and (6.21) are also obtained with a constant concentration of the diffusing substance
on both sides. As shown in Figures 6.11 and 6.12, none of these two assumptions, e.g.,
initial and boundary conditions, meet the experimental requirements.
iii) Generally, there is only one transfer of substance diffusing through the membrane,
although this fact is not mandatory, as several substances may diffuse simultaneously
with different rates of transport. But, in the present case of plasticised PVC, the benecial
retardation in the plasticiser release does not only come from the absence of plasticiser in
a hypothetical membrane. The process is as follows: the liquid enters the PVC, dissolves
the plasticiser, enabling the plasticiser to diffuse out of the solid. Thus, the retardation
in the release of plasticiser is associated with a retardation in the absorption of the
liquid. The diffusivity of the liquid being concentration-dependent, this concentration
concerning not only that of the liquid but also that of the plasticiser, it means that when
the concentration of plasticiser is low, the diffusivity of the liquid is also low.
Figure 6.11. Proles of concentration of plasticiser, di(2-ethylhexyl)phthalate (DEHP)

developed through the 0.3 cm thick sheet of plasticised PVC at various times, initially
at 50% plasticiser, immersed in n-heptane at 30 C. (Reprinted from J.L. Taverdet and
J-M. Vergnaud, Journal of Applied Polymer Science, 1984, 29, 3391, Figure 5 [17]
with permission from John Wiley & Sons).
243
Figure 6.12. Proles of concentration of n-hexane and plasticiser (DEHP) developed

through the 0.06 cm thick sheet of plasticised PVC at various times, initially at 30%
plasticiser, when immersed in the liquid at room temperature (Reprinted from A.
Aboutaybi, J. Bouzon and J-M. Vergnaud, European Polymer Journal, 1990, 26, 285,
Figure 5d [23], with permission from Elsevier).
iv) The average diffusivity D1 obtained by using Equation (6.24), or the diffusivity D2
drawn from Equation (6.23) which would represent the maximal value of D1 [26-29],
are not representative of the process, neither for the membrane nor for the complex
process of double transfer with concentration-dependent diffusivities. The values of
D1 and D2 differ from each other by more than 10 times, while the diffusivity D2 is
more than 100 times larger than the diffusivity D0 of the original untreated plasticised
PVC sheet.
v) The optimisation of the process of release of plasticiser is surely of great interest [29],
provided that it would be applied to the complex process itself, based on a double
transfer of the liquid and plasticiser with a concentration-dependent diffusivity for
each component.
vi) To come to the end with this problem, there is another stage which may take place
in the retardation of the mass transport, with the wettability. Putting on the surface
of the treated plasticised PVC an agent that prevents it being wetted by the liquid in
which the solid is immersed gives supplementary benet to the retardation process
244
[30]. Note that putting a very thin layer on the plasticised PVC does not replace the
pre-treatment with absorption in a solvent and drying; more simply, this layer is able
to be absorbed into the PVC sheet so-treated. The problem is to nd the nature of
the liquid to be used for this layer which will not wet the other liquid in which the
plasticised PVC sheet is due to be immersed.
6.6 Heat Transfer: Conduction or Convection
6.6.1 The Problem Considered in the Literature [31]
An interesting problem is how to select the way through which heat is transferred from
one medium to another. This problem is of some importance, as it is concerned with the
operation of co-extrusion that is necessary to use in preparing multi-layer lms: is there
conduction or convection at their interface?
Two parts are worth noting in this paper [31], the one with the techniques used for
measurement, the other with the theoretical approach.
6.6.1.1 Experimental Part
Two systems are described and used for evaluating the effect of heat transfer in the process
of co-extrusion, and a third one for measuring the proles of concentration:
i) The rst system which mimics the co-extrusion process is based on a pre-form in which
the PET polymer is injected. This pre-form is a mould in the shape of a bottle, and the
polymer is injected at its bottom. Thus, three PET polymers are injected in succession,
the rst and the third being made of virgin polymer, while the second is a contaminated
polymer, leading as a result to a three-layer PET sample. The thickness of the mould is
rather large, around 0.43 cm, while the external radius of the polymer bottle is 1.321
cm. The mould (core and walls) is said to be kept at 8 C. Thus the PET polymers are
extruded in a dynamic way.
ii) The second system, on the laboratory scale, is classical, based on a static method. It
consists of a mould made of two iron plates heated under a slight pressure up to the testing
temperature for 10 minutes. Two layers of the same PET polymer, whose thickness ranges
between 0.01-0.05 cm, one contaminated and the other virgin, are placed in the mould,
parallel with the iron heated plates. The main difculty of the test is to avoid blending
of the polymer layers during their melting, this transfer being made by convection and
not diffusion. Therefore, the total PET sample thickness is slightly lower than that of
the mould, in order to compensate a possible thermal expansion during melting.
245
iii) Evaluation of the diffusion effect. The sample removed from the mould ii) is analysed
by UV spectrometry with the help of a microscope unit for determining the position
when the concentration measurement is made [32].
6.6.1.2 Theoretical Approach
In both cases, e.g., the bottle-shaped pre-form and the plated mould, the heat and mass
transfers had to be considered. Various facts should be noticed:
i) In the pre-form, cylindrical in shape, the radial diffusion is considered through the
circular cross section of the bottle.
ii) For the boundary conditions, which represent the rate of heat transfer at the mould-
PET interface, convection is assumed to be the correct process with either a perfect
convective transfer (hh = ) and a nite value of this coefcient (hh = 0.0074) for a poor
convective transfer, without saying something about the unit of this coefcient.
iii) For the other boundary condition, expressing the contaminant transfer between
the PET layers, the convection equation is also used, with a coefcient of matter
convection hc.
iv) The same equation is obtained for heat diffusion, by replacing C by T, D by , hc

by hh.
6.6.2 Recall of the Theory of Mass and Heat Transfers
6.6.2.1 Heat Transfer
Recalling what is written in (Section 3.2 Principles of One-dimensional Heat Transfer)

and widely described elsewhere in other books [33-35], the process of heat transfer
is controlled either by conduction through solid materials (metals or polymers) or by
convection at the interface between a solid (metal or polymer) and the surrounding
atmosphere (gas or liquid). Moreover, the convective heat transfer is achieved either in
free convection (when the surrounding uid is motionless) or in forced convection (when
the surrounding uid is stirred). The equations which apply, with a one-directional heat
transfer, are the following:
T

x
(
= h h Ts Tsurrounding ) (6.25)
246
where hh is the coefcient of heat convection at the solid-uid interface, Ts is the

temperature of the solid surface, and Tsurrounding the temperature of the surrounding uid
far away from the surface which is kept constant.
Unidirectional heat transfer by conduction takes place through the lm, by assuming that
the heat conductivity is independent of the temperature:
T 2T 2T
= 2 = 2 (6.26)
t c x x
with the thermal diffusivity dened by:

= (6.27)
c
At the interface between two media 1 and 2, consisting of solids (mould and polymer),
the condition being that there is no loss or accumulation of heat, is written as follows:
T T
1 = 2 (6.28)
x 1 x 2
6.6.2.2 Mass Transfer controlled by diffusion
By analogy with heat transfer, the mass transfer is controlled either by diffusion through
the solid or by convection through the solid-uid interface. Following this, diffusion takes
place through solids in perfect contact. Finally, the equations for the one-directional mass
transfers, are:
Through the solid:
C C
= D (6.29)
t x x
When the diffusivity D is constant, independent of the concentration, this equation

reduces to:
C 2C
= D 2 (6.5)
t x
247
At the polymer-uid interface, the relationship is:
C
D
x
(
= h c CL , t Ceq ) (6.30)
where: hc is the coefcient of transfer by convection in the liquid next to the surface,
CL,t is the concentration of the diffusing substance on the surface of the solid,
Ceq is the concentration of the diffusing substance on this surface required to
maintain equilibrium with the concentration of this substance in the liquid, at time t.
At the interface between two solids, there is:
C C
D1 = D2 (6.31)
x 1 x 2
6.6.3 Conclusions on Convection-Conduction Heat Transfers
Two conclusions can be drawn from this subject, one on the experimental part, the other
on the theoretical treatment.
i) If the multilayer pre-form processing has the advantage of being run on a semi-plant
scale, it appears likewise as a complex system either in the process of lling itself or for
making analysis. The method of cutting the slices of polymer and the analysis of the
contaminant concentration after extraction from the PET seems to be tedious as well.
ii) In spite of the precautions taken in the process based on using the mould, it is said that
at least 50% of the samples could not be used for analysis, due to blending. Another
difculty may arise in achieving the complete lling of the mould, because a continuous
layer of air inserted at the PET-mould surface totally modies the heat transfer at this
interface. In another study [36], special care was taken to make sure that the surface
between a pre-cured thermosetting resin and an uncured resin was perfectly adjusted:
by pre-moulding under pressure the two pieces which are due to be in contact at room
temperature or at higher temperature in the same mould, in order to get samples with
adjusted shapes; by pressing the two pieces under a high pressure at room temperature in
order to evacuate the residual air; and by using a mould consisting of two parts made in
such a way that the upper part which enters the lower part would be constantly applied
to the polymeric layers under constant pressure.
248
6.6.3.2 Theoretical attempt
i) Several contradictions to a correct theoretical treatment appear, especially for the heat
transfer process at the PET-mould interface. Taking for granted that this heat transfer
is controlled by convection without specifying the nature of this convection is one
thing, but taking for this transfer a coefcient of forced convection is another thing.
In fact, as stated in Section 6.6.2, the heat transfer at this interface is expressed in
terms of conduction. But a PET polymer, even if it is melted over a given time is so
highly viscous that it necessitates a high pressure for extrusion - cannot be considered
as a gas or a strongly stirred liquid.
ii) The statement made for the heat transfer which takes place in the pre-form, is dened
as the mould (core and walls) is kept at constant temperature equal to 8 C seems to
be optimistic. Generally, when two bodies which are initially at different temperatures
are put in contact, the cooler body heats up while the heater body cools down, because
of the exchange of heat between them. In fact, the essential knowledge is concerned
with the internal wall of the mould that is in contact with the melted PET. What would
be of interest are the following data: the thickness of the mould, and the way through
which its external wall is kept at 8 C.
iii) Another remark about the coefcient of convection used in the pre-form system
should be added. If some perplexity could arise in a few minds about the behaviour
of the melted polymer considered either as a liquid or a solid, there is no doubt about
the nature of the mould: heat conduction denitely takes place into and through the
metallic mould.
iv) It seems that the authors wanted to get rid of the general equation of heat transfer,
in writing that it is derived from the equation of diffusion (Section 1.3), because by
replacing C by T, D by , and hc by hh, in doing so, the following is obtained:
T
= h h ( Ts Texternal )
x
where the two coefcients and hh have the following dimensional equations:
: cm2/s
hh: cal/(cm2s.deg)
expressed for example in the CGS system (centimetre, gram, second) units.
249
6.7 Profiles of Concentration in Two Semi-infinite Media
6.7.1 Description and Study of the Moisans Method
There is a kind of recognition when a method is associated with the surname of its author.
The apparatus described [37] looks very simple, however it is efcient, at least at rst
glance. It consists of two parts pressed together under a pressure around 5 kg/cm2.
A sheet of a polymer (0.1-0.15 cm) thick containing up to 2-10% of a diffusing substance

is used as the source. The polymer through which the substance should diffuse is made
of more than 20 thin lms, 0.006 cm thick for each, pressed together, giving a kind of
thick sheet.
The concentration of the diffusing substance is very high in the source, so that the saturation
could be attained in the polymer lm in contact with it.
6.7.1.2 Theoretical Part
The two parts of the system, e.g., the source and the packed polymer lms, are considered as
two semi-innite media. Moreover, because of the very high concentration of the diffusing
substance in the source, the surface of the rst lm in contact with the source is saturated,
with a concentration denoted as S. The equation expressing the prole of concentration
of the diffusing substance developed with time through the source is:
Cx,t x
= erfc 0.5
(6.8)
S 2(D t)
By integrating this concentration between a nite position e and , the ratio of the amounts
of diffusing substance is obtained at these positions, at time t.
6.7.2 Study of the Technique
The apparatus seems simple and efcient. However, the concentration of the diffusing
substance in the source is much larger than the concentration used for the additives in
250
a polymer package. Thus it appears that the two polymers located either in the source
and the packed lms are not of the same nature. Moreover, it seems necessary that the
concentration of the diffusing substance in the rst lm layer in contact with the source
is at least equal to its solubility in this polymer.
Before 1980, this kind of apparatus was certainly innovative. Now, with the technique
based on a microscope for determining the position at which the measurement is made,
and spectrometry for evaluating the concentration, this part of the apparatus may appear
outdated.
6.7.2.2 Theoretical Part
Two facts are clear: There is a matter transfer through the polymer sheets of nite thickness.
The concentration of the diffusing substance in the polymer source is very high, much
larger than its solubility in the rst lm in contact with the source.
Nevertheless, the transfer at the interface between the polymer source and the packed
lm is given by:
C C
D1 = D2 (6.31)
x 1 x 2
meaning that the rate of transfer is equal on each side of the interface.
As the concentration in the source is larger than the solubility in the rst lm in contact
with it, a partition factor should be found.
But, as shown in Chapter 2 (Figure 2.23) when the diffusivities are equal in the two polymers
in contact, and Figure 2.24 when the diffusivity is higher in the polymer source than in the
polymer lm, a decrease in the concentration appears in the source next to the interface, as
well as in a lesser way on the surface of the polymer lm in contact with the source.
6.7.3 Conclusions on Moisans Method
6.7.3.1 Apparatus
There is little to say about the technique employed at that time [37]. It was a perfect
apparatus, but it could perhaps, be used in a better way by considering the purpose of
food packages, with a much lower concentration of diffusing substance as well as a thicker
251
thickness of the source. Moreover, using the same polymer for the source and the packed
lms may be useful at the present time [38], and the new technique for the concentration
measurement of the diffusing substance is more efcient and takes less time. Nevertheless
the press system is still in use nowadays.
6.7.3.2 Theoretical
It is always surprising, even problematical, to use semi-innite media for very thin sheets.
The mathematical treatment is possible and easy to apply, by using the equations shown
in Chapter 2 obtained with the separation of variables with nite thicknesses [39, 40].
Moreover, in order to keep the concentration constant on the surface in contact with the
source (C = S), it is necessary to nd a polymer source which is able to absorb a large
quantity of diffusing substance, and to make sure that the concentration on this surface
is maintained equal to the solubility of the substance in the source.
6.8 Double Transfer of Substances in a Sheet
6.8.1 Study Carried Out in a First Paper [41]
6.8.1.1 Experimental
Tedious but also sophisticated methods are described and used. The following experiments
are used for determining either the kinetics of transfer or the proles of concentration of
the additive and of the food simulant in various cases:
The food simulant sorption (glyceryl tripelargonate) is obtained by measuring at various

times the concentration of the amount of liquid entering the PP lm (56 m thick)
resulting from the increase in concentration in the polymer determined by FTIR.
The food simulant sorption was determined by weighing at intervals, the amount
absorbed by the same polymer (55 m thick), which reached up to 3.2% in weight
after innite time.
The kinetics of release of the additive from the polymer immersed in the liquid, were
determined by measuring the increase in concentration of the additive in the liquid
by UV spectrometry.
The concentration proles developed at various times through the thickness of the
polymer (75 m thick) by UV spectrometry, after cutting thin slices.
252
The kinetics of transfer of the additive through a solid-solid contact without

interaction of the liquid, by using a tri-layer system with a loaded polymer sheet
inserted between two virgin sheets (0.037 cm thick for each sheet). From time-to-time,
the concentration of the additive is measured in the sheets. The so-called plateau,
or value at equilibrium, is attained after a three month experiment using a 57 m
thick lm.
The kinetics of transfer of the additive through the polymer pre-saturated with the
solution made of the liquid (simulating the food) and additive, by immersing this
pre-saturated polymer into the pure liquid. A somewhat symmetrical experiment
is also made by immersing into the solution of the additive in the liquid, the pre-
saturated polymer with the pure liquid.
6.8.1.2 Theoretical Treatment
Various studies are made in this paper: some are directly concerned with the problem of
food pollution, but others however, are of concern as they prompt some questions. Let
us consider the transfer of the additive into the liquid.
In the study [41], two mass transfers take place simultaneously, the liquid into and the
additive out of the polymer sheet. The amount of the additive is very low, while the
amount of liquid entering the polymer does not exceed 3.2%, and thus no swelling
is considered. However, the following is stated the model described here takes into
account possible swelling effects of the polymer by the food or by the food stimulant.
Swelling does not necessarily mean that there is a visible change in the dimensions of
the sample . This term swelling is constantly used in the paper, but no relationship
indicates the change in dimension, the program being established with increments of
space of constant thicknesses x, by following an explicit method [22]. In fact, the
numerical model is built with a concentration-dependent diffusivity of both the additive
and the liquid, their diffusivity varying exponentially with the local concentration of
the liquid in a correct manner, as the change in volume is negligible. However, it should
be noted that various numerical models have been previously built and tested, in still
more complex situations with plasticised PVC, when the amount of liquid absorbed
and plasticiser released are of around 50% [17-20, 22-25]. Other numerical models
have also been previously built and tested by considering the swelling of the polymer,
resulting from the absorption or evaporation of a liquid whose percentage is 230% of
the volume of the polymer free from liquid, this polymer having the shape of either a
sheet or a sphere [42-45], moreover, the concentration-diffusivity has also been used in
some of these cases [44, 45].
253
6.8.1.3 Analysis of the Study [41]
The method of writing the equations is very cumbersome as well as the presentation of
the numerical model [41]. Surely, a more simple way is based on using integers i and
j, so that the following is obtained for the position of the very thin sheet in which the
concentration is constant: x = i. x, and for the time t = j, t. By using these symbols, the
concentration is written as Ci,j.
A few misinterpretations are made in the text, and some of them are worth noting:
i) During t, all variables are supposed to vary linearly with time [41]. In fact, during each
increment of time t, all the variables, e.g., the concentrations and the diffusivities are
kept constant during this short time increment, while the variables are discontinuously
changed from one increment to another.
ii) The following text is correct in principle: the convection affects mainly the beginning of
the kinetics, the diffusivity affects all the kinetics, the coefcient BS (which accounts for the
dependence of the diffusivities with the liquid concentration) affects principally the end of
the kinetics. But the presentation of these facts is nave and leads to a wrong conclusion,
showing in the following gure a discontinuous increase in the kinetics of sorption
(Figure 6.13). Fortunately, the kinetics obtained either from experiments or calculation,
are continuously shown in the paper [41], without exhibiting this anomaly.
Figure 6.13. Scheme of the process of migration of additives and liquid, by

decomposing the effects of the convection (1), diffusion (2) and concentration-
dependent diffusivity (3).
254
iii) The effect of the swelling and of the increase in concentration of the liquid absorbed
in the polymer should be precisely noted. The diffusivity of the additive and of the
liquid varies with the concentration of the liquid, but not with the swelling, as stated
in the paper swelling of the polymer increases the additives mobility [41]. In fact,
an increase in the dimensions of the polymer is responsible for an increase in the time
of the diffusion of the additive.
iv) In the case concerned with the release of the additive into the liquid, it would have been
of interest to draw the proles of concentrations of the liquid and of the additives, in
the same way as shown in Figures 6.11 and 6.12. These proles are able to provide a
fuller insight into the nature of the process. The liquid diffuses into and through the
polymer with a low concentration at the forefront of the prole, thus dissolving the
additive, and so it can be said that the additive in solution diffuses through the liquid
inserted in the polymer. But the concentration of the liquid at the forefront is very low,
especially for a package whose polymer is selected for its resistance to the transfer
of the liquid food. In this case, the solubility of the additive in the liquid plays the
main role, and it should be very high. On the whole, both these transfers are driven
by in a counter-current. Nevertheless, the problem of the diffusion of the liquid into
and through the polymer package is of great concern, especially for long-term basic
studies made for the purpose of selecting the right polymers.
v) The last study made on the diffusion of the additive from the pre-saturated polymer
with the additive-liquid solution into the pure liquid is of no use in the present case.
It was considered to be quite a different problem [46, 47], to establish a method able
to evaluate the diffusivity of an antibiotic into and through a heart with endocarditis
(inammation of tissues located in the heart [48]), which is constantly saturated with
blood. Of course, these two problems are quite different, since the polymer package
does not contain any amount of liquid food.
6.8.2 Analysis of a Somewhat Similar Study [49]
The present study [49] is similar to the previous one [41] with the same gures, except
for the extension of the method to various other molecules.
The following conclusions can be drawn:
The mathematical approach, as well as the numerical treatment, described in the previous
paper [41], is used and the same results are published. However, the method has been
extended to a wide number of molecules, such as linear alkanes, commercial additives
including a plasticiser and a variety of Irganox and Irgafos additives, as well as other
255
chemicals. In that sense, a large amount of work has been achieved, leading to the following
two results of interest: good linearity is attained for linear alkanes when the diffusivity
is plotted versus the molecular weight, either with a virgin PP or with the same polymer
pre-saturated with the food simulant.
The kinetics of sorption of the food stimulant is expressed by assuming that the coefcient
of convection at the polymer-liquid interface is innite. But the times of experiments are
rather long: 1, 2 and 5 days. Surely a shorter time for the rst measurements, e.g., hours,
should have shown that this coefcient is nite, as was previously obtained [32]?
6.9 Methodology for Measuring the Reference Diffusivity
6.9.1 Presentation of the Ideas and the Methods [50]
In a paper [50] somewhat similar to the previous one [41], the interesting idea emerges
again about what could be the right diffusivity of a surrogate (diffusing substance) in a
polymer. It is understandable that the diffusivity of a substance could be different whether
it diffuses through a solid-solid system or it diffuses in a solid-liquid operation. The main
difference between these two cases comes from the fact that the liquid could intervene in
the process in various ways: by plasticising the polymer (a euphemism for a slight transfer
of the liquid into the PET polymer), no possible pollution of the liquid when the diffusing
substance is not soluble in it, without forgetting the convective effect which takes place
at the solid-liquid interface.
The factors of interest are:
The concentration of the pollutant initially in the package;
The partition coefcient for a pollutant between the package and the food;
The diffusivity. A proposal is made for correlating the diffusivity with the molecular
weight of the diffusing substance. This work done with parafns diffusing through
polyolens as polymers [9, 10] should be repeated using PET.
The initial distribution of the pollutant. This factor appearing essentially in the case
of bi-layer or tri-layer package made of recycled and virgin layers co-extruded.
256
Two types of experiments are made, the one with non-swollen PET lms, and the other
with swollen PET lms.
Very thin lms, around 10 m thick, are prepared for diffusivity measurements. Great
care is taken to make sure that the physical properties of these lms (expanded by air
blowing) are similar to those of PET bottles, by using thermal mechanical analysis (TMA)
and modulated differential scanning calorimeter (MDSC).
6.9.1.2 Diffusion Experiments in Swollen and Non-swollen PET
Various data are given with different potential contaminants obtained either with
solid-solid polymer or with pre-swollen polymers in contact with the liquid located
in the polymer.
A typical example is shown for the diffusion of phenol at 60 C considered as the

diffusing substance. A plateau is reached at only 33% of the theoretical plateau.
The question put by the authors, coming from discussions between various authors
[51, 52] is: which is the value for the amount of matter transferred at equilibrium?
But another question arises in terms of the provisional answer: what is the so-called
theoretical plateau? Is it obtained by assuming without any proof that the whole
amount of additive initially located in the polymer would be perfectly distributed
between the polymer and the liquid, according to the obvious relationship:
Vl
M100 = M in (6.32)
Vp + Vl
6.9.2 Analysis of the study
6.9.2.1 Value of the Diffusivity with the Plateau Value
Surely, by considering Equation (6.33), which can be used only when the coefcient of
convection is innite, the value of the diffusivity depends on the value given to M:
0.5
Mt 2 D t Mt
= for < 0.6 (6.33)
M L M
257
Thus two values are obtained for this diffusivity called M100 and M33 [50, 51]. As the
diffusivity D is inversely proportional to the square of the value given to M, the two values
of this diffusivity vary by around 10. In fact, the value of M100 is obtained by forgetting
that the solubility of the diffusing substance is also a limiting factor, this difference in the
value of the solubility in the two media giving rise to the partition factor (the fact is true
in the same way, either when the diffusing substance enters or leaves the polymer).
In Equation (6.33), as well as in the other Equations (6.1), (6.4) or (6.14), the term M, as
indicated by its name, represents the amount of the diffusing substance which is transferred
from one medium to another after infinite time. The amount of additive initially located
in one medium, Min, in the polymer for instance, is another quite different thing.
6.9.2.2 Question About the Diffusivity in the Non-swollen and the

Swollen Polymer
The swollen polymer behaves towards the diffusion of any surrogate in a way different
from that of the same polymer under non-swelling conditions.
6.9.3 Conclusions
6.9.3.1 Question Concerning the Two Values of the Diffusivity
In fact, this result is not uncommon, and the conclusion is easy to draw: the process of
diffusion is characterised by more than one parameter: the diffusivity D coupled with
the amount at equilibrium, M, without forgetting the coefficient of convection at the
polymer-liquid interface and the possible partition factor.
6.9.3.2 Effect of the Presence of the Liquid in the Polymer
This fact is perhaps more important than those concerned with the so-called worst case
scenario. This is a worst case scenario for the reason that the presence of a solvent in
the polymer increases considerably the diffusivity of any surrogates. This should be the
basis for the implementation of a further legislation rule for food packages, which stands
already for the drugs in their packages with their time-limitation defined for the patients
safety. Thus a condition should be defined for this time, allowing for the shelf life of the
food-bottle system. This time can be defined by thinking of the following:
The diffusion of the liquid food into the polymer bottle over a long time period
(experimentally, this time can be reduced by considering that the time of diffusion necessary
for a given transport is proportional to the square of the thickness of the sample).
258
The variation of the diffusivity of the surrogates with the concentration of the
liquid food.
Let us note that in this case, the problem is far more complex than that described
with a totally swollen polymer [50]. As already shown [17, 18, 22], the two transfers
of the contaminant into the liquid and of the food into the polymer are not only
coupled with each other, but they take place simultaneously, making the problem far
more complex, as especially proved by the proles of concentration of the liquid and
plasticiser (diffusing substance) shown in Figure 6.12 for plasticised PVC.
6.9.3.3 Diffusivity-Molecular Weight Relationship for PET
It is true that this kind a relationship, already obtained with polyethylene and its surrogates
[10] should be considered for the PET bottle. The attempt made [49] is the rst example.
Nevertheless, it should be noted that the diffusivity values versus molecular weight
obtained for various surrogates are far from being accurate, the values of the diffusivity
lying between one order of magnitude when expressed in a logarithm form (by more than
10 for the values), but far much precise than the relationship dened previously [10].
6.10 Conclusions on the Remarks Made in Chapter 6
This part, with Chapter 6, which is perhaps not so usual in a book, has been necessary,
for the following reasons:
i) Two categories of workers are making attempts to develop the potential of the food
packages through their own research:
The theoreticians who would keep their knowledge at a constant level, if new
problems were not set up by the experimentalists.
The experimentalists who have the exciting task of discovering and developing
new ways of improving our knowledge by using more sophisticated and precise
techniques.
ii) The experimentalists are much occupied in doing their own work, but some of them
are inclined to build their own mathematical treatment.
iii) The hard task of the theoreticians is to show the best way of obtaining more accurate
data from the experiments. It is very important to get at the end of the experimental
259
work, precise data which can be used in the future. The relevance to attaining this
objective appears when it is seen that the values of the diffusivity collected in the
literature vary to such a large extent (by ten times, or a hundred times, according to
who did the work) that they should be used with circumspection [10].
iv) The problem of diffusion is becoming so important in the case of food packaging, as
well as for membranes, that the number of researchers is growing more and more, with
some contradictory results: the literature has expanded so much that is has become
impossible to cite all the authors needed because of this every researcher has built
his own anthology of authors and papers.
v) The researchers, for various reasons, have been tempted to simplify the theoretical
treatment in order to get precise data from their experiments. The following have
been described:
semi-innite medium for sheets whose thicknesses do not exceed 0.05 cm.
innite coefcient of convective transfer at the food-package interface.
taking forced convection for conduction in heat transfer.
vi) There has been a trend to say without denite proof that a worst case for the release
of the polymer additives in the food should be the best solution. A kind of statement
often holds in various situations: simplication is only possible after the precise results
have been obtained, and the choice of the worst case then emerges as a result, in a
quantitative manner. As already stated in Section 6.4 about the paper [9], neglecting
the presence of the coefcient of convective transfer either for evaluating the diffusivity
or calculating the time of protection of the food, leads to a vicious circle and nally
does not provide complete protection.
vii) The problem of recycling old packages in new packages is growing more important.
And nally, it arises as a new task for the researchers. Dening a list of polymer
additives which are not permitted is one thing which resolves the problem of food
contamination in the rst run, when these polymers, considered as being in virgin
state, are used for the rst time. For the stage of recycling, the problem becomes
different and the task grows immensely as the empty bottle, before its recycling
stage, could be used to store chemicals as herbicides, enabling them to diffuse into
the polymer and nally to remain in the new package.
viii) The theory and model based on Equation (6.14), using , the ratio of the volumes
of liquid and package, has been developed. It is used without making clear that the
coefcient of convective transfer at the package-liquid interface is innite. Moreover,
it has been shown in Chapter 4, especially through the Figures 4.4-4.7 that the effect
260
of the parameter becomes sensible only when it is lower than 20. Now, the values
of are 166 and 16.6 for cubes of 1 litre and 1 cm3, respectively, when the thickness
of the package is 100 m, and 35.9 for a cube of 10 cm3. These values mean that it
is absolutely necessary to take into account when the volume of the liquid is equal
or less than that of a thimble.
ix) Rivalry exists between researchers, if not competition, and this occurrence is the best
thing that could be. Discoveries could not be made without emulation or concurrence
between the researchers. In the same way, when some people nd a result, others
have to repeat them; this is necessary to make sure that the theory is set up in a
right way and the data are correct. This is the reason why it is necessary to make a
thorough analysis of a few selected papers, those relevant papers emerging from the
main laboratories which are of consequence in the research community.
References
1. R. Dagani, Chemical & Engineering News, 2005, 83, 26, 50.
2. M. Limam, L. Tighzert, F. Fricoteaux and G. Bureau, Polymer Testing, 2005, 24,

3, 395.
3. Programme de Calcul du Coefficient de Diffusion a Partir de Mesures

Experimentales, Software developed by the Swiss Federal Ofce of Public Health,
Bern, Switzerland, http://www.bag.admin.ch/verbrau/gebrauch/info/f/exdif.htm

Systems: Mathematical and Numerical Treatments, CRC Press, Boca Raton, FL,
USA, 2005.
5. M. Siewert, European Journal of Drug Metabolism and Pharmacokinetics, 1993,

18, 7.
6. R. Franz, M. Huber and O. Piringer, Food Additives and Contaminants, 1997, 14,
6-7, 627.
7. J. Crank, The Mathematics of Diffusion, Clarendon Press, Oxford, UK, 1975.
8. O. Piringer, R. Franz, M. Huber, T.H. Begley and T.P. McNeal, Journal of

Agricultural Food Chemistry, 1998, 46, 4, 1532.
261
9. J. Brandsch, P. Mercea, M. Rter, V. Tosa and O. Piringer, Food Additives and

Contaminants, 2002, 19, Supplement, 29.
10. J. Brandsch, P. Mercea, and O. Piringer in Food Packaging: Testing Methods and
Applications, Ed., S.J. Risch, ACS Symposium Series No.753, Washington, DC,
USA, 1999, p.27-36.
11. O-G. Piringer in Plastic Packaging Materials for Food: Barrier Function, Mass
Transport, Quality Assurance and Legislation, Ed., O-G. Piringer and A.L. Baner,
Wiley-VCH, Weinheim, Germany, 2000, p.159.
12. T. Begley, L. Castle, A. Feigenbaum, R. Franz, K. Hinrichs, T. Lickly, P. Mercea,

M. Milana, A. OBrien, S. Rebre, R. Rijk and O. Piringer, Food Additives and
Contaminants, 2005, 22, 1, 73.
13. D. Messadi and J-M. Vergnaud, Journal of Applied Polymer Science, 1981,
26, 7, 2315.
14. D. Messadi and J-M. Vergnaud, Journal of Applied Polymer Science, 1982, 27,
10, 3945.
15. H.L. Frisch, Journal of Polymer Science: Polymer Physics Edition, 1978, 16, 9, 1651.
16. D. Messadi, J-M. Vergnaud, and M. Hivert, Journal of Applied Polymer Science,
1981, 26, 2, 667.
17. J.L. Taverdet and J-M.Vergnaud, Journal of Applied Polymer Science, 1984, 29,
11, 3391.
18. J.L. Taverdet and J-M. Vergnaud, Journal of Applied Polymer Science, 1986, 31,
1, 111.
19. J.L. Taverdet and J-M.Vergnaud, Journal de Chimie Physique, 1985, 82, 2, 643.
20. J.L. Taverdet and J-M. Vergnaud in Instrumental Analysis of Foods, Volume 1,
Eds., G. Charalambous and G. Inglett, Academic Press, New York, NY, USA,
1983, p.367-378.
21. J-M. Vergnaud, Drying of Polymeric and Solid Materials: Modelling and
Industrial Applications, Springer-Verlag, London, UK, 1992.
22. J-M. Vergnaud, Liquid Transport Processes in Polymeric Materials: Modelling

and Industrial Applications, Prentice Hall, Englewood Cliffs, NJ, USA, 1991.
262
23. A. Aboutaybi, J. Bouzon and J-M. Vergnaud, European Polymer Journal, 1990,
26, 3, 285.
24. Y. Khatir, J.L. Taverdet and J-M. Vergnaud, Journal of Polymer Engineering,
1988, 8, 1-2, 111.
25. J.L. Taverdet and J-M. Vergnaud, European Polymer Journal, 1986, 22, 12, 959.
26. A. Bichara, J.L. Fugit and J.L. Taverdet, Journal of Applied Polymer Science,
1999, 72, 1, 49.
27. A. Bichara, J.L. Fugit, I. Ouillon and J.L. Taverdet, Journal of Applied Polymer
Science, 1999, 74, 14, 3492.
28. J-L. Fugit and J.L. Taverdet, Journal of Applied Polymer Science, 2001, 80, 10,
1841.
29. J-L. Fugit, J.L. Taverdet, J-Y. Gauvrit and P. Lanteri, Polymer International, 2003,
52, 5, 670.
30. A. Senoune and J-M. Vergnaud, European Polymer Journal, 1993, 29, 5, 679.
31. P.Y. Pennarun, Y. Ngono, P. Dole and A. Feigenbaum, Journal of Applied Polymer
Science, 2004, 92, 5, 2859.
32. A.M. Riquet, N. Wolff, S. Laoubi, J-M. Vergnaud and A. Feigenbaum, Food
Additives and Contaminants, 1998, 15, 6, 690.
33. H.S. Carslaw and J.C. Jaeger, Conduction of Heat in Solids, 1st Edition,
Clarendon Press, Oxford, UK, 1978.
34. W.H. McAdams, Heat Transmission, 3rd Edition, McGraw-Hill, New York, NY,
USA, 1954.
35. J-M. Vergnaud and J. Bouzon, Cure of Thermosetting Resins: Modelling and
Experiments, Springer-Verlag, London, UK, 1992.
36. J. Ben Abdelouahab, A. El Bouardi, R. Granger and J-M. Vergnaud, Polymers and
Polymer Composites, 2001, 9, 8, 515.
37. J.Y. Moisan, European Polymer Journal, 1980, 16, 10, 979.
38. A. Reynier, P. Dole and A. Feigenbaum, Food Additives and Contaminants, 1999,
16, 4, 137.
263

Science, 1997, 66, 3, 597.
40. I-D. Rosca, J-M. Vergnaud and J. Ben Abdelouahab, Polymer Testing, 2001, 20, 1, 59.
19, 1, 89-102.
42. A. Bakhouya, A. El Brouzi, J. Bouzon and J-M. Vergnaud, European Polymer

Journal, 1992, 28, 7, 809.
43. A. Bakhouya, A. El Brouzi, J. Bouzon and J-M. Vergnaud, Plastics, Rubber, and
Composites Processing Applications, 1993, 19, 77.
44. N. Bakhouya, A. Sabbahi and J-M. Vergnaud, Computational and Theoretical

Polymer Science, 1996, 6, 109.
45. N. Bakhouya, A. Sabbahi and J-M. Vergnaud, Plastics, Rubber and Composites,
1999, 28, 6, 271.
46. A. Benghalem and J-M. Vergnaud, Polymer Testing, 1994, 13, 1, 35.
47. A. Senoune, A. Benghalem, K. Erdogan, A. El Brouzi and J-M. Vergnaud,

International Journal of Bio-Medical Computing, 1994, 36, 1-2, 69.
Systems, Mathematical and Numerical Treatment, CRC Press, Boca Raton, FL,
USA, 2005.
19, Supplement, 42.
50. P.Y. Pennarun, P. Dole and A. Feigenbaum, Journal of Applied Polymer Science,
2004, 92, 5, 2845.
51. A. Reynier, P. Dole, S. Humbel and A. Feigenbaum, Journal of Applied Polymer

Science, 2001, 82, 10, 2422.
52. J. Brandsch, P. Mercea and O-G. Piringer in Plastic Packaging Materials for Food,
Barrier function, Mass Transport, Quality Assurance and Legislation, Eds., O-G.
Piringer and A.L. Baner, Wiley, VCH, Weinheim, Germany, 2000.
264
Abbreviations
ratio of the volume of liquid and polymer sheet, dimensionless number
b, d thickness of the layers in the package (see Section 6.2)
ns positive roots of Equation (6.2)
Cx,t concentration of diffusing substance at position x and time t
Cin initial concentration of the diffusing substance
CGS Centimetre, gram, second system of units
D diffusivity (cm2/s)
D1 diffusivity in the medium 1
D2 diffusivity in the medium 2
DEHP di (2-ethylhexyl)phthalate
h coefcient of matter convective transfer at the package-liquid interface

(cm/s)
hh coefcient of convective heat transfer (cal/(cm2/s/deg)
K partition factor, dimensionless number
1 thermal conductivity in the medium 1
2 thermal conductivity in the medium 2
L thickness of the layer (cm)
LDPE Low-density polyethylene
Mt amount of diffusing substance released at time t
M amount of diffusing substance released at innite time, at equilibrium
MDSC modulated differential scanning calorimeter
MIC Maximum initial concentration
265
PET Polyethylene terephthalate
PP Polypropylene
PVC Polyvinyl chloride
qns non-zero positive roots of Equation (6.15)
R dimensionless number, dened in Equation (6.3)
x dened position
t dened time
TMA thermal mechanical analysis
Vl volume of liquid
Vp volume of the package
266
7
Conclusions
As was said many times, after the rst book by Crank [1], laying the way of diffusion, or
rather the mathematical treatment at least, various studies have been conducted by using
mass transfer whose driving force is diffusion. These works have been oriented in many
directions for example:
i) in pharmacy with dosage forms whose drug release is controlled by diffusion as well
as with the drug transfer through various human tissues [2, 3];
ii) in various materials, such as wood which exhibits a typical anisotropy in three-
directions and with three values of diffusivity [4];
iii) in elastomers and rubbers where sometimes the swelling largely exceeds 100%
in volume;
iv) in thermosetting resins - those materials which are replacing iron or steel more and
more and thus becoming metal substitutes [5];
v) and last but not least, in food packages made of polymers.
In the last application of diffusion, with the food packages where the protection of the
consumers safety is concerned, various orientations have been followed in research.
The rst is devoted to the usual food package, when the virgin polymer is used for the rst
time, and the problem which occurs is the diffusion of the additives disseminated into the
polymer in order to provide the essential qualities of the polymer. For this reason, a list of
non-authorised additives has been drawn under the guidance of the European Community
and the Food and Drug Administration (FDA, Washington, DC, USA).
As the pollution of the surrounding atmosphere, this time, by the polymer packages
and polymer bags has been more and more pressing, a solution to this problem has
been considered based on recycling the polymer, and especially in reusing the old food
packages in new packages. But this solution is not simple as another contamination of
the food package may occur from this recycling. Thus, as a nal result, bi- or tri-layer
packages should be prepared, where a virgin polymer layer is inserted between the recycled
267
polymer layer and the food to give the protection. And following this, as these multi-layer
packages are obtained by co-extrusion at a temperature at which the polymers are melted,
an additional transfer (by diffusion or perhaps by convection) takes place between the
recycled and the virgin polymer layers. At the time of the study, heat transfer has to be
looked at, and the effect of the temperature-dependency of the diffusivity estimated.
In the third chapter, the problems of heat transfer have been briey, but seriously described,
with heat conduction taking place between two solids as well as through each of them,
and heat convection between a solid and a uid; moreover, in this second case, depending
on whether the uid (gas or liquid) is stirred or not, the convection is either forced or free
(natural), while in both cases the process is driven in laminar or in turbulent condition.
At this time, it is of interest to recall that in science history, heat conduction was studied
rst by Fourier (1822) who put this transfer of random molecular motion on a quantitative
basis with his well-known equation. A few decades later, Fick (1855) recognising the
analogy between the two processes, put diffusion on a quantitative basis by adopting the
mathematical equation for matter diffusion. The analogy between the two processes was
prolonged, when Crank applied in the Mathematics of Diffusion a way of calculation
introduced by Carslaw and Jaeger in the Heat Conduction. The analogy between the heat
and mass transfers is obviously extended to the convection which takes place either at the
surface of a heated solid in contact with a surrounding atmosphere or at the package-liquid
interface. Thus, the convective transfer taking place either into the liquid food or at the
liquid-solid interface is characterised by the coefcient of convection. And nally, without
any shadow of doubt, the process of transfer of the polymer additives into the food is
controlled either by diffusion through the thickness of the polymer (whatever its nature,
with multi-layer and recycled layers) or by convection into the liquid at the polymer-liquid
interface. Another example has been cited to explain this fact, with the phenomenon of
evaporation. Contrary to a permanent gas which exhibits such a high rate of evaporation,
any liquid should be dened by a nite rate of evaporation. Thus, the process of drying
a solid is controlled either by diffusion through the solid and evaporation at the surface,
without forgetting that this nite rate of evaporation is still controlled by the rate of stirring
of the atmosphere, a high motion of the surrounding atmosphere increasing the rate of
evaporation to a nite limit (without forgetting that evaporation being an endothermic
process, the temperature on the surface decreases). With the package-liquid problem, by
following up the previous metaphor of evaporation, the additives appearing on the surface
of the polymer should overcome the resistance offered to any transfer by the liquid, this
resistance leading to the convective transfer.
On the other hand, while thinking of what could be a worst case, meaning the possible
experiment which might lead to the faster release of the additives, many thoughts should be
expressed. A case can be called worst only when the true case is perfectly known. In other
268
Conclusions
words, in the same way as people building a bridge, the right conditions are calculated for the
parts of the bridge, and afterwards a multiplication factor is introduced so as to ensure the
safety of the passengers. The work dealing with the problems of food safety should follow
this way of thinking: rst, to get the best knowledge of the actual facts which are possible,
and afterwards to increase the constraints which are believed necessary for a better safety.
By contrast with the position of Crank who, before the researchers, had carried out
experiments and dealt with the mathematical treatment, we had to carefully examine various
papers and to call attention to a few misconceptions of the process and misuses of equations
which have been made. Precise attention has been focused on the following facts:
i) The innite coefcient of convection at the solid-liquid interface which - by the way-
leads to a worst case scenario but also to an unknown worst case scenario, which is
of little use, if not useless. Moreover, calculating the diffusivity by assuming that the
rate of the convection is innite leads to a lower diffusivity, but taking this last value
in evaluating the time of food protection and by using the same equation with innite
convection, leads back in a so called vicious circle. Incidentally, this assumption is
not clearly put forth in various equations, and the experimentalists can use these
equations without thinking that this fact is applied. The problems put by the effect of
the convective transfer associated with the rate of stirring of the liquid has been judged
so essential by the FDA that standardised apparatuses have been built and tested (with
the shape of the ask, the rate of stirring due to the paddle system) in pharmacy, so
as to determine precisely the rate of release of the drug out of dosage forms. As food
protection is also relevant for the consumers safety, the FDA has paved the way for
what is to be done with food packages.
ii) In terms of heat transfer, taking heat convection for heat conduction leads one to
consider the metal mould behaving as either a liquid or a gas.
iii) The concept of innite or even semi-innite medium seems unreasonable when applied
to a food package whose thickness does not exceed a few hundred microns. The use
of the parameter called , expressing the ratio of the volumes of liquid food and
package, becomes mandatory only when it is lower than 20. This result means that it
is useless for a bottle of 1 litre stored in a package whose thickness is 100 m, as in
the case of = 166; nally, the equations dealing with would be necessary for a 1
cm3 cube wrapped in the same 100 m thick package for which = 16.6.
iv) And nally, the problem of great concern, with the effect of the possible transfer of
the food itself into the polymer. This factor is so important that it should be one of
the factors, if not the main factor, which are considered in dening the shelf lifetime
of the package-food system, as far as the additives transport is relevant.
269
These misuse of equations, which generally follow the misconceptions of the process, have
been pointed out with great care. The present authors have not wanted to criticise other
authors who are often highly competent experimentalists, but after a careful analysis of
their concepts, want to propose a better way of doing things.
There is a common responsibility of the researchers with regard to science, and the economy
as well, according to the pressing necessity that only true results should be obtained.
Moreover, it should not be forgotten that the people in important laboratories are considered
as leaders by the other researchers, and especially by the younger; and thus, these young
people could be tempted to follow the way paved by these elder workers, because they are
well known, and to take misuses for truth. Of course, as occurring in many elds, researchers
are submitted to emulation, if not competition or even rivalry. This fact is essential. But
publishing in scientic journals a lot of papers without verifying their accuracy is one thing,
it is far better is to make sure that the paper published contributes something new in terms of
ideas or of improved techniques. As far as the theory is concerned, only a few developments
are possible, as the essential ideas have been expressed already, but not always correctly
applied. On the other hand, the techniques have advanced in precision and feasibility. It is
a pleasure to recall that the Moisans method for evaluation of the proles of concentration
can be applied now far more easily and accurately by using a spectrometer coupled with a
microscope. In the same way, small asks described for measuring the kinetics of release,
are so pretty that they seem to be coming from a jewel even if they necessitate the use of
both the dimensionless numbers for the small volume and R for convection.
In conclusion, this book has been written with the purpose of helping authors and researchers,
the well-known as well as new ones, in nding their way through the tangled web that is
the process of diffusion, by making the theoretical treatment clear, by playing the role of
Ariadnes thread.
References
1. J. Crank, The Mathematics of Diffusion, Clarendon Press, Oxford, UK, 1975.
2. J-M. Vergnaud, Controlled Drug Release of Oral Dosage Forms, Ellis Horwood,
London, UK, 1994.

Systems, CRC Press, Taylor & Francis, Boca Raton, FL, USA, 2005.
4. J-M. Vergnaud, Liquid Transport Processes in Polymeric Materials, Prentice Hall,

Englewood Cliffs, NJ, USA, 1991.
5. J-M. Vergnaud and J. Bouzon, Cure of Thermosetting Resins, Springer-Verlag,

London, UK, 1992.
270
Appendix
The First Six Roots* n of tan = R

R 1 2 3 4 5 6
0 0 3.1416 6.2832 9.4248 12.5664 15.7080
0.001 0.0316 3.1419 6.2833 9.4249 12.5665 15.7080
0.002 0.0447 3.1422 6.2835 9.1250 12.5665 15.7081
0.004 0.0632 3.1429 6.2338 9.4252 12.5667 15.7105
0.006 0.0774 3.1435 6.2841 9.4254 12.5668 15.7083
0.008 0.0803 3.1441 6.2845 9.4256 12.5670 15.7085
0.01 0.0998 3.1448 6.2848 9.4258 12.5672 15.7086
0.02 0.1410 3.1479 6.2864 9.4269 12.5680 15.7092
0.04 0.1087 3.1543 6.2895 9.1290 12.5696 15.7105
0.06 0.2125 3.1606 6.2927 9.4311 12.5711 15.7118
0.08 0.2791 3.1668 6.2959 9.4333 12.5727 15.7131
0.1 0.3111 3.1731 6.2901 9.4354 12.5743 15.7143
0.2 0.4328 3.2039 6.3148 9.4459 12.5823 15.7207
0.3 0.5218 3.2311 6.3305 9.4565 12.5902 15.72711
0.4 0.5932 3.2636 6.3161 9.4670 12.5981 15.7334
0.5 0.6033 3.2923 6.3616 9.4775 12.0060 15.7397
0.6 0.7051 3.3204 6.3770 9.4879 12.6139 15.7460
0.7 0.7506 3.3477 6.3923 9.4983 12.6218 15.7524
0.8 0.7910 3.3744 6.4074 9.5087 12.6296 15.7587
0.9 0.8274 3.4003 6.4224 9.5190 12.6375 15.7650
271
1.0 0.8603 3.4256 6.4373 9.5293 12.6453 15.7713

1.5 0.9882 3.5422 6.5097 9.5801 12.6841 15.8026
2.0 1.0769 3.6430 6.5783 9.6296 12.7223 15.8336
3.0 1.1925 3.8088 6.7040 9.7240 12.7966 15.8945
4.0 1.2646 3.9352 6.8110 9.8119 12.8678 15.9536
5.0 1.3138 4.0336 6.9096 9.8928 12.9352 16.0107
6.0 1.3496 4.1116 6.9924 9.9667 12.9988 16.0654
7.0 1.3766 4.1746 7.0640 10.0339 13.0584 16.1177
8.0 1.3978 4.2264 7.1263 10.0949 13.1141 16.1675
9.0 1.4149 4.2694 7.1806 10.1502 13.1660 16.2147
10.0 1.4289 4.3058 7.2281 10.2003 13.2142 16.2594
15.0 1.4729 4.4255 7.3959 10.3898 13.4078 16.4474
20.0 1.1961 4.4915 7.4954 10.5117 13.5420 16.5864
30.0 1.5202 4.5615 7.6057 10.6543 13.7085 16.7691
40.0 1.5325 4.5979 7.6647 10.7334 13.8048 16.8794
50.0 1.5400 4.6202 7.7012 10.7832 13.8666 16.9519
60.0 1.5451 4.6353 7.7259 10.8172 13.9094 17.0026
80.0 1.5514 4.6543 7.7573 10.8606 13.9644 17.0686
100.0 1.5552 4.6658 7.7764 10.8871 13.9981 17.1093
1.5708 4.7124 7.8540 10.9956 14.1372 17.2788
*The roots of this equation are all real if R > 0.
272
Author Index
A El Kouali, M 219
Erdogan, K 264
Aboutaybi, A 244, 263
Al-Ati, T 219
Appendini, A 219 F
Feigenbaum, A 55, 96, 143, 198, 262,
B 263, 264
Fick, A 7, 57, 59, 73, 101, 146. 268
Bakhouya, N 264
Fourier, JBJ 7, 101, 268
Bakhouya, A 264 Franz, R 143, 261, 262
Begley, TH 261; 272 Fricoteaux, F 261
Ben Abdelouahab, J 96 Frisch, HL 262
Benghalem, A 264 Fugit, JL 263
Bichara, A 263
Bouzon, J 143; 244; 263; 264, 270
Brandsch, J 237, 262, 264 G
Brody, A, 219 Gauvrit, JY 263
Bureau, G, 261 Granger, R 263
Hinrichs, K 262
C
Carslaw, HS 6, 143, 263; 268
H
Castle, LJ 143, 262 Hivert, M 262
Crank, J 2, 5, 6, 55, 87, 96, 197, 261, 267, Hotchkiss, JH 219
268, 269, 270 Huber M 143, 261
Humbel S 264
D
Dagani, R 261
J
Damant, AP 143 Jaeger JC 6, 143, 268, 263
Dole, P 143, 263, 264 Jickells, S 143
E K
El Bouardi, A 263 Khatir, Y 263
El Brouzi, M 219, 264 Kline, L 219
273
L S
Labidi, F 219 Sabbahi, A 264
Lanteri, P 263 Salouhi, M 219
Laoubi, S 55, 96, 143, 197, 198, 263, 264 Senoune, A 263, 264
Lickly, T 262 Siewert, M 198, 261
Limam, M 261 Strupinsky, E 219
M T
McAdams, WH 6, 143, 219, 263 Taverdet, JL 96, 243, 262, 263
McNeal, TP 261 Tighzert, L 261
Mercea, P 237, 262, 264 Tosa, V 237, 262
Messadi, D 96, 197, 262
Milana, M 262 V
Miltz, J 143
Moisan, JY 50, 55, 250, 251, 263, 270 Vergnaud, J-M 6, 55, 96, 143, 197, 198,
164, 219, 243, 244, 261, 262, 263,
264, 270
N
Ngono, Y 143, 263 W
Nicolson, P 87
Nir, NM 143 Wilkinson, SL 219
Wolff, N 55, 263
O
Z
OBrien, A 262
Ouillon, O 263 Zobel, MRG 96
P
Pennarun, PY 143, 263, 264
Perou AL 143, 198
Piringer, O 143, 237, 261, 262, 264
R
Ram, A 163
Rebre, S 262
Reynier, A 263, 264
Rijk, R 262
Riquet, AM 55, 263
Rooney, M 219
Rosca, I-D 55, 96, 143, 197, 198, 219,
261, 264, 270
Rter, M 262
274
Subject Index
A Coefcient of convection 10, 30, 39, 40,

150, 153, 155, 269
Active packages 201 Innite value 149
Antimicrobial properties 203 Coextrusion
Conclusions 218 Heat transfer 174
Food protection 207 Mass transfer 174
Mathematical/numerical treatment of 207 Of multi-layer lms 99
Theoretical 206 Copper 103
Transfer 201 Concentration
Analogy of contaminant 64, 66, 71
Diffusion with heat conduction 7 proles 61, 87, 250
Matter convection with heat convection 9 Contaminant transfer 70
Antimicrobial agents 204, 205 Contamination 184
Coating of polymer 204 Convection
Antimicrobial packages 203, 205 Of heat 103
Regulatory issues 205 Of matter 7
Antimicrobial polymers 205 Properties 9
Approximate value of the diffusivity 41 Rate of 235
Asbestos board 103 Convective transfer 229
Coefcient of 159
B Equation based on 222
Basic equations
Of heat 101
D
Of matter 8 Di(2-ethylhexyl)phthalate 243
Bi-layer lm 99 Differential equations 10, 11
Bi-layer package 58, 67, 85, 165, 166 Differential scanning calorimeter
Bottle Modulated 257
One-layer 189 Diffusion 54, 58, 247
Tri-layer 100, 177, 181 Basic equations 8, 13, 147
Boundary conditions 9 Determination 29, 49
Application of 148 Differential equation 150
Kinetics of transfer 89
Parameters of 148
C Principles of 147
Chlorobenzene 229 Diffusion-convection process 185
275
Diffusivity 29, 36, 41, 256, 258, 259 G

Experimental 50
Glyceryl tripelargonate 252
Molecular weight relationship 259
Gradients of concentration 51
Theoretical 50
Measurement 49, 250
Dimensionless numbers 217
Use for measuring the kinetics 41, 49,
Dimensionless time 184 250, 238
Double transfer of substances 238, 252 Gradients of temperature 106, 118
Grashof number 105
E
Effect of
H
Co-extrusion 174, 185 Heat convection 103
The coefcient of convective transfer 159 Coefcient of 104, 109, 118
The ratio of the volumes of liquid and of Heat transfers 108, 135, 269
package 163 Basic equations 101
The thickness of the lm 114 By conduction 101, 245, 248
Ethylacetate 66 By convection 103, 125, 245, 248
Ethylene vinyl acetate 103 Coupled with mass transfers 107, 142
Ethlene vinyl alcohol 202 In bi-layer lms 105, 108
Evaluation of In tri-layer lms 120, 122
In tri-layer bottles 123, 133
Heat and mass transfers
Theoretical 122, 246
In bi-layer lms 108
Unidirectional 101
In tri-layer lms 120
Heptane 242, 244
In tri-layer bottles 123, 133 Hexane 242, 244
The parameters of diffusion 29 High-impact polystyrene 229
From the proles of concentration 49
From the kinetics of transfer 31,
I
36, 38
Innite value of the
Rate of convection 10, 13, 19, 39, 41,
F 222, 229
Film With innite volume of liquid 13, 19
Thickness of 229 With nite volume of liquid 20, 235
Finite values of Thickness of the lm 229, 233
The coefcient of convection 9, 40 Irgafos 255
with innite volume of the liquid 26 Irganox 255
Food
Liquid of innite volume 13, 19, 26 K
Liquid of nite volume 20 Kinetics of mass transfer
Solid 186, 187, 188 Basic equations 8
Food packaging Innite volume of liquid and of rate of
Ratio of volume/area 28 convection 13, 19
Forced convection 104 Finite volume of liquid and innite rate
Functional barrier 57, 58, 67, 142, 183, 258 of convection 20, 235
276
Subject Index
Innite volume of liquid and nite rate In tri-layer lms 120, 122
of convection 26 In tri-layer bottles 123, 133
Innite thickness of the lm and of the Mould kept at constant temperature
rate of convection 229, 233 on the external surface 123, 245
Kinetics of heat transfer Mould under usual conditions 133
Basic equations for heat conduction 101 Matter transfer
Basic equations for heat convection 103 kinetics of 63, 80
Kinetics of coupled heat and mass transfers mathematical treatment 73, 85
In bi-layer lms 105 Media
In tri-layer lms 120 Semi-innite 233
In tri-layer bottles 123, 133 Membranes 41, 42, 43, 45, 47, 238, 239,
242
L Methane 66
Methanol 66
Limonene 66 Microbes
Linen 206, 207, 208, 209, 213 Detection of 206
Liquid Misconceptions worth to be avoided 221
Finite volume of 233 Innite convective rate 222, 229, 233,
235
M Innite thickness of the package 229
Semi-innite media 233
Mass transfer 125, 135
Convection or conduction of heat 245
Between food and packages 145
Membrane as a package 238
By diffusion 247
Reference diffusivity 252, 256
Effect of coextrusion 185
Moisans Method 250-252
Effect of co-moulding 185
Motiers number 213, 214, 218
From tri-layer packages 171
Multi-layer lms
In food
Coextrusion of 99
Effect of coextrusion 174
Tri-layer bottles 174, 177
In liquid food 157, 171. 172 N
Theoretical study 122, 246 Nanocomposites
Through a membrane 239 Clay-polyimide 202
Mass transfers controlled by diffusion and Natural rubber 103
convection Numerical Model 30, 31
Basic equations 7 Nsselt number 104, 105, 109
Between food and packages 145
With nite rate of convection 26
Mass transfers controlled by diffusion alone O
Through multi-layers alone 57 Olive oil 50, 52, 53
With innite rate of convection 13, 20,
222, 229, 235
Mass transfers coupled with heat transfers
P
99, 142 Packages
In bi-layer lms 108 Active packages 201
277
Antimicrobial 203 By conduction 101

Modied atmosphere 202, 203 By convection 105
Process of transfer 206 Rate of transfer of heat and matter
Passive packages 7, 201 coupled 105
Bi-layer 58, 108, 165 Ratio of the volumes of liquid and package
Mono-layer 7, 157 28, 163
Multi-layer alone 57 Recycled polymers 58, 67
Process of transfer 7 Recycling of waste polymer 57
Tri-layer lms 73, 120 Regulatory issues
Tri-layer bottles 123, 133, 171 Antimicrobial packaging 205
Packaging Reynolds number 104, 109, 114
Polypropylene 66
Single layer 157
S
Parallelpipeds
Diffusion through 38 Savoie number 210, 212, 215, 216, 217
Partition factor 10, 149 Shape of the package
Polyamide 103, 202 Films 7, 57, 99,120
Polyethylene Bottles 123, 133
Low-density 103, 235, 236, 237 Rectangular 38
High-density 103, 235 Sherwood number 209, 211, 212, 214,
Naphthalate 202 215, 216
Polyethylene terephthalate 108, 124-141, Silicone rubber 103
201, 259, 178, 181, 185, 201, 202, Single layer package
222, 245, 246, 248, 249, 256, 259 In contact with liquid food 157
Non-swollen 257 In contact with solid food 186
Swollen 257 Solid food 186
Polyolens 145 Solid-liquid interface 8
Polypropylene 50, 52, 53, 66, 202, 235, Basic equation 147
256 Solutions of equations
Polystyrene 145 Methods with the separation of
Polyvinyl chloride 3, 58, 103, 146, 202, variables 12
238, 239, 242, 244, 245, 259 With innite volume of liquid and of the
Prandtl number 105 rate of convection 19
Process With nite volume of liquid and innite
Of co-extrusion of lms 99 rate of convection 20
Of co-moulding of bottles 123, 133 With innite volume of liquid and nite
rate of convection 26
R Steel 125, 135
alloy 103
Rate of transfer of matter
Basic equations 7, 10
By diffusion alone 13, 20, 57
T
By diffusion and convection 26 Theoretical treatment
Rate of transfer of heat Of heat transfer 108
Basic equations 101, 103 By conduction 101
278
Subject Index
By convection 103
Of matter transfers
Basic equations 7
In various systems 12, 19, 20, 26,
38, 42, 50, 58, 145
Of heat and matter transfers 122, 123,
133
Thermal conductivity 102, 103
Thermal mechanical analysis 257
Thermal parameters 106
Temperature dependent 107
Thickness of the lms 67, 114, 118
Toluene 229
Tri-layer packages 73
Heat and mass transfers
Through lms 120
For bottles 123, 133
Matter transfer alone 73
279
280
ISBN: 098-1-84735-026-8
Jean-Maurice Vernaud and Iosif-Daniel Rosca

Assessing Food Safety of Polymer Packaging
Rapra Technology Assessing
Rapra Technology is a leading international
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ISBN: 1-85957-527-7

Jean-Maurice Vernaud and Iosif-Daniel Rosca

Rapra has extensive processing, analytical and of Polymer

Shawbury, Shrewsbury, Shropshire SY4 4NR, UK

Food Safety Cover 2.indd 1 17/5/06 1:58:22 pm

Smithers Rapra Limited

Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom

Smithers Rapra Limited

2006, Smithers Rapra Limited

All rights reserved. Except as permitted under current legislation no part

Typeset by Smithers Rapra Limited

1. A Theoretical Approach to Experimental Data...................................................... 7

1.1 Mass Transfer by Diffusion or Convection: Basic Equations ........................ 7

1.3 Methods of Solution with the Separation of Variables ............................... 12

1.4 Solution of the Equation of Diffusion: Sheet of Thickness 2L

1.6 Solution of the Equation of Diffusion: Sheet of Thickness 2L

1.6.1 The Diffusing Substance Enters the Sheet ...................................... 21

1.9 Determination of the Parameters of Diffusion ........................................... 29

2. Mass Transfer Through Multi-layer Packages Alone ........................................... 57

2.1 Recycling Waste Polymers and Need of a Functional Barrier ..................... 57

3. Process of Co-Extrusion of Multi-Layer Films ..................................................... 99

3.1 Scheme of the Process of Co-Extrusion ...................................................... 99

3.2 Principles of Unidirectional Heat Transfer ............................................... 101

3.4.1 Consideration of the Process of Heat Transfer ............................ 108

4. Mass Transfers Between Food and Packages ..................................................... 145

4.1 General Introduction to the Various Problems ......................................... 145

4.2 Theoretical Treatment ............................................................................. 147

Infinite (or Finite) Volume and a Finite Value of the

4.4 Bi-layer Packages Made of a Recycled and a Virgin Polymer Layer,

4.5 Mass Transfer from Tri-layer Packages (Recycled Polymer Inserted

4.7 Conclusions on the Functional Barrier ..................................................... 183

4.8 Conclusions on the Diffusion-Convection Process ................................... 185

4.9 Problems Encountered with a Solid Food ................................................ 186

5. Active Packages for Food Protection ................................................................. 201

5.1 Process of Transfer with Active Packages ................................................. 201

6. A Few Common Misconceptions Worth Avoiding ............................................. 221

6.1 Using Equations Based on Infinite Convective Transfer ........................... 222

6.4 Innite Rate of Convection in a Finite Volume of Liquid ......................... 235

7. Conclusions ....................................................................................................... 267

Appendix: The First Six Roots n of tan = R ....................................................... 271

i) Describing the problems of diffusion is highly complex, because various equations

the release of a drug from diffusion-controlled release dosage forms in

Dimensionless numbers are introduced as much as possible, in order to build master

Chapter 3 is devoted to the problems set up by the process of co-extrusion or co-moulding

Chapter 6 is devoted to the most striking misconceptions of the processes or misuses of

as he has to face many mistakes. The theoretician should be neither a mathematician, as

1. J. Crank, The Mathematics of Diffusion, 2nd Edition, Clarendon Press, Oxford,

2. J-M. Vergnaud, Liquid Transport Processes in Polymeric Materials: Modelling

3. J-M. Vergnaud, Drying of Polymeric and Solid Materials: Modelling and

5. W. McAdams, Heat Transmission, 3rd Edition, McGraw-Hill, London, UK 1954.

1.1 Mass Transfer by Diffusion or Convection: Basic Equations

1.1.3 Analogy With Heat Transfer

1.1.4 Basic Equations

By expressing F, the amount of diffusing substance, and C, the concentration, in terms of

(length)2/(time) or cm2/s (1.2)

1.1.5 Solid-Liquid Interface

1.1.6 Properties of Convection

The coefcient of convection has the dimensional cm/s.

As previously noted, two kinds of convection exist:

Natural convection, when the liquid is motionless, and

1.1.7 Applications of the boundary conditions

1 - When the coefcient of convection, h, is innite, the following facts appear:

CL , t > Ceq release of additives in the liquid (1.6)