J. Comyn (Auth.), J. Comyn (Eds.) - Polymer Permeability-Springer Netherlands (1985)

POLYMER PERMEABILITY
POLYMER
PERMEABILITY
Edited by
J. COMYN
School of Chemistry, Leicester Polytechnic, UK
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First edition 1985

Reprinted 1994
© 1985 Chapman & Hall
Softcover reprint of the hardcover 1st edition 1985
ISBN·13:978-94-010-8650-9 e-ISBN-13:978-94-009-4858-7
DOl: 10.1007/978-94-009-4858-7
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Preface
Polymers are permeable, whilst ceramics, glasses and metals are gener-
ally impermeable. This may seem a disadvantage in that polymeric
containers may allow loss or contamination of their contents and
aggressive substances such as water will diffuse into polymeric struc-
tures such as adhesive joints or fibre-reinforced composites and cause
weakening. However, in some cases permeability is an advantage, and
one particular area where this is so is in the use of polymers in drug
delivery systems. Also, without permeable polymers, we would not
enjoy the wide range of dyed fabrics used in clothing and furnishing.
The fundamental reason for the permeability of polymers is their
relatively high level of molecular motion, a factor which also leads to
their high levels of creep in comparison with ceramics, glasses and
metals.
The aim of this volume is to examine some timely applied aspects of
polymer permeability. In the first chapter basic issues in the mathema-
tics of diffusion are introduced, and this is followed by two chapters
where the fundamental aspects of diffusion in polymers are presented.
The following chapters, then, each examine some area of applied
science where permeability is a key issue. Each chapter is reasonably
self-contained and intended to be informative without frequent outside
reference. This inevitably leads to some repetition, but it is hoped that
this is not excessive.
J. COMYN
v
Contents
Preface v
List of Contributors viii
1. Introduction to Polymer Permeability and the Mathematics

of Diffusion 1
J. COMYN
2. Permeation of Gases and Vapours in Polymers 11

C. E. ROGERS
3. Case II Sorption 75
A. H. WINDLE
4. Effects of Oxygen Permeation and Stabiliser Migration on

Polymer Degradation 119
J. Y. MOISAN
5. Diffusion and Adhesion. 177

J. COMYN
6. The Role of Polymer Permeability in the Control of Drug

Release . 217
JOHN H. RICHARDS
7. Permeability and Plastics Packaging . . 269

R. J. ASHLEY
vi
Contents vii
8. Permeability of Coatings and Encapsulants for Electronic

and Optoelectronic Devices 309
M. T. GOOSEY
9. The Role of Water Transport in Composite Materials. 341

GAD MAROM
Index 375
List of Contributors
R. J. ASHLEY
Research and Development Division, Metal Box Ltd, Denchworth
Road, Wantage, axon OX12 9BP, UK
J. COMYN
School of Chemistry, Leicester Polytechnic, PO Box 143, Leicester
LEI9BH, UK
M. T. GODSEY
Morton Thiokol Inc, Dynachem Corporation, 2631 Michelle Drive,
Tustin, California 92680, USA
GAD MAROM
Casali Institute of Applied Chemistry, School of Applied Science and
Technology, The Hebrew University of Jerusalem, 91904 Jerusalem,
Israel
J. Y. MOISAN
ROC-TAC, Centre National d'Etudes de Telecommunications, BP
40, 22301 Lannion, France
JOHN H. RICHARDS
School of Pharmacy, Leicester Polytechnic, po Box 143, Leicester
LEI 9BH, UK
C. E. ROGERS
Department of Macromolecular Science, Case Western Reserve Uni-
versity, Cleveland, Ohio 44106, USA
A. H. WINDLE
Department of Metallurgy and Materials Science, University of
Cambridge, Pembroke Street, Cambridge CB2 3QZ, UK
viii
Chapter 1
Introduction to Polymer Permeabllity and the

Mathematics of Diffusion
1. COMYN
1. Fick's Laws of Diffusion . . . . . . 1

2. Film Permeation. . . . . . . . . . 3
3. Dimensions of Transport Parameters. 6
4. Diffusion into a Film or Slab . . 7
S. Diffusion into a Fibre . . . . . 8
6. Diffusion at a Concentration Step 9
References . . . . . . . . . . 10
1. FICK'S LAWS OF DIFFUSION
Fick's first law is the fundamental law of diffusion. It states that (eqn
(1» the flux in the x-direction (FJ is proportional to the concentration
gradient (ac/ax).
Fx = -D(ac/ax) (1)
Flux is the amount of substance diffusing across unit area in unit time
and D is the diffusion coefficient. The first law can only be directly
applied to diffusion in the steady state, that is, where concentration is
not varying with time.
Fick's second law of diffusion describes the non-steady state and it
has several forms; first to be examined is diffusion into a box shaped
element in Cartesian coordinates. A point P is at the centre of a
volume element which has edges of length 2 dx, 2 dy and 2 dz (Fig. 1).
The fluxes which cross the six faces of the element control the build-up
or decay of diffusant. If there is a flux gradient aF/ax in the x-direction
and the x-direction flux at P is F, then the actual flux at the face
ABCD is (Fx -(aF)ax)) dx and at the face abcd it is (Fx + (aFx/ax» dx.
2 1. Comyn
B
,\-0 '\
A a
----+ p
2dz 0 d
2dx
dr
dz
rd8
Fig. 1. Volume elements for the derivation of Fick's second law of diffusion.
So the material entering face ABeD in unit time is 4 dy dz(Fx -·

(aF)ax» dx and that leaving face abcd is 4 dy dz(Fx + (aF)ax» dx.
Hence the material accumulating in the volume element due to diffu-
sion in the x -direction is
Rx = -8 dx dy dz(aFxfax) (2)
Similarly, eqns (3) and (4) can be derived for the y- and z-directions.
R" = - 8 dx dy dz(aF)ay) (3)
Rz = -8 dx dy dz(aFz/az) (4)
So the rate of concentration increase in the element is given by
ac Rx + Rv + R z
(5)
at 8 dx dy dz
So
ac _ aFx_ aFy _ aFz
(6)
at ax ay az
Introduction to polymer permeability and the mathematics of diffusion 3
The flux gradients are obtained by differentiating eqn (1), for example
aFxfax = - D a2e/ax2, so that
ae = D(a2e+ a2e+ a2e) (7)
at ax 2 ay2 az 2
Equation (7) is known as Fick's second law of diffusion. Under
circumstances where diffusion is limited to the x-direction it simplifies
to
(8)
However, if D depends upon the concentration of the diffusant and

hence on location, it may be written as
(9)
If the volume element is a segment cut from a cylinder with sides dr,
r de and dz (Fig. 1) then the appropriate form of the second equation
IS
ae
at
1[aar (rD arae) + aea (D--;. aeae) + aza (rD azae)]
= -;
(10)
but if diffusion is entirely radial this reduces to
ae _!~ (rD ae) (11)

at r ar ar
In any situation, the problem is to find a solution to the appropriate
form of the second equation. Solutions can be found in Crank's book 1
on the mathematics of diffusion or in that by Carslaw and Jaeger2 on
the analogous situation of heat conduction in solids. Some of the more
frequently used solutions are examined below.
2. FILM PERMEATION
If a film of thickness I and area A separates two chambers containing a

permeable gas or vapour at different pressures, then the gas will
permeate from the high pressure chamber to the low pressure
chamber. This situation is of particular interest in that it illustrates the
4 1. Comyn
difference between steady state and non-steady state diffusion, and it is

also the basis of the time-lag method for the determination of diffusion
coefficients. 3
If, initially, the system is free of permeant but, at zero time, gas at
pressure PI is introduced into chamber 1 then the amount of gas to
permeate the membrane Q is given by eqn (12).
Q Dt 1 2 ~ (-It 2 2 2
- = 2 - - - 2 L. - 2 - exp(-Dn 7r til) (12)
IC I I 6 7rn~I n
Here C I is the concentration of permeant in the face of the film

adjacent to chamber 1. It is an assumption in the derivation of eqn (12)
that equilibrium is instantaneously established at the interface. A plot
of eqn (12) appears in Fig. 2, and it can be seen that there is an initial
build-up period but eventually a linear relationship develops as t~oo.
Under these conditions eqn (12) simplifies to
Q=DCI (t-~) (13)

I 6D
05,---------------,-,
0'4
Q/IC,
0-3
02
I
I
I
0·1 /
I
I
O'-----"---L-J-----'-_ _ _- L _ - '
o 0-2 0'4 0·6
Fig. 2. Permeation through a film approaching the steady state.
which has an intercept on the time-axis known as the time lag. This is
simply related to the diffusion coefficient by eqn (14) which provides
the basis for the determination of D by the time lag method.
(14)
In the curved region of Fig. 2 the concentration of diffusant is
building up within the film (i.e. ac/at>O) and this is an example of
steady state diffusion. In the linear region concentrations in the film
are now static, ac/at = 0, and Fick's first equation can be directly
applied to this steady state diffusion in the following manner.
If the gas pressures are now PI and P2 then the concentrations in the
film surfaces are C 1 and C 2 (Fig. 3). The flux is given by Fick's first law
(eqn (1)) i.e.
(15)
so that the total permeant to have passed through a film of area A

after time t is
Q = - DAt( C 2 - C1)!l (16)
It is assumed that Henry's law applies at both interfaces i.e.
·l· coefficlent,
So Iu b llty . K =C-1 =C-2 (17)
Pl P2
Hence, eqn (16) can be written as
Q = - DKAt(P2 - PI)/ I (18)
~--l--------;,
(1
Pz
Fig. 3. Permeation through a film in the steady state.

6 f. Comyn
As the permeability coefficient P, which equals DK, can be determined

from the steady state slope, use of the time lag means that both D and
K can be evaluated from permeation experiments. Apart from apply-
ing the method to the permeation of gases and vapours, it has also
been used for the permeation of dyes between two solutions. 4
Experimental conditions often arrange for P1» P2 where eqn (18)
simplifies to
Q = DKAtpdl = PAtpdl (19)
3. DIMENSIONS OF TRANSPORT PARAMETERS
D has dimensions length2 time-' and is usually expressed as m 2 s-'.

The dimensions of P and K which are used are much more varied and
a source of some confusion. Equation (19) shows the dimensions of P
to be
P = (amount of gas under stated conditions) (film thickness)
(film area) (time) (driving pressure) (20)
In the following chapters no attempt has been made at standardisation.

Huglin and Zakaria s have noted 29 different units for P which appear
in the literature and, as well as some others which are ambiguous or
incorrect, they have provided a table of conversion factors. They
propose that a recommended permeability unit should be within one
system of units and should not give inconvenient numerical values for
D. Their choice for the recommended permeability unit is
10 10(cm 3 at STP) cm
cm 2 scmHg
In these units P for oxygen ranges from about 0·1 in polymethyl-

methacrylate to about 500 in poly(dimethylsiloxane).
Yasuda 6 recommended that P be expressed in the same units as D,
especially cm2 S-1, in which case K is dimensionless. This can be
arranged if K = (concentration of permeant in polymer)/(concentration
of gas), the two concentrations being in the same units.
Collected values of transport parameters in polymers have been
assembled by Yasuda and Stannetf and Hwang, Choi and Kammer-
meyer. 8
4. DIFFUSION INTO A FIl,M OR SLAB
If a film of polymer is placed in an infinite bath of diffusant, then

concentrations, C, at points within the film at time t are given by eqn
(21); this is another solution to eqn (8).
C 4 f (-l)n (-D(2n+1f1T2t) (2n+1)1TX)
-= 1-- 1.. ---exp cos
C1 1T n~O 2n + 1 4t 2 2t
(21)
The film is of thickness 2t, its faces being located at +t and - t and
x = 0 at the centre of the film. C 1 is the concentration at the faces of
the film, which are established instantaneously. The effects of diffusion
at the edges of the film are not taken into account. Values of C/C1
against x/t for several values of Dt/t2 appear in Fig. 4. Equation (21)
can be integrated to yield eqn (22) which gives the mass uptake by the
film, M,.
M, = 1- f 8 (- D(2n + 1)21T2t)
(22)
1.. ( 2 2 exp 2
M= n~O 2n+1) 1T I
Here M= is the mass uptake at equilibrium, and I is again film
thickness. At short times this equation reduces to
M, = ~ (D) 1/2 (23)
Moo I 1T
10 -- ---
~
0·7
OB
05
~
(,
0·6
0·3
04
01
02
-L..-
0
0 0·2 04 0'6 O'S 1·0
x/I
Fig. 4. Concentration-distance curves at various values of Dt/£2 for a slab of
thickness 2£ with a uniform surface concentration Ct.
8 1. Comyn
which provides a convenient way (as later chapters will show) of

measuring D from mass uptake experiments.
5. DIFFUSION INTO A FIBRE
If a long cylindrical fibre of radius r is placed in an infinite bath of

diffusant at zero time, then the uptake is described by eqn (24) which is
due to Hill. 9
~
- = 1 - A exp ( - aDt/ r2 ) - B exp ( - bDt/ r~)
0
M=
- C exp (-cDt/r2) - . .. (24)
This is a solution to eqn (11); A, B, C and a, b, c are numerical

constants with the following values.
A =0·692 a = 5·785
B=0·131 b = 30·5
C = 0·0536 c = 74·9
In this equation as in previous ones (eqns (12), (21) and (22)) the
higher terms rapidly diminish. A plot of the Hill equation appears in
Fig. 5.
10 r----------========J
0·8
0·6
04
02
ot I r 2
o
o 01 0·2 03 04 os 06
Fig. 5. Mass uptake for long cylindrical fibres in an infinite bath, from eqn
. (24).
6. DIFFUSION AT A CONCI~NTRATION STEP
If a slab of polymer doped with a diffusant at concentration Co, is

placed in contact with a diffusant-free polymer, then there will be a
concentration step at the interface. Diffusion will cause this step to
change shape with time (Fig. 6) according to eqn (25). The step is
located at x = O.
c(x, t) = ~Co erfc (x/)4Dt) (25)
1·0 r - - - = = = - - - - - - - - - - - - - - - - - - - - ,
0·5
x/V40t
0.0 L-.._ _ _L _ _ _ _L--_ _ _ _L - - - = = = _ '
-2 -1 o
Fig. 6. Concentration-distance curve for semi-infinite doped and undoped
slabs in contact.
An alternative experimental arrangement would be to sandwich a

doped polymer between two semi-infinite un doped slopes. Here the
solution is
1 (h-X h+X) (26)

c = "Co erf ~+erf 2 ~
~ 2vDt vDt
The origin of coordinates is at the centre of the doped slab which is of
thickness 2h. Where the undoped slabs are finite with their outer face
located at x = + I and x = - { the relevant equation is
. _I ~ (h+2n{-X h-2nl+X)
( - "Co erf
L.., ~ +erf 2 ~ (27)
- 11 ~ -= 2 v Dt v Dt
Expressions (26) and (27) are sometimes referred to as top hat

equations (Fig. 7). In the last three equations there appears error
function erf (z) and error function complement erfc (z). These are
10 1. Comyn
xJh
Fig. 7. Concentration-distance curves for a doped slab of thickness 2h
sandwiched between semi-infinite undoped slabs, for some values of mtlh.
defined as
erf(z)= ~
2 l'
0 exp(-w 2 )dw (28)
erfc (z) = l-erf (z) (29)
REFERENCES
1. J. Crank, The Mathematics of Diffusion, 2nd Edn, Oxford University Press,

Oxford, 1975.
2. H. S. Carslaw and J. C. Jaeger, Conduction of Heat in Solids, 2nd Edn,
Oxford University Press, Oxford, 1959.
3. H. Daynes, Pr0Ci. Roy. Soc. A fYI, 286 (1920).
4. C. L. Bird, F. Manchester and D. F. Scott, J. Soc. Dyers and Colorists, 72,
49 (1956).
5. M. B. Huglin and M. B. Zakaria, Angew. Makromolek. Chem., 117 (1983).
6. H. Yasuda, J. Appl. Polym. Sci., 19, 2529 (1975).
7. H. Yasuda and V. T. Stannett, In: Polymer Handbook, 2nd Edn, eds J.
Brandrup and E. H. Immergut, Interscience, New York, 1975.
8. S. T. Hwang, C. K. Choi and K. Kammermeyer, Separation Sci., 9, 461
(1974).
9. A. V. Hill, Proc. Roy. Soc. B, 104, 39 (1928).
Chapter 2
Permeation of Gases and Vapours in Polymers

C. E. ROGERS
Department of Macromolecular Science, Case Western Reserve

University, Cleveland, Ohio, USA
1. Introduction . . . . . . . . . 11
2. Definitions and Basic Equations 13
3. Measurement and Calculation . 21
4. Temperature and Concentration Dependence 27
4.1. Sorption . . . . . . . . . . 29
4.2. Diffusion and permeation. . . 34
4.3. Concepts and models for penetrant immobilisation 50
4.4. Effects of polymer relaxation. ..... 55
5. The Physicochemical Nature of the Components 56
5.1. Penetrant size and shape . . . ..... 56
5.2. Molecular composition, symmetry and polarity 60
5.3. Crosslinking, orientation and crystallinity. . 65
5.4. Heterogeneous and muiticomponent systems 67
References . . . . . . . . . . . ..... 69
1. INTRODUCIION
The solution and transport behaviour of low molecular weight sub-

stances in polymeric materials is a topic of interest for many fields of
science and technology. The importance and relevance of such be-
haviour has become more apparent in recent years with the accelerat-
ing development of separation membrane systems, highly impermeable
or selectively permeable packaging or barrier films, and the overall
increase in the use of polymeric materials for diverse applications with
consequent exposure to various environmental agents.
The selection or development of polymeric materials for use
in applications with stringent design specifications relating to their
soll1tion and transport behaviour requires knowledge and appreciation
11
12 C. E. Rogers
of the many factors which affect those phenomena. There are, unfortu-
nately, many examples of products designed and produced with an
apparent lack of proper consideration of the effects of the end use
environment on properties and lifetime performance or of limitations
imposed upon performance due to unfavourable solution or transport
characteristics. The plasticisation of polymers by sorption of ambient
vapours or liquids resulting in the decrease in mechanical properties
and the loss of bottled beverage components (e.g., COb alcohol, etc.)
are but two of many examples which could be cited.
An objective of research in this field is to establish mechanisms and
expressions relating solubility and transport with the molecular proper-
ties and characteristics of the components. Conversely, the nature of
the solution and diffusion processes can help elucidate inherent charac-
teristics of the polymeric material such as the flexibility and conforma-
tion of the chain segments, interactions and structural and morphologi-
cal features. This is the 'molecular probe' aspect which has been
employed to advantage in conjunction with more usual characterisa-
tion techniques.
This chapter is concerned with aspects of the solution, diffusion and
permeation of gases and vapours ('penetrants') in effectively non-
porous polymeric materials. Only brief mention will be made of
systems involving liquid solvents or higher concentrations of sorbed
solvent vapours. Those systems, especially initially glassy or semi-
crystalline polymers, often show behaviour which seemingly deviates
strongly from that observed with gases or low concentrations of sorbed
vapours. Such deviations (classified as anomalous diffusion, Case II, or
Super Case II behaviour) have been the subject of many investigations,
particularly during the last decade. The present status of our under-
standing is the concern of Chapter 3.
No claim is made that this chapter is a comprehensive review.
Indeed, a recent computer literature search covering Chemical Ab-
stracts from 1967 to early 1983 disclosed over 7000 apparently relev-
ant papers, with patents excluded from the search. This indicates the
magnitude of the research efforts and the difficulty of establishing a
comprehensive knowledge base. More extensive reviews pertaining to
these topics have been written by several authors. 1- 17 An historic
perspective 16. 18 should be of considerable interest for present workers.
Compilations of solubility, diffusion and permeability coefficients
and more limited compilations of related parameters, such as apparent
activation energies and concentration-dependence coefficients, have
Permeation of gases and vapoui'S in polymers 13
been tabulated 3 ,6,8,9,12,14,19-2H in addition to data for specific polymers

in brochures provided by various manufacturers,
It should be noted that caution must be exercised in accepting
absolute values of solubility, diffusion and permeability parameters as
published in the literature or industrial brochures. The sensitivity of
solution and transport processes to otherwise minor variations in
polymer composition and structure, add:itives, processing conditions
and other variables means that published parameters should be viewed
only as guides in lieu of values for a particular system of interest.
However, the general behaviour and dependence of parameters on
component characteristics and experimental conditions should be a
reasonable indication of the underlying physicochemical basis of solu-
tion and transport behaviour.
2. DEFINmONS AND BASIC EQUATIONS
The diffusive flux, J, of a penetrant in a polymer can be defined as the

amount passing through a plane (surface) of unit area normal to the
direction of flow during unit time, independent of the state of aggrega-
tion of the polymer. That is,
J= Q/At (1)
where Q is the total amount of penetrant which has passed through
area A during time t. By analogy with the transfer of heat by
conduction, the transfer of matter by diffusion can be expressed 29 as
proportional to the negative gradient of concentration at any point or
plane in the diffusion medium with a proportionality coefficient, D,
thereby defined as the diffusion coefficient:
J=-D(ac!ax} (2)
x is the space coordinate normal to the reference plane and D
describes the interdiffusion of the components with units of length2
time-I, e.g. cm2 S-I.
As diffusion proceeds, the rate of change of penetrant concentration
at any point or plane within the medium (x> 0) is given by:
(3)
This is the fundamental differential equation for unidirectional diffu-
sion' in an isotropic continuum when the diffusion coefficient is a
14 C. E. Rogers
constant independent of x, t or c. Comparable equations describe

multidirectional (x, y, z) fluxes and cylindrical or spherical geometries
or the expressions can be in vector notation independent of any special
coordinate system. 13
There are extensive discussions of mathematical methods for solving
the diffusion equation and solutions for many of the more common
situations. 1 •2 •13 The classical treatise on heat conduction by Carslaw
and Jaeger 30 provides solutions to a wide range of diffusion problems.
The temperature and thermal diffusivity in that work may be replaced
by c and D, respectively. Analysis of many diffusion systems can be
achieved by using an analogous electrical network considering flux to
be current flow, diffusion to be conductance and the gradient driving
force as voltage. Appropriate solutions are to be found in electrical
and electronic literature sources.
For many penetrant-polymer systems, D is not a constant but rather
is a function of c, and in some cases, of spatial coordinates and/or the
lapsed time since diffusion started. The concentration-dependence is a
reflection of the plasticising action of sorbed penetrant and/or various
mechanisms which localise (immobilise) a portion of the sorbed pene-
trant. The spatial and time dependences are usually ascribed to struc-
tural relaxations on a time scale equal to or greater than that of the
diffusion process. A different type of spatial dependence may arise
when the medium possesses a fixed gradient of composition, structure,
temperature, etc.
In the most common case, D is dependent only on the sorbed
penetrant concentration, D(c). Equation (2) remains unchanged, but
eqn (3) becomes:
(ac/at) = a(D(c)(ac/ax»/ax (4)
There are relatively few rigorous solutions of the diffusion equation for
a concentration-dependent D. The usual method to estimate D(c) is to
utilise solutions for a constant D and then extract a value of D(c) from
those data. One guide to such procedures is to transform eqn (4) into:
(4a)
Experiments are then performed over sufficiently small intervals of c

such that a(D(c))/ac is small compared with D(c) so that the second
term may be neglected. This gives a mean, or integral, value of the
diffusion coefficient, D, over the concentration range, Cl to C2, defined
Permeation of gases and vapours in polymers 15
as:
jj may be determined over several ranges of concentration to obtain

an estimate of D(c).
It should be noted that these equations apply strictly only for
diffusion in two-component systems in which the partial specific vol-
umes of the components are independent of pressure and composition.
An approximation to such an incompressible mixture with no volume
change on mixing, mayor may not be achieved in practice. Even a very
dilute penetrant concentration may show marked deviations due to
localisation mechanisms, etc.
A more fundamental and comprehensive approach to the diffusion
process is afforded by the theory of irreversible thermodynamics?1-33
A rigorous development on that basis is beyond the scope of this
chapter but certain aspects will be noted where appropriate. In any
case, it should be remembered that the formalism of the mathematics
of diffusion does not involve considerations of structure, morphology
and other factors affecting transport. Those factors are usually ac-
counted for by the development of models in terms of relevant
parameters with a continuum-defined D. The success of such models to
represent diffusion data does not necessarily prove the validity of the
specific model-many models may be developed to represent a given
data set. A survey of the literature reveals many cases of polemics
between different investigators advocating different models for the
same data, and in many cases both groups are probably not correct.
For most experimental and predi-ctive purposes it is convenient or
necessary to relate the sorbed concentration, c, to the ambient pene-
trant concentration, C, in contact with the polymer surface. The dis-
tribution of penetrant between the ambient and polymer phases is
described by the Nernst distribution function
c=KC (6)
where K is a function of temperature and may be a function of c. For

gases and vapours, C is proportional to pressure, p, through the ideal,
or a real, gas law equation. The equilibrium concentration, c, of a
penetrant in a polymer then can be related to the ambient pressure by
c = S(p)p (7)
16 C. E. Rogers
where the solubility coefficient S(p) is a function of temperature and

may be a function of P (or c). For sufficiently low penetrant concentra-
tions, c is directly proportional to P, and S is the Henry's law solubility
coefficient, denoted here as S(O), independent of P and c.
When Henry's law is obeyed, it follows that the steady-state flux can
be expressed as
(8)
where PI and P2 are the ambient pressures on the two sides of a film of
thickness I and the product DS == P defines the permeability coefficient
(constant). More generally, either D or S or both will vary with c, P, x
or t so that the permeability 'constant' will also be dependent on those
variables. Thus,
J=P(PI-P2)/1 (9)
where P = DS, with D as defined by eqn (5) and

S= (c I - C2)/(PI - P2) (10)
S reduces to S = cdpI for the usual experimental conditions of P2 and

C2 =0, but S may still vary as a function of C I (or PI)'
When diffusion occurs in a system in which the penetrant swells the
polymer, the total flow through a given reference plane fixed in space
is not only due to pure diffusion fluxes but is complicated by a
concurrent mass flow of the components. The significance and in-
terpretation of a measured value of D for such a system then depends
upon the conditions of the experimental method, and the specific range
of c, T and other experimental variables. Since an ultimate aim of
diffusion studies is to interpret D in terms of the molecular properties
of the components, it is necessary to define clearly the reference plane
in terms of the units of concentration and space coordinate appropriate
to a given experimental situation. 4 ,6,13 Such 'frame of reference' cor-
rections have seldom been made in practice with the result that many
published papers are subject to reappraisal in terms of the validity of
the stated interpretations.
A consideration of even greater significance is based on the ther-
modynamics of irreversible processes which indicate that the funda-
mental driving forces for diffusion in a multicomponent system are the
gradients of the chemical potential (partial molar free energies) of each
component. Cross terms appear in the overall diffusion equation which
relate the flux of a given substance with the chemical potential gra-
dients of each of the system components, This dependence may be
assumed as linear for systems near equilibrium. Most often, the cross
terms have betn considered negligible or neglected. These terms may
be significant in certain cases and should be considered to obtain a
better understanding of diffusion phenomena.
In a binary mixture, the driving force causing diffusion of a given
component is taken as proportional to the negative of the chemical
potential gradient (-a/.L/ax) of that component at any given point. The
Gibbs chemical potential is given by the usual expression:
/.L = RT In a + constant (11)
where a is the thermodynamic activity of the component in the
mixture. The total force on all molecules of the component at a given
point is therefore proportional to -c(a/.L/ax), and the flux due to pure
diffusion (through a reference frame to correct for mass flow, etc.) is:
J = -(mc/N)(a/.L/ax) (12)
or since
a/.L = RTain a (13)
then
J= -(mRT/N)(oln a/oln c)(ac/ax) (14)
The quantity N is Avogadro's number and m is the intrinsic mobility
of a component molecule for unit force. The mobility is inve~ely
proportional to the frictional resistance characterising the relative mo-
tion of the two components in the mixture. It is to be emphasised that
m not only depends upon temperature but usually is strongly depen-
dent on concentration and other factors such as component interac-
tions, polymer structure and morphology, etc. Indeed, it can be antici-
pated that in any mixture there is a range of mobilities, m(c), of a given
penetrant corresponding to the 'mode of sorption' of the penetrant in
the polymer matrix. Thus, a mean mobility can be defined as:
(15)
In the absence of any detailed knowledge of the distribution of

mobilities, the usual assumption has been to approximate the situation
by the dual-sorption mode model (e.g. refs 4, 13, 16, 17, 34-39). In
the simplest case, this assumes that a portion of the penetrant
molecules are sorbed in a mode which effectively immobilises them
within the polymer matrix, thereby removing them from the net
18 C. E. Rogers
permeation process but not from the rate of sorption process. If the
concentration of free-to-diffuse molecules is denoted by c' , then the
pure diffusive flux is:
J = -m' RT(a In a'/a In cl)(ac'jac)(ac/aC)(aC/ax) (16)
where (ac/aC) = S is the overall solubility coefficient which is a meas-

ure of the total sorbed concentration of both mobile and 'bound'
penetrant and
D' = m'RT(iJ In a'/a In c') (17)
is the 'true' diffusion coefficient as a measure of the average mobility of
the mobile penetrant molecules. The experimentally measured value of
the diffusion coefficient from the definition J = - DS(aC/ax) is
D =D'(ac'lac) (18)
so that the measured D is equal to the true D' only when all sorbed
penetrant molecules are mobile. Otherwise, the measured D, calcu-
lated on the basis of the total sorbed concentration, is less than the
true D ', calculated on the basis of the mobile concentration only.
The concentration (and temperature) dependence of the diffusion
coefficient is seen to arise from three sources: the concentration
dependence of the true mobility (m/), the variation of mobile concent-
ration with total concentration (ac'/ac), and a concentration depen-
dence attributed to the thermodynamic ideality of the mixture
(a In a'Ia In c /). When the mixture is thermodynamically ideal,
a In a'Ia In c' is unity, Henry's law is obeyed and the diffusion coefficient
is equal to the self-diffusion coefficient, D*, defined as:
(19)
which is a measure of the mean square distance a molecule travels in
the x direction during time t. Since it is difficult to determine D*
directly for most systems, a 'thermodynamic' diffusion coefficient
DT = D(d In c/d In a) (20)
has often been used in theories regarding the concentration and
temperature dependence of diffusion.
The term (a In a/a In c) can also be expressed as (1 + 0 In ),/0 In c),
where )' is the activity coefficient defined as )' = a/ c. If, for any reason,
these thermodynamic terms become negative in sign, diffusion may
occur against the concentration gradient. 40 -42 This so-called 'uphill'
diffusion behaviour, often observed in biological systems, is related to

the directional flux effects observed in systems with a polymer mem-
brane possessing a gradient of chemical composition,43-46 or tempera-
ture, or stress, or other variable which affects diffusion in terms of
irreversible thermodynamics.
The transport of a penetrant through a homogeneous membrane, in
the absence of gross defects such as pores or cracks, is usually
considered to occur by the following process: solution (condensation
and mixing) of the gas or vapour in the surface layers, migration to the
opposite surface under a concentration (chemical potential) gradient,
and evaporation from that surface into the ambient phase. The migra-
tion of the penetrant can be visualised as a sequence of unit diffusion
steps or jumps during which the particle passes over a potential barrier
separating one position from the next.
The unit diffusion or jump involves a cooperative rearrangement of
the penetrant molecule and its surrounding polymer chain segments. It
is not necessary that a 'hole' per se be formed in the polymer structure
between two successive penetrant positions (although this is often the
basis for model calculations); the penetrant molecule and its surround-
ing chain segments may share some common volume before and after
the diffusion jump. However, a certain number of van der Waals type
or other interactions between the component molecules and chain
segments must be broken to allow a rearrangement of the local
structure. The amount of energy required for this rearrangement (or
'hole formation') will increase as the size and shape of the penetrant
molecule increase. Several jumps may need to occur in the same
direction before the molecule has been displaced by a distance equal to
its size.
This process requires a localisation of energy to be available to the
diffusing molecule and its polymer chain segment neighbours to pro-
vide the energy needed for rearrangement against the cohesive forces
of the medium with effective movement of the penetrant for a success-
ful jump. In a polymer above its glass temperature, as in simple liquids,
fluctuations in density ('holes') are constantly disappealing and reform-
ing as a result of thermal fluctuations. Low density regions resulting
from an outward expansion of chain segments from a central point can
be associated with a localised accumulation of energy causing the
expansion.
Diffusive motion thus depends on the relative mobilities of penetrant
molecules and polymeric chain segments as they are affected by
20 C. E. Rogers
changes in size, shape, concentration, component interactions, temper-

ature and other factors which affect polymeric segmental mobility.
Since diffusion requires rearrangement of the relative molecular con-
formations within a mixture, the behaviour is closely related to the
rheological and mechanical properties of the solid in the presence of
penetrant. In many cases, relatively long-term relaxation processes
may delay the rate of approach to equilibrium with consequent marked
effect on concurrent diffusion and solution behaviour.
Studies of concurrent solution/diffusion and stress relaxation or
creep in a given system can be used to advantage for elucidating the
nature of polymer chain segmental motions as they affect both vis-
coelastic and transport behaviours. 4 .47-S0 However, it must be emphas-
ised that the molecular and segmental motions are somewhat different
for the two processes, especially when diffusion is compared with the
bulk viscosity of the polymer. For the diffusion of small molecules only
relatively local coordination of segmental motions are involved. In
viscous flow processes, there is an actual displacement of polymer
molecules requiring more coordination of these segmental motions.
The two processes utilise different spectra of the distribution of seg-
mental motions (or free volume fluctuation distribution). It is to be
expected that any correlation between the processes will be closer for
low penetrant concentrations or large-size penetrants where the seg-
mental motions involved in the two processes are more nearly
equivalent.
The overall transport process in a polymer therefore depends on two
major factors which, in turn, are governed by a wide variety of factors
related to composition, fabrication and experimental conditions. One
factor is polymer chain segmental mobility and the other is defect
structures, such as voids, microcracks and other non-thermodynamic
variations in polymer structure and morphology. Defect structures are
usually difficult to either define or characterise, but their effect on
transport and solution behaviour can be profound. Gross defects, such
as pinholes and cracks, are of great experimental concern but are not
to be considered here since their effects on transport are overwhelming
and usually obvious to the investigator-the film leaks profusely. It is
the smaller defects which give more subtle, but important, contributions
to the overall transport and solution processes that we need to con-
sider. These include spherulitic and lamellar boundary regions in
semi-crystalline polymers and permanent or transient voids (excess
free volume, 'frozen holes', etc.) found in glassy polymers.
After a brief discussion of experimental procedures, we will consider

various phenomena, interpretations and theories which give some
insight into factors which affect chain segmental mobility and defect
structures in polymers with consequent effects on S, D, and P. Changes
in temperature and sorbed concentration are major factors which have
pronounced effects. The physicochemical natures of the components
also are important with the additional aspect of guiding the selection
and development of polymer materials for specific solution and trans-
port applications.
3. MEASUREMENI AND CALCULATION
Experimental methods and apparatus for the measurement of S, D and

P have been described by many investigators?·6,8,16 A particularly
good discussion, including descriptions and analysis of many techni-
ques with methods of calculation and sources and minimisation of
errors, has been given by Felder and Huvard,l6
Unfortunately, there are relatively few instruments available com-
mercially. The commercial gas and vapour transmission instruments
include the ASTM standard test Dow-Park cell, the Linde cell, cells
for use with a mass spectrometer detector, various water vapour
transmission cells and the Mocon instruments for Cab O 2 and water.
These instruments are adequate for determination of steady-state
permeability but measurements of diffusion coefficients require modifi-
cation and careful techniques. 16.51 Consequently, many studies of diffu-
sion behaviour per se have been carried out using custom-made gas or
vapour transmission instruments, usually with vacuum systems, al-
though a carrier gas rate of permeation system can be used.
A common alternative has been to use commercially available
vacuum recording microbalances to measure rates of sorption and
desorption. Other types of systems using volumetric, optical, radio-
tracer, weighing cup and a variety of other measurement methods are
described in the literature. As noted by Felder and Huvard,16 particu-
lar methods have often been lost and then rediscovered, their origins
forgotten. This apparently is especially true of the isostatic method of
permeation rate measurement (the total pressures on both sides of the
membrane are kept approximately equal) which has been reinvented a
number of times since Mitchell used it in 1831.
Many of the more common transmission methods are such that
22 C. E. Rogers
---L---·~ TIME t
Fig. 1. Typical permeation and time lag curve. Amount of permeated pene-
trant, Q, as a function of time, 1. Extrapolation of the steady state line AB to
the time axis gives the time lag as intercept L.
PI » P2 = 0 so that IJ.Q/!lt can be calculated from IJ.P2/ IJ.t found from a

plot of the pressure (or concentration or volume) at the low-pressure
side versus time (Fig. 1). When pressure is the measured quantity, the
volume, V, of the receiving side is kept constant so that the amount of
gas transmitted at standard temperature and pressure (STP) is:
IJ.Q = IJ.Pz V 273/760 (273 + T) (21)
where T is the receiving volume temperature. The permeability con-
stant is then calculated as:
(22)
where IJ.Q is the quantity of gas at STP which has permeated in the
time interval IJ.t in the steady state of flow, A is the effective film area,
and I is the average film thickness. The determination of film thickness
is often the least accurate part of the permeation test. Typical units for
Pare (cm 3 (STP) cm)/(s cm 2 cm Hg) (those units x 10- 10 are defined as
the barrer, the standard unit of P adopted by ASTM). A bewildering
variety of units are found in the literature; a table of conversion factors
has been given 3 ,8 for several of the more frequently used sets of units.
Estimates of D, and hence of S = P/D, may be obtained using steady
state and/or transient state transmission data. Most values of S for
gases above their critical temperature in polymers have been deter-
mined by the combination of P and transient state D values from the
same experiment.
In gas or vapour transmission methods:, in the steady state of flow
through a planar membrane, the flux is constant
J = -D(c)(dc/dx) = constant (23)
so that even if D(c) is a function of eoncentration and dc/dx is
therefore non-linear, the product of the two is a constant. Integration
between C 1 and Cz, the two surface concentrations of the membrane of
thickness 1 (and let Cl» C2 = 0), gives:
D(c) = d(11)/dc (24)
An estimate of the dependence of D(c) on c can be obtained from the
slope of a plot of 11 versus Cl'
If independent solubility data (e.g. sorption balance) are available,
another estimate of fj follows as:
(25)
When a penetrant diffuses through a polymer film in which it is
soluble, there is a transient state from the time the penetrant first
enters the film untiHhe steady state of flow is established (Fig. 1). The
intercept on the time axis of the extrapolated linear steady state
portion of the curve is called the time lag, L.
For the common experimental case when the film is initially free of
penetrant and the receiving volume is maintained at essentially zero
concentration (relative to the feed volume) it has been shown 1 •13 that:
L = [2/6D (26)
so that all three parameters can be calculated from the single
experiment-P from the steady state flux, D from the time lag, and S
as P/D.
Under ordinary conditions, for a constant D, the steady state of flow
24 C. E. Rogers
is reached after a period amounting to about 2·7L. Failure to continue

a transmission experiment to obtain the real steady state of flow, plus
inaccuracy of thickness determination (here squared), constitute major
sources of error in the subsequent estimation of D.
If the diffusion coefficient is not constant, but depends upon c, x or t,
then a value of D from transient state data must be viewed with
caution. Frisch,52 Petropoulos and Roussis 53.54 and others have
developed expressions which allow the calculation of diffusion coeffi-
cients from time lag data for systems in which the functional depen-
dence of D on any or all of the variables is known or can be assumed.
It has been shown 55 that, with some minor restrictions, the following
inequality holds for a large class of functional dependencies of D(c) on
c:
(27)
Thus, an estimate of 15 made using eqn (26) may be too small by a
factor of 3. For many purposes, especially if interpretations are made
on the basis of ratios of diffusion coefficients obtained within a certain
range of conditions for a given system, this order of accuracy may be
sufficient.
Another estimate of D from transient state data can be made using
the expression of Rogers et al.,56 based on the Holsteill relation,13 for
the approximate solution of the diffusiC'n equation valid at small times:
(28)
The slope of a plot of In (t 1/2J) versus lit yields (-12/4D) with D
taken as D(O), the limiting value of D(c) as c ~ O. The intercept yields
a value of Cl so that S(O) may be calculated by eqn (7). This relation-
ship also has been adapted for analysis of transient rate of permeation
data,57 which is useful for experimental methods involving measure-
ment of permeation into carrier gas streams. Other calculation proce-
dures may also be used to estimate D from transient permeation
rate data. 16
A major method for studying diffusivity and solubility in vapour-
polymer systems is to detetmine the rates of sorption and desorption of
penetrant. This is usually done gravimetrically, but volumetric and
other techniques 16 can be used.
Data are plotted as the relative weight gain or loss, M,I M~, versus
t 1/ 2 /1, where M, and M= are the cumulative masses sorbed or desorbed
from a planar sample of thickness 1 at r = t and t = 00, respectively, as
8 1.0 , . . . - - - - - - - - - - . - - - - - - - ,
~
.......
~
~ t.8
'"
'"
9
a: 0.6
o
w
lI::
~ 0.4
Q.
:;)
...J
«
z 0.2
Q
~
~
a:
II.. 0.2 0.4 0.6 0.8 1.0
[0 (O)t/t2]"2
Fig. 2. Some typical sorption and desorption plots for D, a function of
concentration only. (I) D = D(O), sorption and desorption plots coincide; (II)
sorption (s) and desorption (d) for D = D(O) exp (ac/co) with exp (a) = 10; (III)
D = D(O)(1 + ac/co) with a = 10. (Reproduced, by permission, from ref. 4.)
illustrated in Fig. 2. Moo is obtained in the practical sense when there is

no sensible change in weight over a time interval comparable to the
interval required to obtain that value. However, caution must be
exercised, since some systems with long relaxation times exhibit a
second stage of sorption following initial uptake to a quasi equilibrium
stage. The second stage is characterised by sorption occurring without
a measurable concentration gradient across the membrane; the uptake
is governed by (he rate of polymer relaxation (swelling creep) in
response to the swelling (osmotic) stress imposed on the system by the
initially sorbed penetrant. This type of behaviour is most distinct when
sorption is carried out over successive intervals of concentration
('differential sorption') where the equilibrium sorbed content from the
previous sorption cycle is the starting concentration for the next cycle
initiated by an increase in the ambient vapour pressure. The behaviour
is very closely related to the sigmoid 'anomalous' sorption curves
obtained in such systems when increments of penetrant are sorbed in a
single cycle ('integral sorption'). This behaviour will be discussed in
some more detail in Section 4.
26 C. E. Rogers
In the absence of complicating polymer relaxation rate behaviour,

plots of ~/M~ versus t1!2Jl are typically linear out of the origin up to
50% or more of the total concentration change (Fig. 2). Above the
linear portions, the curves are concave to the time axis and there are
no inflections in the curves. If D is a constant, the sorption and
desorption curves coincide. If D is an increasing function of c, the
curves do not coincide, with sorption usually faster than desorption
and with the sorption curve often exhibiting a linear relation to higher
concentrations. Sorption curves for the same concentration range in
membranes of differing thickness 1 are superimposed when data are
plotted as MJM~ versus t1!2Jl. There are other characteristic features
of such so-called 'Fickian' behaviour. 4 ,13 Systems which show deviations
from this behaviour have been termed 'non-Fickian' or anomalous.
The calculation of diffusion coefficients for the latter systems must
account for the concurrent relaxation processes with appropriate cau-
tion in subsequent interpretation of the results. Some aspects of these
procedures are discussed elsewhere in the book.
When the process is Fickian, the value of tJl2 for which ~/ M~ = O· 5
is given as:
(tW) 1/2 = -(1/rr2D) In [( rr2/16) - (1/9)( rr2/16)9] (29)
approximately, the error being about 0·001 %? Thus:
J5 = 0'04939/(tW)l/2 (30)
When M,/M= is greater than about 0·4, the sorption rate equation
can be written as
(31)
A value of J5 may then be calculated 13 from the limiting slope of a plot
of In (M=- M,) versus t or tJl 2.
The initial stage of sorption or desorption corresponds to diffusion in
a semi-infinite medium; a plot of Mt/M~ versus t 1/2 /l is linear. The
diffusion equation is then
~/M~= (4/rrI/2)(DtW) 112 (32)
and the diffusion coefficient is
(33)
where G is the slope of the initial sorption or desorption curve. If the
curves are linear up to the half-time, (t/l 2) 1/2, eqns (30) and (33) are
equivalent.
The simple average of values of D calculated from sorption and

desorption data has often been accepted as a better approximation to
the system parameter value of D than the individual values separately.
This assumption may be questionable, especially when the individual
values are quite different, when one wants to make predictive esti-
mates of sorption/desorption rate behaviour for design and perfor-
mance purposes. The calculation of a single system D parameter may
be carried out with greater accuracy using other procedures, such as
successive approximations or the 'weighted mean' method as described
elsewhere. 13
It should be noted that the usual expressions for calculation of D
values based on solutions of these continuum equations for various
initial and boundary conditions apply strictly only for diffusion in
two-component homogeneous systems in which the partial specific
volumes of the components are independent of pressure and composi-
tion. These conditions, describing an incompressible mixture with no
volume change on mixing, are not often satisfied, except as an approxi-
mation, for real systems involving different concurrent or sequential
modes of sorption. Indeed, solution and diffusion behaviour in mul-
tiphase systems may be very complex. 5 ,53,58 The practical need to use
mathematical expressions solved for a constant D to calculate values
for systems in which D varies, for which rigorous solutions invoke
intractable mathematics, further complicates the interpretation of D
values in terms of system characteristics. Caution in interpretation is
advisable for these and other reasons.
4. TEMPERATURE AND CONCENTRATION DEPENDENCE
Two major factors which affect polymer chain segmental motion are
temperature and the concentration (and its temporal and spatial dis-
tribution) of sorbed penetrant within the polymer. An increase in
temperature provides energy for a general increase in segmental mo-
tion. If the energy density is sufficient, the polymer may pass through
structural transitions, such as the glass and melting transitions, which
further affect solution and diffusion processes. The effects of an in-
crease in temperature may also be expressed in terms of the increase in
free volume directly related to the bulk expansion of the polymer due
to the increased segmental motions.
The presence of sorbed penetrant also increases the free volume of
28 C. E. Rogers
the system. In the absence of specific component interactions, polymer

chain segmental motion is thereby enhanced to the same extent that it
would be by a corresponding temperature increase leading to the same
free volume increase. Polymer segments and penetrant molecules
jointly utilise the combined free volume of the components in the
mixture.
Concentration dependence does, or may, differ from the tempera-
ture dependence due to the possibility (probability) of specific compo-
nent interactions (modes of sorption) which affect component
mobilities per se and the relative free volume contribution to the
mixture by components involved in different modes of sorption. If the
solution process is ideal, with no volume change on mixing, the change
in system free volume with increasing concentration will be propor-
tional to that obtained by an increase in temperature. In this type of
system there is a temperature-concentration equivalence ('superposi-
tion') for transport behaviour just like the well known temperature-
time equivalence for viscoelastic behaviour. This implies that there is a
concentration-time equivalence relationship also. Hence, there is a
temperature-time-concentration equivalence principle identical for
both viscoelastic and transport behaviour in which the shape of the
modulus curve is maintained with an increase in any of the three
variables. A plot of modulus (In modulus) versus temperature (the
'master curve' of viscoelastic behaviour) is merely shifted to a lower
temperature, corresponding to the change in Tg , with no change in
shape when a constant concentration of penetrant is sorbed as an ideal
solution.
Somewhat similar relationships, but with a slower increase in free
volume with concentration, will be observed for systems in which the
amount of penetrant in different sorption modes are maintained in
constant ratios to the total concentration with changing overall con-
centration. If the ratios are not constant, then the relationships be-
tween concentration and temperature dependencies will be more com-
plex. In any case, the shape of the viscoelastic master curve will change
with changing sorbed concentration due to the effects of specific
sorption modes, involving polymer-penetrant interactions, on certain
polymer segmental motions and their related relaxation behaviour and
times.
These relationships between temperature and concentration effects
on viscoelastic and penetrant transport behaviour in polymer-
penetrant systems can serve as a basis for elucidation of the natures of
both processes and their interdependence. The magnitude and effi-

ciency of sorbed penetrant effects on viscoelastic and transport be-
haviour are directly determined by the thermodynamics of the solution
as it relates to the magnitude of sorption and the distribution of
penetrant in various sorption modes.
4.1. Sorption
Sorption is a generalised term used to describe the penetration and
dispersal of penetrant molecules in a polymeric matrix to form a
mixture. The sorption process can be described phenomenologically as
the distribution of the penetrant between two or more phases to
include adsorption, absorption, incorporation into micro-voids, cluster
formation, solvation-shell formation and other modes of mixing.
It is important to note that penetrant molecules may experience
more than one concurrent or sequential mode of sorption in a given
polymer material. Furthermore, the distribution of penetrant between
different modes of sorption may change with changes in sorbed con-
centration, temperature, swelling-induced structural states, time of
sorption to equilibrium, and other factors.
The equilibrium amount of penetrant sorbed and its sorption mode
distribution, in a polymer under given conditions, are governed by the
thermodynamics of the system. The literature concerning relevant
solution thermodynamic relations and phenomena is huge, so that any
attempt to present a comprehensive survey is clearly beyond the scope
of this chapter. We will give only a brief description of certain common
types of isotherms whose physical interpretations have been invoked to
explain or rationalise penetrant transport behaviour in polymers. In-
terested readers may wish to refer to more detailed discussions of the
thermodynamics of polymer solutions4 •6 ,59,6o to gain further insight into
these and other isotherms, their equations and interpretations.
The simplest case is that of ideal solution behaviour with sorbed
penetrant randomly dispersed within the polymer such that Henry's
law is obeyed. The solubility coefficient is then a constant independent
of sorbed concentration at a given temperature and the sorption
isotherm is a linear relation of concentration versus pressure (or
vapour activity). The term 'randomly dispersed' refers to the molecular
scale such that, if the molecular pair distribution function F2 is consi-
dered, neither polymer-penetrant nor penetrant-penetrant pairs are
preferred. In a mixture of molecules of type 1 and 2 (where 1 refers to
the penetrant) the probability that molecules i and j are at the
30 C. E. Rogers
posItions specified by the coordinates (i, j) in the range of these

coordinates d(i) and d(j) is (1/v 2 )F2 (i, j) d(i) d(j) where v is the total
volume of the mixture. The cluster integral for penetrant-penetrant
pairs G l l is defined by
G l1 =; JJ[F2 (i, j) -1] d(i) d(j) (34)
where i and j now both refer to penetrant molecules. G ll is related to

equilibrium sorption isotherm data for an incompressible system61 by
(35)
where VI and cPI refer, respectively, to partial molecular volume and
volume fraction and a l is the thermodynamic activity of the sorbed
component.
For an ideal solution a l varies linearly with cP1 and it follows from
eqn (35) that G l1 /VI = -1. This means that a penetrant molecule
excludes its own volume to other penetrant molecules but does not
otherwise affect their distribution. The quantity Gll/VI is a measure of
the clustering tendency such that when Gll/VI> -1 (isotherm convex
towards the pressure axis) there is an overall tendency for penetrant-
penetrant pairs to be preferred.
It must be emphasised that the above procedure yields little infor-
mation concerning the detailed physical mechanism of the sorption
process and cannot be used to predict sorption isotherms as can the
equations described in the next section. However, eqn (35) can be used
to interpret measured isotherm data for a given system in terms of
mean molecular clustering tendencies, although great caution should
be exercised with using eqn (35) to compare two different systems in
any quantitative manner.
Ideal solution behaviour is observed in practice when permanent
gases are sorbed by polymers provided the gas pressure does not
exceed about an atmosphere. This behaviour is readily understood
since the solubility of permanent gases in polymers is very small
« - 0·2%) due to the lack of strong polymer-penetrant interactions.
As a result, specific gas-gas interactions are also negligible and ideal
solution behaviour is observed.
Three other general types of sorption isotherm found for sorption by
polymers are illustrated schematically in Fig. 3. The figures on these
isotherms also allude to the BET classification of isotherms in genera1. 4
In terms of the molecular pair distribution approach type II represents
I n
f
z
o
!(
G:
~
ZF-------------______~------------------~
ILl
m
~
U
o
ILl
10
~
II)
PRESSURE -+
Fig. 3. Typical isotherm plots of sorbed concentration versus ambient vapour
pressure. (I) Henry's law, S = a constant; (II) Langmuir equation; (III) Flory-
Huggins equation; (IV) BET equation, site saturation at point B. (Reproduced,
by permission, from ref. 4.)
a preference for polymer-penetrant pairs to be formed at relatively

small pressures with a smaller amount of sorption of more nearly ideal
solution behaviour at higher pressures. In physical terms, this repres-
ents initial sorption on some kind of specific sites in the polymer.
When the sites are nearly all occupied, a small amount of penetrant
dissolves in the polymer with a more or less random distribution. This
situation is exemplified by the sorption of some dyes by ionic polymers
or polymers containing polar groups. It also may occur when certain
gases and vapours are sorbed in composite or heterogeneous media
which have a polymer as the continuous phase with dispersed particles
of a porous, high-area inorganic filler such as carbon black or silica gel.
If the filler particles are incompletely 'wetted' by polymer, their
32 C. E. Rogers
surfaces provide a limited number of sites on which the gas is preferen-

tially sorbed. Type II isotherms also result when gases are sorbed at
high pressures by glassy polymers containing voids. Two modes of
sorption have been considered62 to be involved: true solution plus
sorption into pre-existing voids which act in a manner equivalent to
that of specific sites.
Type III isotherms represent a preference for penetrant-penetrant
pairs to be formed such that the solubility coefficient increases continu-
ously with pressure. There are two principal physical interpretations of
this behaviour. One is that the first molecules sorbed tend to loosen
the polymer structure locally and make it easier for subsequent
molecules to enter in the neighbourhood of the first than to go
elsewhere. This interpretation implies that the sorbed penetrant effec-
tively plasticises the polymer and type III isotherms are observed when
a liquid or vapour penetrant is a strong solvent or swelling agent for
the polymer. Although polymer-penetrant interactions are relatively
strong, they are not specific in the sense of site-penetrant interactions.
Another physical interpretation of type III behaviour is reserved for
systems in which penetrant-penetrant interactions are inherently
stronger than the corresponding polymer-penetrant interactions. An
example is that of water in relatively hydrophobic polymers (e.g.
polyalkylmethacrylates).59.63 Water is vastly associated through hyd-
rogen bonding in the liquid state and association of clustering of water
molecules inside a polymer is obviously an important consideration. It
might be anticipated that stable clusters or aggregates of sorbed
penetrant molecules would be relatively less mobile in comparison with
isolated molecules. Hence, if the proportion of clustered molecules
increases with increasing sorbed concentration c as implied by a type
III isotherm, then it would be expected that the diffusion coefficient D
of the polymer-penetrant system would decrease with increasing c.
This has been observed in a number of water-polymer systems 59.63 and
contrasts with the behaviour of sorbed solvents or swelling agents
when D increases with c.
Type IV isotherms may be considered as a combination of type II at
low pressures and type III at higher pressures. Such isotherms fre-
quently describe the sorption of water by the more hydrophilic poly-
mers such as wool, silk and cellulosic materials. 59 Initially, water
molecules are strongly sorbed on sites corresponding to the polar
groups (usually hydroxyl, carboxyl or amide) in the polymer. At higher
relative vapour pressures solution or clustering processes predominate.
For water in natural fibres and proteins an approximate 1: 1 relation

exists between the number of BET sites and the number of polar
groups in the polymer indicating that each polar group interacts
strongly with only one water molecule.6.~'9
It is to be emphasised that the above physical interpretations are
probably oversimplified. In particular, it is likely that two or more
modes of sorption will occur concurrently. No information on the
degree of overlap of the two modes can be deduced from the simple
molecular pair distribution treatment.
The temperature dependence of solubility over relatively small
ranges of temperature can be represented by an Arrhenius-type rela-
tion:
S = So exp (-t!t.HsIRT) (36)
where t!t.Hs, the heat of solution, may be expressed as the molar heat of
condensation, t!t.Hcond , and the partial molar heat of mixing, t!t.H1 : 64
(37)
A value of t!t.H1 can be estimated from th'e cohesive energy densities of
the penetrant and the polymer by means of the Hildebrand 65 equation:
Mil =t!t.EI = 1)1(Sl-S2)2<1>i (38)
The solubility parameters Sl and S2 are the square roots of the
cohesive energy densities of the penetrant and polymer,65 VI is the
partial molar volume of the penetrant and <1>2 is the volume fraction of
polymer in the mixture. Other estimates of t!t.H1 can be obtained from
various theories of polymer solutions.
For gases well above their critical point (e.g. H 2 , He, O 2 , N2 at room
temperature) the hypothetical value of t!t.Hcond would be very small and
t!t.Hs is governed by t!t.H 1. Values of t!t.H1 for permanent gases are small
and positive so that S increases slightly with temperature. For more
condensable gas and vapours (e.g. S02, NH 3 , hydrocarbons) ilHs is
negative, due to the contribution of t!t.Hcond , and S decreases with
increasing temperature. The solubility of liquid penetrants generally
increases with temperature (solvent action) but may decrease depend-
ing on the nature of component interactions in the system.
As a consequence of the dependence of t!t.Hs on t!t.H cond and t!t.H1 , at
a given temperature more easily condensible vapours are more soluble
in a given polymer. Thus, approximately linear relationships are
obtained66--68 between log S and either boiling temperature, critical
temperature, the force constant in the Lennard-lones 6-12 potential
34 C. E. Rogers
field equation, or other parameters which give a measure of the

condensibility of a gas or vapour. Likewise, there is a linear relation-
ship between log Sand tlRs which is well-defined for the case of
elastomers.
4.2. Ditlusion and Permeation

The dependence of the diffusion coefficient on sorbed penetrant con-
centration for systems in which the solubility essentially follows
Henry's law has usually been empirically represented by equations of
the form:
D = D(O) exp (yc) (39)
where D may be fj or D(c), y is a characteristic parameter of the
system at the given temperature, and D(O) is D in the limit as c ~ O.
This type of equation is generally only applicable to systems where the
concentration of sorbed vapour is small or the temperature sufficiently
high such that Henry's law is a reasonable approximation. For suitably
low concentrations, the exponential in eqn (39) may be expanded as a
series to give:
D =D(0)(1 +2yc) = D(0)(1 +bc) (40)
A linear dependence of D on c has been observed in some systems,69
e.g. rubber-benzene, over substantial ranges of c.
For systems in which Henry's law does not adequately represent the
sorption isotherm, the dependence of D on concentration is generally
more complex. In a simple case, when there are no specific component
interactions, the sorption data may be represented by a Flory-Huggins
type of isotherm equation or the related70 expression:
S = S(O) exp (O"c) (41)
where S(O) is the value of S as c ~ 0 and 0" is a parameter charac-
terising the concentration dependence of S. The concentration depen-
dence of D can often be represented70 by its dependence on vapour
activity (usually taken as Pl/P~):
D = D(O) exp (aal) (42)
Since S = c/p, substitution of eqn (41) into eqn (42) gives:
D = D(O) exp [yc/exp (O"c)] (43)
with y = alp~S(O). Expanding the exponential term in O"C and neglect-
ing higher order terms (small (Ic) gives:

D = D(O) exp [ac/(l + (Ic)] (44)
when Henry's law is obeyed, (I = 0 and eqn (44) reduces to eqn (39).
When the system conforms to the Flory-Huggins isotherm equation
(I ~ 1 and then:
D = D(O) exp (Ot' cPI) (45)
where cPI = penetrant volume fraction = cl/(l + CI), with C I expressed
in units of sorbed penetrant in the condensed (liquid) state, and a' is
dimensionless.
Combination of eqns (41) and (42) gives for the permeability:
P = P(O) exp «(IC + mal) (46)
with P(O) = S(O)D(O). When Henry's law is obeyed this dependence
reduces to an exponential dependence upon activity or vapour pres-
sure. At low pressures, the dependence may reduce to a linear depen-
dence on pressure, as has been found?l
The temperature dependence of pemleability and diffusion coeffi-
cients over small temperature ranges can be represented by:
D =Doexp (-ED/RT) (47)
P= Po exp (-Ep/RT) (48)
where ED and Ep are the apparent activation energies for the diffusion
and permeation processes. It follows that:
(49)
and
(50)
A comparison of eqns (39), (42) and (45) with eqn (47), and with
the assumption that the pre-exponential (entropy-related) terms are
not affected by changes in concentration, suggests the relationship:
ED = ED(c ~ 0) -- yRT (51)
where y is 'YC, aa l or a'cPI' The value of ED(c ~ 0) is a measure of the
apparent activation energy for diffusion in a polymer matrix which is
otherwise unaffected by the presence of penetrant in terms of its chain
segmental motions, etc. The quantities yRT are the amounts by which
the apparent activation energy is reduced by the sorption of penetrant.
36 C. E. Rogers
The parameters ,¥, a and a' characterise the effectiveness with which
equal amounts of various penetrants plasticise a polymer to facilitate
segmental mobility and, hence, to increase the rate of diffusion of the
penetrant.
The plasticising action of a sorbed penetrant would be expected to
increase (an increase in ,¥, a and a') as the inherent polymer chain
segmental mobility decreased (e.g. decrease in temperature, increase in
polymer-polymer interactions, etc.) and as the solvent power of the
penetrant increases. It is also generally observed72 that the efficiency of
plasticisation increases as the penetrant mobility increases with de-
creasing penetrant size and shape.
When permeability or diffusion coefficients are measured over wider
ranges of temperature, plots of In D or In P versus liT often are
non-linear, concave to the temperature axis. This type of temperature
dependence is common with rates of reaction, k, for which:
k = ko TA/R exp (- Eol RT) (52)
where the apparent (Arrhenius) activation energy is given by:
E=Eo+AT (53)
It has been suggested66 that for the case of diffusion, ED can be
considered as the energy required to loosen the molecular chain for a
given distance. This involves the cohesive energy of the chain element
which, like the heat of vaporisation, must depend on the temperature.
An insight into the underlying thermodynamic basis of the activated
diffusion process is obtained by consideration of the fact that data for
Do and ED (Arrhenius equation) for a wide range of elastomers and
glassy polymers for a variety of gases give very good linear plots of
log Do versus EDI R. The range of D extends over nine orders of
magnitude. The representative equations are,25 for elastomers:
log Do = [(ED X 10- 3 )1 R] - 4·0 (54)
and for glassy polymers:
log Do=[(ED x 1O- 3 )/R]- 5·0 (55)
2
with D in cm S-l and EDI R in K.
This corresponds to a linear relationship between an enthalpic term
and an entropic term which is a corollary of a linear free energy
relationship. This implies that a general constant mechanism of diffu-
sion is utilised in all the systems, differing only in magnitude or
frequency and not in type.
An immediate consequence is that if either Do or ED can be

estimated by some model calculation or other procedure, then the
other parameter is given byeqns (54) or (55). Therefore, values of D
may be calculated via eqn (47). This linear free energy relationship has
been used directly, or tacitly, as the basis for several semi-empirical
methods for the estimation and prediction of D and P values.25.26.73-75
Theories and models to represent or estimate diffusion coefficients
and/or their dependence on temperature or concentration generally
have a basic premise that the diffusing molecule makes a successful
diffusion jump of length d in a random direction every t* s. The
diffusion coefficient, characterising a solid-state jump mechanism, is:
(56)
The jump of the moving molecule from one equilibrium position to the
next can be regarded as equivalent to passage of the system over a
potential-energy barrier. For one degree of translational freedom, the
probability is exp (- E/ RT) that the system will possess energy equal or
greater than E (Boltzmann equation); thus:
D = (d 2 v/6) exp (-E/RT) (57)
where v is the vibration frequency of the molecule in the diffusion
coordinate.
These representations are of the general form:
(58)
Ad is a parameter characteristic of the penetrant or, more exactly, of
the volume occupied by the penetrant during the jump. It is expected
that it will depend on the penetrant size and shape. w is the probability
of a successful jump.
Theories and models seek to estimate these parameters either in
terms of the energy required for a critical volume disturbance or,
conversely, the availability of a favourable distribution of localised
excess volume (free volume) to allow a diffusive jump. The approach
can be in terms of models of specific molecular motions using statistical
mechanics to calculate the thermodynamic parameters. The other
approach is to consider the system, not on a molecular level, but as a
statistical thermodynamic region characterised by system parameters
such as energy distributions or free volume fractions.
Rather than a detailed presentation of major models and theories
concerning diffusion, the main features and assumptions to illustrate
38 C. E. Rogers
their general utility and limitations will be presented. As will be

seen, more rigorous treatments require proportionally more system or
model parameter inputs. Recourse must be made to the relevant
literature citations for more complete understanding.
The representation by eqn (57) is perhaps the simplest one in terms
of a thermodynamic approach. Its use is limited by the fact that d 2 v is
composed of an unspecified jump distance and frequency such that the
product is best considered as an adjustable data fitting parameter.
The transition-state theory of rate processes76 leads to an expres-
sion:
D =K(kT/h)d 2 exp (-I1Gf/RT) (59)
where k is the Boltzmann constant, h is the Planck constant, K is the
transmission coefficient (usually conveniently assumed to be unity) and
I1G f is the free energy of activation. In terms of the entropy and
enthalpy of activation, the Arrhenius parameters are:
ED =I1Hf+RT (60)
Do = e(kT/h)d 2 exp (11S'#<'jR) (61)
If reasonable values of d are assumed (about equal to the diameter
of the penetrant molecule, 5-8 A), then values of I1S f are very large
(40-120 J mol- 1 K- 1). Such large values, indicating that the activated
state is considerably disordered, usually do not seem reasonable in
terms of physical reality. This is a result of the assumption that the
entropy contribution is in a single translational degree of freedom and,
correspondingly, that the energy is concentrated in the activated com-
plex.
In the activated-zone theory,t a larger number of degrees of free-
dom are involved, the activation energy density is low and the en-
tropies of activation have more reasonable values. The equations for
the diffusion coefficient
D = [(vd 2 /6)(f' -1)!](E/RT),,-1 exp (-E/RT) (62)
and the apparent activation energy
ED = E -(f' -l)RT (63)
are based on an approximation which is rigorously true if E»

(f - 1)RT. The quantity f' is the optimum number of degrees of
freedom as calculated from the temperature dependence of ED by the
derivative of eqn (63). The theory assumes that the activation energy
(~E) is shared with chain segments and penetrant in a zone of
activation characterised by the degrees of freedom. Values of fare
typically of the order of 13 or 14 for diffusion of simple penetrants in
elastomers.
As mentioned previously (relating to eqns (52) and (53)), the activa-
tion energy can be considered as the energy to 'loosen' the polymer
structure. An increase in temperature provides energy to increase
segmental mobility which increases the penetrant diffusion rate. A
comparable loosening or increase in segmental mobility is brought
about by the plasticising action of sorbed penetrant which serves to
lower the apparent activation energy for diffusion.
Prager and Long77 suggested that, when the chemical natures of
penetrant and polymer are not too different, the fraction of penetrant-
polymer contacts should be proportional to c or cPl' If these contacts
are weaker than polymer-polymer contacts, the energy required for a
diffusive jump should decrease linearly with increasing c (eqn (51)) and
the concentration dependence of D would be an exponential function
of c or cPl (eqns (39) and (45)).
Vasenin 78 derived an equation under essentially these assumptions
to represent the dependence of the intrinsic diffusion coefficient4 ,13
over the entire range of concentration:
(64)
where (3 is a characteristic system parameter. At low penetrant con-
centrations eqn (64) reduces to
Qill = D(O)[Qil1fD(O)](3cPl (65)
and comparison of eqns (65) and (45) gives
a' = (3 In [Qil1fD(O)]
A major, and limiting assumption is that the energy, E, in the
Boltzmann relation (see eqn (57)) varies as a continuous function from
E2 in pure polymer to E~ in pure solvent according to:
-dEfdC= (3(E- E~) (66)
The physical significance of (3 is not clear and it is considered as an
empirical parameter. Extension of the theory and some elucidation of
the definition and properties of (3 have been presented.63 ,79
There are a number of different definitions of free volume and
40 C. E. Rogers
related treatments of diffusion processes based on those defini-

tions. 4 ,6,13,17,63,79 These treatments generally have the advantage of
adequate data representation without the need of specifying specific
diffusion mechanisms. The extra volume required for a diffusion step is
considered as being more or less uniformly distributed about a diffu-
sion site.
Wilkins and Long80 ,81 considered the diffusion rate as proportional
to the occurrence of local regions of high free volume in the mixture.
The free volume was defined as equal to the change in volume, with
the free volume a linear function of the component mole fractions. The
theory of fluctuations gives the expression:
log D = log D(O) + AcPl - BcPi (67)
where A and B are characteristic parameters. The approximately
linear dependence of log D on penetrant volume fraction cP1, with
downward curvature at higher concentrations, is in agreement with
experimental results.
PeterIin 82 invoked the Hilbebrand concept of fractional free volume:
(68)
where f1 and f2 are the fractional free volumes of penetrant and
polymer and f is the resultant free volume fraction in the mixture.
Utilisation of the Flory-Huggins equation leads to an expression for
the solubility coefficient:
(69)
where p~ is the saturated vapour pressure of penetrant and Xl is the
Flory-Huggins interaction parameter. From an expression similar to the
Doolittle equation as modified for diffusion:
(70)
where Ad is a parameter which is dependent on the size and shape of
the penetrant and Bd is a parameter characterising the 'efficiency' of
use of the available free volume fraction f in the diffusion process; an
expression for D follows as (where Peterlin's nomenclature has been
changed for purposes of consistency):
D = D(O) exp (adc) (71)
where D(O)=RTAd exp[-Bd/(cP2fJJ and ad=Bdl/(cP~f~). It is to be
noted that D is much more dependent on f than is S.
In the most widely used free volume treatment, Fujita and cowor-
kers 83 .84 employed the Williams-Landel-Ferry (WLF) modification 47 ,85
of the Doolittle equation. The free volume is defined as:
[(<1>1 T) = [(0, T) + (3<1>1 (72)
and
[(0, T) = [(0, Tg) + (X2(T - Tg)
where [(0, T) is the free volume fraction of undiluted polymer at
temperature T, [(0, Tg) is the value at the glass temperature, (X2 is the
difference in thermal expansion coefficients above and below Tg , and (3
is a parameter characterising the contribution of sorbed penetrant to
increasing the free volume. With D defined as the thermodynamic
diffusion coefficient (eqn (20)), the expression is:
[In (DT/D(0))r 1 = [(0, T)/Bd + [f(0, T)]2/Bdf3<1>l (73)
and
In D(O)/ RT = In Ad - Bd/[(O, T)
This equation can represent data very well, as illustrated in Fig. 4.
jr---------~-----------r--------~
¥o·C
.'
/o·C
o /0 cO flO
(Volume {'rod/on Dr benzene, VI)-
Fig. 4. Correspondence of experimental data with the Fujita free volume
theory for benzene in poly(methyl acrylate) at various temperatures. (DT is the
thermodynamic diffusion coefficient, D(O) is the value of D(c) as c --l> 0, and
VI the volume fraction of benzene. (Reproduced from ref. 83.)
42 C. E. Rogers
Values of Ad, B d, and y(T) = (d{/dcf>lh can be evaluated from experi-

mental data. The value of {(a, T) can be calculated if {(a, Tg), Tg and
a2 are known. For amorphous polymers the 'universal' values,
{(a, Tg) = 0·025 and a2 = 4·8 X 10- 4 K- 1 provide a first estimate.
A combination of data for a given system for diffusion and viscoelas-
tic properties in terms of the Fujita and WLF modifications of the
Doolittle equation can provide a useful method for elucidating the
nature of penetrant-polymer systems. The combined expression can be
given for the case of D(O) data and creep or stress relaxation data as: 86
log [D(O, T)/RT] = K log llr + log [D(O, Tg)/RTg] (74)
where Tg has been chosen as the reference temperature, D(O, T) and
D(O, Tg) are the diffusion coefficients in the limit of zero concentration,
at T and Tg , K is the ratio of Bd/ BTl' and aT (T/ (T)/ T/ (TR )) is the
u
•.. 3
......
'"E
u
(0)2
0 A
+ <!> N2
j: G CH"
......
0 Q csH.
(J) n-CSHt2
III 1
0 e lao 'Cslit 2
oJ
ED neo-CISHI2
o~----~----~~----~----~~~
o 3 6 9 12
-Log aT
Fig. 5. Log (DIT) versus -log aT (aT is the viscoelastic modulus-time shift
factor) for different penetrants in 45 mol% methyl methacrylate copolymer
with isoprene. (Reproduced, by permission, from ref. 50.)
viscoelastic shift factor from the time-temperature equivalence treat-

ment of suitable stress relaxation or creep data.
If BTJ is assumed to be unity, a common assumption, then a value of
Bd can be calculated from the slope of plots such as Fig. 5. However,
Frisch and Rogers48 suggested that the slopes of such plots could better
be interpreted as measures of the efficiencies of utilisation of free
volume by a mass transport process relative to its utilisation by a
momentum transfer process in the same polymer. A linear relationship
would hold if the mechanisms of mass and momentum transport were
affected similarly by changes in free volume with changing tempera-
ture. Likewise, plots of diffusion and viscoelastic data for a given
penetrant-polymer system at constant temperature with changing
sorbed concentration should also give linear plots if the mechanisms
respond in unison. In this latter case, however, one may expect
meaningful deviations from linearity due to specific component in-
teractions such as clustering.
The magnitude of the slope parameter K is significant in relating the
nature of the polymer segmental motion required for a diffusion
process to that required for a viscous process. The increase in slope
with increasing penetrant size is evident in Fig. 5. Values of K
approach unity for the larger size penetrant molecules indicating that
the two transport processes are then utilising similar domains of free
volume, or segmental motion size.
An example of the use of the method for studying the effects of
concentration changes on diffusion and viscoelastic behaviour has been
carried out49 with the system poly(n-butyl methacrylate) and benzene
and methyl ethyl ketone (MEK) at 23°C. The ratio
Bd(benzene)jBd(MEK)= 1·22 indicates that the critical free volume
for diffusion is greater for benzene than for MEK in accordance with
the comparative molecular sizes. The ratio ~d(benzene)/~d(MEK) =
0·66 indicates that, at equal volume fraction, the plasticising ability of
MEK for diffusion processes is greater than that of benzene. The value
of BTJ(benzene)jBTJ(MEK) = 1·02 implies that the same proportion of
free volume is required for momentum transfer regardless of the
penetrant. From the ratio ~TJ (benzene)/ ~TJ (MEK) = 0·91, it appears
that MEK is a slightly better plasticising agent but the difference is not
as marked as for diffusion.
Stern, Fang and Frisch87 have extended the free volume model of
Fujita et al. to develop a more general expression for the mean
permeability coefficient P. For that purpose, they modified eqn (72) to
44 C. E. Rogers
account for the dependence of f on total hydrostatic pressure, as well

as temperature and concentration. The applied hydrostatic pressure
may result in two opposing effects, an increase in f from an increase in
concentration or a decrease in f due to compaction. The equations
have been found to hold for a number of systems,17 more importantly
for CO 2, C 2 H 4 and C 3 Hs in polyethylene for pressures up to
30 atmospheres.
Vrentas and Dudass- 91 have developed a more complex free volume
model which represents data over a wide range of concentration and
other experimental variables. The model is based on the free volume
models of Cohen and Turnbull 92 and Fujita,84 with Bearman's93 rela-
tionship between the mutual diffusion coefficient and the friction
coefficient. It also employs the Flory-Huggins polymer solution theory
and aspects of the entanglement theory of Bueche. 94 It is assumed that
the thermal expansion coefficients can be taken as their average value
over a temperature range, that the component partial specific volumes
are independent of concentration, that the change of volume on mixing
is effectively zero, and that the Flory-Huggins theory applies with a
constant interaction parameter Xl. The expression for D is then:
D = DOl (1- 4>1)2(1- 2X14>1) exp [-(W1 vi + w2fvi)/(v FH h)] (75)
where:
vFHh = (K ll /-Y)Wl(K2l + T- Tgl) + (K12/-y)wiK22 + T- Tg2)
and:
4>1 = WIV~/(WlV~+WlV~)
D is the mutual diffusion coefficient, DOl = Do exp (-E/RT), Vi are
partial specific volumes, -y is an overlap factor for free volume, vt
are
specific critical hole free volumes required for a jump, l; = vi/vi, Wi is
the mass fraction and VFH is the average hole free volume per gram of
mixture. In practice the parameters are evaluated from a combination
of density, viscosity, equilibrium sorption and limited diffusion data.
The definition of l; leads to unsatisfactory results so that it is necessary
to calculate l; from the limited D data to fit the equation to those data
points. The equation then is used to predict D values for other (usually
higher) concentrations as shown in Fig. 6. The equation in this form
gives a good predictive fit for data obtained over wide concentration
ranges (Fig. 6) where the Fujita theory does not represent data well.
These models can represent and predict data but they all have the
limitation that the free volume parameters Ad, B d, etc., are
Permeation of gases and vapours In polymers 45
10"5
o
o 110 -C
_ PROPOSED FREE-VOLUME THEORY

_._ FREE-VOLUME THEORY OF FWITA
08
WEIGHT FRACTION TOLUENE

Fig. 6. Test of predictive capabilities of free volume theory proposed by
Vrentas and Duda and the free volume theory of Fujita at a single temperature
using toluene-polystyrene data. Only data points represented by solid symbols
were used to obtain free volume parameters for the two theories. (Repro-
duced, by permission, from ref. 91.)
phenomenological so that they must be determined separately for each

system. In addition, the models which give the better representations
and predictions of data require correspondingly more parameter input
(e.g., the Vrentas-Duda model) which considerably reduces the utility
of the models.
Expressions based on molecular models of the diffusion process
rather than free volume or related approaches would seem to offer the
advantage that the necessary parameters should be predictable from
the inherent properties of the penetrant and polymer components.
However, all such molecular models developed to date have one or
more adjustable parameters except for certain systems in limited
ranges of temperature. In addition, since the molecular models are
46 C. E. Rogers
more detailed, the expressions are more complex requiring con-

siderable parameter input.
In one of the earlier models, Meares 95 considered that Ed is the
energy required to separate the matrix to form a cylinder space of
suitable cross-section to allow the penetrant molecule to make a unit
diffusion jump of length A rather than being the energy for formation
of the 'hole' into which the penetrant jumps. This approach, which
effectively equates the energy to a product of the internal pressure,
Pi = (aE/avh, times an activation volume, V", gives:
(76)
where u is the collision diameter of the penetrant molecule, N is

Avogadro's number and CED is the cohesive energy density of the
polymer.
This expression, which says that Ed varies as the diameter squared,
in accordance with data for most small gas molecule-polymer systems,
allows calculation of the jump distance A. For example, it was found
that A varied from 26·5 A for He to 28·9 A for Ar in poly(vinyl
acetate) above its T g • These values are considerably greater than values
usually assumed, of the order of molecular diameters.
Brandt96 considered that Ed was the energy needed to bend chains
and overcome forces between them to allow the diffusion jump. The
energy is stored in f degrees of freedom, distributed as:
E*=Eb+E;+E, (77)
where Eb = energy for chain bending, E, = energy to overcome interac-

tions, and E, = thermal energy which is not part of Ed' Each energy
contribution is expressed in terms of f and molecular parameters. The
activation energy, Ed = Eb + E j , was found to be a minimum for f
between 12 to 19 which is in the general range found for the
somewhat related zone theory of Barrer (eqns (62) and (63)).
The model was tested initially for the system ethane-polyethylene
where it was found that calculated values of Ed were 25-70% lower
than experimental values. This may imply that there are other molecu-
lar motions involved besides those chosen. In addition, the model
assumes that cooperative motion is required only for larger penetrant
molecules which cannot pass through existing open volumes so that Ed
goes to zero as the penetrant diameter goes to 5-8 A. Finally, Ed is not
proportional to penetrant diameter squared, but rather experimental
RIL
NORMAL STATE AFTER ONE
NORMAL STATE ACTIVATED STATE DIFFUSIONAL JUMP
~
s.gfN/I,-OO
Po/ym.,
NORMAL STATE ACTIVATED STATE
Fig. 7. DiBenedetto and Paul model for the activation process for diffusion
which involves penetrant motion down a corridor bounded by four parallel
polymer segments. (Reproduced, by permission, from ref. 97:)
plots of Ed versus a Z are concave to the (T z axis (nor is it proportional

to the CED, contrary to the model of Meares).
The Meares and Brandt expressions seem to be applicable to several
systems. However, their long-lasting significance is that the approaches
have served as a basis for many subsequent model developments.
In the molecular model of DiBenedetto and Paul97 the matrix is
considered to be a homogeneous phase with NA n-centre polymer
segments corresponding to structural units (e.g. -CHz-). A sorbed
penetrant molecule behaves as a three-dimensional harmonic oscillator
trapped by bundles of parallel segments (Fig. 7). A diffusion jump
occurs when a cylindrical void is formed, so that:
EaJNA = (4ne*p*/2,\)[t/lrc(V*/VA ) - t/lrc(V*/V)] (78)
where t/lrc is a function relating to the potential energy of interaction of
one centre with one neighbouring chain, based on the Lennard-Jones
6-12 potential, V A =V(1+u*Z), u*z=2'\(7T/4)u z /(nV), 2'\=chain
length per centre (approximately a C-C bond length), e*, V* and p*
are the Lennard-Jones energy, volume and pressure parameters, V =
volume per centre, V* = 2,\ (p*f, and n is an adjustable parameter
(- 5-9) = number of participating centres.
The expression predicts that plots of Ed versus U Z are concave to the
U Z axis as is found experimentally but not explained by previous
models. Thus, the forces to form the passage decrease as the passage
48 C. E. Rogers
volume increases. However, the model also predicts that Ed goes to

zero as 0' goes to zero which is not in agreement with experimental
results. The model predicts only the energy for the additional activa-
tion volume formation while the actual volume involved in the diffu-
sion process also includes the local average free volume of the system.
In another model, DiBenedetto and Paul used fluctuation theory
with the homogeneous phase now divided into NA unit cells of volume
v = 2Ap~n, where Po is the average chain separation. Diffusion occurs
along the axis of four parallel segments when a volume fluctuation
equal to or greater than (7r/4)0'22An occurs. The expression predicts
that Ed will go to a constant value, representing the total cohesive
energy of a polymer segment, as 0' goes to zero.
Both models were tested by plotting data for a reduced activation
energy, Ed = E) RT = Eapp/ RT, versus a reduced diameter, (O'*? =
(2A7r/4)0'2(NA /VO)' where Vo is the total equilibrium volume. Plots of
data with predictions from each model (Figs 8 and 9) indicate that the
molecular model is better for elastomeric systems and the other model
is better for glassy systems. The diffusion process involves disruption of
segmental cohesive forces in elastomers and an additional compression
V·=100
- - - Fluctuation analysIS n= 12
20 Mol<2cular modal analYSIS
V·=50
n=6
."
w
10
__ ---n=8
p*=O
~·=020
o 01 0·2 03 04 05 06 07
(0·)2
Fig. 8. Dependence of activation energy E: on penetrant collision diameter

(a*)2 for diffusion in polybutadiene rubber. p* is the external pressure, V* the
average polymer segment volume, (3* the thermal expansion coefficient. All
parameters are dimensionless, except n, the number of molecular centres per
polymer segment. Circles are experimental data and lines are predictions by
the two models. (Reproduced, by permission, from ref. 97.)
50
V*= 700 (n =113)
V*=600 (n =9 8)
(n=9)
V*=500(n=81)
- - - Fluctuation analysis
- - - - Mol",cular mod",1
p*=O
~*=0068
004 05
Fig. 9. Dependence of activation energy E~ on penetrant collision diameter

for diffusion in glassy poly(vinyl acetate). Parameters are the same as in Fig. 8.
(Reproduced, by permission, from ref. 97.)
of neighbouring segments in glassy polymers. The dependence of

activation energy on diameter squared is opposite for the two models.
These models can represent data well while giving some further
insight into the nature of the diffusion process. The equations are
moderately complex, however, and they do involve adjustable parame-
ters that detract from the rigour of interpretation.
A much more recent model has been presented by Pace and
Datyner98 based on aspects of the models of Brandt, and DiBenedetto
and PauL The definition of structure of the latter model is assumed but
diffusion is now considered to occur not only parallel to the chains but
also across them as in Brandt's modeL These parallel and perpendicu-
lar jumps occur in series with the more energy requiring perpendicular
jump taken as rate limiting.
The formulation of this more detailed model is correspondingly
more complex. The expression for Ed involves most of the parameters
of the DiBenedetto and Paul model in terms of the Lennard-Jones
potential plus single chain bending energies and other parameters.
There are a number of input parameters that need to be evaluated.
The expressions indicate that Ed is dependent on temperature since
it is a function of equilibrium chain-centre separation (-density func-
tion), Ed is also approximately proportional to a, not to a 2 , The
50 C. E. Rogers
prediction of D does involve an adjustable parameter, with other

adjustable parameters added to extend the temperature range of
utilisation above and below T g • The model has been extended to include
more complex penetrant molecules 98 with expressions for D(O) and its
dependence on temperature and concentration. The predictions of
these models seem to agree well with the experimental systems that
have been studied. The utility of the model does depend on the
availability of parameter input data as well as the feasibility of the
more involved and complex calculation procedures.
4.3. Concepts and Models for Penetrant Immobilisation

As discussed in Section 2, the mode of sorption, defined as relating to
the position, manner and strength by which a sorbed molecule is held
within a solid, is a primary factor governing molecular mobility. When
penetrant molecules are held by sites of varying energies the driving
force for diffusion contains energy factors which depend on concentra-
tion and the number and distribution of sites within the system. As
sorbed concentration changes with time, external concentration or
temperature, the relative number of component contacts at any given
position may change greatly. The resultant change in the modes of
sorption is often reflected by a marked change in the overall diffusion
rate process.63
Depending on the magnitude and nature of the interaction forces, a
given penetrant molecule may be localised at a site or within a volume
element for periods of time greater than that required for a unit
diffusion step. Such molecules are essentially immobilised and do not
contribute to the overall flux.
Mechanisms for penetrant immobilisation include 4 chemical or phys-
ical interactions with polymer groups and sorption into pre-existing
microvoids or related structures. When there are strong interactions
between the components, penetrant molecules may be involved in
solvation clusters, chemisorption modes or even actual chemical reac-
tion. When cohesive forces between penetrant molecules are greater
than attractive forces between penetrant and polymer, the penetrant
tends to cluster within the polymer. A measure of clustering is given by
eqn (35).
A molecule within a cluster will generally be less mobile than an
isolated molecule owing to the additional energy required to break free
from the cluster. In the absence of pre-existing pores or capillaries, the
energy required for hole formation for the migration of clusters per se
can be expected to exceed the energy for evaporation of single

molecules from the cluster or even complete dissociation of the cluster.
The value of c', the concentration of free molecules (eqns (16)-(18)),
depends then on the equilibrium distribution of molecules between the
bound and free sorption modes and on the rate of exchange between
the two states. When the exchange rate is equal to or greater than the
diffusion rate, the presence of clusters will have little effect on the
transport rate. When the exchange rate is less than the diffusion rate of
free molecules the observed D is dependent on the ratio c'/c (eqn
(18)).
Such a dependence of sorption, diffusion and mechanical properties
on both clustering and exchange rate has been illustrated by a study99
of water and alcohols in nylon. All of the penetrants undergo cluster-
ing, but the diffusion data show little effect of clustering for water
transport and a marked effect on alcohol transport. However, the
effect of clustering of all penetrants is reflected by changes in dynamic
mechanical properties which have a different characteristic relaxation
time than does the diffusion process.
The sorption of penetrant in pre-existing microvoids, or more gener-
ally in fluctuation volumes comprising excess volumes, has received
considerable attention in terms of the so-called 'dual-sorption
model',17,34-39,62,lOo-107 especially for glassy polymer systems. The
model postulates that the penetrant dissolves by two component
processes: an ordinary dissolution similar to that observed above Tg
and a filling of a number of pre-existing microcavities or 'holes'. The
concentration, Co, of the dissolved penetrant is usually represented by
Henry's law, or more generally byeqn (41).37 The concentration, C H,
of penetrant involved in hole-filling can be represented by the Lang-
muir equation: C H = Ckbp/(1 + bp) (79)
where Ck is a 'hole saturation' constant and b is a 'hole affinity'
constant representing the ratio of rate constants for adsorption and
desorption in microcavities. The total concentration c of sorbed pene-
trant is the sum of the two processes so that at sufficiently low values,
where Henry's law is obeyed:
c = kop + Ckbp/(1 + bp) (80)
where ko is the Henry's law solubility constant.

The diffusion process then can be expressed as:
J = - Do(dCo/dx) - DH(dCH/dx) (81)
52 C. E. Rogers
where Do and DH are diffusion coefficients characterising the mobility

of the penetrant in the two sorption modes (see eqns (15)-(18)). The
permeability and time lag follow as:
p= koDo[1 + FK/(1 +bp)] (82)
and
L = OZ/bDo )[1 + f(K, F, b, p)]
where F = DH/ Do, K = CHb/ ko and f(K, F, b, p) is a function of the
parameters listed.
These equations, and other related equations, have been used to
represent the sorption and transport behaviour of gases such as CO2
and C~ in many glassy systems; typical sorption and transport data
are illustrated in Figs 10 and 11. Such gases are relatively insoluble
even at the high pressures (tens of atmospheres) commonly used
experimentally. For more condensible vapours (e.g. water-
polyacrylonitrile39), eqn (81) holds only at low c and an equation such
as eqn (41) must be used for Co ?9 If the diffusion process is concentra-
tion dependent, due to plasticisation of the polymer matrix in addition
to the concentration dependence arising from the hole-filling sorption,
the following expression based on eqns (39) and (41) may be used to
30
5 10 15 20 25
Prassura (atm)
Fig. 10. Equilibrium sorption of carbon dioxide in polycarbonate Ctl.), poly-

styrene (0), and polyacrylonitrile (0). The isotherm concave to the pressure
axis is the feature typical of dual mode sorption behaviour. (Reproduced, by
permission, from ref. 18.)
Permeation of gases and vapours in polymers S3
RELATIVE PRESSURE '\ '''0
Fig. 11. Dependence of effective permeability coefficient, P eff, on relative

vapour pressure of water, P2/PU for water-poly(acrylonitrile). The curves were
calculated from eqn (83). (Reproduced, by permission, from ref. 39.)
calculate an effective permeability coefficient: 39

P eff = [D(O)/-yp]{exp [-ykDp(exp (ae) + FK/(l + bp))]-l} (83)
where -y and a are the parameters characterising the exponential
concentration dependence of the diffusion and solubility coefficients,
respectively, and p and e are the upstream pressure and sorbed
concentration at that surface with the downstream pressure and con-
centration held at zero. When the sorption process obeys Henry's law,
a - 0 and exp (ae)-1.
In many of the studies of dual-mode sorption and transport, it is
assumed that the penetrant in the hole-filling mode is completely
immobilised with DH and F - O. Petropoulos35 and Paul and Koros 36
have suggested that that penetrant population may be only partially
immobilised requiring the use of both diffusion coefficients to represent
data. The assumption of partial immobilisation can be replaced
mathematically36 by the assumption that a fraction, F, of the penetrant
in microcavities is fully mobile with the remaining fraction (1- F)
totally immobile, as stated in eqn (82).
Although the dual-mode sorption concept has provided a satisfac-
tory representation of solubility and transport in glassy polymers, it
54 C. E. Rogers
must be remembered that the concept is based on rather drastic

assumptions and a simple physical picture of what is undoubtedly a
complex solution-diffusion system. The nature and distribution of the
micro cavities is not really known. They have been described as free
volume packets or microdomains of lower density. In addition, the
polymer-penetrant (and penetrant-penetrant) interactions in those re-
gions must differ from those in the polymer matrix to account for the
difference in penetrant mobilities-how is not known.
The suggestion of Vieth et ai.107 that Langmuir isotherms are obeyed
by all the penetrant in different sorption modes (hence all species are
partially mobile in varying degrees) is effectively based on a sorption
site energy distribution which is more in agreement with the concept
leading to eqn (15). It can be noted that diffusion in a system with
sorption governed by a Langmuir-type isotherm was considered much
earlier by Fujita 108 in terms of the general equation for the combined
process of diffusion and immobilisation (reaction):
(84)
where c is the overall concentration free to diffuse and B is the
adsorbed concentration. With some assumptions this leads to:
D(c) = D(O)/(I- AC)2 (85)
where A is characteristic parameter relating to the Langmuir parame-
ters. This form of D(c) is one of the very few which has been derived
formally. 109
The matrix model proposed by Sefcik and Raucher llo also considers
a combined process of diffusion and immobilisation related to less
specifically defined interactions between the components during sorp-
tion and transport in glassy polymers. That model assumes that one
population of penetrant exists in the polymer rather than the two
populations in the dual mode concept. The solubility and diffusion
coefficients are:
S = S(O)/(1 + ac) (86)
and
D = D(O)/(1 + (3c) (87)
where a and {3 are parameters characterising the gas-polymer interac-
tions in the system.
Both the dual-mode and matrix models, as well as other models/- 18
seem to fit sorption and transport data for certain systems. There are
Permeation of gases and vapou.rs in polymers 55
some differences for certain time-lag data and for other derived data.
The relative validity of the two models is not established at this time
but the dual-mode model seems to be favoured. It must be realised
that both models are only approximations which require estimation of
a number of parameters.
4.4. Effects of Polymer Relaxation 4

Sorption and transport in polymers with long relaxation times often
exhibit features which cannot be described adequately by any general-
ised form of Fick's law with constant boundary conditions and with the
diffusion coefficient dependent only on concentration. This so-called
'non-Fickian' behaviour usually occurs with glassy polymers, with
semicrystalline polymers above Tg , and with polymers with more rigid
chain conformations and higher internal viscosity when the penetrant
swells the polymer.
In such cases, D may be a function of concentration, time, the
spatial coordinates and history of the sample. The boundary conditions
for diffusion depend on time and other variables such that the surface
concentrations change with time, applied stress, etc. In some cases,
when the polymer contains microvoids or pores, multiple transport
mechanisms may be operative with contributions to the total flux which
change with time, etc.
Deviations from Fickian behaviour generally arise as a consequence
of the finite rates by which changes in polymer structure occur in
response to stresses imposed upon the medium before and during the
sorption-<iiffusion process. Stresses and strains present initially are the
result of the fabrication process, crystallisation conditions, mechanical
deformations, etc. More important are swelling stresses generated
during sorption and the resultant creep effects to establish swelling
equilibrium. The non-Fickian behaviour may be related to either or
both the change in structure or the stress per se.
Polymers have a wide spectrum of relaxation times related to the
many modes of relaxation. All relaxation times decrease with increas-
ing temperature or concentration, with some decreasing more rapidly
than others. The overall sorption process reflects those relaxation
motions of the polymeric matrix which occur on a time scale compara-
ble to or greater than the time scale of the concurrent diffusion
process. Indeed, a Deborah number can be defined as the ratio of the
relaxation time to the diffusion time. When that number is much less
56 C. E. Rogers
than unity, relaxation is fast, the sorption rate is controlled by diffu-

sion, and the behaviour is Fickian or so-called 'Case 1'. When the
number is much greater than unity, the sorption process is essentially
controlled by polymer relaxation. When the number is near unity,
intermediate behaviour is observed and one can speak of 'coupled'
diffusion-relaxation or just call it 'anomalous'.
The type of behaviour is characterised experimentally by the con-
centration gradient profile during sorption and its time dependence.
The time dependence is conveniently determined by the slope n of a
plot of log M against log time, where M is the amount of penetrant
sorbed. In a sheet geometry for Fickian sorption (n = 1/2), the profile
proceeds with time such that the separation between points of specified
concentration scales with the square root of time. As the Deborah
number increases, a plot of amount sorbed versus t l/2 becomes pro-
gressively more sigmoid in shape. In addition, the concentration
profiles, after an initial formation period, maintain a constant shape
and distance scale identified as an advancing front. When the front
advances at constant speed, n is equal to unity, and the process is
called 'Case II' sorption. Anomalous behaviour can be classified then
as those cases when n is between one-half and unity. 'Super Case II'
classifies cases when n is greater than unity, usually for later stages of
the overall sorption when the advancing Fickian tails preceding the
fronts advancing from the two surfaces meet, overlap and promote an
acceleration of the sorption process. Sorption with n < 1/2 is termed
'pseudo-Fickian' and is characterised by initial curvature of M versus
t I/2 plots out of the origin concave to the time axis.
This major aspect of sorption and transport in polymers is discussed in
detail elsewhere (e.g. refs 4, 6,13, 111-113); Chapter 3 brings together
the most recent results and concepts in this very active area of study.
5. THE PHYSICOCHEMICAL NATURE OF

THE COMPONENTS
5.1. Penetrant Size and Shape

An increase in the size (e.g. average diameter, molar volume) of a
penetrant in a series of chemically similar penetrants generally leads to
an increase in solubility S(O) and a decrease in diffusion D(O)
coefficients. Since the permeability coefficient is the product of these,
its variation with penetrant size is often much less. The increase in
solubility usually results in an increase in the concentration depen-

dence of S, D and P with increasing penetrant size.
The increase in solubility is directly related to the dependence of S
on boiling temperature and related parameters, as discussed in Section
4. An increase in penetrant size requires more energy for vaporisation
and hence the boiling temperature increases.
The decrease in D(O) is a reflection of the need to create or utilise a
critical activation volume in the polymer proportional to that of the
penetrant molecule, again as discussed in Section 4. The activation
energy for diffusion is also found to be proportional to the molecular
dimensions of the penetrant molecule, with correlations varying be-
tween the first and second power of the diameter (or cross-sectional
area).4.6.13.2~ A comparison of available measurements of molecular
diameters shows significant uncertainty and discrepancies between
different methods. 114 Thus, correlations of diffusivity with diameters
may be expected to show scatter or uncertainty from this source alone.
Berens and Hopfenberg114 have studied the diffusion of a wide range
of gases and vapours in poly(vinyl chloride), polystyrene and
polymethylmethacrylate. A plot of log D versus the van der Waals
molar volume b, shown in Fig. 12, displays a very systematic trend
encompassing ten orders of magnitude in D values for little more than
a twofold change in penetrant diameter; ED varies by a factor of about
5 over the same range. Fairly good linear plots of log D versus
diameter, or diameter squared, using average diameter values also
were obtained.
In the same study, it also was found that the diffusivities of n-alkane
and other elongated or flattened molecules are higher, by a factor of
up to 10\ than the diffusivities of spherical molecules of similar
volume or molecular weight. This implies that anisotropic molecules
are oriented and move along their long dimension during diffusion, at
least in glassy polymers. This is in agreement with the results of earlier
studies 115 which established that D(O) could be linearly correlated with
the product 1112, where 11 is the minimum molecular dimension of the
diffusing molecule and 12 is the next smallest perpendicular to II'
A comparable dependence on penetrant shape has also been
found 116 for S(O); plots of log S(O) versus penetrant molar volume
display two linear relationships of identical slope for a given polymer
with one relationship for more spherical organic molecules and the
other for normal paraffins. The extrapolated intercept at zero molar
volume is greater for spherical than for straight-chain molecules.
58 C. E. Rogers
-II
-/2
-/3
-/4
-15
Fig. 12. Diffusivities of gases and vapours in poly(vinyl chloride) as a function

of their van der Waals volume, b. (0) Data of Berens and Hopfenberg,114 (e)
data used by those authors from Tikhomirov et al. '28 (Reproduced, by
The sorption and diffusion processes in the glassy state generally

show a greater dependence On the size and shape of the penetrant
molecule than in the rubbery state. This can be ascribed to a change in
the process of mixing from one of site generation above Tg to the
effective filling of pre-existing sites governed by the excess volume
distribution in the more rigid glassy polymer. This is illustrated 117 by
the change in the sorption of alcohol penetrants in a random
o CH 3 - OH
8 CH 3 CH 2 -OH
[:1
x CH 3 CH 2 CH 2 - OH
7 + CH 3 CH 2 CH 2 CH 2 - OH
~
5 I
OCI
Eo
I
----
I
0 4 ;r
/
><
u .1
/,
. I /
3
/1
2
/ ,I
. I
I;'
I
/
20 40 60 80 100
% MOLE MMA
Fig. 13. Sorption of alcohols in a series of isoprene-methyl methacrylate

random copolymers at room temperature. At 50-55% MMA content and
higher, the copolymer T. is at or above the temperature of the experiment.
copolymer series as the Tg changes with changing copolymer composi-

tion at a given temperature (Fig. 13). In the rubbery copolymers, the
magnitude of sorption increases with increasing penetrant size as
expected from various polymer solution theories. In the glassy
copolymers (MMA content greater than about 55%) the order of
solubility magnitudes is reversed with the smaller molecules being
sorbed more than the larger. This suggests that the distribution of
excess volume provides fewer sorption sites for large molecules than
for small. A corresponding change in apparent diffusion coefficients is
also noted (Fig. 14).
60 C. E. Rogers
o CH.OH
a CHi CHz OH
·7
+ CHi CHI CHI OH
r. CH, CH z CHz CH z OH
-8
so
...
.3 -9
-10
o 20 40 60 80 100
'% MOLE MMA

Fig. 14. Diffusion coefficients of alcohol penetrants in a series of isoprene-
methyl methacrylate copolymers at room temperature. At 50-55% MMA
content and higher, the copolymer T. is at or above the temperature of the
experiment. (Reproduced, by permission, from ref. 117.)
S.2. Molecular Composition, Symmetry and Polarity

Permanent gases interact little, if at all, with organic solids and the
amount sorbed is sufficiently small so that the solid structure does not
undergo any swelling strain or other rearrangement. Therefore, the
solubility, diffusion and permeability coefficients are constants inde-
pendent of pressure at any given temperature.
With other factors equal, the permeation rate of gases can be
expected to decrease as the structural symmetry and cohesive energy
of the polymer increase. In Table 1, data are given for the permeation
of oxygen through several polymers of quite different structure and
polarity. 3 In a comparison of polymers such as polyethylene,
Permeation of gases and l'apours in polymers 61
TABLE 1
Permeability of Polymer Films to Oxygen at 25-30°C
Polymer Ebp
Silicone rubber 5000

Ethyl cellulose 265 16
Methyl cellulose 5
Polyisoprene (natural rubber) 230 30
Polybutadiene 191 30
Poly(butadiene (80% )-acrylonitrile) 82 36
Poly(butadiene (73 % )-acrylonitrile) 39 40
Poly(butadiene (68% )-acrylonitrile) 24 44
Poly(butadiene (61 %)-acrylonitrile) 9·6 50
Polystyrene 15-250
Poly(styrene-butadiene) 172 30
Cellulose acetate-butyrate 60
Teflon (FEP) 59 24
Polyethylene (density 0·922) 55 43
Polyethylene (density 0·922), radiated 35 40
Polyethylene (density 0·965) 0·5 13
Polychloroprene (neoprene) 40 41
Poly(vinyl chloride-vinyl acetate) 24 41
Poly(vinyl chloride), 30 parts 6
dioctylphthalatellOO parts PVC
Poly(vinyl chloride) 1·2
Polypropylene (density 0·907) 21 47
Polydimethylbutadiene 21 47
Butyl rubber 13 45
Cellulose acetate 7·8 21
Polychlorotrifluoroethylene 5·6 46
Rubber hydrochloride, plasticised 5·4 35
Rubber hydrochloride, unplasticised 0·25
Polyacetal 3·8
Polysulphide rubber 2·9 56
Polyamide (nylon 6) 0·38 43
Poly(ethylene-terephthalate) (Mylar) 0·30 27
Poly(vinyl fluoride} (Tedlar) 0·2
Poly(vinylidene chloride) (Saran) 0·05 67
a P is in the following units:
(cm 3 at STP)(mm thickness) x 10 10
(cm2 area)(s)(cm Hg)
h Ep: P = Po exp (- Ep/RT) in units of kJ mol-I.
62 C. E. Rogers
poly butadiene and rubber, which have similar cohesive energies, the
latter is found to be considerably looser in structure due to lack of
symmetry along the chain, which leads to a much larger diffusion
coefficient. Again, in a comparison of two symmetrical polymers, such
as polyvinylidene chloride and polybutadiene, the former is found to
be more polar, which leads to a much lower diffusion coefficient due to
its high cohesive energy. Chemical modification of a polymer can have
a pronounced effect on D and P. The introduction of methyl or polar
side groups onto rubber chains increases the cohesive energy and
decreases the values of P and D but affects the solubility only slightly.
The permeation of more condensable vapours and liquids through a
polymer membrane usually proceeds at much greater rates than does
the permeation of gases. Good solvents swell and plasticise the
polymeric structure, which leads to increased mobilities of both
polymer chain segments and penetrant molecules. In Table 2, data are
given for the permeability of a nitrile rubber to several gases, vapours
and liquids of different molecular size and solvent power; the range of
permeability constants extends over seven orders of magnitude.
The permeation of water vapour varies greatly from polymer to
polymer, as shown in Table 3, depending on the type and degree of
specific interaction that is possible between the water and certain polar
TABLE 2
Permeability of Poly(butadiene-acrylonitrile (35%)) Rubber
to Penetrants at 25-30 D C
(em 3 at STP)(mm x 10 7 )
Penetrant P = ----=-----'---------'-
(em 2 s)(em Hg)
Nitrogen 0·0042
Oxygen 0·016
Methane 0·032
Diisobutylene 0·045
Helium 0·084
Hydrogen 0·095
Carbon dioxide 0·13
Water 17·5
Methanol 246
Carbon tetrachloride 465
Ethyl acetate 3280
Benzene 6050
Methyl ethyl ketone 6100
TABLE 3
Permeability of Polymer Films to Water Vapour (25°C)
(em 3 atSTP)(mm x 10")

Film P = -=-----=-----'--'---
(em 2 s)(em Hg)
Poly(vinylidene chloride) (Saran) 0·3-1·0a
Polytetrafluoroethylene (Teflon) 0·3
Butyl rubber 1·3
Polyethylene (density 0·960) 1·2
Polyethylene (density 0'938) 2·5
Polyethylene (density 0·922) 9·0
Polypropylene (density 0'907) 5·1
Poly(vinyl chloride) 6·1
Poly(vinyl chloride-vinyl acetate) 7·0
Poly(ethylene terephthalate) (Mylar) 13
Polystyrene 12
Polyacrylonitrile 13
Polybutadiene 47
Poly(styrene-butadiene) 9
Poly(butadiene-acrylonitrile (62%» 15
Polyisoprene (natural rubber) 30
Polyamide (nylon 66) (95% relative humidity) 68 b
Cellulose acetate 550
Cellulose acetate (15% dibutyl phthalate) 740
Ethyl cellulose, plasticised 1300
Poly(vinyl alcohol), p = 2·3 cm Hg 4200
a Dependent on grade.
b Dependent on relative humidity.
substituents on the polymer chains. 3 Polymers such as cellulose,

poly(vinyl alcohol), poly(vinyl acetals) and poly(ethylene glycol) have
high water absorptions. Hydrocarbon polymers such as polystyrene,
polyolefins and most common elastomers have low water absorptions.
Intermediate water absorptions, between 1 and 10%, are obtained for
various cellulose derivatives, acrylics, polyurethanes and polyamides.
However, the time required to obtain equilibrium water sorption in
these systems is often a very important practical factor.
Relatively small changes in the chemical nature of the polymer chain
which affect the abundance of available polar substituents, can have
marked effects on transport of water. An increase in the acetyl content
of a cellulose acetate film from about 34 to 43% by weight decreased
the permeability to water by more than a factor of ten. On the other
hand, an otherwise minor amount of oxidation (0-6% oxygen by
64 C. E. Rogers
weight) of polyethylene can result in a more than fivefold increase in

water absorption.
The magnitudes of the apparent activation energies, ED and E p , also
increase as the chain rigidity and polarity of the polymer increase.
Polymers with weak intermolecular forces and flexible chains allow
segment separation to occur more readily. This behaviour can be
correlated 118 with parameters such as the brittle temperature and the
activation energy for viscous flow since those processes are also
affected by variations in chain segmental mobility.
A more versatile correlation parameter is the glass temperature, T g ,
which can be related to the molecular characteristics of the polymer.
The value of Tg is governed mainly by chemical composition and the
presence of added plasticisers (e.g. ref. 119). Structural features such
as chain branching, crosslinking and crystallinity have a much lesser
effect on Tg • A fairly systematic correlation between activation ener-
gies for diffusion, sizes of the diffusing molecules and Tg for the
polymers has been established 25 for a wide range of gases and low
molecular weight organic vapours in rubbery, glassy and semicrystal-
line polymers. This correlation can be used 25 to estimate values of D.
In general, there is a decrease in the apparent activation energy (and
the value of Do) for diffusion as the temperature of the system
decreases through Tg. Below Tg the range of ED values is about
25-50 kJ mol-I. Above Tg values as high as 170 kJ mol-I have been
observed. This change in ED can be related 4 to the change in thermal
expansivity and the presence of an excess volume distribution in the
polymer below its T g • The activation energy is concentrated in a smaller
number of degrees of freedom in the zone of activation. The excess
volume distribution may allow an effective contribution of convective
flow to the overall flux that requires a smaller (negative) temperature
coefficient than the corresponding activated diffusion process both
above and below T g • This also leads to a greater dependence of both
',orption and diffusion on penetrant size and shape in the glassy state
.han in the rubbery state, as discussed in the previous section.
In !:ertain polymers, the nature of the glass transition structural
changes is such that there is little, if any, change in ED above and
below Tg for suitably small penetrant molecules. This has been shown 18
for the transport of argon and hydrogen in poly(ethyl methacrylate)
which has a rather small difference between the coefficients of thermal
expansion above and below Tg •
5.3. Crosslinking, Orientation and Crystallinity

The presence of crystalline domains in a polymer has at least two
effects on sorption and diffusion behaviour. At temperatures well
below the melting point, crystalline regions are generally inaccessible
to most penetrants. 120 Hence, they act as excluded volumes for the
sorption process and as impermeable barriers for the diffusion process.
The other effect on sorption and diffusion processes is that crystalline
domains act as giant crosslinking regions with respect to those chains
which enter and leave those regions from the surrounding non-
crystalline matrix in which sorption and diffusion take place.
The presence of excluded volumes requires that the effective com-
position be calculated on the basis of the accessible amorphous content
to include the 'surface' regions of the crystalline domains and any voids
or defects arising from the crystallisation process. In nearly every
system, it has been found (e.g. refs 4, 6, 120 and 121) that the
solubility is proportional to the amorphous volume fraction cf>a:
(88)
where Sa is the solubility coefficient for a completely amorphous
polymer (with due consideration of surface and void effects). This leads
to a single isotherm which represents sorption data for chemically
similar polymers with differing degrees of crystallinity, such as
polyethylene 120 ,121 and poly(ethylene terephthalate).105
In the diffusion process, the impermeable regions require penetrant
migration around them which increases the average path length rela-
tive to the nominal dimensions of the membrane. There have been a
number of proposals to account for this tortuosity effect (e.g. ref. 4)
which can be generalised as:
(89)
where Da is the diffusion coefficient for a completely amorphous
polymer. Values of the parameter m have been reported as "arying
from about 0·3 for polyethylene 121 to about unity for PET. lOS
The tortuosity factor, T = 1Il0, where 1 is the actual migration path
length and 10 is the nominal film sample thickness, can be related to
various models for flow through media containing impermeable parti-
cles or porous media with non-linear pores. A particularly useful
model is based on an analogy with electrical conductance theory.121 It
assumes the crystalline domains to be a homogeneous dispersion of
66 C. E. Rogers
ablate or prolate spheroids so that:
(90)
where X is a shape factor related to the axial ratio, whose magnitude

decreases as departure from sphericity increases.
The crosslinking action of crystalline regions on sorption and trans-
port is based on the effects of crosslinking on those processes in
non-crystalline polymers. l .3 --{;,8.13 In those systems, diffusion coeffi-
cients decrease approximately linearly with crosslink density or the
reciprocal of the molecular weight between crosslinks at low to moder-
ate degrees of crosslinking. At higher densities the decrease is non-
linear.67 The solubility is relatively unaffected except at very high
degrees of crosslinking or when the penetrant significantly swells the
polymer.
The restraints of crosslin king on the segmental mobility of the
polymer make the diffusion process more dependent on the size and
shape of the penetrant molecule. Thus, the selectivity of the polymer
membrane is enhanced in agreement with the generally observed
correlation of increased selectivity with a decrease in diffusion rate
from almost any cause. Likewise, the decrease in inherent segmental
mobility makes the diffusion process more concentration dependent.
In crystalline systems the presence of effectively crosslinking regions
affects the sorption of solvents which swell the polymer. Isotherm data
can be represented using equations of the form: 116
(91)
where x~=[ln(al/<I>la)-<I>2aJ/cP~a is the value of Xl calculated for a

system disregarding the effect of the crosslinking restraint of swelling.
cPla and cP2a are the volume fractions of penetrant and amorphous
polymer, respectively, al is the penetrant activity, vl is the molar
volume of liquid penetrant, and Pa is the density of unswollen amorph-
ous regions. Linear plots of X~ versus <1>2;13 then serve to determine Xl
(the Flory-Huggins interaction parameter) from the intercept and Me
(the average molecular weight of amorphous polymer between crystal-
line domains) from the slope.
Equation (88) can be generalised4 by writing:
(92)
where {3' is a factor relating to chain immobilisation. Likewise, any
decrease in diffusivity can be expressed 121 as:

D = Dalr(3 (93)
where (3 > (3' == 1 for gases and poor solvents. The magnitude of (3 and
(3' would increase as the size and shape of the penetrant increase, and
as crystallite size decreases. Their dependence on solvent power and
concentration is more complex due to concurrent plasticisation and
crosslinking effects.
Orientation of polymer materials introduces an asymmetric structure
such that diffusion rates vary relative to the axis of orientation (e.g.
refs 4, 6, 13). Generally, the rate of penetration parallel to the axis is
less than the rate in a randomly oriented sample which is less than the
rate perpendicular to the axis. The validity of this generalisation is
dependent, in part, on the homogeneity of orientation. The generation
or disappearance of voids during orientation can affect subsequent
transport processes.
Deformation of elastomers does not appreciably affect S or D until
elongation results in crystallisation. The effects of orientation of semi-
crystalline polymers depend on the initial degree of crystallinity. The
large relative change of ordered regions by orientation of polymers
with low degrees of crystallinity (10-15%., e.g. PET) causes a signific-
ant decrease in transport rate. The minor relative change in more
crystalline systems leads to negligible changes in transport at low to
moderate elongations.
At higher elongations, the sorption and transport processes can be
significantly affected by deformation of the crystalline domain struc-
ture. 82 Very large decreases in diffusion rate with concurrent increase
in concentration dependence have been found with polyethylene and
certain other polymers. 82 Initial changes to increase transport can be
related to a strain-induced increase in free volume in either semicrys-
talline or glassy polymers. 82 ,122,123 In both types of polymer a subse-
quent decrease in transport rate as a function of time following
deformation was attributed to relaxation recovery of the deformed
structure. In glassy polymers,122.123 the recovery was faster for larger
penetrant molecules, suggesting that larger defects, or free volume
packets, were decaying more rapidly than smaller ones.
5.4. Heterogeneous and Multicomponent Systems

Sorption and transport in systems comprised of two or more compo-
nents or phases can be complex, depending on the nature and mag-
68 C. E. Rogers
nitude of component interactions, the amounts and distribution of the

multiphases, interphase mixing regions and any interfacial phenomena.
Since multiphase systems are very common in commercial practice, it is
a significant problem with, as yet, generally unsatisfactory solutions in
terms of expressions based on more rigorous theories.
Two simple cases can be considered for transport through n layers of
materials in series and in parallel. In series:
(94)
The rate of transport is the same across each layer so that for P not a
function of p or c:
n
lIP = L (x;/l)/P i (95)
where I = total thickness of the laminate of layer thickness Xi with

pressure gradient api and permeability constant Pi.
In parallel systems, each layer contributes to the total flux in an
additive manner. This can be expressed as:
(96)
where Ai is the area fraction of the i species and ap is the pressure
difference across the film of thickness l.
These equations constitute the lower and upper bounds for transport
in a composite mixture in much the same manner as modulus for a
composite. Indeed, a number of treatments of permeation have been
deduced on that basis for polyblends, particulate filler/polymer sys-
tems, fibre/polymer systems, as well as semicrystalline systems.124.125
A consideration of tortuosity effects in particulate filled systems
with particles of length L and thickness w gives: 125
T = 1 + (L/2W)cf>f (97)
where cPf is the filler volume fraction. By analogy to the expressions 121
for semicrystalline polymers this leads to:
(98)
where Pc and Pp are the permeability constants for the filled and
unfilled systems and cf>p is the volume fraction of polymer.
In cases where the filler is not well bonded or when the interfacial or
interphase region sorbs penetrant differently from the polymer matrix,
more complicated expressions must be used. For example, the total
permeation can be expressed as:

Pc == Pr(<pb*) + Pp(<Pp+ <Prp)/T (99)
where Pc, P r and Pp are the permeabilities of the filled polymer,
interface/interphase region and bulk polymer, respectively. The tor-
tuosity factor T* refers to the interphase region with an associated
volume fraction of sorbed penetrant <Pr.
These and related expressions, based generally on rules of mixtures
often accounting for domain shape and orientation, can provide useful
expressions for data representation. However, caution must be taken
when the constituent parameters are interpreted in a more rigorous
manner. For example, equating the transport coefficient in polymer
regions of a filled polymer to that coefficient in an unfilled polymer
neglects the effects on segmental mobility, and hence transport, due to
changes in polymer chain conformations related to polymer adsorption
on filler surfaces. This effect is somewhat akin to the crosslinking effect
on D and S in crystalline systems.
Sorption and transport in block copolymers, polyblends and other
composites generally have been approached along the lines discussed
above. These systems require additional consideration of interphase
effects which tend to complicate sorption and transport behaviour. The
available data regarding transport in polyblends have been re-
viewed. 126 The interphase regions often have higher sorption and
diffusion coefficients than the adjoining phases. A recently published
computer model for sorption and transport in polyblends 127 should be
of interest.
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126. H. B. Hopfenberg and D. R. Paul, In: Polymer Blends, Vol. 1, eds D. R.
Paul and S. Newman, Academic Press, New York, 1978, chap. 10.
127. 1. Sax and 1. M. Ottino, Polym. Engr. Sci., 23, 165 (1983).
128. B. K. Tikhomirov, H. B. Hopfenberg, V. T. Stan nett and J. L. Williams,
Makroll1ol. Che/Il. 118, 177 (I c)6S).
Chapter 3
Case II Sorption
A. H. WINDLE
Department of Metallurgy and Materials Science, University of

Cambridge, UK
1. Introduction . . 75
2. The Fickian Case 77
3. Sharp Boundaries 78
4. Linear Kinetics . 82
5. Theories of Case II Sorption 87
5.1. Established work . . . 87
5.2. Further developments. 89
5.3. Osmotic pressure theories 91
6. The Influence of Temperature and Penetrant Concentra-
tion . . . . . . . . . . . . . . . 99
7. The Induction Period . . . . . . . 103
8. Internal Stresses and Shape Changes 105
9. Super Case II. . . . . . . . . 107
<l.1. Overlapping precursors . . . . 109
9.2. Differential swelling stresses . . 110
10. Sensitivity of Case II Processes to the Physical State of
the Glass . . . . . . . . 111
10.1. Thermal history . . . . . 111
10.2. Mechanical history . . . . 112
11. The Limits of Case II Sorption 114
12. Conclusions. . . . 115
Acknowledgements .. 116
References . . . . . 116
1. INTRODUCTION
Since the advent of synthetic high polymers there have been many
observations of their ability to absorb substantial quantities of pene-
trating liquids. In some cases the equilibrium swelling is sufficient to
dOl'ble the original volume or more, and materials which are originally
75
76 A. H. Windle
hard and perhaps glassy become rubbers or gels. The early develop-
ment of interest in sorption phenomena was reflected in a general
discussion of the Faraday Society on Swelling and Shrinking in 1946. 1
At this meeting there were several reports of moving boundaries in
swelling polymer systems and linear, as opposed to Fickian, sorption
kinetics. A growing recognition of the reality and significance of linear
kinetics was marked some 20 years later by Professor Alfrey (a
participant at the 1946 meeting) who christened such behaviour 'Case
II'.2 Once named, the process has appeared to attract increasing
interest. The essential attrihutes, namely sharp step-like penetrant
profiles moving inwards from the surfaces with constant velocity which
give, for sheet specimens, weight gain plots which are also linear with
time, have now been frequently observed and widely recorded (e.g.
Fig. 1). Also, further detailed features of the process, such as the
induction period and front acceleration in the latter stages, have
recently been noted for some conditions. The last few years have also
shown significant developments of the theories of Case II kinetics
Fig. 1. A thin cross-section cut from a sheet of PMMA partially penetrated by

methanol showing the: sharp fronts associated with Case II sorption. The top
and bottom edges of the section are the faces of the sheet specimen, and the
right-hand extremity one edge of the sheet. The methanol was stained with
iodine to darken the penetrated regions.~
Case II sorption 77
which, while drawing on already established views as to the importance

of solvent generated stress and the resultant time dependent mechani-
cal response, have enabled the essential features of the process as well
as some more detailed aspects to be predicted for a wide range of
conditions.
2. THE FICKIAN CASE
Fick's adaptation of Fourier's heat transfer equations has led to the

renowned law:
aC_~(Df)C) (1)
at ax ax
As written the equation applies to diffusion in one dimension. It is
also based on the assumption that no volume changes are associated
with the movement of the penetrant. For the case where the diffusivity,
D, is independent of the penetrant concentration, C, it is possible to
write down solutions of the form:
C(x, t) = C o(1- erf x/(2mt)) (2)
where boundary conditions C(O, t) = Co and C(x, 0) = 0 have been
applied.
The concentration profile at any time, t, will have constant
mathematicai form differing only in scale as penetration proceeds with
time. It can thus be plotted against a reduced distance function as in
Fig. 2. The rate at which the concentration profile moves into the
material can be determined by using the Boltzmann transformation 4 of
1·0.--------~-------___,
c
c(x~O) 0·5
~__~__~~~--~==c=====d
o 20 4·0
X x (Ot)-t
Fig. 2. Concentration profile for unidirectional penetration as predicted by

Fick's equations.
78 A. H. Windle
1·0r------------==~__,
~
M~ 0·5
o 0·5 1-0
t~ x(D'tl)
Fig. 3. Plot of the fractional weight increase against t 1/2 for penetration of a
sorbant into a plane sheet. The curve is calculated for constant sheet thickness
(no swelling) and constant diffusion coefficient.
eqn (1) to give:
G:) c = [(D, C)t 1l2 (3)
Hence taking a particular value of concentration, say C o/2, to define

the depth of penetration, it is apparent that the penetration will
increase with t 1/ 2 •
Consequently, for a semi-infinite medium the mass of penetrant
sorbed will also be dependent on t 1/ 2 . In the case of a sheet sample of
thickness l, but of unbounded lateral extent, immersed in an appro-
priate penetrant, the two profiles will approach each other from the
opposite surfaces. It follows that the low concentration tips of the
profiles, which in accord with eqn (2) are of potentially infinite extent
at all finite times, will overlap immediately and as sorption proceeds
the rate mass uptake will fall behind the t 1 / 2 law eventually approach-
ing the equilibrium sorption at long times. Such behaviour is illustrated
in Fig. 3 as a plot of M,/Moo versus t1l2 calculated for a sheet of finite
thickness but infinite area. (Here M, is mass uptake at time t and Moo is
mass uptake at equilibrium.)
3. SHARP BOUNDARIES
The transparency of many polymers, allied with their ability to absorb

substantial amounts of penetrant liquids without dissolving, means that
it is possible to observe and measure the sorption process optically.
Such information can then be related to the results of the more
traditional mass/time measurements. Comparatively early studies of
Case [/ sorption 79
C A
-----
o B
Fig. 4. Experimental plot adapted from Robinson (1946),7 of optical retarda-
tion as a function of depth for the unidirectional penetration of acetone into
cellulose acetate film sandwiched between glass slides and constrained so that
swelling i!> only possible in the direction of penetration. The penetration is into
the edge of the film and from the right on the diagram. The sharp front
marking the limit of penetration is apparent as the discontinuity in optical
retardation at A-B. The protected edge (to the left) is marked by C-D.
sorption by cellulosic polymers showed that liquids appeared to move

into the material behind sharply delineated fronts.
First observations of boundaries in polymer systems were made by
Hartley5,6 and by Robinson,7 Figure 4 shows the variation of optical
retardation associated with the edgewise sorption of acetone by cellu-
lose acetate held between microscope slides. The acetone is entering
from the right and the line A-B marks the position of the advancing
front. A photograph 5 of a front of methylene chloride advancing
radially into a disc of cellulose acetate clamped between glass sheets is
reproduced in Fig. 5. The liquid has entered the constrained disc of
polymer at its circumference and the circular front is clearly visible
inside the birefringent zone. The four-fold contrast in this zone is
associated with the radial extension of the polymer on swelling and its
transient nature in this system is presumably due to the relaxation of
this orientation.
Although moving boundary phenomena are well known in cases of
reaction fronts and phase changes such as the melting of ice, the
concentration profiles predicted by Fick's equations with constant
diffusion coefficients are in no sense sharp boundaries. It is important
to note, however, that any assumption of constant diffusion coefficient
is likely to be highly inappropriate for swelling polymer systems. In
80 A. H. Windle
Fig. 5. A photograph, between crossed polars, of a front of methylene chloride

advancing radially into a disc of cellulose acetate film with the plane surfaces
protected by glass. The front is the innermost circle and the birefringence
generated by its passage decays a short distance behind it. (Reproduced, with
many cases swelling penetrants plasticise a polymer glass to the extent

that it becomes a gel, and the consequent increase in diffusion coeffi-
cient (D) can be several orders of magnitude. Solutions of Fick's
equations are possible where D is a given function of the penetrant
concentration C. In general, it is apparent that where D increases with
C there is a tendency for the concave Fickian concentration profiles to
become convex. This trend can be seen in a series of profiles calculated
by Crank8 and reproduced in Fig. 6. In this example the diffusion
coefficient is exponentially related to the concentration as D =
Do exp (kC/Co) and the values on the curves are exp (k). The distance
scale is normalised to (4D ot)1!2. Where D is steeply dependent on C,
as in the profile for exp (k) = 200, it is possible to begin to identify a
front, albeit a diffuse one, which would become more clearly defined
for yet steeper dependence of D upon C. Crank8 has taken the logical
extension to this argument and calculated the profiles where D in-
creases discontinuously at a critical value of concentration. Sharp
fronts are obtained as shown in Fig. 7 for the particular condition
where D is zero until the critical concentration Cx is reached where it
Case II sorption 81
0·7
0·6
0'0'5
G
0·4
0·3
oJ
0·1
Fig. 6. Concentration profiles calculated for the case where the diffusion
coefficient (D) increases exponentially with concentration. The numbers on the
curves are the ratios of D at the equilibrium concentration, Co, to that at zero
concentration. (Reproduced, with permission, from ref. 8.)
becomes D\ and remains at this value for increasing concentration up

to the equilibrium value C\. The fractions on the curves denote the
ratios Cx/C\.
It is possible, therefore, by choice of suitable relationships between
diffusion coefficients and concentration, to obtain from Fick's equa-
tions predictions of moving boundaries similar to those observed by
Hartley and Robinson. It is important, however, to enquire as to the
kinetics of such moving boundaries. Firstly, the Boltzmann transforma-
tion, eqn (3), is true for a varying diffusion coefficient provided that it
is a unique function of concentration and not independently influenced
by either time or concentration gradient. It follows that a point of fixed
concentration marking the advancing front will move as t 1 / 2 , as is in
fact implied by the normalisation of the ordinates of both Figs 6 and 7
to (4Dt)I/2. Correspondingly, the fractional weight gain for Fickian
moving boundarie~ is still initially proportional to t \/2; moreover, this
relationship is maintained to much larger values of M,/M= than in the
82 A. H. Windle
10
075
~050
0·25
c, c,
0-0 0-2 0-4 0-6 08

x/(4D,r)!
Fig. 7. Concentration profiles calculated for a discontinuous dependence of the

diffusion coefficient (D) on concentration as shown in the inset. The fractions
on the curves are values of the ratio CxfC l (Reproduced, with permission, from
ref. 8.)
case of a constant diffusion coefficient and diffuse concentration

profiles.
The sharp boundaries observed in polymer-penetrant systems can
thus be predicted from Fick's equations where D increases discontinu-
ously with C. However, the predictions also define the kinetics, namely
that both the positions of the fronts and the initial fraction weight gain
are dependent on t1l2.
4. LINEAR KINETICS
From the earliest studies of polymer-penetrant systems, the expected

t 1/2 weight gain kinetics have been observed, as have sharp fronts
moving with the same time law (e.g. ref. 5). However, it rapidly
became clear that some systems, especially those with larger equilib-
rium uptakes, show an entirely different type of kinetics in which the
sorption was directly proportional to time. Probably the first observa-
tions of linear rather than t 1 / 2 behaviour were made by J. R. Scott in
Case II sorption 83
.....-_ _ _ _ _ _ _ _ _~- _ _ _ _ _- I I
90
10
Time of Immersion-Hours
Fig. 8. The first observation of linear swelling kinetics for sheet specimens
recorded by Scott (1937).9 The polymer was ebonite and the penetrant
benzene. The different curves cover a range of crosslink densities from 26%
combined sulphur (specimen 11) to 32% (specimen 4). The vertical dashed line
marks a change in the (linear) time scale.
1937.9 He worked with ebonite, a heavily crosslinked natural rubber

which is a glass at room temperature, and found that many organic
penetrants gave weight increase-time curves which were substantially
linear. A set of his curves for sorption of benzene by ebonites of
different crosslink densities are shown in Fig. 8. In general the higher
the crosslink density (measured as percentage combined sulphur) the
slower the rate and the smaller the equilibrium swelling. The speci-
mens were 2 cm x 2 cm x 5 mm sheets and no correction for edge
effects was made which can explain in part some of the residual
curvature of the near linear plots. Observations of sharp penetrant
fronts which moved linearly with time were also reported, initially by
Hartley6 for the sorption of methylene chloride along the extension
axis of oriented cellulose acetate.
In recent years, the existence of linear kinetics in many polymer-
penetrant systems has been firmly established and widely accepted.
84 A. H. Windle
The vast majority of evidence has come from measurements of weight-

gain, although there have also been some microscopic observations of
front movement. It is interesting to note that the practice of plotting
sorption data against t 1/2 in order to test for Fickian characteristics, has
meant that linear kinetics have sometimes been overlooked. For exam-
ple, the sigmoidal mass versus (time)li2 curves of Andrews et al.lO for
the sorption of a series of alcohols by PMMA did in fact become
excellent straight lines when simply replotted against time. 11
Alfrey and co-workers,2.12 in addition to reporting linear kinetics in
the polystyrene-acetone system and also discussing possible stress
effects, took the very significant step of calling such behaviour Case II
sorption. In thus identifying a second limiting type of diffusion, charac-
terised by linear kinetics and distinct from Fickian (or Case I) be-
haviour, they have helped to establish a framework within which yet
more complex examples of behaviour can be understood.
The PMMA (Perspex)-methanol system has been extensively
studied by Thomas and Windle. 3.13- 17 It has the advantages that the
polymer glass is available in a reproducible form and the time scale of
the sorption is convenient for specimens 1 mm thick over the tempera-
ture range 0-65°C. At 30°C and below, the system shows linear mass
sorption kinetics and a sharp penetrant front which moves at constant
velocity. It thus provides an excellent example of Case II behaviour.
Figure 9 shows the weight gain with time compared with the measure-
ments of front position. The time at which the weight gain abruptly
ceases corresponds to the observed meeting of the opposing fronts. In
these experiments the fronts were rendered more visible by staining
the methanol with 15 g dm"3 of iodine. The iodine entered the polymer
along with the methanol, and experiments in which its concentration
was varied showed that it had no effect on the rate of front traverse,
although the increased density of methanol containing iodine meant
that the apparent equilibrium weight gain was increased. It is also
noteworthy that there are two ways of defining the front position;
either in relation to the original position of the specimen surface
before swelling commenced, which will give the rate of front penetra-
tion into the glass ahead of it, or in relation to the position of the
actual specimen surface as it swells. These parameters, defined as d
and I, respectively, are both plotted in Fig. 9. Further experiments also
demonstrated that the colour density of the iodine across a section cut
from the specimen was a reliable indicator of methanol concentration,
Case II sorption 85
-----------------.---~,
2-0
"E
~
01 • : fronts
have
I met
(II
~
f 1·0 I
?
'Ii
I
I
01 I
~
E I
r
E o·s I fronts
.e
c
o
o
I met
~
I have
I
~02S I
QI o I
a..
10 20 30
time - hrs
Fig. 9. Experimental plots of weight increase per unit area and the front
penetration parameters I and d against time for absorption of liquid methanol
by PMMA at 30°C. The specimens were 40mmx20mmxO·93rnrn thick and
the equilibrium absorption was 24% W/W.14
and remained as such even though the methanol itself may subse-
quently desorb from the thin section. Optical densitometer scans across
the sections (Fig. 10) showed the fronts, which were sharp to within the
resolution of the optical microscope, and also the negligible concentra-
tion gradients behind them. Examination between crossed polars while
sorption was taking place indicated that the swollen material had
deformed by stretching in a direction normal to the front, in agreement
with the original observations of Hartley. 6 This extension is understood
as the consequence of swelling under conditions of area constraint,
provided in this case by the unpenetrated glassy core.
The most simple defining characteristic of Case II sorption is the
occurrence of a linear relationship between the mass of penetrant
86 A. H. Windle
.,c:
'5 c
.2
'0
!:
.;;;
.,c:
-c
Iii
.~
C.
.,>
0
"Z
"§'"
t=22 Hrs t =24 Hrs
distance
Fig. 10. Optical density scans across thin sections cut from 1 mm sheets of
PMMA after penetration at 30°C by methanol coloured by iodine for the times
indicated,14
absorbed and time, It is apparent that such linear kinetics require that:
(a) there is a negligible concentration gradient behind the sharp fronts
and hence step-type profiles;
(b) the fronts advance with constant velocity; and
(c) an infinite sheet sample so that the direction of penetration is
along one 'axis only.
The inclusion of a particular sample geometry as a requirement for
the Case II process is not especially satisfactory and it is probably
better to recognise the process in terms of the two conditions (a) and
(b), Hence a sorb ant penetrating a sphere with a constant velocity front
behind which there is no significant concentration gradient, while not
giving rise to linear weight gain kinetics, should nevertheless be classed
Case II.
Case II sorption 87
5. THEORIES OF CASE II SORPTION
5.1. Established Work

So far we have focussed on the essence of Case II behaviour, that is,
sharp penetrant fronts which move linearly with time. There are many
more detailed aspects of the process, some of them very significant,
which have been recorded. They will be discussed later. This section
describes the approaches developed to model and understand the basic
linear Case II kinetics.
Scott9 considered his linear sorption plots to be the consequence of a
diffusion coefficient which increased on swelling, and incidentally drew
attention to the possible contribution to linear behaviour from the
formation of cracks which he sometimes observed. Hartley6 went
further and suggested that as a constant velocity front violated
Boltzmann's formulation of Fick's law, the diffusion coefficient could
no longer be a single-valued function of concentration, but must also
be history dependent. He also proposed that 'in the extreme limit' the
rotational diffusion of molecules may become the rate determining
process. The basis for the development of theories was thus laid.
The idea of a history dependent diffusion coefficient was developed
by Crank. 18 The dependence is expressed by:
(-aD) = (aDi)
-
at z aC at z
(ac)
- +ex(De- D ) (4)
where Di is the component of Dwhich changes instantly with concent-

ration, De is the equilibrium value of D and Z is a position coordinate.
Hence, the final term represents a change in diffusion coefficient with
time which is proportional through the rate parameter, ex, to the
amount by which D is less than the eqUilibrium value. With suitable
choice of parameters, it was possible to predict many of the features of
Case II sorption plots although not directly the sharp fronts. In the
same paper, another important idea was introduced: that of the
influence of differential swelling stress. It is an experimental fact that
the area of the swollen part of a sheet is effectively the same as that of
the unpenetrated core, so that elastic deformation necessary to com-
pensate for the swelling will lead to an internal stress distribution. The
stress on the swollen material will have a compressive component, that
on the core a tensile component, and the components must integrate to
zero. By assuming that the diffusion coefficients were simply dependent
88 A. H. Windle
on the stress levels he was again able to predict sorption curves which
showed aspects of observed Case II behaviour.
Another step in the prediction of anomalous sorption phenomena in
general was taken by Long and Richmond. IQ Their efforts were di-
rected at explaining the two stage sorption phenomenon in which
initial up-take appears Fickian, but subsequently settles down to linear
kinetics typical of Case II. They approached the problem by assuming
that the concentration in the surface layers of the polymer, Co,
increased with time beyond its initial instantaneous equilibrium value
of CoCO) according to:
(5)
where Co(oo) is the equilibrium concentration and (3 a rate parameter

which is assumed to be constant.
Incorporation of the time dependent surface concentration into the
boundary conditions in the solution of the diffusion equation, with D
constant, yielded two-stage sorption relations. It was found that the
stages were only clearly distinct when Dj/2 (21 is the specimen thick-
ness) is significantly greater than (3. If the two parameters were similar,
then a single 'anomalous' absorption process was observed. In one way
the model is unsatisfactory in that it is difficult to see why a relaxation
process should only apply to the surface; however, the significance of
the contribution is that it introduces the idea of a relaxation control on
concentration, rather than on diffusion coefficient as in Crank's
theories.
A different approach was introduced by Peterlin. 20 The diffusion
equation was rewritten to incorporate a term to describe the move-
ment of a front with constant velocity v:
ac =.~ (D ac _ vc) (6)

at ax ax /
There has beel) some disagreement over the hest solution of the
equation in this form. 21 - 2 :1 However, the equation is designed to be
descriptive of the observed phenomena and, despite later modifications
and incorporation of aspects of the differential swelling stress treat-
ment,24 it still lacks any firm physical basis. Hence, even while it is seen
to provide an excellent fit to experimental data of the Case II type, it
does not at the same time increase our understanding of the process.
Case 1I sorption 89
5.2. Further Developments

In a series of papers25~27 Petropoulos and Roussis have extended the
development of Crank. They first rewrote the diffusion equation in
terms of activity gradient instead of concentration gradient:
ac a ( caa)
at = ax D-;; ax (7)
where the ratio Cia is often referred to as the solubility parameter, S.

They then followed Long and Richmond in applying relaxation control
to concentration, although with an equation which was an exact
analogue of Crank's for the time dependent diffusion coefficient, viz:
aC(a,
- - - t)
= aC(a, O) (aa) {( oo) -Cat
-+{3Ca ( )} (8)
at aa at ' ,
In this way the penetrant concentration profile is affected by the
relaxation process throughout the polymer, not just at the surface. The
two simultaneous differential equations can be solved by numerical
routines, but first it is necessary to specify the instantaneous relation~
ship between a and C and more significantly decide on the form of the
concentration dependence of D and (3. Using somewhat empirical
functions to reduce computing time-that is D(C)= 1 + 999(CICo?
and (3 (C) = 10 + 9000( CI Co? which mean that both parameters in~
crease very steeply with concentration-~Petropoulos28 obtained the
plots of Fig. 11. The sorption plot shows classic linear Case II kinetics
and the concentration profiles are sharp steps which move linearly with
time. There is a small gradient behind the front which could no doubt
be reduced if the diffusion coefficient was set to accelerate yet more
rapidly with concentration. (These curves, while possibly representing
the first successful prediction of all essential elements of Case II, have
not yet been published and the author is indebted to Dr Petropoulos
for his permission to reproduce them here.)
The fact that the 'rate constant' {3 must increase rapidly with
concentration in order to successfully predict Case II behaviour is
physically very reasonable, for increasing penetrant concentration will
tend to plasticise the polymer and thus enhance the rate of molecular
relaxations. However, possibly in order to provide addition rationale in
the choice of the form of the {3 function, Petropoulos has also
considerably extended the differential swelling stress approach. While
determining internal stresses in much the same way as Crank, the
90 A. H. Windle
A i" 0·0045
B i" 0·011
C i" 0·021
0 j" 0 031
E i" 0 041
0-6
,,0
Q
0·3
C
o 4
Fig. 11. Sorption plot (weight gain versus time) and concentration profiles
calculated by the simultaneous solution of equations for aC/at. These results,28
although unpublished, are based on the methods of Petropoulos and
Roussis2s-27 and represent one of the first successful predictions of sharp
penetrant fronts which move linearly with time. (Reproduced, with permission,
© J. Petropoulos.)
additional step is taken to describe the relaxation of stress in terms of a
mechanical equivalent model of a standard linear solid. The form of
the model used has a Maxwell element of elastic modulus G 1 and
viscosity 'Tj in parallel with a 'weaker' spring of modulus G 2 • The
characteristic rate constant, (3 = G1/'Tj; and (3 as well as both elastic
moduli are functions of concentration (C). The evolution of the stress
function, <T(X, t) is thus obtained by solving the constitutive equation
of the model. For a given position, X, it depends in a complicated way
on the detailed sorption history of the sample. However, once ob-
tained, the stress function is used to control the diffusion process
through its perceived influence on either the diffusion coefficient, D, or
the solubility parameter, S (= C/ a)
viz:
D(C, <T) = D(O, 0) exp (k1C+ k2<T)
or (9)
Case II sorption 91
t
Qt
Q-
0.16
t-
Fig. 12. A set of sorption curves calculated on the basis of eqn (9) for different
dependences of the diffusion coefficient (D) on the relaxing stress. 29 Curve 1
corresponds to zero stress dependence and all curves in this example incorpo-
rate the same increase in D with increasing concentration.
Here kl' k2' k3 and k4 are constants. By substitution of these equations

into the diffusion eqn (7) with the correct choice of parameters, it is
possible to obtain sorption-time curves with linear portions (Fig. 12).
However, some curves can show a tendency to curve upwards despite
the linear rather than t l/2 timescale. Such an appearance is reminiscent
of so-called Super Case II behaviour observed in some systems and
discussed in Section 9. However, for this model the quasi-linear
sorption plots are not associated with the sharp penetrant fronts
characteristic of Case II processes. It seems that, although the presence
of differential swelling stresses can cause sorption kinetics to be
profoundly non-Fickian, their influence in not 'of the essence' in
determining Case II behaviour.
5.3. Osmotic Pressure Theories

The description of an equilibrium swollen molecular network in terms
of an osmotic pressure component in the absorbed liquid which is
balanced by the residual elasticity of the network itself, as developed
by Flory,30 is relevant to sorption phenomena where the swelling of the
polymer is constrained for kinetic or structural reasons. The osmotic
pressure over and above that which balances the entropic forces of the
92 A. H. Windle
molecular network at equilibrium swelling is given by:

7T(X, t) = (RT/V) In [a (X, t)/a(X, (0)] (10)
where a(X, t) is the penetrant activity in the polymer, a(X, 00) is equal
to the activity of that same concentration of penetrant after complete
relaxation of the polymer and V is the partial molar volume. The fact
that the rate of volume relaxation of the polymer could be related to
the osmotic pressure through the stress sensitivity of thermally acti-
vated mechanical deformation was originally suggested by Newns 31 in
the context of the phenomenon of two-stage absorption curves, and
subsequently underlined by Park?2 This basic idea is at the root of
explanations of Case II sorption developed by Peterlin,33.34 Thomas
and Windle13·15.35 and, for the specific case of samples which craze as
they swell, by Sarti?6.37
Peterlin's mathematical treatment is based on the assumption of a
sharp penetrant front which moves at constant velocity. Given such a
situation, it is able to predict profiles both for concentration, which
show a discontinuity (the sharp front), and for activity, which do not.
The step-type profiles which are reproduced in Fig. 13 result from
discontinuities in the dependence of both the diffusion coefficient and
the solubility parameter (C/a) on penetrant activity. The calculations
are important in that they predict a Fickian type precursor penetrating
ahead of the sharp front, but the theory in general is limited in scope in
0.5
vX!D,
OL-__ ~ ______ ~ ____ ~~=- __ ~~
-2 o 2 4
Fig. 13. Diagram due to Peterlin" showing the calculated form of profiles,
both concentration (the lower profile with the discontinuity) and activity
(expressed as a ratio of vapour pressures, PIPo) , associated with a penetrant
front moving at constant velocity.
Case II sorption 93
that it does not independently predict the central aspect of Case II

transport, that is, the linear kinetics themselves.
Thomas and Windle 15.35 have modelled the processes occurring at
the front in terms of the viscous response of a swelling element of glass
to the osmotic pressure of the penetrant. The first small amount of
swelling in the precursor ahead of the front creates space for further
penetrant molecules to enter the element; the plasticising effect of
these molecules causes the viscous creep to occur at a greater rate; the
next penetrant molecules enter more rapidly and so on. This 'au-
tocatalytic' response, which is a consequence of a strongly
concentration-dependent viscosity, continues until the concentration in
the element reaches an equilibrium value. Thus, most of the build-up
of penetrant in an element of polymer occurs in a time which is much
shorter than the time increment between the 'filling' of successive
elements. This is the condition for a sharp front. In developing the
model quantitatively, these authors have used the simple relation for
osmotic pressure (eqn (10)) but with the fractional (actual/equilibrium)
concentration v(X, t) instead of a (X, 00). The next step has been to
consider the swelling of a glassy surface element thin enough so that
diffusional resistance can be neglected. They therefore assume that on
immersion in the pure penetrant liquid, the activity of this liquid is
immediately unity throughout the element, and hence
7T(t) = - (RTf V) In v(t) (11 )
Being a glass, the element is seen as initially resistant to swelling,
either on account of the rearrangements of the molecular network
required to increase its volume or because of the shape change
necessarily associated with volume increase where the area is con-
strained by the unpenetrated rigid glassy polymer ahead of the ele-
ment. The mechanical response of the element is initially taken as
viscous, with the viscosity exponentially dependent on concentrations
according to:
where M is a constant and TJo the viscosity of the pure polymer. Hence,
the rate of strain
and is proportional to aVjat which it effectively controls. Thus,

av 7T - RT
-=-=---In ii exp[Mv] (12)
at TJk VkTJo
(Here k is a constant of proportionality between E and ii, i.e. Ek = ii.)
94 A. H. Windle
'·0..--------,------,
I> 0·5
5
Time h
v with time for a
Fig. 14. The increase in fractional penetrant concentration
very thin sample from eqn (12) using parameters appropriate to the system
PMMA-mcthanol."
Estimates of parameters for the PMMA-methanol system at 24°C give

the prelog factor as 1· 35 x 10- 6 m 3 S-1 and M = 15. Numerical integra-
tion of eqn (12) gives the concentration-time plot of Fig. 14. An
induction time during which swelling is slow, followed by a sudden
increase in concentration to the equilibrium value after 4 h, is clearly
apparent.
The extension of the model to account for sorption by bulk speci-
mens involved the simultaneous solution of eqn (12), rewritten for the
Xth element and thus involving the actual activity in that element
which will not be unity as in the surface element:
( av) = -= RT In (~) exp [Mv] (13a)

at x VkTJo a x
and the diffusion equation:
( av\) =~ {D(V)(~) aa} (l3b)

at x ax a ax
The method of solution of these equations, using an alternating
approximation method, produced convergent results under the major-
ity of conditions; however, very recent work has shown that a standard
finite difference approach, while giving equivalent predictions, is able
to avoid stability problems. 38
Figure 15 shows the results of the Thomas-Windle theory using
parameters for PMMA-methanol at 24°C compared with experimental
a
a
10~ -~
Of
Thlckrltl'ilS at PMMA sh~li!t (I 18 mm bli'torC/' sWII'II,ng)------i
o
O.stanct:
b
51 ~~
I ()
I
r I
a. I
E I
'"'"'"
~ 20 I ::::
I
I Q
'"
£ I
E I ~
E I
a)
- I
g.
,.......-
j Front~ hoyt'm(t
!'I
~ I 1i
I
'"
I
/ 10 I
I
I
~ I
g, I
I
;: I
100 150 200 250 I
T,ml!' (hours)
I
.l.......c..-
50 75 100
T'lnt' (tlours)
Fig. 15. Concentration profiles and sorption plot predicted by the Thomas-Windle theory (left-hand diagrams)
compared with experimental measurements made on the PMMA-methanol system. 35 The parameters used in the
calculations were those corresponding to this system with 1 mm thick specimens at 24°C, namely, a diffusion coeffi-
cient of 10- 14 m 2 S-1 which increases with concentration according to the factor exp (6·2 v), a viscous deformation rate
'-0
for the unpenetrated polymer of 5 x 10- 15 S-1 MPa- 1 and a factor M of 15. The calculated concentration profiles are u.
plotted at 10 h intervals, and the measured profile is for 60 h.
96 A. H. Windle
results under these conditions. The agreement is satisfying. In fact, it is

better than that entitled on the basis of the uncertainty of the values
for the various materials parameters. This theory is thus able to predict
sharp diffusion fronts propagating at constant velocity as well as linear
weight gain kinetics, in fact it accounts for the essential features of
Case II sorption, both qualitatively and quantitatively. The calculated
profiles of Fig. 15 (top left) show the precursors ahead of the fronts,
which although not visible on the experimental traces are of very
similar form to those calculated by Peterlin. A small concentration
gradient is predicted behind the fronts but there is substantial variabil-
ity in the slopes from time element to time element. The variations are
a consequence of the limited number of positional elements (fifty). The
rapid 'filling' of an element takes much less time than the interval
between the filling of successive elements, and when an element fills,
there is a transient steepening of the gradient behind it. The precise
relative positions of the front and the elements are not the same at
each time increment and thus differences in concentration gradient are
apparent.
It is interesting to note that the two theories which have been most
successful in predicting sharp fronts which move linearly with
time,27,28,35 have both employed simultaneous solutions of two equa-
tions for iJC/iJt, one being the diffusion equation, the other a descrip-
tion of relaxation control. The relaxation equations differ and invite
comparison (i.e. eqns (8) (Petropoulos and Roussis) and (12) (Thomas
and Windle), Firstly the equation of Petropoulos and Roussis has an
additional term (the first) which involves the relationship between
concentration and activity, as iJC/iJa, in the absence of any relaxation.
For a polymer glass this factor is likely to be small (of the order of a
few percent) and so may not be especially significant. However, it
represents an omission from the Thomas and Windle theory and
should ideally be incorporated. The relaxation terms have some simi-
larity in form; the {C(a, (0) - C(a, t)} term of Petropoulos and Roussis
plays the same role as the (In v -In a) osmotic pressure term of
Thomas and Windle. Correspondingly, the (3 term of Petropoulos and
Roussis [10+9000(C/Cn?] is equivalent to the Thomas and Windle
viscous response relation [(1/'T)())(exp [Mv])].
Thomas and Windle 35 have been able to use their model to explore
the osmotic pressure distribution ahead of the front. For the system
considered the pressure reaches a maximum, of the order of the yield
stress of the polymer glass. 70 fL m ahead of the front as defined by
Case II sorption 97
the discontinuity in concentration. The pressure increases most rapidly

with distance at the front itself, and it is apparent that the front is
stabilised by the balance of a very steep concentration gradient in one
direction and an equivalently steep pressure gradient in the other. The
net result is the absence of any rapid change in activity (or chemical
potential). Another important aspect of this model is the demonstra-
tion that a sharp front is still predicted even if the diffusion coefficient
is unrealistically assumed to be constant across both swollen and
unswollen regions. The profiles (Fig. 16) show substantial precursors
and also large concentration gradients behind the fronts, so that the
weight gain kinetics would be far from linear; also, it is apparent that
the sharp fronts would not survive beyond a particular depth of
penetration. At this stage it becomes clear that although the model can
account for sharp fronts, a diffusion coefficient which increases mar-
kedly with concentration, albeit without discontinuity, is a necessary
I>
_ _ ~L-~~~~~~~
o
~~~~_~
01 02 03
Distance (m m)
Fig. 16. Calculated penetrant concentration profiles, corresponding to the

PMMA-methanol system, except that the diffusion coefficient is held indepen-
dent of penetrant concentration at a value of D = 8 x 10 "m2 S-I. The sharp
front is still predicted."
98 A. H. Windle
additional criterion for Case II behaviour which requires step-like

profiles to give linear sorption kinetics.
From the first observations by Scott9 it has been recognised that
cracking may be associated with Case II type processes. However,
Michaels, Bixler and Hopfenberg 39 found that sorption of Ii-heptane in
polystyrene led to extensive bulk crazing in the swollen regions. Such
craze networks, which consist of interconnected microvoids, appear to
nucleate at the Case II front and represent localised plastic instability
in the polymer. Crazing as a consequence of Case II sorption has been
observed in several n-alkane polystyrene systems. The reason why
polystyrene has this rather special property is not properly understood
although it may be associated with its known propensity to develop
highly localised regions of plastic flow such as shear bands.
Sartj36 has developed a theory of Case II sorption especially applica-
ble to polystyrene systems which craze as they swell. His calculation of
the osmotic pressure driving forces has taken into account the chemical
non-ideality of the system, through the Flory-Huggins interaction
parameter, x. The critical step is the use of the reported kinetics of
planar craze propagation in the dry polymer as a function of the
applied tensile stress, to predict the rate of Case II front traverse in
response to the tensile component on the polymer generated by the
osmotic pressure.
Given that craze propagation is described by:
Ac = K(O' - O'J
where the critical stress, 0'0' is a linear function of the difference
between test temperature and the glass transition temperature and K is
dependent on temperature through an activation rate equation, the
corresponding traverse rate for a Case II front is held to be:
(14)
The parameter a relates tensile stress to osmotic pressure and is
taken to be between 1 and 3; it is also used as a model parameter in
that its value is calculated from eqn (14) where AI- is experimentally
observed, and its reasonableness can be used as a measure of the
predictive success of the model. Used in this sense a is found to range
from 0·85 to 7·0 for four different polystyrene-alkane systems over a
range of temperatures. A later modification 37 introduces an additional
'out of equilibrium component' of the osmotic pressure, '/T E , which is
seen as being associated with the excess free volume frozen into the
Case II sorption 99
polymer glass. However, whatever its exact physical basis, its inclusion
reduces the variation of the parameter a to between 1·4 and 2·6 which
is most satisfactory.
The work of Sarti is important in that, as well as being the first
successful development of the osmotic pressure approach, it provides a
way of modelling linear front kinetics in terms of another, albeit
equally complicated, mechanical phenomenon. Its limitation, however,
is that it is only useful when Case II sorption is accompanied by crazing
at the penetrant front, and it is thus not strictly relevant to systems
other than those based on polystyrene.
6. THE INFLUENCE OF TEMPERATURE Ac~

PENETRANT CONCENTRATION
Not surprisingly, increasing temperature enhances the rate of Case II

sorption and, for many systems, it also increases the equilibrium
sorption. However, there is another effect of temperature which is also
significant: a system which shows linear weight gain kinetics at ambient
temperature will tend towards Fickian, t 1 / 2 dependence as the temper-
ature is increased. In fact, as Hopfenberg and Frisch pointed out,40
given a sufficiently wide range of temperature a particular system could
be expected to show a full spectrum of behaviour from linear to t 1 / 2
kinetics. The behaviour at elevated temperature of an otherwise Case
II system is shown clearly by PMMA-methanol where the front
profiles are rendered visible by the iodine staining technique. Figure
1714 shows both weight gain and front position measurements at 52°e.
The weight gain kinetics are far from linear and the fronts are
observed to meet when the sorption is little more than half complete.
The front velocity also decreases as penetration proceeds. The meas-
ured penetrant profiles of Fig. 18 provide the link between the weight
gain and front position plots. The concentration gradient behind the
fronts is steep and it is clear why the time at which they meet does not
mark the achievement of equilibrium sorption. The reason for this
changed behaviour also becomes apparent, for whereas increasing
temperature leads to an increase in diffusion coefficient, it in fact leads
to a greater increase in front velocity. Hence, the penetrant supply to
the advancing fronts becomes relatively more difficult and steeper
gradients develop.
Quoted values for the activation energy for the process controlling
100 A. H. Windle
a
40
"E
~
!?}
0 30
~
0
c
.2. I
c
0
20 I
'" I
~ r---- Fronts hove met
'"
~
c;, I
I
I
I
I
b
050
B
E
E
I
c
I
g
0
025
r- Fronts have met
..'"
c
a.
I
I
I
I
0 100 200
Time (min)
Fig. 17. Weight gain and front penetration measured for PMMA-methanol at
S2°e. The solid points on the weight-gain plot are calculated from measured
penetration profiles. 3
front velocity have ranged as high as 425 kJ mor- 1 for PMMA-fl-

butane,41 but their measurement presents problems as the concentra-
tion at the front is not constant with time and in any case the
equilibrium concentration itself varies with temperature. The availabil-
ity of profile measurements for PMMA-methanol and hence the full
relationship between penetrant concentrations at the front, front veloc-
ity and temperature, means that it is possible to construct a plot from
which the log rate-temperature relation can be inferred at any fixed
concentration. An Arrhenius plot for this system gives a reasonably
straight line and an apparent activation energy of around 105 kJ mol-I.
Case 1I sorption 101
I>
32 min
61 min
°1~.~==~~~~~====~~·1
Thickness of PMMA sheet (I 14 mm before swelling)
Fig. 18. Concentration profiles measured for PMMA-methanol at S2°C."
This value is within the range of those reported for creep of glassy
PMMA, i.e. 80-125 kJ mor- 1 42.43 but clearly larger than those held to
be typical for diffusion processes, i.e. 40-60 kJ mol-I.
The theory of Thomas and Windle has been used to explore the effects
of changing the ratio of diffusion coefficient (based on that in the
unswollen glass) to viscous flow rate at the front. Figure 19 shows
calculated profiles and a sorption-time plot for the case where the
viscous flow rate has been increased by an order of magnitude and the
diffusion coefficient decreased by the same factor with respect to the
values appropriate to room temperature which predicted the classic
Case II behaviour of Fig. 15. The high temperature process is thus
modelled to give good agreement with the experimental behaviour at
52°C shown in Figs 17 and 18. There is, however, another prediction
of this theory which should be noted. Under conditions where the
sorption is completely Case II, the front velocity is shown to depend
equally on the diffusion coefficient, D, and the viscous flow rate E
(figure 15 of ref. 35), and an equal change in each (in the same sense)
is required to produce an equivalent change in front velocity. Hence,
front velocity
d = A(iD)I/2
where A is a constant.
A consequence of this dual dependence of front velocity is that an
apparent activation energy derived from velocity measurements will be
c
o
;;
I> Q.
o
III
~
,
f
Distance o 50 100 150 200 250

a Time (hours)
b
D =
10- 15 D·IO- 15
1/'10=5 x 10- 14 1/'1]0- 5 x 10 14
Fig. 19. (a) Concentration profiles and (b) equivalent sorption plot calculated for PMMA-methanol," with the diffusion
coefficient decreased by an order of magnitude and the viscous deformation rate increased by the same factor with respect
to the values used in predicting the room temperature Case II behaviour (Fig. 15).
Case II sorption 103
the arithmetic mean of the activation energies for both viscous flow
and diffusion. It may thus be necessary to modify the activation
energies for viscous flow previously measured from front velocities.
Another approach to this issue is to measure the initial sorption
rates as a function of penetrant activity. A set of sorption curves due to
Kirby44 has been obtained as a function of the activity of the penetrant
vapour. The equilibrium swelling in the PMMA-methanol system is
very sensitive to the activity such that a reduction from 1·0 to 0·9
reduces the equilibrium volume fraction sorbed from 0·3 to 0·15. For
these experiments the initial rate of front traverse is not proportional
to the equilibrium concentration. Rather, it is more dependent on the
square of the concentration, although it is not easy to be certain about
the exact function.
7. THE INDUcnON PERIOD
Many reported Case II sorption plots show an induction period before

the linear portion of the curve is properly established. The effect is
apparent in the experimental sorption plot of Fig. 15. Examination of
this initial region with higher time resolution shows that the sorption
rate builds up gradually until the characteristic Case II rate is estab-
lished. Extrapolation of the linear portion back to intercept the time
axis gives a useful measure of the effect, the induction time. Wein-
berg45 fitted the early acceleration of the sorption to the empirical
relation:
(15)
where v is the front velocity, 1 the semi-thickness of the specimen, tj

the induction time and T a characteristic time. He also noted that tj was
independent of film thickness. Measurements of the induction time in
the PMMA-methanol system showed it to be very dependent on
temperature with an apparent activation energy of 120 kJ mol-I.
Perhaps not unreasonably, the induction period has often been
ascribed to a 'surface effect', and sometimes with the implication that it
is associated with a non-typical polymer structure in the surface layers
of the polymer. Such a view is strongly countered by the Thomas-
Windle theory which predicts an induction period as an intrinsic aspect
of Case II behaviour (see, for example, the calculated sorption plot of
I0 I-t---+--t~
,,
I
tI
~
§ ,,
~
I> o ,
'" ,, ""
o
~ ,/
,
,,
f
o +
Distance
LJ
o 50 100 150
Time (hours)
200 250
a b --13
D ~10-13 ~D -10 -16
- I/'1a~ 5 x 10- 16 1/'10=5xI0
Fi~. 20. (a) Concentration profiles and (b) equivalent sorption plot calculated for PMMA-methanoI 3 :i for the condition
of a diffusion coefficient D, an order of magnitude greater than for the room temperature case (Fig, 15), and a viscous
deformation rate an order of magnitude less.
Fig. 15). For conditions in which the viscous flow rate of the glass is
slow compareo with the diffusion coefficient (corresponding to low
temperature behaviour in the PMMA-methanol system) the induction
time is predicted to be almost as long as the time required for the
fronts, once established, to traverse to the specimen centre. The
concentration profiles and sorption plot shown in Fig. 20 are calculated
for conditions in which the viscous flow rate is an order of magnitude
less, and the diffusion coefficient an order of magnitude more, than for
the calculated plots of Fig. 15. Under these conditions the profiles
show a substantial Fickian precursor ahead of the front, and the
induction period is a dominant feature of the sorption plot. A further
prediction of the same theory is that, unlike the front velocity, the
induction time depends only on the viscous response of the glass and
not on the diffusion coefficient. It thus appears that not only is the
induction period itself an important feature of Case II sorption, but the
induction time provides the most direct indication of the rate of the
viscous deformation component of the process.
8. INTERNAL STRESSES AND SHAPE CHANGES
Consider the swelling of a sheet specimen of a glassy polymer by a

penetrant which plasticises the glass sufficiently to render it a rubber.
The swollen rubber will have increased in volume but not in area (or
very little) because it is attached to the yet unpenetrated and thus rigid
glassy core. It thus experiences a biaxial compressive stress in the plane
of the sheet which maintains it in a non-equilibrium shape with the
molecular axes aligned normal to the front. Such orientation leads to
birefringence which can be detected between crossed polars and was
used in the early experiments of Hartley 6 and of Robinson. 7 When the
fronts meet in the centre of the specimen the constraint of the glassy
core is lost and the shape of the swollen regions returns to equilibrium
with the same ratio of thickness to lateral dimensions as in the initial
specimen. This return to equilibrium shape is seen as a sudden increase
in area and a reduction in thickness. An example of such behaviour,
which has been reported for several systems, is shown in Fig. 21 for
PMMA-methanol at 42°C. 16 Before penetration is complete, the pla-
nar compressive stresses will be balanced by equivalent tensile ones in
the glassy core so that the opposing forces exactly balance. In the early
stages of penetration the thickness of the core is large compared with
106 A. H. Windle
a
04 Fronts
have
met
E
..
E 03
'"0~
u
'"'""
. 02
c
-"
u
E
I-
01
150
't
..
E
~ 100
~
u c
"o
Q
~c
«
~
50
.
u
c
o
U
Distance
BOO 1000
Fig. 21. Measurements of (a) increase in thickness and (b) area of PMMA
sheet specimens as a function of time in methanol at 42°C. The inset shows the
concentration profile just before the fronts meet. 16
the swollen rubber; the tensile stress on the core will therefore be
comparatively small, but as the fronts move closer together it will
increase on account of both the greater force required to hold the
thicker swollen rubber to the area of the core and the smaller amount
of glass left to provide the constraint. The planar stress systems in the
core and the swollen regions can each be resolved into a deviatoric
component which results from the non-equilibrium shapes of the
rubber and (to a much smaller degree) the glass, and a hydrostatic
component which is compressive in the swollen rubbery layers and

tensile in the glassy core. The possible influence of such differential
stresses on the diffusion coefficient was explored by Crank l8 as a
possible explanation of Case II kinetics, and has since been refined to
that end. However, even though it now seems that theories based on
the creep response of the glass to the osmotic swelling pressure are
able to provide more accurate and detailed predictions of the observed
Case II behaviour, it is important not to lose sight of the fact that the
components of hydrostatic stress are still present. It is probable that the
compressive stress in the swollen layers will at least influence the
equilibrium swelling, and the tension in the glass add to the effect of
internal osmotic pressure and thus the front velocity. However, these
effects are seen as modifiers of the Case II process rather than the
underlying cause.
So far, we have not questioned the assumptions that the swollen
polymer behaves as a rubber with negligible viscous flow on the
timescale of the experiment. In the case of PMMA (which as a cast
sheet has a particularly high molecular weight) the swollen and con-
strained rubber does not lose its orientation with time, although at
24°C there is a transient region of higher birefringence immediately
behind the front. The increased orientation is associated with the fact
that the polymer at the front is deformed in a timescale within which
even the fully swollen polymer is glassy. After an interval of a few
hours (at this temperature) the orientation then decays to a value
typical of rubber deformed to the same strain. 16 On the other hand,
the early experiments of Hartley on cellulose acetate showed that the
orientation produced at the front decayed completely a short distance
behind it (Fig. 5), presumably because the instability of the molecular
network permitted complete relaxation of orientation. In polystyrene
systems, the exact level of preferred molecular orientation in the
swollen regions is difficult to assess on account of the heavy crazing,
and additionally there is evidence that hot n-hexane, for example, may
leach out some lower molecular weight components during sorption.
9. SUPER CASE II
The first experimental report of Super Case II sorption is that of

Jacques et al. 46 who, working with the systems n-hexane-polystyrene,
n-hexane-polyphenylene oxide, and blends of these, observed in some
108 A. H. Windle
'.0~----------------------------~----~==~~=r.~0.--,
0.8
0.6
0.4
n-Hexane
PIP 0= 0.775
T = 30°C
0.2
,y, Mil Polystyrene Film
°0~-----2~0~O~----4~0~0----~6~0~0------~------~-----'~200
Time (hours)
Fig. 22. Sorption plot for the n-hexane vapour (activity = O'775)-polystyrene
film (37 /Lm thick) system which shows Super Case II behaviour. 4ti
N
'E
v
E 20
0'
0
~
...c
0
-2. 10
c
0
...
0'
.t::
Q'
'"
3:
0
Time (days)
Fig. 23. Experimental sorption plot for PMMA-methanol at ODC showing

some acceleration in rate; the PMMA sheet was 1 rom thick. 15
samples a very distinct acceleration in sorption rate in the later stages

of the process (Fig. 22). It seems that the effect is most apparent in thin
samples when the initial front penetration rate is low, perhaps on
account of annealing treatments. 47 Super Case II is not observed so
readily in the PMMA-alcohol series, although an experiment at OCC
where the front was moving at only 0·9 nm S-I did show an increase in
rate as the fronts moved near to each other (Fig. 23). It should be
underlined that Super Case II is recognised as a steepening of a more
or less established linear sorption plot. The increase in slope associated
with the transition from an initial induction portion of the plot to the
linear region should not be considered Super Case II.
There are a number of possible causes of an acceleration of the
hitherto linear kinetics in the later stages of sorption; these will now be
considered.
9.1. Overlapping Precursors

The process of rate control governing the front velocity mainly oper-
ates in the region of the Fickian precursor ahead of the front. The
parameters of importance are both the ratio of activity to concentra-
tion, which determines the osmotic driving force, and the activity
gradient, which is the other control on the rate at which the concentra-
tion increases. When two opposing Fickian profiles meet (as discussed
in the first section) the overall rate of sorption will decrease, yet the
concentration in (say) a central element of the polymer will increase
more rapidly if it is being fed from both surfaces. For the overlap of
precursors ahead of Case II fronts, there may well be a decrease in
overall sorption rate as the contribution due to each precursor is
reduced, but the more rapid increase in activity in the central elements
will, through the steep dependence of the deformation rate on driving
force, lead to an acceleration of the fronts. The acceleration will
dominate the reduction in sorption rate due to the purely Fickian
argument, and the linear mass sorption plot can be expected to turn
upwards in the final stages. This mechanism for Super Case II is
essentially that envisaged by Jacques et al. 46 It is shown that under
conditions where the viscous response of the polymer is slow in
relation to the diffusion rate, such acceleration is predicted by the
Thomas-Windle theory (see for example the calculated sorption plot of
Fig. 20). It should be noted that the theory, as applied, did not include
differential swelling stresses.
110 A. H. Windle
9.2. Differential SweUing Stresses

In many systems showing Case II behaviour, the swollen regions are
rubbery and constrained to a non-equilibrium shape by the unpene-
trated rigid core. The constraint means that the swollen regions are in
compression and the unpenetrated core in tension. If one neglects the
possibility of viscous relaxation of the rubber network, the stress in the
swollen region will be reasonably constant but disappear after the
fronts have met, whereas that in the core will increase as the fronts
approach. Both these effects of differential stress can potentially in-
fluence the Case II process and lead to departures from linearity of the
Super Case II type. In fact, one limitation of some of the theories of
Case II based on differential swelling stresses is that linear kinetics
appear rather as a transient between Fickian and Super Case II
)ehaviour. The loss of the compressive stre~s component in the swollen
material as the fronts meet can lead to an increase in the equilibrium
penetrant content of the rubber and thus to its readjustment, by
Fickian ingress. For example, measurements of the dimensions of
PMMA specimens swollen by methanol at room temperature indicate
that the equilibrium swelling increases from 0·23 to 0·27 as the
constraint is 10st. 16 The rate at which the new equilibrium is attained
once the fronts have met remains a matter for conjecture. However, if
it is sufficiently rapid, a weight-gain plot will show pseudo Super Case
II behaviour. Possible variations are illustrated schematically in Fig.
24.
The increase in the tensile stress component on the remaining
portion of the core in the latter stages of sorption can also lead to an
acceleration in the Case II process. 45 In simple terms this differential
stress component must be added to the internal osmotic component in
determining the driving force which elicits the viscous creep response.
That it can be significant can be shown by an estimate for PMMA-
methanol assuming a rubber modulus of 10 MPa and 20% swelling.
When the thickness of the glassy core is reduced to 10% of that of the
swollen region it will experience a tensile stress of 20 MPa, if reduced
to 1%, then 200 MPa. These values should be compared with the
calculated osmotic stress ahead of a moving front which, in this system,
peaks at 100 MPa reducing to about 10 MPa 200/-Lm ahead of the
front. A much more detailed treatment of this Super Case II mechan-
ism has recently been given by Gostoli and Sarti 4R who recognise it as
the primary explanation.
It is clear. however, that the effects of overlapping precursors, as
l----fTTI
Adjustment In I~~~/
? IsotropIc
r---t -----------
c equilibrium
io equilibrium llV Equilibrium tor

~~~~~~Ined
~
Fronts
meet
Time
Fig. 24. Schematic diagram illustrating how the adjustment in equilibrium

volume after the Case II fronts have met might cause a change in slope in the
weight-gain-time relationship just prior to final equilibrium. The lines joining
the two equilibrium weights illustrate the possible paths which might occur,
although there is no reason why this upper portion of the plot should be
linear. 16
well as those associated with differential swelling stress, can all contri-
bute to apparent Super Case II behaviour. It is likely that the three
mechanisms are all present in varying degrees, and the question is
which is dominant under any given set of conditions.
10. SENSITIVITY OF CASE II PROCESSES TO THE

PHYSICAL STATE OF THE GLASS
10.1. Thermal History

It is well established that the efficiency of molecular packing in a glass
depends on the rate at which it has been cooled through the glass
transition temperature (TJ. For fast cooling the glass density is less,
and the material is considered to contain a greater amount of 'free
volume'. In this state it is recognised that mechanical relaxation
processes such as creep are greatly enhanced49 and it is not surprising
that Case II sorption is similarly affected. Figure 25 shows combined
data for PMMA-methanol from refs 15 and 17. The initial sorption
rate, measured as front velocity increases by a factor of 3 for three
orders of magnitude increase in prior cooling rate through Tg , while
the induction time (plotted as its reciprocal on the figure), is reduced
by a similar factor. Similar effects have been reported by Enscore et
al. 50 who found that annealing of sub-micron diameter polystyrene
112 A. H. Windle
~-----------
t,1
.2:-
.B
0·6
04
£
§
~ uOJ
c ]
g
02 '-
0h---~~---3~1---~4- 5 0
Fig. 25. Plot showing the dependence of measured initial front penetration
rate and the reciprocal of the induction time for PMMA-methanol at 24°C on
the rate at which the specimens had been cooled through the glass transition
temperature.
spheres before swelling in n-hexane caused a reduction in sorption rate

relative to that measured in the 'as-received' material. The effects of
thermal history underline the controlling role played by mechanical
deformation processes in Case II sorption; they also suggest that
observation of Case II behaviour can provide a ready and sensitive
measure of the physical state of the glass, which otherwise requires
sensitive density or thermal equipment.
10.2. Mechanical History

The early observations of Hartley6 of sharp fronts in the cellulose
acetate-methylene chloride system demonstrated the marked aniso-
tropy in penetrant velocity as a result of prior stretching of the film. The
front velocity was lower along the tensile axis and it was in this
direction that the linear kinetics became apparent. That the mechanical
history should profoundly influence a process which depends on the
mechanical response of the material is perhaps to be expected and,
indeed, highlights the unique aspects of Case II behaviour. However,
more recent studies of the effects of prior deformation have added
detail to the picture. It is known that regions of the polymer glass
which have been deformed through the yield point, show much en-
hanced penetration rates, and this effect can be dramatically illustrated
in PMMA-methanol by use of the iodine staining technique. 51 Meas-

urements on s<lmples of PMMA deformed at room temperature show
that the Case II kinetics are influenced in two distinct ways.7 Firstly,
the process of plastic yield itself increases the sorption rate by a factor
of between 2 and 3. This increase appears independent of whether the
hydrostatic component of the deforming stress system is compressive
or tensile. Secondly, the plastic strain after yield either further in-
creases the sorption rate or leads to a decrease depending on whether
the prior molecular extension was normal to or parallel to the direction
of front movements. Figure 26 shows a collection of results for PMMA
deformed in tension, axial compression and plane strain compression.
The continuous line plot is for uniaxial compression. Values of Af , the
plastic strain in the front direction, are greater than unity where they
correspond to measurements of relative front velocity normal to the
compression axis (i.e. for the sides of a cylindrical specimen). They are
less than unity, in fact axial compression ratios. for measurements of
-- -----.--------r------------,
50
I·
20 o
Fig. 26. Plots of the ratio change in Case II front penetration rate (dido) for
PMMA-methanol, as a function of prior plastic strain (deformation at 24°C)
measured as a strain ratio normal to the plane of the front (A,). The continuous
curve represents uniaxial compression, the chain dotted curve and the isolated
round point represent axial tension and the three square points correspond to
plastic strain along the three axes of a (single) plane-strain compression
sample. 17
114 A. H. Windle
relative front velocity along the compression axis. The chain-dotted

line and isolated circular point relate to tensile experiments and the
square points to plane strain compression specimens. The similarity
between the results for the different deformation geometries provides
the evidence that the increment due to the onset of plastic yield of the
glass is not related to the direction of deformation in relation to that of
front traverse, while changes of front rate caused by increasing plastic
deformation are dependent on both the sign and magnitude of the
prior plastic strain in the direction of the moving front. The types of
hydrostatic stress state (i.e. compressive or tensile) associated with the
different deformation geometries appear to have no influence on the
subsequent Case II process although they are known to affect the
plastic yield stress itself.
11. THE LIMITS OF CASE D SORPTION
Although Case II is thought of as the consequence of relaxation or

deformation control, it really represents a balance between these local
processes and the diffusive process described by Fick's equations. Such
a view is clearly incorporated in theories based on the simultaneous
equations for dC/dt. If, in a typical Case II system, the diffusive process
becomes much slower in both the swollen and unpenetrated regions,
then the front will move more slowly (as the square root of the
reduction in D 35 ) and the gradients behind the fronts will steepen and
destroy the rectangular step-like nature of the profiles. Hence the
linearity of the sorption plots will be lost and Case II behaviour tends
towards Fickian with the familiar tl/2 kinetics. In thicker specimens
there is a greater opportunity for the diffusion gradient behind the
fronts to significantly reduce the concentration at the front, and any
system which is Case II in a thin specimen will not indefinitely
maintain linear kinetics for deep penetrations in a thick specimen;
again, the behaviour will gradually become Fickian. An increase in
specimen thickness is equivalent to a pro rata reduction in both diffu-
sion coefficient and viscous deformation rate where concentration
profiles are plotted using a normalised distance ordinate.
The effects of a significant reduction in viscous deformation rate, and
thus an increase in its relative influence, on a normal Case II process
are, if anything, less straightforward. Firstly, the induction time
changes as the reciprocal of the deformation rate, while the time for
the front to move a unit distance changes only as the square root of
this reciprocal rate. With a fixed diffusion coefficient, the induction
period will thus become a relatively more significant feature of the
sorption plot as the deformation rate is decreased. Taken to the limit,
the diffusional resistance will become negligible on the timescale
necessary for the deformation process both in the glass ahead of the
advancing fronts as well as in the swollen regions. The total sorption
behaviour will then be dependent on the deformation kinetics alone,
and thus be independent of sample thickness. In the context of the
Thomas-Windle theory35 a sorption plot would appear as depicted in
Fig. 14 and could hardly be called Case II. Observations of thickness
independent effects were reported by Newns 31 for the regenerated
cellulose-water system in which the polymer was already plasticised by
a limited quantity of penetrant. Recently Lewis52 demonstrated a
similar thickness independence for cellulose nitrate-isopropyl nitrate,
preplastiyised by penetrant and als0 53 when the polymer was plasti-
cised by nitroglycerine. He also put forward the idea of a Case III
classification to describe systems in which the swelling kinetics are
determined by deformation alone, according to some functional
characteristic of the system, but the timescale of the swelling process is
independent of sample thickness. It is probable that in the cellulosic
system the deformation is controlled by the timescale of the dissolution
of small ordered regions by the imbibed penetrant, a process which,
unlike plasticisation of a glass, could remain slow even after high
degrees of preswelling or plasticisation. In classic glassy systems an
approach to thickness independent behaviour can be observed where
the samples are extremely thin, as in the sorption studies using
sub-micron polystyrene particles by Hopfenberg, Berens and co-
workers. 50
12. CONCLUSIONS
It has long been recognised that where sorption of a penetrant is

accompanied by significant swelling, any time dependent resistance to
the increase in volume of the solid will lead to a modification of the
behaviour predicted by Fick's equations. Case II sorption occurs over a
range of conditions for which there is both diffusional and deformation
(often called relaxation) control. The Case II swelling process is
characterised by movement into the specimen of sharp, step-type
116 A. H. Windle
penetrant fronts at constant velocity. For sheet specimens of suffi-

ciently large aspect ratio, the weight-gain kinetics are also linear with
time. The theories which most successfully predict the linear ingress of
sharp fronts appear to be those based on the simultaneous solution of
two equations for dC/dt: 26•35 one which is Fick's second law rewritten
in terms of activity gradient, and the other a relation which describes
the rate of increase in volume of an element in response to the
osmotic-type swelling stress. It now appears that the induction period,
apparent before the sharp fronts develop and linear kinetics are
established, is an intrinsic characteristic of the Case II process. Super
Case II behaviour, where fronts approaching each other appear to
accelerate before they meet, can be explained in a number of ways, but
it is probable that the existence of differential swelling stresses, due to
the area constraint imposed on the swollen layers by the unpenetrated
glassy core, is most significant in this respect.
The unique linear kinetics of the Case II process, while providing an
excellent example of dual control of a transport phenomenon, are also
capable of exploitation. For example, a drug incorporated in a polymer
glass which is capable of swelling with linear kinetics in body fluids,
will be released at a constant rate with time. 54 Suitable hydrophilic
copolymers have now been developed 55 and actual application in the
treatment and control of biological processes should be established in
the near future.
ACKNOWLEDGEMENTS
While drawing widely on the work of others, the author wishes to

thank particularly Dr Noreen Thomas who was responsible for most of
the Cambridge data and Dr John Petropoulos for several stimulating
discussions on the development of the theory of Case II. In addition,
Professor Harold Hopfenberg has played a large part in encouraging
the author's interest in this subject. His enthusiasm and friendship has
been much valued. The processing of the manuscript has been a
substantial task, and grateful thanks are due to Mrs Carole Bishop for
her expertise.
REFERENCES
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2. T. Alfrey, Chern. Eng. News, 43, 64 (11 October 1965).
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4. L. Boltzmann, Ann. Physik, 53, 959 (1894).
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9. J. R. Scott, Trans. Inst. Rubber Industries, 13, 109 (1937).
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17. A. H. Windle, J. Membrane Sci., 18, 87 (1984).
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(1969).
23. A. Peterlin, Makromol. Chem., 124, 136 (1969).
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26. J. H. Petropoulos and P. P. Roussis, J. Polym. Sci., C22, 917 (1969).
27. J. H. Petropoulos and P. P. Roussis, In: Permeability of Plastic Films and
Coatings, ed. H. B. Hopfenberg, Plenum, New York, 1974.
28. J. H. Petropoulos, unpublished work.
29. J. H. Petropoulos and P. P. Roussis, J. Membrane Sci., 3, 343 (1978).
30. P. J. Flory, Principles of Polymer Chemistry, Cornell, Ithaca, 1953, p. 576.
31. A. C. Newns, Trans. Faraday Soc., 52, 1533 (1956).
32. G. S. Park, In: Diffusion in Polymers, eds J. Crank and G. S. Park,
Academic Press, London, 1968, p. 141.
33. A. Peterlin, J. Research NBS, 81A (2), 243 (1977).
34. A. Peterlin, J. Polym. Sci., Polym. Phys. Ed., 17, 1741 (1979).
36. G. Sarti, Polymer, 20, 827 (1979).
37. G. Sarti and A. Apicella, Polymer, 21, 1031 (1980).
38. R. P. Collins and A. H. Windle, Polymer, in press.
39. A. S. Michaels, H. J. Bixler and H. B. Hopfenberg, J. Appl. Polym. Sci.,
12, 991 (1968).
40. H. B. Hopfenberg and H. C. Frisch, J. Polym. Sci., B7, 405 (1969).
41. L. Nicolais, E. Drioli, H. B. Hopfenberg and G. Caricati, J. Membrane
Sci., 3, 231 (1978).
42. E. L. Morris and N. G. McCrum, J. Polym. Sci., Cl, 393 (1963).
43. J. A. Roetlin, Polymer, 6, 311 (1963).
118 A. H. Windle
44. A. W. Kirby, M.Phil. Thesis, Cambridge University, 1980.

45. D. Weinberg, 1. Membrane Sci., 3, 309 (1978).
46. C. H. M. Jacques, H. B. Hopfenberg and V. T. Stannet, In: Permeability of
Plastic Films, ed. H. B. Hopfenberg, Plenum, New York, 1974.
47. H. B. Hopfenberg, V. T. Stan net and G. M. Folk, Polymer Eng. Sci., 15,
261 (1975).
48. C. Gostoli and G. C. Sarti, Chem. Eng. Comm., 21, 67 (1983).
49. L. C. E. Struik, Physical Ageing in Amorphous Polymers and Other
Materials, Elsevier, Amsterdam, 1978.
50. D. J. Enscore, H. B. Hopfenberg, V. T. Stan net and A. R. Berens,
Polymer, 18, 1105 (1977).
51. C. C. Chau and J. C. M. Li, Phil. Mag., 44, 493 (1981).
52. T. J. Lewis, Polymer, 19, 285 (1978).
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(1981).
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55. N. M. Franson and N. A. Peppas, Polymer Preprints, ACS, 24(1), 53
(1983).
Chapter 4
Effects of Oxygen Permeation and Stablliser

Migration on Polymer Degradation
J. Y. MOISAN
Centre National d'Etudes des Telecommunications, Lannion, France
1. Introduction . . . . . . . . . . . . . . . . . 119
2. Oxidation Ageing and Stabilisation of Polyolefins 120
3. Distribution of Additives in Polymers . . . . . 123
4. Permeability of Polyolefins to Oxygen . . . . . 125
4.1. Values of permeability to oxygen . . . . . . . 126
4.2. Effect of oxygen permeability on the kinetics of oxida-
tion . . . . . . . . . . . . . 129
5. The Kinetics of Diffusion of Additives 130
5.1. Methods of measurement 130
5.2. Results . . . . . . . . . . 134
5.3. Theories and interpretations 150
6. Solubility of Additives . . . . 154
6.1. Methods of measurement. . 154
6.2. Results . . . . . . . . . . 155
6.3. Discussion . . . . . . . . 162
7. Migration of Stabilisers and Natural Ageing 166
8. Concluding Remarks . . . . . . . . . . . 169
References . . . . . . . . . . . . . . . 171
1. INTRODUcnON
Most polymers are oxidisable materials, whether synthetic or natural.
Many of them must be stabilised to withstand environmental condi-
tions (temperature, oxygen, radiation) and this can be achieved by
adding components to the resin, with a view to retarding the kinetics of
degradation. Organic or mineral absorbers (carbon black) may also be
used as a protection against radiation.
The most widely used plastics are very easy to colour with only very
small quantities of organic pigment. Occasionally a mineral oxide
(titanium or zinc oxide) is used to intensify the colour. Only rather
small quantities of additives are required in many cases, but where the
119
120 1. Y. Moisan
mechanical properties of a material must be modified, the additives

may represent an important proportion of the final mixture. This is
particularly true in the case of plasticisers for PVC and reinforcing
agents (glass-fibre, carbon-fibre). Some fillers only act to increase the
density or make the material cheaper, for instance various sulphates,
carbonates or oxides of alkali or transition metals. Although an addi-
tive is intended to improve a given property of the material it may also
affect other properties; for instance, an antioxidant stabiliser may
modify electrical performance. It is therefore necessary to take some
precautions before using them.
It is convenient to classify additives as mineral or organic. Mineral
additives such as carbon black, titanium dioxide or zinc oxide form a
dispersion of non-agglomerated particles. Organic additives, such as
plasticisers, antioxidants, u.v. absorbers, colouring or antistatic agents,
can be dissolved in the polymer provided they are compatible with it.
It is easy to see that organic additives can be extracted from the
matrix, especially if they are soluble in a solvent which may be in
contact with the material or they are volatile. This property of the
additive being extracted is often called migration, a well known exam-
ple being the migration of PVC plasticisers.1,2 This phenomenon is so
important that standards 3 have been defined, making it possible to test
the various plasticisers under well defined conditions. The same prob-
lem is encountered in fibres coloured with disperse dyestuffs,4.6 where
the dyes are dispersed inside the matrix. 7 - 9 There are test methods to
evaluate the colour fading. 1O With food packages, it is necessary to
select additives which cannot be extracted by foods. I 1-13
Migration in polyolefins is an important problem which has already
been investigated. 14 The interest in using polyethylene is because it has
a rather simple chemical structure, and its physical structure is fairly
well known. It is therefore possible to try and interpret the results of
the diffusion and solubility of stabilisers as a function of the structure
of materials. Currently lvailable results on natural ageing also add to
this interest. It should thus be possible to ensure the long term
efficiency of a stabilising process using parameters ohtained from
laboratory measurements.
2. OXIDATION AGEING AND STABILISATION

OF POLYOLEFINS
The processes involved in the thermal oxidation of polyethylene are
now fairly well known [',16 although the basic chemical reactions are
O 2 permeation and stabiliser migration effects on polymer degradation 121
still being investigated. Different methods, which are now conventional

have been used to estimate the efficiency of a stabilising process. The
two main methods are differential thermal analysis (DTA) which
permits measurement of the time for the onset of thermal oxida-
tion17~19 at a temperature between 180 and 220°C and oxygen absorp-
tion which measures the same time but at lower temperatures between
100 and 160°c. 15 The time is called the oxidation induction time.
These methods revealed the action of some parameters which mod-
ify the kinetics of oxidation. For instance, the induction time is
significantly reduced when the polymer comes into contact with cop-
per,17.18 and titanium dioxide used together with some colouring agents
can induce degradation. 17
Figure 1 is a plot of oxidation induction time against temperature,
obtained using various antioxidants. It can be noted that the antioxid-
ants seem to have a very high efficiency., from a chemical viewpoint,
and that extrapolating towards the usual operating temperatures pro-
vides satisfactory induction times.z o
The results obtained in a similar paper dealing with the stabilisation
of polypropylene can be arranged as an Arrhenius plot allowing
extrapolation to lower temperatures. However, these processes are
rarely caused by temperature and oxygen alone. Reports pub-
lished 17 ,18.22 about the insulating sheath of telephone cables which was
prematurely degraded showed that the cause might be the migration of
150
100
50
ld 1m Time 1y
Fig. 1. Dependence of oxidation induction time on temperature. (----)

Results of the author; (--) results obtained by Pusey et al. 17 and Gilroy. 19
122 1. Y. Moisan
antioxidants, perhaps induced by leaching by rainwater or condensa-

tion. Hence, some authors 17 ,21 have measured induction time after a
specific processing of the sample such as dipping in boiling water and
storing in water at room temperature. A decrease in the efficiency of
the stabiliser can be observed.
Gilroy conducted a study of great interest,19 on the decrease in the
oxidation induction time of samples at 200°C, after they had been
exposed to the air for up to 200 days at 90°C or up to 700 days at
40°C. For each temperature the decrease in the induction time varies
linearly with the square root of the time of storage, so showing the
importance of diffusion. A linear relation could be established between
the oxidation induction time and the antioxidant percentage. 23 Com-
parative measurements confirmed the negative effect of losses of
antioxidants by migration (or by volatilisation). Blumberg et al?4
showed that in the case of polypropylene samples exposed to a
temperature of 140°C, the oxidation appears earlier in an oven with air
circulation than in a sealed tube. Newland and Tamblyn 25 also had to
take the losses by volatilisation of u.v. absorbers into account. Plant
and Scott26 discovered a close relationship between the lifetime of
polypropylene samples and antioxidant volatility. In the same way,
blooming of low solubility additives at temperatures of about 60°C was
associated with short stock life. 22,27 In contrast, when the antioxidant
molecule has a chemical link with the polymer chain,28,29 preliminary
leaching has no effect on the kinetics of oxidation, since the extraction
of the stabiliser is not possible.
The chemical efficiency of the antioxidant is not the only parameter
to take into account when considering the efficiency of an antioxidant.
Several studies already deal with the volatility of these compounds,
which are vacuum-extracted from polyethylene. The losses of antioxid-
ants 39 or u.v. absorbers 31 from polypropylene samples by volatilisation
have been measured at various temperatures. Increasing molecular
weight brings a reduction of volatility and hence the efficiency is
improved.
The same measurements were carried oue2- 34 with rubber additives
(antioxidants and ozone absorbers), They revealed that the influence of
sample thickness is to decrease additive loss by evaporation. The
volatility of pure additives 35 ,36 varies with temperature, following an
Arrhenius type equation. Schmitt and Hirt37 observed the occurrence
of a discontinuity in the Arrhenius plot at the melting temperature of
the additive, the heat of evaporation being generally lower at higher
temperatures. At the same time, other studies were conducted on the

water extraction of these additives. Hawkins et al. 38 showed that the
induction time of polyethylene samples which had undergone a water
extraction at 60°C decreased significantly, except when polymeric
antioxidants were used. Tests carried out on polypropylene films 39
showed it was easier to extract antioxidants of the hindered phenolic
type or thiodipropionic esters than u.v. absorbers such as ben-
zophenone or benzotriazole. It was also noticed that polypropylene
fibres are less resistant to photooxidation 30 when being leached in
water containing detergents, or in benzene. The migration of the
various additives from the sample is not the only parameter to take
into account for these experiments; solubility in the extracting solvent
must also be considered.
These latter studies show that it is not possible to consider the
chemical efficiency of the stabiliser in isolation. There was a discre-
pancy between the reports concerning seriously damaged materials 17,18
and estimates derived from laboratory studies 20 in which only the
chemical reactivity was measured. These experiments on volatilisation
or extraction of additives highlight the necessity of taking into account
physical parameters expressing the stabiliser-polymer compatibility.
Researchers hesitate to start natural ageing tests in view of the
predicted protection time. Recently, Akay et al. 41 reported the results
of polyethylene photooxidation under natural climatic conditions. They
did not mention the percentages of additives, but after 15 months all
the samples presented a noticeable oxidation, showing that oxidation
had started and the stabilisers had lost efficiency. In view of their initial
concentrations they were expected to act much longer.
3. DISTRIBUTION OF ADDITIVES IN POLYMERS
Most of the materials mentioned in this chapter are semi-crystalline

materials (polyethylene, polypropylene, polyamides, etc.). It is already
known 42 that polyethylene chains are arranged in crystalline lamellae
originating at a nucleus. Hence, these lamellae radiate and grow from a
common point until they meet the lamellae growing from another
nucleus. Structures called spherulites are so formed. Their sizes range
from 1 ~m for polyethylene to over 150 ~m for polypropylene, de-
pending on the crystallisation conditions and on the material. The
amorphous phase consisting of chains without any special organisation
takes up the interlamellar and interspherulitic space.
124 1. Y. Moisan
The distribution of the additive between the two phases poses a

problem when accounting for the semicrystalline structure of the
material. The problem is to know whether the concentration is uni-
form, whether the additive is soluble only in the amorphous phase, or
whether it forms a precipitate between the spherulites. The results of
observations answering these questions have been published by several
authors.
Small crystals of Santonox R ((4,4'-thiobis)2-tert-butyl-5-methyl
phenol) of about 5 /-Lm can be observed, using a scanning electron
microscope, when the concentration in polyethylene exceeds a given
percentage. 43 Frank and Lehner44 observed the distribution of a u.v.
stabiliser (Tinuvin 328 or 2-(2'hydroxy-3,5'-di-tert-amylphenyl) ben-
zotriazole) during crystallisation, using u.v. microscopy. They noticed
that this compound, which was uniformly distributed in the melt was
not uniformly distributed in the solid material, depending to a great
extent on the crystallisation conditions. Hence they concluded that the
amorphous phase can dissolve this compound at the concentration
chosen (3%) but it is rejected by the crystalline phase. Billingham et
al. 45 recently confirmed this result for poly(4-methyl pentene-1) and
Cyasorb UV 531 (2-hydroxy-4-octaoxybenzophenone); the additive is
markedly rejected by the crystalline phase. Calvert et al. conducted a
thorough study46-49 of the distribution of two additives during poly-
propylene crystallisation. These were Uvitex OB (2,5-di(5-tert-butyl-2-
benzoxalolyl)thiophene) and Cyasorb UV 1084 (2,2'-thiobis(4-tert-
octylphenolato)-butylaminonickel (II)). They also proposed a model
for the distribution of additives in spherulites, which takes into account
the kinetics of diffusion of this additive, and the spherulite growth rate.
Their model was confirmed by observations made using scanning
electron microscopy. They came to the conclusion that the additive is
totally rejected by the crystalline phase of the polymer, and seems to
be evenly distributed in the amorphous phase. Precipitates may occur
when the overall concentration is such that the amorphous phase
becomes supersaturated.
The effect of this inhomogeneous distribution of the stabiliser must
now be considered and two cases can be made out, depending on the
expected influence of the stabiliser. The absence of stabiliser additive
from the crystalline phase will be a nuisance if the additive acts as a
screen against the u.v. radiation. The radiation may induce degradation
in the crystalline phase which is not protected. Conversely it may be
thought that if the crystalline phase is impermeable to oxygen, only the
amorphous phase will undergo thermal oxidation. Yet the stabiliser

will be isolated in the amorphous phase so that the inhomogeneous
distribution of the stabiliser will be beneficial provided of course the
crystalline phase really is impermeable to oxygen, a point which still
has to be demonstrated.
4. PERMEABILITY OF POLYOLEFINS TO OXYGEN
We have seen that additives are unevenly distributed in polyolefins,

and may wonder whether the crystalline phase is devoid of oxygen, as
c
( O·5mm--H---Q-5mm _ _
+- .- -,--- --
1"""' __ ~ _I"~l'~'d
o
.;:;
o
~
x
o -
.t-
- -- -
I
- - -..
- ______e _
---
•
-
• •
• • • i
• Distance
1-----
I
0
\
\ -"
10 --
0'-...0
........ 0 Depth
o -0_0_
_0
o 0-25 O·5mm
Fig. 2. Oxidation levels estimated from 0=0 absorption at 1720 cm-'. Top:
natural and accelerated aging of 1 mm thick samples at 90°C. Bottom: oxida-
tion level curve for a sample exposed for 6 days to air at 100°C.
126 J. Y. Moisan
it is of stabilisers. In such a case, u.v. radiation may generate reactive

sites in crystallites which may not be oxidised. The consequence would
be a limitation of the kinetics of photooxidation.
In the case of thermal oxidation of the amorphous phase the
permeability of surface layers may reduce the consumption of oxygen
inside the sample. Again, a limitation of the kinetics of oxidation could
be observed. Figure 2 shows some observations of oxidation level and
depth.60 The accelerated ageing of the sample and natural ageing
(ambient outdoor temperature) give quite different results. An
homogeneous oxidation can be observed on 1 mm thick samples after
natural ageing, whereas the surface is much more oxidised than the
core, in samples of 1 mm or more, exposed at a temperature of 90°C
and above. Permeation of oxygen seems to be the only reason for this,
since the accelerated ageing is characterised by thermal factors and not
photochemical ones for which the transparency of the material to
excitation wavelengths would probably have to be accounted for. It is
therefore important to know the oxygen permeation within the
material.
4.1. Values of Permeability to Oxygen

Techniques for the measurement of gas permeability have been availa-
ble for a long time already. Meares 51 described a measuring device for
polyvinylacetate films in 1953. Michaels and Bixler52 later discussed
methods involving the evaluation of equilibrium, or of the time-lag,
which give similar results. Indirect methods were also proposed,s3
based on physicochemical reactions due to oxygen; these methods are
really interesting when dealing with materials containing slightly solu-
ble gases.
A most interesting result was reported by Michaels et al.,52.s4.ss who
showed that the relation between polyethylene crystallinity and the
oxygen solubility is:
S=aS* (1)
Nhere S is the solubility in the material, S* is the solubility in the
amorphous phase and a the fraction of the amorphous phase. The
range of values of a which can be observed is wide enough to deduce
that oxygen is insoluble in the crystalline part of the polymer. Hence
oxygen only exists in the amorphous phase, along with the additives.
As diffusion will occur only in the amorphous phase, the crystallites act
as a screen against the transport of diffusants.
O2 permeation and stabiliser migration effects on polymer degradation 127
TABLE 1
Diffusion Coefficients of Oxygen in Some Polymers at 25°C
Polymer Ref·
Polyethylene, density = 0·964 1·70 54
Polyvinylacetate 0·4 51
Polymethylmethacrylate 3·8 (20°C) 53
Natural rubber 1·58 57
Polybutadiene 1·5 57
Butyl rubber 0·081 57
Tables 1 and 2 give several values of the diffusion coefficient and of

the oxygen solubility. Van Amerongen56,57 published a study on elas-
tomers in which the values were computed as a function of the nature
of polymers, or of the composition of copolymers. Permeability coeffi-
cient is the product of diffusion coefficient and solubility, thus:
P=DS (2)
and it gives a measure of the amount of gas which can flow through a
membrane of material. Permeability will be low in polyolefins, in view
of the very low solubility and hence the progress of oxidation is
expected to be slower inside a thick sample, since only a small flow of
oxygen can reach this part of the sample and maintain the reaction.
These parameters will each vary with temperature in accordance
with an Arrhenius type equation, and hence the following relationship
TABLE 2
Solubilities of Oxygen in Some Polymers at
25°C
Polymer S (ppm) Ref·
Amorphous polyethylene 110 52,55
Natural rubber 160 57
Polybutadiene 140 57
Butyl rubber 175 57
Polyvinylacetate 90 51
128 J. Y. Moisan
will be valid:
(3)
Here Ep is the activation energy for permeation, Ed the activation

energy for diffusion and toRs the heat of solution.
Table 3 gives some values for oxygen in polymers. The effect of the
polymer nature and structure on Ep and Ed can be observed, e.g. the
influence of the polyethylene density. The most important fact, how-
ever, is the very small value or often negative value of toR" the latter
meaning that solubility will decrease with increasing temperature. It is
interesting to compare these with the value of the oxidation activation
energy18.20 which is about 160 kJ mol- 1 for polyethylene.
TABLE 3
Activation Energies of Diffusion and Permeation, and Heat of Solution for
Oxygen in Polymers, Between 25°C and 50°C
Polymer Ep(kJmol- 1 ) Ed (klmol- 1 ) ilR Ref.

(klmoZ- 1)
Polyethylene, density = 0·964 35·1 36·8 54

Polyethylene, density = 0·914 42·6 40·1 54
Natural rubber 31·4" 34·7 -3·3 56
Butyl rubber 44·7" 49·7 -5·0 56
Polypropylene 46 59
Polyvinyl acetate 56·0" 60·6 -4'6 51
" Valu'e computed according to eqn (3).
It can be seen that the permeation of surface layers controls oxida-

tion of a thick polyethylene sample. However the limit thickness for
this phenomenon will be smaller as the temperature is increased, due
to faster oxidation kinetics.
The phenomenon observed by Meares,51 concerning the diffusion of
ight gases in polyvinyl acetate, is interesting. Arrhenius plots of
diffusion coefficient or solubility against temperature show a discon-
tinuity always at about the same temperatures (26 and 17°C), the
highest temperature being associated with the second order transition
of the polymer.
4.2. Effect of Oxygen Permeability on the Kinetics of Oxidation

The influence of the thickness of the sample on the kinetics of
oxidation is often reported 60 and it is generally considered that oxygen
permeation is rate limiting. Boss and Chien61 showed that the oxida-
tion kinetics of polypropylene at 150°C decrease with samples exceed-
ing 125 /Lm in thickness. Similarly, Billingham et a1. 45 ,62 observed that
at 140°C a 200/Lm film of poly-4-methyl pentene-1 absorbs less
oxygen than a 40 I-Lm thick film. The same phenomenon is observed for
polystyrene,63 Two interesting studies on the photooxidation of low
density polyethylene were recently published, Furneaux et al. 64 ex-
posed 3 mm thick samples and then analysed the oxidation profiles,
Photooxidation could be observed in the samples after they had been
exposed at various sites in Australia, The overall oxidation depends on
the photon energy reaching the sample, which varies with the site, All
of the samples have about the same oxidation profile, however; that is,
only a small amount of oxidation appears in the centre of the sample
and on each side there is a section about 1 mm thick, in which the
oxidation rate remains almost constant. There is considerable surface
oxidation.
The same oxidation profile is obtained when performing an artificial
photooxidation of identical samples using a fluorescent lamp. But when
this ageing process is performed in a pure oxygen atmosphere, the
oxidation profile is flat and at the same level as for the surface layer of
other samples aged under the same conditions but in the air. The
kinetics of oxidation are then obviously diffusion limited at the centre
of the samples; it is, however, easy to assume that this phenomenon
will not occur for the natural ageing of films less than 1· 5 mm thick.
Cun liffe and Davis65 proposed a model for the oxidation profile of
low density polyethylene samples, accounting for the thickness of the
sample, diffusion, solubility and pressure of oxygen. The profiles are in
good agreement with those reported in their previous publication,
although no satisfactory explanation is given for the high surface
oxidation.
Huvet et al. 66 and Verdu 67 may have shed some light on the matter.
They show that when computing the kinetics of oxidation one should
also consider the fact that the permeability of oxygen seems to signific-
antly increase beyond a given threshold of oxidation. Thus, when
exposing a stack of identical films (about 1 mm overall thickness) to
u.v, in air, the oxidation profile is similar to those observed previ-
ously.64 However, when the back film (the remotest one from the
130 J. Y. Moisan
radiation source} is filled with carbon black (and hence insensitive to

oxidation), the oxidation rate of the front layers decreases significantly.
The present author assumes that permeation of oxygen occurs on both
sides of the film stack, but oxidation of the film filled with carbon black
is small and hence the permeability to oxygen does not increase, so
that the oxidation rate of the films at the front cannot be as high as in
the previous experiment.
Photooxidation profiles are symmetrical with respect to the centre of
the stack.64.66.67 Permeation of oxygen is symmetrical but exposure to
one face usually means that irradiation is not.
5. THE KINETICS OF DIFFUSION OF ADDITIVES
From the above, it can be seen that in the case of thick samples,
permeation to oxygen may be the limiting factor to the kinetics of
degradation of polyethylene. In the case of thin samples, however,
many authors have observed an inhomogeneous distribution of stabilis-
ers in the material due to limited solubility. Others suggest that the
early degradation is induced by stabiliser migration. Let us now study
more thoroughly the diffusion and solubility parameters of additives
and try to explain the results obtained.
A series of diffusion coefficients without solubility data were pre-
sented in a recent publication. 68
5.1. Methods of Measurement

The 'time lag' method is the most used for the diffusion of gases in
polymers69-71 and methods involving an increase in the weight of the
sample are used to determine the diffusion coefficient of organic
vapours in polyethylene.72.73 These methods cannot be envisaged for
additives in polyolefins, which remain solid in the temperature range of
concern. More specific methods have been developed, the most sophis-
ticated using radioisotopes in the diffusing molecule. 13
Gromov et al.74 measured the decrease in {3 activity of 14C or of 35S
in the additive deposited at the surface of the polymer sample as it
diffused inwards. In contrast, Jackson et al.,75 and also Westlake and
Johnson,76 measured the radioactivity on the back face of a film.
Dubini et al. 77 and Cicchetti et al. 78 obtained the concentration profile
of the diffuser in a thick sample by measuring the radioactivity of thin
films from that sample after a given diffusion time. 14C labelling has
been used with polyethylene and polypropylene, as well as for

molecules of low solubility in rubbers,79 polyethylene and poly-
propylene, but it can also be used for other types of polymers, for
instance molecules having a very low solubility in rubbery polymers ,79
stabilisers80 and plasticisers81 in PVC, and stabilisers in polyurethane. 82
Besides the use of radiotracers, other methods can be used to obtain
concentration profiles during diffusion. For instance, Klein83- 85 plotted
the concentration profile by moving the sample in the beam of an i.r.
spectrophotometer, the wavelength of which was set to a specific
absorption band of the diffuser. This enabled him to obtain the
diffusion coefficient of long chain esters in a low density polyethylene.
Andress and Rohl86 obtained the concentration profile of phenolic
antioxidants by using u.v. spectrophotometry.
These two last spectrophotometric methods can also be applied to
the techniques of Dubinj17 or Cicchettj18 as was done by Roe et al. 87 •88
and Moisan. 89 Figure 3 shows the experimental arrangement. A source
is kept in contact with a stack of films; th(: concentration in the source
must be at least twice as high as the solubility. The whole equipment is
kept at a chosen temperature T for a time t, then the films are
separated and the quantity of diffuser which has passed into the films is
measured. Roe et al. used a slightly different assembly in which the
films are inserted between two sources.
The polymer diffusant combination determines the type of analysis
needed. In the case of esters in polyethylene or polypropylene, i.r.
C
Co - .
SOURCE FILMS
2 Phases
S I
1\
"- ~
--
1 Phase
o --
I
o e x
Fig. 3. Model for the measuremeIY of diffusion coefficitmt and solubility. Co is
the diffuser concentration in the source and x the penetration depth.
132 J. Y. Moisan
spectroscopy can be used. Ultraviolet spectroscopy is used with antiox-

idants in polyolefins and liquid chromatography after extraction where
concentrations are very low.
The initial and boundary conditions for the system shown in Fig. 3
are
t =0, x>O, c=O
t>O, x =0, c=s
The appropriate solution to Fick's second law is
c{x, t) = S(l-erf (x/K» (4)
where c(x, t) is the concentration at position x and time t and S is the
solubility. K is given by
K=2.fi5t (5)
r
The amount of diffusant in the region x = 0 to x = e is given by
Qe = c(x, t) dx (6)
whence
Q e = KS l 0
X/K
(l-erf (x/K) d(x/K) (7)
The total amount of diffusant to have entered the stack is given by
(8)
Equation (7) can be rewritten thus
Q e = KS loo(l-erf (x/K)) d(x/K)- KS roo (l-erf (x/K)) d(x/K)

o J X/ K
(9)
or
Qe = KS
, - KS
foo (l-erf (x/K)) d(x/K) (10)
V'lT x/K
so that the ratio Q,/Q, becomes

Q roo
Q' = l-y''/T]. (l-erf (x/K)) d(x/K) (11)
t x/K
---
CT
x
CT
05
500 1000 X ()Jm)
Fig. 4. Graphical determination of K. (x) K = 0·098; hence D =

1·1 X 10-7 cm 2 5- 1 with t = 6 h at 50°C.
QelQt can be obtained by chemical analysis and then compared with

values computed from eqn (11) using different values of e.
The results presented in Fig. 4 show that the results comply with
Fick's laws. The value of this method is that it is easy to implement,
provided polymer films are available and no special method of analysis
is required. AHara and White90 used various analytical methods when
studying the diffusion of copper carboxylates in polyethylene, for
instance, reflective i.r. spectrophotometry, atomic absorption spectros-
copy and Rutherford back scattering.
Specific methods may be necessary for definite needs. For instance
Price et al. 91 used x-ray fluorescence with a scanning electron micros-
cope to study the diffusion of PVC molecules by observing the progress
of chlorine. A recently published holographic method is very interest-
ing: it is possible to observe diffusion of macromolecules linked to a
dye molecule 92,93 or diffusion of the dye molecule itself. The coefficient
of diffusion of vapours or volatile additives, in a polymer constituting
the stationary phase of the assembly, can also be calculated by using
the gas chromatography technique. The results obtained by Braun et
al. 94 for low density polyethylene are discussed by Millen and
Hawkes. 95 Finally, Zupancic et al. 96 determined the kinetics of diffusion
of butane in linear polyethylene, by using nuclear magnetic resonance.
134 f. Y. Moisan
5.2. Results
The only studies on polyethylene which are of note are those con-
ducted by Jackson et al./ s Roe et al.,88 Westlake and Johnson,76.97
Braun et al. 94 and Moisan. 89 On polypropylene, let us mention the
studies of Gromov et al.,74 Cicchetti et al.78 and of Dubini et al. 77 The
results are rather difficult to compare, in view of the different struc-
tures of polymers, due to crystallinity or thermal history and the
various ranges of temperatures.
5.2.1. Coefficient of Diffusion Independent of Concentration

It has apparently not been suggested yet, that the diffusion coefficient
of molecules which are not easily soluble in polyolefins might depend
on concentration. The kinetics of diffusion of some organic vapours
strongly depend on concentration; examples are benzene, hexene,
heptane or o-xylene in polyethylene,98-1oo and methyl chloride, ben-
zene, n-pentane and hexane in the case of ethylene-propylene
copolymers. 101
The same phenomenon can be observed 102 for the diffusion of
butane or pentane in rubber, of plasticisers and some PVC stabilis-
ers,103 carbon tetrachloride, acetone, benzene, methanol and propanol
in polyvinyl acetate 104 and methyl chloride, carbon tri- and tetra-
chloride, ethyl bromide and methyl iodide in polystyrene. lOS It seems that
the diffusion of some products which are solvents of the polymer or
highly compatible with the polymer (plasticisers, for instance) is differ-
ent from that of far less soluble products such as stabilisers.
5.2.2. Influence of Temperature on the Diffusion Coefficient

In general, the Arrhenius law (eqn (12)) is obeyed when plotting the
diffusion coefficient as a function of temperature.
D = Do exp (-Ed/RT) (12)
Here Ed is the activation energy of diffusion and Do the pre-
exponential factor. A plot for Topanol CA in low density polyethylene
is shown in Fig. 5. Studying the diffusion coefficient as a function of
temperature will give a value of the activation energy in the tempera-
ture range under investigation.
Table 4 89 gives the values of Ed and Do of several stabilisers for the
same low density polyethylene and Table 5 gives the chemical names
of the stabilisers used.
I I
\ i
1\
--
--;; I
N \ I
1\
E
u
I
'\. I
\{ I
rOF ~NO LeA

1\
r\
I
10- 9
3 3.2 x 10- 3
lIT (K)
Fig. 5. Temperature dependence of the diffusion coefficient for Topanol CA in

low density polyethylene. 89
5.2.3. Diffusant Melting Temperature

Melting points of some of the stabilisers are given in Table 4. Figure 6
shows that a discontinuity occurs in the Arrhenius plot at the melting
point (except for lonol) and the activation energy is lower at tempera-
tures above the discontinuity. Hence, there are different activation
energies, Bd(hT), BilT), for high and low temperatures (see Table 4).
On looking at this discontinuity more thoroughly it is seen that it
occurs at a temperature which is slightly higher than the melting
temperature of the additive. It should be noted that the author 106
observed the phenomenon with very different products, namely
hexadecanone-3, stearic acid, methyl stearate, elaidic acid and lrganox
1076, at temperatures varying from 39 to 70°C. Polyethylene does not
usually present any first order or second order modification at these
temperatures. There is no relation between heat of fusion of the
additive and the variation of activation energy for diffusion. Schmitt
and Hirt 37 observed a similar phenomenon when studying the volatility
of benzophenones. The vapour pressure varies with temperature, fol-
lowing an Arrhenius relationship but a discontinuity occurs near the
melting temperature of the compound.
136 J. Y. Moisan
TABLE 4
Diffusion Parameters for Some Stabilisers in a Low Density Polyethylene.
Do (em 2 S-I) log Do Ed(kJmol I) t..Ed Tm (ac)
= Eil T) - Ed(h T)
e·89X 10 3 3·84 73·2

Ionol (BHT) 36·4 74
1·83x 10 9 9·26 109·6
Plastanox 2246 1·72 x 10" 8·24 102·6
Santonox 6·91 x 10 5 5·84 88·0
Plastanox 425 7·80x 10' 8·89 107·3
r
NonoxWSP 2·66x10 7 7·42 99·7
Ionox 220 9·17x10 7 7·96 101·7
Al x 10 9 9·15 108·0
Irganox 1076 36·9 62
r
2·87xl0 3 3·46 71·1
Topanol CA 1·71 x 10" 6·23 92·5
·01 x 10 14 14·00 34·17
Irganox 1035 65·2 74
1·39x 104 4·14 77·7
Ionox 330 2·69x 10" 6·43 93·6
HPM12 6·01 x 10 ' " 16·78 160·7
e'
Irganox 1010 9·19 x 10 8 8·96 115·4
64X 9 9·94 108·8
DLTDP 106 22·1 40
1·70x 10 6·23 86·7
r·09X1015 15·04 144·2
DSTDP 81·0 66
3·21x10 2 2·51 63·2
e'02 x 10' 5·95 84·3
Cyasorb UV531 5 10·5 50
1·80 x 10 4·25 73·8
Tinuvin 327 5·96 x 10 6 6·77 93·7
.----~-
5.2.4. Polymer Melting Temperature

The melting of a polymer is expected to have an influence on the
kinetics of diffusion. Lowell and MacCrum72 showed clear evidence of
this phenomenon in several alkanes of low molar mass. Again, the
activation energy at temperatures exceeding the melting temperature is
less important than that obtained with polyethylene in solid condition.
But the discontinuity cannot be observed below 120°C with linear
polyethylene; this temperature is much higher than the 107°C ob-
served by Klein 83 with low density polyethylene.
The influence of the melting of a polymer has also been reported by
Van Amerongen 56 for the diffusion of gases such as hydrogen or
nitrogen in natural rubber, where the activation energy follows the
same pattern.
a
TABLE 5 "
List of Stabilisers Referred to in the Text '"
'"~
Trade mark Chemical name Molecular Molar 'g.'""
;:
length (A) mass
;:
'l:>.."
lonol (BHT) 2,6-Ditert.butyl-4-methylphenol 7·6 220 '"
B
<::>-
Plastanox 2246 3,3' - Ditert. butyl-2,2' -dihydroxy-5 ,5' -dimethyldiphenylmethane 13·3 340
Santonox 5,5' -Ditert.butyl-4,4' -dihydroxy-2,2' -dimethyldiphenylsulphide 13·9 358 ~
Plastanox 425 3,3' -Ditert.butyl-2,2' -dihydroxy-5,5' -diethyldiphenylmethane 13·3 368 '~..,"
Nonox WSP 3,3' -Di(methylcycIohexyI)-2,2' -dihydroxy-5 ,5' -dimethyldiphenylmethane 15·0 420 QQ'
Ionox 220 3,5,3' ,5' -Tetratert.butyl-4,4-dihydroxydiphenylmethane 13·3 424 ~
g.
Irganox 1076 Octadecyl 3-(3,5-ditert.butyl-4-hydroxyphenyl)propanoate 35·1 530 ;:
Topanol CA 1,1,3-Tri (2- tert.butyl-4- hydroxy-6-methylphenyl )bu tane 13·4 544 ~
Irganox 1035 2,2' -Thiodiethyl bis[3( 3,5-di tert. butyl-4-hydroxy)phenyl ]propanoate 29·0 642 ~
<"l
0;-
Ionox 330 1,3,5-Tri( 3,5 -ditert. butyl-4-hydroxy) benzyl-2,4,6-trimethylbenzene 14·8 774
;:
HPM12 2,2' -Methylene bis( 4-methyl-6-tert.butyl)phenol terephthalate 810 "
Irganox 1010 Tetramethylene 3-(3',5' -di-tert.butyl-4' -hydroxyphenyl)propionate 25·9 1177
~
'""
DLTDP Didodecanyl 3,3' -thiobispropanoate 43·0 514 ~
Dioctadecanyl 3,3' -thiobispropanoate

...'"
DSTDP 50·5 682 l:>..
'"..,
Cyasorb UV 531 2-Hydroxy-4-octoxybenzophenone 19·4 326 ""
Tinuvin 327 5-Chloro-2-(3,5-ditert.butyl-2-hydroxy )phenylbenzotriazole 357 '"l:>..
'g."
;:
~
(;.)
-~
138 J. Y. Moisan
'""'. ~\
'\~
--
--
i'\
III
~\
N
E
B Cl
c
....~
o 4J
10- 8 I ~ \.~
~
\
~ I~
TOP
10- 9 DST \
\ \
\
\
2.8 3 33x10-3
l/T (K)
Fig. 6. Temperature dependence of the diffusion coefficient for DLTDP and

DSTDP in low density polyythylene. 89 Note the effect of the melting tempera-
ture of the diffuser.
5.2.5. Polymer Glass Transition Temperature

A discontinuity in the Arrhenius plot can also be expected at the glass
transition temperature, Tg • This was clearly demonstrated by Meares,51
who studied the diffusion of helium, hydrogen, neon, oxygen and argon
between 4 and 44°C in polyvinyl acetate. This discontinuity is easily
observed at 26°C; it is ascribed to the polymer Tg , which is generally
between 25 and 31°C. Meares also observed a similar phenomenon
at 17°C, which he could not explain.
Johnson and Hauserman 80 could not measure the diffusion coeffi-
cient of 2,4-dihydroxybenzophenone below the Tg in plasticised PVC
because it was too low. Hence, it is only known that the Arrhenius law
is obeyed above Tg • Kumins and Roteman 107 studied vinylchloride-
vinylacetate copolymers; they did not show any clear discontinuity in
the diffusion of polyatomic gases.
On the other hand Chen 108 clearly showed the influence of Tg in
polycarbonate by diffusion of propane, isobutane and neopentane. In
this case, the activation energy seems to be greater above the Tg • Chan
and Paul 109 also studied polycarbonate and showed that the diffusion
of nitrogen and carbon dioxide is not significantly modified on anneal-
ing polycarbonate.
The diffusion coefficient usually seems to follow the Arrhenius law
as long as there are no polymer transitions. Several authors have
published results in which this is not so, the activation energy seeming
to increase as temperature decreases. This was observed by Fujita et
al.,110 in the diffusion of alkyl acetates in polymethylacrylate.
Their interpretation was questioned by Boyer et a1. 111 as it is quite
possible to draw two lines in the temperature range being investigated
defining the temperature of discontinuity for each diffuser. This tem-
perature is almost constant for the same polymer with any diffuser and it
probably corresponds to transition at a temperature ranging between
Tg and the melting temperature. At this temperature, a modification
should occur in the behaviour of the amorphous network which can be
revealed by measuring creep.
Boyer et al. discuss the diffusion of acetates in polymethylacrylate, of
benzene in polyethylacrylate, of pentane in polystyrene and of
methanol in polyvinylacetate in this way.
It is expected that any modification of the molecular mobility of the
diffuser or of the matrix will affect the kinetics of diffusion, and that
every first order or second order transition will modify the activation
energy of diffusion.
5.2.6. Size of the Diffusing Molecule

Roe et al. 88 obtained the following empirical relation between the
diffusion coefficient and molar mass (M) of some antioxidants in low
density polyethylene.
(13)
In spite of their assertion to the contrary, this relationship depends on
temperature, since the activation energies of diffusion of the additives
were all different. According to the author,89 Fig. 7 shows the relation
between D and M at 50°C for the stabilisers described in Table 5; it
can be seen that the empirical law is rather difficult to apply. The
relation between D and molecular length (Fig. 8) is no clearer.
In the presence of diffusing molecules from different chemical
families, or of a small number of products from the same family, the
only certainty is that the diffusion coefficient decreases with the in-
creqsing size of the different molecules as revealed by Allara and
10.8 I--I--*"'d---+--+--+--+--+
N
--
2-
III
E
o
10. 9 1--1_--+__ 1-_
f--t--+-.. ~.--- +-
I
I I
10.10 f---+--+-
---+ I
I
2.5 3 logM
Fig. 7. Dependence of diffusion coefficient at 50°C on molecular weight of the
diffusant. 89 (~) DLTDP, DSTDP-'linear antioxidants'; (e) other phenolics •
,,
•
,,
10·8~_~.~\~_ _ _ _ _ _ _1--___~
\
.,\
\
,
\
,
~----~-~\-----~~r----+~
--
\
III
N
.-
\
E \
'-' \
o \
,
\
,
\
\
."
\
10- 9 1--_ _ _ _1--______--'\.-___ >--__ f---

,
,
\
f-------f---------------c---
10
Fig. 8. Dependence of diffusion coefficient on the molecular length of the
diffusing additive at 50°c. 89 ( - - - - ) represents the relation D = f(L -2); (~)
DLTDP, DSTDP-'linear antioxidants'; (e) other phenolics.
10- 9
Fig. 9. Diffusion coefficient of methyl esters as a function of molecular length

at various temperatures. 106 ( ....) Values of D below the melting temperature of
the diffusant.
White 90 for the case of copper carboxylates in polyethylene, by Rhee et

al. 112 with heavy alkanes (C 16 to ClOO) in rubbers, or by Dubini et al. 77
with thiodipropionic esters or hydroxybenzophenones in poly-
propylene.
On the other hand, it is possible to have a better indication of the
influence of size, with diffusers from the same chemical family. For
instance, Fig. 9 represents the dependence of diffusion coefficient on
length for methyl esters at various temperatures. 106 Again, the in-
fluence of the melting temperature of the additive can be observed, but
the most noticeable effect is the sudden change at a length of about
26-27 A. Klein 85 observed the same phenomenon in the diffusion of
alkanes or of low molar weight deuterated polyethylene in
polyethylene at a temperature of 176°C. The author considers that
self-diffusion occurs beyond this limit, in agreement with the following
relation:
(14)
Unfortunately, this IS at a variance with the studies conducted by
142 1. Y. Moisan
Douglass and MacCall 113 who observed the following relationship from
a study of the self-diffusion of normal alkanes.
(15)
However, only one product (dotriacontane C 32H 66 ) is likely to have a
length exceeding the critical length observed by Klein and Moisan.
At a later stage, MacCall et al. 1l4 studied the self-diffusion of low
molar weight polyethylene (degree of polymerisation, N = 290 or 415),
and although some difficulties arose, they found D proportional to
M- 5 / 3 •
In addition, Klein lIS observed that the diffusion coefficient of
deuterated polyethylenes having low molar weights remains unchanged
when the mean molar mass of the polyethylene constituting the matrix
changes, but provided that it remains significantly greater than that of
the diffusant.
Finally, only products such as DLTDP or DSTDP among the usual
stabilisers have a suitable length to be compared with egns (14) and
(15). The size of the molecule has a great influence, as it decreases the
diffusion coefficient significantly. This has been observed for the diffu-
sion of gases51.56.116 and for alkanes.I02.105 Chen and Edin 117 recently
measured the diffusion of gases in polycarbonate below T g • They
obtained a linear relation between log D and d 2 (d being the diameter
of the gas molecule). A linear relation was observed between activa-
tion energy Ed and d 2 • Meares 51 observed it for gases in polyvinylace-
tate below and above T g • Other authors 56,118 noticed only the influence
of the size of the diffusing gas on Ed' Such a simple relation will
probably not hold with stabilisers for polyolefins.
It has already been mentioned that the value of Ed is less above the
polymer melting temperature than it is below. Figure 10 reports the
values of the activation energy at lower temperatures Ed(l T) obtained
with antioxidants of the hindered phenolic type in low density
polyethylene89 and also with methyl esters in the same polyethylene.
Ed(l T) increases with the length of the molecule and reaches about
140 kJ mol- l at 50 A. This value is much higher than expected; from
measurements of self-diffusion in paraffins,113,114 above the melting
temperature' EaChT), it seems to be slightly less than 25 kJ mol-I.
According to Klein 85 and Lowell and MacCrum,72 the ratio between
the two values of Ed is 3·3, The maximum value of Ed(lT) is thus
expected to be about 85 kJ moll, but there will be some effect due to
the ester or phenol groups.
, ~~
. -
,
./ . -
' ---:
120 ---
. ,
<5
--
E
~80
w
"0
,Y
V ,
I I
I
I
40 I
I
I
I
I
I
I
20 40
Fig. 10. Ed(I T) as a function of the length of difIusant in low density
polyethylene. (e) Phenolic antioxidants;89 (L'-.) methyl esters. 106
The variation of BiIT) with molecular length is reported in Fig. 11,

for some methyl esters in low density polyethylene,106 hydroxyben-
zophenones in isotactic polypropylene77 and dipropionic esters in the
same polypropylene. 77 The values of BiIT) increase with the length of
the diffusing molecule in polypropylene, whereas a sudden change
~30
.--.. --
-~
'0
E
-,
'0
u
"" ,..-t.-
-'"
•
-- - A_--
"0
UJ 20 J. ~t. 0-0-"
9''' ~"''''~.>oc:.-''
p'
~
0 , ..............
9-
_0' '0-_
0
10
0
10 20 30 40 L(A)
Fig. 11. Ed(lT) as a function of the length of difIusant. (0) Methyl esters in
low density polyetbylene;106 (L'-.) dipropionic esters in isotactic poly-
propylene;77 (e) hydroxybenzophenones in isotactic polypropylene.77
144 1. Y. Moisan
seems to occur in polyethylene at a molecular length at which a sudden

change in D has also been observed (see Fig. 9).
5.2.7. Effect of Polymer Structure

Barrer 102 reported a decrease in the diffusion coefficient with the
crosslin king of a rubber. Recently, Nah and Thomas 119 also observed a
significant decrease in the diffusion of waxes in a rubber as the
crosslinking is increased. In the same way, the diffusion of organic
vapours 98 is decreased by radiation, which induces crosslinking in
polyethylene. The study published by Cicchetti et a/. 77 •78 is of great
interest; they compare the diffusion of several hydroxybenzophenones
in high and low density polyethylene. With the same diffusant, the
diffusion coefficient is greater in low density polyethylene, but Ed is
smaller. However, two polymers are not sufficient to draw satisfactory
conclusions on the influence of crystallinity.
Moisan 120 reports the behaviour of only one antioxidant, Plastanox
2246, as a function of the density of six different high density, medium
density and low density polyethylenes. It can be seen from Fig. 12 that
2246 :
N
-- Vl
E
u
i
----t--.'"-..""--+-~>-----f--------"-",-+-
---------+ ----
I
o
10-10
,-----1.-
092 094 d
Fig. 12. Variation of diffusion coefficient for Plastanox 2246 at various tem-
peratures as a function of the polyethylene density. 120
120 r - - - - r - - - , - - - - , - - - - - , - - - ,
PLASTANOX
o
~80
..,
~
"0
W
0.92 094 d
Fig. 13. Eil T) as a function of the polyethylene density for Plastanox 2246. 120
the diffusion coefficient decreases as the density increases at each

temperature. The ratio of D at extreme densities is about 10. Figure
13 shows that Ed increases linearly with the density of the polymer.
Michaels and Bixler54 obtained a similar result with gases in
polyethylenes having different crystallinities. The behaviour of Irganox
1076 is more surprising than that of Plastanox 2246 in the same
polymers,12o as can be seen from Figs 14 and 15. Figure 15 shows that
above a given density, Ed(lT) and EihT) seem to reach maximum
values.
This experimental result needs to be explained as does the influence
of annealing low density polyethylene on the diffusion of Irganox
1076, as shown in Fig. 16. Except at the lowest temperatures, the
10- 9
10- 8
N
--.In
--.111
N
E
u
E
(5 2-
0
10- 9
10-11
0.94 d 0..94 d
Fig. 14. Diffusion coefficient for Irganox 1076 at various temperatures, as a

function of the polyethylene density. 120
146 J. Y. Moisan
IRGANOX 1076
V
160
'0
.....
E
...., A
-'"
't:l
I.JJ 120 --
--.?
•
80 / • •
V
/
0.92 0.94 d
Fig. 15. Values of EiIT) (&) and Bd(hT) (e) for Irganox 1076 as a function
of the polyethylene density.120
'. An ealedl PE
~~~~--+-~---+---+---+-~
E
2~-~.~~+-~r-~---+---+~
o
10-10~l---j--+--+--+--+---l
I
2.8 3.3x10- 3
3 11T(K)
Fig. 16. Influence of annealing low density polyethylene on Irganox 1076

diffusion coefficient. 12o 2 and 4, after annealing; 1 and 3, after quenching.
diffusion coefficient is higher in an annealed material than in a

quenched sample, which may seem to be in contradiction with the
results obtained previously. The same phenomenon was observed by
Klein 84 in a low density polyethylene, with the docosanyl ester of
docosanoic acid as diffusant. The interpretation given by Klein will be
taken up in the next section. Density, or even degree of crystallinity,
are obviously crude characterisations of polyethylene.
5.2.8. Orientation and Diffusion

Polyethylene is often oriented, that is the polymer chains are not
randomly distributed but they tend to be parallel to a selective direc-
tion depending on the conditions of processing. This phenomenon of
orientation is most important in the case of fibres, such as polyamide
textile fibres, where it has been observed that D decreases, but activa-
tion energy increases, with draw ratio (A).121
Takagi 122,123 has published an interesting study on the kinetics of the
dyeing of nylon 6 fibres. He observed that the diffusion coefficient in
the direction of draw decreases continuously with draw ratio, whereas
the activation energy increases. In the cross direction, D reaches a
maximum value at A = 1'5-2,123 and then decreases. The activation
energy comes down to a minimum with A approaching 2-3, and then
increases.
Yasuda and Peterlin 124 also observed the diffusion coefficient reach-
ing a maximum, but with CO 2 diffusing in monoaxially oriented low
density polyethylene. On the other band, Araimo et al. 12S did not
notice any maximum value, but a continuous decrease of D with
elongation as they studied the diffusion of methylene chloride in low
density polyethylene. De Candia et al. 1S7 rev~aled different behaviour
for crosslinked low density polyethylene; the maximum diffusion
coefficient is observed with the draw ratio approaching 2, as are the
minimum values of density and elastic modulus. Williams and Peter-
lin 126 consider that when polyethylene is drawn, the spherulites distort at
A up to 7 or 8, but beyond this the material has a fibrillar structure.
These studies of low density polyethylene have been conducted
using carbon dioxide or methylene chloride as diffusers. Can the same
phenomenon be observed with stabilisers of polyolefins?
Moisan 127 used low density polyethylene films which had been
quenched under different conditions; the orientation of mac-
romolecules was assessed by measuring dichroism in the absorption
band at 1368 cm- 1 which is characteristic of the amorphous phase,
1.1
+ 01 • OIl
Fig. 17. Diffusion coefficients against dichroism ratio at 1368 cm- 1 for Irganox
1076 in films of slightly drawn low density polyethylene. 127
N
..!!!
E
o
Cl
10- 9 f--f----+---+---+--'-..l---+------l
15 01
Fig. 18. Diffusion coefficients against dichroism ratio at 1368 em-I for Irganox
1076, in direction perpendicular to stretch for highly drawn polyethylene. 127
From Fig. 17 it can be seen that at low draw ratios, the diffusion
coefficient parallel to orientation decreases while the perpendicular
one increases. Figure 18 shows that a maximum value of D is obtained
as with dyes in nylons.
5.2.9. Relation between Activation Energy and the Pre-exponential

Factor
In early studies of the diffusion of gases through elastomers, Barrer
and Skirrow 1l6 pointed out a relation between Ed and log Do of the
form
log Do = a + b(Ed/T) (16)
which is interpreted as a linear relation between free energy and

entropy. Van Amerongen confirmed this relation 56 and Meares 51 de-
monstrated it in the diffusion of gases in polyvinyl acetate. Dubini et
al. 77 observed it while studying the diffusion of thiodipropionic esters
and hydroxybenzophenones in polypropylene. Cicchetti et s found ae
it applied to the diffusion of hydroxybenzophenones in several
polyolefins.
In examining the results obtained by Dubini et al. 77 a relation is
revealed which is typical of thiodipropionic esters and hydroxyben-
zophenones in polypropylene. It is thatS9.106.120.128 the coefficients a
and b are typical of a chemical family of diffusants in a given polymer
(see Fig. 19).
15
Cl
o
~ 5
40 120 Ed (kJjmol)
Fig. 19. Experimental relation between log Do and Ed for low density
polyethylene. (e) Phenolic antioxidants; (.A.) thiodipropionic esters. 89
150 J. Y. Moisan
5.3. Theories and Interpretations

The first theories which were proposed to explain diffusion phenomena
dealt with the diffusion of gases in polymers (mostly in amorphous
polymers). An example is the activated zone theory as described by
Barrer 1l6,129 and investigated by Brandt. 130 This theory expresses the
diffusion coefficient as a function of the square of the diffusing
molecule diameter and activation energy as the sum of several energies
representing interactions between molecules.
Michaels et al. 54,55,69 were concerned with the permeation of gases in
polyethylene and wrote
D = D*/(T{3) (17)
where D* is the diffusion coefficient in totally amorphous materials, T
a 'geometrical impedance' factor and {3 an 'immobilisation' factor. {3 is
almost equal to 1 for helium, that is a diffuser having very low atomic
radius. In view of the results obtained in the diffusion of gases in
different polyethylenes, these authors come to the conclusion that T
increases very rapidly with crystallinity, and that the two factors
increase much more rapidly with crystallinity in large molecules than in
small ones. This is considered as an increase in the crystalline order as
crystallinity increases; Brownian motion in the amorphous phase is
thus hindered when the lamellae are more perfectly arranged and the
interlamellar space decreases.
Peterlin 131 gave almost the same description and wrote
D=DalfJ/{3 (18)
where Da is the diffusion coefficient in 'pure' amorphous phase, 1/1 the
tortuosity factor expressing the necessity for the diffuser to avoid
crystallites and {3 the 'blocking' factor, which gives the narrowing of
the amorphous phase between crystallites.
Where diffusant-polymer compatibility is high the diffusion coeffi-
cient can be concentration dependent and D may not change with
temperature in accordance with the Arrhenius equation. FujitallO
suggests that this phenomenon should be described by means of the
William-Landel-Ferry (WLF) equation. It should be noted, however,
that such deviations from the Arrhenius equation have probably not
been observed with the low compatibility additives used in polyolefins.
Pace and Datyner132-134 very recently proposed a description of
diffusion in polymers. They consider a semicrystalline structure, that is
the macromolecular chains are locally almost parallel, in the amorph-
ous as well as in the crystalline phase. Diffusion parallel to the chains is
supposed to have a zero activation energy, but perpendicular diffusion

requires distortion of the chains and so has a finite activation energy.
They give an expression for the diffusion coefficient and the activation
energy for a small 'spherical molecule which takes some characteristics
of the polymer into account. Results are in good agreement with the
theory for polyethylene, natural rubber, polyisobutylene, polyethylene
terephthalate and polydimethylsiloxane, but not so satisfactory for
polypropylene, polyvinyl acetate, polystyrene, polyvinyl chloride or
polyethylmethacrylate.
The values of Ed(l T) seem to support this theory. The molecule
cannot be distorted below the melting temperature; only a temperature
above melting will produce enough energy to cause the molecule to be
distorted. This helps to explain why the discontinuity observed in the
Arrhenius plot does not occur at the melting temperature of the crystal
but at a slightly higher temperature.
Pace and Datyner also studied the diffusion of more complex
molecules,135,136 but they only considered a diffusion coefficient de-
pending on the concentration and having a variation with temperature
independent of the Arrhenius law. The results obtained are in rather
good agreement with those published and corresponding to the same
criteria.
Klein 137-139 recently published a different presentation of the diffu-
sion phenomenon. In a description of the amorphous phase he pro-
posed that the macromolecular chains partly belong to a crystallite, be
they entangled, or tied to two crystallites ('tie-molecules'). Finally,
several 'fixed obstacles' appear in this amorphous phase which are
separated by a distance h. A small molecule will diffuse without being
concerned with this distance h. On the other band, a long molecule will
have to avoid these obstacles. Any action likely to modify this distance
h will affect the kinetics of diffusion. From the model of reptation
discussed by several other authors14o-142 and proposed by De Gennes,
Klein139 came to the conclusion that D must vary as 1-2 in molecules
of length I greater than h.
Several authors143-145 have been concerned with the intercrystallite
phase and have revealed the existence of these 'fixed obstacles' show-
ing that diffusion was dependent or independent of the relative size of
the lamellae and of interlamellar spaces. Klein 84 examined the in-
fluence of annealing of low density polyethylene on the diffusion of
molecules of great length. A greater 'order' of the polymer amorphous
phase was expected and hence less and more widely spaced obstacles.
152 J. Y. Moisan
Annealing should lead to a higher diffusion coefficient. Klein checked

this by diffusing the decosanyl ester of decosanoic acid and of the
dodecyl ester of dodecanoic acid. This was also confirmed,120 using
Irganox 1076 in low density polyethylene (see Fig. 16). The decrease
in D with the increasing crystallinity of the polyethylene can be
explained by a decrease in the length h. This would explain the various
behaviours of Plastanox 2246 and of Irganox 1076 (see Figs 12 and
14). The length of the Plastanox 2246 molecule would always be
smaller than h but the molecule of Irganox 1076 is shorter than h in
low density polyethylene and longer in high density polyethylene.
Klein found D to be proportional to 1- 2 (eqn (14» for molecules
having a length exceeding 25-30 A. In semi-dilute solution, where the
model presented by De Gennes is still valid, this result was confirmed
by the diffusion of polystyrene. 146 On the other hand MacCall 1l4 found
D proportional to 1- 513 for self-diffusion of molten polyethylene, and
Kumagai et al. 147 obtained 1- 1 . 7 with polystyrene. Do these two experi-
ments reveal a decrease in the density of obstacles, as discussed by
Doi 148 ?
The molecular distortions of the chains in the amorphous phase and
of the diffuser may affect the activation energy for diffusion Ed' When
the length I of the diffusant is smaller than h, Ed increases with I,
whereas it remains constant when I is greater than h. In addition, an
increase in Ed may be expected when h decreases. The mobility of
molecules in an amorphous phase which is highly 'influenced' by
lamellae will be decreased, hence a greater energy will be necessary for
the movement of the diffusant. This would explain the different be-
haviours of Plastanox 2246 and Irganox 1076 (see Figs 13 and 15) and
confirm that the length of a Plastanox molecule is always smaller than
h, which is not always true with Irganox 1076. The material is greatly
altered by transitions such as the melting of the polymer and the glass
transition; a greater mobility enables the obstacles to be 'avoided'
more easily and induces a smaller activation energy.
It is worth discussing the various activation energies obtained. Let
Ep be the energy required to distort a polymer chain of length h in the
amorphous phase, and Ea the energy required to distort the diffusing
molecule. We have, when 1<11
(19)
when l>h
(20)
Assuming that Ea is almost equal to zero above the additive melting

temperature, we obtain, when I < h
(21)
when l>h
Ed(hT) = Ep (22)
With a rigid molecule (such as lonol with I < h):
Ed(lT)<Ep (23)
Examining Fig. 15 shows that Ed(lT) and Ed(hT) seem to reach a limit
when h = I. The results presented in Fig. 11 concern the variation of
Ed(h T) in several methyl esters in a low density polyethylene. Only the
activation energy required for an element of the macromolecular chain
of length 1 (when I::;,; h) to be distorted needs to be considered. An
increase in Ed(h T) with 1 is observed, which is the energy of distortion
of a chain of length I. It should be noted that on extrapolation the
curve passes through the urigin, which means that the energy is zero
when 1 equals zero. The critical h at about 27-28 A (that is about 25
-CH 2- chain links) corresponds to an energy of about 88 kJ mol- 1. The
energy Ed(lT) of lonol is much smaller (73 kJ mol-t, see Table 5) since
the length is smaller than h.
Frisch 149,15o has proposed that the activation energy of a diffusing
gas in a polymer is the sum of two energies, one of which is specific to
the diffuser, the other to the polymer. Lowell and MacCrum (62 com-
pared the 'Y-relaxation of polyethylene and the diffusion of butane in
that polymer showing that the mechanism responsible for both is the
distortion of four carbon atoms in the chain. The activation energies
are almost identical; Ed is 62 kJ mor 1 and the activation energy of 'Y
relaxation is 60 kJ mol- 1.
It is now possible to compare the {3 relaxation of polyethylene with
distortion length for diffusion. The {3 relaxation is only observed in low
density polyethylene and is specific to the amorphous phase. In addi-
tion it is sensitive to any modification of that phase such as annealing
or oxidation and the presence of additives. 152 The activation energy of
{3 relaxation is generally153 considered as ranging from 80 to
100 kJ mol- 1. There does not seem to be a relationship between
distortion length and relaxation for polypropylene.
On stretching polyethylene to A > 6 the spherulites are destroyed
and only fibrils remain.154-156 At low values of A, orientation of the
154 J. Y. Moisan
crystalline phase seems greater than that of the amorphous phase, as

can be shown by i.r. dichroism.127.155 Orientation of crystallites can be
shown to cause a shrinking of the amorphous phase in the direction
parallel to stretching. This is revealed by an increase in D which
depends on a decrease in h. In the perpendicular direction, the
amorphous phase seems to be stretched; the density first decreases 157
up to A = 2 and then increases. The distance h thus seems to be
greater, until the amorphous phase is orientated in its turn, and the
number of obstacles in the material increases. This could explain why
the diffusion coefficient increases and then decreases perpendicularly
to stretching. This interpretation was recently confirmed by Akay et
al. 151 Crystallinity, measured by i.r. spectrophotometry, first decreases
and then seems to increase for A > 2. At the same time, the rate of
oxidation in stretched samples decreases; this is interpreted as a
decrease in the permeation of oxygen on drawing.
In conclusion, it may be stated that the kinetics of diffusion of
stabilisers in polyolefins depends on parameters related both to the
structure of the diffusant and to that of the polymer. These diffusants
are not model materials; thus it is impossible to easily extrapolate
already known results. Therefore, it is rather difficult to provide the
value of D and Ed in an additive-polymer pair without measuring
them.
6. SOLUBILITY OF ADDITIVES
The preceding section illustrated that diffusion in polymers has been

widely studied; the same is not true of solubility. This parameter will
nevertheless prove important for the effectiveness of stabilisation. If, in
fact, too great a proportion of the stabiliser is in the form of precipi-
tates and not in solution in the material, the effectiveness will certainly
be reduced. Some publications have given solubility values of stabilis-
ers in polyolefins and these will now be examined.
6.1. Methods of Measurement

Methods of measurement differ according to whether interest lies in
gases, organic vapours or stabilisers. In general, methods of measure-
ment of the permeation of gases enable solubility values to be ob-
tained. 52 The establishment of an unsteady state enables D to be
measured, then the steady state measurement of permeability, P,
O2 permeation and stabiliser migration effect.~ on polymer degradation 155
permits the evaluation of solubility, S, by eqn (2). A method more

often employed to measure the solubility of solvents or organic vap-
ours entails following the gain in weight of a polymer sample submitted
to an atmosphere of this product.72.73.102
For additives and in particular antioxidants of polyolefins, three
methods have been used to ascertain solubility in polymers. The first
has been described by Roe et al. 87 •88 and more recently by Billingham
et al. 158 The solubility of the additive is measured in a series of solvents
of similar chemical structure to that of the polymer-normal alkanes
for polyethylene, for example. In this way the solute-solvent interac-
tion parameter, Xl> can be evaluated. The hypothesis that Xl is
invariant for these different product-solvent combinations at all tem-
peratures enables solubility in the polymer to be calculated from molar
volumes and heats of fusion. The enthalpy of solution, aHs , is consi-
dered to be the same for the polymer and for the solvents.
The second method is an equilibrium one, and consists of dissolving
the maximum quantity of solute in the amorphous phase of the
material. For this purpose, Billingham et al. 158 constructed an assembly
similar to that used by Roe et al. 88 for measuring diffusion. The
polymer sample is placed between two sources with high additive
concentration, and the assembly is left for several weeks at a given
temperature until constant concentration in the sample is obtained. In
the method employed by Frank,21.159 solute is dispersed in the
polymer and turbidimetry used to find the temperature at which it
dissolves.
The third method could be called dynamic and has been used by
Roe et al. B?88 and by the author 89 and is described in Section 5.1 for
the graphical determination of the parameter K. Equation (5) leads
directly to the diffusion coefficient, and solubility S is easily calculated
with the aid of eqn (9).
6.2. Results
6.2.1. Influence of Temperature

The effect of temperature on the solubility of gases in polyolefins has
been dealt with extensively in the literature;55.69.72.l60 an Arrhenius
type equation (eqn (24)) is always obeyed
S = Soexp (-aHJRT) (24)
Here So is the pre-exponential factor and aHs is the enthalpy or
156 1. Y. Moisan
,
Ul
0.1
1\ ~
'\
t\.
"\
SANrON( X
2.7 3><10- 3
1/T (K)
Fig. 20. Solubility of Santonox in low density polyethylene. 89
heat of solution. It must be noted that for light gases, tt.Hs is generally
very small and often negative. This relation is however not obeyed for
vapours which are also solvents of the polymer, as is the case with
benzene, hexane and heptane for polyethylene. 161
In polyethylene,89.158 as in polypropylene,21.159 the relationship for
stabilisers is as shown in Fig. 20 for the case of Santonox in
polyethylene. Lowell and MacCrum72 have illustrated the effect of the
~I ij1B~I~~IR1076
3 3.2><10- 3 1/T
3 1/T
Me St ~
10
-
Ul
I Ac St
! 5
............ 4 .i-:.
~ [S"'! ~
3
.........
3.1 11T 3.3><10- 3

2
2.9 1/T '"
3><10. 3
Fig. 21. Solubility of hexadecanone-3(Hd3). Irganox 1076 (IR. 1076), methyl

stearate (MeSt) and stearic acid (AcSt) in low density polyethylene. 106
fusion of polyethylene on the solubility of C 3 H 6 , C 4 H lO and C(CH3 )4'

Solubility increases sharply by almost a factor of 10 at the fusion
temperature of the polymer, but dRs remains the same on either side
of this temperature. A discontinuity in the Arrhenius plot at a temper-
ature close to the fusion temperature of the additive is therefore to be
expected under these conditions. Figure 21 106 shows this for solutes as
different as hexadecanone-3, methyl stearate, stearic acid and Irganox
1076 in low density polyethylene. The discontinuity does not take
place at the fusion temperature of the additive but, as for diffusion,
slightly above it. dRs has different values above and below the
discontinuity.
Table 6 89 gives the parameters So and dRs for a series of stabilisers
in polyethylene. It therefore appears that in studying solubility in
polymers, as in the case of diffusion, every modification of the molecu-
lar mobility of solute or solvent has to be taken into account. One must
undoubtedly realise that solute-solvent interactions are not indepen-
dent of molecular mobilities.
The reason for the Arrhenius type of behaviour of solubility is that
TABLE 6
Solubility Parameters for Some Stabilisers in Polyethylene
So (ppm) tlHs (kJ mol-I) 8 tlH,
Plastanox 2246 2·2 x 107 15·9

Santon ox 1·3x10 15 80·7
Plastanox 425 9'Ox 107 26·8
Nonox WSP g·lx10 8 32·8
Ionox 220 1·6 x 109 38·5
{ 4'Ox 1011 45·4
Irganox 1076 -27'3
9·3x10 14 72·6
Topanol CA 2'Ox 10 10 47·2
{ l'Ox10 l3 61·4
Irganox 1035 14·6
6·1 x 10 10 46·8
Ionox 330 1·lx107 28·0
Irganox 1010 4·0x 10'2 62·3
{1'6 x 109 53·0
DLTDP 42·3
1.4x 102 10·7
{ 1·0x10s 29·2
DSTDP 21·5
4·4x 10' 7·7
Tinuvin 327 3.9x 105 10·9
158 I. Y. Moisan
15 1 - - - - - - 4 - - - - - - - - - + - - - - - - + - - - - -____"Il----l
o
(f)
•
10
5 1-----=--------1---"E--
20 40 60 t> Hs (kJ/moll
Fig. 22. Experimental relation between dR, and log So for low density
polyethylene. 89 ( .... ) Thiodipropionic esters; (e) phenolic stabilisers.
the equilibrium obeys the laws of thermodynamics, and in particular

the Van't Hoff equation.
log S = - LlHs LlSs (25)
RT R
where LlHs and LlSs are respectively the enthalpy and entropy of
solution. A relation between LlHs and So has observed, and is shown in
Fig. 22. However, it is to be noted that the experimental relationship
obtained for phenolic stabilisers is different from that obtained for
thiodipropionic esters.
6.2.2. Structure of the Diftusant
Some time ago, Barrer and Skirrow noticed the influence of the length
of the chain of normal paraffins on their solubility in rubbers. In this
case, Sand LlH, increase with chain length. Later on Aitken and
Barrer to2 showed the negative influence of the branching of paraffin
chains on soluhility.
The stabilisers which have been studied H9 belong to a variety of
chemical groups, but can be broadly compared on the basis of molar
mass as shown in Fig. 23.
6.2.3. Structure of the Polymer
The influence of polymer crystallinity on the solubility of gases has
been thoroughly studied by Michaels et al. 52 .5 5 ,69 and Lowell and
~ , , I
Ul
1\ • I
0.1
1-------
f---
".~
'\..
~
5P ·C
-- I----
• "-
'\ •
.
""
0-01
25 3 logM
Fig.l3. Solubility at 50°C in low density polyethylene as a function of molecular

weight. 89 (.&) Thiodipropionic esters; (e) hindered phenolic antioxidants .
I
•A;neai PE
5
.., I --- f--
'r--..~~~
i:
I' I
4
i
I
!~ ,
,
2.8 3.3x10- 3
3 1/T (K)
Fig. 24. Solubility of Irganox 1076 in low density polyethylene. 2 and 4,

annealed polyethylene; 1 and 3, quenched polyethylene.
160 1. Y. Moisan
+
•
OL-____-L_____ ~ ______~____~__~
0.92 094 d
Fig. 25. Solubility of Plastanox 2246 in various quenched polyethylenes. l1 (J
MacCrum72•162 for polyethylene, showing that eqn (1) is obeyed. It

seems that such a simple relation is not valid for additives in
polyolefins. Calvert et al. 46•48 illustrated that separation occurs during
crystallisation and the formation of spherulites in polypropylene indi-
cates that only the amorphous phase is a solvent for these substances.
The conditions of crystallisation have a perceptible effect on the
solubility of gases in polyethylene69 or of vapours such as carbon
U1
IRGANO 1076
o
35 ~__-+~__ --~-----+------~~~
~
3 ~__--+---=~;..
•
092 091. d
Fig. 26. Solubility of Irganox 1076 in various quenched polyethylenes. 'to

"'"~I
PLASTAN( X 2246
-040
--...,
E
-"
III
•
I----
:r:
<l
20
0.92 0.94 d
Fig. 27. Dependence of b.Hs on density for Plastanox 2246 in various
quenched polyethylenes. 11o
tetrachloride in polypropylene. 163 Figure 24 shows that an important

difference in the solubility of Irganox 1076 in low density polyethylene
is evident; according to whether the sample has been quenched or
annealed, not only are the values of S different, but also the values of
llH.. Figures 25 and 26 give the solubilities of Plastanox 2246 and
Irganox 1076 in a series of quenched polyethylenes and shows that eqn
(1) is not obeyed, assuming of course that density and crystallinity are
linearly linked. Moreover, eqn (1) supposes that llH. is constant
whatever the value of a. This is not the case for either Plastanox 2246
IRGA OX 1076.
-0
--
E
~ 40 -----.-f-----I---="""'-00;;;;;;;::::1---
L
III
:r:
1---1-<--1
<l
-+----1
20
092 094 d
Fig. 28. Dependence of b.Hs(lT) and b.Hs(hT) for Irganox 1076 in various
quenched polyethylenes. 110
162 f. Y. Moisan
or Irganox 1076, above or below the fusion temperature (see Figs 27

and 28).
6.2.4. Orientation
Peterlin124.126.164 showed that the solubility of methylene chloride in
stre,tched polyethylene increases for draw ratios up to 7 or 8, only
to decrease abruptly beyond these values. Figure 29 shows that the
solubility of stabilisers undoubtedly develops in the same way, l27 and is
due to a more rapid orientation of the crystalline phase leading to an
increase in 'free volume' in the amorphous phase.
5r-.-----r----,----,-----r----,~
o
Ul
0.5 r--+-----+-----+----+---r---+-1
DI 15
Fig. 29. Plot of the solubility against dichroism ratio at 1368 cm·- 1 for Irganox
1076 in low density polyethylene. 127
6.3. Discussion
It appears that one cannot validly apply the first method of measure-
ment to the evaluation of solubility in semicrystalline polymers.
Perhaps it is nevertheless applicable to entirely amorphous polymers.
This method supposes tha~ dRs is the same, even if the solvent is a
polymer. Table 7, however, records the published values for dRs for
four antioxidants and shows that the above hypothesis is not justified.
Billingham et al. 158 have already s!lggested that this method of measur-
ing the solubility of additives in polyethylene is not acceptable. This is
easily understandable in view of the description of the structure of the
amorphous phase of polyethylene. This amorphous phase is too much
subjected to the influence of the crystalline phase to be classed as a
liquid organic solvent.
TABLE 7
Heats of Solution for Antioxidants in Some Alkanes
Octane 158 Dodecane 158 Octadecane 158 Low density polyethylene
According According
to ref. 158 to ref. 89
Topanoi CA 20±2 19±2 19±2 50±1 47·2

Irganox 1010 77±6 76±17 67±2 39±4 62·3
Ionox 330 35±1 39±2 44±3 28·7
Plastanox 2246 42±6 38±1 41±4 26·7
The two other methods can be discussed on the basis of solubility

values of two antioxidants,87-89.158 Topanol CA and Irganox 1010.
Table 8 summarises the available values, namely solubility at 25°C,
S(25°C) and 70°C, S(70°C), and tlHs for low density polyethylene
(LDPE), atactic polypropylene (APP) and isotactic polypropylene
(IPP). Roe et al. 87 •88 recognise that their dynamic method does not give
an accurate solubility value. The results published by Billingham et
al. 158 and the author 89 for Topanol CA, and represented in Fig. 30, are
identical. The two values of tlH. are equal within experimental error.
Figure 31 shows values for Irganox 1010, for low density
polyethylene and for atactic polypropylene-the last result being given
TABLE 8
Solubilities of Antioxidants in Polyolefins at Two Temperatures
S at 25°C S at 70°C ~Hs Ref.

(%) (%) (kJmoZ- 1 )
{ O'009 0·12 50±1 158

Topano\ CA LDPE
0·011 0·125 47·2 89
0'00006 U
O'012 u -100} 87, 88
LDPE { 0·026 -62
0·020 0·24 39±4 158
{
Irganox 1010 0·003 0·14 62·3 89
APP 0·25 1·5 24·4 21,40
IPP 0·15 0·40 32·6 158
a These values were obtained from the solubilities of organic
solvents; they only concern a totally amorphous material.
164 J. Y. Moisan
0.1
'i\~ ~"
r"i..'
0.01
\ 1'\.
~
25 3 1/Txl0 3 35
Fig. 30. Solubility of Topano) CA with temperature. (--) according to

ref. 158; (----) according to ref. 89.
(1)
( 2)
o1 ~_ _+_-+-.-+
(3)
2.4 l/Tx 10 3
Fig. 31. Solubility of Irganox 1010 with temperature. 1, according to refs 21

and 40; 2, according to ref. 158; 3, according to ref. 89.
by Frank?1.40 It appears immediately that these three curves are

distinct but seem to lead to a single value of solubility for a tempera-
ture close to the fusion temperature of polyethylene (about 130°C). It
is also seen that the 'equilibrium' method (curve 2) always gives a
higher value than the dynamic method (curve 3). One might therefore
wonder if the equilibrium method which enables the maximum of
solute to be placed in the semi-crystalline matrix, does not modify the
amorphous phase. This modification would be undoubtedly ever
weaker as the fusion temperature was approached and perhaps ever
greater as Tg was approached.
It remains to be seen why Irganox 1010 behaves in this way whereas
Topanol CA does not. Arguments based on the size of the solute
molecule cannot be sufficient. On the other hand, we noted in a
preceding section that phenolic antioxidants modify the dielectric {3
and 'Y relaxations of low density polyethylene which amounts to saying
that these products modify the amorphous phase of this polymer.
Concurrent studies of dielectric loss165 between 1 and 60 MHz at room
temperature show that the effect of antioxidants is very different
according to the additive. Thus for Irganox 1010 losses linearly
increase with concentration so modifying the relaxation {3 of the
polymer. In contrast, Topanol CA has a weak effect which is near the
limit of experimental measurement. This fact leads one to estimate that
Topanol CA has a very weak effect on the structure of the amorphous
phase.
Solubility varies according to the method of measurement employed.
Irganox 1010 plasticises the amorphous phase of polyethylene whereas
Topanol CA does not. It can be also underlined that the solubility of
Irganox 1010 in isotactic polypropylene measured by Billingham et
al. 158 by the equilibrium method, shows that the variation with temper-
ature is not perfectly 'Arrhenius'. If the interpretation given above is
valid for all the semicrystalline materials, it is exactly what one would
expect for isotactic polypropylene. On the other hand, for a perfectly
amorphous material such as atactic polypropylene, an Arrhenius plot is
observed. Around the fusion temperature of polyethylene, solubility is
the same whatever the measurement method and is of the same order
of magnitude as the solubility in atactic polypropylene. In these cases,
the matrix will be a completely amorphous material and the differences
in chemical nature between polyethylene and polypropylene are un-
doubtedly not sufficient to influence the behaviour of a phenolic
compound.
166 1. Y. Moisan
7. MIGRATION OF STABIUSERS AND

NATURAL AGEING
Certain authors166.167 when dealing with the subject of natural ageing

in polyolefins, are primarily concerned with climatic factors. However,
most17-20.38.168 stress the importance of the migration of stabilisers.
Two recent studies go further. Akay et al. 41 examined the photodegra-
dation of polyethylene samples containing different concentrations in
an anti-u.v. agent. The period of time after which oxidation of the
material becomes evident depends upon the stabiliser; however, it does
not double when the initial concentration is doubled. This experimen-
tal fact cannot be explained except by the effect of losses by migration
during exposure in outdoor climatic conditions. Likewise, Cunliffe and
Davis65 have illustrated the effect of the permeation of oxygen on the
kinetics and oxidation profile of thick samples of low density
polyethylene.
Luston 14 has reinvestigated a set of published values concerning the
compatibility of additive-polymer systems. He considers the physical
loss of stabiliser to be linked to low solubility, the kinetics of diffusion
and extractability by solvents and additive volatility. If the values
quoted in previous sections are considered, it can be ascertained that in
terms of the effectiveness of stabilisation, physical loss emerges as the
most important parameter. The notions of solubility and kinetics of
diffusion now have to be translated into the practice and protection
time considered.
The model proposed by Calvert and Billingham60.158 considers the
form of the sample (film or fibre) and losses by surface evaporation,
and calculates the period of time after which concentration in the
sample will be no more than 10% of the initial concentration. Unfortu-
nately, values of solubility, diffusion coefficient and volatility of the
stabiliser, have never been measured by the same author under the
same conditions. Nevertheless, the results of their calculations are
interesting for the evaluation of the order of magnitude of the effective
protection time of an additive. Thus BHT (butylated hydroxy toluene)
or lonol would only have a protection time of 50 days in a sheet of low
density polyethylene of 1 mm thickness. On the other hand, Cyasorb
UV 531 would give a protection time of 7·6 years for a 1 mm sample
but the protection time for a film of 100 ILm thickness is no more than
9 months.
Akay et al. 41 observe the beginning of oxidation after only 5 months,
for samples Qf 170 ,...m thickness in the process of natural ageing, when
the initial concentration of stabiliser is 0·5 or 1 %. This is a shorter
time than calculated from the diffusion coefficient and solubility89 and
therefore it seems that volatility has been underestimated. It is regret-
table that they did not measure the remaining additive concentration
after exposure.
Moisan and Lever I69 took samples of low density polyethylene, in
the form of sheets 1 mm thick and containing 0·05%, 0·1% and
0·15% of six phenolic antioxidants, and exposed them to outdoor
natural ageing, which included washing by rainwater. Samples were
taken every three months and the remaining antioxidant concentration
was measured by gel permeation chromatography (Fig. 32) and the
oxidation rate by measuring the absorption of the i.r. band at
1720 cm-I. The presence of degraded forms of this product is apparent
adjacent to the characteristic peak of the antioxidant in Fig. 32. The
absence of any protection on the fifth chromatogram is noticeable; this
sample was examined after a year of exposure. Figure 33 presents the
concentration against time for six antioxidants. It can be seen that
disappearance time is independent of the initial concentration, except
in the case of Irganox 1076 and Ionox 330. Figure 34 confirms the
preceding results by showing that oxidation appears as soon as the
stabiliser concentration becomes too low. During the course of the
experiment, no deposit was observed on the surface of the samples.
This is in accordance with the solubility169 or volatility 158 of phenolic
./ If' /'
TOPANOL CA
x2 1500 ppm
x5
x5 x2
56
min
Fig. 32. Gel permeation chromatogram of Topanol CA from the same sample
at different ageing times. From left to right: 0, 3, 6, 9 and 12 months.
SANTONOX TOPANOL CA IRGANOX 1010
020 020 020
~0.15 015 0.15 f--

z
0
fi 010 0.10 '\ 010 1\
Cl:
>-
~n05 0.05
,.~
0.05 '\\
l
u
z r-~! '0\
~
"~.
0
uO.OO 0.00 000
0 6 12 18 24 o 6 12 18 U 0 6 12 18 21.
IRGANOX 1035 IRGANOX 1076 IONOX 330

0.20 0.20 r---r--r---r-~ 020
~015 0.15 I't---j--t--+---j 0.15

_x\
z
~ 0.10 ~-\-r---t--j---j
«
010 0.10
-', \
Cl:
>-
t5005l"-<,--\\~_--+_-+
u
0.05 " ..... /'\
-x
'::,~ ....
z
o
.....0 .....
'
-0
u 0.00 '-----'----"""""_~_ _:_' 000 0.00
o U C 6 m U 0 6 U m U
months months months
Fig. 33. Antioxidant content against ageing time for different initial loadings.
(x) Initially 1500 ppm; (fl.). initially 1000 ppm; (0) initially 500 ppm. 169
SANTONOX TOPANOL CA IRGANOX 1010

10 10 1.0
0.8 08 i 0.8
-
z
w
-
-.--'
-
!;? 0.6 0.6 r-- - - - - 06
1:§
0.4 - /' 0.4 / 0.4
~ /. 1//
I
!
.'
0.2 0.2 02
0.0 / 0.0
'/' 00
o 3 6 9 12 15 o 9 12 15 0
IRGANOX 1035 1.0 .--,1R_G_A,N_O_X,l_07_6,---, IONOX 330

1.0 1.0
1li:T
; I
0.8 08 08
-
--- ---
z iI
w
-
~ 06 r--- r----: --t-- - 06 06
x
0 0.4
iL -
0.4 04
-+-+--l---L -
~
--+-i~F-f
..-.-
(V ,-
0.2 0.2 02
0.0 /' 0 0 L-_"'--L---L.-,-L--,J 00

o 3 6 9 12 15 0 0 6 9 12 15
months months months
Fig. 34. Oxidation level against ageing time for different initial antioxidant
contents. (x) Initially 1500 ppm; (fl.) initially 1000 ppm; (0) initially
500ppm. '69
Fig. 35. Relation between antioxidant protection time and its solubility and
diffusion coefficient. 169
antioxidants. If the concentration data for Irganox 1076 (the only

additive with a concentration always less than its solubility) are re-
corded against the square root of time, three straight lines are ob-
tained, thus showing that a diffusion process which is undisturbed by a
deposit on the surface of the sample is taking place. Topanol CA and
Irganox 1076 have practically the same diffusion coefficient but very
different solubilities. This results in protection times which are very
different. On the other hand, Topanol CA and Irganox 1035 have
diffusion coefficients differing by two tens, but their similar solubilities
lead to similar protection times.
The parameter S2/D seems to be empirically linked to protection
time as is shown in Fig. 35. Here values of Sand D at 10°C were used,
as this temperature is considered to be an average for outdoors. This
shows the importance of solubility in relation to the diffusion coeffi-
cient and can be used in estimating protection time.
8. CONCLUDING REMARKS
A number of points remain to be discussed by way of conclusion.

Many of the results presented in preceding sections concern low
170 J. Y. Moisan
density polyethylene without mineral filler, simply stabilised by a single

constituent. Other polymers which require stabilisation will often have
a filler.
Stabilising systems for polyolefins are often composed of several
additives which are sometimes supposed to act in synergy. A recent
study by Ivanov et al. 171 shows that the synergy observed between a
u.v. absorber and an antioxidant is due more to migration of the
antioxidant from the inner part of the material towards the surface. At
the surface it has greater efficiency than when in the bulk, so the
interior serves as a reservoir of antioxidant for the surface. The authors
support this interpretation by showing that synergy appears greater
with thicker samples.
On the other hand, Kovacs and Wolkober 180 assume an interaction
between the active centres on carbon black filler particles and stabilis-
ers. Carbon black would thus have an effect on the antioxidant in
addition to its screening effect. Their measurements, however, were
carried out in a closed system at high temperature. In other conditions,
Hawkins and Winslow 15 always observed a positive effect of the
presence of carbon black on the efficiency of an antioxidant at 140°C;
this has also been seen at 200°c. 173
Nury170 looked at the effect of carbon black on the natural ageing of
low density polyethylene containing a phenolic antioxidant. He ascer-
tained that losses by migration are considerably reduced by the pres-
ence of carbon black. However, one might also consider that this
effect, which is beneficial from the point of view of stabilisation, will
depend on the quality of carbon black employed. This also explains the
superior stability of carbon black filled cable insulations. 22
Since solubility is the most important practical parameter, choice of
stabiliser will tend to depend upon it. The presence on the stabiliser of
organic functions similar to those on the polymer will increase its
stability. This is the case for Irganox 1076 in relation to phenolic
antioxidants or hydroxybenzophenones linked to octoxyl or stearyl
radicals.
Another approach is to increase the molar mass of additives by
polymerisation. l72 A polymerised Santonox (2·5-4 monomer units) has
thus been proposed for which migration is appreciably diminished.
Migration can be prevented by chemically bonding the stabiliser to the
polymer as is frequently suggested28.174.175 for rubber, polyethylene,
polypropylene and even polystyrene. Chemical bonding can occur
during vulcanisation of the polymer, or by grafting with the aid of an
intermediary.176 Albarino and Schonhorn177-179 used silane coupling

agents to improve compatibility.
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Chapter 5
Diffusion and Adhesion

J. COMYN
1. Theories of Adhesion. . . . . . . . . . . . 177

2. Diffusion Theory of Adhesion . . . . . . . . 181
2.1. Evidence for diffusion across the interface 181
2.2. Measurement of self-diffusion coefficients 184
2.3. Tack, diffusion and viscosity. . . . 185
2.4. Solvent welding of glassy polymers. . . 189
3. Diffusion and Joint Durabilitv . . . . . . . 190
3.1. Kinetics of water entry: . . . . . . . 192
3.2. Calculated and measured water uptake. 197
3.3. Dependence of joint strength on water content 202
3.4. Effect of water on the adhesive 203
3.5. Effect of water on the interface 207
4. Concluding Remarks 211
References. . . . . . . . . . . . 211
There are two quite distinct aspects of diffusion in the field of adhesive
bonding. The first of these is the diffusion theory of adhesion, which is
just one of several current approaches to a general understanding of
bonding. The second is the role of the diffusion of water in the
weakening of joints, and this is of particular importance in that
sensitivity of joints to atmospheric water vapour is one of the factors
which limits the further exploitation of the bonding of structures.
1. THEORIES OF ADHESION
There are six theories of adhesive bonding in current use, and these
are the diffusion, mechanical interlocking, electrostatic, adsorption,
177
178 1. Comyn
chemical bonding and weak boundary layer theories, although the last
of these is more a theory of non-adhesion than of adhesion. As these
have recently been reviewed by Kinloch! and by Wake 2 •3 only a brief
discussion of them is given here, but it is hoped that this will be
sufficient to place the diffusion theory in context.
Weak boundary layers certainly occur on contaminated substrates,
rust on iron and lubricating oils on other surfaces being well-known
examples. However, weak boundary layers may be more common in
polymers because of their tendency to reject foreign substances to their
surface by the process of diffusion. An important foreign substance
which might be a general source of weak boundary layers is low molar
mass polymer. Schonhorn and his collaborators have supported the
weak boundary concept. Surface treatment prior to bonding4 is widely
regarded as an essential practice in the preparation of durable joints
and Schonhorn and Hansen5 demonstrated that corona discharge treat-
ment is very effective for the pretreatment of polyethylene. The
treatment significantly increased the molar mass of the material and
introduced some crosslinking, but did not at the same time change the
wettability of the surface. Hence, it was suggested that corona dis-
charges increase the cohesive strength of an otherwise weak surface,
and that many semicrystalline polymers have a weak boundary layer,
between 0·02 and 0·10 Illll thick, composed of low molar mass mater-
ial which is rejected during crystallisation. However, recent work by
Briggs and Brewis6 using electron spectroscopy for chemical analysis
(ESCA) found no evidence for failure at the interface with treated
polyethylene substrates, and they further demonstrated that effective
surface treatments introduce various polar groups into the polymer
surface which can account for improved adhesion.
The mechanical interlocking theory places importance on the pene-
tration of the adhesive into surface irregularities of the substrate. The
fact that good adhesion can be obtained with flat surfaces rules out the
general applicability of the theory, but there are many instances where
the contribution of interlocking may be important. One case is the
adhesion of polymers to textiles where the former penetrates the yarn.
A second is the electroless plating of modified styrene plastics, where
the surface can be roughened by chemical etching. Later in this chapter
reference will be made to the adhesive bonding of aluminium and its
alloys, materials which have been widely studied because of their use
in the building of aircraft. Surface treatments for aluminium produce a
honeycomb of aluminium oxide with pores typically 400 nm deep. The
Diffusion and adhesion 179
application of a structural adhesive to such a surface at moderate

temperatures (e.g. IS0°C) and under slight pressure might not seem
ideal conditions for the adhesive to penetrate the honeycomb, but this
has been demonstrated to be the case for some systems by Knock.7
Charge transfer across the interface which gives rise to an electrical
double layer is the basis of the electrostatic theory of adhesion, which
was first proposed by Deryaguin. 8 It is well known that when adhesive
tapes are quickly stripped from substrates in the dark, light emissions
occur which might be due to electrical discharges. It was upon evidence
of this kind that the theory was first proposed but controversy still
exists as to whether such charges are the cause of adhesion or merely
the result of it. Upon placing dissimilar materials in contact, transfer of
electrons from one to the other will give rise to the anticipated double
layer, but good adhesion can also be obtained with the same material.
Further the nature of the charge carriers in most polymers is uncertain,
and additives and impurities might have a large effect on their ability
to form double layers. A variant of the electrostatic theory is due to
Fowkes9 who proposed that donor-acceptor pairs may occur at some
interfaces. These included copolymers with acrylic or maleic acid units
bonded to metal oxide or hydroxide surfaces where the -COO-
groups constitute an array of negative charges in the polymer. In
general terms, atoms with lone pairs can be regarded as donors and
groups containing chlorine or fluorine as acceptors. Comyn 10 has
proposed that ion-pairs may arise at the interface between aluminium
and epoxide adhesives in the following manner. An amine group will
add to an epoxide group to produce a zwitterion, thus:
0-
+ I
---+ -NH2-CH2-CH-
In the bulk of the adhesive proton transfer will occur to eliminate the
charges but at the interface ion exchange can occur, thus:
so providing an electrostatic attractive force across the interface.

Exchangeable ions (X-) could arise on the surface of aluminium during
pretreatment in an acid solution. Surface treatments for aluminium
180 J. Comyn
which give the best durability involve acid solutions; these include
etching or anodising in chromic-sulphuric or phosphoric acid.
The adsorption theory proposes that for materials in intimate con-
tact, van der Waals's forces between the molecules on the two sides of
the interface are sufficiently strong to give good adhesion. Whilst van
der Waals's forces are amongst the weakest of intermolecular forces it
has heen demonstrated that their combined strength may greatly
exceed measured joint strengths; however, it is a general property of
materials that their strengths are much less than the sum of the
component interatomic or intermolecular forces and the presence of
flaws or defects is given as the reason for this. Van der Waals's forces
include dispersion forces which are due to the attraction between
fluctuating dipoles and will thus occur between all materials, and also
the generally stronger polar forces which are due to permanent di-
poles. The non-polar polyolefins and polytetrafluoroethylene do not
make strong bonds, but bond strength can be greatly improved by
treating polyolefins by corona discharge, with a gas-air flame or by
oxidising in solutions containing chromic acid, where it has been
demonstrated4 that polar groups are introduced into the surface.
Similarly, the polarity of polytetrafluoroethylene surfaces can be in-
creased by chemical or electrochemical defluorination. 11
Covalent bonds are much stronger than van der Waals's forces and
their presence across an interface should lead to strong adhesive
bonds. There is some evidence for these when silane coupling agents
are used as primers on steel. These primers have the general formulae
XSi(OR)3 where R is methyl or ethyl and X contains a group which
will react with the adhesive such as an amine, epoxide or vinyl group.
When applied to a metal surface some hydrolysis of the alkoxide
groups occurs and there may be some condensation of the resulting
silanols to polysiIoxanes at the metal surface. For mild steel treated
with 3-glycidoxypropyltrimethoxysilane, Gettings and Kinloch 12 de-
tected FeSiO+ ions hy secondary ion mass spectrometry, and showed
that this was accompanied by an improvement in the water durability
of adhesive joints.
The presence of covalent bonds across the interface may be a factor
in the superior durability of phenolic adhesives. Such bonds might be
formed by the coordination of phenolic oxygens to aluminium ions, as
has been observed by the formation of complexes between aluminium
and some phenolic compounds.13 Further support for this view comes
from inelastic electron tunnelling spectra of phenol and hydroquinone
on aluminium oxide. 14
2. DIFFUSION THEORY OF ADHESION
Like the theories just presented the diffusion theory of adhesion is not
a general theory but probably applies to some adhesive bonds and not
to others. Its chief advocate is Voyutskii 15 and its basis is that diffusion
takes place across the interface to eventually obliterate it (Fig. 1). For
this to occur it is necessary for the level of molecular motion in the
adhering surfaces to be high, and for there to be sufficient compatibil-
ity for mixing to take place at the interface. Because of these restric-
tions the theory is most appropriate to the self adhesion of unvu1can-
ised elastomers. The term autohesion has been used to describe this
phenomenon.
Fig. 1. Diffusion across the interface between two polymers in contact.
2.1. Evidence for Diffusion Across the Interface

Diffusion at the interface between polyviny1chloride(PVC) and' poly(e-
caprolactone)(PCL) has been demonstrated 16 . 17 using energy dispersive
x-ray analysis (EDX) combined with t:lectron microscopy. These
polymers are compatible in the melt at all concentrations, but phase
separation occurs on cooling to room temperature. The EDX techni-
que measures the characteristic x-ray fluorescence of chlorine atoms in
PVC (they are excited by an electron beam) and it permits the
measurement of the concentration-distance curve for PVC in the
interfacial region. The high spatial resolution of EDX makes it applica-
ble to interfacial diffusion, where the mixing layer may be very thin.
The existence of interfacial diffusion is demonstrated by the results
182 J. Comyn
C- Co
~ .0 0·8 (,- Co
o.
L_
Q:!' «J
0·6
0
.e .0
0·4 o •0 0
eo o.0.0
02
-8 -6 -4 -2
°O S
2
7
4
x/2t · (x 10 )
6 8
Fig. 2. Master curve for interdiffusion at the interface between PVC and poly-
(E-caprolactone) at 70°C.'b
shown in Fig. 2. This shows the results of experiments with different

diffusion times at 70°C, but plotted in the form of a master curve.
Analysis of the data gives a mutual diffusion coefficient of (1·59±
0·13) x 10- 16 m 2 S-I; number-average molar masses were about 12,500
for PCL and 3000 for PVc, Experiments in the temperature range
70-11O°C with number-average molar masses of 19,200 for PCL and
40,600 for PVC gave an activation energy for diffusion of 49 kJ mol-I.
In fending off Anand's criticism of the diffusion theory of adhesion,
Voyutskii 18 has shown some electron micrographs of the interfaces of
polymethacrylate-PVC and polybutylmethacrylate-PVC prepared at
210-220°C. Mixing at the interface is much greater with the first pair
of polymers; a microdensitometer trace of the electron micrographs
appears in Fig. 3, where the gentler slope for the polymethyl-
methacrylate-PVC interface indicates greater diffusion. Voyutskii
Fig. 3. Microdensitometer traces of electron micrographs of (1)

polybutylmethacrylate-PVC and (2) polymethylmethacrylate-PVC inter-
faces.'"
has claimed that even completely incompatible polymers can give good
adhesive bonds because of 'local compatibility.'
Solubility parameter is a simple but not particularly reliable guide to
the possibility of mixing. Forbes and McLeod 19 measured the tack
between three different rubbers, taken in pairs. Tack bctween a pair of
polymers was less than the average tack between identical rubbers, but
the difference was less as the difference in solubility parameters of the
polymers making the bond decreased (Fig. 4). As the optimum condi-
tion for mixing is when the solubility parameters are equal, this
indicates that maximum adhesion occurs when mixing is greatest.
100r-------------------------~~
Mean tack- observed tack x 100

Mean tack 0
o
50 o o
o
1'2 2·4
d(SOLUBILITY PARAMETER)/(J cm- 3 )V2
Fig. 4. Effect of differences in polymer solubility parameter on tack. (After

Forbes and McLeod. 1 ")
Optical microscopy is reported to show the disappearance of the

interface between polyethylene and polyisobutene. 2o Ultraviolet mic-
roscopy showed a blurring of the interface between non-polar poly-
mers of like structure which increased on heating. With polymers which
differ greatly in chemical structure blurring at the interface still occurs
but the width of the blurred zone is less.
184 J. Comyn
2.2. Measurement of Self-diftusion Coefficients

In cases where the diffusion theory of adhesion is valid, the rate of tack
development will be controlled by the rate of self or mutual diffusion.
It is therefore appropriate to examine methods by which diffusion
coefficients in polymers can be measured. The use of EDX has been
mentioned above for the measurement of mutual diffusion coefficients.
Most measurements of self diffusion coefficients have involved label-
ling with radioisotopes.
Skewis22 spread a thin layer of 14C_ or 3H-Iabelled polymer on a
base of unlabelled material. Coant rate can be measured with a
Geiger-Muller tube placed over the sample, and this decreases as the
labelled polymer diffuses into the base. Both isotopes are (3 -emitters
and the absorption coefficients for (3-particles for the two in styrene-
butadiene rubbers are different (300 cm- I for 14C and 3600 cm- I for
3H). It is therefore a confinnation of the reliability of the technique
that the same value of diffusion coefficient results from each isotope
(Fig. 5). This method of measurement was first proposed by Rayner,
Thomassen and Rouse 23 and it was used for the self diffusion of
polymers by Bueche, Cashin and Debye24 for a copolymer of n-butyl
acrylate with 1% of 14C-Iabelled styrene. They demonstrated that self
diffusion coefficients are inversely proportioned to polymer viscosity,
and that the activation energies for self diffusion (55·2 kJ mol-I) and
40 Dt/1O- 6 cm 2
0
30
0
•
0
0
20 0
10
5 10
tl10 5 s
Fig. 5. Self diffusion measurements of 14C_ and 3H-labelled styrene-butadiene
rubber at 25°C, (0) 14C; (e) 3H. (After Skewis. 22)
viscous flow (57·7 kJ mol-I) are very similar. McCall, Douglass and
Anderson 25 used a proton n.m.r. spin-echo technique to measure
self-diffusion coefficients of a low molecular mass polyisobutene
(viscosity-average molar mass = 1660) and found the activation energy
of diffusion (23 kJ mol-I) to be less than the activation energy for
viscous flow (65 kJ mol-l). Diffusion coefficients of nylon 12 in the
melt were measured using a dye-tagging technique by Veno et a/?6
who observed that the activation energy for diffusion was much smaller
than that for viscous flow.
The relationship between diffusion coefficient (D) and viscosity ('TJ)
has been considered by Bueche?7 D can be related to a friction
constant f by the Einstein relationship (eqn (1)), where x is the number
of chain segments per molecule, k is Boltzmann's constant and T the
absolute temperamre.
D = kT/xf (1)
Debye's free draining model leads to the following expression for the
bulk viscosity of a polymer.
_ r 2xp N. f (2)
'TJ- 36M
Here r2 is the mean square end-to-end distance, M the molar mass and
p the polymer density. N is Avogadro's number. Eliminating f from
the above equations leads to eqn (3).
D'TJ = N~~T (f~) (3)
As r2/ M is constant for a bulk polymer the inverse proportionality

between D and 'TJ should prevail.
2.3. Tack, Diffusion and Viscosity

Skewis22 measured the tack of rubber to rubber and rubber to glass as
a function of contact time and his results are shown in Fig. 6. The two
factors which may contribute to tack in this case are the development
of intimate contact between the two surfaces by viscous flow of the
polymer and diffusion of polymer segments across the interface. Diffu-
sion will not occur between polymer and glass, and the low levels of
tack which develop between styrene-butadiene rubber and butyl rub-
ber indicate low levels of diffusion. Higher levels of autohesion de-
velop with the like polymer pairs and this is attributed by Skewis to
186 J. Comyn
BREAKING LOAD /9
400
200
o~------------~------------~~
o 10 20
HONTACT TlME/rs
Fig. 6. Adhesion at various contact times of styrene-butadiene and butyl
rubbers. (0) SBR/SBR; (e) butyl/butyl; (0) SBR/butyl; (II) SBR/gJass?2
diffusion across the interface. As both viscous flow and diffusion are
controlled by the same friction constant, factors which change D will
change TJ in a similar manner, so making it difficult to distinguish
between the effects of the two parameters.
The development of intimate interfacial contact is the mechanism
proposed for autohesion in a series of papers by Anand and his
collaborators,28-32 and a summary of Anand's objections to Voyutskii's
diffusion theory has also been published. 33 Anand makes the signific-
ant point that the instantaneous autohesive strength exceeds zero.
Skewis22 shows that self diffusion coefficients of some styrene-
butadiene, butyl, ethylene-propylene and natural rubbers fallon the
same log D against log(molar mass) locus, so demonstrating that
molecular size is the prime factor which controls D in these non-polar
materials. The effect of molar mass on autohesion and on the tensile
strength of the material is shown for some natural rubber fractions in
Fig. 7. Whilst the tensile strength of the rubber rises with molar mass,
tack tends to fall once the molar mass exceeds 300,000. A similar
relationship between peel strength and molar mass has been shown for
some butadiene-acrylonitrile copolymers by Voyutskii and Vakula. 34
.y
200
• •
p.s.i.
[]
100
•
.~
OL----k--~~--~·--~----~~
0 1 2
MOLAR MASS /10 6
Fia. 7. Dependence of tensile strength (.,I:::J) and tack strength (e,O) of

natural rubber upon molar mass. (0,0) Milled rubber; (., e) unmilled. (After
Forbes and McLeod. 19)
Skewis proposed that only molecules with a mass below 300,000 are
sufficiently mobile to 'flow' across the interface in the 30 s contact
time.
Vasenin 35 explained the effect of molar mass by suggesting that only
the terminal parts of the molecules are capable of diffusion; Bueche
believes, however,24.27 that chain ends loosen the structure of the
polymer.
Certainly self diffusion coefficients depend quite strongly on molar
mass. Using tritium labelled unvulcanised natural rubber, Bresler36
showed the following relationship between D and M at lOO°C.
(4)
For the self diffusion of polyethylene at IS0°C D is proportional to
M-S/3.37
The dependence of tack upon contact time is illustrated in Fig. 6 and

similar relationships have been reported by Forbes and McLeod, 19
Voyutskii and Margolina38 and Voyutskii and Vakula. 34 The essential
188 1. Comyn
features of these are that instantaneous tack is greater than zero and
that as time passes a maximum tack develops, possibly due to inter-
diffusion. However, the contact time required for tack to reach the
cohesive strength of the rubber varies considerably; Forbes and
McLeod give values of 3-5 min for butyl rubber, 4-5 h for natural
rubber and 14-17 h for styrene-butadiene rubber.
Gent and Vondnicek 39 observed that the peel strength of bonds
between lightly crosslinked silicone rubber and either glass, quartz or a
second sample of the rubber increased linearly with time over a period
of days, to eventually reach the fracture strength of rubber. The rate of
increase of peel strength with temperature gave an activation energy of
ahout 60 kJ mol-t, and the process was also accelerated by water and
ammonia. The behaviour is not too dissimilar to the systems where
adhesion has been ascribed to diffusion, but the interpretation put
forward by Gent and Vondnicek is hydrolysis of the polymer which
leads to the formation of reactive groups which interlink with surface
groups on the substrate.
From the point of view of the diffusion theory, the effect of bonding
pressure is simply to provide intimate contact of the adherends. Thus,
there should be, for any bond, a critical pressure above which no
further increases in autohesion will take place. Voyutskii40 has shown
that the critical pressure for two polyisobutene surfaces is as low as
50 g cm- 2 . Although diffusion coefficients vary with pressure, pressures
very much greater than this are needed to cause any effect.
This has been illustrated by a recent Japanese study41 on the effect
of hydrostatic pressure on the diffusion of some dyes in polyethylene
terephthalate (PETP) and nylon 6. For 3-amino-azobenzene diffusing
in nylon 6 at 80°C, and for 3-nitroaniline in PETP at 120°C, they
observed that the lowering of D with pressure p obeys eqn (5) in
which t:. Vi is the activation volume for diffusion.
(olnD) = _ t:.V*
(5)
op T RT
Values of t:. Vi for the two systems are, respectively, 20 em 3 mor- I and
93 cm 3 mar-I; in familiar units this means that a pressure of about
1000 atm will reduce D by half in the first case, whilst only 80 atm is
needed for the second. Voyutskii40 examined the autohesion of
polyisobutene of molar mass 150,000 pressed together for 5 min at
various temperatures with a pressure of 40 g cm- 2 • Peel strengths
closely fitted an Arrhenius plot with an activation energy of autohesion
of 11·7 kJ mol-I, which Voyutskii claims to be 'characteristic of the

activation energy of diffusion processes,' a point of view which is not
easy to substantiate. Using low molar mass polyisobutene McCall et
al. 25 give the much higher value for the activation energy for self
diffusion of 23 kJ mol- 1 whilst activation energies for the diffusion of
some small non-polar molecules are about 70 kJ mol- 1 for n-butane
and n-pentane in butyl rubber42 and 71·5kJmor- 1 for 1,1-
diphenylethane in polyisobutene. 43 How€!ver, basically there is little
information in the literature on self diffusion in polymers, and com-
parisons are difficult because of differences in molar mass or level of
crosslinking used by different experimenters. Some data by Voyutskii
(p. 35 of ref. 15) shows that the activation energy for autohesion is the
same for polyisobutenes with molar mass in the range 20,000-200,000.
The structure of the repeat unit affects D and Tj in a similar manner.
The introduction of polar groups increases inter- and intramolecular
forces and this leads to the poor self adhf:sion of polychloroprene and
nitrile rubbers in comparison with natural rubber. Peel strengths of
nitrile rubbers with different levels of acrylonitrile are reported by
Voyutskii and Shtarkh.44 Increasing the acrylonitrile content not only
lowers peel strength but also increases the activation energy for peel.
With 11·7% of acrylonitrile the activation energy is 6·4 kJ mor l which
increases to 69 kJ mol- l when the level of acrylonitrile is 36·9%.
Crosslinking reduces molecular motion and prevents viscous flow;
vulcanised rubbers have no appreciable autohesion. Similarly crystal-
linity limits molecular motion. Two pairs of polymers which are similar
in structure are polyisobutene and polyethylene, and natural rubber
(poly-cis-1,4-isoprene) and gutta percha (poly-trans-1,4-isoprene), but
the first member of each pair is amorphous and the second partially
crystalline. The amorphous polymers show autohesion whilst at am-
bient temperatures the crystalline ones do not;38.44 however, above
their crystalline melting points both exhibit autohesion.
2.4. Solvent Welding of Glassy Polymers

Two polymers which can be joined by swelling with a solvent and then
pressing together are polystyrene and bisphenol-A polycarbonate.
Here solvent has the effect of depressing the glass transition tempera-
ture to below the working temperature, so that when adherends are
pressed together there is an adequate level of molecular motion for
interdiffusion to occur. After bonding most solvent diffuses from the
bond and eventually evaporates.
190 J. Comyn
o o
B
Fig. 8. Bond zone in solvent welded polycarbonate. 45 Vertical arrow marks
original interface. B = Bond zone (containing original solvent), C =
morphologically modified central bond. 0 = unmodified original material.
Titow et al. 45 have examined the strength and structure of joints in

polycarbonate welded with either dichloromethane or 1,2-
dichloroethane. The total bond zone (Fig. 8) corresponds to the region
containing 99% of the original solvent and is about 1 mm wide. A
central zone, about 0·2 mm wide, is slightly birefringent, and this
corresponds to the region which is initially highly swollen by solvent.
The original interface is completely removed and there is no evidence
of a residual parting plane.
3. DIFFUSION AND JOINT DURABILfIY
Water is the substance which gives the greatest problem in the en-
vironmental stability of adhesive joints. The great majority of bonded
structures are exposed to moist air, and if the relative humidity is high
then over a period of time the strength of joints usually declines. There
have been many studies in the literature4 6-50 which have demonstrated
this by exposing adhesive joints either to natural or laboratory cli-
mates; in almost every case joints are weakened. However, joints
exposed to labotatory air, which is, in fact, quite humid (50-60%
relative humidity), were unaffected. The typical behaviour of adhesive
lap joints in moist air is illustrated by Fig. 9. It can be seen that, at the
o o o
o o o
500 10'00
Exposure Ii me (h)
Fig. 9. Typical behaviour of the strength of lap joints on exposure to high and
ambient humidity. Here the adhesive was FM 1000 with a nylon carrier and
the adherend aluminium. 49
higher humidity, strength falls with time, but it tends to level out rather
than fall to zero.
There seem to be two fundamental problems which arise with water,
these are its widespread occurrence and the fact that adhesives are
hydrophilic because they contain polar groups.
Surface treatment of adherends has been seen as the best means of
maintaining strength in the wet. 46 ,48,51.52 Materials which are based on
epoxides, phenolics or acrylics are used as structural adhesives. Epox-
ides have been the most widely studied as regards their durability
whilst acrylic adhesives are relative newcomers. 53
What, therefore, is the mechanism by which water alters the strength
of adhesive joints? It would seem that water may enter and alter a
joint by one of a combination of the following processes. Firstly, water
may enter the joint by
(a) diffusion through the adhesive;
(b) diffusion through the adherend if it is permeable, such as might
be the case with a composite;
(c) transport along the interface, a process which is often referred
to as wicking; in this context the interface ~ould be the
adhesive-adherend interface, or if a fibrous carrier is incorpo-
rated in the adhesive then also the carrier-adhesive interface;
(d) capillary action through cracks and crazes in the adhesive; this
192 1. Comyn
process is more likely to occur in joints which have been aged

rather than in freshly prepared ones.
Secondly, having entered a joint, water may cause weakening by one
or a combination of the following. It may
(e) alter the properties of the adhesive in a reversible manner;
plasticisation of the adhesive is such a process:
(f) alter the properties of the adhesive in an irreversible manner,
either by causing it to hydrolyse, to crack or to craze;
(g) attack the adhesive-adherend interface either by displacing the
adhesive or by hydrating the metal or metal oxide surface of
the adherend;
(h) induce swelling stresses in the adhesive joints.
These will now be examined.
3.1. Kinetics of Water Entry

If water enters a joint by diffusion, then it is possible to calculate the
distribution of water using standard equations. 54 If two films or slabs
intersect at right angles, then their volume of intersection is a rectan-
gular prism and the adhesive layer in a lap joint can be considered as a
normal section of such a prism. These relationships are illustrated in
Fig. 10. When placed in an infinite bath of diffusant, concentrations at
points through slab 1 are given by the following solution to Fick's
second law of diffusion. Diffusion at the edges of the slab is neglected.
C~ _ 1 - -
---
4 L.~ (-1)" exp [- D(2n + 1)27Tt] cos [(2n -1- 1hrx] (6)
C= 7T n~O (2n + 1) 4£i 2fl
Here Cx is the concentration at a point distance x measured from the

centn: of the slab, C= is the equilibrium concentration, D the diffusion
coefficient and t the time. A similar equation exists for slab 2 in which Cx
is replaced by Cy , £1 by £2 and x by y. Concentrations at point Cx.y in
the prism (or adhesive layer) are then given by
Equation (6) may be integrated to give the total uptake by slab 1 at

time t; this is usually expressed as the fractional uptake MdM=
Ml=l'_~
M= 7T 2
f
n~O (2n
1
+ 1?
ex p [-(2n+1?7T 2 Dt]
4£i
(8)
Adhesive
~ layer
Fig. 10. Illustration that the adhesive layer in a lap joint is a section of a
rectangular prism formed by the volume of intersection of two slabs at right
angles.
There is again a parallel equation for slab 2. The total amount of water
uptake by the adhesive layer is given by
(9)
The use of these equations obviously requires reliable values of the

diffusion coefficient, and we now examine how these can be obtained.
If a thin film of adhesive is placed in liquid water or water vapour at
a static pressure, then both the diffusion coefficient and the solubility
of water within the adhesive can be determined by following mass
uptake of water as a function of time. An initial problem is to prepare
thin films (0·1-0·5 mm thick) of even thickness and in the author's
194 J. Comyn
laboratories polytetraftuoroethylene, silicone rubber and tin have been

found to be suitable substrates upon which adhesive films may be cast
and subsequently removed.
Brewis and Comyn S5 and their group in Leicester examined the
liquid water uptake by a series of epoxide adhesives based on the
diglycidyl ether of bisphenol-A (DGEBA). Films were periodically
removed for careful surface drying and weighing; plots of mass uptake
against Jt are initially linear and diffusion coefficient can be obtained
from the slope.
An example of a mass uptake plot for an epoxide in water at 45°C is
shown in Fig. 11. Linear uptake of this type is termed Fickian and is
typical of diffusion in a polymer in the leathery state (that is, above its
glass transition temperature) and not, therefore, what might be ex-
pected for diffusion in glassy epoxides. In general, glassy polymers
show non-Fickian sigmoid shaped uptake plots. Fickian and non-
Fickian sorption have been compared by FujitaS6 and characteristics of
Fickian diffusion which are of relevance to water uptake by adhesive
films are as follows:
(i) For both absorption and desorption plots of Mtl Moo against Jt
are initially linear, and this linearity extends to at least
MtfMoo = 0·6 for absorption.
o
1-0 •
OS
-......
8
L
L
o 50 100
t1/2 C1 .10 5s1/2 m-1
Fig. 11. Uptake of liquid water at 45°C by the DGEBA-tris(dimethyl-
aminomethyl)phenol epoxide. Results of two experiments are shown."
(ii) Above the linear region, curves are concave against the abs-
cissa.
(iii) Plots of M,I M= against .Jill, which are termed reduced sorption
curves, should coincide for films of different thickness.
(iv) Plots of M,/Moc against .Ji for sorption and desorption will only
coincide when D does not vary with concentration of the
sorbant.
In recent years quite a large number of uptake plots for water in

adhesives or in composites have appeared in the literature, and very
frequently the characteristics of Fickian sorption as described in (i) and
(ii) above have been evident, even though the glass transition tempera-
ture was in many cases considerably above the experimental tempera-
ture, so making non-Fickian diffusion likely.57-62
Manson and Chiu63 measured the water permeability of some films
based on DGEBA, phenylglycidylether and the polyamide Versamid
140, over a range of temperatures covering Tg. They found that plots
of log (permeability) against reciprocal temperatures consisted of two
straight line regions which intersected at about T g , and that the
activation energy was greater for the leathery than for the glassy state.
Such a relationship between activation energies for the diffusion of
helium, neon, argon, oxygen arid hydrogen in high molar mass
polyvinyl acetate was reported by Meares64 who accounted for the
lower activation energy in the glassy state by there being a smaller
zone of activation than in the leathery state.
Should samples of the same adhesive film be exposed to liquid water
or its saturated vapour in equilibrium, then the zeroth law of ther-
modynamics requires their equilibrium uptakes to be the same. Equa-
tions (6) and (8) assume that saturation of the surface layer is instan-
taneous and hence identical rates of uptake should be recorded for the
liquid and vapour exposed films; in fact, identical uptake plots should
be seen. Liquid and vapour uptake by the adhesive from DGEBA with
di(1-aminopropyl-3-ethoxyether) (DAPEE)S5.65 by the epoxide
polyamide adhesive FM 100047 and by some carbon fibre composites66
give support to this view. If an uptake experiment is undertaken from a
single infinite bath, e.g. liquid water, with which the epoxide estab-
lishes an equilibrium uptake M=, then the diffusion coefficient obtained
from the plot of M,I Moc against .Ji is an average over the concentration
range O-M=. On account of the large fraction of free volume associated
with liquids, they generally plasticise polymers. Because of this it might
196 J. Comyn
be anticipated that D might depend quite strongly on M=, and this is

the situation which has been observed for many polymer-liquid combi-
nations. 56
The dependence of D upon concentration can be evaluated by
performing uptake experiments from vapours at different pressures.
This was done by Comyn et al. 65 on the adhesive based on DGEBA-
DAPEE at 48°C. Films of adhesive were suspended in water vapour
from the arm of a recording microbalance. In all cases uptake was
found to be Fickian, and although results show some experimental
scatter, they clearly indicate that D is independent of concentration in
this particular system. Although this may be unusual it greatly simp-
lifies the calculation of water distribution in joints. It has been observed
for some other water-epoxide systems,67 but there are reports of
systems where D increases with water concentration.68.69
Comyn et al. 65 also reported the dependence of equilibrium uptake
upon vapour pressure for the DGEBA-DAPEE resin. Their results
are similar to a BET type III isotherm. They pointed out that a
possible interpretation of the constant D and the shape of the uptake
isotherm is that most of the water exists in clusters within the epoxide.
A relatively small amount of water remains molecularly dispersed in
the adhesive, and except at very low overall concentrations, its amount
remains constant over the whole range of vapour pressure. Only the
dispersed water molecules will contribute to the diffusion process.
Whilst many adhesives do attain an equilibrium uptake with water,
as demonstrated by a level plateau region in uptake plots, this is not
always the case. Clearly the lack of eqUilibrium in film uptake experi-
ments is a source of doubt in calculating D and also in evaluating
saturation levels in adhesive joints.
Some adhesives show a second uptake stage. An example is the
adhesive based on DGEBA and 4,4' -diaminodiphenylmethane in
water at 100°C but the same resin shows a single Fickian uptake stage
at 25, 45 and 700C. 55 This tendency to undergo a second uptake
process at higher temperatures was noted for the adhesive FM 73 by
AlthoCO who observed that at 70°C and 95% relative humidity (r.h.) a
distinct second sorption stage appeared, but at lower temperatures (20,
40 and 50°C), at 95% r.h., this was absent. Mijovic71 observed a
second uptake stage for acetone in an epoxide resin, and attributed this
to the solvent entering a relatively impermeable nodular phase.
Other adhesives show weight losses after the initial uptake. One
example is the DGEBA-borontriftboride monoethylamine resin at
70°C in water. At 25°C this resin gave an equilibrium plateau, but
weight loss persisted at some intermediate: temperatures. 55 The uptake

plot from liquid water at 50°C by the adhesive FM 1000 shows weight
loss, but uptake from the saturated vapour at the same temperature
gives a Fickian uptake plot with a plateau. In the liquid, weight loss is
due to leaching out of some component which is not lost to the vapour
phase. This is completely removed in the first liquid sorption process so
that re-exposure after drying gave an uptake plot with a plateau.
Knowledge of the mechanisms of these secondary sorption or de-
sorption processes is slight, but speculation on them is permissible.
Leaching out has already been noted, and this may be the leaching out
of an unreacted component in the adhesive or of a product of hyd-
rolysis. Another possibility is the further crosslinking in the water
plasticised adhesive at high temperature. Cracking or crazing of the
adhesive is a possible reason for increased uptake which is discussed
later on.
3.2. Calculated and Measured Water Uptake

Althof 2 ,73 made some aluminium-adhesive-aluminium sandwiches
with the modified epoxide adhesives BSL 313A and FM 73, the epox-
ide nitrile adhesives AF 126-2 and FM 123-5, and the vinyl phenolic
adhesive Redux 775. It should be noted that FM 73, AF 126-2 and
FM 123-5 contained fibrous carriers designed to assist in the handling
of the adhesives and in controlling glue line thickness. These
sandwiches were 100 mm in length and 5, 10, 20 or 30 mm in width
and their uptake from unsaturated watl~r vapour was followed by
weighing and values of D and M were obtained which compared
reasonably well with values from film uptake experiments. In some
cases opening of the sandwich edges was observed, and in others
corrosion at the edges took place. Both these effects could contribute
to the significant differences hetween diffusion coefficients noted in
some instances.
Further, Althof took sandwiches measuring 30 x 100 mm and ex-
posed them to water vapour. After removing and discarding 15 mm
from each end, the remainder was cut into strips measuring 3 x 70 mm.
Water levels in the strips were determined by weighing before and
after careful drying. Figure 12 compares some measured water dis-
tributions in sandwiches with those calculated from a diffusion coeffi-
cient obtained by film uptake experiments.
Brewis, Comyn and their co-workers74 made sandwiches of adhe-
sives between aluminium alloy measuring 25 x 12·5 mm. The adhesives
used were the epoxide-polyamide adhesive FM 1000 and the modified
198 J. Comyn
0~
...... 3
c
OJ
......
C
0
u
2
OJ
<-
......
::l
I
VI
0
I
:L I
I
0 15
U 30
Distance, mm
Fig. 12. Moisture distribution across sandwiches bonded with the adhesive
FM 73 after 60 days exposure to air at 70°C and 95% r.h. Experimental points
are compared with a line calculated using eqn (6). (After Althof.73)
epoxide adhesive BSL 312, as well as versions of both these adhesives

containing knitted nylon carriers. The sandwiches were exposed to
isotopically labelled water vapour 3HOH, at 50°C for periods up to six
weeks, after which they were cut into 5 x 5 identically shaped rectang-
les and fractional uptake measured by liquid scintillation counting after
swelling the piece in dioxan. Because of the symmetry of the
sandwiches, some pieces are identical to others. Measured uptakes are
compared with those calculated from eqn (6) in Tables 1 and 2;
individual values of CrlC were calculated at several points within each
piece and an average taken. There are three entries for each piece, the
upper one is calculated from the diffusion coefficient and the middle
and lower ones were measured for the uncarried and carried adhesives,
respectively. With FM 1000, uptake in the outer pieces was the same
for both carried and un carried adhesives, and these values agreed with
the calculated values. In the inner pieces measured water was signific-
antly less than predicted levels, and this was particularly the case when
TABLE 1
Fractional Uptake by Aluminium Sandwiches Bonded with
FM 1000 and FM 1000/EP 15 (with Carrier) after Six Weeks
Exposure to Labelled Wate:r Vapour74
A 0·93 B 0·83 C 0·79

0'91±0'37 0·77±0·36 0·79
0·86±0·19 0·70±0·13 0·32
D 0·85 E 0·61 F 0·51
0·81±0·21 0·57±0·19 0·49
0·85±0·06 0·39±0·1O 0·32
G 0·83 H 0·55 I 0·45
0·75 0·36 0·20
0·66 0·09 0·02
Overall mean values 0·75
for joint 0·69
0·60
In each case the top value is calculated from D, the next

measured for the adhesive without carrier, and the lower one
for the carried adhesive.
TABLE 2
Fractional Uptake by Aluminium Sandwiches Bonded with
BSL 312 and BSL 312/5 (with Carrier) after Six Weeks Expos-
ure to Labelled Water Vapour 74
A 0·87 B 0·68 C 0·61

0·57±0·06 0·31±0·06 0·32
0·99±0·23 0·55±O·07 0·53
D 0·75 E 0·37 F 0·23
0·39±0·08 0·06±O·01 0·08
0·61±0·08 0·095 ±0·006 0·21
G 0·74 H 0·27 I 0·18
0·44 0·02 0·04
0·60 0·045 0·07
Overall mean values 0·58
for .ioint 0·28
0·47
In each case the .top value is calculated from D, the next

measured for the adhesive without caITier, and the lower one
for the carried adhesive.
200 1. Comyn
carrier was present. Overall mean levels of uptake by the sandwiches

were in quite good agreement.
With BSL 312, the carried adhesive had uptake levels which again
were comparable with the calculated values in the outer pieces, but
uptake with the uncarried adhesive was distinctly lower. Towards the
centre of the joint, measured water levels fall below calculated ones
and again levels for uncarried adhesive were lowest.
It would seem from these results that the carrier in the FM 1000
adhesive hinders the passage of water. The capacity of a material to
transmit a permeant is indicated by its permeability coefficient, which
is the product of the diffusion and the solubility coefficient; the product
DC was used as an approximate estimation of this quantity, and it is
compared for the adhesives and carriers in Table 3. It illustrates that
the FM 1000/EP 15 combination represents a relatively impermeable
carrieJ in a permeable matrix, and the carrier so provides an obstacle
to wat.::r diffusing through the adhesive, which is in accordance with
the observed results. In the BSL 312/5 system, however, carrier and
adhesive have much closer permeabilities, and would be expected to
have similar efficiencies in transporting water into joints. This is again
in accord with the results presented. Support for the relative inertness
of carriers in the process of water entry into joints comes from a study
of their effect on the strength of double lap joints in aluminium alloy,
exposed to saturated air at 50°c.47.50 Adhesives based on BSL 312 and
FM 1000 were used in this study, and joints were exposed for up to
10,000 h. It was found that carriers did not alter the durability charac-
teristics of unstressed joints.
Schulte and DeIasi75 exposed sandwiches of a carbon fibre epoxide
composite bonded with FM 300 epoxide adhesive to a D 2 0 environ-
ment at 70% r.h. and 77°C for various exposure times and then
sectioned them by cutting with a diamond wheel at liquid nitrogen
TABLE 3
Diffusion Coefficients and Equilibrium Water Uptake at 50~C74 in Compo-
nents of Some Structural Adhesives
Component D(lO 13 m 2 s-') C(g 100 g ') DC

FM 1000 34 ±6 13·4 460
BSL312 18 ±5 2·2 40
Carrier EP 15 4·4±0·9 7·2 32
Carrier from BSL 312/5 2·9±0·6 7·3 21
-----
temperatures. The deuterium concentration at points on the cut faces

could be measured by bombardment with 3He+ ions and measuring the
protons produced by the following reaction:
D+3He+ -+ H+ +4He
The sandwiches measured approximately 25 x 12·5 rum and were
about 1· 9 mm thick, with a thin glue line. Diffusion coefficients of D 2 0
in composite and adhesive measured by mass uptake were 3·7 x
10- 13 m 2 s- 1 and 1·3 x 10- 12 m 2 s-l, respectively. They compared
measured moisture content along the glue line with that calculated on
the basis of one-dimensional diffusion along the glue line. Some results
shown in Fig. 13 show measured water levels to exceed the calculated
value, and this is due to diffusion through the adherend which has not
been taken into account in calculation.
These various studies demonstrate that water distribution in joints
with impermeable adherends can be accounted for by assuming Fickian
diffusion in the adhesive layer, and where one or more adherends is
permeable then this provides a further path for water to diffuse into
the joint. It also seems clear that carrier fibres do not generally have
much effect on the rate of water entry. The contribution of carriers to
3.----------------------------------,
2
o
N
o
-;;e.
X
,
L.J '0
O~ ______ ~~ ___ r - - - - - - L - - - - - - _ . - J
o 12
x/mm
Fig. 13. Measured and predicted moisture profile for the adhesive layer in a
composite lap joint after exposure to 70% Lh. at 77°C for 12 days_ The solid
line is calculated with the assumption that diffusion occurs only through the
adhesive_ 75
202 1. Comyn
the rate of ingress can be accounted for by diffusion along the fibres so
making it seem that water is not transported along the fibre-adhesive
interface.
However, these studies employed carefully prepared substrates,
whereas it is in joints with less rigorous surface treatments that
transport along the substrate-adhesive interface would seem more
likely. Certainly, on the basis of the studies so far reported, interfacial
transport cannot be excluded as a possible mechanism of water entry
into adhesive joints.
Transport along the interface may be important when a silane
primer has been applied to the substrate. Silanes have been used for
some time to treat glass fibres in order to improve the durability of
composites and it has been suggested that water diffusion along the
glass-resin interface may be at least 450 times as fast as through the
resin. 76 Kadotanf 7 has claimed that an abnormal resin layer exists at
the fibre-matrix interface in a glass-epoxide composite, and that this
layer has a higher water absorption and permeability. Silanes have
been used to pretreat metal surfaces prior to adhesive bonding with
consequent improvements in durability78-81 and it has also been de-
monstrated that they produce polysiloxane coatings on iron,8o.81
steel,82 aluminium80 and aluminium oxide in the form of sapphire.83 .84
It may well be the case that silanes lead to more durable interfaces but
they may greatly assist the entry of water into adhesive joints. This is
because polysiloxanes are about the most permeable polymers known.
A detailed study by Barrie and Machin8s examined water transport in
three polydimethylsiloxanes; the diffusion coefficient of water in a
Midland Silicone product seems typical with D = 3·5 X 10-9 m2 S-1 at
26· 3°e whereas a typical value for water in an epoxide at this tempera-
ture would be 1· 5 x 10- 13 m 2 s- \ ss making it seem that water diffusion
in the interfacial primer layer would be about 20,000 times faster
than in the adhesive.
3.3. Dependence of Joint Strength on Water Content

Comyn, Brewis and their co-workers have observed a linear depen-
dence of joint strength upon total water uptake for a number of
adhesively bonded aluminium alloy lap joints. Some results are shown
in Fig. 14 for the adhesive DGEBA-DAPEE48 which has been de-
monstrated to have a diffusion coefficient independent of concentra-
tion, so adding confidence to the calculated water uptakes. It can be
seen that the linearity persists to high levels of water uptake. The
8-,-------
l---hII
~
.c
+-
en 4
c
OJ
'-
+-
l/)
~-~4
0
0 (}S lO
Mt/M ao
Fig. 14. The linear relationship between joint strength and fractional water
uptake for aluminium alloy lap joints bonded with DGEBA-DAPEE. Surface
treatments: (0) anodising; (II) sandblasting. 48
joints in this study were 12·5 x 12·5 mm single lap joints and exposure
for about one year was required to achieve the high levels of uptake. A
similar linear relationship was observed for joints using the modified
epoxide adhesive BSL 312 with chromic acid etched aluminium alloy
adherend,50 but in the case of the epoxide-polyamide adhesive FM
100047 .49 a marked departure from linearity occurred at high uptake.
This probably represents the attack of water on the interface after
longer exposure.
3.4. Effect of Water on the Adhesive

Having examined the rate of water entry into adhesive joints, it
remains to consider the mechanism whereby it causes weakening.
Water could influence the adhesive or the interface and in the case of
permeable adherends changes in substrate properties could also occur.
Some of the processes which might occur would be reversible and so
be accompanied by recovery in strength on removal of water but
others would be irrecoverable.
204 J. Comyn
Plasticisation and swelling are both reversible processes. Water

depresses the glass transition temperature of adhesives and lowers the
modulus and strength.
Several attempts have been made to relate the depression of the Tg
of adhesives by water to free volume theories of the glass transition
using the equations of Kelley and Bueche86 and Fox. 87 The application
of such equations requires a value for the glass transition temperature
of water and this has been reported in the range -134 to _138°C.88-91
Using a Tg (H2 0) in this region, Morgan and Mones 92 applied the
Kelley-Bueche theory to some experimental data of Browning on the
TGDDM-DDS-water system and found that the actual glass transition
of wet resins was well below predicted values. However, Brown-
ing62,93,94 found very good agreement between measured and predicted
values of Tg if a value of +4°C was used for the glass transition
temperature of water.
Water is an unusual fluid, and is more complex in structure and
behaviour than the organic plasticisers used to modify the properties of
commercial plastics. It may well be that equating its Tg parameter to
the temperature of maximum density is a better measure of its free
volume contribution to a polymer-water mixture. Brewis, Comyn et
al. 55 analysed the Tg depression of a range of epoxides using the Fox
equation. All Tg values were depressed on first absorbing water and
agreement between the predicted and experimental values was proba-
bly within experimental error when DAPEE, DAB (1,3-
diaminobenzene), DMP and borontrifluoride monoethylamine were
used as hardeners. In other cases there was less plasticisation than
predicted, and this could be interpreted by water being clustered
within the adhesive rather than being completely dispersed. On pro-
longed exposure to water, the Tg values of all adhesives studied
increased, and in two cases they increased to values which exceeded the
Tg of the dry adhesives. Thus it would seem unlikely that plasticisation
can satisfactorily explain the long term durability of joints, although
doubtless it is a contributory factor in some cases.
Water entering a joint may cause swelling and thereby introduce
stresses into a joint which could weaken it. There are several studies in
the literature demonstrating dimensional changes of adhesive materials
on exposure to water, including those of Gazit95 and Shirrell and
Halpin. 96
Weitsman 97 has undertaken an analysis of the stresses introduced
into adhesive joints by water swelling caused by Fickian diffusion but it
seems unlikely that they contribute significantly to long term weaken-

ing of joints.
Kinloch et al. proposed that an outer water-containing zone of an
adhesive layer might constitute a crack. This notion had its roots in the
observation that while exposure of adhesive joints to high humidity
usually causes weakening, it has frequently been observed that they
can withstand exposure to lower humidities for long periods without
any weakening. De Lollis 98 has referred to some epoxide-aluminium
joints which showed no loss of strength after exposure to laboratory
humidity for up to 11 years. Kinloch et al. 99 exposed butt joints with an
epoxide adhesive to 55% r.h. at 20 e for 2500 h and found no
0
weakening; similarly, eomyn et al. 47 .49,50 found no significant weaken-

ing effect after 10,000 h at about 200 e and 45% r.h. for joints bonded
with carried and uncarried variants of the adhesives FM 1000 and
BSL 312. From a knowledge of water sorption isotherms of other
adhesives it would be expected that joints would absorb significant
quantities of water under these conditions.
Kinloch et al. proposed that there must be a critical water concentra-
tion in the adhesive layer, below which environmental weakening does
not occur. The outer zone, where this critical concentration is ex-
ceeded, is regarded as a crack in the bond line. Kinloch tested this
hypothesis with some butt joints bonded with an adhesive based on
DGEBA and the tri-2-ethyl hexanoate of 2,4,6-tris(dimethylamino-
methyl) phenol, exposed to water at 20, 40, 60 and 90 e and also to
0
air at 20 e and 55% r.h. All the water immersed joints had a reduction
0
in strength and Kinloch was able to show, using a fracture mechanics

approach, that the strengths of the various joints could be interrelated
by using a critical water concentration of 1·35%. This would mean that
the outer zone which constitutes a crack has a water concentration
exceeding this value, and that joints exposed to humidities too low to
induce this level of water would not be weakened.
The physical ageing of adhesives in the form of cracking or crazing is
probably more important than hydrolysis and it seems that exposure to
varying climates is an important cause of this. This has been demon-
strated on many occasions by the exposure of epoxide-fibre composites
to so called thermal spikes, which are intended to simulate the flight
conditions of military aircraft. A supersonic dash will cause an aircraft
skin temperature to rise from below zero to about 1500 e as it acceler-
ates, but as it resumes its cruising speed the temperature will have
returned to below zero within a few minutes. Adhesives within the
206 1. Cornyn
aircraft will contain some water from contact with the atmosphere,
which will tend to produce voids at temperatures above boiling point.
A study by Browning62 exposed epoxide composites to thermal spikes
and found equilibrium water uptake to increase with spiking.
In one experiment, in which samples were s).lbjected to one or four
spikes per day, weight gains were proportional to the total number of
spikes. This behaviour was attributed to microcracking, with water
entering the cracks. The microcracks were demonstrated by scanning
electron microscopy. The glass transition temperature was not changed
by spiking, so indicating that the extra water absorbed was not con-
tributing to plasticisation.
Mazor, Broutman and Eckstein 100 demonstrated damage to epoxide
based composites after exposure to salt or distilled water for 11 years.
Samples were dried out and then re-exposed to water. Higher weight
gains and diffusion coefficients shown by 11 year samples indicated the
possible occurrence of microdamage. This was supported by observed
changes in mechanical properties.
Small amounts of electrolyte may be responsible for the formation of
cracks or crazes, and this could be sodium chloride remaining from the
reaction of epichlorohydrin with the sodium salt of bisphenol-A in the
production of DGEBA. The attempt by water to dilute this electrolyte
could set up osmotic pressures capable of causing internal fracture.
Ashbee and his co_workerslOl.102 showed that the incorporation of
finely ground potassium chloride into an epoxide resin led to the
formation of disc-shaped cracks upon exposure to hot water. Cooling
the wet epoxides to - 95·1 °C caused further propagation of the cracks
as the water which they contained turned into ice. Fedors103 demon-
strated cracking in epoxides due to embedded sucrose or some electro-
lytes.
Apicella et al. 104--106 demonstrated Fickian uptake with an equilib-
rium plateau for water uptake by an adhesive based on DGEBA and
TETA at 23, 45 and 75°C. However, on changing the temperature of
an equilibriated sample, weight always increased and so did not move
necessarily towards the level of equilibrium uptake first associated with
the new temperature. For example, the M= value for samples first
equilibriated at 23, 45 and 75°C and the temperature then lowered to
23°C; weight loss would be anticipated. In fact, an increase was
observed and this was attributed to the formation of microcavities. On
the basis of no microcavities being formed at the lowest temperature,
amounts of water contained in microcavities at 45 and 75°C were
0·23% and 0·94%, respectively. Again the water apparently isolated

within microcavities did not cause any lowering of the glass transition
temperature.
Comyn et al. 65 exposed films of the epoxide DGEBA-DAPEE to
five successive sorption-desorption cycles from saturated water vapour
at 48°C. Their results indicated that the diffusion coefficient decreased
with cycling, and solubility increased slightly. For both parameters the
greatest change took place during the first cycle. Again, these results
were ascribed as being due to microcracks, but a search for these by
electron microscopy failed to reveal them.
Cracks may of course increase the rate of water transport and so
lead to an apparent increase in D; they may also grow causing an
adhesive joint to fail.
3.5. Etlect of Water on the Interface

Using the following argument, Kinloch and his co_workersl07.108 have
demonstrated that water may displace an adhesive from the interface.
The thermodynamic work of adhesion, W, that is, the work required to
separate the unit area of two phases x and y in contact, is related to
the surface free energies and by the Dupre equation. Here 'Yx and 'Yy
are the surface free energies of x and y and 'Yxy is the interfacial free
energy. If the phases are separated in an inert medium such as dry air
the equation has the form:
W = 'Yx + 'Yy - 'Y"y (10)
but if separation takes place in a liquid then the form is
W = 'YxL + 'YyL - 'YXy (11)
where 'YxL and 'YyL are interfacial free energies between the two phases
and the liquid. In Table 4 there appear some calculated values of the
work of adhesion. A negative value of W indicates that an interface is
unstable in the presence of water and that water is capable of displac-
ing adhesive from the substrate. However, the kinetics may be such
that displacement by water does not occur spontaneously or even after
a long period. Table 4 shows that this theory predicts that bonds
between epoxides and glass, aluminium and iron or steel are ther-
modynamically unstable in the presence of water. However, bonds to
carbon-fibre composites are stable, although a case 'is shown where
surface treatment (CFRP treated with nitric acid) seems to actually
reduce stability. Although bonds to CFRP may be thermodynamically
208 J. Cornyn
TABLE 4
Work of Adhesion in Air and in Water for Some Inter-
faces 10
Interface W(rnJm- 2 ) W L (mJm- 2 )
Epoxide-Si02 178 -57

Epoxide-Ah0 3 232 -137
Epoxide-Fe 2 0 3 291 -255
Epoxide-CFRP 88-90 22-44
Epoxide-CFRP (heavily 92 18
sanded)
Epoxide-CFRP (RN0 3 95 -20
treated)
PMMA-Ah03 216 -102
PMMA-Fe 2 0 3 270 -167
stable and indeed interfacial failure is not widely observed, loss of

strength may be observed and might be due to other processes such as
plasticisation.
One disadvantage with this approach is that it implies that joint
strength will fall to zero, whereas in many cases strength is seen to
level out at a moderate fraction of the initial dry strength. Another
disadvantage is that it does not allow for the recovery of strength on
drying, as once displaced from the substrate it seems unlikely that
there would be sufficient molecular mobility for a glassy adhesive to
re-establish contact with the adherend. Joints are frequently observed
to increase in strength on drying out, and the fact that complete
recovery is not always reported is due in part to the fact that drying
times are usually too short. The duration of exposure and drying out
times are controlled by the rate of water diffusion, and for lap joints
measuring about 10 x 10 mm bonded with epoxide adhesives, then
about one year is needed to reach a high level of water uptake, and a
similar period needed for drying out. Nevertheless, the extent of
strength maintained during a cycle could provide valuable information
on the role of irreversible processes both within the adhesive and at
the interface. Sorption-<iesorption cycles on joints which have ap-
peared in the literature have mostly been fairly short duration and
have generally shown that some recovery can take place, although it
seems doubtful whether all water was removed in the drying stage.
Comyn et a1. 47 .49 exposed 25 x 12· 5 mm double lap joints with
FM 1000 and BSL 312 adhesives to 1000 h exposure followed by
1000 h drying. Some strength recovery occurred in all cases. Etching

or anodising in chromic or phosphoric acid is known to give strong
bonds with the best durability and the reason for this could be due, to
some extent, to the fact that they produce exchangeable ions on
alumina, as described earlier. Water will enter the adhesive and
increase the relative permittivity at the interface, and so weaken the
electrostatic force.
Deimonte 109 reported the relative permittivity of epoxides cured
with diethylene tetramine (DETA) MPD and phthalic anhydride as 4·6
and values of about 4 have been reported for triethylenetetramine
cured epoxide. 110 Kadotani 77 reported a value of 2·96 for an anhydride
cured cycloaliphatic epoxide. All these values are at room tempera-
ture, where the relative permittivity of water is about 80. 111 Thus, the
addition of a small amount of water could cause the relative permittiv-
ity of an epoxide to increase significantly.
Thus, the advantages of considering ion-pairs at the interface as a
major contributor to the strength of epoxide to aluminium bonds are
that (i) a reduction in strength is predicted which is similar to observed
strength losses, (ii) partial weakening rather than total strength is
indicated and (iii) strength should be recoverable on removal of water.
Water is the most important fluid in joint durability, but other
liquids may throw light on the validity of opposing theories. Kerr,
MacDonald and Orman 112 found that whilst ethanol severely deterior-
ated the mechanical properties of an epoxide adhesive, its effect on
joint strengths was slight. Water on the other hand severely weakened
joints but had little effect on the adhesive. This behaviour can be
ascribed to water but not ethanol having the ability to displace the
adhesive, but the ion-pairing approach also offers an explanation
because of the low relative permittivity (K = 24,2)113 of ethanol. The
adsorption theory also predicts 107 that formamide should displace an
epoxide adhesive from a metal oxide, but the high relative permittivity
of this fluid (K = 109)113 also would imply a large weakening effect by
the ion-pair theory.
Reference has also been made to water attacking adherends consist-
ing of fibres in plastic matrices, but with metallic adherends water may
(i) attack the oxide layer or (ii) be involved in corrosion of the bulk
adhcrend. In most cases gross corrosion of a metallic substrate is not a
problem and its occurrence in failed joints is often taken as a sign of
post-debonding corrosion107 rather than as a primary cause of failure.
Possible exceptions to this are when the environment is particularly
210 1. Comyn
corrosive, such as saltwater, or when two different metals are in

electrical contact within an adhesive as is the case with aluminium alloy
clad with pure aluminium. 114 Here differences in electrode potential
will give the possibility of one metal being preferentially corroded.
Adhesive joints generally have to bear loads at least sometime
during their working life and this of course may have an effect both on
the kinetic and mechanistic processes which have been discussed
above. Firstly, stress might modify the rate of water diffusion. How-
ever, the evidence which exists indicates that this is not likely to be a
large effect. Kim and Broutman 115 measured the diffusion coefficient in
some stressed tensile bars of graphite-epoxide composites. The level of
stress was 25% of ultimate and exposure was to liquid water. Their
results show that D increases with stress, whilst there is a small
increase in M=. Interestingly, the activation energy for diffusion was
not signipcantly altered by the application of stress, but the pre-
exponential factor in the Arrhenius equation, Do, was increased. The
enhanced diffusion rate for stressed samples could be due to stress
causing microscopic defects of interfacial separation.
Gillat and Broutman 116 undertook a similar experiment but went to
65% of the ultimate stress of some epoxide-graphite composites.
Uptake remained Fickian at all levels of stress, but whilst equilibrium
uptake was not significantly altered by stress, there was a tendency for
D to increase.
The effect of stress upon double lap joints exposed to saturated air
at 50°C has been examined47 •50 for some adhesives based on FM 1000
and BSL 312. Joints were stressed to 20% of their mean initial dry
strength and exposed for periods up to 10,000 h. Joints became weaker
during exposure, but stressed and unstressed joints were weakened to
the same extent, which points to the diffusion coefficient of water
having the same value in both stressed and unstressed joints. A few
stressed joints did fail during exposure, but other members of their set
which remained intact had strengths comparable with unstressed joints.
Cotter46 has shown a number of strength against time plots for
aluminium double lap joints with six adhesives described as epoxide-
novolac, modified epoxide, nitrile-phenolic, epoxide-polyamide, vinyl-
phenolic and epoxide-phenolic, exposed for up to 6 years to either a
hot-wet, hot-dry or temperate natural climate. Some joints were
exposed without stress but others were stressed to 20% of their mean
initial dry strength; however, this was 15% in the case of the vinyl-
phenolic joints in the hot climates. Most joints did not show much
sensitivity to stress, the exceptions being the epoxide-polyamide joints

in all climates, the modified epoxide in the temperate climate and
the vinyl-phenolics in hot-wet surroundings. A factor which may lead to
stress insensitivity is the possible occurrence of a critical stress level
below which no environmental attack takes place. 117
4. CONCLUDING REMARKS
Diffusion is an important process in adhesion and it is clear that the

entry of water into well prepared adhesive joints is by diffusion. As all
adhesives are permeable, diffusion will always occur along the glue
line. Diffused water can cause changes in the adhesive, such as plasti-
cisation, cracking, crazing or hydrolysis, but it is the effect of water at
the interface which is the most significant in causing the long term
weakening of adhesive joints. Our knowledge of the nature of the
adhesive interface is far from complete, and in the future the use of
surface analytical techniques such as x-ray photoelectron spectroscopy,
inelastic electron tunnelling spectroscopy, Auger electron spectroscopy
or secondary ion mass spectrometry may assist in its growth.
The diffusion theory of adhesion remains fairly controversial and it
will always be difficult to distinguish between the establishment of
intimate contact and interdiffusion as the causes of autohesion, because
of the interdependence of viscous flow and diffusion. However, strong
support for the diffusion theory is given by the observation of inter-
diffusion, even between some unlike polymers.
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101. N. R. Farrar and K. H. G. Ashbee, l. Phys. D., 11, 1009 (1978).
102. J. Nicholas and K. H. G. Ashbee, l. Phys. D., 11, 1015 (1978).
103. R. F. Fedors, Polymer, 21, 713 (1980).
104. A. Apicella, L Nicolais, G. Astarita and E. Drioli, Polymer 20, 1143
(1979).
105. A. Apicella and L. Nicolais, Ind. Eng. Chern. Prod. Res. Dev., 20, 138
(1981).
106. A. Apicella,'L. Nicolais, G. Astarita and E. Drioli, Polymer Eng. Sci., 21,
17 (1981).
107. R. A. Gledhill and A. J. Kinloch, J. Adhesion, 6, 315 (1974).
108. A. J. Kinloch, W. A. Dukes and R. A. Gledhill, Poly. Sci. and Techno!.,
9B (Adhes. Sci. and Techno!.), 597 (1975).
109. J. Delmonte, J. Appl. Polymer Sci., 2, 108 (1959).
110. J. Daly and R. A. Pethrick, Polymer, 22, 37 (1981).
111. c. G. Malmbery and A. A. Maryott, J. Res. Nat. Bur. Standards, 56, 1
(1956).
112. C. Kerr, N. C. MacDonald and S. Orman, J. App!. Chern., 17,62 (1967).
113. R. A. Robinson and R. H. Stokes, Electrolyte Solutions, Butterworths,
London, 1955.
114. F. J. Riel, SAMPE J., 7, 16 (1971).
115. R. H. Kim and L. J. Broutman, 4th Int. Conf. on Deformation, Yield,
Fracture in Polymers, Cambridge, 1971.
116. O. Gillat and L. J. Broutman, ASTM Spec. Tech. Publ. 685, 61 (1978).
117. B. W. Cherry and K. W. Thomson, Adhesion-1, ed. K. W. Allen,
Applied Science Publishers, London, 1977, p. 251.
Chapter 6
The Role of Polymer Permeability in the

Control of Drug Release
H. RICHARDS
JOHN
School of Pharmacy, Leicester Polytechnic, UK
Symbols and Definitions . . . . . . . . . . . . 217

1. Introduction. . . . . . . . . . . . . . . . . . 219
2. Methods of Controlling Drug Release . . . . . . 226
3. Control of Drug Release by Polymer Permeability. 227
3.1. Reservoir (membrane) devices for controlling drug
release . . . . . . . . . . . . . . . . . . . . 229
A. Reservoir devices with non-porous membranes 231
B. Reservoir devices with microporous membranes 242
C. Reservoir devices with hydrogel membranes 245
3.2. Matrix (monolithic) devices for controlling drug
release. . . . . . . . . . . . . . . 245
A. Release from non-porous matrices . 246
B. Release from porous matrices . . . 254
C. Examples of matrix devices . . . . 255
4. Other Polymeric Controlled Release Systems 256
4.1. Biodegradable or bioerodible system~ 256
4.2. Microencapsulated products. . 258
4.3. Osmotically controlled systems 259
4.4. Polymer bound drugs 259
References . . . . . . . . . . . 260
SYMBOLS AND DEFINITIONS
A Total surface area of a polymeric slab excluding edge effects

C Total concentration of drug (i.e. solid plus dissolved drug) in
a matrix device
~C Difference between the concentration of drug in the core of
a reservoir device and that in the surrounding aqueous phase
C Aq Solubility of drug in aqueous receptor phase
c'n Uniform concentration of drug that exists in a polymeric
217
218 John H. Richards
membrane surrounding a reservoir device after prolonged

storage
Concentration of drug at inner surface of a polymeric
membrane that surrounds a reservoir device when steady
state release occurs
Cp Solubility of drug in a polymer
Cplasma(t) Concentration of drug in plasma at time t
C~lasma Desired concentration of drug in plasma
Cs Solubility of drug in the suspending medium of a core
formulation in a reservoir device
D Aq Diffusion coefficient of drug in a stagnant aqueous boundary
layer or in the aqueous phase filling the pores of a porous
matrix
Diffusion coefficient of drug in a polymer
Diffusion coefficient of drug in a stagnant boundary layer of
the suspension medium used in the core of a reservoir device
Diffusion coefficient of drug in a liquid filling the pores of a
microporous membrane
Porosity of a microporous membrane or a porous matrix
Length of a cylindrical reservoir device
Transport flux through a membrane
First-order rate constant for drug absorption
First-order rate constant for drug elimination
Zero-order rate constant for release of drug from a control-
led release device
K Aq/s Partition coefficient of a drug between an aqueous receptor
phase and the suspending medium used in the core formula-
tion of a reservoir device
KL/S Partition coefficient of a drug between a liquid in the pores
of a microporous membrane and the suspending medium
used in the core formulation of a reservoir device
Partition coefficient of a drug between a polymer and the
suspending medium used in the core formulation of a reser-
voir device
K s/s Partition coefficient of a drug in the suspending medium of a
core formulation in a reservoir device with respect to the
same medium (Le. K s/s = 1)
Thickness of a boundary layer in an aqueous receptor phase
Thickness of a slab matrix
Thickness of a polymeric membrane
The role of polymer permeability in the control of drug release 219
Thickness of a boundary layer in the suspending medium of

a core formulation in a reservoir device
Mt Amount of drug released from a controlled release device
after time t
Amount of drug remaining within a reservoir after time t
Amount of drug transported to a receptor phase from a
reservoir device after time t
Amount of drug released from a controlled release device
after infinite time
Ot Cumulative amount of drug released per unit area of a
controlled release device after time t (Ot = MJ A)
Radius of a spherical or cylindrical matrix device
Diffusional resistance of a stagnant boundary layer in an
aqueous receptor phase
Radius of the inner core of a spherical or cylindrical reser-
voir device
Overall radius of a spherical or cylindrical reservoir device,
i.e. core plus membrane
Diffusional resistance of a polymeric membrane
Diffusional resistance of a stagnant boundary layer in the
suspending medium of a core formulation in a reservoir
device
Rtotal Total resistance of a series of barriers to diffusion
T Tortuosity of a microporous membrane or a porous matrix
t1/2 Half-life of a first-order release system
tB Negative intercept on the time axis of Fig. 5
tL Positive intercept on the time axis of Fig. 5
too Time taken for all solid drug dispersed in a polymeric matrix
to dissolve
Volume of distribution of a drug in the body
Volume of the reservoir in a reservoir device
Volume of a receptor phase or sink
1. INTRODUCflON
Polymer permeability causes a number of problems in various areas of
pharmaceutical interest, such as the loss of drugs or other formulation
ingredients by diffusion controlled sorption into plastic containers l - 3 or
into plastic components of delivery systems,4,5 the uptake of preserva-
tives from cleansing and soaking solutions by soft contact lenses and
their subsequent release into the eye 6 . 7 and the release of residual
ethylene oxide and its reaction products from plastic devices sterilised
by exposure to that gas. 8 However, permeability, together with other
properties of polymers, form the basis of a number of important
applications, such as tablet coatings,9 haemodialysis 10 and wound dres-
sings. 11 In addition to these applications a considerable amount of
research and development has been and continues to be concerned
with the use of polymers as agents for controlling the release of drugs
from various types of formulated product or dosage form, e.g. tablets,
implants, injectables and topically applied adhesive strips. Evidence of
the high degree of current interest in the design of such dosage forms
and parallel studies in the fields of agriculture and pest control is
provided by the number of recent reviews,12-29 books 3 O-34 and sym-
posia35-40 that have been concerned with these subjects.
The impetus for seeking ways of controlling the release of drugs
from dosage forms arises from the knowledge that such control would,
in certain circumstances, improve the efficiency of drug therapy over
that provided by conventional dosage forms. The specific improve-
ments and other advantages that may be obtainable are indicated in
the following list.
(a) A continuous input of drug into the body can ensure that the
concentration of drug in appropriate body tissues or organs, in
which the specific receptor sites for a given drug are located, i.e.
the biophase, remains above the lowest limit that is required to
provide the required response but does not exceed a higher
value that would produce an excessive and possibly dangerous
level of this response as is shown in Fig. 1. Furthermore, since
systemically active drugs are transported to several parts of the
body they frequently elicit responses additional to the desired
one by interaction with receptors located in other tissues, and
high concentrations of drugs in such tissues should be avoided if
side effects are to be minimised or eliminated. A continuous
input can ensure that the side effects generated by these alter-
native interactions do not become too severe. These situations
are sometimes difficult to achieve with conventional dosage
forms that must of necessity be administered repeatedly at
regular intervals in many treatments, because such administra-
tion provides a pulsed input. Consequently, troughs and peaks
appear in the concentration versus time profile of a drug in the
i TIME
Fig. 1. Biophasic concentrations versus time profiles of a drug following (A)
administration of successive doses in a conventional dosage form (arrows
indicate times of administration) and (B) a single administration of a controlled
release dosage form.
appropriate biophase, as is also shown in Fig. 1. The amplitude

and frequency of this wavy profile depends on a number of
factors, which include the size of each dose and the frequency
of administration. An excessive amplitude can be reduced in
theory by administering smaller doses at more frequent inter-
vals but this may not be practicable.
(b) The total amount of drug administered during a prolonged
period of therapy is reduced if a controlled release dosage form
is used instead of a conventional one particularly when the
former can be positioned close to the appropriate biophase.
This reduction in drug intake will contribute to the decrease in
side effects that was referred to in section (a).
(c) One of the major obstacles to effective drug therapy arises from
the non-compliance of patients with the directions for taking
their prescribed medicines. For example, in normal cir-
cumstances better compliance is usually observed with .,elf-
administered oral dosage forms if the frequency of dosage can
be adjusted to not more than once every 12 or 24 h. Such
adjustment may often be achieved by the development of a
controlled release product.
(d) Extension of the duration of therapeutic effects following a
single administration often provides better management of a
patient's condition. For example, the benefits of an anaJges:r;
product that provides undisturbed overnight relief from pain in
cancer patients should be obvious, whilst overnight duration of

action of theophylline reduces the problems experienced on
awakening by asthmatic patients.
(e) Controlled release dosage forms are usually more expensive
than conventional ones. However, Lee and Robinson 41 point
out that a more complete appraisal of the savings to health
services and patients arising from shorter recovery periods and
better disease management may show that controlled release is
the more economic approach. Evidence is already available that
savings in time for nurses and pharmacists can accrue and
storage space can be reduced if the number of dose administra-
tions per patient can be decreased. 42.43
(f) In circumstances where continuous or adequate medical super-
vision is not readily available, e.g. underprivileged or isolated
areas, then controlled drug release over long periods may
provide for better therapy.
The potential disadvantages of controlled release dosage forms should
be taken into account, however, in specific situations. These disadvan-
tages, as indicated by Langer and Peppas,22 include
(a) the necessity to ensure that drug leakage, and other factors
which would cause inadequate control and possibly lead to
dangerous situations, do not occur:
(b) the necessity to ensure adequate safety of the devices with
respect to device components and their degradation products
together with the biocompatibilities of the actual devices;
(c) the necessity for surgical operations in the case of implantable
devices and subsequent operations for the removal of
exhausted, non-biodegradable devices;
(d) the pain caused by the presence of an implant;
(e) the difficulty in shutting off drug release if required after a
device has been implanted;
(f) the relatively high costs of components and methods of produc-
tion of devices, although with respect to this point the com-
ments made in section (e) of the previous list of advantages
should be borne in mind.
Mention has been made in section (a) of the list of advantages, and
also indicated in Fig. 1, that controlled drug release can maintain a
certain concentration of drug in the biophase surrounding a desired
receptor site in the body. In fact, maintenance of this concentration,

between the limits imposed by the minimum effective concentration
and the maximum safe concentration for an appropriate period, forms
what is presently the most readily achievable of the two main aims of
controlled release drug therapy. The second aim is to ensure that all,
or at least a substantial proportion, of the active drug is released in the
correct biophase at a controlled and satisfactory rate, or is transported
only to that biophase, again at a satisfactoryl rate, following its absorp-
tion into the body at some distant site of administration. In cases
where the controlled release dosage form can be positioned in, or
adjacent to, the appropriate biophase, e.g. in instances where dosage
forms are inserted into the conjunctival sac for the treatment of eye
diseases, then a reasonable degree of achievement of this aim can
already be realised. However, in other cases where the released drug
can only reach the required receptor site after being transported some
distance via the blood or lymphatic systems then methods of achieving
the aim, i.e. the targetting of drugs to their receptor sites, are still in
their infancy.2o.44
Measurement of drug concentrations in tissues and organs, that
contain the specific receptor sites of a given drug, at various times after
drug administration, is often difficult or impossible. Use is therefore
made of the concentration versus time profiles of drug in accessible
body fluids, particularly blood plasma, to monitor the time course of
the drug in the body. The validity of this approach is improved if a
correlation can be established between the drug concentration in
plasma and the pharmacological effect of the drug. 45 Such correlations
have been demonstrated in a number of cases and usually result in the
recognition of a therapeutic range for a given drug. 24 This range
defines the lower and higher limits of drug plasma concentration that
correspond to the minimum effective and maximum safe concentra-
tions, respectively. In such cases, as is shown in Fig. 2, the plasma
concentration versus time curves will have similar profiles to that for
the specific biophase (Fig. 1). It should be noted that maximum safe
concentrations, that are designated with respect to the plasma curves,
are influenced by the necessity to avoid undesirable side effects as well
as unacceptably excessive primary responses.
The shapes of drug concentration versus time curves for plasma and
body tissues reflect the effects of absorption, distribution, metabolism
and excretion processes. Quantitative analysis of the relative contribu-
tions of these processes to the overall disposition of drug in the body
- I:- - - -
I
TOXiC
range
~---+-----\---+----+--t----+----- ;:~~':1'eutic
---- 0---V-
Min~u~ 1ffective concentration
'J 'Ineffective
l range
t t
TIME
Fig. 2. Plasma concentration versus time profiles of a drug following ad-

ministration of (A) successive doses in a conventional dosage form (arrows
indicate times of administration) and (B) a controlled release dosage form.
forms the basis of pharmacokinetic studies. 46- 48 These studies attempt

to obtain reliable estimates of various parameters, such as absorption,
distribution and elimination rate constants, that may be used in con-
junction with realistically chosen mQdels to describe the kinetics of
drug disposition throughout the body. Knowledge of relevant phar-
macokinetic parameters is useful in the design of controlled release
dosage forms because they may indicate the essential characteristics of
a required release process. 49
The most simple pharmacokinetic model of drug disposition in the
body is known as a one compartment open model, in which drug input
(e.g. absorption) and output (i.e. elimination) occur by first order
processes. This model can be represented diagrammatically by Scheme
1, where ka and ke represent the first order rate constants associated
with absorption and elimination, respectively. The single box or com-
partment represents the plasma plus any other body fluids and tissues
into which the drug is distributed so rapidly that a concentration
equilibrium can be regarded as existing between them and plasma. A
Drug at Drug in
k,. Drug in
absorption body --+ .
unne
site Cplasmalt) Vd
Scheme 1. One compartment open model of drug disposition.

sample of plasma consequently represents an aliquot of the total

volume of distribution (Vd ) of the drug in the body. Thus, multiplica-
tion of Vd by the plasma concentration at a given time (Cplasma(t)
yields the total amount of drug in the body at that time. The rate of
drug elimination in terms of amount of drug per unit time is given,
therefore, by kcCplasma(t) Yd' In this case it follows that if a desired
plasma concentration C~lasma is required to be maintained for
therapeutic purposes by a controlled release dosage form then the rate
of drug input from the dosage form should equal the rate of drug
elimination from the body, i.e.
Required rate of drug input = keC~lasma Vd
This requirement is most readily achieved in theory by the use of a

dosage form that releases the drug at a constant rate that is indepen-
dent of the amount of drug remaining in the dosage form at any given
time, i.e. at a zero-order rate ko, where
The previously described one compartment model can be modified

in order to include the input of drug from a controlled release dosage
form as shown in Scheme 2. Since two consecutive mass transfer
Drug in Drug at Drug in

absorption body _~ Drug in
dosage
urine
form site Cp1ao:.;ma
Scheme 2. One compartment open model of drug disposition with zero-order

input.
processes occur before the drug enters the body then effective control
over Cplasma can only be exerted by drug release from the dosage form
if this process is the rate determining stage.
It should be borne in mind that the above comments assume that (a)
the one compartment model provides an adequate representation of
the way in which the drug is distributed in the body and (b) complete
absorption of the released drug occurs at a first-order rate. In addition,
inferences made in earlier parts of this chapter may be questionable in
certain circumstances. For example, the assumption that a constant
plasma concentration is required during the therapeutic period may
not necessarily be the most desirable concentration profile for all cases.
For example, an oscillating profile may be preferable in the treatment

of bacterial infections by antibiotics. In spite of these limitations the
majority of controlled release studies have aimed to provide plasma
concentrations of drugs that either remain essentially constant at some
value within the therapeutic range of a given drug for an appropriate
period or, if the concentration declines with time, the rate of decline
should be small enough to ensure that a satisfactory period occurs
whilst the concentration remains within the therapeutic range. As
indicated previously, constant concentration profiles can be achieved
with dosage forms that release drugs at zero-order rates. However,
studies have also involved products that provide either first-order
release rates or rates that are linearly related to (time) 1/2. In fact, it has
been shown that satisfactory approximations to a constant plasma
concentration can be achieved by using a first-order controlled release
dosage form in combination with an immediate release of drug. 50•51
2. METHODS OF CONTROLLING DRUG RELEASE
A controlled release dosage form consists essentially of a drug contain-

ing device that permits the release of the drug at a predetermined rate
when the dosage form is placed in the body. The drug in the device
should also be protected against the possibility of degradation, particu-
larly during its active life in the body.
In the majority of modern systems control of release is effected by
utilising various properties of polymeric materials. The usefulness of
these materials arises from the tremendously wide and often subtle
variations that can be obtained in the properties of polymers by
varying the natures and/or concentrations of comonomers, crosslinkers
and plasticisers or by using laminated combinations of different poly-
mers. Although most studies have tended to centre on the use of
polymer permeability as the mechanism for controlling drug release
other systems, which rely on the biodegradability of polymers and on
the properties of polymer-drug complexes, have been introduced. A
review of polymer controlled drug release should obviously deal with
all of these different types of mechanism. However, in view of the
general theme of this book emphasis has been placed, in the following
sections, on the role of polymer permeability as a release controlling
mechanism and on the applications and problems associated with this
type of system. This emphasis should not be interpreted as a suggestion
that polymer permeability is more important than the other mechan-

isms. The reader should appreciate that, at present, the different
systems possess individual advantages and disadvantages that make
each of them likely to be more suitable for some purposes than others.
In addition, the need to assess the performance and possible side
effects of these systems in long-term clinical trials and toxicological
studies is responsible for considerable delay in their possible appear-
ance as acceptable products so that relatively few systems have, so far,
received approval from drug licensing authorities and become available
commercially.
3. CONTROL OF DRUG RELEASE BY POLYMER

PERMEABILITY
The majority of polymer-based controlled release systems have been

designed for use as subcutaneous implants, devices for insertion into
body cavities, such as the uterus and vagina or into the conjunctival sac
of the eye, or adhesive strips that permit controlled absorption of drugs
through the skin. The feasibility of obtaining substantial periods of
control over drug release with many of these systems, e.g. over 1 year
for some intrauterine contraceptive devices, is aided by the fact that
the devices remain in a fixed position in or on the body during their
period of use. However, the rate of gastrointestinal transport precludes
the effective control of drug levels in the body over long periods by
means of orally administered dosage forms and the maximum period of
drug activity that is feasible at present is approximately 12 h plus the
length of time that the released drug exerts its activity. In addition, the
performance of orally administered dosage forms will be affected by
variations in factors such as pH, enzyme activities, gastric emptying
rates, intestinal transit times and the effects of gastrointestinal con-
tents, e.g. food, that will be encountered. The blood concentrations of
those drugs with short biological half-lives will be more sensitive to
these variations. Unfortunately, the therapeutic need for a sustained
release product increases as the biological half-life of the drug de-
creases. This quandary has led Boxenbaum 52 to conclude that the level
of success that may be expected from an orally administered sustained
release product is inversely proportional to the therapeutic need for
such a product. Furthermore, the use of drugs with long half-lives in
the design of sustained or controlled release dosage forms is undesira-
ble because of the possible occurrence of drug accumulation in the
body and the inherent dangers associated with this possibility. In spite
of these limitations and because the oral route offers such a convenient
means of administration, that does not, in contrast to the previously
mentioned routes, require sterilisation of intended dosage forms, vari-
ous attempts have been made to design suitable products that provide
a sustained period of drug release in the gastrointestinal tract and some
of these depend on the properties of polymeric materials, including
polymer permeability. However, many of these oral products rely on
more than one mechanism to sustain drug release and permeability and
dissolution of polymeric materials are often involved simultaneously.
For this reason more emphasis has been placed in the following
sections on examples of controlled release devices that are adminis-
tered via routes other than the oral one. In view of this limitation the
chapter by Lee and Robinson 41 is recommended for more information
on orally administered, sustained release dosage forms.
Polymer-based controlled release systems are normally classified as
either reservoir (membrane) devices or matrix (monolithic) devices. In
the former type release is controlled by a polymeric membrane that
surrounds a drug containing reservoir, whereas in matrix devices the
drug is either dissolved in or dispersed homogeneously as solid parti-
cles throughout a polymer matrix. Such classification can be readily
applied to many examples of controlled release systems. However, the
separation of microencapsulated products into the two subclasses is
more difficult because it is not always easy to decide if this type of
product consists of a core surrounded by a distinct membrane or if it
consists, at least in part, of particles of drug embedded in a matrix of
the encapsulating material. For this reason examples of microencapsu-
lated products, that are intended to control the release of drugs, are
considered separately in the later sections of this ·chapter.
Selection of appropriate polymers for both types of device is in-
fluenced not only by biocompatibility and safety aspects but also by
solubility and stability characteristics, since neither dissolution nor
degradation of the polymer should occur during the active life of a
device that relies on diffusion control of drug release. However, the
occurrence of biodegradation after the end of this lifetime may be a
desirable feature in certain instances, because it would, for example,
avoid the necessity of surgical removal of implanted devices at the end
of their useful lifetimes or avoid the possibility of blockage of the
gastrointestinal tract by inert matrices, as has been observed in some
case studies on patients receiving orally administered sustained release
products. 53
Dense, i.e. non-swollen, hydrophobic polymers, swollen hydrophilic

polymers (hydrogels) and microporous membranes and matrices have
been used in the construction of reservoir and matrix devices. Silicone
rubber and polyethylene, which formed the basis of some of the
earliest studies on controlled release,54.55 are satisfactory for the re-
lease of hydrophobic drugs with relatively low molecular weights
«600). These polymers have since been augmented by the introduc-
tion of materials such as ethylene-vinyl acetate copolymer (EV A)56 for
intrauterine devices 57 and various hydrogels, which may be used to
construct devices that release larger molecules in a controlled manner.
For example, a copolymer of hydroxyethyl methacrylate (HEMA) and
ethylene glycol dimethacrylate (EGDMA), which was patented as an
implantable hydrogel by Wichterle and Lim,58 can be used for ionisa-
ble drugs with molecular weights of up to 8000. Hydrogels of the latter
type are not only suitable for use with hydrophilic drugs but may also
be used to control the release of hydrophobic agents such as proges-
terone. 15 In addition, microporous membranes and matrices have
formed the basis of some important and commercially available con-
trolled release devices and further comments on these systems are
given in later sections.
3.1. Reservoir (Membrane) Devices for Controlling Drug Release

As previously mentioned, a reservoir device consists of a core formula-
tion of the drug surrounded by a polymeric membrane. Drug release
rate is controlled by diffusion across this surrounding membrane so
that neither dissolution nor degradation of the polymer should occur
during the active lifetime of the device.
The profile of drug release rate versus time is dependent on the
thermodynamic activity of the drug inside the device. Thus, in order to
obtain a constant release rate over a prolonged period, this activity
must be maintained at a constant value. In the case of a solid drug this
is most readily achieved by using either a saturated solution of the drug
with excess solid or simply solid drug as the core formulation, since
either of these systems would yield a thermodynamic activity of unity
whilst some solid drug remained within the core. If the drug happened
to be a liquid at body temperature then pure liquid would also provide
a constant activity of unity. Under these circumstances the profile of
release rate versus time would reach a steady level after an initial
period, during which transient higher or lower release rates ma.v be
observed (see sub-section A(i), and this steady level would be main-
tained until all the solid drug in the core had been removed. In this
W Burst effect
~
~ \ I
~ ~
>:
Steady state I Exponential decline
(zero order release) I (first order release)
I I
~~
!\
I
( I
Lag effect
TIME
Fig. 3. Overall profile of release rate versus time for a reservoir device.
event the rate of release would decline exponentially with time as the
thermodynamic activity of the core drug decreased. The overall profile
can therefore be represented diagrammatically, as in Fig. 3. From
analogies with chemical kinetics the steady and finally declining parts
of this profile are usually referred to as zero-order and first-order
release, respectively.
The ease with which zero-order release kinetics can be achieved with
reservoir systems is the main advantage of this type of device. How-
ever, thes(: devices do suffer from a number of disadvantages. For
example, t hey are often more expensive to make than other types of
controlled release device and ensurance of membrane integrity is
particularly important because of the dangers that may arise if rapid
release of drug occurs through imperfections in the membrane. Finally,
the polymers that are used are often non-biodegradable so that sub-
cutaneous implants must be removed surgically. In fact, it has been
suggested 22 that this disadvantage may restrict the use of non-
biodegradable devices to subcutaneous implantation into easily excised
sites in animals (e.g. the ear) and to insertion into human body cavities
(e.g. uterus, vagina, eye, nose and mouth), from which they can be
removed without surgery. In other words, human subcutaneous im-
plantation would not be considered except for the possible treatment
of chronic diseases (e.g. diabetes) when reservoirs containing large
supplies of drug or refillable reservoirs would be required.
Various types of polymeric membrane may be used in the construc-
tion of res ~rvoir devices. In general, these types may be sub-divided
into hydrophobic, non-porous membranes, microporous membranes
and water-swollen, hydrophilic membranes (hydrogels). The following

sections give an indication of the mechanism of drug release in each
case and the factors that may affect the rates of release, together with
some examples of the use of these different membranes in the design
of reservoir devices. In the case of non-porous membranes, equations
which describe the kinetics of release that occur during the various
stages of the overall profile illustrated in Fig. 3 are presented, together
with others that describe the effects of boundary layers.
A. Reservoir Devices with Non-porous Membranes
(i) Release mechanism. In the case of these membranes the release

process involves the consecutive processes of drug partition between
the core formulation and the membrane, diffusion of drug in solution
across the latter and subsequent partition of drug into an aqueous
environment.
During the zero-order phase of the overall release profile the rates
of drug release from devices having the simple geometries that are
shown in Fig. 4, i.e. infinite slabs, infinite cylinders and spheres, may
be described by eqns (1)-(3), respectively. 59 (However, equations are
applied in practice to slabs and cylinders of reasonable dimensions.)
dM, ADp K p/s l1C
Slab: (1)
dt lp
dM. 27ThlJpKp/s.1.C
Cylinder: (2)
dt In (ro/rJ
Sphere: (3)
where M t is the amount of drug released after time t, dMrfdt is the

steady state release at time t, Dp is the diffusion coefficient of the drug
in the polymeric membrane, K p/s is the partition coefficient of drug
between the polymer and the solvent in the core formulation, I1C is
the difference between the concentration of drug in the core formula-
tion and the aqueous phase that surrounds the device, lp is the
thickness of the polymeric membrane and the geometric terms A, h, ro
and rj are defined as follows:
Siab-A is the total surface area, i.e. both sides but ignoring edge
effects;
• •,M• • t/p
M_ _ _ t '*"
______ t t , '
SI.A8
~l r
h
- - - >"- ; i
! j
21'1 21'0
! l ..,
____ J,;
. _i
SPHERE
Fig. 4. Reservoir devices with simple geometries (M = membrane; R =

reservoir of drug).
Sphere-ro is the overall radius of the core plus surrounding mem-

brane and rj is the radius of the core only;
Cylinder-h is the length and ro and rj have the same definitions as for
a sphere.
In the case of a sphere with a very thick membrane, such that ro »rj,
eqn (3) reduces to eqn (4):
dM,
dt = 47TDpK P/sa Cr; (4)
and the rate of release is then independent of the overall radius of the
device. Baker and Lonsdale 59 have shown that this independence is
realised if ro >4r;. In addition, the same authors indicate that two small
reservoirs placed a short distance on either side of the centre of a
sphere will have almost twice the release rate of a single central
reservoir. In other words, the release rate can be altered by the
distribution and shape of the reservoirs.
In order to obtain constant, i.e. zero-order, release all the terms on
the right-hand sides of eqns (1)-(4) must remain constant. Thus, the
diffusion and partition coefficients Dp and K p/s and the concentration
difference aC must remain constant as well as the geometrical dimen-
sions that determine the diffusional path-lengths and surface areas of
the devices.
As mentioned previously, the initial release rate from a constant
activity reservoir device may be greater or less than the zero-order rate
that is attained eventually. The initial behaviour will depend on the

degree of saturation of the membrane by the drug that is achieved
before the device is put into use. The extremes of behaviour will
therefore correspond to conditions in which the membrane is either
saturated by, or devoid of, drug, respectively.
In the former extreme the release rate versus time profile will exhibit
an initial high rate that declines with time until the zero-order rate is
observed in the steady state, as shown in Fig. 3. This is known as the
'burst effect' and the corresponding shape of a plot of amount of drug
released (M,) versus time (t) is given in Fig. 5. The linear relationship
between M, and t that occurs when the steady state is reached in the
release of drug from a device with slab geometry is given by eqn (5)
(5)
where em is the uniform concentration of drug that exists initially in

the membrane. In addition, the diffusion coefficient of the drug in the
membrane can be derived from eqn (6),
(6)
where tB is the negative intercept on the time axis in the plot shown in
Fig. 5.
h
/- BURST EFFECT
/0
/' '" '" ,/

/'
/'
/'
,,-
/'
/'
/'
9'
?' LAG EFFECT
/'
/'
/'
/' /'
/' /'
/' /'
- - te = 2 t l - -.. -tL----:-+ TIME
Fig. S. Approach to the steady state during initial stages of drug release from a
reservoir device.
If the device is used immediately after preparation so that little or no

drug has partitioned into the membrane then establishment of a
concentration gradient across the membrane will take some time and
will therefore give rise to a lag effect. The release rate versus time
profile will initially exhibit slow rates that increase with time until the
steady state is reached, as shown in Fig. 3. Equation (7) describes the
linear relationship that exists between M, and t in the steady state that
is depicted in Fig. 5,
M, = DpCo (t -l~) (7)
A lp 6Dp
where Co is the concentration of drug that exists at the inner surface of
the membrane.
In the case of a lag effect Dp may be determined from eqn (8),
l~
tL = 6Dp (8)
where tL is the positive intercept on the time axis in the plot shown in
Fig. 5.
Equations (7) and (8) indicate that the time required before a
constant rate of release commences in the steady state is not influenced
by the amount of drug in the device but is only dependent on the
thickness of the membrane and the diffusion coefficient of the drug in
the polymer.
Equations that describe the lag times given by cylindrical and
spherical devices have also been derived. 60
If a reservoir device is stored for insufficient time to ensure complete
saturation of the membrane by the drug then more complex initial
profiles than that given in Fig. 5 may be observed. 59
As mentioned previously when all of the solid drug has been
removed from a reservoir device then the terminal part of the release
process declines exponentially as shown in Fig. 3. During this stage the
constancy of terms on the right-hand-sides of eqns (1)-(4) is not
maintained since aC decreases with time. A similar situation would
occur if the original reservoir contained only a solution of drug rather
than a suspension of solid drug. Derivation of equations, which de-
scribe the resulting first-order release rates, involves substitution of the
. eqns (1-
aC term m ) () VIi , - M
4 by M h
V 22 ,' were V· h
1 IS t e volume of the
reservoir that is separated by a rate controlling membrane from a

receptor phase or sink of volume V 2 , M 1t represents the mass of drug

that remains within the reservoir at time t and M2t is the mass that has
been transported to the sink in the same time. Thus, the total mass of
drug M= is given by the sum of M 1t + M2t and if all the drug is initially
contained in the reservoir then M= = M 1t at t = O.
For example, in the case of a system with a slab geometry then
substitution for t:.C in eqn (1) yields eqn (9).
(9)
Further substitution for M 2, (=M=-M},) followed by rearrangement

gives eqn (10).
dM}, ADpK p/s dt
(10)
M I ,(V} + V 2 ) - M= VI lp V 1 V 2
The integration constant of eqn (10), can be evaluated if it is remem-

bered that M= = Mit at t = 0; it is represented by eqn (11).
(11)
Differentiation of eqn (11) gives eqn (12),

dMI ,
--=
-M~DpKp/s
exp
(- ADpKp/S(Vi + V 2 )t) (12)
dt VIl p VI V21p
which describes the release rate from the system in terms of changes in
the mass of drug remaining in the reservoir, i.e. not, as in eqns (1)-(4),
in terms of the mass of drug released.
When the receptor phase volume V 2 is sufficiently large so that it
can be regarded as an infinite sink then V 2 » V 1 and eqns (11) and (12)
can be simplified to give eqns (13) and (14), respectively.
(13)
(14)
The time required to release half the drug from the reservoir, i.e. the
half life (t l/2 ), of a first-order release system, is often useful to know
and may be derived from eqn (13) by substituting M=/2 for MI. and
rearranging to give eqn (15),
In 21p VI O·6931pVI
tl/2 = (15)
ADpK PIS ADpK PIS
(ii) Boundary layer effects. In the derivation of eqns (1)-(3) it is

assumed that the rate of drug release is determined only by the rate of
diffusion across the polymeric wall of the reservoir device. This may
not be so, particularly in vivo where the degree of agitation by body
fluids may be very low. The resultant stagnant boundary layer that
surrounds the device may constitute an additional resistance to mass
transfer. Furthermore, in order to account for all such resistances then
the effects of a stagnant boundary layer in the liquid suspending
medium used in the reservoir formulation should be considered. The
concentration (or thermodynamic activity) gradient between the inner
reservoir and the outer eluting fluid may be represented by Fig. 6.
Thus, the total diffusional resistance (r total) is given by the sum of the
resistance in the polymeric membrane (rp) and those in the boundary
layers that exist in the inner suspending medium (rs) and the outer
aqueous phase (rAq) as shown by eqn (16).
rtotal=rS+rp+rAq (16)
Since each resistance is equal to the thickness of the diffusion layer
~ ~ I~
-----_.--- -- - -----+--..
RESERVOIR MEMBRANE
SUSPENSION I
OF DRUG
AQUEOUS
SINK
Fig. 6. Concentration profile between inner reservoir of a reservoir device and

aqueous eluting phase. Is, lp and IAQ are the respective thicknesses of the
boundary layer in the inner suspending medium, the polymeric membrane and
the aqueous boundary layer.
divided by the permeability (DK) of the diffusant in that layer, where

D is the appropriate diffusion coefficient and K is a partition coeffi-
cient that reflects the relative affinity of a given layer for the diffusant,
then eqn (16) may be rewritten as eqn (17)
Is Ip IAq
'total = ~~- + +------=-=--- (17)
DsKs/s DpKp/s DAqKAq/S
where the subscripts S, P and Aq refer to the suspending medium,
polymer and aqueous eluting phase, respectively, I represents the
thickness of a diffusion pathway, D is the diffusion coefficient of the
drug in a given phase and K represents the partition coefficient of the
drug in each phase with respect to the suspending medium, i.e.
Ks/s = 1.
In the steady state the rate of release into an infinite sink is given by
eqn (18).
dO, Cs
(18)
dt 'total
where 0, is the cumulative amount of drug released per unit area of

the device (i.e. 0, = M,/ A), C s is the solubility of the drug in the inner
suspending medium and substitution for 'total in eqn (18) yields
dO, DsDpDAqKp/sKAq/SCS
(19)
dt IsDpDAqKp/s + IpDsDAqK Aq/S + IAqDsDpKp/s
In most reservoir systems ip > is and IAq and Dp<Ds and D Aq so that
the first and third terms in the denominator of eqn (19) are small when
compared with the middle term and simplification can be carried out to
give eqn (20),
dO,
(20)
dt
where Cp is the solubility of the drug in the polymer. The latter
equation is an alternative version of eqn (1) and indicates that drug
release rate is controlled by membrane limited diffusion and follows
zero-order kinetics. The equation also shows that the release rate is
linearly related to both the diffusivity and solubility of the drug in the
polymer and is inversely proportional to the membrane thickness.
Neglect of the diffusional resistance of the inner boundary layer is
not unreasonable (except perhaps if a very viscous and very poor
solvent for the drug were selected). However, if K Aq/s is very low, K p/s
is very high and if lAq is large then the third term in the denominator of
eqn (19) may exceed the sum of the other two terms and the resulting
simplification is given by eqn (21),
dO, DAqKAq/SCS
(21)
dt lAq
and since KAq/SCS = C Aq (solubility of drug in aqueous eluting phase)

then dO, DAqCAq
(22)
dt IAq
These latter equations define the rate of drug release when it is

controlled by boundary layer limited diffusion. Zero-order release
kinetics are again predicted but in this situation the release rate is
linearly related to the diffusivity and solubility of the drug in the
surrounding aqueous phase and is inversely proportional to the thick-
ness of the boundary layer. Alternatively, since CAq = KAq/PCp, it
follows from eqn (22) that
dO, D AqKAq/pCp
(23)
dt lAq
thus indicating that the partition coefficient of the drug between the
aqueous phase and the polymer (K Aq/P ) may be an important factor
when drug release is controlled by the properties of the boundary
layer, i.e. a boundary layer-limited, partition-controlled, release pro-
cess can be envisaged.
(iii) Examples of reservoir devices with non-porous, hydrophobic mem-

branes. Polydimethylsiloxane (PDMS) exhibits good biocompatibility
with body tissues and ever since Folkman and his colleaguess4.61-M
reported its permeability to a variety of drugs, such as anaesthetics and
cardiovascular agents, it has been used extensively in the preparation
of reservoir devices. These devices usually consist of capsules made
from PDMS tubing (silicone rubber tubing), particularly the medical
grades (Silastic®) that are available from the Dow Corning Corp.
Various sizes of Silastic tubing are available with different degrees of
hardness. The elastomeric polymer, that is used in the manufacture of
the tubing, is composed of dimethylsiloxy units with small amounts of
methylsiloxy copolymers in the hard, medium and soft grades. The
latter grade also contains small amounts of methylphenylsiloxy
copolymer. A mixture of the elastomer, a filler consisting of very fine
silica powder (particle size approximately 20-30 nm) and vulcanising

agent (dichlorobenzoyl peroxide) is heated and the dichlorophenyl free
radicals produced from the vulcanising agent cause crosslinking be-
tween the copolymers. 65
Sections of Silastic tubing may be converted into reservoir devices by
sealing one end with a thin layer of Silastic medical adhesive. This
adhesive consists of a relatively low molecular weight silicone polymer
with hydroxyl end groups with methyltriacetoxysilane as the crosslink-
ing agent. Polymerisation occurs on contact with water since the
triacetoxy group on the crosslinking agent is hydrolysed to a trihyd-
roxyl group, which then condenses with hydroxyl groups on the prim-
ary polymer. Crosslinking is only fully achieved when water has
completely penetrated the mixture so that curing periods of the order
of 24 h in a humidified atmosphere may be required. The open capsule
may then be filled with the required drug formulation and sealed with
a further layer of adhesive, which is allowed to cure as before.
Many of the controlled release studies that have utilised reservoir
systems based on Silastic tubing have been concerned with steroid
hormones, particularly those that act as contraceptive agents. This
interest arose from the advantages that could be obtained by providing
a considerably sustained contraceptive activity with such potent sub-
stances, which only required release rates of the order of a few
micrograms per day in order to produce their physiological effects.
Subcutaneous implantation of devices containing such agents as pro-
gesterone received particular attention after Kincl et al. 66 showed that
PDMS had a much higher permeability for this agent than other
polymeric materials such as nylon and polystyrene. Since progesterone
sometimes causes adverse effects when administered subcutaneously,67
together with the fact that it is metabolised rapidly so that large
amounts would be required in a reservoir to give considerably ex-
tended periods of activity, more recent studies have involved the
subdermal implantation of PDMS capsules containing other contracep-
tive agents, e.g. megestrol acetate,68 norgestrienone,69 norethindrone7o
and d-norgestrel?l
Subcutaneously implanted PDMS capsules have also been used to
inhibit oestrus in animals via the delivery of male hormones, such as
testosterone and androstenedione. 72
Progesterone exerts its contraceptive effect by altering the endomet-
rial tissue that lines the uterus in such a way that the implantation of
fertilised ova into this tissue is resisted. A close proximity between a
controlled release device and the required receptor site of the drug
contained in the device is desirable in order to minimise the possible
side effects of the drug. Consequently, variously shaped contraceptive
devices that utilise PDMS membranes surrounding reservoirs of
steroids, such as progesterone,73 d-norgestreC 4 and chlormandinone,75
have been tested.
The high permeability of PDMS to steroids coupled with the low
water solubility of these drugs may lead to partition controlled rather
than membrane controlled release rates, i.e. the rate of drug clearance
from the surface of the membrane tends to control the overall release
process rather than the rate of drug diffusion through the polymeric
membrane. This problem may be overcome by the formation of
laminates of PDMS and other polymers such as polyethylene76 .7 7 and
polytetrafluoroethylene,77 which exhibit much lower permeabilities for
steroids than does PDMS, so that effective membrane controlled
release is achieved.
Because of the long standing interest in the diffusion of steroidal
contraceptive agents through PDMS, many of the previous studies on
factors that influence the diffusion of drugs through this polymer have
been concerned with such agents. 78- 84 A list of references to investiga-
tions on the transport of other drugs has been compiled by O'Neill. 85
More recent additions to such a list include studies on nicotine,86
antiarrhythmic agents,87 prostaglandins 88 and gentamicin. 89 The latter
reference is of interest because of its particular attention to the effects
of fibrous capsule formation around an implanted reservoir device.
Such tissue reaction is often regarded as a major problem in the use of
implanted controlled release devices because the diffusional resistance
offered by a fibrous envelope may have serious effects on the release
profile of a drug.
The disadvantage of PDMS, that arises from the high permeability
of this polymer to steroids, has also been overcome by the introduction
of ethylene-vinylacetate (EY A) copolymers, which exhibit lower per-
meabilities than PDMS for steroids such as progesterone. 57
In addition, the EY A copolymers possess advantageous thermoplas-
tic properties with regard to the formation of device components. The
potential usefulness of these materials, including toxicological and
biocompatibility aspects. in the design of controlled release drug
delivery devices was developed by the Alza Corp. This research and
development effort has led to the commercial introduction of a con-
traceptive reservoir device for intrauterine insertion and an ocular
i Isert for the treatment of glaucoma.
The former device (Progestasert®) delivers 65 I-Lg of progesterone

per day from a reservoir mixture of drug, barium sulphate and oil
through an EVA membrane to the uterine fluids. The drug delivery
rate remains virtually constant for 1 year. Further details of the design
and performance of the Progestasert Intrauterine Therapeutic System
are available in a number of publications. 19.8s ,9o,91 These publications
also provide similar information on the pilocarpine-containing Ocular
Therapeutic System (Ocusert®) that is intended for insertion into the
upper or lower cul-de-sac of the eye. Two systems are available, which
deliver essentially constant rates of either 20 I-Lg or 40 I-Lg of pilocar-
pine per hour for one week, for the reduction of intraocular pressure in
the treatment of chronic, open-angle glaucoma, the higher rate being
achieved by means of a plasticiser, di(2-ethylhexyI)phthalate, that is
incorporated into the EVA copolymer.
The problems that arise from the use of water-soluble drugs such as
pilocarpine, which generate adverse osmotic effects if the reservoir
membranes are permeable to water, and the extent to which these
problems are overcome by the EV A membrane in the Ocusert system
are discussed by Shell. 92 This author also provides information on the
release of chloramphenicol and hydrocortisone from an Ocusert de-
vice.
The Ocusert and Progestasert systems provide examples of control-
led release devices that are placed in close proximity to the receptor
sites of their contained drugs. Thus, they approximate to ideal control-
led release systems since not only is the concentration of drug in the
appropriate biophase maintained at a safe and effective level for an
acceptable period of time but also a substantiai proportion of the
active drug reaches that biophase.
The use of EVA in devices intended to provide a controlled release
of fluoride into the mouth for the prevention of tooth decay has been
investigated. 93 The EVA was applied from a solution in chloroform by
dipcoating on to hydrophilic polymer matrices containing NaF or
Na2P03F.
Hydrophobic polymers other than PDMS and EVA have received
varying degrees of attention as membrane materials for reservoir
devices. In the case of polyurethane containing compositions the
copulyether-urethane combinations possess suitable permeability and
biocompatibility characteristics for use as rate controlling mem-
branes94.95 and they are permeable to both lipophilic and hydrophilic
drugs.% Zentner et al. 97 have investigated the permeation of proges-
terone through two polyurethanes and Baker et al. 98 have tested an
intrauterine reservoir device with a polyurethane membrane for the

release of oestriol in animals and humans.
The low permeability of polyethylene to drug molecules precludes its
general usefulness in controlled release dosage forms. However, this
property may occasionally be advantageous, for example, as indicated
previously, in providing a possible means of counteracting the high
permeability of PDMS via lamination of both polymers. 76•77
Studies have also been carried out on polyamides99 • lOo but PDMS
and EVA are by far the most widely used membrane materials in
pharmaceutical controlled release devices. However, in the agricultural
sphere, polyethylene, polyviny1chloride and nylon membranes have
been used in the design of laminated reservoir devices for the control-
led release of pesticides. 10 1
B. Reservoir Devices with Microporous Membranes
(i) Release mechanisms. The diffusional stage in the release of drug

from this type of device involves transfer of dissolved drug through
discrete, liquid-filled pores rather than through successively formed
spaces between segments of polymeric macromolecules as in the case
of the dense hydrophobic membranes. Partition of drug between a core
formulation and the liquid in the pores of the membrane must occur
before membrane transport can proceed.
Porous polymeric membranes can be produced by appropriate pro-
duction processes, incorporation of readily leachable or volatile com-
ponents into the initial membrane formulation, or by careful micro-
deformation of crystalline or glassy polymers. Thus, various cel-
lulosic materials, such as cellulose triacetate, and other polymeric
materials, such as polycarbonate and polypropylene, can be used in the
formation of membranes that contain discrete, continuous micropores
having diameters of the order of 1· 5 x 10-3 ILm up to several microns.
The number and size of the micropores is extremely dependent on the
method of preparation and subsequent storage conditions. These
membranes can be used to provide a support network, in which liquids
may be entrapped. The transport properties of such liquid-filled net-
works are determined mainly by the properties of the liquid phase.
Drug transfer from a reservoir device surrounded by a liquid-filled
microporous membrane occurs by diffusion through the liquid-filled
pores. The transport flux (J) through such membranes may be de-
scribed by eqn (24),

dO, £DLKL/sLle
J=-= (24)
dt Tip
where E, T and lp are the porosity, tortuosity and thickness of the

microporous membrane, respectively, DL is the diffusion coefficient of
the diffusant in the liquid that fills the micropores, K LIS is the partition
coefficient of the diffusant between that liquid and the one that is used
as the suspending medium in the core formulation and Lle is the
concentration difference that exists across the membrane.
Equation (24), like eqn (1), predicts that release rates will be time
independent, i.e. zero-order kinetics will be exhibited. However, eqn
(24) differs from eqn (1) in the following respects:
(a) the area of the diffusional path is limited by the porosity of the
membrane,
(b) the diffusion coefficient in eqn (24) refers to the transfer of drug
through a liquid in distinct pores in the membrane rather than
through spaces formed between mobile segments of mac-
romolecules,
(c) the partition coefficient in eqn (24) also reflects this change to a
liquid continuum through the membrane, and
(d) the length of the diffusion pathway is increased by the irregu-
larly channeled pores so that a tortuosity factor might be
introduced to allow for this effect.
(ii) Examples of reservoir devices with microporous membranes. Mic-

roporous membranes have been used in the design of dosage forms
that adhere to the skin and control the rate of absorption of drugs
through unbroken skin into the systemic circulation.
The first commercially available dosage form, known as a Transdermal
Therapeutic System (TIS), was introduced by the Alza Corp. and contains
scopolamine (hyoscine) for the prevention and treatment of motion
induced nausea. Human skin is sufficiently permeable to scopolamine
to allow the design of a practically sized reservoir that can provide
adequate drug for the prevention of motion sickness in adults for 3
days whilst reducing the side effects of the drug (drowsiness, visual
impairment and dry mouth), that arise from the wide fluctuations of
scopolamine plasma levels when the drug is administered either by
intramuscular injection or orally.19 The TIS-scopolamine device is a
thin, laminated structure, 2· 5 cm3 in area, which is stuck on to the skin

behind the ear lobe. Detailed descriptions and illustrations of the
device have been given previously.19.85 Briefly, it consists of a reservoir
of scopolamine in a gel sandwiched between a rate controlling, mic-
roporous membrane, the nature of which is undisclosed, and an
external metal foil, which is impermeable to drug and moisture. A
layer of adhesive gel is also present on the dermal side of the
membrane. This gel contains additional scopolamine and serves not
only as a means of fixing the device to the skin but also as a reservoir
for an initial dose of drug that is released rapidly in order to saturate
skin binding sites so that steady state is reached more quickly when
drug is released from the main reservoir.
Other transdermal drug delivery devices that are based on controlled
release, reservoir systems containing glyceryl nitrate have been intro-
duced recently for the prophylaxis of angina pectoris, e.g. Transiderm-
Nitro® (Ciba-Geigy).102.103 In addition, current interest in the use of
polymers as rate-controlling films for transdermal drug therapy is
indicated by recent patent reports, which relate, for example, to
polyacrylate and vinyl polymers,104 polyurethanes 105 and cellulose de-
rivatives. 106
As indicated previously micropores may be created in a polymeric
membrane by the leaching out of soluble or volatile components. The
work of Donbrow and his colleagues 107- 109 on drug release from
ethy1cellulose films containing polyethylene glycol (PEG) 4000, which
is leached out by an aqueous environment, suggests that it may be
feasible to produce microporous membranes in situ. The results ob-
tained by Coletta and Rubin llo and Wood and Syarto 1l1 for the release
of aspirin from granules coated with films composed of ethyl- and
methy1cellulose support this suggestion. O'Neill85 reports that mic-
roporous membranes are also claimed to be formed when Diffulac®
membranes (Eurand Corp., Milan), which are used to microencapsu-
late active ingredients in the production of Diffucap® dosage forms,
are placed in water.
The use of ultramicroporous cellulose triacetate (Poroplastic®,
Molecular Research Corp., USA) as a rate-controlling membrane for
reservoir devices has been investigated by Obermayer and Nichols. 112
The structure of this material is d~scribed as essentially a molecular
sponge with a cellulose triacetate matrix and it can be impregnated
with high contents (70-98%) of almost any liquid. Evaporation of
impregnated liquid causes progressive collapse of the pore structure.
The resultant shrinkage is irreversible but can be stopped at any time

by preventing the further loss of liquid. Thus, controlled shrinkage can
be used to modify the rate of solute diffusion through such a mem-
brane and this diffusion rate is presumably maintained during use
because the collapsed membrane will not absorb water. The mechani-
cal properties of the ultramicroporous membrane are reasonable when
the high liquid content is taken into consideration and gelatin capsule-
like shapes can be fabricated. However, Obermayer and Nichols 112
indicate that osmotic pressure effects may cause problems with encap-
sulated reservoir devices.
C. Reservoir Devices with Hydrogel Membranes
(i) Release mechanisms. The large amount of water imbibed by certain

hydrophilic polymers, that arc known as hydrogels, provides the main
diffusional pathway for substances through these swollen polymers.
Thus, permeability is affected markedly by the solubility of the diffus-
ant in the aqueous continuous phase of these systems, which may be
considered as intermediates between non-porous and porous mem-
branes. The percentage volume of water in the hydrogel is also an
important determinant of permeability 113 and this volume is affected in
turn by the concentration of any crosslinking agent.114 When this latter
concentration is sufficiently high then permeability may involve a
partition process instead of porous transport. 97 . 1l5
(ii) Examples of reservoir devices with hydrogel membranes. The hyd-
rogel membranes used in most studies on potential reservoir systems
appear to have been based on polymethacrylates, particularly poly(2-
hydroxyethyl methacrylate) (HEMA), which has been referred to
earlier. 58 Thus, copolymers of HEMA and methylmethacrylate (MMA)
have been used in studies on the design of controlled release systems
containing fluorides for the treatment of dental caries,17.116 cyclazocine
for use in the treatment of narcotic addiction 1l7 and tetracycline. 118 In
addition, poly-HEMA membranes have been used by Kim et al. 15 to
control the release of progesterone from core formulations in which
the drug was dispersed in silicone fluid, methoxyethoxyethyl methacry-
late (MEEMA) or a combination of MEEMA and HEMA.
3.2. Matrix (Monolithic) Devices for Controlling Drug Release

These devices consist of solid polymers containing uniform distribu-
tions of drugs. They may be classified with regard to the mechanism of
drug release, since this may involve diffusion in solution through either
the polymeric matrix material itself or through water-filled pores.
Subclassification may then be made depending on whether the drug is
present solely as a solution in the device or as a dispersion of solid
particles in equilibrium with the dissolved drug.
A. Release from Non-porous Matrices
(i) Matrices containing dissolved drug. The theoretical release profiles

of drugs from devices with slab, cylindrical or spherical geometries are
shown in Fig. 7 in terms of the fractional release, M,/ M= versus t, and
//......--------
Sphere
Cylinder--
Slab ---
Time
Fig. 7. Fractional release and release rate versus time profiles for slab,
cylindrical and spherical matrices containing dissolved drug.
dM,/M= .
the rate of release dt versus t, where M, IS the amount of drug
released after time I and M= is the total amount released at infinite
time. Approximate equations that describe the early and later stages of
these profiles are usually preferred for practical purposes because-
complete mathematical descriptions of the curves are rather unwieldy.
The approximate relationships that may be applied to the profiles
given in Fig. 7 are given by eqns (25)-(36?9
Slabs
Early time
approximation M, = 4 (Dpt) liZ
(25)
(M,/M",~0·6)
M= 'Tre
dM,1 M= = 2( Dp ) 1/2
(26)
dt 7T1 2t
Late time
(-7T D pt)
2
approximation M, 8 (27)
M= = 1- 7T2 exp [2
(MJM=~0'4)
dMJM= p (-7T 2D pt)
dt r8D exp [2
(28)
Cylinders
Early time
approximation M, = 4 (Dpt) 1/2 _ Dpt
(29)
M= 7Tr2 r2
(M,IM=~0'4)
dMJM= = 2( Dp ) 1/2 _ Dp
(30)
dt 7Tr 2t r2
Late time
M, =1 4 [ -(2'405)2.Dpt]
approximation (2.405f exp ,2
(31)
(M,/M= > 0·6) M=
dM,/M=_ 4Dp
dt - r 2 exp
[-(2'405 f D p
,
2
t] (32)
Spheres
Early time
approximation M, = 6(Dpt) 1/2 _ 3D pt (33)
M= 7Tr2 r2
(M,/M=<0·4)
dM,/M== 3( Dp y/2 _ 3Dp (34)

dt 7Tr 2t r2
Late time
approximation M, = 1-~ exp ( _ 7T 2 Dpt) (35)
M= 7T 2 r2
(M,/M=>0'6)
dM,/M", 6D pt 2
--exp (7T
- -Dpt)
- (36)
dt r2 r2
where I is the thickness of a slab matrix, r is the radius of a cylindrical

or spherical matrix and the other terms are defined as before.
The use of matrices containing only dissolved drug as controlled
release devices has not received much attention probably because the
relatively low solubilities of drugs in suitable polymers limits the total
amount of drug that can be incorporated and hence limits the useful
lifetime of such devices. This type of system is, however, employed in
the design of some pharmaceutical ointments and creams.119.120
(ii) Matrices containing suspended drug. When equilibrium has been

attained in these devices after their manufacture the drug is present as
uniformly dispersed particles in contact with a matrix that is saturated
with dissolved drug. When drug release occurs into an aqueous envi-
ronment dissolved drug at the interface partitions into the aqueous
phase. Diffusion of matrix dissolved drug towards the interface then
takes place and subsequently dissolution of drug particles occurs in the
matrix in an attempt to re-establish the equilibrium. Scheme 3 may
therefore be considered as a representation of the various stages
involved in the overall release process.
Solid Drug Dissolved

drug dissolved drug in
embedded Dissolution ) In Diffusion ) surface
in matrix layer
matrix of matrix
1I
Partition
Dissolved Dissolved
drug Diffusiondrug in
removed across aqueous
(
into boundary solution
aqueous layer at
sink interface
Scheme 3. Stages in the release of suspended drug from a matrix device.
Most studies on drug release from this type of system have attemp-
ted to correlate their results with an equation derived by Higuchi from
consideration of a physical model of release from ointment bases. 121 A
diagram of this model as applied to a matrix with slab geometry is
Fig. 8. Development of concentration profiles with time (0 < t, < t2 ) within a

matrix device containing suspended drug. Y = matrix containing solid plus
dissolved drug; Z = zone of depletion containing dissolved drug only; C = total
concentration of drug, i.e. solid plus dissolved drug; C p = solubility of drug in
polymeric matrix.
given in Fig. 8. The model is based on the assumption that solid drug
dissolves first from the surface layer of the matrix and when this layer
is exhausted then depletion of drug from the next layer begins. Thus, a
so-called zone of depletion, which contains only dissolved drug, is set
up in the outermost layers of the matrix. The interface between this zone
and an inner one, that contains dispersed particles of solid drug, moves
inwards as release progresses. Higuchi pointed out that the sharpness
of this interface would be a function of the fineness and state of
dispersion of the solid particles. Assuming that (a) a pseudo steady-
state exists, (b) the drug particles are small compared to the average
distance of diffusion, (c) the diffusion coefficient of the drug in the
polymeric matrix (Dp) is constant, and (d) the external medium is
immiscible with the matrix and constitutes an infinite sink for the
released drug it is possible to derive eqns (37) and (38), which describe
the amount and rate of drug release at any time t, respectively,
Ot = ~' = [D p tCp (2C - C p )]1/2 (37)
dOt = dM, = ~ [DpCp (2C _ C )] 1/2 (38)

dt Adt 2 t p
where C is the total concentration of drug (i.e. solid plus dissolved

drug) in the matrix and the other terms are defined as be ·ore. If
C » Cp then eqns (37) and (38) may be simplified to give eqns (39) and
(40), respectively.
(39)
and
(40)
Equations that describe the release from cylindrical and spherical

matrices containing suspended drug have been given by Roseman 122
and Higuchi,123 respectively.
A comparison of eqn (39) with eqn (41),
Ot = 2C(D;t) 1/2 (41)
which is an alternative to eqn (25) as a description of the release from

a device that contains dissolved drug only, shows that the relationship
between release and initial concentration of drug (C) differs for the
two types of matrix device. Thus, the amount of drug released at any
time t increases with the square root of the initial concentration when
the solid drug is present and is directly proportional to the initial
concentration when only the dissolved drug is present.
In the case of the relationships between drug release and time both
types of device exhibit similar behaviours in the early stages of release
in that the amounts released and the rates of release are related to t 1l2
and t- 1I2 , respectively. However, these relationships are maintained for
most of the overall release profile when solid drug is present, whereas
an exponential decrease with increase in time occurs in the latter half
of the profile when only dissolved drug is present initially. In fact, the
time when all the solid drug has just dissolved (too) can be calculated
from eqn (39) and is given by
l2C
too = 8Dp Cp (42)
where l is the thickness of a polymer slab.

Although the release rate is less variable when solid rather than
dissolved drug only is present in a matrix the rate is not maintained at
a constant level as it is with reservoir devices. This absence of zero-
order release characteristics is a disadvantage of matrix devices. How-
ever, the ease and relatively low cost of preparation of such devices
renders them attractive and rates of drug release can generally be

tailored to adequate values for many practical purposes.
The reason for the decrease in release rate with time from matrices
containing solid drug particles is that the zone of depletion, and hence
the diffusional pathway as visualised in the Higuchi model, increases
progressively during the release process. Attempts have therefore been
made to achieve zero-order release by using geometrical shapes that
provide an increasing area between the depletion zone and that
containing residual particles in order to compensate for the increasing
diffusional pathway.124.125
The applicability of the Higuchi model has been demonstrated many
times. 121 ,124,126,127 In fact, Roseman and Higuchi 128 have presented
photographic evidence of the development of a depletion zone in
cylinders of PDMS containing medroxyprogesterone acetate particles.
The influence of the assumption regarding a pseudo steady-state has
been examined. 129 It was concluded that although an exact analysis
may provide some advantages in cases where the initial drug concent-
ration is low this analysis gives almost identical results to that of the
Higuchi approach when the concentration is large.
Higuchi's model assumes that diffusion of dissolved drug through the
matrix is the rate-controlling stage in the overall release process.
However, some studies have indicated that dissolution of drug in the
polymer matrix may become the rate-controlling stage and in such
cases particle size effects therefore become important. 130-132 A rela-
tively complex mathematical model, which allows for dissolution con-
trolled as well as diffusion controlled release, has been developed by
Ayres and Lindstrom. 133 ,134 A simplified model has since been formu-
lated by Chandrasekaran and Paul 135 and this gave good agreement
with the experimental results obtained using a polyisobutylene-rnineral
oil matrix containing different particle sizes of a dispersed drug. Thus,
as predicted by the model, the rate of release becomes constant, i.e. it
is time independent, when dissolution controlled release is operative.
The Higuchi model has been extended by Roseman and Higuchi 128
and Chien et aI. 136 ,137 to take into account the effects of diffusion
across unstirred boundary layers. A diagram of the diffusional pathway
across the depleted zone in a matrix and across a boundary layer is
shown in Fig. 9. In these circumstances and when C» Cp the amount
of drug release can be defined by eqn (43)138
(43)
REC~PTOR PHASE
Fig. 9. Concentration profile during release from a matrix containing solid

drug across an unstirred boundary layer into a receptor phase. Y = matrix
containing solid plus dissolved drug; Z = zone of depletion within matrix
containing dissolved drug only. C = total concentration of drug in matrix, i.e.
solid plus dissolved drug; C p = solubility of drug in polymeric matrix; IAq =
thickness of boundary layer.
and the rate of release by eqn (44)

dQ,
(44)
dt
where a = 2CDp and (3 = DplAqC/ D Aq.
When (32K~/Aq« Cpt then eqns (43) and (44) reduce to eqn (39) and
(40), respectively, and release exhibits a dependency on the square
root of time. This is usually referred to as matrix controlled release.
However, when (32K~/Aq» Cpt then
dQ,= CpDAq CAqDAq
(45)
dt lAqKp/Aq lAq
since
and
(46)
This latter situation will occur when the boundary layer (IAq) is
relatively thick or if K p/Aq is large so that the concentration of drug in
aqueous solution at the interface with the matrix is low. Thus, Q, is
related directly to time and the release kinetics become zero-order.
LU
~
f-------....:::....-==---= ~_- - - - - - -zero-order
.
release
~a:
~
IL
o
~
a:
Fig. 10. Profile of drug release rate from a matrix device containing suspended
drug versus the square root of time showing initial zero-order release at low
times.
These circumstances are usually referred to as boundary layer or

partition controlled release. Such circumstances will also occur in the
early stages of release when t is small. Consequently, on the basis of
eqn (44), the overall release profile will be expected to consist of an
initial period of zero-order release followed by a dependency on the
square root of time as shown in Fig. 10.
The significance of the partition coefficient and boundary layer
thickness with respect to the shape of drug release profiles has been
investigated by Roseman and Yalkowsky 139 using silicone rubber mat-
rices containing a series of alkyl esters of p-aminobenzoic acid. These
workers extended their findings to a con~ideration of the release of
medroxyprogesterone acetate from silicone rubber vaginal rings. Their
results illustrate the problems that occur in attempts to correlate in
vitro release data with results obtained from in vivo experiments.
These problems often arise from the existence of thick boundary layers
around implanted devices so that not only are slower release rates
observed in vivo but also the period of initial zero-order, boundary
layer controlled release is considerably extended. This situation may be
exacerbated by the build-up of fibrous tissue around the devices. 14o
These factors are of importance in the design of controlled release
devices because ideally the release rates should be controlled by the
properties of the device and not by the environmental conditions.
Additional extension of the original Higuchi model of drug release
from a matrix has been described by Flynn et al. 141 Their model
encompasses not only matrix and unstirred boundary layers but also
absorption through a biological membrane and relates specifically to
the design of intravaginal controlled release devices.
B. Release From Porous Matrices

Release from such matrices involves diffusion of drug through liquid-
filled pores. The pores may be an inherent part of the structure of the
matrix as in swollen hydrogels and monoliths formed by compression
of polymeric granules or by evaporation of a solvent containing dissol-
ved polymer and drug. In addition, pores may be formed in situ by
dissolution of a soluble component from a heterogeneous monolith into
an eluting liquid. In this latter case the soluble component may be the
drug itself if it constitutes a high volume fraction of the original
monolith.
Equations describing the release from these systems are similar to
those presented earlier for non-porous matrices but other terms are
included to account for the degree of porosity (e) and the tortuosity of
the pores (-r). In addition, the solubility (CAq ) and diffusion coefficient
(DAq) of the drug in the eluting liquid are used rather than the
corresponding parameters in the polymer phase. Thus, for a matrix
with slab geometry containing the dissolved drug only, the rate of
release is given by:
dM, = C (DAq) 1/2 (47)

Adt 'T7Tt
whilst the Higuchi equation 142 for a similar device containing solid
drug particles is given by:
dM;=dQ,=~[DAqec (2C-C )J1I2 (48)

Adt dt 2 Tt Aq Aq
or
(49)
where C» C Aq.
A re-examination of the release of water-soluble drugs from hyd-
rophobic porous matrices has been carried out by Gurny et al. 143 In
those cases where the initial drug loading exceeds the solubility of the
drug in the eluting liquid, i.e. when C> eCAq , the transition from a
dissolution controlled to a diffusion controlled release process takes

place when a certain degree of drug depletion has occurred. In
addition, these workers pointed out that when depletion is almost
complete then major changes in the void fraction and porosity of the
matrix may lead to a considerable increase in the release rate.
Hatem Fessi et al. 144 have considered drug release from porous
matrices when C < fOCAq- However, these circumstances are not very
common in the design of pharmaceutical controlled release devices.
Higuchi and his colleagues have also presented equations to describe
the effects of drug-matrix binding on release and the simultaneous
release of non-interacting and interacting drugS.145-147
C. Examples of Matrix Devices

The polymers used as the basis of matrix devices are mainly the same
as those used for reservoir systems. Thus, polydimethylsiloxane
TABLE 1
Examples of Studies on Controlled Release Matrix Devices
Polymer Drug Reference
PDMS Anti-tumour agents 148

Chloroquine diphosphate 149
Desoxycorticosterone acetate 150, 151
d-Norgestrel 152
Morphine sulphate 153
Progesterone and derivatives 141, 154, 155
Prostaglandins 156, 157
Testosterone 158
EVA Macromolecules 159-162
Poly-HEMA Anti-thrombotic agents 163
Progesterone 164
Salicylic acid 165
Ethy1cellulose Caffeine 166
Chlorhexidine 167
Salic ylic acid 166
Tripelennamine 109
Hydroxypropyl Pilocarpine 168
cellulose
Polyethylene Progesterone 169
Vinylpyrrolidone Erythromycin 170
viny1copolymer
(PDMS) is the most commonly cited material. In addition, steroidal

drugs have been involved in many investigations on matrix devices for
the same reasons that encouraged the development of reservoir devices
containing such drugs. Some examples of recent studies on polymeric
matrix devices are given in Table 1. References 159-162 are of particular
interest at present because they indicate that polymers such as EVA
can be used to control the release of macromolecular agents. The
technique for obtaining such control is based on solvent casting of the
polymer in a volatile solvent, such as methylene chloride, along with
powdered macromolecular material. A series of interconnecting chan-
nels, that are sufficiently large to permit release of the macromolecules,
are formed in the matrix and release periods of 100 days have been
achieved. The incorporation of small magnetic beads in polymeric
matrices is also of interest since it has been shown that exposure to an
oscillating external magnetic field causes an increase in the rate of drug
release. 161
4. OrnER POLYMERIC CONTROLLED RELEASE SYSTEMS
Release from the reservoir and matrix devices, that have already been
described, is controlled by diffusion of the drug through a device
provided that the eifects of drug dissolution in a polymer matrix and
transport across boundary layers are negligible. However, other prop-
erties of polymers and of drug:polymer compounds have been utilised
in the design of controlled release systems. The contents of each of the
following sections are intended to give a brief account of the rationale
underlying the design of a given type of system together with some
references for further information. It should be noted that the permea-
bfiity of polymers to drugs or to body fluids may still be particularly
significant with respect to the control of release in some of these
systems whereas in others its effects are insignificant.
4.1. Biodegradable or Bioerodible Systems

In these systems the drug is dissolved or dispersed in a polymeric
matrix, which erodes by dissolution in aqueous body fluids, thus
allowing release of entrapped drug. The main advantage of these
systems over non-erodible devices arises from the fact that surgical
removal of a device after its useful life is obviated because the products
of polymer degradation are eventually absorbed by the body. How-
The role of polymer permeability ill the control of drug release 257
ever, the safety of these products with respect to toxicity, im-

munogenicity and carcinogenicity must b(~ established.
Polymers that have been investigated for controlled release purposes
may he classified on the basis of their dissolution mechanisms into
three types.171
Type 1 polymers consist of water soluble compounds that are
rendered insoluble by means of hydrolytically unstable crosslinks, e.g.
copolymers of acrylamide or N -vinyl pyrrolidone with N,N'-
methylenebisacrylamide. 171 Such systems are considered to be poten-
tially useful for the slow release of water-soluble macromolecules.
The type 2 polymers include all those that are initially water insolu-
ble but become soluble on hydrolysis, ionisation or protonation of
pendant side groups, e.g. partially esterified copolymers of methyl vinyl
ether and maleic anhydride.
The type 3 category includes all water-insoluble polymers that
undergo hydrolytic backbone cleavage and degrade into water-soluble
molecules. Polylactic acid and lactic/glycolic acid copolymers are ex-
amples of this type and are the most commonly used biodegradable
polymers. Other examples include polyorthoesters, polY(E-capro-
lactone) and polyamino acids.
If the kinetics of the degradation process are known it is possible to
define mathematical expressions of drug release rate. In order to
obtain zero-order release, erosion must be limited to the surface of a
matrix having a geometry that does not change in surface area as
erosion proceeds, e.g. a slab in which edge effects are neglected. l72
Surface limited erosion has been achieved using the partially esterified
copolymers of methyl vinyl ether and maleic anhydride (type 2
polymer). However, erosion of most of the biodegradable polymers
that have been used for controlled release purposes is not limited to
the surface of the matrix and bulk erosion occurs simultaneously. In
addition, diffusional release of a drug may occur and prediction of the
overall release profile becomes difficult in such cases. However, it is
possible to select polymer permeabilities and erosion rates in order to
permit the design of systems that release drug by a diffusion controlled
mechanism and then the polymer erodes after the drug is exhausted.
This approach has been applied to the design of reservoir devices that
utili:.;e membranes of po!y(c-caprolactone) copolymers with polY(DL-
lactic acid) to provide constant diffusion controlled delivery rates of the
contraceptive agent levonorgestrel for 1 year and the narcotic antagon-
ist naltrexone for 1-2 months.173
Further information on studies concerned with the use of biodegrad-

able polymers for controlling drug release may be obtained from
refs 172-177 whilst Lee and Robinson41 discuss the control of release
from orally administered dosage forms via dissolution of polymeric
matrices and coats.
4.2. Microencapsulated Products

Microencapsulation of drugs by polymers provides a potential means of
obtaining satisfactory control over the release of drugs. Techniques for
the production of microcapsules have been well described I78 and the
size range of this type of product has been extended at the lower end
by the introduction of nanocapsules. 179,180
Unlike the larger-sized devices that require surgical incision in order
to effect implantation the small size of microcapsules allows adminis-
tration by injection through hypodermic needles. However, and again
unlike larger devices, removal of exhausted microcapsules is not feasi-
ble. Thus, biodegradable encapsulating materials are more favourable
than non-degradable ones for parental use. This limitation does not
apply in the case of orally administered products since exhausted cells
will be removed from the body in the faeces.
It might be expected that release from a microencapsulated product
would correspond to that from a reservoir system if diffusion through
the encap:;ulating polymer were the rate-controlling stage. For exam-
ple. the results obtained by Gardner et al. 18I on the release of steroids
from cellulose butyrate microcapsules are explainable on this basis,
However, the structure of microcapSUles may vary from single cores
surrounded by a polymeric film to multi cored systems embedded in a
polymeric mass. 178 Thus, release characteristics similar to those of
matrix systems may be encountered. For example, the mathematical
model employed by Gupta and Sparks182 to explain the release of
progesterone encapsulated by poly(lactic acid) assumes that the mic-
rocapsular structure can be described as a polymeric matrix containing
evenly dispersed drug particles.
Difficulties arise in the prediction of drug release because of these
possible variations in structure. The situation may be further compli-
cated during the initial stages of drug release by conventional burst
effects and by rapid release from incompletely encapsulated particles,
and during subsequent stages by differences in the thickness of encap-
sulating layers on individual cores and by film rupture under the
influence of osmotic pressure. In addition, when biodegradable poly-
mers are used their rate of erosion may affect release,
In spite of these difficulties in predicting release from microencapsu-

lated systems many studies have indicated the potential usefulness of
these systems as a means of controlling drug release. This potential is
likely to be realised to a greater extent in the light of knowledge
gained from further studies on the effects of process variables on the
structures of microcapsules and on the factors that may influence drug
release in vivo.
Further information on microencapsulated systems is given in Chap-
ters 4-8, Volume II of ref. 34. Recent studies on drug release from
such systems include those given by refs 183-190.
4.3. Osmotically ControUed Systems

In the previously described systems control of release is dependent on
the diffusion of drugs through polymeric barriers. However, the use of
polymeric membranes that are permeable to water and that are pierced
by a single small orifice allows drug release to proceed under the
influence of osmotic pressure. Thus, a solution of drug is forced out
through the orifice at a rate that remains constant as long as excess
solid osmotic agent remains in the system.
This concept has been applied to the design of orally administered
dosage forms and to implantable devices. Further details of these
systems and their performances are given in refs 13, 19, 24, 191 and
192.
4.4. Polymer Bound Drugs

The properties of chemical combinations of drugs and polymers may
be used as the basis for controlling the release and/or the activity of
drugs. For example, the rate of hydrolysis of a drug-polymer linkage
may act as the rate controlling stage in the release of a drug from an
insoluble polymer. Alternatively, the properties of a soluble drug-
polymer compound may result in different rates of absorption, dis-
tribution and elimination when compared with an unbound drug so
that changes in drug activity and toxicity may be observed. In general,
the behaviour of this latter type of drug-polymer compound will
depend on the nature of the polymer, the type of spacer groups
between the polymer and drug, the nature of the linkage between the
drug and the terminal spacer group and the amount of drug incorpo-
rated. In addition, increases in the specificity of the compound for
particular sites in the body can be achieved by the attachment of
further groups, termed homing devices, on to the polymer chain. These
homing devices, which include antibodies against specific cell mem-

brane proteins and hormones provide a means of improving the
delivery of drugs to selected sites. Further information on the design of
these systems and examples of their use is given by Kim et al. 15
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Chapter 7
Permeabllity and Plastics Packaging

R. J. ASHLEY
Metal Box Ltd, Research and Development Division, Wantage, UK
1. Introduction. . . . . . . . . . . 269
2. The Importance of Permeation . . 270
2.1. Effect of time and temperature 273
2.2. Effect of moisture . 274
2.3. Effect of oxygen . . . . 278
2.4. Choice of materials . . 280
3. Rate of Transmission . . . . 281
3.1. Variables of the polymer 284
3.2. Effect of permeating species 289
3.3. Temperature and pressure . 289
3.4. Wall thickness. . . . . . . 290
4. Measurement of Permeability . . 291
4.1. Water vapour transmission rate 292
4.2. Gas transmission rate . . . 294
5. Selection of Packaging Materials. 295
6. Prediction of Shelf-life . 300
7. Materials Development. 303
References . . . . . . 306
1. INTRODUCTION
The food packaging industry is one which places particular demands on

the performance of the packaging materials selected, especially in
terms of the barrier requirements. The ability of modern food retail
outlets, such as hypermarkets, to offer and distribute a wide selection of
products is dependent on the preservation of product quality. To this
end the function of the packaging material is multifarious and includes
protection of the product over the required shelf-life both in the shop
and at home, promotion of the product by attractive graphic design
269
270 R. 1. Ashley
and the ability to dispense the product satisfactorily. Product protec-

tion must account for factors that arise during storage, distribution,
shop and home shelf-life.
By a combination of design and material selection, foodstuff packag-
ing must provide an environment which stabilises the system used to
preserve the product and maintain an adequate barrier effective
against external deteriorative influences. Within the scope of plastics
packaging there are a number of processes that lend themselves to the
production of containers, e.g. thermoforming, injection and blow
moulding, for tubs, trays and bottles. Also plastics materials may be
combined together by processes such as lamination, extrusion coating
or coextrusion to form multilayer structures which can be subsequently
formed into flexible pouches, wraps, tubes or deep drawn containers.
The choice of plastics materials suitable for conversion by these
processes is wide and hence the selection of a particular material for a
given application will be made as a result of consideration of physical
properties, processability, barrier properties and cost. In cases where a
barrier to a number of agencies is required it is unlikely that a single
polymer will be satisfactory, hence a number of different polymers in
combination will often be employed when their individual properties
can be of benefit in providing part of the required protection. This
ability to combine polymers offers further scope to the number of
materials that are available for packaging and enables manipulation of
the barrier properties to suit individual product requirements.
2. THE IMPORTANCE OF PERMEATION
The packaging requirements of a biological system such as foodstuffs

and pharmaceuticals are more diverse and complex than those for
other products. The main functions of the package are to keep, present
and dispense the product. Protection of the product may be regarded
as the rate of change of quality and this includes both 1 physical
(mechanical damage during transit or storage, loss of consistency or
crispness, loss of appearance and sales appeal) and organoleptic
changes (loss of taste, colour, odour).
Thus the deterioration rate of a product is related to composition
and processing factors and to environmental factors, which in turn are
affected by direct and indirect agencies. A direct agency leads to
immediate food spoilage (e.g. off-taste or colour) and leads to termina-
Permeability and plastics packaging 271
tion of shelf-life. The indirect agency brings about some change (e.g.
softening or caking) in the product which does not necessarily render it
useless. Some of these agencies are listed below.
Physical
Biochemical
/ Microbiological
Direct
agency
Product
deterioration
Indirect
agency Time
Temperature
Moisture
Light
Gases
Pressure
Most food systems are complex blends of various components and

part, if not all, usually experience deterioration by all three forms of
direct attack. These factors act independently or in conjunction with
each other, but one of them frequently terminates useful shelf-life of
the product before other factors become serious. Some deterioration
mechanisms will continue over a long period of time at a rate governed
by product characteristics and environmental conditions and at a given
stage the extent of deterioration will be detected by a degree of
product spoilage such as an off-flavour or odour, change in appearance
or form (e.g. discoloration, softness of crisp products or caking of
powders) and at this period of time the shelf-life has been reached.
This bears a relationship to the significance of terms such as 'best
before', 'eat by' and 'use within [so many] days' which are now required
on many forms of packaging.
Thus the package must protect the product against physical hazards
and atmospheric environmental influences, such as rain, water vapour,
gases and odours. It should also be remembered that barriers to the
emission of aromas from the product to the environment may also be
required (e.g. coffee). Materials are therefore required to act as bar-
riers between the outside environment and the interior atmosphere of
the package in order to maintain food quality. The design of a pack
272 R. J. Ashley
,----------------
Outside environment
Fig. 1. Container--environment interactions.
often necessitates a headspace above the product. An important vari-

able in barrier measurements or calculations of shelf-life is the product
volume to packaging surface area ratio. The interactions, which are
illustrated in Fig. 1, include
(A) Interactions between headspace and outside environment
through container closure.
(B) Interactions between inside environment (headspace) and pro-
duct.
(C) Interactions between product and outside environment
through container wall.
Materials are primarily selected for their resistance to gases, vapours
and odours. Further selectivity of the materials will depend on the
other properties required such as abuse resistance, appearance and
cost. Of the gases, oxygen, carbon dioxide, nitrogen and sulphur
dioxide are the main ones of interest in packaging; and the main
vapour is water. In terms of odour barrier, flavour aromas, essential
oils and perfumes are important. In some cases a barrier against liquids
such as water, alcohol, oils and greases may be required, against solids
such as fats, and general spoilage by dirt. Many products require
barriers to protect them against contamination by bacteria and mould
growth. Finally there are instances where a barrier to certain
wavelengths of light and other radiations may need to be taken into
consideration.
A consideration of the overall structure of a pack includes the
combination of materials for the body of the container and, if appro-

priate, any closure or seals. The plastic materials used will contribute
towards pack quality through their physical characteristics and barrier
properties. As stated earlier several indirect factors, such as time,
temperature and moisture, lead to product deterioration, and these are
now considered.
2.1. Effect of Time and Temperature

All foodstuffs require time before the onset of deterioration or its
noticeable effects and it is the function of the packaging material to
delay the process as much as possible by protecting the food product
against spoilage caused by microorganisms and chemical reactions
often catalysed by enzymes.
Modern food preservation techniques are aimed at destroying mic-
roorganisms by heat (pasteurisation or sterilisation), or reducing their
activity by a number of processes, such as chilling (slowing down),
freezing (immobilisation), drying (effect of water reduced), vacuum or
gas flushing (effect of oxygen reduced), pickling or fermenting (acid
conditions), adding chemicals (such as antioxidants, sugar or salt).
Through these processes it is possible to enjoy seasonal food pro-
ducts all year round. Temperature is one of the main factors in
controlling microorganism activity.
Bacterial growth and chemical activity increase significantly when
the temperature reaches 20-35°C. Lower temperatures or freezing will
-
a
20 40 60 80 100
Temperature .• (
Fig. 2. Effect of temperature on bacterial growth.
274 R. 1. Ashley
cause slowing down or immobility while at higher temperatures bacter-

ial growth is reduced and finally destroyed when temperatures during a
preservation cycle reach in excess of 80°C for pasteurisation or 120°C
for sterilisation (see Fig. 2). These conditions of no bacterial growth
following a specific preservation method will prevail for a certain
period of time depending on the type of microorganism involved, e.g.
is it heat sensitive or heat resistant, food spoiling or food poisoning?
2.2. Eftect of Moisture

When considering the effects of moisture on bacterial activity it is
necessary to take into account the original moisture content of the
product and the humidity conditions inside and outside the pack. The
inside humidity conditions will be determined by the water vapour
permeability of the packaging material selected.
In the case of the moisture content of the product it should be noted
that even so-called dry products such as instant soups and desserts or
dried meals contain moisture. Where the relative humidity (r.h.) ex-
ceeds 80% foods are considered to be biologically active. Since an r.h.
below 60% does not promote significant mould growth, most of the
dry food products (r.h. = 30-40%) are microbiologically stable. It is
therefore necessary to prevent too much uptake of water vapour by the
product by controlling permeation through the packaging material.
CII
d'-
-
.c
~
o
'-
l::I
o 20 40 60 80 100
Relative humidity (%)
Fig. 3. Effect of moisture on the growth of A, mould; B, yeast; and C,
bacteria.
Bacteria, moulds and yeast react differently2 to the r.h. of the inside
environment, as shown in Fig. 3.
The r.h. of an environment is expressed as the ratio of the actual
humidity to the maximum humidity required to saturate that environ-
ment at a given temperature and pressure. The basis for consideration
of moisture loss or gain can be viewed in terms of the concept of water
activity of foods. 3 The physiochemical binding of water as measured
by water activity (a w ) can be defined as follows:
P %ERH
a =-=--- (1)
w Po 100
where P = vapour pressure of water exerted by the food, Po = vapour

pressure of pure water and % ERH = equilibrium relative humidity of
the food.
In essence, the a w of a product determines whether it will gain or
lose moisture in a given environment. For example if a dried biscuit and
a slice of meat were independently transferred into an atmosphere of
75% r.h., over a period of time the biscuit would gain water and the
meat lose water. The products will not come to equal water content,
but rather to equal a w • The functioJ;l of a packaging material is to delay
this process as much as possible within economic as well as food safety
and quality limits. To do this it is necessary to know both the sorption
isotherms (moisture content against a w ) of the product as shown in Fig.
4 and the permeability properties of the packaging material.
As an inducement to further consider these characteristics regula-
tions have been proposed by the US Food and Drug Administration
stating that 'Foods such as but not limited to dry mixes, nuts, inter-
mediate moisture foods and dehydrated foods that rely on the control
of a w for preventing the growth of microorganisms shall be processed
to and maintained at a safe moisture level,.4 It is accepted that this
may be achieved by any effective means including protecting the
finished product from moisture pick-up so that aw does not increase to
the unsafe level. The safe level is defined as a level low enough to
prevent the growth of microorganisms in the finished product.
Two basic principles have evolved from studies on foods that are
relevant to packaging. s,6 These are:
(i) Certain critical values for a w exist. If the food gains or loses
moisture above or below these values, its quality will become
unacceptable.
276 R. 1. Ashley
I
1·0
Tissue foods
I""""
Cheese. sausages
o·a
t:I
)<
',NP'
06
~
>
.;::
u
t:I
L
01.
ClJ
~
t:I Dry foods

3
02
L -_ _ _ _~_ _ _ _J __ _ _ _ _ _ _ _ _ _~_ _ _ _ _ _ _ ~
00
0 3
MOisture content (gH 20/g dry solids)
Fig. 4. Water activity and moisture content for some foods.
(ii) Even for the products in which the rate of gain or loss of
moisture is so slow that the critical limit is never reached, the
change in a w during that period affects the rate of chemical
reactions, and can lead to quality losses.
The general effects of a w on packed foods are now considered. If a
dry food gains moisture to reach an aw of above 0·7-0'75, then
pathogens will grow, whilst within the range 0·6-0·7 it would be
spoiled by mould growth. Dry, crisp products become 'soggy' at an aw
of 0·35-0·5,7 and caking and lumping of powders occurs at an awof
0.4-0.5. 8
Pasta dried below an a w of 0·4-0· 5 becomes brittle and fractures
during cooking. When semi-moist pet foods, bakery items and confec-
tionery are dried to an a w of 0,5-0,8 they harden and become
organoleptically unacceptable. Loss of moisture can also affect the
legal net weight with respect to under stated value.
It has also been shown that for many foods, when the food gains
moisture above the Brunauer-Emmett-Teller (BET) moisture
monolayer value, 0·2-0·3aw , the rates of reaction increase for many
enzyme and chemical reactions that lead to loss of quality. For each
O·la w increase, the rate of a reaction may double or triple; hence

protection against moisture gain is essential. 9 - 11
Packaging cannot improve or completely preserve the quality of
foodstuffs indefinitely, but serves to slow down or decrease the rate at
which the mechanisms of deterioration take place, or delay the onset
of deterioration. Certain products will be deteriorated by the effects of
exposure to excessive levels of oxygen, moisture and light; for instance,
powdered desserts and soups can produce off-flavours or discoloration
and mixing difficulties due to moisture pick-up and light exposure. Fats
in certain powdered soups, dehydrated meals, or as spreads may
become rancid as a result of oxygen pick-up, and fresh meats lose their
red colour and sales appeal due to gas pick-up. Carbonated beverages
can become flat due to loss of carbon dioxide through the bottle walls.
In order to preserve food for future use it is necessary to exclude
moulds, yeast and bacteria. These have to be killed by chemical means
or denied growth by dryness or low temperature storage conditions.
The cheapest means for short-term storage, e.g. 6 months, is drying of
the product. Some of the water is removed so as to prevent growth of
the organisms, but not all water is removed since the last traces are
very firmly held; for instance, biscuits may contain about 2% residual
water.
Having removed water from the product it is then necessary to
prevent it from returning. It is easily observed that dried foods, such as
biscuits, soon re-absorb water and become soft, or that bread becomes
mouldy usually when exposed to the atmosphere for a relatively short
period, i.e. a matter of a few days.
The atmosphere always contains moisture vapour and the natural
polymers contained in foodstuffs absorb water back from the air.
Such foods are called hygroscopic and the amount of water they hold
depends on the amount of water available in the air which in turn is
governed by the levels of humidity in the environment. If the air is not
very humid the amount of water absorbed may be small and insuffi-
cient to permit the growth of microbes. However, some loss of crisp-
ness in certain products may be noticed which could aesthetically mar
the quality of the food. The packaging material is therefore selected to
provide an arid atmosphere around the product so as to preserve
palatability .
In order to select a suitable packaging material for protection against
permeation of water vapour it is necessary to consider the following
278 R. 1. Ashley
factors:
(a) How hygroscopic is the product?
(b) How humid is the anticipated environment?
(c) How effective is the selected material as a barrier to moisture
vapour?
2.3. Effect of Oxygen

Whilst water is only lightly and reversibly held to the product (by
hydrogen bonding), oxygen is absorbed strongly and irreversibly. The
ingress of oxygen leads to a permanent change in the nature of the
product. In the case of fresh vegetables a packaging material that is a
relatively poor barrier to oxygen is useful since vegetables are usually
packed slightly before they ripen fully and they can breathe inside the
pack. Respiration consumes oxygen in the pack and if this is not
replaced by permeation through the packaging material, bacteria can
flourish and decomposition begins. It is also desirable for fresh vegeta-
bles to retain water in the product since loss of water causes wilting
and loss of texture. Thus the ideal packaging material for fresh fruit
and vegetables is one having high permeability to oxygen but low
permeability to water vapour. Even with such materials the shelf-life
for such products can only be prolonged for a few days. For longer
shelf-life it is necessary to resort to other methods of protection using
food preservation techniques such as steam sterilisation, chilling or
deep freeze, and pasteurisation. 12
Vegetable or animal fats are affected by oxygen in a different way.
When the fat is sensitised by exposure to light or trace impurities,
active sites are produced in the polymer chain where oxygen can be
absorbed resulting in the formation of a peroxide which is unstable and
changes to a more stable aldehyde. This alters the nature and flavour
of the fat, making it rancid. 12
The permeation process for the packaging in this case is different
from that of water vapour transmission. Oxygen in the headspace of
the pack is consumed, creating a maximum pressure gradient across
the packaging medium, thereby accelerating ingress of the gas. The
effect is less serious for bulk packs since only the surface of the product
is affected and diffusion into the bulk is slow. However, it is considera-
bly worse when a small amount of fat is exposed over a large surface
area in a bulky pack as in the case of a packet of crisps or similar snack
foods. For the packaging of fats it is usual to select materials of good
water vapour and oxygen barrier properties since dry oil does not go
rancid as rapidly as moist oil. To compromise a certain amount of
product formulation is carried out whereby antioxidants are included
with the fat or oil.
However, in meat packaging, antioxidants are not permitted in the
cured meats such as bacon, and the curing treatment does not protect
the fat. For extended shelf-life it is necessary to exclude air from the
pack. Thus a high barrier material to air and oxygen is used to prevent
the loss of vacuum. Similar protection is required for the oils in nuts
and vacuum packaging techniques or nitrogen flushing of the head-
space are common in this type of packaging. In the case of fresh meat
products the oxygen permeability problem is more acute since the fat is
still liable to oxidise and become rancid. If gas flushing or vacuum
techniques were used the tissues of the meat would no longer be able
to suppress the growth of anaerobic microbes and putrefaction would
set in. In addition to this the colour of the meat product while on
display on the supermarket shelf or chill cabinet is of aesthetic impor-
tance. A good blood red colour is generally indicative of a really fresh
product and an incentive for the customer to purchase, but this
changes to brown within a short period of time if further oxygen is not
available to replace that absorbed, by permeation into the pack. Fresh
meat when cut is purple due to myoglobin and the red colour develops
within a few hours as a result of oxygen exposure forming oxymyoglo-
bin. However, this is an unstable colour because the meat slowly
consumes its absorbed oxygen and the brown colour of metmyoglobin
is produced. 13
One of the more recent methods for the presentation of food
products, such as fresh meat portions, bacon, sausages, liver, kidney,
fish fillets and salads, is a system known as controlled atmosphere
packaging. In this method of packaging the air surrounding the product
contained in a package is evacuated and replaced with a controlled
mixture of gases. The gaseous mixture inhibits bacterial growth within
the pack providing the pack is kept at low temperatures. For meat
products such as mince or cut portions the package usually consists of a
PVC tray overwrapped in transparent polyethylene film formulated
with antifogging additives. Shelf-life is extended from a few days to at
least a week by replacing the air entrapped in the package with a
mixture of 20% carbon dioxide/80% oxygen or 20% carbon
dioxide/69% oxygen/II % nitrogen. Other gas mixtures are used for
fish and bakery products. 14
280 R. I. Ashley
2.4. Choice of Materials

A casual glance at the shelves of a supermarket show that the forms of
plastics packaging and the materials used are many and diverse; a few
examples are detailed below:
(a) Single ply polythene bags or cellulose wraps for biscuits and
vegetables.
(b) Laminated films or coated films for cooked meats and cheese
vacuum packs.
(c) Thermoformed tubs for fats, butter, spreads, dairy produce
such as cream and yogurt, salad dressings, ice-cream, dehyd-
rated water regenerated meals.
(d) Laminates converted into pouches for dried soups, desserts,
instant drinks, dehydrated foods and stand-up packs of fruit
juice.
(e) Blow-moulded bottles for soft drinks, cooking oils, milk.
When considering a packaging material for a particular product it is
necessary to balance the barrier properties with the suitability for the
form of package, the method of preservation and any subsequent
handling after purchase (such as boil-in-bag, oven re-heat, freezer
storage). Such a balance is often not achieved by the use of a single
polymeric layer; hence it is necessary to combine several polymeric
materials or incorporate special barrier layers such as polyvinylidene
chloride, poly(ethylene-vinyl alcohol) or aluminium foil, where each
layer provides part of the total pack property requirement.
The materials used in packaging virtually cover the full range of
commOn polymers; a few examples of their use are:
(a) Films and laminates

(i) Cellulose, polyethylene, polypropylene, polyvinylidene
chloride (PVdC) coated films, acrylic coated films.
(ii) Coextruded polyolefins with polyamides, polyethylene
terephthalate (PETP), including barrier resins such as
PVdC or poly(ethylene-vinyl acetate) (EVAL).
(iii) Adhesive laminates of polyolefins with polyesters,
polyamides and PVdC coated films.
(b) Tubs and containers-Polystyrene, polyvinyl chloride (PVC),
polyethylene, polypropylene, acrylonitrile-butadiene-styrene
(ABS)-as homopolymers, copolymers or co extruded struc-
tures, incorporating PVdC or EVAL.
(c) Trays-PVC, polyesters, or expanded polystyrene.

(d) Bottles-PVC, polyesters, polyethylene, polyacrylonitrile; mul-
tilayer coextruded struli:tures including PVdC or EVAL.
However, the total barrier is not only attributable to the material
from which the body of the package is made but also includes, where
appropriate, closures and joints. For instance, glass or metal containers
may be perfect barriers but if fitted with a low barrier lid the material
may become practically useless for storage. The final selection of
materials will thus be governed by consideration of the following
factors:
(i) physical properties of the materials and pack requirements in
terms of strength, rigidity, etc;
Oi) process ability (compatibility with the process of preservation,
machine handling during filling, heat sealing, storage condi-
tions, after purchase handling such as boil-in-bag or re-heat);
(iii) barrier properties relative to anticipated shelf-life;
(iv) cost of the materials and conversion processes relative to the
cost of the product.
The physical and chemical properties of polymeric materials make
them ideally suited for combining their advantages by coating, lamina-
tion, extrusion and moulding techniques to meet specific product
requirements. It is also possible to tailor-make polymers with respect
to permeability by consideration of chemical composition, morphology
and molecular topography or the use of additives which strongly
influence permeability properties. The polymeric material may be used
as a support layer, adhesive layer between other polymers or addi-
tional barrier layer. This leads to more imaginative use of existing
polymers and scope for development of specialised polymers and
structures.
3. RATE OF TRANSMISSION
The rate at which a gas, vapour or liquid will pass through a polymeric
material is governed by several factors, some of which are dependent
on the properties of the permeating species, some controlled by the
properties of the polymer, and others by the degree of interaction
between polymer and gas, or environmental conditions.
Crystalline struc!ures have a greater degree of molecular packing
and the individual lamellae may be considered as almost impermeable
282 R. f. Ashley
to a diffusing molecule. Thus, diffusion can only occur in the amorph-

ous zones or at regions of imperfection in the crystal structure.
Therefore, semi crystalline polymers tend to be less permeable.
Permeation of a gas or vapour through a polymeric material is
generally of the activated diffusion type, the presence of cracks,
pinholes and voids leading to rather catastrophic loss of barrier proper-
ties.
The process by which a small molecule permeates through a polymer
film involves the following four stages:
(i) absorption of the permeating species on to the surface of the

polymer;
(ii) solution of the gas or vapour into the polymer matrix;
(iii) diffusion through the wall along a concentration gradient;
(iv) desorption from the other surface.
Such a view of the diffusion of gases through solids was first proposed
in 1866 by Graham.ls
The permeability coefficient (P) is the product of the diffusion
coefficient and the solubility coefficient (eqn (2)).
P=DS (2)
Three assumptions are made in the simple treatment of permeation

(see Chapter 1). These are that diffusion is in a steady state condition,
the concentration-distance relationship through the polymer is linear,
and diffusion takes place in one direction only (that is, through the film
with no net diffusion along or across it).
Thus, for example, polyethylene will be more permeable to liquids
of similar solubility parameter, e.g. hydrocarbons, than to liquids of
differing solubility parameter but of similar molecular size and shape.
The permeabilities of a number of polymers to different gases are
given in Table l.
It has been argued that the permeability coefficient is a product of a
factor F determined by the nature of the polymer, a function G
determined by the nature of the gas and an interaction function H.16
The latter is considered to be of little significance according to the
general assumptions of the theory and is taken as unity.
Hence the permeability of a polymer can be expressed by:
P=FG (3)
TABLE 1
Permeability Data for Various Polymers 16
Polymer a P «cm 3 mm)/(s cm 2 em Hg)) Po, Pea, Nature of

polymer
°
P N, P N2
N 2, 2
CO 2 , H 2 0, 90% r.h.
,
30°C 30°C 30°C 25°C
LDPE 19 55 352 800 Some
crystallinity
HDPE 2·7 10·6 35 130 3·9 13 Crystalline
PP 23 92 680 Crystalline
Unplasticised 0·4 1·2 10 1,560 3·0 25 Slightly
PVC crystalline
Cellulose 2·8 7·8 68 75,000 2·8 24 Glassy,
acetate amorphous
PS 2·9 11 88 12,000 3·8 30 Glassy
Nylon 6 0·1 0·38 1·6 7,000 3·8 16 Crystalline
PET 0·05 0·22 1·53 1,300 4·4 31 Crystalline
PVdC 0·0094 0·053 0·29 14 5·6 31 Crystalline
Butyl rubber 64·5 191 1,380 3·0 21 Rubbery
Natural 80·8 233 1,310 2·9 16 Rubbery
rubber
aLDPE. low density polyethylene; HDPE, high density polyethylene; PP, polypropylene;
PS, polystyrene; PET, polyethylene terephthalate; PVdC, polyvinylidene chloride.
and the permeability of a polymer x to gas a can be expressed as:

(4)
Hence the ratio of the permeability of a polymer x to gases a and b
can be shown to be the same as the ratio between their respective G
factors:
P xa = G a (5)
P xb G b
Similarly for the permeability of two polymers x and y and for a gas a:
P xa Fx
(6)
P~a F~
From a knowledge of various values of P it is possible to calculate F
values for specific polymers and G values for specific gases. For
non-condensable gases it has been predicted that the permeability
ratios of a pair of gases will be relatively constant over a series of
polymers as shown for the ratios shown in Table 1.
284 R. J. Ashley
Equation (3) assumes that both D and S are independent of con-

centration. For many gases (e.g. oxygen, hydrogen and nitrogen) this
assumption is true and for gases that deviate slightly from the gas laws
(e.g. carbon dioxide) the theory is reasonably accurate. However,
where considerable interaction between polymer and diffusing species
takes place (e.g. water and cellulose film or many solvent vapours
diffusing through plastic films) the theory breaks down.
Factors which can affect the permeability values of a polymer may
be divided into those associated with the polymer itself and those
affecting the constant D and solubility S.
3.1. Variables of the Polymer

The permeation rate should be inversely proportional to the thickness
of the polymer sample or the permeability coefficient should be inde-
pendent of thickness. Whilst this is true for many systems, there are
exceptions to this rule and cases can be found where the permeability
coefficient increases or decreases with thickness.
Examples of P increasing with thickness are usually coated films
where not all of the measured thickness contributes to the permeability.
Examples of P decreasing with thickness are irregular surfaces of
defective films where a pinhole may occur giving an apparently high
localised transmission rate. For many packaging applications it is
common to use coated, laminated or multilayer structures on the basis
that the probability of two pinholes being superimposed is very small
so that passage of a gas is interrupted.
There are certain specific molecular structures which give rise to
good barrier properties in polymers. 17- 19 However, a structure that
leads to a good gas barrier often results in a poor water vapour barrier.
An example of this is the effect of polarity in a polymer. Highly polar
polymers such as those containing hydroxyl groups (polyvinyl alcohol
or cellulose) are excellent gas barriers but the poorest water barriers.
In addition their effectiveness as gas barriers becomes reduced when
the polymer is plasticised by water. On the other hand, non-polar
hydrocarbon polymers such as polyethylene have excellent water bar-
rier but poor gas barrier properties. In order to be a good all-round
barrier material the polymer must possess the following properties:
(i) some degree of polarity such as found in the nitrile, chloride,
fluoride, acrylic or ester groups; .
(ii) high chain stiffness;
TABLE 2
Effect of Functional Groups on Oxygen Permeability
Nature of X in Po, (cm 3 /(mil day 100 in 2 atm»

-fCH2 -CHXt-n
-OH 0·01
-CN 0·04
-CI 8·0
-F 15·0
-COOCH3 17·0
- CH3 150·0
-C6 H S 420·0
-H 480·0
Here and throughout this chapter the unit of film thickness

is the mil. 1 mil = 25 IL m.
(iii) inertness to the permeating species;

(iv) close chain-to-chain packing ability brought about by molecu-
lar symmetry or order, crystallinity or orientation;
(v) some bonding or attraction between chains;
(vi) high glass transition temperature.
Table 2 indicates that permeation varies considerably depending
upon the presence of certain chemical groups in the polymer. 2o
The effect of packing can be seen from Table 3. Linear polymers
with a simple molecular structure lead to good chain packing and lower
TABLE 3
Effect of Chain Packing and Side Groups
Polymer Structure Packing ability Po, (cm 3 /(mil

day 100 in 2 atm»
HOPE Good 110

PP Fair, hindrance 150
of CH 3 group
Poly-4-methyl Poor, bulky 4000

pentene-1 side groups
286 R. J. Ashley
TABLE 4
Effect of Polymer Crystallinity on Oxygen Permeability
Polymer % Crystallinity Po, (cm 3 /(mil day 100 in 2 atm»

LDPE 50 480
HDPE 80 110
Nylon 66, quenched 20 8·0
Nylon 66, annealed 40 1·5
gas permeability than a polymer where the backbone contains bulky

side groups leading to poor packing ability, such as poly-4-
methylpentene-1.
Certain polymers can have varying degrees of crystallinity. A high
degree of crystallinity gives a better barrier since crystallites are
impermeable. Table 4 compares polyolefins and polyamides at various
degrees of crystallinity and the effect this has on gas barrier. In
general, the higher the degree of crystallinity the lower the
permeability.
In Table 5 the effect of molecular orientation of crystalline polymers
is shown. For amorphous polymers orientation decreases permeation
by about 10-15%, but in crystalline polymers reductions of over 50%
can be observed. The permeability of an amorphous polymer below or
not far above its Tg is dependent on the degree of orientation of the
molecular segments and is normally reduced as compared to high
temperatures, but sometimes some small strains increase the permea-
bility. Orientation is particularly relevant to bottle blowing processes
where it is possible to improve the barrier properties of a bottle simply
TABLE 5
Effect of Molecular Orientation on Oxygen Permeability
Polymer % Elongation Po, (cm 3 /(mil day 100 in 2 atm))

150
PP Log 80
420
PS { 30g 300
10
PET { 50g 5
Styrene-acrylonitrile 1·0
copolymer { 30g 0·9
TABLE 6
Effect of Fillers
% CaC0 3 Type of CaCO, Po, (cm 3 j(mil day 100 in 2 atm))
a 480
;~} Untreated 1000
2000
15} Treated to enhance 250
25 adhesion to polythene 150
by controlling the degree of orientation during the moulding cycle

rather than resort to overcoatings with barrier polymer latices.
The use of inert fillers in polymers can either increase or decrease
barrier properties, depending on the degree of compatibility and
adhesion between the polymer matrix and filler. In Table 6 some
results are given for the use of calcium carbonate added to
polyethylene, in one case treated to aid adhesion to the polymer, and
in the other case untreated. In many cases fillers will be added to a
formulation to cheapen it, reinforce its mechanical properties or pro-
vide opacity.
In order to manufacture a particular container to be used as a
package it is usual to incorporate some additive in the polymer to
modify properties. These may include plasticisers, impact modifiers
and other monomeric or polymeric additives and their presence usually
increases permeation, depending on the system. Very often rubber is
incorporated into a glassy polymer as an impact modifier, for example
in the case of yogurt containers and thin-walled tubs, and the reduction
in barrier properties observed is due to the dilution effect of the
barrier and the flexibilising effect of the rubber. Some of these effects
are shown in Table 7. Copolymerisation can also decrease barrier
properties especially if the comonomer is flexibilising or is a poor
barrier material.
Many polymers, in particular those containing polar groups, can
absorb moisture from the atmosphere or from liquids in contact with
the polymer. This has the effect of swelling or plasticising and reduces
the barrier properties as illustrated in Table 8.
In general the density of a polymer is related to the free volume
content and is a good measure of the pre-existing hole volume or
looseness of the structure. The lower density polymers are generally
more permeable.
288 R. J. Ashley
TABLE 7
Effect of Additives on Oxygen Permeability
Polymer Type Po, (cmJ/(mil

day 100 in 2 atm))
. __. __._--- - - -
SAN Unmodified 70
ABS SAN + rubber 100
PMMA Unmodified 17
XT polymer PMMA + rubber 20-40
PVC Unmodified 8
PVC bottle capped PVC+rubber 15
PVC flexible PVC t plasticiser 150
PVdC Unmodified 0·1
Saran film PVdC + plasticiser 1·3
PVdC Homopolymer 0·1
PVdC/PVC Copolymer 1·0
PAN Homopolymer 0·04
PAN/styrene Copolymer 1·0
The molecular weight of a polymer has been found to have little

effect upon the rates of diffusion and permeation except for very low
values of molecular weight, but these are not normally encountered in
barrier polymers used in packaging.
Crosslin king of polymer chains will decrease the permeability due
to the decrease in the diffusion coefficient and the effect is more
pronounced for large molecular size vapours.
TABLE 8
Effect of Humidity on Oxygen Permeability
------------------------------ - - - - - -
Polymer P (crn 3 /(mil day 100 in 2 atm))
Dry, at 0% r.h. At 100% r.h.
Polyvinyl alcohol 0·01 25·0

Uncoated cellulose 0·13 200·0
Nylon 6 1·0 5·0
Polyvinylacetate 55·0 150·0
Acrylonitrile-styrene copolymer 1·0 1·0
Polyester 7·0 6·0
HDPE 110·0 110·0
3.2. Effect of Penneating Species

As indicated above the composition and molecular structure of the
polymer can play an important part in determining the permeability of
a barrier material. Likewise, the molecular structure of the permeating
gas or liquid is of importance in the following manner. Small molecules
diffuse faster than large ones whilst streamlined molecules diffuse
faster than ones with bulky shapes. Non-polar molecules diffuse more
rapidly than polar ones and the effect is more pronounced in polar
polymers. The solubility of a penetrant will be greatly affected by these
factors and the similarity of these with the polymer into which it
dissolves?1-23
3.3. Temperature and Pressure

For gases and vapours that show no interaction with the polymer the
permeability coefficient is independent of the pressure of the diffusing
gas. However, in cases where strong interactions occur the permeabil-
ity constant is found to be pressure dependent and generally increases
as pressure increases. This results from an increase in the diffusion
constant D caused by the plasticising effect of the sorbed vapour and
an increase in the solubility coefficient S caused by the shape of the
sorption isotherm?4
The permeability coefficient increases rapidly as temperature in-
creases. 2S Dewar 26 found that log P gave a linear relationship when
plotted against temperature in °C. The currently accepted relationship
was revealed by Barrer who demonstrated that log P is linear with
reciprocal temperature 27 i.e.
(7)
where Po is a temperature independent factor, Ep is the activation

energy for p.ermeation, R is the gas constant and T the absolute
temperature. The dependence of both the diffusion and solubility
coefficients on temperature follow similar relationships:
D = Do exp (--Ed/RT) (8)
S = So exp (-6.Rsf RT) (9)
where Ed is the activation energy of the diffusion process and Il.Rs is

the heat of solution. Consequently
(10)
290 R. J. Ashley
The diffusion constant always increases when the temperature in-

creases. Sorption of a gas or vapour in a polymer may be considered as
two processes, condensation of the vapour followed by mixing. AHs
can be expressed as the sum of the heat of condensation, I1He, and the
heat of mixing, I1Hm
(11)
For permanent gases, such as hydrogen, oxygen and nitrogen, AHe is
negligible and I1Hs is determined by I1H for these gases the heat of
lTl ;
solution is small and positive and hence S increases slightly with

increasing temperature. For condensable vapours such as water AHs is
negative due to the large value of il.Hc and S decreases with increases
in temperature.
The activation energy, Ed, is always positive; therefore the overall
permeation activation energy Ep is positive for permanent gases. 'With
a condensable vapour such as water in polystyrene I1Hc is negative and
nearly equals Ed' The net result is permeability which is nearly
independent of temperature.
3.4. Wall Thickness

The permeability coefficient should be independent of thickness, but
there is an inverse relationship between thickness and the number of
pinholes. Although polymeric films may be considered relatively free
of pinholes they may still be present in very thin films. Electrical
conductivity indicates that there are pinholes or microvoids in polymer
films below a certain critical thickness « 10 p,m).
In addition the thickness of polymer films, especially semicrystalline
polymers may alter the morphology of the film and the result of this
change in morphology could be interpreted as the effect of the thick-
ness of the film. Non-linear dependence of the permeability of vapours
on the reciprocal of the thickness of polyolefin bottles has been
reported. 28 .29
The permeability coefficient is independent of thickness. Thus, as a
guide it is possible to assume that if the thickness of a barrier layer is
doubled the transmission rate of a gas or vapour is halved. But as the
film thickness is increased beyond a certain value it becomes un-
economical to increase it further to obtain lower permeation.
Many packaging materials consist of coated polymer layers, lami-
nated films or multilayered structures. 30- 32 For the purpose of assessing
barrier properties these materials may be considered as a number of
membranes arranged in series. For the simplest case of a laminate

consisting of two plies it can be demonstrated that if the permeabilities
of the two layer~ are PI and P 2 , respectively, and the thickness of the
layers 11 and 12 so that 11 + 12 = I, total thickness, then the total
permeability for the structure may be determined by the following:24
1 11 12
-=-+- (12)
P lP 1 lP2
If a barrier polymer is used as a thin coating in a multilayer
structure, normal layer materials will have different characteristics
which depend on the grade and thickness of the material and the
number of pinholes. To generalise for the case of multilayer structures,
there is a direct relationship between the permeability rate of a
multilayer material and the permeability rates of the separate layers in
that structure. It is
111 1
-=-+-+- ... . (13)
P t p" P y Pz
where P t = total permeability of the laminate and P ", P y and P z are the
permeabilities of the separate layers. Equation (13) only holds where
the separate layers are of the same thickness.
4. MEASUREMENT OF PERMEABILITY33-35
When designing containers for packaging applications it becomes

necessary at some stage to record details of the permeability of suitable
containers and relate these to properties of the intended contents so
that a realistic shelf-life can be estimated. Since packaging materials are
often complex combinations of several plastics layers it is desirous to
measure the permeability of individual layers and the final container.
In general, the permeability to water vapour and gas (usually oxygen
but, of increasing importance, carbon dioxide and nitrogen also) is
primarily required. However, permeability to volatile liquids, oils and
odours may also be required. Methods are needed for rapid assessment
of the permeability using flat sheets or films of material prior to any
forming operation so that early selection of suitable polymers can be
made in the laboratory. After container manufacturing trials, methods
are required whereby a thermoformed tub or a moulded bottle can be
assessed.
292 R.1. Ashley
4.1. Water Vapour Transmission Rate

Earliest methods were based on BS 3177 (1959) which involved mois-
ture gain by test dishes containing desiccants and covered by a sheet of
barrier material. The dish was exposed to test atmospheres and the
water vapour transmission rate determined by the rate of increase in
weight after several days or weeks of exposure. Modern equipment
facilitates the ability to make measurements in less than a day. When
dynamic equilibrium conditions of water vapour transfer have been
established within and across a homogeneous non-porous barrier ma-
terial, the quantity of water vapour, 0, permeating through the
medium in time t is given by:
(14)
Here (PI - P2 ) is the difference in water vapour pressure across the

sheet, A is the area of test sample and I its thickness. The test
temperature is usually 25 or 38°C. Interest usually centres on the water
vapour transmission rate, Of At, under specific conditions of tempera-
ture and pressure difference rather than the permeability coefficient.
The rapid methods of determination depend on detecting small
changes in the relative humidity of the atmosphere on the dry side of
the barrier. A schematic diagram of a rapid water vapour transmission
cell is illustrated in Fig. 5. 36
The lower section of the cell contains water to provide a saturated
atmosphere. The test sample is clamped between the two halves of the
r-----:J-----++Humldlty
sensor
Test sample
'O~rings
Water
Fig. 5. Apparatus for steady state permeability.

Dry~
I I ~JI
T~st film
ru U r- 'O'-ring
100%R.H.
~. ( MOist pad ")
Fig. 6. Water vapour transmission cell.
cell and secured by rubber rings. When clamped together the cell is
placed in a controlled temperature environment. The upper section of
the cell contains a humidity sensor and is dried by flushing with dry
air. When sufficiently dry the air inlet and outlet tubes are closed to
isolate the section. The relative humidity of the upper part can only
rise as a result of transmission of water vapour through the test
material and the time for a given rise in R.H. can be recorded to
calculate water transmission rate.
Figures 6 and 7 show how this principle is adapted on a commercial
Package
s~led to
base of cell
11
Fig. 7. Water vapour transmission measurement of a container.
294 R. I. Ashley
instrument for the measurement of water transmission rate through a

film and a container.
A moist pad is placed in the lower half of the cell to create a
saturated atmosphere. Having loaded the cell with a test film the cell is
placed in a conditioning rack to allow the sample to come to equilib-
rium with the new temperature and R.H. conditions to which it is
exposed. After the sample has achieved equilibrium (typically 5 min
for 25 tLm polyethylene to 24 h for 250 tLm rubber modified
copolymer of acrylonitrile and methylacrylate) the cell is clamped into
the test chamber to measure the amount of water vapour diffusing
through the film by means of an infrared sensor. A dry air stream
enters the test chamber at a constant rate and picks up the water
vapour permeating through the film. The gas leaving the chamber
contains a mixture of air and water vapour in a ratio determined by the
dry air purge rate and the rate of transmission of water vapour through
the film. The water vapour in this emergent gas mixture is measured by
the sensor and is proportional to the transmission rate for the film. A
recorder details the transmission rate directly. 36
To measure the water vapour transmission rate of a finished package
a modified cell is used. The package is fixed to the base of the cell
(possibly with the use of a hot melt adhesive to ensure leakproof
conditions) and encased in an outer shell containing a moist pad to
create a saturated atmosphere. The cell is conditioned as before and
then the sampling tubes connected to a test chamber so that dry air can
be purged in one tube and emergent air/water vapour analysed from
the other tube.
4.2. Gas Transmission Rate

The rate of permeation of a gas through a non-porous barrier layer is a
function of the partial pressure differential of that gas across the layer
and not of the total pressure difference between the two surfaces. In a
given fixed volume, the total pressure results from all the constituents
of a mixture of gases whilst the partial pressure of any specific
component is the pressure that would result if that specific component
occupied the same volume.
Various methods are documented for the measurement of gas trans-
mission rate and a few are briefly noted here. As with water vapour
transmission rate measurement rapid determination techniques are
required. It is usual to clamp a film or container sample in a diffusion
cell and expose one surface of known area to oxygen (or particular gas
--IllI
REFERENCE GAS [
) To detector
Fig. 8. Gas transmission cell.
required). The gas transmission rate is expressed as the volume of gas

passing through the sample per unit of area. A cell is divided into two
compartments with a test sample between the divisions. Oxygen is
continuously flushed through the lower half of the cell and a vacuum is
drawn above the sample. The cell is placed in a controlled atmosphere
to come to equilibrium and the upper half of the cell isolated. The
pressure rise in this volume due to permeation of the gas through the
sample is measured by a pressure gauge and the rate of increase per
minute recorded.
In methods based on concentration increase two gases are used, a
reference gas and a test gas, for which the permeability rate is
required. Concentration changes can be determined by the use of gas
chromatography techniques.
It is common practice to use a sweep gas technique as shown
diagrammatically in Fig. 8.
5. SELECI10N OF PACKAGING MATERIALS38
The barrier function of a packaging material is multifarious. In the case

of dried products it is necessary to prevent the ingress of moisture,
whilst for moist products loss of moisture through the package has to
296 R.I. Ashley
TABLE 9
Examples of Polymer Barrier Properties
Resin Po, (cm 3 j(mil PH,n (g/(mil

day 100 in 2 atm», day' 100 in2)),
25°C 38°C, 90% r.h.
-----_._----------
Hydrolysed (ethylene-vinyl 0·02 (dry only) 13-9
acetate) (EVAL)
High barrier Saran resins 0'05-0'15 0,1-0,15
(PVdC)
Nitrile barrier resin 0·8 5·0
Nylon 6 2·6 16-22
Polyester 3-4 1'0-1'3
Rigid PVC 5-20 0'9-5'1
Polypropylene 150 0·25
HDPE 150 0·3-0·4
Polystyrene 350 7'0-10'0
LDPE 420 1,0-1·5
be prevented. For products containing fats and oils, such as fried

snacks and fresh and cured meats, protection against the effects of
oxygen and light is required. In certain cases a package may have to
contribute moisture and oxygen barrier properties. To provide the
wide range of properties required use is made of all the major
polymeric materials. A representative selection of materials is given in
Table 9 in jicating the degree of protection in terms of oxygen and
moisture transmission rates that can be achieved from a single wrap of
these polymers for a given thickness. In order to improve upon the
basic property a number of techniques may be adopted which can be
taken into consideration when designing a suitable container. These
include:
(a) increasing the thickness of a polymer layer;
(b) improving barrier by introducing crystallinity into the polymer
which may be achieved by orientation, such as in a stretch blow
moulding process or control of blow-up ratio in a film extrusion
process;
(c) introduction of suitable fillers into a polymer formulation;
(d) use of polymer blends and copolymers;
(e) coating of one polymer with another;
(f) lamination of several polymeric layers in adhesive, extrusion or
coextrusion processes.
In addition to control of polymer properties through chemical com-

position and method of processing, it is possible to extend pack
shelf-life by selection of food processing technique or storage condi-
tions. Thus it will be necessary for the selected packaging materials to
demonstrate physical properties sufficient to withstand the process
cycle or storage conditions.
Whilst single- or multilayered polymeric packages can be produced
and their barrier properties accurately determined over a range of
environmental conditions so that the likely shelf-life for a given
package construction can be estimated, the required degree of protec-
tion for the product is another matter. In many cases food manufactur-
ers cannot specifically define the requirements of water vapour and gas
barrier that their products require, although guidelines may be gained
based largely on experience with traditional forms of packaging with
which they are familiar. The matter is further complicated since many
convenience foods are complex blends of materials and additives which
react differently to a given environment. A detailed knowledge of the
response of each component to atmospheric conditions would be useful
in designing the right pack for a given shelf-life so that adequate
protection at an economic price can be maintained.
For some products guidelines have been suggested to serve as a
starting point, and part of this data is shown in Table 10 where the
degree of permeation protection required for a one year shelf-life is
illustrated. The data shown indicates that the most oxygen sensitive
products would have a one year shelf-life if oxygen gain is limited
within the range 1-5 ppm. Less sensitive products would tolerate
greater oxygen concentrations or would exhibit longer shelf-life. The
table further indicates that the common low-acid foods are most
sensitive and these products are generally retort processed or hot filled,
and represent the major part of the food market.
Apart from oxygen sensitivity, water gain or loss is offered as a guide
to product stability. Values range from a maximum tolerable gain of
1 % for dry foods to a maximum tolerable loss of 3% for wet food
products.
In selecting a particular plastic or combination of plastics materials
inertness is very important since the container must neither impart nor
remove any flavour or odour through chemical interaction or physical
extraction or migration, nor may it transfer any component that will
adulterate or render the foods packed unsafe. Thermal resistance is
vital when foods are filled hot, aseptically or retort processed at
298 R.I. Ashley
TABLE 10
Degree of Permeation Protection for One Year at 25°C
Product Maximum estimated Maximum acceptable

acceptable oxygen water gain or loss
gain (ppm) (%)
Canned meats
Canned fish
Canned milk
Poultry 1-5 3, loss
Canned vegetables
Soups
Sauces
Canned fruits 5-15 3, loss
Nuts 5-15 5, gain
Snack foods 5-15 5, gain
Dried foods 5-15 1, gain
Fruit juices 10-40 3, loss
Soft drinks 10-40 3, loss
Oils and fats 50-200 10, gain
Salad dressings 50-200 10, gain
Preserves 50-200 3, loss
Pickles 50-200 3, loss
temperatures up to 135°C for periods up to 1 h, or deep frozen at

temperatures down to -40°C for storage for periods up to or greater
than 1 year.
For a rigid container stiffness is required, and because plastics have
considerably lower moduli than metals and glass they have to be
moulded in thicker wall sections to compensate for the difference. For
bottles and jars barrier properties and clarity are important.
Figure 9 gives examples of four barrier structures that are commer-
cially viable and by adjustment of the layer thickness may be used as a
flexible film laminate, a thick thermoformed or blow moulded structure
for a rigid container. Figure 9(a) shows a high impact polystyrene
which contributes structural strength and enables thermoformability of
the composite. A suitable barrier layer of Saran or EVAL is included
and adhesive layers selected to produce good bond strengths for the
pack requirements. In Fig. 9(b) low density polyethylene replaces one
layer of high impact polystyrene in order to improve moisture barrier
properties and provide a heat sealable layer so that various lidding
membranes can be attached. Figure 9(c) shows a structure based on
f¢
b
'~b"';"
LOPE
-S S S S S S
S \
'Y".
I
\ \ S S \ \ Sllrlln or EVAL
HIPS I
'I------------------~Ic
I HOPEor PP
S \' \ \ -\ \ S ~
~s •
S S \
-.'
\ .S
.
S \ \;
1
HOPE or PP __ ---.J
Fig. 9. Some typical barrier structures. (a) Thermoformable and rigid, oxygen
and moisture barrier, filled below 80°C; (b), as (a), but heat sealable and with
improved moisture barrier properties; (c) can be filled at above 80°C with very
good barrier properties, transparent or opaque, ftexible or rigid; (d) general
layer structure to determine performance characteristics. (HIPS = high impact
polystyrene.)
HDPE or polypropylene which is for improved heat resistance and

high barrier requirements. The fourth structure is a generalised ap-
proach where the inner and outer layers mayor may not be identical.
The structure has a barrier core and may include a scrap layer of
reclaimed material for economy or a black pigmented layer for u.v.
light protection. The structure may be rigid or flexible depending on
selection and thickness of inner and outer ply materials. The inner ply
is generally a heat sealable material such as polyethylene, poly-
propylene, EVA or ionomer film. For the outer layer abuse resistance of
300 R. 1. Ashley
the package can be improved by the use of polyester, polyamide or

oriented polypropylene films.
Using the criteria described in Table 10 a high barrier multilayer
plastic material may be evaluated for its protective qualities. Equation
(15) may be used to approximate the annual gain of oxygen through
any plastics container providing the oxygen permeability of the struc-
ture, the dimensions of the container and the weight of the contents
are known:
10,500APo
ppm O 2 per year = (273 + T)tW (15)
Similarly for annual water vapour gain or loss eqn (16) may be used:
12'9APw
% Water vapour per year = tW (16)
where A = plastic area of container (in2), t = barrier layer thickness

(mils), P 02 = oxygen permeability constant of the barrier (cm3 /mil/day
100 in 2 atm), P w = water vapour permeability (g/mil/day 100 in 2) at
38°C and 90% R.H., T = temperature eC) and W = weight of container
contents (ounces).
6. PREDICflON OF SHELF-LIFE39-45
In previous sections it has been indicated that the quality of a food

product depends on its moisture content, extent of oxidation, concent-
ration of certain components (flavour, odour, etc.) and a combination
of these factors.
Maintenance of these factors at acceptable levels is governed by the
conditions of transport and storage and the permeability of the packag-
ing system. The required shelf-life will also depend on marketing
considerations. The problem of the packaging technologist is to predict
the shelf-life for a product and to select the optimum package, bearing
in mind economic and market presentation factors.
In order to give some meaning to the term shelf-life it is necessary to
have knowledge of, and be able to measure, the distribution life of the
product, factors governing product spoilage over a given period of time
(i.e. relating to ingredients), and permeability of the packaging
materials.
The most accurate method to predict shelf-life is actual shelf-life
testing in which the product concerned is packed in the proposed

packaging system and sent through the distribution environment for a
defined period, after which, quality checks are carried out to determine
acceptability of the product. Since this is a lengthy and expensive
exercise it is rarely carried out and accelerated test procedures are
used. This generally involves testing the product under more severe
conditions than are likely to be encountered in practice (i.e. higher
temperature and relative humidity).
Whilst this method reduces the testing time significantly, the as-
sumption on which the principle is based (i.e. that the ratio of shelf-life
under accelerated and actual conditions is constant for any product
package), is unsound and leads to errors.
In reality this means that every product to be marketed should be
exposed to an accelerated test programme to assess the suitability of
the packaging system, or series of alternatives, prior to commercial
distribution. This may be possible for some large companies with
extensive research centres, but would be very expensive for smaller
companies to consider, such that some products would probably never
appear on the market.
To overcome some of the problems associated with accelerated
testing, mathematical models and computer aided systems of predic-
tion have become useful. The basic principle is to develop a model
which incorporates the nature of the product, the package system (or
options), distribution environment and the interrelation of these fac-
tors. Thus using computer techniques the total system can be studied
and optimised in terms of cost by determining the significance of
changes to individual factors used in the model. The accuracy of the
model can be enhanced by incorporating historical data obtained by
practical experience under similar circumstances.
This system may be used because rapid changes to materials prices
necessitates package changes and the competitive nature of the indus-
try requires shorter development periods. The technique can also be
useful as a decision-making tool to check, at an early stage, market
opportunities and alternative packaging approaches or materials.
The shelf-life simulation model relies on several assumptions:
(a) Shelf-life of the product depends on qualities which can be

controlled by the permeability of the package.
(b) The environmental factors of importance are temperature, oxy-
gen and humidity.
302 R. J. Ashley
(c) The package is of plastic, is plastic-coated or is a laminate with

measurable permeability.
(d) The elements of the model and their interaction are known or
can be estimated with reasonable accuracy.
As shown in Fig. 1 the package containing the product is in contact

with the distribution environment, and a headspace above the product
represents the internal environment being in contact with the product.
Therefore, the concentration of the components in the headspace
influence the shelf-life of the product. In addition to the interaction
between headspace and product the internal environment depends on
the initial conditions of packaging, external environment, seal quality
and permeation rate through the package wall. In turn all these relate
to a series of sub-elements, such as mechanical properties and methods
of manufacture, which must be determined and included in the model
system. The use of mathematical models enables decisions about
modification of the environment or storage system, use of higher
quality product or use of more expensive packaging materials to obtain
the necessary shelf-life to be made.
The key elements of a model system are shown in Fig. 10 where
many factors are involved; unfortunately some of them are often
ignored during selection of a barrier package. The permeability of the
package for a given environment is governed by the permeability
coefficient of the selected materials, the wall thickness and the surface
area for a perfectly sealed container. Models generally assume per-
fectly formed and sealed containers with no abuse damage arising from
transit. Some correction factor should be included to account for
mechanical abuse, creasing, scratching, etc., which could significantly
increase permeability and reduce shelf-life. Other factors to be consi-
dered include mechanical properties, chemical resistance to the pro-
duct, thermal and optical properties, in addition to marketing and legal
limitations, or consumer appeal.
The mathematical simulation model is not an instant or perfect
solution for shelf-life prediction, but is a useful concept to study the
significance of many factors, where practical evaluation would be
difficult for initial assessment of package development. The accuracy of
the results depends on the accuracy of the data input and the error
introduced by estimated values or assumptions. At some stage actual
shelf-life testing needs to be carried out to prove the validity of the
model.
Marketing Size and volume

requirements of product
Legal Optimisation of
limitations dimensions
Physical Limitation of
properties packaging operation
Chemical Method of product

resistance presentation
Manufacturing
methods
Sealing
methods
Internal
environment environment
Shelf-life
Fig. 10. Example of model for shelf-life prediction.
7. MATERIALS DEVELOPMENT
The packaging industry is by far the largest user of plastics materials

among the five major industries where plastics are consumed. In
Western Europe it is estimated that about 45% of the plastics pro-
duced are converted by the packaging industry. The most significant
materials used as raw materials for packaging are low density
304 R.I. Ashley
polyethylene, high density polyethylene, polypropylene, polystyrene,

polyamide, polyvinyl chloride and polyester. Currently polyethylene
accounts for about 50% of the plastics used with LDPE primarily used
for film applications and HDPE for blown or formed containers. To a
certain extent linear low density polyethylene is gaining importance
over the other polyethylene grades. About 25% of the polypropylene
output is used in packaging mainly as film, but more in the future
where its high temperature resistance can be exploited such that
coextrusions of polypropylene with a suitable barrier layer of, for
example polyvinylidene chloride or poly(ethylene-vinyl alcohol), can
provide long shelf-life containers for retortable food products. Of the
polystyrene output about 45% is converted into packaging materials
chiefly short shelf-life snack foods (water regenerable) and many dairy
products. 46
Europe consumes a considerable amount of polyvinyl chloride for
bottles and formed containers, but more recently this has been
threatened by the rapid rise in the use of polyester (polyethylene
terephthalate) bottles for carbonated beverages and other liquids such
as oils, beer and spirits.
An essential requirement for the use of plastics in food packaging is
the absence of any additive which in any way can impart an off-flavour
to the product or present a health hazard. Whereas polyolefins can be
formulated so as not to raise problems other plastics materials have
fared less fortunately. Doubts have been expressed over the effects of
the high monomer contents of polyvinyl chloride and certain stabiliser
and plasticiser systems. However, monomer contents of less than
1 ppm and, in some cases, less than 0·01 ppm can now be attained in
the end product which has accounted for the popularity of PVC in
packaging. Progress has been made with the stabilisers needed in PVC
processing and calcium-zinc based systems have proved successful.
The level below which a content of monomeric acrylonitrile can be
tolerated in PAN polymers has not been so clearly defined until very
recently. This may promote an upsurge in the use of PAN for bottles
for carbonated beverages where the outstanding gas barrier properties
can be exploited. At present for products such as beer it has been
necessary to coat polyester bottles with suitable barrier formulations
such as polyvinylidene chloride.
An average growth rate of about 4· 5% per annum is expected for
plastics materials in the packaging sector which ranks the industry
second amongst the five major plastics consumers. However, during

the early 1980s there has been a spectacular increase in the consump-
tion of polyester for stretch blow moulded bottles. These materials
have largely encroached on the glass bottle market especially for 1 litre
and 2 litre containers where lightweight properties are an advantage.
But with improvements in barrier properties, beer and spirits can be
safely packaged and provided the economics are right the production
of 0·25 and 0·5 litre sizes becomes feasible opening up attack on the
canned beverage market. Both poly(ethylene terephthalate) and
poly(butylene terephthalate) are used in these applications. These
materials are being further exploited by conversion into jars, contain-
ers and trays for a variety of other food products, such as coffee, dried
foods, preserves and microwave cooked foods.
Where the basic plastics material has been inadequate in providing
the required barrier property, polyvinylidene chloride (PVdC) has
been widely used as a component of a coating or extruded composite
film where its outstanding gas barrier has been useful. However, a
relatively new plastic material, EV AL, a partially saponified polyvinyl
acetate, is challenging its position in structures requiring extreme gas
protection. At a specific saponification level and molecular weight
range the good gas barrier properties of polyvinyl alcohol can be
combined with the thermoformability of polyvinyl acetate. Thus
EV AL can be used as an interlayer for coextruded film or coextrusion
blow moulded articles. However, the gas barrier properties of EV AL
can only be maintained whilst the polymer is kept dry; hence it must
be surrounded by good moisture barrier layers. Work is in progress to
offer grades that can maintain their gas barrier in humid environ-
ments.47
In conjunction with materials development, improvements to water
vapour and gas barrier properties have been achieved by process
engineering developments. New blow moulding techniques such as
stretch blow moulding have enabled biaxial stretching within the
polymer and an increase in barrier properties. The coextrusion techni-
que has been widely adopted for sheet and blown film extrusion. Thin
coextruded structures combine the packaging properties of two or
three plastics differing greatly in barrier properties. So far coextrusion
has shown limited use in the hlow moulding sector due to equipment
costs. In the field of thermoforming a technique whereby the polymer
is held just below its crystallite melting point and biaxially stretch-draw
306 R.I. Ashley
oriented is being used to improve barrier properties. Above all the use
of computerised control methods in process engineering enables grea-
ter control of layer thickness and production procedures to improve
package quality.
With regard to the use of various packaging materials and packages,
competition of plastics against metals and glass will inevitably occur as
also will replacement of one polymer for another polymer on account
of the variety of plastics available for packaging applications and
versatility of combining techniques. It is also assumed that the require-
ments of increased customer demands leading to more stringent
specifications and arguments for recycling will be easier to satisfy with
plastics than other materials. Further progress in the packaging indus-
try is expected as a result of increasing demand for materials savings,
energy conservation, improved barrier requirements, better protection
and changes in shopping and distribution habits.
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20. E. J. Mayor and K. Kammermeyer, Modem Plastics, 39, 136-79 (1962).
21. A. S. Michaels and H. J. Bixler, 1. Poly. Sci., 50, 393 (1961).
22. H. Yasuda and V. Stannett, 1. Poly. Sci., 57, 907 (1962).
23. V. Stannett and H. Yasuda, 1. Poly. Sci. (B), 1, 289 (1963).
25. Edwards and Pickering, Sci. Paper Bur. Standards, 16, 327 (1920).
26. Dewar, Proc. Roy. Instn., 21, 813 (1914-1916).
27. R. M. Barrer, Diffusion In and Through Solids, Cambridge University
Press, Cambridge, 1941.
28. F. S. Charlton and F. F. Delong, Mod. Pkg, 29(7), 227 (1956).
29. J. Pinskey, A. R. Nielsen and J. H. Parliman, Mod. Pkg, 28(2), 145 (1954).
30. c. L. Brickman, A. W. Saunders, and J. G. Rate, Jr., Mod. Pkg, 31(8),
149, 196 (1958).
31. M. R. Rogers, E. Pillion and A. M. Kaplan, Mod. Pkg, 31(3), 176, 238
(1957).
32. V. C. Simril and A. Hershberger, Mod. Plastics, 27(10), 97 (1950).
33. H. J. Bixler and O. J. Sweeting, The Science and Technology of Polymer
Films, Vol. 2, Interscience, New York, 1965, chapter 1.
35. V. Stannett and H. Yasuda, Testing of Polymers, Interscience, New York,
1965.
36. Trade Literature, Permatran W, Modem Controls Inc.
37. Trade Literature, Oxtran 100, Modem Controls Inc.
38. S. A. Marcus, Multi-layer plastics food containers, Food and Drug Pack-
aging, August 1982.
39. C. R. Oswin, The kinetics of package life-I. Package life, 1. Soc. Chem.
Ind., 64, 67 (1945).
40. C. R. Oswin, The kinetics of package life-II. Temperature factor, 1. Soc.
Chem. Ind., 64, 224 (1945).
41. c. R. Oswin, The kinetics of package life-III. The isotherm, 1. Soc.
Chern. Ind., 65, 419 (1946).
308 R.I. Ashley

43. C. R. Oswin, Food packaging in relation to moisture exchange, Chern.
Ind., 1042 (December 1976).
44. R. Heiss, Shelf-life determinations, Mod. Pkg, 31(8), 119 (1958).
45. S. M. Gyeszly, Permeability and shelf-life, Packaging Encyclopedia, 36-9
(1982).
46. K. Stoeckhert, Plastics in the packaging sector, Kunststoffe, 72, 575-83
(1982).
47. Special Report, Packaging Engineer, 63-7 (January 1983).
Chapter 8
Permeability of Coatings and Encapsulants for

Electronic and Optoelectronic Devices
M. T. GOOSEY
Morton Thiokol Inc., Tustin, California, USA
1. Introduction . . . . . . . . . . . . . . . . 309
2. Determination of Coating Penneability . . . . 310
3. Factors Affecting Polymer Penneability. . . . 315
4. Coating Penneability and Corrosion Protection 321
5. Penneability and Optical Data Storage Media. 328
6. Penneability Effects in Electrical and Electronic Compo-
nent Coatings 331
7. Conclusions 337
References. . . . . . . . . . . . . . . . . . . . . . 338
1. INTRODUCTION
Polymeric coatings are now widely encountered in all aspects of life

from the protection of the largest bridges and ships by paints to the
protection of the smallest electronic microcircuits by specially formu-
lated epoxides and silicones. The purpose of such coatings is usually to
protect the underlying substrate from the effects of moisture, oxygen
or other gases which can lead to the degradation of the properties of
the coated material and thus shorten its service lifetime. Unfortunately
all polymeric coatings possess the ability to transmit liquids, gases and
vapours to a greater or lesser extent and this permeability is an
important factor in determining the suitability of a particular polymer
for a specific application.
Permeability in polymers occurs by an activated process in which the
permeant dissolves in the coating on the side of highest concentration.
It then diffuses through the coating towards the side of lowest concent-
ration, where it may become desorbed if there are voids present. In
309
310 M. T. Goosey
films of polymers desorption readily occurs from the side of lowest

concentration, but precisely what happens with coatings onto another
material depends upon the properties of the two materials and in
particular on the nature of the interface between them.
The permeability coefficient (P) is a product of the diffusion coeffi-
cient (D) and the solubility coefficient (S). The diffusion coefficient,
solubility and permeability of a coating with various gases, liquids and
vapours is very important in determining the degree of protection that
it will impart on an underlying substrate. Absorption of a permeant
involves two processes: firstly the permeant dissolves in the polymer at
the permeant/coating interface and secondly it is transported into the
bulk of the polymer by diffusion. The diffusion process occurs as a
result of random molecular motions and is closely analogous to ther-
mal conduction.
If the diffusion coefficient is high and the solubility low, as is the case
with polysiloxanes, the material may be perfectly acceptable. Similarly
if the diffusion coefficient is very low and the solubility high, the
material may also be acceptable. The ideal coating will have both a low
solubility and a low diffusion coefficient. This is exactly what is aimed
for in the commonly used highly filled epoxide novolac transfer mould-
ing compounds. By introducing large amounts of the correct kinds of
fillers the diffusion and solubility coefficients can both be reduced
because the sorbant molecules have a longer path length to travel in
order to penetrate the film and because the amount of permeable
epoxide resin is greatly reduced.
2. DETERMINATION OF COATING PERMEABILITY
There have been many techniques reported for the determination of

coating permeabilities and these either involve the measurement of the
penetrant transmission rate through a thin film of the coating or a
gravimetric method. A film of the coating material is used as a
partition between two chambers one of which contains the penetrant
and the other which is initially penetrant free. With gaseous penetrants
the transmission rate is usually determined by following the increase in
pressure in a constant volume receiving chamber or by following the
increase in volume in a receiving section kept at constant pressure. If
the amount of penetrant that has permeated the membrane is plotted
Permeability of coatings for electronic/optoelectronic devices 311
against time the permeability, diffusion and solubility coefficients can

be determined. This is known as the 'time lag' method and was initially
developed by Barrer and Daynes. 1 ,2
Many gravimetric methods of determining coating permeabilities
have been reported and these have been reviewed by Newns. 3 Two
such methods for determining the diffusion and solubility coefficients
of moisture in polymer films have been successfully employed by the
author. The first method allows sorption from liquids to be investigated
and can be used for most non-reactive, involatile penetrants. The
determination of solubility and diffusion coefficients from liquids by a
gravimetric method is one of the most convenient and straightforward
methods available and is ideally suited to the rapid assessment of a
variety of materials prior to selection for a particular application. A
thin film of the material is cast and should ideally have thickness
variations of less than ±5%. The sample is weighed as accurately as
possible and suspended in a thermostated bath of the desired pene-
trant. At regular intervals the sample is removed from the liquid,
blotted dry with a tissue to remove surface wetness, and weighed. The
weighings show successive increases in weight until equilibrium absorp-
tion has occurred and a plateau is reached. Depending upon the
thickness of the film the experimental temperature and the sample
permeability, the time for equilibrium uptake to be achieved may vary
from several minutes to months or even years and allowances should
be made when deciding what thickness of film to use.
Whilst the above method is to be recommended for initial examina-
tions it may not be capable of producing the accuracy required by
some workers. Errors are introduced because the change in mass of the
sample is not measured continuously and also because, depending
upon the material and the penetrant, various compounds such as
impurities, unreacted hardeners or decomposition products can be
leached out of the film causing a loss in mass which masks the true
amount of penetrant absorbed.
The second method utilises a vacuum microbalance to give a con-
tinuous recording of sorbed vapour uptake versus time. The high
sensitivity of the balance allows much smaller amounts of sorption to
be accurately recorded and thus thinner films of the coating to be
examined. The use of thinner films means that equilibrium uptake can
be achieved for samples with low diffusion coefficients in a matter of
hours rather than months using a liquid method. This method also has
312 M. T. Goosey
the advantage of allowing sorption experiments to be carried out at

reduced activities because penetrant vapour is used. The vapour pres-
sure of the diffusing species can be depressed by mixing it with another
liquid that has no appreciable vapour pressure at the experimental
temperature. In this way sorption isotherms can be easily examined
and these often give information about the types of penetrant-polymer
interactions occurring.
A sample of the polymer coating under investigation is placed on
one arm of the microbalance with a counterweight on the opposite
arm. The balance is mounted in an evacuable chamber with good
temperature stability. Once the balance chamber has been evacuated a
tap connecting it to a reservoir containing the degassed penetrant is
opened and the output of the microbalance recorded continuously on a
chart recorder until equilibrium uptake is achieved. The vapour of the
penetrant is conveniently read from a mercury manometer using a
cathetometer or directly using a vacuum gauge. A schematic diagram
of the microbalance equipment used by the author is shown in Fig. 1.
With either gravimetric method eqn (1) can be used to obtain
diffusion coefficient from the linear part of a plot of mass uptake, M"
against root time.
M, = ~ (Dt) 1/2
(1)
M= I 7r
Here Moo is mass uptake at equilibrium and I is film thickness. A

typical plot of uptake against time is shown in Fig. 2 for an epoxide
coating at 50°C and the linearity over this range demonstrates the
diffusion to be Fickian.
Many other methods for determining the diffusion coefficients of
penetrants in coatings have been developed for specific applications.
Dcwydov, Eremeeva and Kiselev 4 examined the permeability of
polyurethane films to water vapour using infra-red spectroscopy to
monitor the deuterium exchange reaction and the disappearance of
isocyanate groups. This work was based on the fact that the
polyurethane films contained residual functional groups with active
hydrogens capable of undergoing an exchange reaction with D 2 0
vapour leading to a corresponding change in the infra-red absorbance
spectrum (Fig. 3). The rate of deuterium exchange is very high com-
pared to the rate of diffusion. The sorbed water also reacted with
residual isocyanate groups and their disappearance could also be
monitored by infra-red spectroscopy.
A 1------240V AC
r--- -----------------,
I I
I I
I I
I C I
I
I
I
I ~ I
I
R I
I
I
~==~~~==~=--Q
s J K
Fig. 1. Electronic vacuum microbalance. A, Relay and rheostat; B, control

heaters; C, contact thermometer; D, fan; E, balance arm; F, isolating tap; G,
sample; H, counter weight; I, tap to water reservoir; J + K, manometer taps; L,
mercury manometer: M, water reservoir; N, fan; 0, background heaters; P,
rheostat; Q, to vacuum pumps; R, balance control; S, matching circuit; T,
chart recorder; U, thermostated cabinet.
314 M. T. Goosey
0·6
Mt 04
MOO
02
0
0 40 eo 120 160
t'/2/S'/2
Fig. 2. Uptake of bulk water by an amine cured epoxide at 50°C.
Various workers have used tritiated water to measure the water

vapour permeabilities of various films, coatings and paints. Gildes
determined the amounts of water diffusing through a film in a system
of constant vapour content by using tritiated water and measuring the
activities. Using this method the permeability constants of cellulose
and rubber derivatives as well as an epoxide and a polyurethane were
determined.
Marshall and Marsha1l 6 also used tritiated water to determine the
diffusion coefficient and the concentration profile of a diffusant at any
time without the need for equilibrium to be achieved. After exposure
c:
.
o
'OJ
.
E
.....
c:
II
4000 3000 2000

Wave numbers (cm- ' )
Fig. 3. Infrared spectra of polyurethane films before and after D 2 0 exposure.
1, Before exposure; 2, after 2 h; 3, after 168 h. (After ref. 4.)
to labelled water the polymer was cut into thin slices, pyrolysed in
oxygen at 900°C and then passed through a catalyst bed at 700°C to
ensure complete combustion. The water so formed was frozen out at
-80°C and a suitable scintillation cocktail added. The activity of the
water was then determined by means of a liquid scintillation counter.
3. FACfORS AFFECflNG POLYMER PERMEABILITY
When coatings are used as a means of protecting an underlying

substrate the vapour and moisture permeability is one of the most
important factors determining the likely performance. As well as the
chemical structure of the coating, factors such as temperature, humid-
ity, degree of crystallinity, the nature of any additives or impurities and
even stress can all playa major part in affecting the permeability.
The temperature at which permeation takes place is very important
since Barrer7 demonstrated that the variation of diffusion with temper-
ature was an activated process which could be represented by an
Arrhenius type equation.
The temperature dependence of solubility can be similarly rep-
resented. Increases in temperature activate the polymer molecules
creating voids by the movement of polymer segments which can be
occupied by diffusant molecules and thus the diffusion coefficient
increased with increasing temperature. When selecting a polymer
coating for a specific application the likely operating temperature
range of the material should be assessed in terms of its glass transition
temperature {Tg }. The temperature coefficient of permeability is usu-
ally lower when the coating is in the glassy state than in the rubbery
state. Consequently any temperature excursions through the Tg to the
rubbery state may significantly increase the rate of permeation.
The Arrhenius type behaviour for the permeability of gases in
polyethylene is clearly shown in Fig. 4. The nature of the penetrant
obviously plays an important part in determining its permeability in a
coating. Quite simply for a permanent gas or a vapour which is hard to
condense the permeability increases with decreasing size of the per-
meating molecule. 9 In contrast to permanent gases, liquids and easily
condensed vapours show a high degree of interaction with the coatings
they are permeating. When considering the permeability of a vapour in
a coating the important parameters are the size of the penetrant
molecule, its ease of condensation and any structural similarity with
316 M. T. Goosey
3·0
.0
-~ 2·0
x
Jl..
01
~co,
o
- 1·0
0~3~1--~3~'3~--~3~'5~--~3~'7~----
103 , T (K)
em' (STP) mm)

Fig. 4. Permeability, p ( 2 ( ) , versus temperature, for gases in
em s emHg
polyethylene."
the coating. The permeability will generally increase with decreasing

molecular size, ease of condensation and increasing structural
similari ty .
Where a permeant and coating are dissimilar, as is the case with
polypropylene or polyvinyl chloride and water, the interactive forces
between the polymer and moisture will be less than the cohesive forces
between the water molecules and the water will tend to aggregate and
form clusters. In the opposite case where the polymer actually contains
functional groups similar to those of the diffusing species the cohesive
forces between the penetrant and coating molecules are greater than
the penetrant-penetrant interactive forces and the solubility of the
penetrant in the film will be large. This causes a corresponding increase
in the permeability constant because the high concentration of the
penetrant in the coating causes it to swell, loosening up the polymer
network, allowing easier diffusion and thus an enhanced diffusion
coefficient. As the permeability is the product of the solubility and
diffusion coefficients it is increased by contributions from both the
increased diffusion and solubility. These two types of behaviour are
clearly demonstrated with the case of moisture permeability in
polyethylene and regenerated cellulose where the permeability of
water in polyethylene is between 70 and 400 times greater than that of
regenerated cellulose.
Various workers 10 . ll have shown that, for carbon dioxide, nitrogen
TABLE 1
Permeabilities of Nitrogen, Oxygen, Carbon Dioxide and Water in Various
Polymers!3
Polymer Room temperature ((em' STP) mm x 10 10)

permeability em 2 s (em Hg)
Nitrogen Oxygen Carbon dioxide Water
Polyvinyl alcohol 29,000-140,000

Ethyl cellulose 84 265 410 14,000-130,000
Polyurethane 5 15-48 140-400 3,500-125,000
Cellulose acetate 2-5 4-8 24-180 15,000-106,000
Polypropylene 4 23 92 700
Polychlorotrifluor- 0·1-1·3 0·3-5 0·5-12·5 3-360
ethylene
Polyvinyl fluoride 0·04 0·2 0·9 3,300
Fluorinated ethylene 21·5 59 17 500
propylene copolymer
and oxygen, the ratio of one gas permeability to another through the
same coating under the same conditions is virtually constant (within a
factor of three or less) even though for the materials examined the
permeability constants varied over a 1200 fold range. Similar reg-
ularities were observed for the activation energies of the gases by
Frisch. 12
This is not the case however with liquids and easily condensed
vapours because they often show the high degree of polymer permeant
interactions mentioned above. Some typical examples of permeabilities
to nitrogen, oxygen, carbon dioxide and water are shown for a variety
of polymers in Table 1.
The choice of barrier coating will be made by considering the nature
of the penetrant. Various properties of the barrier material itself will
influence the rate of permeation of a given penetrant. These not only
include its chemical composition and compatibility with the penetrant
but also the degree of crystallinity, the amount of crosslinking, the
presence of a plasticiser and the history of the material before
exposure.
If a coating is to possess the best barrier properties to a penetrant it
must be such that it interferes with the ease of the diffusion process
and the polymer must not possess any functional groups chemically
similar to the penetrant molecule.
A highly crosslinked structure will inhibit the diffusion process more
318 M. T. Goosey
than a linear polymer because the polymer chains are more tightly
bound together and resist the separation necessary to form a void
capable of accommodating a diffusing molecule. The energy to create
such voids will therefore be large and the permeability small. Such
structural tightness is found not only in highly crosslinked polymers but
also in those possessing a high degree of crystallinity, symmetry or
strong cohesive forces brought about by polarity. The opposite effect
will occur if there are none of these features and the polymer network
is loose. This is usually most evident in plasticised materials and those
containing double bonds.
If there are regions within a coating that are inaccessible to the
diffusing species the permeability is reduced. The presence of such
regions effectively increases the diffusion path length and it is normally
achieved by incorporating fillers into the coating or using a material
with large areas of crystallinity. Crystallites can generally be consi-
dered to function as inert fillers and the decrease in diffusion coeffi-
cient with increasing crystallinity is at least partly due to the more
tortuous nature of the diffusion path. The variation of gas permeability
with crystallinity in polyethylene is clearly demonstrated in Table 2.
Stannett and Yasuda 15 found that the permeability of polyethylene
to gases decreased by a factor of two between uncrosslinked and
crosslinked material. Also, low density polyethylene has been found to
be about five times more permeable than the corresponding high
density material. The effect of polarity is conveniently demonstrated by
comparing polyethylene with butyl rubber and Saran. Butyl rubber is
essentially a polyethylene in which half the hydrogens have been
replaced by methyl groups. Its permeability is about one fifth that of
the equally non-crystalline polyethylene. Saran is essentially a
polyethylene in which half of the hydrogens have been replaced by
TABLE 2
Variation of Polyethylene Gas Permeability with Crystallinity 14
Crystallinity (%)
em 3 STP) mm x 1010)
Permeability at 30°C ( - - - - - 0 :2-- - - ' - - - - - -
em s (em Hg)
Nitrogen Oxygen Carbon dioxide
60 1.90x 10- 9 5·5 x 10- 9 25·2x 10- 9
69 0·66 2·1 7·4
78 0·33 1·1 4·3
81 0·27 1·06 3·5
chlorine atoms and its permeability is between 200 and 1000 times less
than that of polyethylene. Carfagna et al. 16 found increased water
solubilities in amine hardened epoxy resins cured with an excess of
hardener and this was attributed to the high degree of hydrophilicity
imparted to the polymer by the amine. The effect of double bonds is
illustrated by polybutadiene which has a permeability some three times
greater than that of low density polyethylene.
In a real life application a coating is likely to be exposed to more
than one penetrant at a time. It is therefore interesting to speculate to
what extent the presence of gas in a mixture affects the transmission
rate of another component. Little or no interaction would be expected
in the case of gas mixtures. For instance it would not be expected that
an excess of carbon dioxide would effect the permeability to nitrogen
but it has been found that the presence of water vapour can profoundly
affect the rates of transmission of various gases. The effects of water
vapour on the gas transmission for a number of polymer gas systems
have been studied by Simril and Hershberger 1 ? and they reported large
increases in various gas permeabilities with increasing relative humid-
ity. Such increases in permeability in the presence of moisture can be
explained by the plasticising effect of the sorbed water.
The sorption, diffusion and permeation of organic vapours in a
coating are often strongly dependent upon the vapour activity and the
concentration of sorbed penetrant. In an investigation of hydrocarbon
vapour sorption in polyethylenes of different densities, Rogers et al. 18
found that the data could be represented by a linear function of the
logarithm of the solubility coefficient versus the concentration of the
sorbed vapour.
The present author 19 studied the isothermal sorption of water by
epoxide films based on the diglycidyl ether of bisphenol A and
triethylene tetramine at 50°C. The diffusion coefficient was found to
decrease with increasing water activity in a similar manner to that
observed for several other polymers?O,21 The solubilities of moisture
for samples given different cures both increased with activity (Fig. 5).
Brunauer et al. 22 classified non-ideal sorption isotherms into five types
and the results shown in Fig. 5 clearly indicate type 5 behaviour with
the isotherm levelling out to a finite value at unit activity. These results
are taken to indicate that both clustering and plasticisation occurred in
the epoxide with the clustering becoming more dominant as the water
concentrations increased. In this case the decrease in diffusion coeffi-
cient with increasing water activity is due to clustering at higher
activities.
320 M. T. Goosey
~
:.c::J 3
'0
III
'$.
Activity H20
Fig. 5. Solubility versus H 2 0 activity at 50°C for amine cured epoxide. Cure:
(0) 3 h at 60°C; (0) 3 h at 60°C+4 h at 120°C.
In general the permeability of a permanent gas or hard to condense

vapour is usually proportional to the pressure or partial pressure
differential providing that the coating has been exposed to the gas for a
time sufficient to reach equilibrium and that the pressure is not so high
as to cause deviations from the gas laws. In the case of liquids and
vapours two possibilities exist. The first is where penetrant vapour does
not dissolve to any great extent in the coating. An example would be
the permeation of water through polyethylene and the rate of permea-
tion would be proportional to the vapour pressure differential between
the inside and outside surfaces. The water vapour is behaving in

exactly the same way as the permanent gases do. The second possibil-
ity is where the permeant dissolves appreciably in the coating. An
example of this type of behaviour would be the permeation of moisture
in a nylon coating or alkanes in polyethylene. For these two cases
neither Henry's law nor Fick's law is obeyed and the deviation is such
that the solubility increases faster than proportionally with vapour
pressure. As a consequence the permeation rate increases faster than
linearly with the vapour pressure differential and is dependent not only
on the pressure differential but also on the absolute vapour pressure. It
can thus be appreciated that any attempts to predict behaviour at one
vapour pressure from data at another can lead to erroneous results.
The permeability of acetone in vulcanised rubber is much lower than
that of acrylonitrile if the vapour pressure is low whereas at high
vapour pressures in contact with the liquids acetone has a much higher
permeability than acrylonitrile.
4. COATING PERMEABILITY AND CORROSION

PROTECTION
Corrosion has been a major factor in the use of metals for many
hundreds of years but it is only recently that the enormous replace-
ment costs for corroded structures have prompted serious studies into
its mechanisms and prevention. One of the most important and widely
developed approaches to corrosion control is the use of paints and
protective coatings to prevent deleterious corrosive media from coming
into contact with the metal. Such coatings may be formed either
naturally or synthetically. The natural coatings often consist of pas-
sivating corrosion products and these self-formed protective films
usually result from the conversion of the metal surface into a com-
pound which is joined to the surface by atomic forces. They are
continuous, relatively impermeable and quite often invisibly thin. The
synthetic coatings cover a large variety of compounds which can
conveniently be divided into three common types. One class contains
the non-ferrous metals, the second is comprised of inorganic coating
substances such as the cements, clays and enamels. Thirdly, there is the
organic coatings group, which embraces waxes, lacquers and paints. All
of these types of coating have certain advantages and limitations
322 Mo To Goosey
depending upon the particular application but by far the most impor-
tant group are the organic coatings. It is to these organic coatings that
this discussion relates.
The aim of an organic coating on a metal may be twofold and the
application is usually designed to give not only corrosion protection
but also a suitable cosmetic appearance. Whilst the cosmetic aspects of
a coating can be determined relatively easily the performance of a
protective coating in the protection of an underlying metal depends
upon several important factors. These usually include the nature of the
metal surface, the composition, thickness, adhesion and continuity of
the coating and also the environment to which the coated material is
exposed. In order to prevent corrosion of the underlying metal a
coating must exclude the deleterious components of the atmosphere
from the substrate. As already described all organic films are perme-
able to a certain extent.
The permeation of a paint film by water involves sorption but there
may not be a direct relationship between the amount that is absorbed
and that which permeates. Certain organic materials often only absorb
very small quantities of moisture but permit the diffusion of relatively
large quantities. The opposite may also occur where large quantities of
moisture may be sorbed but very little actually permeates the coating.
The interaction of moisture with a coating can lead to swelling which
may influence its physical structure resulting in enhanced per-
meabilities not only to moistw·e but other species as wello The sorption
of moisture may also influence the structural properties of a coating,
sometimes with an accompanying loss of adhesion. The use of pig-
ments in coatings is not only for cosmetic purposes since their incorpo-
ration also reduces the mixture permeability. Table 3 gives permeabil-
ity data for an organic coating medium containing various pigments in
a concentration of 25% by volume.
TABLE 3
The Effects of Various Pigments on Moisture Penneability
Pigment D
rermea bOZO
I Ity
(_m..:;:g,-o=-oO_o_l_i_n)
2
day
0
In
Unfilled coating 72
Lead chromate 56
Silica 40
Iron oxide 36
Red lead 29
When moisture is sorbed by a paint coating there exists the possibil-

ity of deleterious ions being transported to the interface between the
metal and the coating. The presence of such ions in solution provides a
means of conduction for corrosion currents and subsequent corrosion
of the metal. Vittal Rao and Yaseen23 studied the effects of tempera-
ture on the rates of permeation of chloride ions and water vapour
through alkyd coatings. Chloride ion permeation rates were measured
by clamping a test film between two parts of an ionic permeability cell.
Each side of the cell contained a sodium chloride solution of differing
strengths and the permeation of chloride ions was detected using ion
selective electrodes. The permeation of moisture was also examined
and the results indicated that the rate of permeation of water vapour at
45°C was more than 4 times greater than it was at 30°C. In the case of
chloride ion permeation the rate increased with temperature. The
effect of temperature on chloride ion diffusion rates in a variety of
coatings is shown in Fig. 6.
Koopmans24 studied some new aspects of the relation between
pigments and binders in corrosion protecting coatings. It was found
that the permeability and diffusion coefficients were affected by both
the binder and the pigmentation of the paint coating. The water
0·12
:;: 0·10
-
N
E
E
E OO6
o.o22'::5:-----"J3o~----:3-'::5---4.1.0---4..l.5-
Temperature (·C)
Fig. 6. Temperature dependence of chloride ion permeation rate through

various alkyd coatings. 23
324 M. T. Goosey
absorption of paints is well known to be affected by the binder but the

effect of pigmentation was not expected. Koopmans explained this
effect by the adsorbed binder having a different chemical composition
from the mass. These differences in chemical composition resulted in
different mobilities and solubilities of water in the paint.
It has been shown that the electrical resistance of a paint film may be
inversely proportional to the ionic permeability, that the capacity
increases for films of high polarity and that these two parameters vary
linearly with the thickness of the film and the area exposed. Vetere et
a1. 25 measured the conductivity, capacity, electrical resistivity and
moisture permeability of paint films immersed in an aqueous medium
in order to characterise the physical and electrical qualities of the film
either when isolated or applied to a metallic substrate. From the results
of this work it was found that resistance measurements may be used to
determine:
(a) the compatibility between current density and paint systems in

the case of cathodic protection.
(b) adjustments in the formulations of anticorrosive paints with an
adequate choice of pigments and binders in order to obtain a
greater barrier effect as well as a better inhibiting power.
(c) failures of a paint film due to mechanical deterioration.
Ruggeri and Beck 26 investigated the mass transfer characteristics of

polyurethane paints both by experimental methods and by the use of a
comprehensive mass transport model. Three experimental methods
were reported for the investigation of diffusion in films of the
polyurethane. These were the Hittorf, concentration gradient and
pressure gradient techniques. In the Hittorf experiments the current
and concentrations were monitored as functions of time while a fixed
potential was applied across the membrane. The concentration changes
were followed using radioisotopes of sodium and chlorine. Water
sorption isotherms were also obtained by exposing paint films to con-
stant humidity atmospheres and measuring the uptake with an elec-
trobalance. The results of these experiments support the findings of
Vittal Rao and Yaseen above that the ionic species permeated the
paint much more slowly than did the water. These observations may
well support the proposition by Mayne 27 that ionic permeability is the
rate determining step in the corrosion of the underlying substrate
metal. Another possibility is that residual ionic contamination of the
metal surface is simply covered over by the coating when it is applied

and the rate determining step is the diffusion of oxygen or moisture.
Most discussions of corrosion and coatings concentrate upon the
permeation of water, oxygen and ions and there are various theories as
to which of these processes is the controlling factor. Bacon 28 and
Cherry29 both agreed with Mayne in concluding that while water and
oxygen were essential components of the corrosion process their
permeabilities were not rate determining as they were relatively fast
and could not be prevented from reaching the underlying metal by the
coating. They proposed that protection was due to the high electrical
resistance of the coating which resulted from low ionic permeability.
Further work by Kreusse 30 disregarded both oxygen and ion per-
me abilities as the controlling factors and attributed the rate determin-
ing step to water diffusion but contrary to Kreusse, Haagen and
Funke 31 published papers concluding that oxygen permeability was the
rate controlling factor and that water was the rate controlling factor for
the loss of adhesion but not corrosion.
It was once thought that small molecules and ions could not signific-
antly permeate an organic coating but it is now perfectly clear that not
even a compact and non-porous coating can prevent ion penetration.
This means that it is impossible to impart a full barrier type protection
to the surface of a metal by giving it an organic coating. Current
thinking supports the idea that ions and small molecules may permeate
a polymer coating by travelling in the spaces between the polymer
molecules in the free volume.
The permeation of ions in a coating obviously depends upon its
dielectric constant. This wili normally be low and the passage of ions is
controlled by the action of active ionisable groups fixed on the polymer
chains of the film which function as transition stages for oppositely
charged ions in the coating film. However in the presence of diffusing
moisture those fixed ionisable groups became ionised by the sorbed
water. Free counter ions of opposite charge are also formed and it is
these ions which may then become mobile. If the coating contains a
large quantity of water its permittivity increases further and passages
along the polymer chains of the coating are formed which allow the
penetration of large hydrated ions within the film?2
Murray 33 studied chloride ion penetration in three coatings using an
ion selective electrode technique and the results indicated that the
penetration dependence upon time and penetration rate could be
divided into three groups. These are represented by cellulose acetate,
326 M. T. Goosey
iSk:=:
15
'~ 12 '~ 72
....L :!:!
~9 ~ 56
on 6 '$:! 40 ~6
~
x 3 x 24 ~4
x
IjO
r,-o '1'2
.Q. Q, 8 ..Q
o 2 4 6 8
L--:c!:""":::7-::-:'7~7
48 96 144 192 240 0 2·5 5'0
h h h
(A) (9) (e)
Fig. 7. The three types of chloride ion permeation behaviour reported by

Murray. 33 A, Cellulose acetate; B, epoxy/polyamide (1: 1); C, polyvinyl
chloride/acetate copolymer.
an epoxide polyamide and a polyvinyl chloride-vinyl acetate

copolymer and their behaviour is shown in Fig. 7. This separation of
coatings into three groups was found to be determined by the type of
interactions occurring between the coating films and the water or
chloride ions.
Just as the addition of pigments and fillers affects the permeability of
a coating to gases and vapours so they effect the diffusion rates of
sodium and chloride ions. This has been shown by measuring the
diffusion of sodium chloride labelled with sodium-22 and chlorine-36
isotopes into various pigmented and unpigmented films. The rate of
sodium and chloride ion diffusion decreased with increasing pigment
content up to a critical volume concentration above which there was an
increase in the diffusion in the coatings. The diffusion of sodium ions
was found to be greater than that of the chloride ions into epoxide
polyamide coatings34 whereas the sodium and chloride diffusion occur-
red in a stoichiometric ratio in non-pigmented acrylonitrile cellulose
coatings.
The diffusion ratio of sodium to chloride ions in pigmented as well as
non-pigmented coatings is not affected by the pigment but is depen-
dent upon the nature of the polymeric component of the coating. The
diffusion rate of chloride and sodium ions in a crosslinked epoxide
polyamide film is lower than in a linear acrylonitrile cellulose film.
Addition of fillers or pigments reduced the ionic diffusion rate in both
coatings owing to the decreased polymer mobility and the increased
diffusion path length. The degree of the decrease in the diffusion rate
was lower for the epoxide polyamide coating than for the cellulose
acrylonitrile films because the active parts of the polymer segments
have already been fixed in the crosslinked polymer whereas the linear
polymer may contain many active groups. Addition of pigments or
fillers provides adsorption sites for these groups by which segment
mobility is reduced and thus also ionic mobility.
As with the diffusion of moisture and gases conflicting results have
been obtained for chloride diffusion in coatings. Kittelberger and
Elm 35 examined the permeation of sodium chloride through phenolic,
polyvinylbutyral and alkyl clear varnish films. The diffusion coefficients
were found to increase remarkably when pigments were added to the
paint films.
Whilst the permeability of a coating to ionic impurities, oxygen and
moisture is undoubtedly extremely important in determining the de-
gree of protection afforded to an underlying metal the role of adhesion
cannot be overemphasised and it has been reported 36 that in certain
cases, even if a coating is highly permeable to moisture, it can still give
good protection if adhesion is maintained . There is, however, evidence
that when a protective coating is exposed to high humidities or
immersed in an aqueous medium a loss of adhesion can take place
which is often very severe. After short periods of exposure Walker 36
found that the adhesion of coatings dropped sharply and this
phenomenon occurred even before water permeation had taken place
to any significant extent in the paint film. Similar results were noted by
the author 19 on single bonded epoxy lap joints exposed to high
temperature and humidity. In this case the large initial loss of adhesion
was compensated for by a gradual recovery possibly caused by further
curing of the resin. It has also been found that films having large
moisture absorptions and high permeabilities lose adhesion fastest.
Walker also demonstrated the importance of the curing process in the
way adhesion was lost and recovered after subsequent drying. Coatings
which cure chemically, e.g. epoxy polyamides and polyester isocyan-
ates have their adhesion greatly affected by humidity.
Whilst there has been much interesting work carried out in the study
of small molecule and ion permeabilities in paints and their relation-
ships with corrosion the results go only part way in explaining the
dependency of permeability upon fillers, pigments and chemical com-
position. Further investigations into the factors which influence the
penetration of corrosion causing species are undoubtedly required.
328 M. T. Goosey
5. PERMEABILITY AND OPTICAL DATA STORAGE MEDIA
With the ever increasing need to store and retrieve large amounts of
data there is a growing requirement for an economical, compact,
high-speed storage system. Further improvements in magnetic record-
ing media will become much more difficult to achieve and hopes are
now centred on new optical technologies to meet the challenge.
Various systems have been proposed and in particular an attractive
new technique is emerging which may be a solution to the problem.
This uses a highly focused laser beam for optically recording data on a
disc at very high data rates with extremely high packing density.
Playback-only systems have been available for some years but the
greatest challenge is with record/playback systems where the recording
materials represent the key component.
Many different optical recording media have been investigated and
among these polycrystalline tellurium films have several attractive
properties but unfortunately they also show rapid degradation in high
humidity or oxygen?7 Like most metals tellurium is oxidised upon
exposure to air but under dry conditions a stable passivating layer is
rapidly formed and oxidation does not proceed any further. Water
destabilises this thin oxide layer and oxidation of the tellurium layer
proceeds until it is all consumed. Smith et al. 38 examined the feasibility
of protecting thin metal layers from oxidation in the light of known
vapour permeability characteristics of selected organic polymeric ma-
terials. Attempts have been made to increase the tellurium stability by
using various polymers as overcoats and to form sandwich-type struc-
tures. The air sandwich structure utilises a substrate on which the
tellurium metal is deposited. Annular spacers then provide the supports
for the top polymer film and leave a cavity immediately above the
metal (Fig. 8).
Overcoated or encapsulated structures have also been used but only
a few materials can be utilised without the metal film suffering a
signifi<.:ant loss in marking sensitivity (Fig. 9). The concept of prevent-
ing metal oxidation by encapsulation is very much the same as for
Top polym~r lay~r
I~_b[ I
S::s\:;:::<S;:SS:::SS:::S±2;~=1r---'~:I~~;ium
s;:ss::s::s: s: ss::ss:;:::<s;:ss::s::s::s::s lay~r
. . Substrate
Fig. 8. Air sandwich type film structure.
~ncapsulating
~
top layer
f
_
\\\\\\\\\\\\\\\\\\\\\\~0_~+--_
~
Tellurium layer
Substrate
Fig. 9. Overcoated (encapsulated) type film structure.
previous samples cited in that if water and oxygen can be prevented

from reaching the metal surface no oxidation will occur. Since all
polymers are permeable to moisture and gases the problem is one of
kinetics, i.e. for how long oxidation of the metal will be insignificant
enough not to affect the marking or read out sensitivity. It is thus
important that the polymeric coating materials selected have the
optimum barrier properties against detrimental species.
Recent work carried by Plessey Ltd has taken the concept of optical
read-write data storage systems one step further. This has involved the
use of a range of novel organic photochromic materials as the basis for
a reversible optical data storage system. The main reason for the
development of such a system was the hope that optical methods
would increase the power of computers by allowing parallel processing,
giving very high data rates together with a greatly increased capacity.
The low cost of optical data storage resulted from the use of a high
resolution storage medium; for example, photographic emulsions are
capable of recording in excess of 10 6 bits mm- 2 with the result that the
contents of The Concise Oxford Dictionary could be contained in a
strip of 35 mm film only a few tens of millimetres long. The system
developed by Plessey utilised holographic recording techniques for
storing images on photosensitive materials. For reversible storage a
photochromic film was used with the recording operation carried out
by first exposing with ultraviolet light to impart a colour to the film and
then recording by bleaching areas of the colour with green light.
Erasure was achieved by re-exposure to the ultraviolet light and data
read out utilised a weak green light source of sufficiently low power to
cause no further bleaching.
The organic photochromic materials were coated onto both cellulose
acetate and polyethylene terephthalate film bases. Unfortunately most
organic photochromic materials eventually suffer from fatigue prob-
lems which limit the achievable number of read-write cycles. This has
been directly related to the presence of oxygen which has permeated
the coating material causing a decrease in the photochromic response
by the formation of unwanted side products. Wilson 39 examined the
330 M. T. Goosey
Saran (PVdC)
E
c:
~0.8
~
~
u
c:
ra
.Q
L.
o
'"
~ 0-4
o 10 20 30 40
Exposur,z (min)
Fig. 10. Effect of matrix on photochromic fatigue due to oxygen.
Polymer P((em 3 em x 1O-- 1")/(s em 2 (em Hg»
Estane 5715 70
Diatcon MGIOI 10
Epikote 1009 2
Saran 310 0·3
photoinduced fatigue of these photochromics in various polymeric

matrices and correlated this with the oxygen permeability of the
polymers. Figure 10 clearly shows that the rate of fatigue is greatest for
the photochromic in the polymer matrix with the highest oxygen
permeability. Material developments have now produced photo-
chromics of greater fatigue resistance and with the correct selection of
film base materials and the judicious use of antioxidants the problems
of oxygen induced fatigue have been significantly reduced.
6. PERMEABILITY EFFECfS IN ELECfRlCAL AND

ELECfRONIC COMPONENT COATINGS
Polymeric coatings are widely used in the electrical and electronics

industries because of their excellent electrical properties. One of their
most important functions is to provide electrical insulation and dielec-
tric isolation for active and passive electronic components. Another
important function is to provide protection from deleterious environ-
ments such as moisture, heat, salt spray, oxygen, radiation, microor-
ganisms and solvents. Such coatings thus play a vital role in the
successful operation of electronic equipment and the possibility of
penetrant permeation in such coatings is obviously of serious concern.
In the early days of integrated circuit manufacture these devices
were encased in hermetically sealed metal or ceramic packages in
order to impart protection from the outside environment and to allow
easy handling. However this procedure was expensive and not suited to
the rapid rates of production required by the cost conscious electronics
industry. During the 1960s an alternative method, plastic encapsula-
tion, began to become an increasingly important and much cheaper
method of packaging circuits. This method involves mounting the
device or chip on to a metal preform known as a lead frame which is
then placed in a transfer moulding press and a rigid thermosetting
polymer moulded around it. The main attractions are the relative cost
compared to the labour intensive hermetic packaging methods and the
compatibility with mass production techniques which allows several
hundred devices to be moulded in less than 2 min. Transfer moulding
has become increasingly popular and today a large proportion of the
total production of solid-state devices is now encapsulated in plastic.
Unfortunately, plastic encapsulated devices are less reliable than
hermetically sealed devices because the plastic encapsulants are
permeable to atmospheric gases and moisture. As these encapsulants
are in intimate contact with the chip surface diffused moisture may
cause corrosion and eventual failure of the microcircuit. Hence the
process of encapsulating devices in plastic to protect them from hostile
and potentially corrosive environments may itself give rise to corrosion
induced failures.
The increasing demands for further miniaturisation of electronic
circuitry have caused the electronics industry to produce smaller and
smaller integrated circuits to meet these requirements. Consequently
332 M. T. Goosey
the size of the aluminium metalisation that interconnects the various

active regions of the chip has been reduced to the order of only a few
microns wide. The accompanying increases in packing density mean
that conductors will be packed as close as possible and tracks
separated by several microns would be considered well spaced. If a
voltage is applied to a device in normal operation the potential
gradient between adjacent tracks will typically be around several
million volts per metre. Such a high potential gradient is one of the
fundamental requirements for corrosion problems to occur on the chip
surface. The other requirement is the presence of an aggressive solu-
tion so that electrolytic corrosion can take place. In the case of the
originally hermetically sealed devices there is no possibility of any
moisture from the atmosphere reaching the circuit because the metal
and ceramic packages are impervious to both moisture and gases.
Unfortunately plastic encapsulating compounds are not impervious and
moisture can permeate through the bulk of the package to the circuit
surface. This, whilst in itself being undesirable, is not as bad as an
electrolyte appearing at the chip surface, since the neutral pH of the
water would not cause any serious attack on the aluminiums passivat-
ing oxide layer. An aggressive electrolyte is unfortunately produced
because the encapsulating resins contain impurities from their man-
ufacture which are transported to the circuit surface by the diffusing
moisture. This is particularly the case with epoxide resins which are the
most commonly used microcircuit coatings, although the same occurs
to a lesser extent with silicones which are also used for certain
applications.
In the case of epoxide encapsulants their preparation involves a
multistage synthesis and sodium hydroxide is extensively used in the
initial stages. An olefin is converted to a chlorohydrin with hypochlor-
ous acid. The chlorohydrin is then treated with sodium hydroxide to
give the epoxide ring and sodium chloride.
Various amounts of sodium and chloride ions are thus found in the
final product, depending upon the methods of purification used. Ionic
impurities are also introduced at a later stage when the resin is
formulated into a moulding compound by the addition of fillers,
thixotropic agents, catalysts, hardeners and flame retardants. Any

moisture diffusing through the encapsulating material will pick up
these ionic impurities and become a corrosive electrolyte by the time it
has permeated the bulk of the encapsulant and reached the microcir-
cuit surface.
Aluminium generally possesses a very good resistance to corrosion
even though it has a high free-energy of oxidation which is usually
indicative of a strong tendency to corrode. Aluminium does in fact
corrode very rapidly but it quickly becomes covered with a thin
« 10 nm) passivating oxide layer which renders it resistant to further
corrosion. This oxide layer is normally stable but at low and high pH,
dissolution and precipitation as aluminium hydroxide at a more neutral
site can occur. In the presence of chloride ions a self-sustaining
corrosion reaction can be initiated which may lead to eventual device
failure. The autocatalytic corrosion reaction occurring between mois-
ture, chloride and aluminium can be represented by the following
equations.
AI(OHh + cr ~ Al(OHhCI + OH- (2)
The underlying aluminium then reacts:

Al+4Cr ~ AlCI4+3e- (3)
which then reacts with moisture

2Al(OHh + 6H+ + 8cr (4)
1
eqn (2)
The diffusion of moisture in the plastic of an encapsulated device has
been demonstrated by several workers using a variety of techniques.
Dycus40 reported two major uptake rates in plastic moulding com-
pounds, one fast and one slow. The fast rate was ascribed to.. the
moisture uptake mechanism that is responsible for moisture dependent
failures in standard encapsulated devices. The slower rate of sorption
was thought to be due to uptake by the filler. Moisture permeation was
studied in this case by a gravimetric method on a variety of standard
moulded packages and 2 in ASTM standard plastic discs. Seven epox-
ide novolac formulations were studied and they all behaved in a similar
manner.
Yamaguchi41 examined the water sorption and permeabilities of a
variety of epoxide resins in the context of their use as electronic device
334 M. T. Goosey
encapsulants. The effects of both the curing agents and fillers upon the
diffusion coefficients and solubilities of the epoxide were examined.
The results not only confirmed that the diffusion coefficients for
moisture were decreased by the use of fillers but that the use of a
surface treated filler decreases the solubility coefficient more than if a
non-surface-treated filler were used. Diffusion coefficients were found
to decrease with increasing filler contents up to a limiting volume
concentration. Above this figure there was an extraordinary increase in
the diffusion coefficient, presumably because macroscopic cavities were
created in the material. This work also showed a large variation in the
water vapour permeabilities of the epoxides for the various curing
agents used. Acid anhydride cured epoxides had large diffusion coeffi-
cients whilst amine cured resins had large solubility coefficients.
Various methods have been developed for testing the acceptability
of a given moulding compound in terms of the reliability it imparts to
an encapsulated device. It is usually impractical to assess the effects of
moisture permeability on device performance using normal service
conditions because the results take such a long time to obtain. Conse-
quently accelerated life tests are used to evaluate plastic encapsulated
devices in relatively short time periods. The devices are subjected to
conditions of temperature, humidity and electrical bias which will
cause failures within a few hundred hours rather than several years.
One such set of conditions requires the devices to be exposed to 85%
relative humidity at 85°C, usually with some form of applied bias. The
electrical properties of the device are monitored during the exposure
and it is deemed to have failed when either it ceases to function or
some of its electrical properties exceed those laid down in the specifi-
cations for that device.
In order to evaluate the properties of encapsulating resins various
workers have utilised passive chips consisting of a metallisation pattern
to which a bias can be applied and the resistance measured. Any
corrosion occurring at the chip is revealed by an increase in the
resistance of the metallisation as the aluminium is corroded away. Berg
and Paulson 42 used such a device to investigate chip corrosion in
plastic encapsulated devices exposed to accelerated life test conditions
of 85°C and 85% r.h. and they found that there was an induction time
before failure occurred which was a strong function of the polymeric
class of encapsulant used. The induction period was taken as being
indicative of the time required for moisture to penetrate the plastic
coating and initiate corrosion. Their results for three different types of
Epoxy A
Epoxy 8
100
/
80
..
c:
~ 40
~
20
Silicone epoxy
a 1000 2000
h
Fig. 11. Failure versus time for devices encapsulated in different materials.
(After ref. 42.)
epoxide moulding compound and a silicone epoxide copolymer are

shown in Fig. II.
Another method of monitoring the permeation of moisture and ionic
contaminants through the encapsulation of a device is to monitor the
leakage current at the chip-moulding compound interface by applying
a potential to two conductors on the chip surface and monitoring the
current flowing between them. Sim and Lawson 43 studied the influence
of plastic encapsulants and passivation layers on the corrosion of thin
aluminium films subjected to humidity stress. Part of this work utilised
an interdigitated metallisation test structure which allows surface con-
ductivities to be measured. When devices were exposed to an environ-
ment of 110°C and 90% relative humidity the die surface leakage
current was initially low but rose as water began to permeate the resin
and reach the chip. This work examined epoxide novolacs, epoxides
cured with anhydrides, silicone epoxides and silicones. The increase in
surface conductivity after the initial induction period was particularly
large for the epoxide novolac resin. One of the epoxide anhydrides
showed steadily increasing surface conductivity with time from the
beginning of the exposure. This behaviour may have been due to the
hydrolysis of residual anhydride groups to acid groups by the diffusing
moisture.
A particular variety of electronic devices known as complementary
metal oxide semiconductors (CMOS) are sometimes extremely sensi-
tive to moisture and ionic contaminants in a plastic encapsulating
336 M. T. Goosey
compound. (The term CMOS refers to the method of fabrication of the

semiconductor elements on a device and further description is beyond
the scope of this article.) The two main reasons for this enhanced
sensitivity are the properties of the gate oxide and the higher operating
voltages that are used. One common failure mechanism in these
devices is known as parasitic MOS formation. In CMOS devices
sensitive to surface effects the accumulation of charge on the silicon
oxide surface causes an inversion layer or channel to form in the silicon
beneath the oxide as though a metal electrode with d.c. voltage were
provided on the oxide layer. Wakashima et al. 44 studied the effects of
plastic encapsulant properties on the parasitic MOS formation
phenomenon. The main conclusions of this work were that bulk charge
motion in the encapsulant was a dominant factor in causing parasitic
MOS formation. The major carrier of the mobile charge in the epoxide
resin was not electrons or dipoles but negatively charged ions and the
principal suspect was the chloride ion. CMOS devices are also sensitive
to the presence of sodium ions and the diffusion of these from the
plastic coating to the chip can cause an increase in the threshold
voltage of p-channel transistors and a decrease in the threshold voltage
of n-channel transistors or a decrease in the field inversion voltage of
n-type resistors. Koshiba et al. 45 investigated the reliability of resin
coated electronic components in terms of the moisture proof charac-
teristics of the coating. Various kinds of epoxide resin coatings for
CMOS large-scale integration integrated circuits were studied. It was
found that the deterioration in moisture permeability characteristics
tended to stop at a certain level and that chloride ions and moisture
permeabilities were closely related to the reliability of the compounds.
Polymer coatings are not only used as encapsulants for electronic
components; they find uses in all areas of the electrical and electronics
industries. One of the most common and also most important uses of
coatings in this area is as sheaths for cables and wires. The perfor-
mance of such a coating is of the utmost importance since the cable
sheath will be required to impart dielectric properties for many years
often in the most inhospitable and inaccessible places. Undersea tele-
rhone cables, once layed, cannot easily be serviced and the cable
slleathing must be able to protect the conductors from the corrosive
components of seawater.
A common problem encountered with polyethylene or crosslinked
polyethylene insulated cables is that of electrochemical treeing. Tree-
ing is attributed to the simultaneous action of an electric field and
moisture which is either initially present in the cable or has permeated

through the sheathing and shielding. Bobo et al. 46 studied the migra-
tion of water in such a cable coating system and found that one of the
major influencing factors was the permeation of moisture.
Enamels are also extensively used as wire coatings in the windings of
motors, coils and transformers. In order to obtain optimum perfor-
mance from such a component the individual windings must be as
closely wrapped as possible and this means that very thin enamel
coatings are employed. Such components must function with high
reliability under diverse environmental conditions and so the wires
require stable insulation. Minami et al. 47 investigated the deterioration
of motor windings under environmental stress and the results indicated
that such enamel wire coatings have weak insulative points due to the
presence of imperfections on the underlying wire. The insulative
capabilities of the coatings were greatly reduced with the application of
electrical stress under high humidity conditions because the moisture
penetrated the coating at its weak points by electro-osmosis. A de-
terioration of the mechanical and electrical properties of the enamel
was also noted and this was attributed to hydrolysis of the coating by
permeating moisture.
7. CONCLUSIONS
Whilst there has been much interesting and revealing work carried out
on the permeability of organic protective coatings to moisture, gases
and ions, there are still many confusing aspects and unanswered
questions. Much of the published data only partially explains the
mechanisms of substrate protection and there is no doubt that in a lot
of the systems studied the protective role of the coating is very
complex and little understood. In particular there is still no clear
correlation between coating permeability, interfacial adhesion and the
onset of corrosion. Further work needs to be done to clarify the
dependence of corrosion upon adhesion and the influence of permea-
tion and permeating species on adhesive strength degradation. There is
obviously also a need for new high purity materials wl:J.ich possess low
permeabilities to deleterious species and yet also have good adhesion.
These two aims are somewhat mnflicting because it is generally agreed
that the introduction of polar groups into a coating structure, whilst
improving its adhesive properties, also increases the moisture permea-
bility.
338 M. T. GODsey
With continued effort further knowledge of all the factors influenc-

ing the protective properties of a coating will be gained and this may
not only enable better use to be made of available coatings but also
lead to the development of new materials.
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34. A. L. Glass and J. Smith, J. Paint Techno/., 39, 490 (1967).
35. W. W. KitteIberger and A. C. Elm, Ind. Eng. Chem., 44, 326 (1952).
36. P. Walker, Paint Technol., 31, 15, 22 (1967).
37. D. Y. Lou, G. M. Blom and G. C. Kenney, J. Vac. Sci. Technol., 18, 78
(1981).
38. T. W. Smith, G. E. Johnson, A. T. Ward and D. J. Luca, Proc. Spie. Int.
Soc. Opt. Eng., 329, 236 (1982).
39. A. E. J. Wilson, Private communication, Plessey Research (Caswell) Ltd,
1983.
40. D. W. Dycus, Proc. 18th Annual Reliability Physics Symposium, IEEE,
1980, p. 293.
41. H. Yamaguchi, Proc. 15th Electrical/Electronic Insulation Conference,
Chicago, 1981, p. 159.
42. H. M. Berg and W. M. Paulson, Microelectron. Reliab. 20, 247 (1980).
43. S. P. Sim and R. W. Lawson, Proc. Int. Rei. Phys. Symp., 1979.
44. Y. Wakashima, H. Inayoshi, K. Nishi and S. Nishida, Proc. 14th Annual
Reliability Physics Symposium, IEEE, 1976, p. 223.
45. S. Koshiba, S. Yamashita and K. Kanol, Bull. Electrotech. Lab., 40, 3
(230).
46. J. C. Bobo, E. Papirer, M. Prigent and J. Schulz, lEE Cont. Publ., 177
(Int. Cont. Dielec. Mater. Meas. Appl. 3rd) 235, 1977.
47. M. Minami, M. Maeda and H. Yamaguchi, Proc. 14th
Electrical/Electronics Insulation Conference, IEEE, October 1979, p. 56.
Chapter 9
The Role of Water Transport in

Composite Materials
GAD MAROM
Casali Institute of Applied Chemistry, School of Applied Science and
Technology, The Hebrew University of Jerusalem, Israel
1. Introduction. . . . . . . . . . . . . . . . . . . . . 341
2. Mechanisms of Moisture Penetration. . . . . . . . . . 342
2.1. Water transport in the matrix phase. . . . . . . . 342
2.2. Mechanisms of moisture penetration in composites. 349
2.3. Effect of external loading . . . . . . . . . 357
3. Hygroelasticity and Dimensional Changes . . . . . . . 362
3.1. Hygroelasticity of the matrix phase . . . . . . . . 363
3.2. Hygroelasticity of fibre-reinforced composites . . 366
4. Hygrothermal Ageing and Effects on Mechanical Perfor-
mance . . . . . . . . . . . . . . . . . 368
4.1. Chemical effects. . . . . . . . . . . . . . . 368
4.2. Effects on glass transition temperature. . . . . 369
4.3. Internal stresses and micro-damage . . . . . . 371
4.4. Durability of composites in moisture conditions. 372
References . . . . . . . . . . . . . . . . . . . 373
1. INTRODUCTION
The last few years have witnessed a tremendous growth in the use of
composite materials in various fields, spanning the whole range from
sporting goods to structural materials for the aerospace industry. Such
applications almost invariably entail contacts with liquids or vapours-
either aqueous or organic-bearing on both the immediate and the
long-term performance of the material. Hence, problems pertinent to
the role of permeability of composite materials must be of prime
consideration as limiting factors. This applies particularly to the most
common phenomenon of moisture penetration.
The broad subject of interactions between polymeric composite
materials and liquid or vapour environments has been and currently is
341
342 Gad Marom
the theme of numerous studies. Most of them can be classified into

three topics representing three conceptual approaches. The first fo-
cuses on the actual mechanisms of penetration, where emphasis is
given to questions related to transport kinetics and to diffusional
processes. The theme of the second topic is the studying of the
dimensional response of the composite, termed hygroelasticity, where
one is confronted with questions such as how much the structure
swells, and what is the magnitude of the internal stresses which
develop in it. The third topic is concerned with the deterioration of the
original properties due to the attack of moisture and it investigates the
environmental effect on the residual properties.
A systematic method for investigating and understanding these
phenomena in composite materials is to initially define and character-
ise them in the unreinforced polymeric matrix. Thereafter, additional
effects contributed by the presence of the reinforcement and of the
interface appear clearly.
In the next sections the three topics outlined above are reviewed
with emphases on effects typical of the polymeric matrix, and on those
derived from the presence of the reinforcement. The review is divided
into two parts: the first-Section 2 below-deals with the essence of
moisture permeability in composites mostly from a mechanistic view-
point. The second part discusses the results of the moisture
presence-Section 3 presents the aspect of dimensional change (swell-
ing) and Section 4 addresses the effect of moisture on deteriorating
the mechanical performance.
2. MECHANISMS OF MOISTURE PENETRATION
2.1. Water Transport in the Matrix Phase

Matrices for advanced composite materials usually comprise
crosslinked polymers with high glass transition temperatures, so that
the polymer under the variable service conditions is mostly in its glassy
state. It is therefore relevant to examine water transport in glassy
polymers.
Diffusion is the process by which matter is transported from one part
of the system to another as a result of random molecular motion. The
motion of a single molecule can be described in terms of the 'random
walk' picture. It is possible, statistically, to calculate the mean-square
distance it has travelled in a given time interval, but it is impossible to
The role of water transport in composite materials 343
predict in what direction a given molecule will have moved In that

time.
In general, diffusion behaviour and transport in glassy polymers have
been classified according to the relative rates of mobility of the
penetrant and of the polymer segments. 1 Such classification produces
three basic categories of behaviour as follows:
(i) Case I, or Fickian diffusion, in which the rate of diffusion is
much less than that of the polymer segment mobility. Sorption
equilibrium is rapidly established, leading to time-independent
boundary conditions which exhibit no dependence on swelling
kinetics.
(ii) Case II (or Super Case II) , the other extreme in which diffu-
sion and penetrant mobility are much greater compared with
other relaxation processes. Sorption processes are strongly
dependent on swelling kinetics.
(iii) Non-Fickian, or anomalous diffusion which occurs when the
penetrant mobility and polymer segment relaxation are com-
parable. This diffusion is related to the fact that the polymers
in which it is observed are hard or glassy, and it vanishes at
and above the glass transition temperature.
Case I (Fickian) and Case II can be viewed as the two limiting types
of transport processes with anomalous diffusion being between them.
They can be distinguished by the shape of the sorption-time curve
represented by
(1)
where M t is the relative weight gain at time t, Moo is the eqUilibrium
relative weight gain and k and n are constants. 1 For Fickian systems
moisture moisture
Fig. 1. A schematic presentation of one-dimensional diffusion of a specimen

exposed on both sides to moisture.
344 Gad Marom
n =!, while for Case II n = 1 (and for Super Case II n > 1). For
anomalous systems ! < n < 1. For Fickian uptake by a specimen of
thickness b exposed on both sides to the same environment, as shown
schematically in Fig. 1, mass uptake is related to time by the following
eqn (2) where D is the diffusion coefficient.
M, = ~ (Dt) 1/2
(2)
M= b 7T
2.1.1. Fickian Diffusion

Some of the characteristic features of Fickian diffusion are as follows: 3
(i) Both sorption and desorption curves as functions of the square
root of time are linear in the initial stage.
(ii) Above the linear portion both absorption and desorption
curves are concave to the abscissa.
(iii) The sorption behaviour obeys the film thickness scaling law,
i.e. reduced sorption curves for films of different thicknesses
are all superimposable.
(iv) When D is constant the absorption and the desorption curves
coincide over the entire range of t.
(v) The temperature dependence of D can be expressed by the
Arrhenius relation
D = Do exp (-Ea/RT) (3)
where the pre-exponential term, Do, is the permeability index,

Ea is the activation energy of the diffusion process and R is the
gas constant.
The moisture diffusion coefficient, for example, may be determined
readily by exposing a thin dry specimen (after recording its dry weight)
to a consta 1t moisture environment, monitoring and plotting its weight
gain versu~ /1/2. Such results for an epoxy resin are demonstrated in
Fig. 2. The diffusion coefficient is then calculated by
(4)
where k is the slope of the linear portion of the plot of M, versus t 1/2
(Fig. 2). This experiment obviously assumes one-dimensional penetra-
tion and therefore a thin specimen (compared with the other dimen-
sions) should be employed to minimise the edge effect.
30
20
10
k·4~" il
6 8 10 12 14 16 18 20
«( h'lZ)
Fig. 2. Moisture gain as a function of square-root of time for an epoxy resin of
the diglycidylether of bisphenol A cured with a stoichiometric amount of
m-phenylenediamine. Water immersion at 95°C, D = 6·3 X 10- 12 m 2 S-1.
2.1.2. Case II and Non-Fickian Diffusion

Deviations from Fickian diffusions usually accompany diffusion of
organic vapours into glassy polymers. According to a recent review of
sorptbn and transport in glassy polymers,4 the non-Fickian, anomalous
diffusion, Case II and Super Case II behaviour as well as the dual
mode sorption (see below) are interrelated and are direct consequences
of the glass transition in these systems. The nature of that glass
transition is as yet far from being fully understood and there exists no
general theory for anomalous diffusion in polymers. Extensive reviews
have been published of experimentally observed diffusion anomalies in
various polymer systems. 5 ,6 These reviews contain many references to
original papers and the readers are referred to these works for further
discussion. As indicated below these anomalies by and large do not
apply to composites, and thus in view of the almost classical Fickian
behaviour of most water-composite material interactions we shall only
point out the typical features of anomalous phenomena and the
principles of the various existing theoretical modes.
Case II diffusion, originally studied by Alfrey, 1 is characterised by
the development of a sharp boundary between the outer swollen shell
surrounding the inner glassy core of the polymer. The polymer glass on
the swollen side of the boundary attains equilibrium immediately,
while at the boundary there is a discontinuity in the solvent penetrant
concentration. The boundary advances at a constant velocity-being
the basic parameter of Case II diffusion-and the core diminishes in size
346 Gad Maram
Fig. 3. A cross-section of a polymethylmethacrylate specimen exposed to

methanol (containing iodine to improve contrast) at 60°C. The swollen shell
and the unswollen core typical of Case II diffusion are evident.
until all the polymer attains equilibrium penetrant content. An exam-

ple of Case II diffusion is shown in Fig. 3.
Figure 4 presents a schematic description of the major sorption
anomalies that have been reported. 2 They are
(i) Pseudo-Fickian behaviour: The sorption and desorption curves
when plotted against t 1/2 show anomalously short initial linear
portions, and/or the sorption curves depart from the film
thickness scaling law.
(ii) Sigmoid behaviour: The sorption curves are sigmoid in shape
with a single inflection point at about 50% equilibrium sorp-
tion. The initial rate of desorption exceeds that of sorption, but
desorption then becomes slower and the curves cross.
_ ~------~t---------1
Fig. 4. A schematic presentation of some major sorption anomalies.

(iii) Two-stage sorption behaviour: The initial uptake is rapid and a

linear function of t 1/2. The sorption curve then approaches a
quasi-equilibrium followed by a slow approach to a final true
equilibrium.
A number of models have been proposed to describe anomalous

behaviour, but all of them are designed to only describe certain
features of the behaviour. Following is a very brief outline of the
principal assumptions of some of the models.
According to the time dependent boundary conditions modeC the
sorption process is still diffusion-controlled. The surface concentration
attains an initial value instantaneously then rises exponentially to a
new equilibrium value. The Berens-Hopfenberg first order relaxation
model 8 considers absorption as a contribution of two independent
processes, namely, Fickian diffusion and molecular relaxation. The
combination of Case I and Case II models9 takes into account the
internal stresses that arise from the swelling of the polymer, and
considers the velocity of solvent penetration as a direct consequence of
the internal stress effect. Both the diffusion coefficient and the velocity
are assumed to be constant. The dual mode sorption models 10- 13
assume that the penetrant molecules are divided into two populations,
one which is dissolved in the polymer and is able to diffuse and another
which is sorbed into microvoids (holes) and is at least partially im-
mobilised.
2.1.3. Applicability to Composites

The applicability of anomalous diffusion to composites has two
aspects: the first is its occurrence in systems of water and crosslinked
resins (such as epoxies), and the second is its occurrence in water-
composite systems. Recent studies of water-resin interactions under
various exposure conditions have shown various kinds of anomalous
behaviour. In Fig. 5, for example, sorption data for two epoxy resins
immersed in water at 98°C are presented. Since only one sorption
curve is needed to adequately represent the data for each resin, one
can conclude that the diffusion processes are essentially Fickian. How-
ever, concentration dependencies of the diffusion coefficients are ob-
served when the sorption data are compared to theoretical curves
based on constant diffusion coefficients. Another typical example of
deviation from Fickian behaviour in water-epoxy systems is the evi-
dence of a two-stage sorption process under immersion conditions or
348 Gad Maram
Calculated Fickian
/~l-------=-:==--_
/
I
I
I
I
o 5 10
'It (days) 1/2
Fig. 5. Experimental moisture absorption data for DGEBA/DDM and

TGDDM/DDS epoxies immersed at 98°C, compared with calculated Fickian
curves assuming constant diffusion coefficients of 7·0 x 10- 3 and 2·7 x 10- 3 cm 2
day-I (8·1 x 10- 12 and 3·1 x 10- 12 m 2 S-I), respectively.
1-1.02mm
2-0.76 mm
3-051 mm
4-030 mm
10 20 30 40 50
{fIb (h I/2 mm- l )
Fig. 6. Moisture absorption data by immersion at 70°C for DGEBA/m-

phenylenediamine epoxies of four thicknesses showing that only the linear
stage is scaled by the film thickness (ref. 15).
high relative humidities. 14 Also, typical anomalous behaviour is the

breakdown of the film thickness scaling law (itself a valuable diagnostic
for Fickian diffusion), stating that the reduced sorption curves of
samples of different thicknesses are superimposable. This is demon-
strated in Fig. 6.
As far as composite materials are concerned the most striking
phenomenon with regard to the anomalous behaviour is its diminishing
or even complete disappearance with the introduction of the reinforce-
ment. Considering the complexity of the sorption behaviour of the
bulk resin, the almost classical Fickian behaviour of the composites
comes as a surprise and represents a welcome simplification. An
explanation drawn by analogy with the size dependence of relaxation
controlled diffusion effects,16 suggests that the matrix sections between
the fibres and, therefore, the path length are too small, hence the
contribution of the relaxation controlled behaviour disappears. 17
2.2. Mechanisms of Moisture Penetration in Composites

Moisture penetration into composite materials is conducted by one
major mechanism, namely diffusion. This mechanism involves direct
diffusion of water molecules into the matrix and, to a much lesser
extent, into the fibres. It depends on the angle between the penetration
direction and the fibres, the angular dependence resulting from the
variation with the angle of the matrix cross-section available for direct
diffusion.
The other common mechanisms of moisture penetration into compo-
site materials are capillarity and transport by microcracks. Each of
them becomes active only after the occurrence of specific damage to
the composites. Frequently, that damage, which enhances moisture
penetration by activating those additional mechanisms, is in itself a
direct consequence of the exposure of the composite to moisture. The
capillarity mechanism involves flow of water molecules along the
fibre-matrix interface followed by diffusion from the interface into the
bulk resin. It is not active unless debonding between the fibres and the
matrix has occurred, often as a result of water attack at the interface.
Transport of moisture by microcracks involves both flow and storage of
water in microcracks or other forms of microdamage which result from
environmental effects or from service conditions. The activation of
these mechanisms is distinguished in increasing both the rate and the
maximum capacity of moisture absorption in an auto-accelerative
manner.
350 Gad Maram
2.2.1. The Diffusion Mechanism

The diffusion of moisture into fibre-reinforced composites comprising
glassy crosslinked resin matrices such as epoxy resins is experimentally
shown to be Fickian (or anomalous Fickian), and to be governed by a
diffusion coefficient. The analysis is based on the analogy between the
thermal diffusivity (heat transfer) and mass diffusivity.18 The
diffusivities of the composite material depend on those of the matrix,
D m , and of the fibres, D f, and on the volume fraction of the fibres, cf>f.
For fibre-reinforced composites two diffusivities are defined, one paral-
lel (longitudinal) and another perpendicular (transverse) to the fibre
direction, denoted Du and D 22 , respectively.
The directional diffusivities depend on the geometry and composi-
tion of the cross-section of the composite perpendicular to the diffusion
direction. Hence, for a unidirectionally reinforced material the lon-
gitudinal diffusivity is simply given by a rule-of-mixtures expression
(5)
The transverse diffusivity is a more complex function of cf>f, as follows:
where
(7)
Since moisture diffusion in most fibres used for reinforcement is zero
or very small compared with that of the matrix D f « Dm and eqns (5)
and (6) reduce to
(8)
and
(9)
Equations (8) and (9) merely express the longitudinal and transverse
diffusivities of the unidirectional composite as a function of the
diffusivity of the matrix and of its available cross-section in the
diffusion direction.
Let us now consider a unidirectionally reinforced composite plate
whose sides are aligned with the x, y and z axes of a coordinate
)',-'-"'---- )(
Fig. 7. A unidirectionally reinforced composite plate whose sides are aligned

with the x, y and z axes of a coordinate system and its fibres forming the
angles 0/, /3 and y with respect to the three axes.
system, and whose fibres form the angles a, (3 and 'Y with respect to
the three axes, as shown in Fig. 7. The axial diffusivities are expressed
by a transformation of the directional diffusivities, Dll and D 22 , as
follows:
Dx = Dll cos 2 a + D22 sin 2 a }
D, = Dll cos 2 (3 + D22 sin2 (3 (10)
D z = Dll cos 2 'Y + D22 sin2 "!
The total moisture diffusion into the specimen shown in Fig. 7
results from diffusion into the six sides, and it therefore depends on the
directional diffusivities and relative dimensions of the plate. (The
interactions of the different sides are neglected.) By analogy with eqn
(2) we obtain
(11)
which, in terms of a total (overall) diffusion coefficient for the compo-

site, Dc, may be re-written as
(12)
where
(13)
Equation (13) which expresses the total diffusion coefficient may also
352 Gad Maram
be useful for determining the edge effect in a diffusion experiment

carried out with a thin plate of homogeneous material. Here the
diffusion is isotropic with Dx = Dv = D z, resulting in
(14)
where Dx is the isotropic diffusion coefficient of the homogeneous

material.
Coming back to the anisotropic case presented by eqn (13), we
further notice that the axial diffusivities may be expressed in terms of
the directional coefficients (eqn (10)), which in turn are functions of the
diffusivity of the resin and of the volume fraction of the fibres (eqns
(8) and (9)). Incorporation of those equations in eqn (13) results in
Dc = D [(I- cl>f) cos 2 a + (1- 2";cl>r/7r) sin 2 a]

II1
X [1 +~ (I-cI>f) cos 2 (3 + (1-2..r;;;;;;) sin 2 (3)1/2

I (1- cl>f) cos 2 a + (1- 2";cl>br) sin 2 a
+k (1- cl>f) cos 2y+ (1- 2..r;;;;;;) sin2y)I/2]2 (15)
W (1- cl>f) cos 2 a + (1- 2";cl>f/'IT) sin2 a
When the diffusion experiment is carried out with a very thin plate
b b
/« 1 and w « 1 and eqn (15) reduces to
Dc = D «I- cl>f) cos 2 ex + (1- 2../cl>r/'IT) sin 2 a)
II1 (16)
It is noted that the common case with composite structures is that
the reinforcement lies within the plane of the structure, that is a = 90°.
In such cases and provided that the edge effect is negligible we obtain
(17)
Finally, it is possible to generalise eqn (15) to accommodate for a

laminate constructed of laminae with various fibre orientations. How-
ever, as long as the structure thickness is small compared with the
other dimensions and ex = 90°, eqn (17) applies.
In conclusion, Fig. 8 presents a typical diffusion curve for a unidirec-
tional graphite fibre-epoxy composite, and Table 1 lists some typical
values of diffusion coefficients.
The role of water transport In cumposite materials 353
2.4
22
2.0
18 .
~ 1.6
~ 14
":f 1.2
10
0.8
0.6 k=O.157 %h-" 2
0.4
0.2
8 12 16 20 24 28 32 36
ft (h"2)
Fig. 8. A typical diffusion curve for a unidirectional graphite fibre-reinforced

epoxy, <PI = 0·60 (Scotchply SP-313) in water at 98°C, D = 0·72 X 10- 12 m 2 s 1.
2.2.2. Damage Dependent Mechanisms

We now turn to discuss the two damage dependent mechanisms: (i) the
capillary flow of moisture along the fibre-matrix interface; and (ii) the
diffusion through cracks, pores or small channels present in the mater-
ial. These two mechanisms are active in addition to the diffusion.
However, it is pointed out that although moisture penetration is
composed of three mechanistically different components, the overall
empirical picture is one of Fickian diffusion and can be conveniently
treated accurdingly. In other words, the penetration is characterised by
a diffusion coefficient measured experimentally as described in Figs 2
and 8.
The theoretical and experimental problems of determining capillary
flow and transport through micro-damage have not been solved yet,
and only a few direct measurements of interfacial flow and its effects
are available. However, there are clear indications and indirect evi-
dence of the occurrence of these mechanisms.
Such indirect evidence has recently been provided based on two
separate calculations of the diffusion coeffi~ients of glass fibre rein-
forced epoxies and of graphite fibre reinforced epoxie~? I The first
calculation is based on the value of Dm as measured experimentally for
the pure resin. The second calculation is based on the value of Dm
derived from that of Dc by eqn (15). The results (and the experimental
conditions) presented in Table 2 show that the values of Dll and D 22 ,
w
V>
.j:>.
TABLE 1
Examples of Diffusion Coefficients (10- 12 m 2 s-') for Composite Materials
Material Exposure conditions D11 D22 Reference
Carbon-epoxy, <Pf=0'55 98% relative humidity, 60°C
After 11 years immersion in OSS}
distilled water 98% relative humidity, 60°C 1·26 19
After 11 years immersion in
seawater 98% relative humidity, 60°C 1·33
Graphite-epoxy, <Pf= 0·60 Immersion, 75°C 1·62 063}

Second cycle Immersion, 75°C 4·89 1·36 23
~
Third cycle Immersion, 75°C 7·14 1·75
'"'-"
Graphite-epoxy, (0/90)~so <Pf = 0·60 Immersion, 25°C ~
Immersion, 60°C 0·20
OOS) Cl
~
Immersion, 80°C 0·46
26
Stressed to 25% of uts,a 60°C 0·39
Stressed to 45% of uts, 60°C 0·37
Stressed to 60% of uts, 60°C 1·17
Glass-epoxy, <Pf = O· 50 Immersion, 98°C 1·69 0·68 } 21

Under 3·6 MPa stress 1·75 0·71
Kevlar-epoxy, (0, 90±45), <Pf= 0·52 76% relative humidity, 21°C 6·10 (in plane) 0·02 20
a uts = ultimate tensile strength.
h 2s, according to the conventional notation for composite laminations denotes double and symmetrical; thus the
particular laminate has a structure of 0/90/0/90/90/0/90/0.

TABLE 2
Comparisons of Dll and D22 Values (10- 12 m 2 S-I) Obtained from
Dm by a Direct Measurement of Resin Diffusivity with those Ob-
tained from the Diffusivities of the Composites Through eqn (15)
(Experimental Conditions: Immersion at 98°C) (Ref. 21)
Material Dm Dll D22
Glass-epoxy composites, <Pf = O· 50 1·90 a 0·95 0·38

3·45 b 1·73 0·70
Graphite-epoxy composites, <Pf = 0·60 1·90 a 0·76 0·24
3·45 b 1·38 0·43
a Result of a direct measurement with unreinforced epoxy.
b From the diffusivity of the composite material.
calculated from those of Dc, are almost twice as high as those calcu-
lated from the experimental value of Dm. It can be shown that this
difference is accounted for by absorption rate, k, higher by 35% in the
composites. The higher Dll and D22 values in the composites are
indicative of a damage mechanism occurring typically in the compo-
sites and not in the pure matrix. Measured changes in thermal expan-
sivities of glass and graphite composites 22 show that a debonding
process starts immediately upon exposing the composites to water. The
debonding enhances moisture penetration by capillary flow along the
interface accounting for the relatively high moisture concentration at
the interfacial region.
In a recent study on graphite epoxy composites of <PI = 0·60, values
of 2,37,1·62 and 0·68xlO-- 12 m 2 s-- 1 have been reported for the
diffusivities of the resin and of Dll and D 220 respectively, at 75°C?3
The diffusivities of the composites are much higher than what would be
expected from the resin. Moreover, when several successive cycles of
absorption and desorption are performed large increases in the diffu-
sion coefficients of moisture absorption are observed, while the value
of the maximum moisture content remains relatively stable. These
results are indeed indicative of a damage mechanism in the composite
microstructure enhancing moisture take-up from the dry state.
When D l l and D22 are measured independently and not calculated
from Dc it is found that DlJ is much higher than D 22 . For example, for
a unidirectional glass fibre reinforced epoxy Dn/D22 ratios of two
orders of magnitude have been reported. 24 These ratios are much
higher than those predicted by eqns (8) and (9) accounting for diffusion
only.
356 Gad Maram
Fig. 9. Debonding at the fibre-matrix interface of a unidirectional E-glass

fibre-reinforced DGEBA epoxy. The debonding is revealed by transverse
fracture testing.
The damage dependent penetration of moisture by flow along the

fibre-matrix interface, shown in the higher D)) values, is, in fact,
auto-accelerative since the presence of water is responsible for de-
bonding and other types of damage at the interface. Figure 9 shows an
example of such damage developed at the surface of a glass fibre of a
reinforced epoxy composite.
-5
--
0~
~
4
3
2
... •
I
o 10 20 30 40 50
(fi" Ib)xIO- 3 ( 5"2 em-I)
Fig. 10. Moisture absorption data for DGEBA/triethylenetetramine epoxy at
45°C. Effect of damage occurring in the first cycle on moisture absorption in a
successive cycle (ref. 25).
The second damage dependent mechanism, namely the flow of

moisture through micro-damage, is best distinguished by comparing
the sorption behaviour of a virgin sample with that of another sample
with a history of a swelling-drying cycle. Figure 10 shows this for an
epoxy resin, and it is seen that the preswelled-dried sample absorbs
about 0·5% more moisture. A similar observation is the so-called
'reverse thermal effect', where after equilibrating a sample at a higher
temperature, reducing the temperature immediately results in addi-
tional absorption. 25 These phenomena are explained by a hygrother-
mal history-dependent microcavity formation process, facilitating
moisture penetration. Since this process occurs in the bulk matrix its
effect on the moisture penetration into the composite is isotropic.
2.3. Effect of External Loading

The effect of external loading on moisture penetration into composite
materials is a markedly relevant issue since it is difficult to imagine any
application of composite materials (even non-structural) which does
not result in SUbjecting them to some form of static or dynamic
loading. The general effect of such loading is to enhance each of the
three main moisture penetration mechanisms discussed in Section
2.2.26,27
The main penetration mechanism, diffusion, may be considered

mechanistically as transport of water molecules through holes in the
polymer structure. The ease of transport mobility depends on the size
of these holes which in turn depends on the free volume, being the
difference between the specific volume of the polymer and the actual
volume of its molecules. The effect of the external loading on the
diffusion mechanism is expected to result from changes in the free
volume of the matrix concomitant with the volume strain of the
composite. The volume strain depends on the level of the external
stress, on its direction with respect to that of the fibre, and on the
Poisson's ratios of the constituents.
With regard to the damage dependent mechanism, capillary flow and
flow-through micro-damage, the external loading is expected to prom-
ote these mechanisms through enhancement of the type of damage on
which they depend. Capillarity depends on debonding, which under
loading at an angle (J -=f 0 to the fibre direction is affected by the
normal-to-the-fibre stress component, while at (J = 0 it is affected by
the shear stress at the interface. The creation of micro-damage in the
matrix, and henco, the acceleration of the corresponding transport
358 Gad Maram
mechanism is obviously directly related to the loading history of the

composite.
2.3.1. Stress Dependent Diffusion of the Matrix

We initially considered the effect of stress on the diffusion coefficient
of the unreinforced matrix. The results presented below derive from a
calculation of the change of the free volume as a function of stress?S
The calculation is based on a model representing a polymer by an
assembly of thick spherical shells as in Fig. 11. Regardless of the size
distribution of holes the shells are assumed to have the same ratio of
inner to outer radii. The volume fraction of the spherical cavity is thus
the same for all shells and represents the free volume fraction. One
such spherical shell would then represent polymer behaviour (Fig. 11).
Applying the Doolittle equation 29 ,3o to the stressed and unstressed
states, successively, and combining the results we obtain
In -
Do
(D,,) (
-a -1 --
VfO
1)
Vf"
(18)
where a is a constant, D" and Do are the diffusion coefficients and V f "
and VfO are the free volume fractions in the stressed and unstressed
states, respectively. The free volume fractio~ increases under tension
and decreases under compression according to
V f" = VfO [ 1 + a(l+v)]

2E = VfO
[ a]
1 + 4G (19)
Fig. 11. Representation of the free volume of a polymer by an assembly of

thick-walled spherical shells (ref. 28.)
where G is the shear modulus, v is Poisson's ratio, E is Young's

modulus and IJ is the external stress. Incorporating eqn (19) into eqn
(18) results in
_
Dcr-Doexp
[(6 toG10)IJ] (20)
which for moderate stresses approximates to
Dcr = Do( 1 + (6 tOGI0)a) (21)
In addition to the functional relationship between the diffusion

coefficient and stress, the rate of moisture absorption, k, and the
equilibrium concentration, M=, are also related to the stress level.
Those relationships have not been fully studied yet, however; since
D ex: (k/M=f it is clear that, only when the stress effect on k is greater
than that on M=, is D affected.
2.3.2. Stress Dependent Diffusion of the Composite 21 •27

Figure 12 describes a unidirectional composite specimen loaded at an
angle 8 to the fibre direction. Here, also, the effect of stress on the
diffusivity is linked to the free volume change of the matrix. In
composite materials the free volume change is a much more complex
function of the stress, being dependent on its direction with respect to
that of the fibre and on the Poisson's ratios of the constituents.
However, two relatively simple cases of longitudinal (8 = 0 0 ) and
IJ
Fig. 12. A schematic description of a unidirectional composite specimen
loaded at an angle (J to the fibre direction.
360 Gad Maram
transverse (8 = 90°) loadings of unidirectionally reinforced composites

are considered below.
The change in free volume fraction of the matrix is in fact equal to
the volume strain experienced by the matrix as part of the volume
strain of the composite. Accordingly, eqn (18) can be rewritten as
follows:
In~:)~b~~ (m~ +vJ (22)
where (A V/VO)rn is the volume strain of the matrix, theoretically given

by Cl'rn/Ern (1-2vrn ), and Cl'rn is a function of 8 and <Pt, resulting in
Cl'JEL (1-- 2vrn) for 8 = 0°. However, this cannot explain experimental
evidence of reduction in moisture absorption under load for low values
of 8. 27 It may be explained by assuming that the Poisson's ratio of the
moisture flexibilised matrix increases, or that in the composite some
interaction between the load carrying fibres and the matrix places the
matrix under lateral compression, producing a negative matrix volume
strain. Postulating that the matrix strain is given by the difference
between those of the composite and the fibres, we have
(23)
where the subscripts c and f denote composite and fibre, respectively.

It is noted that eqn (23) is assumed instead of the rule-of-mixtures
(A V/Vo)c = (A V/VO)m<Pm + (A V/VO)t<Pf
For the longitudinal case (8 = 0°) the fibre volume change can be
written as follows:
( -A~ Cl'f Cl'L

=-(l-2Vf)--(1-2vf) (24)
Vo f E f EL
where L denotes a longitudinal composite property. Also,
(-A~ =Cl'L
- (l-2vLT) (25)
Vo c EL
where VLT is the longitudinal Poisson's ratio of the composite, and thus
( -A~
Vo m
Cl'L
=2-(v -v )
EL f IT
(26)
which, combined with eqn (22), results in a functional relationship

between the external stress, <TL, and the diffusIon coefficient D rr • The
complexity of the composite case is realised noting that a positive
volume strain of the composite does not necessarily result in a positive
strain in the matrix. For example, in a glass fibre composite of
<Pf = 0· 50, VLT = O· 25 and VI = 0· 2, producing a negative value of the
right-hand side of eqn (26) and implying (see eqn (22)) that DO" is a
decreasing function of <T. Similarly, for a graphite fibre composite of
<Pf=O·50, VLT=vf=0·30 and (.:1V/VO)m=O, implying (see eqn (22))
that for that composite D(J" = Do.
In the transverse case (8 = 90°) the volume strain of the matrix is
directly proportional to the external stress, <T,., as follows:
(27)
which is positive for tensile stresses.
°
For other values of 0, (.:1 V/VO)m and, in turn, DO" are expected to
increase as is increased from 0 to 90°. However, it is difficult to
devise an experiment to prove this point since it is difficult to isolate
the effect of the external stress on (.:1 V/VO)m from its other effects, such
as debonding. Indeed, a comparison of the moisture diffusivity of
stressed and unstressed graphite fibre reinforced epoxy (Table 3) shows
that while D" is higher than Do, it is independent of 0, which may be
TABLE 3
Moisture Diffusivities of Free and Stressed (6·7 MPa) Unidirectional Graphite-
epoxy Composites of cPt = 0·60 (ref. 21)
Unstressed Stressed
k M~ 10 1~ m2 s k Moc 10 12 m 2 s- 1
8 (%h l) (%) D, Dll D22 (%h l) (%) Dc DlI D22
0° 0·157 2·32 0·72 1·50 0·47 0·162 2·07 0·96 2·00 0·63
15° 0·133 2·08 0·64 1·30 0·41 0·183 2·28 1·01 2·05 0·65
30° 0·145 2·17 ()·70 1·35 0·42 0·185 2·31 1·01 1·94 0·61
45° 0-151 2-19 0·75 1-36 0·43 0-197 2-40 1·06 1·92 0-60
60° 0-155 2-23 0-76 1-31 0·41 0-214 2-57 1·09 1-88 0-59
75° ()·171 2·20 ()-95 I-58 0·50 0-215 2-46 1·20 2·00 0-63
90° 0-166 2·20 0-90 1-48 0-47 0·215 2·58 1-09 1-80 0-57
Average: 2-20 1-41 0·44 1·94 0-61
~---- - ---------.-~ - - - - - _ . -------------_._---- - - - - - - - - - --- - - - - -
362 Gad Marom
an indication that k, the rate, is affected by some additional mechanism

accelerated by external loading, thereby masking the effect of
(a V/VO)m with f) on k and in turn on DO".
3. HYGROELASTICITY AND DIMENSIONAL CHANGES
Section 2 discusses the main moisture penetration mechanisms in

polymers and composites, while the effects of the moisture presence in
the material are treated only in the narrow sense of their influence on
the penetration mechanism itself. In this section, as well as in Section
4, we focus on specific outcomes of the moisture presence. These are
the dimensional stability, discussed below, and the mechanical integ-
rity, discussed in Section 4.
The hygroelasticity of a polymer or composite is defined as its
reversible dimensional response to liquid or vapour penetration. 31 A
guideline employed in studies of dimensional changes due to swelling is
to develop an analogy between this phenomenon and thermoelasticity.
In thermoelasticity, deformation (strain) is determined by a tempera-
ture change, aT. Correspondingly, hygroelasticity is treated by exa-
mining the relative dimensional change in relation to the absorption
which may be expressed by a number of different ways. Expressing the
absorption in terms of the relative weight gain results in the following
definition of the coefficient of hygroelasticity
aL/Lo
(28)
f.L = aM/Mo
where aL/Lo is the relative length change and aM/Mo is the relative
weight change. Expressing the absorption in terms of weight increase
relative to the original volume results in
aL/Lo
(29)
f.L = aM/Vo
where Vo is the original volume of the material. The second definition
of f.L is more appropriate for composite materials, since Vo is indepen-
dent of the fibre volume fraction. Finally, for convenience, yet another
modification of f.L is sometimes used, namely
aL/Lo
(30)
f.L = av*/v ()
where a v* is the volume occupied outside the polymer by the

penetrating liquid, weighing ilM. It should be noted that il V* is

usually greater than the actual volume change of the material. Thus,
il V* = il V + 8, where 8 accounts for the volume of penetrant
molecules which occupy the free volume or micro-damage sites of the
polymer without causing any volume increase, and for the different
density of the penetrant within the polymer. It can be shown that for a
homogeneous material the upper bound for /.L (for 8 = 0) is 1/3.
Each of the above definitions of /.L ignores, in actual fact, the
problem of the distribution of the penetrant molecules in the polymer.
A perfect analogy between hygroe1asticity and thermoelasticity re-
quires a uniform distribution which is not always the case. The dis-
tribution of the penetrant molecules within the polymer is determined
by and large by the transport mechanism in action and by the geometry
of the specimen. For example, Case II diffusion experienced by a
polymer rectangular plate results, as shown below, in anisotropic hygro-
elastic behaviour.
The process of obtaining /.L requires measurements of ilL/Lo and of
ilM/ Mo for a period of time, and then plotting them against one
another; /.L is worked out from the slope of the resulting curve. In
many cases it is a straight line, in others /.L is a function of ilM/ Mo.
3.1. Hygroelasticity of the Matrix Phase i,
The hygroelastic behaviour of the matrix phase varies with the pene-
tration mechanism, and two categories of behaviour are discussed
below pertaining to Fickian and Case II diffusion.
3.1.1. Fickian Diffusion

Hygroelastic behaviour under Fickian diffusion is isotropic and the
value of /.L is affected by the rigidity (modulus) of the polymer and by
its morphology?2 One aspect of morphology, for example, is the free
volume, which in epoxy resins may be varied by varying the
hardener/epoxy ratio. A decrease in that ratio may generally result in
an increase in the free volume through increasing of the chain
molecular weight between adjacent crosslinks, and ultimately in induc-
ing micro-phase separations. Such morphological changes are reflected
in the value of /.L as exemplified in Table 4. Another aspect of
morphology is molecular orientation which results in anisotropic hygro-
elastic behaviour even under Fickian conditions as shown in Fig. 13.
The anisotropic hygroelasticity of oriented polymers is analogous to
their anisotropic thermoelasticity. The two phenomena depend on the
364 Gad Ma,om
TABLE 4
Coefficients of Hygroelasticity (Defined by
eqn (30)) for Diglycidyl Ether Bisphenol-
A/Diaminodiphenylmethane Epoxies at Var-
ious Epoxy/hardener Ratios (ref. 32)
Hardener/100 g epoxy (g)

---------
18 0·266
27 (stoichiometric) 0·321
36 0·148
intermolecular forces and distance, which contrarily to the interatomic

bonds are affected by both the temperature and the volume of the
diffused water. Orientation of a polymer results in a situation whereby
the longitudinal behaviour is controlled by interatomic bonds while
transverse behaviour is marked by intermolecular forces. Thus, as the
degree of orientation increases the longitudinal thermal expansion and
swelling decrease, and the transverse properties increase.
>.0.25
o=E
_ ~0.20
~.2
:Q
.......~0.15
~
u~C' 0
.1 JUl
0~~2~4~6~8~~IO~12~14
Birefringence (10- 4 )
Fig. 13. Longitudinal and transverse coefficients of hygroelasticity (defined by

eqn (30)) as a function of orientation for oriented poly methyl me thacrylate in
water at 21°C. (Reproduced, with permission. from ref. 31.)
3.1.2. Case II Diffusion

The hygroelastic behaviour under Case II diffusion is basically aniso-
tropic, and the value of each directional I.t is determined by the
proportional dimension of the specimen in that direction. 33 The aniso-
tropy of the swelling strains is caused by the mechanical constraints
exerted mutually by the two regions of the specimen, namely the
swollen shell and the core. Such swelling stresses developing during the
process are evident (e.g., in Fig. 14) and may eventually lead to failure
of the polymer specimen. 34
Since the swelling strain in each direction is affected by the direc-
tional constraint imposed by the core on the shell and transferred at
Fig. 14. A view through cross polaroids of an epoxy plate partially swollen
with methylene chloride, showing the developing stresses (ref. 34).
the interface, the dimensions of the interfacial surfaces are essential in

determining the anisotropic response of the specimen. The analytical
model for predicting the directional coefficient of hygroelasticity con-
siders the deviations of the initial dimensions of the specimens from
those of a cube with an identical surface area regarded as an 'equival-
ent cube' :~4 On this basis a simple expression for the directional
coefficients of hygroelasticity was developed
(31)
IL, = IIJ1/I)
where ILv = I lLi (i = x, y, z), and I is the actual specimen length in the
ith direction (J = X, Y, Z). Since the upper bound for isotropic IL is
0·33, that of ILv is 1, hence eqn (31) reduces to
1
(32)
IL, = I'i. (1/1)
Table 5 contains a comparison of theoretical and experimental direc-

tional coefficients of hygroelasticity for different epoxy specimens
swollen by methylene chloride at 35°C.
TABLE 5
Theoretical and Experimental Directional Coefficients of Hygroelasticity of
Different Epoxy Specimens Swollen hy Methylene Chloride at 35°C (ref. 34)
Specimen 1-', 1-', 1-', /-Lv
geometry (em) Theory Experimellt Theory Experiment Theory Experiment
10·0 X 1·9 X 0·9 0·299 0·290 0·060 0·064 0·665 0·670 1·024
10'Ox 1·9xO·2 ()'086 0·097 0·017 0·022 0·865 0·845 0·964
4·0x 1·9x()·9 0'26R 0·266 0·134 0·148 (J·600 0·583 0·997
4·0x 1·9xO·2 0·083 0·089 0·042 0·048 0·834 0·820 0·959
--------- ----~----- ------
366 Gad Maram
3.2. Hygroelasticity of Fibre-Reinforced Composites

The hygroelasticity of fibre-reinforced composites is naturally aniso-
tropic and dependent on the fibre volume fraction. Prediction of
hygroelastic behaviour as a function of constituent material properties
and phase geometry is based on the principle analogy between that
behaviour and thermoelasticity. Hence, the convenient approximate
expressions derived by Schapery35 for thermal expansions are success-
fully used for predicting the longitudinal and transverse coefficients of
hygroelasticity fL~' and fL ~, respectively36,37
fL ~ = EmfLmcf>m + EffLfcf>f (33)

Emcf>m + Efcf>f
fL ~ = (1 + Vm)fLmcf>m + (1 + Vf)fLfcf>f - fL ~'(Vfcf>f+ vmcf>m) (34)
(Here the subscripts m and f are used to indicate parameters for the
matrix and fibre phases, respectively.) For example,37 based on the
definition of fL as in eqn (29), the value of fLm for a typical DGEBA
based epoxy resin exposed to boiling water is fLm = 0·28 cm3 g-l. With
eqns (33) and (34) the values of fL ~ and fL ~ for a glass fibre reinforced
resin of cf>f=0'42 are 0·015 and 0·21cm3 g-t, respectively, assuming
fLf = O. The experimental values are 0'013 and 0·19 cm 3 g-t, respec-
tively.
The analogy between hygroelasticity and thermoelasticity is man-
ifested further by their angular dependence. Since thermoelastic and
hygroelastic strains are second rank tensors, the coefficient of a uni-
directional composite in a direction fJ with respect to the fibre direc-
tion is given by the following transformation. 38 ,39
(35)
Figure 15 presents an example of the angular dependence of the
coefficient of hygroelasticity of a unidirectional glass fibre-reinforced
epoxy.
An important aspect of hygroelasticity is its interrelation with
diffusivity.40 This interrelation is realised by combining eqn (2) with
eqn (28), considering that M = 6.M/ Mo. Hence,
(36)
where kL and L= are obtained from a plot of 6.Lj Lo versus square root
of time as shown in Fig. 16, and fL and fL= are the initial and
0.30
~'
/
0.25 /
0.20
0.15
I
,l
I
I
I
I
0.10 ~'
I
I
I
0.05
/
I
o 153045607590
Fig. 15. The angular dependence of the coefficient of hygroelasticity of a

unidirectional glass~poxy composite, cPt = 0·51 (ref. 39).
equilibrium values of the coefficient of hygroelasticity. For many
composite materials, /-L is independent of I1M/ Mo, and it is therefore
constant throughout the swelling process, resulting in /-L = /-too. Hence,
D = 1T(bkL)2 (37)
4L~
which is the essence of a new technique for measuring the coefficient of

diffusion of composite materials based on recording their dimensional
response against the square root of time, as in Fig. 16. This technique,
although of particular applicability, provides a very convenient metho.d
for measuring D in many material-liquid systems whose coefficients of
hygroelasticity are independent of the level of the absorbed penetrant.
11>
c:r>
<=
o 0
...J
" .....
.£;
"O...J
<= <I
o -I
"en "
:5
E
(5
Square root of time

V
Fig. 16. Illustration of the relative length change as a function of square root
of time. The coefficient of diffusion is calculated from the slope of the linear
portion of the curve and from the maximum relative length change.
368 Gad Maram
4. HYGROTHERMAL AGEING AND EFFECTS ON

MECHANICAL PERFORMANCE
In this section we address the theme of the deterioration of the

mechanical performance and integrity of composite materials due to
the presence of moisture. The deterioration of the mechanical proper-
ties, or alternatively, the question of residual properties after a particu-
lar exposure cycle are generally referred to as hygrothermal ageing,
implying the combined action of water and heat. Naturally, hygrother-
mal ageing has two sources, one which is chemical and another which
is physical.
The former results from chemical interactions between the penetrat-
ing water and one of the constituent materials of the composite. In
addition, chemical interactions also include moisture attack at the
fibre-matrix interface. Chemical interactions are mainly hydrolyses of
polymer bonds and dissolution and leaching of water-soluble species.
In secondary chemical interactions hydrolysis or dissolution products
react further with the polymers. Due to the wide variability of compo-
site materials we witness innumerable reports of different kinds of
chemical interactions. Hence, only representative examples are pre-
sented below.
The physical source of hygrothermal ageing of composite materials is
reflected in the plasticisation of the matrix, resulting in a reduction in
its glass transition temperature. Another significant physical phenome-
non is the generation of internal stresses due to the accumulation of
water molecules within the polymer network. Both physical
phenomena are discussed below.
4.1. Chemical Effects

The chemical effects on the constituent materials obviously depend on
their chemical composition and it is feasible that there exists a wide
range of examples from highly moisture sensitive to inert materials.
The first type of material may be exemplified by most styrene-based
polyester resins, which exhibit very poor hygrothermal resistance, and
the second type by graphite fibres which are practically insensitive to
the presence of water.
The chemical effects of moisture on the reinforcement can be
demonstrated by the example of glass fibres. It is established that
degradation of glass in the presence of water occurs mostly where the
former contains alkali ions. Equation (38) presents a sequence of
reactions leading to cleavage of silicon-oxygen bonds and to their

conversion to hydroxysilane. 41
.Si-ON~ + H 2 0 __ S~-OH + ~aOH}

Sl-O-Sl + OH- __ Sl-OH + Sl-O- (38)
Si-O- + H 2 0 ----? Si-OH + OH-
The overall reaction, which is autocatalytic due to the gradual increase
in the pH level, results in degradation and flaw formation at the glass
fibre surface, and in significant strength reduction.
Moving from the reinforcement to the interface it is well known that
a fundamental prerequisite for high composite strength is good fibre-
matrix bonding. This is achieved either by direct chemical bonding
between the fibre and the matrix or by the intermediary of a coupling
agent. 42 With carbon fibres, for example, a range of active functional
groups like -C02 H, -C-OH and -C=O are produced by various
oxidative surface treatments such as in nitric acid or sodium hypochlo-
rite. The functional groups which form chemical bonds directly or
through silane and other coatings with resins, are liable to hygrother-
mal chemical attack, and to interfacial moisture degradation. 43 ,44 In
addition to the chemical bonding, the physical morphologies of the
constituents at their interface determine the type of physical bonding
which is formed, and whose strength is sensitive to physical processes
such as the build-up of destructive internal swelling stresses (see
Section 4.3).
Finally, the chemical source of the hygrothermal ageing of the
matrix also depends on its chemical composition. Thus, epoxy resins
are generally hydrolysis-stable, and although indications of moisture-
induced conversion of the crosslinked structure do exist, their durabil-
ity depends mostly on physical processes such as crazing. 45 Contrarily,
polyesters are hydrolysis-prone resins due to the ester groups which
are highly susceptible to saponification 46
4.2. Effects on Glass Transition Temperature

The sorption of moisture by resins and polymers lowers their Tg
values, and correspondingly causes them to soften at lower tempera-
tures. Two major mechanisms for the lowering of Tg by water are
considered. The first is a result of the action of water as a lower
molecular weight plasticiser. The water acts as an internal lubricant
decreasing the energy barrier for chain segment movements. The glass
370 Gad Maram
.-? 140
120
100 0
2 3 4 5 6
MCD ("to)
Equilibrium weight gain
Fig. 17. Theoretical and experimental plots of Tg versus equilibrium moisture

weight gain for a TGDDM/DDS epoxy-moisture system (ref. 47).
transition temperature of a plasticised polymer is given approximately

by the following rule of mixtures
(39)
where Vp is the volume fraction of the polymer and T gp and Tgd are
the glass transition temperatures of the unplasticised polymer and of
the diluent, respectively. Experimentally, the Tg of water has been
reported in the range 128-142 K. Alternatively, a good empirical rule
for most substances places the ratio of Tg/Trn (crystalline melting point)
in the range i ~. However, experimentally determined Tg values of
TGDDM-DDS epoxy-moisture systems equilibrated at various rela-
tive humidities are much lower than those obtained by eqn (39) even
with a Tgd value of 182 K. This is shown in Fig. 17.47
This discrepancy is attributed to the fact that relationships such as
eqn (38), based on the additivity of some property such as the free
volume, are inappropriate when there are specific interactions between
the polymer and the absorbed species. Indeed, the Tg values of nylons
and of polyvinyl alcohol are greatly reduced by only a percent or so of
water. Strong hydrogen bonds in nylons act similar to crosslinks in
raising Tg , while small amounts of water break these bonds and cause
abnormally large decreases in Tg •48 Similar explanations have been
proposed recently for the anomalously large reductions in Tg with
water absorption in epoxy resins. 49,5o For example, the Tg of a
diaminodiphenylmethane cured diglycidyl ether of bisphenol A epoxy
resin has reportedly decreased from 410 K in the dry state to 378 K for
a moisture content of 2·5 wt%.49 In another example the Tg of an
epoxy based on tetraglycidyl ether 4,4'-diaminodiphenylmethane/4,4'-
diaminodiphenylsulphone reduced from 523 K in the dry resin to
473 K for a moisture content of 7 wt%.50 In both examples the Tg

reduction has been attributed to the breaking of the hydrogen bonds
by the sorbed water, making chain segment rotation possible.
4.3. Internal Stresses and Micro-damage

Low molecular weight liquids, including water, generally cause failure
in polymers by inducing crazing or cracking via a mechanism which
comprises three contributions. The first two contributions are the
chemical degradation and plasticisation discussed in Sections 4.1 and
4.2, respectively. The third contribution derives from the generation of
internal stresses due to accumulation of penetrant molecules within the
polymer network structure. When a combination of these three factors
occurs in a particular region it will produce localised failure at stresses
much lower than those observed in the absence of the penetrant
(moisture).
For durability predictions of resin matrices the local magnitude of
the internal stresses and strains and the level of stress or strain which
produces permanent damage must be known. This may be done by
theoretically linking the internal stresses with the dilatational (swelling)
strains of the resin which are either measurable or may be calculated.
One approach is to establish the relationship between fL, the coefficient
of hygroelasticity-representing the swelling strains-and the internal
pressure, P. The proposed model considers P as a positive hydrostatic
pressure developed in a sphere containing the water molecules. 51 In
this case the local directional strains are equal, ex = ey = e z =
P(1- 2v)/E, and in an isotropic material this yields equal hygroelastic
strains, AL/L o. Using eqn (30) for the definition of the coefficient of
hygroelasticity we obtain
P = fLE(A V*/Vo) = 3IL K (A V*/Vo) (40)

1-2v
Since the bulk modulus is defined by K = PICA VI yo) and AV* = AV + S
(see Section 3), P is different from zero only when Sf 0, or in other
words, only when the water molecules are compressed into a smaller
volume within the polymer, thus generating internal stresses.
Now, the internal stress is linked to the swelling strain, and we know
how it increases with moisture absorption. When the internal stress
reaches a critical value, failure by a specific type of micro-damage
occurs. The specific type of micro-damage is a result of the chemical
cOl1'position of the polymer and of the chemical and plasticisation
372 Gad Maram
effects of the penetrating water molecules. The onset of each specific

type of micro-damage may be expressed by a failure criterion, which
singles out a critical value of P. It is already known how P increases
with moisture absorption; when a critical value of P is reached, failure
by the corresponding mechanism will occur. For example, failure by
crazing will occur when P>~Y{1+lnE/(3(1-v)Y)}, where Y is the
yield stress of the water containing polymer. 52 Similarly, other criteria
are used for other anticipated modes of failure.
4.4. Durability of Composites in Moisture Conditions
The above sections discuss the various chemical and physical hygro-
thermal ageing processes which determine the durability of compo-
site materials. Clearly, the complexity of the material and exposure
condition combinations make it very difficult if not impossible to
develop a general theory by which property deterioration or durability
may be predicted. Instead, experimental work under real or simulated
conditions is required in order to establish the rate and extent of the
hygrothermal effect. In many cases accelerated conditions are used to
facilitate the effect (and obtain results in a shorter period of time);
however, the question of the relevance of the accelerated conditions
and of how authentically they represent the reality always arises.
The results of such experimental monitoring of hygrothermal ageing
are usually presented in terms of the residual value of a particular
mechanical property as a function of some parameter related to the
exposure conditions, such as exposure time, level of relative humidity
and temperature. The durabilities of the modulus, the strength and the
fracture toughness are mostly considered. Only one example is given
here which represents, however, the general approach. Figure 18
contains results of the transverse (9 = 90°) buckling modulus of a
moisture content %
'0
0.10
~
II>
::J
~o 5
E
200 300
Temperature K
Fig. 18. The transverse buckling modulus of graphite fibre--epoxy composite as
a function of temperature and moisture content. (Reproduced, with permis-
sion, from ref. 53.)
graphite 'fibre-reinforced epoxy composite as a function of temperature

and moisture content. 53 It is noted that in many cases the experimental
results, such as the data in Fig. 18, are additionally beneficial, in the
sense that they allow fairly accurate extrapolations to close, yet differ-
ent, temperature and moisture levels.
Whereas an understanding of fundamental features of the moisture
penetration mechanisms, of the hygrothermal ageing processes and of
the hygroelastic behaviour are required for the development of more
durable resins and composites, the systematic accumulation of suffi-
cient data for a comprehensive description of the durabilities of the
currently used systems is a crucial task.
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374 Gad Marom
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Index
Acetone sorption, 79 Block copolymers, 69
Acrylics, 63 Boltzmann
Acrylonitrile, 189 equation, 37, 39
Activation energy, 64, 128, 136, 138, transformation, 77, 81
139,149,150,185,188-9,290 Brunauer-Emmett-Teller (BET)
Activity coefficient, 18 equation, 31
Additives, 119, 120, 123, 13G-54, moisture monolayer value, 276
287-8 Butadiene-acrylonitrile copolymers,
distribution of, 123-5 186
solubility of, 154---65 Butyl rubber, 185, 186, 189
Adhesion
adsorption theory, 180 Carbon black, 130, 170
diffusion theory, 181-90 Carbon dioxide equilibrium sorption,
electrostatic theory of, 179 52
mechanical interlocking theory, 178 Carbon-fibre composites, 207
theories of, 177-80 Cellulose, 63
Adhesives, 205 acetate, 63, 107
Aircraft applications, 205 derivatives, 63
Alcohol transport, 51 nitrate-isopropyl nitrate, 115
Aluminium, 333 triacetate, 242
Aluminium-adhesive-aluminium Chemical potential, 16-17, 19
sandwiches, 197-202 Coatings
Annealing effects, 145, 146, 152 barrier properties, 317
Antioxidants, 122, 163,279 effect of humidity, 327
Apparent activation energy, 64 electrical components, 331-7
Arrhenius electronic components, 331
behaviour, 315 electronic/optoelectronic devices,
law, 127, 128, 134, 135,138,151, 309-39
157,165,188,210 factors affecting vapour and mois-
Autohesion, 181, 185, 186, 188,189 ture permeability, 315-21
Avogadro's number, 17 gas permeability, 317-21
ion penetration in, 325-7
isothermal sorption of water, 319
Barrer permeability determination, 31G-15
standard unit of P, 23 see also Corrosion protection
zone theory, 46 Colour, 119
Berens-Hopfenberg first order re- Complementary metal oxide semicon-
laxation model, 347 ductors (CMOS), 335-6
Binders in corrosion protecting coat- Composite materials
ings, 323 anomalous diffusion, 347-9
375
376 Index
Composite materials-contd. Diffusant

carbon-fibre, 207 melting temperature, 135
damage dependent mechanisms of structure effects, 158
moisture penetration, 353-7 Diffusion
durability in moisture conditions, additives, of, 130-54
372-3 concentration step, at, 9-10
effect of external loading on mois- fibre, into, 8
ture penetration, 357-62 Fick's first law of, 1,5
fibre-reinforced, 366 Fick's laws of, 77,133
graphite fibre-reinforced epoxy, Fick's second law of, 1-3
373 film or slab, into, 7-8
moisture gases, of, 130
diffusion, 350-2 two-component systems, in, 15
penetration mechanisms, 342-62 Diffusion analysis, 14
stress dependent diffusion Diffusion behaviour, 27
composite, of, 359-62 Case I, 56, 343, 347
matrix, of, 358-9 Case II, 343, 345-7, 364
water transport in, 341-74 Fickian, 56,343, 344,347.349,363-4
matrix phase, in, 342-9 non-Fickian, 343, 345-7
Computer Super Case II, 343, 345-7
control, 306 temperature and concentration de-
techniques, 301 pendence,34-50
Concurrent solution/diffusion studies, theory of irreversible thermodyna-
20 mics, 15, 19
Contraceptive agents, 240 Diffusion coefficients, 12-14,130,
Corrosion protection, 321-7 151,282,310
Covalent bonds, 180 activated zone theory, 150
Cracking, 205-7, 282, 371 Arrhenius plots, 128
Crazing, 205, 206, 371 composite materials, 354
Creep studies, 20 constant, 79, 82
Crosslinking effects, 65-7, 239, 317 crosslinking effect, 66
Crystallinity effects, 65-7 crystallinity effects, 65
dichroism ratio, and, 148, 149
discontinuous dependence on con-
Deborah number, 55, 56 centration, 82
Defect structures, 20 equilibrium water uptake, and, 200
Desorption fixed, 115
curves, 26 front velocity, and, 101
rate, 21, 24 history dependent, 87
Deuterium exchange rate, 312 increasing exponentially with con-
DGEBA-DAPEE, 196, 202, 207 centration,81
DGEBA/triethylenetetramine epoxy, independent of concentration. 134
356 influence
Di(l-aminopropyl-3-ethoxy)ether annealing. of, 152
(DAPEE), 195, 196 filler content, of, 334
Didodecanyl-3,3' -thiobispropanoate stress, of, 358
(DLTDP),142 temperature on, of, 99, 134, 138,
)iethylenetriamine (DETA), 209 144, 145,289
Index 377
Diffusion coefficients--contd. Drug release--contd.

measurement and calculation of, 4, Type 1 polymers, 257
5,21-7,131,210,312,314, Type 2 polymers, 257
353, 367 Type 3 polymers, 257
molar mass, and, 139 Dupre equation, 207
oxygen in polymers at 25°C, 127
penetrant size and shape effects,
56-9 Effective permeability coefficient, 53
sharp boundaries, 80, 97 Electrical component coatings, 331-7
'true', 18 Electronic component coatings, 331-7
viscosity, and, 185 Electronic devices, 309-39
water transport, 202 Enamels, 337
Diffusion equation, 14,88,89,94,96 Encapsulants for electronic/optoelec-
Diffusion parameters, 136 tronic devices, 309-39
Diffusion problems, 14 Encapsulated devices, 331-5
Diffusive flux, 13, 18 Epoxide-graphite composites, 210
Diglycidylether of bisphenol-A Error function, 9
(DGEBA), 194-6,205,206; Ethanol effect on joint, 209
see also under DGEBA Ethylene glycol dimethacrylate
Dimensional changes, 362-7 (EGDMA),229
Dioctadecanyl-3,3' -thiobispropanoate Ethylene-propylene, 186
(DSTDP),142 Ethylene-vinyl acetate (EVA), 229,
Doolittle equation, 41, 42, 358 240-2,256,299
Drug concentration EVAL,305
measurement of, 223
versus time curves, 223
Drug disposition, pharmacokinetic Fibre-adhesive interface, 202
models of, 224-5 Fillers, 120, 287, 334
Drug release Film permeation, 3-6
control approaching steady state, 3-6
biodegradable or bioerodible sys- steady state, in, 5
tems, by, 256-8 Flory-Huggins
matrix (monolithic) devices, by, equation, 31, 40
245-56 interaction parameter, 40, 66
polymer permeability, by, 227-56 isotherm equation, 34-5
reservoir (membrane) devices, polymer solution theory, 44
by,229 Fluctuation theory, 48
Higuchi model of, 251, 253 Foodstuff packaging, 269-308
impetus for seeking ways of con- accelerated testing, 301
trolling, 220 barrier
methods of controlling, 226-7 function, 295
microencapsulated products, 258-9 properties, 296-300, 305
osmotically controlled systems, 259 structures, 298-9
permeability basic principles of, 275
problems, 219-26 choice of materials, 270
role in, 217-67 container-environment interac-
polymer bound drugs, 259-60 tions,272
potential disadvantages of, 222 controlled atmosphere, 279
378 Index
Foodstuff packaging-contd. Gas permeation, 11-73

deterioration rate, 270-1, 277 Gas transmission
effect of cell, 295
additives, 287-8 rate measurement, 294-5
chain packing and side groups, Geometrical impedance factor, 150
285 Gibb's chemical potential, 17
fillers, 287 Glass transition temperature, 64,
humidity, 287-8 138-9,204,369-71
moisture, 274-8 Gravimetric methods, 311
molecular orientation, 286 Gutta percha, 189
oxygen, 278-9
permeating species, 289
polymer crystallinity, 286 Heat
temperature and pressure, 289 conduction, 14
time and temperature, 273-4 solution, of, 163
wall thickness, 290-1 Henry's law, 5, 16, 18,29,31,34,35,
examples of materials used, 280-1 51,53
gas transmission rate measurement, Heterogeneous systems, 67-9
294-5 n-Hexane-polyphenylene oxide, 107
hygroscopic foods, 277 n-Hexane-polystyrene, 107
importance of permeation, 270-81 Hildebrand
inertness, 297 concept of fraction free volume, 40
materials equation, 33
choice, 280-1 Homing devices, 259
development, 303-6 Humidity effects, 287-8, 327, 334
oxygen permeability, 285-8 Hydroelasticity, coefficients of, 365
permeability Hydrostatic pressure effect, 188
measurement, 291-5 Hydroxyethyl methacrylate (HEMA),
rate, 291 229
polymer variables, 284-8 Hygroelasticity, 362-7
protective role, 271 coefficients of, 362, 366, 367
regulations, 275 fibre-reinforced composites, of, 366
selection of, 277-8 matrix phase, of, 363-5
materials, 295-300 Hygrothermal ageing, 368-73
shelf-life prediction, 300-2 chemical effects, 368-9
thermal resistance, 298 effects on glass transition tempera-
transmission rate, 281-91 ture,369-71
water experimental monitoring of, 372
gain or loss, 297 internal stresses, 371-2
vapour transmission rate micro-damage, 371-2
measurement, 292-4
Fourier heat transfer equations, 77
Fujita free volume Immobilisation factor, 150
model,43 Infrared spectroscopy, 312, 314
theory, 41-2 Integral sorption, 25
Internal stresses, 371-2
Intrinsic mobility, 17
Gas law equation, 15 Ion-pairs, 209
Index 379
Ion penetration in coatings, 325-7 Molecular probe, 12

Ionic contaminants, 335 Multicomponent systems, 67-9
Ionic impurities, 332
Irganox 1010, 163, 165 Natural ageing, 166
Irganox 1076, 145, 152, 159-62, 169 Natural rubber, 136, 151, 186,189
Isoprene-methyl methacrylate co- Nemst distribution function, 15
polymers, 59, 60 Nitrile rubbers, 189
Nylon-6, 147
Joint
durability, 190-211 Optical data storage media, 328-9
strength and water content, 202-3 Optical densitometer scans, 85
Optical retardation, 79
Optoelectronic devices, 309-39
Langmuir Organic additives, 120
equation, 31, 51 Orientation effects, 65-7, 147-9,162
isotherms, 54 Osmotic pressure
Lap joints, 210 effects, 96, 98, 99, 259
Lennard-Jones 6-12 potential, 33--4, theories, 91-9
47 Oxidation
Load effects, 210 ageing, 120-3
kinetics, 129-30
Oxygen
Matrix (monolithic) devices, 245-56 permeability
containing dissolved drug, 246-8 kinetics of oxidation, and, 129-
containing suspended drug, 248-54 30
drug release from, 246 polymer films, of, 60
examples of, 255-6 polyolefins, of, 125-30
porous, 254-5 values of, 126
Mean mobility, 17 solubility, 127
Melting temperature
diffusant, 135 Packaging materials. See Foodstuff
polymer, 136 packaging
Membrane transport, 19 Paint films
Methoxyethoxyethyl methacrylate electrical resistance, 324-5
(MEEMA),245 mass transfer characteristics, 324
Methyl esters, 141 permeation by water, 322--4
Methylmethacrylate (MMA), 245 Parasitic MOS formation, 336
Micro-damage, 371-2 Peel strength, 186, 189
Microencapsulated products, 258 Penetrant
Migration effects, 120, 122, 166-9 concentration, 27-50
Mineral additives, 120 Case II sorption, 99, 103
Moisture effects, 274-8, 322-3, 333, permeation process, 34-50
335 profiles, 77, 80-2,89,97
composite materials, in. See Com- sorption process, 29-34
posite materials immobilisation concepts and mod-
Molar mass, 139, 170, 186, 187 els,50-5
Molecular length, 141, 143 size and shape effects, 56-9
380 Index
Permeability Polyethylene-contd.
coefficient, 12-13,200,284 concentration dependence, 67
effective, 53 crystallinity and oxygen solubility,
influence of temperature, 289 126
measurement and calculation of, density effects, 128
6,21-7,282,310 diffusion
penetrant size and shape effects, coefficient, 65
56-9 kinetics, 130, 131, 133-6, 139,
measurement of, 291-5 141, 143-7, 150-2
plastics packaging, in. See Food- electrochemical treeing, 336
stuff packaging high density, 299, 304
role in drug release. See Drug induction time, 123
release low density, 129, 149, 163,169-70,
Permeation process, temperature and 303-4
concentration dependence, 34- permeability
50 coefficient, 282
Phenolic antioxidants, 149 gases, of, in, 315
Photooxidation, 123, 129, 130 water, of, in, 316, 318
Pigments, 119, 322 photodegradation, 166
Pinholes, 282 self-diffusion, 187
Plastanox 2246, 144, 145, 152, 160, stabiliser solubility, 156, 157, 159-
161 62, 165
Plasticisation, failure due to, 208 thermal oxidation, 120
Plasticisers, 120, 13] Poly(ethylene glycol), 63, 244
PMMA, 6, 57, 76, 84, 106, 107,110, Polyethylene terephthalate, 65, 67,
113 151,188,305
PMMA-alcohol,109 Polyethylmethacrylate, 151
PMMA-n-butane, 100 Poly(2-hydroxyethyl methacrylate)
PMMA-methanol, 94, 97, 99-101, (HEMA),245
103-5, 108, 110-13 Polyisobutane, 188
PMMA-PVC, 182 Polyisobutene, 189
Poisson's ratio, 359, 360 Polyisobutylene, 151
Poly acrylonitrile (PAN), 52, 304 PolY(DL-lactic acid), 257
Polyamides, 63,242, 300, 304 Polymer
Polyblends, 69 chain segmental mobility, 20, 27
Polybutadiene, 62 degradation, 119-76
Poly(butadiene-acrylonitrile (35%)) melting temperature, 136
rubber, 62 structure effects, 144-7,158-61
Poly(butylene terephthalate), 305 swelling kinetics, 83, 105-6, 110-
Polybutylmethacrylate-PVC, 182 11,116
Poly( E-caprolactone), 181, 257 Polymerisation, 239
Polycarbonate, 52, 138, 139, 190,242 Polyolefins
Polychloroprene, 189 activation energy and pre-
Polydimethylsiloxane (PDMS), 6, exponential factor, 149
151,238-40,242,251,255-6 antioxidant solubility, 163
Polyester, 300, 304 migration in, 120
Polyethylacrylate, 139 natural ageing, 166
Polyethylene oxidation ageing and stabilisation,
cohesive energy, 60 120-3
Index 381
Polyolefins--contd. Polyvinylidene chloride, 304, 305

oxygen permeability, 125-30 Pre-exponential factor, 149
stabilisers, 142, 154 Progesterone, 239, 241
Polypropylene Pseudo-Fickian
activation energy and pre- behaviour, 346
exponential factor, 149 sorption, 56
additives, 131
atactic, 163
diffusion factor and activation ener-
Rate constant, 89
gy,151
Recommended permeability unit, 6
distortion length and relaxation. 153 Reinforcing agents, 120
Ed(JT),143 Relaxation
heat resistance, 299 control, 89, 96
isotactic, 163 times, 55-6
lifetime and antioxidant volatility, Reservoir devices, 229-45
122 boundary layer effects, 236-8
migration, 170 hydrogel membranes, with, 245
oriented films, 300 microporous membranes, with,
oxidation kinetics, 129 242-5
packaging, 304 non-porous hydrophobic mem-
permeability, 316 branes, with, 238
photooxidation,123 non-porous membranes, with, 231-
porous membranes, 242 42
stabilisation, 121 simple geometries, with, 232
stabilisers, 156 steady state, 233
Polystyrene, 52 Reverse thermal effect, 357
barrier structures, 298 Rubber, 62, 122, 170
Case II sorption, 98
CO2 sorption, 52
diffusion coefficient, 57, 134,151,
152 Self-diffusion, 141, 142, 152
migration, 170 coefficient, 18, 184-7
packaging, 304 Sigmoid behaviour, 346
Polystyrene-acetone system, 84 Silastic
Polystyrene-alkane system, 98 medical adhesive, 239
Polyurethane, 63, 131,314 tubing, 238-9
Poly( vinyl acetals), 63 Solubility
Polyvinyl acetate, 126, 128, 134, 138, additives, of, 154-65
151 coefficient, 5, 16, 18,200,282,310,
Poly(vinyl alcohol), 63 319
Poly(vinyl chloride) (PVC), 131,138 compilations of, 12-13
diffusion crystallinity effects, 65
coefficient, 151 measurement and calculation of,
gases and vapours, of, 57 21-7
interface, at, 181 temperature dependence, 289
packaging, 304 parameters, 33, 89, 157, 183
permeability, 316 Solution behaviour, 11-13,27,30
plasticisers, 120, 131 Solvent welding, 189-90
stabilisers, 131 Sorbed penetrant effects, 27-9
382 Index
Sorption behaviour Stress

anomalies in, 346 effects, 210
Case II, 56, 75-118 relaxation, 20, 90
cracking in, 98 Styrene-butadiene rubber, 185, 186
craze propagation in, 98, 99 Substrate-adhesive interface, 202
defining characteristic of, 85 Surface
essential features of, 96 effect, 103
Fickian case, 77-8 evaporation, 166
further developments, 89-91 treatment, 191
induction period, 103-5, 115 Swelling
influence of temperature and caused by water, 204
penetrant concentration, 99- polymer systems, 79-80
103
internal stresses and shape
changes, 105-7 Tack effect, 183, 185-9
limits of, 114-15 Temperature
linear kinetics, 82--6 dependence, 27-50
mechanical history effects, 112- penetrant immobilisation, 5G-5
14 permeation process, 34-50
osmotic pressure theories, 91- sorption process, 29-34
9 effects, 99-103, 134, 155,273-4,
sample geometry, 86 289,315,334
sensitivity to physical state of TGDDM-DDS epoxy-moisture sys-
glass, 111-14 terns, 370
sharp boundaries, 78-82 TGDDM-DDS-water system, 204
theories of, 87-99 Thermal diffusivity, 14
thermal history effects, 111-12 Thermal spikes, 205, 206
dual mode, 17,51,52 Thermodynamic diffusion coefficient,
Fickian, 26, 55 18,41
heterogeneous and multicompo- Thiodipropionic esters, 149
nent systems, in, 67-9 Thomas-Windle theory, 94, 96, 103,
non-Fickian, 26 109,115
penetrant size and shape effects, Time dependent boundary conditions
56-9 model, 347
Super Case II, 56, 91, 107 Time lag method, 130
differential swelling stresses, Topanol CA, 165, 167, 169
110 Tortuosity factor, 65, 68
overlapping precursors, 109 Transdermal Therapeutic System
temperature and concentration de- (TIS), 243
pendence,29 Transition-state theory of rate proces-
two-stage process, 347 ses, 38
Sorption curves, 26 Transport
Sorption-desorption cycling, 207 behaviour, 11-12,28
Sorption isotherm, 30 coefficient, 69
Sorption rate, 21, 24, 26 parameter dimensions, 6
Stabilisation, 12G-3 process
Stabilisers, 131,137,142,166-9 heterogeneous and mUlticompo-
Steroids, 240 nent systems, in, 67-9
Index 383
Transport-contd. Water
process-contd. attack on adherends, 209
major factors, in, 20 content and joint strength, 202-3
sensitivity of, 13 effect on interface, 207-11
Transverse buckling modulus, 372 entry
Triethylenetetramine (TETA), 206 joint, into, 204
Type II isotherms, 30, 32 kinetics, 192-7
Type III isotherms, 32 swelling caused by, 20~
Type IV isotherms, 32 transport in composite materials.
See Composite materials
uptake, calculated and measured,
Ultraviolet 197-202
radiation, 124 weakening mechanism, 203-7
stabiliser, 124 Water vapour
permeability; 63, 314
transmission
Vacuum microbalance, 311-12 cell, 293
van der Waals forces, 180 rate measurement, 292--4
Van't Hoff equation, 158 Weight increase-time curves, 83
Vapour permeation, 11-73 Weighted mean method, 27
Vinylchloride-vinylacetate copoly- William-Landel-Ferry (WLF)
mers, 138 equation, 150
Viscoelastic behaviour, 28, 43 modification, 41, 42
Viscosity effects, 185
Voids, 206, 282
Vrentas-Duda free volume model, 44

J. Comyn (Auth.), J. Comyn (Eds.) - Polymer Permeability-Springer Netherlands (1985)

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J. Comyn (Auth.), J. Comyn (Eds.) - Polymer Permeability-Springer Netherlands (1985)

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POLYMER PERMEABILITY

CHAPMAN & HALL

Chapman & Hall. 2-6 Boundary Row. London SE1 8HN. UK

Chapman & Hall Japan. Thomson Publishing Japan, Hirakawacho

First edition 1985

List of Contributors viii

1. Introduction to Polymer Permeability and the Mathematics

2. Permeation of Gases and Vapours in Polymers 11

4. Effects of Oxygen Permeation and Stabiliser Migration on

5. Diffusion and Adhesion. 177

6. The Role of Polymer Permeability in the Control of Drug

7. Permeability and Plastics Packaging . . 269

8. Permeability of Coatings and Encapsulants for Electronic

9. The Role of Water Transport in Composite Materials. 341

Introduction to Polymer Permeabllity and the

School of Chemistry, Leicester Polytechnic, UK

1. Fick's Laws of Diffusion . . . . . . 1

1. FICK'S LAWS OF DIFFUSION

So the material entering face ABeD in unit time is 4 dy dz(Fx -·

However, if D depends upon the concentration of the diffusant and

but if diffusion is entirely radial this reduces to

ae _!~ (rD ae) (11)

If a film of thickness I and area A separates two chambers containing a

difference between steady state and non-steady state diffusion, and it is

Here C I is the concentration of permeant in the face of the film

Q=DCI (t-~) (13)

so that the total permeant to have passed through a film of area A

It is assumed that Henry's law applies at both interfaces i.e.

Fig. 3. Permeation through a film in the steady state.

As the permeability coefficient P, which equals DK, can be determined

3. DIMENSIONS OF TRANSPORT PARAMETERS

D has dimensions length2 time-' and is usually expressed as m 2 s-'.

In the following chapters no attempt has been made at standardisation.

In these units P for oxygen ranges from about 0·1 in polymethyl-

4. DIFFUSION INTO A FIl,M OR SLAB

If a film of polymer is placed in an infinite bath of diffusant, then

which provides a convenient way (as later chapters will show) of

5. DIFFUSION INTO A FIBRE

If a long cylindrical fibre of radius r is placed in an infinite bath of

This is a solution to eqn (11); A, B, C and a, b, c are numerical

6. DIFFUSION AT A CONCI~NTRATION STEP

If a slab of polymer doped with a diffusant at concentration Co, is

An alternative experimental arrangement would be to sandwich a

1 (h-X h+X) (26)

Expressions (26) and (27) are sometimes referred to as top hat

erfc (z) = l-erf (z) (29)

1. J. Crank, The Mathematics of Diffusion, 2nd Edn, Oxford University Press,

Permeation of Gases and Vapours in Polymers

Department of Macromolecular Science, Case Western Reserve

The solution and transport behaviour of low molecular weight sub-

been tabulated 3 ,6,8,9,12,14,19-2H in addition to data for specific polymers

2. DEFINmONS AND BASIC EQUATIONS

The diffusive flux, J, of a penetrant in a polymer can be defined as the

constant independent of x, t or c. Comparable equations describe

Experiments are then performed over sufficiently small intervals of c

jj may be determined over several ranges of concentration to obtain

where K is a function of temperature and may be a function of c. For

where the solubility coefficient S(p) is a function of temperature and

where P = DS, with D as defined by eqn (5) and

S reduces to S = cdpI for the usual experimental conditions of P2 and

In the absence of any detailed knowledge of the distribution of

where (ac/aC) = S is the overall solubility coefficient which is a meas-

diffusion behaviour, often observed in biological systems, is related to

changes in size, shape, concentration, component interactions, temper-