Water Sorption and Diffusion Studies in an

Epoxy Resin System

C. MAGGANA,1 P. PISSIS2
1
National Technical University of Athens, Department of Theoretical and Applied Mechanics, Zografou Campus,
GR 15780 Athens, Greece

2
National Technical University of Athens, Department of Physics, Zografou Campus, GR 15780 Athens, Greece

Received 17 August 1997; revised 6 November 1998; accepted 9 November 1998

ABSTRACT: The kinetics of water absorption in epoxide materials was studied by the
aid of a diglycidyl ether of bisphenol-A–triethylenetetramine (DGEBA–TETA) epoxy–
resin system containing various amounts of the plasticizer THIOCOL (0 – 40 phr). The
presence of plasticizer permits the formation of products with different crosslinking
densities and hydrophilic characters. Dynamic water absorption experiments were
carried out at 15, 40, and 70°C. For the fitting of the experimental results, a new model
was used, based on a model proposed earlier by Jacobs and Jones. This model considers
epoxide product as a two-phase system consisting of a master phase (where the major
part of the water is absorbed), which is homogeneous and nonpolar (phase 1), and of a
second phase with different density and/or hydrophilic character (phase 2). By making
the assumption that water diffusion can take place independently in the different
phases of the material in accordance with Fick’s second law, we can calculate the
diffusion coefficient D and the water content at saturation M ` for each phase sepa-
rately. Equilibrium water sorption measurements were performed at 40°C, and the
data were analyzed and discussed based on the Guggenheim–Anderson– de Boer (GAB)
equation, the results being in support of the two-phase model used in the analysis of
absorption kinetics. The linear expansion coefficient and the glass transition temper-
ature of the materials, employed in the discussion of the results, were measured by
thermomechanical analysis. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37:
1165–1182, 1999
Keywords: epoxy resins; Fickian diffusion; water sorption; water–polymer interac-
tion; Guggenheim–Anderson– de Boer equation

INTRODUCTION ters that strongly influence water sorption mech-

Polymer-based materials are often exposed to hu-
mid environments, where water molecules, as
well as other low-molecular-weight substances,
can easily migrate in the polymeric matrix, even
at ambient temperatures, and modify their phys-
ical properties.1 The chemical composition and
the microstructure of polymers are two parame-
Correspondence to: P. Pissis
Journal of Polymer Science: Part B: Polymer Physics, Vol. 37, 1165–1182 (1999)
© 1999 John Wiley & Sons, Inc.
CCC 0887-6266/99/111165-18
anisms, leading to deviations from the random-
mixing Flory–Huggins theory and from Henry’s
Law.2– 4 In many cases, the second Fick’s Law5,6
fails to describe successfully the kinetics of water
diffusion, which should be analyzed by consider-
ing various mechanisms of sorption that can be
activated.2,7–11
Epoxy resins are widely used as matrices for
structural composite materials, adhesives, and
organic coatings due to their good mechanical
properties.12–15 However, it is well known that
these properties are strongly affected by moisture
1165
1166 MAGGANA AND PISSIS
absorption, which causes plasticization,16,17 low-
ering the glass transition temperature,16 –18 and
diminishes their mechanical strength.18,19 So the
transport of moisture in epoxy resin systems is of
great importance, and the kinetics of absorption
and distribution of water in the polymeric matrix
is still under investigation.
The kinetics of water absorption in epoxy res-
ins is usually assumed to be a concentration-in-
dependent Fickian diffusion process.20 –27 This
model, which is usually applicable to the initial
stages of the diffusion process, fails to describe
the whole phenomenon.28,29 Some authors at-
tempt to explain this by means of a Langmuir-
type diffusion process,30 in which the absorbed
material (water) can be divided into mobile and
strongly bound types.2,30 –32 Other authors accept
the existence of a two-phase structure epoxy ma-
terial composed of areas with different densi-
ties.33,34 Changes in the structure of the material
during the moisture exposure, such as plasticiza-
tion and formation of cavities, should also not be
neglected.27,35
Complex expressions, which take into account
parameters, such as the formation of hydrogen
bonds,2,28,31,32 the heterogeneity of the epoxy
resin system,33,34 changes in free volume,36 relax-
ation phenomena during hydration,10,37 degrada-
tion of epoxide material,38 the depression of T g , 11
and the formation of clusters, crazes, and micro-
cracks during hydration, have been proposed by
many authors.29,33
The physical aspects of the transport process
are also of great importance. Adamson39 has pos-
tulated that the transport of moisture below T g is
a three-stage process in which the absorbed mois-
ture first occupies the free volume. In the second
stage, water becomes bound to network sites,
causing swelling. Finally, water enters the
densely crosslinked regions.
Yang et al. suggest that while the driving force
for the absorption of water is the electrostatic
attraction between water and the functional
groups of the resin (especially hydroxyls produced
during curing reactions or amine groups when
there is an excess of the curing agent), the equi-
librium degree of water uptake is determined pri-
marily by unoccupied volume of the epoxy resin.40
Carfagna et al. also indicate that water sorp-
tion in polymers containing potential hydrogen-
bonding sites is driven by strong interactions be-
tween water molecules and particular segments
or groups present in the polymer.41
In accordance with Gupta and Drzal, the two–
modes sorption involves a Langmuirian mode at
early stages of absorption and at temperatures
far below T g since little energy is needed for water
molecules to enter into preexisting gaps so that
small differences in free volume can make a con-
siderable difference to the amount of moisture
absorbed. At higher temperatures, Henry’s law
mode is more probable as the water molecules
enter in the material through gaps created by
segmental motion, a mechanism which requires
more energy.35
Isothermal equilibrium sorption curves deviate
from Henry’s Law. The experimental data of wa-
ter content versus relative humidity yield para-
bolic or sigmoidal curves, which are better de-
scribed by power law functions.18
Moy and Karasz report that low-temperature
sorption of water by epoxy resins is a multilayer
process,16 usually represented by sigmoidal iso-
thermal curves of type II in the Brunauer–Em-
met–Teller (BET) classification.42 This indicates
that, initially, sorbed water molecules are able to
interact with binding sites of the polymer, while
subsequent molecules associate with the primary
layer in liquid waterlike structures. At more ele-
vated temperatures, isotherms approach linear-
ity, revealing simple solution sorption, which is
asymptotically approximated by Henry’s Law.16
The negative and positive deviations of the ex-
perimental results from Henry’s Law of isother-
mal equilibrium water absorption have been de-
scribed by Galin and Galin,43,44 in other poly-
meric systems by use of the Guggenheim–
Anderson– de Boer (GAB) isothermal absorption
model.45
Infrared (IR) and nuclear magnetic resonance
(NMR) spectroscopy also confirm the formation of
hydrogen bonds between water and the polar
groups of the resin. Antoon and Koenig demon-
strated by Fourier transform infrared (FTIR)
spectroscopy that although some of the changes in
the spectrum of wet epoxy resin specimens may
be attributed to solvent-induced alteration of
the electronic environment or conformational
changes and bond distortion due swelling, others
imply that water molecules interact preferen-
tially with polar species such as hydroxyl-ether
and phenyl-ether units, even with phenyl rings,
while saturated hydrocarbon units remain prac-
tically unaffected.46
In this work, we investigate the characteristics
of isothermal equilibrium and dynamic water ab-
sorption of a model epoxy resin system with dif-
 WATER SORPTION IN AN EPOXY RESIN SYSTEM 1167

ferent amounts of plasticizer. By changing the tion, as relaxation phenomena and changes in the
percentage of plasticizer, we can modify the flex- free volume influence the diffusion coefficient and
ibility, length, and packing density of macromo- the water content at saturation.48
lecular chains between crosslinks and the distri-
bution of hydroxyl groups (formed during the cur-
ing reaction) in the final product. This procedure EXPERIMENTAL
permits a better approach to the factors that in-
fluence the water absorption and gives explana-
Materials and Reactions
tions about the way water penetrates and diffuses
into polymer networks. The investigation of the The system studied was based on diglycidyl ether
hydration procedure can also give useful informa- of bisphenol-A (DGEBA) epoxy resin (Epon 828,
tion about the microstructure of the polymeric Shell), with a number-average molecular weight
material.33,34 M ne ' 370, cured with 8% per weight of the resin
The experimental results of dynamic water ab- triethylenetetramine (TETA), (Dow Chemical).
sorption exhibit deviations from Fick’s law, espe- The plasticizer used was a polysulfide with the
cially at low temperatures and low plasticizer commercial name THIOCOL LP3 (Thiokol Chem.
content. To describe this behavior, a new ap- Corp., Switzerland), 1000 molecular weight, and
proach is used, which is based on the Fickian 2% crosslinking. The proportion of plasticizer was
mode of absorption but also takes into account the 0, 10, 20, 30, 40, 50, and 60% per weight of the
formation of hydrogen bonds and/or the heteroge- resin.49 The chemical structure of the materials
neous structure of the materials, as firstly pro- used is as follows.
posed by Jacobs and Jones. Based on the exis-
tence of bound water forming hydrogen bonds
with hydrophilic sites in epoxy resin sys-
tems26,27,46 and on the heterogeneous structure of
these systems,27,47 it is expected that Jacobs and
Jones (two-phase) type models will successfully
describe dynamic water absorption in our sys-
tem.31,33,34 From the fitting parameters of the
aforementioned model, we can calculate the dif-
fusion coefficient D and the water content at sat-
uration M ` for each phase (or each mode of ab-
sorption) separately. This permits the extraction
of useful results about the way water penetrates
the epoxide network and how the temperature
and the presence of plasticizer modify the struc-
ture of the material.
The negative deviations of the experimental
results from Henry’s Law at the first stages of
isothermal equilibrium water absorption (espe- The aminohydrogen to epoxy ratio r is calculated
cially for specimens with small amount of plasti- from the following equation:
cizer) are attributed to the Langmuirian mode of

S D S D
absorption due to the formation of hydrogen
6m a 2m e
bonds. The amount of bonded water and the po- r5 4 , (1)
tential of the bonds between the different types of M na M ne
absorbed water layers are estimated by use of the
GAB isothermal absorption model,43,44 which can where m a and m e are the initial weights of amine
also describe the positive deviations from Henry’s and epoxy prepolymer, and M na and M ne are
Law at the last stages of absorption due to forma- the number-average molecular weights, respec-
tion of water clusters.4 tively.50 If r equals 1, the amount of TETA is
Thermomechanical analysis (TMA) experi- stoichiometric. In our specimens, r equals 0.64
ments were also performed to detect the glass , 1, and so some of the epoxide groups do not
transition temperature (T g ) and the expansion react with TETA as its amount is less than the
coefficient (a g ) of the materials under investiga- stoichiometric one.
1168 MAGGANA AND PISSIS
The epoxide groups of DGEBA react with the
hydrogens of ONH2 and ONHO groups accord-
ing to the following reaction:
This reaction leads to the formation of hydroxyl
(OOH) groups, which show strong hydrophilic
character. As the amount of TETA is less than the
stoichiometric one, we accept that the final prod-
ucts, after the curing and post curing procedure,
do not contain amino groups. The plasticizer also
reacts with DGEBA, creating longer polymeric
chains between crosslinks.49
All specimens were prepared by the following
procedure. DGEBA, THIOCOL (in the specimens
present), and TETA were mixed at 35°C. The
mixture was vacuum-degassed for 5 min and cast
between parallel plates covered with silicone. Af-
ter 24 h, specimens were cut from the glassy
epoxy plates prepared by following the above pro-
cedure. These specimens were postcured for 24 h
at 100°C in a vacuum (5 3 1022 torr) oven to
remove water from the final product. The speci-
mens after the postcuring process are considered
as dry.
Dynamic Water Absorption
Three series of dynamic water sorption measure-
ments were carried out at 15, 40, and 70°C, by
immersion of dry rectangular samples into deion-
ized water in 50-mL Pyrex glasses. The dimen-
sions of the samples were n equal to 10 mm width,
l equal to 10 mm length, and b equal to 1 mm
thickness (Fig. 1). At appropriate intervals, the
samples were removed from water, blotted dry,
and weighed on an analytical balance (A200S,
Sartorius, accuracy 1024 g). The water content M t
was calculated by eq. (2), as follows:
wt 2 wd
Mt 5 3 100 (2)
wd
where w t is the weight of the wet specimen at
time t, and w d is the weight of the dry specimen.
Figure 1. Typical geometry of the specimens used in
diffusion measurements.
The experimental error in M t was estimated to
0.05% (absolute values). Typical curves obtained
by dynamic sorption experiments are plotted in
Figure 2, and they will be discussed in the Results
and Discussion section.
Equilibrium Water Sorption Experiments
Equilibrium water sorption isotherms were mea-
sured at 40 6 1°C. The samples (cylinders of 13
mm diameter and 1 mm thickness) were allowed
to equilibrate to constant weight in various des-
sicators with increasing values of relative humid-
ity (RH). The RH was monitored between 6 and
98% using different saturated salt solutions.51
The percentage of water content h, defined as
grams of water per 100 g of dry sample, was
determined by weighing on an analytical balance
(A200S, Sartorius, accuracy 1024 g). The experi-
mental error in h was estimated to 0.05% (abso-
lute values). After hydration reached full satura-
tion (at RH 5 1), the samples were dehydrated by
using the reverse procedure. Figure 3 shows the
variation of the percentage of water content h
with RH during a full absorption– desorption cy-
cle for two specimens with 0 and 40% THIOCOL.
The results will be discussed later.
 WATER SORPTION IN AN EPOXY RESIN SYSTEM 1169

of this, we refer to Fujita et al.7 and Vrentas and

Duda10). The one-dimensional case of Fick’s sec-
ond law implies that the material is exposed to
the environment on one side only, or on two sides
with both sides being parallel, as Figure 1 shows.
Using this assumption, the percentage mois-
ture content as a function of time (M t ) can be
calculated from eq. (4), as follows:

M t 5 G~M ` 2 M i! 1 M i (4)

where M i is the initial percentage of moisture

content of the sample, M ` is the percentage of
moisture content at equilibrium, and G is a time-
dependent parameter given by eq. (5), as follows:

G512
8
O
` F exp 2~2j 1 1! 2p S DG
Dt
b2
(5)
Figure 2. Typical results of dynamic absorption mea- p2 j50
~2j 1 1! 2
surements at three different temperatures obtained
with specimens with 20% THIOCOL. Lines are to guide
the eye. G is obtained by integrating the solution of eq. (3)
over the plate thickness b. An analytical approx-
imation for G is given by eq. (6),23 as follows:
TMA Measurements
TMA measurements were carried out on dry sam-
ples using a Du Pont Thermomechanical Ana-
lyzer (model 943) at a heating rate of 10 K min21
to determine the linear expansion coefficient and
the glass transition temperature T g of dry sam-
ples.48

MODELS FOR WATER

SORPTION/DIFFUSION

Fick’s Theory
In most of the cases, the kinetics of moisture
absorption is described by the one-dimensional
case of Fick’s second law, expressed by eq. (3), as
follows:

­c ­ 2c
5D 2 (3)
­t ­x

where c is the concentration of the diffusing sub-

strate, x is the distance through plate thickness, t
is the time, and D is the diffusion coefficient in
the direction of absorption ( x-direction normal to
the plate surfaces).23 D is considered to be inde-
pendent of the moisture content (for a discussion
Figure 3. Water sorption (closed symbols)– desorp-
tion (open symbols) isotherms at 40°C for two speci-
mens with 0 (solid lines) and 40% (dotted lines)
THIOCOL. Lines are to guide the eye.
1170 MAGGANA AND PISSIS

F S D G
0.75 the diffusivity of the fibers (D f ), the volume frac-
Dt
G 5 1 2 exp 27.3 (6) tion of the fibers (V f ), and the orientation of the
b2
fibers with respect to the exposed surface.
At the first stages of diffusion, the moisture con-
tent M t varies linearly with the quantity =t/b,
Modified Jacobs–Jones Model
and the diffusion coefficient D can be calculated
from the initial slope s of the diffusion curve in The Jacobs–Jones model accepts that in each
accordance to eq. (7),23 as follows: phase, the diffusion process is controlled only by
the density of that phase. Possible formation of

D5p S D
sb
4M `
2
(7)
hydrogen bonds between water molecules and hy-
droxyl groups of the resin is neglected because of
the lack of such kind of bonds in their system.
For specimens without moisture-impermeable In the following proposed model, the epoxide
coating at their edges, the calculated diffusion product is also considered as a two-phase sys-
coefficient should be corrected in accordance with tem,47,49 consisting of a master phase (phase 1),
eq. (8), proposed by Shen and Springer,23 as fol- where the major part of water is absorbed, and of
lows: a second phase (phase 2), with a different density
or/and hydrophilic character than phase 1.

S D 22 The Jacobs–Jones model can then be trans-

b b
Dx 5 D 1 1 1 (8) formed to eq. (10), as follows:
l n

H F S D GJ
0.75
where D x is the corrected value of diffusion coef- D 1t
M t 5 M 1 1 2 exp 27.3
ficient, and l and n are the length and the width b2
of the specimen, respectively.
H F S D GJ
0.75
D 2t
1 M 2 1 2 exp 27.3 (10)
b2
Jacobs–Jones Model
The analysis of Jacobs and Jones concerns two- where D 1 and D 2 and M 1 and M 2 are the diffusion
phase materials consisting of one dense and one coefficient and the percentage of absorbed water
less-dense phase.33,34 They propose that diffusion at saturation in the two phases, respectively. Ob-
proceeds by parallel Fickian processes in both viously, M ` equals M 1 1 M 2 . The first term of eq.
phases. Then the variation of the normalized wa- (10) is related to the diffusion of water molecules
ter content M(t) with time t can be described by in the homogeneous and nonpolar phase 1 (mode
the morphology-dependent eq. (9), as follows: 1). The second term of eq. (10) expresses the con-
tribution of water absorption in phase 2 (mode 2)

H F S D GJ
0.75 to the whole diffusion procedure. Figure 4 dem-
D dt
M~t! 5 V d 1 2 exp 27.3 onstrates schematically the evolution of both
b2 mechanisms and their contribution to water ab-

H F S D GJ D lt 0.75 sorption by a specimen with 0% THIOCOL at

1 ~1 2 V d! 1 2 exp 27.3
b2
Mt
where M~t! 5 , D d and D l are the diffusion
M`
coefficients of the less-dense and the dense phase,
respectively, and V d is the volume fraction of the
dense phase.
This analysis is based on the expressions de-
veloped by Shen and Springer23 to describe the
diffusion of moisture into fiber-reinforced compos-
ite materials. According to these authors, the dif-
fusion coefficient of the material (D x ) can be cal-
culated from the diffusivity of the matrix (D m ),
(9) 40°C. This figure is also a good example to dem-
onstrate that the water absorption behavior can-
not be described by only one diffusion coefficient.
The superposition of mode 1 and 2 results in
the solid curve (model), which gives a good de-
scription of the total absorption (details are in the
Result and Discussion section).
In accordance with the J. J. model, the diffu-
sion coefficient D 2 refers to the dense phase and
must be at least one order of magnitude less than
D 1 , as the penetration of water in this region is
hindered by the stiff crosslinking density. This
assumption is correct for systems where water
molecules are not strongly attached to polar
 WATER SORPTION IN AN EPOXY RESIN SYSTEM 1171

RESULTS AND DISCUSSION

Overall Behavior of Dynamic Absorption

Figure 2 shows, as already mentioned, the varia-

Figure 4. Schematic description of the evolution of
the two modes of diffusion and their contribution to the
total diffusion process. Lines express the values pre-
dicted by the proposed model and symbols the experi-
mental results.
groups of the polymer. We will demonstrate that
this is not always true, especially in cases where
hydration takes place at low temperatures or the
material contains strong hydrophilic centers.
tion of M t with the quantity =t/b for a specimen
with 20% THIOCOL at 15, 40, and 70°C. Similar
diagrams are obtained for all specimens. In gen-
eral, a slow positive deviation from an equilib-
rium state is observed at longer times; compare,
for example, the results for the specimen with
20% THIOCOL at 40°C in Figure 2. Such contin-
uous slow absorption processes have been re-
ported by numerous authors and can be attrib-
uted to slow relaxation processes of the glassy
epoxy network,52–54 to the filling of hygrother-
mally induced voids,21,22,25,55 and to further cur-
ing reaction in the system.56 These long-term hy-
grothermal aging processes25,56 have not been
studied in this work. The present investigation is
confined to the early stages of hydration up to the
Fickian pseudoequilibrium state.25 The experi-
mental results are fitted by eq. (9). The values of
fitting parameters M 1 , M 2 , and M ` and D 1 and
D 2 are listed in Table I. The values of D 1 and D 2
have been corrected according to eq. (8). Figures 5
and 6 show the variation of D 1 and D 2 and M 1 ,
M 2 , M ` with plasticizer and temperature.
These results confirm the existence of two dis-
tinguished modes of diffusion and that the whole
procedure should be considered as a superposition
of mode 1 and mode 2.
In all cases, the diffusion coefficient D 1 char-
acterizes the rate of diffusion in the loose regions
of the material. D 1 is the basic mechanism of
diffusion and concerns the major part of absorbed
water (Table I), which is considered as free water.
This observation proves that D 1 describes the

Table I. Fitting Values in Accordance with Eq. (10) of the Diffusion Coefficient and the Percentage of Water
Content at Saturation for Both Phases at 15, 40, and 70°C, for Specimens with Various Amounts of Plasticizer

15°C 40°C 70°C

%
Thiocol log D 1 M1 log D 2 M2 M` log D 1 M1 log D 2 M2 M` log D 1 M1 log D 2 M2 M`

0 213.05 1.95 210.40 0.13 2.08 212.55 1.69 211.66 0.51 2.19 211.90 2.48 213.70 0.96 3.44
10 213.13 2.15 210.60 0.14 2.29 212.54 2.02 211.60 0.41 2.43 211.73 2.98 2.98
20 213.14 1.98 210.88 0.19 2.16 212.29 2.22 213.72 0.54 2.76 211.60 2.70 2.70
30 213.08 2.05 210.09 0.14 2.19 212.18 2.32 213.15 0.29 2.61 211.54 2.70 2.70
40 213.05 1.96 210.26 0.15 2.12 212.13 2.38 212.99 0.02 2.39 211.41 2.70 2.70

Note: D 1 , D 2 are the diffusion coefficients (in m2 s21), and M 1 and M 2 are the percentages of water content at saturation for
phases 1 and 2, respectively.
M ` 5 M 1 1 M 2.
1172 MAGGANA AND PISSIS

water molecules and attach them by hydrogen

bonds. This procedure can be characterized as a
Langmuirian mode of absorption and exhibits sat-
uration immediately after the monolayer capacity
is reached. The attachment of the first water mol-
ecule to the nodule results in its disintegration

Figure 5. Variation of the fitting values of the diffu-

sion coefficients (a) D 1 and (b) D 2 of the two modes with
plasticizer content at 15, 40, and 70°C. Lines are to
guide the eye.

same absorption mechanism in all specimens,

which is affected mainly by the temperature. The
influence of temperature and plasticizer content
on D 1 values will be discussed later.
As mentioned before, D 2 is related with the
diffusion process in the dense and/or polar regions
of the material (mode 2), but it does not describe
the same diffusion mechanism in all cases. When
D 2 . D 1 , as Figure 7 demonstrates, the diffusion
is controlled by the formation of hydrogen bonds
between water and hydrophilic nodules. In this
case, water is considered as bound.
These nodules, formed during curing, are re-
gions with high crosslinking density. The curing Figure 6. Variation of the fitting values of the max-
reaction has as a result the formation of hydroxyl imum water content (a) M 1 and (b) M 2 of the two modes
(OOH) groups. The denser the crosslinking is, the and of the total maximum water content (c) M ` with
larger the concentration of OOH groups in this plasticizer content at 15, 40, and 70°C. Lines are to
region of the material is, so the nodules attract guide the eye.
 WATER SORPTION IN AN EPOXY RESIN SYSTEM 1173

Evolution of Mode 1 with Plasticizer and

Temperature
With increasing temperature, the fitted values of
D 1 increase for all specimens (Table I and Fig. 5).
The variation of D 1 with temperature is in accor-
dance with the Arrhenius eq. (11), as follows:

S D
D 1 5 D 0exp 2
W
kT
(11)

where W is the activation energy, D 0 is the pre-

Figure 7. Description of the evolution of the two
modes of diffusion and of their contribution to the total
diffusion process when the dense phase exhibits a
strong hydrophilic character (D 1 , D 2 ). Lines express
the values predicted by the proposed model, and sym-
bols express the experimental results.
exponential factor, and k is Boltzmann’s constant.
Plotting ln D 1 versus 1/T results in straight
lines (Fig. 10). The variation of the fitting values
of W and ln D 0 with the plasticizer content is
demonstrated in Figure 11. The parallel increase
of ln D 0 and W with the plasticizer content indi-
cates that as the amount of plasticizer increases,
the loose phase becomes looser and exhibits
greater segmental mobility. This permits water
molecules larger motions, which require greater
activation energy.24,57 The increase of D 1 values
with the plasticizer content, especially at higher
temperatures, verifies this assumption.

because the formation of the bond between OOH

groups and water requires breaking of the in-
tramolecular hydrogen bonds between the polar
groups of the resin, which are responsible for the
formation of the nodule. This hydrophilic proce-
dure can take place only at low temperatures
(Fig. 7 and Table I) when the hydrogen bond
formation is thermodynamically preferable.
At high temperatures, the hydrogen bond for-
mation tends to disappear, and the density of the
nodules mainly controls the diffusion of water in
the nodules. The absorption– diffusion mecha-
nism is similar with mode 1, but it develops at a
slower rate, as the nodule density prevents the
entrance of water molecules in the highly
crosslinked regions. In this case, D 2 , D 1 , and
the total result is much like that already de-
scribed by Jacobs–Jones (Fig. 8).
In experiments on specimens with large
Figure 8. Description of the evolution of the two
amounts of plasticizer at high temperatures, the
modes of diffusion and of their contribution to the total
mode 2 diffusion disappears (Table I), and the diffusion process when the dense phase does not exhibit
kinetics of absorption can be described simply by hydrophilic character (D 1 . D 2 ). Lines express the
the first term of eq. (10). This kind of behavior is values predicted by the proposed model, and symbols
schematically represented in Figure 9. express the experimental results.
1174 MAGGANA AND PISSIS

the plasticizer, forces water molecules to diffuse

Figure 9. Description of the evolution of the two
modes of diffusion and of their contribution to the total
diffusion process at elevated temperatures when the
materials become homogeneous (Fick’s Law). Lines ex-
press the values predicted by the proposed model, and
symbols express the experimental results.
faster through the vacancies of the free volume.
So, as the amount of plasticizer content increases,
the diffusion process becomes faster.
The maximum equilibrium water content of
the loose phase (M 1 ) is related to the free volume
of the material. Although all specimens exhibit
the same density at room temperature, their den-
sity decreases at elevated temperatures due to
expansion. The a g values increase as plasticizer
content increases (Fig. 13). So at elevated temper-
atures, specimens with large amount of THIO-
COL expand more than specimens with little or
without plasticizer, and, correspondingly, their
density decreases, and their free volume in-
creases.
For measurements at 15°C, the diffusion tem-
perature is too far from T g , so the relaxation
times for all specimens are much greater than the
time associated with the diffusion mecha-
nism.10,11,59 In addition, the hydrophilic phase is
well separated from the loose hydrophobic matrix.
So, the plasticizer content cannot affect the diffu-
sion coefficient, and all specimens exhibit the
same behavior represented by Figure 7. The dif-
fusion coefficient D 1 and the maximum water con-

As suggested by Figure 11, ln D 0 increase lin-

early with W (Fig. 12, where each point corre-
sponds to a plasticizer content). This linear de-
pendence known as the Mayer–Neldel rule or
compensation law has been observed in several
thermally activated processes.58
The variation of the D 1 values with the plasti-
cizer content should be related to the relaxation
rate, the free volume, and the hydrophobic char-
acter of the polymeric matrix. As the amount of
plasticizer increases, the glass transition temper-
ature (T g ) decreases, whereas both the expansion
coefficient (especially at elevated temperatures)
and the hydrophobic character of the material
increase. The variation of the expansion coeffi-
cient a g and of the glass transition temperature
T g with plasticizer content are plotted in Figures
13 and 14, respectively; a g and T g were obtained
from thermomechanical analysis (TMA) measure-
ments.
For diffusion experiments performed in the
glassy state, the relaxation time of the redistribu- Figure 10. Semilogarithmic plot of diffusion coeffi-
tion of the free volume decreases when the tem- cient D 1 of the loose phase versus the reciprocal of
perature of measurement approaches T g . The hy- temperature, 1/T. (Arrhenius plot) for three specimens
drophobic character of the loose phase, induced by with 0, 20, and 40% THIOCOL.
 WATER SORPTION IN AN EPOXY RESIN SYSTEM 1175

Figure 12. Variation of the pre-exponential factor D 0

with the activation energy W (each point corresponds to
a plasticizer content).

Fig. 5(a)]. As discussed above, the effect of an

increase in plasticizer content on D 1 is two-fold.
First, T g decreases with increasing plasticizer
content (Fig. 14), so that for experiments at the
same temperature, the relaxation time of the ma-
trix decreases. Second, the hydrophobic character
of the matrix increases with increasing plasticizer
content. M 1 values also exhibit an increase both

Figure 11. Variation of (a) the pre-exponential factor

D 0 and of (b) the activation energy W calculated from
the Arrhenius plots, with plasticizer content.

tent at saturation M 1 , which characterize the

loose phase, are nearly unaffected by the plasti-
cizer, with mean values of log D 1 5 213.1 and of
M 1 5 2%. These results indicate that at low
temperatures, the evolution of diffusion is similar
for all specimens and independent of plasticizer
content. It should be considered as a free diffusion
process without any preferable bond formation
between water and epoxy resin. All specimens
exhibit similar structure of the loose phase with
approximately the same free volume and the
same relaxation time of the matrix. The diffusion
coefficient D 2 is greater than D 1 (Table I) for all
specimens. Its evolution with plasticizer and tem-
perature will be discussed later.
At 40 and 70°C, D 1 values exhibit a systematic Figure 13. Variation of the expansion coefficient a g
increase with the plasticizer content [Table I and at 15 and 40°C with plasticizer content.
1176 MAGGANA AND PISSIS
Figure 14. Glass transition temperature T g , deter-
mined by TMA, versus plasticizer content.
with plasticizer content and temperature, related
to the increase of the free volume of the material
[Fig. 6(a)].
At 70°C, specimens with more than 10%
THIOCOL exhibit the same M1 equal to 2.7%,
indicating that the free volume of those mate-
rials is almost the same [Fig. 6(a)].
At 40°C, the specimens with 0 and 10%
THIOCOL exhibit similar values of D 1 . Also, for
both specimens, D 1 , D 2 , indicating that at 40°C,
the structure of the material remains practically
the same with the structure at 15°C. For speci-
mens with a larger amount of THIOCOL, the
increase in D 1 is larger. Additionally, D 1 . D 2 ,
indicating that at 40°C and plasticizer contents
larger than 10%, the hydrophilic character of the
material gradually disappears.
Evolution of Mode 2 with Plasticizer and
Temperature
At 15°C, the hydrophilic diffusion (mode 2) of all
specimens is characterized by similar values of
the diffusion coefficient (log D 2 ' 2 10.5) and of
the maximum water content (M 2 ' 0.15%) [Ta-
ble I and Figs. 5(b) and 6(b)]. Mode 2 is considered
as a very fast and strongly hydrophilic mecha-
nism, which reaches saturation at the very early
stages of diffusion (Fig. 7). The small values of M 2
are attributed to the fact that after the absorption
of water molecules at the primary hydration sites,
the nodules loose their strong hydrophilic charac-
ter and become unable to further attract water.
So, the mode 2 mechanism reaches saturation
and diffusion proceeds according to mode 1. The
independence of the values of D 2 and M 2 on the
plasticizer content indicates that at 15°C, all ma-
terials have the same structure consisting of hy-
drophilic nodules embedded in a loose hydropho-
bic matrix. The two phases are well separated and
behave in a similar manner independently of the
plasticizer content. So, all materials can be char-
acterized by similar values of D 1 and D 2 and M 1
and M 2 (Table I).
At 40°C, the structure begins to diversify. Both
the loose and the dense phases of the material
become looser. The effect of this change on the
loose phase has already been discussed. The effect
on the dense phase is more complicated. As
mentioned before, specimens with 0 and 10%
THIOCOL keep the same structure observed at
15°C; but the diffusion in the nodules is now
slower, although their density has diminished.
The nodules keep their hydrophilic character,
which is now, however, less pronounced, as the
decrease of density and the increase in tempera-
ture suppresses the formation of hydrogen bonds.
The result is a decrease of D 2 values [Fig. 5(b)].
The decrease of the density of the nodules leads to
an increase of their free volume and, thus, to an
increase of the M 2 values [Fig. 6(b)].
In specimens with 20 and 30% THIOCOL, the
nodules begin to disintegrate, loosing, in this way,
their hydrophilic character. Their structure at
40°C becomes similar to that of the loose phase
but denser. So the diffusion of water in the nod-
ules becomes slower without any preferable for-
mation of hydrogen bonds. D 2 values are lower
than D 1 values (Fig. 5), and the diffusion mecha-
nism is similar to that described by the Jacobs
and Jones model.33,34 For even higher plasticizer
content (sample with 40% THIOCOL) at 40°C, the
nodules can no longer be detected. The material
becomes homogeneous, and the diffusion can be
described by the first term of eq. (10) alone or
simply by Fick’s second law.
At 70°C, all plasticized specimens exhibit ho-
mogeneous structure. Water absorption is consid-
ered as a single-phase diffusion into a continuum
without any bond formation between water and
the polar groups of the resin. The first term of eq.
(10) can successfully describe the kinetics of dif-
fusion. In this case, M 2 equals 0 for all plasticized
specimens [Fig. 6(b)]. Only the specimen with 0%
THIOCOL exhibits a deviation from this behav-
ior, as it is the only one where the nodules can
 WATER SORPTION IN AN EPOXY RESIN SYSTEM
still be detected. As it is expected, their hydro-
philic character has disappeared because of the
high temperature, but they remain denser than
the rest of the material with a diffusion coefficient
D 2 , D 1 and maximum water content at satura-
tion M 2 equal to 0.97 [Fig. 6(b)].
Equilibrium Water Sorption
Equilibrium water sorption experiments were
performed at 40°C. In the following, the results of
these experiments will be compared with those
obtained from dynamic absorption measurement
at the same temperature.
As observed in Figure 3, the desorption proce-
dure exhibits hysteresis compared to the absorp-
tion. This phenomenon is more pronounced in
specimens with 0 and 10% THIOCOL. As the
amount of plasticizer increases, the hysteresis
loop decreases and, finally, for the sample with
40% THIOCOL almost disappears (Fig. 3). These
hysteresis phenomena have also been observed in
other polymeric systems.2,60,61 They are usually
attributed to the formation of hydrogen bonds
between water and hydrophilic centers of the
material, which lead to permanent changes in
the structure of the specimen in the absorption–
desorption cycle. When the binding is strong,
the hysteresis loop is large (sample with 0%
THIOCOL in Fig. 3). If the binding is loose, ab-
sorption– desorption cycles tend to become almost
identical (sample with 40% THIOCOL in Fig. 3).
The sorption isotherms of specimens with 0
and 10% THIOCOL are sigmoid and belong to
type III in the Brunauer classification.3,42 All the
rest exhibit a parabolic shape and belong to type
II.3,42– 45 The negative deviation from the linear-
ity (i.e., sorption curves concave to the RH-axis)
is obvious for the specimen with 0 and 10%
THIOCOL and for water content values up to
0.5% and is indicative of the formation of hydro-
gen bonds (the Langmuirian type of absorp-
tion).2,62 This region becomes almost linear in
specimens with more than 10% THIOCOL. For
water content values greater than 1%, sorption
curves of all specimens exhibit positive deviation
from the linear behavior, usually attributed to
clustering of water molecules.4,62
Sorption isotherms of the aforementioned
shapes can be analyzed according to the so-called
Guggenheim–Anderson–De Boer (GAB) equation,
which is an amended form of the classical
Brunauer–Emmet–Teller (BET) equation.42– 45
The GAB equation [eq. (12)] allows one to take
1177
into account the experimental data over the whole
range of water activity a(a 3 1), as follows:
kf a
n 5 nm (12)
~1 2 f a !@1 1 ~k 2 1!f a #
where n is the number of sorbed molecules per
monomeric unit, n m is the number of sorption
sites per monomeric unit (first monolayer sorp-
tion capacity), k is the ratio of the binding con-
stants of water molecule directly bound to the
sorption site in the first layer and of that bonded
indirectly in the succeeding liquid-like layers, and
f is the ratio of the standard chemical potential of
the indirectly bound water molecule and that of
the molecule in the bulk liquid state.
For k values higher than 1, the site-bound wa-
ter molecules may be considered as strongly
bound, while indirectly bound water may be con-
sidered as loosely bound.43,44
For k values higher than 1, the directly bonded
is considered as strongly bound, while the indi-
rectly bound water may be considered as loosely
bound.43,44
The greater the value of k is, the stronger the
bond between the water molecule and the hydro-
philic site. Values of f less than unity imply that
the outermost hydration layer is formed by water
molecules of lower activity than bulk water so
that extra layers of water are required to be as-
sociated with the hydrated specimen before it can
become fully accommodated into normal bulk wa-
ter. Low values of f are indicative of the hydro-
phobic character of the polymer.3 When f equals
1, the GAB equation reduces to the BET.
Our experimental data were fitted by eq. (13),
as follows:
kf ~RH!
h 5 hm (13)
~1 2 f ~RH!!@1 1 ~k 2 1!f ~RH!#
where h is the percentage of water content in the
specimen, and h m is the percentage of water con-
tent directly bound to the hydrophilic sites. RH is
the relative humidity, which is approximately the
same as the activity a. Figure 15 shows the ex-
perimental water content values versus RH (sym-
bols) and the fit of eq. (13) to the experimental
data (solid lines).
The variation of the fitting values with the
amount of plasticizer is listed in Table II and
plotted in Figure 16.
1178 MAGGANA AND PISSIS

Figure 15. Water absorption isotherms at 40°C for

three specimens with 0, 20, and 40% THIOCOL. Lines
are fitting of the GAB equation [eq. (13)].

The results indicate that at 40°C, specimens

with 0 and 10% THIOCOL demonstrate strong
hydrophilic mode of absorption related with the
high values of the k parameter. This behavior
tends to disappear in specimen with 20% or more
THIOCOL (k 3 1). The systematic increase in h m
with plasticizer’s content is followed by a decrease
in k values. This means that the increase of the
amount of plasticizer hinders the aggregation of
the hydrophilic OOH groups and forces them to
disperse in the material. So the strong hydro-
philic centers disintegrate, and although the first
Figure 16. Variation of the fitting parameters of the
GAB equation (h m , k, and f ) with plasticizer content.
Table II. Results of the Analysis Following the
GAB Equation [eq. (13)] of the Sorption Data at 40°C
for Specimens with Various Amounts of THIOCOL
layer of water molecules is bonded to the hydro-
% Thiocol hm k f
philic sites of the polymer, the binding intensity is
almost comparable to that of the indirectly
0 0.57 6.50 0.76 bonded layer.
10 0.72 3.31 0.73 Especially for the specimen with 0% THIOCOL,
20 1.30 1.13 0.64 the amount of water directly bonded to the polar
30 1.32 1.40 0.64 centers is equal to that calculated by the proposed
40 1.36 1.39 0.60 model of dynamic absorption (Table I).
The calculated h m values for the specimens
Note: h m is the percentage of water content directly bound
to the hydrophilic sites; k is the ratio of the binding constants with 0 and 10% THIOCOL should be compared to
of water molecule directly bound to the sorption site in the M 2 values obtained by the proposed model of dy-
first layer and of that bound indirectly in the succeeding namic absorption at 40°C (Table III). For the
liquid-like layers; f is the ratio of the standard chemical po-
tential of the indirectly bound water molecule and that of the specimen with 0% THIOCOL, h m is nearly equal
molecule in the bulk liquid state. to M 2 and k equals 6.5. This is indicative of the
 WATER SORPTION IN AN EPOXY RESIN SYSTEM 1179

Table III. Calculated Values of the Percentage of Table IV. Experimentally Determined Values of the
Water Content Directly Bound to the Hydrophilic Percentage of Water Content at Saturation (h max)
Sites {h m in the GAB equation [eq. (13)] Equilibrium from Equilibrium Water Sorption Experiments at
Water Sorption at 40°C} and of the Percentage of 40°C and the Calculated Values of the Maximum
Water Content at Saturation for Phase 2 [M 2 in Eq. Water Content at Saturation (M ` ) from the Fitting
(10); Dynamic Water Absorption at 40°C] of Dynamic Absorption Results at the Same
Temperature
% Thiocol hm M2
% Thiocol h max M`
0 0.57 0.51
10 0.70 0.41 0 2.04 2.19
20 1.30 0.54 10 2.30 2.43
30 1.30 0.29 20 2.39 2.76
40 1.36 0.02 30 2.48 2.61
40 2.31 2.39

strong hydrophilic mode, which characterizes

both equilibrium absorption and diffusion. For fully in agreement with the results obtained by
the specimen with 10% THIOCOL, the fitting the proposed model of dynamic absorption.
value of h m is higher than M 2 . A possible expla- The systematic decrease of f values with plas-
nation for this is that M 2 and h m do not corre- ticizer content indicates the increase of the hydro-
spond exactly the same quantity. M 2 values are phobic character of the specimen with the amount
attributed to the amount of water absorbed by the of plasticizer.3
strong hydrophilic nodules, while h m values are The results obtained by the isothermal equilib-
attributed to the amount of water bonded to the rium absorption measurements prove the validity
primary positions of hydration. In the specimen of the proposed dynamic absorption model.
with 0% THIOCOL, the primary positions of hy- Table IV and Figure 17 show the experimen-
dration are located on the nodules, and, thus, h m tally determined values of the percentage of wa-
is nearly equal to M 2 . In the specimen with 10%
THIOCOL, the increase of the plasticizer content
leads to a decrease of the number of strong hydro-
philic nodules, resulting in a decrease of the
amount of water absorbed by them. The disinte-
gration of some of the nodules, as mentioned be-
fore, increases the number of hydrophilic sites,
but decreases, at the same time, their binding
intensity. So, only part of the water bound di-
rectly to the hydrophilic sites is strongly bonded
to the nodules, while the rest is loosely bonded to
the dispersed hydrophilic sites, so that h m , M 2 .
The parameter k characterizes the binding
strength of the total amount of water directly
bonded to the primary positions of hydration. Its
decrease in the case of the specimen with 10%
THIOCOL (k 5 3.3) can be attributed to the de-
crease of the percentage of the nodules (compared
with the specimen with 0% THIOCOL).
In the specimens with 20% THIOCOL or more,
M 2 expresses the maximum water content of the
dense phase, while h m is related to the amount of
water directly bonded to the hydrophilic sites. So, Figure 17. Variation of the maximum water content
it is not surprising that M 2 and h m get different at 40°C when absorption takes place in a humid envi-
values (Table III). The small values of k (k 3 1) ronment with 100% RH (h max, experimental values)
calculated for all these specimens are indicative and for immersion into the water (M ` , theoretical val-
of the lack of strong hydrophilic nodules and are ues predicted by the proposed model).
1180 MAGGANA AND PISSIS
ter content at saturation (h max) from equilibrium
water sorption experiments and the calculated
values of the maximum water content at satura-
tion (M ` ) from the fitting of dynamic absorption
results at 40°C. The values of M ` ) are, in all
cases, greater than h max values.
Differences in water content at saturation be-
tween specimens hydrated by immersion into the
water and specimens hydrated by exposure to
environment with 100% RH are also observed in
other polymeric systems. Results to be published
show that in rubber-modified epoxy resins, water
contents determined from immersion experi-
ments are larger than those determined by expo-
sure to water vapor. This difference is usually
attributed to the formation of microcracks and
vacancies22 or to further reaction between water
and epoxy resin.63 These phenomena are more
pronounced when the specimen is immersed into
the water. In our experiments, the difference be-
tween M ` and h max values is small, and, consid-
ering that M ` values are theoretical and h max is
experimental, it can almost be neglected (except
from the specimens with 20% THIOCOL, which
will be discussed later). These results indicate
that hydration by immersion does not provoke
more damage in the specimen at 40°C compared
with absorption by exposure to humid environ-
ment. For the specimen with 20% THIOCOL, the
fitting parameters of the proposed dynamic ab-
sorption model indicate the existence of a dense
phase with log D 2 nearly equal to 13.72 and M `
nearly equal to 0.54. As the calculated diffusion
coefficient of the dense phase is very small, and
the amount of water absorbed in this phase large,
h max probably does not correspond to equilibrium.
This means that more water would be absorbed in
the dense phase if the specimen were exposed for
longer time in the equilibrium water sorption ex-
periment.
CONCLUSIONS
Dynamic water absorption measurements and
isothermal equilibrium sorption measurements
performed on a DGEBA/TETA epoxy resin system
with various amounts of plasticizer THIOCOL
were used to investigate the characteristics of
sorption and diffusion of water in epoxide sys-
tems.
The experimental results of diffusion were an-
alyzed by using a model described by eq. (10).
This model considers epoxide product as a two-
phase system consisting of a master phase (where
the major part of the water is absorbed), which is
homogeneous and nonpolar (phase 1), and a sec-
ond phase with different density and/or hydro-
philic character (phase 2). Although the overall
diffusion process exhibits deviation from Fickian
behavior, the proposed model accepts that the
diffusion of water in each phase is Fickian and
can be characterized by a diffusion coefficient (D 1
for phase 1 and D 2 for phase 2) and a maximum
water content at saturation (M 1 for phase 1 and
M 2 for phase 2).
The main results can be summarized as fol-
lows.
● The diffusion coefficient D 1 characterizes the
rate of diffusion in the loose regions of the
material. At 15°C, all specimens exhibit sim-
ilar values of D 1 equals approximately 8
3 10214 m2 s21 and M 1 equals approximately
2%, independent of the plasticizer content,
indicating that, at this temperature, the
structure of the loose phase is similar for all
materials. At 40 and 70°C, D 1 exhibits an
increase with the plasticizer content, most
pronounced at 70°C. This phenomenon is at-
tributed to the decrease in the relaxation
time and the decrease of hydrophobic char-
acter of the loose phase as the amount of
plasticizer increases. Variations in M 1 val-
ues at 40 and 70°C are related to variations
in the free volume of the specimen.
● The variation of D 1 with temperature follows
Arrhenius behavior. The parallel increase of
ln D 0 (D 0 , the pre-exponential factor) and W
(W, the activation energy), calculated from
Arrhenius plots, with the plasticizer content
indicates that, as the amount of plasticizer
increases, the loose phase becomes looser
and exhibits greater segmental mobility.
● D 2 is related to the diffusion process in the
dense and/or polar regions of the material
(mode 2). When D 2 . D 1 , the diffusion in
phase 2 is controlled by the formation of hy-
drogen bonds between water and hydrophilic
nodules. The small values of M 2 at 15°C are
attributed to the fast saturation of primary
hydration sites of the nodules, which loose
their strong hydrophilic character and be-
come unable to further attract water. This
behavior is observed for all specimens at
15°C and for the specimens with 0 and 10%
THIOCOL at 40°C.
● When D 2 , D 1 , the hydrophilic character of
 WATER SORPTION IN AN EPOXY RESIN SYSTEM
the nodules has disappeared, and the diffu-
sion of water in phase 2 is controlled mainly
by their density. The absorption– diffusion
mechanism is similar to mode 1, but it devel-
ops at a slower rate in the denser nodules. In
this case, observed at 40°C for specimens
with plasticizer concentration larger than
10% and at 70°C for the specimen with 0%
THIOCOL, the total result is very similar to
that already described by Jacobs–Jones.33,34
● At 70°C, in all specimens with THIOCOL
concentration larger than 0%, mode 2 disap-
pears, and the materials are characterized as
homogeneous. Fick’s second law can then de-
scribe the diffusion process.
● Sorption isotherms obtained at 40°C were
analyzed according to the GAB equation.
They exhibit deviations from linearity and
belong to type II or III in the BET classifica-
tion.
● The large values of parameter k in GAB for
the specimens with 0 and 10% THIOCOL
verifies the strong hydrophilic mode of ab-
sorption at the first stages of hydration. The
values of k equals approximately 1 for all the
other specimens indicates that the hydro-
philic centers have disappeared. These re-
sults are in accordance with those obtained
by diffusion measurements at the same tem-
perature.
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