J. POLYMER SCI.: Symposium No.

41,79-93 (1973)

THE DIFFUSION TIME LAG IN POLYMER MEMBRANES

CONTAINING ADSORPTIVE FILLERS

D. R. PAUL and D. R. KEMP

Department of Chemical Engineering,

Uniuersily of Texas, Austin, Texas 78712

SYNOPSlS

Immobilizing adsorption of diffusing penetrants is known to occur in a number of

polymer membrane systems. It will cause very large increases in the diffusion time lag but
will have only minor effects on the steady-state permeation. This effect may be troublesome
in that considerable errors may be incurred when the time lag method is used to analyze
quantitatively the sorption and diffusion behavior in such systems. On the other hand, this
effect can be utilized in a beneficial way to design very effective protective coatings,
packaging materials, timed release mechanisms, etc. for special situations. The time lag in
this case can be predicted very accurately from a theoretical result reported previously. This
point is demonstrated here by comparing theoretical predictions with experimental time lag
data obtained for various gases in a model membrane synthesized by dispersing highly
adsorptive molecular sieves into silicone rubber. The agreement is excellent.

INTRODUCTION

There are numerous situations where small penetrant molecules are present
in polymer systems with at least two different states of molecular mobility. In
all cases there can be penetrant molecules which are simply dissolved and are
thus free to diffuse. But in certain instances a mechanism may be operative
which can bind penetrant molecules to fixed sites and effectively immobilize
them. Examples include binding of dyes to specific sites in fibers by chemical
reaction or strong ionic bonding, adsorption of a penetrant onto a filler or other
high energy site in the polymer, or the proposed clustering of water observed in
some polymers [ 11. Penetrant diffusion in such systems is described by applying
Ficks law to the mobile species and properly accounting for the conversion
from mobile to immobile states and vice versa. The presence of a mechanism for
immobilization will not have much effect on the steady-state rate of transport of
the penetrant but it will have a profound effect o n transient diffusion [2-61.
This is most easily visualized in permeation through membranes where the
transient diffusion prior to the attainment of steady-state results in a time lag, 8.
Immobilization of the penetrant will serve to increase the time lag since more

79

0 1 9 7 3 by John Wiley & Sons, Inc.

80 PAUL A N D KEMP

penetrant has to diffuse in before steady-state is reached. In an earlier paper (21,

we developed a quantitative theory for the time lag in a system with
immobilizing adsorption. Specifically this theory considered the mobile species
to follow a Henrys law isotherm while the immobile species was considered to
follow a Langmuir isotherm. This form has rather widespread applicability. We
will report here on some experimental results recently obtained [7] using a
model system prepared by dispersing highly adsorptive molecular sieves into a
silicone rubber membrane. The sorption characteristics fit exactly that described
above, and the previously mentioned theory can be adapted t o this system rather
easily. The theory predicts the experimental results very nicely using no
adjustable parameters. Before describing these results, it will prove interesting to
consider examples of where this phenomenon occurs and its importance.

EXAMPLES OF PENETRANT IMMOBILIZATION

ACCOMPANYING DIFFUSION

Numerous situations exist in which immobilization of the penetrant occurs.

At least two cases have been reported which illustrate its effect on the diffusion
time lag. A brief description of these systems will serve to place the current
results in better perspective.
Higuchi, et al. [4-51 were interested in developing protective ointments or
creams which could be applied t o the skin for the purpose of providing the
treated area with protection from toxic agents that could be absorbed through
the skin. They presented the novel argument that it would be better t o develop a
coating which created a very long diffusion time lag for the toxic agent rather
than to try t o reduce the steady-state rate of transport of this agent. This is quite
appropriate when any measurable steady rate would produce a lethal effect.
They were able t o create such a barrier by dispersing a high surface area silica gel
in white petrolatum. The silica gel strongly adsorbs the toxic penetrant. They
presented data showing very large increases in the diffusion time lag with coatings
containing the silica gel in comparison to coatings without it. However, the
steady rate of transport occurring on breakthrough after the time lag, was
reduced only slightly by this adsorptive filler. Their data document very nicely
the feasibility of the concept of providing barrier protection via increased time
lags for one type of application. They presented a sound qualitative explanation
of the increased time lag, but the mathematical theory they proposed is
quantitatively inadequate.
Most [6] was interested in the use of silicone rubber as an implantable
sustained-released carrier for medicaments. As part of his evaluation, he
attempted t o employ the standard time lag experiment to determine the
diffusion coefficients (D = Q2/60)of various drugs in this material. Many silicone
rubber formulations employ fillers which would adsorb these agents. He found
that the presence of such fillers increased the diffusion time lag manyfold more
than they affected the steady-state transport. Most recognized what was
occurring and correctly concluded that the simple time lag theory could not be
employed to determine D.
 TIME DIFFUSION LAG 81

Both of these situations provide examples of the effects accounted for

previously [ 2 ] on a theoretical basis. However, neither can be described
quantitatively by this theory owing t o the lack of complete supporting data on
the sorption characteristics of the fillers employed. The current experimental
data provides this opportunity to demonstrate the effectiveness of the theory
since the latter data were obtained.
Other cases in which adsorptive fillers are added to polymers are well known
IS], and it is certain that similar effects on the time lag would be observed. In
fact, it is likely that many data obtained for such systems in the past have been
obscured for just this reason. On a more positive note, it is interesting t o
speculate on the advantages that could accrue by designing coatings or packaging
materials where fillers are added to gain enhanced barrier properties via increased
time lags rather than attempting to select systems with low permeabilities.
Another very interesting example likely to have considerable fundamental
and practical importance is provided by glassy polymers. Michaels, Vieth, e t al.
[9-121 have reported very convincing evidence that a dual sorption mode is
operative for many gases in glassy polymers. One mode is by Henrys law which
generates a mobile population of dissolved penetrant whereas another popula-
tion exists which is described by a Langmuir adsorption isotherm. The latter
population is believed t o be immobilized [3], and the gas molecules are
envisioned as being located in holes which are not well understood but are a
very interesting and apparently real feature of the glassy state.

TIME LAG THEORY

Transient diffusion in a system where the penetrant may exist in either a

dissolved and thus mobile state or an adsorbed and thus immobile state can be
described generally by the following modification of Ficks second law [7]

for unidirectional transport. The concentration of dissolved penetrant, a gas in

our case, is denoted by C, and adsorbed penetrant by C,. For the current
situation it turns out that sorption equilibrium can be described by Henrys law
for the mobile gas and a Langmuirs isotherm for the immobilized gas. It was
shown previously that the diffusion time lag, 8, for conventional transient
permeation through a membrane meeting these conditions is given by [ 2 ]
82 PAUL AND KEMP

provided that ultimately a point by point equilibrium is established in the

membrane between CD and C, . The terminology in eq. (2) is as follows

II = membrane thickness
D = diffusion coefficient
K = CA b/kD
Y = bP2
f(y) = 6y-3[iy2 + y - (1 + y) l n ( 1
f(0) = 1
+
1
y)

f(m) = 0.

The constants C, and b are the parameters in the Langmuir isotherm

and kD is the Henrys law coefficient from

C, = k,p. (4)

The upstream gas pressure in the conventional time lag experiment is p2. It is
assumed that the downstream pressure is zero.
Equation (2) does not explicitly account for the heterogeneous nature of the
membrane as it existed in the experiments t o be described later. These
membranes were composed of a dispersed phase of an adsorptive filler,
molecular sieves, which occupy a volume fraction Vd, and a polymeric
continuous phase of volume fraction vp = 1 - Vd. We may adapt eq. ( 2 ) t o this
situation by writing the total concentraion of gas, C, in the membrane at
equilibrium as follows

C i bP
C = v P k Dp + v d -
1 + bp

where kD and C, are parameters which are applicable to the pure polymer and
dispersed phase respectively. We further require that transport in the hetero-
geneous system can be treated as if it were occurring in a continuum with an
effective diffusion coefficient D,. With these changes eq. ( 2 ) can be written as
[71
 TIME DIFFUSION LAG 83

where the time lag is given the subscript m since it is a property of the mixed
phase just as D, is. The other terms in eq. (6) have the same meaning as in eq.
(2). In subsequent comparisons of experimental data with this theory it will be
convenient t o use the reduced time lag defined by 6DmOm/P2whose rationale
derives from a simple rearrangement of eq. (6).
The membrane geometry. Q, and composition, Vd and vp, are easily
determined. In addition, the parameters k,, b, C I A % and D, can be determined
by independent experiments as will be described in the next section. With this
information, we can effect a quantitative comparison of the experimental time
lag with the prediction of eq. (6) without the use of adjustable parameters. It is
clear from eq. (6) that 8, will depend on the upstream gas pressure, p2, through
the term f (y) and the amount of sieves present through the term (vd/vp). The
experimental data will demonstrate the ability of eq. (6) to describe the response
of Om to these two factors.
The effect of immobilizing adsorption is to increase the time lag beyond that
expected in the absence of this process, i.e., P2/6D, as can be seen from eq. (2)
or ( 6 ) . This reflects the additional time required t o accumulate the excess
penetrant before steady state can be reached. The magnitude of the increase is
related to the amount of gas adsorbed relative t o that dissolved. This ratio will
depend on upstream pressure since the Langmuir isotherm saturates at higher
pressures while Henrys law continues t o increase.

EXPERIMENTAL

Two types of experiments were performed on the membranes loaded with

adsorptive fillers of interest here, viz. sorption and permeation. The sorption of
gas by membrane specimens was followed gravimetrically by a Cahn balance [7].
This determination yielded both kinetic and equilibrium data. The kinetic data
and its analysis will be discussed elsewhere [ 131 since only the equilibrium data
are required here. The permeation experiments were executed in a transient
mode t o yield the time lag and in a steady-state fashion to give the permeability.
The permeation equipment and procedures have been described in detail
elsewhere [7] so only a few essential details will be discussed here.
The permeation cell had a downstream gas collection vessel t o which an
absolute pressure transducer was connected. The pressure versus time record in
conjunction with the known downstream volume, Vcell, was used t o determine
the accumulative amount of gas having diffused through the membrane. The
downstream volume could be changed easily by opening or closing valves to an
interconnecting series of vessels with a range of volumes. This flexibility is useful
to accommodate the wide range of permeabilities encountered. The upstream gas
pressure was maintained constant during an experiment and could be conve-
niently varied over the range from 30 to 130 cm Hg. All experiments were begun
with both sides of the membrane exposed to a vacuum (- 100 p) which had
been held for a time adequate t o insure the membrane was in equilibrium with
this state. The temperature was held at 30C in all measurements.
84 PAUL AND KEMP

The detection o f the amount of gas transmission by allowing the pressure to

build up in the downstream receiving volume can cause errors in the observed
time lag and steady-state transmission rate [14] if this increase in pressure is
large. in this work this problem was of negligilbe concern owing to thc system
design and experimental execution. Likewise errors may be incurred if steady
state has not truly been reached in the portion of the run utilized in
extrapolating t o the time lag and for the determination of the steady-state
transport rate. Normally this problem is averted by making certain that only
data after about three time lags are employed in the calculation. In more
complex systems such as these, there is no assurance that this rule is adequatc. so
we devised an experimental check to assure that steady state was reached. I t
consisted of continuing a run until steady state appeared to be reached as shown
schematically by the first portion of the pressure-time trace shown in Figure 1.
At this point the valve connecting the downstream volume, V c e l l , to the
vacuum pump was opened for a time exceeding several time lags. During this
time a true steady state was reached for sure. Subsequently, this valve was closed
off and the pressure was allowed to build up again as shown by the second
portion of the pressure-time trace i n Figure 1 . If the slope of this line was equal
to that of the apparent linear portion of this first curve, it was certain that the
former was a steady reading. If the latter slope were larger, then the transient
run was repeated gencrally using a larger downstream volume. This approach,
while time consuming, assured accurate data.
The adsorptive filler employed here was a commercially avail able zeolite
(151 designated Molecular Sieve Type 5 A obtained from the Linde Division of
Union Carbide. The sieves are crystalline aluminosilicate particles with an
average size of 14 I-( and a density of 2.03 glcm3 when fully hydrated. The
crystal structure of this particular zeolite is such that there are large caverns
(-925 A3) connected by windows of approximately 4.2 A in opening. It will
adsorb molecules smaller than this, e.g. C 0 2 , N 2 , CH4, H20, and He; however,
polarity is particularly important in the magnitude and strength of the

-I /
-I
W /
/
/

FIG. 1. Illustration of a downstream pressure vs. time record showing test for steady-state.
 TIME DIF1:USION LAG 85

adsorption. Water is adsorbed very strongly and will displace other species
already adsorbed. Adsorbed molecules can be removed by activation under
varying combinations of vacuum and elevated temperature. The degree of
activation will depend on the specific conditions and the molecule adsorbed. The
capacity for the individual gases employed here varies widely as illustrated by
that for COz of
adsorption for He.
- 140 (cc(STP)/cc) at 1 atm as compared to essentially no

A silicone rubber was selected as the polymer matrix for the filled
membranes primarily because of the thermal stability it afforded for the in situ
activation of the molecular sieves to be described subsequently. It was supplied
by the General Electric Co. in the form of a low viscosity, clear liquid
(RTV-602). It was cured into a rubber-like material by 0.3 wt.% of the curing
agent SRC-05. Membranes were prepared by casting on a mercury surface. Prior
to casting, the molecular sieves werc dispersed into the fluid silicone prepolymer.
Microscopic examination of the finished membrane showed that the sieves were
very unformly dispersed. To assure an accurate volume fractional loading of the
filler the sieves were fully hydrated and then weighed into the polymer.
Subsequent activation steps removed this water.
In order to assure that the embedded sieves were at the same level of
activation for all permeation experiments a standard activation procedure was
adopted. It consisted of preparing all membranes with sieves that had been
previously saturated with water and then removing the water in a vacuum oven
after the membrane was formed. To accomplish this the membrane was
maintained at 200C under high vacuum for approximately 3 hr. Subsequently
the oven was flooded with nitrogen and the membrane was removed imme-
diately and assembled into the permeation cell. After this initial thermal
treatment, subsequent activation of the sieves was accomplished by maintaining
the membrane under high vacuum for approximately 2 days at 30C. That is,
COz, N2,or CH4 adsorbed in a previous experiment was desorbed prior to the
next experiment by a vacuum cycle. The level of activation achieved by these
means is referred t o here as vacuum activation and was found to be
reproducible. A comparison of the sorption capacity of the sieves when treated
in this manner and the capacity when thermally activated can be seen in Figure
2. The equilibrium sorption isotherms shown were obtained by performing
sorption experiments with a Cahn microbalance at 30C with samples of the
membranes used in the permeation experiments.
Six different membranes, all approximately 1 mm thick, were prepared
containing from zero to 0.216 volume fraction of sieves. Four gases, He, NZ,
CH4, and COz, were employed as the penetrant.

EVALUATION OF PARAMETERS

The procedures employed to evaluate the parameters kD, b, C A , and D ,

appearing in eq. (6) are described here.
Conventional time lag and permeability experiments were performed on pure
86 PAUL AND KEMP

CI)
a
0

0 20 40 60 80
P (cmHg )

FIG. 2. Equilibrium sorption isotherms for Linde 5A molecular sieves at various states of
activation embedded in silicone rubbcr. The solubility of CO, in the silicone rubber has
becn subtracted out.

TABLE I

Transport Properties of RTV-602 Silicone Rubber

CO, 3.06 x 10-7 2.14 x 10-5 14.5 x 10-3

CH, 0.994 x 10-7 1.77 x 10-5 5.67 x 10-
N2 0.329 X 1.98 x 10-5 1.68 x 10-~
He 0.455 X lo- 7.86 x 10-5 0.582 X lo-

silicone rubber membranes containing no molecular sieves. This permitted

determination of the permeability, P, in the usual fashion, and the diffusivity, D,
was calculated from the time lag by P2/60.The Henrys law coefficient for the
polymer was determined from P/D. The average values of these quantities from
several experiments are given in Table 1.
The sorption of gas by the sieve loaded membranes were determined
gravimetrically by a Cahn microbalance. These experiments were carried t o
equilibrium in a series of experiments where the gas pressure at equilibrium
ranged from about 10 up to 70 cm Hg. The amount of gas dissolved in the
 TIME DIFFUSION LAG 87

membrane matrix k, p vp (membrane volume) was subtracted from the

measured equilibrium uptake. This difference represents the amount of gas
adsorbed by the sieves in situ in the membrane at this pressure. This was divided
by the volume of sieves in the membrane to obtain C,. A typical plot of C,
versus pressure is shown in Figure 2 for C 0 2 . The amount of C 0 2 adsorbed after
vacuum activation is less than that after a more stringent thermal activation
for reasons discussed earlier. A comparison with data from Linde is provided by
the dashed curve.
Langmuirs isotherm can be rearranged t o the linear form

P 1
- + - P. (7)
c, bc;, ci
The data from Figure 2 are replotted in Figure 3 in this form, and it is evident
from the straight lines obtained that the sorption data can be described by this
equation for all states of activiation although different values of the parameters
b and CIA are required. From the slopes and intercepts of similar plots for the
other gases, the values of the parameters b and CIA were obtained for the
vacuum activation state with the results given in Table 11. The effective
diffusivity, D,, was determined from the measured steady-state permeability of
the filled membrane, P,. After saturation with gas the sieve particles are
effectively impermeable barriers t o the gas molecules in comparison to the
polymeric matrix [7]. Van Amerongen [16] has shown that the diffusion
coefficient, D,, in polymer membranes containing a dispersed, impermeable
filler is related to that in the matrix phase, D, by

D, = KD

where K is a structural factor that accounts for the geometric obstruction by the
filler. The same factor along with the volume fraction of the polymer, vp, relates
the permeability of the filled system, P, to that of the unfilled system, P, as
follows

P, = VpKP. (9)

Thus by eliminating K from eqs. (8) and (9) the following relation results

D vpP

, using measured values of D, P, and P,. Values

from w h c h we can obtain D
obtained in this way were used in subsequent comparisons of time lag data with
eq. (6). The values of D, were never less than 0.75 D for the most highly filled
 88 PAUL AND KEMP

U
0
\
a

P (cmHg1

FIG. 3. Lincarizcd Langmuir plot.

TABLE I1

Langmuir Parameters for Sorption on Vacuum

Activated in Situ Molecular Sieves

CA b
Gas (an3(STP)/
(cmHg)-'
cm3 sieve)

co2 102.6 0.0928

CH4 43.4 0.00632
N2 14.6 0.0158

membranes. In a later section these experimental values of D , are compared

with some model predictions.
It is worthwhile t o reiterate herc that the current theory predicts and our
experiments confirm that an adsorptive filler has only a small effect on the
stcady transmission rate owing to the geometric filer effect even through it has a
very large effect on the kinetics of transient transport. The steady transmission
rate is given by
 TIME DIFFUSION LAG 89

TIME LAG RESULTS

Figure 4 provides a clear illustration of the effect an adsorbing filler has on

the results of a time lag experiment. The curve labeled Vd = 0 is for a pure
silicone rubber membrane. The time lag here is quite short. The curve labeled Vd =
0.202 is for a membrane loaded with molecular sieves at this volume fraction.
The time lag for COz with the sieves present is about two orders of magnitude
larger than the value when there are no sieves. Carbon dioxide produces a very
large effect owing t o the great extent it is adsorbed. On the other hand, the
steady-state permeation rate has been reduced by only about 30% owing strictly
to the filler effect the impermeable sieves produce. Figure 5 illustrates how the
time lags for different gases are affected by the different degrees of adsorption.
The time lag in a sieve loaded membrane may be expected to decrease with
increases in upstream gas pressure for reasons discussed earlier (also see [ 2 ] and
171). Figure 6 is a test of the ability of eq. ( 6 ) to predict this quantitatively for
COz in a membrane containing 21.6% sieves. The 0 , versus pz response is
plotted using dimensionless reduced variables suggested by eq. ( 6 ) . The open
circles are experimental data points while the curve was computed from eq. (6).
The parameters required for the construction of this figure were experimentally
derived by the procedures described in previous sections. The agreement of the
experiment and theory are excellent as judged by this stringent test where no
adjustable parameters are employed.
These results show that if the simple relation between the time lag and the
diffusion coefficient, D = P2/6tl, is applied to experimental data where

t, min.

FIG. 4. Transient permeation cspcriments for pure silicone rubber membranes (vd = 0) and
silicone rubber loaded with activated molecular sieves.
90 PAUL AND KEMP

1, rnin

FIG. 5 . Transient permeation experiments for four gases and one silicone rubber membrane
with vacuum activated sieves.

FIG. 6. Response of the diffusion time lag in dimensionless form to the upstream gas
pressure for a membrane loaded with molecular sieves.

immobilizing adsorption is occurring, then the D calculated will be too small and
will depend on the upstream gas pressure. The latter could lead one to
erroneously conclude that D is concentration dependent.
As the sorptive capacity is increased by increasing the sieve loading, Vd , the
time lag will increase. The ability of eq. (6) to predict this is shown in Figure 7
where results for membranes with different sieve loadings are shown for three
gases. Again the points are experimental and the curves are theoretical, with the
necessary parameters experimentally determined. The various gases show
different responses owing to the degree that they are adsorbed by the molecular
sieves. Two theoretical lines are drawn for each gas t o bracket the range of
pressures, p2, used in the experiments. Again the agreement between the
experimental facts and the theoretical predictions is excellent.
No results for He are given here since its adsorption on the sieves is so small
 TIME DIFFUSION LAG 9 1

FIG. 7. The effect of the amuunt of sieve loading on thc diffusion time lag for various
penetrants.

that the parameters C', and b could not be accurately determined. As a result
the increase in the time lag was also small.

PREDICTION OF D
, FROM THEORY

The effective diffusion coefficient, D ,, utilized in the previous section was

determined by experimental data inserted into eq. (10). There are, however,
several theories (see, e.g., [17]) which should allow one to estimate this quantity
since it differs from D only by the filler effect summarized in the parameter K
introduced earlier. We will compare our experimental data with three such
theories t o determine how effective they are at estimating K . Figure 8 shows this
comparison in the form of vpP/Pm versus vd. Rearrangement of eqs. (8)-(10)
reveals that

'pP
- -
D - _1
K
prn Dm

so that the ordinate of Figure 8 is also D/Dm or 1 / ~The

. points in Figure 8 are
92 PAUL A N D KEMP

1.6
-- I I

0 COZ
1.5 - A CH4
N2
1.4- OH;

E
a 1.3-

0 0.I 0.2 0.3 0.4

FIG. 8. Comparison of experimental permeabilities of filled membranes with the indicated

heterogeneous permeability models.

the experimental values of vpP/Pm. The solid lines were calculated from the
following theoretical models for impermeable fillers Maxwell [ I 81 :

1 = 1 .t -1V d
-
K 2

Bruggeman [ 191 :

Higuchi [20] :

2 ( 2 + v,) - K ( l - v,)
_1 -- with K = 0.78 . (15)
K 2+K

The experimental data except for C02 agree well with the Higuchi equation, and
it is clear that quite suitable estimates of Dm could be made from it. The
Higuchi equation is probably superior to the others because even though it has a
theoretical basis, it is somewhat empirical since the value of K was set at 0.78 by
Higuch because it gave the best fit with experimental data. The experimental
Dm for C 0 2 is about 14% lower than the Higuchi equation predicts. This
deviation may be owing t o a strong particle-penetrant interaction which exists
for C 0 2 but not the other gases that the Higuchi equation cannot account for.
Thc exact naturc of this apparently specific effect for C 0 2 cannpt be resolved
from the current data.
 TIME DIFFUSION LAG 93

SUMMARY

Immobilizing adsorption of diffusing penetrants is known t o occur in a

number of situations. It will cause very large increases in the diffusion time lag
but will have only minor effects on the steady-state permeation. This effect may
be troublesome in that considerable errors may be incurred when the time lag
method is used to analyze quantitatively the sorption and diffusion behavior in
such systems. On the other hand, this effect can be utilized in a beneficial way
to design very effective protective coatings, packaging materials, timed release
mechanisms, etc. for special situations. The time lag in this case can b e predicted
very accurately using physical parameters and adaptations of results reported
previously [2,7).

The authors wish to exprcss their appreciation to the National Science Foundation and
the Lubrizd Corporation for financial support.

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