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The Diffusion Time Lag in Polymer Membranes Containing Adsorptive Fillers
The Diffusion Time Lag in Polymer Membranes Containing Adsorptive Fillers
41,79-93 (1973)
SYNOPSlS
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
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.
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
-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
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
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
U
0
\
a
P (cmHg1
TABLE I1
CA b
Gas (an3(STP)/
(cmHg)-'
cm3 sieve)
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
'pP
- -
D - _1
K
prn Dm
1.6
-- I I
0 COZ
1.5 - A CH4
N2
1.4- OH;
E
a 1.3-
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
The authors wish to exprcss their appreciation to the National Science Foundation and
the Lubrizd Corporation for financial support.
REFERENCES