J O U R N A L OF COLLOID AND I N T E R F A C E SCIENCE 9.9.

, 3 6 0 - 3 7 0 (1966)

Dual Sorption Mechanisms in Glassy Polystyrene

W O L F R. V I E T H , P H I M. TAM, AND ALAN S. M I C H A E L S

Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts

Received December 15, 1965

The solubility of CO2, CH4, A, and N~ in oriented and unoriented polystyrene films
at 25°C. has been investigated by the direct sorption method. It has been found that
Henry's law does not apply to sorption of CO~ and CHt4.The results can be quantita-
tively described by the postulation of two concurrent mechanisms for sorption: or-
dinary dissolution and mierovoid-filling.
The dissolution constants are correlated with the gas force constants, e/k. The
abnormally high solubility of CI-I~is probably due to the high polarizability of this
gas. The hole-affinity constants are also correlated with E/k. The deviation of CI-I~is
consistent with the behavior of the dissolution constant. The correlation of hole-fill-
ing constants with surface areas occupied by the individual gas molecules has been
successful.
Stress-induced orientation of polystyrene does not change the nature of the sorption
processes; however, it decreases the level of solubility. Orientation decreases the hole-
filling constants and the Henry's law solubility constants whereas it slightly increases
the hole-affinity constants.

INTRODUCTION where C is the gas concentration, kD is the

The study of the solubility of gases in
polymers serves a twofold objective: it per-
mits the establishment of correlations of gas
solubilities with readily available gas molec-
ular parameters and it also supplies informa-
tion on the morphology of polymers. In this
regard, several investigations dealing with
the solubility and diffusion of gases in rub-
bery crystalline polymers (1-3), in addition
to the work by Fieares (4-6) and the recent
work by Michaels, Vieth, and Barrie (7, 8)
with amorphous glassy polymers, have pro-
vided useful information for a comparison
of the rubbery and glassy states of polymers.
In the case of rubbery crystalline poly-
ethylene, Parker and Bixler (1, 2) have
found that Henry's law is applicable for
N2, 02, CO2, He, A, CO, CH4, C2I-I6,
C~H4, C3H~, C~I-Is, and SF~ up to 1.0 arm.
The solubility is successfully predicted by
Eq. [1]:
C = kDP,
Henry's law solubility constant, and P is
the equilibrium pressure. It was found that
all gases, with the possible exception of He,
dissolve only in the amorphous regions of
polyethylene. Hence, the solubility constant
kD for a particular gas is:
k~ = a k * . , [2]
where a is the volume fraction of amorphous
material and k*o is the solubility constant
in completely amorphous polyethylene. The
values of k*~ correlate satisfactorily with
the Lennard-Jones force constants e/k ac-
cording to the relationship developed b y
Jolley and Hildebrand for organic liquids
(9). The correlations parallel the lines for
organic liquids, indicating that, as regards
solubility behavior, organic polymers m a y
be idealized as high molecular weight or-
ganic liquids.
The above results lead to the concept that
[1] polyethylene consists of a distinct amorphous
360
 DUAL SORPTION MECHANISMS IN GLASSY POLYSTYRENE 361

phase and a distinct crystalline phase, the referred to as the "dual mode" sorption
amorphous phase being continuous, quasi- model.
liquid, and permeable to gas, and the crys- Recent work by Michaels, Vieth, and
talline phase being dispersed and imperme- others (7, 8) with polyethylene terephthalate
able. has contributed to the understanding of the
In certain respects, the molecular model glassy state and to the formulation of a
for sorption in rubbery crystalline poly- molecular model for sorption in glassy
ethylene has been found applicable to glassy polymers. It was found that C02 shows
polymers. One main difference is the postu- deviations from Henry's law in glassy
lation of the existence of "holes," as a stable amorphous polyethylene terephthalate below
phase in the polymer below its glass transi- 1.0 arm. The sorption data at high pressures
tion. However, a satisfactory model for with CO2 are well described by the dual
sorption in the glassy state has been pro- mechanisms of sorption. In addition, the
posed by Meares (4). In this model it is decrease in solubility accompanying crystal-
assumed that, at constant temperature and lization is smaller than the corresponding
pressure, the free energy of the polymer reduction in amorphous volume fraction.
depends on its volume through two micro- With the concept of holes, this can be ex-
seopic variables: the interehaln distance in plained because the crystallization process
closely packed regions and the number and leaves a higher volume concentration of
size of holes present. Above the glass transi- microvoids (per unit volume of amorphous
tion temperature, the two mentioned varia- phase) than that present in the completely
bles are continually adjusted to represent amorphous polymer. With the exception of
the minimum free energy. Below the glass He, the heat of sorption is more exothermic
transition temperature, one degree of too- in glassy polyethylene terephthalate than in
bility, segmental rotation, is lost, immobiliz- rubbery polyethylene terephthalate and it
ing the holes in the polymer matrix. becomes more negative with increasing e/k.
Meares (4) has found that the heats of The solubility constants correlate well with
sorption of N2, Ne, A, and O2 in polyvinyl
acetate below its Tg are negative. The exo- The effects of chain orientation have also
thermic heats observed are attributed to the been investigated (8). The sorption mech-
dispersion interactions between gas mole- anism is similar in oriented and unoriented
cules and the polymer as the dissolved gas is polyethylene terephthalate, but the solu-
sorbed into holes. Barter (t0) has also ob- bility of gas is higher in the oriented film.
served highly exothermic heats of sorption An analysis of the sorpfion data gives higher
of organic vapors in ethyl cellulose. In addi-Henry's law solubility constants, higher
tion, the isotherms obtained show the char- hole-filling constants, and higher hole a~nity
aeteristie curvature of the Langmuir iso- constants in the oriented polyethylene
therm. From these pieces of evidence, terephthalate film. However, the marked
Barrer originally postulated two concurrent increase in solubility in the thinnest oriented
sorption mechanisms: ordinary dissolution film cannot be accounted for by the effects
and hole-filling. Thus, Eq. [3] has been of orientation alone. Different thermal his-
proposed (7, 8) to describe quantitatively tory in the film preparation has been ad-
the solubility of gas in glassy polymers. vanced as a possible explanation.
A useful result of this work is the develop-
C'nb P ment of supplementary evidence supporting
C= C~+C~=]c~P+-- [31
1 "~bP" the existence of stable mierovoids in the
Ordinary dissolution CD is represented by glassy state. In addition, the work has dem-
the Henry's law term and the sorption of onstrated the applicability of the dual
gas into holes, CH, is represented by the mechanisms of sorption to explain the effects
nonlinear Langmuir expression where C'~r of crystallization and orientation on sorption
is the hole-filling constant and b is the hole behavior in a glassy polymer. The successful
al~nity constant. This may be conveniently use of this concept with polyethylene ter-
362 VIETH, TAM, AND MICHAELS
PRESSURE GAUGE
\
TO G~S 'CYLINDER
:RMOMETE;
THERMONITOR
CONSTANT -
SAMPLE BOMB
Fro. 1. Schematic diagram of the sorptiorl apparatus.
ephthalate motivates further study of this
model for sorption. The present investiga-
tion seeks to establish whether this concept
applies equally well to polystyrene, a well-
characterized amorphous polymer. With the
available information on polyethylene ter-
ephthalate, a comparison of the solubility
behavior of polystyrene and polyethylene
terephthalate may also be obtained and the
effects of orientation on their microstructures
may be illustrated.
EXPERIMENTAL
A. MATERIALS
Biaxially oriented polystyrene (7.5 rail)
film was supplied by the Dow Chemical
Company, Midland, Michigan. The film
density, determined by weighing a film
sample in air and in water, is 1.0490 g./c.c.
The oriented fihn is washed with water,
dried, and then used without any pretreat-
ment.
Cast anneMed polystyrene film is pre-
pared from the same stock as the oriented
film. A solution of about 20 % by weight of
polystyrene in methylene chloride is cast on
L,~ RECORDER
MCLEOD GAUGE
TO PUMP
TEMPERATURE BATH
glass plates with a 20 mil casting bar. The
cast film is air-dried and removed from the
glass plate under a jet of cold water. To re-
move the strain and residual orientation, the
film is annealed at 110°C. for 15 minutes.
The average film thickness is 5.2 mil, and
the density 1.0474 g./e.c.
The following gases were used in this
study: N2, A, CH4, and C02. The mini-
mum purity for all gases is 99.99 %. No
attempt was made to further purify the
gases before use.
B. APPARATUS AND PROCEDURE
A schematic diagram of the sorption
apparatus is shown in Fig. 1.
With the film sample placed in the sorp-
tion bomb, the sorption system is evacuated
and flushed with gas several times. Then the
system is evacuated to 0.02 mm. Gas is then
introduced rapidly and the initial pressure
recorded. Sorption takes place instantane-
ously and proceeds until the equilibrium
pressure is established. To increase the
efficiency of experimentation, sequential
runs are made by incrementally raising the
 D U A L S O R P T I O N M E C H A N I S M S IN GLASSY P O L Y S T Y R E N E 363
2O
I I I I [ [ I I e/~Pu
0 • BIAX/ALLY O~.iENTED FILM
0 ~ CAST ANNEALED FILM
Q 0 FIRST RUNS
• A SECOND RUNS
co~
"Is ,~
_J
m
B
~0

~ z ~ / ~ z ~--

-- ~O / CH4 ~ J
- /

A _~

Lx N _

=~--I I I t I [ I I
0 5 ]O 15 20
PRESSURE (ATm)

FI~ 2 S o l u b i l i t y of gases in p o l y s t y r e n e s~t %°C.

pressure of the equilibrated system until an
equilibrium pressure of about 20 arm. is
attained. The amount of gas sorbed in the
fihn sample at each equilibrium pressure is
determined from the initial and final pres-
sures and temperatures.
RESULTS AND DISCUSSION
GENERAL CONSIDERATIONS
The scope of data was restricted, in a
practical sense, by two factors: (a) Diffusion
constants of molecules with higher force
constants, such as ethane or propane, are
very low and would have resulted in sorp-
tion equilibration times of weeks to months
with polymer film specimens which can be
regarded as homogeneous, e.g., 1 rail or
thicker films. Thus, although it would have
been desirable to obtain sorption isotherms
for ethane or propane to seek still more
obvious evidence of isotherm curvature, it
was not possible to accomplish this within a
reasonable period of time. (b) The upper
limit on pressure with the current system is
about twenty atmospheres, which coincides
the isotherms at higher pressures and be-
cloud rather than clarify the picture. Despite
these restrictions, it was found that the
isotherms of CO2 and CIt4, in both oriented
and unoriented polystyrene films at 25°C.
(Figs. 2, 3, 5), exhibited definite deviations
from Henry's law. Although the isotherms
for N2 and A did not display marked curva-
tin'e, they too were analyzed according to
the dual-mode sorption model, and all the
results were compared with theoretical pre-
dictions, as will be described later.
The first step in analyzing the results
requires the determination of the constants
for sorption in Eq. [3] for each gas-poly-
styrene system.
The slope of the linear portion of the iso-
therm in the high-pressure region is equal
to k . . By subtracting k~P from the total
solubility C, the hole-filling contribution
C~ is determined for each pressure.
CP~bp
C. - [4]
l+bP'
OF

with the limit of the experimental data. P 1 P

Although the apparatus could be modified + -- [5]
C/~- C'Hb C'H"
to allow for data collection at higher pres-
sures, one must face the possibility of strue- Then, plots of P/C~ versus P yield C'si and
rural changes within the polymer; i.e., com- b. Such plots are shown in Figs. 4 and 6.
paction, which could alter the character of This procedure is continued until the best
 364 VIETH, TAM, AND MICHAELS

~° 1 I I r i I I T I I,,.,I~
I Q A BIAXLA.LLY ORIENTED FILNI ~,..~'z~. - -

~E

-_ . -

- 1-"'/ .-o" ~

-- ~// / CH C'HbP//0+ bP)

I r ; I i i I I I I I I -
0 I0 15 20
PRESSURE (Ai-rn)

FIG. 3. Solubility of CO2 in polystyrene at 25°C.

~.o
E o /

~ 2.0

J
~ E N T'~D FIL~

hO

I0 15 ZO
PRESSURE (.A'l-rn )

FIG. 4. Langmuir plots for CO2 sorption by hole filling in polystyrene at 25°C.

(least-mean-squares) fit of the data or the
Langmuir plot is achieved, and the values
of kD, C%, and b so determined for each
gas-polymer system are presented in Table I.
An analysis of the accuracy of the direct
sorption method indicates that the initial
pressures are the main source of error. At the
95 % level of confidence, the following error
limits on solubility C are obtained: -4-8.1%
for CO2, ±6.3% for CH4, ~i0.5% forA,
and -4-15 % for N2. The faster rate of sorp-
tion of CO2 is responsible for its larger error
than the error of CI-I~, owing to the un-
certainty in the measurement of initial pres-
sure.
SOLUBILITY CONSTANTS
The over-all solubility constant can be
approximated for very low pressures. At Iow
pressures, Eq. [3] reduces to Eq. [6].
C = kDP + C%bP; [6]
 DUAL SORPTION MECHANISMS IN GLASSY POLYSTYRENE 365

I I I I I I I I I I I I I
z~z;:>
UNORIENTED F ~ ~

FED FLM
V'D ~_

I I r I I I I I
0 5 I0 15 20
PRESSURE (Atm)

FIG. 5. Solubility of CH~ in polystyrene at 25°C.

ORIENTED FILN

°~ / ,©r

0 5 I0 15 20
PRESSURE (Atnn)

FIG. 6. L~ngmuir plots for CH4 sorption by hole filling in polystyrene at 25°C.

C = KP; [7] C = K'P; [7]

where where
K = k~÷C'.b. [8] K ' = kD + C'H/P ~--" lc~. [10]

Thus, at low pressures, the over-all solu-
bility constant K is made up of ]Ca and
C'Hb, which is usually much larger than
kD. Hence, at low pressures, hole-filling is
more important than ordinary dissolution.
At high pressures, Eq. [3] becomes:
C = kDP -t- C ' , ,"
Hence at high pressures, hole-filling becomes
less important and ordinary dissolution is
the main sorption mechanism.
The Lennard-Jones force constant E/k,
which measures the tendency of a gas to
condense, would also be a measure of the
gas solubility. In fact, Jolley and Hilde-
[9] brand (9) have successfully correlated the
366 VIETtt, TAM, AND MICtIAELS

TABLE I
CONSTANTSFOR SORPTIONIN POLYSTYRENEAT 25°C.
e.c. STP )
Gas e/K (°K.) kD c.c. Polymer Attn. b(atm.-~)
Oriented Unoriented Oriented Unoriented Oriented Unoriented

CO~ 229 0.57 0.65 0.40 0.37 6.05 7.7

CI-I4 150 0.13 0.16 0.08 0.108 5.88 7.4
A 113 0.06 0.065 0. 021 0.021 7.55 9.1
N2 95 0.02 0.025 0.015 0.013 6.65 8.3

i°
o."

.~c
J

-2

j
-3 /"

50 100 150 2_00 250

LENNARD-JONES FORCE CONSTANT, ~/k (OK)

F l a . 7. Correlation of over-all solubility constants (data for PET from Michaels (7)).

solubility constants of gases in nonpolar is related to e/K by the use of empirical

organic solvents with e/k. Michaels and
Bixler (2), and Michaels, Vieth, and Barrie
(7), in their correlations of solubility con-
stants of gases in polyethylene and poly-
ethylene terephthalate with e/k, have re-
garded the amorphous phase, in which gas
is sorbed, as of liquid-like structure. The
success of these correlations has encouraged
the attempt of the same correlation with
polystyrene. The data are plotted in Fig. 7,
according to a relationship derived at 25°C.
(11).
In K = 0.026E/k -- 1.68 AHm -~- I,
where 'AHm is the heat of mixing and I is a
system constant. Equation [11] is obtained
from the integrated Clausins-Clapeyron
equation where the heat of condensation
AH¢, a component of the heat of sorption,
thermodynamic relationships (7). At the
95 % level of confidence for all gases except
CH4, the slopes of the correlations of K are
0.0246 ± 6.1% for oriented polystyrene
film and 0.0247 ± 6.4 % for the unoriented
film, in remarkable agreement with Eq. [11].
The high solubility of CH4 in both oriented
and unoriented films is probably due to the
relatively high polarizability of this gas (12)
and its plasticizing effect on polystyrene, as
observed by Lundberg (13). The Henry's
law solubility constants k, are also corre-
lated within the precision limits of =t=13%
[11] for the oriented film and 4-9 % for the un-
oriented film (Fig. 8). Greater difficulty in
the accurate estimation of the derived quan-
tity k9 is responsible for the wider precision
limits.
Within the stated precision limits, which
 DUAL SORPTION MECHANISMS IN GLASSY POLYSTYRENE
I FIGURE 8
CORRELATION OF HENRY'S LAW SOLUBILITY CONSTANTS
C Ddta ~or Benzene ~rom JolicLj & Hildebrand f 3 ) )
e
50 IO0
FIG. 8. Correlation of Henry's law solubility constants. (Data for PE from ]3ixler (2) ; data for ben-
zene from Jolley and Hildebrand (9).)
are reasonably narrow, considering the size
of the statistical sample, all correlation lines
agree with the theoretical line predicted by
Eq. [11] and parallel the lines for benzene,
polyethylene, and polyethylene terephtha-
late. This again supports the validity of Eq.
[11] as applicable not only to organic liquids
but also to polymers in the rubbery and
glassy states.
HOLE AFFINITY CONSTANTS
The hole affinity constant b represents the
ratio of rate constants of sorption and de-
sorption of gas in holes. Qualitatively, the
amount of gas sorbed in holes should depend
on the specific gas-polystyrene interaction.
By a similar thermodynamic analysis, using
the definition of the isosteric heat of sorp-
lion, a relationship between b and e/k can
be established as for the solubility constants
at 25°C.
In b = O.026e/k + in 1 ~e z'
where O = C,/C'H is the fraction of surface
area bounding the free volume occupied by
gas molecules and I' is a system constant
dependent on the choice of the reference
state for the gas-polymer system.
The plots of b versus e/k are shown in
367
L] /
,//
J
~ ~
150 200 250
LENNARD-JONES FORCE CONSTANT, ~ / k (°K)
Fig. 9. At the 95 % level of confidence for all
gases except CH4, the slopes of the correla-
tion lines agree with the calculated slope of
0.026 i.e., 0.0252 ~ 4.7 % for the oriented film
and 0.0255 =E 4.0 % for the unoriented film.
The higher affinity of CH4 in both oriented
and unoriented film is consistent with the
previously described behavior; i.e., the high
specific CH4-polystyrene interaction due to
the apparently high polarizability of this
gas.
The establishment of the exponentiM de-
pendence of b on e/k explains the different
shapes of isotherms. For CO2 with high eric
and thus high b, the characteristic curvature
of Langmuir adsorption occurs within a small
range of pressure and the second portion of
the isotherm can be observed at about a
pressure of 10 arm. For N2 or A with low
e/k and thus very small b, the isotherm ap-
pears linear in the pressure range under
consideration and only starts to become non-
[12] linear near the end of the range. Thus, the
second linear portion is not exhibited. How-
ever, at higher pressures (> 20 arm.), the
deviations would be expected to become
more obvious and the second linear portion
exhibited. With this observation, it is very
probable that the dual processes of sorption
in glassy polymers apply to M1 gases. How-
368 VIETH, TAM, AND MICHAELS
T~
E -I
-3
-4
-5 , i
50 I00
FIG. 9. Correlation of hole affinity constants.
ever, it is more difficult to differentiate the
two mechanisms for low e/k gases than for
high eric gases.
HOLE-FILLING CONSTANTS
The hole-filling constant C'~ represents
the saturation limit of gas which can be
sorbed into holes. Experimental evidence
tends to indicate that sorption by hole filling
is a monolayer process. The characteristic
shape of the isotherms and the behavior of
heat of sorption bear many similarities to
Langmuir adsorption. More convincingly,
holes of the order of 10 A or smaller, as are
estimated for polystyrene (14), would pre-
vent accommodation of more than one layer
of gas molecules on the surface of holes.
Additional evidence of this monolayer
sorption process is supplied by the correla-
tions of hole-filling constants. Hole-filling
constants, C'n, are inversely proportional to
the surface areas occupied by the individual
sorbate gas molecules according to Eq. [13]:
c ' . = [~T~Ss . !
N.~P~ As '
where R is the gas constant; N~ the Avo-
gadro number; T~ and P~, the standard
temperature and pressure; Ss, the surface
bounding the free volume; and A 2 the area
occupied by one sorbate gas molecule calcu-
lated on the assumption that the molecules
adsorbed have the same hexagonal packing
150 2_00 250
LENNARD-JONES FORCE CONSTANT, ~/k ( oK )
as the plane of closest packing of liquid (15).
Figure 10 shows the plots of C'n versus
1 / A 2 for oriented and uno~iented polystyrene
films. The good agreement of the experi-
mental slopes with the theoretical prediction
(within 4-15% for the oriented film and
4-8.5 % for the unoriented film, all at the
95 % level of confidence) gives support to the
monolayer sorption mechanism, since this
implies a constant value of S/, unchanging
with the type of sorbate. The calculated
values in square meters per cubic centimeter
of polymer of Si are 32.5 for the unoriented
film and 25.6 for the oriented film.
EFFECTS OF ORIENTATION OF CHAINS ON
MICROSTRUCTURE OF POLYMERS
The similar shapes of the isotherms in both
oriented and unoriented films indicate that
orientation does not change the nature of
the sorption process. However, the changes
in microstructure are reflected in the changes
in the levels of the sorption constants. Ori-
[13] entation decreases the solubility of CO2 in
polystyrene whereas, from previous work, it
increases the solubility in polyethylene
terephthalate (8).
Considering COs as a typical gas, in both
polymers the hole affinity constants, b, are
slightly higher in the oriented film, 0.40
versus 0.37 for polystyrene and 0.52 versus
0.44 for polyethylene terephthalate (7). This
 DUAL SORPTTON MECHANISMS IN GLASSY POLYSTYRENE
~o I I I I [ I
~=:
5 I I I I I 1
5.0 5.5
FIG. 10. Correlation of hole-filling constants with areas occupied by individual sorbed gas molecules.
seems reasonable because the strained
amorphous regions bounding holes could
have a higher affinity for gas, especially if
the molecular details of the hole periphery
change upon stretching of the film.
The hole-filling constant C'H is smaller in
oriented polystyrene film, 6.05 versus 7.7 for
the unoriented film, indicating a decrease in
free volume, while C'H in the oriented film is
larger for polyethylene terephthalate, 5.7
versus 5.5 for the unoriented film (7), indi-
eating an increase in free volume. More sig-
nificantly, the quantity C's/a = 10.6 for
oriented polyethylene terephthalate film
(7) indicates a much larger saturation
capacity per unit volume of amorphous
phase. However, orientation of chains in
polyethylene terephthalate by stretching is
accompanied by crystallization. The crystal-
lites formed exert large stress on chains in
neighboring amorphous regions, thereby en-
larging holes present or creating new holes
and making those amorphous regions
"loose." B y contrast, in polystyrene, orienta-
tion of chains reduces the interchain dis-
tance, makes certain amorphous regions
more compact, and hence reduces the num-
ber and size of holes.
Another difference between oriented and
unoriented films appears in the Henry's law
solubility constants los. For polyethylene
terephthalate, "loose" amorphous regions of
lower cohesive energy density than the un-
oriented amorphous film, created as second-
369
1 I I I I I I I I I
~ FILM
CO 2 N2 A
1 1 r 1 1 I 1 1 1 r
6.0 6,5 7.0
A-zxlo ~8 (cr~2)
ary effects of crystallization, are responsi-
ble for the higher kD/a in the oriented flm,
0.65 versus 0.38 for the unoriented film (7).
For polystyrene, kD is smaller in the oriented
film, 0.57 versus 0.65 for the unoriented film,
as a result of the closer packing and higher
cohesive energy density of the oriented
amorphous regions.
In summary, the solubility data of poly-
styrene are satisfactorily described by the
sorption model for glassy polymers and the
correlations of the constants for sorption
have been successful. Orientation decreases
the level of solubility and changes the values
of the constants for soprtion, reflecting the
change in the microstrueture of polystyrene.
ACKNOWLEDGMENTS
The financial assistance of the National Science
Foundation (Grant GP-707) is gratefully acknowl-
edged.
NOMENCLATURE
A2 surface area occupied by one sorbate gas
molecule, A2.
b hole affinity constant, arm. -1.
C concentration, e.e. STP/c.e. Polymer.
CD concentration by ordinary dissolution, c.c.
STP/e.c. Polymer.
CH concentration by hole-filling, c.e. STP/c.e.
Polymer.
C'n hole-filling constant, e.c. STP/e.e. Polymer.
AH~ heat of condensation, kcal./g, mole.
AH~ heat of mixing, kcal./g, mole.
AH~ heat of sorption, kcal./g, mole.
370 VIETH, TAM, AND MICHAELS

I constant of integration. 3. SzwAnc, M., AND STANNETT, V., Mod. Plastics

I' constant of integration. 34, 157 (1957).
k Boltzmann's constant, ergs/°K. 4. MEAliES, P., J. Am. Chem. Soc., 76, 3415
kD Henry's law solubility constant, c.c. STP/ (1954).
c.c. Polymer-arm. 5. MEARES, P., Trans. Faraday Soc., 53, 101
k*D Henry's law solubility constant in com- (1957).
pletely amorphous polymer. 6. MEARES,P., Trans. Faraday Soc., 54, 40 (1958).
K over-all solubility constant at low pressure, 7. MICItAELS,A. S., VIETH, W. R., AND BARRIE,
c.c. STP/c.c. Polymer-atm. J. A., J. Appl. Phys. 34, 1 (1963).
K' over-all solubility constant at high pres- 8. VIETH, W. R., ALCALAY,I-I. H., AND FRABETTI,
sure, c.c. STP/c.c. Polymer-arm. A. J., J. Appl. Polymer Sci. 8, 2125 (1964).
M molecular weight of gas, g./g. mole. 9. JOLLEY, J. E., AND HILDEBRANE,J. H., J. Am.
NA Avogadro's number. Chem. Soe. 80, 1050 (1958).
P pressure, arm. 10. BARBER, R. M., BARRIE, J. A., ANn SLATER,
R gas constant, kcal./g, mole °K. J., J. Polymer Sci. 23, 315 (1957).
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