Fluid Phase Equilibria 158–160 Ž1999.

1029–1034

Solubility and diffusion of carbon dioxide in polymers

)
Kimberly F. Webb, Amyn S. Teja
School of Chemical Engineering, Georgia Institute of Technology, 778 Atlantic DriÕe, Atlanta, GA 30332-0100, USA
Received 6 April 1998; accepted 17 December 1998

Abstract

We have measured the solubility and diffusion coefficients of carbon dioxide in four polymer substrates at
313 K and 10.5 MPa. The polymer substrates included polyŽchlorotrifluoroethylene., cross-linked polyŽdimeth-
ylsiloxane., polyŽmethylmethacrylate., and cross-linked polystyrene. Solubilities were determined from maxi-
mum mass gain measurements when a film of each polymer was contacted with carbon dioxide, and diffusion
coefficients were determined from timed absorption experiments. The highest solubility and the highest
diffusivity were obtained with polyŽmethylmethacrylate.. q 1999 Elsevier Science B.V. All rights reserved.

Keywords: Supercritical; Carbon dioxide; Polymer; Absorption; Solubility; Diffusion

1. Introduction

We are investigating the formation of conducting blends of polypyrrole and polyŽ 3-undecylbi-
thiophene. with several host polymers using supercritical carbon dioxide. In these experiments,
carbon dioxide acts both as a solvent and as a carrier gas for the in situ polymerization of the
monomer in the host substrates. The solubility of carbon dioxide in the host substrates and its ability
to diffuse through the host polymer are properties that are obviously of interest in these investigations.
The experimental determination of the solubility of carbon dioxide in four host polymers wpolyŽ chloro-
trifluoroethylene., polyŽ dimethylsiloxane. , polyŽ methylmethacrylate. , and polystyrenex and the mea-
surement of its diffusivity in these polymers are described in the present work.

)
Corresponding author. Tel.: q1-404-894-3098; fax: q1-404-894-2866; e-mail: amyn.teja@che.gatech.edu

0378-3812r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 1 2 Ž 9 9 . 0 0 1 5 3 - 3
1030 K.F. Webb, A.S. Teja r Fluid Phase Equilibria 158–160 (1999) 1029–1034

2. Experimental

2.1. Materials

Coleman grade carbon dioxide Ž 99.9% purity. and nitrogen were purchased from Air Products and
used as received. A sheet of polyŽchlorotrifluoroethylene. Ž PCTFE. was purchased from Modern
Plastics Ž Springfield, MA.. PolyŽdimethylsiloxane. ŽPDMS., a GE Plastics product, was purchased
from Electrical Insulation Suppliers ŽAtlanta, GA. and then cross-linked with GE-purchased cross-lin-
king agent, and made into thin films. PolyŽ methylmethacrylate. Ž PMMA. was obtained from Laird
Plastics Ž Atlanta, GA. . Cross-linked, porous polystyrene Ž PS. was synthesized as described below.
AIBN initiator and styrene used in the synthesis were purchased from Aldrich Ž Milwaukee, WI. ,
sorbitane monooleate was purchased from Fluka Ž Milwaukee, WI. , and divinylbenzene was purchased
from Polysciences ŽWarrington, PA..

2.2. Cross-linked PDMS synthesis

One part of a cross-linking agent and 10 parts of silicone rubber were added to a beaker containing
hexane. A solution of 14 wt.% polymer in hexane was then prepared by adding the appropriate
amount of hexane to the beaker. The resulting solution was stirred on a hot plate at low heat until it
became viscous, when it was quenched. Equal amounts of solution were placed into petri dishes and
dried in a fume hood for several days to form films of the desired thickness. The films were removed
from the petri dishes, heated to 373 K, and allowed to dry in a vacuum oven for several more days for
additional cross-linking and removal of hexane.

2.3. Porous, cross-linked PS synthesis

The procedure for emulsion polymerization of porous, cross-linked polystyrene by Ruckenstein and
Park w1x was adopted in this work. The polymerization reaction was carried out under nitrogen with an
oil column to control the nitrogen flow. AIBN initiator Ž 0.20 g. and divinylbenzene Ž 4 g. were
thoroughly mixed in a three-necked round bottom flask; sorbitane monooleate Ž 4 ml. and styrene Ž 20
g. were then added to the flask, followed by dropwise addition of deionized water Ž 100 ml. to control
the reaction. Any evaporated monomer was trapped in a condenser and allowed to flow back into the
solution. The emulsion was stirred for a few hours and then placed in covered petri dishes for 24 h at
323 K to allow further polymerization to occur. Afterwards, the covers were removed and the
polystyrene was allowed to dry for 3 days in order to remove excess water.

2.4. Apparatus

The equipment used in the experiments consisted of an ISCO SFX 2-10 vessel connected to two
ISCO 260D and 500D pumps for pressurizing the carbon dioxide to supercritical conditions. A cooler
with a circulating system ŽPrecision Scientific model 254. was used to circulate coolant to the pumps.
Temperature was controlled with a temperature controller Ž Fuji PYZ4-TCY1-4V. , calibrated with a
digital thermometer ŽFluka model 2180A. . A pressure gauge Ž Heise CMM 51848. was used to
measure the pressure in the vessel. The Heise gauge was calibrated with a dead weight tester
ŽBudenburg model 380 H. .
 K.F. Webb, A.S. Teja r Fluid Phase Equilibria 158–160 (1999) 1029–1034 1031

3. Results

3.1. Solubility

The solubility of carbon dioxide in the polymer hosts was determined by measuring the maximum
amount of carbon dioxide absorbed by the polymer at 313 K and 10.5 MPa. The amount of carbon
dioxide absorbed as a function of time was obtained from a series of desorption experiments described
below. The experimental procedure was similar to that employed by Berens et al. w2x and Watkins and
McCarthy w3x.
Briefly, a host polymer was loaded into the ISCO SFX 2-10 vessel, the vessel was evacuated, and
then pressurized by the addition of carbon dioxide for a specified time period. The temperature was
maintained at 313 K during these experiments and the final Žequilibrium. pressure was 10.5 MPa.
Next, the vessel was depressurized quickly, and the host polymer transferred to a Mettler AE163
balance, where the weight loss was monitored to "0.0001 g as a function of time. Time was
measured with a stopwatch, starting at the instant when the pressure vessel was depressurized. Weight
loss and time data were recorded until no further weight loss occurred. A typical weight loss–time
curve is shown in Fig. 1. The initial desorption of carbon dioxide from the polymer is linear with time
w4x, and the y-intercept yields the amount of carbon dioxide absorbed by the host substrate in the
specified time period Žof the experiment.. Several of these experiments Ž conducted over different time
periods. were performed with each host polymer to obtain the curve plotted in Fig. 2 for PCTFE. In
Fig. 2, the amounts of carbon dioxide absorbed at different time periods are plotted as a function of
the square root of time. The maximum in the curve represents the maximum amount of carbon
dioxide absorbed by PCTFE Ž 4.34 wt.%., and can be directly converted to the equilibrium solubility
Ž4.16 wt.%. of carbon dioxide in PCTFE at 313 K and 10.5 MPa. Also shown in Fig. 2 are the
measurements of Watkins and McCarthy w3x. The two sets of measurements agree within "0.1%, and
lend validity to the experimental procedure used in this work.
The experiments described above were repeated for cross-linked PDMS, PMMA, and porous,
cross-linked PS. The maximum mass gain of carbon dioxide in cross-linked PDMS at 313 K and 10.5

Fig. 1. Desorption of carbon dioxide from PCTFE after soaking for 1 h at 313 K and 10.5 MPa.
1032 K.F. Webb, A.S. Teja r Fluid Phase Equilibria 158–160 (1999) 1029–1034

Fig. 2. Absorption of carbon dioxide into PCTFE at 313 K and 10.5 MPa. Also shown are the data of Watkins and McCarthy
w3x.

MPa was 11.34 wt.%. By comparison, Wissinger and Paulaitis w5x obtained a mass gain of 22.5 wt.%
at 323 K and 10 MPa. However, it should also be noted that their PDMS was synthesized via a
different route and was probably cross-linked to a different extent. The maximum mass gain of carbon
dioxide in PMMA in our experiments was 22.2 wt.%, corresponding to a solubility of 18.17 wt.%. By
comparison, Vincent et al. w6x found that carbon dioxide concentration in PMMA is 17 wt.% at 308 K
and 9 MPa. The polystyrene Ž PS. synthesized in the present work was very porous, so that carbon
dioxide was able to diffuse through the pores and was not absorbed by the polymer. The solubility of
carbon dioxide in this polymer could not therefore be measured. All solubility data obtained in the
present work are summarized in Table 1.

3.2. Diffusion coefficient

Diffusivities of carbon dioxide into the host polymers were determined using the following
equation for Fickian diffusion w7x through a flat plate:
1r2
M Ž t . rM Ž ` . s 4 Ž Dtrp l 2 . , Ž1.
where M Ž t . is the mass gain Žby the polymer film. at time t, M Ž`. is the maximum mass gain, D is
the diffusivity Žof carbon dioxide in the polymer. , and l is the thickness of the film. M Ž `. is
effectively the equilibrium solubility of carbon dioxide at the conditions of the experiment.

Table 1
Solubility of CO 2 in polymers at 313 K and 10.5 MPa
Host substrate Solubility Žwt.%.
PCTFE 4.16
Cross-linked PDMS 10.19
PMMA 18.17
Cross-linked, porous PS –
 K.F. Webb, A.S. Teja r Fluid Phase Equilibria 158–160 (1999) 1029–1034 1033

Fig. 3. Diffusion of supercritical carbon dioxide into host polymers at 313 K and 10.5 MPa.

The diffusion coefficient of carbon dioxide in a host polymer may be obtained from the slope of
M Ž t . rM Ž `. when plotted against Ž t 1r2rl .. This is shown in Fig. 3 for PMMA, PCTFE, and PDMS.
No results are reported for cross-linked PS because carbon dioxide was able to diffuse through the
pores of this polymer, as discussed previously. Diffusion was most rapid in PMMA, followed by
PCTFE and PDMS in decreasing order. Diffusivities in PMMA, PCTFE, and PDMS are shown in
Table 2, and these values agree with the diffusivity of rubbery polymers in the range 10y6 –10y7
cm2rs reported by Berens et al. w2x. The host polymers were assumed to be in their rubbery states at
313 K and 10.5 MPa, since their glass transition temperatures Tg are all below 313 K in the presence
of carbon dioxide. Carbon dioxide lowers the Tg values of the polymers by plasticization, as discussed
by Chiou et al. w8x and Wissinger and Paulaitis w9x who found the glass transition temperature of
PMMA to be about 275 K after absorption of carbon dioxide.

3.3. Swelling

The dimensions of the polymer samples in the present work were measured with a cathetometer
before and after contact with carbon dioxide. Initially, all samples were 4.0 cm = 0.5 cm and of
varying thickness between 0.032 cm and 0.290 cm. Most samples showed a small change in volume
upon contact with carbon dioxide. However, a large change in volume Ž27.3 vol.%. was exhibited by
PMMA. This compares with volume changes in this system of 22 vol.% reported by Wissinger and
Paulaitis w5x at 305.7 K and 10 MPa and 21.5 vol.% reported by Vincent et al. w6x at 308 K and 9
MPa.

Table 2
Diffusion coefficients of CO 2 in polymers at 313 K and 10.5 MPa
Host substrate D Žcm2 rs.
PMMA 1.04=10y6
PCTFE 7.08=10y8
Cross-linked PDMS 7.08=10y10
1034 K.F. Webb, A.S. Teja r Fluid Phase Equilibria 158–160 (1999) 1029–1034

4. Conclusions

The solubilities of supercritical carbon dioxide in several host substrates were determined at 313 K
and 10.5 MPa. The maximum mass gains in PCTFE, cross-linked PDMS, and PMMA were 4.34
wt.%, 11.34 wt.%, and 22.2 wt.%, respectively. The highest solubility occurred in the case of PMMA,
which was also swollen to the greatest extent Ž27.3 vol.%. by carbon dioxide. Diffusivities of carbon
dioxide in PMMA, PCTFE, and PDMS were found to be 1.04 = 10y6 , 7.08 = 10y8 , and 7.08 = 10y10
cm2rs, respectively.

References

w1x E. Ruckenstein, J.S. Park, J. Appl. Polym. Sci. 42 Ž1991. 925–934.

w2x A.R. Berens, G.S. Huvard, R.W. Korsmeyer, F.W. Kunig, J. Appl. Polym. Sci. 46 Ž1992. 231–242.
w3x J.J. Watkins, T.J. McCarthy, Macromolecules 28 Ž1995. 4067–4074.
w4x A.R. Berens, G.S. Huvard, in: K.P. Johnston, J.M.L. Penninger ŽEds.., Supercritical Fluid Science and Technology,
American Chemical Society, Washington D.C., 1989.
w5x R.G. Wissinger, M.E. Paulaitis, J. Polym. Sci.: Part B: Polym. Phys. 25 Ž1987. 2497–2510.
w6x M.F. Vincent, S.G. Kazarian, C.A. Eckert, AIChE J. 43 Ž1997. 1838–1848.
w7x J. Crank, G.S. Park, Diffusion in Polymers, Academic Press, New York, 1968.
w8x J.S. Chiou et al., J. Appl. Polym. Sci. 30 Ž1985. 2633–2642.
w9x R.G. Wissinger, M.E. Paulaitis, J. Polym. Sci.: Part B: Polym. Phys. 29 Ž1991. 631–633.