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Journal of Membrane Science 204 (2002) 413419

Short communication
Effect of extraction and drying on the structure of microporous
polyethylene membranes prepared via thermally
induced phase separation
Hideto Matsuyama
a,
, Myung-man Kim
b
, Douglas R. Lloyd
b
a
Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan
b
Department of Chemical Engineering, The University of Texas at Austin, Austin, TX 78712, USA
Received 7 September 2001; received in revised form 31 January 2002; accepted 31 January 2002
Abstract
The objective of the study reported here is to demonstrate that it is possible to manipulate membrane porosity, pore size, and
permeability through the choice of extractant and drying conditions in the thermally induced phase separation (TIPS) process
for makingmicroporous membranes. Todoso, tendifferent extractants were usedtoremove mineral oil frompolyethylene lms
and two different evaporation conditions were used to remove the extractant and produce microporous membranes. The di-
mensions, microstructure, and permeability of the membranes were used to measure the impact of extractant choice and drying
conditions on the membrane morphology. The solubility parameter was used to represent the afnity between the extractant and
the polymer. Boiling point was used to represent the volatility of the extractant and therefore, the kinetics of extractant removal.
Surface tension was used to represent the force exerted by the extractant on the solid matrix as the extractant is removed fromthe
membrane. Eachof these properties was relatedtothe membrane morphology. 2002Elsevier Science B.V. All rights reserved.
Keywords: Thermally induced phase separation; Extractant; Evaporation; Membrane shrinkage; Membrane morphology
1. Introduction
The thermally induced phase separation (TIPS)
process is used in industry to make microporous poly-
meric membranes [13]. The TIPS process begins by
dissolving a polymer in a diluent at an elevated tem-
perature. The solution is then cast or extruded into the
desired shape (at sheet, hollow ber, etc.) and cooled
to induce phase separation and polymer solidication
(crystallization or glass transition). The diluent is
extracted by solvent exchange and the extractant is
usually evaporated to yield a microporous structure.

Corresponding author.
While many studies have been presented on the struc-
ture of membranes resulting from the TIPS process,
the thermodynamics of polymer-diluent systems, and
the phase separation kinetics [413], to our knowl-
edge no systematic study on the combined extraction
plus evaporation steps has been reported. This short
communication demonstrates the signicance of these
two steps in determining the microporous structure
and performance of membranes formed via TIPS.
In this work, polyethylenemineral oil lms were
extracted using 10 different extractants. The effects
of extractant choice and evaporation conditions on
membrane shrinkage, porous structure, and transport
properties of the membrane were investigated.
0376-7388/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S0376- 7388( 02) 00052- 2
414 H. Matsuyama et al. / Journal of Membrane Science 204 (2002) 413419
Table 1
Physical properties of polymer and extractants
Solubility parameter (MPa
1/2
) Boiling point (K) Surface tension at
298 K (mN/m)
Total Dispersive
Polyethylene 16.2
a
16.2
a

Trichloroethylene 18.7
b
11.7
b
360 28.70
c
Pentane 14.4
b
14.4
b
308 15.49
d
Hexane 14.9
b
14.9
b
342 17.89
d
Heptane 15.3
b
15.3
b
371 19.65
d
Cyclohexane 16.8
b
16.4
b
354 24.65
d
Tetrahydrofuran 18.5
b
13.3
b
339 26.40
e
2-Butanone 19.3
b
14.1
b
353 23.97
d
p-Xylene 18.1
b
16.5
b
411 28.01
d
Toluene 18.3
b
16.4
b
383 27.93
d
Ethyl acetate 18.2
b
13.4
b
350 23.39
d
a
[14].
b
[15].
c
[16].
d
[17].
e
[18].
2. Experimental materials and methods
2.1. Materials
Polyethylenemineral oil lm prepared via TIPS
was kindly supplied by 3M. The lm was prepared
by extruding a 35 wt.% polymer melt-blend. The
resulting solid lm thickness was 250 m. The extrac-
tants used were trichloroethylene, pentane, hexane,
heptane, cyclohexane, tetrahydrofuran, 2-butanone,
p-xylene, toluene and ethyl acetate. All extractants
were used without further purication. General ex-
tractants which are volatile and compatible with the
mineral oil diluent were used in this work. Selected
physical properties of the extractants are listed in
Table 1.
2.2. Membrane shrinkage test
The lm was cut into 6.0 cm machine direction
(MD) 4.0 cm transverse direction (TD) samples and
the dimensions of each sample were measured. Ten
bottles, each containing approximately 150 ml of ex-
tractant, were prepared. Two samples were immersed
in each bottle and the bottle was sealed. After soaking
overnight to allow diluent-extractant exchange, the
membrane size was measured again and then air-dried
at room temperature to a constant mass (typically
achieved within 16 h). The sample was not restrained
during the evaporation. The length and width of the
dry membranes were measured with a ruler (accurate
to 0.05 cm) and the membrane thickness was mea-
sured with a micrometer (Japan Micrometer MFG
Co. Ltd., DMII; accurate to 0.0025 cm). The rela-
tive measurements reported below represent the nal
dimensions (length, width, thickness, and volume)
divided by the initial dimensions. The dimensions of
each pair of samples agreed to within the accuracy of
the measurement devices.
2.3. SEM observation
The dry membrane was fractured in liquid nitrogen
and coated with Au/Pd. An SEM (Hitachi Co., S-800)
with an accelerating voltage set to 15 kV was used to
examine the cross-section of each membrane.
2.4. Transport experiments
The transport experiments were done using a stirred
cell (Advantec Co., UHP-25K) for several membranes.
The feed was 1-propanol pressurized by nitrogen gas
at 4.0 atm. The volumetric ow rate of propanol trans-
ported through the membrane was measured.
H. Matsuyama et al. / Journal of Membrane Science 204 (2002) 413419 415
3. Results and discussion
Replacing diluent with extractant can cause the
lm to either swell, contract, or remain the same size,
depending on the afnity of the extractant for the
polymer relative to the afnity of the diluent for the
polymer and the freedom of the polymer molecules
to rearrange. If the polymer and extractant have a
stronger afnity than the polymer and diluent, the
amorphous regions of the semi-crystalline lm can
swell. For the samples reported here, there was no
measurable difference between the dimensions before
and after exchanging the extractant for the diluent.
This lack of dimensional change is attributed to the
high crystalline content of the sample (67%). Con-
sequently, in this study, all dimensional changes are
attributed to the subsequent evaporation of extractant.
Table 2 lists the relative dimensions of the mem-
brane after drying. The original membrane was pre-
pared by extruding the polymer solution through a slit.
The extrusion direction is called MD and the direction
perpendicular to MD is TD. The shrinkage was only
marginally greater in the MD than in the other two di-
rections, indicating that the lm was not signicantly
oriented during processing.
Fig. 1 shows the relation between the membrane
porosity and the relative membrane volume. The mem-
brane porosity was calculated from the dry membrane
mass and volume. The porosity increased from 0.059
for p-xylene (with relative volume 0.39) to 0.53 for
pentane (with relative volume 0.82). For comparisons
sake, Fig. 1 also indicates the point represented by the
Table 2
Relative dimensions after the shrinkage
Extractant MD
a
TD
b
Membrane
thickness direction
Trichloroethylene 0.74 0.80 0.84
Pentane 0.91 0.94 0.96
Hexane 0.89 0.92 0.93
Heptane 0.83 0.88 0.90
Cyclohexane 0.80 0.85 0.87
Tetrahydrofuran 0.81 0.85 0.87
2-Butanone 0.84 0.88 0.89
p-Xylene 0.67 0.75 0.78
Toluene 0.72 0.80 0.80
Ethyl acetate 0.86 0.88 0.90
a
Extrusion direction.
b
Direction perpendicular to MD.
Fig. 1. Relation between membrane porosity and relative mem-
brane volume. (): Trichloroethylene; (): heptane; (): tetrahy-
drofuran; (): hexane; (): cyclohexane; (): pentane; ():
2-butanone; (): p-xylene; (): toluene; (): ethyl acetate; ():
volume fraction of diluent in original polyethyene membrane. Den-
sities of polyethylene (0.96 g/cm
3
) and mineral oil (0.85 g/cm
3
)
were used in the calculation of membrane porosity.
hypothetical case of removing the diluent without any
dimensional change. Fig. 1 indicates that it is possible
to inuence membrane porosity through the choice of
extractant used in membrane production.
To illustrate the structural signicance of the sam-
ple contraction, cross-section micrographs were taken
of the dry membranes. Fig. 2 shows cross-sections
of three representative membranes that were extracted
and dried in the air as described above; all micro-
graphs are at the same magnication. At the membrane
surface, there was no skin layer and porous structure
formed similar to that in the cross-section although
the porosity at the membrane surface was lower than
that in the cross-section. Based on the data in Table 2
and Fig. 1, the sample extracted with pentane showed
the least contraction; Fig. 2(a) shows this membrane
to be the most open of those presented here. Accord-
ing to Table 2 and Fig. 1, the sample extracted with
p-xylene underwent the most contraction; Fig. 2(c)
shows this membrane to be the most dense of those
presented here. Table 2and Fig. 1 indicate 2-butanone
caused moderate collapse, as conrmed by comparing
Fig. 2(b) to Fig. 2(a) and (c). Thus, the pore size in the
micrographs follows the trend indicated in Fig. 1; that
is, the pore size decreases as the porosity and relative
volume decreased.
To illustrate the signicance of the drying method
on structure, a second sample extracted with 2-buta-
none was freeze-dried rather than air-dried. The sam-
ple containing the 2-butanone was immersed in liquid
nitrogen, removed from the liquid nitrogen, and
416 H. Matsuyama et al. / Journal of Membrane Science 204 (2002) 413419
Fig. 2. Cross-sections of membranes: (a) prepared with pentane; (b) prepared with 2-butanone; (c) prepared with p-xylene; (d) prepared
by freeze-drying process.
freeze-dried at low temperature condition. During the
freeze-drying, the glass bottle containing the sample
was contacted with vapor of liquid nitrogen. The rela-
tive dimensions of the freeze-dried sample were 0.98
(MD) by 0.99 (TD) by 0.99 (thick). The structure
shown in Fig. 2(d) shows that the collapse is signif-
icantly less for the freeze-dried sample than for the
air-dried 2-butanone sample.
To relate performance to pore collapse, the 1-pro-
panol permeability of three of the membranes shown
in Fig. 2 is summarized in Table 3. The trend of the
Table 3
1-Propanol permeation through representative membranes
Membrane preparation condition Permeance 10
12
(m
3
/(m
2
s Pa))
Freeze-drying 2-butanone 6.2
Air-drying pentane 4.7
Air-drying 2-butanone 2.6
Air-drying p-xylene 0
H. Matsuyama et al. / Journal of Membrane Science 204 (2002) 413419 417
permeability results agrees with the expectations from
the previous plots and micrographs. The sample ex-
tracted with p-xylene had no ux, which is in keeping
with the extreme collapse shown in the previous plots
and micrograph. Table 3 indicates that it is possible to
inuence membrane performance through the choice
of extractant and drying method used in membrane
production.
All of the data presented earlier indicate that evap-
oration of the extractant resulted in contraction of the
lm. This contraction can be attributed to a combina-
tion of two physical phenomena: densication of the
amorphous regions of the lm and collapse of pores
due to capillary forces. For the purposes of this pre-
liminary study, it is the cumulative effect of these two
phenomena on membrane structure and performance
that is of interest. Additional detailed studies are re-
quired to distinguish accurately the magnitude of each
of these phenomena, but because the polymer under
study here has such high crystallinity (67%), the im-
pact of densication of the amorphous regions is prob-
ably much less important than the collapse of pores.
The afnity between the extractant and the amor-
phous polymer in the membrane can affect the ease
with which the extractant is removed during the
evaporation process. One measure of such afnity
is the square of the difference between the solubil-
ity parameter of the extractant and the polymer. A
small difference between solubility parameters means
high afnity between the polymer and the extrac-
tant. Fig. 3(a) shows relative membrane volume after
diluent extraction and evaporation plotted against the
square of the difference in solubility parameters. Since
the polymer is dispersive in nature, the relative volume
Fig. 3. Relation between relative membrane volume and solubility parameter difference between extractant and polymer. Symbols are the
same as shown in Fig. 1. (a) Total solubility parameter; (b) dispersive solubility parameter.
Fig. 4. Relation between relative membrane volume and surface
tension of extractant. Symbols are the same as shown in Fig. 1.
was also plotted against the square of the difference
between the dispersive component of the polymer and
extractant solubility parameters (Fig. 3(b)). Neither
of the plot shows a discernable trend. The scatter in
Fig. 3(a) and (b) suggests that factors in addition to
thermodynamic afnity need to be considered.
Capillary forces can lead to pore collapse, and such
forces are proportional to the surface tension of the
liquid being evaporated from the pore. The surface
tension values of the extractants used in this study are
listed in Table 1. The relative membrane volume after
extraction and evaporation is plotted in Fig. 4 against
the surface tension of the extractants. The decrease in
relative volume with increasing surface tension (cor-
responding to increasing capillary force) is evident,
although there is minor scatter in Fig. 4.
One factor that may contribute to the scatter in
Fig. 4 and may play a role in determining the mem-
brane structure is the length of time during which
the capillary force is exerted on the pore wall. It is
418 H. Matsuyama et al. / Journal of Membrane Science 204 (2002) 413419
Fig. 5. Relation between relative membrane volume and boiling
point of extractant. Symbols are the same as shown in Fig. 1.
hypothesized that pore collapse involves rearrange-
ment of the amorphous polymer molecules within the
matrix phase. Since such a rearrangement requires
time, it is hypothesized that the longer the capillary
force is in effect, the greater the time for rearrange-
ment of polymer chains in the matrix phase and the
greater the extent of pore collapse. Fig. 5 shows the re-
lation between the relative membrane volume and the
boiling points of the extractants, where boiling point
was used to represent the volatility of the extractants
and the evaporation rate, i.e. a low boiling point cor-
responds to a rapid evaporation. Fig. 5 shows that the
higher the boiling point (i.e. slower evaporation) the
greater the shrinkage of the lm.
Additional research is required to evaluate and
quantify the relationship between the force and du-
ration of the force on pore collapse and membrane
structure.
The hypothesis presented above is based on the
results for air-dried membranes. The fact that the
membranes extracted with 2-butanone produced
membranes of different properties depending on the
drying conditions suggests that the mechanism by
which extractant is removed from the pore can affect
membrane structure. In air-drying, the liquid extrac-
tant interact with the amorphous portion of the matrix
phase, thereby softening the matrix phase that sur-
rounds the pore. Since the liquid leaves the pore via
evaporation over some period of time, the pore is able
to collapse due to capillary forces and densication
of the amorphous regions of the matrix phase. Since
the extractant is a solid throughout the drying period
in freeze-drying, the pore wall does not soften and the
pore does not collapse when the extractant is removed.
4. Conclusion
In this work, 10 different extractants were used to
remove the diluent used in the TIPS process for mak-
ing polyethylene membranes. This preliminary study
demonstrated that it is possible for membrane manu-
facturers to manipulate membrane porosity, pore size,
and permeability through the choice of extractant and
drying conditions. Membrane dimensions were shown
to decrease with increasing surface tension and in-
creasing boiling point, while no discernable trend was
observed between membrane shrinkage and solubility
parameter of the extractant. Scatter in the plots indicate
that a combination of thermodynamics, kinetics, and
forces play a role in determining membrane shrink-
age. Membrane dimensions decreased less when the
extractant was removed via freeze-drying as opposed
to air-drying, conrming the inuence of kinetics.
Decreasing membrane dimensions were shown to in-
dicate decreasing porosity, pore size, and permeability.
Acknowledgements
The authors thank Gene Shipman of 3M for the lm
used in this study.
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