Journal of Membrane Science 325 (2008) 92–97

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Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Correlation between macrovoid formation and the ternary phase diagram for
polyethersulfone membranes prepared from two nearly similar solvents
Jalal Barzin ∗ , Behrouz Sadatnia
Department of Biomaterials, Iran Polymer and Petrochemical Institute, P.O. Box 14965/115, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The morphological structure of membranes prepared from two nearly similar systems consisting
Received 5 March 2008 of water/N,N-dimethylacetamide (DMAc)/polyethersulfone (PES) and water/N-methyl-2-pyrrolidone
Received in revised form 17 June 2008 (NMP)/polyethersulfone (PES) has been studied. The morphology of the prepared membranes showed that
Accepted 2 July 2008
both systems exhibit an instantaneous liquid–liquid demixing that leads to the formation of macrovoids
Available online 10 July 2008
in the resulting structures. Nevertheless, the resulting macrovoid structures were contrary to the gen-
erally accepted concepts concerning macrovoid formation. The membranes morphologies showed that
Keywords:
in spite of better miscibility between water and DMAc, which must promote the formation of channel-
Macrovoid
Morphology
and finger-like structures, more sponge-like structures were observed in membranes prepared from the
Phase diagram water/DMAc/PES system compared to those prepared from the water/NMP/PES system. To find the source
Vitrification of this unexpected phenomenon, the complete ternary phase diagrams consisting of theoretical binodal
Polyethersulfone curves, vitrification boundaries, and gelation boundaries were constructed for both systems and it was
shown that gelation process occurs earlier in the water/DMAc/PES system compared to the other system,
which inhibits the growth of macrovoids in this system.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
Today most of the industrially used polymeric membranes are
prepared via the phase separation (phase inversion) method. In this
process, a homogeneous polymer solution is separated into two
phases: a solid, polymer-rich phase that forms the matrix of the
membrane and a liquid, polymer-lean phase that forms the mem-
brane pores [1]. The phase separation process can be accomplished
by a wide variety of techniques such as nonsolvent induced phase
separation (NIPS), thermally induced phase separation (TIPS), vapor
induced phase separation (VIPS), and evaporation induced phase
separation (EIPS) [2]. Among these techniques, the NIPS process is
without doubt the most widely used technique for the preparation
of polymeric membranes. In the NIPS process, a homogenous poly-
mer solution is cast as a thin film or spun as a hollow fiber and then
immersed in a coagulation bath (typically water). The exchange of
nonsolvent and solvent induces the phase separation phenomena
in the polymer solution, which usually leads to the formation of
an anisotropic (asymmetric) structure with a relatively thin skin
supported on a much thicker substrate in the resulting membrane.
∗ Corresponding author. Tel.: +98 21 44580050; fax: +98 21 44580161.
E-mail address: j.barzin@ippi.ac.ir (J. Barzin).
Membranes that are prepared by the NIPS process usually con-
tain large elongated voids (macrovoids) in their sublayer structure
[3]. The type and structure of these macrovoids has a large effect on
the performance and mechanical strength of the resulting mem-
branes and several studies have been performed to discover the
mechanism of macrovoid formation and to determine the effect of
various parameters on the structure of the resulting macrovoids
[3–32].
Usually, macrovoids occur under instantaneous demixing but, in
delayed demixing, the formation of macrovoids is suppressed and
sponge-like structures are observed in the membrane structure [3].
Experimental results have shown that increasing the concentration
of polymer in the casting solution [4,5,12,16,19,28,30], increas-
ing the evaporation time [5,18,19], choosing nonsolvent–solvent
pairs with low mutual affinity [5,7,13], addition of solvent to the
coagulation bath [6,7,9,21], and addition of nonsolvent to the poly-
mer solution [3,5,12,13,16–18,21,23,24] suppress the formation of
macrovoids in membranes prepared by the NIPS process.
One of the most efficient ways to obtain different morpholog-
ical structures in membranes prepared by the NIPS process is to
use different solvents with varying mutual affinity with the non-
solvent present in the coagulation bath. Nevertheless, generally,
in these types of studies the morphological structures obtained
from a nonsolvent–solvent pair which has high mutual affin-
ity and induces an instantaneous demixing is compared with

0376-7388/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2008.07.003
 J. Barzin, B. Sadatnia / Journal of Membrane Science 325 (2008) 92–97 93

those obtained from a nonsolvent–solvent pair which has low
mutual affinity and induces the delayed demixing [25,33,34].
For example, Shieh and Chung [33] have studied the morphol-
ogy of membranes prepared from water/N-methyl-2-pyrrolidone
(NMP)/cellulose acetate (CA) and water/tetrahydrofuran (THF)/CA
systems and by adjusting the ratio of NMP and THF in the
water/NMP-THF/CA system, they succeeded in suppressing the for-
mation of macrovoids in the resulting membranes. Li et al. [34]
have studied the morphological structure of water/NMP/CA and
water/␥-butyrolactone (GBL)/CA systems and reported that when
ratio of NMP to GBL was increased to 80% in the water/NMP-GBL/CA
systems, the macrovoids were eliminated and typical sponge-like
structures were observed in the resulting membranes.
Kim et al. [35] have investigated the phase behavior of
water/NMP/polyimide and water/DMSO/polyimide systems and
reported that despite of higher mutual affinity between water
and DMSO compared to that of water and NMP, macrovoid-free,
sponge-like membrane was prepared from water/DMSO/polyimide
system, whereas a finger-like membrane was obtained from a
water/NMP/polyimide system.
In the present study, the morphological structure of two nearly
similar membrane-forming systems consisting of water/N,N-
dimethylacetamide (DMAc)/polyethersulfone (PES) and water/N-
methyl-2-pyrrolidone (NMP)/polyethersulfone (PES) has been
evaluated. Both of these systems exhibit an instantaneous
liquid–liquid demixing that leads to the formation of macrovoids
in the resulting membranes. Nevertheless, some unexpected struc-
tures were observed in the structure of the prepared membranes.
To find an explanation for this unusual phenomenon, the complete
ternary phase diagrams of these systems were constructed theo-
retically and according to the mechanism of gelation of amorphous
polymers the source of these observations has been explained. To
the best of our knowledge, there is no report concerning evalua-
tion of the effects of two nearly similar and strong solvents on the
structures of membranes prepared from the NIPS process in the
literature.
2. Experimental
2.1. Materials
Polyethersulfone (PES) Ultrason E 6020 P (BASF, Germany)
was used as the polymer. This polymer has Mw = 58,000 g/mol
and Mn = 16,000 g/mol as reported by the manufacturer. N,N-
dimethylacetamide (DMAc) (Merck) and N-methyl-2-pyrrolidone
(NMP) (Riedel-de-Haën) were used as solvent and double-distilled
water was used as the nonsolvent.
Qian and Rudin [39]. The nonsolvent/polymer interaction parame-
ter, g13 , was determined by a swelling measurement according to
Flory–Rehner theory [38]. Details of the required procedures for
determination of interaction parameters and numerical calcula-
tions for construction of theoretical phase diagrams are presented
elsewhere [40].
2.3. Membrane preparation
Polymer solutions of 10, 12, 18, and 20 wt% of PES in DMAc and
NMP were cast at room temperature on glass plates with a uniform
thickness of 120 ␮m by a casting knife. Immediately after casting,
the glass plates were immersed in a coagulation bath containing
distilled water at 25 ◦ C. After polymer coagulation, the prepared
membranes were transferred to a second bath containing fresh
water and then they were dried in air.
2.4. Scanning electron microscopy analysis
The morphology of the membranes was studied by scanning
electron microscopy (Philips XL 30). Before analysis, the samples
were fractured in liquid nitrogen, coated with gold in a sputtering
device (SCD 005, BAL-TEC), and then transferred into the micro-
scope chamber.
3. Results and discussion
3.1. Interaction parameters
In theoretical studies on ternary membrane-forming systems for
the construction of theoretical ternary phase diagrams, the non-
solvent/solvent interaction parameter, g12 , is usually considered
concentration dependent. There are several reports concerning g12
values of water/DMAc and water/NMP systems in the literature
but, these reports are not in accordance with each other and some
inconsistencies are observed in the reported values and relations
[41–46].
In Fig. 1 the g12 values which have been used in our numerical
calculations are presented for water/DMAc and water/NMP sys-
tems. According to the results of numerical calculations presented
in the following sections, it has been shown that these two set
of g12 values result in theoretical binodal curves that are in good
agreement with the experimental cloud point data.

2.2. Construction of ternary phase diagrams

The theoretical ternary phase diagrams for water/DMAc/PES and

water/NMP/PES systems were constructed based on an extended
form of Flory–Huggins theory of polymer solutions [36,37]. Accord-
ing to this theory, the binodal and spinodal curves and tie lines of
these systems were determined by numerical calculations based
on the Newton–Raphson method.
Binary interaction parameters are the main input parameters
of the Flory–Huggins theory. The nonsolvent/solvent interac-
tion parameters, g12 , were determined from excess Gibbs free
energy, GE , data. GE can be determined from activity coefficients,
vapor–liquid equilibrium data, or it can be obtained directly from
data that are available in the literature [38]. The solvent/polymer
interaction parameters, g23 , were determined through measure- Fig. 1. Concentration-dependent nonsolvent/solvent interaction parameter of
ment of the intrinsic viscosity based on a model proposed by water/DMAc (䊉) and water/NMP () systems.
94 J. Barzin, B. Sadatnia / Journal of Membrane Science 325 (2008) 92–97
Fig. 2. Theoretical binodal (—) and spinodal (– –) curves for water/DMAc/PES and
water/NMP/PES systems. To verify the theoretical calculations, the experimental
cloud point data (䊉) are presented as well.
For the water/NMP system, the g12 values were determined
through GE data reported by Zeman and Tkacik [44] and for the
water/DMAc system, these values were determined through GE
data which have been determined by activity coefficients calculated
from the van Laar equation [43]. The required relation for determi-
nation of g12 values through GE data is available in the literature
[38].
It can be seen from Fig. 1 that in all compositions the g12 values
of water/DMAc system are smaller than those of the water/NMP
system, which indicates that there is a better miscibility between
water and DMAc compared to water and NMP system.
For the solvent/polymer interaction parameters, g23 , and non-
solvent/polymer interaction parameter, g13 , no concentration
dependencies were considered; therefore, these parameters have
been shown with the symbol of  in the preceding sections.
The solvent/polymer interaction parameters, 23 , were deter-
mined through measurement of the intrinsic viscosity of the
Fig. 3. Micrographs of the cross-sections of membranes prepared from NMP/PES solutions coagulated in water. The compositions of polymer solutions were (a) 10, (b) 12,
(c) 18, and (d) 20 wt% PES in NMP.
desired polymer solutions based on Qian and Rudin model [39]. For
NMP/PES and DMAc/PES pairs this parameter was determined to be
0.37 and 0.39, respectively. These values show that the interaction
parameter of NMP/PES pair is lower than that of DMAc/PES system
which confirms that NMP is a better solvent for PES compared to
DMAc.
The nonsolvent/polymer interaction parameter, 13 , was deter-
mined by the equilibrium swelling measurement. This method is
perhaps the most widely used technique for determination of this
parameter. These measurements result in a value of 2.83 for 13
of water/PES system. In spite of its widespread popularity, the
equilibrium swelling measurement results in 13 values that are
somewhat larger than the real values for this parameter [40]. To
find a reasonable value for this parameter, the theoretical bin-
odal curves were fitted on the experimental cloud point data for
both water/DMAc/PES and water/NMP/PES systems. This process
resulted in a value of 1.6 for this parameter and therefore this value
of 13 were used for the construction of theoretical ternary phase
diagrams in the following sections.
3.2. Phase diagram of water/DMAc/PES and water/NMP/PES
systems
In Fig. 2 the theoretical binodal and spinodal curves for the
water/DMAc/PES and water/NMP/PES systems are presented. These
curves were constructed by numerical calculations based on an
extended form of Flory–Huggins theory of polymer solutions
[36,37] by the determined binary interaction parameters as input
data. To verify the theoretical calculations, the results of experimen-
tal cloud point data, which have been determined by the titration
method [40], are also presented in Fig. 2.
This figure shows that the theoretical binodal curve of
water/DMAc/PES system is closer to the polymer–solvent axis com-
pared to that of water/NMP/PES system; therefore less water is
needed for the precipitation of PES in the former system com-
pared to the latter one. It is widely accepted that higher values
of g12 and lower values of g23 shift the binodal curve toward the
nonsolvent–polymer axis and produce larger homogenous regions
in the phase diagram of a ternary system [40,47].
 J. Barzin, B. Sadatnia / Journal of Membrane Science 325 (2008) 92–97
Fig. 4. Micrographs of the cross-sections of membranes prepared from DMAc/PES solutions coagulated in water. The compositions of polymer solutions were (a) 10, (b) 12,
(c) 18, and (d) 20 wt% PES in DMAc.
The interaction parameter values which have been determined
for these two systems show that water/NMP/PES system has higher
g12 and lower 23 values compared to water/DMAc/PES system.
These two factors cause the binodal curve of the latter system be
closer to the polymer–solvent axis.
3.3. Membrane morphology
In Figs. 3 and 4 the morphology of the membranes prepared from
water/NMP/PES and water/DMAc/PES systems are shown. These
figures show that macrovoids are observed in the sublayer of all
the prepared membranes. The presence of macrovoids proves that
there is a high mutual affinity between water and the solvents in
these systems as it has been shown in the nonsolvent/solvent inter-
action parameters of water/NMP and water/DMAc pairs (Fig. 1).
This high mutual affinity between nonsolvent and solvent induces
an instantaneous demixing in the aforementioned systems that
leads to the formation of macrovoids in the resulting membranes
structure.
A look at different morphologies of Fig. 3 shows that channel-
like structures with open ends are observed in membrane prepared
from a solution with a polymer concentration of 10 wt% (Fig. 3a).
Membranes with these irregular morphological structures are not
suitable membranes regarding mechanical strength and handling
[48]. As the polymer concentration increases to 12 wt%, the pores
structure changes to regular channels with closed ends (Fig. 3b).
At a concentration of 18 wt%, the size of the channels decreases
and more sponge-like structures are observed in the membrane
structure (Fig. 3c). In high concentration of 20 wt%, the structure
changes again and small channel-, finger-, and tear-like structures
are observed in the membrane structure (Fig. 3d).
In membranes prepared from DMAc (Fig. 4), a similar trend can
be observed. Albeit, in this case more sponge-like structures are
observed in the membrane structures compared to the correspond-
ing concentrations in the NMP/PES membranes.
As a general rule, in membranes prepared from nonsol-
vent/solvent/polymer systems, increasing the polymer concentra-
tion in the casting solution, which leads to an increase in the
95
solution viscosity, suppresses the formation of macrovoids and
causes long, open channel-like macrovoids turn to finger- and
tear-like structures with more sponge-like areas in the resulting
membranes [4,5,12,16,19,28,30].
When the morphological structures of membranes prepared
from these two nearly similar solvents were compared with each
other, the most important finding of this study was revealed. A
comparison between the morphologies in Figs. 3 and 4 shows that
in all polymer concentrations, especially in high polymer concen-
trations, more sponge-like structures are observed in membranes
prepared from DMAc compared to those prepared from NMP. This
observation is contrary to the generally accepted concepts regard-
ing macrovoid formation and suppression. It is widely accepted that
a low tendency of mixing between nonsolvent–solvent pair sup-
presses the formation of macrovoids [5,7,13]. The mixing tendency
between the nonsolvent–solvent pair is reflected in the nonsol-
vent/solvent interaction parameter of these components. Materials
with low g12 values have a higher tendency to mix with each
other and materials with high g12 values have a lower tendency
to mix. As it has been shown in Fig. 1, in all compositions the
g12 values of the water/NMP system are higher than those of the
water/DMAc system, which proves that there is a higher mutual
affinity between water and DMAc in comparison to water and
NMP. Therefore, according to the concept of macrovoid suppres-
sion in nonsolvent–solvent pairs with lower tendency of mixing,
more sponge-like structures with smaller fingers and tears must
be observed in membranes prepared from water/NMP/PES system
but, completely opposite results are observed in Figs. 3 and 4.
To find an explanation for these unusual observations, it’s
necessary that mechanisms of physical gelation of amorphous
polymers in presence of a solvent and nonsolvent are considered.
According to the gelation mechanism proposed by Arnauts and
Berghmans [49], gelation of an amorphous polymer in a solvent
results from liquid–liquid phase separation arrested by vitrifica-
tion of the polymer-rich phase. Li et al. [50] extended this concept
of gelation to a ternary system consisting of a nonsolvent, a solvent,
and an amorphous polymer. According to this extended concept,
the structure of a phase-separated polymer solution is set when
96 J. Barzin, B. Sadatnia / Journal of Membrane Science 325 (2008) 92–97
Fig. 5. Theoretical binodal curve, vitrification boundary, and gelation boundary for
water/DMAc/PES (—) and water/NMP/PES (– –) systems.
the polymer-rich phase of demixed polymer solution reaches its
glass state (i.e. vitrifies). In a ternary phase diagram, a line that
separates the one-phase solution region from the one-phase glass
region is the vitrification boundary [51]. The intersection of the
vitrification temperature curve and binodal curve is called Bergh-
mans’ point and the tie line that crosses through the Berghmans’
point determines the gelation boundary. Li et al. [50] have per-
formed comprehensive studies concerning the physical gelation of
PES in a mixture of different solvents and water systems. Accord-
ing to the differential scanning calorimetry (DSC) measurements,
these authors determined the polymer concentration at which the
Tg is equal to the system temperature (25 ◦ C) for DMAc/PES and
NMP/PES systems. These polymer concentrations can be used to
determine the vitrification boundary in a ternary phase diagram.
In the present work we have shown the results of our
numerical calculations regarding theoretical binodal curves for
water/DMAc/PES and water/NMP/PES systems in Fig. 2. Based on
these calculations and data reported by Li et al. we have suc-
ceeded to construct complete ternary phase diagrams consisting
of the theoretical binodal curve, vitrification boundary, and gela-
tion boundary for water/DMAC/PES and water/NMP/PES systems
and the results are presented in Fig. 5.
According to this figure, a reasonable explanation for the unex-
pected structures observed in Figs. 3 and 4 can be presented. As
this figure shows the polymer-rich phase concentration at the
intersection of binodal curve with the vitrification boundary is
lower in the case of water/DMAc/PES system. On the other hand,
the binodal curve of this system is closer to the solvent–polymer
axis. Therefore, the vitrification curve of the water/DMAc/PES sys-
tem intersects the binodal curve of this system at lower polymer
concentration which results in the gelation boundary of the sys-
tem being closer to the solvent–polymer axis compared to the
water/NMP/PES system. Therefore, after liquid–liquid demixing the
polymer-rich phase of the water/DMAc/PES system vitrifies earlier
than that of water/NMP/PES system; this phenomenon suppresses
the growth of macrovoids in the former system and membranes
with more sponge-like structures are observed in this case. Recently
Pekny et al. [26] have studied macrovoid development in the
water/acetone/CA solutions and hypothesized that macrovoid for-
mation requires a significant supersaturated region exist within the
casting solution. The earlier vitrification phenomenon observed in
the water/DMAc/PES system studied in the present work causes
solidification of the interface and therefore greatly reduces the
mass transfer of solvent into the nonsolvent bath and the transfer of
nonsolvent into the casting solution. This phenomenon suppresses
the formation of a significant supersaturated region near the inter-
face, which Pekny et al. claim is essential for promoting macrovoid
growth.
4. Conclusions
Morphological studies on membranes prepared from
water/DMAc/PES and water/NMP/PES systems showed that
both systems exhibit an instantaneous demixing that leads to the
formation of macrovoids in the resulting membranes. Neverthe-
less, in spite of higher mutual affinity between water and DMAc,
it was observed that membranes prepared from DMAc had more
sponge-like structures compared to those prepared from NMP. It is
contrary to this widely accepted concept that nonsolvent–solvent
pairs with lower tendency of mixing with each other suppress the
formation of macrovoids. To find an explanation for this unex-
pected observation, the vitrification lines and theoretical binodal
curves and gelation boundaries of these systems were determined
and compared with each other. It was shown that despite higher
mutual affinity between water and DMAc compared to water
and NMP, the vitrification boundary in the former case intersects
the binodal of this system in lower polymer concentration com-
pared to the latter case. This phenomenon leads to the earlier
vitrification of the polymer-rich phase of the water/DMAc/PES
system compared to that of the water/NMP/PES system, which
suppresses the formation of macrovoids in the former system.
The results of this study show that in membrane-forming systems
consisting two nearly similar solvents, in addition to the extent
of nonsolvent–solvent pairs affinity, the position of vitrification
and gelation boundaries play an important role in determining the
type of macrovoid structures in the resulting membranes.
Acknowledgement
The authors gratefully acknowledge support of this research by
Iran National Science Foundation (INSF) grant 84122.
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