ORIGINAL PAPER

Effect of preparation conditions on the morphology,

polymorphism and mechanical properties of polyvinylidene
fluoride membranes formed via thermally induced
phase separation
Jie Liu & Xiaolong Lu & Chunrui Wu & Chen Zhao
Received: 30 July 2013 / Accepted: 7 November 2013 / Published online: 29 November 2013
#Springer Science+Business Media Dordrecht 2013
Abstract Polyvinylidene fluoride (PVDF) membranes were
prepared from PVDF/sulfolane (SFL) solutions using the
thermally induced phase separation (TIPS) method. The ef-
fects of PVDF concentration and dissolving temperature on
the morphology, polymorphism and mechanical properties of
such prepared membranes were investigated. Field emission
scanning electron microscopy (FESEM) was performed to
observe the membrane morphology, and X-ray diffraction
(XRD) along with differential scanning calorimetry (DSC)
was used to analyze the crystalline structure and thermal
behaviors of membranes, respectively. Based on the experi-
mental results, PVDF mainly crystallized into phase in the
overall membranes for all the investigated cases. As the PVDF
concentration in the casting solution was raised, the total
crystallinity and tensile strength of the membranes increased,
while the porosity decreased. With the increase in dissolving
temperature, the total crystallinity and porosity of the mem-
branes increased slightly; however, the tensile strength de-
creased. The FESEM photomicrographs of cross-sections of
membranes indicated that an interconnected bi-continuous
structure was obtained in the PVDF/SFL (30 wt.% PVDF)
system with a dissolving temperature of 120 C, while the rest
of the investigated membranes showed spherical or irregular
particle structure, consequently, the tensile strength was
improved from 3.5 to 7.5 MPa, and the energy consumption
of membrane preparation was reduced.
Keywords Polyvinylidene fluoride
.
Membranes
.
Polymorphism
.
Tensile strength
.
Thermally induced phase
separation
Introduction
Polyvinylidene fluoride (PVDF) as a semi-crystalline poly-
mer, is a favorable material for membrane products due to its
excellent physical and chemical properties [16]. PVDF ex-
hibits a well-known polymorphism depending on crystalliza-
tion conditions, and the chains can crystallize into four distinct
conformations, known as , , , and [710]. The most
common polymorph is the nonpolar phase with a chain
conformation of trans-gauche (TG
+
TG
-
). The polar phase
has an all trans-planar zigzag conformation (TTT). Conver-
sion between the distinct PVDF phases may occur via conve-
nient thermal or mechanical treatments.
Recently, plenty of investigations have been focused on
controlling the polymorph of PVDF in processes, such as the
solutioncast method, melt crystallization and the nonsolvent
induced phase separation (NIPS) mothod. Salimi et al. [11]
studied the supra-molecular crystal structure in PVDF solu-
tioncast films by changing crystallization conditions in two
solvents (N, N-dimethylacetamide and cyclohexanone) of
different structures and polarities. Gregorio et al. [12] investi-
gated the effects of crystallization time and temperature on the
morphology and phase transition of high melt temperature
crystallized PVDF. Buonomenna et al. [13] discussed the
J. Liu
:
X. Lu (*)
:
C. Wu
:
C. Zhao
State Key Laboratory of Hollow Fiber Membrane Materials and
Membrane Processes, Institute of Biological and Chemical
Engineering, Tianjin Polytechnic University, Tianjin 300387,
Peoples Republic of China
e-mail: luxiaolong@263.net
C. Wu
e-mail: wuchunrui79@aliyun.com
J Polym Res (2013) 20:321
DOI 10.1007/s10965-013-0321-3
effects of several parameters such as precipitation tempera-
ture, composition of the polymer solution (concentration, type
of solvent), exposure time before immersion in the coagula-
tion bath, and type of coagulant on the crystallization of NIPS
PVDF membranes. Nevertheless, corresponding studies on
the thermally induced phase separation (TIPS) PVDF mem-
branes have seldom been reported.
The thermally induced phase separation (TIPS) method is a
well-known technique for the preparation of porous PVDF
membranes. In this process, PVDF is dissolved in a diluent at
a high temperature of 200220 C and then the solution is
cooled to induce phase separation. Phase separations during
the TIPS process can occur via liquidliquid or solidliquid
demixing [14, 15]. There are several factors affecting the
morphology and performance of fabricated membranes via
TIPS, including the concentration of polymer in casting solu-
tion, the type of diluents, and the cooling conditions, etc. An
increasing attention has been paid to the TIPS process in
recent years; however, the spherical particles are always
formed [1618]. For PVDF/sulfolane (SFL) system, Cui
et al. [19] had reported that only solidliquid phase separation
was observed in the TIPS process, and the membranes with
spherical particles were obtained. Hence, it is still difficult to
prepare TIPS PVDF membranes with a bi-continuous struc-
ture using single diluent.
Cheng [20] had demonstrated that the dissolving tempera-
ture of the casting solution had a great effect on the morphology
of prepared membranes in the NIPS process. Wang et al. [21]
found that the dissolving temperature had an important role on
macromolecular chains, and its influence on the properties of
dopes remained in the process of immersion precipitation and
led to the formation of different membrane morphologies.
However, the dissolving temperature of dope has seldom been
considered as a parameter influencing the membrane structure
in TIPS process.
The current work is aimed at developing PVDF mem-
branes with interconnected bi-continuous structure via TIPS
method using SFL as a diluent. In the fabrication process, the
effects of PVDF concentration and dissolving temperature on
the morphology, polymorphism and mechanical properties of
TIPS membranes were investigated.
Experimental
Materials
The PVDF resin used is SOLEF 6010 from Solvay
Solexis Company (French), which has a melt flow index
of 6 g/10 min (230 C, 5 kg). The crystallizing point
(crystallizing point is the onset of polymer melting [22])
and melting temperature of the as-received resin are
138 C and 173 C, respectively, according to the product
introduction. Chemically pure grade SFL is used as dilu-
ent without further purification, and it is purchased from
Guangfu Chemical Reagent, Tianjin, China.
Membrane preparation
A mixture of PVDF/SFL was dissolved in a hermetically
sealed glass flask, followed by stirring until the solution
became homogeneous, then the solution was degassed to
remove bubbles. After that, the solution was cast into flat
sheet membranes by a glass blade on a hot plate at a special
temperature. The flat sheet membranes were solidified by
quenching in 30 C water bath for 0.5 h with no residence
time in the air. Finally, SFL was extracted with water for 48 h.
Flat sheet membranes were dried in ambient air. The prepara-
tion conditions for various membranes are listed in Table 1.
Because SFL was water soluble, during membrane prepara-
tion, the NIPS process inevitably occurred with the TIPS
process theoretically as a result of the exchange of solvent
(SFL) and nonsolvent (water) as the PVDF membranes were
immersed into the water bath.
Membrane characterization
The cross-sectional morphologies of membranes were observed
by a field emission scanning electron microscope (FESEM,
Hitachi S-4800, Japan) using an acceleration voltage of 5 kV.
Cross-sections were prepared by fracturing the membranes in
liquid nitrogen, and sputtered with gold under vacuum.
Crystalline structures of the overall membranes were in-
vestigated through an X-ray diffractometer (Bruker D8 ad-
vance, Germany), using Cu K radiation at a voltage of
40 kVand a current of 40 mA. Intensities were measured in
the range 10<2<45, typically with step scans of 0.05.
The characteristic diffraction peaks of and phases were at
2 (17.8, 18.3, 19.9 and 26.7) and 2 (20.6), respectively
[23, 24].
Table 1 Preparation conditions for membranes
Membrane label PVDF
concentration
(wt.%)
Dissolving
temperature
(C)
Hot plate
temperature
(C)
M1 20 200 200
M2 30 200 200
M3 40 200 200
M4 50 200 200
M5 60 200 200
M6 70 200 200
M7 30 120 120
M8 30 150 150
M9 30 180 180
321, Page 2 of 10 J Polym Res (2013) 20:321
Fig. 1 FESEMphotomicrographs of TIPS membranes with different PVDF concentrations. a1, a2 M1, b1, b2 M2, c1, c2 M3, d1, d2 M4, e1, e2 M5,
f1, f2 M6
J Polym Res (2013) 20:321 Page 3 of 10, 321
The melting temperature and total crystallinity of PVDF
membranes were characterized by a differential scanning cal-
orimeter (Perkin-Elmer DSC-7, USA). The heating rate was
set to 10 Cmin
1
.
The PVDF total crystallinity X
c
was calculated by [25]:
X
c

H
f
H
f

100% 1
Where H
f
*
=104.7 J g
1
, is the melting enthalpy for a
100 % crystalline PVDF, H
f
is the melting enthalpy of
PVDF membranes measured in DSC.
The overall porosity was calculated according to the
equation:

W
w
W
d
=
H
2
O
W
w
W
d
=
H
2
O
W
d
=
p
100% 2
Where W
w
and W
d
are the wet and dry weight of the
membranes, respectively,
H2O
=1.0 gcm
3
,
p
=1.78 gcm
3
.
Tensile strength was measured by an Electronic Single-
yarn Tensile Tester (room temperature, 500 mmmin
1
).
Results and discussion
Effect of PVDF concentration
Morphology
Figure 1 shows the cross-sectional morphologies of TIPS
membranes with different PVDF concentrations (from 20 to
70 wt.%). With reference to Fig. 1, spherical particles and
irregular particles are formed in the cross-section of mem-
branes, which are the typical membrane structures for TIPS
process, that is to say, the predominant phase separation
process is the TIPS process when membranes are solidified
in water bath. The membranes (M1 and M2) demonstrate
relatively similar morphologies with clear spherical particles
and non-spherical structure. For M1 and M2 membranes, the
boundary among spherical particles is quite clear. For M3
membrane, the spherical particle morphology becomes indis-
cernible, and the morphology tends to be irregular. As the
PVDF concentration reaches 50 wt.% (M4), only irregular
morphologies are observed.
Fig. 1 (continued)
Fig. 2 XRD patterns of TIPS membranes with different PVDF concen-
trations. a M1, b M2, c M3, d M4, e M5, f M6
Fig. 3 DSC curves of TIPS membranes with different PVDF concentra-
tions. a M1, b M2, c M3, d M4, e M5, f M6
321, Page 4 of 10 J Polym Res (2013) 20:321
This change may be related to the higher viscosity and
reduction of the mobility of chains caused by increasing
PVDF concentration, which prevent the formation of spheri-
cal particles during the TIPS process [19]. With the concen-
tration increasing from 50 to 70 wt.%, the change of mem-
brane morphology is slight. It indicates that the effect of the
higher PVDF concentration on the cross-sectional structure is
insignificant. All these structures of membranes present dif-
ferent crystallization morphologies of PVDF. There is another
important phenomenon that should be noted. For all the in-
vestigated membranes in Fig. 1, pore structures are observed
on the particle surface. In the cooling process, PVDF crystals
precipitated from the high temperature casting solution be-
cause of S-L phase separation; hence, spherical particles were
formed. With the continuous crystallization of the polymer,
more perfect or bigger crystallites would push much more
diluent to the growth front of the polymer, which induced the
decrease in the polymer concentration of the growth front. As
the temperature was further reduced, L-L phase separation
happened in the growth front of spherical particles, conse-
quently, pore structure on the spherical particle surface was
formed after the coarsening process.
Crystalline structures of the overall membranes
The XRD measurements were performed to examine the crys-
talline phases of the overall membranes. Figure 2 shows the
XRD patterns of TIPS membranes prepared with different
PVDF concentrations. As illustrated in Fig. 2, PVDF concen-
tration in casting solution exerts a significant influence on the
crystalline structure of the overall membranes. For the mem-
branes with PVDF concentration of 30, 40, 50, 60 and 70 wt.%,
phase is definitely predominant for PVDF crystalline with
the three most distinctive diffraction peaks at around 18.3,
19.9 and 26.7 in the XRD patterns, corresponding to the
reflections of (020), (110) and (021) planes of phase, respec-
tively. The reflection peak of the (020) plane at 18.3 becomes
insignificant, and the reflection peak of (021) plane at 26.7
disappears when PVDF concentration decreases to 20 wt.%.
These changes suggest that the c-axis of the crystals is prefer-
entially oriented parallel to the surface at lower polymer con-
centration [26]. As reported, it seemed that the resulting crys-
talline phase of PVDF was determined by the crystallization
rate [22]. An explanation for this phenomenon might be given
considering that the phase in PVDF was thermodynamically
meta-stable, however, phase was thermodynamically more
stable [26]. In the TIPS process, the casting solution was
quenched in a 30 C water bath, resulting in a high crystalliza-
tion rate. PVDF chains did not have sufficient time and thermal
energy to form the thermodynamically meta-stable phase,
consequently, phase was formed in the overall membranes.
Thermal behaviors of the membranes
Figure 3 shows the DSC curves of TIPS membranes prepared
with different PVDF concentrations. The heat of fusion (H
f
)
and total crystallinity (X
c
) are summarized in Table 2. As can
be seen, all the membranes have one broad melting peak at
156 C175 C. The total crystallinity and melting tempera-
ture increase as PVDF concentration is increased (Fig. 3). The
results indicate that the mass exchange rate in viscous casting
solutions is not comparable to that in the lower concentration
case [26], and the increase of PVDF concentration would
Table 2 Heat of fusion
(H
f
) and total crystal-
linity (X
c
) of TIPS
membranes with differ-
ent PVDF concentrations
Membrane label H
f
(J/g) X
c
(%)
M1 44.8 42.8
M2 70.3 67.1
M3 70.4 67.2
M4 73.2 69.9
M5 76.2 72.8
M6 76.4 73.0
Fig. 4 Porosity of TIPS membranes with different PVDF concentrations
Fig. 5 Mechanical properties of TIPS membranes with different PVDF
concentrations
J Polym Res (2013) 20:321 Page 5 of 10, 321
promote the contact of PVDF chains that leads to larger
molecular coils and more entanglements among them [19],
allowing the crystallization process to commence much earlier
to yield higher crystallinity.
Porosities of the membranes
The porosity results of the TIPS membranes prepared with
different PVDF concentrations are shown in Fig. 4. With the
increase of PVDF concentration, the porosity of the whole
membrane decreases. This development trend is predictable.
The membrane pore structure mainly comes from the space
occupied by diluent. The content of diluent decreases with the
increase of PVDF concentration, consequently, the porosity
decreases.
Tensile strength of the membranes
Figure 5 shows the effect of PVDF concentration on the
mechanical properties of TIPS membranes. The tensile
strength of the membrane increases from 1.4 to
17.7 MPa with the increase in PVDF concentration up
to 70 wt.%. The differences in the tensile strength are
directly related to the increase in total crystallinity and
compaction of TIPS PVDF membranes. The break elon-
gation increases as the PVDF concentration is increased
Fig. 6 FESEM
photomicrographs of TIPS
membranes with different
dissolving temperatures. a1, a2
M7, b1, b2 M8, c1, c2 M9, d1,
d2 M2
321, Page 6 of 10 J Polym Res (2013) 20:321
from 20 to 40 wt.%, when the PVDF concentration is
as high as 50 wt.%, break elongation decreases, with
the PVDF concentration increasing from 50 to 70 wt.%,
and break elongation changes slightly. As discussed
above, the porosity decreases and crystallinity increases
as PVDF concentration is increased from 20 to
70 wt.%. An explanation for the change in break elon-
gation might be that: The decrease in porosity is favor-
able to the increase in break elongation [27, 28], while
the increase in crystallinity induces the decline in break
elongation [2931]. These two factors result in the
change in break elongation. To clearly understand the
detailed mechanisms of such behavior presented in the
membrane, further investigation is still needed.
Effect of dissolving temperature of casting solution
Morphology
The membranes were prepared by dissolving PVDF at differ-
ent temperatures with 30 wt.% PVDF concentration. Figure 6
shows the FESEM photomicrographs of the formed mem-
branes. The membranes with dissolving temperature of
150 C, 180 C and 200 C demonstrate similar morphologies
with spherical particles both with and without surface pores.
The spherical particles become bigger and more perfect as the
dissolving temperature increases from 150 to 200 C. An
interconnected bi-continuous structure is obtained with dis-
solving temperature of 120 C. As shown in Fig. 7, the inter-
connected structure is composed of small leaf-like crystallites.
When a polymer was dissolved in solvent, small crystalline
structures were formed in the solution owing to the partial
dissolution of the crystals or the refolding of the dissolved
macromolecular chains. The crystallization process happened
because small crystals acted as nuclei when the solution re-
crystallized [32]. In the dissolving process, the solution state
was closely related to the dissolving temperature. Therefore,
the different dissolving temperatures could result in a remark-
able variation both in crystal nucleus size and available con-
centration, which initiated the crystallization process. In Wang
et al.s experiment [21], PVDF's dissolving temperature was
Fig. 7 Higher magnified FESEM photomicrograph of TIPS membrane
with dissolving temperature of 120 C
Fig. 8 XRD patterns of TIPS membranes with different dissolving
temperatures. a M7, b M8, c M9, d M2
Fig. 9 DSC curves of TIPS membranes with different dissolving tem-
peratures. a M7, b M8, c M9, d M2
Table 3 Heat of fusion
(H
f
) and total crystal-
linity (X
c
) of TIPS
membranes with differ-
ent dissolving
temperatures
Membrane label H
f
(J/g) X
c
(%)
M7 66.7 63.7
M8 66.7 63.7
M9 69.8 66.7
M2 70.3 67.1
J Polym Res (2013) 20:321 Page 7 of 10, 321
varied from 50 to 120 C, and they found that the increase of
the PVDF dissolving temperature would lead to larger molec-
ular coils and more entanglement among them, the macromo-
lecular chain would pervade a larger region in the solution due
to the expansion of the coils. Therefore, in the membrane
formation process, the higher dissolving temperature resulted
in a less and a bigger crystal nucleus. Ahmad et al. [33]
reported the similar result that low dissolving temperature
led to a higher nuclei concentration.
The differences in the crystallization process account for
the different membrane morphologies. The dissolving temper-
ature of 120 C is far below the crystallizing point of PVDF
138 C. As mentioned before, the crystallizing point is the
onset of polymer melting. The casting solution with lower
dissolving temperature of 120 C does not melt, which results
in a higher crystal nucleus concentration. With a higher crystal
nucleus concentration, the growth of the crystalline is slower
because of competition between the nuclei [33], which leads
to smaller leaf-like crystallites of PVDF at the same cooling
condition. On the contrary, as the dissolving temperature is
increased, the number of crystal nucleus decreases. The PVDF
crystallites can grow simultaneously to all directions in space
from finite crystal nucleus. Therefore, TIPS membranes pres-
ent obvious spherical particles with bigger size.
Crystalline structures of the overall membranes
The XRD patterns of TIPS PVDF membranes with different
dissolving temperatures are presented in Fig. 8. It can be
clearly seen that all the membranes exhibit similar diffraction
patterns. The predominant presence of phase is confirmed
by the occurrence of three most distinctive diffraction peaks at
around 18.3, 19.9, and 26.7. The diffraction peak of
phase at 18.3 becomes stronger as the dissolving temperature
increases. The major reason for this change is attributed to the
higher mobility of PVDF chains at higher dissolving temper-
atures, which facilitates the formation of phase.
Thermal behaviors of the membranes
Figure 9 shows typical DSC curves for TIPS membranes with
different dissolving temperatures. The heat of fusion (H
f
)
and total crystallinity (X
c
) are summarized in Table 3. The
DSC curves of the membranes present very similar thermo-
grams, they all have one endotherm with a peak at around
169 C172 C. The total crystallinity increases slightly and
the melting temperature shifts towards higher temperature as
the dissolving temperature increases. In the case of higher
dissolving temperature, the polymer chains have better mobil-
ity, which is favorable to the crystallite growth. Thus, PVDF
crystallites grow faster and bigger that might promote the
crystallization to obtain higher crystallinity.
Porosities of the membranes
Dissolving temperature also has an influence on the porosities
of the membranes. The porosity of the whole membrane
increases with increasing the PVDF dissolving temperature
as shown in Fig. 10. It is well known that higher temperature is
favorable to the crystallization of polymer. This would influ-
ence the microstructure of the membrane, that is to say, the
higher dissolving temperature promotes the formation of big-
ger crystallites, which results in larger gaps between the
PVDF crystallites and consequently, generates a higher poros-
ity of TIPS membrane. The shrinkage of the membrane is
another important factor to affect the porosity. As illustrated in
Fig. 6, when the dissolving temperature increases, the shrink-
age of the membrane decreases, hence, porosity increases.
Tensile strength of the membranes
Figure 11 shows the effect of dissolving temperature on me-
chanical properties of TIPS PVDF membranes. As the
Fig. 10 Porosity of TIPS membranes with different dissolving
temperatures
Fig. 11 Mechanical properties of TIPS membranes with different dis-
solving temperatures
321, Page 8 of 10 J Polym Res (2013) 20:321
dissolving temperature is elevated from 120 to 200 C, the
tensile strength decreases from 7.5 to 3.5 MPa. This change in
tensile strength is mainly due to the structure of membranes as
the total crystallinity changes slightly. It is commonly believed
that the interconnected bi-continuous structure usually has
better mechanical properties than the spherical particle, con-
sequently, the membrane with the dissolving temperature of
120 Chas a higher tensile strength. The result is in agreement
with Rajabzadeh et al. [6]. They demonstrated that the
membrane with interconnected structure exhibited better
maximum stress than spherulite-like structures. The size
of spherical particles becomes bigger and the packing
density of spherical particles decreases when the dis-
solving temperature is raised from 150 to 200 C, thus,
the tensile strength decreases.
Conclusions
In this study, PVDF membranes with interconnected bi-
continuous structure were prepared through the TIPS method
with the diluent of SFL. The effects of PVDF concentration
and dissolving temperature on the morphology, polymor-
phism and mechanical properties of PVDF membranes were
investigated. It was found that PVDF mainly crystallized into
form crystalline structure in the overall membranes. As the
PVDF concentration in casting solution was raised, the total
crystallinity and tensile strength of the membranes increased,
while the porosity decreased. When the dissolving tempera-
ture increased, the total crystallinity and porosity of the mem-
branes increased slightly, however, the tensile strength de-
creased. An interconnected bi-continuous structure was ob-
tained bya PVDF/SFL (30 wt.% PVDF) system with a lower
dissolving temperature of 120 C. Hence, the energy con-
sumption of membrane preparation was reduced, and the
tensile strength was improved from 3.5 to 7.5 MPa.
Acknowledgments This work was supported by the National Natural
Science Foundation of China (21176188, 21106100, 51278336), Special-
ized Research Fund for the Doctoral Program of Higher Education of
China (20111201110004), Research Program of Application Foundation
and Advanced Technology, Tianjin, China (11JCYBJC04700).
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