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Membrane Separations Division, Center of Excellence in Polymer Science, Karnatak University, Dharwad 580003, India
b Organic Coatings and Polymers Division, Indian Institute of Chemical Technology, Hyderabad 500007, India
Received 21 October 2004; received in revised form 13 March 2005; accepted 14 March 2005
Available online 3 May 2005
Abstract
Novel nanocomposite polymeric membranes containing nanosized (30100 nm) polyaniline (PANI) particles dispersed in poly(vinyl alcohol) (PVA) were prepared and used in the pervaporation separation of waterisopropanol feed mixtures ranging from 10 to 50 mass% of water
at 30 C. Of the three nanocomposite membranes prepared, the membrane containing 40:60 surface atomic concentration ratio of PANI:PVA
produced the highest selectivity of 564 compared to a value of 77 observed for the plain PVA membrane. Flux of the nanocomposite membranes was lower than those observed for the plain PVA membrane, but selectivity improved considerably. Membranes were characterized
by differential scanning calorimetry, dynamic mechanical thermal analyzer, X-ray photoelectron spectroscopy, Fourier transform infrared
spectroscopy and scanning electron microscopy. The highest selectivity with the lowest flux was observed for 10 mass% water containing
feed mixture. Flux increased with increasing amount of water in the feed, but selectivity decreased considerably. These results were attributed
to the acid-doped PANI particles in the PVA membrane as a result of change in the micromorphology of the nanocomposite membranes. In
addition, molar mass between cross-links and fractional free volume of the membranes are responsible for the varying membrane performance.
Temperature effect on permeability was investigated for 10 mass% water containing feed with the membrane containing higher concentration
of PANI particles, the presence of which could be responsible for varied effect of water permeation through the membrane. Membranes of
this study could remove as much as 98% of water from the feed.
2005 Elsevier B.V. All rights reserved.
Keywords: Nanocomposite membrane; Polyaniline; Poly(vinyl alcohol); Diffusion; Pervaporation
1. Introduction
Dehydration of isopropanol by pervaporation (PV)
technique has been widely studied [13]. One of the key
successes of PV is that, if suitable membranes can be fabricated with high permeability and good selectivity to water, it
is possible to achieve an excellent separation, particularly at
the azeotropic composition. However, more number of novel
polymeric membranes are needed for a successful operation
This paper is Center of Excellence in Polymer Science Communication
# 57.
Corresponding author. Tel.: +91 836 2215372/2778279;
fax: +91 836 2771275/747884.
E-mail address: aminabhavi@yahoo.com (T.M. Aminabhavi).
0376-7388/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2005.03.037
B. Vijaya Kumar Naidu et al. / Journal of Membrane Science 260 (2005) 142155
143
2. Experimental
2.1. Materials
Laboratory reagent grade PVA (87% degree of hydrolysis)
with a molecular weight 125,000 was procured from s.d. Fine
Chemicals, Mumbai, India. AR grade aniline (Loba Chemicals, Mumbai, India) was vacuum distilled and stored in an
amber colored bottle under cold conditions. Glutaraldehyde
(GA), hydrochloric acid, acetone, isopropanol, ammonium
persulfate and all other chemicals used in this work were
of AR grade samples, purchased from s.d. Fine Chemicals,
Mumbai, India. These were used as received. Deionized water having a conductivity of 20 S/cm was produced in the
laboratory from the Permionics pilot plant (Vadodara, India)
using the nanofiltration membrane module.
2.2. Preparation of PVAPANI nanocomposite
membranes
Polymerization of aniline in PVA was carried out as per the
published report [21] to obtain the nanocomposite. To prepare
three different nanocomposites, a 3 mass% solution of PVA
prepared in water, 0.6, 0.9 or 1.2 mL of aniline were added.
The pH of the solution was adjusted to 1 by adding dil. HCl.
To this mixture, an aqueous solution of ammonium persulfate
was added at 5 C under constant stirring by maintaining the
equimolar ratio of aniline to ammonium persulfate. The mixture was stirred for 4 h to obtain the colloidal PANI particles
suspended in PVA. This reaction mixture was then poured
onto a clean glass plate to cast the membranes. The dried
PVAPANI nanocomposite membranes were cross-linked
with GA by dipping them in 200 mL aqueous acetone mixture containing 1 mL of GA and 1 mL of con. HCl for 12 h.
Membranes were removed from the bath, washed three times
with distilled water and dried in an oven at 40 C for 4 h. The
nanocomposite membranes prepared with 0.6, 0.9 or 1.2 mL
of aniline were designated as PVAPANI-I, PVAPANIII and PVAPANI-III, respectively. Plain PVA membrane
was prepared by using 3 mass% PVA solution in a similar
manner.
2.3. Characterization
2.3.1. Fourier transform infrared (FT-IR) spectroscopic
studies
FT-IR spectra of the pure aniline, PVA and PVAPANI
membranes in KBr pellets were recorded on a Nicolet, Model
Impact 410 (Milwaukee, WI, USA) in the wavelength region
of 4000400 cm1 .
2.3.2. X-ray photoelectron spectral (XPS) studies
The core level XPS spectra of polyaniline salts and bases
and membranes were recorded using KRATOS AXIS 165
(Shimadzu) with Mg K X-ray source 253.6 eV. The X-ray
power supply was operated at 75 W and 5 mA. Pressure
144
B. Vijaya Kumar Naidu et al. / Journal of Membrane Science 260 (2005) 142155
W
At
PA
1 PA
(1)
1 FA
FA
(2)
B. Vijaya Kumar Naidu et al. / Journal of Membrane Science 260 (2005) 142155
145
Fig. 1. FT-IR spectra of plain PANI, plain PVA and PVAPANI-II nanocomposite membrane.
Sample
Deconvoluted N(1s)
binding energy (eV)
PVAPANI-I
PVAPANI-II
PVAPANI-III
0.78
0.73
0.52
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Table 2
Melting onset temperatures and molar mass between cross-links (Mc ) of
different membranes
Membrane
PVA
PVAPANI-I
PVAPANI-II
PVAPANI-III
Melting onset ( C)
Mc 104 (kg/mol)
Uncross-linked
Cross-linked
175
196.1
196.6
194.0
143
193.0
195.7
199.0
886
285
115
15
B. Vijaya Kumar Naidu et al. / Journal of Membrane Science 260 (2005) 142155
147
Fig. 3. tan curves of (a) uncross-linked PVAPANI, (b) cross-linked PVAPANI, and (c) plain and cross-linked PVA membranes.
148
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Fig. 5. E curves of (a) uncross-linked PVAPANI, (b) cross-linked PVAPANI, and (c) plain and cross-linked PVA membranes.
modulus at a temperature above Tg ) and R is the universal gas constant (8.314 107 cal/mol deg). Calculated values of Mc are also given in Table 2. For the plain PVA
membrane, Mc = 886 104 kg/mol, the highest among all the
membranes. For PVAPANI-I, the Mc = 285 104 kg/mol, a
value that is almost three-times smaller than that observed
for the plain PVA. Such a decrease in Mc of the nanocomposite membrane could indicate changes in the morphological
setup of the membranes. These changes are directly related
to the pervaporation performance (to be discussed in Section 3.10). It can be seen that with an increasing amount
of PANI particles in the PVA matrix, the Mc values tend
to decrease considerably. Thus, for the PVAPANI-III, the
Mc = 15 104 kg/mol, the smallest of all the membranes prepared.
3.8. Free volume
(3)
B. Vijaya Kumar Naidu et al. / Journal of Membrane Science 260 (2005) 142155
149
Vsp V0
Vsp
(4)
PVAPANI-I
PVAPANI-II
PVAPANI-III
0.5798
0.5809
0.5831
V0 = 1.3VW
0.114
0.074
0.084
(5)
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Fig. 7. Number average particle size distribution of (a) PVAPANI-I, (b) PVAPANI-II, and (c) PVAPANI-III nanocomposites.
Fig. 8. Plots of swelling vs. time at 10 mass% of water in water containing isopropanol mixtures. Symbols: () pure PVA, () PVAPANI-I, ( )
PVAPANI-II and () PVAPANI-III nanocomposite membranes.
Selectivity
Permeate
10
20
30
40
50
89.57
88.2
87.62
85.43
84.63
PVA
0.095
0.216
0.320
0.366
0.398
77.3
29.9
16.5
8.8
5.5
10
20
30
40
50
67.44
78.38
81.04
86.38
89.02
PVAPANI-I
0.035
0.068
0.091
0.116
0.156
18.6
14.5
10
9.5
8.1
10
20
30
40
50
98.28
87.97
63.02
80.73
87.13
PVAPANI-II
0.061
0.090
0.084
0.127
0.194
514.3
29.3
4.0
6.3
6.8
10
20
30
40
50
98.43
92.56
84.82
71.75
67.8
PVAPANI-III
0.069
0.221
0.243
0.219
0.218
564.2
49.8
13.0
3.8
2.1
B. Vijaya Kumar Naidu et al. / Journal of Membrane Science 260 (2005) 142155
151
152
B. Vijaya Kumar Naidu et al. / Journal of Membrane Science 260 (2005) 142155
Fig. 11. Comparison of vapor liquid equilibrium curve (), with PV data ()
for water (l)-isopropanol (2) mixtures at 30 C for PVAPANI-III membrane.
Table 5
Comparison of PV performance of the present nanocomposite membranes with literature data on PVA-based membranes for water + isopropanol mixtures at
30 C
Membrane
Flux (kg/m2 h)
Selectivity
Reference
PVAPANI-III
NaAlg/PVA (75:25)
NaAlg/PVA (50:50)
NaAlg/PVA (25:75)
PVA + KA
PVA + NaA
PVA + CaA
PVA + NaX
PVA cross-linked with glutaraldehyde
PVA cross-linked with citric acid
10
10
10
10
20
0.069
0.025
0.034
0.039
0.179
0.183
0.190
0.216
0.194
0.095
564
195
119
91
410
328
233
133
116
741
Present work
[4]
10
5
PVA: poly(vinyl alcohol); PANI: polyaniline; NaAlg: sodium alginate; KA, NaA, CaA, NaX: zeolites.
[55]
[56]
B. Vijaya Kumar Naidu et al. / Journal of Membrane Science 260 (2005) 142155
our earlier results [4] on sodium alginate/PVA blend membranes, the present nanocomposite membranes could offer
an improved flux and better selectivity to water. The plain
PVA membrane cross-linked with glutaraldehyde developed
by Burshe et al. [56] had a selectivity of 116 with a flux
of 0.194 kg/m2 h for the separation of waterisopropanol
mixture. On the other hand, 5 mass% water-containing
feed mixture of waterisopropanol had a selectivity of 741,
when the plain PVA was cross-linked with citric acid [56].
Comparing with the PVA membranes incorporated with
KA, NaA, CaA and NaX type zeolites [55], which gave
an improved flux with reasonable selectivites ranging from
410 to 133 at 20 mass% water containing feed mixture, the
present PVAPANI-III nanocomposite membranes gave
much superior values (see Table 5).
3.11. Temperature-dependent permeation rate
Another method of increasing the permeation rates of
liquids through a membrane module is by increasing the temperature of the permeating solution. Temperature-dependent
permeation rate, selectivity and mass% of water in the
permeate for 10 mass% water and 90 mass% isopropanol
feed mixture through the PVAPANI-III membrane are given
in Table 6. A two-fold increase in the permeation rate (flux)
is observed upon raising the temperature from 30 to 40 C,
with an appreciable loss in selectivity from 564 to 181. Upon
further increasing the temperature to 50 C, an increase in
flux, but not a drastic decrease in selectivity is observed. The
increase in flux over the studied temperature range is likely
due to an increased diffusion rate of the feed molecules.
Additionally, in the complex nanocomposite membrane of
the type prepared in this study, slight changes in the fractional
free volume with increasing temperature could result in their
increased permeation flux. These observations are consistent
with the observed systematic decrease in mass% of water
in permeate with increasing temperature. The Arrhenius
activation energy, EP for the PV process was computed using:
JP = JP0 exp(EP /RT )
(6)
Water flux
(kg/m2 h)
Mass% of water
in permeate
Selectivity
30
40
50
0.069
0.144
0.158
98.43
95.26
92.87
564.2
180.9
117.2
153
4. Conclusions
The present study addresses the development of novel
nanocomposite membranes of poly(vinyl alcohol) dispersed with the doped polyaniline nanoparticles used for
the pervaporation separation of waterisopropanol feeds
ranging in composition from 10 to 50 mass% of water.
SEM micrographs confirmed the uniform distribution
of polyaniline nanoparticles in the poly(vinyl alcohol)
matrix. The solution-cast membranes were cross-linked with
glutaraldehyde as confirmed by Fourier transform infrared
spectra. Membranes could exhibit an increased selectivity
to water about five-folds compared to the plain poly(vinyl
alcohol) membrane at the expense of reduced water flux. The
PVAPANI-III nanocomposite membrane could successfully
separate waterisopropanol feed mixture at the azeotropic
composition compared to simple distillation. The membrane
performance was also studied at higher temperatures (40
and 50 C). The results of this study were explained in terms
of the acid doping effects of the PANI particles in the PVA
matrix. However, the parameters like molar mass between
cross-links, fractional free volume and extent of swelling
are important to explain the pervaporation results.
Acknowledgements
Professor T.M. Aminabhavi and Dr. B.V.K. Naidu (RA)
thank the Council of Scientific and Industrial Research
(CSIR), Grant No. 80(0042)/02/EMR-II for a financial support of this study. Authors thank the University Grants Commission (UGC), New Delhi, India for a major funding (F141/2001/CPP-II) to establish the Center of Excellence in
Polymer Science.
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