Modification of chitosan membranes with

nanosilica particles as polymer electrolyte

membranes
Cite as: AIP Conference Proceedings 1725, 020037 (2016); https://doi.org/10.1063/1.4945491
Published Online: 19 April 2016

Ella Kusumastuti, Widasari Trisna Siniwi, F. Widhi Mahatmanti, Jumaeri, Lukman Atmaja, and Nurul
Widiastuti

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AIP Conference Proceedings 1725, 020037 (2016); https://doi.org/10.1063/1.4945491 1725, 020037

© 2016 Author(s).
 Modification of Chitosan Membranes with Nanosilica
Particles as Polymer Electrolyte Membranes

Ella Kusumastuti1, a), Widasari Trisna Siniwi1, b), F. Widhi Mahatmanti1, Jumaeri1,
Lukman Atmaja2 and Nurul Widiastuti2

1
Department of Chemistry, Faculty of Mathematics and Natural Sciences, State University of Semarang
D6 Building 2nd floor, Sekaran Unnes Campus, Gunungpati, Semarang, Indonesia
2
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Tenth November Institute of Technology
Keputih ITS Campus, Sukolilo, Surabaya, Indonesia

a)
ella.kusuma@gmail.com
b)
wsiniwi@gmail.com

Abstract. Chitosan has been widely used as polymer matrix for Polymer Electrolyte Membrane (PEM) application
replacing Nafion which has shortcomings in terms of high methanol permeability that degrades the performance of fuel
cells. Chitosan membranes modification is performed by adding nanosilica to prevent methanol transport through the
membrane. Nanosilica is synthesized by sol-gel method and the particle diameter is obtained by analysis using Breunner
Emmet Teller (BET) that is 6.59 nm. Nanosilica is mixed with chitosan solution to obtain nanosilica-chitosan as polymer
electrolyte membrane. The membranes are synthesized through phase inversion method with nanosilica composition
including 0; 0.5; 1; 2; 3; 5; and 10% w/w of chitosan. Characterization of the membranes indicate that the results of water
swelling, proton conductivity and methanol permeability of the membrane with 3% nanosilica respectively were 49.23%,
0.231 S/cm, and 5.43 x 10-7 cm2/s. Based on the results of membrane selectivity calculation, the optimum membrane is
the composition of 3% nanosilica with value 5.91 x 105 S s cm-3. The results of functional groups analysis with FTIR
showed that it was only physical interaction that occurred between chitosan and nanosilica since no significant changes
found in peak around the wave number 1000-1250 cm-1.

INTRODUCTION

The development of human civilization today has led to the increasing consumption of energy over time. Fossil
fuels dominate human needs throughout the world. The primary human dependence on this energy source has
caused the scarce and shortage of the world’s crude oil supply, so it requires serious attention to look for alternative
sources of fuel energy. Fuel cell is one of potential alternatives to overcome these problems [1].
Fuel cell is a device that produces electricity generator directly through an electrochemical process with
hydrogen gas (H 2 ) as fuel and oxygen gas (O 2 ) as oxidant. In a fuel cell, electrolyte membrane is the main
component that separates the reactants and the means of hydrogen ions transport produced by the anode reaction
towards the cathode reaction that produces electrical energy [2]. This membrane is called Polymer Electroyte
Membrane (PEM) [3]. The main properties owned by the membrane is its ability to exchange ions. In the application
of fuel cell, the electrolyte membrane must have high cation exchange capacity, low permeability and high thermal
stability [4]. This research will synthesize PEM for Direct Methanol Fuel Cell (DMFC).

The 3rd International Conference on Advanced Materials Science and Technology (ICAMST 2015)
AIP Conf. Proc. 1725, 020037-1–020037-9; doi: 10.1063/1.4945491
Published by AIP Publishing. 978-0-7354-1372-6/$30.00

020037-1
 Nafion membranes provide maximum performance of many membrane types that have
been investigated, however nafion membranes have drawbacks including the limited working temperature, being
uneconomical, and have not been able to prevent methanol crossover as well [5]. Therefore, it is necessary to
conduct further research in order to obtain alternative membrane that has a high separation efficiency and is more
economical.
Chitosan is a polymer compound of 2-amino-2-dioksi-ȕ-D-glucose that can be produced
from chitin which removes the acetyl group using concentrated alkaline [6]. Chitosan is readily
available and has a high thermal stability, but modifications to the chitosan needs to be done in order to produce a
material that can be used as a charged proton exchange membrane. Chitosan has amino and hydroxyl groups
that were allowed to be modified [4]. According to [7], it is also known that the chitosan methanol crossover is
lower than Nafion. Although chitosan membrane does not provide advantages over Nafion when viewed from the
proton conductivity, it decreases the permeability of methanol that makes these polymers suitable for application in
DMFC [8]. Modifications to the chitosan as sulphonated, phosporilasi or cross belt makes it more effective as a
polymer membrane electrolytes with low methanol permeability and ionic conductivity suitable for high temperature
[9].
In order to increase the ionic conductivity, particularly, to promote ions migration through the membrane, it is
necessary to make chitosan membrane modification. Modifications made by adding silica to the membrane. The
silica can reduce hydrophilic degree of the chitosan primary chain as the impact of free amine acid group and a
hydroxyl at carbon atom [10]. Silica can absorb methanol on the membrane surface so that most of the methanol
does not pass through the membrane. Silica can close the membrane pores so that the displacement of methanol
through the membrane is small. It has been reported that the addition of silica into the base polymer matrix can
reduce the crystallinity of the polymer matrix and increase mechanical strength such as water resistance, strong
stretching and tensile strength [11]. Methanol crossover of chitosan-silica composite is also reduced with a decrease
in the degree of methanol swelling [12]. The swelling of chitosan membrane is largely influenced by the ionic
interaction between chitosan chains that depend on the density of crosslink achieved during crosslink framework
formation. The increasing density of crosslink can reduce the degree of swelling [13]. In addition, swelling methanol
degrades in the presence of these particles and it is useful for maintaining water absorption so that the membrane
remains in a state of moist when operated at a high temperature in fuel cell [14].
Nanoparticles has been widely used as filler in the nanocomposite membrane [8]. This study will conduct
modifications to the chitosan membrane. Modifications made by adding nanosilica into the membrane matrix.
Nanosilica is chosen because of its small size and large surface area making it possible to penetrate the polymer
matrix easily. Any addition of nanosilica into the polymer matrix can reduce the crystallinity of the polymer matrix
and increase mechanical strength such as water resistance, strong stretching and tensile strength [11]. There are
many materials as a source of nanosilica. Tetraethyl orthosilicate (TEOS) with the chemical formula Si(OC 2 H 5 ) 4 is
pure silica sources that is readily available and widely used as a precursor for the synthesis of silica-based material.
TEOS is easily converted into silica particles by reaction with water. The hydrolysis reaction occurs in the sol-gel
process. TEOS is used as a cross linking agent on inorganic polymer synthesis because of its ability to form chains
of Si-O-Si.
This study will synthesize nanosilica from TEOS by sol-gel method. The obtained nanosilica will be composited
on chitosan membranes to get the PEM cheaper than by nafion. It is expected that by adding
nanosilica with specific composition in the structure of chitosan membrane, it will reduce
the methanol crossover and increase the membrane proton conductivity when applied for direct methanol fuel cell.

020037-2
 METHODOLOGY

Tools and Materials

Some tools are used such as a set of glassware (glass beaker, measuring cups, pipette, flask),
a glass plate 20x20 cm for casting, a magnetic stirrer (IKAMAG), an oven (Memmert),
a furnace (Barnstead Thermolyne 1400), an incubator (Mammert), an analytical balance (Ohaus),
a digital calipers (Krisbow), and a pycnometer. For membrane characterization, the apparatus permeability test is
used, a FTIR spectrophotometer (Shimadzhu 8201),
a Surface Area Analyzer (Quantachrome instruments Nova E series), and a tool for measuring conductivity
is LCR meter (Agilent U1733C).
The materials are Tetraethyl Orthosilicate (TEOS, 99% MERCK), absolute ethanol (C 2 H 5 OH 99% -
100%, ȡ  l/kg MERCK), Ammonia (NH 3 25%, ȡ  l/kg), aqua
demineralization, Chitosan, acetic acid (CH 3 COOH 99% E, ȡ  l/kg MERCK), Methanol (99.9%, ȡ  l/kg M
ERCK), and sodium hydroxide (NaOH, MERCK).

Nanosilica Preparation

A total of 2.26 mL of TEOS was dissolved in 46 mL absolute ethanol at a speed of 6000 rpm at room
temperature for 15 minutes. Then ammonia was added dropwise until pH 10. After 1 hour, 1 mL aquademin was
then added dropwise into the solution. The stirring process was continued for 6 hours. Then the solution was
allowed to stand for 24 hours during the aging process. After the aging process, the obtained gel was then roasted at
a temperature of 80°C for 24 hours. The crystals were crushed into powder in further calcined for 2 hours at a
temperature of 600°C [15]. Nanosilica was analyzed using the Surface Area Analyzer with BET method.

Membrane Preparation

The synthesis of composite membranes was made with the phase of inversion method [29]. First, each
nanosilica composition 0; 0.5; 1; 2; 3; 5; 10% w/w chitosan was dissolved in 55 mL of 2% acetic acid and was
stirred at a temperature of 60°C for 7 hours. Secondly, as many as 1 gram of chitosan was dissolved in 50 mL
of 2% acetic acid at a room temperature for 4 hours. Then 50 mL of chitosan solution was poured into nanosilica
solution and was stirred for 4 hours at a temperature of 60qC. The solution which had been referred to as a
homogeneous dope solution that had no air bubbles, then was poured in the mold of glass size 20x20 cm and
was dried in an incubator at a temperature of 50qC for 24 hours that produced dry membrane. The dry membrane
was soaked with 1 N NaOH and was then washed with neutral pH aqua and dried up at a room temperature.

Membrane Characterization

The characterization of nanosilica-chitosan membrane is performed with swelling water measurement, methanol
permeability determination, proton conductivity analysis (by LCR meter), membrane selectivity determination and
functional groups analysis (by Fourier Transform Infrared or FTIR).

020037-3
 RESULT AND DISCUSSION

Average Diameter of Nanosilica Particles

Nanosilica preparation was done by sol gel method that produces silica powder with particles diameter average is
6,59 nm. BET method can be used to predict the average diameter of the particles in the powder if considered
particle size is spherical [23]. The average diameter of the silica particles (D) is determined from the data of silica
GHQVLW\ȡDQGWKHVXUIDFHDUHDVLVREWDLQHGIURPWKH%(7PHWKRGPHDVXUHPHQWDQGLVWKHQFDOFXODWHGXVLQJWKH
BET equation.

Water Swelling of Nanosilica-chitosan Membrane

Figure 1 shows the relationship water swelling value (%) and nanosilica-chitosan composition (%). The water
swelling test was conducted to determine how much water is absorbed by the membrane. The water on the
membrane serves as a proton transport medium, but if is it too high it will damage the membrane easily [1]. Fig. 1
shows the greater amount of nanosilica in chitosan membrane, the greater water swelling will be. It can be caused by
hygroscopic affinity of silica so that the water absorption capacity increases. In addition, another factors that affects
this is the hydrophilic properties of the Si-OH groups in silica. The high silica composition in the membrane matrix
increases the water charges relatively due to the amount of Si-OH groups, and the amount of water that is absorbed
through the pores [16].
According to the theory, the higher the water swelling value, the higher proton conductivity as more and more
water molecules in the membrane can be the proton transfer medium. But the increase in water swelling can increase
stability and decrease methanol permeability of the membranes that cause PEM’s performance degradation [17]. The
US Department of Energy has set the water swelling of the membrane to the required PEM target that is 50% water
absorption degree [18]. If the water swelling is too high (over 50%), the membrane will turn to be soft or spongy so
that the membrane’s life time is getting shorter [10]. Based on the test results, the most optimum composite
membrane is 3% nanosilica of chitosan membrane with water swelling 49.23%.

FIGURE 1. The relationship between water swelling value (%) and nanosilica-chitosan composition (%)

Proton Conductivity of Nanosilica-chitosan Membrane

The conductivity of nanosilica-chitosan membrane can be seen in Figure 2. The membrane conductivity is
measured by using the LCR-Meter to determine the impedance of membrane. Before being tested, the membrane
should be in a state of fully hydrated or completely wet [10] with relative humidity 98% [12] since ionic
conductivity will only occur when the membrane in a wet state (hydrated) [5]. Proton conductivity indicates the
ability of the membrane to conduct protons, the larger the value, the better the membranes used in fuel cell systems
[19].

020037-4
 FIGURE 2. The relationship between nanosilica-chitosan composition (%) and proton conductivity (S/cm)

From Figure 2, it can be seen that the proton composite conductivity increases with nanosilica addition to the
chitosan membrane. It shows that nanosilica moving into the polymer matrix is a proton conductor [20]. There are
two types of proton conduction in PEM, they are vehicle mechanism and Grotthuss (hopping) mechanism. In the
vehicle mechanism, proton travels on a carrier such as water (H 3 O+ and H 5 O 2 +) and solvent. While in the Grotthuss
mechanism, proton conduction occurs through hydrogen bonding (proton hopping). Proton transfer through a
solvent is not required, however reorganization of proton environment consisting of hydrogen bond reorientation of
one or more are needed for the formation of an uninterrupted path for proton transfer [20].
The higher the composition of nanosilica, the higher of the proton conductivity due to the influence of ionic
groups Si-OH nanosilica which may facilitate proton conduction, but there is a decrease in the composition of
nanosilica 10%. The conductivity decrease due to the silica addition. It can lead to an excessive formation of silicic
acid. The more concentrated acid that formed, the more dissociated ion H+ diminished, thus the smaller the proton
conductivity [2].
Although the membrane on nanosilica composition of 5% has the highest conductivity values, this membrane has
a large water swelling value that is 62.23%. It is not good to be used in DMFC. So for conductivity values it has to
be based on the value of water swelling composite membrane that is on the composition of nanosilica 3% with
proton conductivity of 0.231 S / cm.

Methanol Permeability of Nanosilica-chitosan Membrane

Figure 3 shows that methanol permeability decreases with the increasing composition of nanosilica. Nanosilica
influences the chitosan polymer matrix so it can reduce methanol crossover which is characterized by decreasing
methanol permeability values based on nanosilica-chitosan composition [20]. The addition of nanosilica can close
the membrane pores so it prevents the displacement of methanol through the membrane. This phenomenon indicates
that methanol is only absorbed on the membrane surface and does not penetrate or pass through the membrane [1].
On the 5% nanosilica-chitosan composition, methanol permeability begins to increase. The increase in methanol
permeability is in line with previous water swelling characteristics which also builds up on 10% nanosilica-chitosan
composition. The more nanosilica added to the chitosan membrane, the more pore formation builds porous
aggregate. These pores contribute in increasing methanol permeability, because the mass transfer (methanol) can
occur through the porous aggregate [10].

020037-5
 FIGURE 3. The relationship between nanosilica-chitosan composition (%) and methanol permeability (×10-6 cm2/s)

Permeability is defined as a product solubility and diffusivity penetrant (methanol/gas), which occurs through
diffusion mechanism. It is further dependent on the volume of pore in the membrane. There are two types of pores in
the polymer membrane: pore network or ionic clusters and aggregate pores. Proton transport occurs through two
types of pore, while the mass transport (methanol, water, and gas) occurs only through the porous aggregate [25].
The pore network is a small cavity between the polymer chains that are responsible for proton conduction, while the
aggregate pores are large cavity surrounding the polymer aggregates that cause the transport period (methanol) [24].
The 3% nanosilica-chitosan composition has the lowest methanol permeability that is 5.43×10-7 cm2/s. When
compared with nafion methanol permeability value of 4.9×10-5 cm2/s, it is clear that the nafion methanol
permeability value is greater than nanosilica-chitosan membrane. The best condition of PEM for DMFC
applications, its methanol diffusion coefficient have to be smaller than 5.6 ×10-6 cm2/s [21].

Membrane Selectivity

Table 1 shows that all synthesized membranes have met the requirement as PEM. From all nanosilica-chitosan
membranes that are synthesized, 3% of nanosilica-chitosan membrane shows the most optimum value selectivity of
5.91x10-5 S s cm-3. In DMFC applications, proton conductivity and methanol permeability are used to determine the
3(0VHOHFWLYLW\WKDWFDQEHGHILQHGDVȕ ı3ZLWKȕLVWKHPHPEUDQHVHOHFWLYLW\ıLVWKHSURWRQFRQGXFWLYLW\DQG3
is the methanol permeability [22].

TABLE 1. Comparison of nanosilica-chitosan membrane selectivity by Nafion

Nanosilica-chitosan Water Swelling Proton Conductivity Methanol Membrane

(% w/w) (%) (S/cm) Permeability (cm2/s) Selectivity
0 40.66 0.174 8.64 x 10-6 2.02 x 104
0.5 40.79 0.206 2.001 x 10-6 1.03 x 105
1 46.59 0.209 1.902 x 10-6 1.92 x 105
2 47.93 0.22 1.2 x 10-6 1.83 x 105
3 49.23 0.231 5.43 x 10-7 5.91 x 105
5 62.22 0.234 7.75 x 10-7 3.02 x 105
10 63.56 0.231 8.52 x 10-7 2.71 x 105
Nafion 117 - 1 x 10-2 1.76 x 10-6 5.7 x 103
Requirements less than 50% more than 1x10-5 less than 5.6 x 10-6 -

020037-6
 Functional Groups Analysis of Nanosilica-chitosan Membrane

The functional groups analysis by using FTIR is to prove the interaction between the polymer matrix and the
silica network. Fig. 4 is a comparison of the FTIR spectrum of a nanosilica-chitosan membrane (w/w) 0% and 3%.
The presence of nanosilica filler on chitosan membrane is shown by the emergence of FTIR spectra in the
wavenumber range 1000-1250 cm-1 that indicates the siloxane groups (Si-O-Si) absorption, which appears precisely
at a wavenumber at of 1026.13 cm-1. Absorption band of silanol (Si-OH) which are the characteristic
of silica appears at a wavenumber of 894.97 cm-1 [26]. The presence of hydrogen bonds between the silicon (Si-
H) are shown at a wavelength of 2152.56 cm-1 [27]. The absorption band around a wave number of 1000-1100 cm-1
indicates the group –C-O-C [28]. This –C-O-C Group appears precisely at a wave number of 1087.85 cm-1 for 0% of
nanosilica-chitosan membrane and it shifts to 1080.14 cm-1 on the 3% nanosilica-chitosan membrane. Based on the
comparison of absorption band in 3% and 0% nanosilica-chitosan membrane, there is no significant change in the
wave number of 1000-1250 cm-1. It indicates that there is no chemical interaction between chitosan and nanosilica,
but it is only physical interaction with the formation of pores in the chitosan membrane that affect the composite
membrane characteristics.

100

80

60

1427,32
, 0%
%T 1635,64 1257,59
1087,85
40 3448,72

20
3%
1427,32 941,26
1604,77 1265,30 1026,13
26,13
3448,72 1080,14
0,14
0

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber
enum (cm
cm )

FIGURE 4. FTIR spectra of 0% and 3% of nanosilica-chitosan (b/b)

CONCLUSION

The modification of chitosan membrane by adding nanosilica produces membranes with better properties for the
PEM application. Based on the analysis, the membranes selectivity reaches their optimum at 3% (w/w) nanosilica-
chitosan with a value of 5.91×105 S s cm-3. The results of water swelling determination, proton conductivity analysis
and methanol permeability analysis on 3% (w/w) nanosilica-chitosan membrane which is the most suitable for PEM
application are respectively 49.23%, 0.231 S/cm, and 5.43×10-7 cm2/s. The characterization of nanosilica-chitosan
membrane such as water swelling and proton conductivity increases with the increasing of nanosilica

020037-7
composition. However, methanol permeability decreases with the increasing of nanosilica composition. The FTIR
spectra indicates that there is no chemical interaction between chitosan and nanosilica, but it occurs only physical
interaction with the formation of pores in the membrane that affects their characteristics. The modification of
chitosan membrane with a ratio of 3% nanosilica-chitosan prospectively serving as the Polymer Electrolyte
Membrane for further applications on Direct Methanol Fuel Cell.

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