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FABRICATION OF CHITOSAN/NATURAL ZEOLITE COMPOSITE-BASED

POLYMER ELECTROLYTE MEMBRANES

Article  in  Rasayan Journal of Chemistry · October 2020

DOI: 10.31788/RJC.2020.1345906

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 Vol. 13 | No. 4 |2181-2187| October - December | 2020
ISSN: 0974-1496 | e-ISSN: 0976-0083 | CODEN: RJCABP
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FABRICATION OF CHITOSAN/NATURAL ZEOLITE

COMPOSITE-BASED POLYMER ELECTROLYTE
MEMBRANES
Y.A. Sihombing1,2,*, Susilawati1,2, S.U. Rahayu1,3 and A. Siahaan1
1
Department of Physics, Universitas Sumatera Utara, Medan 20155, Indonesia
2
Center of Excellence Chitosan and Advanced Materials, Universitas Sumatera Utara, Medan
20155, Indonesia
3
Cellulosic and Functional Materials Research Centre, Universitas Sumatera Utara, Medan
20155, Sumatera Utara, Indonesia
*E-mail: yuan@usu.ac.id
ABSTRACT
Natural materials, such as chitosan (CS) and natural zeolite (NZ), are widely used for energy applications such as
fuel cells because of their favorable properties. This study reported the fabrication of chitosan/natural zeolite
composite (CS/NZ)-based polymer electrolyte membranes. The solution casting method was used to produce the
membranes. There are 5 variations of NZ mass based on the dry weight of CS (5% w/w, 10% w/w, 15% w/w, 20%
w/w, 25% w/w). The results show that the addition of NZ as filler to the matrix of CS can improve the mechanical
properties of the resulted membranes. The highest tensile strength of CS/NZ-based membranes is 1.6 MPa, which
comes from CS/NZ (10% w/w), while CS/NZ (5% w/w) gives the highest elongation at break of all samples
(18.2%). Related to the oxidative stability, the CS/NZ-based membranes 5% w/w has the highest oxidative stability
at 103.2 minutes in Fenton’s reagent (3wt% hydrogen peroxide and iron sulfate 2 ppm). Besides, the thermal
properties of CS/NZ-based membranes are more favorable than that of the CS-based membranes. These results
imply that the addition of NZ provides the enhanced performance of composite membranes and has good potential
to be used as a membrane for fuel cell application.
Keywords: Chitosan, Natural Zeolite, Polymer Electrolyte Membranes, Solution Casting Method, Fuel Cell.
© RASĀYAN. All rights reserved

INTRODUCTION
Chitosan (CS) is a natural polymer that is widely used for fuel cell membrane application because it has
good thermal, mechanical and chemical stability. Also, CS is a low-cost material that is easy to be made
as a film; it is also biodegradable and hydrophilic.1,2 The use of CS as membranes is limited due to its low
conductivity. As explained, the lack of hydrogen ions mobility in a membrane causes the conductivity of
CS to be small.3 To enhance its electrical, physical and chemical properties to be membranes, it needs
modification.
There is numerous research conducted to improve CS. Wang et al. found that the addition of organic and
inorganic as a filler, such as carbon nanotubes (CNT) increased the proton conductivity4; Li et al.
transplanted polyaniline into CS to improve the capacity of cation exchange.5 Polyaniline/nanosilica
(PAni/SiO2), which was ionic cross-linked to CS-based membranes, increased the mechanical properties
and improved the oxidation stability.6 Also, quaternized poly(ether ketone) was used as exchange
membranes with high temperatures.7 Sulfonated graphene oxide was constructed to decrease the
permeability and increase the conductivity.8 From those methods, the most effective one is by adding
inorganic materials with extremely good stability of thermal and mechanical properties into organic
materials that have the flexibility and acceptable chemical reactivity; this method is also called as the
complex method.9
Related to that, natural zeolite (NZ), which consists of an aluminosilicate compound, can be promised as
inorganic filler in the CS matrix. NZ is an environmentally friendly natural material and comes from
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mountain mineral rock, which is abundant. It has favorable ion exchange, mechanical, and thermal
properties; thus, NZ can improve the thermal and mechanical stability of hybrid membranes due to the
presence of hydrogen bonds between zeolite and CS.10 Besides, it can enhance the conductivity of
materials; Wu et al. found the conductivity of membranes added by zeolite raised to 25.8 mS/cm.11
Poltarzewski et al. also investigated zeolites in poly(tetrafluoroethylene) matrix, which showed high ionic
conductivity.12 Other research suggested that it can be modified into membranes; for example, NZ with
addition sulfonated polysulfone was possible to be used as a proton conductivity membrane.13 Also,
zeolite has been used widely as a filter, such as a water vapor filter for hydrogen-fueled motorcycle,14
water vapor filter to purify hydrogen,15,16 and ethanol purification.17
In this research, CS provides as a matrix and NZ was employed as filler to form CS/NZ-based
membranes. The method used was the casting method, which is proved to be an efficient method to
produce membranes; for instance, Dharmadhikari et al. used this method to fabricate proton exchange
membranes (PEMs) from polyethylene glycol (PEG), polyvinyl alcohol (PVA), CS, and orthophosphoric
acid (OPA).18 In this report, CS/NZ-based membranes were varied in NZ’s mass based on the dry weight
of CS. The resulted membranes, which have were tested to determine the mechanical properties, thermal
and oxidative stability, surface morphology, functional group, and crystalline structure. To date, there are
limited research mentioning the use of CS/NZ composite as polymer electrolyte membranes; many
studies, however, used other materials to be polymer electrolyte membranes, such as Pulungan et al.
which conducted the research about sulfonated polystyrene (sPS) as polymer electrolyte membranes,
resulting proton conductivity of 3.37 x 10-2 Scm-1.19 Therefore, the results of this research will also
provide the potential polymer electrolyte membranes that can be applied for fuel cells.
EXPERIMENTAL
Materials
The materials used in this research were chitosan (CS), sulphuric acid, hydrogen peroxide, iron (II)
sulfate, and acetic acid; all materials were from Sigma Aldrich. Natural zeolite (NZ) was collected from
Tarutung, North Sumatera, Indonesia.

Preparation of Natural Zeolite Powder

Natural zeolite was ground by using a mortar before being sifted with 200 mesh of particle size to yield a
powder form. Then, it was chemically activated by immersing it in a solution of 6% sulfuric acid. This
solution was stirred for 2 hours. The obtained powder was then washed by using purified water until
reaching a neutral pH. Finally, the powder was burned at a temperature of 100°C for 5 hours to remove
the water.

Preparation of Chitosan/Natural Zeolite Composite (CS/NZ)-Based Membranes

The solution casting method was used to obtain CS/natural zeolite composite (CS/NZ)-based membranes.
In brief, as much as 1.5 g of CS was dissolved in an acetic acid solution (75 ml, 2 wt%). After obtaining
the homogenous solution, the NZ powder was poured into the solution and stirred for 24 hours. There are
five variations of NZ mass added to the solution based on dry weight of CS, namely 0.075 g (5% w/w),
0.150 g (10% w/w), 0.225 g (25% w/w), 0.300 g (20% w/w), and 0.375 g (25% w/w). The solution was
then cast in a glass template and allowed to dry at room temperature under the atmospheric condition to
form a solid membrane. For comparison, CS-based membranes were also produced using the same
method.

Characterization
The resulted spectra for Fourier Transform Infra-Red (FTIR) were assessed by Agilent/Cary 630 with
transmittance mode. The wavenumber range is 700-4000 cm-1 at room temperature with a resolution of 16
cm-1. The crystal structures were performed by analyzing XRD pattern resulted from XRD Malvern
Panalytical Empyrean Model with anode material Cu Kα radiation and generator setting of 30 mA and 40
kV. The angle of 2theta was from 5° to 90° with a scan rate of 0.07°/min at a temperature of 25°C.
Scanning electron microscopy (SEM) pictures were obtained from Zeiss/SEM EVO MA10 with the
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magnification of 2000 times. The membrane thermal stability was examined by using the
thermogravimetric analysis (TGA) instrument. The average heating speed was 5°C/min; the heating
temperature ranges from 30°C to 450°C using platinum as a reference under nitrogen. RTF-1350
machine was used to determine the mechanical properties (elongation at break and tensile strength) of
membranes with a rate test speed 5 mm/min at a temperature of 25°C. The dimension of each sample was
3 cm × 5 cm × 1 mm. The membrane oxidative stability was examined by soaking in Fenton’s reagent
(hydrogen peroxide 3 wt% with 2 ppm iron II sulfate). The time of the rupture of the membrane and the
mass loss was recorded after heating the Fenton’s reagent for 1 hour at a temperature of 80°C.

RESULTS AND DISCUSSION

Analysis of Fourier Infra-Red Transform (FTIR) Spectra
Figure-1 shows the FTIR spectra of CS-based membrane and CS/NZ-based membranes. The absorption
peak at around 3354 cm-1 is assigned to hydroxyl (-OH) groups stretching of CS for all samples. The
amino bands (C=O stretching and –NH2 bending) of CS are confirmed at 1640 cm-1 and at 1543 cm-1,
respectively.20 As for zeolite, the one that contains HEU and mordenite should show a vibration peak of
T-O stretching in the range of 1045–1070 cm−1, which represents the aluminum content of HEU. The
intensity of this peak should be proportional to Si/Al Ratio.21 The mentioned peak, however, is not seen in
the resulted membrane due to the interaction with CS. Also, the three characterized peaks from CS were
found to have weakened intensities. It shows that there are the interactions of hydrogen bonds between
hydroxyl and amino groups from CS with surface hydroxyl groups of NZ since the acid intensity of NZ
surface was improved with the increase of Si/Al ratio.20
Furthermore, there are other peaks of CS shown in the CS-based membranes as well as CS/NZ-based
membranes, namely the peak at 2877 cm-1 (attributed to aliphatic groups (CH2 and –CH3)); the peak at
1401 cm-1 (contributed to C-O stretching); and the peak at 1014 cm-1 (represented glycosidic groups (-C-
O-C-)). All of these groups also have weakened absorption intensity after introducing NZ to the CS
matrix due to the interaction of CS molecules groups and NZ.

Fig.-1: The FTIR Spectra of CS-based Membranes and CS/NZ-based Membranes

Analysis of Scanning Electron Microscopy (SEM) Pictures

As depicted in Fig.-2(a), the CS-based membrane has a homogenous and smooth surface without any
aggregation. The addition of NZ gives a rougher surface as pictured in Fig.-2(b to f) to confirm the
existence of NZ particles. It is seen from those figures that the NZ particles are evenly distributed through
the surface of the membranes without any defects and aggregation. These results proved that the CS/NZ-
based membranes were produced successfully by using the casting solution method.
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(a) (b)

(c) (d)

(e) (f)

Fig.-2: SEM Pictures of (a) CS-based Membranes, (b) CS/NZ (5% w/w), (c) CS/NZ (10% w/w), (d) CS/NZ (15%
w/w), (e) CS/NZ (20% w/w), and (f) CS/NZ (25% w/w)
Analysis of X-Ray Diffraction (XRD) Pattern
The XRD patterns were provided in Fig.-3. As shown, there are six main peaks in CS-based membranes
and CS/NZ-based membranes. The 2θ angles at 11.8°, 18.8°, and 21.6° is assigned to CS peaks,10 while
the diffraction angles at 9.4°, 16.4°, and 23.3° are due to the amorphous semicrystalline of CS. The
presence of NZ in the CS/NZ-based membranes causes decreased intensity and crystalline degree of
membranes. It can be explained as the NZ particle intruded the ordered chains of CS, the interaction of
hydrogen bonds between CS and NZ exists so that the crystalline structure of CS breaks down. This result
is in agreement with the previous research.10 The membranes of CS/NZ (20% w/w) depicted the smallest
intensity of all; thus, one can say that there is no relation between the amount of NZ added to the
membranes with intensity and the crystalline degree of resulted membranes.
Analysis of Thermal Properties
Figure-4 shows the thermal stability of the membranes measured by thermogravimetric analysis (TGA).
There are three main stages of all samples. The first stage, which is at temperatures of 30°C–100°C,
represents the membranes’ loss of water molecules6,10,22,23 with the average weight loss of less than 10%
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for CS/NZ-based membranes and 14% for CS-based membranes. The second stage indicated the CS chain
decomposition, which occurs at temperatures ranged from 175°C to 350°C. CS/NZ-based membranes
have a weight loss of less than 53%, while CS-based membranes have a weight loss of 55%. The
intramolecular and intermolecular hydrogen bonds could establish a good contribution to the membrane
thermal stability.24 The third stage takes place at a temperature of up to 450°C, which is owing to
membrane degradation. The membrane thermal stability indicated a strong hydrogen bond between CS
and NZ. As depicted, CS/NZ (25% w/w) shows the best thermal stability because the mass composition
of zeolite particles in CS matrix was larger than that of others.

Fig.-3: XRD Patterns of CS-based Membranes and CS/NZ-based Membranes

Fig.-4: TGA Curve of CS-based Membranes and CS/NZ-based Membranes

Analysis of Mechanical Properties
From Fig.-5, CS-based membrane has appropriate mechanical properties with elongation at break and
tensile strength of 12.6% and 1.0 MPa, respectively. The addition of NZ is proved to enhance the
elongation at the breakpoint and the tensile strength. The highest tensile strength (1.6 MPa) was
confirmed by CS/NZ (10% w/w). This value is 1.6 times larger than that of CS-based membranes. The
highest elongation at break percentage (18.2%), which is 1.4 times larger than that of CS-based
membranes, occurred in the CS/NZ (5% w/w).
The increase of tensile strength in the membrane is due to the reinforcing effect of NZ as filler in the
matrix of CS. On the other hand, the NZ particles, which are evenly distributed in CS, provide good
interaction between CS chain and NZ, thus, they can bind properly. This bond can enhance the tensile
strength of the membrane. The reduction of elongation at break was determined by the decrease of chain
flexibility. The decrease in the chain flexibility occurs due to the inhibition of CS chain motion by the
existence of NZ as a filler and the formation of polymer filler bonds.

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Fig.-5: Stress-strain Curves of CS-based Membranes and CS/NZ-based Membranes

Analysis of Oxidative Stability
The oxidative stability of the resulted membranes is provided in Fig.-6. The oxidative stability of the CS-
based membrane was confirmed by the time of 63.4 minutes. The oxidative stability of CS/NZ-based
membranes increased when the added NZ was of 5% w/w and 15% w/w. The best oxidative stability of
all membranes was presented by CS/NZ (5% w/w) at 103.2 minutes. This value is 60% larger than the
oxidative stability of CS-based membranes. This result is in agreement with the results of elongation at
the break of the CS/NZ (5% w/w) that implies a strong hydrogen bond between NZ particles and CS
chains, resulting in a more stable oxidative property against the oxidizing of Fenton's reagent.

Fig.-6: The Oxidative Stability of CS-based Membranes and CS/NZ-based Membranes

CONCLUSION
Chitosan/natural zeolite composite (CS/NZ) has been successfully employed to produce polymer
electrolyte membranes by using the solution casting method. The addition of NZ to CS is proved to
enhance the oxidative and thermal stabilities of membranes. As for thermal properties, there is an increase
in thermal stability due to the strong hydrogen bond between CS and NZ. Also, the CS/NZ-based
membranes perform better oxidative stability than that of CS-based membranes. In terms of mechanical
properties, the tensile strength of all CS/NZ-based membranes is enhanced compared to the CS-based
membrane. Even though the maximum tensile strength comes from the elongation at break reaches
maximum value from CS/NZ (5% w/w). Based on these results, the addition of NZ to CS-based
membranes can improve the performance of polymer electrolyte membranes and has potential use for fuel
cell membranes.
ACKNOWLEDGEMENT
This research was funded by the TALENTA research scheme from Universitas Sumatera Utara with
granted number 2590/UN5.1.R/PPM/2018 on March 16th, 2018 and 4167/UN5.1.R/PPM/2019 on April
1st, 2019.
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[RJC-5906/2020]

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