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Broad Exposure to Science and Technology 2019 (BEST2019) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 673 (2019) 012017 doi:10.1088/1757-899X/673/1/012017

Cellulose extracted from water hyacinth and the application

in hydrogel

L Setyaningsih*, E Satria, H Khoironi, M Dwisari, G Setyowati, N Rachmawati,

R Kusuma and J Anggraeni
Department of Chemical Engineering, Islamic University of Indonesia, Yogyakarta,
Indonesia
*
E-mail: [email protected]

Abstract. This paper present the conversion of cellulose based on water hyacinth into hydrogel.
The water hyacinth cellulose was prepared using acid-alkaline treatment and bleaching. The
cellulose properties was optimized by varying the extraction condition such as solvent
concentration and temperature. The analysis method of FTIR and XRD were used for
characterizing the functional groups and crystallinity of cellulose. The effective condition of
extraction were achieved at solvent concentration 17.5% w/w of NaOH, 8% v/v of H2O2 as
bleaching agent and temperature of 80oC. The extracted cellulose was used to produced
hydrogels using polyvinyl alcohol and glutaraldehyde as crosslinker agent. The research revealed
that adding of glutaraldehyde with ratio 1:2 at 25oC give the highest water absorption capacity
of 285%.

1. Introduction
Cellulose is a natural polymer that have been used in a wide range of application due to its own
advantages such as readily available, non-toxic, biocompatible, hydrophilic and biodegradable[1,2].
Cellulose from natural sources have main potential application in production of biodegradable
membranes, filters, adsorbent, etc. [3]. Cellulose is composed of β-1,4-glucosidic bond contains
lignocellulosic fibers which are formed by lignin, hemicellulose and cellulose [4]. Cellulose biomass
can be derived from wood and nonwood biomass with chemical or physical extraction process that
carried out to break the complex lignocellulosic bond without destruction of the cellulose fibrils [5].
One of natural sources that contain high cellulose (10% lignin, 33% hemicellulose and 25% cellulose)
is water hyacinth.
Water hyacinth (Eichhornia crassipes) is an aquatic weed species that grow rapidly and form thick
layer on whole water surface [6]. Its rapid growth cause particular impacts on open water bodies such
as clogging irrigation and hydropower systems, limiting livestock access to water, blocking water rivers
and canals, removing native aquatic plants, changing water condition (oxygen level, pH and
temperature) and reducing sunlight infiltration [7]. Water hyacinth removal by chemical, mechanical
and biological method requires a huge amount of money and provide detrimental effect on the water
environment like destruction of other useful plants and environmental pollution. However, water
hyacinth is rich in cellulose content and easily converted chemically into useful derivative product and
make this species an excellent candidate for cellulose base natural polymers. In this project cellulose
fiber from water hyacinth was extracted according to method of Hu [12] with some modification
including hydrolysis, delignification, pulping and bleaching.

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Broad Exposure to Science and Technology 2019 (BEST2019) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 673 (2019) 012017 doi:10.1088/1757-899X/673/1/012017

Hydrogel is defined as polymeric material with three-dimensional structure capable of absorbing and
releasing large amount of water. Nowadays, the application of hydrogels has been widely used in various
industries such as cosmetics, food industry and drug delivery system. Compared to hydrogels made from
synthetic polymers, hydrogels from natural materials such as starch, chitosan and cellulose have more
superiority properties such as good biocompatibility, biodegradable, good permeability, low friction and
toxicity factor [8]. Due to these superiority, the development of hydrogel from cellulose is promising
for application to the pharmaceutical and biomaterial field. Superabsorbent hydrogel obtained by
chemical or physical crosslinking between polymer and crosslinker agent [9]. Recently, other natural
source of cellulose have been studied in the hydrogels production such as rice husk [9]; oat husk [4];
bamboo shoot [2]; pineapple peel [1]; tea residue [11]. However, the application of cellulose from water
hyacinth as hydrogel feed stock has not been reported. In this study, cellulose fibers from water hyacinth
was isolated and characterized and used to produce hydrogels.

2. Methodology
2.1. Material
Water hyacinth was collected from Kulon Progo coast in Yogyakarta and dried under the sunlight for 3
days. 99.8% ethanol, 99.9% toluene, acetic acid, nitric acid, sodium hydroxide, sodium sulphite,
hydrogen peroxide, sodium hypochlorite, hydrochloric acid and glutaraldehyde as crosslinker agent
were purchased from Merck and Sigma-Aldrich.
2.2. Cellulose fiber isolation
Firstly, the stem of water hyacinth were washed, dried under the sunlight for 3 days, grinded and sieved
through a 40 mesh sieve. The dried stem was then mixed with ethanol and toluene for dewaxing process
at 75oC for 6 h. After dewaxing, the sample hydrolyzed with HNO3 solution 3.5% (v/v) at 90 oC for 2 h.
For removal of the lignin, an alkaline treatment with Na2SO3 solution (2% w/v) and NaOH solution (2%
w/v) was carried out using magnetic stirrer at 50 oC for 1 h. Furthermore, bleaching process using various
type of solvent (H2O2 10%, NaOCl 8% and HCl 3% v/v) was performed for remaining lignin and
hemicellulose removal and stirred at 60oC for 15 minutes.
2.3. Preparation of hydrogel
Hydrogel was prepared from water hyacinth cellulose referring the method of Oliveira [4]. The
cellulose was dissolved into NaOH solution (8.5% w/v) until the uniform viscous mixture was
obtained and frozen for 24 hours. Furthermore, the mixture was melted and mixed with (2%,
4% and 6%) wt crosslinker agent (glutaraldehyde or poly vinyl alcohol) and stirred for 4 h to
avert bubble formation. A sample of the gel was then casted onto a acrylic plate and placed in
oven at 50oC for 6 h.
2.4. Cellulose fiber and hydrogel characterizations
Functional groups of cellulose fiber and hydrogel were investigated by Fourier Transform Infrared
Spectometer (FT-R). X-ray diffraction (XRD) were performed to analyzed relative crystallinity of the
cellulose and hydrogel. The swelling capacity of the hydrogels was evaluated in distilled water by
measuring the weight of samples before and after soaked in water at 4oC, 25oC and 50oC for 24 h. The
swelling ratio of the hydrogel was performed according to the equation:
𝑊𝑠 − 𝑊𝑑
𝑆𝑅 = 𝑥 100 (1)
𝑊𝑑

Where 𝑊𝑑 is the weight of initial dried sample and 𝑊𝑠 is the weight of the swollen hydrogel.

3. Result and discussion

3.1. Characterization and extraction yield of cellulose
3.1.1. FTIR and XRD analysis on extracted cellulose fibre. The comparison of functional groups of
cellulose extracted from water hyacinth with different solvent were presented in Figure 1. From figure

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Broad Exposure to Science and Technology 2019 (BEST2019) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 673 (2019) 012017 doi:10.1088/1757-899X/673/1/012017

1, it was observed that the samples with H2O2 solvent exhibited the absorption peak around 3447.65 cm-
1
and 2901.37 cm-1 were related to the –OH and C-H stretching vibration. The spectra of extracted
cellulose also showed a band at 1161.5 cm-1 and 1112.88 cm-1 which more intense than the band
exhibited by raw water hyacinth. The same phenomenon was reported in isolation of cellulose from oat
and rice husk carried out by Oliveira [4]. According to Halal [13], the band at 1161.5 cm-1 indicate of
C3 carbon vibrations and the band at 1319.44 cm-1 indicate the vibration of the glycosidic C-O-C bond
on cellulose fibers. The presence of functional groups of cellulose constituent components was also seen
with the appearance of bands at 1060.7 and 893.79 cm-1 which related to C-O and C-H stretching
vibration, in which spectra of cellulose fibres exhibited greater absorption peak resolution compared to
peak from raw material [14].
Based on the FTIR analysis, the final result of extraction with H 2O2 solvent still represent character
of cellulose by presence of O-H, C-H, C-O and C-H stretching vibration. However, the band at 893.79
cm-1 shows that the cellulose contained β-cellulose which insoluble at NaOH concentration below 17.5%
wt. The absorption peak at 1637.96 cm-1 was related to the C=O stretching vibration of carboxylate ions.
According to Zhang [15], a number of carboxylic groups were produced due to the presence of oxidizing
agents (HNO3) during extraction process of cellulose. According to Hassan [16] the bands at 1500-1600
cm-1 are associated to the presence of aromatic ring and carbonyl groups which indicate the lignin
constituent structure. While the absorption peak around 1700 cm-1 can be assigned to the acetyl and ester
functional groups as part of the lignin compound. From figure 1, it is confirmed that lignin and
hemicellulose constituent were completely removed during delignification and pulping process.
130
Raw Water Hyacinth
125 HCl
NaOCl
120 H2O2
115
Intensity (%)

110
105
100
95
90
85
80
0 1000 2000 3000 4000 5000
Wavenumber (cm-1)

Figure 1. FTIR spectra of the cellulose of water hyacinth.

The X-ray diffraction which present relative crystallinity of the raw water hyacinth and cellulose
fibers are presented in Figure 2 and Figure 3, respectively. The XRD pattern of raw material was found
exhibiting the peaks around 15.3o, 21.2o, 33.4o which indicate the characteristics of lignocellulosic
materials. The extracted cellulose showed the peaks around 17.8o, 21.2o, 34o due to its crystal structure.
The relative crystallinity of raw material was found lower compared to the cellulose which evidenced
that the removal of lignin and hemicellulose promote an increasing crystallinity ratio. According to
Abraham [17], the presence of cellulose caused crystallinity of lignocellulose, which has a crystal
structure. In the other hand, another component including lignin and hemicellulose are amorphous. In

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IOP Conf. Series: Materials Science and Engineering 673 (2019) 012017 doi:10.1088/1757-899X/673/1/012017

addition, the crystallinity affects the swelling ratio of hydrogels, because the higher crystallinity the
higher water absorption capacity of hydrogels.

Figure 2. X-ray diffraction of the cellulose of Figure 3. X-ray diffraction of the cellulose
water hyacinth. fibers.

3.1.2. Extraction yield of extracted cellulose fibers. The yield of the cellulose from water hyacinth with
different solvent are shown in Table 1. In this work, the highest percentage of mass reduction was found
in hydrolysis step compared to another steps in cellulose extraction process. This is because
hemicellulose has short chain and can be hydrolysed easily using nitric acid (HNO3) compared to
cellulose and lignin, therefore the acids can break the hemicellulose polymers into simple monomers. It
was also observed that difference result obtained between NaOCl and H 2O2 as solvents in bleaching
process, where the highest percentages of mass reduction obtained with the variation of NaOCl. NaOCl
has strong chemical content that can degrade cellulose in high amount. On the other hand, the lowest
percentages of mass reduction was found in bleaching process with H2O2 as solvent, it can be caused by
the H2O2 characteristic that tends not to damage cellulose and more environmentally friendly. The
cellulose yield of the water hyacinth was 12.45 g cellulose/100 g of water hyacinth.
Table 1. Percentages of mass reduction and yield of extracted cellulose fibre.
Steps of cellulose Precentage of mass reduction (%)
extraction process H2 O 2 NaOCl HCl
Dewaxing 32.13 31.07 32.27
Hidrolisis 60.03 62.60 67.83
Delignification 15.75 23.40 15.47
Pulping 10.35 12.86 6.74
Bleaching 5.90 18.90 10.34
Yield (g cellulose/100 12.45 8.95 10.76
g water hiacynth

3.2. Characterization of hydrogel

3.2.1. FTIR analysis on hydrogel. Figure 4 shows the FTIR characteristic of hydrogel prepared using
glutaraldehyde and poly vinyl alcohol as crosslinker agent. The spectra of hydrogels with glutaraldehyde
showed band at 3302 cm-1 can be assigned to the stretching of –OH, while the absorption band at 2935
cm-1 is associated to the stretching of the aldehyde groups. The absorption band at 1705 cm-1, which is
related to the C=O and C-O stretching of carboxylate groups.
The spectra of hydrogels with poly vinyl alcohol shows the absorption peak at 2915 cm-1 and 3318
cm-1 are respectively related to the C-H stretching of methyl in cellulose and O-H stretching in the
cellulose molecule chain, while the peak at 2916 cm-1 is related to the PVA alkyl groups stretching. The
band at 1724 cm-1 was due to the contribution of the C=O and C-O stretching vibration in carboxyl
groups. According to Oliveira, the interaction between cellulose and poly vinyl alcohol was affirmed by
the band around 1076 cm-1 associated with C=O, where in the PVA spectrum was more intense.

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Broad Exposure to Science and Technology 2019 (BEST2019) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 673 (2019) 012017 doi:10.1088/1757-899X/673/1/012017

130
PVA
125
Glutaraldehide
120
115
Intensity (%)

110
105
100
95
90
85
80
0 1000
2000 3000 4000 5000
Wavenumber (cm-1)
Figure 4. FTIR spectra of the hydrogel using glutaraldehyde and polyvinyl alcohol.

3.2.2. Swelling Capacity. The swelling capacity of hydrogels observed at various additive concentration
and temperature. Table 2 shows analyzed swelling ratio result of the hydrogel which soaked in distilled
water at temperature 25oC. These result indicate that the higher glutaraldehyde concentration exhibited
significant lower equilibrium swelling ratio (ESR). This might occur due to the uniform and compact
structure do not form during hydrogel formation and the hydrogels have bigger micrometer pores. Water
is absorbed and restricted in the structure of hydrogel through smaller micrometre pores and swelling
ratio depends on the size of pores. This phenomenon is similar to the poly vinyl alcohol addition as
additive, however, compared with PVA, addition of glutaraldehyde showed that hydrogel preserved
more water in their three-dimensional structure.

Table 2. Swelling capacity of hydrogel at different additive concentration.

Additive Ratio ESR %
Glutaraldehyde 1:2 285
1:4 234
1:6 202
Poly vinyl alcohol 1:2 186
1:4 110
1:6 128

From table 3, it was found that swelling capacity increase with increasing temperature up to 30 oC,
and significantly decrease at temperature 45oC for both additive addition. At temperature, the chain
movement on the hydrogel matrix was occurred due to formation of hydrogen bond from water
molecules which has polar functional group. However, at high temperature these structure decrease due
to the breakage of hydrogen bonds between chains on the matrix and water molecules.

5
Broad Exposure to Science and Technology 2019 (BEST2019) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 673 (2019) 012017 doi:10.1088/1757-899X/673/1/012017

Table 3. Swelling capacity of hydrogel at temperature.

Additive Temperature, oC ESR %
Glutaraldehyde 15 256
25 285
35 298
45 195
50 212
Poly vinyl alcohol 15 115
25 186
35 173
45 124
50 122

3.2.3 Maximum stress compression. The mechanical properties of hydrogel was investigated by
measuring the allowable maximum stress during compression. The hydrogel prepared from cellulose
with glutaraldehyde as crosslinker agent had lower maximum stress compression compared to hydrogel
with poly vinyl alcohol. This result obtained due to the poly vinyl alcohol can lead an increasing of
crystalline structure within hydrogel network which effected in strength of hydrogel. Some papers which
studied the mechanical behaviour of hydrogel reported that the hydrogen bond between functional
groups of polymer chain in hydrogel network are broken during the first compression reducing hydrogel
stiffness [18]. These result revealed that hydrogel based on poly vinyl alcohol and cellulose was more
impervious to force applied during compression. Therefore it is suggested that a stable network was
formed [19].

Table 4. Maximum stress compression of hydrogel.

Additive Ratio Maximum stress compression
Glutaraldehyde 1:2 1.8 kPa
1:4 1.56 kPa
1:6 1.88 kPa
Poly vinyl alcohol 1:2 2.67 kPa
1:4 3.15 kPa
1:6 2.89 kPa

4. Conclusion
Hydrogel prepared from water hyacinth cellulose exhibite different structural, crystallinity, absorption
capacity and maximum stress compression depend on the type of additive. The application of
glutaraldehide (1:2) produce hydrogel with high swelling capacity (285%) at 25oC, while the highest
maximum stress compression (3.15 kPa) was presented by hydrogel prepared with poly vinyl alcohol
(1:4) as additive.

References
[1] Dai H, Ou S, Liu Z and Huang H 2017 Carbohydrate Polymers 169 504-514
[2] Liu Z and Huang H 2016 Carbohydrate Polymers 147 226-233
[3] Sundari M T and Rames A 2012 Carbohydrate Polymers 87, 1701-1705
[4] Oliveira J P, Bruni G P, Lima K O, Halal S L M, Rosa G S, Dias A R G and Zavarese E R 2017
Food Chemistry 221 153-160
[5] Brasileiro L B, Colodette J L, and Piló-Veloso D 2001 Quimica Nova 24 819–829

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IOP Conf. Series: Materials Science and Engineering 673 (2019) 012017 doi:10.1088/1757-899X/673/1/012017

[6] Mochochoko T, Oluwafemi O S, Jumbam D N and Songca S P 2013 Carbohydrate Polymers 98

290-294
[7] Bourton J, Van O E, and Ensbey R 2010 Water Hyacinth: Weed of National Significance
http://www.dpi.nsw.gov.au/agriculture/pests-weeds/weeds/profiles/water-hyacinth; 2010
accessed on 28 August 2014.
[8] Kwon S S, Kong B J and Park S N 2015 European Journal of Pharmaceutics and
Biopharmaceutics 92 146–154
[9] Masruchin N, Park B, and Causin, V Journal of Industrial and Engineering Chemistry 29 265–
272
[10] Ooi S Y, Ahmad I and Amin M C I M 2016 93 227-234
[11] Liu Z, Li D, Dai H and Huang H 2017
[12] Hu X, Hu K, Zeng L, Zhao M and Huang H 2010 Carbohydrate Polymers 82 62-68
[13] Halal S L M, Colussi R, Deon V G, Pinto V Z, Villanova, F A and Carreno N L V 2015
Carbohydrate Polymers 133 644-653
[14] Alemdar A and Sain M 2008 Bioresource Technology 99 1664-1671
[15] Zhang X, Wang Y, Lu C and Zhang W 2014 Carbohydrate Polymers 114 166-169
[16] Hassan M, Mathew A, Hassan E and Oksman K 2010 Wood and Fiber Science 42 362-376
[17] Abraham E, Deepa B, Pothan L, Jacob M, Thomas S, Cvelbar U 2011 Carbohydrate Polymers
86 1468–1475
[18] Buyanov A L, Gofman I V, Khripunov A K, Tkachenko A A and Ushakova E E 2013 Polymer
Science Series A 55 302–312
[19] Huang H C, Chen L C, Lin S B, Hsu C P and Chen H H 2010 Bioresource Technology 101
6084–6091