5298

Journal of Applied Sciences Research, 8(11): 5298-5305, 2012

ISSN 1819-544X
This is a refereed journal and all articles are professionally screened and reviewed

ORIGINAL ARTICLES
Effect of Chemical Treatment on Water Absorption of Areca Fiber
1
Dhanalakshmi Sampathkumar, 1Ramadevi Punyamurth, 2Srinivasa C. Venkateshappa and
3
Basavaraju Bennehalli
1
Research Scholar, Department of Chemistry, Jawaharlal Nehru Technological University, Hyderabad-500 085,
Andhra Pradesh, India and Department of Chemistry, KLE Society’s BVB College of Engineering &
Technology, Hubli-580031, Karnataka, India.
2
Department of Mechanical Engineering, GM Institute of Technology, Davangere-577006, Karnataka, India.
3
Department of Engineering Chemistry, Alva’s Institute of Engineering & Technology, Moodbidri-574225,
Karnataka, India.

ABSTRACT

Today, the benefit of composites can be made by replacing synthetic fibers with various types of cellulose
fibers. The significant factor in finding good fiber reinforcement in the composite is the strength of adhesion
between polymer matrix and fiber. Due to the presence of hydroxide and other polar groups in various
constituents of natural fiber, the water absorption is high and this leads to poor wettability and weak interfacial
bonding between fibers and the more hydrophobic matrices. Hence, in order to develop composites with suitable
and better mechanical properties, it is most important to impart hydrophobic nature to the fibers by suitable
chemical treatments. In the present work, investigation on the effect of alkali-treatment and acetylation on water
absorption characteristics of single areca fiber has been carried out. The results indicate that the acetylation of
areca fibers drastically reduces the water absorption whereas alkali treatment of areca fibers improves the water
absorption.

Keywords: lignocellulosics, areca fibers, water absorption, acetylation, alkali treatment, hydrophobic nature

Introduction

In the plant, waste fibers can be described as lignocellulosic. Lignocellulosic materials include agricultural
residue, wood, water plants, grasses, and other plant substances. Plant waste fibers have the composition,
properties, and structure that make them suitable for usage of fibers in composites. Currently, hard cellulose
fibers like flax, jute, banana, sisal, pineapple leaf fibers are used in textile, packaging, low-cost housing, paper
manufacturing industries, and other general applications. These fibers are considered as hard cellulose fibers
because of their high tensile modulus and low elongation at break.
Scientists and technologists made many attempts in utilizing natural fibers in the fabrication of composites
and found that these natural fibers-reinforced composites possess better chemical resistance, electrical
resistance, good thermal, acoustic insulating properties, and high resistance to fracture. This has stimulated the
use of hard natural cellulose fibers as an attractive alternative to synthetic fibers because of their low cost, less
weight, and density. Due to the hydrophilic nature of natural fibers, the potential of using natural fibers as
reinforcing agent is based on the interfacial properties between fiber and polymer matrix. Chemical
modifications are considered to optimize the interface of fibers (Stocchi et al., 2007; Aziz and Ansell, 2004).
The water absorbed by the fibers can be reduced by chemical modifications of fibers such as acetylation,
methylation, cyanoethylation, benzoylation, permanganate treatment, and acrylation (Ramadevi et al., 2012).
Acetylation of natural fibres is a well-known esterification method causing plasticisation of cellulosic
fibres. Polymer hydroxyl groups of the cell wall with acetyl groups, modify the properties of these polymers so
that they become more hydrophobic which could stabilise the cell wall against moisture, improving dimensional
stability and environmental degradation.
Few attempts have been made to study the properties of chemically treated natural fiber-reinforced polymer
composites. The flexural properties, storage modulus, and glass transition temperature of acrylated fiber
reinforced composites were found improved. Also, water absorption of composites made using treated fiber
found to decrease when compared to untreated fiber composites (Vilay et al., 2008; Jannah et al., 2009;
Srinivasa et al., 2010).
Ghali et al., (2011) reported the effect of chemical modification of luffa cylindirica fibers on the mechanical
and hygrothermal behaviours of polyester-luffa composites. The water absorption behaviour of luffa fibers

Corresponding Author: Basavaraju Bennehalli, Department of Engineering Chemistry, Alva’s Institute of Engineering &
Technology, Moodbidri-574225, Karnataka, India
E-mail: basavaraju_b@yahoo.co.in
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J. Appl. Sci. Res., 8(11): 5298-5305, 2012

followed Fick’s law early in the immersion and a degradation process was observed later in the immersion. An
investigation on the effect of acetylation on the properties of flax fiber and its polypropylene composites shown
that the acetylation of flax fibers resisted up to 50% water absorption depending on degree of acetylation of flax
fibers (Bledzki et al., 2008).
Areca belongs to the species Areca catechu Linnaeus under the family palmecea and originated in the
Malaya peninsula, East India. In India, areca cultivation is coming up in a large scale with a view to attaining
competence in medicine, paint, chocolate, etc. The husk of the areca constitutes about 60–80% of the total
weight and volume of the fresh fruit. The husk fiber is composed of cellulose with varying proportions of
hemicellulose (35–64.8%) and lignin (13.0–26.0%), pectin and protopectin (Rajan and Kurup, 2005;
Dhanalakshmi et al., 2012). Areca appears to be a budding fiber amongst all natural fiber-reinforcing materials,
because it is inexpensive, abundantly available and a very high potential perennial crop. The present use of this
highly cellulose material is as a fuel in areca nut process. Thus the use of this husk fiber as structural material
requires a detailed study on physical, chemical and thermal characteristics.
Many considerations have to be taken into account in the design of natural fiber composites. One of the
most important issues is the degrading behaviour of the composites exposed to environmental conditions such as
humidity, sunlight, and microorganisms. Also, the poor resistance of the fibers to water absorption can have
undesirable effects on the mechanical properties and the dimensional stability of the composites. Therefore, it is
important to study in detail the water absorption behaviour in order to estimate not only the consequences that
the water absorbed may have, but also the durability of natural fibers composites aged under water. Currently,
there is no information on the water absorption studies of areca fibre. Therefore, this study seeks to determine
the water absorption of single areca fibre. A better understanding of water absorption property of fibres will help
to develop a productive use of fibres in composite materials. In the present work, a detailed investigation on
water absorption of single areca fibre and the effect of alkali treatment and acetylation on water absorption of
areca fibre was carried out.

Materials and Methods

Materials:

Areca empty fruits were obtained from Madhu Farm House, Nilogal, Davangere, Karnataka, India, and
analytical grade reagents were purchased from Qualigens Company and used as received.

Fiber extraction:

The dried areca empty fruits were soaked in de-ionised water for about five days. The soaking process
loosens the fibers and can be extracted out easily. Finally, the fibers were washed again with de-ionised water
and dried at room temperature for about 15 days. The dried fibers were designated as untreated fibers.

Morphological study:

Scanning electron microscopic (SEM) photographs of untreated and alkali-treated areca fibers were
obtained with a JEOL JSM-T330A scanning electron microscope at the accelerating voltage of 20 KV.

Alkali treatment of fibers:

The fibers were dewaxed by soaking in 1:2 mixtures of ethanol and benzene for 72 h at 50 oC, followed by
washing with deionised water and then air dried. The dewaxed fibers were immersed in NaOH solutions of
different concentrations, where the total volume of the solution was 15 times the weight of the fibers. The fibers
were kept in alkaline solution for 72 h at a temperature of 30 oC; they were thoroughly washed in running water
and then neutralized with 2% acetic acid solution. Lastly, the fibers were washed again in running water to
remove the last traces of acid sticking to it, so that the pH of the fibers was approximately 7. Then, they were
dried at room temperature for 48 h to obtain alkali-treated fibers.

Acetylation of areca fiber:

The acetylation of areca fiber was carried out according to Bledzki et al., (2008). The areca fibers were
placed in a round bottom flask containing acetylating solution. Acetylating solution consists of 250 ml toluene,
125 ml acetic anhydride and a small amount of catalyst perchloric acid (60%). The process temperature of
acetylation was 60 oC and duration was 1-4 h. After modification, the fiber was washed periodically with
distilled water until acid free. Finally acetylated areca fibers were air dried for certain time before investigation.
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J. Appl. Sci. Res., 8(11): 5298-5305, 2012

To determine the degree of acetylation, acetylated areca fibers were saponified by 0.5N sodium hydroxide
solution. After saponification, the excess alkali was titrated by using 0.5N hydrochloric acid. Similar method has
been considered for untreated areca fibers and the degree of acetylation was calculated from the difference.

Water absorption measurements:

The study of water absorption on untreated, alkali treated, and acetylated fibers were carried out in water
from various sources such as pond water, borewell water, river water & sea water. The pH values of water
samples were, pond water: 8.20, borewell water: 7.40 river water: 7.74, sea water: 7.76. Humidity chambers
(desiccators) were set up at 100% humidity using water from various sources. The specimens were prepared
from bundles of single fibers bound together. The specimens (untreated, alkali treated and acetylated areca fiber)
were dried in hot air oven at 60 oC for 24 h, weighed in a balance accurate to 4 decimal places (± 0.1 mg) and
were then placed in the humidity chamber. The humidity chamber was held at room temperature. After 24 h,
each fiber bundle was taken out from the humidity chamber and excess water was carefully mopped with filter
paper. Finally, the weight of the fibers was measured and the water absorption was calculated by weight
difference. Then again the sample is immersed in water and the same process is repeated after every 24 h. A
graph is plotted between percentage of water absorption and square root of immersion time.

where ma is the mass of the sample after exposing to water, and md is the mass of the dry sample. More details
about the technique can be found in the literature (Bismarck et al., 2002; Jimenez and Bismarck, 2007; Stana-
Kleinschek and Ribitsch, 1998).

Results and Discussion

Chemical composition of fiber:

Lignocellulosics are three-dimensional, polymeric composites made up primarily of cellulose,

hemicellulose and lignin. In natural fibers, semicrystalline cellulose is the main reinforcement material. The
cellulose is held together by amorphous hemicelluloses and fibers are cemented together in the plant by lignin
which is commonly known as plant cell adhesive. Lignocellulosic fibers may differ in chemical composition,
but have very similar properties such as flammability, thermoplasticity, they swell and shrink as the moisture
content of the cell wall changes, they degraded by acids, bases and ultraviolet radiation. All of these
characteristics will result in specific end use of lignocellulosics in composite formulation (Rowell et al., 1998).
The areca husk fiber is composed of 35-65% hemicellulose, 13-26% lignin and does not contain noticeable
cellulose.

Morphological study:

The SEM micrographs of untreated and treated areca fibers are presented in Figure 1. In Figure 1a, it can be
observed that untreated areca fiber presents a network structure in which the fibrils are bound together by
hemicellulose and lignin. It clearly demonstrates the presence of longitudinally oriented unit cells with more or
less parallel orientations. The intracellular space is filled up by the binder lignin and fatty substances, which
hold the unit cells firmly in a fiber. The micrograph of alkali-treated areca fiber (Figure 1b) clearly shows a
large number of pin holes or pits on the surface, which are due to the removal of fatty deposits from the fiber. A
large number of globular fatty deposits lie hidden below the surface of the untreated fiber and these are not
revealed by the SEM pictures of untreated fibers and are only revealed in alkali-treated fibers (Prasad et al.,
1983; Bismarck et al., 2001). The surface morphology of acetylated areca fiber viewed in Figure 1c. Upon
acetylation treatments the wax and cuticle in the surface is removed by the interaction with acetyl group and
surface becomes smoother. The fibrillation is also found to arise as the binding materials removed and some
micro-pores appear in the acetylated fiber. It was also observed from Figure 1d that at the higher degree of
acetylation, the fibrillation increased but fiber damage and crack were also observed.
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J. Appl. Sci. Res., 8(11): 5298-5305, 2012

Fig. 1: SEM photograph of untreated and treated areca fiber: a) untreated, b) alkali treated, c) acetylated fiber,
d) fiber damage at higher degree of acetylation.

Water absorption measurement:

Lignocellulosics change dimensions with changing moisture content because the cell wall polymers contain
hydroxyl and other oxygen containing groups that attract moisture through hydrogen bonding. The
hemicellulose is mainly responsible for moisture sorption, but the accessible cellulose, noncrystalline cellulose,
lignin and surface of crystalline cellulose also play major roles. Moisture swells the cell wall, and the fiber
expands until the cell wall is saturated with water (fiber saturation point). Beyond this saturation point, moisture
exists as free water in the void structure and does not contribute further expansion.
To measure the water absorption, the fiber was immersed in a water sample from various sources. After
every 24 h, the fiber was taken out and excess water on the fiber surface was removed before weighing. Three
replicates were tested and the results were presented as an average of three. The untreated areca fiber was used
as a control in this study. The study on the water absorption of untreated areca fiber showed that the untreated
areca fiber absorbs more water in bore water than in other water samples. The maximum water absorption of
untreated areca fiber was found to be 78.5%, 69.5%, 69%, and 67% in borewell water, pond water, river water
and sea water respectively. The water absorption by the fiber is due to the fact that areca fiber contains very high
percentage of hemicellulose in its structure. Also, in all natural cellulose fibers, a hollow cavity called lumen
exists in the unit cell of the fibers which generates more pathways for water to diffusing into the fiber (Reddy
and Yang, 2005).

Effect of alkali-treatment of water absorption:

Figure 2 shows the effect of the square root of immersion time, , on water absorption of alkali-treated
areca fiber. For both untreated and alkali-treated fiber, the percentage of water absorption increased initially
with before reaching a maximum. It also shows that the percentage of water uptake decreased with an
immersion time. This is attributed to the fact that the initial and second absorption phases are governed
respectively by the wetting of fibers and the capillary absorption process where the water diffuses into the fibers
until reaching a maximum absorption. When the immersion time becomes significant, a decrease in the water
absorption is due to the hydrophilic property of cellulosic fibers as more water molecules penetrate into the
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micro cracks present in these fibers, making the fibers swell and eventually leading to failure (Nosbi et al.,
2011; Saika, 2010).

Fig. 2: Comparison of water absorption studies of alkali-treated areca fiber in Bore well water.

The effect of alkali treatment on water absorption of areca fibers is presented in Figure 3. It shows that
alkali treatment had improved the ability of areca fibers to absorb water. This improvement is likely due to the
removal of the gummy and waxy substances from the raw fibers. As stated in the literature an alkali treatment
results in the partial dissolution of hemicellulose (Rong et al., 2001). Hemicellulose, however, is responsible for
the water absorption of the fiber (Nabi and Jog, 1999). The alkali treatment leads to a partial removal of waxes
and therefore an increased accessibility of the protanable surface functions. An increased number of ‘polar’
surface functionalities will increased the amount of water absorbed on the fibers (Prasad et al., 1983; Bismarck
et al., 2001). As observed for an alkalisation 5%, 10%, 15%, 20% NaOH solutions leading the removal of all
other hydrophobic compounds from the fibers, the fiber treated with 15% NaOH shown maximum water uptake
in pond water and river water; fiber treated with 10% NaOH shown maximum water absorption in borewell
water; and fiber treated with 5% NaOH shown maximum water absorption in sea water. This means that
swelling process was much faster leading to higher water uptake and also the alkali treatment had removed the
protecting cell-fibers, thus increasing the water absorption. This improvement could also be explained by both
the change in the quality of the surface of the areca fibers after alkali treatment (Figure 1b) and the presence of
several hydroxyl groups on this surfaces (Bal et al., 2004).

Fig. 3: Effect of alkali-treatment on water absorption of areca fiber.

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J. Appl. Sci. Res., 8(11): 5298-5305, 2012

Influence of acetylation on water absorption:

The acetylation of areca fibers was conducted at 60 oC. The percentage of catalyst was in the range 0 to
0.052%. The effect of catalyst concentration on the degree of acetylation of areca fiber is presented in the Figure
4. It was observed that the degree of acetylation increased with the increase in catalyst concentration. The
similar results were reported for acetylation of flax fiber (Bledzki et al., 2008; Zafeiropoulos et al., 2001). The
maximum degree of acetylation was reached up to 47.65% in the presence of 0.052% catalyst in four hours
process.

Fig. 4: Influence of catalyst concentration on degree of acetylation.

The water absorption study of acetylated areca fiber was determined at room temperature. Prior to the water
absorption studies, the untreated areca fiber was subjected to acetylation process for 3 h with different catalyst
concentration as mentioned in the experimental procedure. The influence of degree of acetylation of areca fibre
on the water absorption is presented in Figure 5. The 4.0, 10.12, 18.56, 26.52 and 37.48% degree of acetylated
areca fibres respectively showed about 15.25, 21.48, 32.28, 40.18 and 50.34% lower water absorption properties
than untreated areca fibres. It was observed that the water absorption property of areca fiber was inversely
proportional to the degree of acetylation which is because of reduction of hydrophilicity of the fibre. The results
obtained clearly point out that acetylation process decreased the dissemination of water into the fiber and fiber
become more hydrophobic. This is due to the replacement of hydroxyl groups by hydrophobic acetyl groups.
Chemical modification takes place as the acetic anhydride substitute the cell wall hydroxyl groups with acetyl
groups, making the surface more hydrophobic (Bessadok et al., 2007; Paul et al., 1997).

Fig. 5: Influence of degree of acetylation of areca fibre on the water absorption.

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J. Appl. Sci. Res., 8(11): 5298-5305, 2012

Conclusion:

The potential of using natural fibers as reinforcing agents is based on the interfacial properties between
fiber and polymer matrix. Also, the poor resistance of the fibers to water absorption can have undesirable effects
on the structure, dimensional and mechanical properties of the natural fiber reinforced composites. It is possible
to reduce the water absorption property of areca fiber through chemical treatment. The results presented in this
work indicate that the acetylated areca fiber absorbs less water than the untreated fiber. Hence, Mechanical
properties of areca fiber-reinforced composites can be improved through acetylation.

Acknowledgments

The authors would like to thank Madhu Farm House, Nilogal for providing a good quality areca fruit husk.
The first author would like to thank the Management of KLE Society’s BVB College of Engineering and
Technology, Hubli, Karnataka, India for the kind encouragement and constant support provided. She sincerely
thanks Prof. Ashok Shettar, Principal, KLE Society’s BVB College of Engineering and Technology, without his
encouragement and motivation, this work would not have been possible. The second author would like to thank
Sri G. M. Lingaraju, Secretary, GM Institute of Technology, Davangere, India, for their encouragement and
support throughout this work. The third author would like to thank Dr. M. Mohan Alva, Chairman, Alva’s
Education Foundation, Moodbidri and Dr. Peter Fernandes, Principal, Alva’s Institute of Engineering &
Technology, Moodbidri, Karnataka, India, for their kind encouragement and support provided.

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