Carbohydrate Polymers 142 (2016) 158–166

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Isolation and characterization of cellulose nanofibrils from arecanut

husk fibre
Julie Chandra C.S. a,b , Neena George a,c , Sunil K. Narayanankutty a,∗
a
Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology, Kochi, 682022 Kerala, India
b
Department of Chemistry, K.K.T.M. Govt. College, Pullut, Kodungallur, Thrissur, India
c
Department of Chemistry, Govt. College Chittur, Palakkad, India

a r t i c l e i n f o a b s t r a c t

Article history: The isolation of cellulose nanofibres from arecanut husk was achieved by a chemo-mechanical method
Received 3 October 2015 thereby opening up a means for utilizing a waste product more effectively. The chemical processes
Received in revised form involved alkali treatment, acid hydrolysis, and bleaching. The mechanical fibrillation was performed via
22 December 2015
grinding and homogenization. The chemical constituents at different stages of treatment of fibres were
Accepted 10 January 2016
Available online 12 January 2016
analyzed according to the ASTM standards. Morphological characterization was done using the scanning
electron microscopy (SEM), field emission scanning electron microscopy (FE-SEM) and transmission elec-
tron microscopy (TEM). The isolated nanofibers had an average diameter of below 10 nanometres and
Keywords:
Arecanut a very high aspect ratio in the range 120–150. Fourier transform infrared spectroscopy (FT-IR) showed
Cellulose nanofibrils the effective removal of the non cellulosic components. The crystallinity was increased with successive
Cellulose nanofibres treatments as shown by the X-ray diffraction analysis (XRD). The TGA studies revealed a good thermal
Homogenization stability for the isolated nanofibres.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction & Takemura, 2010; Fahma, Iwamoto, Hori, Iwata, & Takemura,
2011; Khalil et al., 2014; Nazir, Wahjoedi, Yussof, & Abdullah,
With the development of nanotechnology, cellulose, one of the 2013) wood pulp (Siddiqui, Mills, Gardner, & Bousfield, 2011),
most ancient and abundant natural polymer on earth, attracts more kenaf, (Chan, Chia, Zakaria, Ahmad, & Dufresne, 2012; Jonoobi,
attention in a new form: ‘nanocellulose’. Based on the dimension Khazaeian, Tahir, Azry, & Oksman, 2011), bamboo (Yu et al., 2012),
and morphology, nanocellulose is grouped as cellulose nanocrystals flax (Khalil, Mahayuni, Rudi, Almulali, & Abdullah, 2012; Qua,
(CNC), cellulose nanofibers, (nanofibrillated cellulose) and bacte- Hornsby, Sharma, & Lyons, 2011) and rice straw (Lu & Hsieh,
rial cellulose or microbial cellulose (Dufresne, 2012; Klemm et al., 2012). Utilization of these lignocellulosic fibres increase rapidly
2011). Among these cellulose nanofibers have gained much atten- due to their abundance and ease of recyclability and attractive
tion from academic and industrial researchers, especially for the properties.
development of new bio nanocomposite materials (Charreau et al., Several methods have been reported for the extraction of
2013; Khalil et al., 2014; Missoum, Belgacem, & Bras, 2013; Song, nanocellulose fibres from these renewable sources. A chemo-
Winter, Bujanovic, & Amidon, 2014). Cellulose nanofibre compos- mechanical method was used by Alemdar et al. for the extraction
ites find applications in many areas such as printed and flexible of cellulose nanofibres from the agricultural residues such as
electronics films and coatings for packaging, drug delivery, water wheat straw and soy hulls for use as reinforcement in biocompos-
treatment, optical media, barrier films, etc. The use of nanocel- ites. (Alemdar & Sain, 2008). They obtained cellulose nanofibres
lulose based composites in automotive and building products is with 10–80 nm diameter and 35% improvement in crystallinity
increasing. Over the years, numerous studies have been carried out for wheat straw nanofibres and only 16% for soyhull nanofi-
for the extraction of cellulose nanofibres from various cellulosic bres. Farah Fahma and co-workers extracted cellulose nanofibers
sources, such as oil palm biomass (Fahma, Iwamoto, Hori, Iwata, by hydrolysing oil palm empty fruit bunch with sulphuric acid
hydrolysis (Fahma et al., 2010). They observed a decrease of crys-
tallinity and DP with sulphuric acid treatment time. Fatah et al.
∗ Corresponding author. explored a chemo-mechanical technique to isolate cellulose nanofi-
E-mail address: [email protected] (S.K. Narayanankutty). bres from oil palm empty fruit bunch (OPEFB) and succeeded in

http://dx.doi.org/10.1016/j.carbpol.2016.01.015
0144-8617/© 2016 Elsevier Ltd. All rights reserved.
 J.C. C.S. et al. / Carbohydrate Polymers 142 (2016) 158–166 159

obtaining cellulose nanofibres of diameter in the range 5–10 nm 2. Experimental

and found a reduction in crystallinity which is influenced by the
pressure of mechanical treatment (Fatah et al., 2014). Chemi- 2.1. Materials and methods
cal ultrasonic method was adopted by Chen et al. for isolating
cellulose nanofibres from four different fibres, wood, bamboo, Dried arecanut husk was collected from the western coastal
wheat straw and flax fibres. They succeeded in isolating nanofi- region of Kerala, South India. The fibres were separated from the
bres with diameter ranging from 10 to 40 nm from wood, bamboo husk by the biological retting process. Toluene, ethanol, sodium
and wheat straw whereas flax fibres with high cellulose con- hydroxide, con hydrochloric acid, sodium chlorite, acetic acid and
tent were not uniformly nanofibrillated (Chen et al., 2011). Saito all other chemicals used for the extraction process were of analyt-
et al. introduced an oxidation pre treatment of cellulose with ical grade.
2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated
system. They obtained cellulose nanofibres with 3–4 nm width 2.2. Isolation of cellulose nanofibrils
from hardwood celluloses (Saito et al., 2009). The defibrillation
of nanofibrillated cellulose usually require intensive mechanical Fig. 1 shows the overall process flow chart. The dried areca
methods such as microfluidization, cryocrushing, grinding, high husk fibres were dewaxed with a (2:1, v/v) mixture of toluene and
intensity ultrasonication, high pressure homogenization or a com- ethanol for 48 h at 50 ◦ C followed by washing with boiling water
bination of these (Khalil et al., 2014). Kanoth et al. obtained highly and dried in air. The dried fibres were then cut into short fibres of
crystalline nanofibrillated cellulose of diameter 18–20 nm from 6 mm length. The major part of the lignin and hemicelluloses was
coir by using a commercial kitchen grinder for pulping followed removed by treating with 5% NaOH solution at a temperature of
by chemical treatment. An Ultra Turrax homogenizer was used 50 ◦ C for 4 h. It was then washed free of alkali and treated with 3.5 M
for nanofibrillation of the chemically pretreated and bleached con HCl to break up the cell walls and thus to separate microfibrils
pulp (Kanoth, Thomas, Joseph, Kuthirummal, & Narayanankutty, (Boldizar, Klason, Kubat, Näslund, & Saha, 1987). The fibres were
2015). washed well with deionised water to get rid of acid. Then it was
Among all lignocellulosic fibres, areca appears to be a promis- grinded into a pulp form and treated again with alkali to remove the
ing material because of its abundance being a perennial crop and remaining noncellulosic constituents followed by acid hydrolysis
less cost. Areca belongs to the species Areca catechu under Are- with 5 M acid (Bipinbal, 2012; Kanoth et al., 2015).
caceae family and believed to have originated in either Malaysia The delignification was further carried out by the bleaching
or Philippines. It is found in much of the tropical Pacific, Asia and process proposed by Wise, Murphy, & D’Addieco (1946). The delig-
parts of East Africa. Areca nut is used for chewing in some Asian nified fibres with a solvent to fibre ratio of 25:1 by weight were
countries. In India, areca cultivation is increasing in a large scale bleached with a 4:1 mixture of sodium chlorite (NaClO2 ) and glacial
to attain self sufficiency in paint, medicine, chewable gudka, etc. acetic acid for 2 h at 60 ◦ C. The bleaching was repeated with half the
Arecanut husk constitutes about 60–80% of its total weight and initial amount of bleaching agent. After bleaching, the fibres were
volume of the fresh fruit. Arecanut husk is a waste product and washed with deionised water until the pH 7. The white suspension
is mostly used as a fuel for areca nut processing. Areca husk left obtained was then homogenized in an Ultra Turrax homogenizer
unnoticed in the plantation causes bad odour and other decay (IKA Homogenizer model T25 digital S22) at 12,000 rpm for 2 h to
related issues. A few articles have been reported to utilize the get nanofibrillated cellulose.
arecanut husk fibre as a reinforcing material in epoxy, UF and
PF composites (Srinivasa & Bharath, 2011; Srinivasa et al., 2011).
The utilization of this lignocellulosic fibre in polymeric compos- 3. Characterization
ites will open up a new way of disposing off a waste product. A
better understanding of chemical composition, morphology, phys- 3.1. Analysis of chemical composition
ical and thermal properties of the nanofibres after isolation from
arecanut husk fibre will be useful in developing new bionanocom- Chemical constituents of the raw fibre and at each stage of treat-
posites. ment were measured according to ASTM standards. ␣-cellulose
Arecanut husk consists mainly of cellulose, hemicelluloses, (ASTM D 1103-55T), hemicelluloses (ASTM D 1104-56), lignin
and lignin. The cellulose contains much more crystalline regions (ASTM D1106-56), moisture content (ASTM D 4442-92) of raw and
whereas hemicelluloses and lignin are amorphous in nature. The treated fibre along with the pectin content and ash content of the
noncellulosic constituents of fibres are removed during the extrac- raw fibre were determined.
tion process. The amorphous regions easily absorb chemicals and
undergo hydrolysis while the compactness of crystalline regions 3.2. Fourier transform infra red spectroscopy (FT-IR)
resists the penetration of chemicals (Klemm et al., 2006). Alkaline
treatment is usually done to remove the hemicelluloses and lignin. FT-IR spectra were recorded on a Fourier transform infrared
It is well known that when acid hydrolysis is used the properties, (FT-IR) instrument (Thermo Nicolet, Avatar 370) in the range of
the structure and the size of the nanocellulose depend on the raw 400–4000 cm−1 with a resolution of 4 cm−1 . FT-IR spectra of the raw
material, concentration and the time of hydrolysis (Habibi, Lucia, & fibre, alkali treated, acid hydrolysed after grinding and bleached
Rojas, 2010). This study aims at isolating cellulose nanofibres from pulp were taken by attenuated total reflection (ATR) technique. The
a renewable, inexpensive and underutilized raw material-arecanut. peak heights were determined from the absorbance spectra using
To date, no study has been reported on the isolation of cellu- EZ OMNIC software.
lose nanofibres from arecanut husk. Controlled hydrolysis using
hydrochloric acid coupled with mechanical pre treatment (using a
simple kitchen grinder) followed by homogenization (using ultra 3.3. Scanning electron microscopy (SEM)
Turrax homogenizer) was adopted for the isolation of cellulose
nanofibres (Kanoth et al., 2015). The resultant nanofibres were The morphological analysis of raw fibre and treated fibres
characterized by various techniques. The morphology and physio- was done using a JEOL Model JSM.6390 LV scanning electron
chemical properties were analyzed by SEM, FE-SEM, TEM, XRD, DLS, microscope. The fibre surfaces were gold coated prior to SEM inves-
FTIR and TGA. tigation to make them conductive.
160 J.C. C.S. et al. / Carbohydrate Polymers 142 (2016) 158–166

Fig. 1. Preparation procedure for arecanut nanocellulose fibrils.

3.4. Field emission scanning electron microscope (FESEM) Debye–Scherrer Equation (Amiralian, Annamalai, Memmott, &
Martin, 2015).
The nanocellulose dispersion in the bleached as well as homog-
k
enized state was analyzed by Field Emission Scanning Electron D=
Microscopy using “NOVA NANO SEM 450 FE-SEM” instrument. A ˇCos
drop of the dispersion was placed on the carbon tape and allowed where k is the shape factor and is approximately = 0.89,  is the
water to evaporate completely. The specimen was sputter coated wave length of the radiation (0.154 nm), ˇ is the line width in radi-
with gold (10 nm thickness) to suppress charging inside the FESEM. ans at half the maximum intensity of I200 to which the background
and the amorphous component have been subtracted, and  is the
3.5. Transmission electron microscopy analysis (TEM) scattering angle of the peak (2 0 0).

Transmission electron micrographs of cellulose fibres were 3.7. Dynamic light scattering
made on a JOEL 2100 microscope. The nanofibrils were deposited
from an aqueous dilute dispersion on a micro grid covered with a The particle size of nanocellulose dispersion in water was
thin carbon film and allowed to dry at room temperature for 24 h. recorded by dynamic light scattering (DLS) system using Microtrac
The deposited fibres were subsequently stained with a 2% uranyl Nanotrac Wave. The technique is also referred as photon correlation
acetate solution to enhance the microscopic resolution. The sample spectroscopy (PCS) in which particle size is determined by measur-
was then dried before TEM analysis. ing the random changes in the intensity of light scattered from a
suspension or solution. The sample is illuminated by a laser beam
3.6. X-ray diffraction technique (XRD) followed by detection of the resultant fluctuations of the scattered
light at a known scattering angle  by a fast photon detector.
XRD patterns of the fibres at different stages were obtained
using a Bruker AXS D8 Advance X-ray powder diffractometer 3.8. Thermogravimetric analysis (TGA)
equipped with Cu K␣ radiation at the operating voltage and cur-
rent of 40 kV and 35 mA respectively. The diffraction intensities Thermogravimetric analysis of the fibres was carried out on
were recorded between 3 and 80◦ (2 angle range) at increments TA Instruments TGA Q50 with a heating rate of 20 ◦ C/min. About
of 0.02◦ at a wavelength of 1.541 Å. 5–8 mg of dried samples were heated from room temperature to
The crystallinity index was calculated using the Segal’s method 600 ◦ C under nitrogen atmosphere.
as given below (Segal, Creely, Martin, & Conrad, 1959).
I − Iam
 4. Results and discussion
200
Crystallinity index, ICr = × 100
I200
4.1. Chemical composition
where I200 is the maximum intensity of diffraction at 200 peak
(2 = 22.6◦ ) and Iam is the intensity of diffraction at 2 = 18◦ . I200 The chemical constitution of the raw arecanut husk fibre
represents both crystalline and amorphous regions of the material determined is given in Table 1. The raw fibre contains 34.18 wt% cel-
whereas Iam represents only the amorphous regions. lulose, 20.83 wt% hemicelluloses, 31.6 wt% lignin, low percentage of
Further the effect of different treatments on the crystalline pectin, ash and about 10.95 wt% of moisture content. From the liter-
structure of fibres can be evaluated by another parameter, ature reports, it is clear that the cellulose content of arecanut husk
the mean size of crystalline regions, and was calculated using fibre is comparable with that of some of the agricultural residues
 J.C. C.S. et al. / Carbohydrate Polymers 142 (2016) 158–166 161

Table 1
Compositional analysis of the raw arecanut husk fibre. Bleached
Components Content % (w/w)

␣-Cellulose 34.18
Hemicellulose 20.83 1426
Lignin 31.60
Moisture 10.95 897
1155
Pectin 1.26
Ash 2.34
Acid treated 996

3370
Table 2
Chemical composition at each stage.

Fibre ␣-Cellulose Hemicellulose Lignin (%, Moisture

(%, w/w) (%, w/w) w/w) Content

Transmittance (a.u)
(%, w/w)

Raw 34.18 (±1.93) 20.83 (±0.66) 31.6 (±2.36) 10.95 (±0.55)

Alkali 34.5 (±1.5) 14 (±2) 21.83 (±2.18) 16.2 (±0.2) Alkali treated
treated
Alkali 67.78 (±6.22) 4.78 (±0.57) 16.85 (±2.85) 6.22 (±0.17)
treated and
Acid hydro
pulp
Bleached 85.47 (±1.63) – 2.3 (±1.04) 7.09 (±0.03)
Raw fibre

such as wheat straw (39%), (Sun, Xu, Sun, Fowler, & Baird, 2005), rice
straw (38%), (Hessien, Rashad, Zaky, Abdel-Aal, & El-Barawy, 2009),
rice husk (35 wt%), (Johar, Ahmad, & Dufresne, 2012), hardwood
(31–64%) and softwood (30–60%) (Jawaid & Khalil, 2011) where as
a lower percentage of cellulose is seen in orange peels (13.6 wt%), 2907

1509
1734
lemon peels (12.7 wt%) and algae biomass (7.1 wt%), etc. (Ververis

1254
3364 1049
et al., 2007). Table 2 describes the chemical composition of fibres
at different stages of processing. It is found that the raw fibre has 3500 3000 2500 2000 1500 1000 500
the lowest percentage of cellulose content and highest percentage -1
of non-cellulosic components such as hemicellulose and lignin. The Wave numbers cm
purpose of pre-treatment of fibres is to remove the non cellulosic
Fig. 2. FT-IR spectra of fibres at various stages of processing.
components and thus the embedded cellulose get exposed. When
the fibres are subjected to alkaline treatment, the hemicellulose
and lignin are removed. This is due to the breakdown of ether link- et al., 2013). The highest percentage of cellulose content is observed
ages between hemicelluloses and lignin (Xiao, Sun, & Sun, 2001). after the bleaching process and since the cellulose contains O H
The hemicellulose content is decreased from 20.83% to 4.78% and groups the moisture content increases slightly.
the lignin content from 31.65 to 16.85% on two successive alkali
treatments. It is reported that the alkali treatment is an efficient 4.2. Fourier transform infra red spectroscopy (FT-IR)
method for removing the non cellulosic components like hemicel-
luloses, pectin and lignin (De Rodriguez, Thielemans, & Dufresne, The FT-IR spectroscopy was done for studying the changes in
2006; Dufresne, Cavaillé, & Vignon, 1998). The crystalline regions the chemical structures after the various treatments of fibres. FT-
of the cellulose are compact and resist the penetration of chemi- IR spectra of the raw, alkali treated, acid hydrolysed and bleached
cals. The shear forces developed in grinding can lead to fibrillation fibres are shown in Fig. 2. The FT-IR spectrum shows major absorp-
by breaking down of hydrogen bond of cell wall structure. This also tions corresponding cellulose and lignin functional groups. As
helps further removal of cementing materials from the interior by we have discussed earlier, the arecanut husk fibre consists of
the second time chemical treatment. The repeated acid hydrolysis mainly cellulose, hemicelluloses, and lignin. Alkanes, esters, aro-
of fibres helps in the individualization of microfibrils from the cell matics, ketones and alcohols, with different oxygen-containing
wall. The remaining hemicelluloses and lignin can be removed by functional groups are the main functional groups present in these
bleaching with NaClO2 . When lignin reacts with NaClO2 , an oxida- three materials. Disappearance of some peaks in the spectra indi-
tive fragmentation takes place and some of the lignin will form cates the removal of some of the components after the chemical
lignin chloride which is easily dissolvable. From raw to bleached treatments of the fibre. There are two main absorption regions
fibres it is observed that the percentage of cellulose component observed for all the fibres, one at low wavelength region from 600
increased drastically to 85.47% as it is exposed by the removal to 1750 cm−1 and other at high wavelength region between 2800
of non-cellulosic components. The yield of nanocellulose obtained and 3400 cm−1 . The absorption bands in the range 3348–3404 cm−1
with respect to the initial amount of arecanut husk fibres is found and 2890–2980 cm−1 found in the spectra of all the fibres represent
to be about 22–26%. the O H stretching vibrations of the hydrogen bonded hydroxyl
Moisture content at each stage is also clear from Table 2. The raw groups and the C H groups of cellulose respectively (Avolio et al.,
fibre shows moisture content of 10.95%. When the fibre is subjected 2012; Jonoobi et al., 2011). The peaks at 1254, 1508, 1604 cm−1
to alkali treatment, the moisture content rises. Then it decreases found in the spectrum of raw fibre correspond to the aromatic
and finally increases slightly. Alkali exposure induces swelling of skeletal vibrations of lignin (Morán, Alvarez, Cyras, & Vázquez,
the fibres which promotes moisture absorption. The swelling of 2008). The appearance of a significant peak at 1730 cm−1 also in
fibres facilitates the breakdown during acid hydrolysis (Abraham the raw fibre is due to the acetic and uronic ester groups of the
162 J.C. C.S. et al. / Carbohydrate Polymers 142 (2016) 158–166

Table 3 (Marchessault, 1962). Additionally, the most significant intense

Absorbance peak height ratio for various fibres.
peak at 996 cm−1 and a shoulder peak in the region 897 cm−1
Fibre Peak height ratio Acellulose /Alignin correspond to the C H glycosidic deformation of cellulose com-
Raw 0.43 ponent (Avolio et al., 2012). Moreover two sharp signals at 1426
Alkali treated 0.66 and 897 cm−1 reflect the crystalline band of cellulose (Fan, Dai, &
Acid treated 1.7 Huang, 2012). The absorption bands in the region 890–1200 cm−1
are not much significant in the spectra of all other fibres except
the bleached and acid-treated fibres which indicates the increase
hemicelluloses or the ester linkages of the carboxylic group of fer- of cellulose content with different chemical treatments.
ulic and p-coumaric acids of lignin or hemicelluloses as reported Due to the hydrophilic nature, all the fibres in the spectra show
in the literature (Cherian et al., 2008; Fatah et al., 2014; Sun et al., signals in the range 1603–1640 cm−1 which represents the O H
2005). The main observation from the spectrum of the bleached bending vibration of absorbed water (Nacos et al., 2006). It can be
fibre is that these peaks are absent indicating the complete removal observed that the absorption maximum of water peak is slightly
of hemicelluloses and lignin. The peak ratios are calculated based shifted to higher wave number as moisture increases (Velazquez,
on the peak height of the absorbance peaks (Acellulose /Alignin ) for Herrera-Gómez, & Martın-Polo, 2003). Also the peak assigned to the
untreated as well as treated fibre. From Table 3 it is clear that O H stretching vibration (near 3400 cm−1) also becomes more
the peak height ratio (Acellulose /Alignin ) increases from raw fibre to intense and widens towards the lower wavenumber side with the
acid treated fibre. This again confirms the removal of lignin from rise in moisture absorption. This is evident from the spectrum of
the fibre during chemical treatment. The peaks appearing at 1155 alkali-treated fibre which has higher moisture content as men-
and 1094 cm−1 are due to the C O C stretching vibrations of the tioned earlier. The reduction of the peak intensity by successive
␤-1,4-glycosidic ring linkages between the d-glucose units in cel- treatments can be attributed to the inter and intra molecular hydro-
lulose which are more pronounced after the bleaching treatment gen bonding formed by most of the hydroxyl groups resulting

Fig. 3. SEM images of (A) raw fibre, (B) alkali treated fibre, (C) acid treated fibre, (D) alkali treated pulp, (E) acid treated pulp and (F) bleached pulp.
 J.C. C.S. et al. / Carbohydrate Polymers 142 (2016) 158–166 163

Fig. 4. FESEM images of (A) bleached pulp (high magnified image in the inset) and (B) homogenized pulp.

in lower moisture absorption (Abraham et al., 2013; Sun et al., FESEM images validate the effective disintegration of microfibrils
2005). by bleaching. A high magnification image of bleached fibre with a
diameter of around 11 nm is shown in the inset of Fig. 4(A). Homog-
enization results in the formation of nanofibres, confirmed by the
4.3. Scanning electron microscopy analysis (SEM)
entangled network of fibres of nano dimension as seen in the FE-
SEM image (Fig. 4(B)). As can be seen, most of the fibres have a
The morphology and dimension of the fibres are believed to be
diameter in the range 3–5 nm. Thus the morphological investiga-
affected by the chemo-mechanical treatment. Fig. 3 show the SEM
tion supports the evidence of the isolation of cellulose nanofibres
images of the fibres at different stages of processing. Fig. 3(A) shows
from arecanut husk and highlighting the success of the chemo-
the SEM image of the raw fibre. The surface of the raw fibre seems
mechanical treatment employed.
uneven due to the presence of binding materials like hemicellu-
loses, lignin, pectin, etc. These binding materials are removed and
thereby fibres get detached from the surface by the alkali treat- 4.5. Transmission electron microscopy analysis
ment (Fig. 3(B)). Fig. 3(C) clearly shows the defibrillation of fibres
occurring during acid hydrolysis. TEM micrographs of the cellulosic nanofibrils obtained after
Fig. 3(D) and (E) represent the alkali treated and acid treated homogenization are shown in Fig. 5. It clearly supports the evidence
fibre, respectively after mechanical grinding. The surface rough- of isolation of cellulose nanofibrils from arecanut husk. Long fibrils
ness shown in the image indicates the removal of the cementing with diameter in the nanometer range (1–10 nm) are observed from
materials (Chan et al., 2012). Furthermore the mechanical grind- the figure. The aspect ratio (length to diameter ratio) plays a major
ing increases the surface area and facilitates the ease of access of role in determining the reinforcing capability of nanofibres. The
alkali and acid into the interior part of the fibre. This contributes the aspect ratio of the nanofibrils is measured using image processing
effective defibrillation which is clearly demonstrated in the figure. software image J. Most of the fibres display a very high aspect ratio
As seen in the figures the diameter is reduced from 15 to 7 ␮m. in the range of (120–150). This value is rather high compared to one
Bleaching with NaClO2 after the acid hydrolysis helps to elim- reported for cellulose nanofibrils extracted from other sources such
inate the rest of lignin and further disintegration leading to the as coconut husk (60) (Rosa et al., 2010) or wheat straw (90–110)
development of cellulose micro fibrils. This is clearly observed from (Alemdar & Sain, 2008).
Fig. 3(F). The bleached pulp exhibits smoother and uniform fibril
surface, confirming the removal of non cellulosic components.
4.6. X-ray diffraction analysis

4.4. Field emission scanning electron microscope (FE-SEM) Fig. 6 represents the XRD patterns of the raw fibre and the
chemo-mechanically treated fibres. The crystalline structure of cel-
Fig. 4(A) and (B) show the FESEM images of bleached pulp lulose can be well studied by the XRD patterns. Two characteristics
and cellulose nanofibrils after homogenization respectively. The peaks at around 22◦ and 15◦ found in all the diffractograms are

Fig. 5. TEM micrographs of arecanut husk cellulose nanofibrils.

164 J.C. C.S. et al. / Carbohydrate Polymers 142 (2016) 158–166

1200

1100 Raw fibre

Alkali treated pulp
1000
Acid treated pulp
900 Bleached pulp
800
Intensity Count

700

600

500

400

300

200

100

0
0 5 10 15 20 25 30 35 40

2 theta (degree) Fig. 7. Particle size distribution from DLS spectrum.

Fig. 6. XRD pattern of fibres at various stages of treatment.

and analyzed by the DLS particle size analyzer. The size distribu-
Table 4 tion of the nanocellulose fibrils is given in Fig. 7. The data clearly
Crystallinity index and crystalline domain size of fibres at different stages of reveals that fibrils isolated are in the nano range and also a nar-
treatment. row size distribution of the particles is seen. The DLS spectrum of
Fibre stage Crystallinity index Crystalline domain nanocellulose suspension from Isora fibre also behaved in a similar
(%) size (nm) manner (Chirayil et al., 2014). Homogenization plays a key role in
Raw fibre 37 2.8
obtaining nanocellulose dispersion with narrow size distribution.
Alkali treated pulp 35 3.5
Acid treated pulp 60 3.7
4.8. Thermo gravimetric analysis (TGA)
Bleached pulp 67 3.4
Homogenized pulp 73 4.3
TGA was carried out to study the degradation characteristics
of fibres at various stages of treatment. Thermogravimetric (TG)
likely to be associated with the crystalline structure of cellulose and derivative thermogravimetric (DTG) curves of raw fibre, alkali
I (Nishiyama, 2009). The ordered crystalline arrangements in the treated fibre and acid hydrolysed fibre before grinding, alkali and
cellulose appears due to the formation of inter and intramolecular acid treated pulp after grinding, bleached and homogenized (i.e.
H-bonding by the hydroxyl groups (Chirayil et al., 2014). The H- nanocellulose) are shown in Fig. 8. The thermal degradation of raw
bonding restricts the free movement of the cellulosic chains and fibre is a multi-stage process since different non cellulosic and cel-
chains align close together in an orderly manner which tends to lulosic components with different decomposition temperatures are
have the crystallinity. In the case of raw fibre, these crystalline present in the raw fibre. Initial weight loss starting at 35 ◦ C and
domains are embedded in the matrix of amorphous components continuing up to around 120 ◦ C is due to the evaporation of loosely
like hemicelluloses, lignin and pectin thus a low crystallinity is bound moisture on the surface and the intermolecular hydrogen
shown. It is clear from the figure that the crystallinity increases bonded chemisorbed water. The FT-IR spectrum has confirmed the
with the consecutive chemical treatments. This is attributed to the presence of the chemisorbed water. The next stage of degradation
effective removal of the non crystalline components. begins at 223 ◦ C which is caused by the thermal depolymerisation
The crystallinity index and the crystalline domain size are of hemicelluloses and the breakdown of glycosidic linkages of cel-
enhanced for the chemo-mechanically treated fibres as shown in lulose (Chirayil et al., 2014). The third stage of degradation is likely
Table 4. to be associated with the main cementing material lignin which
Alkali treatment causes the dissolution of the amorphous hemi- decomposes over a broader temperature range than cellulose and
celluloses and lignin. Their removal helps in realigning a significant hemicelluloses. The DTG of raw fibre shows two broad exothermal
portion of the crystalline domains. The remaining randomly ori- peaks, one at 283 ◦ C and another peak at around 350 ◦ C and goes
ented amorphous regions are easily prone to acid attack. This on till 500 ◦ C. This broader decomposition range of lignin is because
is possible because the hydronium ions can penetrate into the of the presence of various oxygen functional groups from its struc-
amorphous regions promoting the hydrolytic cleavage of glyco- ture with different thermal stabilities and their cleavage occurring
sidic bonds of cellulose and thus releasing individual crystallites (de at different temperatures (Brebu & Vasile, 2010). The degradation
Souza Lima & Borsali, 2004; Park, Baker, Himmel, Parilla, & Johnson, of alkali treated pulp starts at 232 ◦ C and the rate of degradation
2010). This leads to 62% of improvement in crystallinity after the reaches a maximum at 364 ◦ C owing to the decomposition of cellu-
acid hydrolysis. Additionally bleaching finds effective in the elimi- lose where as for acid hydrolysed pulp starts at 262 ◦ C and a peak at
nation of the remaining amorphous constituents and thus giving a 377 ◦ C corresponds to the maximum rate of degradation. The rise
maximum CI of 73%. It is also evident from the intense sharp peak in the onset temperature of degradation of acid hydrolysed pulp is
observed in the XRD pattern. due to the removal of non cellulosic components which makes the
cellulose more dense and compact. The onset of degradation further
4.7. Dynamic light scattering rises in the case of bleached pulp (261 ◦ C) and that of the nanocellu-
lose obtained after homogenization (273 ◦ C). This shift in the onset
Dynamic light scattering is popularly used for the determination degradation temperature from raw fibre to homogenized is because
of size of particles in suspension, emulsions, colloids, polymer etc. in raw fibre the cellulose microfibrils are embedded in the soft
The advantage of this is it allows the particle sizing down to 1 nm matrix consisting of hemicelluloses, lignin and pectin (Chen et al.,
diameter. The water suspended nanocellulose sample was diluted 2011; Mandal & Chakrabarty, 2011). These components can form
 J.C. C.S. et al. / Carbohydrate Polymers 142 (2016) 158–166 165

components from the raw fibre was responsible for observed

increase in cellulose content. The increase in crystallinity to 73%
was confirmed by the XRD analysis. SEM, FE-SEM and TEM showed
the morphology of nanofibrils obtained. An entangled network of
cellulose fibres with a diameter in the range 3–5 nm was seen in
the FE-SEM images. Long nanofibrils with very high aspect ratio
(120–150) was clearly observed in the TEM images. The aspect ratio
of nanofibres obtained is found to be very high compared to that
from other sources. The nanofibres also exhibited enhanced ther-
mal properties. Based on the results, it can be concluded that highly
crystalline and thermally stable cellulose nanofibrils with very high
aspect ratio can be prepared from arecanut husk fibre through
hydrochloric acid hydrolysis followed by mechanical fibrillation.
The cellulose nanofibrils obtained is considered to be a potential
candidate for many industrial applications.

Acknowledgement

We gratefully acknowledge the University Grants Commission,

India for financial support and SAIF-STIC CUSAT for characteriza-
tion. We are thankful to Dr. Sailaja G.S., Dept of Polymer science &
Rubber technology, CUSAT for assistance in TEM characterization.

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