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Effect of Chemical Treatments on

Physicochemical Properties of Prosopis
juliflora Fibers
a b c
S. S. Saravanakumar , A. Kumaravel , T. Nagarajan & I. Ganesh
d
Moorthy
a
Department of Mechanical Engineering , Kamaraj College of
Engineering and Technology , Virudhunagar , Tamil Nadu , India
b
Department of Mechanical Engineering , K.S. Rangasamy College of
Technology , Thiruchengode , Tamil Nadu , India
c
Click for updates Research and Development, Biological E. Limited , Hyderabad ,
Andhra Pradesh , India
d
Department of Biotechnology , Kamaraj College of Engineering and
Technology , Virudhunagar , Tamil Nadu , India
Accepted author version posted online: 25 Mar 2014.Published
online: 16 Jul 2014.

To cite this article: S. S. Saravanakumar , A. Kumaravel , T. Nagarajan & I. Ganesh Moorthy (2014)
Effect of Chemical Treatments on Physicochemical Properties of Prosopis juliflora Fibers, International
Journal of Polymer Analysis and Characterization, 19:5, 383-390, DOI: 10.1080/1023666X.2014.903585

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 International Journal of Polymer Anal. Charact., 19: 383–390, 2014
Copyright # Taylor & Francis Group, LLC
ISSN: 1023-666X print/1563-5341 online
DOI: 10.1080/1023666X.2014.903585

Effect of Chemical Treatments on Physicochemical

Properties of Prosopis juliflora Fibers

S. S. Saravanakumar,1 A. Kumaravel,2 T. Nagarajan,3 and I. Ganesh Moorthy4

1
Department of Mechanical Engineering, Kamaraj College of Engineering and Technology,
Virudhunagar, Tamil Nadu, India
Downloaded by [Innasi Muthu Ganesh Moorthy] at 04:06 24 April 2015

2
Department of Mechanical Engineering, K.S. Rangasamy College of Technology,
Thiruchengode, Tamil Nadu, India
3
Research and Development, Biological E. Limited, Hyderabad, Andhra Pradesh, India
4
Department of Biotechnology, Kamaraj College of Engineering and Technology,
Virudhunagar, Tamil Nadu, India

Incompatibility between hydrophilic natural fibers and hydrophobic matrix is known to affect the
adhesion of the fiber and matrix. Therefore, it becomes necessary to modify the surface of natural
fibers for improved adhesion between the fiber and matrix. Prosopis juliflora fibers (PJFs) are
known to possess desirable properties for use as reinforcement in polymer matrices. Using chemical
analysis, the optimal condition for alkali treatment of the PJFs was found to be 5% (w=v) of NaOH
concentration with 60 min soaking time. Chemical modifications favorably changed the physiochem-
ical properties of PJFs and undoubtedly diminished the amorphous and wax contents.

Keywords: Chemical treatment; Crystallinity index; Prosopis juliflora fiber; Thermal stability

INTRODUCTION

Increased environmental awareness of the general public about reducing carbon footprints and
the use of nonnaturally decomposed solid wastes has resulted in increasing use of biodegradable
natural materials and recyclable polymers and their composites for a wide range of engineering
applications.[1] In recent years, fiber-reinforced polymer composites have become important in
industries and fundamental research.[2] Natural fibers such as hemp, flax, sisal, kenaf, and jute
are highly hydrophilic due to the presence of hydroxyl (OH) groups of anhydroglucose repeating
unit in the cellulose structure. However, these fibers are covered with pectin and waxy materials,
thus hindering the OH groups from reacting with polymer matrices. This can lead to the forma-
tion of deficient interfaces between the fibers and matrices with consequent problems such as

Submitted 12 February 2014; accepted 3 March 2014.

The authors gratefully acknowledge the management of Kamaraj College of Engineering and Technology,
Virudhunagar, Tamil Nadu, India, for providing necessary facilities to carry out this research work.
Correspondence: S. S. Saravanakumar, Department of Mechanical Engineering, Kamaraj College of Engineering and
Technology, Virudhunagar-626001, Tamil Nadu, India. E-mail: sankarameena@yahoo.co.in
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpac.
 384 S. S. SARAVANAKUMAR ET AL.

debonding and voids in composites.[3–5] Interfacial adhesion between the fiber and the matrix
largely determines the mechanical properties of the composites.[6] To enhance interfacial
bonding, many chemical treatments have been successfully explored for natural lignocellulosic
fibers. Alkaline treatment, also known as mercerization, is one of the most common chemical
treatments of cellulosic fibers intended to be used as reinforcement in polymers.[7] Exposing
pre-alkali-treated sisal fibers to permanganate solution resulted in reduced hydrophilicity.[8]
Peroxide treatments induced grafting of polyethylene adhering on the fiber surface and imparted
reduced moisture content and improved thermal stability.[6] Stearic acid (CH3(CH2)16COOH)
in ethyl alcohol solution when used for treating flax fibers caused removal of noncrystalline
constituents of the fibers and reduction of the fiber surface free energy. The treated fibers seemed
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more crystalline than the untreated ones.[9]

The present study is aimed at better understanding the effect of different chemical treatments
on physicochemical properties of Prosopis juliflora fibers (PJFs). Chemical treatments per-
formed using alkali, benzoyl peroxide, potassium permanganate, and stearic acid are discussed.
The chemically modified PJFs were analyzed using several techniques: chemical assays,
Fourier-transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), and thermogravi-
metric analysis (TGA).

MATERIALS AND METHOD

Extraction of PJFs

Bark of the Prosopis juliflora plant was immersed in water to allow microbial degradation for a
maximum period of two weeks during which time the bark degraded sufficiently to enable fiber
extraction. The fibers were isolated from the degraded bark by employing a traditional combing
process with the aid of fine, long metal teeth.[10]

Chemical Modifications of PJFs

Optimally Alkali-Treated PJFs (Optimally APJFs)

The alkali treatment of PJFs involved 5% (w=v) NaOH for 60 min soaking time.[11]

Benzoyl Peroxide–Treated PJF (BPJF)

The optimally APJFs were soaked in 6% benzoyl peroxide in acetone for 30 min. The treated
fibers were then recovered and dried in air for 24 h.[8]

Potassium Permanganate–Treated PJF (PPJF)

The optimally APJFs were soaked in 0.5% potassium permanganate in acetone for 30 min.
The treated fibers were then recovered and dried in air for 24 h.[12]
 CHEMICAL TREATMENTS OF PROSOPIS JULIFLORA FIBERS 385

Stearic Acid–Treated PJF (SPJF)

First, 1% stearic acid was dissolved in ethyl alcohol. The solution was then added dropwise to
the optimally APJFs placed in a stainless steel vessel with continuous stirring. These fibers were
then dried in an oven at 80
C for 45 min.[8]

Characterization of Chemically Modified PJFs

Chemical Constituents and Density Analysis

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The chemical constituents (cellulose and hemicellulose) of raw and various chemically modified
PJFs were determined by employing standard methods.[13,14] Lignin in the fibers was determined
as Klason lignin according to ASTM method D1106-96[15] and moisture content following a
method described elsewhere.[16] Density of the fibers was evaluated employing the meltbertole-
doxsz05 balances method,[17] and its wax content was quantified as per the standard protocol.[18]

Fourier Transform-Infrared (FT-IR) Spectroscopy

FT-IR analysis of the raw and various treated PJFs samples was done using a Shimadzu
FTIR-8400S spectrum spectrometer (Japan). Three grams of powdered PJFs were mixed with
250 mg of potassium bromide (KBr) and compressed into pellets before analysis. The FT-IR
spectra were recorded at wave numbers from 4000 to 400 cm1 resolution with an average of
32 scans; each spectrum has a regime in the transmittance mode as a function of wave number.

X-ray Diffraction (XRD) Analysis

Wide-angle X-ray diffraction patterns were determined using a X’pert PRO-PANalytical

spectrometer and diffraction intensity of Cu Ka radiation wavelength of 0.1542 nm over
the range of 10
 2h  80
. The crystallinity index (CI) was estimated using the following
expression:
H22:67  H18:12
CI ¼ ð1Þ
H22:67
where H22.67 is the height of the peak at 2h ¼ 22.67, which is contributed by the crystalline
fractions, and H18.12 is the diffracted intensity at 2h ¼ 18.12 and is attributed to the amorphous
fraction.[19]

Thermogravimetric Analysis

Thermal degradation was observed in terms of global weight loss using a Jupiter simul-
taneous thermal analyzer (model STA 449 F3, Netzsch, Germany). High-purity nitrogen gas
was continuously passed into the furnace at a flow rate of 20 mL=min. All the measurements
were made with an alumina crucible in a programmed temperature range from 10
to 500
C
at a heating rate of 10
C=min.
 386 S. S. SARAVANAKUMAR ET AL.

RESULTS AND DISCUSSION

Chemical Properties of Modified PJFs

The principal chemical constituents of the natural fiber cell walls are embedded with semicrys-
talline polysaccharides of cellulose, branched amorphous polymers of hemicellulose, and highly
complex aromatic structures of lignin. The chemical compositions of modified and raw PJFs are
listed in Table I. The raw and various chemically modified PJFs were found to contain levels of
cellulose in the order: SPJF > BPJF > PPJF > optimally APJF > raw. The improved cellulose
content and diminished amorphous (hemicellulose and lignin) content and higher moisture
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resistance properties in all the modified PJFs resulted in a tendency to highly packed crystalline
order. Relatively higher density of the modified PJFs than the raw fibers could be due to
(i) densification of walls of fiber as a result of the removal of impurities (less dense fats and
waxes) by solvents and (ii) filling of the pores with grafted molecules.[20]

FT-IR Study of Modified PJFs

The typical functional groups of the raw and modified PJFs in the form of infrared spectra are
shown in Figure 1. The hydrophilicity of raw and modified PJFs is evidenced by broad absorption
bands in the 3700–3100 cm1 region, which is associated with the –OH stretching of a-cellulose.
The intensity peak at 2850 cm1, attributed to C–H (aldehyde), and the noticeable peak at
2355 cm1 are seen only in raw PJF and disappeared in the spectra of all the modified PJFs that
are exemplified by CC stretching (wax).[11] A peak signal at 1734 cm1 in the raw fiber is due to
the acetal and uronic ester groups of the hemicellulose.[21] The noticeable peak at 1734 cm1,
which is the most evident in the diminished region of hemicellulose in each spectra, could be
due to the chemical modifications. Two gradually decreasing peaks in all the modified PJFs
observed at 1635 and 1508 cm1 correspond to C=C stretching of lignin and C=C aromatic sym-
metrical stretching. An absorption peak at 1429 cm1 was assigned to CH in plane deformation
with aromatic ring stretching. However, the band region at 1381 to 1373 cm1 suggested CH
bending of lignin, and the peak at 1313 cm1 represented CH2 wagging. A sharply decreasing
peak noticed in the modified PJFs spectrum at 1255 cm1 indicates the CH bending of hemicel-
lulose. This perfect peak, seen only for the modified PJFs, shows leaching of hemicellulose. The
two peaks at 1157 and 1109 cm1 can be ascribed to asymmetric C–O–C stretching of lignin, and

TABLE I
Chemical composition of raw and chemically modified PJFs

Cellulose Hemicellulose Lignin Wax Moisture Density

Fiber (wt.%) (wt.%) (wt.%) (wt.%) content (wt.%) (g=cm3) Reference

Raw 61.65 16.14 17.11 0.61 9.48 0.580 [10]

Optimally APJF 72.27 4.02 12.09 0.10 6.36 0.648 [11]
BPJF 82.09 2.6 9.12 0.07 4.67 0.921 —
PPJF 78.84 3.32 11.67 0.09 5.88 0.744 —
SPJF 82.16 2.3 9.06 0.06 4.61 0.933 —
 CHEMICAL TREATMENTS OF PROSOPIS JULIFLORA FIBERS 387
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FIGURE 1 FT-IR spectra of raw and chemically modified PJFs.

the strong vibration peak at 1051 cm1 is attributed to symmetric CO stretching of lignin. The
spectrum peak at 896 cm1 represented b-glycosidic linkages between the monosaccharides.
The peaks in each spectrum at 2355, 1734, and 1508 cm1 strongly confirmed the reduction of
wax, hemicellulose, and lignin contents caused by the chemical modifications of PJFs.

FIGURE 2 X-ray diffractograms of raw and chemically modified PJFs.

 388 S. S. SARAVANAKUMAR ET AL.
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FIGURE 3 (a) TG curves of raw and chemically modified PJFs; (b) DTG curves of raw and chemically modified PJFs.

Crystal Structure of Modified PJFs

X-ray diffractograms, as illustrated in Figure 2, were used to investigate the crystallinity of modi-
fied PJFs. The noticeable major crystalline peak for various treated PJFs occurred at 2h ¼ 22.67
,
and well-defined peaks present at 2h ¼ 15.07
and 2h ¼ 16.9
corresponded to the typical diffrac-
tion of cellulose-I. The minimum intensity peaks were observed at 2h ¼ 18.12
. However, the fiber
contains a higher percentage of amorphous fraction (lignin, pectins, hemicellulose, and amorphous
cellulose). The CI values of the raw and various treated PJFs as evaluated by Equation (1) are in the
 CHEMICAL TREATMENTS OF PROSOPIS JULIFLORA FIBERS 389

order: SPJF (88.70%) > BPJF (87.43%) > PPJF (74.67%) > optimally APJF (73%) > raw PJF
(46%). This order suggests improved CI mainly due to two reasons. First, the treatments may have
caused removal of some of the hemicellulose and noncrystalline region of the fiber, thereby
increasing the presence of relatively crystalline cellulose. Second, there may be a rearrangement
of the crystalline regions in such a way that the fiber acquires a more crystalline nature.[22]

Thermal Stability of Modified PJFs

Thermogravimetric performance of various modified PJFs is shown in TG and DTG curves

(Figure 3). Typically, two main stages of degradation were observed in all the chemically modi-
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fied and raw PJFs. The initial degradation noticed between 32
and 100
C could be due to the
evaporation of moisture from the fiber, and the second major degradation proceeded from about
220
to 400
C. The temperature region of 220
–300
C is related to thermal depolymerization of
hemicellulose with different weight losses of SPJF (9.45%), BPJF (11.32%), PPJF (10.94%),
optimally APJF (13.72%), and raw PJF (16.54%). The strong promising peaks at 332.2
C,
351.4
, 357.2
, 363
, and 365.3
indicate the depolymerization of cellulose with corresponding
weight losses of raw PJF (38.58%), optimally treated PJF (40.85%), PPJF (42.32%), BPJF
(45.22%), and SPJF (47.31%), respectively. The crystalline structure contained strong intramol-
ecular and intermolecular hydrogen bonding, which requires higher energies to break down.[23]
Moreover, all chemical modifications resulted in thermal stability of PJFs in the order: SPJF
(10%) > BPJF (9.27%) > PPJF (7.52%) > optimally APJF (5.77%) in comparison to raw PJFs,
which could be due to retention and improvement of the structural order and reduction in the
amorphous content. In general, lignin degradation takes place over a broader temperature range
of 200
to 500
C. The weak bonds break at the temperature range from 200
to 300
C, whereas
at higher temperatures the cleavage of strong bonds in aromatic rings occurs.[24] However, the
residue at 500
C was marginally higher in the chemically modified PJFs than the raw PJFs.
Taken together, these findings clearly show that chemically modified PJFs can preferably be
used as reinforcement in polymer matrices whose processing temperature is below 250
C.

CONCLUSIONS

In this preliminary study, PJFs were chemically modified by alkali, benzoyl peroxide, potassium,
permanganate, and stearic acid treatment to reduce hydrophilicity, which may improve the
adhesion between the fiber and matrix. The chemical treatments effectively influenced and
enhanced the physicochemical properties of PJFs through improvement of CI, higher thermal
stability, and removal of wax and cementing materials (hemicellulose and lignin). It is evident
from the results that SPJF has superior physicochemical properties to the others. In conclusion,
the improved properties of PJFs make them potential reinforcement for polymer matrices in
composite structures.

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