J Polym Environ (2012) 20:361–371
DOI 10.1007/s10924-011-0370-9
ORIGINAL PAPER
A Study on Benzoylation and Graft Copolymerization
of Lignocellulosic Cannabis indica Fiber
A. S. Singha • Ashvinder K. Rana
Published online: 28 October 2011
Ó Springer Science+Business Media, LLC 2011
Abstract Present work deals with the surface modifica-
tion of Cannabis indica fiber through benzoylation and
graft copolymerization of acrylonitrile (AN) onto C. indica
fibers under the influence of microwave radiations. The
Benzoylation of C. indica fiber was carried out by treating
raw fiber with varying concentrations of benzoyl chloride
solution. Different reaction parameters for graft copoly-
merization, such as reaction time, initiator concentration,
nitric acid concentration, pH and monomer concentration
were optimized to get the maximum percentage of grafting
(25.54%). A suitable mechanism to explain benzoylation
and graft copolymerization has been also proposed. Raw C.
indica fiber, graft copolymerized and benzoylated fibers
were subjected to evaluation of some of their properties
like swelling behavior, moisture absorbance and resistance
towards chemicals. Cannabis indica fibers treated with 5%
benzoyl chloride solution and AN graft copolymerized
fibers have been found to show more resistant towards
moisture, water and chemicals when compared with that of
untreated fibers. Morphological, structural changes, ther-
mal stability and crystallanity of raw, graft copolymerized
and benzoylated fibers have also been studied by SEM,
FTIR, TGA and XRD techniques. It has been observed that
the crystallinity of fiber decreases but thermal stability
increases on surface modification.
Keywords Benzoylation  Crystallinity 
Thermal stability  Microwave radiation
A. S. Singha (&)  A. K. Rana
Applied Chemistry Research Laboratory,
Department of Chemistry, National Institute of Technology,
Hamirpur 177005, Himachal Pradesh, India
e-mail: assingha@gmail.com
Introduction
Over the last few years, world has turned its attention
towards renewable and sustainable resources. This trend
has resulted not only in the utilization of alternative
shaping processes or the property design of the cellulose
derivatives, but also the utilization of the new cellulose
sources. The rapidly increasing environmental awareness,
growing global waste problem, geometrically increasing
crude oil prices and high processing cost trigger the
development concepts of sustainability and reconsideration
of renewable sources. Natural fibers have already estab-
lished a record of accomplishment as reinforcing material
in automotive parts. Plant fiber reinforced polymer com-
posites have attracted more and more research interests
owing to their potential of serving as alternative for arti-
ficial fiber composites [1–3]. The availability, renewability,
low density, price and satisfactory mechanical properties
make the natural fibers an attractive ecological alternative
to glass, carbon and other manmade fibers used for the
manufacturing of the composites [4, 5]. However, hydro-
philic natures of hydroxyl groups present on cellulose
molecules hamper the application of native cellulosic fibers
as tailored material. This has resulted in increased demand
for the surface modification of natural cellulosic fibers in
order to reduce their hydrophilic character and thus
increasing compatibility between fibers and polymer
matrices. A variety of physical (Corona, cold plasma) and
chemical treatments for surface modification have been
reported in literature [6–8]. Different chemical treatments
include dewaxing, mercerization, acetylation, Benzoyla-
tion, silanation, cyanoethylation and graft copolymeriza-
tion. Among various methods for surface modification of
cellulosic fibers graft copolymerization is an attractive
method to impart a variety of functional groups on the
123
362
polymer backbone [9–14]. Vinyl monomers have great
potential to graft onto cellulose fiber using different sys-
tems i.e., chemical, ionic and radical initiators. Among
these initiation systems the chemical initiation of the
grafting involving oxidizing agents such as KMnO4,
Na2S2O3, Ce(IV), V(V) etc. are promising from the eco-
nomic point of view [15–18]. In comparison to conven-
tional techniques of grafting, the microwave radiation
induced grafting is one of the efficient methods for graft
copolymerization of vinyl monomers as it not only con-
sume less time but also causes minor change in the texture
of the fiber [19]. Different researchers have studied ben-
zoylation and grafting of vinyl monomers reactions onto
natural fibers and reported increase in thermal, moisture,
chemical resistance behavior and better interlocking
between the fibers and matrices [10, 14, 20–22].
Cannabis indica fibers collected from higher reaches of
the Himalayan Region have been found to contain
approximately 68% cellulose. Traditionally this fibrous
material belonging to Himalayan region has been used by
local people for making low cost articles like ropes, bags,
socks, boots, mats, etc. C. indica is a short plant, usually
less than 6 ft in height but rarely over 8 ft and is found in
India, Pakistan, Afganistan and other surrounding South
Asian countries. Literature survey has revealed that not
much work has been done on benzoylation and graft
copolymerization of the C. indica fiber [23, 24].
The specific objective of the present investigation is to
study the effect of Benzoylation and graft copolymeriza-
tion onto C. indica fiber on physico-chemical behavior and
crystallinity properties of fibers so that these fibers could be
used for various industrial applications including synthesis
of bio-composites.
Experimental
Cannabis indica fibers were at first washed thoroughly with
2% detergent solution and then dried in a hot air oven at
70 °C for 24 h. The dried fibers were designated as
untreated fibers. Then these fibers were further subjected to
soxhlet extraction with acetone for 72 h followed by
washing with double distilled water and air drying to
remove waxes and other water soluble impurities prior to
various chemical treatments.
Materials
Acrylonitrile (AN) was purified by initially washing with
5% sodium hydroxide and then drying over anhydrous
Na2SO4. Finally it was subjected to distillation and the
middle fraction of distillate was used for further studies.
Ceric ammonium nitrate (CAN) obtained from Merck
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J Polym Environ (2012) 20:361–371
chemicals was used as initiator. Weighing of the samples
was done on Libror AEG-220 (Shimadzu) electronic bal-
ance. Humidity chamber of Swastika make was used to
study the moisture absorbance behavior of the graft
copolymers.
Surface Modification of Fiber
The surface modification of C. indica fibers was carried
through the following chemical treatments:
Benzoylation
Fibers were pretreated with10% (w/v) NaOH solution for
210 min in order to activate the OH groups of cellulose and
lignin in the fiber. The fibers were then washed several
times with distilled water to remove any traces of NaOH
sticking to the fiber surface, neutralized with dilute acetic
acid and finally washed again with distilled water. The
fibers were then dried at room temperature for 48 h fol-
lowed by oven drying at 70 °C to a constant weight. One
gram of pretreated fiber was suspended in 100 mL of 10%
NaOH solution and agitated well with different benzoyl
chloride concentrations (1, 2, 3, 5, 7 and 9%) for
10–15 min, followed by filtration, washing thoroughly with
water and finally drying between the folds of filter papers.
The isolated fibers were then soaked in ethanol for 1 h to
remove any unreacted benzoyl chloride and finally washed
with distilled water and then dried.
Graft Copolymerization of AN
Activation of the C. indica fiber was done by immersing it
in 100 mL of distilled water at room temperature for 24 h
prior to carrying out graft copolymerization. Grafting was
then carried out under the influence of microwave radia-
tions in a microwave oven at 110 W microwave power. A
known amount of the CAN (2.27 9 10-2 mol L-1) and
nitric acid (2.88 9 10-2 mol L-1) was added to the reac-
tion mixture followed by addition of the monomer
(3.05 9 10-1 mol L-1) with continuous stirring of the
reaction mixture. The reaction flask was then put in the
microwave oven for a definite period of time. Optimum
conditions of time, pH, CAN concentration, nitric acid and
monomer concentration were worked out so as to get
maximum graft yield (25.54%). Homo-polymer formed
during the graft copolymerization was removed by
extraction with dimethylformamide (DMF). The grafted
samples were dried in a hot air oven at 60 °C to a constant
weight. The amount of graft added onto the fiber was
determined gravimetrically. The percent grafting (Pg) and
percent efficiency (Pe) were then calculated as per the
following methods.
J Polym Environ (2012) 20:361–371
Wg  W
% Grafting Pg ¼  100
W fiber.
Wg  W
% Efficiency Pe ¼  100
Wm
where W is the weight of raw fiber, Wg is the weight of
grafted fiber, Wm is weight of monomer.
Evaluation of Physical and Chemical Properties
Chemical Resistance
The chemical resistance of raw and grafted fiber was
studied as a function of percent weight loss of fiber when
treated with different chemicals. A known amount (Wi) of
raw and grafted fiber was treated with a definite volume of
hydrochloric acid and sodium hydroxide of different
strengths for a time interval of 24 h. The fibers were then
washed 2–3 times with distilled water and finally dried in
oven at 70 °C to a constant weight to get the final weight
(Wf). The percent weight loss was determined by using the
following formula:
Wi  Wf
% Wt:loss ¼  100
Wi
Swelling Behavior
The swelling behavior of the raw and surface modified
samples of C. indica fiber was studied in different solvents
such as water, butanol, dimethyl formamide and carbon
tetra chloride. Dry samples of grafted as well as raw fibers
(1.0 g) were suspended in 100 mL of the solvents kept at
35 °C for 24 h. The solvent that adhered on the surface of
the samples was removed by softly pressing between the
folds of the filter paper. The samples were then weighed to
get the final weight. The percent swelling was calculated
by using the following relationship:
Wf  Wi
% Swelling ¼  100
Wi
where Wi = initial weight of the dried fiber and Wf = final
weight after the swelling.
Moisture Absorption
The moisture absorption study of grafted as well as raw
fiber was performed at different humidity levels ranging
from 20 to 80% for a fixed time period of 2 h. The percent
moisture absorption was studied as a function of weight
gain and was calculated using the following formula:
Wf  Wi
% Moisture absorbance (Mabs) ¼  100
Wi
363
where Wf and Wi are the final and initial weights of the
Crystallinity Index (C.I)
Crystallanity index (C.I) was determined by using the wide
angle X-ray diffraction counts at 2h angle close to 22° and
15°. The counter reading of peak intensity close to 22° and
15° is said to represent the crystalline and amorphous
contents in cellulose, respectively. Percent crystallinity and
crystallinity index (C.I) were calculated using the follow-
ing equation [25].
IC
% Cr ¼  100
IC þ IA
IC  IA
C:I ¼
IC
where IC and IA are the crystalline and amorphous inten-
sities at 2h scale close to 22° and 15° angles.
Results and Discussion
Benzoylation of Cannabis Indica Fiber
Benzoylation is the introduction of the aryl radical
(C6H5CO.) into a molecule. Benzoyl chloride is most often
used for this purpose. C. indica fibers were mercerized first
in order to activate the hydroxyl groups of cellulose and
lignin [26, 27]. Mercerized fibers were then well agitated
with benzoyl chloride in NaOH solution. This treatment
helps in replacing hydroxyl groups of the cellulosic fibres
with benzoyl groups and makes them hydrophobic in nat-
ure. The reaction between the hydroxyl group of the fiber
and benzoyl chloride is shown in Eq. 1 and 2 [28].
Graft Copolymerization of Cannabis Indica Fiber
with AN
Grafting reaction proceeds through redox mechanism in
which Ce(IV) ions are reduced to Ce(III) ions by the
transfer of electron from the cellulose molecules. This
creates active sites on the polymeric backbone which are
then attacked by monomer radicals.
Ceric ions form complexes with the carbon chain of
polymer backbone as well as monomer chains and generate
free radicals (Eq. 3, 4). Free radicals then result in the
formation of graft copolymer [CIC-g-poly (AN)] as per the
reaction sequence given (Eq. 5, 6). Monomer free radicals
also combine with more monomer molecules to form
homopolymer [poly (AN)] free radicals (Eq. 7), which
further react with the cellulose chain to form homopolymer
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364 J Polym Environ (2012) 20:361–371

and CI free radicals (Eq. 8). On the other hand the ceric ion Pg
combines with the free radical to form a stable poly (AN) Pe 5
28
(Eq. 10) chain as well as CIC-g-poly(AN) (Eq. 9) and 4
terminates the polymerization process. 23
3

Pe
Pg
18
2
Effect of Time 13 1

The graft copolymerization has been recorded at different 8 0

timings ranging from 5 to 30 min at 110 W power under
definite concentrations of ceric ammonium nitrate
(2.27 9 10-2 mol L-1), AN (3.05 9 10-1 mol L-1), and
nitric acid (2.88 9 10-2 mol L-1) (Fig. 1). Initially the Pg
increased with the increases in time up to 15 min. but
then decreased with the further increase in reaction time.
This probably happens due to the generation of more and
more monomer radicals with increase in time which
interacts with the active sites on the polymeric backbone
resulting in increased in Pg. Grafting in the presence of
MWR took lesser time because of passage of electro-
magnetic wave in solution, which oscillates speed of
molecules. But after the optimized value further increase
in the reaction time, Pg decreases due to the availability
of lesser number of the reactive sites for grafting. It may
also due to the mutual destruction of growing polymeric
chains leading to homo polymerization at the exposure of
grafting.
Effect of Nitric Acid
Figure 2 shows the effect of nitric acid concentration on
grafting parameters. It can be seen that Pg increased sig-
nificantly with the increase in nitric acid concentration up
to acid concentration of 2.88 9 10-2 mol L-1. However,
Pg decreased with the further increase in nitric acid con-
centration probably due to hydrolysis of the fiber and early
degeneration of the radicals.
1 2 3 4 5
[HNO3]X10-2 (mol L-1)
Fig. 2 Effect of nitric acid concentration on Pg and Pe. [CAN]:
2.27 9 10-2 mol L-1; [AN]: 3.05 9 10-1 mol L-1; Power: 110 W;
Time: 15 min; pH: 7
Effect of Initiator
From Fig. 3 it can be established that Pg increased with the
increase in CAN concentration up to 2.73 9 10-2 mol L-1
at constant concentration of monomer (3.05 9 10-1 mol
L-1) and nitric acid (2.88 9 10-2 mol L-1), and after that
Pg showed a decreasing trend. This behavior can be
explained by the logic that increase in CAN concentration
will result in generation of more free radical sites on the
polymeric backbone, which may lead to increased Pg.
However, with further increase in CAN concentration, it
accelerates the dissociation rate of Ce(IV), which reduces
the concentration of CAN participating in graft copoly-
merization and hence low graft yield.
Effect of pH
With increase in pH of the reaction medium, Pg increases
up to pH of 7, but beyond pH 7 there is a decrease in the
graft yield as depicted in Fig. 4. This may be due to the fact
that at higher pH the OH radical are generated in basic
medium which combine with the backbone free radicals to
terminate the chain reaction.

30 5
Pg 22 Pg 7
25 Pe 4 Pe
20 6
20 18
3 5
Pg

Pe

Pg

15
Pe

16
2 4
10 14

5 1 12 3

0 0 10 2
0 5 10 15 20 25 30 35 0.6 1.6 2.6 3.6 4.6
Time (min) [CAN]X10-2 (mol L-1 )

Fig. 1 Effect of time on Pg and Pe. [CAN]: 2.27 9 10-2 mol L-1; Fig. 3 Effect of CAN concentration on Pg and Pe. [HNO3]:
[HNO3]: 2.88 9 10-2 mol L-1; [AN]: 3.05 9 10-1 mol L-1; Power: 2.88 9 10-2 mol L-1; [AN]: 3.05 9 10-1 mol L-1; Power: 110 W;
110 W; pH: 7 Time: 15 min; pH: 7

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J Polym Environ (2012) 20:361–371 365

Pg 9
H2 O [ C2 H5 OH [ DMF [ CCl4
26
Pe
7
21 A high percent swelling in water is expected because
Pg

Pe
16 5 water enters into hydrogen bonding with the hydroxyl
11 3
6 1
4 6 8 10 12
pH
Fig. 4 Effect of pH on Pg and Pe. [HNO3]: 2.88 9 10-2 mol L-1;
[CAN]: 2.73 9 10-2 mol L-1; [AN]: 3.05 9 10-1 mol L-1; Power:
110 W; Time: 15 min
Effect of Monomer Concentration
Figure 5 shows the effect of monomer (AN) concentration
on various grafting parameters. It can be established from
the figure that Pg increased with increase in AN concen-
tration up to 4.27 9 10-1 mol L-1 and after that Pg showed
a decreasing trend. The above behavior of the monomer
concentration may be explained on the basis that initially
more and more free radicals reach onto the polymeric
backbone, resulting increase in Pg. However, with further
increase in the monomer concentration, Pg decreases due to
increase in the viscosity of the reaction medium and lesser
availability of active sites on polymer backbone which led
to homo-polymerization.
Physical and Chemical Properties
Swelling Behavior
The percent swelling of raw, benzoylated and grafted
C. indica fibers in different solvents such as water, meth-
anol, DMF and carbon tetrachloride at temperature 35 °C
was studied as a function of the percentage of grafting and
results are depicted in Figs. 6 and 7. The following order of
different solvents toward the swelling of the raw C. indica
fiber was observed.
30 12
25 10
20
8 Water
Pg
groups of the C. indica fiber. Amorphous region of the fiber
is generally responsible for H-bonding where hydroxyls
group are exposed to such kind of interactions. The
dielectric constant values of different solvents also have the
great effect on the swelling behavior of the fiber. As
regards the dielectric constants, the order of the solvents
studied is as follow:
H2 O [ DMF [ C2 H5 OH [ CCl4
ðe ¼ 78:35Þ ðe ¼ 36:71Þ ðe ¼ 24:30Þ ðe ¼ 2:24Þ
Water having a higher e value easily enters into the
H-bonding with the fiber leading to maximum swelling.
DMF, although it is an aprotic solvent, is polar with high e,
interacts with the hydroxyl groups of the fiber lead to
substantial increase in percentage swelling. In case of
carbon tetra chloride which has a lower e = 2.24, a lower
percentage of swelling has been observed.
The percent swelling of the C. indica-g-poly(AN) in
different solvents varies as a function of maximum grafting
and follow the trend: DMF [ H2O [ CCl4 [ C2H5OH
(Fig. 6). In case of the grafted fiber, the reverse swelling
trend has been found in various solvents when compared
with that of raw fiber. This happens due to increase in
hydrophobicity of fiber on account of the blockage of the
hydroxyls groups (active sites) by poly acrylonitrile chains.
Higher percent swelling in the case of the DMF occurs by
solvolysis of grafted fiber in DMF due to its dipolar aprotic
nature as comparison to water and ethanol. Percent swell-
ing of the C. indica-g-poly (AN) with carbon tetrachloride
increases as a function of Pg because of the development of
the hydrophobic character on the polymeric backbone.
In case of benzoylated fiber decrease in swelling with
polar solvent and increase with the non polar solvents
has been observed. Further 5% benzoyl chloride treated
C. indica fiber showed maximum hydrophobic charac-
ter which could be due to maximum penetration of
120

Pe

15 100
% Swelling

6 butanol
10 80
Pg
5 4 60 DMF
Pe
0 2 40
Carbon
2 3 4 5 6 20 tetra chloride
-1 -1
[AN]X10 (mol L ) 0
0 10 20 30
Fig. 5 Effect of monomer concentration on Pg and Pe. [HNO3]: Pg
2.88 9 10-2 mol L-1; [CAN]: 2.73 9 10-2 mol L-1; Power: 110 W;
Time: 15 min; pH: 7 Fig. 6 Effect of Pg on swelling against different solvents

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366 J Polym Environ (2012) 20:361–371

120 14
Water
100
12
% Swelling

% Weight loss
butanol
80
10
60 DMF
40 Carbon tetra 8 0.5 N
20 chloride
6 1.0 N
0
0 2 4 6 8 10 4
% Benzoyl chloride treated fiber 0 5 10 15 20 25 30
Pg
Fig. 7 Effect of percent Benzoylation on swelling behavior behavior
against different solvents Fig. 9 Effect of Pg on resistance to acid

the benzoyl groups into fiber pores and resulting in
mechanical interlocked coating on the fiber surface. With
further increase in benzoyl chloride concentration beyond
5% a decrease in the hydrophobic character has been
observed. This could be due to increase in the viscosity
of reaction medium which may cause hindrance in the
penetration of benzoyl molecules and lesser availability
of active sites for penetration onto cellulosic backbone.
From the above discussion it is clear that grafting results
in decrease in the hydrophilic character of lignocellulosic
fibers, and thus may lead to fabrication of natural fiber
reinforced biodegradable composites with good mechan-
ical properties.
Chemical Resistance
The chemical resistance has been studied in terms of
weight loss of the fiber with dilute solutions of strong acids
and bases. The effect of acid (HCl) and the base (NaOH)
was studied by keeping the raw, benzoylated and AN graft
copolymerized fibers in acid or base for a period of 24 h
and the result obtained showed the same trend in case of
AN graft copolymerized fibers. It is clear from the Figs. 8
and 9 that with increase in Pg the weight loss of the fiber
decrease and the minimum weight loss was found at high
Pg (25.54%). This probably could be due to the fact that
with the increase in the Pg the active sites on fiber
backbone which are prone to attack got blocked and hence
showed maximum resistance.
From Fig. 10 it is also evident that chemical resistance
behavior of benzoylated fiber with base decreases initially
with increase in benzoyl chloride concentration in the
reaction mixture. Further maximum weight loss was found
at 5% benzoyl chloride concentration. This probably could
be due to the formation of corresponding sodium salt
(hydrolysis of ester). But increase in concentration beyond
5% led to decrease in % weight loss. This could be
explained on the same basis as discussed in ‘‘Swelling
Behavior’’. It has also been observed that the benzoylated
fiber shows maximum resistance towards the action of acid
as compared to that of base (Fig. 11).
Moisture Absorption
Raw C. indica fibers absorb maximum moisture due to
affinity of –OH groups on cellulosic backbone with water.
However, moisture absorbance has been found to decrease
upon acrylonitrile graft copolymerization and benzoylation
of C. indica fiber (Figs. 12, 13). It has been also found that
moisture absorbance decreases with increase in Pg. Further
among 1, 2, 3, 5, 7 and 9% treated fiber, 5% benzoylated
fiber showed best result. These results can also be
explained on the same basis as discussed above in
‘‘Chemical Resistance’’.

16
14
% Weight loss

25
% Weight loss

12 20
10 15
0.5 N 10
8 0.5 N
1.0N 5
6 1.0N
0
4 0 2 4 6 8 10
0 5 10 15 20 25 30 % Benzoyl chloride treated fiber
Pg
Fig. 10 Effect of %benzoyl chloride treated fiber on resistance to
Fig. 8 Effect of Pg on resistance to base base

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J Polym Environ (2012) 20:361–371 367

14 stretching vibration and CH stretching vibrations were

12 obtained. The band near 1252.1 cm-1 is due to –C–O–C–

% Weight loss
10 bond in cellulose chain. The peak near 900 cm-1 which is
8 characteristics of b-linkages also was obtained.
6 From Fig. 14b it is evident that strong band around
0.5 N
4
1.0 N
1735.1 cm-1 and 1252 cm-1 disappears when C. indica
2 fiber is pretreated with dilute NaOH solution. These
0 changes occur due to the removal of the waxy epidermal
0 2 4 6 8 10
% Benzoyl chloride treated fiber tissues, substational portion of uranic acid, lignins, adhe-
sive pectins and hemicelluloses that bind fiber bundles to
Fig. 11 Effect of %benzoyl chloride treated fiber on resistance to each other and to the pectins and hemicelluloses rich sheet
acid
core. The peak at 1,735 is assigned to carbonyl group of
pectins, while the peak at 1,252 is assigned to –C–O–C–
and –C=O stretching in xylan side substituent and lignin
4 aromatic C=O stretching.
%Moisture absorbance

3.5 In case of FTIR study on benzoylated fiber (Fig. 14c), it

is observed that hydroxyl vibration adsorption at 3395.9
3
20%
decreased due to the esterification of hydroxyl group.
2.5 The ester group is identified by presence of peaks at
40%
2 1727.6 cm-1 and 1275.9 cm-1, while absorption bands
1.5
60% obtained at 1,600 cm-1 and 709.5 cm-1 were assigned to
80% aromatic rings. However, in the FTIR spectra of C. indica–
1
0 5 10 15 20 25 30 g–poly (AN) additional characteristic absorption band at
Pg 2244.1 cm-1 has been obtained due to the presence of
nitrile group in the grafted structure (14d). A band with
Fig. 12 Effect of AN graft copolymerization on moisture absorbance increased intensity at 2922.9 characteristic for –CH2 group
behavior at different humidity levels
was also observed.

Morphological Studies
% Moisture Absorbance

4
3.5
3 pretreated, benzoylated and grafted C. indica fibers were
2.5
2
1.5
1 80%
0 2
% Benzoyl chloride treated fiber
Fig. 13 Effect of % benzoylation on moisture absorbance behavior at
different humidity levels
FTIR Analysis
IR spectra of raw, pretreated, benzoylated and AN graft
copolymerized C. indica fibers were recorded with KBr
pellets on PERKIN ELMER RXI Spectrophotometer and
the results are shown in Fig. 14a–d. The IR absorptions
peaks and its relation to various functional groups in the
constituents of the fibers are shown in Table 1. For
untreated fiber, strong peaks at 3395.9 cm-1 and
2922.3 cm-1 characteristics of hydrogen bonded –OH
Scanning electron microscopic (SEM) studies of raw,
20%
carried out on a LEO 435 VP electron microscope and
40% results are shown in Fig. 15a–d. Prior to conduct SEM
60% studies all the samples were gold plated in order to make
them conducting. Scanning was synchronized with micro-
4 6 8 10 scopic beam for the maintenance of small size over large
distance relative to the specimen. All the images were
taken at a resolution of 1,0009. From these figures it has
been observed that untreated fibers contain micro fibril
aggregates. The untreated fiber surface also showed the
presence of oil and waxy substances. Treatment of the
fibers with alkali (Pretreated fiber) causes dissolution and
swelling of fiber. The fiber surface showed more fibrillation
because of the removal of lignin, waxes and hemicelluloses
during alkali treatment of the fibers as shown in the SEM
micrograph 15b. However, after benzoylation surface
morphology is not clear because of grafting of benzoyl
molecules onto polymer backbone. Further comparison of
the scanning electron micrographs of the raw and acrylo-
nitrile grafted C. indica fiber clearly showed that the chains
of polymeric AN have been grafted onto C. indica fiber.

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Fig. 14 FTIR spectrum of

(a) raw (b) pretreated and
(c) Benzoyl chloride treated and
(d) AN graft copolymerized
Cannabis indica fiber

Table 1 Peak position and assignment of chemical groups in the were conducted on a TGA with auto sampler (Mettler
raw, pretreated, benzoylated and Cannabis indica-g-poly(AN) fiber Toledo) analyzer at a heating rate of 15 °C/min. Thermo-
Wavenumber Functional group grams were recorded over a temperature range of 0 °–
cm-1 900 °C under nitrogen atmosphere with the flow rate of
20 mL/min. Thermal behavior of raw, pretreated, benzoy-
3395.9 OH stretching
lated and AN graft copolymerized C. indica fiber were
2922.3 C–Hn symmetric and asymmetric stretching
vibrations
studied as a function of % weight residue with increase in
temperature (Fig. 16). In case of raw fiber, weight loss
1733.1 Carbonyl group of pectins
between 60 and 120 °C occurs due to the heat of vapori-
1635 C=O stretching mainly ketones and estors
zation of water in the sample. The second weight loss at
1429.3 C=C stretching
about 330 °C is due to depolymerization of hemicelluloses
1,063 and CH bending
1,169 and cleavages of glucosidic linkages of cellulose [29]. The
1,252 –C–O–C– and –C=O stretching in xylan side third weight loss at about 460 °C may be due to further
substituent and lignin aromatic C=O stretching decomposition of the product of stage II leading to for-
1,000–1,500 C–O-C stretching aromatic region related to mation of tar through levoglucosan [30]. Some of the
lignin. results of TG analysis for raw, pretreated, benzoylated and
2244.1 cm-1 Nitrile group (-CN) stretching AN graft copolymerized C. indica fiber are summarized in
1727.6 and Ester group Table 2. For raw fibers, the initial decomposition temper-
1275.9 ature (IDT) has been found to be 256.33 °C (6.91% weight
1,600 and Aromatic rings loss) and final decomposition temperature (FDT) to be
709.5
383.25 °C (61.12% weight loss). For pretreated fibers the
value of IDT and FDT were 223.76 °–395.95 °C, respec-
tively. In case of benzoylated fiber the IDTand FDT were
Thermal Analysis found to be 236.15 °–394.1 °C respectively. From the
above data it is establish that there is decrease in the
Thermogravimetric analysis (TGA) of the raw, pretreated, thermal stability of benzoylated fiber in comparison to raw
benzoylated and AN graft copolymerized C. indica fiber fiber but slightly more stable as compared to pretreated

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J Polym Environ (2012) 20:361–371 369

Fig. 15 Surface morphology of raw, pretreated, benzoylated and Cannabis indica-g-poly(AN) fibers. a Raw b Pretraeted c Benzoylated
d Cannabis indica-g-poly(AN)

120 Table 2 Thermal analysis of the raw, pretreated, benzoylated and

AN-g-poly-Cannabis indica fibers
100
Sr. Sample IDT FDT DT DT Residual
% Residue

80
no designation (°C) (°C) (°C) at (°C) at weight
60 20% 60% (%) at
wt loss wt loss 600°C
40
1 Raw 250.33 383.25 329.61 383.25 27.04
20
Cannabis
0 indica fiber
0 200 400 600 800 1000 2 Pretreated 223.76 395.95 329.61 382.25 1.19
Temp in degree celsius fiber
Grafted fiber Raw fiber Pretreated fiber Benzoylated fiber 3 Benzoylated 236.15 394.1 314.89 354.38 10.48
fiber

Fig. 16 TGA thermogram of the raw, pretreated, benzoylated and 4 AN-g-poly- 263.82 382.2 342.73 551.54 37.10
AN graft copolymerized Cannabis indica fiber Cannabis
indica fiber

Fiber OH + NaOH Fiber O-Na++ H2O (1)

fiber. However, in case of AN graft copolymerized C.
indica fiber, IDT and FDT values have been found to be
263.82 °C (6.98% weight loss) and 382.2 °C (48.04% O O
weight loss), respectively (Schemes 1, 2). Fiber O-Na+ + Cl C Fiber O C + NaC l
(2)
From these results it is clear that graft copolymeriza-
tion enhance the thermal stability of C. indica fibers as Scheme 1 A possible mechanism for the grafting of the Benzoyl
compared to Benzoylation process. These results also find chloride onto Cannabis indica fiber [28]

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Step 1: Initation Table 3 Percentage crystallinity (%Cr) and crystallinity index (C.I.)
OH OH OH of raw, pretreated, benzoylated and Cannabis indica-g-poly(AN) fiber
OH O O
HO O O O + Ce4+ HO O
O O Sr. Sample At 2h scale % C.I
OH HO OH OH HO Ce4+OH
CI Cellulose
Complex (CI no Crystallinity
Cellulose-
Ce4+)
I22 I15

OH OH 3+ 1 Raw 709 348 67.07 0.5091

HO OH O O + Ce
O O 2 Pretreated 882 375 70.16 0.5748
OH OH
CI Cellulose free radical (3) 3 Benzoylated 1,601 797 66.76 0.5021
4 Cannabis indica-g- 1,514 969 60.97 0.3600
MWR Ce4+ N
poly(AN)
N + Ce4+ N
AN Complex (AN-Ce4+) AN free radical (4)

Step 2: Propagation X-Ray Diffraction Study

OH OH OH
HO OH O O HO
OH
OH O O X-ray diffraction studies were performed on X-ray dif-
O O O
OH OH OH
O OH fractometer (Brucker D8 Advance), using Cu Ka (1.5418
+N
CI Cellulose free radical
AN (5) Å) radiation, a Ni-Filter and a scintillation counter as a
detector at 40 kV and 40 mA on rotation from 10° to 50° at
OH OH OH 2h scale. X-ray diffraction studies of the raw, pretreated,
OH O O
O O+ HO OH
HO
O
OH
O OH
nN O O OH benzoylated and AN graft copolymerized C. inidca fiber
OH N OH N
N have been shown in Table 3. Since cellulosic fibers gen-
n
(6) erally contain both crystalline and amorphous region so it
is evident that X-ray diffraction patterns of such materials
N + nN
N will show both region in the form of sharp peak and dif-
N
N fused pattern. The main aim of X-ray diffraction study was
n +1
Poly(AN) (7) to analyze effect of treatment on the texture and crystal-
linity of fiber.
OH OH N From the table it has been observed that % crystallinity
HO O O O +
O N
OH
HO OH N of pretreated fiber is higher than raw fiber. This could be
CI Cellulose n+1
due to the removal of waxy, cementing materials and
hemicelluloses, which leads to the interfibrillar regions to
OH N
be less dense and less rigid and better packing of the
OH
O O +
HO
O
OH N cellulose chains [31]. However, upon benzoylation of
N
OH O OH
H pretreated fiber a slight decrease in percent crystallinity of
CI Cellulose free radical n+1 (8) the fiber has been observed. This could be due to dis-
Step 3:Termination
turbance in structure of polymer backbone by penetration
of bulky benzoyl groups into the polymer backbone. In
OH OH
O O OH OH case of C. indica-g-poly(AN) decrease in C.I has also
HO OH HO OH O O
O O OH+ 4+ O been observed which could also be due to the reason
OH Ce O OH
N N OH
n
N N explained above.
n

CIC-g-poly(AN) (9)

N N
N + Ce4+ N Conclusion
N N
n+1 n+1H
Poly(AN) free radical Poly(AN) (10) Benzoylation and acrylonitrile graft copolymerization
causes modification of the C. indica fiber and the same has
Scheme 2 A possible mechanism for the graft copolymerization of been confirmed by FTIR, SEM, XRD and TGA analysis.
the Acrylonitrile(AN) onto Cannabis indica fiber
XRD study showed that C.I of the raw fibers increases after
the pretreatment but decreases considerably on subsequent
support if we consider decomposition temperature (DT) at benzoylation and graft copolymerization. Thermal stability
20 and 60% weight loss as a standard of comparison for all of AN graft copolymerized fiber has been found to be
samples (Table 2). higher than that of benzoylated and raw fiber. It has also

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J Polym Environ (2012) 20:361–371
been observed that there is an enhancement in the chemical
resistance and hydrophobic behavior of surface modified
C. indica fibers. All these properties of modified fibers
could help in their applications especially in the synthesis
of fiber reinforced composites for better end use.
Acknowledgments Authors are highly thankful to the Director,
National institute of Technology Hamirpur (H.P) India for providing
the laboratory facilities and Ministry Of Human Resources and
Development for financial support.
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