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Carbohydrate Polymers 125 (2015) 69–75

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

Hydrophobic modification of cellulose isolated from Agave angustifolia


fibre by graft copolymerisation using methyl methacrylate
Noor Afizah Rosli a , Ishak Ahmad a,∗ , Ibrahim Abdullah a ,
Farah Hannan Anuar a , Faizal Mohamed b
a
School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia (UKM), Bangi 43600, Selangor,
Malaysia
b
School of Applied Physic, Faculty of Science and Technology, Universiti Kebangsaan Malaysia (UKM), Bangi 43600, Selangor, Malaysia

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

Article history: Graft copolymerisation of methyl methacrylate (MMA) onto Agave angustifolia was conducted with ceric
Received 18 September 2014 ammonium nitrate (CAN) as the redox initiator. The maximum grafting efficiency was observed at CAN
Received in revised form 1 March 2015 and MMA concentrations of 0.91 × 10−3 and 5.63 × 10−2 M, respectively, at 45 ◦ C for 3 h reaction time.
Accepted 2 March 2015
Four characteristic peaks at 2995, 1738, 1440, and 845 cm−1 , attributed to PMMA, were found in the IR
Available online 7 March 2015
spectrum of grafted cellulose. The crystallinity index dropped from 0.74 to 0.46, while the thermal stability
improved upon grafting. The water contact angle increased with grafting yield, indicating increased
Keywords:
hydrophobicity of cellulose. SEM images showed the grafted cellulose to be enlarged and rougher. The
Cellulose
Graft copolymerization
changes in the physical nature of PMMA-grafted cellulose can be attributed to the PMMA grafting in the
Hydrophobic amorphous regions of cellulose, causing it to expand at the expense of the crystalline component.
Free radical © 2015 Elsevier Ltd. All rights reserved.
Methyl methacrylate

1. Introduction promising leaf fibres that can be used in new materials. The suc-
cessful isolation and characterisation of cellulose from this plant
In recent years, environmental sustainability, industrial ecol- was previously reported in the literature (Rosli, Ahmad, & Abdullah,
ogy, eco-efficiency, and green chemistry have become mainstream 2013).
research areas, driving the development of new materials and Despite all these attractive properties, cellulose possesses some
products from renewable resources. The use of natural fibres limitations in its applications owing to a lack of thermoplastic-
as reinforcement agents in composites presents numerous ben- ity and high hydrophilicity. To overcome these major drawbacks,
efits over the use of synthetic fibres (e.g. glass fibres), owing chemical modification of the cellulose structure is necessary. One
to their favourable properties. Some advantages of natural fibres cellulose modification method that shows great promise is graft
over synthetic fibres include low cost, low density, biodegradabil- copolymerisation, which offers an attractive means for incorporat-
ity, non-toxicity, and recyclability. Natural fibres comprise three ing a wide variety of functional groups onto the cellulose backbone.
main components, namely cellulose, hemicellulose, and lignin, and The modification of cellulose by graft copolymerisation alters its
cellulose constitutes the main fraction. physical and chemical properties, in addition to increasing its
Cellulose is the most abundant polymeric material on earth functionality.
and possesses several valuable physicochemical properties such Among the known methods of graft copolymerisation, free-
as a fine cross-section, good biocompatibility, high durability and radical polymerisation has received the greatest amount of
thermal stability, and good mechanical properties. Cellulose is a attention due to many attractive characteristics such as its appli-
reactive chemical due to the presence of three hydroxyl groups in cability to a wide range of monomers, ability to provide an
each glucose residue, which are mainly responsible for the reac- unlimited number of copolymers, tolerance to water, and opera-
tions of cellulose (Roy, Semsarilar, Guthrie, & Perrier, 2009). Agave tional simplicity (Roy et al., 2009). The formation of free radicals
angustifolia, which has a high cellulose content, is one of the more on the cellulose backbone by direct oxidation using Ce(IV) ions has
gained appreciable importance due to its ease of application and
high grafting efficiency compared to other redox systems such as
∗ Corresponding author. Tel.: +60 3 89215441; fax: +60 3 89215410. Fe(II)–hydrogen peroxide (Gupta & Khandekar, 2006; McDowall,
E-mail address: gading@ukm.edu.my (I. Ahmad). Gupta, & Stannett, 1984). Most of the cellulose grafting methods

http://dx.doi.org/10.1016/j.carbpol.2015.03.002
0144-8617/© 2015 Elsevier Ltd. All rights reserved.
70 N.A. Rosli et al. / Carbohydrate Polymers 125 (2015) 69–75

involve the formation of free radicals on the cellulose molecules methanol, and then dried to a constant weight in an oven at 40 ◦ C.
by utilising redox systems (Gupta and Khandekar, 2006; Kumar, After a constant weight was achieved, the homopolymer in the
Naithani, & Pandey, 2011). The grafting of methyl methacrylate dried product was extracted with acetone in a Soxhlet apparatus
(MMA) onto cellulose materials such as commercial cellulose (Xin, for 24 h. The suspension was filtered and the filtrate was washed
Yuan, Xioa, & He, 2011), bamboo (Wan et al., 2011), and Grewia with acetone and dried to a constant weight.
optiva fibres (Thakur, Thakur, & Gupta, 2014) using different redox The free radical polymerisation of MMA monomer onto cel-
systems has been reported. However, no work has been directed lulose surface will result in formation of both cell-g-PMMA and
towards the grafting of the MMA monomer onto cellulose isolated its homopolymer PMMA. The optimum graft copolymerisation
from Agave angustifolia. Previous studies have shown that Agave was determined by the percent of graft yield (GY) and graft effi-
angustifolia can be considered as one of the most promising new ciency (GE). %GY was evaluated by increasing sample weight after
natural fibre sources due to its high cellulose content (67%) (Rosli homopolymer removal and was calculated according to eq. (1)
et al., 2013). (Princi et al., 2005).
In this study, cellulose was isolated from the wild-growing
(W2 − W1 )
perennial plant Agave angustifolia, followed by the grafting of MMA % Graft yield = × 100% (1)
W1
onto the agave-derived cellulose using graft copolymerisation. A
number of variables involved in the graft copolymerisation pro- where W1 is the initial mass of cellulose (g) and W2 is sample mass
cess, such as different reaction conditions, including temperature after removal of homopolymer (g).
and time, as well as the concentrations of the monomer, initiator, The grafting efficiency was defined as the ratio between the
and HNO3 , were investigated. Further, the physicochemical prop- amounts of grafted monomer after removal of homopolymer and
erties of the PMMA-grafted cellulose were evaluated and compared the total polymerised monomer before removal of homopolymer.
to those of native cellulose. %GE was calculated according to eq. (2).
(W2 − W1 )
2. Materials and methods % Graft efficiency = × 100% (2)
(W3 − W1 )

2.1. Materials where W3 is the mass of graft copolymer before removal of


homopolymer (g).
The agave leaves were harvested in Kajang, Selangor (Malaysia).
Sodium chlorite (NaClO2 ), sodium hydroxide (NaOH), and glacial 2.3. Characterisation of cellulose and grafted cellulose
acetic acid (99%) were used for the isolation of cellulose. HNO3
(63%), acetone, methanol, ceric ammonium nitrate (CAN), and MMA 2.3.1. Contact angle measurements
(stabilised) were used for graft copolymerisation. All the chemicals, Measurements of the contact angle of water on the cellulose and
except for MMA, were used without further purification. MMA was grafted cellulose samples were carried out using a FECA Contact-
passed through a column of basic Al2 O3 , in order to remove the Angle Meter. For standard contact angle measurements, a 2 ␮l
stabiliser. All the chemicals were purchased from Sigma-Aldrich, E. water drop was used and the tests were done at room temperature
Merck, and System ChemAR. with at least five liquid drops.

2.2. Preparation of grafted cellulose 2.3.2. Fourier-transform infrared (IR) spectroscopy


FTIR spectra of the cellulose and grafted cellulose samples were
2.2.1. Fibre extraction recorded on a Perkin–Elmer (SpectrumGX) spectrophotometer.
The thorns in the margins and tips of the agave leaves were The cellulose and grafted cellulose samples were mixed with KBr,
removed and the leaves were dried for one week to remove the ground into a powder, and pressed into ultra-thin pellets. The pel-
excess moisture. The fibres were extracted from the leaves using a lets were then characterised using the FTIR spectrophotometer in
fibre-extracting machine and were retted for one week. They were the wavenumber range of 500–4000 cm−1 , with a scanning resolu-
subsequently combed and shadow dried for 4–6 h. The long fibres tion of 1 cm−1 .
were cut to a length of 5 cm and ground using a mill.
2.3.3. X-ray diffraction (XRD) measurements
2.2.2. Isolation of cellulose XRD analyses were performed with a Bruker AXS D8 Advance
The ground and graded agave fibres were treated with 4% NaOH diffractometer at a voltage of 40 kV and a current of 40 mA, using
at 70–80 ◦ C for 2 h. The purpose of alkali treatment is to remove Cu-K␣ radiation ( = 0.1541 nm) and the data were acquired in
hemicellulose content from the fibres. A bleaching treatment was the 2 range of 5◦ –60◦ . The crystallinity indices (Ic ) of cellulose
then carried out using 1.7 w/v% NaClO2 at 70–80 ◦ C for 4 h. The and grafted cellulose were calculated using the following formula
ratio of the fibres to the liquor was kept constant at 1:25 (g/ml). (Segal, Creely, Martin, & Conrad, 1959):
Each fibre treatment procedure was performed twice and the fibres I002 − Iam
were washed with distilled water after each treatment. Ic = (3)
I002

2.2.3. Graft copolymerisation where I002 is the maximum diffraction intensity of the (0 0 2) lat-
The grafting reaction was carried out in a three-necked flask tice peak between 22◦ and 23◦ and Iam is the minimum diffraction
equipped with a reflux condenser, dropping funnel, and a gas inlet intensity of the amorphous material between 2 values 18◦ and 19◦ .
system immersed in a water bath. In a typical reaction, 1 g of cel- Percent crystallinity (%Cr) was calculated using the formula
lulose was dispersed in 50 ml of water with constant stirring and shown in eq. (4) (Mwaikambo & Ansell, 2002).
nitrogen bubbling for 1 h at 45 ◦ C. A freshly prepared solution of I002
%Cr = (4)
CAN (10 ml, 0.91 × 10−3 mol) in 0.3 N HNO3 was added to the cel- I002 + Iam
lulose dispersion and stirred for an additional 15 min. The MMA
monomer (5.63 × 10−2 mol) was gradually added to the above solu- 2.3.4. Thermogravimetric analyses (TGA)
tion over a period of 30 min and the mixture was stirred for 3 h. The thermal stabilities of cellulose and grafted cellulose
The grafted cellulose was washed sequentially with water and were analysed using a Mettler Toledo model TGA/SDTA851e
N.A. Rosli et al. / Carbohydrate Polymers 125 (2015) 69–75 71

thermogravimetric analyser. Approximately, 2–12 mg of each sam- with an increase in the CAN concentration from 0.18 × 10−3 to
ple was heated from room temperature to 600 ◦ C at a heating rate of 0.91 × 10−3 mol, with a maximum %GY of 282% achieved at the
10 ◦ C/min. All the measurements were performed under a nitrogen latter concentration. A further increase in the CAN concentra-
atmosphere with a gas flow of 10 ml min−1 . tion beyond 0.91 × 10−3 mol led to a decrease in %GY and %GE.
In the range of CAN concentrations studied, minimum %GY and
2.3.5. Scanning electron microscopy (SEM) %GE values of 137 and 30%, respectively, were observed at a con-
Variable-pressure scanning electron microscopy (VPSEM) centration of 1.6 × 10−3 mol. The initial increase in the %GY and
micrographs of the cellulose and grafted cellulose samples were %GE values was due to the generation of free-radical sites on the
recorded on a Leo 1450VP scanning electron microscope with an cellulose backbone as a result of the increase in the total num-
accelerating voltage of 15 kV. The samples were coated with gold ber of Ce(IV)–cellulose complexes, which decompose to yield more
prior to the measurements, to avoid charging. active sites. The generation of the active sites on the cellulose back-
bone was immediately followed by the grafting copolymerisation
of MMA onto the backbone. On the other hand, the decrease in the
2.3.6. Polarised light microscopy (PLM)
%GY and %GE values beyond the optimum CAN concentration can be
PLM observations were performed using a Leica ICC50 HD. The
attributed to the formation of Ce(IV)–monomer complexes rather
image of cellulose and cell-g-PMMA fibre structure under a PLM
than Ce(IV)–cellulose complexes, which resulted in the increased
was obtained at 10× magnification at 180◦ bright field polarising
formation of the homopolymer. There is also a high possibility of
angle.
termination of the backbone radicals before grafting takes place at
increased CAN concentrations, due to the scavenging of the free-
3. Results and discussion radical sites on the cellulose backbone (Scheme 1) (Kaur, Kumar, &
Sharma, 2010).
3.1. Determination of the optimum reaction conditions

3.1.1. Effect of CAN concentration 3.1.2. Effect of nitric acid concentration


The effect of CAN concentration on the percent grafting yield Fig. 1b shows the effect of HNO3 concentration on the values of
(%GY) and grafting efficiency (%GE) is shown in Fig. 1a. As observed %GY and %GE. An increase in the values of %GY and %GE was noted
from Fig. 1a, the values of %GY and %GE increased initially initially as the HNO3 concentration was increased, until maximum

Fig. 1. The effect of (a) CAN concentration, (b) HNO3 concentration, (c) MMA concentration, (d) reaction time, and (e) temperature on the percent grafting yield and grafting
efficiency.
72 N.A. Rosli et al. / Carbohydrate Polymers 125 (2015) 69–75

Scheme 1. Mechanism of Ce4+ ion promoted grafting of methyl methacrylate onto cellulose.

values were reached. Beyond the maxima, further increases in the 3.1.5. Effect of temperature
HNO3 concentration caused a decrease in the %GY and %GE val- Fig. 1e shows the results of graft copolymerisation of PMMA onto
ues. The ceric ions that exist in the form of [Ce4+ ], [Ce(OH)]3+ , and cellulose as a function of temperature. Both %GY and %GE increased
[Ce–O–Ce]6+ species in aqueous solutions are less effective to form initially with an increase in temperature, reaching optimum values
a cellulosic complex due to their large size. In the grafting tech- at 45 ◦ C, after which they decreased with further increases in tem-
nique used in this study, the Ce(IV) ions produce free radicals on perature. As the kinetic energy of the molecules increases with an
the cellulose backbone in the presence of HNO3 . In the presence of increase in the temperature, more radicals are able to form on the
HNO3 , the equilibrium shifts towards the Ce4+ ion, which is smaller cellulose backbone at a faster rate, which leads to an increase in the
in size, resulting in an increase in the %GY and %GE values with an %GY and %GE values. A further increase in the temperature beyond
increase in the HNO3 concentration. However, at higher concentra- the optimal value leads to the occurrence of the termination pro-
tions of Ce4+ , the oxidative termination of the growing polymeric cess and the thermal initiation of the monomer, resulting in the
grafting chain takes place instead of the propagating process, as formation of a homopolymer, thereby causing a decrease in %GY
shown in eq. (5) (Goyal, Kumar, & Sharma, 2008; Sharma, Kumar, and %GE.
& Soni, 2002).
3.2. Water contact angle analysis
Ce4+ + Mn · → Ce3+ + Mn + H + (5)
Fig. 2a–c shows the images of the water contact angle (WCA)
measurements on the surface of unmodified cellulose, grafted cel-
3.1.3. Effect of monomer concentration
lulose with a high %GY, and grafted cellulose with a low %GY,
The %GY and %GE values for the grafting of PMMA onto cellulose
respectively. The WCA on the surface of unmodified cellulose was
were next studied as a function of the monomer concentration and
found to be less than 10◦ , whereas the contact angles of the high
the results are presented in Fig. 1c. Both %GY and %GE were found
%GY and low %GY grafted cellulose were 84◦ and 70◦ , respectively.
to increase with an increase in the MMA concentration, reach-
The low WCA of agave-derived cellulose can be attributed to the
ing maximum values at an MMA concentration of 5.63 × 10−2 mol.
instant absorption of water upon contact, due to the hydrophilic
However, beyond an MMA concentration of 5.63 × 10−2 mol, the
nature of cellulose. Balu, Kim, Breedveld, and Hess (2009) stated
%GY and %GE values decreased with further increases in the MMA
that the receding contact angle could not be obtained for substrates
concentration. This enhancement in grafting by increasing the
with values less than 10◦ , due to drop breakup. The increase in the
MMA concentration could be explained by the greater availabil-
WCA upon grafting suggests that the PMMA successfully imparted
ity of grafting sites on the cellulose macroradicals compared to the
hydrophobicity to the cellulose surface. As seen in Fig. 5b and c,
monomer molecules. Increases in the MMA concentration beyond
the contact angle increased with increasing %GY. Since the %GY
an optimum value may, however, result in the formation of a three-
represents the amount of monomer grafted on the cellulose, the
component complex consisting of a substrate, monomer, and water,
above results prove that the increase in the hydrophobicity of the
which rearranges to provide a requisite free radical site with the
surface was a direct result of the increase in the amount of PMMA
liberation of atomic hydrogen. This initiates homopolymerisation
grafted on the surface of cellulose.
over the cellulose macroradicals (Kumar et al., 2011).

3.3. FTIR spectroscopic analysis


3.1.4. Effect of reaction time
The effect of reaction time on %GY and %GE values is shown FTIR spectroscopic analysis of the cellulose and grafted cellulose
in Fig. 1d. As seen in Fig. 1d, both %GY and %GE increased with samples are shown in Fig. 3. The spectra for both the samples exhib-
an increase in the reaction time, reaching maximum values at 3 h, ited a broad band centred around 3330 cm−1 , which was attributed
and decreased thereafter. The initial increase in %GY and %GE with to the free stretching vibration of the OH group. In addition, the
reaction time could be explained by the increased contact time peak detected at 2900 cm−1 in both the spectra was attributed to
of the monomer molecules with the cellulose macroradical sites a C H stretching vibration. A comparison of the spectra revealed
at higher reaction times. However, beyond the optimum reaction that compositional changes occurred upon grafting, as evident from
time, homopolymer formation and backbiting by the active radi- the four additional peaks at 2995, 1738, 1440, and 845 cm−1 in the
cal due to the mutual destruction of the growing polymeric chains grafted cellulose sample, which were characteristic of PMMA (Duan
occurs, resulting in a decrease in the %GY and %GE values (Kumar et al., 2008). The peaks at 2995 and 1738 cm−1 were attributed
et al., 2011). to the stretching vibrations of C H and C O (ester) in the PMMA
N.A. Rosli et al. / Carbohydrate Polymers 125 (2015) 69–75 73

Fig. 2. The images of the water droplet formed on the surface of (a) cellulose, (b) grafted cellulose with a high % grafting yield, and (c) grafted cellulose with a low % grafting
yield.

Fig. 3. FTIR spectra of (a) cellulose and (b) grafted cellulose.


Fig. 4. X-ray diffraction patterns for (a) cellulose and (b) grafted cellulose.

chains, respectively. The vibration peak detected at 1440 cm−1 was


indicative of CH3 and CH2 deformation vibrations, while the peak Table 1
Crystallinity index and % crystallinity of cellulose and grafted cellulose.
at 845 cm−1 was attributed to the deformation vibration of C O C
single bonds. Also, worthy of note is that the absorbance peak at Sample Crystallinity index % Crystallinity
1630 cm−1 , which was attributed to the O H bending of absorbed Cellulose 0.74 80.14
water (Le Troedec et al., 2008), almost disappeared in the grafted Grafted cellulose 0.46 67.68
cellulose spectrum. The incorporation of PMMA onto the cellu-
lose backbone improved the hydrophobicity, as discussed before,
thereby decreasing the amount of absorbed water. decreased upon grafting. The decrease in the percent crystallinity
with the graft copolymerisation of PMMA onto the cellulose back-
3.4. XRD measurements bone indicated a reduction in the crystallinity of the sample and the
presence of a larger amorphous region compared to the unmod-
Fig. 4 shows the XRD patterns of cellulose and grafted cellulose. ified sample, due to the incorporation of the monomer moieties
The diffraction patterns for both of the samples showed peaks at 2 onto the cellulose backbone (Kaith, Jindal, & Maiti, 2009). Concern-
values of 16◦ and 22◦ , with large differences in the peak intensities, ing the crystallinity index, which is used to indicate the order of
indicating changes in the crystallinity of cellulose. The results of crystallinity, the lower crystallinity index observed for grafted cel-
the crystallinity analyses shown in Table 1 clearly revealed that lulose is suggestive of a poor crystal lattice order in the cellulose. We
both the crystallinity index and the percent crystallinity values believe that a misorientation of the crystal lattice to the cellulose
74 N.A. Rosli et al. / Carbohydrate Polymers 125 (2015) 69–75

axis during graft copolymerisation resulted in the low crystallinity ␤ scission rather than main chain scission (Manring, 1991). At the
index observed for the grafted cellulose. end of the test (600 ◦ C), the remained residues for the cellulose and
grafted cellulose are 17 and 5 wt%, respectively. The higher amount
3.5. Thermogravimetric analysis of residues in the cellulose is due to the presence of lignin as well as
ash, which have a slow degradation rate (Ashori, Jalaludin, Raverty,
The presence of PMMA during the degradation of the grafted & Mohd Nor, 2006). On the contrary, the low residues in grafted
cellulose was investigated using thermogravimetric analysis. The cellulose are due to the absence of lignin content since cellulose
thermal degradation of cellulose and grafted cellulose was deter- grafting mainly occurred in the amorphous region of cellulose.
mined from the TGA and DTG thermograms, which are shown in
Fig. 5a and b. Both the samples showed two degradation steps 3.6. Morphological analysis
related to moisture evaporation and cellulose degradation. The first
step, occurring at a low temperature, is due to the evaporation of SEM images visually showing the evolution of the cellulose and
moisture from the cellulose and grafted cellulose samples. How- grafted cellulose morphologies are shown in Fig. 6a and b, respec-
ever, the percent weight lost due to moisture evaporation in the tively. Further evidence of grafting was furnished by examining the
case of grafted cellulose was found to be much less than that for surface morphologies of the samples using VPSEM. An examination
the unmodified cellulose. This is attributed to the increase in the of the micrographs of the unmodified and grafted cellulose sam-
hydrophobicity of the grafted cellulose, which is discussed in the ples revealed a highly rough surface in the case of grafted cellulose
next section. The decomposition step that occurred at 235 ◦ C in due to the deposition of PMMA on the cellulose surface. Wróbel,
the unmodified cellulose sample shifted to 240 ◦ C in the case of Kryszewski, Rakowski, Okniewski, and Kubacki (1978) demon-
grafted cellulose. The shift in the decomposition temperature can strated that the adhesion of grafted fibres to a polymer matrix was
be attributed to an improvement in the thermal stability owing to improved as the surface roughness was increased due to an increase
the presence of the PMMA polymer. Two additional degradation in the surface area for mechanical interlocking. Thus, the rougher
steps appeared in the grafted cellulose thermogram that were not surface on the grafted cellulose is expected to improve its adhesion
present in the case of unmodified cellulose. The first step occurred to other polymer matrices and thereby, improve the mechanical
at 200 ◦ C and was thought to be due to the unsaturated ends of properties of composites prepared using grafted cellulose. The fibre
PMMA (Manring, 1989). The degradation is due to the small size diameter also increased with grafting, from a range of 5–9 ␮m for
of the free radicals transferred from the impurities, H H bonds, ungrafted cellulose, to a range of 7–20 ␮m for grafted cellulose.
scission of ␤ to the vinyl group at the unsaturated ends, and ran-
dom scission (Ferriol, Gentilhomme, Cochez, Oget, & Mieloszynski, 3.7. Polarised light microscopy
2003). The random scission of PMMA at around 360 ◦ C is initiated by
the homolytic scission of a methoxycarbonyl side group followed by An optical method to characterise cellulose fibre microstruc-
tural alignment is through qualitative PLM. The PLM is used to
determine the double refraction of an optical anisotropic material
such as crystal, organic tissues, polymers, etc. Micrographs reveal
that the crystalline fibre in cellulose and cell-g-PMMA are bire-
fringent as shown in Fig. 7a and b. The control sample exhibits

Fig. 5. (a) TGA and (b) DTG thermograms of cellulose and grafted cellulose. Fig. 6. SEM micrographs of (a) cellulose and (b) grafted cellulose.
N.A. Rosli et al. / Carbohydrate Polymers 125 (2015) 69–75 75

Fig. 7. PLM micrographs of (a) cellulose and (b) grafted cellulose.

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Hamid from the Malaysian Agriculture Research & Development for green composites. Carbohydrate Polymers, 104, 87–93.
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