International Journal of Biological Macromolecules 62 (2013) 44–51

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

Development of functionalized cellulosic biopolymers by graft

copolymerization
Vijay Kumar Thakur a,∗,1 , Manju Kumari Thakur b,1 , Raju Kumar Gupta c,1
a
Department of Materials Science and Engineering, Iowa State University of Science and Technology, Ames, IA 50011, USA
b
Division of Chemistry, Govt. Degree College Sarkaghat, Himachal Pradesh University, Shimla 171005, India
c
Department of Chemical Engineering, Indian Institute of Technology Kanpur, 208016, India

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

Article history: Natural lignocellulosic polymers are one of the most promising biodegradable, non-toxic and eco-friendly
Received 2 July 2013 polymeric materials which have been used to develop various products for number of applications espe-
Received in revised form 18 August 2013 cially in green composites. However, these cellulosic materials have certain drawbacks, like sensitivity
Accepted 19 August 2013
to water and moisture, and need to be modified. So in this article, a treatment of lignocellulose biopoly-
Available online 27 August 2013
mers with suitable acrylate monomer was investigated. The influence of different reaction parameters
on efficiency (grafting) was investigated. SEM, TGA and Fourier transform infrared spectroscopy (FT-IR)
Keywords:
were used to study the graft copolymerization between the monomer and hydroxyl groups of lignocellu-
Green cellulosic polymers
Graft copolymerization losic biopolymers. This article also discusses swelling, and chemical resistance properties of the both the
Thermal grafted/ungrafted cellulosic biopolymer and their potential candidature for green composite applications.
Morphological and physico-chemical
properties Published by Elsevier B.V.
Green materials
Vinyl monomer

1. Introduction cellulosic polymers especially natural fibers in a number of sys-

Surface functionalization of biopolymers through graft copo-
lymerization of synthetic polymers is one of the most convenient
methods to add new desired properties to the polymers depend-
ing upon the applications with minimum loss of their initial
properties [1–4]. As is evident from the existing literature the
incorporation of any biopolymeric macromolecules results into
eco-friendly materials with good biodegradability, eco-efficiency
and low cost [5–10]. So it is generally assumed that a combina-
tion of synthetic macromolecules with natural macromolecules
might yield green composite materials with enhanced properties
combining the properties of both materials: mechanical stability
and biological acceptability [11–14]. The advantages of polymer
composite systems with cellulosic biopolymer as one of the essen-
tial component for a number of applications may include efficient
utilization of the natural polymers, biocompatibility, no health haz-
ards, easy fabrication of materials etc. [15–19]. The addition of
∗ Corresponding author. Tel.: +1 5154415018.
E-mail addresses: vijayisu@hotmail.com (V.K. Thakur), shandilyamn@gmail.com
(M.K. Thakur), guptark@iitk.ac.in (R.K. Gupta).
1
Tel.: +1 0512 259 6972; fax: +1 0512 259 0104.
tems has been found to improve the existing properties of the
parental materials [20–23]. These cellulosic fibers represents the
most viable renewable resources available in the universe capa-
ble of reducing environmental pollution by absorption of CO2 from
the atmosphere due to their inherent properties like low cost,
non-toxic, non corrosive nature, eco-friendliness, biodegradabil-
ity, easy availability, and enhanced energy recovery [24–27]. In
combination with appropriate biocompatibity cellulosic materi-
als are being used for biomedical applications [27–29]. Natural
fibers are also presently being used extensively in automotive
industry replacing the commonly used synthetic fibers [30–32].
However the sensitivity of cellulosic fibers toward water/moisture
absorption and poor chemical resistance inhibit their use in out-
door applications, and to make them work under these condition,
their surface modification is very essential [32–35]. The graft copo-
lymerization of cellulosic polymers with suitable hydrophobic
monomers incorporates desired functionalities into the cellulosic
backbone, thus improving the existing physico-chemical proper-
ties of the cellulosic polymers [1,2,36]. Furthermore the grafted
cellulosic polymers results in better mechanical interlocking with
the polymer matrix and increasing the mechanical strength of the
composites [10–12,36].
So keeping this in mind, the present study is an attempt
to prepare the butyl acrylate grafted Hibiscus sabdariffa fibers

0141-8130/$ – see front matter. Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.ijbiomac.2013.08.026
 V.K. Thakur et al. / International Journal of Biological Macromolecules 62 (2013) 44–51 45

(butyl acrylate-g-H. sabdariffa) meant for green polymer compos- 2.4.2. Moisture absorbance behavior
ite applications. The H. sabdariffa fibers prior to and after graft Moisture absorbance studies were made for particular time
copolymerization synthesis have been characterized by Fourier interval under different humidity levels ranging from 20% to 90%.
transform infrared spectroscopy (FTIR), thermo gravimetric anal- Final weights of the grafted and ungrafted H. sabdariffa fibers
ysis (TGA), morphological (SEM) and the physico-chemical studies. exposed to different humidity levels were then noted. The percent
moisture absorbance (% Mabs) was calculated from the increase in
initial weight in the following manner:
2. Experimental
Wf − Wi
%moisture absorbance (%Mabs ) = × 100
2.1. Materials Wi

Butyl acrylate (BA), ferrous ammonium sulphate (FAS),
potassium per sulphate (KPS), sodium hydroxide (NaOH), and
tetrahydrofuran were procured from Qualigens Chemicals Ltd. H.
sabdariffa fibers were collected from local resources of Himalayan
region and purification of the fibers as well as chemical modifi-
cation through mercerization was done by the standard method
reported in our earlier studies [12,35].
2.2. Graft copolymerization
The graft copolymerization synthesis reaction was initiated by
immersing surface modified (mercerized) H. sabdariffa fibers in
a definite amount of distilled water for 24 h in order to activate
the cellulosic backbone. This process was followed by addition of
known amount of initiator (FAS-H2 O2 ) and monomer. Different
reaction conditions such as amount of solvent, time, pressure, ini-
tiator (FAS:KPS ratio) and monomer concentration were optimized
by varying one parameter while keeping other constant in order to
get the maximum percentage of grafting. After the completion of
the reaction, flask was cooled under running tap water and the final
product was filtered. The rudimentary product was washed several
times with distilled water and oven-dried at 90 ◦ C to a constant
weight.
2.3. Removal of homopolymer and determination of graft level
where Wf is the weight of grafted H. sabdariffa fibers; Wi is the
weight of raw H. sabdariffa fibers.
2.4.3. Acid and base resistance study
Known weight (Tw ) of raw and grafted H. sabdariffa fibers were
immersed in fixed volume of 1 N HCl and 1 N NaOH and the weights
of the samples were noted down after certain intervals in order
to determine the acid and base resistance studies. The chemical
resistance was studied in the following manner:
Tw − Waci
Percent chemical resistance (Pcr ) = × 100
Tw
where Tw = total weight and Waci = weight after certain interval.
2.5. FTIR analysis
Infrared (IR) spectra of raw and grafted H. sabdariffa were
recorded using KBr pellets on PERKIN-ELMER RXI Spectrophotome-
ter. Scanning was carried out in the range of 400-4000 cm−1 .
2.6. Scanning electron microscopy (SEM) examination
The SEM photographs of the fiber surfaces (raw and grafted
Hibiscus sabdariffa) were observed by using scanning electron
microscopy machine (LEO 435 VP).

The rudimentary product of the grafted fibers was purified

with tetrahydrofuran using a Soxhlet extractor for 72 h followed
by washing with distilled water to remove the homo-polymer
formed during graft copolymerization reaction. The pure grafted
copolymers were then dried at 60 ◦ C to constant weight. The per-
centage grafting (Pg ) was calculated as per procedure reported
earlier [32–35].

Wg − W
Percent grafting (Pg ) = × 100
W

where W is the weight of raw H. sabdariffa fibers, Wg is the weight

of grafted H. sabdariffa fibers.

2.4. Physico-chemical studies of the raw and grafted fibers

Swelling, moisture absorbance and chemical resistance studies

of butyl acrylate grafted H. sabdariffa fibers and their raw counter-
parts was carried out as per methods reported earlier [32–35].

2.4.1. Swelling behavior

Grafted and ungrafted H. sabdariffa fibers were subjected to
swelling studies in different solvents such as dimethyl formamide;
water; methanol and isobutyl alcohol. The percent swelling was
calculated in the following manner:

Wf − Wi
Percent swelling (PS ) = × 100
Wi Scheme 1. Mechanism for graft copolymerization of butyl acrylate (BA) onto Hibis-
cus sabdariffa fibers.
46 V.K. Thakur et al. / International Journal of Biological Macromolecules 62 (2013) 44–51

Fig. 1. (a) Optimization of solvent amount for optimum graft copolymerization butyl acrylate (BA) onto Hibiscus sabdariffa fibers. (b) Optimization of time for optimum
graft copolymerization of butyl acrylate (BA) onto Hibiscus sabdariffa fibers. (c) Optimization of temperature for optimum graft copolymerization of butyl acrylate (BA) onto
Hibiscus sabdariffa fibers. (d) Optimization of initiator ratio for optimum graft copolymerization of butyl acrylate (BA) onto Hibiscus sabdariffa fibers. (e) Optimization of
monomer ratio for optimum graft copolymerization of butyl acrylate onto Hibiscus sabdariffa fibers.
 V.K. Thakur et al. / International Journal of Biological Macromolecules 62 (2013) 44–51 47

Fig. 2. (a) Swelling behavior of raw and butyl acrylate (BA) grafted Hibiscus sabdariffa fibers in different solvents. (b) Moisture absorbance behavior of raw and butyl acrylate
(BA) grafted Hibiscus sabdariffa fibers at different humidity levels. (c) Acid resistance behavior of raw and butyl acrylate (BA) grafted Hibiscus sabdariffa fibers in 1 M HCl at
different time intervals. (d) Base resistance behavior of raw and butyl acrylate (BA) grafted Hibiscus sabdariffa fibers in 1 M Na OH at different time intervals.

2.7. Thermogravimetry analysis (TGA)
Thermogravimetry experiments were carried out using a
Perkin-Elmer Thermal Analyzer. Thermo gravimetric study
(TGA/DTA/DTG) was carried out at a heating rate of 10 ◦ C/min. The
sample weights of raw and grafted H. sabdariffa fibers for thermal
studies were 10 mg each.
3. Results and discussion
The graft copolymerization synthesis reactions of butyl acry-
late monomer onto mercerized H. sabdariffa fibers were carried
out using a water-soluble initiator in an aqueous medium. The
mixture was continuously stirred in the reaction vessel to have inti-
mate contact between the initiator and the fiber, and active centers
formed on the cellulosic fiber with the butyl acrylate monomer.
The optimum conditions were determined by varying the different
reaction parameters. The presence of poly (butyl acrylate) on the
grafted fiber was studied by FTIR spectroscopy, SEM and Thermo-
gravimetry analysis.
3.1. Reaction mechanism
Butyl acrylate grafted H. sabdariffa fibers were synthesized
through a free-radical polymerization mechanism. The proposed
mechanism for reaction is based on the same principle as of that
reported in our previous studies [12,32–35]. The first step in the
graft copolymerization mechanism is the generation of radicals by
the decomposition of the initiator (FAS:KPS) [1]. Different reaction
steps involved in the graft copolymerization of butyl acrylate onto
cellulosic fibers are depicted in Scheme 1. The radical formation
for the initiation reaction can occur cellulosic polymer or on the
monomer. In the active center formation, the radical species may
attack the cellulosic hydroxyl to produce macro radicals. Once the
cellulosic radicals and phenolic radicals are produced on the H.
Sabdariffa fibers, they react with the monomers to give the graft
copolymer (H. sabdariffa -graft-poly (butyl acrylate) fibers.
48 V.K. Thakur et al. / International Journal of Biological Macromolecules 62 (2013) 44–51
Fig. 3. (a) FTIR spectrum of raw Hibiscus sabdariffa fibers. (b) FTIR spectrum of butyl acrylate (BA) grafted Hibiscus sabdariffa fibers.
Effect of reaction parameters such as monomer concentration,
initiator, reaction time, pressure and solvent was assessed to get
the optimum grafting. Fig. 1(a–e) shows different values of grafting
percentage during optimization of the reaction parameters.
3.1.1. Effect of solvent
The effects of solvent amount on the percentage of grafting
are shown in Fig. 1(a). The results suggest that copolymerization
should be carried out in sufficient amount of water. An increase
in the amount of water from 50 to 175 mL give maximum grafting
in 100 mL and then decreases slightly with further increase in the
amount of solvent. This can be explained on the basis that higher
amount of water may decrease the interaction between reaction
component such as lignocellulosic backbone as well as the graft
chains, which leads to a lower percentage of grafting.
3.1.2. Effect of reaction period
The effect of grafting period on the percentage on grafting at
constant temperature is shown in Fig. 1(b). The percentage of graft-
ing onto H. sabdariffa fibers increased with reaction periods of up
to 110 min and then decreases/leveled off. Beyond the optimum
time period, the amount of monomer decreases and the poly (butyl
acrylate) graft on the lignocellulose backbone acts as a barrier in
preventing further diffusion of the monomer onto the fiber as well
as shortage of available grafting sites as the reaction proceeds. This
trend is in agreement with our previous reports.
3.1.3. Effect of reaction temperature
The graft copolymerization of BA onto H. sabdariffa fibers was
carried out at different temperatures ranging from 40 to 70◦ C and
the results are presented in Fig. 1(c). The percentage of grafting
increases with temperature between 40◦ C and 60◦ C. Further
increase in temperature led to a decrease in percentage grafting.
The decrease in percent grafting as the reaction temperature
increased beyond 60 ◦ C may be due to an increase in free radical
termination.
3.1.4. Effect of initiator
Fig. 1(d) shows the effect of initiator concentration on the graft-
ing process. It is obvious from the figure that the percentage of
grafting increased with increase in the initiator concentration up
to 1:1. The increased percentage of grafting for this ratio is due to
the formation of sufficient number of grafting cites on the cellulosic
H. sabdariffa fibers which in the presence of monomer induced graft
copolymerization. The decrease in percentage of grafting after the
optimized ratio might be due to the enhanced rate of termination.
 V.K. Thakur et al. / International Journal of Biological Macromolecules 62 (2013) 44–51 49

Fig. 4. (a) Thermal analysis of raw Hibiscus sabdariffa fibers. (b) Thermal analysis of butyl acrylate (BA) grafted Hibiscus sabdariffa fibers.

3.1.5. Effect of monomer concentration
Fig. 1(e) shows the changes of percent grafting with the vari-
ation of the monomer (BA) quantity over the different ranges.
It is observed that the percentage of grafting is linearly propor-
tional to monomer concentration up to 0.81 mol/L indicating a
simple monomer dependence of the grafting reactions. This behav-
ior is expected due to the generation of more monomer radicals
to reach onto the active sites on the lignocellulosic H. sabdariffa
fibers. Beyond optimum concentration, the percentage of grafting
increases slowly/becomes almost constant due to the predomi-
nance of homo polymerization.
greater affinity for water resulting in the swelling of H. sabdariffa
fibers due to presence of large number of hydroxyl groups. Fur-
ther the dielectric constant (ε) values of different solvents also
have great effect on the swelling behavior of the cellulosic fiber.
Water, having a higher ε value easily enters into H-bonding with the
fiber leading to maximum swelling. The swelling behavior in differ-
ent solvents follows the trend as H2 O >CH3 OH > iso-BuOH > DMF.
In case of grafted fibers, swelling behavior follow the trend;
DMF > CH3 OH > H2 O > iso-BuOH which is due to the blockage of
active sites on polymeric substrate by poly buytylacrylate (PEA)
chains which cause change in the sorption of the different solvents.

3.2. Physico-chemical study

3.2.1. Swelling behavior
Fig. 2(a) represents the swelling behavior of the butyl acrylate
grafted H. sabdariffa fibers as well as raw fibers in different sol-
vents studied at room temperature. Raw H. sabdariffa fibers possess
3.2.2. Moisture absorbance behavior
Fig. 2(b) shows the moisture absorbance behavior of raw and
grafted H. sabdariffa fibers at different humidity levels. The raw H.
sabdariffa fibers show more Mabs as compared to grafted fibers, as
attachment of poly butyl acrylate (PEA) chains grafted onto the H.
50 V.K. Thakur et al. / International Journal of Biological Macromolecules 62 (2013) 44–51
Fig. 5. (a) Scanning electron micrograph of raw Hibiscus sabdariffa fibers. (b) Scan-
ning electron micrographs of butyl acrylate (BA) grafted Hibiscus sabdariffa fibers.
sabdariffa fibers lessen the affinity of grafted fibers toward mois-
ture.
3.2.3. Chemical resistance behavior
The chemical resistance behavior has been studied in terms of
weight loss of the fibers with dilute solutions of strong acid and base
(1 M HCl and 1 M NaOH). It has been observed that the chemical
resistance of lignocellulosic fibers increased with chemical induced
graft copolymerization (Fig. 2c and d) and can be attributed to
blockage of active sites vulnerable to the chemical attack by poly
(BA) chains onto the polymeric backbone resulting in more resis-
tance toward the chemicals.
3.3. Analysis and characterization of raw and grafted H.
sabdariffa fibers
3.3.1. Characterization by FT-IR spectroscopy
The presence of poly (butyl acrylate) on the H. sabdariffa fibers
was verified by studying the FTIR spectra of the raw H. sabdariffa
fibers and poly (butyl acrylate)-g- H. sabdariffa fibers, as shown
in Fig. 3(a) and (b). Characteristic broad absorption bands of the
hydroxyl group in the range of 3600–3400 cm−1 are easily seen in
both spectra and can be attributed to the O H stretching vibra-
tions of cellulose, hemicelluloses, lignin and the absorbed water
constituent of H. sabdariffa fibers. H. sabdariffa fibers showed broad
peaks at 3400 cm−1 due to hydrogen bonded ( OH) groups and
the bands located in the region 1225-1295 cm −1 and at 1739 cm−1
can be assigned for the C O ring of lignin and carboxylic groups
of pectin and hemicellulose present in the raw H. sabdariffa fibers
(Fig. 3a). While the presence of two new peaks at 2963 cm−1 and
2375 cm−1 in the spectrum of poly (butyl acrylate)-g- H. sabdariffa
fibers indicates the presence of the aliphatic chain from poly (butyl
acrylate) and provides strong evidence of grafting (Fig. 3b). A new
sharp peak around 1736 cm−1 was due to C O stretching of an ester,
which also provides strong evidence of grafting.
3.3.2. Characterization by thermal analysis
The thermal behavior of raw H. sabdariffa fibers and poly
(butyl acrylate)-grafted- H. sabdariffa fibers was examined by the
Thermo-gravimetric analysis (TGA) analysis under ambient labo-
ratory conditions at a heating rate 10◦ C per minute (Fig. 4a and
b). Initially 1-3% weight loss was observed in the ungrafted H.
sabdariffa fibers and can be attributed to the dehydration of the
fiber. In the case of ungrafted fibers, the initial decomposition (IDT)
temperature has been found to be 198 ◦ C with a percent weight
loss of 12% and the final decomposition temperature (FDT) to be
503 ◦ C with a percent weight loss of 91% (Fig. 4a). However in
case of the poly (butyl acrylate) -grafted -H. sabdariffa fibers, the
thermal stability increases with an initial decomposition temper-
ature (IDT) of 203 ◦ C with percentage weight loss of 9.7% and the
final decomposition temperature of 524 ◦ C with percentage weight
loss of 87% (Fig. 4b). Differential Thermal Analysis (DTA)/Derivative
thermogravimetric (DTG) study also support the TGA results. The
increase in thermal stability in poly (butyl acrylate)-grafted raw
H. sabdariffa fibers may be due to: (1) the late decomposition of
poly(butylacrylate),as well as the formation of grafted polymers
entangle and crosslinked type of network, which when heated
forms an insulative carbonaceous char barrier on the surface, thus
inhibiting degradation.
3.3.3. Characterization by scanning electron microscopy
Fig. 5a and b shows SEM photograph of the raw and grafted H.
sabdariffa surface. The fiber surface is rough, with bloated portions
in raw fibers. On the other hand the surface of the H. sabdariffa
fibers is almost covered by PBA after the graft copolymerization
process indicating that the synthetic polymer (polybutylacrylate)
is strongly attached onto the fiber as it is chemically bonded.
4. Conclusions
The graft copolymerization synthesis of poly (butyl acrylate)-
grafted- H. sabdariffa has been carried out successfully using
FAS:KPS as redox initiator and proved to be efficient in modify-
ing the properties of H. sabdariffa fibers. The incorporation of poly
(butyl acrylate) chains onto H. sabdariffa fibers results in higher
thermal, acid and base resistance. It also decreases the water and
moisture absorbance in the grafted fibers as compared to the raw
fibers. The spectroscopic data and SEM/TGA confirmed the presence
of poly (butyl acrylate) on the H. sabdariffa fibers. The graft copo-
lymerization reactions depend on the amount of solvent, initiator,
monomer as well as reaction period and reaction temperature.
Acknowledgement
Authors wish to thanks their parental institutes for providing
the necessary facilities to accomplish the present research work.
References
[1] V.K. Thakur, M.K. Thakur, R.K. Gupta, Carbohydrate Polymers 97 (2013) 18–25.
[2] V.K. Thakur, M.K. Thakur, R.K. Gupta, International Journal of Biological Macro-
molecules 61 (2013) 121–126.
 V.K. Thakur et al. / International Journal of Biological Macromolecules 62 (2013) 44–51
[3] M.D. Teli, J. Sheikh, Carbohydrate Polymers 88 (2012) 1281–1287.
[4] C.H. Unlu, N.S. Oztekin, O.G. Atici, Carbohydrate Polymers 90 (2012)
1120–1126.
[5] J.-F. Zhong, X.-S. Chai, S.-Y. Fu, Carbohydrate Polymers 87 (2012) 1869–1873.
[6] C.-S. Wu, Carbohydrate Polymers 87 (2012) 1249–1256.
[7] E.S. Abdel-Halim, Carbohydrate Polymers 90 (2012) 316–321.
[8] E.S. Abdel-Halim, S.S. Al-Deyab, Carbohydrate Polymers 87 (2012) 1863–1868.
[9] Y. Bao, J. Ma, Y. Sun, Carbohydrate Polymers 88 (2012) 589–595.
[10] V.K. Thakur, A.S. Singha, B.N. Misra, Journal of Applied Polymer Science 122
(2011) 532–544.
[11] V.K. Thakur, A.S. Singha, M.K. Thakur, Journal of Polymers and the Environment
20 (2012) 164–174.
[12] V.K. Thakur, A.S. Singha, International Journal of Polymer Analysis and Charac-
terization 16 (2011) 153–164.
[13] H.A. Cheema, A. El-Shafei, P.J. Hauser, Carbohydrate Polymers 92 (2013)
885–893.
[14] S. Kamel, Carbohydrate Polymers 90 (2012) 1538–1542.
[15] T. Arimura, Y. Omagari, K. Yamamoto, J. Kadokawa, International Journal of
Biological Macromolecules 49 (2011) 498–503.
[16] M.C. Popescu, M. Totolin, C.M. Tibirna, A. Sdrobis, T. Stevanovic, C. Vasile, Inter-
national Journal of Biological Macromolecules 48 (2011) 326–335.
[17] V.K. Thakur, A.S. Singha, International Journal of Polymer Analysis and Charac-
terization 16 (2011) 390–398.
[18] A.S. Singha, V.K. Thakur, International Journal of Polymer Analysis and Charac-
terization 15 (2010) 137–146.
[19] C. Jiang, X.L. Wang, P.D. Sun, C. Yang, International Journal of Biological Macro-
molecules 48 (2011) 210–214.
[20] M.D. Teli, J. Sheikh, International Journal of Biological Macromolecules 50
(2012) 1195–1200.
51
[21] V.K. Thakur, A.S. Singha, International Journal of Polymer Analysis and Charac-
terization 16 (2011) 153–164.
[22] E. Akar, A. Altinisik, Y. Seki, Carbohydrate Polymers 90 (2012) 1634–1641.
[23] S. Mishra, G.U. Rani, G. Sen, Carbohydrate Polymers 87 (2012) 2255–2262.
[24] M.C. Khoathane, E.R. Sadiku, P.M. Wambua, Journal of Reinforced Plastics and
Composites 31 (2012) 1261–1269.
[25] M.C. Khoathane, O.C. Vorster, E.R. Sadiku, Journal of Reinforced Plastics and
Composites 27 (2008) 1533–1544.
[26] S. Ifuku, T. Miwa, M. Morimoto, H. Saimoto, International Journal of Biological
Macromolecules 52 (2013) 14–19.
[27] T. Zhang, G.Y. Li, L. Guo, H. Chen, International Journal of Biological Macro-
molecules 51 (2012) 1109–1115.
[28] M.D. Oza, R. Meena, A.K. Siddhanta, Carbohydrate Polymers 87 (2012)
1971–1979.
[29] X. Qiu, X. Ren, S. Hu, Carbohydrate Polymers 92 (2012) 1887–1889.
[30] P.K. Bajpai, I. Singh, J. Madaan, Materials & Design 35 (2012) 596–602.
[31] P.K. Bajpai, I. Singh, J. Madaan, Journal of Reinforced Plastics and Composites
31 (2012) 1712–1724.
[32] V.K. Thakur, A.S. Singha, M.K. Thakur, Advances in Polymer Technology 31
(2012) E741–E748.
[33] V.K. Thakur, A.S. Singha, M.K. Thakur, Polymer-Plastics Technology and Engi-
neering 51 (2012) 1598–1604.
[34] V.K. Thakur, A.S. Singha, M.K. Thakur, International Journal of Polymer Analysis
and Characterization 17 (2012) 133–143.
[35] V.K. Thakur, A.S. Singha, M.K. Thakur, International Journal of Polymer Analysis
and Characterization 17 (2012) 48–60.
[36] V.K. Thakur, M.K. Thakur, R.K. Gupta, Carbohydrate Polymers 98 (2013)
820–882.