Industrial Crops and Products 33 (2011) 63–66

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Industrial Crops and Products

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

Sugarcane bagasse whiskers: Extraction and characterizations

Eliangela de Morais Teixeira a , Thalita Jessika Bondancia a,b , Kelcilene Bruna Ricardo Teodoro a,b ,
Ana Carolina Corrêa a , José Manoel Marconcini a , Luiz Henrique Caparelli Mattoso a,∗
a
National Nanotechnology Laboratory for Agriculture (LNNA), Embrapa Agricultural Instrumentation, P. O. Box 741, CEP: 13560-970, São Carlos, SP, Brazil
b
Federal University of São Carlos (UFSCar), Chemistry Department, P. O. Box: 676, CEP: 13565-905, São Carlos, SP, Brazil

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

Article history: This work evaluates the use of sugarcane bagasse (SCB) as a source of cellulose to obtain whiskers. These
Received 15 June 2010 fibers were extracted after SCB underwent alkaline peroxide pre-treatment followed by acid hydrolysis
Received in revised form 13 August 2010 at 45 ◦ C. The influence of extraction time (30 and 75 min) on the properties of the nanofibers was inves-
Accepted 28 August 2010
tigated. Sugarcane bagasse whiskers (SCBW) were analyzed by transmission electron microscopy (TEM),
X-ray diffraction (XRD) and thermogravimetric analysis (TGA) in air atmosphere. The results showed
that SCB could be used as source to obtain cellulose whiskers and they had needle-like structures with
Keywords:
an average length (L) of 255 ± 55 nm and diameter (D) of 4 ± 2 nm, giving an aspect ratio (L/D) around 64.
Sugarcane bagasse
Sugarcane bagasse whiskers
More drastic hydrolysis conditions (75 min) resulted in less thermally stable whiskers and caused some
Acid hydrolysis damage on the crystal structure of the cellulose as observed by XRD analysis.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction the production of nano-sized cellulose-like microfibrils, such as

There has been increasing interest in cellulose based-materials
due to the abundance, renewable and eco-friendly nature of cel-
lulose (Hubbe et al., 2008). Currently, by diversifying the use of
cellulosic fibers, a new research trend has been seen for obtain-
ing whiskers from several cellulose sources, whether from animal
origin (such as tunicin) (Anglès and Dufresne, 2000), cotton plant
fibers (Dong et al., 1998), sisal (De Rodriguez et al., 2006; Morán et
al., 2008; Siqueira et al., 2009a) and capim dourado (Siqueira et al.,
2009b).
One way to obtain such whiskers is by acid hydrolysis where
the cellulose is exposed to sulfuric acid for a controlled period of
time and temperature. This process removes the amorphous parts
of the cellulose, leaving single and well-defined crystals in a stable
colloidal suspension. The negative sulfate groups on the surface of
the nanofibers guarantee the stability of this suspension due to the
electrostatic repulsion (Lima and Borsali, 2004; Dufresne, 2006).
The whiskers’ high stiffness, surface area and crystallinity are suit-
able for applications in polymeric matrices, acting as reinforcing
elements (Gardner et al., 2008).
Sugarcane bagasse (SCB) is a residue from the refining process
of sugarcane that contains about 40–50% of cellulose in its compo-
sition (Sun et al., 2004). This characteristic suggests the possibility
of using the SCB as a source of cellulose fibers for the extraction
of whiskers structures. Agroindustrial residues have been used for
banana residues (Zuluaga et al., 2007) and wheat straw (Alemdar
and Sain, 2008) and nanofibrils from cassava bagasse (Teixeira et al.,
2009). Bhattacharya et al. (2008) obtained microfibrils from sugar-
cane bagasse by acid hydrolysis through the use of sulfuric acid at
60 ◦ C for 2.5 h, after bleaching the sugarcane bagasse with sodium
chlorite and glacial acetic acid.
The aim of this work was to isolate and characterize cellulose
whiskers from sugarcane bagasse pre-bleached with alkaline per-
oxide solution (free-chlorine reagent) by acid hydrolysis conditions
at a mild temperature (45 ◦ C), and to investigate the influence of
extraction time (30 and 75 min) on the morphology, crystallinity
and thermal stability in air atmosphere of the resulting whiskers.
2. Experimental
2.1. Materials
Unpurified sugarcane bagasse (SCB) containing about 43.6, 27.7
and 27.7% of cellulose, lignin and hemicelluloses, respectively, were
kindly supplied by Edra Eco Sistemas (Ipeúna-SP, Brazil). Hydrogen
peroxide (Nuclear) and NaOH (Qhemis) was used for bleaching the
bagasse. The cellulose was hydrolyzed with sulfuric acid (Synth)
and the cellulose membrane (Sigma–Aldrich: D9402) was used to
dialyze the products.
2.2. Purification of cellulose from sugarcane bagasse

∗ Corresponding author. Tel.: +55 1621072804. The sugarcane bagasse (used as received) was submitted to a
E-mail address: mattoso@cnpdia.embrapa.br (L.H.C. Mattoso). bleaching process. This process was adapted by Sun et al. (2004)

0926-6690/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.indcrop.2010.08.009
64 E.d.M. Teixeira et al. / Industrial Crops and Products 33 (2011) 63–66
Fig. 1. Images of SCB (a) before and (b) after the bleaching with alkaline peroxide solution.
and is describes below. About 5 g of SCB were sonified in 300 mL of
distilled water for 30 min. Next, the SCB was filtered to remove the
excess of water. Then, this pre-washed material was put in a flask
containing 100 mL of NaOH 5 wt% solution at 55 ◦ C. Next, 100 mL of
hydrogen peroxide solution (11%, v/v) was added to the flask. The
system was vigorously stirred for 90 min. After that, the SCB was
filtered and washed with distilled water until neutral pH. The SCB
was dried at 50 ◦ C until constant weight. This product was sub-
mitted again to the same bleaching process for a more effective
discoloration.
2.3. Determination of residual lignin
The residual lignin content of bleached SCB was analyzed by
reaction with sulfuric acid, using a standard method as recom-
mended by TAPPI-T222 om-88.
2.4. Preparation of the cellulose nanofibers from SCB
About 5.0 g of bleached SCB were dispersed in 100 mL of 6 M
sulfuric acid at 45 ◦ C and vigorously stirred for 30 min or 75 min.
Next, 500 mL of cold distilled water was added to stop the reaction.
The sulfuric acid was partially removed from the resulting suspen-
sion by centrifugation at 10,000 rpm for 10 min. The non-reactive
sulfate groups were removed by centrifugation followed by dialy-
sis in tap water with a cellulose membrane, until the pH reached
6 to 7. The neutral suspension was ultrasonicated for 5 min and
stored in a refrigerator after adding chloroform drops. The cellulose
whiskers were labeled SCBW30 or SCBW75 depending on the time of
extraction. The yield of whiskers was determined by weighting an
aliquot of 10 mL of the supernatant of the suspension after standing
overnight to dry. The yield (%) was calculated from the difference
between the initial and final weight. For XRD and TG analysis an
aliquot of 25 mL was dried at 35 ◦ C for 12 h in an air-circulating
oven.
2.5. Scanning transmission electron microscopy (STEM)
The whiskers samples were examined by TEM in a TecnaiTM
G2 F20 equipment. The images were acquired in STEM (scanning
transmission electron microscopy) mode, with a bright-field (BF)
detector. A droplet of diluted suspension was deposited on a car-
bon microgrid (400 mesh) and allowed to dry. The grid was stained
with a 1.5% solution of uranyl acetate and dried at room tempera-
ture.
2.6. X-ray diffraction (XRD)
The X-ray diffraction patterns were obtained in an X-ray diffrac-
tometer (VEB Carl Zeiss-Jena URD-6 Universal Diffractometer),
´ at 40 kV and 20 mA. Scattered
using CuK␣ radiation ( = 1.5406 Å)
radiation was detected in the range of 2 = 5–40◦ , at a scan rate of
2◦ /min. The extent of crystallinity (CI% ) was estimated on the basis
of areas under crystalline and amorphous peaks after an appropri-
ate baseline correction and the applying of a devolution technique
through the use of the Origin 7.5 software and a Gaussian line shape
to the peaks.
2.7. Thermogravimetric analysis (TGA)
Dried whiskers were subjected to TGA in a TA Q500 ther-
mal analyzer (TA Instruments, New Castle, DE, USA). The samples
(10.0 ± 1.0 mg) were heated in a Pt crucible from 25 to 600 ◦ C in air
flowing at 60 mL min−1 . The heating rate was 10 ◦ C min−1 .
3. Results and discussion
Fig. 1 shows the physical aspect of the original SCB and after
the bleaching with alkaline peroxide solution. The great effective-
ness of the process was observed because a white colored SCB was
obtained. The lignin content after the bleaching was calculated to
be 5.8 wt%, indicating that a great part of the initial lignin was
removed, resulting in a purer cellulose, hence more suitable for
extracting whiskers.
The resulting suspensions and the morphology of whiskers are
shown in Fig. 2. After acid hydrolysis, the suspensions were sta-
ble but the sample hydrolyzed for 75 min (SCBW75 ) presented a
brown coloring in the suspension, indicating some level of cellulose
degradation. TEM micrographs presented needle-like whiskers,
especially sample SCBW30 . The dimensions were calculated with
the ImageJ software. Both whiskers had a length (L) of around
255 ± 55 nm and the diameters (D) of 4 ± 2 and 8 ± 3 nm for SCBW30
and SCBW75 , respectively. No significant difference in length or
diameter among the whiskers could be detected by STEM among
the whiskers, if the standard deviation of each value is taken
into account. A slight larger diameter for SCBW75 sample could
be due to some small agglomerations of whiskers. The diame-
ters measured were similar to the nano-sized structures derived
from other sources of agro-residues such as nanofibrils from cas-
sava bagasse (2–11 nm) (Teixeira et al., 2009) and banana residues
(5 nm) (Zuluaga et al., 2007) and smaller than microfibrils from
wheat straw (10–80 nm) (Alemdar and Sain, 2008) and sugarcane
bagasse (30 nm) (Bhattacharya et al., 2008). The yield was 58% for
SCBW30 and 50% for SCBW75 .
 E.d.M. Teixeira et al. / Industrial Crops and Products 33 (2011) 63–66 65

Fig. 2. Suspensions of SCB whiskers: (a) extracted at 30 min (SCBW30 ) and (b) extracted at 75 min (SCBW75 ).

The X-ray diffraction patterns of the bleached SCB and their

respective nanofibers are shown in Fig. 3 and the crystallinity val-
ues are shown in Table 1. The diffractograms display a mixture
of polymorphs of cellulose I (typical peaks at 2 ∼ 15◦ and 22.6◦ )
and cellulose II (peaks at 12.3◦ and 22.1◦ ) (Klemm et al., 2005).
An increase in crystallinity of SCBW30 with respect to bleached SCB
was observed, indicating that the hydrolysis was effective. The sam-
ple SCBW75 presented a decrease in crystallinity and a little change
in the diffractogram profile, with the disappearance of the peak at
2 = 15.3◦ . This observation, added to the physical aspect of SCBW75
suspension (brown coloration, Fig. 2), suggests that the extraction
time of 75 min was severe enough to remove not only the amor-
phous phase but also to destroy part of the cellulose crystalline

Table 1
Crystallinity index (CI% ) and initial temperature of thermal degradation (Tid , air
atmosphere) for SCB bleached and their whiskers.

Sample CI% (%) Tid (◦ C)

SCB bleached 76.0 270.0

SCBW30 87.5 255.0
SCBW75 70.5 210.0
Fig. 3. X-ray diffraction patterns of bleached SCB, SCBW30 and SCBW75 .
66 E.d.M. Teixeira et al. / Industrial Crops and Products 33 (2011) 63–66
Fig. 4. The TG (a) and DTG (b) curves of bleached SCB and whiskers. Analysis in air
atmosphere, heated at 10 ◦ C min−1 .
regions. Similar effect of hydrolysis time in excess was observed by
Chen et al. (2009) for whiskers from pea hull fibers, although the
rod-like structures were maintained.
The TG curves for the bleached SCB and nanofibers (Fig. 4a)
in air atmosphere exhibit an initial small drop between 50 and
150 ◦ C, which corresponds to absorbed moisture, with a mass loss of
approximately 5%. The initial temperatures of thermal degradation
(Tid ) of the samples are presented in Table 1 and were attributed to
cellulose depolymerisation. In this step, the thermal degradation of
nanofibers proceeded at lower temperatures than for the bleached
SCB. This behavior was expected given that the introduction of
sulfate groups in the cellulose diminishes the thermostability of
cellulose crystals (Roman and Winter, 2004). As observed in the
data of Table 1, sample SCBW75 had lower thermal stability than
sample SCBW30 . The DTG curves of the nanofibers (Fig. 4b) show
a large peak at the range of 235–365 ◦ C for SCBW30 and multiples
peaks of around 200–370 ◦ C for SCBW75 , respectively. This reveals a
greater heterogeneity of the samples due to the different content of
sulfate groups incorporated on the cellulose surface. More sulfated
regions of cellulose degrade at lower temperatures, while regions
less accessed by the sulfate groups of the acid tend to be more ther-
mally stable (Wang et al., 2007; Li et al., 2009). Thus, the condition of
hydrolysis for 75 min resulted in a major cellulose sulfonation, also
contributing to the cellulose degradation by dehydration reactions,
hence causing damages in the crystal structure of cellulose, as was
verified by XRD analysis. Because less sulfonation occurred when
hydrolysis was carried out for 30 min, this effect was minimized.
4. Conclusions
SCB could be the source of cellulose for the attainment of
whiskers. SCB was successfully bleached by a less aggressive to
the environment reagent (alkaline peroxide solution). SCB whiskers
were obtained at a mild temperature (45 ◦ C) and at a shorter
extraction time (30 min). The SCB whiskers presented a length
(L) of around 255 ± 55 nm and average diameter (D) of 4 nm, and
good thermal stability (255 ◦ C) and high crystallinity (87.5%). SCB
whiskers obtained by a longer extraction time (75 min) damaged
the crystalline structure of cellulose, resulting in a decrease of their
thermal stability.
Acknowledgements
The authors gratefully acknowledge the financial support pro-
vided by FAPESP (Process No. 07/50863-4), FINEP, MCT, CNPq and
EMBRAPA.
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