Macromol. Symp. 2012, 319, 191–195 DOI: 10.1002/masy.

201100158 191

Extraction and Characterization of Cellulose

Nanowhiskers from Balsa Wood
Carolina Lipparelli Morelli,1 Jose´ Manoel Marconcini,2 Fabiano Vargas Pereira,3
Rosario Elida Suman Bretas,1 Márcia Cristina Branciforti*4

Summary: In this study cellulose nanowhiskers were obtained from balsa wood. For
this purpose, fibers of balsa wood were exposed to hydrolysis reactions for lignin and
hemicellulose digestion and acquisition of nano-scale cellulose. Transmission elec-
tron microscopy (TEM) results demonstrated that the obtained cellulose nanocrystals
had average length and thickness of 176 (
68 nm) and 7.5 (
2.9 nm), respectively.
Infrared spectroscopy (FTIR) and wide angle x-ray diffraction (WAXD) showed that the
process for extracting the nanowhiskers digested nearly all the lignin and hemi-
cellulose from the balsa fiber and still preserved the aspect ratio and crystallinity
satisfactory enough for future application as nanofillers in polymer nanocomposites.
The thermogravimetric analysis (TGA) showed that the onset temperature of thermal
degradation of the cellulose nanocrystals (226 8C) was higher than the onset
temperature of the balsa fiber (215 8C), allowing its use in molding processes with
polymers melts.

Keywords: balsa wood; cellulose; crystallinity; nanowhiskers; renewable resources

Introduction and renewable character. The increase in

the stiffness of the thermoplastic matrix
Cellulose nanocrystals or nanowhiskers will also depend on the ratio between
(CNW) consist of particles with high length and thickness of the nanowhiskers
crystallinity and high specific surface area (aspect ratio). In this study we chose to
that can be obtained from various sources extract CNW from balsa wood, because of
of natural fibers such as cotton, bamboo, its high cellulose content (52%[4]) and
wood and some marine animals such as because it is a fast-growing tree, abundant
tunicates.[1,2] The crystallinity and the in the Amazon region and used as a pioneer
dimensions of these nanocrystals depend tree in the reforestation and recovery of
on the origin of the cellulose fibers as well degraded areas. One study showed that
as the procedure used to obtain them. The balsa tree grew 14 meters in 14 months in
theoretical elastic modulus of cellulose a plantation in a degraded pasture near
nanowhiskers is 167.5 GPa,[3] which makes Manaus, in Brazil.[5] Due to its rapid
them an interesting choice for the reinfor- growth, the shadow of the crown of the
cement of thermoplastics. In addition, balsa tree provides favorable conditions
CNW are biodegradable, have low density for the development of other plants of
slow growth, contributing to reforestation
and sustainable management.[6] The balsa
1
wood (Ochroma pyramidalis) is the lightest
Federal University of São Carlos, São Carlos – SP,
Brazil
wood of commercial use that exists and can
2
Embrapa Instrumentation, São Carlos – SP, Brazil weigh around 48 kg.m3, which is equiva-
3
Federal University of Minas Gerais – UFMG, Belo lent to one third of the weight of cork.
Horizonte – MG, Brazil
4
The balsa wood is largely used in the
University of São Paulo – USP, São Carlos – SP,
Brazil manufacture of boats and wind blades and
E-mail: [email protected] in aeromodelling.

Copyright ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com
192 Macromol. Symp. 2012, 319, 191–195

Experimental Part 24 h at 115 8C. Thermogravimetric analysis

(TGA) was also done using equipment Q50
Extraction of Cellulose Nanocrystals from TA Instruments between 28 8C and
Initially, the balsa wood slats were grounded 800 8C, at a heating rate of 20 8C min1,
into fine powder by using a Cremasco DPC-4 under nitrogen atmosphere (50 mL s1).
mill and washed with hot water (90 8C). Wide angle x-ray diffraction (WAXD) was
Sequentially, the balsa powder was treated done on dried samples of CNW and balsa
with 2 wt % of NaOH aqueous solution, at wood powder, in a Siemens diffractometer
90 8C, for 3 h, under mechanical stirring. This D5005 operating at 40 kV and 40 mA. The
procedure was done four times in order to scans were done between 58 and 408, with a
purify the cellulose pulp by removing others scan rate of 28 min1.
components present, like lignin and hemi-
cellulose. A bleaching treatment was done
later using a solution consisting of equal parts Results and Discussion
of acetate buffer solution and an aqueous
sodium chloride solution (1.7 wt %). This Figure 1 presents a TEM micrograph of
procedure was repeated twice, at 908C, each the cellulose nanocrystal extracted from
procedure lasting 3 h. For the extraction of the balsa wood and Figure 2 presents the
cellulose nanocrystals, an aqueous solution distribution of lengths and thicknesses
of sulfuric acid (65 wt %) was used with of the CNW. The micrographs and the
constant and vigorous stirring during 75 min measurements confirmed the nanometer
at 50 8C. After this period the suspension was dimensions of the obtained cellulose crys-
repeatedly centrifuged at 3500 rpm for tals, which had an average thickness (D)
10 min in a Heraeus Megafuge 2.0 centrifuge; of 7.5 (
2.9 nm, standard deviation) and
the supernatant was discarded until it an average length (L) of 176 (
68 nm,
became cloudy, indicating the presence of standard deviation). These values result in
the CNW in the suspension. The cloudy an aspect ratio (L/D) of 25. These values
suspension was then submitted to dialysis can be used to calculate the percolation
with water until neutrality was attained. volumetric fraction fv, using equation 1,
After this, the suspension of nanocrystals was given by the percolation theory:[7,8]
freeze-dried for the analysis of the CNW.
0:7
fV ¼ (1)
Characterization of Cellulose Nanocrystals L=D
Transmission electron microscopy (TEM)
was done using a Philips CM 120 microscope
with acceleration voltage of 120 kV. For
this analysis, a drop of aqueous suspension
with 0.01 wt % of cellulose nanocrystals
was deposited on a carbon-coated grid and
stained with a uranyl acetate solution
(2 wt%). The length and thickness of
approximately 100 nanocrystals were mea-
sured using the Image-Pro Plus 4.5 software.
Infrared spectroscopy (FTIR) was made in a
ThermoScientific Nicolet 6700 spectrometer,
between a wavelength range of 750 to
4000 cm1, with 32 scans and resolution of
4 cm1. For this purpose, samples of CNW
were grounded with liquid nitrogen and Figure 1.
dried for 24 h at 50 8C. They were then mixed TEM micrograph of the CNW obtained from balsa
(1 wt %) with KBr previously dried during wood.

Copyright ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ms-journal.de
Macromol. Symp. 2012, 319, 191–195 193

a) 20 b)
35
30
15
25
Frequency

Frequency
20
10
15

5 10
5
0 0
50 100 150 200 250 300 350 400 450 2 4 6 8 10 12 14 16 18
Length (nm) Thickness (nm)

Figure 2.
Histograms of distribution of (a) lengths and (b) thicknesses of the CNW.

The density of the CNW is 1.6 g cm3[9] vibration bands. The presence of lignin
and the density of the most part of conven- can be identified mainly by the absorption
tional polymer matrices lays between 0.8 and peaks related to the C¼C bond of the
2 g cm3; therefore, to achieve the formation aromatic ring, which absorbs in the
of a percolating network in the polymer range between 1460 and 1600 cm1.[10–12]
matrix, it would be necessary to add between The presence of hemicellulose can be
2 and 6 wt % of CNW to the polymer matrix. identified mainly through the peak corre-
These values justify the application of CNW sponding to the C¼O bond, which occurs
from balsa wood in polymer matrices, which around 1730 cm1.[10–12] In the infrared
will be the next step of this work. spectrum of the CNW, these peaks are
The infrared spectra of balsa wood not observed, which would prove the
and CNW are shown in Figure 3. Table 1 efficiency of the extraction of lignin and
shows the peak assignments of the main hemicellulose from the balsa wood.
1378

1.0
1323
1159
1115
1426

0.9
3373

0.8
1506
1646

1247
Absorbance (a.u.)

1054

0.7
2920

1597
1736

0.6
899

0.5
Balsa
0.4
0.3
0.2 CNW
0.1
0.0
4000 3500 3000 2500 2000 1500 1000
-1
Wavenumber (cm )
Figure 3.
Infrared spectrum of balsa wood and CNW.

Copyright ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ms-journal.de
194 Macromol. Symp. 2012, 319, 191–195
Table 1.
Frequencies of vibration of the infrared spectra[10,11,12].

Wavenumber Peak assignment Wavenumber Peak

(cm1) (cm1) assignment
3373 OH (stretching) 1378 CH (bending)
2920 CH (stretching) 1323 CH (bending)
1736 C¼O (stretching) 1247 CO (stretching), related to phenol
1646 HOH (bending due to H2O) 1159 CO (stretching), related to alcohol
1597 C¼C aromatic (stretching) 1115 CO (stretching), related to alcohol
1506 C¼C aromatic (stretching) 1054 CO (stretching), related to alcohol
1462 C¼C aromatic (stretching) 899 CH (bending)
1426 CH (bending)

In the WAXD diffractograms of balsa of lowest thermal resistance of the fiber,

wood and CNW, shown in Figure 4, having degradation between 200 and
diffraction peaks characteristics of cellulose 260 8C.[15] However, the maximum degra-
I around 158 (001), 22.58 (002) and 348 dation temperature of balsa (357 8C) was
(040)[13,14] can be observed. The deconvo- higher than that for CNW (337 8C), what
lution of the peaks allowed obtaining the can be clearly visualized in the DTG curves.
degree of crystallinity by the ratio between This is probably due to the presence of
the area corresponding to the crystalline lignin in the balsa wood, that was extracted
peaks and the total area. The balsa wood for the CNW acquisition. Lignin is the
powder showed a crystallinity index of 42% constituent of higher thermal stability of
while the CNW had 62% of crystallinity. wood, between 300 and 5008C.[15] The first
Curves obtained by TGA, shown in mass loss (about 6% for both samples)
Figure 5, indicated that the CNW had a occurred between 28 and 100 8C and refers
higher onset temperature of thermal degra- to the evaporation of water and volatile
dation (226 8C) than the balsa fibers products. The residue obtained at 800 8C
(215 8C). This is probably due to the was 19% for balsa fiber and 30% for the
absence of hemicellulose in the CNW, CNW, probably relative to inorganic con-
since the hemicellulose is the component stituents of wood, like Ca and K. Once the

(002) CNW
400
22,5
o Balsa powder
350

300
CNW
Intensity (a.u.)

250 (101)
o
15
200
Balsa (040)
150
powder o
34
100

50

5 10 15 20 25 30 35 40
o
2θ ( )
Figure 4.
X-ray diffraction patterns of balsa wood and CNW.

Copyright ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ms-journal.de
Macromol. Symp. 2012, 319, 191–195 195

100 CNW 1.0

90 Balsa wood
80 0.8

dm/dT (%/ C)
Mass loss (%)
70

o
60 0.6

50
0.4
40
30 0.2
20
10 0.0

0 100 200 300 400 500 600 700 800

o
Temperature ( C)

Figure 5.
TGA curves of balsa wood and CNW.

most part of constituents of balsa had [2] K. Oksman, A. P. Mathew, M. Sain, Plastics, Rubber
already been digested in the obtaining and Composites 2009, 38, 9/10.
[3] K. Tashiro, M. Kobayashi, Polymer 1991, 32, 1516.
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[4] D. Fengel, G. Wegener, Wood: Chemistry, Ultrastructure,
residual mass of CNW is proportionally Reactions, Berlin; New York 1984.
higher than the residual mass of the raw [5] A. Barbosa, Instituto Nacional de Pesquisas da
balsa. Amazônia 2004.
[6] M. C. Branciforti, A. L. Marinelli, M. Kobayashi, J. D.
Ambrosio, M. R. Monteiro, A. D. Nobre, Sustainability
Conclusion 2009, 1, 1431.
[7] V. Favier, R. Dendievel, G. Canova, J. Y. Cavaille,
P. Gilormini, Acta Mater 1997, 45, 1557.
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successfully used as a source to obtain molecules 2005, 6, 612.
cellulose nanocrystals that can be incorpo- [9] J. Araki, M. Wada, S. Kuga, T. Okano, Colloids and
rated into polymer matrices to manufacture Surfaces A: Physicochemical and Engineering Aspects
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[10] C. J. Pouchert, The Aldrich Library of Infrared
this work had average length and thickness
Spectra, 1975.
of 176 (
68 nm) and 7.5 (
2.9 nm), respec- [11] M. F. Rosa, E. S. Medeiros, J. A. Malmonge, K. S.
tively, crystallinity of 62% and onset tem- Gregorski, D. F. Wood, L. H. C. Mattoso, G. Glenn,
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Acknowledgements: The authors thank CAPES [12] D. L. Pavia, G. M. Lampman, G. S. Kriz, Introduction
for financial support (project Nanobiotec No. 13 to Spectroscopy, Saunders College Publishing, 1996.
and Ph.D. scholarship) and the company Orion [13] S. Park, J. O. Bakerl, M. E. Himmel, P. A. Parilla, D. K.
Balsa Wood for supplying the balsa wood. Johnson, Biotechnology for Biofuels 2010, 3, 10.
[14] C. J. Garvey, I. H. Parker, G. P. Simon, Macromol.
Chem. Phys. 2005, 206, 1568.
[1] R. Silva, S. K. Haraguchi, E. C. Muniz, A. F. Rubira, [15] F. Tomczak, T. H. D. Sydenstricker, K. G. Satyanarayana,
Quı́mica Nova 2009, 32, 661. Composites: Part A, 2007, 38, 1710.

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