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Cellulose
Cellulose
a r t i c l e
i n f o
Article history:
Received 7 April 2013
Received in revised form 8 August 2013
Accepted 16 August 2013
Keywords:
Pineapple leaf
Cellulose nanocrystals
Agricultural residue
Reuse
a b s t r a c t
Pineapple leaf (PL) is an annually renewable agricultural residue, available in abundance, which is used
very rarely and is of limited value at present. Therefore, this agro-waste deserves to be better and/or
properly used. The aim of this study was to explore PL as a source of raw material for the production of
cellulose nanocrystals (CN). The CN were extracted by acid hydrolysis at 45 C for 5, 30 or 60 min, using
20 mL of H2 SO4 (9.17 M) for each gram of material. The resulting CN were characterized by crystallinity
index, FTIR, morphology (shape and size) and thermal stability. Among the hydrolysis conditions carried
out, the best extraction time was 30 min. At this extraction time, the CN presented a needle-shaped
nature, high thermal stability (225 C), high crystallinity (73%), an average length of 249.7 51.5 nm and
a diameter of 4.45 1.41 nm, giving an aspect ratio (L/D) of around 60. Therefore, CN obtained from PL
has great potential as reinforcement in the manufacture of nanocomposites. The production of CN from
this underutilized agro-waste has commercial application potential that can add value to the pineapple
cultivation, generate extra income for farmers and also help in agribusiness diversication. In addition,
the reuse of these residues allows a signicant reduction in both the volume of waste accumulated in the
environment and in the extraction of raw materials.
2013 Elsevier B.V. All rights reserved.
1. Introduction
In recent years, the quest for sustainable development has motivated efforts toward maximizing the efciency of the use of raw
materials and minimizing the creation of waste (Ashori, 2008). In
this context, the use of biomass residues as feedstock for the production of energy and materials has been the object of intensive
academic and industrial research (Mishra et al., 2004; Reddy and
Yang, 2005; Schievano et al., 2009; Silva et al., 2009). The reuse of
these residues allows a signicant reduction both in the volume of
waste accumulated in the environment and in the extraction of raw
materials. Thus, an efcient reuse of these wastes is of great importance, not only for minimizing the environmental impact, but also
for obtaining a higher prot.
Agriculture is an important sector in the Brazilian economy
(Rahman, 2011). Diversication of the industry is crucial in encouraging economic stability and growth. The utilization of these crop
Corresponding author. Tel.: +55 34 3239 4143; fax: +55 34 3239 4208.
E-mail addresses: pasquini@iqufu.ufu.br, danielpasquini2005@yahoo.com.br
(D. Pasquini).
0926-6690/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.indcrop.2013.08.049
708
uses for leaves that can generate extra income for these farmers
(de Aquino, 2006; Mishra et al., 2004).
The practices of decomposing and burning the pineapple leaf
(PL) in situ do not contribute to the improvement of plantation yield,
as reported in previous literature (Ahmed et al., 2002; Mohamed
et al., 2009).
PL is an annually renewable agricultural residue, that is
biodegradable, available in abundance (inexpensive), used very
rarely and of limited value at present. In addition, after harvesting, PL waste remains, causing various problems for farmers to deal
with. There is a great demand to nd other end uses for these agricultural cellulosic wastes (Cherian et al., 2010, 2011; Kengkhetkit
and Amornsakchai, 2012; Maniruzzaman et al., 2011). Hence, without any additional cost input, PL bers can be obtained for industrial
purposes.
Several processes and products have been reported that utilize PL as a raw material. These include the extraction of cellulose
ber and nanober, the production of paper, textiles and composites (Banik et al., 2011; Cherian et al., 2010; Chollakup et al.,
2011; Kengkhetkit and Amornsakchai, 2012; Mishra et al., 2004;
Threepopnatkul et al., 2009). However, there is not yet any published work on the extraction of cellulose nanocrystals (CN) from
PL.
CN have attracted immense interest as a novel nanostructured material during recent years. CN are very high crystallinity
nanoparticles derived from cellulosics bers. CN are a very highvalue material, since they can transform the performance of
existing products as well as helping to create new, unique and
improved products. The unique combination of amazing physicochemical properties and environmental benets allows that the CN
offer a wide range of potential applications. At present, the main
application of CN is as a reinforcing agent in the nanocomposite
eld. Others elds of potential applications are packaging, paints,
coatings, special papers, cosmetics, pharmaceuticals, biomedical
materials, textiles, the automotive industry, aerospace, building
materials, the electronic and electrical industry, and many others
(Moon et al., 2011; Peng et al., 2011; Podsiadlo et al., 2005; Silvrio
et al., 2013). One specic example of the application of CN is the
solidication of liquid crystals for optical applications, e.g. security
paper (Beck et al., 2011; Revol et al., 1998).
It is known that the morphology and properties of the CN
depend mainly on the source of the original cellulose, of the extraction process and their parameters (Beck-Candanedo et al., 2005;
Elazzouzi-Hafraoui et al., 2008). Therefore, the isolation and further
analysis of the characteristics of CN from many kinds of cellulosic
resources is necessary and relevant for the efcient comparison and
exploitation of these resources (Chen et al., 2011; Flauzino Neto
et al., 2013; Silvrio et al., 2013).
CN have been isolated from different vegetable sources, such
as cotton and wood pulp (Beck-Candanedo et al., 2005; Teixeira
et al., 2010), and from animal sources such as tunicates (Berg et al.,
2007). In addition, there are only a few papers which describe the
isolation of whiskers from agricultural byproducts, such as soy hulls
(Flauzino Neto et al., 2013), corncob (Silvrio et al., 2013), rice husk
(Rosa et al., 2012) and sesame husk (Purkait et al., 2011).
In this work, CN were extracted from PL under different conditions of sulfuric acid hydrolysis in order to obtain a material with
a high crystallinity index, thermal stability, aspect ratio and yield.
Different techniques were employed to characterize the PL at different stages of treatment. The characteristics investigated were
the chemical composition, crystallinity index, thermal stability,
surface charge and morphology (shape and size). The aim in this
study was to investigate the viability of this agricultural residue as
a simple and low-cost source of CN and the possibility of adding
value to the pineapple cultivation through a new approach to their
utilization.
2. Experimental
2.1. Materials and methods
The PL used in this study was obtained from residues after harvesting pineapple in the So Mateus farm (Comendador Gomes,
Minas Gerais, Brazil). The plant species used was Ananus cosomus belonging to the Bromeliaceae family. The other reagents
employed in this study were: sulfuric acid (95.098.0 wt.%, Vetec,
P.A.), sodium hydroxide (Vetec), potassium hydroxide (Vetec),
sodium chlorite (NaClO2 , technical grade, 80%, SigmaAldrich),
glacial acetic acid (Synth), and cellulose membrane (D9402,
SigmaAldrich).
709
Fig. 1. Photographs of (a) the pineapple cultivation, (b) untreated pineapple leaves, (c) ground pineapple leaves, and (d) treated pineapple leaves.
y = y0 + A mu
2.5. Chemical composition
wL
2
4(x xc )2 + w2
L
4 ln 2
+ (1 mu )
WG
(4 ln 2/w2 )(xxc )2
G
(1)
where wL and wG are the width at half maximum for Lorentz and
Gauss components of the above equation, respectively, A is the area
and mu is the prole shape factor.
Considering this model, the crystallinity indexes (CrI) of the
samples were calculated using Eq. (2):
CrI =
Ac
Ac + Aa
100
(2)
where Ac and Aa are the areas under the crystalline peaks and the
amorphous halos, respectively determined by the deconvolutions.
2.6.1. Atomic force microscopy (AFM)
AFM measurements were performed with Shimadzu SPM-9600
equipment for evaluating the morphology of CNPL5 , CNPL30 and
CNPL60 . A drop of a diluted nanocrystals aqueous suspension (to
about 5.105 g mL1 ) was deposited onto a freshly cleaved mica
surface and air-dried. AFM images were obtained at room temperature in the dynamic mode with a scan rate of 1 Hz and using Si
tips with a curvature radius of less than 10 nm and a spring constant of 42 N m1 . The dimensions of nanocrystals were determined
using VectorScan software (software for Shimadzus SPM-9600).
To eliminate the effect of tip radius on width measurements, we
measured the heights of the nanocrystals, which are not subject
to peak broadening artifacts, and assumed the nanocrystals to be
cylindrical in shape (Beck-Candanedo et al., 2005). Seventy-ve
nanocrystals were randomly selected to determine the average
length, width and aspect ratio. For each nanocrystal, one measurement of the length and two measurements of the diameter were
performed and the aspect ratio was calculated.
2.6.2. Thermal characterization (TG)
Thermal stabilities of PL, TPL, CNPL5 , CNPL30 and CNPL60 were
evaluated using Shimadzu DTG-60H equipment. The analysis
710
Fig. 3. The resulting colloidal suspensions for CNPL5 , CNPL30 and CNPL60 after a few
hours of rest.
711
CNPL30
CNPL60
Length (nm)
Diameter (nm)
249.7 51.5
190.2 36.5
4.45 1.41
4.18 1.44
60.1 19.5
50.4 20.7
712
Fig. 7. Length (L), width (D) and aspect ratio (L/D) histograms of CNPL30 and CNPL60 obtained by several AFM images.
713
Acknowledgements
The authors thank CAPES/PROAP, CNPq and FAPEMIG for nancial support.
References
Fig. 8. Thermogravimetric (TG) curves of the PL, TPL, CNPL5 , CNPL30 and CNPL60 .
it was actually almost the same (245 vs. 244 C). This can be clearly
explained by the higher cellulose content of CNPL5 compared to
TPL and the small hydrolysis time (small amount of sulfate groups)
of sample CNPL5 .
The CNPL30 sample presented a decrease in initial degradation
temperature with respect to CNPL5 , as expected since the CNPL30
sample had a higher sulfate content than CNPL5 . Similar behavior
was observed when comparing the initial degradation temperature of samples CNPL30 and CNPL60 . These results are consistent
with results obtained from the Chemical Composition, XRD and
FTIR measurements.
4. Conclusions
The present work shows that PL is an interesting source of
raw material for the production of CN, due to the characteristics
of the obtained nanocrystals. Chemical treatment performed with
sodium chlorite and alkali removed the non-cellulosic components
resulting in bers with a low content of lignin and a high content of cellulose, which were therefore suitable for extracting CN.
Through the AFM images it was observed that there was an incomplete isolation of CN after 5 min of hydrolysis by the employed
conditions (sample CNPL5 ). However, above 30 min of hydrolysis it was possible to obtain stable aqueous suspensions of CNPL
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The yields of acid hydrolysis, with respect to the initial amount of
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55 wt%, respectively. The increase in the hydrolysis time resulted
in a decrease in the dimensions and also in the aspect ratio (L/D) of
the CNPL.
For an extraction time of 30 min, the CN presented a needleshaped nature, high thermal stability (225 C), high crystallinity
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4.45 1.41 nm, giving an aspect ratio of around 60 (which is among
the largest values reported in the literature). It can be concluded
from these results that the CN obtained from PL has great potential to be used as reinforcement agents for the manufacture of
nanocomposites and also for diversied applications.
The production of CN from this underutilized agro-waste has
commercial application potential that can add value to the pineapple cultivation, generate extra income for farmers and also help
in agribusiness diversication. In addition, the reuse of these
residues allows a signicant reduction both in the volume of
waste accumulated in the environment, as in the extraction of raw
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