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Cellulose nanocrystals from pineapple leaf, a

new approach for the reuse of this agro-waste

Article in Industrial Crops and Products October 2013

DOI: 10.1016/j.indcrop.2013.08.049


31 22

6 authors, including:

Wilson Pires Flauzino Neto Daniel Pasquini

Grenoble Institute of Technology Universidade Federal de Uberlndia (UFU)


All in-text references underlined in blue are linked to publications on ResearchGate, Available from: Wilson Pires Flauzino Neto
letting you access and read them immediately. Retrieved on: 24 October 2016
Industrial Crops and Products 50 (2013) 707714

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Industrial Crops and Products

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Cellulose nanocrystals from pineapple leaf, a new approach for the

reuse of this agro-waste
Roni Marcos dos Santos a, Wilson Pires Flauzino Neto a, Hudson Alves Silvrio a,
Douglas Ferreira Martins a , Nolio Oliveira Dantas b , Daniel Pasquini a,
Instituto de Qumica, Universidade Federal de Uberlndia, Campus Santa Mnica, Av. Joo Naves de vila, 2121, 38400-902, Uberlndia, Minas Gerais,
Instituto de Fsica, Universidade Federal de Uberlndia, Campus Santa Mnica, Av. Joo Naves de vila, 2121, 38400-902, Uberlndia, Minas Gerais, Brazil

a rti c l e in f o abstrac t

Article history: Pineapple leaf (PL) is an annually renewable agricultural residue, available in abundance, which is used
Received 7 April 2013 very rarely and is of limited value at present. Therefore, this agro-waste deserves to be better and/or
Received in revised form 8 August 2013 properly used. The aim of this study was to explore PL as a source of raw material for the production of
Accepted 16 August 2013
cellulose nanocrystals (CN). The CN were extracted by acid hydrolysis at 45 C for 5, 30 or 60 min, using
20 mL of H2SO4 (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
Pineapple leaf
out, the best extraction time was 30 min. At this extraction time, the CN presented a needle-shaped
Cellulose nanocrystals
Agricultural residue nature, high thermal stability (225 C), high crystallinity (73%), an average length of 249.7 51.5 nm and
Reuse 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 residues in industrial processes for the generation of value-added

products, such as in the production of high performance materi-
In recent years, the quest for sustainable development has moti- als, could be an additional source of revenue for farmers and also
vated efforts toward maximizing the efciency of the use of raw help in agro-industry diversication by providing a non-food-based
materials and minimizing the creation of waste (Ashori, 2008). In market for agro-wastes (Alemdar and Sain, 2008; Flauzino Neto
this context, the use of biomass residues as feedstock for the pro- et al., 2013; Rahman, 2011; Reddy and Yang, 2005; Silvrio et al.,
duction of energy and materials has been the object of intensive 2013).
academic and industrial research (Mishra et al., 2004; Reddy and Pineapple is one of the most popular tropical fruits in the world
Yang, 2005; Schievano et al., 2009; Silva et al., 2009). The reuse of and their crop occupies a prominent position in the Brazilian
these residues allows a signicant reduction both in the volume of agricultural sector. Brazil is one of the main producers of this
waste accumulated in the environment and in the extraction of raw crop, accounting for approximately 10.9% of the world production
materials. Thus, an efcient reuse of these wastes is of great impor- ( Mundo 2010.
tance, not only for minimizing the environmental impact, but also pdf). Currently, the main focus of the pineapple industry in this
for obtaining a higher prot. country is the fruits and related foodstuffs and consequently the
Agriculture is an important sector in the Brazilian economy other plant parts (stems, roots and especially leaves) are consid-
(Rahman, 2011). Diversication of the industry is crucial in encour- ered agricultural residues of pineapple cultivation (dos Santos
aging economic stability and growth. The utilization of these crop et al., 2001; Fagundes and Fagundes, 2010). The post-harvest
residue comprises mainly pineapple leaves, which are mostly
burned to eliminate fungi and other parasites, composted or just
Corresponding author. Tel.: +55 34 3239 4143; fax: +55 34 3239 4208. crammed to rot (de Aquino, 2006; Maniruzzaman et al., 2011). This
E-mail addresses:, is due to the lack of adequate technology for this purpose, as well
(D. Pasquini). as the ignorance of the farmers about the existence of commercial

0926-6690/$ see front matter 2013 Elsevier B.V. All rights reserved.
708 R.M.d. Santos et al. / Industrial Crops and Products 50 (2013) 707714

uses for leaves that can generate extra income for these farmers 2. Experimental
(de Aquino, 2006; Mishra et al., 2004).
The practices of decomposing and burning the pineapple leaf 2.1. Materials and methods
(PL) in situ do not contribute to the improvement of plantation yield,
as reported in previous literature (Ahmed et al., 2002; Mohamed The PL used in this study was obtained from residues after har-
et al., 2009). vesting pineapple in the So Mateus farm (Comendador Gomes,
PL is an annually renewable agricultural residue, that is Minas Gerais, Brazil). The plant species used was Ananus coso-
biodegradable, available in abundance (inexpensive), used very mus belonging to the Bromeliaceae family. The other reagents
rarely and of limited value at present. In addition, after harvest- employed in this study were: sulfuric acid (95.098.0 wt.%, Vetec,
ing, PL waste remains, causing various problems for farmers to deal P.A.), sodium hydroxide (Vetec), potassium hydroxide (Vetec),
with. There is a great demand to nd other end uses for these agri- sodium chlorite (NaClO2, technical grade, 80%, SigmaAldrich),
cultural cellulosic wastes (Cherian et al., 2010, 2011; Kengkhetkit glacial acetic acid (Synth), and cellulose membrane (D9402, Sigma
and Amornsakchai, 2012; Maniruzzaman et al., 2011). Hence, with- Aldrich).
out any additional cost input, PL bers can be obtained for industrial
Several processes and products have been reported that uti- 2.2. Preparation of cellulose nanocrystals
lize PL as a raw material. These include the extraction of cellulose
ber and nanober, the production of paper, textiles and com- 2.2.1. Purication
posites (Banik et al., 2011; Cherian et al., 2010; Chollakup et al., The raw PL was ground in a mill. After that, the PL was treated
2011; Kengkhetkit and Amornsakchai, 2012; Mishra et al., 2004; with a sodium hydroxide aqueous solution of 2% (w/w) for 4 h at
Threepopnatkul et al., 2009). However, there is not yet any pub- 100 C under mechanical stirring, washed several times with dis-
lished work on the extraction of cellulose nanocrystals (CN) from tilled water until the alkali was completely removed, and nally
PL. dried at 50 C for 12 h in an air-circulating oven. After this treat-
CN have attracted immense interest as a novel nanostruc- ment, the material was bleached with a solution made up of equal
tured material during recent years. CN are very high crystallinity parts (v:v) of acetate buffer (27 g NaOH and 75 ml glacial acetic
nanoparticles derived from cellulosics bers. CN are a very high- acid, diluted to 1 L of distilled water) and aqueous sodium chlorite
value material, since they can transform the performance of (1.7 wt% NaClO2 in water). This bleaching treatment was performed
existing products as well as helping to create new, unique and at 80 C for 4 h. The bleached material was washed repeatedly in
improved products. The unique combination of amazing physico- distilled water until the pH of the material became neutral and
chemical properties and environmental benets allows that the CN subsequently dried at 50 C for 12 h in an air-circulating oven. The
offer a wide range of potential applications. At present, the main material content throughout these chemical treatments was about
application of CN is as a reinforcing agent in the nanocomposite 46% (w/w). The material which resulted after the purication was
eld. Others elds of potential applications are packaging, paints, the treated pineapple leaf (TPL). The bleaching process utilized has
coatings, special papers, cosmetics, pharmaceuticals, biomedical been used/adapted by other authors (de Rodriguez et al., 2006;
materials, textiles, the automotive industry, aerospace, building Siqueira et al., 2010a; Flauzino Neto et al., 2013; Silvrio et al.,
materials, the electronic and electrical industry, and many others 2013).
(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 2.2.2. Isolation of cellulose nanocrystals
paper (Beck et al., 2011; Revol et al., 1998). After the chemical treatment was completed, the TPL was milled
It is known that the morphology and properties of the CN with a blender and then used for the extraction of CN by acid
depend mainly on the source of the original cellulose, of the extrac- hydrolysis. The hydrolysis was performed at 45 C for 5 min, 30 min
tion process and their parameters (Beck-Candanedo et al., 2005; or 60 min under vigorous and constant stirring. For each gram of
Elazzouzi-Hafraoui et al., 2008). Therefore, the isolation and further TPL we used 20 mL of H2SO4 64% (w/w) (9.17 M). Immediately fol-
analysis of the characteristics of CN from many kinds of cellulosic lowing the hydrolysis, the suspension was diluted 10-fold with
resources is necessary and relevant for the efcient comparison and cold water to stop the hydrolysis reaction, and centrifuged twice
exploitation of these resources (Chen et al., 2011; Flauzino Neto for 10 min at 7000 rpm to remove the excess acid. The precipitate
et al., 2013; Silvrio et al., 2013). was then dialyzed with tap water to remove non-reactive sulfate
CN have been isolated from different vegetable sources, such groups, salts and soluble sugars, until the neutral pH (4 days) was
as cotton and wood pulp (Beck-Candanedo et al., 2005; Teixeira reached. Subsequently, the resulting suspension of dialysis process
et al., 2010), and from animal sources such as tunicates (Berg et al., was ultrasonicated for 10 min and stored in a refrigerator at 4 C.
2007). In addition, there are only a few papers which describe the Some drops of chloroform were added in the CN suspension to avoid
isolation of whiskers from agricultural byproducts, such as soy hulls any bacterial growth. The cellulose nanocrystals from pineapple
(Flauzino Neto et al., 2013), corncob (Silvrio et al., 2013), rice husk leaf were labeled CNPL5 or CNPL30 or CNPL60, depending on the
(Rosa et al., 2012) and sesame husk (Purkait et al., 2011). time of extraction.
In this work, CN were extracted from PL under different condi-
tions of sulfuric acid hydrolysis in order to obtain a material with
a high crystallinity index, thermal stability, aspect ratio and yield. 2.3. Characterizations and measurements
Different techniques were employed to characterize the PL at dif-
ferent stages of treatment. The characteristics investigated were 2.3.1. Birefringence analysis
the chemical composition, crystallinity index, thermal stability, Aliquots of CN suspensions at same concentration
surface charge and morphology (shape and size). The aim in this (7.103 g mL1) were placed in a glass bottle, and then these
study was to investigate the viability of this agricultural residue as bottles were placed in front of a source of polarized light
a simple and low-cost source of CN and the possibility of adding and photographed by a camera equipped with a polarized
value to the pineapple cultivation through a new approach to their light lter while being agitated with the aid of a magnetic
utilization. stirrer.
R.M.d. Santos et al. / Industrial Crops and Products 50 (2013) 707714 709

Fig. 1. Photographs of (a) the pineapple cultivation, (b) untreated pineapple leaves, (c) ground pineapple leaves, and (d) treated pi neapple leaves.

2.4. Gravimetric analysis These deconvolutions were obtained using the Pseudo-Voigt 2 peak
function from Origin 7.0, which is shown in Eq. (1), and these
The hydrolysis yields were calculated by drying aliquots of the deconvolutions were evaluated according to the two-phase model
CN suspensions with a known volume at 105 C for 12 h in an air- (Cerqueira et al., 2006).
circulating oven. 2 wL
y = y0 + A mu w
4(x xc)2 + w2
2.5. Chemical composition L
4 ln 2 ( 4 ln 2/w2 )(x x )2

The chemical composition of PL and TPL was investigated as + (1 mu ) , e G c (1)
follows: the lignin content was measured according to a standard wWG
method of the Technical Association of Pulp and Paper Indus-
try TAPPI T13M-54; the holocellulose (a-cellulose + hemicellulose) where wL and wG are the width at half maximum for Lorentz and
content was estimated by the acid chlorite method (Browning, Gauss components of the above equation, respectively, A is the area
1967); the a-cellulose content was determined treating the holo- and mu is the prole shape factor.
cellulose with potassium hydroxide solutions of 5 and 24% (w/w), Considering this model, the crystallinity indexes (CrI) of the
according Browning (Browning, 1967); the hemicellulose content samples were calculated using Eq. (2):
was found by subtracting the a-cellulose part from the holocellu- . .
CrI = Ac 100 (2)
lose content; and the ash content was measured by considering the Ac + Aa
percentage difference between the initial weight of the dried ber
where Ac and Aa are the areas under the crystalline peaks and the
of the sample and that after calcination for 4 h at 800 C (Trindade amorphous halos, respectively determined by the deconvolutions.
et al., 2005). An average of three replicates was calculated for each
sample. 2.6.1. Atomic force microscopy (AFM)
AFM measurements were performed with Shimadzu SPM-9600
2.5.1. Fourier transform infrared spectroscopy (FTIR) equipment for evaluating the morphology of CNPL 5, CNPL30 and
A Shimadzu IRPrestige-21 Infrared spectrophotometer was used CNPL60. A drop of a diluted nanocrystals aqueous suspension (to
to obtain spectra for the PL, TPL, CNPL5, CNPL30 and CNPL60. The KBr about 5.105 g mL1) was deposited onto a freshly cleaved mica
disk (ultra-thin pellets) method was used in taking the IR spectra. surface and air-dried. AFM images were obtained at room temper-
Samples were ground and mixed with KBr (sample/KBr ratio, 1/100) ature in the dynamic mode with a scan rate of 1 Hz and using Si
to prepare pastilles. The experiments were carried out in the range tips with a curvature radius of less than 10 nm and a spring con-
of 5004000 cm1 with a resolution of 4 cm1 and a total of 32 scans stant of 42 N m1. The dimensions of nanocrystals were determined
for each sample. using VectorScan software (software for Shimadzus SPM-9600).
To eliminate the effect of tip radius on width measurements, we
2.6. X-ray diffraction (XRD) measured the heights of the nanocrystals, which are not subject
to peak broadening artifacts, and assumed the nanocrystals to be
The X-ray diffractograms of PL, TPL, CNPL5, CNPL30 and CNPL60 cylindrical in shape (Beck-Candanedo et al., 2005). Seventy-ve
were obtained at room temperature within a 2& range from 5 to 40 nanocrystals were randomly selected to determine the average
and a scan rate of 2 min1. The equipment used was a diffractome- length, width and aspect ratio. For each nanocrystal, one measure-
ter Shimadzu LabX XRD-6000, operating at a power of 40 kV with a ment of the length and two measurements of the diameter were
current of 30 mA and Cu Ka radiation (1.5406 A). Before performing performed and the aspect ratio was calculated.
the XRD, all samples were dried at 50 C for 12 h in an air-circulating
oven. 2.6.2. Thermal characterization (TG)
The diffractograms were deconvoluted into peaks and halos Thermal stabilities of PL, TPL, CNPL5, CNPL30 and CNPL60 were
referring to the crystalline and amorphous regions, respectively. evaluated using Shimadzu DTG-60H equipment. The analysis
710 R.M.d. Santos et al. / Industrial Crops and Products 50 (2013) 707714

Fig. 3. The resulting colloidal suspensions for CNPL5, CNPL30 and CNPL60 after a few
Fig. 2. FTIR spectra of PL, TPL, CNPL5, CNPL30 and CNPL60.
hours of rest.

conditions were: a nitrogen atmosphere with ow 30 mL min1, in ether, ester, and phenol groups are present (Siqueira et al.,
heating rate of 10 C min1, temperature range from 25 to 600 C, 2010b). Comparing the data shown in the FTIR spectra for PL and
sample mass between 5 and 7 mg and aluminum pans. TPL, it could be noted that the lack of peaks at 1742 cm1, 1514 cm1
and 1254 cm1 in the spectrum of TPL is due to the signicant
3. Results and discussion removal of hemicelluloses, and mainly lignin, by the purication
process (alkali and bleaching treatments).
3.1. Purication, chemical composition and FTIR The peak at 1061 cm1 is assigned to the C O stretching and the
C H rock vibrations of the cellulose (Alemdar and Sain, 2008). The
A diluted alkali treatment was performed to remove the lignin, small increase in this peak for TPL in relation to PL indicates that the
hemicelluloses, waxes, pectins, proteins, soluble mineral salts, sil- TPL have higher cellulose content. Similar behavior was observed
ica and ash, while bleaching was applied to remove the lignin when comparing the spectra of TPL with CNPL5, CNPL30 and CNPL60.
residues (Dufresne et al., 1997; Flauzino Neto et al., 2013; Sheltami This peak appeared in all of the spectra and the differences pre-
et al., 2012). The yield of purication was 40% (by dry mass). Fig. 1 sented suggest that the CNPL5, CNPL30 and CNPL60 samples has a
shows the physical aspect of the PL before and after purication very high content of cellulose.
(TPL). Visually, the white color of the material after purication
indicates that a great part of the initial non-cellulosic components 3.2. Isolation of Cellulose nanocrystals, gravimetric and
was removed. The contents of the cellulose were 36.3 3.8% and birefringence analysis
74.5 4.2%, of the hemicelluloses were 22.9 2.0% and 20.4 2.6%,
of the lignin were 27.53 1.94% and 8.72 1.63%, and ash were The yields of the CNPL, with respect to the initial amount of dried
2.85 0.24% and 2.28 0.11%, for PL and TPL respectively (the val- TPL bers, for CNPL5, CNPL30 and CNPL60 were 77, 65 and 55 wt%
ues are based on dry basis). respectively; these values are consistent with the literature data
It was veried that the percentage of mass consumption of the (Silvrio et al., 2013; Teixeira et al., 2011, 2010).
main components of the PL due to the purication process was 18.0, Among the several methods for preparing CN, acid hydroly-
64.4 and 87.4% for a-cellulose, hemicelluloses and lignin, respec- sis is the most well-known and widely used (Peng et al., 2011).
tively. The mass loss of cellulose during the purication process This process breaks down the disordered and amorphous parts of
can be related to two factors: (i) the breakdown of cellulose chains the cellulose, releasing single and well-dened crystals. Thus, this
during bleaching and (ii) the loss of material inherent in various process is based on the quicker hydrolysis kinetics presented by
ltering processes and mass transfer (Flauzino Neto et al., 2013). amorphous regions, as compared to crystalline ones (Habibi et al.,
Taking into account that purication was performed to remove 2010; Peng et al., 2011; Teixeira et al., 2011).
non-cellulose components and mainly lignin, which acts as a natu- During the hydrolysis process with sulfuric acid, sulfate groups
ral agglutinative hindering acid hydrolysis, the purication process are introduced on the surface of the CN by esterication of the
has reached its goal because the composition of TPL is suitable for hydroxyl groups from cellulose. This allows an anionic stabilization
the extraction of cellulose nanocrystals (low content of lignin and by repulsive forces, leading to the achievement of stable aque-
high content of cellulose). ous dispersions of CN (Beck-Candanedo et al., 2005; Lima and
Fig. 2 shows the FTIR spectra of PL, TPL, CNPL5, CNPL30 and Borsali, 2004; Silva and DAlmeida, 2009). Also, it is known that
CNPL60. The prominent peak at 1742 cm1 in the spectrum of PL the increased extraction time results in higher sulfate content in
is attributed to the acetyl and uronic ester groups of the hemi- the CN (Flauzino Neto et al., 2013; Roman and Winter, 2004). Only
celluloses or the ester linkage of carboxylic group of ferulic and the hydrolysis times of 30 and 60 min led to stable aqueous suspen-
p-coumaric acids of lignin and/or hemicelluloses (Kejun et al., 2011; sions being obtained (as shown in Fig. 3). The suspension obtained
Sun et al., 2005). In the same spectrum, the peak at 1514 cm1 is with 5 min of hydrolysis tended to aggregate after a few hours (as
associated with the C C aromatic skeletal vibration of lignin (Kejun seen in Fig. 3), probably this particle agglomeration is related to the
et al., 2011; Sun et al., 2005; Vargas et al., 2011; Xiao et al., 2001), large size and small amount of surface charges of these particles.
and the band near 1254 cm1 corresponds to the axial asymmetric Birefringence was used to conrm the presence of isolated
strain of C O C, which is commonly observed when C O e.g. nanowhiskers in a suspension and is considered by some authors as
R.M.d. Santos et al. / Industrial Crops and Products 50 (2013) 707714 711

of the diffractograms proles (Fig. 5), there is a predominance of

type I cellulose, veried by the presence of peaks at 2& = 15 (plane
1 0 1), 17 (plane 101), 21 (plane 0 2 1), 23 (plane 0 0 2) and 34
(plane 0 0 4) (Borysiak and Garbarczyk, 2003; Flauzino Neto et al.,
2013). The peak at 2& = 26.5 present in all the spectra is related to
the sample holder.
The CrI was found to be about 49, 64, 69, 73 and 68% for the
PL, TPL, CNPL5, CNPL30 and CNPL60, respectively. The higher CrI
value of TPL compared to PL can be well understood by the reduc-
tion and removal of amorphous non-cellulosic compounds induced
by the alkali and bleaching treatments performed in the puri-
cation process. The increase in the CrI value of CNPL5 in relation
to TPL was also observed, due to the partial removal of the para-
crystalline domains during the acid hydrolysis. A similar behavior
was observed when comparing the diffraction patterns of CNPL5
and CNPL30 samples.
The CNPL60 sample presented a decrease in crystallinity with
respect to CNPL30. A similar effect of hydrolysis time in excess was
observed by some authors for cellulose nanocrystals from sugar-
cane bagasse bers and pea hull bers (Chen et al., 2009; Teixeira
et al., 2011), although the rod-like structures were maintained,
supported by AFM images.

Fig. 4. Photograph of aqueous suspension of CNPL 5, CNPL30 and CNPL60 observed 3.4. Atomic force microscopy (AFM)
between cross nicols showing the formation of birefringent domains.
An accurate morphological examination of the CN is essential
a good dispersibility criterion in suspension (Silva and DAlmeida, not only for the promoters of the manufacturing process of the CN,
2009; Silvrio et al., 2013). This birefringence results from two ori- but also for developers of functional applications. In this way, AFM
gins: (1) a structural anisotropy form of cellulose and (2) a ow topography measurements were performed in order to have a pre-
anisotropy resulting from the alignment of the nanocrystals under cise characterization of the dimensions of the individual crystallites
ow, generally operated before observation. Fig. 4 shows a bire- (Flauzino Neto et al., 2013).
fringence of different cellulose suspensions in water, indicating Determining the exact dimensions of CN is complicated by the
that CN were isolated in all three isolation conditions. The birefrin- specic limitations of the different analytical methods used. In the
gence was somewhat weaker for CNPL 5 suspension compared to case of AFM, tip/sample broadening represents the main limitation,
the CNPL30 and CNPL60 suspensions. It is possible that the hydroly- resulting in an overestimation of CN dimensions. Since the CN are
sis time was not sufcient to separate single CN from TPL bers assumed to be cylindrical in shape, the height of the CN was taken
as effectively as the others hydrolysis times and, therefore, the to be equivalent to the diameter, to compensate for image widening
birefringence is not as strong (Oksman et al., 2011). due to the convolution of the tip and the particle (Beck-Candanedo
et al., 2005; Flauzino Neto et al., 2013; Kvien et al., 2005). However,
the tip broadening effects causes an error in the length measure-
3.3. X-ray diffraction
ments, but this is unavoidable (Beck-Candanedo et al., 2005).
Fig. 6 shows AFM images of CNPL5, CNPL30 and CNPL60. For the
The XRD patterns of PL, TPL, CNPL5, CNPL30 and CNPL60 are
samples CNPL30 and CNPL60, the AFM images presented needle-
shown in Fig. 5. These patterns are typical of semi-crystalline mate-
like nanoparticles throughout, conrming that the extraction of
rials with an amorphous broad hump and crystalline peaks. In all
CN from PL was successful. However, the AFM images of sample
CNPL5 showed micro-sized bers and some needle-like nanoparti-
cles. Therefore, it is clear that the hydrolysis conditions employed
for this sample (CNPL5) were not sufcient to completely isolate CN
from TPL bers. This is in agreement with the weak birefringence
and particle agglomeration observed for this suspension sample
Fig. 7 shows the length (L), width (D) and aspect ratio (L/D) his-
tograms of CNPL30 and CNPL60 obtained by several AFM images, as
described in the Experimental Section. The statistics of the length,
width and aspect ratio are shown in Table 1.
The increase in extraction time resulted in a slightly shorter
length for CNPL60 when compared with CNPL30. This was expected,
since the long extraction time (60 min) partially destroyed areas of
the crystalline domains, as seen by XRD analysis.

Table 1
Length, width, aspect ratio, for CNPL 30 and CNPL60 obtained by AFM pictures.

Length (nm) Diameter (nm) Aspect ratio (nm)

CNPL30 249.7 51.5 4.45 1.41 60.1 19.5

CNPL60 190.2 36.5 4.18 1.44 50.4 20.7
Fig. 5. X-ray diffractograms of PL, TPL, CNPL 5, CNPL30 and CNPL60.
712 R.M.d. Santos et al. / Industrial Crops and Products 50 (2013) 707714

Fig. 6. AFM images of CNPL5, CNPL30 and CNPL60.

By studying histograms it is clear that the increase in hydrolysis these crystals is a key factor in order for them to be used as effective
time resulted in a reduction in particle size, but no signicant dif- reinforcing materials (Roman and Winter, 2004). The thermogravi-
ference in width among the CNPL30 and CNPL60 could be detected, metric (TG) results of the PL, TPL, CNPL5, CNPL30 and CNPL60 are
when the standard deviation of each value was taken into account. shown in Fig. 8. In all cases, a small weight loss was found in the
As a consequence of the whiskers preparation conditions, range of 25150 C, due to the evaporation of the water of the
a decrease in the aspect ratio (L/D) of CNPL60 compared with materials or low molecular weight compounds (about 7%). The ini-
CNPL30 was observed. This suggests that CNPL30 can give a bet- tial degradation temperatures were found to be around 216, 244,
ter reinforcing effect than CNPL60 at the same ller loading levels 245, 225 and 220 C for the PL, TPL, CNPL5, CNPL30 and CNPL60,
(Eichhorn et al., 2010). The average aspect ratio for the CNPL found respectively.
in this work is close to the largest values ever reported in the lit- The initial degradation temperature of the TPL (244 C) was
erature; therefore, these particles have great potential to be used appreciably increased compared to that of the original PL (216 C).
as reinforcing agents in nanocomposites (Kalia et al., 2011; Silvrio Due to the low initial decomposition temperatures of hemicellu-
et al., 2013). loses, lignin and pectin, the higher initial temperature of thermal
The results of the morphological investigation by AFM are decomposition of the TPL is related to the partial removal of hemi-
consistent with other reports in the literature, where CN were celluloses, lignin, and pectins by purication processes (alkali and
extracted from different sources (Bai et al., 2009; Beck-Candanedo bleaching treatments) (Alemdar and Sain, 2008; Chen et al., 2011;
et al., 2005; de Rodriguez et al., 2006; Elazzouzi-Hafraoui et al., Flauzino Neto et al., 2013).
2008; Kvien et al., 2005; Rosa et al., 2010; Siqueira et al., 2010a; As reported in previous studies, treatment with sulfuric acid
Teixeira et al., 2011). leads to a remarkable decrease in thermal stability of CN. This
occurs because the incorporation of sulfate groups on the surface
3.5. Thermogravimetric analysis (TGA) of the cellulose after hydrolysis has a catalytic effect in its reactions
of thermal degradation (Roman and Winter, 2004).
At present, the main application of CN is as a reinforcing agent Taking into account that acid hydrolysis leads to a remarkable
in the nanocomposite eld, and typical processing temperatures decrease in thermal stability of CN, it was expected that the initial
for thermoplastics rise above 200 C, thus the thermal stability of degradation temperature of CNPL5 were smaller than for TPL, but

Fig. 7. Length (L), width (D) and aspect ratio (L/D) histograms of CNPL 30 and CNPL60 obtained by several AFM images.
R.M.d. Santos et al. / Industrial Crops and Products 50 (2013) 707714 713


The authors thank CAPES/PROAP, CNPq and FAPEMIG for nan-

cial support.


Ahmed, O.H., Husni, M.H., Anuar, A.R., Hana, M.M., 2002. Effect of residue man-
agement practices on yield and economic viability of Malaysian pineapple
production. Journal of Sustainable Agriculture 20 (4), 8394.
Alemdar, A., Sain, M., 2008. Isolation and characterization of nanobers from agri-
cultural residues wheat straw and soy hulls. Bioresource Technology 99,
Ashori, A., 2008. Wood-plastic composites as promising green-composites for auto-
motive industries. Bioresource Technology 99, 46614667.
Bai, W., Holbery, J., Li, K.C., 2009. A technique for production of nanocrystalline
cellulose with a narrow size distribution. Cellulose 16, 455465.
Banik, S., Nag, D., Debnath, S., 2011. Utilization of pineapple leaf agro-waste for
extraction of bre and the residual biomass for vermicomposting. Indian Journal
of Fibre & Textile Research 36, 172177.
Fig. 8. Thermogravimetric (TG) curves of the PL, TPL, CNPL5, CNPL30 and CNPL60. Beck, S., Bouchard, J., Berry, R., 2011. Controlling the reection wavelength of irides-
cent solid lms of nanocrystalline cellulose. Biomacromolecules 12, 167172.
Beck-Candanedo, S., Roman, M., Gray, D.G., 2005. Effect of reaction conditions on the
properties and behavior of wood cellulose nanocrystal suspensions. Biomacro-
it was actually almost the same (245 vs. 244 C). This can be clearly molecules 6, 10481054.
explained by the higher cellulose content of CNPL 5 compared to Berg, O., Capadona, J.R., Weder, C., 2007. Preparation of homogeneous disper-
TPL and the small hydrolysis time (small amount of sulfate groups) sions of tunicate cellulose whiskers in organic solvents. Biomacromolecules 8,
of sample CNPL5. Borysiak, S., Garbarczyk, J., 2003. Applying the WAXS method to etimate the super-
The CNPL30 sample presented a decrease in initial degradation molecular structure of cellulose bres after mercerization. Fibres & Textiles in
temperature with respect to CNPL 5, as expected since the CNPL 30 Eastern Europe 11, 104106.
Browning, B.L., 1967. Methods of Wood Chemistry, 1st ed. Interscience Publishers,
sample had a higher sulfate content than CNPL 5. Similar behavior
New York.
was observed when comparing the initial degradation tempera- Cerqueira, D.A., Rodrigues Filho, G., Assunc o, R.M.N., 2006. A new value for the
ture of samples CNPL30 and CNPL60. These results are consistent heat of fusion of a perfect crystal of cellulose acetate. Polymer Bulletin 56, 475
with results obtained from the Chemical Composition, XRD and 484.
Chen, Y., Liu, C., Chang, P.R., Cao, X., Anderson, D.P., 2009. Bionanocomposites based
FTIR measurements.
on pea starch and cellulose nanowhiskers hydrolyzed from pea hull bre: effect
of hydrolysis time. Carbohydratre Polymers 76, 607615.
Chen, W., Yu, H., Liu, Y., Hai, Y., Zhang, M., Chen, P., 2011. Isolation and char-
4. Conclusions acterization of cellulose nanobers from four plant cellulose bers using a
chemical-ultrasonic process. Cellulose 18, 433442.
The present work shows that PL is an interesting source of Cherian, B.M., Leo, A.L., de Souza, S.F., Thomas, S., Pothan, L.A., Kottaisamy, M.,
2010. Isolation of nanocellulose from pineapple leaf bres by steam explosion.
raw material for the production of CN, due to the characteristics Carbohydrate Polymers 81, 720725.
of the obtained nanocrystals. Chemical treatment performed with Cherian, B.M., Leo, A.L., de Souza, S.F., Costa, L.M.M., de Oliveira, G.M., Kottaisamy,
sodium chlorite and alkali removed the non-cellulosic components M., Nagarajan, E.R., Thomas, S., 2011. Cellulose nanocomposites with nano-
bres isolated from pineapple leaf bers for medical applications. Carbohydrate
resulting in bers with a low content of lignin and a high con- Polymers 86, 17901798.
tent of cellulose, which were therefore suitable for extracting CN. Chollakup, R., Tantatherdtam, R., Ujjin, S., Sriroth, K., 2011. Pineapple leaf
Through the AFM images it was observed that there was an incom- ber reinforced thermoplastic composites: effect of ber length and ber
content on their characteristics. Journal of Applied Polymer Science 119, 1952
plete isolation of CN after 5 min of hydrolysis by the employed
conditions (sample CNPL5). However, above 30 min of hydroly- de Aquino, M.S., 2006. Desenvolvimento de uma Desbradeira para Obtenc o da
sis it was possible to obtain stable aqueous suspensions of CNPL Fibra da Folha do Abacaxi. Master Thesis. Federal University of Rio Grande do
which are negatively charged, due the presence of sulfate groups. Norte.
de Rodriguez, N.L.G., Thielemans, W., Dufresne, A., 2006. Sisal cellulose whiskers
The yields of acid hydrolysis, with respect to the initial amount of reinforced polyvinyl acetate nanocomposites. Cellulose 13, 261270.
dried TPL bers, for CNPL5, CNPL30 and CNPL60 were 77, 65 and dos Santos, M.A.T., Nepomuceno, I.A.S., de Abreu, C.M.P., de Carvalho, V.D., 2001.
55 wt%, respectively. The increase in the hydrolysis time resulted Teores de polifenis de caule e folha de quatro cultivares de abacaxizeiro. Revista
Brasileira de Fruticultura 23 (2), 274276.
in a decrease in the dimensions and also in the aspect ratio (L/D) of Dufresne, A., Caville, J., Vignon, M., 1997. Mechanical behavior of sheets prepared
the CNPL. from sugar beet cellulose microbrils. Journal of Applied Polymer Science 64,
For an extraction time of 30 min, the CN presented a needle- 11851194.
Eichhorn, S.J., Dufresne, A., Aranguren, M., Marcovich, N.E., Capadona, J.R., Rowan,
shaped nature, high thermal stability (225 C), high crystallinity S.J., 2010. Review: current international research into cellulose nanobres and
(73%), an average length of 249.7 51.5 nm and a diameter of nanocomposites. Journal of Materials Science 45, 133.
4.45 1.41 nm, giving an aspect ratio of around 60 (which is among Elazzouzi-Hafraoui, S., Nishiyama, Y., Putaux, J.L., Heux, L., Dubreuil, F., Rochas, C.,
2008. The shape and size distribution of crystalline nanoparticles prepared by
the largest values reported in the literature). It can be concluded acid hydrolysis of native cellulose. Biomacromolecules 9, 5765.
from these results that the CN obtained from PL has great poten- Fagundes, N.S., Fagundes, N.S., 2010. Restos culturais do abacaxizeiro na alimentac o
tial to be used as reinforcement agents for the manufacture of de ruminantes. Revista Eletrnica Nutritime 7 (3), 12431247.
Flauzino Neto, W.P., Silvrio, H.A., Dantas, N.O., Pasquini, D., 2013. Extraction and
nanocomposites and also for diversied applications.
characterization of cellulose nanocrystals from agro-industrial residue soy
The production of CN from this underutilized agro-waste has hulls. Industrial Crops and Products 42, 480488.
commercial application potential that can add value to the pineap- Habibi, Y., Lucia, L.A., Rojas, O.J., 2010. Cellulose nanocrystals: chemistry, self-
assembly, and applications. Chemical Reviews 110, 34793500.
ple cultivation, generate extra income for farmers and also help
Kalia, S., Dufresne, A., Cherian, B.M., Kaith, B.S., Avrous, L., Njuguna, J., Nassiopou-
in agribusiness diversication. In addition, the reuse of these los, E., 2011. Cellulose-based bio- and nanocomposites: a review. International
residues allows a signicant reduction both in the volume of Journal of Polymer Science 2011, 135.
waste accumulated in the environment, as in the extraction of raw Kejun, S., Juntao, Z., Ying, C., Zongwen, L., Lin, R., Cong, L., 2011. Accelerating the
degradation of green plant waste with chemical decomposition agents. Journal
materials. of Environmental Management 92, 27082713.
714 R.M.d. Santos et al. / Industrial Crops and Products 50 (2013) 707714

Kengkhetkit, N., Amornsakchai, T., 2012. Utilisation of pineapple leaf waste for plas- Rosa, S.M.L., Rehman, N., de Miranda, M.I.G., Nachtigall, S.M.B., Bica, C.I.D., 2012.
tic reinforcement: 1. A novel extraction method for short pineapple leaf ber. Chlorine-free extraction of cellulose from rice husk and whisker isolation. Car-
Industrial Crops and Products 40, 5561. bohydrate Polymers 87, 11311138.
Kvien, I., Tanem, B.S., Oksman, K., 2005. Characterization of cellulose whiskers Schievano, A., DImporzano, G., Adani, F., 2009. Substituting energy crops with
and their nanocomposites by atomic force and electron microscopy. Biomacro- organic wastes and agro-industrial residues for biogas production. Journal of
molecules 6, 31603165. Environmental Management 90, 25372541.
Lima, M.M.S., Borsali, R., 2004. Rodlike cellulose microcrystals: structure, properties, Sheltami, R.M., Abdullah, I., Ahmad, I., Dufresne, A., Kargarzadeh, H., 2012. Extraction
and applications. Macromolecular Rapid Communications 25, 771787. of cellulose nanocrystals from mengkuang leaves (Pandanus tectorius). Carbohy-
Maniruzzaman, M., Rahman, M.A., Gafur, M.A., Fabritius, H., Raabe, D., 2011. Modi- drate Polymers 88, 772779.
cation of pineapple leaf bers and graft copolymerization of acrylonitrile onto Silva, R., Haraguchi, S.K., Muniz, E.C., Rubira, A.F., 2009. Aplicac es de bras lig-
modied bers. Journal of Composite Materials 46, 7990. nocelulsicas na qumica de polmeros e em compsitos. Qumica Nova 32,
Mishra, S., Mohanty, A.K., Drzal, L.T., Misra, M., Hinrichsen, G., 2004. A review on 661671.
pineapple leaf bers, sisal bers and their biocomposites. Macromolecular Mate- Silva, D.J., DAlmeida, M.L.O., 2009. Cellulose whiskers. O Papel 70, 3452.
rials and Engineering 289, 955974. Silvrio, H.A., Flauzino Neto, W.P., Dantas, N.O., Pasquini, D., 2013. Extraction
Mohamed, A.R., Sapuan, S.M., Shahjahan, M., Khalina, A., 2009. Characterization of and characterization of cellulose nanocrystals from corncob for application as
pineapple leaf bers from selected Malaysian cultivars. Journal of Food, Agricul- reinforcing agent in nanocomposites. Industrial Crops and Products 44, 427436.
ture & Environment 7 (1), 235240. Siqueira, G., Abdillahi, H., Bras, J., Dufresne, A., 2010a. High reinforcing capability
Moon, R.J., Martini, A., Nairn, J., Simonsen, J., Yougblood, J., 2011. Cellulose nano- cellulose nanocrystals extracted from Syngonanthus nitens (Capim Dourado).
materials review: structure, properties and nanocomposites. Chemical Society Cellulose 17, 289298.
Reviews 40, 39413994. Siqueira, G., Bras, J., Dufresne, A., 2010b. Luffa cylindrical as lignocellulosic source of
Oksman, K., Etang, J.A., Mathew, A.P., Jonoobi, M., 2011. Cellulose nanowhiskers ber, microbrillated cellulose, and cellulose nanocrystals. Bioresources 5 (2),
separated from a bio-residue from wood bioethanol production. Biomass & 727740.
Bioenergy 35, 146152. Sun, X.F., Xu, F., Sun, R.C., Fowler, P., Baird, M.S., 2005. Characteristics of degraded
Peng, B.L., Dhar, N., Liu, H.L., Tam, K.C., 2011. Chemistry and applications of nanocrys- cellulose obtained from steam-exploded wheat straw. Carbohydrate Research
talline cellulose and its derivatives: a nanotechnology perspective. The Canadian 340, 97106.
Journal of Chemical Engineering 9999, 116. Teixeira, E.M., Corra, A.C., Manzoli, A., Leite, F.L., Oliveira, C.R., Mattoso, L.H.C., 2010.
Podsiadlo, P., Choi, S., Shim, B., Lee, J., Cuddihy, M., Kotov, N.A., 2005. Molecularly Cellulose nanobers from white and naturally colored cotton bers. Cellulose
engineered nanocomposites: layer-by-layer assembly of cellulose nanocrystals. 17, 595606.
Biomacromolecules 6, 29142918. Teixeira, E.M., Bondancia, T.J., Teodoro, K.B.R., Corra, A.C., Marconcini, J.M., Mat-
Purkait, B.S., Ray, D., Sengupta, S., Kar, T., Mohanty, A., Misra, M., 2011. Isolation toso, L.H.C., 2011. Sugarcane bagasse whiskers: extraction and characterizations.
of cellulose nanoparticles from sesame husk. Industrial Engineering Chemistry Industrial Crops and Products 33, 6366.
Research 50, 871876. Threepopnatkul, P., Kaerkitcha, N., Athipongarporn, N., 2009. Effect of surface
Rahman, M.A., 2011. Study on modied pineapple leaf ber, journal of textile and treatment on performance of pineapple leaf berpolycarbonate composites.
apparel. Technology and Management 7 (2), 116. Composites Part B 40, 628632.
Reddy, N., Yang, Y., 2005. Biobers from agricultural byproducts for industrial appli- Trindade, W.G., Hoareau, W., Megiatto, J.D., Razera, A.T., Castellan, A., Frollini, E.,
cations. Trends in Biotechnology 23, 2227. 2005. Thermoset phenolic matrices reinforced with unmodied and surface-
Revol, J.-F., Godbout, L., Gray, D.G., 1998. Solid self-assembled lms of cellulose with grafted furfuryl alcohol sugar cane bagasse and curaua bers: properties of bers
chiral nematic order and optically variable properties. Journal of Pulp and Paper and composites. Biomacromolecules 6, 24852496.
Science 24, 146149. Vargas, A.M.M., Cazetta, A.L., Garcia, C.A., Moraes, J.C.G., Nogami, E.M., Lenzi, E., Costa,
Roman, M., Winter, W.T., 2004. Effect of sulfate groups from sulfuric acid hydrolysis W.F., Almeida, V.C., 2011. Preparation and characterization of activated carbon
on the thermal degradation behavior of bacterial cellulose. Biomacromolecules from a new raw lignocellulosic material: amboyant (Delonixregia) pods. Journal
5, 16711677. of Environmental Management 92, 178184.
Rosa, M.F., Medeiros, E.S., Malmonge, J.A., Gregorski, K.S., Wood, D.F., Mattoso, L.H.C., Xiao, B., Sun, X.F., Sun, R.C., 2001. Chemical, structural, and thermal characteri-
Glenn, G., Orts, W.J., Imam, S.H., 2010. Cellulose nanowhiskers from coconut zation of alkali-soluble lignins and hemicelluloses, and cellulose from maize
husk bers: effect of preparation conditions on their thermal and morphological stems, rye straw, and rice straw. Polymer Degradation and Stability 74, 307
behavior. Carbohydrate Polymers 81, 8392. 319.