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Industrial Crops and Products 50 (2013) 707714

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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,
a Instituto de Qumica, Universidade Federal de Uberlndia, Campus Santa Mnica, Av. Joo Naves de vila, 2121, 38400-902, Uberlndia, Minas Gerais, Brazil b Instituto de Fsica, Universidade Federal de Uberlndia, Campus Santa Mnica, Av. Joo Naves de vila, 2121, 38400-902, Uberlndia, Minas Gerais, Brazil

a r t i c l e

i n f o

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.

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

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:, (D. Pasquini). 0926-6690/$ see front matter 2013 Elsevier B.V. All rights reserved.

residues in industrial processes for the generation of value-added products, such as in the production of high performance materials, could be an additional source of revenue for farmers and also help in agro-industry diversication by providing a non-food-based market for agro-wastes (Alemdar and Sain, 2008; Flauzino Neto et al., 2013; Rahman, 2011; Reddy and Yang, 2005; Silvrio et al., 2013). Pineapple is one of the most popular tropical fruits in the world and their crop occupies a prominent position in the Brazilian agricultural sector. Brazil is one of the main producers of this crop, accounting for approximately 10.9% of the world production ( Mundo 2010. pdf). Currently, the main focus of the pineapple industry in this country is the fruits and related foodstuffs and consequently the other plant parts (stems, roots and especially leaves) are considered agricultural residues of pineapple cultivation (dos Santos 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 crammed to rot (de Aquino, 2006; Maniruzzaman et al., 2011). This is due to the lack of adequate technology for this purpose, as well as the ignorance of the farmers about the existence of commercial


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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).

2.2. Preparation of cellulose nanocrystals 2.2.1. Purication The raw PL was ground in a mill. After that, the PL was treated with a sodium hydroxide aqueous solution of 2% (w/w) for 4 h at 100 C under mechanical stirring, washed several times with distilled water until the alkali was completely removed, and nally dried at 50 C for 12 h in an air-circulating oven. After this treatment, the material was bleached with a solution made up of equal parts (v:v) of acetate buffer (27 g NaOH and 75 ml glacial acetic acid, diluted to 1 L of distilled water) and aqueous sodium chlorite (1.7 wt% NaClO2 in water). This bleaching treatment was performed at 80 C for 4 h. The bleached material was washed repeatedly in distilled water until the pH of the material became neutral and subsequently dried at 50 C for 12 h in an air-circulating oven. The material content throughout these chemical treatments was about 46% (w/w). The material which resulted after the purication was the treated pineapple leaf (TPL). The bleaching process utilized has been used/adapted by other authors (de Rodriguez et al., 2006; Siqueira et al., 2010a; Flauzino Neto et al., 2013; Silvrio et al., 2013).

2.2.2. Isolation of cellulose nanocrystals After the chemical treatment was completed, the TPL was milled with a blender and then used for the extraction of CN by acid hydrolysis. The hydrolysis was performed at 45 C for 5 min, 30 min or 60 min under vigorous and constant stirring. For each gram of TPL we used 20 mL of H2 SO4 64% (w/w) (9.17 M). Immediately following the hydrolysis, the suspension was diluted 10-fold with cold water to stop the hydrolysis reaction, and centrifuged twice for 10 min at 7000 rpm to remove the excess acid. The precipitate was then dialyzed with tap water to remove non-reactive sulfate groups, salts and soluble sugars, until the neutral pH (4 days) was reached. Subsequently, the resulting suspension of dialysis process was ultrasonicated for 10 min and stored in a refrigerator at 4 C. Some drops of chloroform were added in the CN suspension to avoid any bacterial growth. The cellulose nanocrystals from pineapple leaf were labeled CNPL5 or CNPL30 or CNPL60 , depending on the time of extraction.

2.3. Characterizations and measurements 2.3.1. Birefringence analysis Aliquots of CN suspensions at same concentration (7.103 g mL1 ) were placed in a glass bottle, and then these bottles were placed in front of a source of polarized light and photographed by a camera equipped with a polarized light lter while being agitated with the aid of a magnetic stirrer.

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

2.4. Gravimetric analysis The hydrolysis yields were calculated by drying aliquots of the CN suspensions with a known volume at 105 C for 12 h in an aircirculating oven. 2.5. Chemical composition

These deconvolutions were obtained using the Pseudo-Voigt 2 peak function from Origin 7.0, which is shown in Eq. (1), and these deconvolutions were evaluated according to the two-phase model (Cerqueira et al., 2006). y = y0 + A mu 2 wL
2 4(x xc )2 + wL

The chemical composition of PL and TPL was investigated as follows: the lignin content was measured according to a standard method of the Technical Association of Pulp and Paper Industry TAPPI T13M-54; the holocellulose (-cellulose + hemicellulose) content was estimated by the acid chlorite method (Browning, 1967); the -cellulose content was determined treating the holocellulose with potassium hydroxide solutions of 5 and 24% (w/w), according Browning (Browning, 1967); the hemicellulose content was found by subtracting the -cellulose part from the holocellulose content; and the ash content was measured by considering the percentage difference between the initial weight of the dried ber of the sample and that after calcination for 4 h at 800 C (Trindade et al., 2005). An average of three replicates was calculated for each sample. 2.5.1. Fourier transform infrared spectroscopy (FTIR) A Shimadzu IRPrestige-21 Infrared spectrophotometer was used to obtain spectra for the PL, TPL, CNPL5 , CNPL30 and CNPL60 . The KBr disk (ultra-thin pellets) method was used in taking the IR spectra. Samples were ground and mixed with KBr (sample/KBr ratio, 1/100) to prepare pastilles. The experiments were carried out in the range of 5004000 cm1 with a resolution of 4 cm1 and a total of 32 scans for each sample. 2.6. X-ray diffraction (XRD) The X-ray diffractograms of PL, TPL, CNPL5 , CNPL30 and CNPL60 were obtained at room temperature within a 2 range from 5 to 40 and a scan rate of 2 min1 . The equipment used was a diffractometer Shimadzu LabX XRD-6000, operating at a power of 40 kV with a Before performing current of 30 mA and Cu K radiation (1.5406 A). the XRD, all samples were dried at 50 C for 12 h in an air-circulating oven. The diffractograms were deconvoluted into peaks and halos referring to the crystalline and amorphous regions, respectively.

+ (1 mu )

4 ln 2 WG

(4 ln 2/w2 )(xxc )2


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


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Fig. 2. FTIR spectra of PL, TPL, CNPL5 , CNPL30 and CNPL60 .

Fig. 3. The resulting colloidal suspensions for CNPL5 , CNPL30 and CNPL60 after a few hours of rest.

conditions were: a nitrogen atmosphere with ow 30 mL min1 , heating rate of 10 C min1 , temperature range from 25 to 600 C, sample mass between 5 and 7 mg and aluminum pans. 3. Results and discussion 3.1. Purication, chemical composition and FTIR A diluted alkali treatment was performed to remove the lignin, hemicelluloses, waxes, pectins, proteins, soluble mineral salts, silica and ash, while bleaching was applied to remove the lignin residues (Dufresne et al., 1997; Flauzino Neto et al., 2013; Sheltami et al., 2012). The yield of purication was 40% (by dry mass). Fig. 1 shows the physical aspect of the PL before and after purication (TPL). Visually, the white color of the material after purication indicates that a great part of the initial non-cellulosic components was removed. The contents of the cellulose were 36.3 3.8% and 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 2.85 0.24% and 2.28 0.11%, for PL and TPL respectively (the values are based on dry basis). It was veried that the percentage of mass consumption of the main components of the PL due to the purication process was 18.0, 64.4 and 87.4% for -cellulose, hemicelluloses and lignin, respectively. The mass loss of cellulose during the purication process can be related to two factors: (i) the breakdown of cellulose chains during bleaching and (ii) the loss of material inherent in various ltering processes and mass transfer (Flauzino Neto et al., 2013). Taking into account that purication was performed to remove non-cellulose components and mainly lignin, which acts as a natural agglutinative hindering acid hydrolysis, the purication process has reached its goal because the composition of TPL is suitable for the extraction of cellulose nanocrystals (low content of lignin and high content of cellulose). Fig. 2 shows the FTIR spectra of PL, TPL, CNPL5 , CNPL30 and CNPL60 . The prominent peak at 1742 cm1 in the spectrum of PL is attributed to the acetyl and uronic ester groups of the hemicelluloses or the ester linkage of carboxylic group of ferulic and p-coumaric acids of lignin and/or hemicelluloses (Kejun et al., 2011; Sun et al., 2005). In the same spectrum, the peak at 1514 cm1 is associated with the C C aromatic skeletal vibration of lignin (Kejun et al., 2011; Sun et al., 2005; Vargas et al., 2011; Xiao et al., 2001), and the band near 1254 cm1 corresponds to the axial asymmetric strain of C O C, which is commonly observed when C O e.g.

in ether, ester, and phenol groups are present (Siqueira et al., 2010b). Comparing the data shown in the FTIR spectra for PL and 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 removal of hemicelluloses, and mainly lignin, by the purication process (alkali and bleaching treatments). 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 small increase in this peak for TPL in relation to PL indicates that the TPL have higher cellulose content. Similar behavior was observed when comparing the spectra of TPL with CNPL5 , CNPL30 and CNPL60 . This peak appeared in all of the spectra and the differences presented suggest that the CNPL5 , CNPL30 and CNPL60 samples has a very high content of cellulose. 3.2. Isolation of Cellulose nanocrystals, gravimetric and birefringence analysis The yields of the CNPL, with respect to the initial amount of dried TPL bers, for CNPL5 , CNPL30 and CNPL60 were 77, 65 and 55 wt% respectively; these values are consistent with the literature data (Silvrio et al., 2013; Teixeira et al., 2011, 2010). Among the several methods for preparing CN, acid hydrolysis is the most well-known and widely used (Peng et al., 2011). This process breaks down the disordered and amorphous parts of the cellulose, releasing single and well-dened crystals. Thus, this process is based on the quicker hydrolysis kinetics presented by amorphous regions, as compared to crystalline ones (Habibi et al., 2010; Peng et al., 2011; Teixeira et al., 2011). During the hydrolysis process with sulfuric acid, sulfate groups are introduced on the surface of the CN by esterication of the hydroxyl groups from cellulose. This allows an anionic stabilization by repulsive forces, leading to the achievement of stable aqueous dispersions of CN (Beck-Candanedo et al., 2005; Lima and Borsali, 2004; Silva and DAlmeida, 2009). Also, it is known that the increased extraction time results in higher sulfate content in the CN (Flauzino Neto et al., 2013; Roman and Winter, 2004). Only the hydrolysis times of 30 and 60 min led to stable aqueous suspensions being obtained (as shown in Fig. 3). The suspension obtained with 5 min of hydrolysis tended to aggregate after a few hours (as seen in Fig. 3), probably this particle agglomeration is related to the large size and small amount of surface charges of these particles. Birefringence was used to conrm the presence of isolated nanowhiskers in a suspension and is considered by some authors as

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of the diffractograms proles (Fig. 5), there is a predominance of type I cellulose, veried by the presence of peaks at 2 = 15 (plane , 21 (plane 0 2 1), 23 (plane 0 0 2) and 34 1 0 1), 17 (plane 101) (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 reduction and removal of amorphous non-cellulosic compounds induced by the alkali and bleaching treatments performed in the purication process. The increase in the CrI value of CNPL5 in relation to TPL was also observed, due to the partial removal of the paracrystalline 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 sugarcane 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 CNPL5 , CNPL30 and CNPL60 observed between cross nicols showing the formation of birefringent domains.

3.4. Atomic force microscopy (AFM) An accurate morphological examination of the CN is essential not only for the promoters of the manufacturing process of the CN, but also for developers of functional applications. In this way, AFM topography measurements were performed in order to have a precise characterization of the dimensions of the individual crystallites (Flauzino Neto et al., 2013). Determining the exact dimensions of CN is complicated by the specic limitations of the different analytical methods used. In the case of AFM, tip/sample broadening represents the main limitation, resulting in an overestimation of CN dimensions. Since the CN are assumed to be cylindrical in shape, the height of the CN was taken to be equivalent to the diameter, to compensate for image widening 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 measurements, but this is unavoidable (Beck-Candanedo et al., 2005). Fig. 6 shows AFM images of CNPL5 , CNPL30 and CNPL60 . For the samples CNPL30 and CNPL60 , the AFM images presented needlelike nanoparticles throughout, conrming that the extraction of CN from PL was successful. However, the AFM images of sample CNPL5 showed micro-sized bers and some needle-like nanoparticles. 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 (CNPL5 ). Fig. 7 shows the length (L), width (D) and aspect ratio (L/D) histograms 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 CNPL30 and CNPL60 obtained by AFM pictures. Length (nm) CNPL30 CNPL60 249.7 51.5 190.2 36.5 Diameter (nm) 4.45 1.41 4.18 1.44 Aspect ratio (nm) 60.1 19.5 50.4 20.7

a good dispersibility criterion in suspension (Silva and DAlmeida, 2009; Silvrio et al., 2013). This birefringence results from two origins: (1) a structural anisotropy form of cellulose and (2) a ow anisotropy resulting from the alignment of the nanocrystals under ow, generally operated before observation. Fig. 4 shows a birefringence of different cellulose suspensions in water, indicating that CN were isolated in all three isolation conditions. The birefringence was somewhat weaker for CNPL5 suspension compared to the CNPL30 and CNPL60 suspensions. It is possible that the hydrolysis time was not sufcient to separate single CN from TPL bers as effectively as the others hydrolysis times and, therefore, the birefringence is not as strong (Oksman et al., 2011). 3.3. X-ray diffraction The XRD patterns of PL, TPL, CNPL5 , CNPL30 and CNPL60 are shown in Fig. 5. These patterns are typical of semi-crystalline materials with an amorphous broad hump and crystalline peaks. In all

Fig. 5. X-ray diffractograms of PL, TPL, CNPL5 , CNPL30 and CNPL60 .


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

By studying histograms it is clear that the increase in hydrolysis time resulted in a reduction in particle size, but no signicant difference in width among the CNPL30 and CNPL60 could be detected, when the standard deviation of each value was taken into account. As a consequence of the whiskers preparation conditions, a decrease in the aspect ratio (L/D) of CNPL60 compared with CNPL30 was observed. This suggests that CNPL30 can give a better reinforcing effect than CNPL60 at the same ller loading levels (Eichhorn et al., 2010). The average aspect ratio for the CNPL found in this work is close to the largest values ever reported in the literature; therefore, these particles have great potential to be used as reinforcing agents in nanocomposites (Kalia et al., 2011; Silvrio et al., 2013). The results of the morphological investigation by AFM are consistent with other reports in the literature, where CN were extracted from different sources (Bai et al., 2009; Beck-Candanedo et al., 2005; de Rodriguez et al., 2006; Elazzouzi-Hafraoui et al., 2008; Kvien et al., 2005; Rosa et al., 2010; Siqueira et al., 2010a; Teixeira et al., 2011). 3.5. Thermogravimetric analysis (TGA) At present, the main application of CN is as a reinforcing agent in the nanocomposite eld, and typical processing temperatures for thermoplastics rise above 200 C, thus the thermal stability of

these crystals is a key factor in order for them to be used as effective reinforcing materials (Roman and Winter, 2004). The thermogravimetric (TG) results of the PL, TPL, CNPL5 , CNPL30 and CNPL60 are shown in Fig. 8. In all cases, a small weight loss was found in the range of 25150 C, due to the evaporation of the water of the materials or low molecular weight compounds (about 7%). The initial degradation temperatures were found to be around 216, 244, 245, 225 and 220 C for the PL, TPL, CNPL5 , CNPL30 and CNPL60 , respectively. The initial degradation temperature of the TPL (244 C) was appreciably increased compared to that of the original PL (216 C). Due to the low initial decomposition temperatures of hemicelluloses, lignin and pectin, the higher initial temperature of thermal decomposition of the TPL is related to the partial removal of hemicelluloses, lignin, and pectins by purication processes (alkali and bleaching treatments) (Alemdar and Sain, 2008; Chen et al., 2011; Flauzino Neto et al., 2013). As reported in previous studies, treatment with sulfuric acid leads to a remarkable decrease in thermal stability of CN. This occurs because the incorporation of sulfate groups on the surface of the cellulose after hydrolysis has a catalytic effect in its reactions of thermal degradation (Roman and Winter, 2004). Taking into account that acid hydrolysis leads to a remarkable decrease in thermal stability of CN, it was expected that the initial degradation temperature of CNPL5 were smaller than for TPL, but

Fig. 7. Length (L), width (D) and aspect ratio (L/D) histograms of CNPL30 and CNPL60 obtained by several AFM images.

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Acknowledgements The authors thank CAPES/PROAP, CNPq and FAPEMIG for nancial support.

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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 which are negatively charged, due the presence of sulfate groups. The yields of acid hydrolysis, with respect to the initial amount of dried TPL bers, for CNPL5 , CNPL30 and CNPL60 were 77, 65 and 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 (73%), an average length of 249.7 51.5 nm and a diameter of 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 materials.


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