Elsevier

Carbohydrate Polymers

Volume 181, 1 February 2018, Pages 1038-1051
Carbohydrate Polymers

Research paper
Isolation and characterization of nanocrystalline cellulose from sugar palm fibres (Arenga Pinnata)

https://doi.org/10.1016/j.carbpol.2017.11.045Get rights and content

Abstract

Cellulose was extracted from sugar palm fibres (Arenga pinnata) by conducting delignification and mercerization treatments. Subsequently, sugar palm nanocrystalline celluloses (SPNCCs) were isolated from the extracted cellulose with 60 wt% concentrated sulphuric acid. The chemical composition of sugar palm fibres were determined at different stages of treatment. Structural analysis was carried out by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Morphological analysis of extracted cellulose and isolated nanocrystalline cellulose (NCCs) was investigated by using field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), and transmission electron microscopy (TEM). The thermal stability of sugar palm fibres at different stages of treatment was investigated by thermogravimetric analysis (TGA). The results showed that lignin and hemicellulose were removed from the extracted cellulose through the delignification and mercerization process, respectively. The isolated SPNCCs were found to have length and diameters of 130 ± 30 nm and 9 ± 1.96 nm, respectively.

Introduction

Nanocrystalline celluloses (NCCs) isolated from plant fibers attracted a tremendous interest in material science due to its appealing intrinsic properties including nano-dimension, high surface area (100 m2 g−1) (Islam, Alam, & Zoccola, 2013; Savadekar & Mhaske, 2012; Silvério, Flauzino Neto, Dantas, & Pasquini, 2013), high aspect ratio of 100 (Rosa et al., 2010; Savadekar & Mhaske, 2012; Tee et al., 2013a, Tee et al., 2013b), high crystallinity, low density, high mechanical strength, unique morphology along with availability, renewability and biodegrability (Azizi Samir, Alloin, & Dufresne, 2005; Ilyas, Sapuan, Ishak, & Zainudin, 2017; Ng et al., 2015). Cellulose is the product of biosynthesis from bacteria and plants, whereas the general term “nanocrystalline cellulose” refers to cellulosic isolation or extraction materials, with the outstanding feature of nano-scale structural dimension. The main component of plant fibres is cellulose, semicrystalline polymer, which composed of poly(1,4-β-d-anhydroglucopyranose) units. These units are formed from strong hydrogen bond between hydroxyl groups. Other main components that made up natural fibres structure are lignin and hemicellulose. Lignin is a highly cross-linked phenolic polymer, whereas hemicellulose is a branched multiple polysaccharide polymer composed of different types of sugars comprising xylose, glucose, arabinose, mannose and galactose. However, both lignin and hemicellulose are amorphous polymers. Strong acid hydrolysis is a well-known process for the removal of the amorphous region and isolation of NCCs from natural fibers. Under controlled conditions, acid hydrolysis allows removal of the amorphous regions of cellulose fibres whilst keeping the crystalline domains intact in the form of crystalline nanoparticles. In fact, removing the amorphous region influences the structure, thermal stability, crystallinity as well as surface morphology of the fibres (Ilyas Rushdan et al., 2017). Previous studies done by Deepa et al. (2011a) and Li et al. (2009), have shown improvement in the thermal stability and crystallinity during the isolation of NCCs.

In the past decades, many different resources have been used to prepare NCCs, such as hard- and softwood fibres (Beck-Candanedo, Roman, & Gray, 2005), wheat straw (Dufresne, Cavaillé, & Helbert, 1997), sisal (Garcia de Rodriguez, Thielemans, & Dufresne, 2006a; Garcia de Rodriguez, Thielemans, & Dufresne, 2006b; Morán, Alvarez, Cyras, & Vázquez, 2008), pineapple leaves (Cherian et al., 2010a), coconut husk fibres (Rosa et al., 2010), mulberry (Li et al., 2009), bananas (Deepa et al., 2011a), sugarcane bagasse (de Morais Teixeira et al., 2011), bamboo (Brito, Pereira, Putaux, & Jean, 2012), mengkuang leaves (Sheltami, Abdullah, Ahmad, Dufresne, & Kargarzadeh, 2012), jute (Cao, Ding, Yu, & Al-Deyab, 2012), rice straw (Lu & Hsieh, 2012), eucalyptus wood (Tonoli et al., 2012), soy hull (Flauzino Neto, Silvério, Dantas, & Pasquini, 2013), cotton linter (Morais et al., 2013) and kenaf bast (Zaini, Jonoobi, Tahir, & Karimi, 2013). The purpose of the isolation of NCCs is as reinforcements in the field of nanocomposite that has gained tremendous attention since it was first examined by Favier et al. (1995). However, no studies on the production, composition, or properties of natural nanocrystalline cellulose fibres from sugar palm fibres have been found in the literature.

Sugar palm tree also known as Arenga Pinnata is a popular multipurpose tree dominantly found in tropical regions. It belongs to the Palmae family which has about 181 genera with around 2600 known species (Ishak et al., 2013). The fruit can be eaten as sweet meal and the fibres can be used for weaving hat and mats, making ropes, brooms, road construction, brushes, roof materials, cushion and shelters for fish breeding. Besides that, its stem core can be used for making sago flour and root as tea to cure bladder stones; insect repellent and posts for pepper, boards, tool handles, water pipes, musical instruments like drums (Adawiyah, Sasaki, & Kohyama, 2013; Ishak et al., 2013, Martini et al., 2012; Mogea, Seibert, & Smits, 1991). Up to the present time, the usage of sugar palm fibres has progressed to another successive level especially to numerous engineering applications. In example, it is being used for underground and underwater cables, substitution of geo-textile fiberglass reinforcement in road construction for soil stabilization as well as a used as reinforcement in polymer matrix composite in material engineering (Ishak et al., 2013). Several studies have shown that sugar palm fibres have a huge potential to be used in various polymer composite application (Bachtiar, Sapuan, & Hamdan, 2008, Bachtiar, Sapuan, & Hamdan, 2010, Bachtiar, Salit, Zainudin, Abdan, & Dahlan, 2011; Ishak, Leman, Sapuan, Salleh, & Misri, 2009; Sahari, Sapuan, Ismarrubie, & Rahman, 2011, Sahari, Sapuan, Zainudin, & Maleque, 2013a, Sahari, Sapuan, Zainudin, & Maleque, 2013b). This study continues with sugar palm-derived cellulose reinforced with starch polymer (Sanyang, Sapuan, Jawaid, Ishak, & Sahari, 2016). To the best of our knowledge, no study on sugar palm nanocrystalline cellulose (SPNCCs) has been found in the literature. Thus the aim of the current study was to extract and characterize nanocrystalline cellulose (NCCs) from sugar palm fibres.

In this paper, cellulose and NCCs were extracted from sugar palm fibres by chemical and mechanical methods. The effects of different chemical treatments on sugar palm fibres were investigated by determining their chemical composition (TAPPI standard), thermogravimetric analysis (TGA), X-ray diffraction (XRD), surface area by Brunauer-Emmett-Teller (BET), degree of polymerization (DP), Fourier transform infrared (FT-IR) spectroscopy and field emission scanning electron microscopy (FESEM). The aspect ratio and dimensions of the isolated NCCs were determined by using zeta potential nanoparticle sizer, atomic force microscopy (AFM) and transmission electron microscopy (TEM).

Section snippets

Materials

Sugar palm fibres gathered in Bahau (Negeri Sembilan, Malaysia) were used in this study. The chemical reagents used were sodium chlorite, acetic acid, sodium hydroxide and sulphuric acid (purchased from Sigma–Aldrich).

Extraction of cellulose

Cellulose fibres can be extracted from sugar palm fibres (SPF) using two main processes, which are delignification and mercerization (Ilyas et al., 2017, Sanyang et al., 2016; Tawakkal, Talib, Abdan, & Ling, 2012; Tee et al., 2013a, Tee et al., 2013b). The initial process was

Results and discussion

The chemical compositions of the sugar palm fibres were affected by the chemical extraction process, NaClO2 followed by NaOH. From raw sugar palm fibres as feedstock, the initial stage of the extraction process was bleaching treatment. This treatment was done to remove lignin (Dufresne, Dupeyre, & Vignon, 2000; Sheltami et al., 2012). The bleaching treatment effects are depending on the temperature and pH. Usually, the reaction happens at high temperature and low pH. The second stage was alkali

Conclusion

SPNCCs was successfully extracted and isolated from sugar palm fibers using the treatment of delignification (NaClO2), mercerization (NaOH) and hydrolysis (H2SO4). The chemical composition analysis showed an increase trending in the cellulose content after each chemical treatment; it therefore changed from 43.88%% in the raw sugar palm fiber to 81.5% in the bleached fibres and to 82.33% in the alkali-treated fibres. FTIR results also showed that the chemical treatments of delignification (NaClO2

Acknowledgments

The authors would like to appreciate University Putra Malaysia for financial support through the Graduate Research Fellowship (GRF) scholarship. The authors are thankful to Dr. Muhammad Lamin Sanyang for guideline throughout the experiment. The authors also thanks the Forest Research Institute Malaysia (FRIM) and Dr. Rushdan Ibrahim for their advice and fruitful discussions.

References (115)

  • B. Deepa et al.

    Structure, morphology and thermal characteristics of banana nano fibers obtained by steam explosion

    Bioresource Technology

    (2011)
  • W.P. Flauzino Neto et al.

    Extraction and characterization of cellulose nanocrystals from agro-industrial residue -Soy hulls

    Industrial Crops and Products

    (2013)
  • C.A. Hubbell et al.

    Effect of acid-chlorite delignification on cellulose degree of polymerization

    Bioresource Technology

    (2010)
  • M.R. Ishak et al.

    Sugar palm (Arenga pinnata): Its fibres, polymers and composites

    Carbohydrate Polymers

    (2013)
  • S. Julien et al.

    Influence of acid pretreatment (H2SO4, HCl, HNO3) on reaction selectivity in the vacuum pyrolysis of cellulose

    Journal of Analytical and Applied Pyrolysis

    (1993)
  • R. Jumaidin et al.

    Effect of seaweed on mechanical, thermal, and biodegradation properties of thermoplastic sugar palm starch/agar composites

    International Journal of Biological Macromolecules

    (2017)
  • R. Jumaidin et al.

    Thermal, mechanical, and physical properties of seaweed/sugar palm fibre reinforced thermoplastic sugar palm starch/agar hybrid composites

    International Journal of Biological Macromolecules

    (2017)
  • R. Kumar et al.

    Physical and chemical characterizations of corn stover and poplar solids resulting from leading pretreatment technologies

    Bioresource Technology

    (2009)
  • R. Li et al.

    Cellulose whiskers extracted from mulberry: A novel biomass production

    Carbohydrate Polymers

    (2009)
  • P. Lu et al.

    Preparation and characterization of cellulose nanocrystals from rice straw

    Carbohydrate Polymers

    (2012)
  • J.P.S. Morais et al.

    Extraction and characterization of nanocellulose structures from raw cotton linter

    Carbohydrate Polymers

    (2013)
  • H.M. Ng et al.

    Extraction of cellulose nanocrystals from plant sources for application as reinforcing agent in polymers

    Composites Part B: Engineering

    (2015)
  • M.Z. Rong et al.

    The effect of fiber treatment on the mechanical properties of unidirectional sisal-reinforced epoxy composites

    Composites Science and Technology

    (2001)
  • M.F. Rosa et al.

    Cellulose nanowhiskers from coconut husk fibers: effect of preparation conditions on their thermal and morphological behavior

    Carbohydrate Polymers

    (2010)
  • J. Sahari et al.

    Mechanical and thermal properties of environmentally friendly composites derived from sugar palm tree

    Materials & Design

    (2013)
  • N.R. Savadekar et al.

    Synthesis of nano cellulose fibers and effect on thermoplastics starch based films

    Carbohydrate Polymers

    (2012)
  • R.M. Sheltami et al.

    Extraction of cellulose nanocrystals from mengkuang leaves (Pandanus tectorius)

    Carbohydrate Polymers

    (2012)
  • H.A. Silvério et al.

    Extraction and characterization of cellulose nanocrystals from corncob for application as reinforcing agent in nanocomposites

    Industrial Crops and Products

    (2013)
  • S. Soares et al.

    Comparative study of the thermal decomposition of pure cellulose and pulp paper

    Polymer Degradation and Stability

    (1995)
  • A. Sonia et al.

    Celluloses microfibres (CMF) reinforced poly (ethylene-co-vinyl acetate) (EVA) composites: Dynamic mechanical, gamma and thermal ageing studies

    Chemical Engineering Journal

    (2013)
  • R.C. Sun et al.

    Characterization of hemicelluloses obtained by classical and ultrasonically assisted extractions from wheat straw

    Carbohydrate Polymers

    (2002)
  • X.F. Sun et al.

    Characteristics of degraded cellulose obtained from steam-exploded wheat straw

    Carbohydrate Research

    (2005)
  • ASTM D1103-60

    Method of test for alpha-cellulose in wood

    (1977)
  • ASTM D1104-56

    Method of test for holocellulose in wood

    (1978)
  • M.A.S. Azizi Samir et al.

    Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field

    Biomacromolecules

    (2005)
  • M. Börjesson et al.

    Crystalline nanocellulose—Preparation, modification, and properties

    Cellulose − Fundamental aspects and current trends

    (2015)
  • D. Bachtiar et al.

    Flexural properties of alkaline treated sugar palm fibre reinforced epoxy composites

    International Journal of Automotive and Mechanical Engineering

    (2010)
  • D. Bachtiar et al.

    Effects of alkaline treatment and a compatibilizing agent on tensile properties of sugar palm fibrereinforced high impact polystyrene composites

    BioResources

    (2011)
  • S. Beck-Candanedo et al.

    Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions

    Biomacromolecules

    (2005)
  • A. Bhatnagar

    Processing of cellulose nanofiber-reinforced composites

    Journal of Reinforced Plastics and Composites

    (2005)
  • D. Bondeson et al.

    Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis

    Cellulose

    (2006)
  • D. Bondeson et al.

    Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis

    Cellulose

    (2006)
  • B. Braun et al.

    Cellulosic nanowhiskers. theory and application of light scattering from polydisperse spheroids in the Rayleigh-Gans-Debye regime

    Biomacromolecules

    (2008)
  • B.S.L. Brito et al.

    Preparation, morphology and structure of cellulose nanocrystals from bamboo fibers

    Cellulose

    (2012)
  • M. Chauve et al.

    Evolution and impact of cellulose architecture during enzymatic hydrolysis by fungal cellulases

    Advances in Biosciences and Biotechnology

    (2013)
  • B.M. Cherian et al.

    A novel method for the synthesis of cellulose nanofibril whiskers from banana fibers and characterization

    Journal of Agricultural and Food Chemistry

    (2008)
  • A.C. Corrêa et al.

    Cellulose nanofibers from curaua fibers

    Cellulose

    (2010)
  • A. Dufresne et al.

    Thermoplastic nanocomposites filled with wheat straw cellulose whiskers. Part II: Effect of processing and modeling

    Polymer Composites

    (1997)
  • A. Dufresne et al.

    Cellulose microfibrils from potato tuber cells: Processing and characterization of starch-cellulose microfibril composites

    Journal of Applied Polymer Science

    (2000)
  • S.J. Eichhorn et al.

    Review: Current international research into cellulose nanofibres and nanocomposites

    Journal of Materials Science

    (2010)
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