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Preparation and characterization of nanocrystalline cellulose via low-intensity ultrasonic-assisted sulfuric acid hydrolysis

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Abstract

Nanocrystalline cellulose (NCC) was extracted from microcrystalline cellulose via low-intensity ultrasonic-assisted sulfuric acid hydrolysis process. NCC samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), particle size distribution (PSD) analysis, Fourier-transformed infrared spectra (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and rheological measurement. It was found that NCC yield reached 40.4 % under the optimum process of low-intensity ultrasonic-assisted sulfuric acid hydrolysis, while it was only 33.0 % in the absence of ultrasonic treatment. Furthermore, the results showed that the two NCC samples obtained from ultrasonic-assisted hydrolysis and conventional hydrolysis were very similar in morphology, both exhibiting rod-like structures with widths and lengths of 10–20 and 50–150 nm, respectively. XRD result revealed that the NCC sample from ultrasonic-assisted hydrolysis contained a small amount of cellulose II and possessed a Segal Crystallinity Index of 90.38 % and a crystallite size of 58.99 Å, higher than those of the NCC sample from conventional hydrolysis. Moreover, PSD analysis demonstrated that the former exhibited a smaller value in average particle size than the latter. In addition, rheological measurements showed that the NCC suspensions from the ultrasonic-assisted process exhibited a lower viscosity over the range of shear rate from 0.1 to 100 s−1 in comparison with that prepared in the absence of ultrasonic treatment.

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References

  • Ahmadi F, McLoughlin IV, Chauhan S, Ter-Haar G (2012) Bio-effects and safety of low-intensity, low-frequency ultrasonic exposure. Prog Biophys Mol Biol 108(3):119–138

    Article  Google Scholar 

  • Bai W, Holbery J, Li K (2009) A technique for production of nanocrystalline cellulose with a narrow size distribution. Cellulose 16(3):455–465

    Article  CAS  Google Scholar 

  • Beck-Candanedo S, Roman M, Gray DG (2005) Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. Biomacromolecules 6(2):1048–1054

    Article  CAS  Google Scholar 

  • Bondeson D, Mathew A, Oksman K (2006) Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis. Cellulose 13(2):171–180

    Article  CAS  Google Scholar 

  • Brinchi L, Cotana F, Fortunati E, Kenny JM (2013) Production of nanocrystalline cellulose from lignocellulosic biomass: technology and applications. Carbohydr Polym 94(1):154–169

    Article  CAS  Google Scholar 

  • Cha R, He Z, Ni Y (2012) Preparation and characterization of thermal/pH-sensitive hydrogel from carboxylated nanocrystalline cellulose. Carbohydr Polym 88(2):713–718

    Article  CAS  Google Scholar 

  • Chen W, Yu H, Liu Y (2011a) Preparation of millimeter-long cellulose I nanofibers with diameters of 30–80 nm from bamboo fibers. Carbohydr Polym 86(2):453–461

    Article  CAS  Google Scholar 

  • Chen W, Yu H, Liu Y, Chen P, Zhang M, Hai Y (2011b) Individualization of cellulose nanofibers from wood using high-intensity ultrasonication combined with chemical pretreatments. Carbohydr Polym 83(4):1804–1811

    Article  CAS  Google Scholar 

  • Chen W, Yu H, Liu Y, Hai Y, Zhang M, Chen P (2011c) Isolation and characterization of cellulose nanofibers from four plant cellulose fibers using a chemical-ultrasonic process. Cellulose 18(2):433–442

    Article  CAS  Google Scholar 

  • Chen P, Yu H, Liu Y, Chen W, Wang X, Ouyang M (2013) Concentration effects on the isolation and dynamic rheological behavior of cellulose nanofibers via ultrasonic processing. Cellulose 20(1):149–157

    Article  CAS  Google Scholar 

  • Cintas P, Luche J (1999) Green chemistry. The sonochemical approach. Green Chem 1(3):115–125

    Article  CAS  Google Scholar 

  • de Campos A, Correa AC, Cannella D, de Morais Teixeira E, Marconcini JM, Dufresne A, Mattoso LH, Cassland P, Sanadi AR (2013) Obtaining nanofibers from curauá and sugarcane bagasse fibers using enzymatic hydrolysis followed by sonication. Cellulose 20(3):1491–1500

    Article  Google Scholar 

  • de Morais Teixeira E, Corrêa AC, Manzoli A, de Lima LeiteF, de Oliveira CR, Mattoso LHC (2010) Cellulose nanofibers from white and naturally colored cotton fibers. Cellulose 17(3):595–606

    Article  Google Scholar 

  • Deepa B, Abraham E, Cherian BM, Bismarck A, Blaker JJ, Pothan LA, Leao AL, de Souza SF, Kottaisamy M (2011) Structure, morphology and thermal characteristics of banana nano fibers obtained by steam explosion. Bioresour Technol 102(2):1988–1997

    Article  CAS  Google Scholar 

  • Driemeier C, Calligaris GA (2010) Theoretical and experimental developments for accurate determination of crystallinity of cellulose I materials. J Appl Crystallogr 44(1):184–192

    Article  Google Scholar 

  • Elazzouzi-Hafraoui S, Nishiyama Y, Putaux J, Heux L, Dubreuil F, Rochas C (2007) The shape and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native cellulose. Biomacromolecules 9(1):57–65

    Article  Google Scholar 

  • Eronen P, Österberg M, Heikkinen S, Tenkanen M, Laine J (2011) Interactions of structurally different hemicelluloses with nanofibrillar cellulose. Carbohydr Polym 86(3):1281–1290

    Article  CAS  Google Scholar 

  • Fan J, Li Y (2012) Maximizing the yield of nanocrystalline cellulose from cotton pulp fiber. Carbohydr Polym 88(4):1184–1188

    Article  CAS  Google Scholar 

  • Fatehi P, Liu X, Ni Y, Xiao H (2010) Interaction of cationic modified poly vinyl alcohol with high yield pulp. Cellulose 17(5):1021–1031

    Article  CAS  Google Scholar 

  • Filson PB, Dawson-Andoh BE (2009) Sono-chemical preparation of cellulose nanocrystals from lignocellulose derived materials. Bioresour Technol 100(7):2259–2264

    Article  CAS  Google Scholar 

  • French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose. doi:10.1007/s10570-013-0030-4

    Google Scholar 

  • French AD, Santiago Cintrón M (2013) Cellulose polymorphy, crystallite size, and the Segal Crystallinity Index. Cellulose 20(1):583–588

    Article  CAS  Google Scholar 

  • Hamad WY, Hu TQ (2010) Structure–process–yield interrelations in nanocrystalline cellulose extraction. Can J Chem Eng 88(3):392–402

    CAS  Google Scholar 

  • Hamada H, Bousfield DW (2010) Nano-fibrillated cellulose as a coating agent to improve print quality of synthetic fiber sheets. In: TAPPI 11th advanced coating fundamentals symposium, Munich, TAPPI, Atlanta, GA, pp 7–16

  • Hashaikeh R, Abushammala H (2011) Acid mediated networked cellulose: preparation and characterization. Carbohydr Polym 83(3):1088–1094

    Article  CAS  Google Scholar 

  • Henriksson M, Henriksson G, Berglund LA, Lindström T (2007) An environmentally friendly method for enzyme-assisted preparation of microfibrillated cellulose (MFC) nanofibers. Eur Poly J 43(8):3434–3441

    Article  CAS  Google Scholar 

  • Ishida O, Kim D, Kuga S, Nishiyama Y, Brown RM (2004) Microfibrillar carbon from native cellulose. Cellulose 11(3–4):475–480

    Article  CAS  Google Scholar 

  • Jahan MS, Saeed A, He Z, Ni Y (2011) Jute as raw material for the preparation of microcrystalline cellulose. Cellulose 18(2):451–459

    Article  CAS  Google Scholar 

  • Johar N, Ahmad I, Dufresne A (2012) Extraction, preparation and characterization of cellulose fibres and nanocrystals from rice husk. Ind Crop Prod 37(1):93–99

    Article  CAS  Google Scholar 

  • Klemm D, Schumann D, Udhardt U, Marsch S (2001) Bacterial synthesized cellulose—artificial blood vessels for microsurgery. Prog Polym Sci 26(9):1561–1603

    Article  CAS  Google Scholar 

  • Lam E, Male KB, Chong JH, Leung ACW, Luong JHT (2012) Applications of functionalized and nanoparticle-modified nanocrystalline cellulose. Trends Biotechnol 30(5):283–290

    Article  CAS  Google Scholar 

  • Langan P, Nishiyama Y, Chanzy H (2001) X-ray structure of mercerized cellulose II at 1 Å resolution. Biomacromolecules 2(2):410–416. doi:10.1021/bm005612q

    Article  CAS  Google Scholar 

  • Li J, Wei X, Wang Q, Chen J, Chang G, Kong L, Su J, Liu Y (2012) Homogeneous isolation of nanocellulose from sugarcane bagasse by high pressure homogenization. Carbohydr Polym 90(4):1609–1613

    Article  CAS  Google Scholar 

  • Li W, Yue J, Liu S (2012) Preparation of nanocrystalline cellulose via ultrasound and its reinforcement capability for poly(vinyl alcohol) composites. Ultrason Sonochem 19(3):479–485

    Article  CAS  Google Scholar 

  • Liu D, Chen X, Yue Y, Chen M, Wu Q (2011) Structure and rheology of nanocrystalline cellulose. Carbohydr Polym 84(1):316–322

    Article  CAS  Google Scholar 

  • Liu C, Xiao B, Dauta A, Peng G, Liu S, Hu Z (2009) Effect of low power ultrasonic radiation on anaerobic biodegradability of sewage sludge. Bioresour Technol 100(24):6217–6222

    Google Scholar 

  • Lu P, Hsieh Y (2010) Preparation and properties of cellulose nanocrystals: rods, spheres, and network. Carbohydr Polym 82(2):329–336

    Article  Google Scholar 

  • Lu H, Gui Y, Zheng L, Liu X (2013) Morphological, crystalline, thermal and physicochemical properties of cellulose nanocrystals obtained from sweet potato residue. Food Res Int 50(1):121–128

    Article  CAS  Google Scholar 

  • Morais JPS, Rosa MDF, Nasciment LD, Nascimento DMD, Alexandre LC (2012) Extraction and characterization of nanocellulose structures from raw cotton linter. Carbohydr Polym 91(1):229–235

    Article  Google Scholar 

  • Morán JI, Alvarez VA, Cyras VP, Vázquez A (2008) Extraction of cellulose and preparation of nanocellulose from sisal fibers. Cellulose 15(1):149–159

    Article  Google Scholar 

  • Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose Iβ from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 124(31):9074–9082

    Article  CAS  Google Scholar 

  • Nishiyama Y, Johnson GP, French AD (2012) Diffraction from nonperiodic models of cellulose crystals. Cellulose 19(2):319–336

    Article  CAS  Google Scholar 

  • Okahisa Y, Abe K, Nogi M, Nakagaito AN, Nakatani T, Yano H (2011) Effects of delignification in the production of plant-based cellulose nanofibers for optically transparent nanocomposites. Compos Sci Technol 71(10):1342–1347

    Article  CAS  Google Scholar 

  • Park S, Baker JO, Himmel ME, Parilla PA, Johnson DK (2010) Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol Biofuels 3:1–10

    Article  Google Scholar 

  • Pirani S, Hashaikeh R (2012) Nanocrystalline cellulose extraction process and utilization of the byproduct for biofuels production. Carbohydr Polym 93(1):357–363

    Article  Google Scholar 

  • Pourbafarani S, Mozaffari M, Amighian J (2013) Investigation of phase formation and magnetic properties of Mn ferrite nanoparticles prepared via low-power ultrasonic assisted co-precipitation method. J Supercond Nov Magn 26(3):675–678

    Article  CAS  Google Scholar 

  • Qian L, Guan Y, Ziaee Z, He B, Zheng A, Xiao H (2009) Rendering cellulose fibers antimicrobial using cationic β-cyclodextrin-based polymers included with antibiotics. Cellulose 16(2):309–317

    Article  CAS  Google Scholar 

  • Qua EH, Hornsby PR, Sharma H, Lyons G (2011) Preparation and characterisation of cellulose nanofibres. J Mater Sci 46(18):6029–6045

    Article  CAS  Google Scholar 

  • Roman M, Winter WT (2004) Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose. Biomacromolecules 5(5):1671–1677

    Article  CAS  Google Scholar 

  • Satyamurthy P, Jain P, Balasubramanya RH, Vigneshwaran N (2011) Preparation and characterization of cellulose nanowhiskers from cotton fibres by controlled microbial hydrolysis. Carbohydr Polym 83(1):122–129

    Article  CAS  Google Scholar 

  • Savadekar NR, Mhaske ST (2012) Synthesis of nano cellulose fibers and effect on thermoplastics starch based films. Carbohydr Polym 89(1):146–151

    Article  CAS  Google Scholar 

  • Scherrer P (1918) Bestimmung der Grösse und der inneren Struktur von Kolloidteilchen mittels Röntgenstrahlen. Nachr Ges Wiss Göttingen 26:98–100

    Google Scholar 

  • Sun XF, Xu F, Sun RC, Fowler P, Baird MS (2005) Characteristics of degraded cellulose obtained from steam-exploded wheat straw. Carbohydr Res 340(1):97–106

    Article  CAS  Google Scholar 

  • Tamada Y (2003) Sulfation of silk fibroin by sulfuric acid and anticoagulant activity. J App Poly Sci 87(14):2377–2382

    Article  CAS  Google Scholar 

  • Tang L, Huang B, Lu Q, Wang S, Ou W, Lin W, Chen X (2012) Ultrasonication-assisted manufacture of cellulose nanocrystals esterified with acetic acid. Bioresour Technol 127:100–105

    Article  Google Scholar 

  • Terinte N, Ibbett R, Schuster KC (2011) Overview on native cellulose and microcrystalline cellulose I structure studied by X-ray diffraction (WAXD): comparison between measurement techniques. Lenzingr Ber 89:118–131

    CAS  Google Scholar 

  • Tischer PCF, Sierakowski MR, Westfahl H Jr, Tischer CA (2010) Nanostructural reorganization of bacterial cellulose by ultrasonic treatment. Biomacromolecules 11(5):1217–1224

    Article  CAS  Google Scholar 

  • Tonoli GHD, Teixeira EM, Corrêa AC, Marconcini JM, Caixeta LA, Pereira-da-Silva MA, Mattoso LHC (2012) Cellulose micro/nanofibres from Eucalyptus kraft pulp: preparation and properties. Carbohydr Polym 89(1):80–88

    Article  CAS  Google Scholar 

  • Torvinen K, Sievänen J, Hjelt T, Hellén E (2012) Smooth and flexible filler-nanocellulose composite structure for printed electronics applications. Cellulose 19(3):821–829

    Article  CAS  Google Scholar 

  • Urena-Benavides EE, Ao G, Davis VA, Kitchens CL (2011) Rheology and phase behavior of lyotropic cellulose nanocrystal suspensions. Macromolecules 44(22):8990–8998

    Article  CAS  Google Scholar 

  • Wang N, Ding E, Cheng R (2007) Thermal degradation behaviors of spherical cellulose nanocrystals with sulfate groups. Polymer 48(12):3486–3493

    Article  CAS  Google Scholar 

  • Wang N, Ding E, Cheng R (2008) Preparation and liquid crystalline properties of spherical cellulose nanocrystals. Langmuir 24(1):5–8

    Article  Google Scholar 

  • Yang Q, Pan X, Huang F, Li K (2011) Synthesis and characterization of cellulose fibers grafted with hyperbranched poly (3-methyl-3-oxetanemethanol). Cellulose 18(6):1611–1621

    Article  CAS  Google Scholar 

  • Zaman M, Liu H, Xiao H, Chibante F, Ni Y (2012a) Hydrophilic modification of polyester fabric by applying nanocrystalline cellulose containing surface finish. Carbohydr Polym 91(2):560–567

    Article  Google Scholar 

  • Zaman M, Xiao H, Chibante F, Ni Y (2012b) Synthesis and characterization of cationically modified nanocrystalline cellulose. Carbohydr Polym 89(1):163–170

    Article  CAS  Google Scholar 

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Grant No. 31100442), the Science and Technology Program of Hangzhou City of China (Grant No. 20120433B63), the Science and Technology Program of Zhejiang Environmental Protection Bureau of China (Grant No. 2012B008), Zhejiang Provincial Top Key Academic Discipline of Chemical Engineering and Technology and 521 Talent Cultivation Program of Zhejiang Sci-Tech University (Grant No. 11110132521310).

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Authors and Affiliations

  1. Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou, 310018, China

    Yanjun Tang, Shujie Yang & Junhua Zhang

  2. Limerick Pulp and Paper Center, University of New Brunswick, Fredericton, E3B 5A3, Canada

    Yanjun Tang

  3. Shanghai Tonnor Material Science Co., Ltd., Shanghai, 200092, China

    Nan Zhang

  4. Engineering Research Center for Eco-Dyeing & Finishing of Textiles, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou, 310018, China

    Junhua Zhang

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  1. Yanjun Tang
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Correspondence to Yanjun Tang.

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Tang, Y., Yang, S., Zhang, N. et al. Preparation and characterization of nanocrystalline cellulose via low-intensity ultrasonic-assisted sulfuric acid hydrolysis. Cellulose 21, 335–346 (2014). https://doi.org/10.1007/s10570-013-0158-2

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