Abstract
Cellulose nanocrystal (CNC) production suffers, among other problems, from low yields. The focus of this study was to investigate the universal effect of charge density, centrifugation, and mechanical treatment as limiting causes of yield. Microcrystalline cellulose (MCC) was used as the starting material in order to eliminate the relatively arbitrary yield losses caused by the hydrolysis conditions. To disintegrate MCC into nanocrystals, high surface charge in the form of carboxylic groups was introduced by TEMPO-mediated oxidation, after which the material was mechanically treated, and separated into fine and coarse fractions. The fine fraction collected as supernatant after separation by centrifugation had a yield of 17–20% independent of the mechanical treatment method or time used. The particle sizes of these fractions did not significantly differ from each other, which raises questions on the efficiency of the mechanical treatment (sonication) and centrifugation in traditional CNC production. The results imply that radically new approaches in preparation are needed for truly meaningful increases in the CNC yield.
Similar content being viewed by others
References
Araki J, Wada M, Kuga S, Okano T (1999) Influence of surface charge on viscosity behavior of cellulose microcrystal suspension. J Wood Sci 45:258–261. doi:10.1007/BF01177736
Berggren R, Berthold F, Sjöhoml E, Lindström M (2001) Fiber strength in relation to molecular mass distribution of hardwood kraft pulp. Nord Pulp Pap Res J 16:333–338. doi:10.3183/NPPRJ-2001-16-04-p333-338
Bondeson D, Mathew A, Oksman K (2006) Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis. Cellulose 13:171–180. doi:10.1007/s10570-006-9061-4
Chang M, Pound TC, Manley RSTJ (1973) Gel-permeation chromatographic studies of cellulose degradation. I. Treatment with hydrochloric acid. J Pol Sci 11:399–411. doi:10.1002/pol.1973.180110301
Chen L, Wang Q, Hirth K, Baez C, Agarwal UP, Zhu JY (2015) Tailoring the yield and characteristics of wood cellulose nanocrystals (CNC) using concentrated acid hydrolysis. Cellulose 22:1753–1762. doi:10.1007/s10570-015-0615-1
Chen L, Zhu JY, Baez C, Kitin P, Elder T (2016) Highly thermal-stable and functional cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids. Green Chem 18:3835–3843. doi:10.1039/c6gc00687f
Cherhal F, Cousin F, Capron I (2016) Structural description of the interface of pickering emulsions stabilized by cellulose nanocrystals. Biomacromolecules 17:496–502. doi:10.1021/acs.biomac.5b01413
Diddens I, Murphy B, Krisch M, Müller M (2008) Anisotropic elastic properties of cellulose measured using inelastic X-ray scattering. Macromolecules 41:9755–9759. doi:10.1021/ma801796u
Dong XM, Gray DG (1997) Effects of counterions on ordered phase formation in suspensions of charged rodlike cellulose crystallites. Langmuir 13:2404–2409. doi:10.1021/la960724h
Dong XM, Revol J-F, Gray DG (1998) Effect of microcrystallite preparation conditions on the formation of colloid crystals of cellulose. Cellulose 5:19–32. doi:10.1023/A:1009260511939
Dri FL, Hector LG Jr, Moon RJ, Zavarettieri PD (2013) Anisotropy of the elastic properties of crystalline cellulose Iβ from first principles density functional theory with Van der Waals interactions. Cellulose 20:2703–2718. doi:10.1007/s10570-013-0071-8
Elazzouzi-Harfaoui S, Nishiyama Y, Putaux J-L, Heux L, Dubreuil F, Rochas C (2008) The shape and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native cellulose. Biomacromolecules 9:57–65. doi:10.1021/bm700769p
Fan J-S, Li Y-H (2012) Maximizing the yield of nanocrystalline cellulose from cotton pulp fiber. Carbohydr Polym 88:1184–1188. doi:10.1016/j.carbpol.2012.01.081
Gestranius M, Stenius P, Kontturi E, Sjöblom J, Tammelin T (2016) Phase behaviour and droplet size of oil-in-water Pickering emulsions stabilised with plant-derived nanocellulosic materials. Col Surf A Physicochem Eng Aspects. doi:10.1016/j.colsurfa.2016.04.025
Guo J, Guo X, Wang S, Yin Y (2016) Effects of ultrasonic treatment during acid hydrolysis on the yield, particle size and structure of cellulose nanocrystals. Carbohydr Polym 135:248–255. doi:10.1016/j.carbpol.2015.08.068
Gurnagul N, Page DH, Paice MG (1992) The effect of cellulose degradation on the strenth of wood pulp fibres. Nord Pulp Pap Res J 7:152–154. doi:10.3183/NPPRJ-1992-07-03-p152-154
Habibi Y, Lucia LA, Rojas O (2010) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110:3479–3500. doi:10.1021/cr900339
Hamad WY, Hu TQ (2010) Structure–process–yield interrelations in nanocrystalline cellulose extraction. Can J Chem Eng 88:392–402. doi:10.1002/cjce.20298
Hu TQ, Hashaikeh R, Berry R (2014) Isolation of a novel, crystalline cellulose material from the spent liquor of cellulose nanocrystals (CNCs). Cellulose 21:3217–3229. doi:10.1007/s10570-014-0350-z
Huang YY, Terentjev EM (2012) Dispersion of carbon nanotubes: mixing, sonication, stabilization, and composite properties. Polymers 4:275–295. doi:10.3390/polym4010275
Huang YY, Knowles TPJ, Terentjev EM (2009) Strength of nanotubes, filaments, and nanowires from sonication-induced scission. Adv Mater 21:3945–3948. doi:10.1002/adma.200900498
Isogai T, Saito T, Isogai A (2011) Wood cellulose nanofibrils prepared by TEMPO electro-mediated oxidation. Cellulose 18:421–431. doi:10.1007/s10570-010-9484-9
Kaushik M, Basu K, Benoit C, Cirtiu CM, Vali H (2015) Cellulose nanocrystals as chiral inducers: enantioselective catalysis and transmission electron microscopy 3D characterization. J Am Chem Soc 137:6124–6127. doi:10.1021/jacs.5b02034
Kelly JA, Giese M, Shopsowitz KE, Hamad WY, MacLachlan MJ (2014) The developmetn of chiral nematic mesoporous materials. Acc Chem Res 47:1088–1096. doi:10.1021/ar400243m
Kontturi E, Vuorinen T (2009) Indirect evidence of supramolecular changes within cellulose microfibrils of chemical pulp fibers upon drying. Cellulose 16:65–74. doi:10.1007/s10570-008-9235-3
Kontturi E, Meriluoto A, Penttilä PA, Baccile N, Malho J, Potthast A, Rosenau T, Ruokolainen J, Serimaa R, Laine J, Sixta H (2016) Degradation and crystallization of cellulose in hydrogen chloride vapor for high-yield isolation of cellulose nanocrystals. Angew Chem Int Ed 55:14455–14458. doi:10.1002/anie.201606626
Lin N, Géze A, Wouessidjewe D, Huang J, Dufresne A (2016) Biocompatible double-membrane hydrogels from cationic cellulose nanocrystals and anionic alginate as complexing drugs codelivery. ACS Appl Mater Interfaces 8:6880–6889. doi:10.1021/acsami.6b00555
Lu Q, Cai Z, Lin F, Tang L, Wang S, Huang B (2016) Extraction of cellulose nanocrystals with high yield of 88% by simultaneous mechanochemical activation and phosphotungstic acid hydrolysis. ACS Sustain Chem Eng 4:2165–2172. doi:10.1021/acssuschemeng.5b01620
Lucas A, Zakri C, Maugey M, Pasquali M, van der Schoot P, Poulin P (2009) Kinetics of nanotube and microfiber scission under sonication. J Phys Chem C 113:20599–20605. doi:10.1021/jp906296y
Mao J, Heck B, Reiter G, Laborie M (2015) Cellulose nanocrystals’ production in near theoretical yields by 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO4)– mediated hydrolysis. Carbohydr Polym 117:443–451. doi:10.1016/j.carbpol.2014.10.001
Mohd Amin KN, Annamalai PK, Morrow IC, Martin D (2015) Production of cellulose nanocrystals via a scalable mechanical method. RSC Adv 5:57133–57140. doi:10.1039/c5ra06862b
Niinivaara E, Faustini M, Tammelin T, Kontturi E (2015) Water vapor uptake of ultrathin films of biologically derived nanocrystals: quantitative assessment with quartz crystal microbalance and spectroscopic ellipsometry. Langmuir 31:12170–12176. doi:10.1021/acs.langmuir.5b01763
Okita Y, Saito T, Isogai A (2010) Entire surface oxidation of various cellulose microfibrils by TEMPO-mediated oxidation. Biomacromolecules 11:1696–1700. doi:10.1021/bm100214b
Peyre J, Pääkkönen T, Reza M, Kontturi E (2015) Simultaneous preparation of cellulose nanocrystals and micron-sized porous colloidal particles of cellulose by TEMPO-mediated oxidation. Green Chem 17:808–811. doi:10.1039/c4gc02001d
Rånby BG (1949) Aqueous colloidal solutions of cellulose micelles. Acta Chem Scand 3:649–650. doi:10.3891/acta.chem.scand.03-0649
Rånby BG (1951) III. Fibrous macromolecular systems. Cellulose and muscle. The colloidal properties of cellulose micelles. Discuss Faraday Soc 11:158–164. doi:10.1039/DF9511100158
Sacui IA, Nieuwendaal RC, Burnett DJ, Stranick SJ, Jorfi M, Weder C, Foster EJ, Olsson RT, Gilman JW (2014) Comparison of the properties of cellulose nanocrystals and cellulose nanofibrils isolated from bacteria, tunicate, and wood processed using acid, enzymatic, mechanical, and oxidative methods. ACS Appl Mater Interfaces 6:6127–6138. doi:10.1021/am500359f
Saito T, Isogai A (2004) TEMPO-mediated oxidation of native cellulose. The effect of oxidation conditions on chemical and crystal structures of the water-insoluble fractions. Biomacromolecules 5:1983–1989. doi:10.1021/bm0497769
Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 8:2485–2491. doi:10.1021/bm0703970
Saito T, Hirota M, Tamura N, Kimura S, Fukuzumi H, Heux L, Isogai A (2009) Individualization of nano-sized plant cellulose fibrils by direct surface carboxylation using TEMPO catalyst under neutral conditions. Biomacromolecules 10:1992–1996. doi:10.1021/bm900414t
Saito T, Kuramae R, Wohlert J, Berglund LA, Isogai A (2012) An ultrastrong nanofibrillar biomaterial: the strength of sigle cellulose nanofibrils revealed via sonication-induced fragmentation. Biomacromolecules 14:248–253. doi:10.1021/bm301674e
Samir ASA, Alloin F, Dufresne A (2005) Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field. Biomacromolecules 6:612–626. doi:10.1021/bm0493685
Satyamurthy P, Jain P, Balasubramanya RH, Vigneshwaran N (2011) Preparation and characterization of cellulose nanowhiskers from cotton fibres by controlled microbial hydrolysis. Carbohydr Polym 83:122–129. doi:10.1016/j.carbpol.2010.07.029
Wang Q, Zhao X, Zhu JY (2014) Kinetics of strong acid hydrolysis of a bleached kraft pulp for producing cellulose nanocrystals (cncs). Ind Eng Chem Res 53:11007–11014. doi:10.1021/ie501672m
Yu H, Qin Z, Liang B, Liu N, Zhou Z, Chen L (2013) Facile extraction of thermally stable cellulose nanocrystals with high yield of 93% through hydrochloric acid hydrolysis under hydrothermal conditions. J Mater Chem A 1:3938–3944. doi:10.1039/C3TA01150J
Acknowledgements
We acknowledge Academy of Finland (259500) for financial support.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Salminen, R., Reza, M., Pääkkönen, T. et al. TEMPO-mediated oxidation of microcrystalline cellulose: limiting factors for cellulose nanocrystal yield. Cellulose 24, 1657–1667 (2017). https://doi.org/10.1007/s10570-017-1228-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-017-1228-7