, Volume 26, Issue 5, pp 3127–3141 | Cite as

Preparation of nanofibrillated cellulose and nanocrystalline cellulose from surgical cotton and cellulose pulp in hot-glycerol medium

  • Anju Ramakrishnan
  • Kartik Ravishankar
  • Raghavachari DhamodharanEmail author
Original Research


A simple and green method for the preparation of nanofibrillated cellulose (NFC) by heating surgical cotton in glycerol is demonstrated as an alternative to the existing mechanical degradation method. The heat treatment of cotton in the presence of 9% w/w sulphuric acid in glycerol (1 M), under relatively milder conditions than those reported in the literature in the absence of glycerol, resulted in the formation of nanocrystalline cellulose (NCC) due to extensive hydrolysis of the amorphous segments. The method reported offers certain unique advantages in the preparation of NFC such as high yield (71%) and much easier post-processing compared to the mechanical degradation method of preparation of NFC. It also offers certain unique advantages in the preparation of NCC such as relatively high yield (56%), the use of lesser quantity of sulphuric acid as well as elimination of the quenching of the reaction through the addition of excess water to the reaction mixture. The residual ‘green solvent’, separated by decantation or centrifugal separation, post-reaction, could be reused for several cycles after filtration with activated carbon. A simple utility of the NCC prepared as reinforcing additive to cement is demonstrated. The addition of 1% (w/w of cement) of NCC and tetraethylorthosilicate modified NCC enhanced the workability of cement mortar and the compressive strength of cured cement composite in sharp contrast to the use of microcrystalline cellulose that required 10% (w/w) for the same enhancement in strength but with poorer workability.

Graphical abstract

A sustainable route for preparing NFC through heat treatment in glycerol is reported. In the presence of 1 M (9% w/w) sulphuric acid in glycerol, similar heat treatment resulted in the formation of both NFC and NCC. The residual ‘green solvent’ could be reused for several cycles. The addition of 1% (w/w) of nanocellulose prepared via this method enhanced the workability of cement mortar and the compressive strength of cured cement composite.


Agricultural biomass Nanocellulose Surface modification Filler Cement composite Workability 



The authors thank the Department of Materials and Metallurgical Engineering, IIT Madras for extending the TEM facility and Prof.S. Ramaprabhu, Department of Physics, IIT Madras for enabling zeta potential measurements and dynamic light scattering experiments. The authors thank Prof. K. Ramamurthy of the Department of Civil Engineering, IIT Madras for guiding the work on cement-reinforcement studies and testing. The work presented here is a part of Indian patent application (201841019186) filed by the authors. This work was supported by IIT Madras.

Compliance with ethical standards

Conflict of interest

The authors declare no competing financial interests.

Supplementary material

10570_2019_2312_MOESM1_ESM.docx (4.4 mb)
Supplementary material 1 (DOCX 4498 kb)


  1. Abdelmouleh M, Boufi S, Ben Salah A, Belgacem MN, Gandini A (2002) Interaction of silane coupling agents with cellulose. Langmuir 18:3203–3208. CrossRefGoogle Scholar
  2. Anju TR, Ramamurthy K, Dhamodharan R (2016) Surface modified microcrystalline cellulose from cotton as a potential mineral admixture in cement mortar composite. Cem Concr Compos 74:147–153. CrossRefGoogle Scholar
  3. ASTM C109 (2013) Test method for compressive strength of hydraulic cement mortar. American Society for Testing and Materials, West ConshohockenGoogle Scholar
  4. ASTM C1437 (2013) Test method for flow of hydraulic cement mortar. American Society for Testing and Materials, West ConshohockenGoogle Scholar
  5. Basch A, Lewin M (1973) The influence of fine structure on the pyrolysis of cellulose. I. Vacuum pyrolysis. J Polym Sci Part A Polym Chem 11:3071–3093. CrossRefGoogle Scholar
  6. Chakraborty A (2004) Ph.D. thesis, University of TorontoGoogle Scholar
  7. Collard FX, Blin J (2014) A review on pyrolysis of biomass constituents: mechanisms and composition of the products obtained from the conversion of cellulose, hemicelluloses and lignin. Renew Sustain Energy Rev 38:594–608. CrossRefGoogle Scholar
  8. Dai D, Fan M, Collins P (2013) Fabrication of nanocelluloses from hemp fibers and their application for the reinforcement of hemp fibers. Ind Crops Prod 44:192–199. CrossRefGoogle Scholar
  9. Dinand E, Chanzy H, Vignon RM (1999) Suspensions of cellulose microfibrils from sugar beet pulp. Food Hydrocoll 13:275–283. CrossRefGoogle Scholar
  10. Dufresne A, Cavaille JY, Vignon MR (1997) Mechanical behavior of sheets prepared from sugar beet cellulose microfibrils. J Appl Polym Sci 64:1185–1194.;2-V CrossRefGoogle Scholar
  11. Duran N, Lemes AP, Seabra AB (2012) Review of cellulose nanocrystals patents: preparation, composites and general applications. Recent Pat Nanotechnol 6:16–28. CrossRefPubMedGoogle Scholar
  12. Epure V, Griffon M, Pollet E, Avérous L (2011) Structure and properties of glycerol-plasticized chitosan obtained by mechanical kneading. Carbohydr Polym 83:947–952. CrossRefGoogle Scholar
  13. Espinosa SC, Kuhnt T, Foster EJ, Weder C (2013) Isolation of thermally stable cellulose nanocrystals by phosphoric acid hydrolysis. Biomacromolecules 14:1223–1230. CrossRefGoogle Scholar
  14. Islam MT, Alam MM, Patrucco A, Montarsolo A, Zoccola M (2014) Preparation of nanocellulose: a review. AATCC J Res 1:17–23. CrossRefGoogle Scholar
  15. Jia X, Chen Y, Shi C, Ye Y, Wang P, Zeng X, Wu T (2013) Preparation and characterization of cellulose regenerated from phosphoric acid. J Agric Food Chem 61:12405–12414. CrossRefPubMedGoogle Scholar
  16. Kamel S (2007) Nanotechnology and its applications in lignocellulosic composites, a mini review. Express Polym Lett 1:546–575. CrossRefGoogle Scholar
  17. Kargarzadeh H, Ioelovich M, Ahmad I, Thomas S, Dufresne A (2017) Handbook of nanocellulose and cellulose nanocomposites. Wiley-VCH Verlag GmbH & Co. KgaA, New York. CrossRefGoogle Scholar
  18. Kaushik M, Moores A (2016) Review: nanocelluloses as versatile supports for metal nanoparticles and their applications in catalysis. Green Chem 18:622–637. CrossRefGoogle Scholar
  19. Klemm D, Kramer F, Moritz S, Lindstrom T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of natural-based materials. Angew Chem Int Ed 50:5438–5466. CrossRefGoogle Scholar
  20. Kos T, Anžlovar A, Kunaver M, Huskić M, Žagar E (2014) Fast preparation of nanocrystalline cellulose by microwave-assisted hydrolysis. Cellulose 21:2579–2585. CrossRefGoogle Scholar
  21. Kunaver M, Anzlovar A, Zagar E (2016) The fast and effective isolation of nanocellulose from selected cellulosic feedstocks. Carbohydr Polym 148:251–258. CrossRefPubMedGoogle Scholar
  22. Li W, Wang R, Liu S (2011) Nanocrystalline cellulose prepared from softwood kraft pulp via ultrasonic-assisted acid hydrolysis. BioResources 6:4271–4281. CrossRefGoogle Scholar
  23. Lu Q, Yang XC, Dong CQ, Zhang ZF, Zhang XM, Zhu XF (2011) Influence of pyrolysis temperature and time on the cellulose fast pyrolysis products: analytical Py-GC/MS study. J Anal Appl Pyrol 92:430–438. CrossRefGoogle Scholar
  24. Lu QL, Li XY, Tang LR, Lu BL, Huang B (2015) One-pot tandem reactions for the preparation of esterified cellulose nanocrystals with 4-dimethylaminopyridine as a catalyst. RSC Adv 5:56198–56204. CrossRefGoogle Scholar
  25. Maiti S, Jayaramudu J, Das K, Reddy SM, Sadiku R, Ray SS, Liu D (2013) Preparation and characterization of nano-cellulose with new shape from different precursor. Carbohydr Polym 98:562–567. CrossRefPubMedGoogle Scholar
  26. McCann MC, Wells B, Roberts K (1990) Direct visualization of cross-links in the primary plant cell wall. J Cell Sci 96:323–334Google Scholar
  27. Navell TP, Zeronian SH (1985) Intercrystalline swelling of cellulose. In: Zeronian SH, Nevell TP (eds) Cellulose chemistry and its applications. Wiley, New York. CrossRefGoogle Scholar
  28. Pääkko M, Ankerfors M, Kosonen H, Nykänen A, Ahola S, Österberg M, Ruokolainen J, Laine J, Larsson PT, Ikkala O (2007) Enzymatic hydrolysis combined with mechanical shearing and high-pressure homogenization for nanoscale cellulose fibrils and strong gels. Biomacromolecules 8:1934–1941. CrossRefPubMedGoogle Scholar
  29. 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 3:10CrossRefPubMedPubMedCentralGoogle Scholar
  30. Pastorova I, Arisz PW, Boon JJ (1993) Preservation of d-glucose-oligosaccharides in cellulose chars. Carbohydr Res 248:151–165. CrossRefGoogle Scholar
  31. Patwardhan PR, Satrio JA, Brown RC, Shanks BH (2009) Product distribution from fast pyrolysis of glucose-based carbohydrates. J Anal Appl Pyrol 86:323–330. CrossRefGoogle Scholar
  32. Rajinipriya M, Nagalakshmaiah M, Robert M, Elkoun S (2018) Importance of agricultural and industrial waste in the field of nanocellulose and recent industrial developments of wood based nanocellulose: a review. ACS Sustain Chem Eng 6:2807–2828. CrossRefGoogle Scholar
  33. Sadeghifar H, Filpponen E, Clarke SP, Brougham DF, Argyropoulos DS (2011) Production of cellulose nanocrystals using hydrobromic acid and click reactions on their surface. J Mater Sci 46:7344–7355. CrossRefGoogle Scholar
  34. Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 8:2485–2491. CrossRefPubMedGoogle Scholar
  35. Sannino A, Demitri C, Madahiele M (2009) Biodegradable cellulose-based hydrogels: design and applications. Materials 2:353–373. CrossRefPubMedPubMedCentralGoogle Scholar
  36. Scheirs J, Camino G, Tumiatti W (2001) Overview of water evolution during the thermal degradation of cellulose. Eur Polym J 37:933–942. CrossRefGoogle Scholar
  37. Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794. CrossRefGoogle Scholar
  38. Serizawa T, Sawada T, Okura H, Wada M (2013) Hydrolytic activities of crystalline cellulose nanofibers. Biomacromolecules 14:613–617. CrossRefPubMedGoogle Scholar
  39. Shafizadeh F (1968) Pyrolysis and combustion of cellulosic materials. Adv Carbohydr Chem 23:419–474. CrossRefGoogle Scholar
  40. Shafizadeh F (1982) Introduction to pyrolysis of biomass. J Anal Appl Pyrol 3:283–305. CrossRefGoogle Scholar
  41. Soltes EJ, Wiley AT, Lin SCK (1981) Biomass pyrolysis-towards an understanding of its versatility and potentials. Biotechnol Bioeng Symp Ser 11:125–136Google Scholar
  42. Stöber W, Fink A, Bohn E (1968) Controlled growth of monodisperse silica spheres in the micron size range. J Colloid Interface Sci 26:62–69. CrossRefGoogle Scholar
  43. Tang MM, Bacon R (1964) Carbonization of cellulose fibers—I. Low temperature pyrolysis. Carbon 2:211–220. CrossRefGoogle Scholar
  44. Vom Stein T, Grande P, Sibilla F, Commandeur U, Fischer R, Leitner W, Domínguez de María P (2010) Salt-assisted organic-acid-catalysed depolymerization of cellulose. Green Chem 12:1844–1849. CrossRefGoogle Scholar
  45. Xiao YT, Chin WL, Abd Hamid SB (2015) Facile preparation of highly crystalline nanocellulose by using ionic liquid. Adv Mater Res 1087:106–110. CrossRefGoogle Scholar
  46. Yu H, Qin Z, Liang B, Liu N, Zhou Z, Chen L (2013) Facile extraction of thermally stable cellulose nanocrystals with a high yield of 93% through hydrochloric acid hydrolysis under hydrothermal conditions. J Mater Chem A 1:3938–3944. CrossRefGoogle Scholar
  47. Zhou X, Nolte MW, Mayes HB, Shanks BH, Broadbelt LJ (2014) Experimental and mechanistic modeling of fast pyrolysis of neat glucose-based carbohydrates. 1. Experiments and development of a detailed mechanistic model. Ind Eng Chem Res 53:13274–13289. CrossRefGoogle Scholar
  48. Zimmermann T, Bordeanu N, Strub E (2010) Properties of nanofibrillated cellulose from different raw materials and its reinforcement potential. Carbohydr Polym 79:1086–1093CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Department of ChemistryIndian Institute of Technology MadrasChennaiIndia

Personalised recommendations