pp 1–17 | Cite as

Effects of residual lignin on composition, structure and properties of mechanically defibrillated cellulose fibrils and films

  • Yan Jiang
  • Xiuyu Liu
  • Qiang Yang
  • Xueping Song
  • Chengrong Qin
  • Shuangfei WangEmail author
  • Kecheng Li
Original Research


This study investigated effects of residual lignin on composition, structure and properties of cellulose fibrils and cellulose fibril-based films by comparing two groups of cellulose fibrils which contained different amounts of lignin (15% and 2%, respectively) but were similar in cellulose to hemicellulose ratio. The results showed that lignin affected the size and content of nanofibril in cellulose fibrils through initially delaying but ultimately facilitating the mechanical defibrillation. Due to higher thermal stability and strong UV absorption capability, lignin enhanced the thermal stability and UV blocking properties of cellulose fibril-based film. Hydrophobic lignin also improved the dewatering of cellulose fibrils and the hydrophobicity of cellulose fibril-based film. Lignin interfered with the interfibrillar hydrogen bonding and therefore increased the mesopore diameter of cellulose fibril network. Lignin acting as a cement in cellulose fibril-based film made the film with a more densely packed structure, a higher density and a smoother surface. However, lignin decreased the transparency of cellulose fibril-based film due to its chromophore groups and impaired the mechanical strength of cellulose fibril-based film through interfering with the interfibrillar hydrogen bonding.

Graphical abstract


Lignin Cellulose fibril Film Structure Property 



The authors thank the supports from China Scholarship Council under Grant No. 201706660011 and the Project for Graduate Study Overseas of Guangxi University (1516401004). The research is sponsored by the Innovation Project of Guangxi Graduate Education (YCBZ2018016), the National Natural Science Foundation of China (21766002), the Scientific Research Foundation of Guangxi University (XTZ140551), and the Foundation of Guangxi Key Laboratory of Clean Pulp & Papermaking and Pollution Control (KF201606 and ZR201603).

Supplementary material

10570_2018_2229_MOESM1_ESM.docx (15.5 mb)
Supplementary material 1 (DOCX 15866 kb)


  1. Abu-Danso E, Srivastava V, Sillanpaa M, Bhatnagar A (2017) Pretreatment assisted synthesis and characterization of cellulose nanocrystals and cellulose nanofibers from absorbent cotton. Int J Biol Macromol 102:248–257. Google Scholar
  2. Bai W, Holbery J, Li KC (2009) A technique for production of nanocrystalline cellulose with a narrow size distribution. Cellulose 16(3):455–465. Google Scholar
  3. Besbes I, Vilar MR, Boufi S (2011) Nanofibrillated cellulose from alfa, eucalyptus and pine fibres: preparation, characteristics and reinforcing potential. Carbohydr Polym 86(3):1198–1206. Google Scholar
  4. Bian HY, Gao Y, Wang RB, Liu ZL, Wu WB, Dai HQ (2018) Contribution of lignin to the surface structure and physical performance of cellulose nanofibrils film. Cellulose 25(2):1309–1318. Google Scholar
  5. Brebu M, Vasile C (2010) Thermal degradation of lignin—a review. Cell Chem Technol 44(9):353–363Google Scholar
  6. Browning BL (1967) Methods of wood chemistry. Wiley, New YorkGoogle Scholar
  7. Chen Y et al (2018) Effect of high residual lignin on the properties of cellulose nanofibrils/films. Cellulose. Google Scholar
  8. Delgado-Aguilar M, Gonzalez I, Tarres Q, Pelach MA, Alcala M, Mutje P (2016) The key role of lignin in the production of low-cost lignocellulosic nanofibres for papermaking applications. Ind Crop Prod 86:295–300. Google Scholar
  9. Dorris GM, Gray DG (1978a) Surface analysis of paper and wood fibres by ESCA (electron spectroscopy for chemical analysis). I. Application to cellulose and lignin. Cellul Chem Tehnol 12:9–23Google Scholar
  10. Dorris GM, Gray DG (1978b) Surface analysis of paper and wood fibres by ESCA. II. Surface composition of mechanical pulps. Cellul Chem Tehnol 12:721–734Google Scholar
  11. Eichhorn SJ et al (2010) Review: current international research into cellulose nanofibres and nanocomposites. J Mater Sci 45(1):1–33. Google Scholar
  12. Ferrer A et al (2012) Effect of residual lignin and heteropolysaccharides in nanofibrillar cellulose and nanopaper from wood fibers. Cellulose 19(6):2179–2193. Google Scholar
  13. French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21(2):885–896. Google Scholar
  14. Garcia A, Gandini A, Labidi J, Belgacem N, Bras J (2016) Industrial and crop wastes: a new source for nanocellulose biorefinery. Ind Crop Prod 93:26–38. Google Scholar
  15. Gray DG, Weller M, Ulkem N, Lejeune A (2010) Composition of lignocellulosic surfaces: comments on the interpretation of XPS spectra. Cellulose 17(1):117–124. Google Scholar
  16. Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110(6):3479–3500. Google Scholar
  17. Hambardzumyan A, Foulon L, Chabbert B, Aguie-Beghin V (2012) Natural organic UV-absorbent coatings based on cellulose and lignin: designed effects on spectroscopic properties. Biomacromolecules 13(12):4081–4088. Google Scholar
  18. Henriksson M, Berglund LA, Isaksson P, Lindstrom T, Nishino T (2008) Cellulose nanopaper structures of high toughness. Biomacromolecules 9(6):1579–1585. Google Scholar
  19. Hietala M, Samuelsson E, Niinimaki J, Oksman K (2011) The effect of pre-softened wood chips on wood fibre aspect ratio and mechanical properties of wood–polymer composites. Compos A Appl Sci Manuf 42(12):2110–2116. Google Scholar
  20. Hon DNS (1979) Formation and behavior of mechano-radicals in pulp cellulose. J Appl Polym Sci 23(5):1487–1499. Google Scholar
  21. Hon DN-S (1987) Mechanochemistry of Lignocellulosic Materials. In: Grassie N (ed) Developments in polymer degradation—7. Springer, Dordrecht, pp 165–191. Google Scholar
  22. Hon DNS, Srinivasan KSV (1983) Mechanochemical process in cotton cellulose fiber. J Appl Polym Sci 28(1):1–10. Google Scholar
  23. Huang J, Zhu HL, Chen YC, Preston C, Rohrbach K, Cumings J, Hu LB (2013) Highly transparent and flexible nanopaper transistors. ACS Nano 7(3):2106–2113. Google Scholar
  24. Ishida O, Kim DY, Kuga S, Nishiyama Y, Brown RM (2004) Microfibrillar carbon from native cellulose. Cellulose 11(3–4):475–480. Google Scholar
  25. Iwamoto S, Nakagaito AN, Yano H (2007) Nano-fibrillation of pulp fibers for the processing of transparent nanocomposites. Appl Phys A Mater Sci Process 89(2):461–466. Google Scholar
  26. Jang JH, Lee SH, Endo T, Kim NH (2013) Characteristics of microfibrillated cellulosic fibers and paper sheets from Korean white pine. Wood Sci Technol 47(5):925–937. Google Scholar
  27. Jiang Y, Liu XY, Yang Q, Song XP, Qin CR, Wang SF, Li KC (2018) Effects of residual lignin on mechanical defibrillation process of cellulosic fiber for producing lignocellulose nanofibrils. Cellulose 25(11):6479–6494. Google Scholar
  28. Jimenez-Saelices C, Seantier B, Cathala B, Grohens Y (2017) Spray freeze-dried nanofibrillated cellulose aerogels with thermal superinsulating properties. Carbohydr Polym 157:105–113. Google Scholar
  29. Jin H, Nishiyama Y, Wada M, Kuga S (2004) Nanofibrillar cellulose aerogels. Colloid Surf A Physicochem Eng Asp 240(1–3):63–67. Google Scholar
  30. Jonoobi M, Harun J, Shakeri A, Misra M, Oksman K (2009) Chemical composition, crystallinity, and thermal degradation of bleached and unbleached kenaf bast (Hibiscus cannabinus) pulp and nanofibers. BioResources 4(2):626–639Google Scholar
  31. Kobayashi Y, Saito T, Isogai A (2014) Aerogels with 3D ordered nanofiber skeletons of liquid-crystalline nanocellulose derivatives as tough and transparent insulators. Angew Chem Int Ed 53(39):10394–10397. Google Scholar
  32. Koishi T, Yasuoka K, Fujikawa S, Ebisuzaki T, Zeng XC (2009) Coexistence and transition between Cassie and Wenzel state on pillared hydrophobic surface. Proc Natl Acad Sci USA 106(21):8435–8440. Google Scholar
  33. Kulachenko A, Denoyelle T, Galland S, Lindstrom SB (2012) Elastic properties of cellulose nanopaper. Cellulose 19(3):793–807. Google Scholar
  34. Kuzuya M, Yamauchi Y, Kondo S (1999) Mechanolysis of glucose-based polysaccharides as studied by electron spin resonance. J Phys Chem B 103(38):8051–8059. Google Scholar
  35. Laine J (1996) The effect of ECF and TCF bleaching on the surface chemical composition of kraft pulp as determined by ESCA. Nord Pulp Pap Res J 11:201–210Google Scholar
  36. Laine J, Stenius P, Carlsson G, Ström G (1994) Surface characterization of unbleached kraft pulps by means of ESCA. Cellulose 1(2):145–160. Google Scholar
  37. Le HQ, Dimic-Misic K, Johansson LS, Maloney T, Sixta H (2018) Effect of lignin on the morphology and rheological properties of nanofibrillated cellulose produced from gamma-valerolactone/water fractionation process. Cellulose 25(1):179–194. Google Scholar
  38. Lee SH, Chang FX, Inoue S, Endo T (2010) Increase in enzyme accessibility by generation of nanospace in cell wall supramolecular structure. Bioresour Technol 101(19):7218–7223. Google Scholar
  39. Li Y, Fu Q, Rojas R, Yan M, Lawoko M, Berglund L (2017) Lignin-retaining transparent wood. Chemsuschem 10(17):3445–3451. Google Scholar
  40. Lu P, Hsieh YL (2010) Preparation and properties of cellulose nanocrystals: rods, spheres, and network. Carbohydr Polym 82(2):329–336. Google Scholar
  41. Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40(7):3941–3994. Google Scholar
  42. Nair SS, Yan N (2015) Effect of high residual lignin on the thermal stability of nanofibrils and its enhanced mechanical performance in aqueous environments. Cellulose 22(5):3137–3150. Google Scholar
  43. Nair SS, Zhu JY, Deng YL, Ragauskas AJ (2014a) Characterization of cellulose nanofibrillation by micro grinding. J Nanopart Res 16(4):10. Google Scholar
  44. Nair SS, Zhu JY, Deng YL, Ragauskas AJ (2014b) Hydrogels prepared from cross-linked nanofibrillated cellulose. ACS Sustain Chem Eng 2(4):772–780. Google Scholar
  45. Nechyporchuk O, Belgacem MN, Bras J (2016) Production of cellulose nanofibrils: a review of recent advances. Ind Crop Prod 93(1):2–25. Google Scholar
  46. Niskanen K (1996) Fibre properties as control variables in papermaking. Pap Ja Puu Pap Timber 78(4):180Google Scholar
  47. Nogi M, Iwamoto S, Nakagaito AN, Yano H (2009) Optically transparent nanofiber paper. Adv Mater 21(16):1595. Google Scholar
  48. 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. Google Scholar
  49. Paakko M et al (2008) Long and entangled native cellulose I nanofibers allow flexible aerogels and hierarchically porous templates for functionalities. Soft Matter 4(12):2492–2499. Google Scholar
  50. Park CW, Han SY, Namgung HW, Seo PN, Lee SY, Lee SH (2017) Preparation and characterization of cellulose nanofibrils with varying chemical compositions. BioResources 12(3):5031–5044. Google Scholar
  51. Poletto M, Zattera AJ, Forte MMC, Santana RMC (2012) Thermal decomposition of wood: influence of wood components and cellulose crystallite size. Bioresour Technol 109:148–153. Google Scholar
  52. Qing Y, Sabo R, Zhu JY, Agarwal U, Cai Z, Wu Y (2013) A comparative study of cellulose nanofibrils disintegrated via multiple processing approaches. Carbohydr Polym 97(1):226–234. Google Scholar
  53. Quievy N, Jacquet N, Sclavons M, Deroanne C, Paquot M, Devaux J (2010) Influence of homogenization and drying on the thermal stability of microfibrillated cellulose. Polym Degrad Stab 95(3):306–314. Google Scholar
  54. Rojo E, Peresin MS, Sampson WW, Hoeger IC, Vartiainen J, Laine J, Rojas OJ (2015) Comprehensive elucidation of the effect of residual lignin on the physical, barrier, mechanical and surface properties of nanocellulose films. Green Chem 17(3):1853–1866. Google Scholar
  55. Rouquerol J et al (1994) Recommendations for the characterization of porous solids. Pure Appl Chem 66(8):1739–1758. Google Scholar
  56. Sacui IA et al (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(9):6127–6138. Google Scholar
  57. 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(10):786–794Google Scholar
  58. Sehaqui H, Salajkova M, Zhou Q, Berglund LA (2010) Mechanical performance tailoring of tough ultra-high porosity foams prepared from cellulose I nanofiber suspensions. Soft Matter 6(8):1824–1832. Google Scholar
  59. Sehaqui H, Zhou Q, Berglund LA (2011) High-porosity aerogels of high specific surface area prepared from nanofibrillated cellulose (NFC). Compos Sci Technol 71(13):1593–1599. Google Scholar
  60. Seth RS (2003) The measurement and significance of fines—their addition to pulp improves sheet consolidation. Pulp Pap Can 104(2):41–44Google Scholar
  61. Shao ZL, Li KH (2006) The effect of fiber surface lignin on interfiber bonding. J Wood Chem Technol 26(3):231–244. Google Scholar
  62. Shen W, Parker IH, Sheng YJ (1998) The effects of surface extractives and lignin on the surface energy of eucalypt kraft pulp fibres. J Adhes Sci Technol 12(2):161–174. Google Scholar
  63. Shimada M, Nakamura Y, Kusama Y, Matsuda O, Tamura N, Kageyama E (1974) Electron spin resonance studies of γ-irradiated cellulose. I. Free radicals in decrystallized cellulose. J Appl Polym Sci 18(11):3379–3386. Google Scholar
  64. Silva TCF, Habibi Y, Colodette JL, Elder T, Lucia LA (2012) A fundamental investigation of the microarchitecture and mechanical properties of tempo-oxidized nanofibrillated cellulose (NFC)-based aerogels. Cellulose 19(6):1945–1956. Google Scholar
  65. Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (1985) Reporting physisorption data for gas solid systems with special reference to the determination of surface-area and porosity (recommendations 1984). Pure Appl Chem 57(4):603–619. Google Scholar
  66. Solala I et al (2012) Mechanoradical formation and its effects on birch kraft pulp during the preparation of nanofibrillated cellulose with Masuko refining. Holzforschung 66:477–483. Google Scholar
  67. Stenius P, Laine J (1994) Studies of cellulose surfaces by titration and ESCA. Appl Surf Sci 75(1):213–219. Google Scholar
  68. Tenhunen TM, Peresin MS, Penttila PA, Pere J, Serimaa R, Tammelin T (2014) Significance of xylan on the stability and water interactions of cellulosic nanofibrils. React Funct Polym 85:157–166. Google Scholar
  69. Tripathi A, Ferrer A, Khan SA, Rojas OJ (2017) Morphological and thermochemical changes upon autohydrolysis and microemulsion treatments of coir and empty fruit bunch residual biomass to isolate lignin-rich micro- and nanofibrillar cellulose. ACS Sustain Chem Eng 5(3):2483–2492. Google Scholar
  70. Wach RA, Mitomo H, Nagasawa N, Yoshii F (2003) Radiation crosslinking of carboxymethylcellulose of various degree of substitution at high concentration in aqueous solutions of natural pH. Radiat Phys Chem 68(5):771–779. Google Scholar
  71. Wang QQ, Zhu JY, Gleisner R, Kuster TA, Baxa U, McNeil SE (2012) Morphological development of cellulose fibrils of a bleached eucalyptus pulp by mechanical fibrillation. Cellulose 19(5):1631–1643. Google Scholar
  72. Wenzel RN (1936) Resistance of solid surfaces to wetting by water. Ind Eng Chem 28:988–994. Google Scholar
  73. Widsten P, Laine JE, Tuominen S, Qvintus-Leino P (2003) Effect of high defibration temperature on the properties of medium-density fiberboard (MDF) made from laccase-treated hardwood fibers. J Adhes Sci Technol 17(1):67–78. Google Scholar
  74. Widsten P, Tuominen S, Qvintus-Leino P, Laine JE (2004) The influence of high defibration temperature on the properties of medium-density fiberboard (MDF) made from laccase-treated softwood fibers. Wood Sci Technol 38(7):521–528. Google Scholar
  75. Yang H, Yan R, Chen H, Lee DH, Zheng C (2007) Characteristics of hemicellulose, cellulose and lignin pyrolysis. Fuel 86(12):1781–1788. Google Scholar
  76. Yang WS, Jiao L, Min DY, Liu ZL, Dai HQ (2017) Effects of preparation approaches on optical properties of self-assembled cellulose nanopapers. RSC Adv 7(17):10463–10468. Google Scholar
  77. Zhang HC, Nie SX, Qin CR, Zhang K, Wang SF (2018) Effect of hot chlorine dioxide delignification on AOX in bagasse pulp wastewater. Cellulose 25(3):2037–2049. Google Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.College of Light Industry and Food EngineeringGuangxi UniversityNanningPeople’s Republic of China
  2. 2.Guangxi Key Laboratory of Clean Pulp & Papermaking and Pollution ControlNanningPeople’s Republic of China
  3. 3.Department of Chemical and Paper EngineeringWestern Michigan UniversityKalamazooUSA

Personalised recommendations