Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Original Article
  • Published:

Controlling the surface structure and functionalization of a cellulose nanocrystal film modified by using glycidyloxypropylsilane in a coating process

Abstract

We herein focused on the structural control and surface functionalization of a cellulose nanocrystal (CNC) film by modifying it with silane coupling reagents. Organosilanes containing a glycidyl group such as diethoxy(3-glycidyloxypropyl)(methyl)silane (GPMDES) and triethoxy(3-glycidyloxypropyl)silane (GPTES) in combination with tetraethoxysilane (TEOS) were selected as compounds for CNC surface modification with a spin coating process. Fourier transform infrared (FT-IR) and nuclear magnetic resonance (29Si-NMR) spectra indicated that the silane compounds were chemically bonded to the CNC surface, and both the glycidyl and methyl groups of GPMDES were detected. The surface of the CNC film observed by atomic force microscopy (AFM) retained the rod-shaped structure of the original CNCs. The surface roughnesses of the CNC films using GPMDES/TEOS and GPTES/TEOS as coprecursors were Sa = 4.9 nm and Sa = 3.7 nm, respectively. The water contact angle of the CNC films was 18° for GPMDES/TEOS and 36° for GPTES/TEOS. These results imply that the surface roughness of the silane-modified CNC film contributed to its hydrophilicity despite the existence of the hydrophobic methyl group. The adhesion strength of the silane-modified CNC film with the chitosan cast film was found to be 23 mN/mm for the 180° peel test, suggesting the reaction of glycidyl groups with amino groups.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Zhu Z, Fu S, Lavoine N, Luica LA. Structural reconstruction strategies for the design of cellulose nanomaterials and aligned wood cellulose-based functional materials – a review. Carbohydr Polym. 2020;247:116722.

    Article  CAS  PubMed  Google Scholar 

  2. Calvino C, Macke N, Kato R, Rowan SJ. Development, processing and applications of bio-sourced cellulose nanocrystal composites. Prog Polym Sci. 2020;103:101221.

    Article  CAS  Google Scholar 

  3. Sharma A, Thakur M, Bhattacharya M, Mandal T, Goswami S. Cellulose nanocrystal based multifunctional nanohybrids. Prog Mater Sci. 2020;112:100668.

    Article  Google Scholar 

  4. Yue L, Maiorana A, Khelifa F, Patel A, Raquez JM, Bonnaud L, et al. Surface-modified cellulose nanocrystals for biobased epoxy nanocomposites. Polymer. 2018;134:155–62.

    Article  CAS  Google Scholar 

  5. Zhang P, Lu Y, Fan M, Jiang P, Dong Y. Modified cellulose nanocrystals enhancement to mechanical properties and water resistance of vegetable oil-based waterborne polyurethane. J Appl Polym Sci. 2019;136:48228.

  6. Wang Y, Gao M, Li S, Liu J, Feng A, Zhang L. Recyclable, self-healable and reshape vitrified poly-dimethylsiloxane composite filled with renewable cellulose nanocrystal. Polymers. 2022; 245:124648.

  7. Ranjbar D, Hatzikiriakos SG. Effect on ionic surfactants on the viscoelastic properies of chira nematic cellulose nanocyrtal suspensions. Langmuir. 2020;36:293–301.

    Article  CAS  PubMed  Google Scholar 

  8. Prakash CGJ, Prasanth R. Approaches to design a surface with tunable wettability: a review on surface properties. J Mater Sci. 2021;56:108–35.

    Article  Google Scholar 

  9. Yang W, Pan M, Zhang J, Zhang L, Lin F, Liu X, et al. A universal strategy for constructing robust and antifouling cellulose nanocrystal coating. Adv Funct Mater. 2022;32:2109989.

    Article  CAS  Google Scholar 

  10. Wu MB, Zhang C, Pi JK, Liu C, Yang J, Xu ZK. Cellulose nanocrystals as anti-oil nanomaterials for separating crude oil from aqueous emulsions and mixtures. J Mater Chem A. 2019;7:7033.

    Article  CAS  Google Scholar 

  11. Bai L, Liu Y, Ding A, Ren N, Li G, Liang H. Surface coating of UF membranes to improve antifouling properties: a comparison study between cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs). Chemosphere. 2019;217:76–84.

    Article  CAS  PubMed  Google Scholar 

  12. Cheng H, Li C, Jiang Y, Wang B, Wang F, Mao Z, et al. Facile preparation of polysaccharide-based sponges and their potential application in wound dressing. J Mater Chem B. 2018;6:634.

    Article  CAS  PubMed  Google Scholar 

  13. Li Y, Grishkewich N, Liu L, Wang C, Tam KC, Liu S, et al. Construction of functional cellulose aerogels via atmospheric drying chemically cross-linked and solvent exchanged cellulose nanofibrils. Chem Eng J. 2019;366:531–8.

    Article  CAS  Google Scholar 

  14. Cabrera IC, Berlioz S, Fahs A, Louarnb G, Carriere P. Chemical functionalization of nano fibrillated cellulose by glycidyl silane coupling agents: a grafted silane network characterization study. Int J Biol Macromol. 2020;165:1773–82.

    Article  CAS  PubMed  Google Scholar 

  15. Khanjanzadeh H, Behrooz R, Bahramifar N, Altmutter WG, Bacher M, Edler M, et al. Surface chemical functionalization of cellulose nanocrystals by3-aminopropyltriethoxysilane. Int J Biol Macromol. 2018;106:1288–96.

    Article  CAS  PubMed  Google Scholar 

  16. Dhali K, Daver F, Cass P, Adhikari B. Surface modification of the cellulose nanocrystals through vinyl silane grafting. Int J Biol Macromol. 2022;200:397–408.

    Article  CAS  PubMed  Google Scholar 

  17. Taniyama H, Takagi K. Study on controlling the surface structure and properties of a cellulose nanocrystal film modified using alkoxysilanes in green solvents. Langmuir. 2022;38:5550–6.

    Article  CAS  PubMed  Google Scholar 

  18. Sharma RK, Kumar R. Functionalized cellulose with hydroxyethyl methacrylate and glycidyl methacrylate for metal ions and dye adsorption applications. Int J Biol Macromol. 2019;134:704–21.

    Article  CAS  PubMed  Google Scholar 

  19. Prateepchanachai S, Thakhiew W, Devahastin S, Soponronnarit S. Improvement of mechanical and heat-sealing properties of edible chitosan films via addition of gelatin and CO2 treatment of film-forming solutions. Int J Biol Macromol. 2019;131:589–600.

    Article  CAS  PubMed  Google Scholar 

  20. Zhou S, Liu P, Wang M, Zhao H, Yang J, Xu F. Sustainable, reusable, and superhydrophobic aerogels from microfibrillated cellulose for highly effective oil/water separation. ACS Sustain Chem Eng. 2016;4:6409–16.

    Article  CAS  Google Scholar 

  21. Adbelmouleh M, Boufi S, Salah AB, Belgacem MN, Gnadini A. Interaction of silane coupling agnets with cellulose. Langmuir. 2002;18:3203–8.

    Article  Google Scholar 

  22. Segal L, Creely JJ, Martin AE Jr, Conrad CM. An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J. 1959;29:786–94.

    Article  CAS  Google Scholar 

  23. Xu S, Zuo C, Sun X, Ding X, Zhong Z, Xing W, et al. Enriching volatile aromatic compounds of lavender hydrolats by PDMS/ceramic composite membranes. Sep Purif Technol. 2022;294:121198.

    Article  CAS  Google Scholar 

  24. Sheng J, Li J, Zhao L. Fabrication of grease-resistant paper with non-fluorinated chemicals for food packaging. Cellulose. 2019;26:6291–302.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Koji Takagi.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Taniyama, H., Takagi, K. Controlling the surface structure and functionalization of a cellulose nanocrystal film modified by using glycidyloxypropylsilane in a coating process. Polym J 55, 675–682 (2023). https://doi.org/10.1038/s41428-023-00763-y

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41428-023-00763-y

This article is cited by

Search

Quick links