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Hydrogen bond–induced aqueous-phase surface modification of nanocellulose and its mechanically strong composites

  • Composites & nanocomposites
  • Published:
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Abstract

Aqueous-phase surface modification of nanocellulose is desirable because nanocellulose is generally produced via water-based fibrillation. In this study, a hydrogen bond–induced surface modification of cellulose nanofibrils (CNFs) in water was developed. Tannic acid and polyvinylpyrrolidone were chosen to modify the CNFs because of their strong capacity for hydrogen bond formation. By tuning the hydrogen bond formation between CNFs, tannic acid, and polyvinylpyrrolidone, CNFs with different surface hydrophilicity were achieved. The modified CNFs can assemble into strong and tough composites owing to the hydrogen bond network in the system. Modified CNFs demonstrated 76% higher tensile strength and 100% higher toughness than those of unmodified CNFs, reaching 162 MPa and 12.7 MJ/m3, respectively. This study provides a new water-based modification strategy for the nanocellulose, leading the way toward producing strong nanocellulose composites via noncovalent interaction.

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References

  1. Lu Y et al (2015) A cellulose nanocrystal-based composite electrolyte with superior dimensional stability for alkaline fuel cell membranes. J Mater Chem A 3(25):13350–13356

    Article  CAS  Google Scholar 

  2. Lu Y et al (2015) Improved mechanical properties of polylactide nanocomposites-reinforced with cellulose nanofibrils through interfacial engineering via amine-functionalization. Carbohyd Polym 131:208–217

    Article  CAS  Google Scholar 

  3. Li K et al (2021) Surface-modified and oven-dried microfibrillated cellulose reinforced biocomposites: cellulose network enabled high performance. Carbohydr Polym 256:117525

    Article  CAS  Google Scholar 

  4. Siró I, Plackett D (2010) Microfibrillated cellulose and new nanocomposite materials: a review. Cellulose 17(3):459–494

    Article  Google Scholar 

  5. Thomas B et al (2018) Nanocellulose, a versatile green platform: from biosources to materials and their applications. Chem Rev 118(24):11575–11625

    Article  CAS  Google Scholar 

  6. Sinquefield S et al (2020) Nanocellulose dewatering and drying: Current state and future perspectives. ACS Sustain Chem Eng 8(26):9601–9615

    Article  CAS  Google Scholar 

  7. Li K et al (2021) Alignment of cellulose nanofibers: harnessing nanoscale properties to macroscale benefits. ACS Nano 15(3):3646–3673

    Article  CAS  Google Scholar 

  8. Lamm ME et al (2021) Recent advances in functional materials through nanocellulose fiber templating. Adv Mater 33:e2005538

    Article  Google Scholar 

  9. Navarro JR, Edlund U (2017) Surface-initiated controlled radical polymerization approach to enhance nanocomposite integration of cellulose nanofibrils. Biomacromol 18(6):1947–1955

    Article  CAS  Google Scholar 

  10. Habibi Y (2014) Key advances in the chemical modification of nanocelluloses. Chem Soc Rev 43(5):1519–1542

    Article  CAS  Google Scholar 

  11. Rol F et al (2019) Recent advances in surface-modified cellulose nanofibrils. Prog Polym Sci 88:241–264

    Article  CAS  Google Scholar 

  12. Yoo Y, Youngblood JP (2016) Green one-pot synthesis of surface hydrophobized cellulose nanocrystals in aqueous medium. ACS Sustain Chem Eng 4(7):3927–3938

    Article  CAS  Google Scholar 

  13. Dhuiège B, Pecastaings G, Sèbe G (2019) Sustainable approach for the direct functionalization of cellulose nanocrystals dispersed in water by transesterification of vinyl acetate. ACS Sustain Chem Eng 7(1):187–196

    Article  Google Scholar 

  14. Grygiel K et al (2014) Omnidispersible poly(ionic liquid)-functionalized cellulose nanofibrils: surface grafting and polymer membrane reinforcement. Chem Commun 50(83):12486–12489

    Article  CAS  Google Scholar 

  15. Cheng Y et al (2018) Glycera-inspired synergistic interfacial interactions for constructing ultrastrong graphene-based nanocomposites. Adv Func Mater 28(49):1800924

    Article  Google Scholar 

  16. Hu X et al (2015) Weak hydrogen bonding enables hard, strong, tough, and elastic hydrogels. Adv Mater 27(43):6899–6905

    Article  CAS  Google Scholar 

  17. Song P et al (2015) Bio-inspired hydrogen-bond cross-link strategy toward strong and tough polymeric materials. Macromolecules 48(12):3957–3964

    Article  CAS  Google Scholar 

  18. Li K et al (2019) Strong and tough cellulose nanofibrils composite films: mechanism of synergetic effect of hydrogen bonds and ionic interactions. ACS Sustain Chem Eng 7(17):14341–14346

    Article  CAS  Google Scholar 

  19. Wan S et al (2015) Use of synergistic interactions to fabricate strong, tough, and conductive artificial nacre based on graphene oxide and chitosan. ACS Nano 9(10):9830–9836

    Article  CAS  Google Scholar 

  20. Wan S et al (2017) Superior fatigue resistant bioinspired graphene-based nanocomposite via synergistic interfacial interactions. Adv Func Mater 27(10):1605636

    Article  Google Scholar 

  21. Hu Z et al (2017) One-pot water-based hydrophobic durface modification of cellulose nanocrystals using plant polyphenols. Acs Sustain Chem Eng 5(6):5018–5026

    Article  CAS  Google Scholar 

  22. Jiménez N, Ballard N, Asua JM (2019) Hydrogen bond-directed formation of stiff polymer films using naturally occurring polyphenols. Macromolecules 52(24):9724–9734

    Article  Google Scholar 

  23. Gaikwad A et al (2020) Hydrogen-bonded, mechanically strong nanofibers with tunable antioxidant activity. ACS Appl Mater Interfaces 12:11026–11035

    Article  CAS  Google Scholar 

  24. Erel-Unal I, Sukhishvili SA (2008) Hydrogen-bonded multilayers of a neutral polymer and a polyphenol. Macromolecules 41(11):3962–3970

    Article  CAS  Google Scholar 

  25. Wohlert M. et al. (2021) Cellulose and the role of hydrogen bonds: not in charge of everything. Cellulose 1–23

  26. Li T et al (2019) Inhibiting ice recrystallization by nanocelluloses. Biomacromol 20(4):1667–1674

    Article  Google Scholar 

  27. Kljun A et al (2011) Comparative analysis of crystallinity changes in cellulose I polymers using ATR-FTIR, X-ray diffraction, and carbohydrate-binding module probes. Biomacromol 12(11):4121–4126

    Article  CAS  Google Scholar 

  28. Pu Y, Ziemer C, Ragauskas AJ (2006) CP/MAS 13C NMR analysis of cellulase treated bleached softwood kraft pulp. Carbohyd Res 341(5):591–597

    Article  CAS  Google Scholar 

  29. Tang H, Covington AD, Hancock R (2003) Structure–activity relationships in the hydrophobic interactions of polyphenols with cellulose and collagen. Biopolym Orig Res Biomol 70(3):403–413

    Article  CAS  Google Scholar 

  30. Foston M (2014) Advances in solid-state NMR of cellulose. Curr Opin Biotechnol 27:176–184

    Article  CAS  Google Scholar 

  31. Tian D et al (2017) Conformations and Intermolecular Interactions in cellulose/silk fibroin blend films: a solid-state NMR perspective. J Phys Chem B 121(25):6108–6116

    Article  CAS  Google Scholar 

  32. Masson JF, Manley RSJ (1992) Solid-state NMR of some cellulose/synthetic polymer blends. Macromolecules 25(2):589–592

    Article  CAS  Google Scholar 

  33. Kubo R, Saito T, Isogai A (2019) Dual counterion systems of carboxylated nanocellulose films with tunable mechanical, hydrophilic, and gas-barrier properties. Biomacromol 20(4):1691–1698

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This research is sponsored by the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Office, under contract DE-AC05-00OR22725 with UT-Battelle LLC. Scanning electron microscopy studies were completed at the Center for Nanophase Materials Sciences, a DOE Office of Science User Facility. The authors would like to thank Dr. Harry Meyer for his help on X-ray photoelectron spectroscopy measurement, and Rick R. Lowden for the access to mechanical testing.

Author information

Author notes

  1. Yuzhan Li

    Present address: School of Materials Science and Engineering, University of Science and Technology, Beijing, Beijing, 100083, China

Authors and Affiliations

  1. Buildings and Transportation Science Division, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN, 37830, USA

    Kai Li, Yuzhan Li & Kashif Nawaz

  2. Manufacturing Science Division, Oak Ridge National Laboratory, 2350 Cherahala Blvd, Knoxville, TN, 37932, USA

    Halil Tekinalp, Vipin Kumar & Soydan Ozcan

  3. Environmental Sciences Division, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN, 37830, USA

    Xianhui Zhao

  4. Biosciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, 37830, USA

    Yunqiao Pu & Arthur J. Ragauskas

  5. Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, TN, 37996, USA

    Arthur J. Ragauskas

  6. Center for Renewable Carbon, Department of Forestry, Wildlife and Fisheries, University of Tennessee, Knoxville, TN, 37996, USA

    Arthur J. Ragauskas

  7. Chemical Science Division, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN, 37830, USA

    Tolga Aytug

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  1. Kai Li
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Corresponding authors

Correspondence to Kai Li or Soydan Ozcan.

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The authors declare that they have no known competing financial interests or personal relationships that could have influenced the work reported in this paper.

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This study did not involve any experiments on human subjects or animals.

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Li, K., Li, Y., Tekinalp, H. et al. Hydrogen bond–induced aqueous-phase surface modification of nanocellulose and its mechanically strong composites. J Mater Sci 57, 8127–8138 (2022). https://doi.org/10.1007/s10853-022-07161-4

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  • DOI: https://doi.org/10.1007/s10853-022-07161-4

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