International Journal of Industrial Entomology and Biomaterials

Korean Society of Sericultural Science (한국잠사학회)
권호 표지
DOI QR코드

DOI QR Code

Preparation of Cellulose Nanofibril/Regenerated Silk Fibroin Composite Fibers

  • Lee, Ji Hye (Department of Bio-fibers and Materials Science, Kyungpook National University) ;
  • Bae, Chang Hyun (Department of Bio-fibers and Materials Science, Kyungpook National University) ;
  • Park, Byung-Dae (Department of Wood Science and Technology, Kyungpook National University) ;
  • Um, In Chul (Department of Bio-fibers and Materials Science, Kyungpook National University)
  • Received : 2013.05.10
  • Accepted : 2013.05.20
  • Published : 2013.07.09
Download PDF
⟨ Previous Next ⟩

Abstract

Wet-spun silk fibers have attracted the attention of many researchers because of 1) the unique properties of silk as a biomaterial, including good biocompatibility and cyto-compatability and 2) the various methods available to control the structure and properties of the fiber. Cellulose nanofibrils (CNFs) have typically been used as a reinforcing material for natural and synthetic polymers. In this study, CNF-embedded silk fibroin (SF) nanocomposite fibers were prepared for the first time. The effects of CNF content on the rheology of the dope solution and the characteristics of wet-spun CNF/SF composite fibers were also examined. A 5% SF formic acid solution that contained no CNFs showed nearly Newtonian fluid behavior, with slight shear thinning. However, after the addition of 1% CNFs, the viscosity of the dope solution increased significantly, and apparent shear thinning was observed. The maximum draw ratio of the CNF/SF composite fibers decreased as the CNF content increased. Interestingly, the crystallinity index for the silk in the CNF/SF fibers was sequentially reduced as the CNF content was increased. This phenomenon may be due to the fact that the CNFs prevent ${\beta}$-sheet crystallization of the SF by elimination of formic acid from the dope solution during the coagulation process. The CNF/SF composite fibers displayed a relatively smooth surface with stripes, at low magnification (${\times}500$). However, a rugged nanoscale surface was observed at high magnification (${\times}10,000$), and the surface roughness increased with the CNF content.

Keywords

References

  1. Aksoy EA, Akata B, Bac N, Hasirci N (2007) Preparation and characterization of zeolite eta-polyurethane composite membranes. J Appl Polym Sci 104, 3378-3387. https://doi.org/10.1002/app.25976
  2. Bhat NW, Nadiger GS (1980) Crystallinity in silk fibers: Partial acid hydrolysis and related studies. J Appl Polym Sci 25, 921-932. https://doi.org/10.1002/app.1980.070250518
  3. Bhatnagar A, Sain M (2005) Processing of cellulose nanofiber reinforced composites. J Reinf Plast Compos 24, 1259-1268. https://doi.org/10.1177/0731684405049864
  4. Brown EE, Laborie MPG (2007) Bioengineering bacterial cellulose/ poly(ethylene oxide) nanocomposites. Biomacromolecules 8, 3074-3081. https://doi.org/10.1021/bm700448x
  5. Cho HJ, Um IC (2010) The effect of dissolution condition on the yield, molecular weight, and wet-and electro-spinnability of regenerated silk fibroins prepared by LiBr aqueous solution. Int J Indust Entomol 20, 99-105.
  6. Cho HJ, Yoo HJ, Kim JW, Park YH, Bae DG, Um IC (2012) Effect of molecular weight and storage time on the wet-and electrospinning of regenerated silk fibroin. Polym Degrad Stab 97, 1060-1066. https://doi.org/10.1016/j.polymdegradstab.2012.03.007
  7. Chung DE, Um IC (2011) The relationship between the rheological properites and wet spinnability of regenerated silk fibroin solution with various molecular weights and concentrations, 6th International Workshop for East Asian Young Rheologists, Yamagata, Japan, p 63.
  8. Dufresne A, Vignon MR (1998) Improvement of starch film performances using cellulose microfibrils. Macromolecules 31, 2693-2696. https://doi.org/10.1021/ma971532b
  9. Freddi G, Romano M, Massafra MR, Tsukada M (1995) Silk fibroin/ cellulose blend films-preparation, structure, and physical-properties. J Appl Polym Sci 56, 1537-1545 https://doi.org/10.1002/app.1995.070561203
  10. Huang J, Liu L, Yao JM (2011) Electrospinning of bombyx mori silk fibroin nanofiber mats reinforced by cellulose nanowhiskers 12, 1002-1006. https://doi.org/10.1007/s12221-011-1002-7
  11. Ki CS, Kim JW, Oh HJ, Lee KH, Park YH (2007) The effect of residual silk sericin on the structure and mechanical property of regenerated silk filament.Int J Biol Macromol 41, 346-353. https://doi.org/10.1016/j.ijbiomac.2007.05.005
  12. Kim HJ, Um IC (2011) The effect of sericin content on the rheological properties and wet spinnability of regenerated silk fibroin solution, 6th International Workshop for East Asian Young Rheologists, Yamagata, Japan, p 66.
  13. Kim HJ, Chung DE, Um IC (2013) Effect of processing conditions on the homogeneity of partially degummed silk evaluated by FTIR spectroscopy. Int J Indust Entomol 25, 54-60. https://doi.org/10.7852/ijie.2013.26.1.054
  14. Klemm D, Kramer F, Moritz S, Lindstrom T, Ankerfors M, Gray D et al. (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Edit 50, 5438-5466. https://doi.org/10.1002/anie.201001273
  15. Ko JS, Um IC (2009) The effect of HPMC concentration on the morphology and post drawing of wet spun regenerated SF/HPMC blend filaments. Int J Indust Entomol 19, 181-185.
  16. Ko JS, Yoon K, Ki CS, Kim HJ, Bae DG, Lee KH et al. (2013) Effect of degumming condition on the solution properties and electrospinnablity of regenerated silk solution. Int J Biol Macromol 55, 161-168. https://doi.org/10.1016/j.ijbiomac.2012.12.041
  17. Li RJ, Zhang YH, Zhu LJ, Yao JM (2012) Fabrication and characterization of silk fibroin/poly(ethylene glycol)/cellulose nanowhisker composite films. J Appl Polym Sci 124, 2080-2086. https://doi.org/10.1002/app.35273
  18. Liivak O, Blye A, Shah N, Jelinski LW (1998) A microfabricated wet-spinning apparatus to spin fibers of silk proteins. Structureproperty correlations. Macromolecules 31, 2947-2951. https://doi.org/10.1021/ma971626l
  19. Meinel L, Hofmann S, Karageorgiou V, Kirker-Head C, McCool J, Gronowicz G et al. (2005) The inflammatory responses to silk films in vitro and in vivo. Biomaterials 26, 147-155. https://doi.org/10.1016/j.biomaterials.2004.02.047
  20. Minoura N, Aiba S, Gotoh Y, Tsukada M, Imai Y (1995) Attachment and growth of cultured fibroblast cells on silk protein matrixes. J Biomed Mater Res 29, 1215-1221. https://doi.org/10.1002/jbm.820291008
  21. Nordqvist D, Idermark J, Hedenqvist MS (2007) Enhancement of the wet properties of transparent chitosan-acetic-acid salt films using microfibrillated cellulose. Biomacromolecules 8, 2398-2403. https://doi.org/10.1021/bm070246x
  22. Park DJ, Choi Y, Heo S, Cho SY, Jin HJ (2012) Bacterial cellulose nanocrystals-embedded silk nanofibers. J Nanosci Nanotech 12, 6139-6144. https://doi.org/10.1166/jnn.2012.6371
  23. Phillips DM, Drummy LF, Naik RR, De Long HC, Fox DM, Trulove PC et al. (2005) Regenerated silk fiber wet spinning from anionic liquid solution. J Mater Chem 39, 4206-4208.
  24. Saito T, Nishiyama Y, Putaux JL, Vignon M, Isogai A (2006) Homogeneous suspensions of individualized microfibrils from TEMPOcatalyzed oxidation of native cellulose. Biomacromolecules 7, 1687-1691. https://doi.org/10.1021/bm060154s
  25. Sakabe H, Ito H, Miyamoto T, Noishiki, Ha WS (1989) In vivo blood compatibility of regenerated silk fibroin. Sen-i Gakkaishi 45, 487-490. https://doi.org/10.2115/fiber.45.11_487
  26. Trabbic KA, Yager P (1998) Comparative structural characterization of naturally-and synthetically-spun fibers of Bombyx mori fibroin. Macromolecules 31, 462-471. https://doi.org/10.1021/ma9708860
  27. Um IC, Kweon HY, Park YH, Hudson S (2001) Structural character-istics and properties of the regenerated silk fibroin prepared from formic acid, Int J Biol Macromol 29, 91-97. https://doi.org/10.1016/S0141-8130(01)00159-3
  28. Um IC, Ki CS, Kweon H, Lee GK, Ihm DW, Park YH (2004) Wet spinning of silk polymer II. Effect of drawing on the structural characteristics and properties of filament. Int J Biol Macromol 34, 107-119. https://doi.org/10.1016/j.ijbiomac.2004.03.011
  29. Um IC, Kweon HY, Lee KG, Park YH (2003) The role of formic acid in solution stability and crystallization of silk protein polymer. Int J Biol Macromol 33, 203-213. https://doi.org/10.1016/j.ijbiomac.2003.08.004
  30. Um IC, Kweon HY, Park YH (2012) Hemicellulose removal and crystalline structure transition of flax fiber with alkali treatment. Text Sci Eng 49, 271-278. https://doi.org/10.12772/TSE.2012.49.5.271
  31. Um IC, Kweon HY, Hwang CM, Min BG, Park YH (2002) Structural characteristics and properties of silk fibroin/polyurethane blend films. Int J Indust Entomol 5, 163-170.
  32. Yan JP, Zhou GQ, Knight DP, Shao ZZ, Chen X (2010) Wet-spinning of regenerated silk fiber from aqueous silk fibroin solution: discussion of spinning parameters. Biomacromolecules 11, 1-5. https://doi.org/10.1021/bm900840h
  33. Yoo YJ, Kim U-J, Um IC (2010) The effect of coagulant and molecular weight on the wet spinnability of regenerated silk fibroin solution. Int J Indust Entomol 21, 145-150.

Cited by

  1. Physicochemical properties of cellulose/whey protein fibers as a potential material for active ingredients release vol.49, 2015, https://doi.org/10.1016/j.foodhyd.2015.03.027
  2. Effect of degumming ratio on wet spinning and post drawing performance of regenerated silk vol.67, 2014, https://doi.org/10.1016/j.ijbiomac.2014.03.055
  3. Effect of Surfactant on Homogeneity of Partially Degummed Silk Fiber vol.28, pp.1, 2014, https://doi.org/10.7852/ijie.2014.28.1.19
  4. Effect of different Bombyx mori silkworm varieties on the wet spinning of silk fibroin vol.30, pp.2, 2015, https://doi.org/10.7852/ijie.2015.30.2.75
  5. Structure and properties of silk sericin obtained from different silkworm varieties vol.30, pp.2, 2015, https://doi.org/10.7852/ijie.2015.30.2.81
  6. Review of the recent developments in cellulose nanocomposite processing vol.83, 2016, https://doi.org/10.1016/j.compositesa.2015.10.041
  7. Facile Preparation of Biocompatible Silk Fibroin/Cellulose Nanocomposite Films with High Mechanical Performance vol.5, pp.7, 2017, https://doi.org/10.1021/acssuschemeng.7b01161
  8. Multiscale Hybridization of Natural Silk-Nanocellulose Fibrous Composites With Exceptional Mechanical Properties vol.7, pp.None, 2013, https://doi.org/10.3389/fmats.2020.00098
  9. Porous Silk Fibroin/Cellulose Hydrogels for Bone Tissue Engineering via a Novel Combined Process Based on Sequential Regeneration and Porogen Leaching vol.25, pp.21, 2013, https://doi.org/10.3390/molecules25215097
  10. Co‐Assembly of Cellulose Nanocrystals and Silk Fibroin into Photonic Cholesteric Films vol.5, pp.6, 2013, https://doi.org/10.1002/adsu.202000272