Journal of Materials Science

, Volume 50, Issue 3, pp 1435–1445 | Cite as

Toughening of electrospun poly(l-lactic acid) nanofiber scaffolds with unidirectionally aligned halloysite nanotubes

  • Ning Cai
  • Qin Dai
  • Zelong Wang
  • Xiaogang Luo
  • Yanan Xue
  • Faquan Yu
Original Paper
First Online:
Received:
Accepted:

Abstract

The mechanical properties of the tissue engineering scaffold are important as they are tightly related the regeneration of structural tissue. The application of poly(l-lactic acid) (PLLA) nanofiber scaffolds in tissue engineering has been hindered by their insufficient mechanical properties. In the study, halloysite nanotubes (HNTs) were used to reinforce the mechanical properties of PLLA-based nanofibers. 4 wt% HNT/PLLA nanofiber membranes possess the best mechanical performance, which represents 61 % increase in tensile strength, 100 % improvement of Young’s modulus, 49 % augment of elongation to break, as well as 181 % elevation in energy to break compared with neat PLLA samples. The satisfactory enhancement effect of HNTs can be attributed to the effective dispersion and incorporation of HNTs in PLLA matrix, which have been confirmed by the analysis of SEM, TEM, and FTIR. The addition of HNTs also improves the degree of crystallization and thermal stability of PLLA-based nanofibers. HNT-incorporated PLLA nanofiber membranes possess higher protein adsorption from fetal bovine serum than the neat PLLA specimen. Therefore, the introduction of HNTs can effectively enhance the mechanical properties of PLLA nanofiber scaffolds. HNT/PLLA nanofiber scaffolds possess potential application in skin tissue engineering.

Keywords

PLLA Composite Nanofibers Thermo Gravimetric Analysis Nanocomposite Membrane Ethylene Propylene Diene Monomer 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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Notes

Acknowledgements

This research was supported by the National Natural Science Foundation of China (Grant No. 21071114), the Excellent Program of Activity of Science and Technology for Overseas-Returned Scientists founded by the Ministry of Human Resources and Social Security of the People’s Republic of China, the Program for Innovative Research Teams of Hubei Provincial Department of Education, the Scientific Research Foundation for Returned Overseas Chinese Scholars of State Education Ministry, Key Natural Science Foundation of Hubei Province (Grant No. 2012FFA100), the Innovative Team Incubation Program in High-Tech Industry of Wuhan City (Grant No. 2014070504020244) and Graduate Innovative Fund of Wuhan Institute of Technology (Grant No. CX2013010).

References

  1. 1.
    Ma PX (2004) Scaffolds for tissue fabrication. Mate Today 7:30–40CrossRefGoogle Scholar
  2. 2.
    Hutmacher DW (2000) Scaffolds in tissue engineering bone and cartilage. Biomaterials 21:2529–2543CrossRefGoogle Scholar
  3. 3.
    Vasita R, Katti DS (2006) Nanofibers and their applications in tissue engineering. Int J Nanomed 1:15–30CrossRefGoogle Scholar
  4. 4.
    Rezwan K, Chen QZ, Blaker JJ, Boccaccini AR (2006) Biodegradable and bioactive porous polymer/inorganic composite scaffolds for bone tissue engineering. Biomaterials 27:3413–3431CrossRefGoogle Scholar
  5. 5.
    Xu J, Cai N, Xu WX, Xue YA, Wang ZL, Dai Q, Yu FQ (2013) Mechanical enhancement of nanofibrous scaffolds through polyelectrolyte complexation. Nanotechnology 24:025701CrossRefGoogle Scholar
  6. 6.
    Zhang YZ, Lim CT, Ramakrishna S, Huang ZM (2005) Recent development of polymer nanofibers for biomedical and biotechnological applications. J Mater Sci Mater Med 16:933–946. doi: 10.1007/s10856-005-4428-x Google Scholar
  7. 7.
    McCullen SD, Ramaswamy S, Clarke LI, Gorga RE (2009) Nanofibrous composites for tissue engineering applications. Wires Nanomed Nanobi 1:369–390CrossRefGoogle Scholar
  8. 8.
    Ray SS (2012) Polylactide-based bionanocomposites: a promising class of hybrid materials. Acc Chem Res 45:1710–1720CrossRefGoogle Scholar
  9. 9.
    Wang Z, Cai N, Dai Q, Li C, Hou D, Luo X, Xue Y, Yu F (2014) Effect of thermal annealing on mechanical properties of polyelectrolyte complex nanofiber membranes. Fiber Polym 15:1406–1413CrossRefGoogle Scholar
  10. 10.
    Ionita M, Pandele MA, Iovu H (2013) Sodium alginate/graphene oxide composite films with enhanced thermal and mechanical properties. Carbohydr Polym 94:339–344CrossRefGoogle Scholar
  11. 11.
    Ge JJ, Hou HQ, Li Q, Graham MJ, Greiner A, Reneker DH, Harris FW, Cheng SZD (2004) Assembly of well-aligned multiwalled carbon nanotubes in confined polyacrylonitrile environments: electrospun composite nanofiber sheets. J Am Chem Soc 126:15754–15761CrossRefGoogle Scholar
  12. 12.
    Liu MX, Zhang Y, Wu CC, Xiong S, Zhou CR (2012) Chitosan/halloysite nanotubes bionanocomposites: structure, mechanical properties and biocompatibility. Int J Biol Macromol 51:566–575CrossRefGoogle Scholar
  13. 13.
    Lvov YM, Shchukin DG, Mohwald H, Price RR (2008) Halloysite clay nanotubes for controlled release of protective agents. ACS Nano 2:814–820CrossRefGoogle Scholar
  14. 14.
    Hassan-Nejad M, Ganster J, Bohn A, Pinnow M, Volkert B (2009) Bio-based nanocomposites of cellulose acetate and nano-clay with superior mechanical properties. Macromol Symp 280:123–129CrossRefGoogle Scholar
  15. 15.
    Wang B, Huang H-X (2013) Effects of halloysite nanotube orientation on crystallization and thermal stability of polypropylene nanocomposites. Polym Degrad Stab 98:1601–1608CrossRefGoogle Scholar
  16. 16.
    Logakis E, Pollatos E, Pandis C, Peoglos V, Zuburtikudis I, Delides CG, Vatalis A, Gjoka M, Syskakis E, Viras K et al (2010) Structure–property relationships in isotactic polypropylene/multi-walled carbon nanotubes nanocomposites. Compos Sci Technol 70:328–335CrossRefGoogle Scholar
  17. 17.
    Peng F, Shaw MT, Olson JR, Wei M (2011) Hydroxyapatite needle-shaped particles/Poly(l-lactic acid) electrospun scaffolds with perfect particle-along-nanofiber orientation and significantly enhanced mechanical properties. J Phys Chem C 115:15743–15751CrossRefGoogle Scholar
  18. 18.
    Gorrasi G, Pantani R, Murariu M, Dubois P (2014) PLA/halloysite nanocomposite films: water vapor barrier properties and specific key characteristics. Macromol Mater Eng 299:104–115CrossRefGoogle Scholar
  19. 19.
    Liu L, Ren Y, Li Y, Liang Y (2013) Effects of hard and soft components on the structure formation, crystallization behavior and mechanical properties of electrospun poly(l-lactic acid) nanofibers. Polymer 54:5250–5256CrossRefGoogle Scholar
  20. 20.
    Thompson CJ, Chase GG, Yarin AL, Reneker DH (2007) Effects of parameters on nanofiber diameter determined from electrospinning model. Polymer 48:6913–6922CrossRefGoogle Scholar
  21. 21.
    Zhou C, Shi Q, Guo W, Terrell L, Qureshi AT, Hayes DJ, Wu Q (2013) Electrospun bio-nanocomposite scaffolds for bone tissue engineering by cellulose nanocrystals reinforcing maleic anhydride grafted PLA. ACS Appl Mater Interfaces 5:3847–3854CrossRefGoogle Scholar
  22. 22.
    Joussein E, Petit S, Churchman J, Theng B, Righi D, Delvaux B (2005) Halloysite clay minerals—a review. Clay Miner 40:383–426CrossRefGoogle Scholar
  23. 23.
    Sun XM, Zhang Y, Shen HB, Jia NQ (2010) Direct electrochemistry and electrocatalysis of horseradish peroxidase based on halloysite nanotubes/chitosan nanocomposite film. Electrochim Acta 56:700–705CrossRefGoogle Scholar
  24. 24.
    Tang ZH, Wei QY, Lin TF, Guo BC, Jia DM (2013) The use of a hybrid consisting of tubular clay and graphene as a reinforcement for elastomers. RSC Adv 3:17057–17064CrossRefGoogle Scholar
  25. 25.
    Liu MX, Zhang Y, Zhou CR (2013) Nanocomposites of halloysite and polylactide. Appl Clay Sci 75–76:52–59CrossRefGoogle Scholar
  26. 26.
    Matusik J, Stodolak E, Bahranowski K (2011) Synthesis of polylactide/clay composites using structurally different kaolinites and kaolinite nanotubes. Appl Clay Sci 51:102–109CrossRefGoogle Scholar
  27. 27.
    Zhou SB, Zheng XT, Yu XJ, Wang JX, Weng J, Li XH, Feng B, Yin M (2007) Hydrogen bonding interaction of poly(d, l-lactide)/hydroxyapatite nanocomposites. Chem Mater 19:247–253CrossRefGoogle Scholar
  28. 28.
    Shao D, Wei Q, Zhang L, Cai Y, Jiang S (2008) Surface functionalization of carbon nanofibers by sol–gel coating of zinc oxide. Appl Surf Sci 254:6543–6546CrossRefGoogle Scholar
  29. 29.
    Liu M, Wu C, Jiao Y, Xiong S, Zhou C (2013) Chitosan-halloysite nanotubes nanocomposite scaffolds for tissue engineering. J Mater Chem B 1:2078–2089CrossRefGoogle Scholar
  30. 30.
    Ismail H, Pasbakhsh P, Fauzi MNA, Abu Bakar A (2008) Morphological, thermal and tensile properties of halloysite nanotubes filled ethylene propylene diene monomer (EPDM) nanocomposites. Polym Test 27:841–850CrossRefGoogle Scholar
  31. 31.
    Qu X-H, Wu Q, Zhang K-Y, Chen GQ (2006) In vivo studies of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) based polymers: biodegradation and tissue reactions. Biomaterials 27:3540–3548Google Scholar
  32. 32.
    Morimune S, Kotera M, Nishino T, Goto K, Hata K (2011) Poly(vinyl alcohol) Nanocomposites with Nanodiamond. Macromolecules 44:4415–4421CrossRefGoogle Scholar
  33. 33.
    Zhuang W, Liu J, Zhang JH, Hu BX, Shen J (2009) Preparation, characterization, and properties of TiO2/PLA nanocomposites by in situ polymerization. Polym Compos 30:1074–1080CrossRefGoogle Scholar
  34. 34.
    Yang X, Li L, Shang S, Tao X-m (2010) Synthesis and characterization of layer-aligned poly(vinyl alcohol)/graphene nanocomposites. Polymer 51:3431–3435CrossRefGoogle Scholar
  35. 35.
    Wang Z, Cai N, Zhao D, Xu J, Dai Q, Xue Y, Luo X, Yang Y, Yu F (2013) Mechanical reinforcement of electrospun water-soluble polymer nanofibers using nanodiamonds. Polym Compos 34:1735–1744Google Scholar
  36. 36.
    Kim JY, Park HS, Kim SH (2006) Unique nucleation of multi-walled carbon nanotube and poly(ethylene 2,6-naphthalate) nanocomposites during non-isothermal crystallization. Polymer 47:1379–1389CrossRefGoogle Scholar
  37. 37.
    Pasbakhsh P, Ismail H, Fauzi MNA, Bakar AA (2010) EPDM/modified halloysite nanocomposites. Appl Clay Sci 48:405–413CrossRefGoogle Scholar
  38. 38.
    Liu M, Guo B, Du M, Jia D (2007) Drying induced aggregation of halloysite nanotubes in polyvinyl alcohol/halloysite nanotubes solution and its effect on properties of composite film. Appl Phys A-Mater 88:391–395CrossRefGoogle Scholar
  39. 39.
    Ramaswamy S, Clarke LI, Gorga RE (2011) Morphological, mechanical, and electrical properties as a function of thermal bonding in electrospun nanocomposites. Polymer 52:3183–3189CrossRefGoogle Scholar
  40. 40.
    Wei H-F, Hsiue G-H, Liu C-Y (2007) Surface modification of multi-walled carbon nanotubes by a sol–gel reaction to increase their compatibility with PMMA resin. Compos Sci Technol 67:1018–1026CrossRefGoogle Scholar
  41. 41.
    Dong Y, Bickford T, Haroosh H, Lau K-T, Takagi H (2013) Multi-response analysis in the material characterisation of electrospun poly (lactic acid)/halloysite nanotube composite fibres based on Taguchi design of experiments: fibre diameter, non-intercalation and nucleation effects. Appl Phys A-Mater 112:747–757CrossRefGoogle Scholar
  42. 42.
    Lizundia E, Oleaga A, Salazar A, Sarasua JR (2012) Nano- and microstructural effects on thermal properties of poly (l-lactide)/multi-wall carbon nanotube composites. Polymer 53:2412–2421CrossRefGoogle Scholar
  43. 43.
    Prashantha K, Lacrampe MF, Krawczak P (2011) Processing and characterization of halloysite nanotubes filled polypropylene nanocomposites based on a masterbatch route: effect of halloysites treatment on structural and mechanical properties. Express Polym Lett 5:295–307CrossRefGoogle Scholar
  44. 44.
    Kim I-H, Jeong YG (2010) Polylactide/exfoliated graphite nanocomposites with enhanced thermal stability, mechanical modulus, and electrical conductivity. J Polym Sci Pol Phys 48:850–858CrossRefGoogle Scholar
  45. 45.
    Kontou E, Niaounakis M, Georgiopoulos P (2011) Comparative study of PLA nanocomposites reinforced with clay and silica nanofillers and their mixtures. J Appl Polym Sci 122:1519–1529CrossRefGoogle Scholar
  46. 46.
    Reynaud E, Jouen T, Gauthier C, Vigier G, Varlet J (2001) Nanofillers in polymeric matrix: a study on silica reinforced PA6. Polymer 42:8759–8768CrossRefGoogle Scholar
  47. 47.
    Edwards C, Marks R (1995) Evaluation of biomechanical properties of human skin. Clin Dermatol 13:375–380CrossRefGoogle Scholar
  48. 48.
    Schadler LS, Giannaris SC, Ajayan PM (1998) Load transfer in carbon nanotube epoxy composites. Appl Phys Lett 73:3842–3844CrossRefGoogle Scholar
  49. 49.
    Tang Y, Ye L, Zhang Z, Friedrich K (2013) Interlaminar fracture toughness and CAI strength of fibre-reinforced composites with nanoparticles—A review. Compos Sci Technol 86:26–37CrossRefGoogle Scholar
  50. 50.
    Fu S-Y, Feng X-Q, Lauke B, Mai Y-W (2008) Effects of particle size, particle/matrix interface adhesion and particle loading on mechanical properties of particulate–polymer composites. Compos Part B-Eng 39:933–961CrossRefGoogle Scholar
  51. 51.
    Prashantha K, Lecouvet B, Sclavons M, Lacrampe MF, Krawczak P (2013) Poly(lactic acid)/halloysite nanotubes nanocomposites: structure, thermal, and mechanical properties as a function of halloysite treatment. J Appl Polym Sci 128:1895–1903Google Scholar
  52. 52.
    Qi R, Cao X, Shen M, Guo R, Yu J, Shi X (2012) Biocompatibility of electrospun halloysite nanotube-doped Poly(Lactic-co-Glycolic Acid) composite nanofibers. J Biomater Sci Polym Ed 23:299–313CrossRefGoogle Scholar
  53. 53.
    Nitya G, Nair G, Mony U, Chennazhi K, Nair S (2012) In vitro evaluation of electrospun PCL/nanoclay composite scaffold for bone tissue engineering. J Mater Sci Mater Med 23:1749–1761. doi: 10.1007/s10856-012-4647-x Google Scholar

Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  • Ning Cai
    • 1
  • Qin Dai
    • 1
  • Zelong Wang
    • 1
    • 2
  • Xiaogang Luo
    • 1
  • Yanan Xue
    • 1
  • Faquan Yu
    • 1
  1. 1.Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and PharmacyWuhan Institute of TechnologyWuhanChina
  2. 2.Department of ResearchHunan Xiangjiang Kansai Paint Co., Ltd.ChangshaChina

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