, Volume 25, Issue 1, pp 65–75 | Cite as

Theoretical and experimental study of the stiffness of electrospun composites of poly(vinyl alcohol), cellulose nanofibers, and nanohydroxy apatite

  • Mohammad Saied Enayati
  • T. BehzadEmail author
  • P. Ł. Sajkiewicz
  • R. Bagheri
  • L. Ghasemi-Mobarakeh
  • F. Pierini
Original Paper


The present study aims to theoretically model and verify the mechanical behavior of electrospun fibers of poly(vinyl alcohol) (PVA) reinforced by nanohydroxy apatite (nHAp) and cellulose nanofibers (CNF), the three composites designated as PVA/nHAp, PVA/CNF, and PVA/nHAp/CNF. Tensile tests and AFM nanoindentation studies were used to measure tensile modulus of electrospun scaffolds and single fibers respectively. Halpin–Tsai and Ouali models were applied to predict the stiffness of electrospun mats. Theoretical analysis according to the Halpin–Tsai model showed that CNF have no preferred orientation in the electrospun fibers, particularly at higher filler content. Additionally, this model provided a better prediction than Ouali model, especially at lower filler content. Theoretical models based on the geometry of an unit cell in open-cell structure such as honeycomb, tetrakaidecahedron and cube models simulate electrospun scaffolds. Among the structural models for analysis of porous scaffolds, the honeycomb model showed the best prediction, tetrakaidecahedron model—a moderate one, and cube model was the worst. In general, it was proved by both experiment and theory that the porous structure of electrospun mat caused significant modulus reduction of nanocomposites.


Nanocomposites Cellulose nanofibers Electrospinning Modulus 



We acknowledge the Institute of Fundamental Technological Research, Polish Academy of Sciences (IPPT PAN), Laboratory of Polymers and Biomaterials, and Institute of High Pressure Physics, Polish Academy of Sciences for providing facilities, materials, and their scientific assistance. Part of this research was carried out with the use of CePT infrastructure financed by the European Regional Development Fund within the Operational Program “Innovative Economy” for 2007–2013.


  1. Abdalkarim SYH, Yu H-Y, Wang D, Yao J (2017) Electrospun poly(3-hydroxybutyrate-co-3-hydroxy-valerate)/cellulose reinforced nanofibrous membranes with ZnO nanocrystals for antibacterial wound dressings. Cellulose 24:2925–2938CrossRefGoogle Scholar
  2. Adibzadeh S, Bazgir S, Katbab AA (2014) Fabrication and characterization of chitosan/poly(vinyl alcohol) electrospun nanofibrous membranes containing silver nanoparticles for antibacterial water filtration. Iran Polym J 23:645–654CrossRefGoogle Scholar
  3. Agrawal P, Pramanik K (2016) Chitosan-poly(vinyl alcohol) nanofibers by free surface electrospinning for tissue engineering applications. Tissue Eng Regen Med 13:485–497CrossRefGoogle Scholar
  4. Baji A, Mai Y-W, Wong S-C, Abtahi M, Du X (2010) Mechanical behavior of self-assembled carbon nanotube reinforced nylon 6, 6 fibers. Compos Sci Technol 70:1401–1409CrossRefGoogle Scholar
  5. Barzegar F et al (2015) Preparation and characterization of poly(vinyl alcohol)/graphene nanofibers synthesized by electrospinning. J Phys Chem Solids 77:139–145CrossRefGoogle Scholar
  6. Bazbouz MB, Stylios GK (2010) The tensile properties of electrospun nylon 6 single nanofibers. J Polym Sci Part B Polym Phys 48:1719–1731CrossRefGoogle Scholar
  7. Costa-Júnior ES, Barbosa-Stancioli EF, Mansur AAP, Vasconcelos WL, Mansur HS (2009) Preparation and characterization of chitosan/poly(vinyl alcohol) chemically crosslinked blends for biomedical applications. Carbohydr Polym 76:472–481. CrossRefGoogle Scholar
  8. Degirmenbasi N, Kalyon DM, Birinci E (2006) Biocomposites of nanohydroxyapatite with collagen and poly(vinyl alcohol). Colloids Surf B 48:42–49CrossRefGoogle Scholar
  9. Dong G et al (2010) Preparation and characterization of Ag nanoparticle-embedded polymer electrospun nanofibers. J Nanoparticle Res 12:1319–1329CrossRefGoogle Scholar
  10. Enayati MS et al (2016a) Fabrication and characterization of electrospun bionanocomposites of poly(vinyl alcohol)/nanohydroxyapatite/cellulose nanofibers. Int J Polym Mater Polym Biomater 65:660–674CrossRefGoogle Scholar
  11. Enayati MS et al (2016b) Crystallinity study of electrospun poly(vinyl alcohol) nanofibers: effect of electrospinning, filler incorporation, and heat treatment. Iran Polym J 25:647–659CrossRefGoogle Scholar
  12. Fallahiarezoudar E, Ahmadipourroudposht M, Yusof NM, Idris A (2015) Influence of process factors on diameter of core (γ-Fe2O3)/shell poly(vinyl alcohol) structure magnetic nanofibers during co-axial electrospinning. Int J Polym Mater Polym Biomater 64:15–24CrossRefGoogle Scholar
  13. Fernandes EM, Pires RA, Mano JF, Reis RL (2013) Bionanocomposites from lignocellulosic resources: properties, applications and future trends for their use in the biomedical field. Prog Polym Sci 38:1415–1441CrossRefGoogle Scholar
  14. Halpin JC (1992) Primer on composite materials analysis (Revised). CRC Press, LondonGoogle Scholar
  15. Inai R, Kotaki M, Ramakrishna S (2005) Structure and properties of electrospun PLLA single nanofibres. Nanotechnology 16:208CrossRefGoogle Scholar
  16. Islam MS, Rahaman MS, Yeum JH (2015) Electrospun novel super-absorbent based on polysaccharide–poly(vinyl alcohol)–montmorillonite clay nanocomposites. Carbohydr Polym 115:69–77CrossRefGoogle Scholar
  17. Khalf A, Singarapu K, Madihally SV (2015) Cellulose acetate core–shell structured electrospun fiber: fabrication and characterization. Cellulose 22:1389–1400CrossRefGoogle Scholar
  18. Kim G-M, Asran AS, Michler GH, Simon P, Kim J-S (2008) Electrospun PVA/HAp nanocomposite nanofibers: biomimetics of mineralized hard tissues at a lower level of complexity. Bioinspir Biomim 3:046003CrossRefGoogle Scholar
  19. Koosha M, Mirzadeh H, Shokrgozar MA, Farokhi M (2015) Nanoclay-reinforced electrospun chitosan/PVA nanocomposite nanofibers for biomedical applications. RSC Adv 5:10479–10487CrossRefGoogle Scholar
  20. Kumar V, Rawal A (2017) Elastic moduli of electrospun mats: importance of fiber curvature and specimen dimensions. J Mech Behav Biomed Mater 72:6–13CrossRefGoogle Scholar
  21. Lee J, Deng Y (2013) Nanoindentation study of individual cellulose nanowhisker-reinforced PVA electrospun fiber. Polym Bull 70:1205–1219CrossRefGoogle Scholar
  22. Lee S-T, Ramesh NS (2004) Polymeric foams: mechanisms and materials. CRC Press, LondonCrossRefGoogle Scholar
  23. Linh NTB, Lee B-T (2012) Electrospinning of poly(vinyl alcohol)/gelatin nanofiber composites and cross-linking for bone tissue engineering application. J Biomater Appl 27:255–266CrossRefGoogle Scholar
  24. Linh B, Thuy N, Lee KH, Lee BT (2013) Functional nanofiber mat of poly(vinyl alcohol)/gelatin containing nanoparticles of biphasic calcium phosphate for bone regeneration in rat calvaria defects. J Biomed Mater Res Part A 101:2412–2423CrossRefGoogle Scholar
  25. Liu W, Yee S, Adanur S (2014) Properties of electrospun PVA/nanoclay composites. J Text Inst 105:423–429CrossRefGoogle Scholar
  26. Ma L, Wang L, Wu L, Zhuo D, Weng Z, Ren R (2014) Cellulosic nanocomposite membranes from hydroxypropyl cellulose reinforced by cellulose nanocrystals. Cellulose 21:4443–4454CrossRefGoogle Scholar
  27. Mehrasa M et al (2016) Incorporation of zeolite and silica nanoparticles into electrospun PVA/collagen nanofibrous scaffolds: the influence on the physical, chemical properties and cell behavior. Int J Polym Mater Polym Biomater 65:457–465CrossRefGoogle Scholar
  28. Meng Z, Wang Y, Ma C, Zheng W, Li L, Zheng Y (2010) Electrospinning of PLGA/gelatin randomly-oriented and aligned nanofibers as potential scaffold in tissue engineering. Mater Sci Eng C 30:1204–1210CrossRefGoogle Scholar
  29. Neisiany RE, Khorasani SN, Naeimirad M, Lee JKY, Ramakrishna S (2017a) Improving mechanical properties of carbon/epoxy composite by incorporating functionalized electrospun polyacrylonitrile nanofibers. Macromol Mater Eng. Google Scholar
  30. Neisiany RE, Lee JKY, Khorasani SN, Ramakrishna S (2017b) Towards the development of self-healing carbon/epoxy composites with improved potential provided by efficient encapsulation of healing agents in core-shell nanofibers. Polym Test 62:79–87CrossRefGoogle Scholar
  31. Ouali N, Cavaillé J, Perez J (1991) Elastic, viscoelastic and plastic behavior of multiphase polymer blends. Plast Rubber Compos Process Appl (UK) 16:55–60Google Scholar
  32. Persano L, Camposeo A, Tekmen C, Pisignano D (2013) Industrial upscaling of electrospinning and applications of polymer nanofibers: a review. Macromol Mater Eng 298:504–520. CrossRefGoogle Scholar
  33. Pierini F, Lanzi M, Nakielski P, Pawłowska S, Zembrzycki K, Kowalewski TA (2016) Electrospun poly(3-hexylthiophene)/poly(ethylene oxide)/graphene oxide composite nanofibers: effects of graphene oxide reduction. Polym Adv Technol 27:1465–1475CrossRefGoogle Scholar
  34. Pon-On W, Charoenphandhu N, Teerapornpuntakit J, Thongbunchoo J, Krishnamra N, Tang I-M (2014) Mechanical properties, biological activity and protein controlled release by poly(vinyl alcohol)–bioglass/chitosan–collagen composite scaffolds: a bone tissue engineering applications. Mater Sci Eng C 38:63–72CrossRefGoogle Scholar
  35. Pooyan P, Tannenbaum R, Garmestani H (2012) Mechanical behavior of a cellulose-reinforced scaffold in vascular tissue engineering. J Mech Behav Biomed Mater 7:50–59CrossRefGoogle Scholar
  36. Ramakrishna S, Lim T, Inai R, Fujihara K (2006) Modified Halpin–Tsai equation for clay-reinforced polymer nanofiber. Mech Adv Mater Struct 13:77–81CrossRefGoogle Scholar
  37. Sambudi NS, Sathyamurthy M, Lee GM, Park SB (2015) Electrospun chitosan/poly(vinyl alcohol) reinforced with CaCO3 nanoparticles with enhanced mechanical properties and biocompatibility for cartilage tissue engineering. Compos Sci Technol 106:76–84CrossRefGoogle Scholar
  38. Sheikh FA, Barakat NA, Kanjwal MA, Park SJ, Park DK, Kim HY (2010) Synthesis of poly(vinyl alcohol) (PVA) nanofibers incorporating hydroxyapatite nanoparticles as future implant materials. Macromol Res 18:59–66CrossRefGoogle Scholar
  39. Shokrollahi M, Morshed M, Semnani D, Rezaei B (2014) Development of electro-spun poly(vinyl alcohol)/titanium dioxide membrane-based polymer electrolytes for lithium–ion batteries. Int J Polym Mater Polym Biomater 63:161–171CrossRefGoogle Scholar
  40. Shulmeister V (1998) Modelling of the mechanical properties of low-density foams. Dissertation, Delft University of TechnologyGoogle Scholar
  41. Srivastava V, Srivastava R (2014) On the polymeric foams: modeling and properties. J Mater Sci 49:2681–2692CrossRefGoogle Scholar
  42. Stachewicz U, Bailey RJ, Wang W, Barber AH (2012) Size dependent mechanical properties of electrospun polymer fibers from a composite structure. Polymer 53:5132–5137CrossRefGoogle Scholar
  43. Tan E, Lim C (2004) Physical properties of a single polymeric nanofiber. Appl Phys Lett 84:1603–1605CrossRefGoogle Scholar
  44. Tan E, Goh C, Sow C, Lim C (2005) Tensile test of a single nanofiber using an atomic force microscope tip. Appl Phys Lett 86:073115CrossRefGoogle Scholar
  45. Thelen S, Barthelat F, Brinson LC (2004) Mechanics considerations for microporous titanium as an orthopedic implant material. J Biomed Mater Res Part A 69:601–610CrossRefGoogle Scholar
  46. Usov I et al (2015) Understanding nanocellulose chirality and structure–properties relationship at the single fibril level. Nat Commun 6:7564CrossRefGoogle Scholar
  47. Wang W, Barber AH (2012) Measurement of size-dependent glass transition temperature in electrospun polymer fibers using AFM nanomechanical testing. J Polym Sci Part B Polym Phys 50:546–551CrossRefGoogle Scholar
  48. Wang C, Li Y, Ding G, Xie X, Jiang M (2013) Preparation and characterization of graphene oxide/poly(vinyl alcohol) composite nanofibers via electrospinning. J Appl Polym Sci 127:3026–3032CrossRefGoogle Scholar
  49. Xiao S, Gao R, Gao L, Li J (2016) Poly(vinyl alcohol) films reinforced with nanofibrillated cellulose (NFC) isolated from corn husk by high intensity ultrasonication. Carbohydr Polym 136:1027–1034CrossRefGoogle Scholar
  50. Yang E, Qin X, Wang S (2008) Electrospun crosslinked poly(vinyl alcohol) membrane. Mater Lett 62:3555–3557CrossRefGoogle Scholar
  51. Zhu H, Knott J, Mills N (1997) Analysis of the elastic properties of open-cell foams with tetrakaidecahedral cells. J Mech Phys Solids 45:319327–325343Google Scholar

Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2017

Authors and Affiliations

  • Mohammad Saied Enayati
    • 1
    • 2
  • T. Behzad
    • 1
    Email author
  • P. Ł. Sajkiewicz
    • 2
  • R. Bagheri
    • 1
  • L. Ghasemi-Mobarakeh
    • 3
  • F. Pierini
    • 2
  1. 1.Department of Chemical EngineeringIsfahan University of TechnologyIsfahanIran
  2. 2.Institute of Fundamental Technological ResearchPolish Academy of SciencesWarsawPoland
  3. 3.Department of Textile EngineeringIsfahan University of TechnologyIsfahanIran

Personalised recommendations