Advertisement

Journal of Polymer Research

, 21:605 | Cite as

Enhancing the crystallization and orientation of electrospinning poly (lactic acid) (PLLA) by combining with additives

  • Ahmed M. El-Hadi
  • Saeed D. Mohan
  • Fred J. Davis
  • Geoffrey R. Mitchell
Original Paper

Abstract

PLLA is a thermoplastic biopolymer and can be used in industrial applications for medical and filtration applications. The brittleness of PLLA is attributed to slow crystallization rates and its glass transition temperature (Tg) is high (60 °C); for this reason, its applications are limited. The orientation, morphology, and crystal structure of the electrospun fibers was investigated by SEM, POM, DSC, FTIR, XRD, and SAXS. Combining with additives leads to a large decrease of fiber diameter, viscosity, and changes of fiber morphology and crystal structure compared to pure PLLA. DSC showed that the Tg of PLLA decreased about 15 °C and there was no change in relaxation enthalpy by the addition of plasticizer. FT-IR indicate a strong interaction between PLLA and additives; a new band appears in the PLLA blend at 1,756 cm−1 at room temperature as a crystalline band without any annealing. In addition, WAXD indicated that the intensities of the two peaks at (200/110) and (203) increased for the blend at room temperature without any annealing in comparison with PLLA; this means that PHB crystallizes in the amorphous region of PLLA. The POM experiments agree with the results from DSC, FTIR, and WAXS measurements, confirming that adding PHB results in an increase in the number of nuclei with much smaller spherulites and enhances the crystallization behavior of this material, thereby improving its potential for applications.

Keywords

PHB PLLA Biopolymer blends Electrospinning Nano fibers 

Notes

Acknowledgments

The author thanks SABIC company for petrochemicals (Research & Consulting Center) and Institute of Scientific Research for supporting this project (grant number: 43005001).

References

  1. 1.
    Greiner A, Wendorff JH, Electrospinning (2007) A Fascinating Method for the Preparation of Ultrathin Fibers. Angew Chem Int Ed 46:5670–5703CrossRefGoogle Scholar
  2. 2.
    Ramakrishna S, Kazutoshi F, Teo WE, Lim TC, Ma Z (2005) An introduction to nanofibers. World Scientific Co., Pte. Ltd., SingaporeGoogle Scholar
  3. 3.
    Reneker DH, Fong H (2006) Polymeric nanofibers. In: ACS symposium series 918.Washington, DC: American Chemical SocietyGoogle Scholar
  4. 4.
    Fong H, Reneker DH (2000) Electrospinning and the formation of nanofibers. In: Salem DR (ed) Structure formation in polymeric fibers. Hanser, Munich, pp 225–289Google Scholar
  5. 5.
    Zong X, Kim K, Fang D, Ran S, Hsiao BS, Chu B (2002) Structure and process relationship of electrospun bioabsorbable nanofiber membranes. Polymer 43:4403–4415CrossRefGoogle Scholar
  6. 6.
    Formhals A (1934) Process and apparatus for preparing artificial threads, US patent 1975504Google Scholar
  7. 7.
    Sawicka KM, Gouma P (2006) Electrospun composite nanofibers for functional applications. J Nanoparticle Res 8:769–781CrossRefGoogle Scholar
  8. 8.
    Buschle-Diller G, Hawkins A, Copper J (2006) Electrospun nanofibers from biopolymers and their biomedical applications. In: Edwards JV, Buschle-Diller G, Goheen SC (eds) ‘Modified Fibers with Medical and Specialty Applications’. Springer, Berlin, pp 67–89CrossRefGoogle Scholar
  9. 9.
    Chen J, Chang GY, Chen JK (2008) Colloids and Surfaces A: Physicochemical and Engineering Aspects. 313–314: 183–188. Electrospun collagen/chitosan nanofibrous membrane as wound dressingGoogle Scholar
  10. 10.
    Yang F, Murugan R, Wang S, Ramakrishna S (2005) Electrospinning of nano/micro scale poly(L-lactic acid) aligned fibers and their potential in neural tissue engineering. Biomaterials 26:2603–2610CrossRefGoogle Scholar
  11. 11.
    Wang X, Drew C, Lee S-H, Senecal KJ, Kumar J, Samuelson LA (2002) Electrospun Nanofibrous Membranes for Highly Sensitive Optical Sensors. Nano Lett 2:1273–3CrossRefGoogle Scholar
  12. 12.
    Wang M, Singh H, Hatton TA, Rutledge GC (2004) Field-responsive superparamagnetic composite nanofibers by electrospinning. Polymer 45:5505–5509CrossRefGoogle Scholar
  13. 13.
    Gibson PW, Schreuder-Gibson HL, Rivin D (1999) Electrospun fiber mats: transport properties. AIChE J 45:190–195CrossRefGoogle Scholar
  14. 14.
    Xu CY, Inai R, Kotaki M, Ramakrishna S (2004) Aligned biodegradable nano fibrous structure: a potential scaffold for blood vessel engineering. Biomaterials 25:877–886CrossRefGoogle Scholar
  15. 15.
    El-Hadi AM (2011) The Effect of Annealing Treatments on Spherulitic Morphology and Physical Ageing on Glass Transition of Poly Lactic Acid (PLLA). Mater Sci Appl 2:439–5Google Scholar
  16. 16.
    Nurkhamidah S, Woo EM (2012) Correlation of Crack Patterns and Ring Bands in Spherulites of Highly Crystalline Poly(L-lactic acid. Collied Polym Sci 290:275–288CrossRefGoogle Scholar
  17. 17.
    Kumbar SG, Nukavarapu SP, James R, Nair LS, Laurenin CT (2008) Electrospun poly(lactic acid-co-glycolic acid) scaffolds for skin tissue engineering. Biomaterials 29:4100–4107CrossRefGoogle Scholar
  18. 18.
    Bognitzki M, Czado W, Frese, T A (2001) Schaper, Hellwig M, Steinhart M, Greiner A, Wendorff JH, Nanostructured fibers via electrospinning, Adv Mater 13 :70–2Google Scholar
  19. 19.
    Xu X, Yang Q, Wang Y, Yu H, Chen X, Jing X (2006) Biodegradable electrospun poly(L-lactide) fibers containing antibacterial silver nanoparticles. Eur Polym J 42:2081–2089CrossRefGoogle Scholar
  20. 20.
    Bognitzki M, Czado W, Frese T, Schaper A, Hellwig M, Steinhart M (2001) Nanostructured fibers via electrospinning. Adv Mater 13:70–72CrossRefGoogle Scholar
  21. 21.
    Patra SN, Easteal AJ, Bhattacharyya D (2009) Parametric study of manufacturing Poly(lactic) acid nanofibrous mat by electrspinning. J Mater Sci 44:647–654CrossRefGoogle Scholar
  22. 22.
    Edwards MD, Mitchell GR, Mohan SD, Olley RH (2010) Development of orientation during electrospinning of fibres of poly(epsilon- caprolactone). Eur Polym J 46:1175–1183CrossRefGoogle Scholar
  23. 23.
    Sombatmankhong K, Suwantong O, Supaphol P (2006) Electrospun Fiber Mats of Poly(3-Hydroxybutyrate), Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate), and Their Blends. J Polym Sci B 44:2923–2933CrossRefGoogle Scholar
  24. 24.
    El-hadi AM (2014) Development of novel biopolymer blends based on poly(L-lactic acid ) (PLLA), poly((R)-3-hydroxybutyrate) (PHB) and plasticizer. Polym Eng Sci 54:1394–1402CrossRefGoogle Scholar
  25. 25.
    Mohan SD, Mitchell GR, Davis FJ (2011) Chain extension in electrospun polystyrene fibres: a SANS study. Soft Matter 7:4397–4404CrossRefGoogle Scholar
  26. 26.
    Koombhongse S, Liu W, Reneker DH (2001) Flat Polymer Ribbons and Other Shapes by Electrospinning. J Polym Sci, Part B:Polym Phy 39:2598–2606CrossRefGoogle Scholar
  27. 27.
    Reneker DH, Yarin AL (2008) Electrospinning Jets and Polymer Nanofibers. Polymer 49:2387–2425CrossRefGoogle Scholar
  28. 28.
    Megelski S, Stephens JS, Chase DB, Rabolt JF (2002) Micro- and Nanostructured Surface Morphology on Electrospun Polymer Fibers. Macromolecules 35:8456–8465CrossRefGoogle Scholar
  29. 29.
    Casper CL, Stephens JS, Tassi NG, Chase DB, Rabolt JF (2004) Effect of organosoluble salts on the nanofibrous structure of electrospun poly(3-hydroxybutyrate-co3- hydroxyvalerate). Macromolecules 37:573–578CrossRefGoogle Scholar
  30. 30.
    Medeiros ES, Mattoso LHC, Offeman RD, Wood DF, Orts WJ (2008) Effect of relative humidity on the morphology of electrospun polymer fibers. Can J Chem-Revue Canadienne De Chimie 86:590–599CrossRefGoogle Scholar
  31. 31.
    Bloembergen S, Holden DA (1986) Studies of composition and crystallinity of bacterial poly(β-hydroxybutyrate-co-β-hydroxyvalerate). Macromolecules 19:2865–2871CrossRefGoogle Scholar
  32. 32.
    Padermshoke A, Katsumoto Y, Sato H, Ekgasit S, Noda I, Ozaki Y (2005) Melting behavior of poly(3-hydroxybutyrate) investigated by two-dimensional infrared correlation spectroscopy, Spectrochim. Acta Part A 61:541–550CrossRefGoogle Scholar
  33. 33.
    Bayar S, Severcan F (2005) FTIR study of biodegradable biopolymers: P (3HB), P(3HB-co-4HB) and P(3HB-co-3HV). J Mol Struct 744–747:529–5CrossRefGoogle Scholar
  34. 34.
    Krikorian V, Pochan DJ (2005) Crystallization Behavior of Poly (L-lactic acid) Nanocomposites:Nucleation and Growth Probed by Infrared Spectroscopy. Macromolecules 38:6520–6527CrossRefGoogle Scholar
  35. 35.
    Furukawa T, Sato H, Murakami R, Zhang J, Duan YX, Noda I, Ochiai S, Ozaki Y (2005) Structure, Dispersibility, and Crystallinity of Poly (hydroxybutyrate)/ Poly (L-lactic acid) Blends Studied by FT-IR Microspectroscopy and Differential Scanning Calorimetry. Macromolecules 38:6445–6454CrossRefGoogle Scholar
  36. 36.
    Zhang M, Thomas NL (2011) Blending polylactic acid with polyhydroxybutyrate: The effect on thermal, mechanical, and biodegradation properties. Adv Polym Technol 30:67–77CrossRefGoogle Scholar
  37. 37.
    Saito M, Inoue Y, Yoshie N (2001) Cocrystallization and phase segregation of blend of poly (3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate). Polymer 42:5573–5580CrossRefGoogle Scholar
  38. 38.
    Kim ES, Kim SH, Lee CH (2010) Electrospinning of polylactide fibers containing silver nanoparticles. Macromol Res 18:215–216CrossRefGoogle Scholar
  39. 39.
    Channuan W, Siripitayananon J, Molloy R, Sriyai M, Davis FJ, Mitchell GR (2005) The structure of crystallisable copolymers of L-lactide, ε-caprolactone and glycolide. Polymer 46:6411–6417CrossRefGoogle Scholar
  40. 40.
    Hu Y, Sato H, Zhang J, Noda I, Ozaki Y (2008) Crystallization behavior of poly(L-lactic acid) affected by the addition of a small amount of poly(3-hydroxybutyrate). Polymer 49:4204–4210CrossRefGoogle Scholar
  41. 41.
    El-Hadi AM (2011) Effect of processing conditions on the development of morphological features of banded or nonbanded spherulites of poly (3-hydroxybutyrate) (PHB) and polylactic acid (PLLA) blends. Polym Eng Sci 51:2191–2202CrossRefGoogle Scholar
  42. 42.
    Hoogsteen W, Postema AR, Pennings AJ, ten Brinke G, Zugenmaier P (1990) Crystal Structure, Conformation, and Morphology of Solution-Spun Poly(L-lactide) Fibers. Macromolecules 23:634–652CrossRefGoogle Scholar
  43. 43.
    Puiggali J, Ikada Y, Tsuji H, Cartier L, Okihara T, Lotz B (2000) The frustrated structure of poly(l-lactide). Polymer 41:8921–8930CrossRefGoogle Scholar
  44. 44.
    Sawai D, Takahashi K, Imamura T, Nakamura K, Kanamoto T, Hyon SH (2002) Preparation of oriented β-form poly(l-lactic acid) by solid-state extrusion. J Polym Sci Part B: Polym Phy 40:95–104CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  • Ahmed M. El-Hadi
    • 1
    • 2
  • Saeed D. Mohan
    • 3
  • Fred J. Davis
    • 3
  • Geoffrey R. Mitchell
    • 3
  1. 1.Department of Physics, Faculty of Applied ScienceUmm Al-Qura UniversityMakkahSaudi Arabia
  2. 2.Department of Basic ScienceHigher Institute for Engineering and TechnologyEl ArishEgypt
  3. 3.Centre for Advanced MicroscopyUniversity of ReadingReadingUK

Personalised recommendations