Abstract
Porous thermoplastic polyurethane (TPU) membranes were produced by the electrospinning process. Two different TPUs and their blends were used to investigate the effects of material composition, solution concentration, and rheological properties on the microstructure, fiber diameter, and fiber diameter distribution of the electrospun membranes. The ratios of hard and soft segments in the solutions were adjusted by varying the blend ratios of TPUs dissolved in N, N-dimethylformamide. The solutions with higher TPU concentrations and more hard segments exhibited a higher viscosity, larger storage and loss moduli, and greater electrospun jet stability. Solutions with concentrations around the critical chain entanglement concentration (Ce) produced bead or beaded fiber structures, while bead-free fibers of a uniform diameter were obtained when the concentration increased to about two times that of Ce. Relationships between the electrospun fiber diameter, the Berry number, and the normalized concentration of the solutions were studied as well.
Similar content being viewed by others
References
M. Mohammadian and A.K. Haghi: Fabrication of nontoxic filters from regenerated silk fibroin and polyacrylonitrile fibers. Mater. Plast. 49(2), 90 (2012).
H.X. Wang, H. Ding, B. Lee, X.G. Wang, and T. Lin: Polypyrrole-coated electrospun nanofibre recovery of Au(III) from aqueous membranes for solution. J. Membrane Sci. 303(1–2), 119 (2007).
A. Sotoudeh, G. Jahanshahi, A. Jahanshahi, M.A. Takhtfooladi, I. Shabani, and M. Soleimani: Combination of poly L-lactic acid nanofiber scaffold with omentum graft for bone healing in experimental defect in tibia of rabbits. Acta. Cir. Bras. 27(10), 694 (2012).
A.R. Unnithan, N.A.M. Barakat, P.B.T. Pichiah, G. Gnanasekaran, R. Nirmala, Y.S. Cha, C.H. Jung, M. El-Newehy, and H.Y. Kim: Wound-dressing materials with antibacterial activity from electrospun polyurethane-dextran nanofiber mats containing ciprofloxacin HCl. Carbohydr. Polym. 90(4), 1786 (2012).
J.Y. Park and I.H. Lee: Controlled release of ketoprofen from electrospun porous polylactic acid (PLA) nanofibers. J. Polym. Res. 18(6), 1287 (2011).
H. Jamil, S.S. Batool, Z. Imran, M. Usman, M.A. Rafiq, M. Willander, and M.M. Hassan: Electrospun titanium dioxide nanofiber humidity sensors with high sensitivity. Ceram. Int. 38(3), 2437 (2012).
T.Q. Doan, T.J. Boyle, L.A.M. Ottley, S.M. Hoppe, and T.M. Alam: Synthesis, characterization, electrospinning of novel tin amide alkoxides for lithium-ion battery application. Abstr. Pap. Am. Chem. S. 242 (2011).
X.Y. Geng, O.H. Kwon, and J.H. Jang: Electrospinning of chitosan dissolved in concentrated acetic acid solution. Biomaterials 26(27), 5427 (2005).
J. Han, T.X. Chen, C.J. Branford-White, and L.M. Zhu: Electrospun shikonin-loaded PCL/PTMC composite fiber mats with potential biomedical applications. Int. J. Pharm. 382(1–2), 215 (2009).
S. Megelski, J.S. Stephens, D.B. Chase, and J.F. Rabolt: Micro- and nanostructured surface morphology on electrospun polymer fibers. Macromolecules 35(22), 8456 (2002).
A. Awal, M. Sain, and M. Chowdhury: Preparation of cellulose-based nano-composite fibers by electrospinning and understanding the effect of processing parameters. Composites Part B 42(5), 1220 (2011).
D.H. Reneker and A.L. Yarin: Electrospinning jets and polymer nanofibers. Polymer 49(10), 2387 (2008).
S. De Vrieze, T. Van Camp, A. Nelvig, B. Hagstrom, P. Westbroek, and K. De Clerck: The effect of temperature and humidity on electrospinning. J. Mater. Sci. 44(5), 1357 (2009).
Z.M. Huang, Y.Z. Zhang, M. Kotaki, and S. Ramakrishna: A review on polymer nanofibers by electrospinning and their applications in nanocomposites. Compos. Sci. Technol. 63(15), 2223 (2003).
A.M. Afifi, H. Yamane, and Y. Kimura: Effect of polymer molecular weight on the electrospinning of polylactides in entangled and aligned fiber forms. Sen-I Gakkaishi. 66(2), 35 (2010).
M.G. McKee, T. Park, S. Unal, I. Yilgor, and T.E. Long: Electrospinning of linear and highly branched segmented poly(urethane urea)s. Polymer 46(7), 2011 (2005).
A.C. Vega-Lugo and L.T. Lim: Effects of poly(ethylene oxide) and pH on the electrospinning of whey protein isolate. J. Polym. Sci., Part B: Polym. Phys. 50(16), 1188 (2012).
J.M. Choi, H.C. Jang, J.Y. Hyeon, and J.H. Sok: Fabrication of PCL/MWCNTs nanofiber by electrospinning. Korean J. Met. Mater. 50(10), 763 (2012).
R. Nayak, I.L. Kyratzis, Y.B. Truong, R. Padhye, and L. Arnold: Melt-electrospinning of polypropylene with conductive additives. J. Mater. Sci. 47(17), 6387 (2012).
S.P. Rwei and C.C. Huang: Electrospinning PVA solution-rheology and morphology analyses. Fiber Polym. 13(1), 44 (2012).
C. Mit-uppatham, M. Nithitanakul, and P. Supaphol: Effects of solution concentration, emitting electrode polarity, solvent type, and salt addition on electrospun polyamide-6 fibers: A preliminary report. Macromol. Symp. 216, 293 (2004).
S.L. Shenoy, W.D. Bates, H.L. Frisch, and G.E. Wnek: Role of chain entanglements on fiber formation during electrospinning of polymer solutions: Good solvent, non-specific polymer-polymer interaction limit. Polymer 46(10), 3372 (2005).
M.G. McKee, G.L. Wilkes, R.H. Colby, and T.E. Long: Correlations of solution rheology with electrospun fiber formation of linear and branched polyesters. Macromolecules 37(5), 1760 (2004).
H.W. Tong and M. Wang: An investigation into the influence of electrospinning parameters on the diameter and alignment of poly(hydroxybutyrate-co-hydroxyvalerate) fibers. J. Appl. Polym. Sci. 120(3), 1694 (2011).
T. Groth, K. Klosz, E.J. Campbell, R.R.C. New, B. Hall, and H. Goering: Protein adsorption, lymphocyte adhesion and platelet-adhesion activation on polyurethane ureas is related to hard segment content and composition. J. Biomater. Sci., Polym. Ed. 6(6), 497 (1994).
J.J. Stankus, J.J. Guan, and W.R. Wagner: Fabrication of biodegradable elastomeric scaffolds with sub-micron morphologies. J. Biomed. Mater. Res. Part A 70(4), 603 (2004).
R.R. Klossner, H.A. Queen, A.J. Coughlin, and W.E. Krause: Correlation of Chitosan’s rheological properties and its ability to electrospin. Biomacromolecules 9(10), 2947 (2008).
M. Pakravan, M.C. Heuzey, and A. Ajji: A fundamental study of chitosan/PEO electrospinning. Polymer 52(21), 4813 (2011).
L. Buruaga, M.E. Munoz, L. Irusta, A. Gonzalez, and J.J. Iruin: Role of specific interactions on fiber formation in the electrospinning of poly(vinyl phenol)/poly(vinyl pyrrolidone) blend solutions. J. Appl. Polym. Sci. 114(5), 2922 (2009).
A. Varesano, A. Aluigi, C. Vineis, and C. Tonin: Study on the shear viscosity behavior of keratin/PEO blends for nanofibre electrospinning. J. Polym. Sci., Part B: Polym. Phys. 46(12), 1193 (2008).
U.A. Pinto, L.L.Y. Visconte, and R.C.R. Nunes: Mechanical properties of thermoplastic polyurethane elastomers with mica and aluminum trihydrate. Eur. Polym. J. 37(9), 1935 (2001).
Z.H. Dong, Y.B. Li, and Q. Zou: Degradation and biocompatibility of porous nano-hydroxyapatite/polyurethane composite scaffold for bone tissue engineering. Appl. Surf. Sci. 255(12), 6087 (2009).
O. Buczek, D. Krowarsch, and J. Otlewski: Thermodynamics of single peptide bond cleavage in bovine pancreatic trypsin inhibitor (BPTI). Protein Sci. 11(4), 924 (2002).
S. Chisca, A.I. Barzic, I. Sava, N. Olaru, and M. Bruma: Morphological and rheological insights on polyimide chain entanglements for electrospinning produced fibers. J. Phys. Chem. B. 116(30), 9082 (2012).
Y.L. Ren, D.R. Picout, P.R. Ellis, and S.B. Ross-Murphy: Solution properties of the xyloglucan polymer from Afzelia africana. Biomacromolecules 5(6), 2384 (2004).
I.S. Chronakis and M. Ramzi: Isotropic-nematic phase equilibrium and phase separation of kappa-carrageenan in aqueous salt solution: Experimental and theoretical approaches. Biomacromolecules 3(4), 793 (2002).
H.M. Kopperud, F.K. Hansen, and B. Nystrom: Effect of surfactant and temperature on the rheological properties of aqueous solutions of unmodified and hydrophobically modified polyacrylamide. Macromol. Chem. Phys. 199(11), 2385 (1998).
H.R. Nie, A.H. He, J.F. Zheng, S.S. Xu, J.X. Li, and C.C. Han: Effects of chain conformation and entanglement on the electrospinning of pure alginate. Biomacromolecules 9(5), 1362 (2008).
W.E. Krause, E.G. Bellomo, and R.H. Colby: Rheology of sodium hyaluronate under physiological conditions. Biomacromolecules 2(1), 65 (2001).
F. Bordi, R.H. Colby, C. Cametti, L. De Lorenzo, and T. Gili: Electrical conductivity of polyelectrolyte solutions in the semidilute and concentrated regime: The role of counterion condensation. J. Phys. Chem. B 106(27), 6887 (2002).
P.D. Hong, C.M. Chou, and C.H. He: Solvent effects on aggregation behavior of polyvinyl alcohol solutions. Polymer 42(14), 6105 (2001).
J. Tao and S. Shivkumar: Molecular weight dependent structural regimes during the electrospinning of PVA. Mater. Lett. 61(11–12), 2325 (2007).
P. Rai and S.L. Rosen: An empirical relation between the Mark-Houwink-Sakurada constants. J. Polym. Sci., Part B: Polym. Phys. 35(12), 1985 (1997).
P. Gupta, C. Elkins, T.E. Long, and G.L. Wilkes: Electrospinning of linear homopolymers of poly(methyl methacrylate): Exploring relationships between fiber formation, viscosity, molecular weight and concentration in a good solvent. Polymer 46(13), 4799 (2005).
M.G. McKee, C.L. Elkins, and T.E. Long: Influence of self-complementary hydrogen bonding on solution rheology/electrospinning relationships. Polymer 45(26), 8705 (2004).
Acknowledgments
The authors would like to acknowledge the support of the Chinese Scholarship Council and the Wisconsin Institute for Discovery, the financial support of the National Nature Science Foundation of China (Grant Nos.51073061 and 21174044), the Fundamental Research Funds for Central Universities (Grant No.2011ZZ0011), and the 973 Program (Grant No. 2012CB025902).
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Mi, HY., Jing, X., Jacques, B.R. et al. Characterization and properties of electrospun thermoplastic polyurethane blend fibers: Effect of solution rheological properties on fiber formation. Journal of Materials Research 28, 2339–2350 (2013). https://doi.org/10.1557/jmr.2013.115
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1557/jmr.2013.115