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Modification on crystallization of poly(vinylidene fluoride) (PVDF) by solvent extraction of poly(methyl methacrylate) (PMMA) in PVDF/PMMA blends

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Abstract

The crystallization modification of poly(vinylidene fluoride) (PVDF) was investigated for the blend films of PVDF and poly(methyl methacrylate) (PMMA). The mass crystallinity (χ c) and further, the β-phase content (F (β)) of PVDF, were studied for the asprepared blend films with different mass ratios. In addition, the variations of χ c and F (β) were systematically probed once the PMMA component was removed from the related blend systems. DSC, FTIR and XRD measurements all indicated that 1) χ c, F (β) and even the content of α-phase (F (β)) decreased with the addition of PMMA; 2) with the extraction of PMMA, both χ c and F (β) increased while F (β) decreased. It is worth noting that the increase of χ c and F (β) depended on the relative amount of extracted PMMA (E PMMA), i.e., the more PMMA was removed, the more χ c and F (β) increased. These results reveal the hindrance effect from the PMMA constituent to the crystallization of PVDF, and consequently, this restriction would be released when the PMMA was extracted.

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References

  1. Tashiro K, Tadokoro H, Kobayashi M. Structure and piezoelectricity of poly(vinylidene fluoride). Ferroelectrics, 1981, 32(1): 167–175

    Article  CAS  Google Scholar 

  2. Firmino Mendes S, Costa C M, Sencadas V, et al. Effect of the ceramic grain size and concentration on the dynamical mechanical and dielectric behavior of poly(vinilidene fluoride)/Pb(Zr0.53Ti0.47)O3 composites. Applied Physics A: Materials Science & Processing, 2009, 96(4): 899–908

    Article  CAS  Google Scholar 

  3. Benz M, Euler WB, Gregory O J. The role of solution phase water on the deposition of thin films of poly(vinylidene fluoride). Macromolecules, 2002, 35(7): 2682–2688

    Article  CAS  Google Scholar 

  4. Lin D J, Chang H H, Beltsios K, et al. Effect of postcasting heattreatment on the structure and properties of semicrystalline phaseinversion poly(vinylidene fluoride) membranes. Journal of Polymer Science Part B: Polymer Physics, 2009, 47(19): 1880–1893

    Article  CAS  Google Scholar 

  5. Choi S, Jiang Z W. A novel wearable sensor device with conductive fabric and PVDF film for monitoring cardiorespiratory signals. Sensors and Actuators A: Physical, 2006, 128(2): 317–326

    Article  Google Scholar 

  6. Saunier J, Alloin F, Sanchez J Y, et al. Plasticized microporous poly(vinylidene fluoride) separators for lithium-ion batteries. I. Swelling behavior of dense membranes with respect to a liquid electrolyte-Characterization of the swelling equilibrium. Journal of Polymer Science Part B: Polymer Physics, 2004, 42(3): 532–543

    Article  CAS  Google Scholar 

  7. Saunier J, Alloin F, Sanchez J Y, et al. Plasticized microporous poly(vinylidene fluoride) separators for lithium-ion batteries. II. Poly(vinylidene fluoride) dense membrane swelling behavior in a liquid electrolyte-characterization of the swelling kinetics. Journal of Polymer Science Part B: Polymer Physics, 2004, 42(3): 544–552

    Article  CAS  Google Scholar 

  8. Saunier J, Alloin F, Sanchez J Y, et al. Plasticized microporous poly(vinylidene fluoride) separators for lithium-ion batteries. III. Gel properties and irreversible modifications of poly(vinylidene fluoride) membranes under swelling in liquid electrolytes. Journal of Polymer Science Part B: Polymer Physics, 2004, 42(12): 2308–2317

    Article  CAS  Google Scholar 

  9. Laroche G, Lafrance C P, Prud’homme R E, et al. Identification and quantification of the crystalline structures of poly(vinylidene fluoride) sutures by wide-angle X-ray scattering and differential scanning calorimetry. Journal of Biomedical Materials Research, 1998, 39(2): 184–189

    Article  CAS  Google Scholar 

  10. Scheinbeim J I. In: Mark J E, ed. Poly(Vinylidene Fluoride). New York: Oxford University Press, 1999, 949

    Google Scholar 

  11. Guerra G, Karasz F E, Macknight W J. On blends of poly(vinylidene fluoride) and poly(vinyl fluoride). Macromolecules, 1986, 19(7): 1935–1938

    Article  CAS  Google Scholar 

  12. Kobayashi M, Tashiro K, Tadokoro H. Molecular vibrations of three crystal forms of poly(vinylidene fluoride). Macromolecules, 1975, 8(2): 158–171

    Article  CAS  Google Scholar 

  13. Salimi A, Yousefi A A. Conformational changes and phase transformation mechanisms in PVDF solution-cast films. Journal of Polymer Science Part B: Polymer Physics, 2004, 42(18): 3487–3495

    Article  CAS  Google Scholar 

  14. Shah D, Maiti P, Gunn E, et al. Dramatic enhancements in toughness of polyvinylidene fluoride nanocomposites via nanoclay-directed crystal structure and morphology. Advanced Materials, 2004, 16(14): 1173–1177

    Article  CAS  Google Scholar 

  15. He X J, Yao K. Crystallization mechanism and piezoelectric properties of solution-derived ferroelectric poly(vinylidene fluoride) thin films. Applied Physics Letters, 2006, 89(11): 112909 (3 pages)

    Article  Google Scholar 

  16. Park Y J, Kang Y S, Park C. Micropatterning of semicrystalline poly(vinylidene fluoride) (PVDF) solutions. European Polymer Journal, 2005, 41(5): 1002–1012

    Article  CAS  Google Scholar 

  17. Pae K D, Bhateja S K, Gilbert J R. Increase in crystallinity in poly(vinylidene fluoride) by electron beam radiation. Journal of Polymer Science Part B: Polymer Physics, 1987, 25(4): 717–722

    Article  CAS  Google Scholar 

  18. Andrew J S, Clarke D R. Enhanced ferroelectric phase content of polyvinylidene difluoride fibers with the addition of magnetic nanoparticles. Langmuir, 2008, 24(16): 8435–8438

    Article  CAS  Google Scholar 

  19. Andrew J S, Clarke D R. Effect of electrospinning on the ferroelectric phase content of polyvinylidene difluoride fibers. Langmuir, 2008, 24(3): 670–672

    Article  CAS  Google Scholar 

  20. He L H, Xu Q, Hua C W, et al. Effect of multi-walled carbon nanotubes on crystallization, thermal, and mechanical properties of poly(vinylidene fluoride). Polymer Composites, 2010, 31(5): 921–927

    CAS  Google Scholar 

  21. Liu Y-L, Li Y, Xu J-T, et al. Cooperative effect of electrospinning and nanoclay on formation of polar crystalline phases in poly(vinylidene fluoride). ACS Applied Materials & Interfaces, 2010, 2(6): 1759–1768

    Article  CAS  Google Scholar 

  22. Ma W Z, Zhang J, Chen S J, et al. β-Phase of poly(vinylidene fluoride) formation in poly(vinylidene fluoride)/poly(methyl methacrylate) blend from solutions. Applied Surface Science, 2008, 254(17): 5635–5642

    Article  CAS  Google Scholar 

  23. Nalwa H S. Ferroelectric Polymers: Chemistry, Physics and Applications. New York: Marcel Dekker, 1995, 63–188

    Google Scholar 

  24. He X J, Yao K, Gan B K. Phase transition and properties of a ferroelectric poly(vinylidene fluoride-hexafluoropropylene) copolymer. Journal of Applied Physics, 2005, 97(8): 084101–084106

    Article  Google Scholar 

  25. Ma W Z, Zhang J, Wang X L. Formation of poly(vinylidene fluoride) crystalline phases from tetrahydrofuran/N, Ndimethylformamide mixed solvent. Journal of Materials Science, 2008, 43(1): 398–401

    Article  CAS  Google Scholar 

  26. Gregorio R Jr. Determination of the α, β, and γ crystalline phases of poly(vinylidene fluoride) films prepared at different conditions. Journal of Applied Polymer Science, 2006, 100(4): 3272–3279

    Article  CAS  Google Scholar 

  27. Nakamura K, Nagai M, Kanamoto T, et al. Development of oriented structure and properties on drawing of poly(vinylidene fluoride) by solid-state coextrusion. Journal of Polymer Science Part B: Polymer Physics, 2001, 39(12): 1371–1380

    Article  CAS  Google Scholar 

  28. Humphreys J, Lewis E L V, Ward I M, et al. A study of the mechanical anisotropy of high-draw, low-draw, and voided PVDF. Journal of Polymer Science Part B: Polymer Physics, 1988, 26(1): 141–158

    Article  CAS  Google Scholar 

  29. Gregorio R Jr, Borges D S. Effect of crystallization rate on the formation of the polymorphs of solution cast poly(vinylidene fluoride). Polymer, 2008, 49(18): 4009–4016

    Article  CAS  Google Scholar 

  30. Priya L, Jog J P. Intercalated poly(vinylidene fluoride)/clay nanocomposites: Structure and properties. Journal of Polymer Science Part B: Polymer Physics, 2003, 41(1): 31–38

    Article  CAS  Google Scholar 

  31. He L H, Sun J, Zheng X L, et al. Effect of multiwalled carbon nanotubes on crystallization behavior of poly(vinylidene fluoride) in different solvents. Journal of Applied Polymer Science, 2011, 119(4): 1905–1913

    Article  CAS  Google Scholar 

  32. Ramasundaram S, Yoon S, Kim K J, et al. Preferential formation of electroactive crystalline phases in poly(vinylidene fluoride)/organically modified silicate nanocomposites. Journal of Polymer Science Part B: Polymer Physics, 2008, 46(20): 2173–2187

    Article  CAS  Google Scholar 

  33. Nasir M, Matsumoto H, Danno T, et al. Control of diameter, morphology, and structure of PVDF nanofiber fabricated by electrospray deposition. Journal of Polymer Science Part B: Polymer Physics, 2006, 44(5): 779–786

    Article  CAS  Google Scholar 

  34. Zheng J F, He A, Li J X, et al. Polymorphism control of poly(vinylidene fluoride) through electrospinning. Macromolecular Rapid Communications, 2007, 28(22): 2159–2162

    Article  CAS  Google Scholar 

  35. Nishi T, Wang T T. Melting point depression and kinetic effects of cooling on crystallization in poly(vinylidene fluoride)-poly(methyl methacrylate) mixtures. Macromolecules, 1975, 8(6): 909–915

    Article  CAS  Google Scholar 

  36. Ma W Z, Zhang J, Wang X L, et al. Effect of PMMA on crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate) blend prepared in semi-dilute solutions. Applied Surface Science, 2007, 253(20): 8377–8388

    Article  CAS  Google Scholar 

  37. Patterson G D, Nishi T, Wang T T. Brillouin scattering from poly(vinylidene fluoride)-poly(methyl methacrylate) mixtures. Macromolecules, 1976, 9(4): 603–605

    Article  CAS  Google Scholar 

  38. Yoshida H, Sasaki H, Bala P K, et al. Miscibility of PVDF/PMMA blends examined by crystallization dynamics. Polymer, 1995, 36(25): 4805–4810

    Google Scholar 

  39. Hirata Y, Kotaka T. Phase separation and viscoelastic behavior of semicompatible polymer blends: poly(vinylidene fluoride)/poly(methyl methacrylate) system. Polymer Journal, 1981, 13(3): 273–281

    Article  CAS  Google Scholar 

  40. Salimi A, Yousefi A A. Analysis Method: FTIR studies of β-phase crystal formation in stretched PVDF films. Polymer Testing, 2003, 22(6): 699–704

    Article  CAS  Google Scholar 

  41. Salimi A, Yousefi A A. Conformational changes and phase transformation mechanisms in PVDF solution-cast films. Journal of Polymer Science Part B: Polymer Physics, 2004, 42(18): 3487–3495

    Article  CAS  Google Scholar 

  42. Nakagawa K, Ishida Y. Annealing effects in poly(vinylidene fluoride) as revealed by specific volume measurements, differential scanning calorimetry, and electron microscopy. Journal of Polymer Science Part B: Polymer Physics, 1973, 11(11): 2153–2171

    CAS  Google Scholar 

  43. Kim K J, Cho Y J, Kim Y H. Factors determining the formation of the β crystalline phase of poly(vinylidene fluoride) in poly(vinylidene fluoride)-poly(methyl methacrylate) blends. Vibrational Spectroscopy, 1995, 9(2): 147–159

    Article  CAS  Google Scholar 

  44. Pawde S M, Deshmukh K. Investigation of the structural, thermal, mechanical, and optical properties of poly(methyl methacrylate) and poly(vinylidene fluoride) blends. Journal of Applied Polymer Science, 2009, 114(4): 2169–2179

    Article  CAS  Google Scholar 

  45. Gregorio R Jr, Ueno E M. Effect of crystalline phase, orientation and temperature on the dielectric properties of poly (vinylidene fluoride) (PVDF). Journal of Materials Science, 1999, 34(18): 4489–4500

    Article  CAS  Google Scholar 

  46. Horibe H, Taniyama M. Poly(vinylidene fluoride) crystal structure of poly(vinylidene fluoride) and poly(methyl methacrylate) blend after annealing. Journal of the Electrochemical Society, 2006, 153(2): G119–G124

    Article  CAS  Google Scholar 

  47. Yuan J K, Dang Z M, Yao S H, et al. Fabrication and dielectric properties of advanced high permittivity polyaniline/poly(vinylidene fluoride) nanohybrid films with high energy storage density. Journal of Materials Chemistry, 2010, 20(12): 2441–2447

    Article  CAS  Google Scholar 

  48. Zhao X J, Cheng J, Chen S J, et al. Controlled crystallization of poly(vinylidene fluoride) chains from mixed solvents composed of its good solvent and nonsolvent. Journal of Polymer Science Part B: Polymer Physics, 2010, 48(5): 575–581

    Article  CAS  Google Scholar 

  49. Danno T, Matsumoto H, Nasir M, et al. PVDF/PMMA composite nanofiber fabricated by electrospray deposition: crystallization of PVDF induced by solvent extraction of PMMA component. Journal of Applied Polymer Science, 2009, 112(4): 1868–1872

    Article  CAS  Google Scholar 

  50. Tashiro K, Itoh Y, Kobayashi M, et al. Polarized Raman spectra and LO-TO splitting of poly(vinylidene fluoride) crystal form I. Macromolecules, 1985, 18(12): 2600–2606

    Article  CAS  Google Scholar 

  51. Dikshit A K, Nandi A K. Thermoreversible gelation of poly(vinylidene fluoride) in diesters: influence of intermittentlength on morphology and thermodynamics of gelation. Macromolecules, 2000, 33(7): 2616–2625

    Article  CAS  Google Scholar 

  52. Gregorio R Jr, Cestari M. Effect of crystallization temperature on the crystalline phase content and morphology of poly(vinylidene fluoride). Journal of Polymer Science Part B: Polymer Physics, 1994, 32(5): 859–870

    Article  CAS  Google Scholar 

  53. Benz M, Euler W B. Determination of the crystalline phases of poly(vinylidene fluoride) under different preparation conditions using differential scanning calorimetry and infrared spectroscopy. Journal of Applied Polymer Science, 2003, 89(4): 1093–1100

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Key Laboratory of Surface and Interface Sciences of Henan Province, Zhengzhou University of Light Industry, Zhengzhou, 450005, China

    Jing Sun, Lu Yao, Rui Song & Ling-Hao He

  2. Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China

    Qiao-Ling Zhao, Jin Huang & Zhi Ma

  3. College of Chemistry and Chemical Engineering, Graduate University of Chinese Academy of Sciences, Beijing, 100049, China

    Rui Song & Yong-Mei Hao

  4. Laboratory of Advanced Polymer Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100080, China

    Wei Huang

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  1. Jing Sun
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Correspondence to Rui Song.

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Sun, J., Yao, L., Zhao, QL. et al. Modification on crystallization of poly(vinylidene fluoride) (PVDF) by solvent extraction of poly(methyl methacrylate) (PMMA) in PVDF/PMMA blends. Front. Mater. Sci. 5, 388–400 (2011). https://doi.org/10.1007/s11706-011-0152-2

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