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Induced formation of polar phases in poly(vinylidene fluoride) by cetyl trimethyl ammonium bromide

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Abstract

Poly(vinylidene fluoride) (PVDF) has been widely used as transducers, actuators,and sensors due to its exceptional electroactive properties among polymer materials and the electroactive properties of PVDF heavily depend on its polymorphs. The effects of cetyl trimethyl ammonium bromide (CTAB) on the crystallization behavior of PVDF during isothermal crystallization and annealing process were studied, and the results showed that the polar phases (β, γ) were induced by CTAB when PVDF was isothermally crystallized at 145–160 °C. Increasing the isothermal crystallization temperature resulted in an increased γ-phase formation with a concomitant decrease of α and β phases. A 100 % γ-phase formation occurred when the sample isothermally crystallized at 155 and 160 °C. The crystalline phase transition of the sample annealed at 160 °C for various time revealed that CTAB induced the transformation from α to γ′ phase and a higher concentration of CTAB resulted in shorter transformation time, as well as higher transformation degree.

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References

  1. Kepler RG, Anderson RA (1992) Ferroelectric polymers. Adv Phys 41:1–57

    Article  Google Scholar 

  2. Lovinger AJ (1983) Ferroelectric polymers. Science 220:1115–1121

    Article  Google Scholar 

  3. Murayama N, Nakamura K, Obara H, Segawa M (1976) The strong piezoelectricity in polyvinylidene fluroide (PVDF). Ultrasonics 14:15–24

    Article  Google Scholar 

  4. Takahashi Y, Matsubara Y, Tadokoro H (1983) Crystal structure of form II of poly(vinylidene fluoride). Macromolecules 16:1588–1592

    Article  Google Scholar 

  5. Tashiro K, Tadokoro H (1983) Estimating the limiting values of the macroscopic piezoelectric constants of poly(vinylidene fluoride) form I. Macromolecules 16:961–965

    Article  Google Scholar 

  6. Takahashi Y, Tadokoro H (1980) Crystal structure of form III of poly (vinylidene fluoride). Macromolecules 13:1317–1318

    Article  Google Scholar 

  7. Lovinger AJ (1981) Unit cell of the γ phase of poly (vinylidene fluoride). Macromolecules 14:322–325

    Article  Google Scholar 

  8. Lopes AC, Costa CM, Tavares CJ, Neves IC, Lanceros-Mendez S (2011) Nucleation of the electroactive γ phase and enhancement of the optical transparency in low filler content poly(vinylidene)/clay nanocomposites. J Phys Chem C 115:18076–18082

    Article  Google Scholar 

  9. Gregorio R, Borges DS (2008) Effect of crystallization rate on the formation of the polymorphs of solution cast poly (vinylidene fluoride). Polymer 49:4009–4016

    Article  Google Scholar 

  10. Song R, Xia G, Xing X, He L, Zhao Q, Ma Z (2013) Modification of polymorphisms in polyvinylidene fluoride thin films via water and hydrated salt. J Colloid Interface Sci 401:50–57

    Article  Google Scholar 

  11. Ma W, Zhang J, Wang X (2008) Formation of poly(vinylidene fluoride) crystalline phases from tetrahydrofuran/N,N-dimethylformamide mixed solvent. J Mater Sci 43:398–401. doi:10.1007/s10853-007-2211-8

    Article  Google Scholar 

  12. Tang XG, Hou M, Ge L et al (2012) The preparation, structures, and properties of poly(vinylidene fluoride)/multiwall carbon nanotubes nanocomposites. J Appl Polym Sci 125:E592–E600

    Article  Google Scholar 

  13. Xing CY, Zhao LP, You JC, Dong WY, Cao XJ, Li YJ (2012) Impact of ionic liquid-modified multiwalled carbon nanotubes on the crystallization behavior of poly(vinylidene fluoride). J Phys Chem B 116:8312–8320

    Article  Google Scholar 

  14. Tang C-W, Li B, Sun L, Lively B, Zhong W-H (2012) The effects of nanofillers, stretching and recrystallization on microstructure, phase transformation and dielectric properties in PVDF nanocomposites. Eur Polym J 48:1062–1072

    Article  Google Scholar 

  15. Xie Q, Ke K, Jiang W-R et al (2013) Role of poly(lactic acid) in the phase transition of poly(vinylidene fluoride) under uniaxial stretching. J Appl Polym Sci 129:1686–1696

    Article  Google Scholar 

  16. Strohmeier W, Frank W (1982) The stress-induced crystalline phase transition in poly (tetramethylene terephthalate). Colloid Polym Sci 260:937–948

    Article  Google Scholar 

  17. Hsu TC, Geil P (1989) Deformation and transformation mechanisms of poly (vinylidene fluoride) (PVF 2). J Mater Sci 24:1219–1232. doi:10.1007/PL00020199

    Article  Google Scholar 

  18. Sun LL, Li B, Zhang ZG, Zhong WH (2010) Achieving very high fraction of β-crystal PVDF and PVDF/CNF composites and their effect on AC conductivity and microstructure through a stretching process. Eur Polym J 46:2112–2119

    Article  Google Scholar 

  19. Na B, Xu W, Lv R, Li Z, Tian N, Zou S (2010) Toughening of nylon-6 by semicrystalline poly(vinylidene fluoride): role of phase transformation and fibrillation of dispersed particles. Macromolecules 43:3911–3915

    Article  Google Scholar 

  20. Martins P, Lopes AC, Lanceros-Mendez S (2013) Electroactive phases of poly(vinylidene fluoride): determination, processing and applications. Prog Polym Sci. doi:10.1016/j.progpolymsci.2013.07.006

    Google Scholar 

  21. Lu F, Hsu S (1984) Spectroscopic study of the electric field induced microstructural changes in poly (vinylidene fluoride). Polymer 25:1247–1252

    Article  Google Scholar 

  22. Hasegawa R, Takahashi Y, Chatani Y, Tadokoro H (1972) Crystal structures of three crystalline forms of poly(vinylidene fluoride). Polym J 3:600–610

    Article  Google Scholar 

  23. Lovinger AJ, Keith HD (1979) Electron diffraction investigation of a high-temperature form of poly(vinylidene fluoride). Macromolecules 12:919–924

    Article  Google Scholar 

  24. Pan H, Na B (2012) Polar phase formation in poly(vinylidene fluoride) induced by melt annealing. J Polym Sci B 50:1433–1437

    Article  Google Scholar 

  25. Ramasundaram S, Yoon S, Kim KJ, Park C (2008) Preferential formation of electroactive crystalline phases in poly(vinylidene fluoride)/organically modified silicate nanocomposites. J Polym Sci B 46:2173–2187

    Article  Google Scholar 

  26. Martins P, Costa CM, Benelmekki M, Botelho G, Lanceros-Mendez S (2012) On the origin of the electroactive poly (vinylidene fluoride) β-phase nucleation by ferrite nanoparticles via surface electrostatic interactions. Cryst Eng Comm 14:2807–2811

    Article  Google Scholar 

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

    Article  Google Scholar 

  28. Martins P, Caparros C, Gonçalves R et al (2012) Role of nanoparticle surface charge on the nucleation of the electroactive β-poly(vinylidene fluoride) nanocomposites for sensor and actuator applications. J Phys Chem C 116:15790–15794

    Article  Google Scholar 

  29. Vijayakumar RP, Khakhar DV, Misra A (2011) Phase transformation and enhancement of toughness in polyvinylidene fluoride by onium salts. J Polym Sci B 49:1339–1344

    Article  Google Scholar 

  30. Wang J, Fu Q, Zhang Q (2012) Inducing of dominant polar forms in poly(vinylidene fluoride) with super toughness by adding alkyl ammonium salt. Polymer 53:5455–5458

    Article  Google Scholar 

  31. He L, Sun J, Wang X, Wang C, Song R, Hao Y (2013) Facile and effective promotion of β crystalline phase in poly(vinylidene fluoride) via the incorporation of imidazolium ionic liquids. Polym Int 62:638–646

    Article  Google Scholar 

  32. Xing C, Zhao M, Zhao L, You J, Cao X, Li Y (2013) Ionic liquid modified poly(vinylidene fluoride): crystalline structures, miscibility, and physical properties. Polym Chem 4:5726–5734

    Article  Google Scholar 

  33. Zhu Y, Li C, Na B, Lv R, Chen B, Zhu J (2014) Polar phase formation and competition in the melt crystallization of poly (vinylidene fluoride) containing an ionic liquid. Mater Chem Phys. doi:10.1016/j.matchemphys.2013.12.042

    Google Scholar 

  34. Ince-Gunduz BS, Alpern R, Amare D et al (2010) Impact of nanosilicates on poly(vinylidene fluoride) crystal polymorphism: Part 1. Melt-crystallization at high supercooling. Polymer 51:1485–1493

    Article  Google Scholar 

  35. Lopes AC, Caparros C, Gómez Ribelles JL, Neves IC, Lanceros-Mendez S (2012) Electrical and thermal behavior of γ-phase poly(vinylidene fluoride)/NaY zeolite composites. Microporous Mesoporous Mater 161:98–105

    Article  Google Scholar 

  36. Mohammadi B, Yousefi AA, Bellah SM (2007) Effect of tensile strain rate and elongation on crystalline structure and piezoelectric properties of PVDF thin films. Polym Test 26:42–50

    Article  Google Scholar 

  37. Esterly DM, Love BJ (2004) Phase transformation to β-poly (vinylidene fluoride) by milling. J Polym Sci B 42:91–97

    Article  Google Scholar 

  38. Ke K, Wang Y, Yang W, Xie B-H, Yang M-B (2012) Crystallization and reinforcement of poly (vinylidene fluoride) nanocomposites: role of high molecular weight resin and carbon nanotubes. Polym Test 31:117–126

    Article  Google Scholar 

  39. Yu S, Zheng W, Yu W, Zhang Y, Jiang Q, Zhao Z (2009) Formation mechanism of β-phase in PVDF/CNT composite prepared by the sonication method. Macromolecules 42:8870

    Article  Google Scholar 

  40. Gregorio JR, Cestari M (1994) Effect of crystallization temperature on the crystalline phase content and morphology of poly(vinylidene fluoride). J Polym Sci B 32:859–870

    Article  Google Scholar 

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

    Article  Google Scholar 

  42. Andrew JS, Clarke DR (2008) Effect of electrospinning on the ferroelectric phase content of polyvinylidene difluoride fibers. Langmuir 24:670–672

    Article  Google Scholar 

  43. Manna S, Nandi AK (2007) Piezoelectric β polymorph in poly(vinylidene fluoride)-functionalized multiwalled carbon nanotube nanocomposite films. J Phys Chem C 111:14670–14680

    Article  Google Scholar 

  44. Priya L, Jog JP (2003) Polymorphism in intercalated poly(vinylidene fluoride)/clay nanocomposites. J Appl Polym Sci 89:2036–2040

    Article  Google Scholar 

  45. Pramoda K, Mohamed A, Yee Phang I, Liu T (2005) Crystal transformation and thermomechanical properties of poly (vinylidene fluoride)/clay nanocomposites. Polym Int 54:226–232

    Article  Google Scholar 

  46. Miyazaki T, Takeda Y, Akasaka M, Sakai M, Hoshiko A (2008) Preparation of isothermally crystallized γ-form poly (vinylidene fluoride) films by adding a KBr powder as a nucleating agent. Macromolecules 41:2749–2753

    Article  Google Scholar 

  47. Gregorio R, Ueno E (1999) Effect of crystalline phase, orientation and temperature on the dielectric properties of poly (vinylidene fluoride) (PVDF). J Mater Sci 34:4489–4500. doi:10.1023/A:1004689205706

    Article  Google Scholar 

  48. Zhang GZ, Kitamura T, Yoshida H, Kawai T (2002) The mechanism of α-γ transition of poly- (vinylidene fluoride) in the miscible blends. J Therm Anal Calorim 69:939–946

    Article  Google Scholar 

  49. Gregorio R (2006) Determination of the α, β, and γ crystalline phases of poly(vinylidene fluoride) films prepared at different conditions. J Appl Polym Sci 100:3272–3279

    Article  Google Scholar 

  50. Lee W-K, Ha C-S (1998) Miscibility and surface crystal morphology of blends containing poly(vinylidene fluoride) by atomic force microscopy. Polymer 39:7131–7134

    Article  Google Scholar 

  51. Silva MP, Sencadas V, Botelho G et al (2010) α- and γ-PVDF: Crystallization kinetics, microstructural variations and thermal behaviour. Mater Chem Phys 122:87–92

    Article  Google Scholar 

  52. Wang YD, Cakmak M (1998) Hierarchical structure gradients developed in injection-molded PVDF and PVDF–PMMA blends. I. Optical and thermal analysis. J Appl Polym Sci 68:909–926

    Article  Google Scholar 

  53. El Mohajir B-E, Heymans N (2001) Changes in structural and mechanical behaviour of PVDF with processing and thermomechanical treatments. 1. Change in structure. Polymer 42:5661–5667

    Article  Google Scholar 

  54. Gregorio R, CapitãO RC (2000) Morphology and phase transition of high melt temperature crystallized poly(vinylidene fluoride). J Mater Sci 35:299–306. doi:10.1023/A:1004737000016

    Article  Google Scholar 

  55. Sajkiewicz P (1999) Crystallization behaviour of poly(vinylidene fluoride). Eur Polym J 35:1581–1590

    Article  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (NNSFC Grants 21374065, 51121001), the MOST (Grant No. 2011CB606006, 2012CB025902) and the Fundamental Research Funds for the Central Universities (Grant No. 2011SCU04A03). The authors also thank Mr. Chao-liang Zhang for his kind assistance in morphological observations.

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  1. State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Chengdu, 610065, Sichuan, China

    Cheng-Lu Liang, Qi Xie, Rui-Ying Bao, Wei Yang, Bang-Hu Xie & Ming-Bo Yang

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  1. Cheng-Lu Liang
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Correspondence to Wei Yang.

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Liang, CL., Xie, Q., Bao, RY. et al. Induced formation of polar phases in poly(vinylidene fluoride) by cetyl trimethyl ammonium bromide. J Mater Sci 49, 4171–4179 (2014). https://doi.org/10.1007/s10853-014-8112-8

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