Abstract
Non-isothermal crystallization behavior of poly(vinylidene fluoride) (PVDF) and ethylene–vinyl acetate (EVA) copolymer and their binary blends with different blending ratios were investigated by the use of differential scanning calorimetry (DSC). With the increasing cooling rates, PVDF, EVA and their binary blends showed wide crystallization temperature range and high crystalline enthalpy. Jeziorny and Mo’s models were applied to calculate non-isothermal crystallization kinetics parameters of neat PVDF, EVA and their binary blends. By Jeziorny method, the crystallization process of neat PVDF, EVA and PVDF/EVA = 7/3 blend can be divided into two parts: primary and secondary crystallization processes. The Avrami exponent n 1 indicated that the primary crystallization process was a mixture model of three-dimensional and two-dimensional space extensions. In comparison, PVDF/EVA = 5/5 and PVDF/EVA = 3/7 blends showed a single crystallization process. Through Mo’s analysis, faster cooling rate was demanded to reach higher relative crystallinity. Crystallization rate coefficient (CRC) was used to describe the effect of crystallization rates on the interaction between PVDF and EVA. CRC reached a maximum value when the mass ratio of PVDF and EVA was 7/3. The maximum CRC values of PVDF system and EVA system were 98.1 and 179.9 h−1, respectively. The activation energy was closely related to the extent of conversion and the neat samples had a maximum value of crystallization activation energy. This was consistent with the observation for the parameters from Jeziorny analysis and could be correlated to the heterogeneous nucleation.
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References
Jian K, Pintauro PN (1997) Asymmetric PVDF hollow-fiber membranes for organic/water pervaporation separations. J Membrane Sci 135:41–53
Yang X, Wang R, Shi L, Fane AG, Debowski M (2011) Performance improvement of PVDF hollow fiber-based membrane distillation process. J Membrane Sci 369:437–447
Bonyadi S, Chung TS (2007) Flux enhancement in membrane distillation by fabrication of dual layer hydrophilic–hydrophobic hollow fiber membranes. J Membrane Sci 306:134–146
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
Nunes SP, Peinemann KV (1992) Ultrafiltration membranes from PVDF/PMMA blends. J Membrane Sci 73:25–35
Yousefi AA (2011) Influence of polymer blending on crystalline structure of polyvinylidene fluoride. Iran Polym J 20:109–121
Cheng J, Wang S, Chen S, Zhang J, Wang X (2012) Crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate)/poly(vinyl pyrrolidone) ternary blends. Polym Int 61:477–484
Chen N, Hong L (2002) Surface phase morphology and composition of the casting films of PVDF-PVP blend. Polymer 43:1429–1436
Ma WZ, Zhang J, Chen SJ, Wang XL (2008) Crystallization behavior and hydrophilicity of poly (vinylidene fluoride) (PVDF)/poly (styrene-co-acrylonitrile) (SAN) blends. Colloid Polym Sci 286:1193–1202
Ma W, Wang X, Zhang J (2011) Crystallization kinetics of poly(vinylidene fluoride)/MMT, SiO2, CaCO3, or PTFE nanocomposite by differential scanning calorimeter. J Therm Anal Calorim 103:319–327
Song J, Lu C, Xu D, Ni Y, Liu Y, Xu Z, Liu J (2010) The effect of lanthanum oxide (La2O3) on the structure and crystallization of poly(vinylidene fluoride). Polym Int 59:954–960
Yu W, Zhao Z, Zheng W, Long B, Jiang Q, Li G, Ji X (2009) Crystallization behavior of poly(vinylidene fluoride)/montmorillonite nanocomposite. Polym Eng Sci 49:491–498
Sung YT, Kum CK, Lee HS, Kim JS, Yoon HG, Kim WN (2005) Effects of crystallinity and crosslinking on the thermal and rheological properties of ethylene vinyl acetate copolymer. Polymer 46:11844–11848
Shi XM, Zhang J, Jin J, Chen SJ (2008) Non-isothermal crystallization and melting of ethylene-vinyl acetate copolymers with different vinyl acetate contents. Express Polym Lett 2:623–629
Bianchi O, Oliveira RVB, Fiorio R, Martins JDN, Zattera AJ, Canto LB (2008) Assessment of Avrami, Ozawa and Avrami–Ozawa equations for determination of EVA crosslinking kinetics from DSC measurements. Polym Test 27:722–729
Bianchi O, Martins JDN, Fiorio R, Oliveira RVB, Canto LB (2011) Changes in activation energy and kinetic mechanism during EVA crosslinking. Polym Test 30:616–624
Avrami M (1939) Kinetics of phase change. I General theory. J Chem Phys 7:1103–1112
Avrami M (1940) Kinetics of phase change. II Transformation-time relations for random distribution of nuclei. J Chem Phys 8:212–224
Avrami M (1941) Granulation, phase change, and microstructure kinetics of phase change. III. J Chem Phys 9:177–184
Jeziorny A (1978) Parameters characterizing the kinetics of the non-isothermal crystallization of poly(ethylene terephthalate) determined by d.s.c. Polymer 19:1142–1144
Lang MH, Zhang J (2013) Morphology and properties of poly(vinylidene fluoride) (PVDF)/ethylene–vinyl acetate copolymer (EVA) blends. Plast, Rubber Compos. doi:10.1179/1743289813Y.0000000055
Somrang N, Nithitanakul M, Grady BP, Supaphol P (2004) Non-isothermal melt crystallization kinetics for ethylene–acrylic acid copolymers and ethylene–methyl acrylate–acrylic acid terpolymers. Eur Polym J 40:829–838
Ji GL, Zhu BK, Zhang CF, Xu YY (2008) Nonisothermal crystallization kinetics of poly(vinylidene fluoride) in a poly(vinylidene fluoride)/dibutyl phthalate/di(2-ethylhexyl)phthalate system via thermally induced phase separation. J Appl Polym Sci 107:2109–2117
Mya KY, Pramoda KP, He CB (2006) Crystallization behavior of star-shaped poly(ethylene oxide) with cubic silsesquioxane (CSSQ) core. Polymer 47:5035–5043
Joshi M, Butola BS (2004) Studies on nonisothermal crystallization of HDPE/POSS nanocomposites. Polymer 45:4953–4968
Liu T, Mo Z, Wang S, Zhang H (1997) Nonisothermal melt and cold crystallization kinetics of poly(aryl ether ether ketone ketone). Polym Eng Sci 37:568–575
Ozawa T (1971) Kinetics of non-isothermal crystallization. Polymer 12:150–158
Khanna YP (1990) A barometer of crystallization rates of polymeric materials. Polym Eng Sci 30:1615–1619
Di Lorenzo ML, Silvestre C (1999) Non-isothermal crystallization of polymers. Prog Polym Sci 24:917–950
Kissinger HE (1957) Reaction kinetics in differential thermal analysis. Anal Chem 29:1702–1706
Vyazovkin S (2002) Is the kissinger equation applicable to the processes that occur on cooling? Macromol Rapid Comm 23:771–775
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This research was supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).
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Lang, M., Zhang, J. Non-isothermal crystallization behavior of poly(vinylidene fluoride)/ethylene–vinyl acetate copolymer blends. Iran Polym J 22, 821–831 (2013). https://doi.org/10.1007/s13726-013-0181-z
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DOI: https://doi.org/10.1007/s13726-013-0181-z