Isothermal Melt Crystallization Kinetic Behavior of Poly (vinylidene fluoride)

Document Type : Research Paper


1 Iran Polymer and Petrochemical Institute, Tehran, Iran

2 Department of life science engineering, Faculty of new sciences and technologies, University of Tehran, Tehran, Iran


Isothermal melt crystallization kinetics of PVDF was investigated by differential scanning calorimetry. Thin PVDF film has been fabricated by the solvent casting technique using dimethylformamide (DMF). Then, the samples were melted and subsequently crystallized in the range of the crystallization temperature (Tc) between 138 and 145 °C. The crystallization kinetics was derived from Avrami equation. Avrami parameter (n) was found in a range from 1.5 to 2.4 and the values of the crystallization rate parameters (k) increased with decreasing Tc. So the crystallization rate parameters suggested that PVDF crystallize slower with increasing of Tc. The Hoffman–Weeks equation has used to approximate the equilibrium melting point of PVDF which was concluded to be 182 °C. Likewise, the activation energy was estimated to be 103.2 kJ/mol for isothermal crystallization. In this research, Lauritzen- Hoffmann theory was employed to analyze crystallization kinetics. Accordingly, regime "I" found appropriate to describe the present case of PVDF crystallization.


[1] Song, J., Lu, C., Xu, D., Ni, Y., Liu, Y., Xu, Z. and Liu, J. (2010). "The effect of lanthanum oxide (La2O3) on the structure and crystallization of poly (vinylidene fluoride). " Polym. Int., Vol. 59, pp. 954-960.
[2] Silva, M.P., Sencadas, V., Botelho, G., Machado, A.V., Rolo, A.G., Rocha, J.G. and Lanceros-Méndez, S. (2010). "[alpha]- and [gamma]-PVDF: crystallization kinetics, microstructural variations and thermal behaviour." Chem. Phys., Vol. 122, pp. 87-92.
[3] Ma, W., Wang, X. and Zhang, J. (2011). "Heat capacities and thermodynamic properties of MgNDCJ." Therm. Anal. Calorim., Vol. 103, pp. 365-372.
[4] Buonomenna, M.G., Macchi, P., Davoli, M. and Drioli, E. (2007). "Poly(vinylidene fluoride) membranes by phase inversion: the role the casting and coagulation conditions play in their morphology, crystalline structure and properties." Euro. Polym. J., Vol. 43, pp. 1557-1572.
[5] Mano, J.F., Sencadas, V., Costa, C.M. and Lanceros-Méndez, S. (2004). "Relaxation dynamics of poly(vinylidene fluoride) studied by dynamical mechanical measurements and dielectric spectroscopy."
Mater. Sci. Eng.: A., Vol. 370, pp. 336-370.
[6] Nasir, M., Matsumoto, H., Minagava, M., Tanioka, A., Danno, T. and Horibe, H. (2007). "Preparation of porous PVDF nanofiber from PVDF/PVP blend by electrospray deposition." Polym. J., Vol. 39, pp. 1060-1064.
[7] Mano, J.F., Sencadas, V., Mello Costa, A. and Lanceros-Méndez, S. (2004). "Dynamic mechanical analysis and creep behaviour of β-PVDF films." Mat. Sci. and Eng.: A, Vol. 370, Vol. 1–2, pp. 336–340.
[8] Sencadas, V., Costa, C.M., Go´mez Ribelles, J.L. and Lanceros Mendez, S. (2010). "Effect of poling on the mechanical properties of β-poly(Vinylidene Fluoride)." J. Mater. Sci., Vol. 45, pp. 1328-1335.
[9] Sencadas, V., Lanceros-Mendez, S. and Mano, J.F. (2004). "Influence of ferrite nanoparticle type and content on the crystallization kinetics and electroactive phase nucleation of poly(vinylidene fluoride)." Thermochim. Acta., Vol. 424, pp. 201-202.
[10] Schultz, J.M. (2001). Polymer Crystallization. ACS and Oxford University Press, New York.
[11] Cheng, S.Z.D. and Jin, S. (2002). In Handbook of Thermal Analysis and Calorimetry. Elsevier Amsterdam.
[12] cations_Briefs/TA222.
[13] Miyazaki, T. and Takeda, Y. (2014). "Role of the KBr surfaces in crystallization of poly (vinylidene fluoride) films with a KBr powder as a nucleating agent." Eur. Polym. J., Vol. 61, pp. 1-12.
[14] Kang, J., Chen, Zh., Chen, J., Yang, F., Weng, G., Cao, Y. and Xiang, M. (2015). "Crystallization and melting behaviors of the β-nucleated isotactic polypropylene with different melt structures – The role of
molecular weight." Thermochim. Acta., Vol. 599, pp. 42- 51.
[15] He, D., Wang, Y., Shao, Ch., Zheng, G., Li, Q. and Shen, Ch. (2013). "Effect of phthalimide as an efficient nucleating agent on the crystallization kinetics of poly(lactic acid)." Polym. Test., Vol. 32, pp. 1088–1093.
[16] Ke, K., Wang, Y., Yang, W., Xie, B.H. and Yang, M.B. (2012). "Crystallization and reinforcement of poly (vinylidene fluoride) nanocomposites: Role of high molecular weight resin and carbon nanotubes." Polym. Test., Vol. 31, pp. 117–126.
[17] Yu, W., Zhao, Z., Zheng, W., Long, B., Jiang, Q., Li, G. and Ji, X. (2009). "Crystallization behavior of poly(vinylidene fluoride)/montmorillonite nanocomposite." Polym. Eng. and Sci., Vol. 49, pp. 491-498.
[18] Qiu, Z., Yan, C., Lu, J. and Yang, W. (2007). "Miscible Crystalline/Crystalline Polymer Blends of Poly(vinylidene fluoride) and Poly(butylene succinate-co-butylene adipate):Spherulitic morphologies and crystallization kinetics. " Macromolecules, Vol. 40, pp. 5047-5053.
[19] Chiu, H.J. (2002). "Spherulitic morphology and crystallization kinetics of poly(vinylidene fluoride)/poly(vinyl acetate) blends. " J. Polym. Res., Vol. 9, pp. 169-174.
[20] Fan, W. and Zheng, S. (2007). "Miscibility and crystallization behavior in blends of poly(methyl methacrylate) and poly(vinylidene fluoride): Effect of star-like topology of poly(methyl methacrylate)
chain." J. Polym. Sci. Part B., Vol. 45, pp. 2580-2593.
[21] Liu, J., Qiu, Z. and Jungnickel, B.J. (2005). "Crystallization and morphology of poly(vinylidene fluoride)/poly(3-hydroxybutyrate) blends. III. Crystallization and phase diagram by differential scanning
calorimetry." J. Polym. Sci. B: Polym. Phys., Vol. 43, pp. 287-295.
[22] Asai, K., Okamoto, M. and Tashiro, K. (2008). "Crystallization behavior of nano-composite based on poly(vinylidene fluoride)and organically modified layered titanate." Polymer., Vol. 49, pp. 4298-4306.
[23] Avrami, M. (1939). "Kinetics of phase change, general theory." J. Chem. Phys., Vol. 7, pp. 1103-1112.
[24] Zhang, Q., Zhang, H., Zhang, Z., Zhang, H. and Mo, Z. (2002). "Isothermal and nonisothermal crystallization kinetics of nylon-46." J. Polym. Sci. Part. B: Polym. Phys., Vol. 40, pp. 1784-1793.
[25] Hoffman, J.D. and Weeks, J.J. (1962). "Rate of spherulitiz crystallization with chain folded Polytrifluoroethene." J. Chem. Phys., Vol. 37, pp. 1723-1741.
[26] Lauritzen, J.I. and Hoffman, J.D. (1973). "Extension of theory of growth of chain‐folded polymer crystals to large undercoolings." J. Appl. Phys., Vol. 44, pp. 4340-4352.
[27] Williams, M.L., Landel, R.F. and Ferry, J.D. (1955). "The temperature dependence of relaxation mechanisms in amorphous polymers and other glass-forming liquids." J. Am. Chem. Soc., Vol. 77, pp. 3701-
[28] Hoffman, J.D, Davis, G.T. and Lauritzen, J.I. (1976). "The rate of crystallization of linear polymers with chain folding." New York: Treatise on Solid State Chemistry, Plenum, Vol. 44, pp. 497-617.
[29] Pethrick, R. A. (2007). Polymer Structure Characterization: From Nano to Macro Organization. Chapter 6, Royal Society of Chemistry (RSC) Pub. Co. UK.
[30] Cebe, P. and Hong, S.D. (1986). "Effect of thermal history on mechanical properties of polyether ether ketone below glass transition temperature." Polymer., Vol. 27, pp. 1183-1192.