Abstract
The thermal transitions and the nonisothermal cold crystallization kinetics of poly(ethylene terephthalate) (PET) at constant heating rates were investigated using differential scanning calorimetry. It was found that the glass transition and crystallization temperature increased with the heating rates, while the melting temperature showed a little variation for the heating rates used. Crystallization and melting latent heats were remarkably constant, independent of the heating rate. Kinetics parameters were determined using Ozawa model. Two different kinetic regimes were identified, corresponding to primary and secondary crystallization, at low and high fractional crystallization, respectively, both following Ozawa’s model. Kinetics parameters were determined for the primary and secondary regimes; the pre-exponential constant (KT) and Ozawa’s exponent (m) decreased with increasing crystallization temperature. The combined kinetic parameter Z = K1/mT increased exponentially with temperature; activation energies were estimated using Arrhenius plots for the two PET crystallization regimes.
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References
F. Van Antwerpen and D.W. Van Krevelen: Influence of crystallization temperature, molecular weight, and additives on the crystallization kinetics of poly(ethylene terephthalate). J. Polym. Sci., Part B: Polym. Phys. Ed. 10, 2423 (1972).
O. Verhoyen, F. Dupret, and R. Legras: Isothermal and non-isothermal crystallization kinetics of polyethylene terephthalate: Mathematical modeling and experimental measurement. Polym. Eng. Sci. 38, 1594 (1998).
D.S. Achilias, G.Z. Papageorgiou, and G.P. Karayannidis: Isothermal and nonisothermal crystallization kinetics of poly(propylene terephthalate). J. Polym. Sci., Part B: Polym. Phys. 42, 3775 (2004).
G.C. Alfonso: Crystallization in polymer blends. In Integration of Fundamental Polymer Science and Technology, Vol. 5, edited by P. J. Lemstra and L.A. Keintjen (Elsevier, Amsterdam and London, 1991), p. 143.
L. Mandelkern: Crystallization of Polymers (McGraw-Hill, New York, 1964).
T.Y. Chen, V.W. Wang, and M.J. Bozarth: Crystallization and its effect on the processing of polypropylene. J. Reinforc. Plast. Compos. 12, 686 (1993).
Y.P. Khanna, A.C. Reimschuessel, A. Banerjie, and C. Altman: Memory effects in polymers. II. Processing history vs crystallization rate of nylon 6—Observation of phenomenon and product behavior. Polym. Eng. Sci. 28, 1600 (1988).
A. Elmoumni, H.H. Winter, A.J. Waddon, and H. Fruitwala: Correlation of material and processing time scales with structure development in isotactic polypropylene crystallization. Macromolecules 36, 6453 (2003).
M.L. Addonizio, E. Martuscelli, and C. Silvestre: Study of the non-isothermal crystallization of poly(ethylene oxide)/poly(methyl methacrylate) blends. Polymer (Guildf.) 28, 183 (1987).
S.A. Jabarin: Crystallization kinetics of polyethylene terephthalate. II. Dynamic crystallization of PET. J. Appl. Polym. Sci. 34, 97 (1987).
D.M. Fann, S.K. Huang, and J.Y. Lee: Kinetics and thermal crystallinity of recycled PET. I. Dynamic cooling crystallization studies on blends recycled with engineering PET. J. Appl. Polym. Sci. 61, 1375 (1996).
X. Lu and J.N. Hay: The effect of phisycal aging on the rates of cold crystallization of poly(ethylene terephthalate). Polymer (Guildf.) 41, 7427 (2000).
P. Sajkiewicz, L. Carpaneto, and A. Wasiak: Application of the Ozawa model to non-isothermal crystallization of poly (ethylene terephthalate). Polymer (Guildf.) 42, 5365 (2001).
R.M.R. Wellen and M.S. Rabello: The kinetics of isothermal crystallization and tensile properties of poly(ethylene) terephthalate. J. Mater. Sci. 40, 6099 (2005).
B. Wunderlich: Thermal Analysis of Polymeric Materials (Springer, Berlin, 2005).
J.B. Menard: Thermal transitions and their measurement, in Performance of Plastics, edited by W. Brostow (Hanser, Munich, 2000).
P.D. Hong, W.T. Chung, and C.F. Hsu: Crystallization kinetics and morphology of poly(trimethylene terephthalate). Polymer (Guildf.) 43, 3335 (2002).
R.M.R. Wellen and M.S. Rabello: Non-isothermal cold crystallization kinetics and morphology of PET + SAN blends. J. Appl. Polym. Sci. 116, 1077 (2010).
H.E. Kissinger: Variation of the peak temperature with heating rate in differential thermal analysis. J. Res. Natl. Bur. Stand. 57, 217 (1956).
P. Cebe and S. Hong: Crystallization behaviour of poly(ether-ether-ketone). Polymer (Guildf.) 27, 1183 (1986).
N. Apiwanthanakorn, P. Supaphol, and M. Nithitanakul: Non-isothermal melt-crystallization kinetics of poly(trimethylene terephthalate). Polym. Test. 23, 817 (2004).
P. Cebe: Non-isothermal crystallization of poly(ether ether ketone)—Aromatic polymer composite. Polym. Comp. 9, 271 (1988).
N. Yoshihara, M. Shibaya, and H. Ishihara: Cold crystallization behaviors of poly(ethylene terephthalate). J. Polym. Eng. 25, 97 (2005).
L.W. Jang, K.H. Lee, D.C. Lee, J.S. Yoon, I. Chin, and H.J. Choi: Alternating copolymers as compatibilizer for blends of poly (ethylene terephthalate) and polystyrene. J. Appl. Polym. Sci. 78, 1998 (2000).
A. Metha, U. Gaur, and B. Wunderlich: Equilibrium melting parameters of poly(ethylene terephthalate). J. Polym. Sci., Part B: Polym. Phys. Ed. 16, 289 (1978).
Y. Kong and J.N. Hay: The measurement of the crystallinity of polymers by DSC. Polymer (Guildf.) 43, 3873 (2002).
D.W. van Krevelen: Properties of Polymers (Elsevier, Amsterdam, 1990).
N. Dangseeyun, P. Supaphol, and M. Nithitanakul: Thermal, crystallization, and rheological characteristics of poly(trimethylene terephthalate)/poly(butylene terephthalate) blends. Polym. Test. 23, 187 (2004).
T. Ozawa: Kinetics of non-isothermal crystallization. Polymer (Guildf.) 12, 150 (1971).
C.F. Ou and C.C. Lin: Blends of polyethylene terephthalate with co[poly(ethylene terephthalate-p-oxybenzoate)] I. Crystallization kinetics by DSC study. J. Appl. Polym. Sci. 54, 1223 (1994).
Y. Zhang and L. Gu: Study of non-isothermal crystallization kinetics and sequence distribuition in poly (ethylene terephthalate-co-isophthalate). Eur. Polym. J. 36, 759 (2000).
M. Run, C. Yao, and Y. Wang: Morphology, isothermal and non-isothermal crystallization kinetics of poly(methylene terephthalate). Eur. Polym. J. 42, 655 (2006).
T. Liu, Z. Mo, and H. Zhang: Nonisothermal crystallization behavior of a novel poly (aryl ether ketone): PEDEKmK. J. Appl. Polym. Sci. 67, 815 (1998).
C.A. Hieber: Correlations for the quiescent crystallization kinetics of isotactic polypropylene and poly(ethylene terephthalate). Polymer (Guildf.) 36, 1455 (1995).
P. Supaphol, N. Dangseeyun, P. Srimoaon, and M. Nithitanakul: Nonisothermal melt-crystallization kinetics for three linear aromatic polyesters. Thermochim. Acta 406, 207 (2003).
J. Yang, P. Pan, T. Dong, and Y. Inoue: Crystallization kinetics and crystalline structure of biodegradable poly(ethylene adipate). Polymer (Guildf.) 51, 807 (2010).
Acknowledgments
The authors thank Terphane (Brazil) for providing the polymer used in this work and gratefully acknowledge Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) and Fundação de Amparo à Ciência e Tecnologia do Estado de Pernambuco (FACEPE) (Brazil) for the financial support.
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Wellen, R.M.R., Canedo, E. & Rabello, M.S. Nonisothermal cold crystallization of poly(ethylene terephthalate). Journal of Materials Research 26, 1107–1115 (2011). https://doi.org/10.1557/jmr.2011.44
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DOI: https://doi.org/10.1557/jmr.2011.44