Nonisothermal cold crystallization of poly(ethylene terephthalate)

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

  1. 1.

    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).

    Google Scholar 

  2. 2.

    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).

    CAS  Article  Google Scholar 

  3. 3.

    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).

    CAS  Article  Google Scholar 

  4. 4.

    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.

    Article  Google Scholar 

  5. 5.

    L. Mandelkern: Crystallization of Polymers (McGraw-Hill, New York, 1964).

    Google Scholar 

  6. 6.

    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).

    Article  Google Scholar 

  7. 7.

    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).

    CAS  Article  Google Scholar 

  8. 8.

    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).

    CAS  Article  Google Scholar 

  9. 9.

    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).

    CAS  Article  Google Scholar 

  10. 10.

    S.A. Jabarin: Crystallization kinetics of polyethylene terephthalate. II. Dynamic crystallization of PET. J. Appl. Polym. Sci. 34, 97 (1987).

    CAS  Article  Google Scholar 

  11. 11.

    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).

    CAS  Article  Google Scholar 

  12. 12.

    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).

    CAS  Article  Google Scholar 

  13. 13.

    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).

    CAS  Article  Google Scholar 

  14. 14.

    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).

    CAS  Article  Google Scholar 

  15. 15.

    B. Wunderlich: Thermal Analysis of Polymeric Materials (Springer, Berlin, 2005).

    Google Scholar 

  16. 16.

    J.B. Menard: Thermal transitions and their measurement, in Performance of Plastics, edited by W. Brostow (Hanser, Munich, 2000).

    Google Scholar 

  17. 17.

    P.D. Hong, W.T. Chung, and C.F. Hsu: Crystallization kinetics and morphology of poly(trimethylene terephthalate). Polymer (Guildf.) 43, 3335 (2002).

    CAS  Article  Google Scholar 

  18. 18.

    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).

    CAS  Google Scholar 

  19. 19.

    H.E. Kissinger: Variation of the peak temperature with heating rate in differential thermal analysis. J. Res. Natl. Bur. Stand. 57, 217 (1956).

    CAS  Article  Google Scholar 

  20. 20.

    P. Cebe and S. Hong: Crystallization behaviour of poly(ether-ether-ketone). Polymer (Guildf.) 27, 1183 (1986).

    CAS  Article  Google Scholar 

  21. 21.

    N. Apiwanthanakorn, P. Supaphol, and M. Nithitanakul: Non-isothermal melt-crystallization kinetics of poly(trimethylene terephthalate). Polym. Test. 23, 817 (2004).

    CAS  Article  Google Scholar 

  22. 22.

    P. Cebe: Non-isothermal crystallization of poly(ether ether ketone)—Aromatic polymer composite. Polym. Comp. 9, 271 (1988).

    CAS  Article  Google Scholar 

  23. 23.

    N. Yoshihara, M. Shibaya, and H. Ishihara: Cold crystallization behaviors of poly(ethylene terephthalate). J. Polym. Eng. 25, 97 (2005).

    CAS  Article  Google Scholar 

  24. 24.

    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).

    CAS  Article  Google Scholar 

  25. 25.

    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).

    Google Scholar 

  26. 26.

    Y. Kong and J.N. Hay: The measurement of the crystallinity of polymers by DSC. Polymer (Guildf.) 43, 3873 (2002).

    CAS  Article  Google Scholar 

  27. 27.

    D.W. van Krevelen: Properties of Polymers (Elsevier, Amsterdam, 1990).

    Google Scholar 

  28. 28.

    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).

    CAS  Article  Google Scholar 

  29. 29.

    T. Ozawa: Kinetics of non-isothermal crystallization. Polymer (Guildf.) 12, 150 (1971).

    CAS  Article  Google Scholar 

  30. 30.

    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).

    CAS  Article  Google Scholar 

  31. 31.

    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).

    CAS  Article  Google Scholar 

  32. 32.

    M. Run, C. Yao, and Y. Wang: Morphology, isothermal and non-isothermal crystallization kinetics of poly(methylene terephthalate). Eur. Polym. J. 42, 655 (2006).

    CAS  Article  Google Scholar 

  33. 33.

    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).

    CAS  Article  Google Scholar 

  34. 34.

    C.A. Hieber: Correlations for the quiescent crystallization kinetics of isotactic polypropylene and poly(ethylene terephthalate). Polymer (Guildf.) 36, 1455 (1995).

    CAS  Article  Google Scholar 

  35. 35.

    P. Supaphol, N. Dangseeyun, P. Srimoaon, and M. Nithitanakul: Nonisothermal melt-crystallization kinetics for three linear aromatic polyesters. Thermochim. Acta 406, 207 (2003).

    CAS  Article  Google Scholar 

  36. 36.

    J. Yang, P. Pan, T. Dong, and Y. Inoue: Crystallization kinetics and crystalline structure of biodegradable poly(ethylene adipate). Polymer (Guildf.) 51, 807 (2010).

    CAS  Article  Google Scholar 

Download references

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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Correspondence to Renate M. R. Wellen.

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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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