Polímeros: Ciência e Tecnologia
Polímeros: Ciência e Tecnologia
Scientific & Technical Article

Melting and crystallization of poly(3-hydroxybutyrate): effect of heating/cooling rates on phase transformation

Wellen, Renate M. R.; Rabello, Marcelo S.; Araujo Júnior, Inaldo Cesar; Fechine, Guilhermino J. M.; Canedo, Eduardo L.

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We studied the crystallization and melting phenomena of poly (3- hydroxybutyrate) (PHB), a biodegradable and biocompatible semi-crystalline thermoplastic, obtained from renewable resources. Its high crystallinity motivated several studies on crystallization and melting behavior, and also on ways to increase the amorphous polymer fraction. The effect of heating and cooling rates on the crystallization and melting of commercial PHB was investigated by differential scanning calorimetry. Several rates, ranging from 2.5 to 20 °C min–1, were used to study the phase changes during heating/cooling/reheating cycles. The results showed that PHB partially crystallizes from the melt during the cooling cycle and partially cold crystallizes on reheating, and that the relative amount of polymer crystallizing in each stage strongly depends on the cooling rate. The melt and cold crystallization temperatures, as well as the rates of phase change, depend strongly on the cooling and heating rates.


PHB, DSC, crystallization, melting, kinetics.


1. Bastioli, C. (2005). Handbook of biodegradable polymers. Shawbury: Rapra Technology.

2. Zini, E., & Scandola, M. (2011). Green composites: an overview. Polymer Composites, 32(12), 1905-1915. http://dx.doi.org/10.1002/pc.21224.

3. Reddy, M. M., Vivekanandhan, S., Misra, M., Bhatia, S. K., & Mohanty, A. K. (2013). Biobased plastics and bionanocomposites: current status and future opportunities. Progress in Polymer Science, 38(10-11), 1653-1689. http://dx.doi.org/10.1016/j.progpolymsci.2013.05.006.

4. Doi, Y. (1990). Microbial polyesters. New York: Wiley-VCH.

5. Hocking, P. J., & Marchessault, R. H. (1994). Biopolymers (PHA). In G. J. L. Griffin (Ed.), Chemistry and technology of biodegradable polymers (pp. 1-154). London: Chapman & Hall/Backie.

6. Hodzic, A. (2005). Bacterial polyester-based biocomposites: a review. In A. K. Mohanty, M. Misra & L. T. Drzal (Eds.), Natural fibers, biopolymers, and biocomposites (pp. 597-616). Boca Raton: Taylor & Francis/CRC Press.

7. Philip, S., Keshavarz, T., & Roy, I. (2007). Polyhydroxyalkanoates: biodegradable polymers with a range of applications Journal of Chemical Technology and Biotechnology, 82(3), 233-247. http://dx.doi.org/10.1002/jctb.1667.

8. Gogolewski, S., Jovanovic, M., Perren, S. M., Dillon, J. G., & Hughes, M. K. (1993). The effect of melt-processing on the degradation of selected polyhydroxyacids: polylactides, polyhydroxybutyrate, and polyhydroxybutyrate-co- valerates. Polymer Degradation & Stability, 40(3), 313-322. http://dx.doi.org/10.1016/0141-3910(93)90137-8.

9. Gunaratne, L. M. W. K., & Shanks, R. A. (2005). Multiple melting behaviour of poly(3-hydroxybutyrate-co-hydroxyvalerate) using step-scan DSC. European Polymer Journal, 41(12), 2980-2988. http://dx.doi.org/10.1016/j.eurpolymj.2005.06.015.

10. Reddy, C. S., Ghai, R., Rashmi, & Kalia, V. C. (2003). Polyhydroxyalkanoates: an overview. Bioresource Technology, 87(2), 137-146. http://dx.doi.org/10.1016/S0960-8524(02)00212-2. PMid:12765352.

11. Renstad, R., Karlsson, S., Albertsson, A. C., Werner, P. E., & Westdahl, M. (1997). Influence of processing parameters on the mass crystallinity of poly(3-hydroxybutyrate- co-3-hydroxyvalerate). Polymer International, 43(3), 201-209. http://dx.doi.org/10.1002/(SICI)1097-0126(199707)43:3<201::AID-PI761>3.0.CO;2-7.

12. Yoshie, N., Fujiwara, M., Ohmori, M., & Inoue, Y. (2001). Temperature dependence of cocrystallization and phase segregation in blends of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate). Polymer, 42(21), 8557-8563. http://dx.doi.org/10.1016/S0032-3861(01)00408-6.

13. Ziaee, Z., & Supaphol, P. (2006). Non-isothermal melt- and cold-crystallization kinetics of poly(3-hydroxybutyrate). Polymer Testing, 25(6), 807-818. http://dx.doi.org/10.1016/j.polymertesting.2006.04.009.

14. Abdelwahab, M. A., Flynn, A., Chiou, B., Imam, S., Orts, W., & Chiellini, E. (2012). Thermal, mechanical and morphological characterization of plasticized PLA–PHB blends. Polymer Degradation & Stability, 97(9), 1822-1828. http://dx.doi.org/10.1016/j.polymdegradstab.2012.05.036.

15. Canetti, M., Urso, M., & Sadocco, P. (1999). Influence of the morphology and of the supermolecular structure on the enzymatic degradation of bacterial poly(3-hydroxybutyrate). Polymer, 40(10), 2587-2594. http://dx.doi.org/10.1016/S0032-3861(98)00503-5.

16. El-Hadi, A., Schnabel, R., Straube, E., Müller, G., & Riemschneider, M. (2002). Effect of melt processing on crystallization behavior and rheology of poly(3-hydroxybutyrate) (PHB) and its blends. Macromolecular Materials and Engineering, 287(5), 363-372. http://dx.doi.org/10.1002/1439-2054(20020501)287:5<363::AID-MAME363>3.0.CO;2-D.

17. Wagner, M. (2010). Thermal analysis in practice. Schwerzenbach: Mettler-Toledo.

18. Barham, P. J., Keller, A., Otun, E. L., & Holmes, P. A. (1984). Crystallization and morphology of a bacterial thermoplastic: poly-3-hydroxybutyrate. Journal of Materials Science, 19(9), 2781-2794. http://dx.doi.org/10.1007/BF01026954.

19. Höhne, G. W. H., Hemminger, W. F., & Flammersheim, H. J. (2010). Differential scanning calorimetry (2nd ed.). Berlin: Springer.

20. Wellen, R. M. R., & Rabello, M. S. (2005). The kinetics of isothermal crystallization and tensile properties of poly(ethylene) terephthalate. Journal of Materials Science, 40(23), 6099-6104. http://dx.doi.org/10.1007/s10853-005-3173-3.

21. Ziaee, Z., & Supaphol, P. (2006). Non-isothermal melt- and cold-crystallization kinetics of poly(3- hydroxybutyrate). Polymer Testing, 25(6), 807-818. http://dx.doi.org/10.1016/j.polymertesting.2006.04.009.

22. Wellen, R. M. R., & Rabello, M. S. (2009). Antinucleating action of polyestyrene on the isothrermal cold crystallization of poly(ethylene terephthalate). Journal of Applied Polymer Science, 114(3), 1884-1895. http://dx.doi.org/10.1002/app.29569.

23. Shafee, E. E., & Ueda, W. (2002). Crystallization and melting behavior of poly(ethylene oxide)/poly(n-butyl methacrylate) blends. European Polymer Journal, 38(7), 1327-1335. http://dx.doi.org/10.1016/S0014-3057(02)00018-6.

24. An, Y., Dong, L., Mo, Z., Liu, T., & Feng, Z. (1998). Nonisothermal crystallization kinetics of poly(β-hydroxybutyrate). Journal of Polymer Science: Part B, Polymer Physics, 36(8), 1305-1312. http://dx.doi.org/10.1002/(SICI)1099-0488(199806)36:8<1305::AID-POLB5>3.0.CO;2-Q.

25. Wellen, R. M. R., & Rabello, M. S. (2007). Redução da velocidade de cristalização a frio do PET na presença de poliestireno. Polímeros: Ciência e Tecnologia, 17(2), 113-122. http://dx.doi.org/10.1590/S0104-14282007000200010.

26. Wellen, R. M. R., Canedo, E. L., & Rabello, M. S. (2011). Nonisothermal cold crystallization of poly(ethylene terephthalate). Journal of Materials Research, 26(9), 1107-1115. http://dx.doi.org/10.1557/jmr.2011.44.

27. Blundell, D. J., Liggat, J. J., & Flory, A. (1992). The crystal lamellar morphology of an aromatic polyketone with unusual crystallization and melting behavior. Polymer, 33(12), 2475-2482. http://dx.doi.org/10.1016/0032-3861(92)91127-N.

28. Blundell, D. J., & Osborn, B. N. (1983). The morphology of poly(aryl-ether-ether-ketone). Polymer, 24(8), 953-958. http://dx.doi.org/10.1016/0032-3861(83)90144-1.

29. Varma, P., Lofgren, E. A., & Jabarin, S. A. (1998). Properties and kinetics of thermally crystallized oriented poly(ethylene terephthalate) (PET). II. Physical and optical properties. Polymer Engineering and Science, 38(2), 245-253. http://dx.doi.org/10.1002/pen.10185.

30. Gunaratne, L. M. W. K., & Shanks, R. A. (2005). Melting and thermal history of poly(hydroxybutyrate-co- hydroxyvalerate) using step-scan DSC. Thermochimica Acta, 430(1-2), 183-190. http://dx.doi.org/10.1016/j.tca.2005.01.060.

31. Harding, K. G., Dennis, J. S., von Blottnitz, H., & Harrison, S. T. (2007). Environmental analysis of plastic production processes: comparing petroleum-based polypropylene and polyethylene with biologically-based poly-beta-hydroxybutyric acid using life cycle analysis. Journal of Biotechnology, 130(1), 57-66. http://dx.doi.org/10.1016/j.jbiotec.2007.02.012. PMid:17400318.

32. Papageorgiou, G. Z., & Karayannidis, G. (1999). Multiple melting behaviour of poly(ethylene-co-butylene naphthalate-2,6-dicarboxylate)s. Polymer, 40(19), 5325-5332. http://dx.doi.org/10.1016/S0032-3861(98)00746-0.

33. Renstad, R., Karlsson, S., Albertsson, A. C., Werner, P. E., & Westdahl, M. (1997). Influence of processing parameters on the mass crystallinity of poly(3-hydroxybutyrate- co-3-hydroxyvalerate). Polymer International, 43(3), 201-209. http://dx.doi.org/10.1002/(SICI)1097-0126(199707)43:3<201::AID-PI761>3.0.CO;2-7.

34. Menczel, J. D., & Prime, R. B. (2009). Thermal analysis of polymers. New York: Wiley.
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