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New approach to the double melting peak of poly(l-lactic acid) observed by DSC

  • Carlos A. Gracia-Fernández (a1), Silvia Gómez-Barreiro (a2), Jorge López-Beceiro (a3), Salvador Naya (a3) and Ramón Artiaga (a3)...


Poly(l-lactic acid) (PLLA) is one of the most studied biopolymers nowadays. Due to its good performance, it constitutes an alternative to petrochemical-derived polymers. It was largely studied by differential scanning calorimetry (DSC) and temperature-modulated DSC. Nevertheless, there is an ongoing debate of what happens at the overlapping melting processes. In the present work, the experimental setups are discussed. Different modulation conditions are proposed for the study of the glass transition, cold crystallization, and the two reported melting processes. Finally, the experimental results allowed to measure the heat capacity change at the cold crystallization and a correct interpretation of what happens at the reported double melting peak of PLLA, which involves the existence of three crystalline structures.


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1.Abe, H., Kikkawa, Y., Inoue, Y., and Doi, Y.: Morphological and kinetic analyses of regime transition for poly[(S)-lactide] crystal growth. Biomacromolecules 2, 1007 (2001).
2.Garlotta, D.: A literature review of poly(lactic acid). J. Polym. Environ. 9, 63 (2001).
3.Vainiopaa, S., Rokkanem, P., and Tormala, P.: Surgical applications of biodegradable polymers in human tissue. Prog. Polym. Sci. 14, 679 (1989).
4.Baratian, S., Hall, E.S., Lin, J.S., Xu, R., and Runt, J.: Crystallization and solid-state structure of random polylactide copolymers: Poly(l-lactide-co-d-lactide)s. Macromolecules 34, 4857 (2001).
5.Huang, J., Lisowski, M.S., Runt, J., Hall, E.S., Ken, R.T., Buehler, N., and Lin, J.S.: Crystallization and microstructure of poly(l-lactide-co-meso-lactide) copolymers. Macromolecules 31, 2593 (1998).
6.Loomis, G.L., Murdoch, J.R., and Gardner, K.H.: Polylactide stereocomplexes. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 31, 55 (1990).
7.Zuza, E., Ugartemendia, J.M., López, A., Meaurio, E., Lejardi, A., and Sarasua, J.R.: Glass transition behavior and dynamic fragility in polylactides containing mobile and rigid amorphous fractions. Polymer 49, 4427 (2008).
8.Pyda, M. and Wunderlich, B.: Reversing and nonreversing heat capacity of poly(lactic acid) in the glass transition region by TMDSC. Macromolecules 38, 10472 (2005).
9.Wunderlich, B.: Reversible crystallization and the rigid amorphous phase in semicrystalline macromolecules. Prog. Polym. Sci. 28, 383 (2003).
10.Yasuniwa, M., Tsubakihara, S., Ohoshita, K., and Tokudome, S.: X-ray studies on the double melting behavior of poly(butylene terephthalate). J. Polym. Sci. Pt. B-Polym. Phys. 39, 2005 (2001).
11.Yasuniwa, M., Tsubakihara, S., and Fujioka, T.: X-ray and DSC studies on the melt-recrystallization process of poly(butylene naphthalate). Thermochim. Acta 396, 75 (2003).
12.Yasuniwa, M. and Satou, T.: Multiple melting behavior of poly(butylene succinate). I. Thermal analysis of melt-crystallized samples. J. Polym. Sci., Part B: Polym. Phys. 40, 2411 (2002).
13.Qiu, Z., Komura, M., Ikehara, T., and Nishi, T.: DSC and TMDSC study of melting behaviour of poly(butylene succinate) and poly(ethylene succinate). Polymer 45, 7781 (2003).
14.Gunaratne, L.M.W.K., Shanks, R.A., and Amarasinghe, G.: Thermal history effects on crystallisation and melting of poly(3-hydroxybutyrate). Thermochim. Acta 423, 127 (2004).
15.Gunaratne, L.M.W.K. and Shanks, R.A.: Thermal memory of poly(3-hydroxybutyrate) using temperature-modulated differential scanning calorimetry. J. Polym. Sci., Part B: Polym. Phys. 44, 70 (2006).
16.Orozco, V.H., Brostow, W., Chonkaew, W., and López, B.L.: Preparation and characterization of poly(lactic acid)-g-maleic anhydride + starch blends. Macromol. Symp. 277, 69 (2009).
17.Cebe, P. and Hong, S.D.: Crystallization behaviour of poly(ether-ether-ketone). Polymer 27, 1183 (1986).
18.Bassett, D.C., Olley, R.H., and Raheil, I.A.M.: On crystallization phenomena in PEEK. Polymer 29, 1745 (1988).
19.Lee, Y., Porter, R.S., and Lin, J.S.: On the double-melting behavior of poly(ether ether ketone). Macromolecules 22, 1756 (1989).
20.Jonas, A.M., Russell, T.P., and Yoon, D.Y.: Synchrotron x-ray scattering studies of crystallization of poly(ether-ether-ketone) from the glass and structural changes during subsequent heating-cooling processes. Macromolecules 28, 8491 (1995).
21.Artiaga, R., Lopez-Beceiro, J., Tarrio-Saavedra, J., Gracia-Fernandez, C., Naya, S., and Mier, J.L.: Estimating the reversing and non-reversing heat flow from standard DSC curves in the glass transition region. J. Chemometr. 25, 287 (2011).
22.López-Beceiro, J., Gracia-Fernández, C., Gómez-Barreiro, S., Castro-García, S., Sánchez-Andújar, M., and Artiaga, R.: Kinetic study of the low temperature transformation of Co(HCOO)3[(CH3)2NH2]. J. Phys. Chem. C 116, 1219 (2012).
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Journal of Materials Research
  • ISSN: 0884-2914
  • EISSN: 2044-5326
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