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Calorimetric Analysis of the Multiple Melting Behavior of Poly(L-lactic acid) Maria Laura Di Lorenzo Istituto di Chimica e Tecnologia dei Polimeri (CNR), c/o Comprensorio Olivetti, Via Campi Flegrei 34, 80078 Pozzuoli (NA), Italy Received 17 June 2005; accepted 1 September 2005 DOI 10.1002/app.23136 Published online in Wiley InterScience (). ABSTRACT: This article contains a detailed calorimetric perfected during the heating scan), followed by recrystalli- analysis of the multiple melting behavior of poly(l-lactic zation and final melting of more perfect crystals, partly acid) (PLLA) in dependence of crystallization conditions. grown during primary crystallization, and partly formed PLLA crystals formed upon primary crystallization have a through the reorganization processes occurring during the greater tendency to reorganize into more stable structures heating scan. A detailed map of the melting behavior of during the heating scan that leads to fusion. Depending on PLLA is described in this contribution. © 2006 Wiley Periodi- crystallization temperature, one or multiple melting endo- cals, Inc. J Appl Polym Sci 100: 3145–3151, 2006 therms and/or reorganization exotherms can be evidenced. This complex melting behavior arises from the fusion of a certain amount of the original crystals (already partially Key words: fusion; poly(L-lactic acid); thermal analysis INTRODUCTION more recent analyses report the observation of addi- tional 001 reflections in the form of PLLA, suggest- The recent advances in polymerization technology al- ing some deviation from a “pure” 103 helix conforma- low the production of poly(l-lacti