The non-steady state technique of laser flash analysis (LFA) was used to record the variation of thermal diffusivity with time during the cold-crystallisation of poly(lactic acid), a grade containing 4% D stereoisomer content. The measured diffusivity data was analysed in terms of the Avrami and Hoffman-Lauritzen models for polymer crystallization. Within the temperature range 88 to 109C, mechanistic 'n' values of 2.0±0.1 were calculated and a nucleation constant of 6.58 x 10-5 K 2 was determined; the LFA technique yielded kinetic data that was comparable to that which originated from DSC. Measurements of thermal diffusivity were also recorded over a longer timescale to determine whether thermal diffusivity was a useful indicator of secondary crystallization and this data was analysed using a modified Avrami equation that includes a root-time dependence of the secondary process. Secondary crystallisation rate constants (k s) increased with crystallisation temperature and yielded an activation energy for the secondary crystallisation process of 40 kJ/mol.

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