The thermomechanical properties of poly(lactide) (PLA) are strongly related to its semicrystalline microstructure and morphology. Thermal annealing is a strategy to improve the crystallinity of PLA. However, the different techniques and specimen types needed for each kind of characterization could lead to misleading conclusions. In this work, annealed samples of three PLA grades with different molecular weights were studied by DSC, wide angle X‐ray scattering and polarized optical microscopy (POM) and the results are related to their thermomechanical and impact properties. Special focus is put on the POM results obtained by different approaches and the suitability of each of them to be related to the thermomechanical properties. By annealing medium molecular weight PLA specimens at 140 °C an important increase of the heat distortion temperature was obtained, which was not related to the spherulite size but to the combination of high crystallinity degree together with high α/α′ crystal type ratio. However, the impact properties of annealed PLA decreased with increase in the annealing temperature according to an increment in crystallinity and in the α/α′ crystal ratio. © 2019 Society of Chemical Industry

The influence of temperature on the formation of high molecular weight poly(lactic acid) (PLA) stereocomplex was studied by evaluation of the precipitates from dioxane solutions of PLA enantiomers (PLLA and PDLA). The racemic mixtures were characterized by Gel Permeation Chromatography, Infrared Spectroscopy, Differential Scanning Calorimetry, Scanning Electronic Microscopy, Wide-Angle X-ray Scattering and Vicat Softening Temperature. Precipitation was carried out under different solution temperatures, keeping constant the mixing ratio (X D), the molecular weight, the optical purity of both PLA enantiomers and the stirring rate. It was found that the precipitates contained only pure stereocomplex crystallites (racemic crystallites), without observing crystal phase separation between both homocrystals. The kinetics of the insoluble phase formation could be adjusted with the Avrami model, classically used for polymer crystallization in molten state. It was observed that the maximum PLA stereocomplex production rate was at about 40°C. However, more thermally stable racemic crystallites were formed at high solution temperatures. It was found that all the precipitates were sphere-like at 10 g•dl-1 at the solution temperature of 25, 40, 60 and 80°C.