Impact of Thermal Properties on Crystalline Structure, Polymorphism and Morphology of Polymer Matrices in Composites

Morphological analysis at different levels is fundamental to understand properties of materials, as these latter are dictated not only by the chemical composition but also by the shape. Solid structures arise from a balance between thermodynamic and kinetic factors, which, especially for polymer composites, depend also on interactions amongst components. In particular, morphology is strongly affected by the heat transfer pattern during crystallization and by the difference in thermal behavior between polymer matrix and filler. Polymers show a spherulitic structure, arising from the start of crystallization in several points of the liquid phase. Within a general rounded shape, spherulites show variability in growth patterns, morphology, and geometry of boundaries. The appearance and the number of spherulites, as well as their growth mechanism, may vary not only in dependence of the chemical composition and the crystalline structures but also, for a same polymer, in consequence of experimental conditions and incorporation of fillers. This article reviews the crystallization process of polymer matrices in the framework of crystal growth and heat transport theories, and explains microstructural differences between composites and neat matrices on the basis of the differences in thermal capacity and conductivity between polymers and additives.