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.

Structure and morphology of cellulose fibers in garlic skin.

The knowledge of the texture and morphology of cellulose is essential for reliable modelling of cell growth and mechanical resistance of vegetal systems. Microscopic observations on thin layers of the skin of Allium sativum have shown elongated structures (i.e. cellulose fibers) imbedded in a matrix of more or less rounded cells. Examination by an optical polarizing microscope (OPM) has shown an intermittent high and low birefringence along fibers. Transversal regions with a reduced brightness along fibers are expected to contain a higher amount of amorphous lignin, hemicelluloses and waxes, some of which might also be birefringent, but at a much lower degree than cellulose. Scanning electron microscopy (SEM) has also evidenced an alternating growth of the fibers. Moreover, the negative sign of birefringence suggests a parallel orientation of cellulose nanofibrils transversally to the fiber axis. The characteristic modulation of intensity along lignocellulosic fibers can be due to variation of the cellulose concentration or orientation, perhaps caused by circadian cycles of temperature and light during growth. Indeed, imperfect orthogonal light can be totally reflected at the interface between regions with different values of the refractive index, contributing to the optical effect of banding.

An optical test to unveil twisting of birefringent crystals in spherulites.

Helical conformations and structures are frequently observed in materials. The presence of helices at points of the unit cell of a crystal, on a larger size scale in the crystalline lattice or even in the microscopic structure of crystals, affects the chemico-physical properties of a solid and, hence, also interactions with light. Here, attention has been drawn to the geometrical properties of helices produced by a hypothetical torque of a transparent crystal, and optical properties of twisted crystals easily observed by a polarizing microscope have been discussed. Radially grown spherulites are obtained by most substances crystallized from melt. The circular arrangement of elongated crystals reflects the optical behaviour of each crystal and, because of the larger dimensions of spherulites, allows investigations otherwise hardly feasible on separate crystals. According to the torsional analysis of elongated bodies and the birefringence theory, information on the existence of helically shaped crystals can be deduced, as hereinafter explained, from the microscopic appearance and birefringence pattern of spherulites. Indeed, twisting decreases the birefringence throughout an elongated crystal and, therefore, also the birefringence of spherulites formed by twisted radial crystals is reduced.