Interphases and Mesophases in Polymer Crystallization III
In polymer crystallization the challenge is to identify and clarify the transformations by which chain molecules pass from a disordered, molten state to the ordered supra-molecular organization known as the semi-crystalline state. The subject is highly relevant in terms of both basic science and technology; it is indeed clear that many modern applications require complete control of the structure and the morphology of polymers from macroscopic dimensions down to below the nanoscale. As a simple example, making the crystallites in a polymer fiber equally oriented and reducing the number of chain folds (or hairpins) therein, usually turn out to be very favorable requisites for mechanical performance . .This series presents critical reviews of the present and future trends in polymer and biopolymer science including chemistry, physical chemistry, physics and material science. It is adressed to ali scientists at universities and in industry who wish to keep abreast of advances in the topics covered
Interphases and Mesophases in Polymer Crystallization II
Polymer crystallisation is a field of science whose widespread practica! and technological implications add to its scientific relevance. Unlike most molecular substances, synthetic polymers consist oflong, linear chains usually covering a broad distribution of molecular lengths. It is no surprise that only rarely may they give rise to regularly shaped crystals, if at all. As a rule, especially from the bulk state, polymers solidify as very tiny crystals interspersed in an amorphous matrix and randomly interconnected by disordered chains.This series presents critical reviews of the present and future trends in polymer and biopolymer science including chemistry, physical chemistry, physics and material science. It is adressed to ali scientists at universities and in industry who wish to keep abreast of advances in the topics covered
Interphases and Mesophases in Polymer Crystallization I
Polyethylene forms a two-dimensional hexagonal phase, stable at 3 GPa depending on molecular length, which in recent years has been claimed to intervene in crystallization prior to the formation of the usual orthorhombic phase even at atmospheric pressure. This claim is evaluated and shown to be without substance. There is very little evidence that the theoretical possibility of thin lamellae being more stable in the hexagonal phase than the orthorhombic at atmospheric pressure, if the former has sufficiently low fold surface free energy, does occur in practice. But the existence of single crystals of the orthorhombic phase unambiguously shows that they did not have a hexagonal precursor; that would have made them threefold twins. The overwhelming mass of evidence is that orthorhombic and hexagonal phases crystallize independently in accordance with the phase diagram and kinetic competition during growth, as has been understood since the hexagonal phase was discovered.


