Topomorphic states and phase transitions connected with the crystallization of polymers

The crystallization of flexible‐chain molecules of different degrees of coiling is considered. The nature of the phase transition during crystallization is discussed. The revision of established notions on phase transitions in polymers leads to the concept of crystalline topomorphism, i.e., the existence of two crystalline types with different modes of packing of macromolecules in the macroscopic crystal though they belong to the same lattice class: folded‐chain crystal (FCC) and extended‐chain crystal (ECC). Phase diagrams in coordinates of degree of coiling vs temperature are plotted. The values of molecular orientation and temperatures at which each of both mechanisms of crystallization takes place are evaluated. The mechanisms of ECC growth under equilibrium conditions and under conditions of molecular orientation are discussed. It is shown that the melting of ECC obtained by the process of orientational crystallization is a second order phase transition, being analogous to a crystal‐nematic phase transition. At the same time the melting of FCC provides all the features of a first order transition.