Effects of crystallization behavior on morphological change in poly(trimethylene terephthalate) spherulites

Abstract

In poly(trimethylene terephthalate) (PTT) spherulites during isothermal crystallization, the morphological changed from an axialite/or elliptical banded spherulite to banded spherulite and then non-banded spherulite with temperature decreasing were studied by following the lamellar growth behaviors. We report lamellar growth mechanism on varied crystallization temperature, which explicitly probes the link between microscopic structure and macroscopic morphology in the development of patterns. Fibrillation of the edge-on lamellae was observed on the surfaces of axialite and the convex bands of banded spherulite. Terrace-like lamellae were observed on the surface of the non-banded spherulite and the concave bands of banded-spherulite. In thin film crystallization, PTT banded spherulite exhibits a texture of alternate edge-on and flat-on lamellae, wavy-like surface and rhythmic growth. The deceleration of growth rate takes place in convex bands with a growth habit of fibrillation of the edge-on lamellae for emerging ridge surface. On the other hand, the acceleration of growth rate appears in concave bands with a growth habit of terrace-like lamellae for emerging valley surface. The alternating growth mechanism of the lamellae was considered to be related with the formation of spatiotemporal self-organization patterns far from equilibrium. In order to explain the rhythmic growth and periodic growth of the lamellae, we may conjecture that the emergence of PTT banded spherulite in thin film crystallization is associated with an oscillatory dynamics of the spherulite growth front driven by latent heat diffusion. We present some tentative ideas on the possibility of band-to-nonband (BNB) morphological transition, which might be analogous with the second order transition in non-equilibrium phase transition.