On the formation of lamellae during annealing of extended chain crystals of radiation-polymerized trioxane

Abstract

The structure changes of radiation-polymerized trioxane taking place during annealing have been studied by means of electron microscopy, X-ray small- and wide-angle scattering, and differential thermal analysis. The original fibrillar crystals, supposedly consisting of extended chains, change into lamellar crystals due to annealing at temperatures between 150° and 190°C. Lamella formation can be connected with the appearance of a long period of about 200A which is not observed in the unannealed sample. During annealing within the same temperature range the X-ray reflections due to the twin structure of the original polytrioxane disappear, whereas the orientation of the fraction with its c-axis parallel to the c-axis of the parent trioxane remains unaltered. The melting point of the lamellar crystals obtained by annealing is 186°-187°C and, therefore, considerably higher than the melting point (175°C) of crystals grown during cooling of a polytrioxane melt. The equilibrium melting point of an undisturbed extended-chain poly-oxymethylene single crystal must be still higher and may even approach 200°C. On the basis of the electron-microscopical observations and the X-ray results, it is supposed that the process of lamella formation takes place continuously by reorganization of the whole structure including the already grown lamellae. The rate of this process is the faster the higher the annealing temperature. Some possible mechanisms are discussed but the final reasons for the observed structure changes are not known.