The glass transition in polymer melts

Abstract

AbstractThis paper presents some results of a Monte Carlo simulation for the glass transition in two‐ and three‐dimensional polymer melts. The melt was simulated by the bond‐fluctuation model on a d‐dimensional cubic lattice which was combined with a two‐level hamiltonian favouring long bonds in order to generate a competition between the energetic and topological constraints in the system. This competition prevents crystallization and makes the melt freeze in an amorphous structure as soon as the internal relaxation times match the observation time of the simulation set by the cooling rate. The freezing point of the melt, i.e the glass transition temperature Tg, thus depends upon the cooling rate and additionally upon the chain length of the polymers. The dependence of the glass transition temperature on the cooling rate was closely analysed in three and that on the chain length in both two and three dimensions, resulting in a non‐linear relationship between Tg and the logarithm of the cooling rate and a linear relationship between Tg and the inverse chain length, respectively. In addition to this behaviour of the melt during the cooling process an example for the relaxational properties of the three‐dimensional model is provided by a quantitative analysis of the incoherent intermediate scattering function in the framework of the idealized mode coupling theory.