Stochastic defect diffusion model for relaxation effects in crystalline polyethylene

Abstract

It is suggested that some relaxation processes observed in crystalline polyethylene are consequences of the diffusive motion of a particular defect called a point dislocation or twist dispiration loop along the polyethylene stems in lamellar crystals. The motion of the defect, characterized by a diffusion coefficient and a mobility, is described by solutions of the Smoluchowski diffusion equation with boundary conditions that constrain the defect to move along routes that produce experimentally observable results. The fact that passage of the defect causes both a 180° rotation of the chain and moves an extra CH2 group in the direction of the chain axis is important to the interpretation of the data according to this model. The diffusion coefficient for a defect is estimated to be around 2 × 10-9 cm2 s-1 at 70°C. This value is shown to be reasonable both from the viewpoint of detailed computer modelling of defect motion and contemporary ideas about scaling. © 1982.