Abstract
To study the effect of processing history, molecular weight/molecular weight distribution, and thermal history on solid state properties (in particular fracture properties and orientation), carefully characterized polydisperse and monodisperse polystyrene samples were drawn above T~g~ and the orientation frozen in. The objective was to simulate the incidental orientation of polymer chains after processing, molding, and so forth (e.g., injection or compression, blow molding) as a result of melt flow. A series of polystyrene samples was produced by hot drawing at temperatures of 113 and 148 °C, followed by a relaxation period, and then a quench to below T~g~. The level of segmental orientation imposed in the samples was determined by birefringence measurements. The tear energy of the sheets was measured at 20 °C by tearing along the draw direction, ultimately giving a value for the fracture energy, G~3C~. Samples of high draw ratio and low segmental orientation were unexpectedly found to have highly anisotropic fracture properties despite the low level of optical anisotropy. The fracture properties also depended significantly on whether the samples were drawn with or without lateral constraint. The results are compared with measurements of isotropic samples and the findings of a previous investigation utilizing SANS and birefringence. Modeling the drawing conditions at the chain level using a recent nonlinear tube theory explains how birefringence alone is an inadequate measure of molecular orientation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 377–394, 2007