The effect of temperature on crazing mechanisms in polystyrene

At room temperature scission is the dominant mechanism for the modification of the entanglement network required for craze formation in polystyrene, but as the temperature is increased towardsT_g, there is the possibility that disentanglement processes may contribute. These will be most important for short chains. If disentanglement can occur, a molecular weight dependence of the crazing stress as a function of temperature will result. This prediction is tested by straining thin films of a range of monodisperse samples of polystyrene at temperatures between 40 and 90° C. The nature of the ensuing deformation has been characterized by transmission electron microscopy. It is observed that whereas only crazing occurs over the entire temperature range for the lowest molecular weight sample, shear processes become important for higher molecular weight materials. For the longest chains, crazing is almost entirely suppressed at 80° C, with the preferential formation of shear deformation zones occurring. These observations are consistent with the idea that disentanglement is playing a significant role in craze formation at sufficiently high temperatures.