Small Angle X-Ray Scattering Studies of Fatigue in Polystyrene

Small angle scattering has been used to study the mechanical fatigue of crazes in polystyrene. The high radiation intensity obtainable from a synchrotron has permitted the examination of the processes that occur during the fatigue in real time. Both the short term changes that occur within a single cycle and the long term changes that occur over many cycles have been observed.Most of the craze growth, as measured by the scattering invariant obtained at peak deformation, occurred in the first cycle of fatigue. However the craze fibril diameter, obtained by Porod analysis, doubled over 250 cycles. As the volume of craze was not growing during during the fatigue this fibril diameter increase was believed to occur by change, that is coalescence, of the preexisting fibrils.The SAXS patterns obtained at a number of different deformations within a single cycle were compared with calculated patterns obtained assuming that the fibrils bend in a sinusoidal manner. Good qualitative agreement was obtained so it was concluded that the craze fibrils showed considerable deformation as the craze was unloaded and then straightened out again on reloading. When the ratio of minimum to maximum deformation was decreased from 0.9 to 0.5 the fibril deformation (contraction) increased to 10% with the fibrils remaining straight. As the minimum deformation was decreased below this the craze stress tends to zero and fibril buckling was evident. The main changes in fatigue lifetime occurred over the regions where there fibrils were straight, perhaps because buckling involves relatively small deformations.