Prediction of long-term properties in polymeric systems: I. Slow crack propagation in poly(vinyl chloride). II. Aging of poly(lactide)/poly(ethylene glycol) blends

Slow crack growth in PVC pipe was studied in order to develop a methodology for predicting long-term creep fracture from short-term tension-tension fatigue tests. In all cases, the crack propagated continuously through a crack-tip craze. In fatigue, the density of drawn craze fibrils gradually increased with decreased frequency and increased temperature. At the lowest frequency, 0.01 Hz, the fibril density in fatigue approached that in creep. The kinetics of fatigue and creep crack growth followed the conventional Paris law formulations with the same power 2.7, da/dt = AfDK2.7I , da/dt = BK2.7I , respectively. The effects of frequency, temperature and R-ratio (the ratio of minimum to maximum stress intensity factor in the fatigue loading cycle) on the Paris law prefactors were characterized. A linear correlation allowed extrapolation of the creep prefactor ( B) from fatigue data. The extrapolated values were systematically higher than the values measured directly from creep and only converged at Tg. The difference was attributed to damage of the craze fibrils during crack closure upon unloading in the fatigue cycle.; Blending poly(ethylene glycol) (PEG) with poly(lactide) (PLA) decreases the Tg and improves the mechanical properties. It was demonstrated that a PLA of lower stereoregularity was miscible with up to 30 wt% PEG. Aging was due to slow crystallization of PEG from the homogeneous amorphous blend. Crystallization of PEG depleted the amorphous phase of PEG and gradually increased the Tg until aging essentially ceased when Tg of the amorphous phase reached the aging temperature.; Different aging mechanism was found with a crystallizable PLA of higher stereoregularity.; The effect of cooling rate on crystallization and subsequent aging of high stereoregular PLA blended PEG was studied by thermal analysis and by direct observation of the solid state structure with atomic force microscopy (AFM). The partially crystallized blend obtained with a cooling rate of 30°C min-1 consisted of large spherulites dispersed in a homogeneous matrix. Further from the spherulites, the homogeneous amorphous phase underwent phase separation with formation of a more rigid PLA-rich phase and a less-rigid PEG-rich phase. Decreasing the amount of PEG in the blend decreased the crystallization rate of PLA and increased the nucleation density. (Abstract shortened by UMI.)...