The effects of thermomechanical history and strain rate on antiplasticization of PVC

Antiplasticization is mechanically characterized by an increase in the polymer stiffness and/or yield strength upon the incorporation of a small amount of a low-molecular weight diluent. It is attributed to hindrance of the local β-relaxation motions of the polymer. Here, we have studied the effects of thermal treatment, plastic deformation, and strain rate on the antiplasticization of the yield stress of a 95 wt% poly(vinyl chloride)/5 wt% dioctyl phthalate (PVC/5 wt% DOP) compound. Two thermal treatments were applied to the materials - cooling to room temperature from above T_g by a quench or by a slow oven-cool anneal. When compressed at low to moderate strain rates, antiplasticization was observed in the annealed (physically aged) PVC/5 wt% DOP but not in the quenched (unaged) PVC/5 wt% DOP. Load-unload-reload compression cycles revealed that antiplasticization can be erased by plastic strain; the anomalously high yield stress of PVC/5 wt% DOP observed in the first load cycle softens to a value lower than that of the neat PVC in subsequent cycles. The results indicate that disordered, high free volume microstructural states, obtained either from thermal quenching or from plastic straining, liberate the beta motions of the PVC molecule which, in turn, erase antiplasticization of the yield stress. Earlier work on the rate-dependence of yield has demonstrated that beta motions must be stress-activated in order to yield neat PVC when deformed at high strain rates (>100/s). Hence, we have characterized the rate-dependence of the antiplasticization of the yield stress by testing the annealed materials in uniaxial compression over a wide range of strain rates (10⁻⁴/s-3000/s). Antiplasticization was observed in PVC/5 wt% DOP in the low strain rate regime where beta motions are free in neat PVC but hindered in PVC/5 wt% DOP; however, the antiplasticization (elevation of yield stress) gradually diminished with increasing strain rate.