A MODEL FOR NONLINEAR CREEP AND PHYSICAL AGING IN POLY(VINYL CHLORIDE)

The creep behavior of polymers depends on the physical age of the material at the time of stress application. Creep curves shift to longer times for more highly aged material and, in poly(vinyl chloride), (PVC), this can be modeled by an empirical equation in which the magnitude of an effective mean retardation time parameter is dependent upon, and increases with, the age of the polymer. Creep compliances for PVC also depend on the magnitude of the applied stress when this exceeds about 4 MPa. This nonlinear behavior is caused, at short creep times, by a reduction in the value for the retardation time parameter on application of the creep stress. Specimens appear therefore to be initially de-aged by elevated stresses. Subsequently, this parameter increases with creep time implying that physical aging has been reactivated, but the rate of increase also depends on the stress level. These influences of elevated stresses can be described by an extension of the creep model, and parametric expressions have been derived which relate creep compliance values to time, stress, and the age of the polymer. It is shown how the parameters can be determined from a short series of creep experiments and thus how creep deformations can be calculated over wide ranges of time, stress, and age.