The Effect of Annealing on the Nonlinear Viscoelastic Response of Isotactic Polypropylene

Three series of tensile relaxation tests are performed on isotactic polypropylene at room temperature in the vicinity of the yield point. In the first series of experiments, injection-molded samples are used without thermal pre-treatment. In the second and third series, the specimens are annealed at 130°C for 4 and 24 hours, respectively. Constitutive equations are derived for the time-dependent response of semi-crystalline polymers at isothermal loading with small strains. A polymer is treated as an equivalent temporary network of macromolecules bridged by junctions (physical cross-links, entanglements and crystalline lamellae). Under loading, junctions slide with respect to their positions in the bulk material (which reflects the viscoplastic behavior), whereas active strands separate from their junctions and dangling strands merge with the network at random times (which reflects the viscoelastic response). The network is thought of as an ensemble of meso-regions (MRs) with various activation energies for detachment of chains from temporary nodes. Adjustable parameters in the stress-strain relations are found by fitting the observations. The experimental data demonstrate that the relaxation spectrum (characterized by the distribution of MRs with various potential energies) is independent of mechanical factors, but is altered at annealing. For specimens not subjected to thermal treatment, the growth of longitudinal strain does not affect the volume fraction of active MRs and the attempt rate for detachment of chains from their junctions. For annealed samples, the concentration of active MRs increases and the attempt rate decreases with strain. These changes in the time-dependent response are attributed to broadening of the distribution of strengths of lamellae at annealing.