Nonlinear Stress Relaxation of Plasticized Poly(vinyl chloride)

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Large deformation, nonlinear stress relaxation behavior was examined for poly(vinyl chloride) in di-isononyl phthalate (PVC/DINP) system having PVC content of 45.5 wt% at 180, 190, and 200°C. The PVC/DINP system exhibited power law type relaxation modulus, G(t, γ) ∝ t-n’, over a wide range of time t. The slope n’ increased with elevating temperature T irrespective of step-strain γ. At 190°C, the n’ value of the system was 0.75 showing a critical gel temperature (Tgel), because 0.75 was in agreement with the values obtained from the linear dynamic viscoelasticity reported previously. Time-strain separability G(t, γ) = G(t)h(γ) is applicable over a wide range of t. Here, G(t) is linear relaxation modulus. The magnitude of damping depended strongly on T. Below Tgel, in other words, in a gel state, h(γ) exhibited very weak strain dependence like cross-linking rubbers. In a critical gel state, the magnitude of damping was a little larger than that for the gel state. Above Tgel, in a sol state, h(γ) showed still more stronger strain dependence similar to branch polymers. It was found that h(γ) of PVC/plasticizer system strongly depended on temperature near Tgel.

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