Rheology of PVC Plastisol - VIII: Mechanism of Non-Linear Viscoelastic Behavior

Abstract

Abstract The mechanism of the strain-amplitude dependence (non-linearity) of viscoelastic properties of a PVC plastisol was examined. The range of amplitude was 0.02 to 10.24 and the range of frequency was 0.1 to 100 rad/s. The amplitude dependence of dynamic viscosity was very similar to its frequency dependence in that with the increase of amplitude or frequency it decreased first, reaching a minimum and then increased. In the preceding series of papers, the decrease of viscosity with the increase of frequency, i.e. pseudo-plasticity, was attributed to shear-induced phase separation into immobilized layer and mobile phase. In the present work, it is shown that the same mechanism is responsible for the decrease of viscosity with the increase of amplitude. The increase of viscosity with the increase of amplitude (after the minimum) is explained by the dilatation of the immobilized layer. Subsequently, the normal stress acting on the immobilized layer is calculated from the difference of the osmotic pressure between the mobile phase and immobilized layer. The shear deformation of the immobilized layer is estimated to be extremely small, although the deformation in the normal direction, i.e. the dilatation, is significant.