Rheology of PVC Plastisol: Formation of Immobilized Layer in Pseudoplastic Flow

Hoffman in the early 1970s examined mechanism of dilatancy and fracture of plastisol under high-shear conditions. The samples were monodispersed spherical particles of PVC. He discovered formation of immobilized layer in the pseudoplastic flow preceding dilatancy and subsequent destruction of the layer at the fracture. However, his analysis was focused primarily on the mechanism of the fracture, and the mechanism of pseudoplastic flow remains unexplored. The present work begins with analyses of Hoffman's data to show that pseudoplastic flow, i.e., the decrease of viscosity with the increase of shear rate, is a result of the development of the immobilized layer and creation of a mobile layer of low-viscosity fluid. Hoffman took the mobile layer to consist of pure plasticizer. The present work shows that the mobile layer contains PVC particles. The thickness of mobile layer decreases (and the thickness of immobilized layer increases) with the increase of shear rate. The particle concentration and hence viscosity of the mobile layer decrease with the increase of shear rate. Similar analyses of our dynamic viscosity-frequency relationship show that (1) the pseudoplastic behavior is a result of formation of immobilized layer, which grows thicker with the increasing frequency, and (2) the mobile layer contains dispersed particles, the concentration of which decreases with increasing frequency. (3) A presence of coarse particles results in a tighter packing of the immobilized layer and lower viscosity of the mobile layer for a given volume fraction of particles. This explains why the presence and the amount of the coarse particles are important parameters in plastisol formulation. The elastic modulus-frequency relationship is also interpreted with the development of the immobilized layer, giving strain amplification. Copyright 2001 Academic Press.