Dispersions or solutions? A mechanism for certain thickening agents

Abstract

Abstract Hydrolyzed starch–polyacrylonitrile (H‐SPAN) graft copolymers form highly viscoelastic mixtures with water, even at concentrations less than 1% by weight. In many ways these mixtures behave like ordinary polyelectrolyte solutions, but dilution experiments revealed that linear reduced viscosity–concentration plots could not be obtained even under ostensibly isoionic dilution conditions. This result, combined with a determination of gel content from centrifugation studies, led to the conclusion that high viscosity H‐SPAN water mixtures consist of swollen, deformable gel particles closely packed in intimate contact. Under high dilution or at high ionic strength conditions, the gel particles no longer are tightly packed, solvent is present in excess, the viscosity drops precipitously, and the thickening action effectively disappears. For comparative purposes, a commercial thickening agent (Carbopol 941) was examined and found to act in the same way. All reduced viscosity‐concentration curves obtained by dilution, either with salt solutions or water, can be shifted to a single normalized reduced viscosity plot. This shift is done by using as the concentration variable the quantity cQ , where c is the polyelectrolyte concentration and Q is the swelling which the gel particles undergo in an excess of solvent at the corresponding total ionic strength of the solution of concentration c .