Studies on the viscosity behavior of polymer solutions at low concentrations

Viscosity measurements had been made on poly(vinyl alcohol) (PVA), poly(N-vinyl-2-pyrrolidone) (PVP) and poly(ethylene oxide) (PEO) solutions down to low concentrations. It was found that t0∗ defined as the flow time of the pure solvent in ideal conditions and obtained practically by extrapolating the flow time of polymer solution t to zero concentration, was not equal to the flow time of the pure solvent t0 measured. The reduced viscosity ηsp/C determined by (t/t0-1)/C exhibited either a drastic increase or a significant decrease with dilution, depending upon the polymer solution investigated. On the other hand, ηsp/C determined by (t/t0∗-1)/C was proportional to C even at low concentrations. The anomalous viscosity behavior of neutral polymer solutions at low concentrations, therefore, was due to the incorrect method by which ηsp/C was determined. The detailed experiments indicated that the effective diameter of the viscometer capillary, the surface property of the capillary wall and the additional pressure corresponding to the measurement of t and t0 for PVA, PVP and PEO solutions were not the same. Taking into account the contact anger and the surface tension of the liquid, together with the geometric parameter of the viscometer, the influence of the additional pressure upon the flow time measurement could be studied quantitatively. The calculation was in a good agreement with the experimental result. According to the method presented in this paper, the thickness of the adsorbed polymer layers on the capillary walls could be determined. It was noted that the thickness of the adsorbed polymer layers on the capillary walls was closely related to the solvent in which the polymer molecules were dissolved. The polymer molecular weight, however, had little or no effect on the thickness of the adsorbed polymer layers on the walls of the viscometer capillary.