Dynamic viscosity of dilute aqueous solutions of poly(acrylic acid) at frequencies of 2–500 kHz

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Abstract
The dynamic viscosity of aqueous solutions of poly(acrylic acid) at a polymer concentration of ca. 0.15 g/100 ml has been measured at frequencies from 2 to 500 kHz as a function of degree of polymerization P, degree of neutralization α, and salt (NaCl) concentration Cs. Relaxation spectra have been obtained from the dynamic viscosity. The spectra in the short relaxation time region can be approximated by the Zimm theory for the conformational relaxation of nonionic polymers. The maximum relaxation time τ1 of the Zimm spectra is proportional to P2 and depends rather moderately on α and Cs. Increased deviation is found, however, in the long relaxation time region, in particular for high values of P and α and low values of Cs. The major part of the deviation is interpreted in terms of rotational relaxation of a molecule as a whole. The rotational relaxation time τR is proportional to P3 and increases with increasing α and decreasing Cs. The remaining part of the excess spectra located between τ1 and τR is ascribed to the deviation of the conformational relaxation from the Zimm theory arising from ionization of the polymer.