Broadband ultrasonic spectrometry of polystyrene-cyclohexane critical mixtures.

Mutual diffusion coefficients, shear viscosities, and broadband ultrasonic attenuation spectra in the frequency range 100 kHz to 300 MHz have been measured for solutions of polystyrene in cyclohexane at two degrees of polymerization N and various temperatures near the critical. The exponent y(η) in the power law representation of the critical part in the viscosity deviates substantially from the universal value y(η) = 0.0435: y(η) = 0.028 (N = 288) and y(η) = 0.014 (N = 6242). Also, the adiabatic coupling constant g and the amplitudes ξ(0) and Γ(0) in the power laws of the correlation length and the relaxation rate of fluctuations, respectively, depend on N. This is especially obvious with the relaxation rates, for which Γ(0) = 5.8×10(9) at N = 288 and Γ(0) = 6.1×10(7) with the larger polymer results. A noteworthy feature is the difference between the relaxation rates from the diffusion coefficients and shear viscosities on the one hand and from the ultrasonic spectra on the other. Near the critical temperatures the latter Γ values deviate from power law behavior, indicating a coupling between the concentration fluctuations and structural isomerizations of the polymers.