Broadband dielectric study of dynamics of polymer and solvent in poly(vinyl pyrrolidone)/normal alcohol mixtures

Broadband dielectric measurements of poly(vinyl pyrrolidone) (PVP)-monohydroxyl alcohol mixtures of various normal alcohols with the number of carbon atoms per molecule ranging from 1 to 9 were made in the frequency range of 20 Hz to 20 GHz at 25 degrees C. Two relaxation processes due to the reorientation of dipoles on the PVP and alcohol molecules were observed. The relaxation process at frequencies higher than 100 MHz is the primary process of alcohols, and that at frequencies lower than 10 MHz is attributed to the local chain motion of PVP. For mixtures of alcohol molecules that are smaller than propanol, the relaxation time of the alcohol increases with increasing PVP concentration, whereas for mixtures of alcohol molecules larger than butanol, the relaxation time of the alcohol decreases with increasing PVP concentration. The increase in the density of hydrogen-bonding sites upon the addition of PVP reduces the relaxation time of alcohol in the mixture, and vice versa. The relaxation time of the local chain motion of PVP increases with PVP concentration and solvent viscosity. Different time scales of the molecular motions of polymer and solvent coexist in homogeneous mixtures with hydrogen-bonded polar solvent and polymer.