Effect of Local Heterogeneity on Dielectric Relaxation Spectra in Concentrated Solutions of Poly(vinyl acetate) and Poly(vinyl octanoate)

The effect of local heterogeneity on the distribution of dielectric relaxation times was studied for concentrated solutions of poly(vinyl acetate) (PVAc) in 1-methylnaphthalene (MN) and those of poly(vinyl octanoate) (PVOc) in toluene (Tol). The half-widths Λ of the dielectric loss curves for the primary processes of those systems are compared with those of the PVAc/Tol system reported previously. The data indicate that Λ decreases in order of PVAc/Tol, PVAc/MN, and PVOc/Tol systems if compared at the same temperature T / T g where T g denotes the glass transition temperature of solutions. The half-width of each solution increases with decreasing temperature. The loss curve is calculated by assuming a Gaussian distribution of the local concentration φ which results in the distribution of relaxation times g (τ). The calculated loss curves agree fairly well with the observed ones. The broadening behavior is also explained by assuming that Λ is proportional to the amplitude of the local concentration fluctuation Δφ times the slope of the φ dependence curve of the average relaxation time τ. This assumption leads to a linear relationship between Λ and Δφ/( T − T 0 ) 2 where T 0 is the Vogel critical temperature. Using this relation, we have attempted to estimate Δφ. Small-angle X-ray scattering was also measured on PVAc/MN solutions and found that the scattering intensity was lower than that for PVAc/Tol. This is consistent with the fact that Λ of PVAc/MN solutions is narrower than PVAc/Tol solutions.