Experimental confirmation of oscillating properties of the complex conductivity: Dielectric study of polymerization/vitrification reaction

Abstract

Clear evidence of the existence of fractional kinetics containing the complex power-law exponents were obtained by conductivity measurements of polymerization reaction of polyvinylpyrrolidone (PVP) performed inside a dielectric cell. We established the relationship between the Fourier image R(jω) of the complex memory function K(t) and the time-dependent mean square displacement 〈r2(t)〉. This relationship helps to understand the origin of the different power-law exponents appearing in the real part of complex conductivity Re[σ(ω)] and find a physical/geometrical meaning of the power-law exponents that can form the complex-conjugated values. The complex-conjugated values of the power-law exponents leading to oscillating behavior of conductivity follows from the fractional kinetics suggested by one of the authors (R.R.N.). The relationships [R(jω)⇔Re[σ(ω)]⇔〈r2(t)〉] are becoming very efficient in classification of different types of collective motions belonging to light and heavy carriers involved in the relaxation/transfer process. The conductivity data obtained for Re[σ(ω)] during the whole polymerization process of the PVP at different temperatures (80, 90, 100 °C) are very well described by the fitting function that follows from the suggested theory. Original fitting procedure based on the application of the eigen-coordinates (ECs) method helps to provide a reliable fitting procedure in two stages and use the well-developed and statistically stable linear least square method (LLSM) for obtaining the correct values of the fitting parameters that describe the behavior of Re[σ(ω, Tr)] in the available frequency range for the current time of the chemical reaction Tr measured during the whole process of polymerization. The suggested theory gives a unique possibility to classify the basic types of motions that take place during the whole polymerization process. © 2007.