Ac conductance and capacitance of carbon black polymer composites during thermal cycling and isothermal annealing

The ac electrical properties of acetylene black composites mixed into ethylene butylacrylate copolymer (EBA) and into poly (methyl methacrylate) (PMMA) have been measured in thermal cycling and isothermal annealing experiments. The results show that changes in electrical properties are due to rearrangement of gaps between the carbon black aggregates. This has been concluded using an exponent z that relates the critical frequency ω_c denoting the crossover of the conductivity from the dc-plateau to its frequency-dependent part to the dc conductivity, σ_dc, according to ω_c ∝σ_dc^z. Below the melting range of EBA and the glass transition of PMMA z is about one corresponding to strong variation of the conductivity and weak dependence of the permittivity on the gaps. Above the melting range of EBA z is about 1.5, indicating strong dependence of both the conductivity and the permittivity on the gaps, as predicted by percolation theory. This was not found in the PMMA composites above the glass transition. We conclude that the polymer matrix affects the nature of the gaps between carbon black aggregates, either allowing their size to vary continuously (z about 1) or letting them open and close (z about 1.5).