Carbon black networking in elastomers monitored by simultaneous rheological and dielectric investigations

The rheo-dielectric response of carbon black filled elastomer melts is investigated by dielectric relaxation spectroscopy in the frequency range from 0.1 Hz up to 10 MHz during oszillatory shearing in a plate-plate rheometer. Various concentrations and types of carbon blacks dispersed in a non-crosslinked EPDM melt are considered. It is demonstrated that during heat treatment at low strain amplitude a pronounced flocculation of filler particles takes place leading to a successive increase of the shear modulus and conductivity. Followed up by a strain sweep, the filler network breaks up and both quantities decrease simultaneously with increasing strain amplitude. Two relaxation times, obtained from a Cole-Cole fit of the dielectric spectra, are identified, which both decrease strongly with increasing flocculation time. This behaviour is analyzed in the frame of fractal network models, describing the effect of structural disorder of the conducting carbon black network on the diffusive charge transport. Significant deviations from the predictions of percolation theory are observed, which are traced back to a superimposed cluster-cluster aggregation process (CCA). During flocculation, a universal scaling behaviour holds between the conductivity and the corresponding high frequency relaxation time, which fits all the measured data. The scaling exponent agrees fairly well with the prediction obtained from CCA. It is demonstrated that the underlying basic mechanism is a change of the correlation length of the filler network, i.e. the size of the fractal heterogeneities. This decreases during flocculation due to the formation of additional conductive paths, making the system more homogeneous. An addition less pronounced effect is found from nanoscopic gaps between adjacent filler particles, which decrease during flocculation. The same universal scaling behaviour, as obtained for flocculation, is found for temperature-dependent dielectric measurements of the cured crosslinked systems, which are heated from room temperature up to 200 °C. Thereby, the conductivity decreases significantly and the relaxation time increases, indicating that the filler network breaks up randomly due to the thermal expansion of the rubber matrix.