A main challenge in the development of polymerinsulated HVDC power cables is to achieve a robust insulation, because the accumulation of space charge under electrical and/or thermal stresses can significantly reduce the cable reliability. The space charge formation depends on the electrode-insulation contact which refers to the transition of carbon-black filled host polymer ('semicon', SC) and unfilled polymer. The fundamental processes which govern the contact physics and their dependence on the microstructure properties of the polymer and the interface are still poorly understood. In this paper we present a methodology to probe SC-insulator contact properties on a nanometer scale and to investigate the impact of material processing.