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X-ray refraction reveals the inner surface concentrations of porous materials within the range of (µm- to nm-dimensions. This technique is compared to mercury pressure porosimetry which is a standard method for pore size determination in porous solids. The mean pore size of several ceramics are investigated over a range of porosity between 30% to 60%. Complementary to high pressure mercury intrusion the refraction technique detects the spatially resolved inner surfaces of both, open and closed pores. Furthermore, X-ray refraction scanning topography visualizes integral interface properties up to 50 m spatial resolution by two-dimensional topographic images. Characteristic microstructure parameters, i. e. inner surface density, porosity and mean pore sizes of some Al2O3 and SiC ceramics are presented. The specific surface data of Al2O3 ceramics obtained from X-ray refraction agree well with the results given by mercury porosimetry. In contrast, the related mean pore sizes differs systematically by about 30%.