Here we develop a detailed, quantitative, understanding of the porous structure of rust and attempt to directly measure its evolution over time. Characterization of porosity in rust layers is non-trivial, as pore sizes span many orders of magnitude and there is no single technique that can measure across the size range. Thus, a range of complementary techniques have been utilised to measure pore sizes: gas (BET) sorption, mercury porosimetry and helium pycnometry, each of which measures different porosity characteristics across different length scales from the “microporous” (i.e. < 2 nm) through the “mesoporous (2 – 50 nm) to “macropores” of size > 50 nm. We find that for rusts developed using cyclic corrosion testing up to 50% of the porous volume exists in the mesoporous and microporous size ranges with surface areas between 20 and 40 m2 g-1 and that there is significant stratification of porosity between "inner" and "outer" rust layers
X-ray computerised tomography (XRCT) has been subsequently used to directly image pores at a voxel size of around 1 micron in order to follow the evolution of the pore structure with time as a function of environmental exposure. The figure shows the experimental protocol whereby projection images of a corroded wire sample are obtained using x-ray absorption contrast and later combined to generate the 3D volume reconstruction.