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The role of particle geometry in the structural integrity of sand and rock ilmenite bed particles was studied under prolonged exposure to oxygen carrier-aided combustion (OCAC) conditions in a 12 MWth circulating fluidized bed (CFB) boiler. Woody biomass was used as fuel. Bed particles were collected at different stages of the exposure. Fresh bed particles were used as reference samples. All the materials were examined by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) and X-ray microtomography (XMT). The obtained results showed that over time, sphericity diminishes in sand ilmenite, whereas the sphericity of rock ilmenite particles remains unchanged. For both bed types, it was noticed that cracks are mainly connected to the concave areas on the bed particle surface. It was also observed that in sand ilmenite, the bed particle layer predominantly forms on convex areas, resulting in nonuniform distribution, whereas in rock ilmenite, with infrequent convex and concave features, the layer is thicker and exhibits a more uniform distribution. Consequently, the bed particle layer in rock ilmenite plays a higher protection against the outward migration of iron. This, coupled with a lower frequency of concave areas, contributes to a reduced average volume fraction of porous regions and cracks, which makes rock ilmenite structurally more resistant to breakage than sand ilmenite. Notably, the difference in the structural integrity of the two bed types becomes even more pronounced with longer exposure times.