Self-transformation of solid CaCO3 microspheres into core-shell and hollow hierarchical structures revealed by coherent X-ray diffraction imaging

The self-transformation of solid microspheres into complex core-shell and hollow architectures cannot be explained by classical Ostwald ripening alone. Here, coherent X-ray diffraction imaging and 3D X-ray fluorescence were used to visualize in 3D the formation of hollow microparticles of calcium carbonate in the presence of polystyrene sulfonate (PSS). During the dissolution of the core made from 10-25 nm crystals, the shell developed a global spheroidal shape composed of an innermost layer of 30 nm particles containing high PSS content on which oriented vaterite crystals grew with their c axis mainly oriented along the meridians. The stabilizing role of PSS and the minimization of the intercrystal dipolar energy can explain in combination with Ostwald ripening the formation of these sophisticated structures as encountered in many systems such as ZnO, TiO2, Fe2O3, Co3O4, MnO2, Cu2O, ZnS, CaCO3 and Ca8H2(PO4) (6)center dot 5H2O.

Automated summary

This article uses coherent X-ray diffraction imaging and 3D X-ray fluorescence techniques to visualize the formation process of hollow microparticles of calcium carbonate in the presence of PSS. The dissolution of the core and the development of the shell result in the formation of complex core-shell structures.