Biomimetic Crystallization of Calcium Carbonate Spherules with Controlled Surface Structures and Sizes by Double-Hydrophilic Block Copolymers

Big CaCO3 spherules with controlled surface structures and sizes ranging from several hundreds of nanometers and micrometers can be easily fabricated through a slow gas–liquid diffusion reaction at room temperature by using double-hydrophilic block copolymers (DHBCs) as crystal modifiers. The influence of the DHBCs with different functionalities such as carboxyl, partially phosphated, and phosphorylated groups on the crystallization and structure of calcite formation was investigated. The morphology evolution process and the early stage of the big spherical superstructures were followed. Such big spherules with complex surface structure made of calcite rhombohedra are not easily produced by conventional solution growth methods, and furthermore show high potential for chromatographic purposes due to their exposition of multiple calcite faces and the huge particle sizes suitable for chromatographic column packings.