Mechanical improvement of calcium carbonate cements by in situ HEMA polymerization during hardening

Calcium carbonate cements are a promising alternative for calcium phosphate cements. Due to the higher solubility of calcium carbonate compared to apatite, it is expected to have an improved biodegradation rate; a clear advantage for prospective biomedical applications in a clinical context. As of yet, the poor mechanical performance of calcium carbonate cements precludes their exploitation as a bioceramic. Herein, we report a mechanically enhanced calcium carbonate cement, formulated of vaterite and magnesium-doped amorphous calcium carbonate, which was strengthened by in situ polymerization of incorporated 2-hydroxyethylmethacrylate (HEMA) during setting in simulated body fluid (SBF). This approach allowed us to generate a pronouncedly strengthened polymer-ceramic composite whose mechanical properties can be tuned by the monomer fraction. Varying cement compositions were characterized with respect to their mechanical performance, morphology, and quantitative phase composition. HEMA polymer reinforcement strengthened the calcium carbonate cement distinctly in four-point bending test while, in stark contrast, the brittleness of the polymer-free cement simply made such tests impossible. Our results demonstrate that the chosen polymer-enforcement strategy is an efficient and straightforward approach and allows for tuning the mechanical properties of an otherwise brittle and thus unusable calcium carbonate cement towards biomedical application.