Compositional, microstructural and mechanical effects of NaCl porogens in brushite cement scaffolds

Modification of the setting process of brushite cements by varying the concentration of ions that alter calcium phosphate crystallization kinetics, is known to enable control on the monetite conversion extent and the accompanying microporosity. This is useful because monetite serves as a suitable matrix in macroporous scaffolds due to its higher phase stability and finer crystal morphology compared to its hydrous counterpart brushite. In this study the synergistic effect of NaCl and citric acid on the microstructural evolution of brushite cement was demonstrated and microporosity of macroporous monetite-rich cement blocks was minimized by a variable NaCl porogen size distribution approach. Initially, maximum packing ratio of various combinations of NaCl size groups in PEG were determined by their rheological analysis in a range between 57% and 69%. Statistical analysis revealed a positive correlation between the amounts of NaCl particles under 38μm and 212μm and the maximum packing ratio. Further broadening the size distributions of NaCl porogens with fine cement precursors was effective in increasing the solids packing ratio of cement blocks more than the maximum packing ratio for the porogens. This improvement in packing was accompanied by a reduction in microporosity despite the increase in micropore volume with ion induced monetite formation. The detrimental effect of the microporosity introduced to the structure during monetite formation was balanced for some size distributions and not so much for others, thereby resulting in a wide range of porosities and mechanical properties. Thus, the exponential dependence of mechanical properties on porosity and the mechanical properties of monetite-rich macroporous blocks at the theoretical zero-porosity were determined according to Rice's model. Zero-porosity extrapolations were much higher than those predicted for brushite cement, contrary to the common assumption that brushite is mechanically stronger than monetite.