Effect of grain orientation and magnesium doping on β-tricalcium phosphate resorption behavior

The efficiency of calcium phosphate (CaP) bone substitutes can be improved by tuning their resorption rate. The influence of both crystal orientation and ion doping on resorption is here investigated for beta-tricalcium phosphate (β-TCP). Non-doped and Mg-doped (1 and 6 mol%) sintered β-TCP samples were immersed in acidic solution (pH 4.4) to mimic the environmental conditions found underneath active osteoclasts. The surfaces of β-TCP samples were observed after acid-etching and compared to surfaces after osteoclastic resorption assays. β-TCP grains exhibited similar patterns with characteristic intra-crystalline pillars after acid-etching and after cell-mediated resorption. Electron BackScatter Diffraction analyses, coupled with Scanning Electron Microscopy, Inductively Coupled Plasma–Mass Spectrometry and X-Ray Diffraction, demonstrated the influence of both grain orientation and doping on the process and kinetics of resorption. Grains with c-axis nearly perpendicular to the surface were preferentially etched in non-doped β-TCP samples, whereas all grains with simple axis (a, b or c) nearly normal to the surface were etched in 6 mol% Mg-doped samples. In addition, both the dissolution rate and the percentage of etched surface were lower in Mg-doped specimens. Finally, the alignment direction of the intra-crystalline pillars was correlated with the preferential direction for dissolution. Statement of significance: The present work focuses on the resorption behavior of calcium phosphate bioceramics. A simple and cost-effective alternative to osteoclast culture was implemented to identify which material features drive resorption. For the first time, it was demonstrated that crystal orientation, measured by Electron Backscatter Diffraction, is the discriminating factor between grains, which resorbed first, and grains, which resorbed slower. It also elucidated how resorption kinetics can be tuned by doping β-tricalcium phosphate with ions of interest. Doping with magnesium impacted lattice parameters. Therefore, the crystal orientations, which preferentially resorbed, changed, explaining the solubility decrease. These important findings pave the way for the design of optimized bone graft substitutes with tailored resorption kinetics

Chemically pure beta-tricalcium phosphate powders: Evidence of two crystal structures

The question whether beta-tricalcium phosphate (beta-TCP) can form a solid solution with beta-calcium pyrophosphate (beta-CPP) and/or hydroxyapatite (HA) has still not been solved. For this reason, wet-chemically synthesized beta-TCP powders with only 20 ppm Sr (among 43 tested elements) and with different HA and beta-CPP contents, or in other words Ca/P molar ratios, were used. The graphical relationship between these various Ca/P molar ratios determined by X-ray diffraction and by inductively-coupled plasma mass spectrometry showed no discontinuity, indicating the absence of a solid solution between beta-TCP and beta-CPP or HA. Analysis of the beta-TCP lattice parameters as a function of the Ca/P molar ratio revealed a discontinuity at a Ca/P molar ratio of 1.500 and a maximum microstrain. These results indicated that at least two beta-TCP structures co-existed, with variable mixing ratios depending on the Ca/P molar ratio, and with a distinct jump at a Ca/P molar ratio of 1.500