Surface properties of various powdered hydroxyapatites

Electrophoretic mobilities of various synthetic and semisynthetic hydroxyapatites (Ca-10(PO4)(6)(OH)(2), HAP) suspended in aqueous solutions have been measured as a function of pH and calcium concentration. The studied powders differ in particle size, crystallinity degree and surface contamination (carbonate). When equilibrated in mineral acids or bases, a large plateau of negative mobility is observed in the pH range 5-8, with increasing negative values at higher pH. Only in the case of the sample composed of nanoparticles, positive mobility obtains at pH < 8.9. When Ca2+ is added, positive mobility values are observed for all samples, and a bell-shaped profile results as a function of pH. Two possible models are explored to describe the results: the Nernstian approach, which assumes solubility equilibrium and surface potentials determined by the three potential-determining ions (Ca2+, PO43-, 4 and OH-), and the surface complexation approach, based on the idea of negligible phase transfer of structural phosphate. The Nernstian model is inadequate, whereas a very simple surface complexation model based on the equations Ca-5(PO4)(3)+ Ca-4(PO4)(3)(-) + Ca-2+, Ca-4(PO4)(3)(-) + H+ = Ca-4(PO4)(2)(PO4H), Ca-5(PO4)(3)(+) + OH-=(_) Ca-5(PO4)(3)(OH), coupled with a very simple electrical double layer, model suffices to reproduce the bell-shaped profile of the mobility as a function of pH in the presence of added calcium salts. The results also show that the sample composed of nanoparticles exchanges ions more easily with the solution, without reaching the solubility equilibrium in the explored timespans. In the presence of soluble phosphate salts, it is postulated that the same surface ensembles define the surface charge, with participation of phosphate as described by the equation 4/5Ca(5)(PO4)(3) + 3/5PO(4)(3-)= equivalent to Ca-4(PO4)(-)(3) HAP is just one member of a family of calcium phosphates with different (Ca)/(P) ratios. Electrophoretic mobilities of another member, tricalcium diphosphate, Ca-3(PO4)(2), were also measured and shown to be described by the same basic model. Comparison with previous literature data shows that the negative plateau in the mobility is a general feature of many HAP samples at low Ca2+, again in agreement with the surface complexation model. FTIR data demonstrates that surface phosphate indeed undergoes protonation, as postulated in the model. (c) 2005 Elsevier Inc. All rights reserved.