Kevor S. TenHuisen

Effects of magnesium on the formation of calcium-deficient hydroxyapatite from CaHPO4.2H2O and Ca4(PO4)2O.

Calcium-deficient hydroxyapatite (HA) with a Ca/P molar ratio of 1.50 was synthesized in various concentrations (0.01-75 mM) of MgCl2 at 37.4 degrees C by reaction between particulate CaHPO4.2H2O and Ca4(PO4)2O. The effects of magnesium on the kinetics of HA formation were determined using isothermal calorimetry. All reactions completely consumed the precursor phases as indicated by X-ray diffraction analysis and a constant enthalpy of reaction (240 kJ/mol). Magnesium concentrations below 1 mM had no effect on the kinetics of HA formation. Magnesium concentrations between 1 and 2.5 mM affected the reaction path but did not affect the time required for complete reaction. Higher concentrations extended the times of complete reaction due to magnesium adsorption on the precursor phase(s) and HA nuclei, and stabilization of a noncrystalline calcium phosphate (NCP). HA formation in the presence of magnesium resulted in separation of the following two events: initial formation of HA nuclei and NCP, and consumption of CaHPO4.2H2O. This was indicated by the appearance of an additional calorimetric peak. Variations in calcium, magnesium, and phosphate concentrations and pH with time were determined. Increasing the magnesium concentration resulted in elevated calcium concentrations. After an initial decrease in magnesium owing to its adsorption onto HA nuclei and precursor(s), a period of slow reaction at constant magnesium concentration was observed. Both the magnesium concentration in solution and the proportions of precursors present decreased prior to any evidence of a crystalline product phase. This is attributed to the formation of NCP capable of incorporating magnesium. This noncrystalline phase persisted for more than 1 year for reactions in magnesium concentrations about 2.5 mM. Its conversion to HA resulted in the release of magnesium to the solution.

Variations in solution chemistry during calcium-deficient and stoichiometric hydroxyapatite formation from CaHPO4. 2H2O and Ca4(PO4)2O

This study explores the mechanistic paths taken when calcium-deficient hydroxyapatite, CDHAp (Ca/P = 1.50), and stoichiometric hydroxyapatite, SHAp (Ca/P = 1.67), form by reaction between particulate calcium phosphate salts. The acidic reactant was CaHPO4.2H2O (DCPD) and the basic reactant was Ca4(PO4)2O (TetCP). Variations in pH, calcium and phosphate concentrations, and the solids present during apatite formation, were determined as functions of reaction temperature (25.0 degrees, 37.4 degrees, and 50.0 degrees C) and time. It was found that the dissolution of TetCP was rate limiting for both hydroxyapatite (HAp) compositions at all three temperatures. However, the retrograde solubility and incongruent dissolution of DCPD became increasingly important in influencing the kinetics as the reaction temperature was increased. An amorphous intermediate phase was observed regardless of the HAp stoichiometry. The solutions from which the SHAp formed approached equilibrium at much shorter reaction times (1-2 days) than those from which the CDHAp formed. The latter continued to display changes in pH and in calcium and phosphate concentrations for 6 months. CDHAp was shown to be a thermodynamically stable phase. The dissolution of CDHAp is incongruent, showing a Ca/P molar ratio in solution less than 0.5.

Fluoride uptake by hydroxyapatite formed by the hydrolysis of α-tricalcium phosphate

Although there is interest in forming synthetic analogs of hard tissues at physiologic temperature, significant gaps in knowledge exist with respect to the mechanisms by which precursor solids convert to apatites and also with respect to the apatite compositions that may be formed. In this study calcium-deficient HAp [Ca9(HPO4)(PO4)5OH] was prepared by hydrolysis of tricalcium phosphate (TCP), α-Ca3(PO4)2. The kinetics of HAp formation were studied as a function of temperature by isothermal calorimetry. TCP hydrolyzed completely within about 12 h, and the hydrolysis reaction evolved 133 kJ/mol of HAp formed. Although the kinetics of hydrolysis exhibited a strong temperature dependence, the mechanistic path taken appeared independent of temperature. The fluoridation of hydroxyapatite compositions having Ca/P ratios higher than 1.59 previously has been investigated. However, little work has been done on the fluoridation of more calcium-deficient hydroxyapatite. Ca9(HPO4)(PO4)5OH was formed at temperatures between 37.4° and 55°C to vary its morphology. These preparations then were reacted in NaF solution and the kinetics of fluoride incorporation studied. Solution chemical analyses were used to determine the amounts of fluoride incorporated. The extent of hydroxyl replacement by fluoride ranged from 17 to 72% and correlated with the surface area of the parent HAp.

The formation of hydroxyapatite–calcium polyacrylate composites

Tetracalcium phosphate (TetCP, Ca4(PO4)2O) reacts rapidly with polyacrylic acid (PAA). Complete reaction results in the formation of hydroxyapatite (HAp) and calcium polyacrylate. Consequently, this combination of reactants can react to form a dental cement. However, reaction occurs so rapidly that it would be difficult to achieve a homogeneous mixture of reactants suitable for use in restorations. In order to explore extending the working time, the effects of prehydrating the TetCP to form surface layers of HAp on the TetCP particles was explored. Prehydration was found to be an effective means of allowing workability. Therefore, the effects of the proportions of TetCP and PAA, with and without HAp filler, on cement properties were investigated. The extents of the reactions were investigated by X-ray diffraction analysis; the extents of PAA neutralization were studied by Fourier transform infra-red spectroscopy (FTIR); pore structures were determined by mercury intrusion porosimetry; microstructures were observed by scanning microscopy, and compressive strengths were determined. After curing for 17 days at room temperature PAA neutralization was almost complete; however, residual TetCP could be detected by X-ray diffraction and PAA by FTIR. As expected, the compressive strengths of the cements showed a dependence on the liquid (water+polymer)-to-solid (TetCP+HAp filler) used. The presence of HAp filler caused a significant decrease in compressive strength and increasing the proportion of HAp filler resulted in a decrease in the compressive strength. The characteristics of the load–deflection curves showed a dependence on the presence of HAp filler. In the absence of filler, two slopes were observed in the curves whereas a linear curve, typical of a ceramic, was observed when HAp filler was present. Mercury intrusion porosimetry (MIP) indicated the majority of the porosity was present in pores larger than 0.1 μm. Porosity increased with increasing liquid-to-solids ratio and with an increasing proportion of HAp filler at a constant liquid-to-solids ratio. Microstructural observations indicated the effect of HAp filler on increasing porosity was the result of porosity present in the filler itself. Thus, poorly consolidated HAp filler contributed to increased porosity and reduced compressive strength.

THE KINETICS OF CALCIUM DEFICIENT AND STOICHIOMETRIC HYDROXYAPATITE FORMATION FROM CAHPO4.2H2O AND CA4(PO4)2O

Isothermal calorimetry was performed on intimate mixtures of CaHPO4·2H2O and Ca4(PO4)2O constituted at Ca/P molar ratios of 1.50 and 1.67 to form the hydroxyapatite compositions Ca9HPO4(PO4)5OH and Ca10(PO4)6(OH)2, respectively, at complete reaction. The temperature range investigated was 15–70°C. The effects of the reaction temperature on the rates of heat evolution during hydroxyapatite formation were determined. Reactions were carried out utilizing a liquid-to-solids weight ratio of 1.0. A two-stage reaction mechanism was observed regardless of the Ca/P ratio as indicated by the presence of two reaction peaks in the plots of the rates of heat evolution against time. An Arrhenius relationship was found between the rate and temperature for each reaction stage for both compositions. Apparent activation energies of 120 and 90 kJ/mol (Ca/P=1.67) and 118 and 83 kJ/mol (Ca/P=1.50), respectively, were calculated for the first and second reaction peaks. An Arrhenius relationship was also found between the time of maximum rate and temperature. The following qualitative reaction mechanism is proposed for each of the two reaction stages for both compositions studied. The first stage involves the complete consumption of CaHPO4·2H2O and the partial consumption of Ca4(PO4)2O to form a noncrystalline calcium phosphate and nanocrystalline hydroxyapatite. During the second stage the remaining Ca4(PO4)2O reacts with the noncrystalline calcium phosphate to form the final product, stoichiometric or calcium deficient hydroxyapatite.

LOW TEMPERATURE SYNTHESIS OF A SELF-ASSEMBLING COMPOSITE : HYDROXYAPATITE-POLY BIS(SODIUM CARBOXYLATOPHENOXY)PHOSPHAZENE

The present study was undertaken to investigate the low temperature formation of a hydroxyapatite-polyphosphazene polymer composite likely to be biocompatible. The temperature range studied (25 to 60°C) was selected to bracket physiological temperatures. The composite precursors consisted of CaHPO4·2H2O, Ca4(PO4)2O, and poly[bis(sodium carboxylatophenoxy)phosphazene]. The results indicate that a synergistic relationship exists in the formation of a polyphosphazene network and hydroxyapatite (HAp) matrix phase during composite synthesis. Calcium from the HAp precursors participates in the formation of a Ca crosslinked polymeric network which influences the rate of HAp formation and its morphology. The mechanistic paths taken during composite formation were followed by determining variations in the concentration of species in solution (at physiological temperature), rates of heat evolution, and microstructural development. These analyses indicate that the polymer controls the kinetics of hydroxyapatite formation and the composite microstructure. Low reaction temperatures and a high proportion of polymer facilitate the formation of a highly interconnected composite. The presence of the polyphosphazene allows a metastable calcium phosphate solution to persist for extended periods prior to the formation of hydroxyapatite. The degree of supersaturation and the length of the induction period increase with an increase in polyphosphazene content. The temperature dependence of these induction periods obeyed an Arrhenius relationship.