The clinical use of plasma-sprayed hydroxyapatite (HA) coatings on metal implants has aroused as many controversies as interests over the last decade. Although faster and stronger fixation and more bone growth have been revealed, the performance of HA-coated implants has been doubted. This article will initially address the fundamentals of the material selection, design, and processing of the HA coating and show how the coating microstructure and properties can be a good predictor of the expected behavior in the body. Further discussion will clarify the major concerns with the clinical use of HA coatings and introduce a comprehensive review concerning the outcomes experienced with respect to clinical practice over the past 5 years. A reflection on the results indicates that HA coatings can promote earlier and stronger fixation but exhibit a durability that can be related to the coating quality. Specific relationships between coating quality and clinical performance are being established as characterization methods disclose more information about the coating.

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The amorphous phase in hydroxyapatite coatings has been examined by using X-ray diffractometry, Fourier transform infrared spectroscopy, optical microscopy, and thermal analysis methods. The amorphous phase mostly consists of a dehydroxylated calcium phosphate. When heated, crystallization of hydroxyl-rich areas produces hydroxyapatite, followed by diffusion of hydroxyl ions, thus increasing the amount of crystalline phase. Hydroxyl-deficient amorphous areas crystallize to oxyapatite at 700°C. Thus, crystallization occurs over a range of temperatures and is dependent on the hydroxyl content of the amorphous phase and the partial water-vapor pressure. The activation energies of crystallization to hydroxyapatite, diffusion of hydroxyl ions, and crystallization to oxyapatite are 274, 230, and 440 kJ/mol, respectively. Shrinkage from these processes leads to a crack network and decreases the mechanical strength of the coating.

Thermally processed hydroxyapatite coatings used on dental implants and hip prostheses for enhanced fixation may typically consist of a number of chemical and structural phases. These phases affect coating performance and tissue attachment. Hydroxyapatite was plasma sprayed to examine the phase evolution during processing. Coatings were examined with X-ray diffraction and elemental analysis. Results indicate that phase transformations are produced by (a) preferential removal of hydroxyl and phosphate leading to a change in melt composition, and (b) the high cooling rate due to the thermal spray process. Hydroxyl group removal promotes the amorphous phase and oxyapatite. Further heating produces a less viscous melt facilitating decomposition of hydroxyapatite to tricalcium and tetracalcium phosphate. Phosphate removal during flight produces a more calcium-rich melt preferring tetracalcium phosphate and calcium oxide formation. A proposed model shows the phase location within the lamellae of these coatings. Coating processes must thus prevent removal of hydroxide and phosphate during processing to maximize the hydroxyapatite content.