Effect of pH of Coating Solution on Adhesion Strength of Hydroxyapatite and Octacalcium Phosphate Coatings on AZ31 Magnesium Alloy

Hydroxyapatite (HAp) and octacalcium phosphate (OCP) coatings were formed on a Mg-3Al-Zn (AZ31) alloy with a chemical solution deposition method using a Ca-EDTA solution at various pH levels. The adhesion strength of the coatings was examined using the pull-off method. The microstructures of HAp and OCP coatings were measured X-ray diffraction (XRD). The morphology and composition of the surface and cross section of the samples before and after the adhesion test were characterized using scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), and a 3D profilometer. The results showed that plate-like OCP crystals grew from a continuous OCP layer on the surface of the AZ31 substrate in the case of a pH 6.3 coating solution. At pH values of 7.5 and 8.6, the HAp coating showed a two-layer structure with a HAp rod-like outer layer and a HAp continuous inner layer. Regardless of the pH of the coating solutions, a very thin Mg (OH)2 intermediate layer was formed between OCP or HAp coating and substrate. The highest adhesion strength of the coatings was 6.7±0.5 MPa, achieved at a coating solution pH value of 7.5. A part of Mg (OH)2 layer remained on the substrate, indicating that the delamination occurred in the Mg (OH)2 intermediate layer. The primary particles in the inner layer formed at pH 7.5 was smaller than those at pH 8.6. This result indicates that the initial corrosion of substrate AZ31 at pH 7.5 was more rapidly than that at pH 8.6, presumably leading to the formation of mixed layer of Mg (OH)2 and calcium phosphate. Further investigation is necessary to understand the better adhesion strength at pH 7.5 than that at pH 8.6. This good adhesion could be due to the flawless and rod-like uniform crystal, which had the densest and finest structure on the surface.