Application of the quartz crystal microbalance with dissipation method to a study of oleate adsorption onto a hydroxyapatite surface

The adsorption process, density and structural property of the oleate layer adsorbed onto a hydroxyapatite (HAP) surface at six different concentrations and three pHs (pH 8, 9 and 10) have been studied using the technique of quartz crystal microbalance with dissipation (QCM-D). The present study demonstrated the versatility and accuracy of the QCM-D for surface adsorption characterization. The real-time measurements of frequency and dissipation shifts with a hydroxyapatite-coated sensor revealed changes in the hydroxyapatite surface during the entire adsorption process. Chemisorption and surface precipitation of sodium oleate were also observed on the surface of hydroxyapatite through the use of Fourier Transform infrared spectroscopy(FTIR). Chemisorption dominated at low concentrations and high pH values and formed a rigid and thin adsorption layer. Surface precipitation of calcium oleate and micelles dominated at concentrations higher than critical micelle concentration (CMC) and lower pHs and formed a thick but dissipated adsorption layer with a high hydration level. Three distinct adsorption behaviors were identified from the different slopes of ΔD-Δf plots. The adsorption density was less than a monolayer at concentrations <0.164 mM, but increased significantly at concentrations higher than 0.821 mM at all three pHs. The critical concentration at pH 8 was 0.33 mM, which was lower than at pH 9 (0.821 mM) and pH 10 (3.3 mM).