Self-Assembled Monolayers of Various Alkyl-Phosphonic Acids on Bioactive FHA Coating for Improving Surface Stability and Corrosion Resistance of Biodegradable AZ91D Mg Alloy

The aim of present study is to deposit protective coatings with various surface chemical states on AZ91D Mg alloy. Hydrothermal bioactive ceramic coatings are performed with a surface modification by the chemical bonding of self-assembled monolayers (SAM). The electrochemical corrosion behaviors of various surface-coated AZ91D alloy within DMEM cell culture medium related to their surface chemical states are evaluated through microstructure observations, XPS surface chemical bonding analysis, static contact angles measurements, potentiodynamic polarization curves, and immersion tests. XRD and high resolution XPS of F 1<i>s</i> analysis results show that the hydrothermal FHA coating with a phase composition of Ca₁₀(PO₄)₆(OH)F can be effectively and uniformly deposited on the AZ91D alloy. FHA-coated AZ91D displays better anti-corrosion performances and lower degradation rates than those of uncoated AZ91D alloy in the DMEM solution. Through the high resolution XPS analysis of O 1<i>s</i> and P 2<i>p</i> spectra, it is demonstrated that 1-butylphosphonic acid (BP), 1 octylphosphonic acid (OP), and dodecylphosphonic acid (DP) molecules can be effectively bonded on the FHA surface by a covalent bond to form SAM. BP/OP/DP-SAM specimens display increased static contact angles to show a hydrophobic surface. It demonstrates that the SAM surface treatment can further enhance the corrosion resistance of FHA-coated AZ91D in the DMEM solution. After 2-16 days in vitro immersion tests in the DMEM, the surface SAM-bonded hydrophobic BP/OP/DP-SAM layers can effectively inhibit and reduce the penetration of DMEM into FHA coating. Long alkyl chains of the dodecylphosphonic acid (DP) SAM represents superior enhancing effects on the reduction of corrosion properties and weight loss.