Synthesis and Characterization of Nano-Hydroxyapatite/mPEG-b-PCL Composite Coating on Nitinol Alloy

In this study the bioactivity of hydroxyapatite/poly(ε-caprolactone)–poly(ethylene glycol) bilayer coatings on Nitinol superelastic alloy was investigated. The surface of Nitinol alloy was activated by a thermo-chemical treatment and hydroxyapatite coating was electrodeposited on the alloy, followed by applying the polymer coating. The surface morphology of coatings was studied using FE-SEM and SEM. The data revealed that the hydroxyapatite coating is composed of one-dimensional nano sized flakes and the polymer coating is uniformly covered the sublayer. Also, High resolution TEM studies on the hydroxyapatite samples revealed that each flake contains nano-crystalline grains with a diameter of about 15 nm. The hydroxyapatite monolayer coating was rapidly covered by calcium phosphate crystals (Ca/P=1.7) after immersion in simulated body fluid confirming the bioactivity of the nanostructured flakes. However, the flakes were weak against applied external forces because of their ultra-fine thickness. Scratch test was applied on hydroxyapatite/ polymer coating to evaluate delamination of the coating from substrate. It was shown that, the polymer coating has a great influence on toughening the hydroxyapatite coating. To assess the degradation effect of the polymer layer on hydroxyapatite coating, samples were immersed in phosphate-buffered saline at 37 °C. SEM studies on the samples revealed that the beneath layer of hydroxyapatite appears after 72 h without any visible change in morphology. It seems that, application of a biodegradable polymer film on the nanostructured hydroxyapatite coating is a good way to support the coating during implantation processes.