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Silicon-doped hydroxyapatite-based (Si-HA) coatings were deposited via radio frequency (RF) magnetron sputtering on the surface of titanium that was treated with a pulsed electron beam. This study aimed to evaluate the effect of Si doping on the structure and mechanical properties of thin HA films. The content of the silicon was 1.2 and 4.6 at.% for the coatings prepared using the Si-HA precursor powders with a chemical formula Ca 10 (PO 4 ) 6 − x (SiO 4 ) x (OH) 2 − x where, x = 0.5 and 1.72. Pure HA (Ca 10 (PO 4 ) 6 (OH) 2 ) coatings were deposited for comparison. The as-deposited films were analysed with respect to their composition, state of chemical binding and microstructure using XPS, FTIR, XRD, and SEM. We hypothesized that the addition of Si would affect the mechanical features of the coatings due to microstructure changes. The effect of the introduction of Si on the nanohardness and the Young's modulus as well as the adhesion strength and scratch resistance of the HA coating was investigated using nanohardness testing and a scratch test, respectively. Examination of the coating microstructure using SEM and AFM revealed that Si doping influenced the surface morphology and led to a smaller grain size. The tendency to form an amorphous structure also increased with an increase in the Si content. A monotonous decrease in both the nanohardness and the elastic modulus was observed with an increase in the Si content. A maximum nanohardness of ~ 7 GPa was obtained for the Si-free HA coating, whereas the hardness decreased to ~ 4.3 GPa for the films with a Si content of 1.2 at.%. The addition of 4.6 at.% Si to the HA coating resulted in a reduction in the elastic modulus, whereas the nanohardness was very similar to that of the uncoated substrate. The adhesion behaviour of the coatings demonstrated different responses. In the case of pure HA coatings, failure occurred due to the low cohesion of the coating, whereas the crystalline Si-HA coatings with a Si content of 1.2 at.% deformed plastically without crack formation and without detaching from the titanium substrate, which resulted in a greater coating stability. [ABSTRACT FROM AUTHOR]

This study investigated the effect of the substrate morphology introduced by various substrate preparation techniques, namely acid etching (AE) and pulsed electron beam (PEB) treatments, on the CaP film morphology and mechanical properties. The morphology, nanohardness, and Young's modulus of the CaP coating deposited via radio-frequency (RF) magnetron sputtering were investigated by X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), scanning electron microscopy and nanoindentation studies. The Ca/P ratios of the CaP coating deposited via RF magnetron sputtering onto titanium substrates treated using AE and PEB according to XPS were 1.73 ± 0.03 and 1.72 ± 0.04, respectively, which is close to the Ca/P ratio of 1.67 typical for stoichiometric hydroxyapatite (HA). The AFM experiments and nanoindentation studies revealed significant differences in the morphology and mechanical responses of the CaP films deposited onto acid-etched titanium substrates treated with PEB. Deposition of the CaP coating onto the acid-etched surface resulted in a rough surface with the presence of an island-like morphology. The CaP coating onto a smooth titanium substrate treated by PEB exhibited grains with irregular shapes and decreased size. The nanoindentation hardness and the Young's modulus of the HA coating deposited onto titanium treated by the PEB treatment were determined to be 7.0 ± 0.3 and 124 ± 3 GPa, respectively, which are significantly higher than those of the CaP coating on the acid-etched titanium substrates. Moreover, the elastic strain to failure ( H / E ), the plastic deformation resistance ( H 3 / E 2 ), and the percent elastic recovery % R of the HA coating on titanium after surface irradiation with an electron energy density of 15 J·cm − 2 were determined to increase by ~ 23%, ~ 70% and ~ 53%, respectively, compared to the CaP coating on acid-etched titanium. [ABSTRACT FROM AUTHOR]