The Improvement in Surface Properties of Metallic Implant via Magnetron Sputtering: Recent Progress and Remaining Challenges

Bioceramic coatings on metallic implants provide a wear-resistant and biocompatible layer, that own ability to develop bone-like apatite in physiological environments to ensure bonding with hard tissues. These bioceramics primarily belong to Calcium Phosphates (CaPs), bioactive glasses, and glass-ceramics. Several techniques are used to deposit these coatings such as; electrophoretic deposition (EPD), plasma spray (PS), and Radio frequency magnetron sputtering (RFMS). Most of these techniques require a high-temperature operation or sintering treatment. This causes either thermal decomposition of bioceramic or results in delamination and cracking of the bioceramic coating due to differences in thermal expansion behavior of metals and bioceramics. RFMS is primarily carried out either at room temperature. However, annealing is performed or substrate is heated at various temperatures ∼400–1,200°C for 2 or 4 h under dry argon (very low temperature compared to other techniques) to ensure crystallization of bioceramics and improve coating adhesion. Chemical composition stability and excellent surface finish are the premium features of RFMS, due to less heat involvement. Moreover, RFMS has the unique ability to develop one-unit/ multilayered composite coatings and the flexibility of in-situ reactions to yield oxides and nitrides. Single or multiple targets can be employed with the insertion of Oxygen and Nitrogen to yield versatile coatings. Due to this attractive set of features RFMS has a strong potential in the field of bioceramic coatings. In recent years, several multifunctional bioceramic coatings have been deposited on metallic substrates using RFMS for biomedical applications. This review focuses on the recent efforts made in order to deposit multifunctional bioceramic RFMS coatings with surface characteristics necessary for biomedical applications and highlights future directions for the improved biological performance of RFMS bioceramic coatings.

Effects of La2O3 contents on microstructure and properties of laser-cladded 5wt%CaB6/HA bioceramic coating

In the present work, 5wt%CaB6/HA bioceramic coatings with different La2O3contents (0-0.6wt%) have been fabricated by a laser cladding technique on Ti-6Al-4V. The effects of La2O3 contents on microstructure and properties of the laser-cladded 5wt%CaB6/HA coatings have been carefully investigated. The results show that the microstructure is obviously refined, and the structure is relatively uniform after doping 0.2-0.4 wt% La2O3. As the La2O3 content increases, the corrosion resistance are found to increase firstly and then gradually decrease. The XRD analysis confirms that the amount of HA and TCP in the coating reaches maximum after doping 0.2wt% La2O3. The La2O3-doped coatings show a significantly higher bone-like apatite precipitation after immersion in SBF compared with La2O3-free coating. In vitro experiment also shows that 5wt%CaB6/HA bioceramic coatings with 0.2-0.4wt% La2O3 are more suitable for the attachment and proliferation of MG63 cells, exhibiting superior bioactivity and biocompatibility.

Creation of Bioceramic Coatings on the Surface of Ti–6Al–4V Alloy by Plasma Electrolytic Oxidation Followed by Gas Detonation Spraying

In this work, bioceramic coatings were formed on Ti6Al4V titanium alloy using a combined technique of plasma electrolytic oxidation followed by gas detonation spraying of calcium phosphate ceramics, based on hydroxyapatite. Plasma electrolytic oxidation was carried out in electrolytes with various chemical compositions, and the effect of electrolytes on the macro and microstructure, pore size and phase composition of coatings was estimated. Three types of electrolytes based on sodium compounds were used: phosphate, hydroxide, and silicate. Plasma electrolytic oxidation of the Ti–6Al–4V titanium alloy was carried out at a fixed DC voltage (270 V) for 5 min. The sample morphology and phase composition were studied with a scanning electron microscope and an X-ray diffractometer. According to the results, the most homogeneous structure with lower porousness and many crystalline anatase phases was obtained in the coating prepared in the silicate-based electrolyte. A hydroxyapatite layer was obtained on the surface of the oxide layer using detonation spraying. It was determined that the appearance of α-tricalcium phosphate phases is characteristic for detonation spraying of hydroxyapatite, but the hydroxyapatite phase is retained in the coating composition. Raman spectroscopy results indicate that hydroxyapatite is the main phase in the coatings.

In vitro biological and antimicrobial properties of chitosan-based bioceramic coatings on zirconium

Ca-based porous and rough bioceramic surfaces were coated onto zirconium by micro-arc oxidation (MAO). Subsequently, the MAO-coated zirconium surfaces were covered with an antimicrobial chitosan layer via the dip coating method to develop an antimicrobial, bioactive, and biocompatible composite biopolymer and bioceramic layer for implant applications. Cubic ZrO2, metastable Ca0.15Zr0.85O1.85, and Ca3(PO4)2 were detected on the MAO surface by powder-XRD. The existence of chitosan on the MAO-coated Zr surfaces was verified by FTIR. The micropores and thermal cracks on the bioceramic MAO surface were sealed using a chitosan coating, where the MAO surface was porous and rough. All elements such as Zr, O, Ca, P, and C were homogenously distributed across both surfaces. Moreover, both surfaces indicated hydrophobic properties. However, the contact angle of the MAO surface was lower than that of the chitosan-based MAO surface. In vitro bioactivity on both surfaces was investigated via XRD, SEM, and EDX analyses post-immersion in simulated body fluid (SBF) for 14 days. In vitro bioactivity was significantly enhanced on the chitosan-based MAO surface with respect to the MAO surface. In vitro microbial adhesions on the chitosan-based MAO surfaces were lower than the MAO surfaces for Staphylococcus aureus and Escherichia coli.

Manufacturing of bilayer bioceramic coatings on surface of titanium alloy Ti-6Al-4V

This paper discusses some properties of bioceramic bilayer coatings on Ti-6Al-4V substrates obtained by an integrated technology including microarc oxidation and detonation spraying of calcium phosphate (Ca-P) layers. Ca-P coatings were deposited from feedstock HAp parti-cles. As a result, bilayer systems were obtained: TiO2 (with a thickness of  2–3 μm) and sub-sequent Ca-P (with a thickness of  100–150 μm) coatings. These coatings were characterized by SEM, XRD and EDX. The coatings contained only biocompatible phases – anatase, hy-droxyapatite and tricalcium phosphate. No cytotoxic components have been registered. The stoichiometric ratio was Ca/P  1.56–1.86. The conclusion is made about the prospects of the proposed integrated technology for manufacturing bilayer ceramics to titanium implants.

In Vitro Biological and Antimicrobial Properties of Chitosan-based Bioceramic Coatings on Zirconium

Ca-based porous and rough bioceramic surfaces were coated on zirconium by micro arc oxidation (MAO). Subsequently, an antibacterial chitosan layer was covered on the MAO-coated zirconium surfaces by dip coating method to develop an antibacterial, bioactive and biocompatible composite biopolymer and bioceramic layer for implant applications. The cubic-ZrO2, meta-stable Ca0.15Zr0.85O1.85, and Ca3(PO4)2 were detected on the MAO surface by powder-XRD. The existence of chitosan on the MAO-coated Zr surfaces was verified by FTIR. The micro-pores and thermal cracks on the bioceramic MAO surface were sealed by chitosan coating, while the MAO surface is porous and rough. All elements such as Zr, O, Ca, P and C were homogenously distributed through both surfaces. Moreover, both surfaces indicated hydrophobic properties. However, the contact angle value of the MAO surface was lower than the one of chitosan-based MAO surface. In vitro bioactivity on both surfaces was investigated by XRD, SEM and EDX analyses at post-immersion in simulated body fluid (SBF) up to 14 days. In vitro bioactivity was significantly enhanced on the chitosan-based MAO surface with respect to the MAO surface. In vitro bacterial adhesions on the chitosan-based MAO surfaces were lower compared to the MAO surfaces for Staphylococcus aureus and Escherichia coli.