New TiNb-based alloys, such as Ti–6Al–7Nb, are currently being studied around the world as an alternative to other Ti alloys, e.g., instead of Ti–6Al–4V. We conducted a pilot study where thin (approximately 1.2 micron) CaP coatings containing low doses of Zn2+ (0.4–0.8 wt.%) were prepared by the radio frequency magnetron sputtering (RFMS) of Zn-hydroxyapatite (HA) target on Ti–6Al–4V and Ti–6Al–7Nb substrates and investigated their physicochemical properties, in vitro solubility, cytotoxicity, and antibacterial and osteogenic activities. The thickness of the obtained coatings was approximately 1.2–1.3 microns. Zn substitution did not result in roughness or structural or surface changes in the amorphous CaP coatings. The distributions of Ca, P, and Zn were homogeneous across the film thickness as shown by the EDX mapping of these elements. Zn doping of CaP coatings on both types of Ti-based alloys statistically influenced the results of the scratch-test. However, obtained values are satisfactory to use Zn-CaP coatings on biomedical implants. Increased Zn2+ release vs. tapered output of Ca and phosphate ions occurred during 5 weeks of an in vitro immersion test in 0.9% NaCl solution. Ti–6Al–7Nb alloy, unlike Ti–6Al–4V, promoted more linear biodegradation of CaP coatings in vitro. As a result, CaP-based surfaces on Ti–6Al–7Nb, compared with on Ti–6Al–4V alloy, augmented the total areas of Alizarin red staining in a 21-day culture of human adipose-derived mesenchymal stem cells in a statistically significant manner. Moreover, Zn–CaP coatings statistically reduced leukemic Jurkat T cell survival within 48 h of in vitro culture. Along with the higher solubility of the Zn–CaP surface, a greater reduction (4- to 5.5-fold) in Staphylococcus aureus growth was observed in vitro when 7-day extracts of the coatings were added into the microbial culture. Hence, Zn–CaP-coated Ti–6Al–7Nb alloy with controllable biodegradation as prepared by RFMS is a prospective material suitable for bone applications in cases where there is a risk of bacterial contamination with severe consequences, for example, in leukemic patients. Further research is needed to closely investigate the mechanical features and pathways of their solubility and antimicrobial, antitumor, and osteogenic activities.
Biodegradable materials are currently attracting the attention of scientists as materials for implants in reconstructive medicine. At the same time, ceramics based on calcium silicates are promising materials for bone recovery, because Ca2+ and Si2+ ions are necessary for the mineralization process, and they take an active part in the formation of apatite. In the presented research, the protective silicate biocoatings on a Mg0.8Ca alloy were formed by means of the micro-arc oxidation method, and the study of their morphology, structure, phase composition, corrosion, and biological properties was carried out. Elongated crystals and pores were uniformly distributed over the surface of the coatings. The coated samples exhibited remarkable anti-corrosion properties in comparison with bare magnesium alloy because their corrosion current decreased 10 times, and their corrosion resistance increased almost 100 times. The coatings did not significantly affect the viability of the cells, even without the additional dilution of the extract, and were non-toxic according to ISO 10993-5: 2009. In this case, there was a significant difference in toxicity of the pure Mg0.8Ca alloy and the coated samples. Thus, the results demonstrated that the applied coatings significantly reduced the toxicity of the alloy.
Magnesium-based alloys hold potential for medical applications, but face challenges like rapid bioresorption and limited mechanical strength during early bone healing. In our study, we present a novel Mg–Zn–Zr–Ce alloy with low cerium content (up to 0.1 wt.% Ce) processed using two severe plastic deformation (SPD) techniques. Through an innovative combination of multiaxial forging and multipass rolling, we have achieved a fine-grained structure with an average grain size of the primary α-Mg phase of 1.0 μm. This refined microstructure exhibits improved mechanical properties, including a substantial increase in yield strength (σYS) from 130 to 240 MPa, while preserving ductility. The alloy’s composition includes α-Mg grains, cerium and zinc hydrides, and intermetallic phases with cerium and zinc elements. Tensile testing of the fine-grained alloy demonstrates an enhancement in yield strength (σYS) to 250 MPa, marking a 2.8-fold improvement over the conventional state (σYS = 90 MPa), with a modest 2-fold reduction in ductility. Crucially, electrochemical tests conducted in physiological solutions highlight substantial advancements in corrosion resistance. The corrosion current was reduced from 14 to 2 μA/cm2, while polarization resistance decreased from 3.1 to 8.1 kΩ∙cm2, underlining the alloy’s enhanced resistance to biodegradation. Our results show that the novel Mg–Zn–Zr–Ce alloy, after combined SPD, demonstrates mitigated bioresorption and enhanced mechanical properties. Our findings highlight the fact that the introduction of this innovative alloy and the application of SPD represent significant steps towards addressing the limitations of magnesium-based alloys for medical implants, offering potential improvements in safety and effectiveness.
This study considers the regularities in the formation of amorphous–crystalline coatings with zinc oxide and wollastonite particles via micro-arc oxidation (MAO) on metal substrates made from a Mg-0.8 wt.% Ca alloy. The combination of components with increased antibacterial and osteogenic properties made it possible to obtain a unique bioactive and corrosion-resistant coating that slowed down the bioresorption of a magnesium implant and stimulated the processes of osteointegration. The coating was examined using various methods, including scanning and transmission electron microscopy, X-ray crystallography, scratch testing, energy-dispersive X-ray spectroscopy, and potentiodynamic polarization testing. As a result of plasma-chemical interactions between electrolyte components and the magnesium substrate, a porous amorphous–crystalline coating comprising wollastonite (CaSiO3), zinc oxide (ZnO), forsterite (Mg2SiO4), and periclase (MgO) was formed at varying voltages (350–500 V) during the MAO process. The protective properties of the coating were exceptional, as evidenced by the mass loss values of the coated samples (1.4–2.3%) in 0.9% NaCl solution, which were significantly lower than the mass loss of the uncoated alloy (8.9%). The coating synthesized at a voltage of 500 V was characterized by a maximum zinc content of 8 at.%, which was responsible for the highest antibacterial activity against Staphylococcus aureus (99.1%).