The effect of potential bias on the formation of ionic liquid generated surface films on Mg alloys

An electrochemical approach to the formation of a protective surface film on Mg alloys immersed in the ionic liquid (IL), trihexyl(tetradecyl)phosphonium–bis 2,4,4-trimethylpentylphosphinate, was investigated in this work. Initially, cyclic voltammetry was used with the Mg alloy being cycled from OCP to more anodic potentials. EIS data indicate that, under these circumstances, an optimum level of protection was achieved at intermediate potentials (e.g., 0 or 0.25 V versus Ag/AgCl). In the second part of this paper, a small constant bias was applied to the Mg alloy immersed in the IL for extended periods using a novel cell design. This electrochemical cell allowed us to monitor in situ surface film formation on the metal surface as well as the subsequent corrosion behaviour of the metal in a corrosive medium. This apparatus was used to investigate the evolution of the surface film on an AZ31 magnesium alloy under a potential bias (between ±100 mV versus open circuit) applied for over 24 h, and the film evolution was monitored using electrochemical impedance spectroscopy (EIS). A film resistance was determined from the EIS data and it was shown that this increased substantially during the first few hours (independent of the bias potential used) with a subsequent decrease upon longer exposure of the surface to the IL. Preliminary characterization of the film formed on the Mg alloy surface using ToF-SIMS indicates that a multilayer surface exists with a phosphorous rich outer layer and a native oxide/hydroxide film underlying this. The corrosion performance of a treated AZ31 specimen when exposed to 0.1 M NaCl aqueous solution showed considerable improvement, consistent with electrochemical data.

Microstructural characterization and mechanical properties of Mg-Zr-Ca alloys prepared by hot-extrusion for biomedical applications

This paper investigated the microstructural characterization and mechanical properties of Mg-Zr-Ca alloys prepared by hot-extrusion for potential use in biomedical applications. Mg-Zr-Ca alloys were fabricated by commercial pure Mg (99.9%), Ca (99.9%), and master Mg-33% Zr alloy (mass%). The microstructural characterization of the hot-extruded Mg-Zr-Ca alloys was examined by X-ray diffraction analysis and optical microscopy, and the mechanical properties were determined from tensile tests. The experimental results indicate that the hot-extruded Mg-Zr-Ca alloys with 1 mass% Ca are composed of one single phase and those alloys with 2 mass% Ca consist of both Mg2Ca and α phase. The hot-extruded Mg-Zr-Ca alloys exhibit equiaxed granular microstructures and the hot-extrusion process can effectively increase both the tensile strength and ductility of Mg-Zr-Ca alloys. The hot-extruded Mg-1Zr-1Ca alloy (mass%) exhibits the highest strength and best ductility among all the alloys, and has much higher strength than the human bone, suggesting that it has a great potential to be a good candidate for biomedical application.

Biodegradable Mg-Zr-Ca alloys for bone implant materials

Mg–Zr–Ca alloys were developed for new biodegradable bone implant materials. The microstructure and mechanical property of the Mg–xZr–yCa [x=0·5, 1·0% and y=1·0, 2·0% (wt-% hereafter)] alloys were characterised by optical microscopy, compressive and hardness tests. The in vitro cytotoxicity of the alloys was assessed using osteoblast-like SaOS₂ cells. The corrosion behaviour of these alloys was evaluated by soaking the alloys in simulated body fluid (SBF) and modified minimum essential medium (MMEM). Results indicated that the mechanical properties of the Mg–Zr–Ca are in the range of the mechanical properties of natural bone. The corrosion rate and biocompatibility decreases with the increase in the Ca content in the Mg–Zr–Ca alloys. The solutions of SBF and MMEM with the immersion of the Mg–Zr–Ca alloys show strong alkalisation. The Zr addition to the Mg–Zr–Ca alloys leads to an increase in the corrosion resistance, compressive strength and the ductility of the alloys, and a decrease in the elastic modulus of the Mg–Zr–Ca alloys.

Compressive properties of hot-rolled Mg-Zr-Ca alloys for biomedical applications

This paper investigated the microstructures and compressive properties of hot-rolled Mg-Zr-Ca alloys for biomedical applications. The microstructures of the Mg-Zr-Ca alloys were examined by X-ray diffraction analysis and optical microscopy, and the compressive properties were determined from compressive tests. The experimental results indicate that the hot-rolled Mg-Zr-Ca alloys with 1% Ca are composed of one single α phase and those alloys with 2% Ca consist of both Mg2Ca and α phase. The hot-rolled Mg-Zr-Ca alloys exhibit typical elongated microstructures with obvious fibrous stripe, and have much higher compressive strength and lower compressive modulus than pure Mg. All the studied alloys have much higher compressive yield strength than the human bone (90~140 MPa) and comparable modulus with the human bone, suggesting that they have a great potential to be good candidates for biomedical applications.

Mg-Zr-Sr alloys as biodegradable implant materials

Novel Mg–Zr–Sr alloys have recently been developed for use as biodegradable implant materials. The Mg–Zr–Sr alloys were prepared by diluting Mg–Zr and Mg–Sr master alloys with pure Mg. The impact of Zr and Sr on the mechanical and biological properties has been thoroughly examined. The microstructures and mechanical properties of the alloys were characterized using optical microscopy, X-ray diffraction and compressive tests. The corrosion resistance was evaluated by electrochemical analysis and hydrogen evolution measurement. The in vitro biocompatibility was assessed using osteoblast-like SaOS2 cells and MTS and haemolysis tests. In vivo bone formation and biodegradability were studied in a rabbit model. The results indicated that both Zr and Sr are excellent candidates for Mg alloying elements in manufacturing biodegradable Mg alloy implants. Zr addition refined the grain size, improved the ductility, smoothed the grain boundaries and enhanced the corrosion resistance of Mg alloys. Sr addition led to an increase in compressive strength, better in vitro biocompatibility, and significantly higher bone formation in vivo. This study demonstrated that Mg–xZr–ySr alloys with x and y ⩽5 wt.% would make excellent biodegradable implant materials for load-bearing applications.

Effect of Zn concentration and grain size on prismatic slip in Mg-Zn binary alloys

Mg-Zn binary alloys with concentrations between 0 and 2.8wt% Zn have been prepared and processed via hot rolling and annealing to produce specimens with a strong basal texture and a range of grain sizes. These have been deformed in tension, a condition in which the deformation is dominated by prismatic slip. This data has been used to assess the Hall-Petch parameter as a function of Zn concentration for deformation dominated by prismatic slip. Pure magnesium showed non-linear Hall-Petch behaviour at large grain sizes, and this is compared to the values for prismatic slip measured on single crystals. The differences between critical resolved shear stress measurements made through single crystal, polycrystal and mathematical modelling techniques are also discussed.

Microstructures, mechanical properties and in vitro corrosion behaviour of biodegradable Mg-Zr-Ca alloys

The microstructures, mechanical properties, corrosion behaviour and biocompatibility of the Mg-Zr-Ca alloys have been investigated for potential use in orthopaedic applications. The microstructures of the alloys were examined using X-ray diffraction analysis, optical microscopy and scanning electron microscopy. The mechanical properties of Mg-Zr-Ca alloys were determined from compressive tests. The corrosion behaviour has been investigated using an immersion test and electrochemical measurement. The biocompatibility was evaluated by cell growth factor using osteoblast-like SaOS2 cell. The experimental results indicate that the hot-rolled Mg-Zr-Ca alloys exhibit much finer microstructures than the as-cast Mg-Zr-Ca alloys which show coarse microstructures. The compressive strength of the hot-rolled alloys is much higher than that of the as-cast alloys and the human bone, which would offer appropriate mechanical properties for orthopaedic applications. The corrosion resistance of the alloys can be enhanced significantly by hot-rolling process. Hot-rolled Mg-0.5Zr-1Ca alloy (wt %) exhibits the lowest corrosion rate among all alloys studied in this paper. The hot-rolled Mg-0.5Zr-1Ca and Mg-1Zr-1Ca alloys exhibit better biocompatibility than other studied alloys and possess advanced mechanical properties, corrosion resistance and biocompatibility, suggesting that they have a great potential to be good candidates for orthopaedic applications. © 2012 Springer Science+Business Media New York.

In vitro studying corrosion behaviour of biocorrodible Mg alloys

The idea of bioabsorbable/biocorrodible stents has gained increasing attention in the last decade. Permanent coronary stents, traditionally made from 316L grade stainless steel, are routinely used for the treatment of blocked arteries. However, these stents can cause complications such as restenosis, thrombosis and the need for the patient to undergo prolonged antiplatelet therapy. Biodegradable metal stents provide an opportunity for the stent to remain in place for a period to ensure restoration of function and then degrade through a carefully controlled bio-corrosion process. Among the number of potentially suitable materials, Magnesium alloys have shown great promise as a stent material due to their non-toxicity [1] and the corrosion rates attainable in biological environments. However, a carefully controlled corrosion process is essential in order to avoid hyper hydrogen generation and the fatal consequences that follow. In addition uniform corrosion is a basic requirement to maintain the mechanical integrity and load bearing characteristics. Work being undertaken in our laboratories focuses on controlling the corrosion behaviour of magnesium in a simulated biological environment in the presence of protein. In the investigation reported here the Mg alloy has been examined using Scanning Electrochemical Microscope (SECM) to visualize the corrosion process and identify the corrosion pattern. Complementary bulk electrochemical techniques (EIS and potentiodynamic polarization) have been used to acquire kinetic and mechanistic information. Early results obtained by SECM have revealed the tendency towards pitting corrosion in the early stages which subsequently develops in to filiform corrosion.