M. Bobby Kannan

In vitro degradation and mechanical integrity of calcium-containing magnesium alloys in modified-simulated body fluid

The successful applications of magnesium-based alloys as degradable orthopaedic implants are mainly inhibited due to their high degradation rates in physiological environment and consequent loss in the mechanical integrity. This study examines the degradation behaviour and the mechanical integrity of calcium-containing magnesium alloys using electrochemical techniques and slow strain rate test (SSRT) method, respectively, in modified-simulated body fluid (m-SBF). Potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) results showed that calcium addition enhances the general and pitting corrosion resistances of magnesium alloys significantly. The corrosion current was significantly lower in AZ91Ca alloy than that in AZ91 alloy. Furthermore, AZ91Ca alloy exhibited a five-fold increase in the surface film resistance than AZ91 alloy. The SSRT results showed that the ultimate tensile strength and elongation to fracture of AZ91Ca alloy in m-SBF decreased only marginally (approximately 15% and 20%, respectively) in comparison with these properties in air. The fracture morphologies of the failed samples are discussed in the paper. The in vitro study suggests that calcium-containing magnesium alloys to be a promising candidate for their applications in degradable orthopaedic implants, and it is worthwhile to further investigate the in vivo corrosion behaviour of these alloys.

Potentiostatic pulse-deposition of calcium phosphate on magnesium alloy for temporary implant applications--an in vitro corrosion study.

In this study, a magnesium alloy (AZ91) was coated with calcium phosphate using potentiostatic pulse-potential and constant-potential methods and the in vitro corrosion behaviour of the coated samples was compared with the bare metal. In vitro corrosion studies were carried out using electrochemical impedance spectroscopy and potentiodynamic polarization in simulated body fluid (SBF) at 37 °C. Calcium phosphate coatings enhanced the corrosion resistance of the alloy, however, the pulse-potential coating performed better than the constant-potential coating. The pulse-potential coating exhibited ~3 times higher polarization resistance than that of the constant-potential coating. The corrosion current density obtained from the potentiodynamic polarization curves was significantly less (~60%) for the pulse-deposition coating as compared to the constant-potential coating. Post-corrosion analysis revealed only slight corrosion on the pulse-potential coating, whereas the constant-potential coating exhibited a large number of corrosion particles attached to the coating. The better in vitro corrosion performance of the pulse-potential coating can be attributed to the closely packed calcium phosphate particles.

Influence of circumferential notch and fatigue crack on the mechanical integrity of biodegradable magnesium‐based alloy in simulated body fluid

Applications of magnesium alloys as biodegradable orthopaedic implants are critically dependent on the mechanical integrity of the implant during service. In this study, the mechanical integrity of an AZ91 magnesium alloy was studied using a constant extension rate tensile (CERT) method. The samples in two different geometries that is, circumferentially notched (CN), and circumferentially notched and fatigue cracked (CNFC), were tested in air and in simulated body fluid (SBF). The test results show that the mechanical integrity of the AZ91 magnesium alloy decreased substantially (∼50%) in both the CN and CNFC samples exposed to SBF. Fracture surface analysis revealed secondary cracks suggesting stress corrosion cracking susceptibility of the alloy in SBF.

Improving the packing density of calcium phosphate coating on a magnesium alloy for enhanced degradation resistance

In this study, an attempt was made to improve the packing density of calcium phosphate (CaP) coating on a magnesium alloy by tailoring the coating solution for enhanced degradation resistance of the alloy for implant applications. An organic solvent, ethanol, was added to the coating solution to decrease the conductivity of the coating solution so that hydrogen bubble formation/bursting reduces during the CaP coating process. Experimental results confirmed that ethanol addition to the coating solution reduces the conductivity of the solution and also decreases the hydrogen evolution/bubble bursting. In vitro electrochemical experiments, that is, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization showed that CaP coating produced in 30% (v/v) ethanol containing coating solution (3E) exhibits significantly higher degradation resistance (i.e., ~50% higher polarization resistance and ~60% lower corrosion current) than the aqueous solution coating. Scanning electron microscope (SEM) analysis of the coatings revealed that the packing of 3E coating was denser than that of aqueous coating, which can be attributed to the lower hydrogen evolution in the former than in the latter. Further increase in the ethanol content in the coating solution was not beneficial; in fact, the coating produced in 70% (v/v) ethanol containing solution (7E) showed degradation resistance much inferior to that of the aqueous coating, which is due to low thickness of 7E coating.

In vitro degradation behaviour of a friction stir processed magnesium alloy.

In this study, the in vitro degradation behaviour of a friction stir processed AZ31 magnesium alloy was investigated. Electrochemical experiments in simulated body fluid suggest that friction stir processing marginally enhances the degradation resistance of the alloy, which could be attributed to the dissolution of secondary phase particles. Homogenisation of the microstructure reduces galvanic corrosion. It is envisaged that the beneficial effect would be more pronounced for magnesium alloys which contain high volume fraction of galvanic corrosion inducing secondary phase particles.

Influence of living cells (L929) on the biodegradation of magnesium–calcium alloy

In this study, the influence of living cells (L929) on the in vitro degradation behaviour of a magnesium-calcium alloy was investigated using an electrochemical technique in the Eagles minimum essential medium (EMEM) with 10% foetal bovine serum (FBS) under 5% CO2 atmosphere. The degradation of the alloy increased significantly in the medium containing the cells as compared to that without cells. Post-degradation analysis revealed localized degradation in the vicinity of the cells. It is suggested that the cell metabolic activity has induced local pH drop and as a result increased the alloy degradation.

A mechanistic study of in vitro degradation of magnesium alloy using electrochemical techniques

To understand the in vitro degradation mechanism of magnesium alloy, electrochemical experiments viz., electrochemical impedance spectroscopy and potentiodynamic polarization, were carried out on AZ91 magnesium alloy under different experimental conditions. The study suggests: (i) the body temperature decreases significantly the corrosion resistance of the alloy, (ii) alkali-treatment of the alloy enhances the corrosion resistance, and (iii) although chloride in simulated body fluid minimizes the corrosion resistance, the presence of other constituents viz., phosphate, calcium, and carbonate, enhances the film forming tendency and hence increases the corrosion resistance of the alloy.

Low elastic modulus Ti–Ta alloys for load-bearing permanent implants: Enhancing the biodegradation resistance by electrochemical surface engineering

In this study, the in vitro degradation behaviour of titanium-tantalum (Ti-Ta) alloys (10-30 wt.% Ta) was investigated and compared with conventional implant materials, i.e., commercially pure titanium (Cp-Ti) and titanium-aluminium-vanadium (Ti6Al4V) alloy. Among the three Ti-Ta alloys studied, the Ti20Ta (6.3×10(-4) mm/y) exhibited the lowest degradation rate, followed by Ti30Ta (1.2×10(-3) mm/y) and Ti10Ta (1.4×10(-3) mm/y). All the Ti-Ta alloys exhibited lower degradation rate than that of Cp-Ti (1.8×10(-3) mm/y), which suggests that Ta addition to Ti is beneficial. As compared to Ti6Al4V alloy (8.1×10(-4) mm/y), the degradation rate of Ti20Ta alloy was lower by ~22%. However, the Ti30Ta alloy, which has closer elastic modulus to that of natural bone, showed ~48% higher degradation rate than that of Ti6Al4V alloy. Hence, to improve the degradation performance of Ti30Ta alloy, an intermediate thin porous layer was formed electrochemically on the alloy followed by calcium phosphate (CaP) electrodeposition. The coated Ti30Ta alloy (3.8×10(-3) mm/y) showed ~53% lower degradation rate than that of Ti6Al4V alloy. Thus, the study suggests that CaP coated Ti30Ta alloy can be a viable material for load-bearing permanent implants.

A mechanistic in vitro study of the microgalvanic degradation of secondary phase particles in magnesium alloys

The aim of this work was to understand the effect of microgalvanic degradation on secondary phase particles in magnesium alloys under in vitro condition. Pure magnesium and Mg17 Al12 (β-phase) were galvanically coupled in simulated body fluid and the degradation behavior was studied using electrochemical impedance spectroscopy. The galvanic coupling produced a phosphate/carbonate layer on the β-phase, which initially increased the degradation resistance. However, the deposited phosphate/carbonate layer rapidly degraded once the galvanic coupling was removed, and β-phase exhibited similar degradation resistance to that of pure magnesium. A phenomenological model has been presented, demonstrating the galvanic coupling effect.

Calcium Phosphate Deposition on Magnesium Alloy for Bioimplant Applications

Successful application of magnesium-based alloys as biodegradable biomaterials is critically dependent on controlling the degradation rate of the alloy. The present study suggests that electrochemical deposition of calcium phosphate on magnesium alloy at an optimal voltage enhances the degradation resistance of the alloy significantly.