A critical review of the stress corrosion cracking (SCC) of magnesium alloys

This review aims to provide a foundation for the safe and effective use of magnesium (Mg) alloys, including practical guidelines for the service use of Mg alloys in the atmosphere and/or in contact with aqueous solutions. This is to provide support for the rapidly increasing use of Mg in industrial applications, particularly in the automobile industry. These guidelines should be firmly based on a critical analysis of our knowledge of SCC based on (1) service experience, (2) laboratory testing and (3) understanding of the mechanism of SCC, as well as based on an understanding of the Mg corrosion mechanism.

Formation and mechanical properties of Mg65Cu25Er10 and Mg65Cu15Ag10Er10 bulk amorphous alloys

Mg65Cu25Er10 and Mg65Cu15Ag10Er10 bulk amorphous alloys were produced by a copper mould casting method. The alloys have high glass-forming ability and good thermal stability. The maximum diameter of glass formation (D-c), glass transition temperature (T-g), crystallization onset temperature (T-x), temperature interval of the supercooled region (Delta T-x), melting temperature (T-m), liquidus temperature (T-1) as well as heats of crystallization (Delta H-x) and melting (Delta H-m) are reported for these alloys. Both alloys exhibit high hardness and high strength at room temperature. (c) 2005 Elsevier B.V. All rights reserved.

Microstructure of MmM(5)/Mg multi-layer films prepared by magnetron sputtering

Microstructure of MmNi(3.5)(CoAlMn)(1.5)/Mg (here Mm denotes La-rich mischmetal) multi-layer hydrogen storage thin films prepared by direct current magnetron sputtering was investigated by cross-sectional transmission electron microscopy (XTEM). It was shown that the MMM5 layers are composed of two regions: an amorphous region with a thickness of similar to 4nm at the bottom of the layers and a randomly orientated nanocrystallite region on the top of the amorphous region and the Mg layers consist of typical columnar crystallite with their [001] direction nearly parallel to the growth direction. The mechanism for the formation of the above microstructure characteristics in the multi-layer thin films has been proposed. Based on the microstructure feature of the multi-layer films, mechanism for the apparent improvement of hydrogen absorption/desorption kinetics was discussed. (c) 2005 Elsevier B.V. All rights reserved.

Mg-based nanocomposites with high capacity and fast kinetics for hydrogen storage

Magnesium and its alloys have shown a great potential in effective hydrogen storage due to their advantages of high volumetric/ gravimetric hydrogen storage capacity and low cost. However, the use of these materials in fuel cells for automotive applications at the present time is limited by high hydrogenation temperature and sluggish sorption kinetics. This paper presents the recent results of design and development of magnesium-based nanocomposites demonstrating the catalytic effects of carbon nanotubes and transition metals on hydrogen adsorption in these materials. The results are promising for the application of magnesium materials for hydrogen storage, with significantly reduced absorption temperatures and enhanced ab/desorption kinetics. High level Density Functional Theory calculations support the analysis of the hydrogenation mechanisms by revealing the detailed atomic and molecular interactions that underpin the catalytic roles of incorporated carbon and titanium, providing clear guidance for further design and development of such materials with better hydrogen storage properties.

Interactions between iron, manganese, and the Al-Si eutectic in hypoeutectic Al-Si alloys

Sand-cast plates were used to determine the effect of iron and manganese concentrations on porosity levels in Al-9 pet Si-0.5 pet Mg alloys. Iron increased porosity levels. Manganese additions increased porosity levels in alloys with 0.1 pet Fe, but reduced porosity in alloys with 0.6 and I pet Fe. Thermal analysis and quenching were undertaken to determine the effect of iron and manganese on the solidification of the Al-Si eutectic. At high iron levels, the presence of large beta-Al5FeSi was found to reduce the number of eutectic nucleation events and increase the eutectic grain size. The preferential formation of alpha-Al15Mn3Si2 upon addition of manganese reversed these effects. It is proposed that this interaction is due to beta-Al5FeSi and the Al-Si eutectic having common nuclei. Porosity levels are proposed to be controlled by the eutectic grain size and the size of the iron-bearing intermetallic particles rather than the specific intermetallic phase that forms.

Zirconium alloying and grain refinement of magnesium alloys

Factors that influence alloying zirconium to magnesium with a Mg-33.3Zr master alloy and the subsequent grain refinement are discussed based on a large number of experiments conducted at the laboratory scale (up to 30 kg of melt). It is shown that the zirconium particles released from the Zirmax(R) master alloy must be brought into thorough contact with the melt by an appropriate stirring process in order to attain a good dissolution of zirconium. The influence of alloying temperature on the recovery of zirconium was found to be negligible in the range from 680 to 780 degreesC. An ideal zirconium alloying process should end up with both high soluble and high total zirconium in the melt in order to achieve the best grain refinement in the final alloy. The distribution of zirconium in the final alloy microstructure is inhomogeneous and almost all of the zirconium in solution is concentrated in zirconium-rich cores in the microstructure.

Electrodeposition on aluminium and its alloys

Aluminium alloys S1C, NS4, HE9, LM25 and the 'difficult' zinc containing U.S. specification alloy used for automobile bumpers (X-7046), have been successfully electroplated using pretreatments which utilized either conventional immersion, elevated temperature or electrolytic modified alloy zincate (M.A.Z.) deposits. Satisfactory adhesion in excess of 7•5 KN m -I was only achieved on X-7046 using an electrolytic M.A.Z. pretreatment. The limitations of simple zincate solutions were demonstrated. Growth of deposits ~as monitored using a weight loss technique and the morphology of the various deposits studied using scanning electron microscopy. The characteristics of a specific alloy and processing sequence selected had a significant influence on the growth and morphology of the N.A.Z. deposi t. These all affected subsequent adhesion of electrodeposited nickel. The advantages of double-dip sequences were confirmed. Superior adhesion was associated with a uniform, thin, fine grained M.A.Z. deposit which exhibited rapid and complete surface coverage of the aluminium alloy. The presence of this preferred type deposit did not guarantee adhesion because a certain degree of etching was essential. For a satisfactory combination of alloy and M.A.Z. pretreatment, there was a specific optimum film weight per unit area which resulted in maximum adhesion. An ideal film weight of 0•06 :!: 0•01 mg cm-2was determined for S1C. Different film weights were required for the other alloys due to variations in surface topography caused by pretreatment. S1C was the easiest alloy on which to achieve high bond strength. Peel adhesion was not directly related to tensile strength of the alloy. The highest adhesion value was obtained on S1C which had the lowest strength of the alloys studied. The characteristics of the failure surfaces after peeling depended on alloy type, adhesion level and pretreatment employed. Plated aluminium alloys exhibited excellent corrosion resistance when appropriately pretreated. The M.A.Z. layer was not preferentially attacked. There was a threshold value of adhesion below which corrosion performance ~a8 poor. Alloy type, pretreatment and coating system influenced corrosion performance. Microporous chromium gave better corrosion protection than decorative chromium.

Wear of high aluminium zinc-based alloys in plain bearing applications

Two zinc-based alloys of high aluminium content, Super Cosmal alloy containing 60% Al, 6% Si, 1% Cu, 0.3% Mn and HAZCA alloy containing 60% Al, 8% Si, 2% Cu, 0.06% Mg were produced by sand casting. Foundry characteristics in particular, fluidity, mode of solidification and feeding ability were examined. Metallographic analysis of structures was carried out using optical and scanning electron microscopy and their mechanical properties were determined using standard techniques. Dry wear characteristics were determined using a pin-on-disc test, and boundary-lubricated wear was studied using full bearing tests. Results from casting experiments were evaluated and compared with the behaviour of a standard ZA-27 alloy and those from tribological tests with both ZA-27 alloy and a leaded tin-bronze (SAE660) under the same testing conditions. The presence of silicon was beneficial, reducing the temperature range of solidification, improving feeding efficiency and reducing gravity segregation of phases. Use of chills and melt degassing was found necessary to achieve soundness and enhanced mechanical properties. Dry wear tests were performed against a steel counterface for sliding speeds of 0.25, 0.5, 1.0 and 2 m/s and for a range of loads up to 15 kgf. The high aluminium alloys showed wear rates as low as those of ZA-27 at speeds of 0.25 and 0.5 m/s for the whole range of applied loads. ZA-27 performed better at higher speeds. The build up of a surface film on the wearing surface of the test pins was found to be responsible for the mild type of wear of the zinc based alloys. The constitution of the surface film was determined as a complex mixture of aluminium, zinc and iron oxides and metallic elements derived from both sliding materials. For full bearing tests, bushes were machined from sand cast bars and were tested against a steel shaft in the presence of a light spindle oil as the lubricant. Results showed that all zinc based alloys run-in more rapidly than bronze, and that wear in Super Cosmal and HAZCA alloys after prolonged running were similar to those in ZA-27 bearings and significantly smaller than those of the bronze.

Comparison of crack growth behaviour between spray-formed and commercial plate Al-Zn-Mg-Cu alloy 7150

This paper compares the crack growth resistance of an experimental spray-formed extrusion with that of a commercial aluminium alloy, the two alloys having similar compositions but markedly different grain structures. Tensile and fracture behaviour is similar in both materials and is influenced by inclusion content. The two materials differ in their crack growth resistance, which is shown to be dependent upon grain size and shape. Environmentally-induced crack growth is favoured by aligned grain boundaries and small grain size.

Serrated yielding and the localized shear failure mode in aluminium alloys

A study has been made of serrated yielding in two commercial Al-Zn-Mg alloys in the as-quenched condition. The different serration types produced in the two alloys and the shear failure mechanism observed in both notched-bend and tensile testing are related to the mechanisms of dynamic strain ageing occurring during the test. An estimate of 19.7 kJ/mole for the activation energy for exchange of a solute atom and a vacancy in Al-6.2 wt% Zn, 2.5 wt% Mg has been made. © 1981.

An assessment of novel biodegradable magnesium alloys for endovascular biomaterial applications

Magnesium alloys have been widely explored as potential biomaterials, but several limitations to using these materials have prevented their widespread use, such as uncontrollable degradation kinetics which alter their mechanical properties. In an attempt to further the applicability of magnesium and its alloys for biomedical purposes, two novel magnesium alloys Mg-Zn-Cu and Mg-Zn-Se were developed with the expectation of improving upon the unfavorable qualities shown by similar magnesium based materials that have previously been explored. The overall performance of these novel magnesium alloys has been assessesed in three distinct phases of research: 1) analysing the mechanical properties of the as-cast magnesium alloys, 2) evaluating the biocompatibility of the as-cast magnesium alloys through the use of in-vitro cellular studies, and 3) profiling the degradation kinetics of the as-cast magnesium alloys through the use of electrochemical potentiodynamic polarization techqnique as well as gravimetric weight-loss methods. As compared to currently available shape memory alloys and degradable as-cast alloys, these experimental alloys possess superior as-cast mechanical properties with elongation at failure values of 12% and 13% for the Mg-Zn-Se and Mg-Zn-Se alloys, respectively. This is substantially higher than other as-cast magnesium alloys that have elongation at failure values that range from 7-10%. Biocompatibility tests revealed that both the Mg-Zn-Se and Mg-Zn-Cu alloys exhibit low cytotoxicity levels which are suitable for biomaterial applications. Gravimetric and electrochemical testing was indicative of the weight loss and initial corrosion behavior of the alloys once immersed within a simulated body fluid. The development of these novel as-cast magnesium alloys provide an advancement to the field of degradable metallic materials, while experimental results indicate their potential as cost-effective medical devices.^

An Investigation on Biocompatibility of Bio-Absorbable Polymer Coated Magnesium Alloys

Advances in biomaterials have enabled medical practitioners to replace diseased body parts or to assist in the healing process. In situations where a permanent biomaterial implant is used for a temporary application, additional surgeries are required to remove these implants once the healing process is complete, which increases medical costs and patient morbidity. Bio-absorbable materials dissolve and are metabolized by the body after the healing process is complete thereby negating additional surgeries for removal of implants. Magnesium alloys as novel bio-absorbable biomaterials, have attracted great attention recently because of their good mechanical properties, biocompatibility and corrosion rate in physiological environments. However, usage of Mg as biodegradable implant has been limited by its poor corrosion resistance in the physiological solutions. An optimal biodegradable implant must initially have slow degradation to ensure total mechanical integrity then degrade over time as the tissue heals. The current research focuses on surface modification of Mg alloy (MZC) by surface treatment and polymer coating in an effort to enhance the corrosion rate and biocompatibility. It is envisaged that the results obtained from this investigation would provide the academic community with insights for the utilization of bio-absorbable implants particularly for patients suffering from atherosclerosis. The alloying elements used in this study are zinc and calcium both of which are essential minerals in the human metabolic and healing processes. A hydrophobic biodegradable co-polymer, polyglycolic-co-caprolactone (PGCL), was used to coat the surface treated MZC to retard the initial degradation rate. Two surface treatments were selected: (a) acid etching and (b) anodization to produce different surface morphologies, roughness, surface energy, chemistry and hydrophobicity that are pivotal for PGCL adhesion onto the MZC. Additionally, analyses of biodegradation, biocompatibility, and mechanical integrity were performed in order to investigate the optimum surface modification process, suitable for biomaterial implants. The study concluded that anodization created better adhesion between the MZC and PGCL coating. Furthermore, PGCL coated anodized MZC exhibited lower corrosion rate, good mechanical integrity, and better biocompatibility as compared with acid etched.

Engineering thin films of magnetic alloys and semiconductor oxides at the nanoscale

The thesis aims to exploit properties of thin films for applications such as spintronics, UV detection and gas sensing. Nanoscale thin films devices have myriad advantages and compatibility with Si-based integrated circuits processes. Two distinct classes of material systems are investigated, namely ferromagnetic thin films and semiconductor oxides. To aid the designing of devices, the surface properties of the thin films were investigated by using electron and photon characterization techniques including Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), grazing incidence X-ray diffraction (GIXRD), and energy-dispersive X-ray spectroscopy (EDS). These are complemented by nanometer resolved local proximal probes such as atomic force microscopy (AFM), magnetic force microscopy (MFM), electric force microscopy (EFM), and scanning tunneling microscopy to elucidate the interplay between stoichiometry, morphology, chemical states, crystallization, magnetism, optical transparency, and electronic properties. Specifically, I studied the effect of annealing on the surface stoichiometry of the CoFeB/Cu system by in-situ AES and discovered that magnetic nanoparticles with controllable areal density can be produced. This is a good alternative for producing nanoparticles using a maskless process. Additionally, I studied the behavior of magnetic domain walls of the low coercivity alloy CoFeB patterned nanowires. MFM measurement with the in-plane magnetic field showed that, compared to their permalloy counterparts, CoFeB nanowires require a much smaller magnetization switching field , making them promising for low-power-consumption domain wall motion based devices. With oxides, I studied CuO nanoparticles on SnO2 based UV photodetectors (PDs), and discovered that they promote the responsivity by facilitating charge transfer with the formed nanoheterojunctions. I also demonstrated UV PDs with spectrally tunable photoresponse with the bandgap engineered ZnMgO. The bandgap of the alloyed ZnMgO thin films was tailored by varying the Mg contents and AES was demonstrated as a surface scientific approach to assess the alloying of ZnMgO. With gas sensors, I discovered the rf-sputtered anatase-TiO2 thin films for a selective and sensitive NO2 detection at room temperature, under UV illumination. The implementation of UV enhances the responsivity, response and recovery rate of the TiO2 sensor towards NO2 significantly. Evident from the high resolution XPS and AFM studies, the surface contamination and morphology of the thin films degrade the gas sensing response. I also demonstrated that surface additive metal nanoparticles on thin films can improve the response and the selectivity of oxide based sensors. I employed nanometer-scale scanning probe microscopy to study a novel gas senor scheme consisting of gallium nitride (GaN) nanowires with functionalizing oxides layer. The results suggested that AFM together with EFM is capable of discriminating low-conductive materials at the nanoscale, providing a nondestructive method to quantitatively relate sensing response to the surface morphology.

Low toxicity ionic liquid surface coating for biodegradable Mg-based stents

 Biodegradable Mg stents are a new treatment means for the human coronary artery disease. This study works on investigating a low toxic and corrosion protective surface coating material- phosphate based ionic liquid to control the degradation rate of Mg alloys in the body.

Enhancement of properties in cast Mg-Y-Zn rod processed by severe plastic deformation

Ternary Mg-Y-Zn alloys have attracted considerable attention from researchers due to their excellent mechanical properties and unique microstructures, particularly from the presence of long-period stacking-order (LPSO) phases. Microstructural variations and the resulting mechanical properties can be affected by various processing routes, particularly those involving severe plastic deformation of a cast billet. The approach used in this work was based on subjecting cast Mg92Y4Zn4 (composition in wt%) billet to severe plastic deformation by three different routes, namely equal channel angular pressing (ECAP), high pressure torsion (HPT) and ECAP followed by HPT, with the aim of refining the microstructure and improving mechanical properties. Samples processed by ECAP were annealed by post-processing and tested in compression and tension. The effect of the processing route and the process parameters on the microstructure and the hardness of the Mg-Y-Zn alloy is reported. An overall positive effect of annealing treatment on the mechanical properties of ECAP-processed alloy is demonstrated. © 2014 Elsevier B.V.