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.

Edge-to-edge matching and its applications - Part II. Application to Mg-Al, Mg-Y and Mg-Mn alloys

A model for the crystallography and morphology of diffusion-controlled phase transformations - edge-to-edge matching - has been used to predict the orientation relationships (OR) and habit planes of precipitates Mg17Al12 in Mg-Al alloy, Mg24Y5 in Mg-Y alloy and alpha-Mn in Mg-Mn alloy. Based on the crystal structures and lattice parameters only, the model predicts that the possible ORs between Mg17Al12 and Mg matrix are the near Burgers OR, the Potter OR, the Gjonnes-Ostmoe OR and the Crawley OR. In the Mg-Y alloy, the OR between Mg24Y5 precipitates and the Mg matrix is predicted to be the Burgers OR only. The model also predicts that there are no reproducible ORs between alpha-Mn and Mg in the Mg-Mn alloy. Combining the edge-to-edge matching model and W. Zhang's Deltag approach, the habit plane and side facets of the precipitate for each OR can be determined. All the predicted ORs and the corresponding habit planes in Mg-Al and Mg-Y alloys agree very well with the experimental results. (C) 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Corrosion of magnesium alloys in commercial engine coolants

A number of magnesium alloys show promise as engine block materials. However, a critical issue for the automotive industry is corrosion of the engine block by the coolant and this could limit the use of magnesium engine blocks. This work assesses the corrosion performance of conventional magnesium alloy AZ91D and a recently developed engine block magnesium alloy AM-SC1 in several commercial coolants. Immersion testing, hydrogen evolution measurement, galvanic current monitoring and the standard ASTM D1384 test were employed to reveal the corrosion performance of the magnesium alloys subjected to the coolants. The results show that the tested commercial coolants are corrosive to the magnesium alloys in terms of general and galvanic corrosion. The two magnesium alloys exhibited slightly different corrosion resistance to the coolants with AZ91D being more corrosion resistant than AM-SC1. The corrosivity varied from coolant to coolant. Generally speaking. an oraganic-acid based long life coolant was less corrosive to the magnesium alloys than a traditional coolant. Among the studied commercial coolants. Toyota long, life coolant appeared to be the most promising one. In addition. it was found that potassium fluoride effectively inhibited corrosion of the magnesium alloys in the studied commercial coolants. Both general and galvanic corrosion rates were significantly decreased by addition of KF, and there were no evident side effects on the other engine block materials, such as copper, solder. brass. steel and aluminium alloys, in terms of their corrosion performance. The ASTM D 1384 test further confirmed these results and suggested that Toyota long life coolant with 1%wt KF addition is a promising coolant for magnesium engine blocks.

Hydrogen storage of magnesium-based nanocomposites system

Hydrogen storage in traditional metallic hydrides can deliver about 1.5 to 2.0 wt pct hydrogen but magnesium hydrides can achieve more than 7 wt pct. However, these systems suffer from high temperature release drawback and chemical instability problems. Recently, big improvements of reducing temperature and increasing kinetics of hydrogenation have been made in nanostructured Mg-based composites. This paper aims to provide an overview of the science and engineering of Mg materials and their nanosized composites with nanostructured carbon for hydrogen storage. The needs in research including preparation of the materials, processing and characterisation and basic mechanisms will be explored. The preliminary experimental results indicated a promising future for chemically stable hydrogen storage using carbon nanotubes modified metal hydrides under lower temperatures.

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.

Anodizing treatments for magnesium alloys and their effecton corrosion resistance in various environments

This paper reviews various aspects of anodizing of magnesium alloys, such as the basics, processes, properties and applications. It systematically summarises the existing fundamental studies and technical developments of anodizing of magnesium alloys, and concludes that new anodizing processes based on electrolytic plasma anodizing that convert the surface of a magnesium alloy into a hard ceramic coating in an electrolytic bath using high energy electric discharges can offer improved wear and corrosion resistance. These new anodized coatings are often claimed to perform better than the traditional ones obtained through older anodizing processes, such as DOW17 or HAE. The new anodizing techniques are chromate free and hence environment friendly. It is expected that more cost-effective, environment-friendly and non-toxic anodizing techniques will be developed and applied to magnesium alloy components in the future.

Eutectic grain size and strontium concentration in hypoeutectic aluminium-silicon alloys

Recently it has been shown that modification with strontium causes an increase in the size of eutectic grains. The eutectic grain size increases because there are fewer nucleation events, possibly due to the poisoning of phosphorus-based nuclei that are active in the unmodified alloy. The current paper investigates the effect of strontium concentration on the eutectic grain size. In the aluminium-10 wt.% silicon alloy used in this research, for fixed casting conditions, the eutectic grain size increases as the strontium concentration increases up to approximately 150ppm, beyond which the grain size is relatively stable. This critical strontium concentration is likely to differ depending on the composition of the base alloy, including the concentration of minor elements and impurities. It is concluded that processing and in-service properties of strontium modified aluminium-silicon castings are likely to be more stable if a minimum critical strontium concentration is exceeded. If operating below this critical strontium concentration exceptional control over composition and casting conditions is required. (c) 2005 Elsevier B.V. All rights reserved.

The effect of grain refinement and cooling rate on the hot tearing of wrought aluminium alloys

Using modifications to the Rappaz-Drezet-Gremaud hot tearing model, and using empirical equations developed for grain size and dendrite arm spacing (DAS) on the addition of grain refiner for a range of cooling rates, the effect of grain refinement and cooling rate on hot tearing susceptibility has been analysed. It was found that grain refinement decreased the grain size and made the grain morphology more globular. Therefore refining the grain size of an equiaxed dendritic grain decreased the hot tearing susceptibility. However, when the alloy was grain refined such that globular grain morphologies where obtained, further grain refinement increased the hot tearing susceptibility. Increasing the cooling decreased the grain size and made the grain morphology more dendritic and therefore increased the likelihood of hot tearing. The effect was particularly strong for equiaxed dendritic grain morphologies; hence grain refinement is increasingly important at high cooling rates to obtain more globular grain morphologies to reduce the hot tearing susceptibility.

Effect of over-doped yttrium on the microstructure, mechanical properties and thermal properties of a Zr-based metallic glass

The effects of over-doped yttrium on the microstructure, mechanical properties and thermal behaviour of an oxygen-contaminated Zr51Cu20.7Ni12Al16.3 bulk metallic glass are studied systematically. It has been found that, when yttrium doping is beyond the optimum doping, the glass-forming ability enhancement effect induced by yttrium addition decreases and the mechanical properties are adversely affected. In this study, a new phase with an orthorhombic structure (a = 0.69 nm, b = 0.75 nm and c = 0.74 nm) is identified in the yttrium over-doped alloys. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Enhanced glass-forming ability of a Zr-based bulk metallic glass with yttrium doping

A significant enhancement in glass formation in a newly developed Zr51Cu20.7Ni12Al16.3 alloy has been achieved by yttrium doping. With just 0.5 at.% yttrium doping, the critical diameter of the as-cast alloys for glass formation has been increased from 3 mm to at least 10 mm. In the undoped, large-sized alloys, massive oxygen stabilized crystalline phases are observed but disappear in yttrium doped alloys. Very small amounts of stable alpha-Y2O3 phases found in the yttrium doped alloys, and their negligible effect on the metallic glasses' properties, provide a superior solution to achieve metallic glasses with a high glass formability. (c) 2006 Elsevier B.V. All rights reserved.

The effect of Cu addition and milling contaminations on the microstructure evolution of ball milled Al-Pb alloy during sintering

Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu (x = 0-7.0) bulk alloys were prepared by sintering the mechanically alloyed powders at various temperatures. The microstructure changes of the as consolidated powders in the course of sintering were analyzed by differential scanning calorimetry, scanning electron microscopy, X-ray diffraction analysis and transmission electron microscopy. It has been found that, with respect to the Al-10 wt.%Pb-x wt.%Cu alloy, CuAl2 and Cu9Al4 phases formed in the milling process, and the amount of CuAl2 phase increased while the Cu9Al4 phase disappeared gradually in the sintering process. In both Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu alloys, the sintering process results in the coarsening of Pb phase and the growth rate of Pb phase fulfills the Lifshitz-Slyozov-Wagner equation even though the size of the Pb phase was in nanometer range. The Pb particle exhibits cuboctahedral morphology and has a cubic to cubic orientation relationship with the Al matrix. The addition of Cu strongly depressed the growth rate of Pb. Contamination induced by milling has apparent influence on the microstructure of the sintered alloys. Al7Cu2Fe and aluminium oxide phases were identified in the sintered alloys. The cuboctahedral morphology of Pb particles was broken up by the presence of the oxide phase. (c) 2006 Elsevier B.V. All rights reserved.

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.

The creep properties of a series of zinc-rich zinc-aluminium alloys

The compressive creep behaviour of six sand cast zinc-rich alloys: No3 and No5, corresponding to BS 1004A and BS 1004B, respectively, alloy No2, ILZRO,.16 and two newer alloys ACuZinc5 and ACuZinc10 was investigated. The total creep contraction of the alloys was found to be well correlated using an empirical equation. On the basis of this equation, a parametrical relationship was derived which allowed the total creep contraction to be related to the applied stress, the temperature and the time of test, so that a quantitative assessment of compressive creep of the alloys could be made under different testing conditions. The primary creep and secondary creep rates were found for the alloys at different temperatures and stresses. Generally, the primary creep contraction was found to increase with copper content, whereas secondary creep rates decreased in the order No3, ACuZinc10, ACuZinc5 and No2. ILZRO.16 was tested only at the highest stress and two higher temperatures. The results showed that ILZRO.16 had higher creep resistance than all the other alloys. Thus, based on the above empirical equation, alloy No2 was found to have a substantially better total creep resistance than alloys No3 and No5, and slightly better than ACuZinc5 and ACuZinc10 for strains up to 1%. Both ACuZinc alloys had higher creep strength than commercial alloys No3 and No5. Alloy No5 had much higher creep resistance than alloy No3 under all conditions. The superior creep resistance of alloy No2 was considered to be due to the presence of small precipitates of -phase in the zinc matrix and a regular eutectic morphology. The stress exponents and activation energies for creep under different testing conditions were found to be consistent with some established creep-controlling mechanisms; i.e. dislocation climb for alloy No3, dislocation climb over second phase particles for alloys No5, No2, ACuZinc10, controlled by lattice diffusion in the zinc-rich phase. The lower creep resistance of alloy No3 was mainly due to the lower creep strength of copper-free primary particles having greater volume than eutectic in the microstructure. Alloys No5, ACuZinc5 and ACuZinc10 showed much better creep resistance than alloy No3, based on the precipitation-hardening due to the presence of small -phase precipitates. The primary dendrites in both ACuZinc alloys however were not of much benefit in improving the creep resistance of the alloys.

Control of soundness and mechanical properties in aluminium-silicon-magnesium alloys

Previously, specifications for mechanical properties of casting alloys were based on separately cast test bars. This practice provided consistently reproducible results; thus, any change in conditions was reflected in changes in the mechanical properties of the test coupons. These test specimens, however, did not necessarily reflect the actual mechanical properties of the castings they were supposed to represent'. Factors such as section thickness and casting configuration affect the solidification rate and soundness of the casting thereby raising or lowering its mechanical properties in comparison with separately cast test specimens. In the work now reported, casting shapes were developed to investigate the variations of section thickness, chemical analysis and heat treatment on the mechanical properties of a high strength Aluminium alloy under varying chilling conditions. In addition, an insight was sought into the behaviour of chills under more practical conditions. Finally, it was demonstrated that additional information could be derived from the radiographs which form an essential part of the quality control of premium quality castings. As a result of the work, it is now possible to select analysis and chilling conditions to optimize the as cast and the heat treated mechanical properties of Aluminum 7% Silicon 0.3% Magnesium alloy.

Bulk and surface switching in Mn-Fe-based Prussian blue analogues

Many Prussian Blue Analogues are known to show a thermally induced phase transition close to room temperature and a reversible, photo-induced phase transition at low temperatures. This work reports on magnetic measurements, X-ray photoemission and Raman spectroscopy on a particular class of these molecular heterobimetallic systems, specifically on Rb0.81Mn[Fe(CN)6]0.95_1.24H2O, Rb0.97Mn[Fe(CN)6]0.98_1.03H2O and Rb0.70Cu0.22Mn0.78[Fe(CN)6]0.86_2.05H2O, to investigate these transition phenomena both in the bulk of the material and at the sample surface. Results indicate a high degree of charge transfer in the bulk, while a substantially reduced conversion is found at the sample surface, even in case of a near perfect (Rb:Mn:Fe=1:1:1) stoichiometry. Thus, the intrinsic incompleteness of the charge transfer transition in these materials is found to be primarily due to surface reconstruction. Substitution of a large fraction of charge transfer active Mn ions by charge transfer inactive Cu ions leads to a proportional conversion reduction with respect to the maximum conversion that is still stoichiometrically possible and shows the charge transfer capability of metal centers to be quite robust upon inclusion of a neighboring impurity. Additionally, a 532 nm photo-induced metastable state, reminiscent of the high temperature Fe(III)Mn(II) ground state, is found at temperatures 50-100 K. The efficiency of photo-excitation to the metastable state is found to be maximized around 90 K. The photo-induced state is observed to relax to the low temperature Fe(II)Mn(III) ground state at a temperature of approximately 123 K.