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.

Understanding the crystallography of the eutectoid microstructure in a Zn-Al alloy using the edge-to-edge matching model

The orientation relationship (OR) between the beta(Zn) phase and the alpha(Al) phase and the corresponding habit planes in a Zn-Al eutectoid alloy were accurately determined using convergent beam Kikuchi line diffraction patterns. In addition to the previously reported OR. [11 (2) over bar0](beta)parallel to[110](alpha), (0002)(beta)parallel to ((1) over bar 11)alpha, two new ORs were observed. They are: [11 (2) over bar0](beta)parallel to [110], ((1) over bar 101)(beta) 0.82 degrees from (002)(alpha) and [(1) over bar 100](beta)parallel to[112](alpha), (0002)(beta) 4.5 degrees from (111)(alpha). These ORs can be explained and understood using the recently developed edge-to-edge matching model. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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.

The corrosion performance of anodised magnesium alloys

The corrosion performance of anodised magnesium and its alloys, such as commercial purity magnesium (CP-Mg) and high-purity magnesium (HP-Mg) ingots, magnesium alloy ingots of MEZ, ZE41, AM60 and AZ91D and diecast AM60 (AM60-DC) and AZ91D (AZ91D-DC) plates, was evaluated by salt spray and salt immersion testing. The corrosion resistance was in the sequential order: AZ91D approximate to AM60 approximate to MEZ >= AZ91D-DC >= AM60-DC > HP-Mg > ZE41 > CP-Mg. It was concluded the corrosion resistance of an anodised magnesium alloy was determined by the corrosion performance of the substrate alloy due to the porous coating formed on the substrate alloy acting as a simple corrosion barrier. (c) 2006 Elsevier Ltd. All rights reserved.

Light alloy castings for automotive applications: The case of Al vs Mg

The economical and environmental effects of mass reduction through Al and Mg primary alloys substitutions for cast iron and steel in automotive components are discussed using MF. Ashby's penalty functions method The viability of Mg alloy substitutions for existing Al alloy cast components is also considered. The cost analysis shows that direct, equal-volume, Al alloy substitutions for cast iron and steel are the most feasible in terms of the CAFE liability, followed by substitutions involving flat panels of prescribed stiffness. When the creation of CO2 associated to the production of Al and Mg is considered, the potential gasoline savings over the lifespan of the car compensate for the intrinsic environmental burden of Al in all applications, while electrolytic Mg substitutions for cast iron and steel are feasible for equal volume and panels only. Magnesium produced by the Pidgeon thermal process appears to be too primary energy intensive to be competitive in structural applications. Magnesium substitutions for existing Al alloy beams and panels are generally unviable. The current higher recycling efficiency of Al casting alloys confers Al a significant advantage over Mg alloys.

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.

Lithium-aluminium casting alloys and their associated metal-mould reactions

Aluminium - lithium alloys are specialist alloys used exclusively by the aerospace industry. They have properties that are favourable to the production of modern military aircraft. The addition of approximately 2.5 percent lithium to aluminium increases the strength characteristics of the new alloys by 10 percent. The same addition has the added advantage of decreasing the density of the resulting alloy by a similar percentage. The disadvantages associated with this alloy are primarily price and castability. The addition of 2.5 weight percent lithium to aluminium results in a price increase of 100% explaining the aerospace exclusivity. The processability of the alloys is restricted to ingot casting and wrought treatment but for complex components precision casting is required. Casting the alloys into sand and investment moulds creates a metal - mould reaction, the consequences of which are intolerable in the production of military hardware. The primary object of this project was to investigate and characterise the reactions occurring between the newly poured metal and surface of the mould and to propose a method of counteracting the metal - mould reaction. The constituents of standard sand and investment moulds were pyrolised with lithium metal in order to simplify the complex in-mould reaction and the products were studied by the solid state techniques of powder X-Ray diffraction and magic angle spinning nuclear magnetic resonance spectroscopy. The results of this study showed that the order of reaction was: Organic reagents> > Silicate reagents> Non silicate reagents Alphaset and Betaset were the two organic binders used to prepare the sand moulds throughout this project. Studies were carried out to characterise these resins in order to determine the factors involved in their reaction with lithium. Analysis revealed that during the curing process the phenolic hydroxide groups are not reacted out and that a redox reaction takes place between these hydroxides and the lithium in the molten alloys. Casting experiments carried out to assess the protection afforded by various hydroxide protecting agents showed that modern effective, protecting chemicals such as bis-trimethyl silyl acetamide and hexamethyldisilazane did not inhibit the metal - mould reaction to a sufficiently high standard and that tri-methylchlorosilane was consistently the best performer. Tri-methyl chlorosilane has a simple functionalizing mechanism compared to other hydroxide protecting reagents and this factor is responsible for its superior inhibiting qualities. Comparative studies of 6Li and 7Li N.M.R. spectra (M.A.S. and `off angle') establish that, for solid state (and even solution) analytical purposes 6Li is the preferred nucleus. 6Li M.A.S.N.M.R. spectra were obtained for thermally treated laponite clay. At temperatures below 800oC both dehydrated and rehydrated samples were considered. The data are consistent with mobility of lithium ions from the trioctahedral clay sites at 600oC. The superior resolution achievable in 6Li M.A.S.N.M.R. is demonstrated in the analysis of a microwave prepared lithium exchanged clay where 6Li spectroscopy revelaed two lithium sites in comparison to 7Li M.A.S.N.M.R. which gave only a single lithium resonance.

Cracking in the welding of cupro-nickel alloys

The problem of variation in weld crack susceptibility caused by small variations in alloy and impurity elements for the 70-30 cupro-nickel alloy has been investigated. Both wrought and cast versions of the alloy have been studied, the main techniques employed being the Varestraint test and weld thermal simulation. In the wrought alloys, cracking has been found to occur mainly in the weld metal, whilst in the cast alloys cracking is extensive in both weld metal and heat affected zone. The previously reported effects of certain impurities (P,S,Si) in increasing cracking have been confirmed, and it has also been shown that Ti and Zr may both have a crack promoting effect at levels commonly found in cupro-nickels, whilst C can interact with several of the other elements investigated to produce a beneficial effect. The testing carried out using the weld thermal simulator has shown that a relationship does exist between hot ductility and weld cracking. In particular, the absence of the peak in ductility in the range 1100°C-900°C on cooling from a temperature near to the solidus is indicative of a highly crack susceptible alloy. Principal practical implications of the investigation concern the relationship of weld metal cracking to alloy composition, especially the level of certain impurities. It would appear that the upper limits permitted by the alloy specifications are unrealistically high. The introduction of lower impurity limits would alleviate the current problems of variability in resistance to cracking during welding.

The creep behaviour of pressure diecast zinc-aluminium based alloys

The creep behaviour of three pressure diecast commercial zinc-aluminium based alloys: Mazak 3, corresponding to BS 1004A, and the new alloys ZA.8 and ZA.27 with a series of alloys with compositions ranging from 0% to 30% aluminium was investigated. The total creep elongation of commercial alloys was shown to be well correlated using an empirical equation. Based on this a parametrical relationship was derived which allowed the total creep extension to be related to the applied stress, the temperature and the time of test, so that a quantitative assessment of creep of the alloys could be made under different conditions. Deviation from the normal creep kinetics occurred in alloys ZA.8 and ZA.27 at very low stresses, 150°C, due to structural coarsening combined with partial transformation of ε -phase into T' phase. The extent of primary creep was found to increase with aluminium content, but secondary creep rates decreased in the order Mazak 3, ZA.8 and ZA.27. Thus, based on the above equation, ZA.8 was found to have a substantially better total creep resistance than ZA.27, which in turn was marginally better than Mazak 3 for strains higher than 0.5%, but inferior for smaller strains, due to its higher primary creep extension. The superior creep resistance of ZA.8 was found to be due to the presence of strictly-orientated, thin plate-like precipitates of ε(CuZn4) phase in the zinc matrix of the eutectic and the lamellarly decomposed β phase, in which the precipitation morphology and orientation of ε in the zinc matrix was determined. Over broad ranges of temperature and stresses, the stress exponents and activation energies for creep were found to be consistent with some proposed creep rate mechanisms; i.e. viscous glide for Mazak 3, dislocation climb over second phase particles for ZA.8 and dislocation climb for ZA.27, controlled by diffusion in the zinc-rich phase. The morphology of aluminium and copper-rich precipitates formed from the solid solution of zinc was clearly revealed. The former were found to further increase the creep rate of inherently low creep resistant zinc, but the latter contributed significantly to the creep resistance. Excess copper in the composition, however, was not beneficial in improving the creep resistance. Decomposition of β in copper-containing alloys was found to be through a metastable Zn-Al phase which is strongly stabilised by copper, and the final products of the decomposition had a profound effect on the creep strength of the alloys. The poor creep resistance of alloy ZA.27 was due to the presence of particulate products derived from decomposed β-phase and a large volume of fine, equiaxed products of continuously decomposed α-dendrites.

The fatigue properties of pressure diecast zinc-aluminium based alloys

The fatigue behaviour of the cold chamber pressure-die-cast alloys: Mazak3, ZA8, ZA27, M3K, ZA8K, ZA27K, K1, K2 and K3 was investigated at temperature of 20°C. The alloys M3K, ZA8K and ZA27K were also examined at temperatures of 50 and 100°C. The ratio between fatigue strength and tensile strength was established at 20°C at 107 cycles. The fatigue life prediction of the alloys M3K, ZA8K and ZA27K was formulated at 20, 50 and 100°C. The prediction formulae were found to be reasonably accurate. All of the experimental alloys were heterogeneous and contained large but varying amounts of pores. These pores were a major contribution and dominated the alloys fatigue failure. Their effect, however, on tensile failure was negligible. The ZA27K possessed the highest tensile strength but the lowest fatigue strength. The relationship between the fracture topography and the microstructure was also determined by the use of a mixed signal of a secondary electron and a back-scattered electron on the SEM. The tensile strength of the experimental alloys was directly proportional to the aluminium content within the alloys. The effect of copper content was also investigated within the alloys K1, K2, ZA8K and K3 which contained 0%, 0.5%, 1.0% and 2.0% respectively. It was determined that the fatigue and tensile strengths improved with higher copper contents. Upon ageing the alloys Mazak3, ZA8 and ZA27 at an ambient temperature for 5 years, copper was also found to influence and maintain the metastable Zn-Al (αm) phase. The copper free Mazak3 upon ageing lost this metastable phase. The 1.0% copper ZA8 alloy had lost almost 50% of its metastable phase. Finally the 2.0% copper ZA27 had merely lost 10% of its metastable phase. The cph zinc contained a limited number of slip systems, therefore twinning deformation was unavoidable in both fatigue and tensile testing.

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.

Auto plant closures, policy responses and labour market outcomes:a comparison of MG Rover in the UK and Mitsubishi in Australia

This paper provides a preliminary comparative longitudinal analysis of the impact on workers made redundant due to the closure of the Mitsubishi plant in Adelaide and the MG Rover plant in Birmingham. Longitudinal surveys of ex-workers from both firms were undertaken over a 12-month period in order to assess the process of labour market adjustment. In the Mitsubishi case, given the skills shortage the state of Adelaide was facing, together with the considerable growth in mining and defence industries, it would have been more appropriate if policy intervention had been redirected to further training or re-skilling opportunities for redundant workers. This opportunity was effectively missed and as a result more workers left the workforce, most notably for retirement, than could have otherwise been the case. The MG Rover case was seen as a more successful example of policy intervention, with greater funding assistance available and targeted support available, and with more emphasis on re-training needs to assist adjustment. However, despite the assistance offered and the rhetoric of successful adjustment in both cases, the majority of workers have nevertheless experienced deterioration in their circumstances particularly in the Australian case where casual and part-time work were often the only work that could be obtained. Even in the UK case, where more funding assistance was offered, a majority of workers reported a decline in earnings and a rise in job insecurity. This suggests that a reliance on the flexible labour market is insufficient to promote adjustment, and that more active policy intervention is needed especially in regard to further up-skilling.

Ranibizumab 0.5 mg for diabetic macular edema with bimonthly monitoring after a phase of initial treatment:18-month, multicenter, phase IIIB RELIGHT study

Abstract PURPOSE: To evaluate ranibizumab 0.5 mg using bimonthly monitoring and individualized re-treatment after monthly follow-up for 6 months in patients with visual impairment due to diabetic macular edema (DME). DESIGN: A phase IIIb, 18-month, prospective, open-label, multicenter, single-arm study in the United Kingdom. PARTICIPANTS: Participants (N = 109) with visual impairment due to DME. METHODS: Participants received 3 initial monthly ranibizumab 0.5 mg injections (day 0 to month 2), followed by individualized best-corrected visual acuity (BCVA) and optical coherence tomography-guided re-treatment with monthly (months 3-5) and subsequent bimonthly follow-up (months 6-18). Laser was allowed after month 6. MAIN OUTCOME MEASURES: Mean change in BCVA from baseline to month 12 (primary end point), mean change in BCVA and central retinal thickness (CRT) from baseline to month 18, gain of ≥10 and ≥15 letters, treatment exposure, and incidence of adverse events over 18 months. RESULTS: Of 109 participants, 100 (91.7%) and 99 (90.8%) completed the 12 and 18 months of the study, respectively. The mean age was 63.7 years, the mean duration of DME was 40 months, and 77.1% of the participants had received prior laser treatment (study eye). At baseline, mean BCVA was 62.9 letters, 20% of patients had a baseline BCVA of >73 letters, and mean baseline CRT was 418.1 μm, with 32% of patients having a baseline CRT <300 μm. The mean change in BCVA from baseline to month 6 was +6.6 letters (95% confidence interval [CI], 4.9-8.3), and after institution of bimonthly treatment the mean change in BCVA at month 12 was +4.8 letters (95% CI, 2.9-6.7; P < 0.001) and +6.5 letters (95% CI, 4.2-8.8) at month 18. The proportion of participants gaining ≥10 and ≥15 letters was 24.8% and 13.8% at month 12 and 34.9% and 19.3% at month 18, respectively. Participants received a mean of 6.8 and 8.5 injections over 12 and 18 months, respectively. No new ocular or nonocular safety findings were observed during the study. CONCLUSIONS: The BCVA gain achieved in the initial 6-month treatment period was maintained with an additional 12 months of bimonthly ranibizumab PRN treatment.