Experimental study of phase equilibria in the Al-Fe-Zn-O system in air

The phase equilibria in the Al-Fe-Zn-O system in the range 1250 °C to 1695 °C in air have been experimentally studied using equilibration and quenching techniques followed by electron probe X-ray microanalysis. The phase diagram of the binary Al2O3-ZnO system and isothermal sections of the Al2O3-“Fe2O3”-ZnO system at 1250 °C, 1400 °C, and 1550 °C have been constructed and reported for the first time. The extents of solid solutions in the corundum (Al,Fe)2O3, hematite (Fe,Al)2O3, Al2O3*Fe2O3 phase (Al,Fe)2O3, spinel (Al,Fe,Zn)O4, and zincite (Al,Zn,Fe)O primary phase fields have been measured. Corundum, hematite, and Al2O3*Fe2O3 phases dissolve less than 1 mol pct zinc oxide. The limiting compositions of Al2O3*Fe2O3 phase measured in this study at 1400 °C are slightly nonstoichiometric, containing more Al2O3 then previously reported. Spinel forms an extensive solid solution in the Al2O3-“Fe2O3”-ZnO system in air with increasing temperature. Zincite was found to dissolve up to 7 mole pct of aluminum in the presence of iron at 1550 °C in air. A meta-stable Al2O3-rich phase of the approximate composition Al8FeZnO14+x was observed at all of the conditions investigated. Aluminum dissolved in the zincite in the presence of iron appears to suppress the transformation from a round to platelike morphology.

Morphological features of interfacial intermetallics and interfacial reaction rate in Al-11Si-2.5Cu-(0.15/0.60)Fe cast alloy/die steel couples

Soldering reactions are commonly observed during high pressure die casting of aluminium alloys, and involve the formation and growth of interfacial intermetallics between the die and the cast alloy. It is generally believed that close to 1% Fe is necessary in the aluminium alloy to reduce soldering. However, the role of iron in the interfacial reaction has not been studied in detail. In this investigation, reaction couples were formed between H13 tool steel substrates and an Al-11Si-2.5Cu melt containing either 0.15 or 0.60% Fe. Examination revealed distinctly different intermetallic layer morphology. The overall growth and chemistry of the reaction layer and the reaction rate measured by the consumption of the substrate were compared for the two alloy melts. It was demonstrated that a higher iron content reduces the rate of interfacial reaction, consistent with an observed thicker compact ( solid) intermetallic layer. Hence, the difference in reaction rate can be explained by a significant reduction in the diffusion flux due to a thicker compact layer. Finally, the mechanism of the growth of a thicker compact layer in the higher iron melt is proposed, based on the phase relations and diffusion both within and near the interfacial reaction zone. (C) 2004 Kluwer Academic Publishers.

Influence of Mg content on the microstructure and solid solution chemistry of Al-7%Si-Mg casting alloys during solution treatment

The solution treatment stage of the T6 heat-treatment of Al-7%Si-Mg foundry alloys influences microstructural features such as Mg2Si dissolution, and eutectic silicon spheroidisation and coarsening. Microstructural and microanalytical studies have been conducted across a range of Sr-modified Al-7%Si alloys, with an Fe content of 0.12% and Mg contents ranging from 0.3-0.7wt%. Qualitative and quantitative metallography have shown that, in addition to the above changes, solution treatment also results in changes to the relative proportions of iron-containing intermetallic particles and that these changes are composition-dependent. While solution treatment causes a substantial transformation of pi phase to beta phase in low Mg alloys (0.3-0.4%), this change is not readily apparent at higher Mg levels (0.6-0.7%). The pi to beta transformation is accompanied by a release of Mg into the aluminum matrix over and above that which arises from the rapid dissolution of Mg2Si. Since the level of matrix Mg retained after quenching controls an alloy's subsequent precipitation hardening response, a proper understanding of this phase transformation is crucial if tensile properties are to be maximised.

The microstructure of mechanically alloyed MoSi2 with Ni and Al additions

The effect of Ni and Al additions on grain boundary silica in mechanically alloyed and hot isostatically pressed (HTPed) MoSi2 was investigated. Mechanical alloying Mo and Si in the absence of Al produced finely dispersed silica within a fine grained structure. Mechanically alloyed and HIPed Mo and Si with Ni and Al partially transformed the silica to crystalline oxide phases, including Al2O3. An improvement in high temperature properties is not expected due to the retention of a grain boundary silica film. Rapid grain growth resulted during HIPing, possibly due to the formation of a Ni/Fe/Al liquid phase.

Mass balance characterisation of Al-7Si-Mg alloy microstructures as a function of solution treatment time

Mass balance calculations were performed to model the effect of solution treatment time on A356 and A357 alloy microstructures. Image analysis and electron probe microanalysis were used to characterise microstructures and confirm model predictions. In as-cast microstructures, up to 8 times more Mg is tied up in the pi-phase than in Mg2Si. The dissolution of pi is accompanied by a corresponding increase in the amount of beta-phase. This causes the rate of pi dissolution to be limited by the rate of beta formation. It is predicted that solution treatments of the order of tens of minutes at 540degreesC produce near-maximum T6 yield strengths, and that Mg contents in excess of 0.52 wt% have no advantage.

Strength-ductility behaviour of Al-Si-Cu-Mg casting alloys in T6 temper

A comparative study of the mechanical properties of 20 experimental alloys has been carried out. The effect of different contents of Si, Cu, Mg, Fe and Mn, as well as solidification rate, has been assessed using a strength-ductility chart and a quality index-strength chart developed for the alloys. The charts show that the strength generally increases and the ductility decreases with an increasing content of Cu and Mg. Increased Fe (at Fe/Mn ratio 0.5) dramatically lowers the ductility and strength of low Si alloys. Increased Si content generally increases the strength and the ductility. The increase in ductility with increased Si is particularly significant when the Fe content is high. The charts are used to show that the cracking of second phase particles imposes a limit to the maximum achievable strength by limiting the ductility of strong alloys. The (Cu + Mg) content (at.%), which determines the precipitation strengthening and the volume fraction of Cu-rich and Mg-rich intermetallics, can be used to select the alloys for given strength and ductility, provided the Fe content stays below the Si-dependent critical level for the formation of pre-eutectic alpha-phase particles or beta-phase plates.

Effect of iron on grain refinement of high-purity MG-Al alloys

The effect of iron on the grain refinement of high-purity Mg-3%Al and Mg-91%Al alloys has been investigated using anhydrous FeCl3 as an iron additive at 750degreesC in carbon-free aluminium titanite crucibles. It was shown that grain refinement was readily achievable for both alloys. Fe- and Al-rich intermetallic particles were observed in many magnesium grains. (C) 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

As-cast morphology of iron-intermetallics in Al-Si foundry alloys

The as-cast three-dimensional morphologies of alpha-Al-15(Fe,Mn)(3)Si-2 and beta-Al5FeSi intermetallics were investigated by serial sectioning. Large beta-Al5FeSi intermetallics were observed to grow around pre-existing dendrite arms. The alpha-Al-15(Fe,Mn)(3)Si-2 intermetallic particle was observed to have a central polyhedral particle and an external highly convoluted three-dimensional structure. (c) 2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Iron-rich intermetallic phases and their role in casting defect formation in hypoeutectic Al-Si alloys

Iron is the most common and detrimental impurity in aluminum casting alloys and has long been associated with an increase in casting defects. While the negative effects of iron are clear, the mechanism involved is not fully understood. It is generally believed to be associated with the formation of Fe-rich intermetallic phases. Many factors, including alloy composition, melt superheating, Sr modification, cooling, rate, and oxide bifilms, could play a role. In the present investigation, the interactions between iron and each individual element commonly present in aluminum casting alloys, were investigated using a combination of thermal analysis and interrupted quenching tests. The Fe-rich intermetallic phases were characterized using optical microscope, scanning electron microscope, and electron probe microanalysis (EPMA), and the results were compared with the predictions by Thermocalc. It was found that increasing the iron content changes the precipitation sequence of the beta phase, leading to the precipitation of coarse binary beta platelets at a higher temperature. In contrast, manganese, silicon, and strontium appear to suppress the coarse binary beta platelets, and Mn further promotes the formation of a more compact and less harmful a phase. They are therefore expected to reduce the negative effects of the phase. While reported in the literature, no effect of P on the amount of beta platelets was observed. Finally, attempts are made to correlate the Fe-rich intermetallic phases to the formation of casting defects. The role of the beta phase as a nucleation site for eutectic Si and the role of the oxide bifilms and AIP as a heterogeneous substrate of Fe intermetallics are also discussed.

Influence of calcium on the microstructure and properties of an Al-7Si-0.3Mg-xFe alloy

The effect of Ca addition on the microstructure, physical characteristics (density/porosity), and mechanical properties (tensile and impact strength) has been investigated in an Al-7Si-0.3Mg-xFe (x = 0.2, 0.4, and 0.7) alloy. The size of Al-Fe intermetallic platelets (beta-Al5FeSi) increased with increasing Fe content. The addition of Ca modified the eutectic microstructure and also reduced the size of intermetallic Fe-platelets, causing improved elongation and impact strengths. A low level of Ca addition (39 ppm) reduced the porosity of the alloys. The tensile strength was decreased marginally with Ca addition. However, Ca addition improved the ductility of the alloy by 18.3, 16.7, and 44 pet and the impact strength by 44, 48, and 15.8 pct for Fe contents of 0.2, 0.4, and 0.7 pct, respectively.

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 role of oxides in the formation of primary iron intermetallics in an Al-11.6Si-0.37Mg Alloy

Recent research suggest that the iron-rich intermetallic phases, such as alpha-FeAl15(Fe,Mn)(3)Si-2 and beta-Fe Al5FeSi, nucleate on oxide films entrained in aluminum casting alloys. This is evidenced by the presence of crack-like defects within these iron-rich intermetallics. In an attempt to verify the role of oxides in nucleating iron-rich intermetallics, experiments have been conducted under conditions where in-situ entrained oxide films and deliberately added oxide particles were present. Iron-rich intermetallics are observed to be associated with the oxides in the final microstructure, and crack-like defects are often observed in the beta-Fe plates. The physical association of the Fe-rich intermetallic phases with these solid oxides, either formed in situ or added, is in accordance with the mechanism suggesting that iron-rich intermetallics nucleate upon the wetted sides of double oxide films.

Hydrochemistry, mineralogy and sulphur isotope geochemistry of acid mine drainage at the Mt Morgan mine environment, Queensland, Australia

Mineralogical, hydrochemical and S isotope data were used to constrain hydrogeochemical processes that produce acid mine drainage from sulfidic waste at the historic Mount Morgan Au–Cu mine, and the factors controlling the concentration of SO4 and environmentally hazardous metals in the nearby Dee River in Queensland, Australia. Some highly contaminated acid waters, with metal contents up to hundreds of orders of magnitude greater than the Australia–New Zealand environmental standards, by-pass the water management system at the site and drain into the adjacent Dee River. Mine drainage precipitates at Mt. Morgan were classified into 4 major groups and were identified as hydrous sulfates and hydroxides of Fe and Al with various contents of other metals. These minerals contain adsorbed or mineralogically bound metals that are released into the water system after rainfall events. Sulfate in open pit water and collection sumps generally has a narrow range of S isotope compositions (δ34S = 1.8–3.7‰) that is comparable to the orebody sulfides and makes S isotopes useful for tracing SO4 back to its source. The higher δ34S values for No. 2 Mill Diesel sump may be attributed to a difference in the source. Dissolved SO4 in the river above the mine influence and 20 km downstream show distinctive heavier isotope compositions (δ34S = 5.4–6.8‰). The Dee River downstream of the mine is enriched in 34S (δ34S = 2.8–5.4‰) compared with mine drainage possibly as a result of bacterial SO4 reduction in the weir pools, and in the water bodies within the river channel. The SO4 and metals attenuate downstream by a combination of dilution with the receiving waters, SO4 reduction, and the precipitation of Fe and Al sulfates and hydroxides. It is suggested here that in subtropical Queensland, with distinct wet and dry seasons, temporary reducing environments in the river play an important role in S isotope systematics

Distribution of major, minor, and trace metals in lake environments of Antarctica

The concentrations of major, minor and trace metals were measured in water samples collected from five shallow Antarctic lakes (Carezza, Edmonson Point (No 14 and 15a), Inexpressible Island and Tarn Flat) found in Terra Nova Bay (northern Victoria Land, Antarctica) during the Italian Expeditions of 1993-2001. The total concentrations of a large suite of elements (Al, As, Ba, Ca, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, Gd, K, La, Li, Mg, Mn, Mo, Na, Nd, Ni, Pb, Pr, Rb, Sc, Si, Sr, Ta, Ti, U, V, Y, W, Zn and Zr) were determined using spectroscopic techniques (ICP-AES, GF-AAS and ICP-MS). The results are similar to those obtained for the freshwater lakes of the Larsemann Hills, East Antarctica, and for the McMurdo Dry Valleys. Principal Component Analysis (PCA) and Cluster Analysis (CA) were performed to identify groups of samples with similar characteristics and to find correlations between the variables. The variability observed within the water samples is closely connected to the sea spray input; hence, it is primarily a consequence of geographical and meteorological factors, such as distance from the ocean and time of year. The trace element levels, in particular those of heavy metals, are very low, suggesting an origin from natural sources rather than from anthropogenic contamination.