Corrosion mechanisms of magnesium alloys

The high strength to weight ratio of magnesium alloys makes them extremely attractive for applications in transport or aerospace technology. However, their corrosion behavior is a major issue and one reason why they are still not as popular as aluminum alloys. This papers reviews the corrosion mechanisms of magnesium and provides the basis for the design of new alloys with improved corrosion properties.

Dendrite coherency of Al-Si-Cu alloys

The dendrite coherency point of Al-Si-Cu alloys was determined by thermal analysis and rheological measurement methods by performing parallel measurements at two cooling rates for aluminum alloys across a wide range of silicon and copper contents. Contrary to previous findings, the two methods yield significantly different values for the fraction solid at the dendrite coherency point. This disparity is greatest for alloys of low solute concentration. The results from this study also contradict previously reported tl ends in the effect of cooling rate on the dendritic coherency point. Consideration of the results shows that thermal analysis is not a valid technique for the measurement of coherency. Analysis of the results from rheological testing indicates that silicon concentration has a dominant effect on grain size and dendritic morphology, independent of cooling rate and copper content, and thus is the factor that determines the fraction solid at dendrite coherency for Al-Si-Cu alloys.

Eutectic nucleation and growth in hypoeutectic Al-SI alloys at different strontium levels

The effects of different levels of strontium on nucleation and growth of the eutectic in a commercial hypoeutectic Al-Si foundry alloy have been investigated by optical microscopy and electron backscattering diffraction (EBSD) mapping by scanning electron microscopy (SEM). The microstructural evolution of each specimen during solidification was studied by a quenching technique at different temperatures and Sr contents. By comparing the orientation of the aluminum in the eutectic to that of the surrounding primary aluminum dendrites by EBSD, the eutectic formation mechanism could be determined. The results of these studies show that the eutectic nucleation mode, and subsequent growth mode, is strongly dependent on Sr level. Three distinctly different eutectic growth modes were found, in isolation or sometimes together, but different for each Sr content. At very low Sr contents, the eutectic nucleated and grew from the primary phase. Increasing the Sr level to between 70 and 110 ppm resulted in nucleation of independent eutectic grains with no relation to the primary dendrites. At a Sr level of 500 ppm, the eutectic again nucleated on and grew from the primary phase while a well-modified eutectic structure was still present. A slight dependency of eutectic growth radially from the mold wall opposite the thermal gradient was observed in all specimens in the early stages of eutectic solidification.

Embracing ligands. A synthetic strategy towards new nitrogen-thioether multidentate ligands and characterization of the cobalt(III) complexes

The synthesis of the hexadentate ligand 2,2,9,9-tetra(methyleneamine)-4,7-dithiadecane (EtN(4)S(2)amp) is reported. The ligand is of a type in which bifurcations of the chain occur at atoms other than donor atoms. The cobalt(III) complex [Co(EtN(4)S(2)amp)](3+) (1) was isolated and characterized. The synthetic methodology also results in a number of by-products, notably 2,9,9-tris(methyleneamine)-9-methylenehydroxy-4,7-dithiadecane (Et(HO)N(3)S(2)amp) and an eleven-membered pendant arm macrocyclic ligand 6,10-dimethyl-6,10-bis(methyleneamine)-1,4-dithia-8-azaacycloundec-7- ene (dmatue). The complexes [Co(Et(HO)N(3)S(2)amp)](3+) (2), in which the alcohol is coordinated to the metal ion, and [Co(dmatue)Cl](2+) (4) were isolated and characterized. Et(HO)N(3)S(2)amp also undergoes complexation with cobalt(III) to produce two isomers endo-[Co(Et(HO) N(3)S(2)amp)Cl](2+) (endo-3) and exo-[Co(Et(HO) N(3)S(2)amp)Cl](2+) (exo-3), both with an uncoordinated alcohol group. endo- 3 has the alcohol positioned cis, and exo-3 trans, to the sixth metal coordination site. Reaction of 1 with isobutyraldehyde, paraformaldehyde and base in dimethylformamide results in the encapsulated complex [Co(1,5,5,9,13,13-hexamethyl-18,21-dithia-3,7,11,15-tetraazabicyclo[7.7.6]docosa- 3,14-diene)](ClO4)(3) . 2H(2)O ([Co(Me(6)docosadieneN(4)S(2))](3+) ( 5). All complexes have been characterized by single crystal X-ray study. The low-temperature (11 K) absorption spectrum of 1 has been measured in Nafion films with spin-allowed (1)A(1g) --> T-1(1g) and (1)A(1g) --> T-1(2g) and spin forbidden (1)A(1g) --> T-3(1g) and (1)A(1g) --> T-3(2g) bands observed. The octahedral ligand-field parameters were determined (10Dq = 22570 cm(-1), B = 551 cm(-1); C = 3500 cm(-1)). For 5 10Dq and B were determined (20580 cm(-1); 516 cm(-1), respectively) and compared with those for similar expanded cavity complexes [Co(Me(8)tricosatrieneN(6))](3+) and [Co(Me(5)tricosatrieneN(6))](3+).

trans-Cyano(6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine)cobalt(III) bis(perchlorate) hydrate and trans-hydroxo(6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine)cobalt(III) bis(perchlorate)

The crystal structures of a pair of closely related macrocyclic cyano- and hydroxopentaaminecobalt(III) complexes, as their perchlorate salts, are reported. Although the two complexes, [Co(CN)(C11H27N5)](ClO4)2.H2O and [Co(OH)(C11H27N5)](ClO4)(2), exhibit similar conformations, significant differences in the Co-N bond lengths arise from the influence of the sixth ligand (cyano as opposed to hydroxo). The ensuing hydrogen-bonding patterns are also distinctly different. Disorder in the perchlorate anions was clearly resolved and this was rationalized on the basis of distinct hydrogen-bonding motifs involving the anion O atoms and the N-H and O-H donors.

Modification-related porosity formation in hypoeutectic aluminum-silicon alloys

A series of aluminum-10 wt pet silicon castings were produced in sand molds to investigate the effect of modification on porosity formation. Modification with individual additions of either strontium or sodium resulted in a statistically significant increase in the level of porosity compared to unmodified castings. The increase in porosity with modification is due to the presence of numerous dispersed pores, which were absent in the unmodified casting. It is proposed that these pores form as a result of differences in size of the aluminum-silicon eutectic grains between unmodified and modified alloys. A geometric model is developed to show how the size of eutectic grains can influence the amount and distribution of porosity. Unlike traditional feeding-based models, which incorporate the effect: of microstructure on permeability, this model considers what happens when liquid is isolated from the riser and can no longer flow. This simple isolation model complements rather than contradicts existing theories on modification-related porosity formation and should be considered in the development of future comprehensive models.

Voltammetric determination of cocaine in confiscated samples using a cobalt hexacyanoferrate film-modified electrode

In this work, a fast, non destructive voltammetric method for cocaine detection in acetonitrile medium using a platinum disk electrode chemically modified with cobalt-hexacyanoferrate (CoHCFe) film is described. The deposition of CoHCFe film at platinum disk (working electrode) was carried out in aqueous solution containing NaClO(4) at 0.1 mol L(-1) as supporting electrolite. Stability studies of the film and subsequent voltammetric analysis of cocaine were made in acetonitrile medium with NaClO4 at 0.1 mol L(-1) as supporting electrolite. A reversible interaction between cocaine and CoHCFe at the film produces a proportional decrease of original peak current, due to the formation of a complex between cocaine and cobalt ions, with subsequent partial passivation of the film surface, being the intensity of current decrease used as analytical signal for cocaine. A linear dependence of cocaine detection was carried out in the range from 2.4 x 10 x 4 to 1.5 x 10(-3) mol L(-1), with a linear correlation coefficient of 0.994 and a detection limit of 1.4 x 10 x 4 mol L(-1). The analysis of confiscated samples by the proposed method indicated cocaine levels from 37% to 95% (m/m) and these results were validated by comparison to HPLC technique, being obtained good correlation between both methods. (C) 2009 Elsevier Ireland Ltd. All rights reserved.

Modeling of columnar-to-equiaxed transition in solidified Al-Si alloys

A Cellular-Automaton Finite-Volume-Method (CAFVM) algorithm has been developed, coupling with macroscopic model for heat transfer calculation and microscopic models for nucleation and growth. The solution equations have been solved to determine the time-dependent constitutional undercooling and interface retardation during solidification. The constitutional undercooling is then coupled into the CAFVM algorithm to investigate both the effects of thermal and constitutional undercooling on columnar growth and crystal selection in the columnar zone, and formation of equiaxed crystals in the bulk liquid. The model cannot only simulate microstructures of alloys but also investigates nucleation mechanisms and growth kinetics of alloys solidified with various solute concentrations and solidification morphologies.

Cyanocobalt(III) complexes of penta- and tetradentate-coordinated macrocyclic hexaamines

The pendent-arm macrocyclic hexaamine trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L) may coordinate in tetra-, penta- or hexadentate modes, depending on the metal ion and the synthetic procedure. We report here the crystal structures of two pseudo-octahedral cobalt(III) complexes of L, namely sodium trans-cyano(trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine)cobalt(III) triperchlorate, Na[Co(CN)(C13H30N6)](ClO4)(3) or Na{trans-[CoL(CN)]}(ClO4)(3), (I), where L is coordinated as a pentadentate ligand, and trans-dicyano(trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine) cobalt (III) trans-dicyano (trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diaminium)cobalt(III) tetraperchlorate tetrahydrate, [Co(CN)(2)(Cl4H32N6)][Co(CN)(2)(Cl4H30N6)](ClO4)(4)•-4H(2)O or trans-[CoL(CN)(2)]trans-[Co(H2L)(CN)(2)] (ClO4)(4)•-4H(2)O, (II), where the ligand binds in a tetradentate mode, with the remaining coordination sites being filled by C-bound cyano ligands. In (I), the secondary amine Co-N bond lengths lie within the range 1.944 (3)-1.969 (3) &ANGS;, while the trans influence of the cyano ligand lengthens the Co-N bond length of the coordinated primary amine [Co-N = 1.986 (3) &ANGS;]. The Co-CN bond length is 1.899 (3) &ANGS;. The complex cations in (11) are each located on centres of symmetry. The Co-N bond lengths in both cations are somewhat longer than in (I) and span a narrow range [1.972 (3)-1.982 (3) &ANGS;]. The two independent Co-CN bond lengths are similar [1.918 (4) and 1.926 (4) &ANGS;] but significantly longer than in the structure of (1), again a consequence of the trans influence of each cyano ligand.

Eutectic modification and microstructure development in Al-Si alloys

Recent increasing applications for cast Al-Si alloys are particularly driven by the need for lightweighting components in the automotive sector. To improve mechanical properties, elements such as strontium, sodium and antimony can be added to modify the eutectic silicon from coarse and plate-like to fine and fibrous morphology. It is only recently being noticed that the morphological transformation resulting from eutectic modification is also accompanied by other, equally significant, but often unexpected changes. These changes can include a 10-fold increase in the eutectic grain size, redistribution of low-melting point phases and porosity as well as surface finish, consequently leading to variations in casting quality. This paper shows the state-of-the-art in understanding the mechanism of eutectic nucleation and growth in Al-Si alloys, inspecting samples, both quenched and uninterrupted, on the macro, micro and nano-scale. It shows that significant variations in eutectic nucleation and growth dynamics occur in AI-Si alloys as a function of the type and amount of modifier elements added. The key role of AIP particles in nucleating silicon is demonstrated. (c) 2005 Elsevier B.V. All rights reserved.

Improved VDC casting of aluminium alloys through an understanding of the surface properties of the molten metal

Vertical direct chill (VDC) casting of aluminium alloys is a mature process that has evolved over many decades through gradual change to both equipment design and casting practice. Today, air-pressurised, continuous lubrication, hot top mould systems with advanced station automation are selected as the process of choice for producing extrusion billet. Specific sets of operating parameters are employed on these stations for each alloy and size combination to produce optimal billet quality. The designs and parameters are largely derived from past experience and accumulated know-how. Recent experimental work at the University of Queensland has concentrated on understanding the way in which the surface properties of liquid aluminium alloys, e.g., surface tension, wetting angle and oxide skin strength, influence the size and shape of the naturally-stab le meniscus for a given alloy, temperature and atmosphere. The wide range of alloy-and condition-dependent values measured has led to the consideration of how these properties impact the stability of the enforced molten metal meniscus within the hot top mould cavity. The actual shape and position of the enforced meniscus is controlled by parameters such as the upstream conduction distance (UCD) from sub-mould cooling and the molten metal head. The degree of deviation of this actual meniscus from the predicted stable meniscus is considered to be a key driver in surface defect formation. This paper reports on liquid alloy property results and proposes how this knowledge might be used to better design VDC mould systems and casting practices.

Properties of rapidly solidified binary copper alloys

A number of binary Cu-X alloys (X = Fe, Cr, Si and Al) with alloying elements up to approximate to 12 at % for Fe and Cr, and = 20 at% for Al and Si were cast into thin ribbons (30-50 mu m thickness) by chill block melt spinning. The structural state of the as-cast ribbons was determined by X-ray diffraction (XRD) and microstructures of the quenched alloys were compared with the ingot equivalent, It was possible to achieve solid solution and fine dispersion of secondary phase beyond XRD detection up to approximate to 8 at% solute for Fe and Cr, which is beyond the expected concentration limits from equilibrium phase diagrams. The effects of alloying on resistivity and microhardness are also presented.

Effect of milling conditions on the synthesis of chromium carbides by mechanical alloying

The synthesis of chromium carbides, Cr7C3 and Cr3C2, by mechanically allowing chromium and carbon powders has been investigated. Milling conditions were found to have a strong influence on the evolution of microstructure, with high collision energies being required to form carbide phases. Milling at intermediate energy levels resulted in the formation of an amorphous phase, and with low energy conditions only grain size refinement of Cr occurred with no evidence of any reaction between Cr and C. The amorphous phase was found to be the precursor to carbide formation. (C) 1997 Elsevier Science S.A.

Lymphocyte proliferation testing in chromium allergic contact dermatitis

Background. Lymphocyte proliferation testing (LPT) has some advantages over patch testing to diagnose allergic contact dermatitis. It is harmless, objective and can be used in clinical situations where patch testing is not recommended. Unfortunately, significant success has only been achieved with nickel. There are few studies on chromium LPT and they were performed with different methods, leading to inconsistent results. Methods. To determine the best parameters for chromium LPT, we tested 20 patients with allergic contact dermatitis to the metal and 20 controls, using various protocols. Results. The best sensitivity and specificity ratios were achieved with 6-day cultures stimulated with a range from 7.5 x 10(-4) to 5 x 10(-3) mol/L of nonfiltered chromium chloride solutions. The sensitivity, specificity and accuracy values found within this range were 65%, 95% and 80%, respectively. Conclusion. Further investigation is necessary to achieve better sensitivity values.

Molybdenum carbonyl complexes of pendant-arm polyazamacrocycles

Molybdenum hexacarbonyl reacted with the pendant-arm macrocycles 10-methyl-1,4,8, 12-tetraazacyclopentadecane-10-amine (L-1) and trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6, 13-diamine (L-2) in the absence of air to form complexes fac-[MoL1(CO)(3)] and [Mo2L2(CO)(8)] respectively. The mononuclear complex has the macrocycle bound in a tridentate manner, including the pendant primary amine, whereas the dinuclear complex exhibits a bridging bis(didentate) co-ordination mode, again involving the pendant primary amines. Structures have been defined by crystal structure analyses. The preferential binding of the pendant primary amines rather than additional secondary amines parallels similar behaviour observed earlier with some mercury(II) and rhodium(III) complexes, and points to the important general role of this pendant, despite being fused directly to the macrocyclic ring, in metal-ion binding.