Using ab initio calculations in designing bcc Mg–Li alloys for ultra-lightweight applications

Ab initio calculations are becoming increasingly useful to engineers interested in designing new alloys, because these calculations are able to accurately predict basic material properties only knowing the atomic composition of the material. In this paper, single crystal elastic constants of 11 bcc Mg–Li alloys are calculated using density functional theory (DFT) and compared with available experimental data. Based on DFT determined properties, engineering parameters such as the ratio of bulk modulus over shear modulus (B/G) and the ratio of Young’s modulus over mass density (Y/ρ) are calculated. Analysis of B/G and Y/ρ shows that bcc Mg–Li alloys with 30–50 at.% Li offer the most potential as lightweight structural material. Compared with fcc Al–Li alloys, bcc Mg–Li alloys have a lower B/G ratio, but a comparable Y/ρ ratio. An Ashby map containing Y/ρ vs B/G shows that it is not possible to increase both Y/ρ and B/G by changing only the composition of a binary alloy.     

The crystal structure of the equilibrium Φ phase in Mg–Zn–Al casting alloys

The crystal structure of the equilibrium intermetallic Φ phase formed in a Mg–Zn–Al casting alloy has been characterised using transmission electron microscopy. Electron diffraction patterns recorded from particles of the Φ phase in the casting alloy can be well indexed according to a primitive orthorhombic unit cell, with lattice parameters a=0.90 nm, b=1.70 nm, and c=1.97 nm. Examination of the whole pattern symmetry of principal zone axis diffraction patterns indicates a space group of Pbcm. A model for the decoration of the unit cell of the Φ phase is proposed, in which the Mg₅(Zn,Al)₁₂ Friauf polyhedron is the key structural unit. The Zn and Al atoms are all in icosahedral coordination, but their icosahedral shells are distorted due to the presence of Mg atoms. A total of 84 Mg atoms and 68 Zn/Al atoms can be accommodated in the orthorhombic unit cell, resulting in a formula of Mg₂₁(Zn,Al)₁₇ that is consistent with the composition obtained experimentally. Computer simulations of electron diffraction patterns provide very good agreement with experimental observations.     

Microstructure and microsegregation in Al-rich Al–Cu–Mg alloys

Microstructure and microsegregation in two directionally solidified Al alloys, Al–3.9Cu–0.9Mg and Al–15Cu–1Mg (in wt%), were investigated for cooling rates between 0.78 and 0.039 K/s. Transverse and longitudinal sections were examined to exhibit dendritic microstructures. Fractions of solids formed were determined using quantitative image analysis and solute redistribution in the primary phase was determined using area scans. The model employed to calculate microsegregation is based on the Scheil model but including solid-state diffusion, dendrite arm coarsening and undercooling of the dendrite tip and the formation of eutectic. The model-calculated results were found to be in good agreement with the experimentally determined concentration distributions in the primary α phase and the amounts of phases formed. It was found that the dendrite morphology was best described by a cylindrical arm geometry and that the accuracy of the phase diagram could have a significant influence on the microsegregation predictions. For the alloy with low copper content, two types of embedded droplets were observed.     

New approach to measuring the activation energy of thermal explosion and its application to Mg–Si system

A novel approach to measuring the activation energy of thermal explosion (SHS) in an original Reactive Forging set up has been developed. Applied to a 2Mg–Si powder blend, the method yielded activation energies comparable to the literature data for 2Mg + Si → Mg₂Si reaction determined by the Kissinger approach.     

A simulation study of the shape of β′ precipitates in Mg–Y and Mg–Gd alloys

The metastable β′ phase is a key strengthening precipitate phase in a range of Mg–RE (RE: rare-earth elements) based alloys. The morphology of the β′ precipitates changes from a faceted and nearly equiaxed shape in Mg–Y alloys to a truncated lenticular shape in Mg–Gd alloys. In this work, we study effects of interfacial energy and coherency elastic strain energy on the morphology of β′ precipitates in binary Mg–Y and Mg–Gd alloys using a combination of first-principles calculations and phase-field simulations. Without any free-fitting parameters and using the first-principles calculations, CALPHAD databases and experimental characterizations as model inputs (lattice parameters of the β′ phase, elastic constants and chemical free energy of Mg matrix and interfacial energies of the coherent β′/Mg matrix interfaces), the phase-field simulations predict equilibrium shapes of β′ precipitates of different sizes that agree well with experimental observations. Factors causing the difference in the equilibrium shape of β′-Mg₇Y and β′-Mg₇Gd precipitates are identified, and possible approaches to increase the aspect ratio of the β′ precipitates and thus to enhance the strength of Mg–RE alloys are discussed.     

Pre-precipitate clusters and precipitation processes in Al–Mg–Si alloys

The solute clusters and the metastable precipitates in aged Al–Mg–Si alloys have been characterized by a three-dimensional atom probe (3DAP) and transmission electron microscopy (TEM). After long-term natural aging, Mg–Si co-clusters have been detected in addition to separate Si and Mg atom clusters. The particle density of β″ after 10 h artificial aging at 175°C varies depending on pre-aging conditions, i.e. pre-aging at 70°C increases the number density of the β″ precipitates, whereas natural aging reduces it. This suggests that the spherical GP zones formed at 70°C serve as nucleation sites for the β″ in the subsequent artificial aging, whereas co-clusters formed at room temperature do not. Atom probe analysis results have revealed that the Mg:Si ratios of the GP zones and the β″ precipitates in the alloy with excess amount of Si are 1:1, whereas those in the Al–Mg₂Si quasi-binary alloy are 2:1. Based on these results, the characteristic two-step age-hardening behavior in Al–Mg–Si alloys is discussed.     

GP-zones in Al–Zn–Mg alloys and their role in artificial aging

The structure of GP-zones in an industrial, 7xxx-series Al–Zn–Mg alloy has been investigated by transmission electron microscopy methods: selected area diffraction, conventional and high-resolution imaging. Two types of GP-zones, GP(I) and (II) are characterized by their electron diffraction patterns. GP(I)-zones are formed over a wide temperature range, from room temperature to 140–150°C, independently of quenching temperature. The GP(I)-zones are coherent with the aluminum matrix, with internal ordering of Zn and Al/Mg on the matrix lattice, suggested to be based on AuCu(I)-type sub-unit, and anti-phase boundaries. GP(II) are formed after quenching from temperatures above 450°C, by aging at temperatures above 70°C. The GP(II)-zones are described as zinc-rich layers on {111}-planes, with internal order in the form of elongated <110> domains. The structural relation to the η′-precipitate is discussed.     

A new approach to fabrication of gradient WC–Co hardmetals

WC–Co hardmetals with gradient structure comprising neither η-phase nor grain growth inhibitors were produced for the first time by regulating the WC re-crystallisation and carbon content in their near-surface layer and core. Hardmetals with low Co contents in the surface region were obtained by selective carburisation of the near-surface zone of green articles with the original low carbon content and their consequent liquid-phase sintering. The surface region of such gradient hardmetals has a hardness of up 150 Vickers units higher and fracture toughness significantly superior than those of the core. Gradient hardmetals with high Co contents in the surface region were obtained by selective decarburisation of the near-surface zone of green articles with the original high carbon content and their consequent liquid-phase sintering. The new approach for fabrication of gradient WC–Co materials appears to be a unique tool for increasing both the hardmetal hardness and fracture toughness.     

The in-situ Ti alloying of aluminum alloys and its application in A356 alloys

1. Introduction Titanium is one of the most effective grain refinement elements of aluminum alloys. The grain of aluminum alloys can be effectively refined if containing up to 0.2% titanium, which results in improvement of mechanical properties and performance [1-8]. Titanium is usually added into aluminum melt by melting Al-Ti or Al-Ti-B (Ti/B= 5:1) master alloy. This requires strict control in melting temperature and holding time, resulting in the complicacy to control the quality of allo…     

A model for the yield strength of overaged Al–Zn–Mg–Cu alloys

A model for the yield strength of multi-component alloys is presented and applied to overaged Al–Zn–Mg–Cu alloys (7xxx series). The model is based on an approximation of the strengthening due to precipitate bypassing during precipitate coarsening and takes account of ternary and higher order systems. It takes account of the influence of supersaturation on precipitation rates and of volume fraction on coarsening rates, as well crystallographic texture and recrystallisation. The model has been successfully used to fit and predict the yield strength data of 21 Al–Zn–Mg–Cu alloys, with compositions spread over the whole range of commercial alloying compositions, and which were aged for a range of times and temperatures to produce yield strengths ranging from 400 to 600 MPa. All but one of the microstructural and reaction rate parameters in the model are determined on the basis of microstructural data, with one parameter fitted to yield strength data. The resulting accuracy in predicting unseen proof strength data is 14 MPa. In support of the model, microstructures and phase transformations of 7xxx alloys were studied by a range of techniques, including differential scanning calorimetry (DSC), electron backscatter diffraction (EBSD) in an SEM with a field emission gun (FEG-SEM).     

A new approach to zinc–nickel separation using solution alkalinization method:application to a zinc plant residue

The present investigation involves the separation of zinc and nickel from a sulfate solution using the acidic leaching of zinc plant residue after cadmium removal step as precursor(42.88 wt% Zn,8.50 wt% Cd and 2.33 wt% Ni).Separation of nickel from the solution was done by pouring it into a strong alkaline sodium hydroxide solution due to precipitation of nickel hydroxide and conversion of zinc to the soluble Zn(OH)₄^2-complex.Higher degrees of separation were reached by pou...     

Cavitation during high-temperature deformation in Al–Mg alloys

It has recently been revealed that high-density pre-existing hydrogen micropores, formed during production processes, exhibit premature growth and coalescence under external loading at room temperature, thereby inducing ductile fracture. This process is incidentally supplemented by the well-established ductile fracture mechanism based on particle damage. It is reasonable to assume that the pre-existing hydrogen micropores may also contribute to damage evolution at high temperatures. In the present study, synchrotron X-ray microtomography was applied to the in situ observation of deformation and fracture in Al–Mg alloys at a high temperature. High-density hydrogen micropores were observed in the alloys. Flow localization controlled deformation through the mechanism of solute drag creep. A combined effect of grain boundary sliding and heterogeneous nucleation on particles was also confirmed to accelerate the growth of pre-existing hydrogen micropores and cavities. Although continuous nucleation occurred together with the growth of pre-existing hydrogen micropores, the effects of the pre-existing hydrogen micropores, especially those located on grain boundaries, were predominant in the overall damage evolution. It seemed likely that supersaturated hydrogen in the aluminum alloys might also make an appreciable contribution to cavitation during high-temperature loading.     

Crystal structure and stability of complex precipitate phases in Al–Cu–Mg–(Si) and Al–Zn–Mg alloys

We demonstrate how first-principles total energy calculations may be used to elucidate both the crystal structures and formation enthalpies of complex precipitates in multicomponent Al alloys. For the precipitates, S(Al–Cu–Mg), η′ (Al–Zn–Mg), and Q(Al–Cu–Mg–Si), energetics were computed for each of the models of the crystal structures available in the literature allowing a critical assessment of the validity of the models. In all three systems, energetics were also calculated for solid solution phases as well as other key phases (e.g., equilibrium phases, GP zones) in each precipitation sequence. For both the S and η′ phases, we find that recently proposed structures (based on electron microscopy) produce unreasonably high energies, and thus we suggest that these models should be re-evaluated. However, for all three precipitates, we find that structures based on X-ray diffraction refinements provide both reasonable energetics and structural parameters, and therefore the first-principles results lend support to these structural refinements. Further, we predict energy-lowering site occupations and stoichiometries of the precipitate phases, where experimental information is incomplete. This work suggests that first-principles total energy calculations can be used in the future as a complementary technique with diffraction or microscopy for studying precipitate structures and stabilities.     

Application of cellular automaton–finite element model to the grain refinement of directionally solidified Al–4.15 wt% Mg alloys

Cellular automaton–finite element simulations and Bridgman experiments are used to study the grain refinement of directionally solidified Al–4.15 wt% Mg. The simulations can successfully map the conditions (velocity and temperature gradient) for columnar or equiaxed growth and account for variations in grain size in equiaxed structures. The simulations show that the latent heat released by dendritic solidification gives a quasi-isothermal zone interrupting the temperature gradient. This zone is important in limiting the degree of grain refinement which can be achieved, but also facilitates growth of equiaxed rather than elongated grains. The columnar-to-equiaxed transition is gradual, and its dependence on the addition level of refiner has been characterized. Hunt's model of the transition is supported by microstructural studies of quenched Bridgman samples.     

Determining hot cracking index of Al–Mg–Zn casting alloys calculated using effective solidification range

The possibility of determining the hot cracking index using the calculated value of the effective solidification range is investigated for multicomponent cast aluminium alloys based on the Al–Mg–Zn system with Mn, Ni, Fe and Si additives. The upper limit of the effective solidification range was calculated as the temperature of formation of a 65?wt-% solid phase using the Sheil model. The linear relationship of the hot cracking index and the effective solidification range in the industrial and experimental multicomponent alloys based on the Al–Mg–(Zn) system is demonstrated.