Modeling of precipitation hardening in Mg-based alloys

This work deals with the development of Mg-based alloys with enhanced properties at elevated temperatures. This is achieved by precipitation of binary phases such as MgZn₂ and Mg₂Sn during the aging of these alloys. The aim of the present work is to develop and calibrate a model for precipitation hardening in Mg-based alloys, as different types of precipitates form simultaneously. The modified Langer-Schwartz approach, while taking into account nucleation, growth and coarsening of the new phase precipitations, was used for the analysis of precipitates’ evolution and precipitation hardening during aging of Mg-based alloys. Two strengthening mechanisms associated with particle-dislocation interaction (shearing and bypassing) were considered to be operating simultaneously due to particle size-distribution. Parameters of the model, R _N i and k _{σ i} , were found by fitting of calculated densities and average sizes of precipitates with ones estimated from experiments. The effective diffusion coefficients of phase formation processes, which determine the strengthening kinetics, were estimated from the hardness maximum positions on the aging curves.     

Application of the CALPHAD approach to Mg-alloys design

The CALPHAD method can be applied as a tool for both alloy development and process guideline determination. In this study, two Mg alloys were designed, their process parameters derived and, using the CALPHAD method, the final results simulated. These results were later confirmed using tangible experimental methods. It was found that γ$\gamma$- Mg₁₇Al₁₂ precipitates along the grain boundaries (GB), Mg₂Sn forms both along the GB and as fine precipitates in the α$\alpha$-Mg matrix and the addition of Ce mishmetal (MM) leads to the formation of elongated Al- rare earth (RE) precipitates along the GB. The microstructural stability at 200 ^°C is high, showing no decrease in microhardness for 32 days. It is shown that the CALPHAD method considerably reduces the effort of alloy design and that the reliability of the results is high.     

Effects of supercooling and cooling rate on the microstructure of Cu–Co–Fe alloys

The effects of supercooling and cooling rate on the microstructure of ternary Cu–Fe–Co alloys were investigated. Electromagnetic levitation was used to supercool the liquids down by 180 K. Alloys with 11 at.% Cu and less than 19 at.% Fe contained fcc (Fe, Co) and fcc Cu phases; those with 19 to 23 at.% Fe contained bcc (Fe, Co), fcc (Fe, Co) and fcc Cu; those with more than 23 at.% Fe contained bcc (Fe, Co) and fcc Cu. The primary dendrites contained 10 to 20 at.% Cu, with Fe and Co contents depending on the alloy composition. Supercooling the melt below a certain temperature resulted in metastable separation of the melt into two liquids, one (Co + Fe)-rich, the other Cu-rich. The metastable phase separation temperatures and the two liquid compositions were determined experimentaly, and compared with calculated ones. Isothermal cross-sections at various temperatures were constructed for stable and metastable cases based on thermodynamic and experimental data of the Cu–Co, Cu–Fe, and Co–Fe systems. A peritectic reaction for the ternary alloys was found at approximately 1100°C.     

Solid Solutions within Selected SrO-LnO1.5-TiO2 Systems

A region of selected SrO-LnO_1.5-TiO₂ (Ln = La, Ce, Pr, or Nd) systems was studied experimentally using X-ray diffractometry (XRD). A series of solid solutions with composition Sr_{4 x} Ln_{2 x/ 3}Ti₄O₁₂ having tetragonally distorted per-ovskite structures was found to exist along the tie line connecting SrTiO₃ and Ln₂Ti₃O₉. Reactions of SrLn₂Ti₄O₁₂, representative compounds of the series, with SrO were also studied. Additionally, the solubility of TiO₂ in Ln₂O₃-(3TiO_{2- m} (Ln = La, Pr, or Nd) at 1300°C was investigated using XRD.     

Basic chemistry of a new cycle, based on reactions of Ce(III) titanate, for splitting water

The chemistry of a new thermochemical cycle for splitting water is described. It consists essentially of three reactions: (a) Ce(IV), as CeO₂, is reduced to Ce(III) by reaction with TiO₂, evolving oxygen and forming one or more Ce(III) titanates; (b) the Ce(III) titanates react with molten NaOH to evolve hydrogen, and form CeO₂ and Na-titanate; and (c) the sodium titanate is hydrolyzed by boiling water into a hydrous titanium dioxide and a sodium hydroxide solution. The cycle has been demonstrated with regenerated materials.     

Qualitative model for creep of AZ91D magnesium alloy

Creep properties of specimens taken from the core of AZ91D magnesium alloy ingots (9 pct Al, 1 pct Zn) were examined in the temperature range of 120 °C to 180 °C and stress range of 40 to 115 MPa. Solution-treated and aged creep specimens were also tested. The creep rates observed were about three orders of magnitude lower than those of pure magnesium, and elongations to fracture were seen to be at least twice those of pure magnesium. A minimum creep rate was reached after approximately 2/3 of the creep life of the specimens (except for the aged specimens, in which the minimum creep rate appears at the beginning of the test). A qualitative model for the creep process in proposed on the basis of the creep tests and optical, scanning electron, and transmission electron microscopy. This model proposes that dislocation motion on additional slip systems is the primary creep mechanism and that cracking acts as a stress relief mechanism. Structural instability dictates the amount of hardening and, hence, creep resistance.     

Precipitation processes in a Mg–Zn–Sn alloy studied by TEM and SAXS

The microstructural evolution of a Mg–Zn–Sn alloy was studied by combining X-ray diffraction (XRD), small angle X-ray scattering (SAXS), and transmission electron microscopy (TEM) in order to determine the individual phases, their size and volume fraction of the alloy. Solutionized and aged samples are analysed in detail concerning the nucleation, growth, morphology, and stability of precipitate phases. In the aged samples, firstly MgZn₂ particles with a rod-like shape form, and secondly plate-like MgSn₂ precipitates. The MgZn₂ phase shows a well-defined orientation relationship with the Mg matrix. The formation of two types of precipitates is responsible for the occurrence of two pronounced hardness maxima. The growth behaviour of the MgZn₂ phase is determined by combining TEM and SAXS measurements and the results are compared to the Lifschitz–Slyozov–Wagner (LSW) theory.     

Semiconductor surface doping by electron beam melting of thin evaporated layers

We have studied the distribution profiles of Cu and Sb introduced into Si substrates, and Sb introduced into Ge substrates by electron beam melting of thin (～30nm) layers of the dopant evaporated onto the substrate. Surface evaporation of the dopant during melting was reduced by a cover layer of the substrate material evaporated on top. We propose a novel model which explains solute surface accumulation phenomena oberved in laser and electron beam surface melting experiments. It is based on a mechanism of solute immobilization at the very surface.     

Optimization of composition and heat treatment design of Mg–Sn–Zn alloys via the CALPHAD method

This work is focused on the application of the calculation of phase diagrams method for alloy and heat treatment design. We analyzed the influence of Zn content on the precipitation of Mg₂Sn in Mg–Sn–Zn alloys. A comparison with previous studies in the Mg–Sn–Zn system was made according to the published results and computational thermochemistry simulations. The phase evolution in the Mg–Sn–Zn system was evaluated for the different compositions, and the simulations were used for precise alloy and heat treatment design. The composition of the ternary alloy was set as Mg–8wt%Sn–1.25wt%Zn. The Sn and Zn content was designed and confirmed to be within the α-Mg solubility limit at the solution treatment temperature. The addition of Zn and the heat treatment applied resulted in the enhancement and refinement of the Mg₂Sn precipitation. Three Vickers micro-hardness maxima were detected: precipitation of metastable Mg–Zn phases, heterogeneous precipitation of Mg₂Sn on the Mg–Zn precipitates, and Mg₂Sn precipitation in the α-Mg matrix. The CT simulations were found to be a valuable alloy design tool.