Microstructural Stability of the CoCrFe2Ni2 High Entropy Alloys with Additions of Cu and Mo

New High Entropy Alloys based on the CoCrFe2Ni2 system have been developed by adding up to 10 at. % of Cu, Mo, and Cu + Mo in different amounts. These alloys showed a single face-centred cubic (FCC) structure after homogenization at 1200 °C. In order to evaluate their thermal stability, aging heat treatments at 500, 700, and 900 °C for 8 h were applied to study the possible precipitation phenomena. In the alloys where only Cu or Mo was added, we found the precipitation of an FCC Cu-rich phase or the µ phase rich in Mo, respectively, in agreement with some of the results previously shown in the literature. Nevertheless, we have observed that when both elements are present, Cu precipitation does not occur, and the formation of the Mo-rich phase is inhibited (or delayed). This is a surprising result as Cu and Mo have a positive enthalpy of mixing, being immiscible in a binary system, while added together they improve the stability of this system and maintain a single FCC crystal structure from medium to high temperatures

Thermodynamic properties and phase equilibria in alloys of Bi—Tm system

The thermochemical properties of the melts of the Bi—Tm system at a temperature of 1100 K in the range of compositions 0 ≤ xTm ≤ 0,2 were determined for the first time by the calorimetry method. It is established that the minimum value of the enthalpy of mixing of these liquid alloys is equal to –75,7 ± 0,5 kJ / mol at xTm = 0,65. = = –150,7 ± 16,7 kJ / mol, = –230,9 ± 21,8 kJ / mol. The activities of the components and molar particles of associates were calculated according to the model of an ideal associated solution (IAR), using data on the thermochemical properties of melts of the Bi—Tm system. It was found that the activities of the components in these metallic solutions show very large negative deviations from ideal solutions with a high content of TmBi and Tm2Bi associates. The obtained dependences of the first i i melts of the Bi—Tm system on temperature showed a large steepness of the Bi Bi curve in contrast to the gradual decrease of exothermic values Tm of Tm. This indicates large changes in the structure of the Bi atom with increasing temperature. Excess integral and partial Gibbs energies of Bi-Tm system melt mixing calculated from component activities The absolute values of G in the whole concentration range are smaller than H (G min = –41,8 kJ / mol at xTm = 0,58), and the function G of is more asymmetric, which is caused by the entropy contribution (entropy of mixing of the studied melts is negative, and Smin min = −30,5 J / mol ∙ K at xTm = 0,65). Keywords: thermochemical properties, compounds, melts, Bi, Tm.

Thermodynamic properties of alloys binary In—Pr (Nd) and ternary In—Pr (Nd)—Ni systems

The thermochemical properties of In—Pr system melts in the range of compositions 0 < xIn < 0,4 and In—Nd in the whole concentration range at 1573 ± 1 K were investigated by isoperibolic calorimetry. The obtained data for the In—Pr system melts were extrapolated to the unexplored concentration interval, taking into account that at xPr = 1 the integral and partial mixing for Pr enthalpy are equal to zero. It was found that the first partial for Pr and the minimum enthalpy of mixing are equal to –139 ± 11 and –40,3 ± 0,2 kJ / mol, respectively. For the In—Nd system the first partial for In and Nd, the minimum enthalpy of mixing is equal to −131,7 ± 11, −140,6 ± 12 і –43,3  0,2 kJ / mol, respectively. Comparison of ΔHmin, melts of the five previously studied In—Ln systems from the ordinal number Ln (zLn) together with the data obtained in this work showed that they are described by a single trend line. For ΔHmin of melts of In—Eu (Yb) systems there are very insignificant deviations from the trend line. But for the size factor, these deviations from the trend line are more significant. The enthalpies of formation of some intermetallics of In—Ln systems are known, and most of them belong to the compound LnIn3. But there is no complete agreement between these data. The results of the most modern work show less dependence on the serial number of lanthanide and are more exothermic for heavy lanthanides, compared with other data. Keywords: thermochemical properties, compounds, melts, In, Pr, Nd.

pyMPEALab Toolkit for Accelerating Phase Design in Multi-principal Element Alloys

Multi-principal element alloys (MPEAs) occur at or nearby the centre of the multicomponent phase space, and they have the unique potential to be tailored with a blend of several desirable properties for the development of materials of future. The lack of universal phase diagrams for MPEAs has been a major challenge in the accelerated design of products with these materials. This study aims to solve this issue by employing data-driven approaches in phase prediction. A MPEA is first represented by numerical fingerprints (composition, atomic size difference , electronegativity , enthalpy of mixing , entropy of mixing , dimensionless $$\Omega$$ Ω parameter, valence electron concentration and phase types ), and an artificial neural network (ANN) is developed upon the datasets of these numerical descriptors. A pyMPEALab GUI interface is developed on the top of this ANN model with a computational capability to associate composition features with remaining other input features. With the GUI interface, an user can predict the phase(s) of a MPEA by entering solely the information of composition. It is further explored on how the knowledge of phase(s) prediction in composition-varied $$\hbox {Al}_x$$ Al x CrCoFeMnNi and $$\hbox {CoCrNiNb}_x$$ CoCrNiNb x can help in understanding the mechanical behavior of these MPEAs. Graphic Abstract

Effect of temperature on mixing behavior and stability of liquid Al-Fe alloys

A theoretical model based on the assumption of compound formation in binary liquid alloy has been used to investigate the thermodynamic properties (free energy of mixing, enthalpy of mixing and entropy of mixing), microscopic properties (concentration fluctuation in long wavelength limit and chemical short range order parameter), surface properties (surface tension and surface composition) and dynamic properties ( viscosity and diffusion coefficient). All the properties of Al2Fe binary melt have been measured using the same energy parameters configured for experimental values of free energy of mixing. The energy parameters are detected as independent of concentration, but depend on temperature. The findings are well consistent with the experimental standards.

Phase vapor–liquid equilibrium for the solutions of diethyl selenide and diethylzinc

Using a semi-empirical Wilson’s model, the vapor-liquid equilibrium in the “diethylzinc - diethyl selenide” system is described: the activity coefficients of the solution components, the separation coefficient, the excess functions of the solution (HE, GE, TSE) are calculated, and isothermal P-X diagrams are obtained. The parameters of the Wilson’s model were calculated on the basis of our data on measuring the temperature dependence for saturated vapor pressure of high-purity samples of diethylzinc, diethyl selenide and their equimolecular solution using iterations from the mathematical software package Mathsad 14. Peculiarities of intermolecular interaction in the “diethylzinc – diethyl selenide” system and the presence of a negative deviation from Raoul's law have been found. The studied system is homogeneous in the whole concentration range. The concentration dependence of the enthalpy of mixing is alternating for the researched temperature range (280-340 K).

Design Principles of Large Cation Incorporation in Halide Perovskites

Perovskites have stood out as excellent photoactive materials with high efficiencies and stabilities, achieved via cation mixing techniques. Overcoming challenges to the stabilization of Perovskite solar cells calls for the development of design principles of large cation incorporation in halide perovskite to accelerate the discovery of optimal stable compositions. Large fluorinated organic cations incorporation is an attractive method for enhancing the intrinsic stability of halide perovskites due to their high dipole moment and moisture-resistant nature. However, a fluorinated cation has a larger ionic size than its non-fluorinated counterpart, falling within the upper boundary of the mixed-cation incorporation. Here, we report on the intrinsic stability of mixed Methylammonium (MA) lead halides at different concentrations of large cation incorporation, namely, ehtylammonium (EA; [CH3CH2NH3]+) and 2-fluoroethylammonium (FEA; [CH2FCH2NH3]+). Density functional theory (DFT) calculations of the enthalpy of the mixing and analysis of the perovskite structural features enable us to narrow down the compositional search domain for EA and FEA cations around concentrations that preserve the perovskite structure while pointing towards the maximal stability. This work paves the way to developing design principles of a large cation mixture guided by data analysis of DFT data. Finally, we present the automated search of the minimum enthalpy of mixing by implementing Bayesian optimization over the compositional search domain. We introduce and validate an automated workflow designed to accelerate the compositional search, enabling researchers to cut down the computational expense and bias to search for optimal compositions.

Formation of carbonitrides and precipitation of alloying elements during thermomechanical treatment of high-strength low-alloy steels. Atomistic modeling

Understanding the processes that control the formation of precipitates of alloying element, their composition and morphology is important for the choosing of optimal regimes of thermomechanical treatment, providing the required structural state and properties of low-alloyed steels. The use of modern methods of atomistic modeling and ab initio calculations to study the mechanisms and conditions of precipitation depending on the steel composition and temperature is discussed. The enthalpy of formation of Ti, V, Nb carbides and nitrides in γ-Fe was calculated using the methods of the theory of the electron density functional and the temperatures of their dissolution were determined in dependence on the composition of the steel. The results obtained agree with the experimental data and obtained by the CALPHAD method. Calculations of the electronic structure, enthalpy of mixing, energy of effective interactions between atoms of alloying and impurity elements have been performed. It was shown that an essential factor determining the nature of the interaction between alloying elements was the magnetic state of iron. It has been established that the enthalpy of mixing, which expresses the tendency of the system to decomposition, increases with the transition of α-Fe from the ferromagnetic to the paramagnetic state. In ferromagnetic α-Fe energetically, the formation of precipitates of Cu, as well as particles of a mixed composition of Cu‒Al, Cu‒Ni and an ordered phase of NiAl are preferable. It has been shown that precipitates Cu-based can be formed during technological times. The transition of α-Fe to the paramagnetic state results in increase of interactions between alloying elements (the exception is the interaction of Cu‒Cu and Cu‒Ni). As a result, additional combinations of alloying elements appear, the interaction between which lead to the formation of precipitates. At the same time, in γ-Fe, precipitates can be formed only based on Mo and Nb. The role of magnetism in the formation of precipitates and their influence on the γ→α-transformation is discussed. It has been shown that the results obtained make a base for enhancement technologies of high-strength low-alloyed steel production.

The effect of cooling rate on structure and mechanical properties of Co-Cr-Cu-Fe-Ni-Sn high entropy alloys

The paper examines the structure and mechanical properties of multicomponent high-entropy CoCrCuFeNiSnx alloys in as-cast and splat-quenched states. The compositions of investigated alloys is analyzed by using the criteria for predicting the phase composition of high-entropy alloys available in the literature, based both on calculations of the entropy and enthalpy of mixing and on an estimate of the difference between the atomic radii of the component. The alloy films is fabricated by the known technique of splat-quenching. A cooling rate estimated by a film thickness is ~ 106 K/s. The simultaneous formation of two solid solutions (FCC + ordered BCC) has been established in the alloy structure. An increase in the concentration of Sn favors the formation of the ordered (В2 type) solid solution in the structure of the alloys. High values of the microhardness and dislocation density have been obtained in the splat-quenched samples. It is also shown that an increase in the Sn content positively affects the microhardness.