Entropy Determination of Single-Phase High Entropy Alloys with Different Crystal Structures over a Wide Temperature Range

We determined the entropy of high entropy alloys by investigating single-crystalline nickel and five high entropy alloys: two fcc-alloys, two bcc-alloys and one hcp-alloy. Since the configurational entropy of these single-phase alloys differs from alloys using a base element, it is important to quantify the entropy. Using differential scanning calorimetry, cp-measurements are carried out from −170 °C to the materials’ solidus temperatures TS. From these experiments, we determined the thermal entropy and compared it to the configurational entropy for each of the studied alloys. We applied the rule of mixture to predict molar heat capacities of the alloys at room temperature, which were in good agreement with the Dulong-Petit law. The molar heat capacity of the studied alloys was about three times the universal gas constant, hence the thermal entropy was the major contribution to total entropy. The configurational entropy, due to the chemical composition and number of components, contributes less on the absolute scale. Thermal entropy has approximately equal values for all alloys tested by DSC, while the crystal structure shows a small effect in their order. Finally, the contributions of entropy and enthalpy to the Gibbs free energy was calculated and examined and it was found that the stabilization of the solid solution phase in high entropy alloys was mostly caused by increased configurational entropy

The Effect of Lattice Vibrations on Substitutional Alloy Thermodynamics

A longstanding limitation of first-principles calculations of substitutional alloy phase diagrams is the difficulty to account for lattice vibrations. A survey of the theoretical and experimental literature seeking to quantify the impact of lattice vibrations on phase stability indicates that this effect can be substantial. Typical vibrational entropy differences between phases are of the order of 0.1 to 0.2 k_B/atom, which is comparable to the typical values of configurational entropy differences in binary alloys (at most 0.693 k_B/atom). This paper describes the basic formalism underlying ab initio phase diagram calculations, along with the generalization required to account for lattice vibrations. We overview the various techniques allowing the theoretical calculation and the experimental determination of phonon dispersion curves and related thermodynamic quantities, such as vibrational entropy or free energy. A clear picture of the origin of vibrational entropy differences between phases in an alloy system is presented that goes beyond the traditional bond counting and volume change arguments. Vibrational entropy change can be attributed to the changes in chemical bond stiffness associated with the changes in bond length that take place during a phase transformation. This so-called ``bond stiffness vs. bond length'' interpretation both summarizes the key phenomenon driving vibrational entropy changes and provides a practical tool to model them.Comment: Submitted to Reviews of Modern Physics 44 pages, 6 figure

Automated computation of materials properties

Materials informatics offers a promising pathway towards rational materials design, replacing the current trial-and-error approach and accelerating the development of new functional materials. Through the use of sophisticated data analysis techniques, underlying property trends can be identified, facilitating the formulation of new design rules. Such methods require large sets of consistently generated, programmatically accessible materials data. Computational materials design frameworks using standardized parameter sets are the ideal tools for producing such data. This work reviews the state-of-the-art in computational materials design, with a focus on these automated $\textit{ab-initio}$ frameworks. Features such as structural prototyping and automated error correction that enable rapid generation of large datasets are discussed, and the way in which integrated workflows can simplify the calculation of complex properties, such as thermal conductivity and mechanical stability, is demonstrated. The organization of large datasets composed of $\textit{ab-initio}$ calculations, and the tools that render them programmatically accessible for use in statistical learning applications, are also described. Finally, recent advances in leveraging existing data to predict novel functional materials, such as entropy stabilized ceramics, bulk metallic glasses, thermoelectrics, superalloys, and magnets, are surveyed.Comment: 25 pages, 7 figures, chapter in a boo

Ab-initio simulation and experimental validation of beta-titanium alloys

In this progress report we present a new approach to the ab-initio guided bottom up design of beta-Ti alloys for biomedical applications using a quantum mechanical simulation method in conjunction with experiments. Parameter-free density functional theory calculations are used to provide theoretical guidance in selecting and optimizing Ti-based alloys with respect to three constraints: (i) the use of non-toxic alloy elements; (ii) the stabilization of the body centered cubic beta phase at room temperature; (iii) the reduction of the elastic stiffness compared to existing Ti-based alloys. Following the theoretical predictions, the alloys of interest are cast and characterized with respect to their crystallographic structure, microstructure, texture, and elastic stiffness. Due to the complexity of the ab initio calculations, the simulations have been focused on a set of binary systems of Ti with two different high melting bcc metals, namely, Nb and Mo. Various levels of model approximations to describe mechanical and thermodynamic properties are tested and critically evaluated. The experiments are conducted both, on some of the binary alloys and on two more complex engineering alloy variants, namely, Ti-35wt.%Nb-7wt.%Zr-5wt.%Ta and a Ti-20wt.%Mo-7wt.%Zr-5wt.%Ta.Comment: 23 pages, progress report on ab initio alloy desig

Mechanistic origin of high retained strength in refractory BCC high entropy alloys up to 1900K

The body centered cubic (BCC) high entropy alloys MoNbTaW and MoNbTaVW show exceptional strength retention up to 1900K. The mechanistic origin of the retained strength is unknown yet is crucial for finding the best alloys across the immense space of BCC HEA compositions. Experiments on Nb-Mo, Fe-Si and Ti-Zr-Nb alloys report decreased mobility of edge dislocations, motivating a theory of strengthening of edge dislocations in BCC alloys. Unlike pure BCC metals and dilute alloys that are controlled by screw dislocation motion at low temperatures, the strength of BCC HEAs can be controlled by edge dislocations, and especially at high temperatures, due to the barriers created for edge glide through the random field of solutes. A parameter-free theory for edge motion in BCC alloys qualitatively and quantitatively captures the strength versus temperature for the MoNbTaW and MoNbTaVW alloys. A reduced analytic version of the theory then enables screening over >600,000 compositions in the Mo-Nb-Ta-V-W family, identifying promising new compositions with high retained strength and/or reduced mass density. Overall, the theory reveals an unexpected mechanism responsible for high temperature strength in BCC alloys and paves the way for theory-guided design of stronger high entropy alloys.Comment: This version corrects the theory and provides more extensive explanation

Origin and tuning of the magnetocaloric effect for the magnetic refrigerant MnFe(P1-xGex)

Neutron diffraction and magnetization measurements of the magneto refrigerant Mn1+yFe1-yP1-xGex reveal that the ferromagnetic and paramagnetic phases correspond to two very distinct crystal structures, with the magnetic entropy change as a function of magnetic field or temperature being directly controlled by the phase fraction of this first-order transition. By tuning the physical properties of this system we have achieved a maximum magnetic entropy change exceeding 74 J/Kg K for both increasing and decreasing field, more than twice the value of the previous record.Comment: 6 Figures. One tabl