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It has been observed in both natural and man-made materials that volume sometimes decreases with increasing temperature. Though mechanistic understanding has been gained for some individual materials, a general answer to the question "Why does volume sometimes decrease with the increase of temperature?" remains lacking. Based on the thermodynamic relation that the derivative of volume with respect to temperature, i.e., thermal expansion, is equal to the negative derivative of entropy with respect to pressure, we developed a general theory in terms of multiscale entropy to understand and predict the change of volume as a function of temperature, which is termed as zentropy theory in the present work. It is shown that a phase at high temperatures is a statistical representation of the ground-state stable and multiple nonground-state metastable configurations. It is demonstrated that when the volumes of the major nonground-state configurations are smaller than that of the ground-state configuration, the volume of the phase may decrease with the increase of temperature in certain ranges of temperature-pressure combinations, depicting the negative divergency of thermal expansion at the critical point. As examples, positive and negative divergencies of thermal expansion are predicted at the critical points of Ce and Fe3Pt, respectively, along with the temperature and pressure ranges for abnormally positive and negative thermal expansion. The authors believe that the zentropy theory is applicable to predict anomalies of other physical properties of phases because the change of entropy drives the responses of a system to external stimuli.

This paper underlined the corrosion behavior of aluminum alloy/galvanized steel joints fabricated by resistance spot welding (RSW) and self-piercing riveting (SPR) exposed to different salt-spray cycles. It was found that the crevice generated by different joining methods has an important impact on corrosion behavior. Compared with the RSW joint, less corrosion happened on the coupled regions in SPR joints because of the higher local pH value resulted from the smaller crevice. The crevice, however, has less impact on the types of corrosion products. Galvanic corrosion happened in the coupled region for both RSW and SPR joints. The Pourbaix diagram explained the stable corrosion products of Al and Zn Fe alloy, which are Al2O3, ZnO, and Fe3O4. Additional corrosion products observed from the experiment included α-Al(OH)3, Ca4Al2(CO3)(OH)12(H2O)5, Zn5(OH)8Cl2(H2O), Zn5(CO3)2(OH)6, and Fe2(OH)2(CO3), which can be understood by considering the metastable corrosion products, Pourbaix diagram, and possible chemical reactions.

An unprecedented NiSn2 intermetallic with CoGe2-type crystal structure has been recovered (at ambient conditions) after high-pressure high-temperature treatment of a Ni33Sn67 precursor alloy at 10 GPa and 400 °C. The orthorhombic structure with Aeam space group symmetry is pseudotetragonal. Based on the evaluation of powder X-ray diffraction data, lattice parameters of a = b = 6.2818 Å and c = 11.8960 Å have been determined. Complicated line broadening and results of a further microstructure analysis, however, imply a defective character of the crystal structure. First-principles calculations with different model structures and a comparison with structural trends in the literature suggest that at the high-pressure high-temperature conditions a CuAl2-type crystal structure might be stable, which transforms to the recovered CoGe2-type crystal structure upon cooling or the release of pressure.

In situ growth of pyrochlore iridate thin films has been a long-standing challenge due to the low reactivity of Ir at low temperatures and the vaporization of volatile gas species such as IrO3(g) and IrO2(g) at high temperatures and high PO2. To address this challenge, we combine thermodynamic analysis of the Pr-Ir-O2 system with experimental results from the conventional physical vapor deposition (PVD) technique of co-sputtering. Our results indicate that only high growth temperatures yield films with crystallinity sufficient for utilizing and tailoring the desired topological electronic properties and the in situ synthesis of Pr2Ir2O7 thin films is fettered by the inability to grow with PO2 on the order of 10 Torr at high temperatures, a limitation inherent to the PVD process. Thus, we suggest techniques capable of supplying high partial pressure of key species during deposition, in particular chemical vapor deposition (CVD), as a route to synthesis of Pr2Ir2O7.

The site occupancy of boron (B) in L12 γ′-Ni3Al and its (010) antiphase boundary (APB) are studied by first-principles calculations in the present work. Based on the electronic structures of the (010) APB, 12 initial tetrahedral sites for B are identified and reduced to 6 distinct configurations due to symmetry, which are transformed into 4 octahedral sites presented by the atomic trajectories during relaxations in first-principles calculations. It is revealed that B atoms prefer to occupy a site far away from the fault layers within the (010) APB of γ′-Ni3Al, agreeing well with previous experimental observations. Bonding charge density is utilized to provide a novel insight into the local L12 → D022 structural phase transformation of the APB and the corresponding tetrahedral-octahedral transition. The energetic site occupation of B is dominated by the lower electron density of the octahedral sites than that of tetrahedral sites.

Oxygen (O) is an inevitable impurity in bulk metallic glasses (BMGs) and its influence over the glass-forming ability (GFA) of BMGs is a longstanding controversy. The present ab initio molecular dynamics (AIMD) simulations indicate that the GFA decreases upon introducing 0.78 at. pct O in the amorphous Zr55Cu55Al9Be9 (at. pct), while examining the evolution of atomic configurations and kinetic properties in BMGs. This study includes a comprehensive analysis using pair correlation function (PCF), bond pair analysis (BPA), and Voronoi polyhedra construction. It is concluded that the incorporation of O leads to a decline in the closely packed icosahedral polyhedrons, where the atom O is coordinated with Be and Zr in the first nearest shell to form the O-centered clusters with enhanced ordering. Mean square displacement (MSD) analysis also shows that the trace O could induce remarkable acceleration of atomic mobility, therefore increasing crystallization tendency of the Zr55Cu55Al9Be9 alloy. The present results illuminate the role of O in the metallic glass-forming process and reveal the underlying role of O in the GFA of the Zr-Cu amorphous alloys.

The all-solid-state battery (ASSB) is a promising next-generation energy storage technology for both consumer electronics and electric vehicles because of its high energy density and improved safety. Sulfide solid-state electrolytes (SSEs) have merits of low density, high ionic conductivity, and favorable mechanical properties compared to oxide ceramic and polymer materials. However, mass production and processing of sulfide SSEs remain a grand challenge because of their poor moisture stability. Here, we report a reversible surface coating strategy for enhancing the moisture stability of sulfide SSEs using amphipathic organic molecules. An ultrathin layer of 1-bromopentane is coated on the sulfide SSE surface (e.g., Li

Atomic structure, diffusivity and viscosity of Al1-xMgx (x=0, 0.0039, 0.1172, 0.9180, 0.9961, 1)melts at 875, 1000, 1125, and 1250K were investigated by the ab initio molecular dynamics (AIMD) simulations. The simulated results are compared with available experimental and calculated data in the literature with reasonable agreements. Considering the results of pair correlation function g(r), it can be observed that Mg atoms in Al0.8828Mg0.1172 melt aggregate more obviously at 1000 and 1250K. For Al0.0820Mg0.9180, Al atom segregation is more obvious at 875 and 1000K. The tracer diffusion coefficients of Al or Mg in Al1-xMgx (x=0.1172, 0.9180) melts, and interdiffusion coefficients of Al0.8828Mg0.1172 and Al0.0820Mg0.9180 melts are all close to the self-diffusion coefficients of Al or Mg. With the increasing temperature, the diffusivity increases linearly. In dilute melts, the tracer diffusion coefficients of solute atom and the interdiffusion coefficients increase nonlinearly with the increasing temperature. For Al0.8828Mg0.1172 and Al0.0820Mg0.9180 melts, the viscosities ? are comparatively higher than pure melts. The viscosities of all melts decrease with the increasing temperature, then increase at 1250K. The results obtained in the present work provide an insight into the design of Al and Mg alloys.

Potassium-ion batteries (PIBs) have attracted great interest due to their high-energy-density and low-cost. The lack of stable anode material greatly limits the quick development of PIBs. Phosphorus-metal compounds are regarded as a class of materials with promising prospects as anode material for PIBs with a low operating voltage and high conductivity. Among them, due to the challenging synthesis method, the application of SnP is limited. Herein, a facile approach to synthesize trigonal SnP@C through alloying red phosphorus with tin on carbon material is reported. It is found that carbon substrate can largely reduce vibrational and configurational entropies, playing a critical role on the formation of metastable SnP. When applied as anode in PIBs, the SnP@C composite delivers a high reversible capacity of 478.1 mAh·g−1 at 50 mA g−1 and a stable cycling performance at 1000 mA g−1. The good electrochemical performance is associated with the SnP@C as well as the carbon, which could suppress the phase separation during charge/discharge process to maintain structural stability. This work may open a new avenue for low-cost synthesis of metastable phases for advanced energy storage systems.

Metallic amorphous/crystalline (A/C) nanolaminates exhibit excellent ductility while retaining their high strength. However, the underlying physical mechanisms and the resultant structural changes during plastic deformation still remain unclear. In the present work, the structure-property relationship of CuZr/Cu A/C nanolaminates is established through integrated high-throughput micro-compression tests and molecular dynamics simulations together with high-resolution transmission electron microcopy. The serrated flow of nanolaminates results from the formation of hexagonal-close-packed (HCP)-type stacking faults and twins inside the face-centered-cubic (FCC) Cu nano-grains, the body-centered-cubic (BCC)-type ordering at their grain boundaries, and the crystallization of the amorphous CuZr layers. The serration behavior of CuZr/Cu A/C nanolaminates is determined by several factors, including the formation of dense dislocation networks from the multiplication of initial dislocations that formed after yielding, weak-spots-related configurational-transitions and shear-transition-zone activities, and deformation-induced devitrification. The present work provides an insight into the heterogeneous deformation mechanism of A/C nanolaminates at the atomic scale, and mechanistic base for the microstructural design of self-toughening metallic-glass (MG)-based composites and A/C nanolaminates.

s Fictive associates are widely used to describe and model liquid phases with strong ordering trends. However, little evidence is known about the assumed associates in most cases. In the present work, an ab initio molecular dynamics (AIMD) study is employed to investigate the characters of the Ba-Bi liquid, in which associates have been assumed in existing thermodynamic modeling. It is found that in the Ba rich melt, the Bi atoms are almost completely surrounded by Ba atoms. The Bi-centered coordination polyhedrons are strongly associated to crystalline structures of Ba5Bi3 and Ba4Bi3 with a longer lifetime than other polyhedrons during the AIMD simulations. In addition, these Bi-centered polyhedrons in Ba rich melt connect with each other through vertex, edge, face, and/or bipyramid sharing to form medium range orders (MRO). In the Bi rich melt, the Ba-centered polyhedrons also form MROs, but they are both structurally and compositionally diverse with a shorter lifetime. These findings from AIMD study provide evidences that there exist a strongly ordering Ba4Bi3 associate and a weakly ordering BaBi3 associate in the Ba-Bi liquid. The predicted enthalpy of mixing in the liquid agrees well with the results by the CALPHAD modeling in the literature.

This article presents a brief review of our case studies of data-driven Integrated Computational Materials Engineering (ICME) for intelligently discovering advanced structural metal materials, including light-weight materials (Ti, Mg, and Al alloys), refractory high-entropy alloys, and superalloys. The basic bonding in terms of topology and electronic structures is recommended to be considered as the building blocks/units constructing the microstructures of advanced materials. It is highlighted that the bonding charge density could not only provide an atomic and electronic insight into the physical nature of chemical bond of materials but also reveal the fundamental strengthening/embrittlement mechanisms and the local phase transformations of planar defects, paving a path in accelerating the development of advanced metal materials via interfacial engineering. Perspectives on the knowledge-based modeling/simulations, machine-learning knowledge base, platform, and next-generation workforce for sustainable ecosystem of ICME are highlighted, thus to call for more duty on the developments of advanced structural metal materials and enhancement of research productivity and collaboration.

Thermodynamics of ferroelectric materials and their ferroelectric to paraelectric (FE-PE) transitions including those in PbTiO3 is commonly described by the phenomenological Landau theory and more recently by effective Hamiltonian and various potentials, all with model parameters fitted to experimental or theoretical data. Here we show that the zentropy theory, which considers the total entropy of a system as a weighted sum of entropies of configurations that the system may experience and the statistical entropy among the configurations, can predict the FE-PE transition without fitting parameters. For PbTiO3, the configurations are identified as the FE configurations with 90- or 180-degree domain walls in addition to the ground state of the FE configuration without domain wall. With the domain wall energies predicted from first-principles calculations based on the density functional theory in the literature as the only inputs, the FE-PE transition for PbTiO3 is predicted showing remarkable agreement with experiments, unveiling the microscopic fundamentals of the transition.

Pd-Zn intermetallic catalysts show encouraging combinations of activity and selectivity on well-defined active site ensembles. Thermodynamic description of the Pd-Zn system, delineating phase boundaries, and enumerating site occupancies within intermediate alloy phases, are essential to determining the ensembles of Pd-Zn atoms as a function of composition and temperature. Combining the present extensive first-principles calculations based on density functional theory (DFT) and available experimental data, the Pd-Zn system was remodeled using the CALculation of PHAse Diagrams (CALPHAD) approach. High throughput modeling tools with uncertainty quantification, i.e., ESPEI and PyCalphad, were incorporated in the phase analysis. The site occupancies across the {\gamma}-phase composition region were given special attention. A four-sublattice model was used for the {\gamma}-phase owing to its four Wyckoff positions, i.e., the outer tetrahedral (OT) site 8c, the inner tetrahedral (IT) site 8c, the octahedral (OH) 12e, and the cuboctahedral (CO) site 24g. The site fractions of Pd and Zn calculated from the present thermodynamic model show the occupancy preference of Pd in the OT and OH sublattices in agreement with experimental observations. The force constants obtained from DFT-based phonon calculations further supports the tendency of Pd occupying the OH sublattice compared with the IT and CO sublattice. The catalytic assembles changing from Pd monomers (Pd1) to trimers (Pd3) on the surface of the {\gamma}-phase is attributed to the increase of Pd occupancy in the OH sublattice., Comment: 12 figures

Forming metallurgical phases has a critical impact on the performance of dissimilar materials joints. Here, we shed light on the forming mechanism of equilibrium and non-equilibrium intermetallic compounds (IMCs) in dissimilar aluminum/steel joints with respect to processing history (e.g., the pressure and temperature profiles) and chemical composition, where the knowledge of free energy and atomic diffusion in the Al–Fe system was taken from first-principles phonon calculations and data available in the literature. We found that the metastable and ductile (judged by the presently predicted elastic constants) Al6Fe is a pressure (P) favored IMC observed in processes involving high pressures. The MoSi2-type Al2Fe is brittle and a strong P-favored IMC observed at high pressures. The stable, brittle η-Al5Fe2 is the most observed IMC (followed by θ-Al13Fe4) in almost all processes, such as fusion/solid-state welding and additive manufacturing (AM), since η-Al5Fe2 is temperature-favored, possessing high thermodynamic driving force of formation and the fastest atomic diffusivity among all Al–Fe IMCs. Notably, the ductile AlFe3, the less ductile AlFe, and most of the other IMCs can be formed during AM, making AM a superior process to achieve desired IMCs in dissimilar materials. In addition, the unknown configurations of Al2Fe and Al5Fe2 were also examined by machine learning based datamining together with first-principles verifications and structure predictions. All the IMCs that are not P-favored can be identified using the conventional equilibrium phase diagram and the Scheil-Gulliver non-equilibrium simulations.

Generative deep learning is powering a wave of new innovations in materials design. In this article, we discuss the basic operating principles of these methods and their advantages over rational design through the lens of a case study on refractory high-entropy alloys for ultra-high-temperature applications. We present our computational infrastructure and workflow for the inverse design of new alloys powered by these methods. Our preliminary results show that generative models can learn complex relationships in order to generate novelty on demand, making them a valuable tool for materials informatics.

Zn-based and Mg-based alloys have been considered highly promising biodegradable materials for cardiovascular stent applications due to their excellent biocompatibility and moderate in vitro degradation rates. However, their strength is too poor for use in cardiovascular stents. The strength of these metals can be related to the sizes of the dislocation cores and the threshold stresses needed to activate slip, i.e., the Peierls stress. Using density functional theory (DFT) and an ab initio-informed semi-discrete Peierls–Nabarro model, we investigate the coupled effect of the solute element and mechanical straining on the stacking fault energy, basal dislocation core structures and Peierls stresses in both Zn-based and Mg-based alloys. We consider several biocompatible solute elements, Li, Al, Mn, Fe, Cu, Mg and Zn, in the same atomic concentrations. The combined analysis here suggests some elements, like Fe, can potentially enhance strength in both Zn-based and Mg-based alloys, while other elements, like Li, can lead to opposing effects in Zn and Mg. We show that the effect of solute strengthening and longitudinal straining on SFEs is much stronger for the Zn-based alloys than for the Mg-based alloys. DFT investigations on electronic structure and bond lengths reveal a coupled chemical-mechanical effect of solute and strain on electronic polarization, charge transfer, and bonding strength, which can explain the weak mechanical effect on Zn-based alloys and the variable strengthening effect among these solutes. These findings can provide critical information needed in solute selection in Zn-based and Mg-based alloy design for biomedical applications.

Chrome-molybdenum steel (2.25Cr1Mo steel) is one of the main materials of a steam generator (SG) in high-temperature reactor-pebblebed modules (HTR-PM). It is essential to analyze the source term of tritium in this material, because the behavior of tritium in a SG is important for performing source term analysis in normal and accident conditions. In this article, the diffusion behavior of H atom in 2.25Cr1Mo steel was calculated to estimate the diffusivity of tritium using first-principles density functional theory. To develop and simplify the model of hydrogen diffusion in 2.25Cr1Mo steel, the impact of Cr and Mo on the diffusion of hydrogen in bcc-Fe were first calculated, all the possible diffusion paths were considered, and the minimum energy path was obtained. The diffusion activation energy and pre-exponential factor of the diffusion coefficient were obtained from Vienna Ab initio Simulation Package combined with the climbing image-nudged elastic band method. The results indicate that the minimum energy path for the impurity H atom is from one tetrahedral interstitial site to an adjacent tetrahedral interstitial site. The function of the diffusion coefficient of H in 2.25Cr1Mo steel with temperature T can be expressed as D = 1.486 × 10 − 7 × ( − 16.350 kJ / mol RT ) (m2/s). The diffusion coefficient of our calculation and some of the previous experiments have an excellent quantitative agreement, which indicates the reliability of our crystalline model and the practicability of the present theoretical approach. More importantly, the computational results in this work can be treated as a good screening method to collect reasonable experimental data, which will provide a good reference for tritium source term evaluation in the SG of the HTR-PM.

Effect of solutes of transition metals (TM = Cr, Fe, Hf, Mn, Mo, Nb, Ni, Pt, Rh, Ru, Re, Ta, Ti, V, W, Y and Zr) on the local phase transition between the L12 and D019 structures in superlattice intrinsic stacking fault (SISF) of Co3TM has been investigated. All the models employed herein, i.e. (1) the SISF-containing supercell, (2) the axial nearest-neighbor Ising (ANNI) model, and (3) both the L12- and D019-containing (L12 + D019) supercell, yield the same result regarding the stability of SISF in L12-type Co3TM. In the view of bonding charge density, the atomic and electronic basis of local D019 phase transition in the SISF fault layers of Co3TM are revealed. Especially, the negative SISF energy predicted by the L12 + D019 model suggests that both the SISF fault layers (i.e. the local D019 structure) and the L12 phase of Co3TM can be stabilized through a coupling interaction between the fault layers and the solutes, paving a pathway to stabilize Co-base superalloys via Co3TM precipitate. Moreover, the consist results of ESISF via the ANNI model with the classical SISF-supercell method utilized in first-principles calculations supports the approach to efficiently distinguish various planar faults and predict their corresponding energies, such as SISF, superlattice intrinsic stacking fault, anti-phase boundaries, and so on.

A thermodynamic understanding of Seebeck coefficient was demonstrated in terms of electrochemical potential. It divided the contributions to the Seebeck coefficient into two contributions: the effect of thermal electronic excitations due to Fermi distribution and the effect of charge carrier gradient due to thermal expansion. The procedure is illustrated within the rigid band approximation in terms of the electronic density-of-states and the quasiharmonic approximation in terms of the phonon density-of-states. Numerical results were given using the n-type high temperature thermoelectric material La3-xTe4 at x = 0, 0.25, and 0.33 as the prototype at a variety of carrier concentrations.

The effects of Hf, Y, and Zr additions on the growth of a thermally grown alumina scale formed on NiAlCr and NiAlPt alloys were investigated. Isothermal and thermal cycling oxidation experiments were carried out at 1150 °C, and cross sections of the oxidized samples were characterized using scanning electron microscopy. It was observed that single doping as well as co-doping of Hf, Y, and Zr reduces the rate of alumina scale growth on NiAlCr and NiAlPt alloys, with Hf showing a more significant effect than Y or Zr. The following possible contributing factors to these observations were assessed: (1) the ionic size of the minor alloying elements and (2) the bond strength between the doping elements and oxygen in the oxide grain boundaries in terms of formation and melting enthalpies of oxides. It was concluded that the bond strength between the doping elements and oxygen within the oxide grain boundaries plays an important role in retarding the alumina scale growth.

Thermodynamic modeling of the Si-Y binary system has been performed by the CALPHAD (CALculation of PHAse Diagram) method based on phase diagram and thermochemical data in the literature combined with Gibbs energies of end-members of compounds predicted by first-principles phonon calculations. In particular, non-stoichiometric compounds Si2Y and Si3Y5 are modelled to accommodate their homogeneity ranges in terms of two-sublattice models (Si,Y)2(Si,Y) and (Si)3(Si,Y)5, respectively. Formation of SiY is treated as a peritectic reaction according to experimental results, instead of an eutectic one as described in the previous models. The calculated phase equilibriums and thermodynamic properties are in a satisfactory agreement with available experimental data.

All-solid-state Na-ion batteries (NIBs) that incorporate nonflammable solid-state electrolytes and an inexhaustible alkali metal offer a potential solution to the safety and cost concerns associated with conventional Li-ion batteries that use liquid electrolytes. Na-ion solid-state electrolytes (SSEs) with high ionic conductivity are the key to success for all-solid-state NIBs. Here, we report a new Na-ion SSE, Na11Sn2PSe12, with a superior grain conductivity of 3.04 mS cm−1 and a total ionic conductivity of 2.15 mS cm−1 at 25 °C. Single-crystal X-ray diffraction, first-principles phonon calculations, and the proposed bonding energy model indicate that its superior ionic conductivity stems from the presence of a high density of dispersive Na+ vacancies, three-dimensional Na-ion conduction pathways, and a low bonding energy of the Na+ ion with its neighboring atoms. Na11Sn2PSe12 is used for the first time as the electrolyte in all-solid-state Na-Sn/TiS2 battery cell, which shows excellent rate performance and delivers a high reversible capacity of 66.2 mAh (g of TiS2)−1 after 100 cycles with cycling retention of 88.3% at a rate of 0.1 C at room temperature.

NiSn4 grows in diffusion couples (Ni plates with electrodeposited Sn) in a temperature range from room temperature up to 353 K. Previously, the crystal structure of NiSn4 grown at ambient temperature was identified to be an intermediate stacking variant between the orthorhombic PtSn4-type and the tetragonal β-IrSn4-type structure, with a slight tendency towards the tetragonal type (Schimpf et al., Mater. Design 109 (2016) 324–333). Now it is reported that NiSn4 forming at 333 K and above, exhibits a 12-layer polytype (space group P42/nbc, a = b = 6.250 A, c = 69.00 A) due to ordered incorporation of stacking faults into the structure. This NiSn4 structure was derived by comparison of its diffraction patterns with those of the exhaustively generated NiSn4 polytypes. First-principles calculations on a series of selected NiSn4 polytypes demonstrate that the experimentally observed polytype is energetically favoured as compared to others.