High Entropy Ceramics: Compositionally Predicted Phase Stability and Mechanical Shock Induced Phase Transformations
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Lowry, Daniel Robert↗
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Between Harmonic Crystal and Glass: Solids with Dimpled Potential-Energy Surfaces Having Multiple Local Energy Minima
Solids with dimpled potential-energy surfaces are ubiquitous in nature and, typically, exhibit structural (elastic or phonon) instabilities. Dimpled potentials are not harmonic; thus, the conventional quasiharmonic approximation at finite temperatures fails to describe anharmonic vibrations in such solids. At sufficiently high temperatures, their crystal structure is stabilized by entropy; in this phase, a diffraction pattern of a periodic crystal is combined with vibrational properties of a phonon glass. As temperature is lowered, the solid undergoes a symmetry-breaking transition and transforms into a lower-symmetry phase with lower lattice entropy. Here, we identify specific features in the potential-energy surface that lead to such polymorphic behavior; we establish reliable estimates for the relative energies and temperatures associated with the anharmonic vibrations and the solid–solid symmetry-breaking phase transitions. We show that computational phonon methods can be applied to address anharmonic vibrations in a polymorphic solid at fixed temperature. To illustrate the ubiquity of this class of materials, we present a range of examples (elemental metals, a shape-memory alloy, and a layered charge-density-wave system); we show that our theoretical predictions compare well with known experimental data.
36 MATERIALS SCIENCE↗
Energetics of hydroxylbastnäsite solid solutions, La 1-$\chi$ Nd $\chi$ CO 3 OH
Bastnäsites (LnCO 3 (F,OH)) are a group of common rare earth elements (REE)-bearing minerals and are one of the primary global sources of REE. Due to the chemical similarities among REE, bastnӓsites tend to occur as solid solutions instead of end members in REE containing ores. To better understand the processes and the mechanisms of formation of such deposits, it is essential to determine the thermodynamic properties of bastnӓsites, including hydroxylbastnӓsite (LnCO 3 OH) solid solutions. In this work, we performed detailed structural and calorimetric investigations on synthetic hexagonal La–Nd hydroxylbastnӓsite (La 1-$\chi$ NdCO 3 OH, $\chi$ = 0, 0.25, 0.5, 0.75, 1) solid solutions. X-ray diffraction confirms the crystal structure of the solid solution series in the $\ P$6 space group, and pair distribution function (PDF) analysis reveals local bonding environments characterized by three different types of 9-coordinated metal-oxygen polyhedra. Unit cell parameters of La1–xNdxCO3OH exhibit a nearly linear relation with the Nd content x, suggesting a random distribution of La and Nd in the structure. Their standard enthalpies of formation (Δ$\ H$° f ) were determined by high temperature oxide melt drop solution calorimetry, from which the enthalpies of mixing (Δ$\ H$ mix ) were derived. The Δ$\ H$ mix can be fitted by a regular solution model with an interaction parameter of 12.58 ± 0.16 kJ/mol, suggesting enthalpic metastability of La1–xNdxCO3OH relative to the two endmembers. Combining entropy and enthalpy, we further estimated the Gibbs free energies of mixing (Δ$\ G$ mix ) at relevant temperatures, revealing favorable temperatures under which the intermediate La 1-$\chi$ NdCO 3 OH phases can be stabilized. Such entropy-driven stabilization, as is consistent with our geochemical modeling results, may explain the enhancement of thermal stability of the solid solutions in nature. Additionally, the temperature range constrained from this study may be used to estimate the thermal history of REE bastnӓsite deposit.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
An ultrastable heterostructured oxide catalyst based on high-entropy materials: A new strategy toward catalyst stabilization via synergistic interfacial interaction
Designing high–performance catalysts that can stabilize catalytic active sites against sintering to deactivation at temperature higher than 900°C is significant but challenging. In this work, we report a new strategy to obtain a transition metal oxide catalyst with high temperature stability for CO oxidation. This is achieved through a synergistic interfacial interaction at the interface of a heterostructure between high– entropy oxides (HEO, high temperature stability) and CuCeO x (catalytic site). The catalytic site (CuCeO x ) for CO oxidation is realized by dissolving an amount of Cu species in HEO into CeO 2 via an entropy–driven mechanochemical process. In situ XRD and HAADF–STEM have confirmed the high temperature stability of the heterostructure CuCeO x –HEO, which can remain its CO oxidation catalytic activity at elevated temperatures. It should be expected that this innovative will offer the potential to the synthesis of catalysts with high temperature stability in industry.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structural damage and phase stability of Al 0.3 CoCrFeNi high entropy alloy under high temperature ion irradiation
In this study, an initially single phase high entropy alloy (HEA) Al 0.3 CoCrFeNi was irradiated by 3 MeV Au ions to a fluence of 6 × 10 15 cm –2 (~31 dpa at damage peak) at four different temperatures ranging from 250 °C to 650 °C. Transmission electron microscopy (TEM) and Atom probe tomography (APT) were employed to study the evolution of structural damage and phase stability with irradiation temperature. Al 0.3 CoCrFeNi exhibited a similar evolution of irradiation-induced defects with temperature as compared with conventional FCC alloys. At 250 °C and 350 °C, most of the visible irradiation-induced defects were faulted 1/3$\langle{111}\rangle$ dislocation loops. As the irradiation temperature increased to 500 °C, perfect 1/2$\langle{110}\rangle$ dislocation loops were observed along with the faulted loops. At the highest irradiation temperature 650 °C, only dislocation lines and networks could be observed. Regarding phase stability, the 3 MeV Au irradiation was observed to suppress the precipitation of (Ni, Al)-enriched nano clusters and the L12 ordered structure at irradiation temperatures 250 °C to 500 °C whereas precipitation of the B2 ordered structure was accelerated at 650 °C. This resulted in qualitatively opposite precipitation behavior between the ion irradiated damage region and unirradiated region at 500 °C and 650 °C. The opposite phase stability of the ion-irradiated damage region and unirradiated region at different temperatures is attributed to the competing effects of ballistic dissolution vs irradiation enhanced diffusion on precipitation.
36 MATERIALS SCIENCE↗
New High-Entropy Perovskite Oxides with Increased Reducibility and Stability for Thermochemical Hydrogen Generation
This project aims to design, synthesize, and test a transformative class of High-Entropy Perovskite Oxides (HEPOs) as redox oxides to enable thermochemical hydrogen generation with improved stability, kinetics, and efficiency. These developed HEPOs are expected to demonstrate improved kinetics with oxygen surface exchange coefficient ( k > 7.5×10 -4 cm/s) in Budget Period (BP) 1, retain its structural stability in a broad range of oxygen non-stoichiometry (Δδ > 0.15) at a low operating reduction temperature of T red < 1400°C in BP 2, and deliver a H 2 yield of over 400 µmol per gram of oxide and high stability with less than 20% degradation after at least 50 cycles in BP 3. This project is feasible due to the unique thermodynamic properties (simultaneously increased reducibility and phase stability) and kinetic characters (stability against particle coarsening and potentially enhanced oxygen transport and surface reaction kinetics) of such HEPOs, and it is enabled by a unique active learning computational design approach. Computational studies have been conducted to investigate the oxygen vacancy formation in complex perovskite systems. * Accurate prediction of V O .. concentration with disordered A-site cations in Fe-based high-entropy perovskite oxides * Combined MC/DFT computation elucidates the mechanism of Co preference on the redox due to the strain introduced by local distortion. In this project, we explored a large number (~150) of perovskite compositions, which are listed in Tables 2 – 4). * All perovskite specimens have been synthesized through a high-throughput high-energy ball milling process, followed by the conventional sintering process. * XRD, SEM/EDS and TGA were performed to confirm the crystal structure, phase homogeneity and oxygen non-stoichiometry for compositionally complex perovskite oxides (CCPOs). * 110 compositions show single-phase from XRD * Unusual aliovalent doping effects in medium-entropy perovskite compositions. * V-shape relation between Δδ vs. x (La 1-x Sr x )(Mn 1/3 Fe 1/3 Ti 1/3 )O 3 * The highest reported hydrogen production for the CCPOs made in this project ( T re = 1350 ºC 30 min, T Ox = 1100 ºC 30 min) * B-site mixing (La 0.8 Sr 0.2 )(Mn 0.2 Fe 0.2 Co 0.4 Al 0.2 )O 3 : 89.97 ± 2.73 mmol H2 /mol oxide (395 ± 10 μmol/g oxide ) (i) No phase transformation during reactions when Co molar ratio is less than 61% (ii) Balance between intrinsic kinetics (oxygen surface exchange) and thermodynamics (oxygen non-stoichiometry) (iii) Preference of Co identified by in-situ XPS * A-site mixing (La 1/6 Pr 1/6 Nd 1/6 Gd 1/6 Ba 1/6 Sr1/6)MnO 3 : 98.48 mmol H2 /mol oxid e (~415 μmol/g oxide )
08 HYDROGEN↗
Stabilization and manipulation of highly concentrated copper single atoms by high entropy oxides
Facile and controllable methodologies capable of providing single atom catalysts (SACs) with high-density active metal sites and sintering-resistance under harsh conditions are highly desired and grand challenges in heterogeneous catalysis. Herein, the entropy effect was leveraged to stabilize and manipulate the electronic properties of copper SACs. The as-developed ultrasonication-driven approach could integrate highly concentrated Cu SAs within the lattice of fluorite-structured high entropy oxide (HEFO) under ambient conditions (CuO-HEFO). The dual benefits from the high entropy effect of the support and the in-situ lattice engineering led to the generation of abundant Cu 1+ species and oxygen defects, together with ultra-high stability and sintering-resistance under extremely harsh conditions. This was confirmed by deploying non-high entropy support (CuO-CeO 2 ) or Cu sites located on the surface of HEFO (CuO@HEFO). In conclusion, the catalytic activity of CuO-HEFO surpassed that of CuO-CeO 2 and CuO@HEFO in CO oxidation together with well-maintained long-term stability and resistance to gas impurities.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Exceptional thermal stability of additively manufactured CoCrFeMnNi high-entropy alloy with cellular dislocation structures
CoCrFeMnNi high-entropy alloy (HEA) was additively manufactured (AM) by laser powder-bed fusion (L-PBF). The AM CoCrFeMnNi has prominent cellular dislocation structures with a small number of Mn-rich oxides. The thermal stability of the AM CoCrFeMnNi was investigated by isochronal annealing treatment at various temperatures from 400 to 1300°C for 1h. Microstructural analysis shows slow dislocation recovery, retarded recrystallization process, and precipitation of additional Cr-Mn based oxides during thermal annealing, resulting in exceptional thermal stability and retained high hardness at elevated temperatures. Further, by thermodynamic calculations, a low stored energy of 1.31 MJ/m 3 and a high activation energy of 353 kJ/mol for recrystallization were estimated for the AM CoCrFeMnNi. The exceptional thermal stability of the AM CoCrFeMnNi HEA is mechanistically attributed to the low crystallographic misorientations across the dislocation cell walls, sluggish atomic diffusion, and the pinning effects of the oxide nanoprecipitates.
36 MATERIALS SCIENCE↗
Data-driven discovery of high entropy alloy hydrides with targeted thermodynamic stability.
Abstract not provided.
Witman, Matthew↗
Role of electronic energy loss on defect production and interface stability: Comparison between ceramic materials and high-entropy alloys
High-entropy alloys (HEAs) and some complex alloys exhibit desirable properties and significant structural stability in harsh environments, including possible applications in advanced reactors. Energetic ion irradiation is often used as a surrogate for neutron irradiation; however, the impact of ion electronic energy deposition and dissipation is often neglected. Moreover, differences in recoil energy spectrum and density of cascade events on damage evolution must also be considered. In many chemically complex alloys, the mean free path of electrons is reduced significantly, thus their decreased thermal conductivity and slow dissipation of localized radiation energy can have noticeable effects on displacement cascade evolution that is greatly different from metals with high thermal conductivity. In this work, nanocrystalline HEAs of Ni 20 Fe 20 Co 20 Cr 20 Cu 20 and nonequiatomic (NiFeCoCr) 97 Cu 3 , both having much lower room-temperature thermal conductivity than pure Ni or Fe, are chosen as model HEAs to reveal the role that electronic energy loss during ion irradiation has in complex alloys. The response of nanocrystalline HEAs is investigated under irradiation at room temperature using MeV Ni and Au ions that have different ratios of electronic energy to damage energy, which is the energy dissipated in displacing atoms. Different from previously reported amorphization of nanocrystalline SiC, experimental results on these HEAs show that, similar to the process in nanocrystalline oxide materials, both inelastic thermal spikes via electron–phonon coupling and elastic thermal spikes via collisions among atomic nuclei contribute to the overall grain growth. The growth follows a power law dependence with the total deposited ion energy, and the derived value of the power-exponent suggests that the irradiation-induced instability at and near grain boundaries leads to local rapid atomic rearrangements and consequently grain growth. The high power-exponent value can be attributed to the sluggish diffusion and delayed defect evolution arising from the chemical complexity intrinsic to HEAs. Here, this work calls attention to quantified fundamental understanding of radiation damage processes beyond that of simplified displacement events, especially in simulating neutron environments.
36 MATERIALS SCIENCE↗
The effect of submicron grain size on thermal stability and mechanical properties of high-entropy carbide ceramics
(Hf 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )C high-entropy ceramics (HEC) with a submicron grain size of 400 to 600 nm were fabricated by spark plasma sintering using a two-step sintering process. Both X-ray and neutron diffractions confirmed the formation of single-phase with rock salt structure in the as-fabricated (Hf 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )C samples. The effect of submicron grain size on the thermal stability and mechanical properties of HEC was investigated. The grain growth kinetics in the fine-grained HEC was small at 1300 and 1600°C, suggesting high thermal stability that was possibly related to the compositional complexity and sluggish diffusion in HEC. Compared to the coarse-grain HEC with a grain size of 16.5 µm, the bending strength and fracture toughness of fine-grained HEC were 25% and 20% higher respectively. The improvement of mechanical properties in fine-grained HEC may be attributed to micromechanistic mechanisms such as crack deflection.
36 MATERIALS SCIENCE↗
Entropic lens on stabilizer states
The n-qubit stabilizer states are those left invariant by a 2 n -element subset of the Pauli group. The Clifford group is the group of unitaries which take stabilizer states to stabilizer states; a physically motivated generating set, the Hadamard, phase, and controlled-not (cnot) gates which comprise the Clifford gates, impose a graph structure on the set of stabilizers. We explicitly construct these structures, the “reachability graphs,” at n ≤ 5. When we consider only a subset of the Clifford gates, the reachability graphs separate into multiple, often complicated, connected components. Seeking an understanding of the entropic structure of the stabilizer states, which is ultimately built up by cnot gate applications on two qubits, we are motivated to consider the restricted subgraphs built from the Hadamard and cnot gates acting on only two of the n qubits. We show how the two subgraphs already present at two qubits are embedded into more complicated subgraphs at three and four qubits. We argue that no additional types of subgraph appear beyond four qubits, but that the entropic structures within the subgraphs can grow progressively more complicated as the qubit number increases. Starting at four qubits, some of the stabilizer states have entropy vectors which are not allowed by holographic entropy inequalities. Here, we comment on the nature of the transition between holographic and nonholographic states within the stabilizer reachability graphs.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Interplay between electron localization, magnetic order, and Jahn-Teller distortion dictates LiMnO2 phase stability
The development of manganese (Mn)-rich cathodes for Li-ion batteries promises to alleviate potential supply chain bottlenecks in battery manufacturing. Fundamental challenges in Mn-rich cathodes arise from phenomena such as structural changes due to cooperative Jahn-Teller (JT) distortions of in octahedral environments, Mn migration, and phase transformations to spinel-like order, all of which affect the electrochemical performance. These physically complex phenomena motivate an re-examination of the Li-Mn-O rock-salt space, with a focus on the thermodynamics of the prototypical, polymorphs. It is found that the generalized gradient approximation (GGA-PBEsol) and meta-GGA ( ) density functionals with empirically fitted on-site Hubbard corrections yield spurious stable phases for , such as predicting a phase with -like order ( ) to be the ground state instead of the orthorhombic (Pmmn) phase, which is the experimentally known ground state. Accounting for antiferromagnetic order in each structure is shown to have a substantial effect on the total energies and resulting phase stability. By using hybrid-GGA (HSE06) and GGA with self-consistent Hubbard parameters (on-site and inter-site ) calculated from linear response theory, the experimentally observed phase stability trends are recovered. The calculated on-site between Mn- states in the experimentally observed orthorhombic, layered, and spinel phases are significantly smaller than in and disordered layered structures, by within GGA. The smaller values of are shown to be correlated with a collinear ordering of JT distortions, in which all orbitals are oriented in the same direction. This cooperative JT effect can lead to greater electron delocalization from Mn along the states due to increased Mn-O covalency, which contributes to the greater electronic stability compared to the phases with noncollinear JT arrangements. The structures with collinear ordering of JT distortions also generate greater vibrational entropy, which helps stabilize these phases at high temperature. These phases are shown to be strongly insulating with large calculated band gaps , which are computed using HSE06 and .
Kam, Ronald L↗
Platinum on High-Entropy Aluminate Spinels as Thermally Stable CO Oxidation Catalysts
Thermal degradation is a leading cause of automotive catalyst deactivation. Because high-entropy oxides are uniquely stabilized at high temperatures via an increase in configurational entropy, these materials may offer new mechanisms for preventing the thermal deactivation of precious metal catalysts. In this work, we evaluated platinum loaded on simple and high-entropy aluminate spinels (MAl 2 O 4 , where M = Co, Cu, Mg, Ni, or mixtures thereof) in carbon monoxide oxidation before and after aging at 800 °C. Pt supported on all simple spinels showed significant deactivation after thermal aging compared to the fresh samples, with T 90 increasing by at least 60 °C. However, Pt on high-entropy spinels had nearly the same or better activity after aging, with T 90 increasing by only 6 °C at most. During aging and reduction, copper exsolved from the spinel supports and alloyed with platinum. This interaction promoted low temperature oxidation activity, presumably through weakened CO binding, but did not prevent deactivation. On the other hand, Co, Mg, and Ni constituents promoted stronger CO bonding, as evidenced by apparent negative order kinetics and poor activity at low temperatures. High-entropy spinels, containing a variety of active metals, displayed synergetic reactant adsorption capacity and cooperative effects with supported platinum particles, which collectively prevented thermal deactivation.
CO oxidation↗
Ab Initio Modeling on The Thermodynamic and Temperature-Dependent Elastic Properties of Subsystems of The FCC FeNiCoCr Medium Entropy Alloys (MEAs)
The stability, phonon spectra, thermodynamic, and temperature-dependent elasticity of subsystems of the FCC FeNiCoCr MEAs are systematically studied by the ab initio approach. Especially, the quasi-harmonic approximation (QHA) and the innovative Zentropy theory were utilized to predict the thermodynamic properties and elastic properties of FeNi, NiCo, FeNiCo, and FeNiCoCr MEAs with the consideration of magnetic transition. With the ensemble of the partition function based on the multiplicity of each magnetic configuration, the current work successfully reproduced the Curie temperature and the Schottky anomaly of heat capacity of these four MEAs purely based on the ab initio input. Meanwhile, the elastic properties of these alloys at finite temperatures are also successfully predicted with the consideration of magnetic transition. The overall results agree well with the available experimental data and CALPHAD prediction.
36 MATERIALS SCIENCE↗
Epitaxial stabilization of ultra thin films of high entropy perovskite
High entropy oxides (HEOs) are a class of materials, containing equimolar portions of five or more transition metal and/or rare-earth elements. We report here about the layer-by-layer growth of HEO [(La 0.2 Pr 0.2 Nd 0.2 Sm 0.2 Eu 0.2 )NiO 3 ] thin films on NdGaO 3 substrates by pulsed laser deposition. The combined characterizations with in situ reflection high energy electron diffraction, atomic force microscopy, and x-ray diffraction affirm the single crystalline nature of the film with smooth surface morphology. The desired +3 oxidation of Ni has been confirmed by an element sensitive x-ray absorption spectroscopy measurement. Temperature dependent electrical transport measurements revealed a first order metal-insulator transition with the transition temperature very similar to the undoped NdNiO 3 . Furthermore, since both these systems have a comparable tolerance factor, this work demonstrates that the electronic behaviors of A-site disordered perovskite-HEOs are primarily controlled by the average tolerance factor.
36 MATERIALS SCIENCE↗
A perspective on challenges and opportunities in developing high entropy-ultra high temperature ceramics
The emergence of a new class of high entropy ultra-high temperature ceramics (HE-UHTCs) is expected to possess exceptionally superior mechanical, oxidation, and erosion resistance as compared to conventional UHTCs. The improvement in the properties of HE-UHTCs is attributed to the high configurational entropy of the multi-component system stabilized into a single-phase, but with little discussion on entropy contributions. This perspective article presents a viewpoint on the critical scientific question regarding the actual role entropy plays in stabilizing and enhancing the thermo-mechanical properties of a multi-component system. The high throughput first-principle calculations, which can provide the entropy formation ability (EFA) of thermodynamically stable HE-UHTCs, can prove to be valuable toolset to this puzzle. HE-UHTCs show enhancement in the mechanical properties much higher than the predicted rule of the mixture, which cannot traditionally be explained by a mere solid solution formation effect. Additionally, isothermal oxidation studies of HE-UHTCs limited to furnace testing state remarkable oxidation resistance which is attributed to the passivity of complex, layered structure, and composition of the oxide scale. However, whether all the constituents in the HE-UHTC system react simultaneously or preferential oxidation takes place needs to be addressed. To address all these issues, an integrated computational and experimental approach has been postulated towards designing a thermal protection system (TPS) for re-entry applications. Succeeding the approach will provide new opportunities in the compositional space of HE-UHTCs with tailored properties.
36 MATERIALS SCIENCE↗
Rate Enhancement of Acid-Catalyzed Alcohol Dehydration by Supramolecular Organic Capsules
The presence of a (sub)nanometric environment has been demonstrated to enhance the rate of homogeneous acid-catalyzed reactions. Conventionally, such catalysts are constructed by directly embedding a catalytically active acid site into the structure of a porous material, linking the acid properties with the properties of the embedding solid. Here, a holoenzyme mimicking approach was used, in which a self-assembled hexameric resorcinarene capsule (1.4 nm 3 cavity) acts like an apoenzyme that transforms into a catalytically active site by hosting hydrated HCl as a cofactor. This capsule binds the hydronium ion together with cyclohexanol (CyOH) and catalyzes the dehydration to cyclohexene with enhanced rates that are 2 orders of magnitude higher than those in the unconstrained environment. Kinetic analysis shows that cyclohexanol dehydration proceeds via an E2 mechanism on hydrated HCl in the unconstrained environment, while the constrained environment of the active capsule induces the stabilization of an ionic intermediate, allowing an E1 mechanism to dominate. By comparison with the reaction in zeolite environments, we show that the direct chemical environment of the capsule or a zeolite wall exerts only a minor direct influence. The volume constraint increases the reaction rate by inducing a larger activation entropy, indicating the stabilization of a later transition state in the E1 mechanism, as well as a higher reaction space of the carbenium ion constituting the transition state.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗