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When exposed to severe environments, the short-range order in pyrochlores significantly influences their physicochemical properties. Using the DFT + U method, this study investigates the effect of short-range order on the solubility of actinides (An = Th, U, Np, Pu, Am, and Cm) in Gd 2 Zr 2 O 7 with distinct coordinated Gd and Zr sites. Our findings indicate that all the actinides under consideration are susceptible to being incorporated into the 7-fold Zr-site of quasi -weberite Gd 2 Zr 2 O 7. The weberite-like short-range order also favors immobilization of these actinides in the 6-fold Zr-site. The effect of the weberite-like motif on the solubility of actinides in the Gd-site of quasi -WB Gd 2 Zr 2 O 7 depends on the chemistry of the actinides. Furthermore, the short-range order results in a lower solution energy for An incorporation into the Gd and Zr sites of the quasi -weberite Gd 2 Zr 2 O 7 with cation antisites, thereby favoring An immobilization in a disordered environment. These results strongly demonstrate the importance of the short-range order on the solubility of actinides in disordered pyrochlores. [ABSTRACT FROM AUTHOR]

This contribution investigates the effect of variable copper incorporation (x = 0.2, 1.0, 2.0, and 4.0) in silicate (45 SiO2, 24.5 CaO, 24.5 Na2O, 6P2O5wt%) and modified borate (45 B2O3, 24.5 CaO, 24.5 Na2O, 6P2O5wt%) bioglass materials to be used for bone bonding applications. X-ray absorption fine structure spectroscopy (XAFS) has been used to determine the oxidation states and local coordination structure of Cu atoms in silicate-based and borate-based glasses at the Cu K-edge (~ 8979 eV). The oxidation states of Cu atoms have been determined by near-edge XAFS (XANES) fingerprinting employing reference standard compounds of Cu. Cu (I) and Cu (II) XANES spectra of the standard reference compounds were linearly combined to fit the normalized μ(E) data of the collected XANES spectra using linear combination fitting (LCF approach). The obtained results prove that most of the silicate glass samples contain Cu2O almost exclusively, while modified borate glass samples contain a significant mixture of Cu2O and CuO phases. According to the literature, the remarkable coexistence of Cu2O and CuO phases within the borate sample, particularly when x = 4, promotes the conversion process to allow the more facile formation of hydroxy carbonate apatite (HCA). The best fit structural parameters derived from extended-XAFS (EXAFS) fitting show that the ratio between Cu (I) and Cu (II) in borate glass agreed well with that extracted from XANES analysis. XANES and EXAFS conclude that borate glass with x = 4 is the most suitable composition for bone bonding applications. [ABSTRACT FROM AUTHOR]

Extended X-ray absorption fine structure (EXAFS) conducted on an equiatomic MoNbTaW bcc medium-entropy alloy that was annealed at 2273 K reveals unexpectedly small 1st and 2nd shell element-specific lattice distortions. An experimental size-mismatch parameter, [Formula: see text], is determined to be ca. 50% lower than the corresponding calculated value. Around W, short-range order (SRO) preferring 4d elements in the 1st and 2nd shells persists. A Nb-W ordering is found, which is reminiscent of ordering emerging at lower temperatures in the B2(Mo,W;Ta,Nb)- and B32(Nb,W)-phases. With high-temperature ordering preferences in fcc also foreshadowing low-temperature phase, these findings suggest a general feature of high-temperature SRO.

Fe78B15Sn7 and (Fe3Co1)78B15Sn7 amorphous metallic alloys were prepared using the method of planar flow casting. The amorphous nature of ribbons containing 7 at. % Sn was verified by X-ray diffraction. The resulting chemical composition was checked by flame atomic absorption spectroscopy and by mass spectrometry with inductively coupled plasma. The microstructure of the as-quenched metallic glasses was investigated by 57-Fe and 119-Sn Mössbauer spectrometry. The experiments were performed with transmission geometry at 300 K, 100 K, and 4.2 K, and in an external magnetic field of 6 T. The replacement of a quarter of the Fe by Co did not cause significant modifications of the hyperfine interactions in the 57-Fe nuclei. The observed minor variations in the local magnetic microstructure were attributed to alterations in the topological short-range order. However, the in-field 57-Fe Mössbauer spectra indicated a misalignment of the partial magnetic moments. On the other hand, the presence of Co considerably affected the local magnetic microstructure of the 119-Sn nuclei. This was probably due to the higher magnetic moment of Co, which induces transfer fields and polarization effects on the diamagnetic Sn atoms. [ABSTRACT FROM AUTHOR]

Multi-edge extended X-ray absorption fine structure (EXAFS) spectroscopy combined with reverse Monte Carlo (RMC) simulations was used to probe the details of element-specific local coordinations and component-dependent structure relaxations in single crystalline equiatomic CrMnFeCoNi high-entropy alloy as a function of the annealing temperature. Two representative states, namely a high-temperature state, created by annealing at 1373 K, and a low-temperature state, produced by long-term annealing at 993 K, were compared in detail. Specific features identified in atomic configurations of particular principal components indicate variations in the local environment distortions connected to different degrees of compositional disorder at the chosen representative temperatures. The detected changes provide new atomistic insights and correlate with the existence of kinks previously observed in the Arrhenius dependencies of component diffusion rates in the CrMnFeCoNi high-entropy alloy. [ABSTRACT FROM AUTHOR]

Extended X-ray absorption fine structure (EXAFS) conducted on an equiatomic MoNbTaW bcc medium-entropy alloy that was annealed at 2273 K reveals unexpectedly small 1st and 2nd shell element-specific lattice distortions. An experimental size-mismatch parameter, $ \delta _{exp} $ δ exp , is determined to be ca. 50% lower than the corresponding calculated value. Around W, short-range order (SRO) preferring 4d elements in the 1st and 2nd shells persists. A Nb-W ordering is found, which is reminiscent of ordering emerging at lower temperatures in the B2(Mo,W;Ta,Nb)- and B32(Nb,W)-phases. With high-temperature ordering preferences in fcc also foreshadowing low-temperature phase, these findings suggest a general feature of high-temperature SRO. A medium-entropy MoNbTaW bcc alloy annealed at 2273 K shows still signs of short-range ordering which relate to its segregational behavior at lower temperatures, corroborating observations on fcc alloys. [ABSTRACT FROM AUTHOR]

A classical molecular dynamics method was used to model potassium and calcium metaphosphate glasses to apply an environmentally conscious glass fertilizer. By controlling the K2O–CaO–P2O5 glass composition, the phosphate glasses are predicted to provide the slow-releasing nutrient fertilizers which are environmentally safe and widely applicable. Five models of a composition of 50P2O5−xCaO–(50−x)K2O (x = 0, 10, 20, 30 and 40 mol %) were developed. The model's short-range order parameters results agree with experimental results. The two P-O bond distances are well resolved on average at 1.48 Å and 1.55 Å. The O–O mean bond distance peaked at 2.46 Å with an average coordination number of 4.1. The Ca–O bond distance is well defined at 2.40 Å with the coordination number of 6 on average. Ca acts as a network modifier; the addition of CaO is associated with the disturbance of the bridges P–O–P and therefore depolymerizes the phosphate network. The K–O coordination number changed insignificantly on composition range, with average values between 5.0–5.6. The bond angle distributions for the five models found that the average O–P–O bond angle is tetrahedral, defined to peak at 110˚, while the P–O–P bond angles peaked at around 150˚. As expected in metaphosphate composition, the models show the phosphate network dominated by Q2 units. The network connectivity is also examined through P–P coordination number with an average value of 2 and the bond distance is well resolved at 3 Å. [ABSTRACT FROM AUTHOR]

For the first time, the retrogradation behavior of starch during storage under high moisture content was studied from the perspective of short-range ordering of gelled starch. The study found that under high moisture content, the formation of crystal structure was not detected in short-term (1 day) retrogradation, but the short-range ordered structure of amorphous gelled starch increased. By extending the retrogradation time to 7 days, the starch formed an obvious crystal structure. After further extending the retrogradation time, the degree of starch retrogradation increased. Low-field nuclear magnetic resonance (LF-NMR) and magnetic resonance imaging (MRI) analysis results indicated that free water was separated from the high moisture content starch gel during the retrogradation process. From the above studies and other results, at high moisture content, gelatinized starch cannot form a crystal structure during short-term storage, but its short-range order increased. As the regeneration time increased, the crystal structure could be formed.

Many technologically important material properties are underpinned by disorder and short-range structural correlations; therefore, elucidating structure–property relationships in functional materials requires understanding both the average and the local structures. The latter information is contained within diffuse scattering but is challenging to exploit, particularly in single-crystal systems. Separation of the diffuse scattering into its constituent components can greatly simplify analysis and allows for quantitative parameters describing the disorder to be extracted directly. Here, a deep-learning method, DSFU-Net, is presented based on the Pix2Pix generative adversarial network, which takes a plane of diffuse scattering as input and factorizes it into the contributions from the molecular form factor and the chemical short-range order. DSFU-Net was trained on 198 421 samples of simulated diffuse scattering data and performed extremely well on the unseen simulated validation dataset in this work. On a real experimental example, DSFU-Net successfully reproduced the two components with a quality sufficient to distinguish between similar structural models based on the form factor and to refine short-range-order parameters, achieving values comparable to other established methods. This new approach could streamline the analysis of diffuse scattering as it requires minimal prior knowledge of the system, allows access to both components in seconds and is able to compensate for small regions with missing data. DSFU-Net is freely available for use and represents a first step towards an automated workflow for the analysis of single-crystal diffuse scattering.

Local chemical ordering (LCO) in the CrCoNi medium-entropy alloy was investigated by transmission electron microscopy (TEM) after different annealing treatments and their corresponding mechanical properties by bulk tensile tests and nanoindentation. A cold-rolled alloy was annealed at 1000°C for 0.5 h followed by ice water quenching and then aged at a number of different temperatures (600°C, 700°C, 800°C, 900°C, and 1000°C) under vacuum for 240 h to generate different degrees of chemical ordering. A splat-quenched sample rapidly cooled from the liquid phase was also examined. While bulk mechanical properties did not vary among samples with equivalent grain sizes, nanoindentation tests revealed notable differences. As indicated by the load at first pop-in using a Berkovich tip or the indentation yield strength via continuous stiffness measurements using a 10 μm spherical tip, the nanoindentation tests revealed that the stress for onset of plasticity during indentation varied with heat treatment and peaked in the 900°C aged sample. Energy-filtered TEM characterization indicated the presence of ordering in all specimens, with a higher degree of LCO in the aged samples relative to the splat-quenched and 1000°C-quenched samples. The evolution of LCO during aging was determined to occur on the time scale similar to those of bulk diffusion. The difference in nanoindentation strength was attributed to the difference in dislocation nucleation barriers imposed by different degrees of LCO.

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A systematic study on a face‐centered cubic‐based compositionally complex alloy system Al–Co–Cr–Cu–Fe–Ni in its single‐phase state is carried out, where a mother senary compound Al8Co17Cr17Cu8Fe17Ni33 and five of its suballoys, obtained by removing one element at a time, are investigated and exhaustively analyzed determining the contribution of each alloying element in the solid solution. The senary and the quinaries are compared using experimental techniques including X‐ray absorption spectroscopy, X‐ray diffraction, transmission electron microscopy, and first principles hybrid Monte Carlo/molecular dynamics simulations. Chemical short‐range order and bond length distances have been determined both at the experimental and computational level. Electronic structure and local atomic distortions up to 5.2 Å have been correlated to the microhardness values. A linear regression model connecting hardness with local lattice distortions is presented. [ABSTRACT FROM AUTHOR]

Understanding the effect of glass network structure on the solubility properties of bioactive glasses is fundamental for designing new compositions with tailored biological functions and applications. This paper bridged the composition-structure-property relationship utilizing experimental measurements and molecular dynamics simulations. The Sr atom reorganized the network structures through a partial transformation of tetrahedral to trigonal boron units and the change of the ratio of bridged oxygen/non-bridged oxygen, which modified the glass structures at longer lengths scales, such as through changing the ring size distribution. Our results demonstrated that the evolution of solubility properties can be linked to the atomic structure change in short- and medium-range ordering. The structure-property relationship can be used to design and tune bioactive glass composition with specific properties. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract—The atomic structure of single-crystal samples of soft-magnetic Fe–9 at % Ga alloys (the A2-phase region) subjected to thermomagnetic treatment (TMT) is studied by X-ray diffraction. In the course of TMT, the samples in the ferromagnetic state are annealed at 450°C and slowly cooled to room temperature in an external saturating magnetic field. In the alloys subjected to TMT and in the alloys subjected to heat treatment (HT) in zero magnetic field, B2 clusters are found, which are pairs of bcc cells centered with Ga atoms. The TMT and HT are shown to have virtually no effect on the size and volume fraction of B2 clusters in the alloy under study. The formation and stability mechanisms of B2 clusters and their role in the formation of induced magnetic anisotropy in the Fe–Ga alloys are discussed. [ABSTRACT FROM AUTHOR]

The research community has recently been captivated by the atomic-scale short-range order observed in high- and medium-entropy alloys. However, significant challenges persist in improving the mechanical performance through manipulation of the short-range order. Herein, molecular dynamics simulations are employed to establish the correlation between this ordering and the chemical composition for the Cr–Co–Ni medium-entropy alloys. It is demonstrated that atomic-scale clustering can be tailored through adjusting the chemical composition. Particularly, it can be promoted by decreasing the content of elements that do not participate in the clusters. The short-range ordering plays a significant role in affecting the dislocation evolution and tensile properties. Reducing the tendency to form Cr–Co clusters yields enhanced strengthening due to the increased local unstable stacking fault energy. Increasing the tendency to form Ni–Ni clusters instead results in enhanced strain hardening due to the high sessile dislocation density impeding the movement of dislocations. These findings unveil the crucial role of chemical composition on short-range ordering and have significant implications on the design of high-performance high- and medium-entropy alloys.

The relationship between the local structures and the thermodynamic properties of metallic liquids has been a fundamental issue, which significantly impacts the comprehensive performances of metallic materials. The temperature-induced structure evolution in CoxBy alloy liquids, involving CoB, Co2B, Co3B, and Co23B6, was investigated using ab initio molecular dynamics simulations. The results show that the clusters of icosahedral-like polyhedrons are found predominantly in all alloys at low temperature, while the heating induces the decrease in ideal icosahedral and the increase in defected icosahedral. At high temperature, the polyhedron clusters decrease significantly and the ideal icosahedra transforms into smaller short-range polyhedrons, signifying the temperature-induced chemical structure change from long-range to short-range ordering. The aggregation of B atoms at high temperature is confirmed by atomic configuration, charge density, and B-centered Voronoi polyhedrons, and the α-Co single phase is observed below 1600 K. This study is helpful for understanding the local structure variability in eutectic Co-B alloys and guiding solidification path in theory.

Pulsed electrodeposition modes allowed to obtain amorphous Co-W alloys. Using X-ray phase and spectral analysis methods, it was established that the deposition modes and the concentration of the amorphizing component (sodium tungstate salts) in an aqueous electrolyte solution affect the amorphization of alloys. The short-range atomic order was studied by X-ray diffraction analysis and the sizes of the regions of ordered arrangement of atoms were determined in X-ray amorphous Co-W alloys obtained by pulsed electrodeposition. The radial distribution function of atoms was analysed. The assumption is made that cobalt and tungsten atoms combine into configurations that are irregular polyhedrons.

Relating the synthesis conditions of materials to their functional performance has long been an experience-based trial-and-error process. However, this methodology is not always efficient in identifying an appropriate protocol and can lead to overlooked opportunities for the performance optimization of materials through simple modifications of the synthesis process. In this work, the authors systematically track the structural evolution in the synthesis of a representative disordered rock salt (a promising next-generation Li-ion cathode material) at the scale of both the long-range crystal structure and the short-range atomic structure using various in situ and ex situ techniques, including transmission electron microscopy, X-ray diffraction, and pair distribution function analysis. An optimization strategy is proposed for the synthesis protocol, leading to a remarkably enhanced capacity (specific energy) of 313 mAh g−1 (987 Wh kg−1) at a low rate (20 mA g−1), with a capacity of more than 140 mAh g−1 retained even at a very high cycling rate of 2000 mA g−1. This strategy is further rationalized using ab initio calculations, and important opportunities for synthetic optimization demonstrated in this study are highlighted.

Obsidian is volcanic glass that results from the rapid cooling of silica-rich melt. Nanoscale crystallites precipitate out of the melt prior to solidification and remain embedded in the amorphous matrix. These crystallites provide information on the flow kinetics and composition of the melt. Due to the sparsity and size of nanolites, studies often focus on supramicron crystallites. This research takes advantage of the conchoidal fracture of obsidian by knapping samples with nanometer-thin edges for transmission electron microscopy characterization. Nanolites in the amorphous matrix are studied using energy-dispersive spectroscopy (EDS) and electron diffraction. Certain alkali and alkaline-earth cations exhibit patterns of depletion near Fe-oxide nanolites. EDS is used to identify nanolites and variations in the composition of the matrix. Parallel beam diffraction and radial distribution function analysis of nearest-neighbor distances determine average bond lengths in the matrix near nanolites, showing that nanolites influence the nearby short-range ordering and atomic character of the matrix. Analysis reveals decreased mean nearest-neighbor distances in the matrix adjacent to nanolites compared to the bulk. Our methods exhibit the required sensitivity to detect variations in the composition and structure near nanolites, and our findings indicate that obsidian nanolites contribute to quantifiable localized changes in the amorphous structure.

The paper presents the results of a comparative analysis of the structure of Ti2NiCu alloy subjected to severe plastic deformation by high pressure torsion and subsequent annealing. The structure of the alloy was studied using diffractometry, electron microscopy, X-ray and neutron techniques, as well as transmission electron microscopy. The analysis has revealed the formation of an amorphous-crystalline state within the alloy, with B2-lattice nanocrystallites present in the amorphous matrix. The analysis of diffuse maxima has indicated that the Ti2NiCu alloy, after subjecting to high pressure torsions till five turns, possesses topological and compositional short-range order in the form of nanodomains with a superstructure arranged by B2 and L21 order. [ABSTRACT FROM AUTHOR]

Two routes of the dehydration process of theophylline monohydrate have been proposed in this work from mid-frequency Raman difference spectra (MFRDS) results and experiments. MFRDS can establish short-range order correlations among various theophylline crystal forms. MFRDS results indicate that the short-range order of metastable Form III is most similar to that of monohydrate, which explains that Form III is the main dehydration products in the mild dehydration process. The phenomenon that unstable amorphous theophylline intermediate phase would appear during the dehydration process of theophylline monohydrate was confirmed indirectly by Powder X-ray Diffraction (PXRD) and optical microscope and reported in the previous reports, which could cause the nucleation of Form II, as MFRDS results indicate short-range order of amorphous solid dispersion of theophylline is most similar to that of Form II. MFRDS analysis shows the advantages in studying the phase transformation of small organic molecule crystals. [ABSTRACT FROM AUTHOR]

Despite being effective in unveiling the complicated nanostructure-property relation of (HfNbTaZr)C high-entropy carbide (HEC), applications of atomistic simulations are restricted by the lack of reliable many-body interatomic potentials. In this study, we propose a machine learning (ML) global optimization framework to parameterize an analytical bond-order potential (ABOP) with massive internal parameters for the Hf/Nb/Ta/Zr/C system. The combined distributed breeder genetic algorithm (DBGA), extensive ab initio training data and a normalized objective function markedly accelerate the convergence towards global optimum. By performing a cross-validation for the established potential, we demonstrate that the ABOP can accurately predict fundamental energetic, structural and mechanical properties of metals, intermetallic compounds, alloys and carbides in both the training and test datasets. Moreover, the potential is employed in dynamic simulations such as thermal annealing, simple loadings, nanoindentation and irradiation collision, from which some typical experimental observations are successfully reproduced. This not only further verifies the reliability of ABOP, but also implies its broad future applicability in nanoscale simulations. [ABSTRACT FROM AUTHOR]

The local structure and glass transition of Ge-As-Se, Ge-As-Se-Schalcogenide glasses have been studied by X-ray diffraction and differential scanning calorimetry. By applying the theory of topological constraints and considering chemically ordered network models, it has been determined that Ge10As20S10Se60 (average coordination number ⟨ r ⟩ = 2.4), Ge25As10S25Se40 ( ⟨ r ⟩ = 2.6) are the compositions associated with the more stable glasses. This result is related to the larger differences between the glass transition (Tg) and crystallization-transition (Tcr) temperatures (ΔTg-cr∼ 38 and 43 K) at these compositions. Relatively high values of short-range (d∼5.7–6.34 Å) and medium-range (L∼26.59–33.74 Å) order parameters of the local structure in the glass compositions satisfying the mentioned conditions affect the glass-transition temperature (Tg) and cause its value to increase (Tg∼589–689 K). As a result of comparative analyses of X-ray diffraction and differential scanning calorimetry curves it has been determined that there is a correlation between the glass-transition temperature (Tg) with the short range (d) and medium range order (L) parameters of the local structure. [ABSTRACT FROM AUTHOR]

High entropy alloys (HEAs) are a class of novel materials that exhibit superb engineering properties. It has been demonstrated by extensive experiments and first principles/atomistic simulations that short-range order in the atomic level randomness strongly influences the properties of HEAs. In this paper, we derive stochastic continuum models for HEAs with short-range order from atomistic models. A proper continuum limit is obtained such that the mean and variance of the atomic level randomness together with the short-range order described by a characteristic length are kept in the process from the atomistic interaction model to the continuum equation. The obtained continuum model with short-range order is in the form of an Ornstein-Uhlenbeck (OU) process. This validates the continuum model based on the OU process adopted phenomenologically by Zhang et al. [Acta Mater., 166 (2019), pp. 424-434] for HEAs with short-range order. We derive such stochastic continuum models with short-range order for both (i) the elastic deformation in HEAs without defects and (ii) HEAs with dislocations (line defects). The obtained stochastic continuum models are based on the energy formulations, whose variations lead to stochastic partial differential equations. [ABSTRACT FROM AUTHOR]

The formation of a short-range order in an equiatomic high-entropy alloy (HEA) CoNiCrFeMn during annealing at moderate temperatures is studied by atomistic MD/MC simulation, including the exchange of atoms in the Monte Carlo (MC) scheme and relaxation of their positions by molecular dynamics (MD) simulation. Two types of chemical short-range order (CSRO) regions are found to form during annealing. The first type is mainly represented by Fe–Co atoms, and the second, by Cr-rich regions with Ni and Mn atoms at their boundaries. The short-range order formation is shown to include several stages, the sequence of which is determined by the Cr–Cr, Fe–Co, and Ni–Mn interactions. [ABSTRACT FROM AUTHOR]

A systematic study on a face‐centered cubic‐based compositionally complex alloy system Al–Co–Cr–Cu–Fe–Ni in its single‐phase state is carried out, where a mother senary compound Al8Co17Cr17Cu8Fe17Ni33 and five of its suballoys, obtained by removing one element at a time, are investigated and exhaustively analyzed determining the contribution of each alloying element in the solid solution. The senary and the quinaries are compared using experimental techniques including X‐ray absorption spectroscopy, X‐ray diffraction, transmission electron microscopy, and first principles hybrid Monte Carlo/molecular dynamics simulations. Chemical short‐range order and bond length distances have been determined both at the experimental and computational level. Electronic structure and local atomic distortions up to 5.2 Å have been correlated to the microhardness values. A linear regression model connecting hardness with local lattice distortions is presented.

Fe78B15Sn7 and (Fe3Co1)78B15Sn7 amorphous metallic alloys were prepared using the method of planar flow casting. The amorphous nature of ribbons containing 7 at. % Sn was verified by X-ray diffraction. The resulting chemical composition was checked by flame atomic absorption spectroscopy and by mass spectrometry with inductively coupled plasma. The microstructure of the as-quenched metallic glasses was investigated by 57-Fe and 119-Sn Mössbauer spectrometry. The experiments were performed with transmission geometry at 300 K, 100 K, and 4.2 K, and in an external magnetic field of 6 T. The replacement of a quarter of the Fe by Co did not cause significant modifications of the hyperfine interactions in the 57-Fe nuclei. The observed minor variations in the local magnetic microstructure were attributed to alterations in the topological short-range order. However, the in-field 57-Fe Mössbauer spectra indicated a misalignment of the partial magnetic moments. On the other hand, the presence of Co considerably affected the local magnetic microstructure of the 119-Sn nuclei. This was probably due to the higher magnetic moment of Co, which induces transfer fields and polarization effects on the diamagnetic Sn atoms.

Refractory high entropy alloys (RHEA) are promising potential used as structural materials owing to the remarkable mechanical properties, such as excellent thermal stability and strength. However, the dynamic nanoindentation response of the nanocrystalline RHEA at atomic scale is not fully revealed. Here, the mechanical behaviour of the as-cast and annealed nanocrystalline HfNbTaZr RHEA under nanoindentation is investigated for first time using a large scale molecular dynamics simulation, in the terms of indentation force, microstructural evolution, stress distribution, shear strain distribution, and surface topography. The results show the annealed nanocrystalline HfNbTaZr RHEA has obvious chemical short-range ordered structure (CSRO), including Ta enrichment and Hf–Nb segregation. The elastic modulus of the annealed RHEA is larger than that of random RHEA, agreeing with the previous experiment. CSRO improves the indentation force and work hardening, due to the inhibition of dislocation nucleation and motion. Interestingly, the hardening behavior is found in the unloading stage, which is rarely reported in traditional alloys. The crystal-to-amorphous phase transition takes place under the loading, and the inverse phase transformation occurs under the unloading. The increase rate of high Von Mises stress and hydrostatic stress region is lower than the change rate of the high strain region. Certainly, almost all atoms move to consume stored energy after unloading, leading to the decrease of stress and strain. The current study not only gives an insight into probing the mechanical behavior of the nanocrystalline RHEA, but also provides an avenue to design high performance RHEAs based on the heat treatment process.

An increase in crystal local short-range order (SRO), characterized by obvious diffuse intensity maxima at 1/3{422} in the [111]-axis selected area diffraction pattern, is observed in AL6XN austenitic stainless steel subjected to high-temperature low-cycle fatigue deformation. SRO is an ordered fcc structure with nanometer size, which can be well explained by the ordered arrangement of Cr/Mo atomic layers segregated on the {422} crystal plane in austenite. Many planar slip bands are observed in the fatigue sample, the distribution of SROs is highly related with the distribution of dislocations. In situ high-energy X-ray diffraction (HE-XRD) experiments are performed to investigate the deformation behavior of both as-received and fatigued samples under uniaxial loading. The lattice strain evolution reveals an interesting lattice expansion in the initial elastic stage, which provides direct evidence of a decrease in SRO during further uniaxial tensile deformation, indicating that the deformation modes greatly affect the SRO transition. We believe that the high-temperature fatigue damage originates mainly from the accumulation of planar slip bands, accompanied by a local increase in SRO, which promotes work hardening near the final fatigue fracture.

Extended X-ray absorption fine structure (EXAFS) and neutron diffraction experiments were carried out to clarify the typical features of the local structure of a family of medium-entropy alloys (CrCoNi, MnCoNi, and FeCoNi). A simple random cluster model was constructed for analyzing EXAFS spectra, and static and dynamic components of the mean-square relative displacement (MSRD) were separately extracted. In our analysis, the static MSRD of the MnCoNi sample was slightly larger than those of the CrCoNi and FeCoNi samples, whereas the dynamic MSRDs of these samples were almost identical. Based on the complementary neutron diffraction data, we argued that the origin of the large static displacement in the MnCoNi alloy can be associated with a short-range structural transformation through long-term structural relaxation. [ABSTRACT FROM AUTHOR]

Computational materials design (CMD) based on the first-principles electronic structure calculations is demonstrated for two topics related to the design of high-entropy alloys (HEAs). The first one is a construction of prediction model of elastic constants. By applying machine learning technique with the use of the linearly independent descriptor generation method to the database of elastic constants of 2555 BCC HEAs generated by the full potential Korringa-Kohn-Rostoker coherent potential approximation (FPKKR-CPA) method. The obtained model is used to predict new HEAs with high Young’s modulus. The second topic is a simulation of atomic arrangement in HEAs at finite temperature. In this simulation, HEAs are described by using the Potts-like model and the interaction parameters are determined based on the generalized perturbation method combined with the KKR-CPA method. Monte Carlo simulations for the models of CrMnFeCoNi and CrMnFeCoCu predict atomic arrangements which are consistent to the experimental observations. [ABSTRACT FROM AUTHOR]

Neutron scattering experiments were conducted to reveal the origin of diffuse scattering in a medium-entropy alloy (MnCoNi). Results showed that a time-temperature-dependent short- and long-range structural transformation from a face-centered cubic to a primitive tetragonal structure occurs. In the MnCoNi alloy, the long-range ordered phase with a relatively small c/a ratio of 3.7(1)% can only be grown in a limited temperature range, whereas short-range structural transformation with a short correlation length of 14 nm can be formed in a wide temperature range. On the contrary, no sign of short-/long-range staggered atomic rearrangement, such as L10 and L12 structures, was observed in the CrCoNi alloy at least at room temperature. The difference in the forming ability of short-/long-range ordering between the MnCoNi and CrCoNi alloys was discussed. [ABSTRACT FROM AUTHOR]

Recently, a new family of anti‐perovskite Li2TMSO was discovered as promising cathode materials for Li‐ion batteries (LIBs) with superiorities in high specific capacity, low cost, and environmental friendliness. However, the applications of these anti‐perovskite materials meet severe challenges in the cyclability and rate performance. Herein, a cation‐disordered anti‐perovskite type solid solution Li2Fe1−xMnxSO (LFMSO, x = 0, 0.2, 0.5) with excellent electrochemical performance is reported. On the basis of comprehensive structural characterizations, the role of the cation disordering in LFMSO is clarified. In comparison with Li2FeSO (LFSO), the reduced Li‐ion diffusion barrier and the increased Li‐rich octahedral configurations in LFMSO with higher configurational entropy imply the facilitated long‐range Li‐ion diffusion and the suppressed phase transition, which favor the high‐rate capability and cycling stability. In addition, the large lattice distortion and Coulombic interaction between the anions and cations lead to the breathing of the unit cell during charge/discharge. The variation of the unit cell volume decreases to 2.5% upon Li‐ion delithiation. A superstructure is observed in LFMSO for the first time. These findings help to pave the way for the research and development of novel cathode materials for the next generation LIBs. [ABSTRACT FROM AUTHOR]

Bimetallic alloys could form three typical structures including solid solution, heterostructure, and intermetallic compound, depending on the interactions between identical and different atoms. Although the trend can be predicted by the types of binary phase diagram, different synthetic protocols will trap the system in various kinetic intermediates among the three typical structures. Herein, we studied the phase evolution and elemental segregation in the alloy nanoparticles of immiscible Pd-Ru before and after thermal annealing. By developing an analysis method of local element segregation (LES) based on the energy dispersive spectroscopy (EDS) mapping signals, we were able to quantify the mixing of Pd and Ru atoms during the gradual phase transition from face-centered cubic (fcc) to hexagonal close packed (hcp). Density functional theory was also applied to calculate the energies of all possible PdRu4 structures (93 fcc models and 267 hcp models), which helps to rationalize the phase transition and element segregation. The annealing process also leads to the change of the electronic structure, which further influences the performance in the electrocatalytic hydrogen evolution reaction. The highest activity of PdRu4-400 was largely attributed to the proper interface between the Pd-rich fcc phase and Ru-rich hcp phase, as revolved by the above methods. [ABSTRACT FROM AUTHOR]

The presence, nature, and impact of chemical short-range order in the multi-principal element alloy CrCoNi are all topics of current interest and debate. First-principles calculations reveal that its origins are fundamentally magnetic, involving repulsion between like-spin Co-Cr and Cr-Cr pairs that is complemented by the formation of a magnetically aligned sublattice of second-nearest-neighbor Cr atoms. Ordering models following these principles are found to predict otherwise anomalous experimental measurements concerning both magnetization and atomic volumes across a range of compositions. In addition to demonstrating the impact of magnetic interactions and resulting chemical rearrangement, the possible explanation of experiments would imply that short-range order of this type is far more prevalent than previously realized.

Amorphous metallic alloys, also known as metallic glasses (MGs), are materials with unique physical properties resulting from their disordered yet densely packed atomic structure. The packing density of MGs can be further enhanced by external pressure, forcing the decrease of interatomic distances and modifying both the atomic and electronic structure of an alloy. This work reports on classical molecular dynamics (MD) and density functional theory (DFT) studies of Ni _64 Zr _36 MG in a hydrostatic pressure range of 0–120 GPa. The MD simulations revealed that compression leads to enhanced short-range ordering by increasing the contribution of efficiently packed icosahedral-like clusters. According to the DFT calculations, for pressure above 50 GPa, Zr atoms show a significant change in electronic configuration, with a dominant charge transfer from their s and p to d -states and charge redistribution between Ni and Zr atoms. This variation is correlated with the appearance of pairs with significantly shortened interatomic distances, as detected by the MD. We conclude that the enhanced icosahedral ordering in Ni _64 Zr _36 MG is induced not only by the pressure-driven densification of an alloy but also by a variation of its electronic structure.

A theoretical model based on compound formation in binary alloys has been used to investigate the energetics of liquid Ag–Cu, Ag–Sb and Cu–Sb binaries at 1423, 1250 and 1190 K, respectively. The Gibbs free energies of mixing, component thermodynamic activities, enthalpies and entropies of mixing were fitted with available experimental data to determine the energetics of the liquid mixture. Investigations were done to understand the nature of chemical order in the bulk of the systems and to predict the nature of the alloys' surfaces. Good agreements between the theoretical model and available experimental data were accompanied by satisfactory and reliable predictions of surface properties in the binary systems. This work showed that amongst Ag, Cu and Sb atoms that form the three binaries, tendency of forming heterocoordinated bonds is the highest for Sb atoms, and the studies carried out on the surfaces of Ag–Cu, Ag–Sb and Cu–Sb binaries reveal that the surface of Ag–Cu–Sb ternary will be Sb-enriched and Cu-deficient in most compositions. This work has improved the understanding of the thermodynamics of Ag–Cu, Ag–Sb and Cu–Sb binaries, as well as contributed knowledge for a better understanding of the Ag–Cu–Sb ternary. [ABSTRACT FROM AUTHOR]

It is a long-sought goal to achieve desired mechanical properties through tailoring phase formation in alloys, especially for complicated multi-phase alloys. In fact, unveiling nucleation of competitive crystalline phases during solidification hinges on the nature of liquid. Here we employ ab initio molecular dynamics simulations (AIMD) to reveal liquid configuration of the Mg-Al-Ca alloys and explore its effect on the transformation of Ca-containing Laves phase from Al 2 Ca to Mg 2 Ca with increasing Ca/Al ratio (r Ca / Al). There is structural similarity between liquid and crystalline phase in terms of the local arrangement environment, and the connection schemes of polyhedras. The forming signature of Mg 2 Ca, as hinted by the topological and chemical short-range order originating from liquid, ascends monotonically with increasing r Ca / Al. However, Al 2 Ca crystal-like order increase at first and then decrease at the crossover of r Ca / Al = 0.74, corresponding to experimental composition of phase transition from Al 2 Ca to Mg 2 Ca. The origin of phase transformation across different compositions lies in the dense packing of atomic configurations and preferential bonding of chemical species in both liquid and solid. The present finding provides a feasible scenario for manipulating phase formation to achieve high performance alloys by tailoring the crystal-like order in liquid. [ABSTRACT FROM AUTHOR]

The microstructure of Ti-6Al-4V titanium alloy produced by laser additive manufacturing is generally relatively coarse, so its mechanical properties have not yet achieved satisfactory results. After adding germanium element to titanium alloy, second phase particles can be formed, at the same time, due to strong bonding force between Ti and Ge atoms, there also have other strengthening effects that need to be revealed. Therefore, the effect of Ge addition on the microstructure and mechanical properties of additive manufactured Ti-6Al-4V alloy was studied in detail in this paper, which can provide more reference for optimizing the performance of titanium alloy manufactured with additives manufacturing. The pure Ge powder was ball milled with Ti-6Al-4V powder in several different proportions, and bulk samples were prepared by laser deposition manufacturing (LDM) with the mixed powder. The Germanium alloyed Ti-6Al-4V alloy's tensile strength and plasticity at room temperature increased about 25% and 10%, respectively, compared with LDMed Ti-6Al-4V alloy without Ge. According to the results of TEM and EDS, Ti and Ge reacted to form granular second phase Ti5Ge3, which distributes along the primary β grain boundary inhibit the growth of columnar crystals. Part of Ge solutes into α phase. Both microstructure refinement and solid solution are very effective in impeding the moving of dislocation, so that the Germanium alloyed LDMed Ti-6Al-4V alloy showed excellent tensile property at room temperature. [ABSTRACT FROM AUTHOR]

Neutron diffraction and total scattering are combined to investigate a series of single-phase 10-component compositionally complex fluorite-based oxides, [(Pr0.375Nd0.375Yb0.25)2(Ti0.5Hf0.25Zr0.25)2O7]1-x[(DyHoErNb) O7]x, denoted as 10CCFBOxNb. A long-range order-disorder transition (ODT) occurs at x = 0.81± 0.01 from the ordered pyrochlore to disordered defect fluorite. In contrast to ternary oxides, this ODT occurs abruptly without an observable two-phase region; moreover, the phase stability in 10CCFBOs deviates from the well-established criteria for simpler oxides. Rietveld refinements of neutron diffraction patterns suggest that this ODT occurs via the migration of oxygen anions from the position 48f to 8a, with a small final jump at the ODT; however, the 8a oxygen occupancy changes gradually (without an observable discontinuous jump). We further discover diffuse scattering in Nb-rich compositions, which suggests the presence of short-range order. Using small-box modelling, four compositions near ODT (x =0.75, 0.8, 0.85, and 1) can be better fitted by C2221 weberite ordering for the local polyhedral structure at nanoscale. Interestingly, 10CCFBO0.75Nb and 10CCFBO0.8Nb possess both long-range pyrochlore order and short-range weberite-type order, which can be understood from severe local distortion of the pyrochlore polyhedral structure. Thus, weberite-type short-range order emerges before the ODT, coexisting and interacting with long-range pyrochlore order. After the ODT, the long-range pyrochlore order vanishes but the short-range weberite-type order persists in the long-range disordered defect fluorite structure. Notably, a drop in the thermal conductivity coincides with emergence of the short-range order, instead of the long-range ODT. [ABSTRACT FROM AUTHOR]

Fluorine substitution is a critical enabler for improving the cycle life and energy density of disordered rocksalt (DRX) Li-ion battery cathode materials which offer prospects for high energy density cathodes, without the reliance on limited mineral resources. Due to the strong Li–F interaction, fluorine also is expected to modify the short-range cation order in these materials which is critical for Li-ion transport. In this work, density functional theory and Monte Carlo simulations are combined to investigate the impact of Li–F short-range ordering on the formation of Li percolation and diffusion in DRX materials. The modeling reveals that F substitution is always beneficial at sufficiently high concentrations and can, surprisingly, even facilitate percolation in compounds without Li excess, giving them the ability to incorporate more transition metal redox capacity and thereby higher energy density. It is found that for F levels below 15%, its effect can be beneficial or disadvantageous depending on the intrinsic short-range order in the unfluorinated oxide, while for high fluorination levels the effects are always beneficial. Using extensive simulations, a map is also presented showing the trade-off between transition-metal capacity, Li-transport, and synthetic accessibility, and two of the more extreme predictions are experimentally confirmed.