Lattice Distortion Research Articles

Oxidation Behavior of Lightweight Al0.2CrNbTiV High Entropy Alloy Coating Deposited by High-Speed Laser Cladding

High-temperature oxidation resistance is the major influence on the high-temperature service stability of refractory high entropy alloys. The oxidation behavior of lightweight Al0.2CrNbTiV refractory high entropy alloy coatings with different dilution ratios at 650 °C and 800 °C deposited by high-speed laser cladding was analyzed in this paper. The oxidation kinetic was analyzed, the oxidation resistance mechanism of the Al0.2CrNbTiV coating was clarified with the analysis of the formation and evolution of the oxidation layer, and the effect of the dilution rate on high-temperature performances was revealed. The results showed that the oxide layer was mainly composed of rutile oxides (Ti, Cr, Nb)O2 after isothermal oxidation at 650 °C and 800 °C for 50 h. The Al0.2CrNbTiV coating in low dilution exhibited better oxidation performance at 650 °C, due to the dense oxide layer formed with the synergistic growth of fine AlVO3 particles and (Ti, Cr, Nb)O2, and higher percentage of Cr, Nb in (Ti, Cr, Nb)O2 strengthened the lattice distortion effect to inhibit the penetration of oxygen. The oxide layer formed at 800 °C for the Al0.2CrNbTiV coating was relatively loose, but the oxidation performance of the coating in high dilution improved due to the precipitation of Cr2Nb-type Laves phases along grain boundaries, which inhibits the diffusion of oxygen.

Pseudo-Jahn-Teller Effect Breaks the pH Dependence in Two-Electron Oxygen Electroreduction.

The hydrogenation of small molecules (like O2 and CO2) often exhibits strong activity dependence on pHs because of discrepant proton donor environments. However, some catalysts can show seldom dependence on two-electron oxygen electroreduction, a sustainable route of O2 hydrogenation to hydrogen peroxide (H2O2). In this work, a pH-resistant oxygen electroreduction system arising from the pseudo-Jahn-Teller effect is demonstrated. Thorough operando Raman spectra, local environment analyses and density function theory simulations, the lattice distortion of TiOxFy that introduces the pseudo-Jahn-Teller effect contributing to regulating local pHs at electrode-electrolyte interfaces and the absorption/desorption of key *OOH intermediate is revealed. Consequently, as comparison to 78.6% activity attenuation for common catalyst, the TiOxFy displays minor activity decay (3.2%) in the pH range of 1-13 with remarkable Faradaic efficiencies (93.4-96.4%) and H2O2 yield rates (595-614mgcm-2h-1) in the current densities of 100-1000mAcm-2. Further techno-economics analyses display the H2O2 production cost dependent on pHs, giving the lowest H2O2 price of $0.37kg-1. The present finding is expected to provide an additional dimension to pseudo-Jahn-Teller effect that leverages systems beyond traditional conception.

Microwave dielectric properties of novel Mg3Ga2TiO8 ceramic

Mg3Ga2TiO8 ceramics were prepared using a solid-phase method. The ceramics sintered at 1440 °C exhibited excellent microwave dielectric properties (εr = 12.07, Q × f = 89,270 GHz, and τf = −40.7 ppm/°C). The typical spinel structure of the Mg3Ga2TiO8 ceramic was confirmed through Rietveld refinement and Raman spectroscopy. High-resolution transmission electron microscopy indicated local lattice distortion in the Mg3Ga2TiO8 ceramics, with a Vickers hardness of 12.53 GPa. The values of εr and Q × f for the Mg3Ga2TiO8 ceramics were affected by the relative density. The theoretical εr obtained from the C-M equation was lower than the measured εr, plausibly due to underestimation of the polarizability of the Ti ions. According to the P-V-L theory, Ti2-O1 has the highest fi value, contributing 29.92 % to εr. The contribution rate of the Ga2-O1 bond to U was 35.76 %, with the greatest impact on Q × f.

Fixed-Point Atomic Regulation Engineered Low-Thickness Wideband Microwave Absorption.

Atomic doping is widely employed to fine-tune crystal structures, energy band structures, and the corresponding electrical properties. However, due to the difficulty in precisely regulating doping sites and concentrations, establishing a relationship between electricity properties and doping becomes a huge challenge. In this work, a modulation strategy on A-site cation dopant into spinel-phase metal sulfide Co9S8 lattice via Fe and Ni elements is developed to improve the microwave absorption (MA) properties. At the atomic scale, accurately controlling doped sites can introduce local lattice distortions and strain concentration. Tunned electron energy redistribution of the doped Co9S8 strengthens electron interactions, ultimately enhancing the high-frequency dielectric polarization (ɛ' from 10.5 to 12.5 at 12GHz). For the Fe-doped Co9S8, the effective absorption bandwidth (EAB) at 1.7mm increases by 5%, and the minimum reflection loss (RLmin) improves by 26% (EAB = 5.8GHz, RLmin = -46dB). The methodology of atomic-scale fixed-point doping presents a promising avenue for customizing the dielectric properties of nanomaterials, imparting invaluable insights for the design of cutting-edge high-performance microwave absorption materials.

Realizing large strain at low electric field in Pb(Zr,Ti)O 3-based piezoelectric ceramics via engineering lattice distortion and domain structure

Realizing large strain at low electric field in Pb(Zr,Ti)O ₃-based piezoelectric ceramics via engineering lattice distortion and domain structure

Chromium nano-segregation and intermediate band formation in heavily-doped ZnS:Cr films

X-ray absorption spectroscopy, X-ray diffraction, and UV–Vis spectroscopy were employed to investigate heavily-doped ZnS:Cr films prepared by RF magnetron co-sputtering. EDS indicates ca. 5 at. % Cr incorporation as well as slight S-deficiency. XAS in the Zn K- and Cr K-edges revealed Zn-by-Cr substitution and segregation of Cr nanoclusters which lead to significant lattice distortion. XRD indicates a 44 % increase in the strain, an increase in the lattice parameter, and a decrease in the crystallite size upon Cr incorporation. The presence of Cr nanoclusters contributed to changes in the band gap, a large Urbach tail parameter of 565 meV, and the formation of an intermediate band arising from the Cr 3d spin-up states. The results suggest ZnS:Cr films in the heavily doping regime could lead to applications in photovoltaics and spintronics.

Mechanism of glycine and H2O action in tribochemical mechanical polishing of single-crystal gallium nitride substrate

With the rapid development of the third-generation semiconductors, environmentally friendly tribochemical mechanical polishing (TCMP) is in urgent need and has been a research hot-spot. In this work, the mechanism of glycine (Gly) and H2O action in TCMP of single-crystal gallium nitride (SC-GaN) substrate is systematically studied. The experimental results indicate that the TCMP of SC-GaN substrate with 0.75 wt% Gly exhibits a higher surface quality and a 3-fold improvement in material removal rate than that with H2O. Based on first-principle calculations, the geometric configurations and interfacial interactions of the Gly/SC-GaN and H2O/SC-GaN heterostrutures are further explored. Charge transfer analysis shows that SC-GaN with lattice distortion of 0.4 Å transfers more electrons into Gly (0.202 e) than into H2O (0.128 e), which suggests the reaction between SC-GaN and Gly is more intense under friction by abrasives. The research of differential charge density and geometric properties (bond angles etc.) demonstrates that the –COOH functional group (Gly) has a higher reactivity than the –OH functional group (H2O). Based on the above findings, a microscopic material removal model for the TCMP of SC-GaN substrate with Gly is established. These results have potential applications in the semiconductor and microelectronics industries.

Distinct amorphization resistance in high-entropy MAX-phases (Ti, M)2AlC (M=Nb, Ta, V, Zr) under in situ irradiation

High-entropy materials have been proposed for applications in nuclear systems recently due to their outstanding properties in extreme environments. Chemical complexity in these materials plays an important role in irradiation tolerance since it significantly affects energy dissipation and defect behaviors under particle bombardment. Indeed, better resistance to irradiation-induced amorphization was observed in the high-entropy MAX (HE-MAX) phase (Ti, M)2SnC (M = V, Nb, Zr, Hf). However, in this work, we report an opposite trend in another series of HE-MAX phases (Ti, M)2AlC (M = Nb, Ta, V, Zr). It is demonstrated that the amorphization resistance is sequentially reduced as the number of components increases from single-component Ti2AlC to (TiNbTa)2AlC and (TiNbTaVZr)2AlC. These phenomena are verified through AIMD simulations and interpreted by analyzing the underlying properties combining lattice distortion and bonding characteristics through the first-principle calculation. By developing a machine-learning (ML) model, we can directly predict lattice distortion to screen HE-MAX phases with excellent resistance to irradiation-induced amorphization. We highlight that the elemental species plays a more crucial role in the irradiation tolerance of these MAX phases than the number of constituent elements. Knowledge gained from this study will enable an improved understanding of the irradiation tolerance in HE-MAX phases and other multi-elemental ceramics.

Powder-diffraction-based structural comparison for crystal structure prediction without prior indexing

The objective of crystal structure prediction (CSP) is to predict computationally the thermodynamically stable crystal structure of a compound from its stoichiometry or its molecular diagram. Crystal similarity indices measure the degree of similarity between two crystal structures and are essential in CSP because they are used to identify duplicates. Powder-based indices, which are based on comparing X-ray diffraction patterns, allow the use of experimental X-ray powder diffraction data to inform the CSP search. Powder-assisted CSP presents two unique difficulties: (i) the experimental and computational structures are not entirely comparable because the former is subject to thermal expansion from lattice vibrations, and (ii) experimental patterns present features (noise, background contribution, varying peak shapes etc.) that are not easily predictable computationally. This work presents a powder-based similarity index (GPWDF) based on a modification of the index introduced by de Gelder, Wehrens & Hageman [J. Comput. Chem. (2001), 22, 273–289] using cross-correlation functions that can be calculated analytically. Based on GPWDF, a variable-cell similarity index (VC-GPWDF) is also proposed that assigns a high similarity score to structures that differ only by a lattice deformation and which takes advantage of the analytical derivatives of GPWDF with respect to the lattice parameters. VC-GPWDF can be used to identify similarity between two computational structures generated using different methods, between a computational and an experimental structure, and between two experimental structures measured under different conditions (e.g. different temperature and pressure). VC-GPWDF can also be used to compare crystal structures with experimental patterns in combination with an automatic pre-processing step. The proposed similarity indices are simple, efficient and fully automatic. They do not require indexing of the experimental pattern or a guess of the space group, they account for deformations caused by varying experimental conditions, they give meaningful results even when the experimental pattern is of very poor quality, and their computational cost does not increase with the flexibility of the molecular motif.

Modulating Surface-Adsorbed Oxygen Species of Bismuth Silicate by a Solid Solution Strategy for Efficient Adsorption and Photocatalytic Activity.

Bismuth silicate photocatalysts suffer from insufficient photocatalytic activity due to an insufficient number of surface active sites and low carrier separation and transport efficiency, which can be solved by defect modulation. Herein, Bi12SiO20/Bi2O2SiO3-BiOClxBr1-x (BSOCB) photocatalysts with a high concentration of surface-adsorbed oxygen species (SAOS) are synthesized by introducing a BiOClxBr1-x solid solution to modify nonhomogeneous BSO via an ion exchange strategy. The introduction of a solid solution enables the generation of dispersed nanoflowers and the regulation of SAOS due to the fact that anion-cation copolymerization guides the crystal growth, and the defects generated by the lattice distortion modulate the concentration of SAOS on the catalysts during the solid solution process. The obtained typical BSOCB photocatalyst possesses both high adsorption and photocatalytic properties, and the results show that it not only can almost completely degrade the traditional pollutant RhB within 20 min but also strongly degrades antibiotics, such as CIP (light for 150 min, 96%), NFX (light for 150 min, 87%), and TC (light for 150 min, 77%). This work provides a new approach for obtaining bismuth-based photocatalysts with controllable morphology and a large number of surface active sites and provides a theoretical and experimental basis for expanding the application scenarios of photocatalysts.

Tailoring structural and magnetic properties of NiCu nanowires by electrodeposition

In this work, we investigated the tailoring of structural and magnetic properties of NiCu nanowires through electrodeposition. Continuous (S1) and composition-modulated (S2) wires were fabricated by electrodeposition using porous alumina membranes as a template. Morphological characterization revealed that the total length of the wires was 8 ± 3 µm in both S1 and S2. For the composition-modulated wires, the length of the segments with the lowest and highest Cu concentrations was 1.2 ± 0.4 µm and 226 ± 65 nm, respectively. Mapping by energy dispersive spectroscopy (EDS) revealed that the concentration of copper and nickel varied along the length of the composition-modulated nanowires, while the continuous nanowires contained a relatively constant concentration of both metals. It is demonstrated that the change in Cu concentration along the wire modifies the lattice parameter, average crystallite size (D) and lattice strain (ε) of Ni. This result is pivotal for understanding the magnetic properties of the wires, as nickel is primarily responsible for the magnetic behavior of the wires. From the ferromagnetic resonance (FMR) results, the linewidth and resonance field values for samples S1 and S2 were determined. It was demonstrated that the greater deformation in the nickel lattice in NiCu nanowires increases the angular dependence of the resonance field. Furthermore, the smaller nickel crystallite size was shown to increase spin dispersion and magnetic damping, leading to complex behavior in FMR responses. Finally, it was demonstrated how Cu can influence the magnetic properties such as coercivity (HC) and squareness (MR/MS) of the wires. Overall, this work contributes to understanding the tailoring of structural and magnetic properties of NiCu nanowires through electrodeposition.

Anomalous annealing enables improved strength-ductility-wear resistance in Fe5Co5CrNi14Cu75 alloy

Annealing is a prevalent heat treatment process frequently employed for optimizing alloy properties. Typically, increasing annealing temperature gives rise to an improved ductility but a decreased strength. However, this work reported a synergistic increase in strength-ductility-wear resistance of Fe5Co5CrNi14Cu75 alloy via increasing the annealing temperature. Compared with the unannealed specimen, the yield strength of the specimen annealed at 1100 °C increased by 33.1 %, the elongation increased by 35.3 %, the coefficient of friction decreased by 10.5 %, and the cross-sectional area of wear scars decreased by 33.2 %. Lattice distortion induced by annealing contributed to enhancing hardness, which in turn improved the wear resistance, resulting in a transition of the wear mode from fatigue wear to abrasive wear.

Reassessment of Electrical and Dielectric Properties in the Borophosphate Glass System: A Promising Solid Electrolyte for High-Temperature Batteries.

This study investigates the conduction mechanism of ternary sodium borophosphate glass 30Na2O-(70 - x)B2O3-xP2O5 with 0 ≤ x ≤ 35 mol % from a different perspective, focusing on previously unreported high-temperature electrical and dielectric properties for potential solid electrolytes in high-temperature batteries. The glass composition with B2O3/P2O5 = 1 exhibits a conductivity of approximately 10-4 S/cm at 250 °C. Dielectric analysis supports this improved conduction, showing higher dielectric values and minimal energy dissipation during storage, indicating promising conductivity and favorable dielectric properties. This enhancement is attributed to the large-polaron (QMT) model, deduced from the power law exponent, due to the creation and spreading of lattice distortion of a long-range order with interconnected B4-O-P1 and B4-O-P2 linkages. Contrary to previous results, the glass transition temperature does not vary coherently with the conductivity and activation energy, displaying a discontinuity at 14 mol %. This discontinuity is caused by the initial extreme depolymerization of P2O5, leading to an increase in nonbridging oxygens (NBOs) within the glass network and forming B4-O-P0 linkages. Despite this, the ionic mobility of Na+ is continuously enhanced, correlated with the increase in the molar volume. This new perspective highlights the significant impact of both free volume expansion and reduced Coulombic effects on conduction improvement.

Femtosecond trimer quench in the unconventional charge-density-wave material 1T′−TaTe2

Ultrafast optical switching of materials properties promises future technological applications, enabled by fundamental insights about microscopic couplings and nonequilibrium phenomena. Transition-metal dichalcogenides (TMDCs) combine photosensitivity with strong correlations, furthering rich phase diagrams and enhanced tunability. The compound 1T′−TaTe2 exhibits an electronically and structurally unique set of charge density waves (CDWs), featuring an unusual increase in conductivity and amplitude modes of low prominence. Compared to other charge-ordered TMDCs, only very few studies addressed the ultrafast response of this material to optical excitation. In particular, the question whether such unconventional properties translate to unusual quench dynamics remains largely unresolved. Here, we investigate the structural dynamics in 1T′−TaTe2 by means of ultrafast nanobeam electron diffraction at an unprecedented repetition rate of 2MHz. We reveal a strongly directional cooperative atomic motion during the one-dimensional quench of the low-temperature trimer lattice. These dynamics are completed within less than 500fs, substantially faster than reported previously. In striking contrast, the periodic lattice distortion of the room-temperature phase is unusually robust against high-density electronic excitation. In conjunction with the known sensitivity of 1T′−TaTe2 to chemical doping, we thus expect the material to serve as a versatile platform for tunable structural control by optical stimuli. Published by the American Physical Society 2024

Tailoring Polaron Dimensions in Lead-Tin Hybrid Perovskites.

Charge carriers in the soft and polar perovskite lattice form so-called polaron quasiparticles, charge carriers dressed with a lattice deformation. The spatial extent of a polaron is governed by the material's electron-phonon interaction strength, which determines charge carrier effective mass, mobility, and the so-called Mott polaron density, that is, the maximum stable density of charge carriers that a perovskite can support. Despite its significance, controlling polaron dimensions has been challenging. Here, experimental substantial tuning of polaron dimensions is reported by lattice engineering, through Pb/Sn substitution in CH3NH3SnxPb1-xI3. The polaron dimension is deduced from the Mott polaron density, which can be composition-tuned over an order of magnitude, while charge carrier mobility occurs through band transport, and remains substantial across all compositions, ranging from 10s to 100 scm2V s-1 at room temperature. The effective modulation of polaron size can be understood by considering the bond asymmetry after carrier injection as well as the random spatial distribution of Pb/Sn ions. This study underscores the potential for tailoring polaron dimensions, which is crucial for optimizing applications prioritizing either high charge carrier density or high mobility.

Structural Particularities, Prediction, and Synthesis Methods in High-Entropy Alloys

High-Entropy Alloys (HEAs) represent a transformative class of materials characterized by multiple principal elements and high configurational entropy. This review article provides an in-depth examination of their structural particularities, prediction methodologies, and synthesis techniques. HEAs exhibit unique structural stability due to high-entropy effects, severe lattice distortions, and slow diffusion processes. Predictive models, including thermodynamic and kinetic approaches, are essential for understanding phase stability. Various synthesis methods impact HEA properties, and advanced characterization techniques are crucial for their study. The article highlights current applications and future research directions, emphasizing the potential of HEAs in diverse technological fields.

Exploring the suppression methods of helium-induced damage in tungsten by investigating the interaction between beryllium and helium

Abstract Helium (He)-induced damage is a sensitive concern for the performance of tungsten plasma facing materials (W-PFMs). Recent experiments have revealed that trace impurities in He plasma can effectively prevent the formation of He bubbles and fuzz on W surfaces. To explore its plausibility and underlying mechanism, we performed a multiscale computational study that combines density functional theory calculations and object kinetic Monte Carlo simulations to investigate the effects of a small quantity of beryllium (Be) on the evolution of He bubbles. It is found that there is a strong attractive interaction between He and Be, which can be attributed to the decrease in electron density and the lattice distortion induced by embedded Be atoms. Therefore, the co-implantation of Be continuously introduces trapping centers for He. Due to the low implantation depth and high migration energy of Be, the Be atoms are located close to the surface, leading to the trapping of the majority of He within the near-surface region and the development of a shielding layer for He permeation. The presence of Be facilitates the dispersion of the trapped He, skewing the He clusters into smaller sizes. More importantly, the Be trapping centers bring the He clusters closer to the surface, significantly increasing the probability of bubble bursting and the release of He back to the vacuum. This ultimately leads to a lower retention of He in the case of He + Be co-irradiation, compared with the case of He-only irradiation. Consequently, our findings elucidate the suppressive effect of a low flux of Be atoms on the growth of He bubbles, highlighting the need to focus on synergetic effects between plasma species.

Mn-Ce solid solution growth on Mn2O3 surface to form heterostructure catalysts with multiple active sites for toluene degradation

A solid solution-heterostructure catalyst with abundant active sites was successfully constructed in this study by in situ growth of Mn-Ce solid solution on the surface of Mn2O3. The solid solution structures with optimum physical and chemical properties were synthesized initially by controlling the Mn-Ce ratios. Subsequently, the reaction time was controlled to realize the orderly growth of the solid solution on the Mn2O3 surface. The catalyst (M−CeMn0.5) with solid solution-heterostructure formed by the reaction of Ce3Mn1 and Mn2O3 for 0.5 h could reach more than 90 % toluene degradation rate at 183 °C and was operated continuously for 15 h without deactivation. XRD showed that the appropriate reaction time resulted in the active components on the catalyst surface exhibiting lower crystallinity and reduced grain size. The reduction capacity (2.28 → 10.47 mmol/g) and the mobility of lattice oxygen were significantly enhanced in the M−CeMn0.5 catalyst compared to the Mn-Ce solid solution. Meanwhile, a high content of low valent metal ions (Ce3+/Ce4+ 0.33, Mn3+/Mn4+ 1.64) and reactive oxygen species (Oads/Olatt 0.53) were also present on the catalyst surface. The DFT demonstrated that the Mn atoms and Mn-O bridge sites on the solid solution surface exhibited high adsorption energy values for toluene (−0.8402/-0.8406 eV) and oxygen (−1.6546/-1.661 eV) molecules. The TEM indicated that lattice distortion and oxygen vacancies were formed at the interface between the solid solution and Mn2O3 at the interface. The synergy of multiple active sites favors the generation of reactive oxygen species and thus promotes p-methyl dehydrogenation. Meanwhile, the high mobility of lattice oxygen facilitates the breakage of benzene ring. This study provides a new strategy for the synthesis of efficient Mn-Ce-based catalysts.

Mechanism for Adsorption, Dissociation, and Diffusion of Hydrogen in High-Entropy Alloy AlCrTiNiV: First-Principles Calculation.

To investigate hydrogen behaviors in the high-entropy alloy AlCrTiNiV, density functional theory and transition state theory were used to explore the molecular H2 absorption and dissociation and the atomic H adsorption, diffusion, and penetration progress. The H2 molecule, where the H-H band is parallel to the surface layer, is more inclined to absorb on the top site of the Ti atom site of first atomic layer on the AlCrTiNiV surface, then diffuse into the hollow sites, through the bridge site, after dissociating into two H atoms. Atomic H is more likely to be absorbed on the hollow site. The absorption capacity for atomic H on the surface tends to decline with the increase in H coverage. By calculating the energy barriers of atomic H penetration in AlCrTiNiV, it was indicated that lattice distortion may be one important factor that impacts the permeation rate of hydrogen. Our theory research suggests that high-entropy alloys have potential for use as a hydrogen resistant coating material.

Influence of He injection amount on the microstructure of ion irradiated Cr0.8FeMnNi medium entropy alloy compared with 316L stainless steel

In recent years, medium and/or high-entropy alloys (M/HEAs) have attracted attention due to their excellent mechanical properties, positioning them as potential candidates for structural materials in advanced nuclear reactors. This study investigated the effect of He injection amount on the microstructural evolution in Cr0.8FeMnNi MEA and 316L stainless steel. Helium atoms were injected, followed by Fe2+ irradiation. Transmission electron microscopy was used to characterize the irradiation-induced defects. The primary irradiation-induced defects observed across all He injection amounts were black dots; no voids were seen under any irradiation conditions. In He-injected Cr0.8FeMnNi, the number density of black dots was significantly lower than in non-He-injected Cr0.8FeMnNi, while the average size of black dots increased with higher He injection rates. As the He injection amount increased, the binding energy of the self-interstitial atom (SIA) to the He-V complex decreased. This reduction facilitated the nucleation and growth of numerous SIA clusters within the matrix, consequently increasing the number density of black dots. The change in the number density of black dots in Cr0.8FeMnNi was much smaller than that observed in 316L. This could be ascribed to the enhanced self-healing process caused by the diversity of point defects and higher lattice distortion in Cr0.8FeMnNi.