Diffusion Of Atoms Research Articles

Crystalline-Amorphous Heterophase PdMoCrW Tetrametallene: Highly Efficient Oxygen Reduction Electrocatalysts for a Long-Term Zn-Air Battery.

Metallenes have received sustained attention owing to their unique microstructure characteristics and compelling catalytic applications, but the synthesis of multielement crystalline-amorphous metallenes remains a formidable challenge. Herein, we report a one-step wet chemical reduction method to synthesize composition-tunable crystalline-amorphous heterophase PdMoCrW tetrametallene. As-synthesized PdMoCrW tetrametallene is composed of approximately six to seven atomic layers and has flexible crimpiness, a crystalline-amorphous heterophase structure, and high-valence metal species. Time-dependent experiments show that PdMoCrW tetrametallene follows a three-step growth mechanism that includes nucleation, lateral growth, and atom diffusion, respectively. The novel ultrathin structure, optimized Pd electronic structure, and hydrophilic surface together greatly promote the activity and stability of PdMoCrW tetrametallene in the alkaline oxygen reduction reaction. Pd75.9Mo9.4Cr8.9W5.8/C exhibits excellent mass and specific activities of 2.81 A mgPd-1 and 4.05 mA cm-2, which are 20.07/14.46 and 23.42/16.20 times higher than those of commercial Pt/C and Pd/C, respectively. Furthermore, a Zn-air battery assembled using Pd75.9Mo9.4Cr8.9W5.8/C as a cathode catalyst achieves a peak power density of 156 mW cm-2 and an ultralong durability of 329 h. This study reports an effective strategy for constructing crystalline-amorphous quaternary metallenes to advance non-Pt electrocatalysts toward oxygen reduction reaction (ORR) performance and for a Zn-air battery.

High-Temperature Atomic Diffusion and Specific Heat in Quasicrystals

High-Temperature Atomic Diffusion and Specific Heat in Quasicrystals

Neural network kinetics for exploring diffusion multiplicity and chemical ordering in compositionally complex materials

Diffusion involving atom transport from one location to another governs many important processes and behaviors such as precipitation and phase nucleation. The inherent chemical complexity in compositionally complex materials poses challenges for modeling atomic diffusion and the resulting formation of chemically ordered structures. Here, we introduce a neural network kinetics (NNK) scheme that predicts and simulates diffusion-induced chemical and structural evolution in complex concentrated chemical environments. The framework is grounded on efficient on-lattice structure and chemistry representation combined with artificial neural networks, enabling precise prediction of all path-dependent migration barriers and individual atom jumps. To demonstrate the method, we study the temperature-dependent local chemical ordering in a refractory NbMoTa alloy and reveal a critical temperature at which the B2 order reaches a maximum. The atomic jump randomness map exhibits the highest diffusion heterogeneity (multiplicity) in the vicinity of this characteristic temperature, which is closely related to chemical ordering and B2 structure formation. The scalable NNK framework provides a promising new avenue to exploring diffusion-related properties in the vast compositional space within which extraordinary properties are hidden.

Induced Diffusion Effect Realizes Heterogeneous Separation/Aggregation for In Situ Fabrication of Heterostructure with Enhanced Catalytic Activity

AbstractSpace charge transfer, which can be provided by heterogeneous structure, is the key to efficient electrocatalytic processes. However, difficulty in controlling the relative atomic diffusion rates due to different atomic radii and affinity makes heterogeneous nanostructures difficult to be accurately designed. Herein, an induced diffusion strategy based on affinity differences between elements is proposed to direct the separation/aggregation of different components in the precursor. The key to strategy in this study is the different affinity of Cu and Co to S/P in the precursor of CuCo Prussian blue analogue (PBA). By controlling the molar ratio of S and P during the phosphorization/vulcanization process, induced diffusion can be achieved and leads to directional separation/aggregation of Cu and Co species. As a result, a heterogeneous yolk‐shell Cu2S@CoP2‐C‐N‐S structure is successfully synthesized with a reticular CoP2‐C‐N‐Cu‐S as the shell and a Cu2S nanocrystal as the core. The space charge effect of the semiconductor heterojunction resulting from component separation/aggregation significantly promotes oxygen evolution reaction, resulting in an ultralow overpotential of 180 mV at 10 mA·cm−2. This work not only provides a simple method for efficient separation of key components in gas‐solid systems but also provides a method for fine‐tuning the active site in an active‐site‐engineering approach.

Tensile Deformation Behaviors and Microstructure Evolution Under Various Temperatures for MAR‐M247 Nickel‐Based Superalloy

The study aims to analyze the tensile behavior and microstructural changes in MAR‐M247 nickel‐based superalloy across different temperatures. Tensile behavior is examined under a constant strain rate of 2.5 × 10−4 s−1 at varying temperatures. Results indicate a temperature‐dependent nature of the alloy's tensile properties. At 550 °C, a Portevin–Le Chatelier effect is observed, attributed to twinning nucleation and carbon atom diffusion. Dynamic recrystallization occurs at 950 °C, manifesting in a sinusoidal stress–strain curve. At room temperature, the primary fracture mechanism involves dislocation shearing in the γ matrix, with minor dislocation shearing in the γ′ phase. At 550 °C, carbides along grain boundaries and the γ′ phase impede dislocation motion. Concurrently, dislocations shear the γ′ phase, leading to the formation of superlattice intrinsic stacking faults and Kear–Wilsdorf locks, thereby enhancing tensile strength. However, at 950 °C, dislocation motion primarily involves climb, carbides decompose, the γ′ phase softens and enlarges, resulting in a notable decrease in tensile strength.

Revealing the reconstruction mechanism of AgPd nanoalloys under fluorination based on a multiscale deep learning potential.

The design of heterogeneous catalysts generally involves optimizing the reactivity descriptor of adsorption energy, which is inevitably governed by the structure of surface-active sites. A prerequisite for understanding the structure-properties relationship is the precise identification of real surface-active site structures, rather than relying on conceived structures derived from bulk alloy properties. However, it remains a formidable challenge due to the dynamic nature of nanoalloys during catalytic reactions and the lack of accurate and efficient interatomic potentials for simulations. Herein, a generalizable deep-learning potential for the Ag-Pd-F system is developed based on a dataset encompassing the bulk, surface, nanocluster, amorphous, and point defected configurations with diverse compositions to achieve a comprehensive description of interatomic interactions, facilitating precise prediction of adsorption energy, surface energy, formation energy, and diffusion energy barrier and is utilized to investigate the structural evolutions of AgPd nanoalloys during fluorination. The structural evolutions involve the inward diffusion of F, the outward diffusion of Ag in Ag@Pd nanoalloys, the formation of surface AgFx species in mixed and Janus AgPd nanoalloys, and the shape deformation from cuboctahedron to sphere in Ag and Pd@Ag nanoalloys. Moreover, the effects of atomic diffusion and dislocation formation and migration on the reconstructing pathway of nanoalloys are highlighted. It is demonstrated that the stress relaxation upon F adsorption serves as the intrinsic driving factor governing the surface reconstruction of AgPd nanoalloys.

Theoretical modeling of defect diffusion in wide bandgap semiconductors

Since the 1940s, it has been known that diffusion in crystalline solids occurs due to lattice defects. The diffusion of defects can have a great impact on the processing and heat treatment of materials as the microstructural changes caused by diffusion can influence the material qualities and properties. It is, therefore, vital to be able to control the diffusion. This implies that we need a deep understanding of the interactions between impurities, matrix atoms, and intrinsic defects. The role of density functional theory (DFT) calculations in solid-state diffusion studies has become considerable. The main parameters to obtain in defect diffusion studies with DFT are formation energies, binding energies, and migration barriers. In particular, the utilization of the nudged elastic band and the dimer methods has improved the accuracy of these parameters. In systematic diffusion studies, the combination of experimentally obtained results and theoretical predictions can reveal information about the atomic diffusion processes. The combination of the theoretical predictions and the experimental results gives a unique opportunity to compare parameters found from the different methods and gain knowledge about atomic migration. In this Perspective paper, we present case studies on defect diffusion in wide bandgap semiconductors. The case studies cover examples from the three diffusion models: free diffusion, trap-limited diffusion, and reaction diffusion. We focus on the role of DFT in these studies combined with results obtained with the experimental techniques secondary ion mass spectrometry and deep-level transient spectroscopy combined with diffusion simulations.

On the Surface Helium Abundance of B-type Hot Subdwarf Stars from the WD+MS Channel of Type Ia Supernovae

The origin of intermediate helium (He)-rich hot subdwarfs is still unclear. Previous studies have suggested that some surviving Type Ia supernovae (SNe Ia) companions from the white dwarf + main-sequence (WD+MS) channel may contribute to the intermediate He-rich hot subdwarfs. However, previous studies ignored the impact of atomic diffusion on the post-explosion evolution of surviving companion stars of SNe Ia, leading to the aspect that they could not explain the observed surface He abundance of intermediate He-rich hot subdwarfs. In this work, by taking the atomic diffusion and stellar wind into account, we trace the surviving companions of SNe Ia from the WD+MS channel using the one-dimensional stellar evolution code MESA until they evolve into hot subdwarfs. We find that the surface He-abundances of our surviving companion models during their core He-burning phases are in a range of −1≲log(NHe/NH)≲0 , which are consistent with those observed in intermediate He-rich hot subdwarfs. This seems to further support the notion that it is possible for surviving companions of SNe Ia in the WD+MS channel to form some intermediate He-rich hot subdwarfs.

Structural pathway for nucleation and growth of topologically close-packed phase from parent hexagonal crystal

The solid diffusive phase transformation involving the nucleation and growth of new phase particles is universal and frequently employed but has not yet been fully understood at the atomic level. Here, our first-principles calculations reveal a structural formation pathway of a series of topologically close-packed (TCP) phases within the hexagonally close-packed (hcp) matrix. The results show that the nucleation follows a nonclassical nucleation process, and apart from atomic diffusion, the entire hcp→TCP transformation only involves shuffle-based displacements, with a specific 3-layer unstable hcp-ordering serving as the basic structural transformation unit (BSTU). The thickening of plate-like TCP phases relies on the formation of these unstable hcp-orderings at their coherent TCP/matrix interface to nucleate a ledge, but the ledge lacks the dislocation characteristics which is commonly considered in the conventional view. Additionally, the atomic structure of the critical nucleus for the Mg2Ca and MgZn2 Laves phases was predicted in terms of Classical Nucleation Theory (CNT). The formation of polytypes and off-stoichiometry in TCP precipitates is found to be related to the nonclassical nucleation behavior. These insights contribute to a deeper understanding of solid diffusive phase transformations at the atomic level and provide a foundation for investigating other technologically significant transformations.

Effects of TaCx on the microstructure and properties of WC composites

WC-5vol.%TaCx (where x = 0.5, 0.7, 0.8 and 0.9) binderless cemented carbides with different carbon vacancy contents were prepared by spark plasma sintering (SPS) at a lower sintering temperature of 1800 °C. The phase evolution, microstructure and mechanical properties of these materials were investigated. The results show that the presence of WC, W2C and (Ta1-x, Wx)Cn phases in the sintered body. The formation of (Ta1-x, Wx)Cn solid solution is attributed to the dissolution of WC into TaCx, and the existence of vacancies promotes the atomic diffusion. (Ta1-x, Wx)Cn solid solution was uniformly distributed around the WC matrix, which inhibited the WC grain growth. In terms of fracture mode, the WC-5vol.%TaCx composites exhibit a combination of intergranular and transgranular fracture, with crack deflection and bridging contributing to enhanced fracture toughness. Compared to other WC-TaCx composites with varying carbon vacancy content, the WC-5vol.%TaC0.8 composite possesses the smallest average particle size and highest intrinsic hardness. Additionally, a semi-coherent interface is formed between (Ta1-x, Wx)Cn and WC, leading to improved mechanical properties such as highest hardness (24.4GPa) and fracture toughness (8.5MPa·m1/2). The WC-5vol.%TaC0.8 composite, however, exhibits the lowest oxidation onset temperature attributed to its relatively smaller grain size. The introduction of carbon vacancies serves to facilitate atom diffusion and lower the densification temperature, while also functioning as a toughening agent.

Unveiling the feature of deposition of oxygen and water molecules on the zirconium surface: A molecular dynamic study

Unveiling the feature of deposition of oxygen and water molecules on the zirconium surface at microscale is crucial during the initial stages of zirconium oxide layer formation in Pressurized Water Reactors (PWRs) or Light Water Reactors (LWRs). In this work, we use molecular dynamic simulations to study the feature of deposition of oxygen and water molecules on the zirconium surface. A special focus of this work is a formula our built for the number of atoms adsorbed by the metal surface at the considered moment of time. The results show that the surface density of atoms for the crystallographic plane (10-10) in is 3 times greater than that for the crystallographic plane (11-20). The effective surface density σ(10-10) for the crystallographic plane (10-10) is greater than the similar value σ(11-20) for the crystallographic plane (11-20). Furthermore, in a sufficiently wide range of temperatures, the mechanical properties of zirconium crystals during tensile deformation are practically independent of the diffusion of oxygen atoms along the grain boundaries. This distinct feature may be providing basis understanding for the experimental puzzle of oxidation rate of zirconium alloys.

Microstructure and properties of 316 L lattice/Al composites by additive manufacturing and infiltration with different temperature

Interface between lattice reinforcement and matrix played a key factor on properties of the lattice reinforced aluminum matrix composites. However, the effect of interface composed of intermetallic compounds on the properties of 316L lattice/Al composites was still unclear. In this study, 316L lattice reinforced aluminum composite with continuous interface were prepared by combining laser powder bed fusion (LPBF) and vacuum infiltration, and effect of infiltration temperature on interface evolution and properties of the composite was investigated. Results indicated that a continuous dual-phase interfacial layer consisting of hard intermetallic compounds η-Fe2Al5 and θ-FeAl3 was formed between the reinforcement and matrix due to diffusion and reaction of iron and aluminum atoms, and the size of needle-type FeAl3 phase in the interfacial zone increased when infiltration temperature was up from 800 °C to 900 °C. It also confirmed that reinforced by 316L lattice and hard intermetallic compounds layer, the composite showed excellent mechanical and wear resistant properties, with compressive strength of 657 ± 32MPa and specific wear rate of 0.20 × 10−3 (mm3/N·m) for the sample prepared at 800 °C, which were over 10 times and one fifth of that of the aluminum matrix individually. This study provides a new strategy for developing 316L lattice/Al composites with excellent properties.

An investigation of self-interstitial diffusion in α-zirconium by an on-the-fly machine learning force field

The on-the-fly machine learning force field approach, based on the Gaussian approximation potential and Bayesian error estimation, was used to study the diffusion of self-interstitial atoms in α-zirconium. Ab initio molecular dynamics simulations of lattice vibration and interstitial diffusion at different temperatures were employed to develop the force field. The radial and angular descriptors of the potential were further optimized to achieve better agreement with first-principles results. Subsequent long-term diffusion simulations were performed to assess the diffusion behavior based on the obtained force field. Tracer diffusion coefficients and diffusion anisotropy were studied at temperatures of 600–1200 K, and the Bayesian errors were estimated throughout the diffusion simulations. The mean and maximum estimated Bayesian errors of atomic force were approximately twice as large as those observed during the learning period. The basal diffusion was greatly favored compared to the interstitial diffusion along the c-axis, consistent with previous simulations based on first-principles results and classical potentials. The accuracy and applicability of the current on-the-fly machine learning approach were critically evaluated.

Surface nanoprecipitation induced by severe plastic deformation in the Fe49.3Co23Ni23C0.85Mn1Si2.85 biphasic multicomponent alloy

Precipitation strengthening plays a vital role in enhancing the mechanical properties of metallic materials, typically achieved through heat treatment. However, deformation-induced precipitation (DIP) in multicomponent alloys (MAs) without the assistance of annealing is rarely reported, owing to their inherent high entropy and sluggish diffusion effects. This work reveals the significant formation of nanoscale and microscale precipitates in dual-phase Fe49.3Co23Ni23C0.85Mn1Si2.85 MA triggered by surface severe plastic deformation (SSPD) through industrial shot blasting. The SSPD process leads to the formation of ultrafine gradient structures comprising nanocrystalline and submicron-crystalline zones. Submicron SiO2 precipitates emerge at the interfaces of both these zones, while various Mn5Si3 and Si nanoparticles precipitate within the nanocrystalline zone. This phenomenon can be ascribed to the high density of generated substructures, the accelerated diffusion of atoms, and the reduction in solid solubility limits in the SPD-driven non-equilibrium state.

Enhanced Thermal Stability and Power Factor in Layered Bi2Se0.5Te2.5 Thin Films Across a Broad Temperature Range

Bi2Te3-based n-type thin films with high thermoelectric performances are typically synthesised through the formation of dense structures, a process conventionally conducted at high temperatures. However, this method compromises thermal stability. In this study, structural design and multiple-step annealing were employed to enhance the thermal stability of high-performance Bi2Se0.5Te2.5 thin films. Post-annealing, the disparity in the values of the Seebeck coefficient over the entire test temperature range, was reduced to 20 μV K−1, which is approximately 32% compared to pre-annealing measurements. The layered Bi2Se0.5Te2.5 thin film demonstrated an elevated power factor (28 × 10−4 W m−1 K−2), which was maintained across a broad temperature spectrum. This multiple-step annealing approach not only refines the structural integrity by extending the atomic diffusion duration but also mitigates defects and augments compositional uniformity at reduced temperatures. Consequently, layered Bi2Se0.5Te2.5 films emerge as promising candidates for thermoelectric materials, offering enhanced long-term stability for diverse applications, including electric and hybrid electric vehicles, and portable electronic devices.

Exceptional load-bearing capability of Al FPCB/Cu FPCB lap joints using instantaneous laser-based large area facial soldering: Experimental and numerical investigations

This study introduces a novel method for integrating aluminum flexible printed circuit boards (FPCBs) and copper FPCBs into battery management systems (BMS) using and instantaneous large area facial laser source soldering. Achieving a robust bonding strength of 65 MPa involved applying 600 W of laser power for 2 seconds, enhancing atom diffusion and promoting intermetallic compound (IMC) growth. Finite Element Method (FEM) simulations revealed variations in heat transfer between Al and Cu, affecting IMC thickness at interfaces. Formation of the (Cu, Ni)3Sn4 phase within solder, and variations in laser output significantly influenced solder joint orientation and Al electrode nucleation. Excessive laser power (>800W) caused critical damage, such as delamination at the Al-PI interface, altering fracture modes and bonding strength. Furthermore, with a detailed examination of the laser soldering phenomenon through both experimental and numerical investigations, this study provides a thorough understanding of the different soldering mechanisms in conventional reflow soldering compared to instantaneous uniform large-area heat source laser soldering. These insights provide new design and material considerations to replace the conventional wiring harness with Al/Cu FPCB lap joints which optimize the circuitry and reducing BMS volume.

Enhancement in interfacial bonding quality of CoCrFeMnNi high-entropy alloy vacuum hot-compression bonding via surface shot peening

Vacuum hot-compression bonding (VHCB) is an advanced solid-state bonding technique. To expand its application in high-entropy alloys (HEAs), a new strategy to enhance the interfacial bonding quality of CoCrFeMnNi HEA VHCB joints by surface shot peening (SP) was proposed, and the effects of SP treatment on the interfacial bonding behavior and mechanical properties of VHCB joints were investigated. The results revealed that SP treatment introduced a nanocrystalline layer and plastic deformation layer with non-uniform strain on the specimen bonding surface, and a hierarchical grain size gradient fine microstructure was formed by a static recrystallization process under the thermal activation condition before VHCB. During the bonding process, the fine microstructure of the SP-treated layer was retained and provided a large number of grain boundaries and dislocations, which facilitated atomic diffusion and plastic flow in the interfacial region and promoted the closure of interfacial voids and the dissolution of interfacial oxide particles. Additionally, interfacial crystallographic and tensile test analyses indicated that the SP treatment induced a multiple interfacial grain boundary (IGB) migration mechanism in the VHCB joints, which dramatically improved the IGB migration level and ultimately led to a complete recovery of the mechanical properties of the CoCrFeMnNi HEA VHCB joints.

Nanoporous silver fabricated with pretreated Ag-Al alloy toward surface enhanced raman sensing.

Nanoporous silver (NPS), characterized by its three-dimensional bi-continuous interpenetrating ligament channel structure, is a good candidate for surface enhanced Raman scattering (SERS), attributed to its exceptional surface-to-volume ratio and significant SERS enhancement capabilities. Here, we have successfully fabricated NPS through the dealloying of α-terpineol (α-TPN) coated Ag55Al45 alloy. The resulting α-NPS exhibits uniform ligaments and nanopore sizes, maintaining high SERS performance even after being exposed to air for more than one month. The pretreatment of precusor alloy with α-TPN is crucial not only for the formation of nanoporous structure but also for ensuring the long term stability of α-NPS. Specifically, α-TPN functions as a surfactant, facilitating atomic diffusion to achieve a superior interconnected NPS. Furthermore, during the dealloying process, the carbonization of α-TPN serves as a protective layer, effectively inhibiting the oxidation of silver. &#xD.

Electrical control of the switching layer in perpendicular magnetic tunnel junctions with atomically thin Ir dusting

The use of magnetic tunnel junction (MTJ)-based devices constitutes an important basis of modern spintronics. However, the switching layer of an MTJ is widely believed to be an unmodifiable setup, instead of a user-defined option, posing a restriction to the function of spintronic devices. In this study, we realized a reliable electrical control of the switching layer in perpendicular MTJs with 0.1 nm Ir dusting. Specifically, a voltage pulse with a higher amplitude drives the magnetization switching of the MTJ's bottom electrode, while a lower voltage amplitude switches its top electrode. We discussed the origin of this controllability and excluded the possibility of back-hopping. Given the established studies on enhancing the voltage-controlled magnetic anisotropy effect by adopting Ir, we attribute this switching behavior to the significant diffusion of Ir atoms into the top electrode, which is supported by scanning transmission electron microscopy with atomic resolution.

Study on the impact of hydrogen storage temperature on iron-based thermochemical hydrogen storage technology

Thermochemical hydrogen storage technology based on iron-based materials has received significant attention owing to its low cost, safety features, and high volumetric hydrogen storage density. However, no consensus has been established on the optimal temperature range for hydrogen storage. This study investigated the impact of hydrogen storage temperature on hydrogen consumption capacity, hydrogen release capacity, and hydrogen storage energy consumption. The hydrogen storage temperature was optimized with the objectives of low energy consumption and high hydrogen storage density. The experiments were conducted using thermogravimetric analyzer and gram-scale packed-bed reactor setups, accompanied by thermodynamic and kinetic calculations. The research indicated that at 550 °C, the optimal hydrogen storage temperature, the lowest relative energy demand was 32.30 %, with the hydrogen consumption capacity reaching the theoretical maximum value of 4.8 %, and the hydrogen release capacity reaching 4.04 %. Furthermore, achieving the theoretical maximum value of hydrogen consumption capacity became exceedingly difficult when the hydrogen storage temperature exceeded 570 °C. Microstructural characterization and kinetic calculations revealed that this phenomenon was attributed to the formation of a dense iron layer on the particle surface, which impeded the solid-state diffusion of oxygen atoms. The formation of the intermediate phase wüstite was identified as the cause of the formation of the dense iron layer. Overall, this study provided theoretical support for iron-based thermochemical hydrogen storage processes and offered a perspective into the reaction behavior of the reduction of magnetite with hydrogen.