Diffusion Of Atoms Research Articles

Influence of Solid Solution Treatment on Microstructure and Mechanical Properties of 20CrNiMo/Incoloy 825 Composite Materials

The utilization of 20CrNiMo/Incoloy 825 composite materials as high-pressure pipe manifold steel can not only improve the strength and hardness of the steel, but also improve its corrosion resistance. However, research on the heat treatment of 20CrNiMo/Incoloy 825 composite materials is still scarce. Thus, the aim of this study was to investigate the influence of solid solution treatment on the microstructure and properties of 20CrNiMo/Incoloy 825 composite materials. Firstly, the composite materials were subjected to solid solution treatment at temperatures ranging from 850 to 1100 °C with varied holding times of 1 h, 4 h, and 6 h. Microstructural analysis revealed that the solid solution treatment temperature had a more pronounced effect than the treatment time on the interface decarburization layer, carburization layer, and grain size. It was observed that the carburized layer thickness decreased while the decarburized layer thickness increased with an increase in the solid solution treatment temperature, oil cooling was found to enhance the hardness of the base layer of the composite materials, and the size of the original austenite grains of 20CrNiMo steel and Incoloy 825 increased with an increase in the solid solution treatment temperature. Secondly, the tensile properties, microhardness, and fracture morphology were evaluated after the composite materials underwent solid solution treatment at temperatures between 950 °C and 1100 °C for 1 h. The results indicated that increasing the solution temperature initially led to an increase in tensile strength and elongation after fracture, followed by a decrease; furthermore, the hardness of Incoloy 825 exhibited a declining trend, while the hardness of 20CrNiMo first decreased then increased. Thirdly, the shear properties and interfacial element diffusion of the composite materials were analyzed following solid solution treatment in a temperature range of 950 °C to 1100 °C for 1 h. The findings demonstrated that higher solid solution treatment temperatures induced full diffusion of Cr, Ni, and Fe atoms at the interface and softened the matrix, leading to an increase in the thickness of the diffusion layer and toughening of the composite interface. Therefore, the shear strength increased with an increase in the solid solution treatment temperature. Finally, the optimal solid solution treatment process for 20CrNiMo/Incoloy 825 composite materials was determined to be 1050 °C/1 h oil cooling, following which the composite materials had good comprehensive mechanical properties.

Broad Instantaneous Bandwidth Microwave Spectrum Analyzer with a Microfabricated Atomic Vapor Cell

We report on broad instantaneous bandwidth microwave spectrum analysis with hot Rb87 atoms in a microfabricated vapor cell in a large magnetic field gradient. The sensor is a MEMS atomic vapor cell filled with isotopically pure Rb87 and N2 buffer gas to localize the motion of the atoms. The microwave signals of interest are coupled through a coplanar waveguide to the cell, inducing spin-flip transitions between optically pumped ground states of the atoms. A static magnetic field with large gradient maps the frequency spectrum of the input microwave signals to a position-dependent spin-flip pattern on absorption images of the cell recorded with a laser beam onto a camera. In our proof-of-principle experiment, we demonstrate a microwave spectrum analyzer that has ≈1 GHz instantaneous bandwidth centered around 13 GHz, 3 MHz frequency resolution, 2 kHz refresh rate, and a −23 dBm single-tone microwave power detection limit in 1 s measurement time. A theoretical model is constructed to simulate the image signals by considering the processes of optical pumping, microwave interaction, diffusion of Rb87 atoms, and laser absorption. We expect to reach more than 25 GHz instantaneous bandwidth in an optimized setup, limited by the applied magnetic field gradient. Our demonstration offers a practical alternative to conventional microwave spectrum analyzers based on electronic heterodyne detection. Published by the American Physical Society 2024

Hydrogen diffusion on Ni(100): A combined machine-learning, ring polymer molecular dynamics, and kinetic Monte Carlo study.

We introduce a methodological framework coupling machine-learning potentials, ring polymer molecular dynamics (RPMD), and kinetic Monte Carlo (kMC) to draw a comprehensive physical picture of the collective diffusion of hydrogen atoms on metal surfaces. For the benchmark case of hydrogen diffusion on a Ni(100) surface, the hydrogen adsorption and diffusion energetics and its dependence on the local coverage is described via a neural-network potential, where the training data are computed via periodic density functional theory (DFT) and include all relevant optimized diffusion and desorption paths, sampled by nudged elastic band optimizations and molecular dynamics simulations. Nuclear quantum effects, being crucial for processes involving hydrogen at low temperatures, are treated by RPMD. The diffusion rate constants are calculated with a combination of umbrella samplings employed to map the free energy profile and separate samplings of recrossing trajectories to obtain the transmission coefficient. The calculated diffusion rates for different temperatures and local environments are then combined and fitted into a kMC model allowing access to larger time and length scales. Our results demonstrate an outstanding performance for the trained neural network potential in reproducing reference DFT energies and forces. We report the effective diffusion rates for different temperatures and hydrogen surface coverages obtained via this recipe in good agreement with the experimental results. The method combination proposed in this study can be instrumental for a wide range of applications in materials science.

Scanning Transmission Electron Microscopy Analysis of the Si(111)–AlN–GaN Nanowire Interface Grown by Polarity‐ and Site‐Controlled Growth Method

In GaN‐on‐Si nanowire integration schemes, where the nanowires are contacted through the substrate, the interfaces between silicon substrate, AlN buffer layer, and GaN nanowire are of high interest. Herein, analysis by scanning transmission electron microscopy (STEM) of GaN nanowires grown on Si(111) by metal–organic vapor phase epitaxy using a polarity‐ and site‐controlled growth method is presented. This method is based on prestructuring the substrate, ex situ oxidation of the surface, and in situ oxide layer desorption. First, an AlN layer is grown to prevent melt‐back etching. Samples are prepared for STEM by focused ion beam cutting. STEM measurements in three different regions reveal that the AlN buffer material is polycrystalline. The degree of polycrystallinity is found to depend on the observed region: the highest degree exists at the field area between nanowires and the lowest at the sidewall of the Si‐pillars. On the sidewall, the ‐direction of the AlN grain is tilted by 30.1° with regard to the Si{111} sidewall plane, leading to reduced lattice mismatch at this location. The growth of GaN is competing with diffusion of Ga atoms through grain boundaries. The dominant mechanism is dependent on the region, leading to site‐controlled growth of nanowires.

The role of surface substitution in the atomic disorder-to-order phase transition in multi-component core-shell structures.

Intermetallic phases with atomic ordering are highly active and stable in catalysts. However, understanding the atomistic mechanisms of disorder-to-order phase transition, particularly in multi-component systems, remains challenging. Here, we investigate the atom diffusion and phase transition within Pd@Pt-Co cubic nanoparticles during annealing, using in-situ electron microscopy and ex-situ atomic resolution element analysis. We reveal that initial outward diffusing Pd partially substitutes Pt, forming a (Pt, Pd)-Co ternary system in the surface region, enabling the phase transition at a low temperature of 400 °C, followed by shape-preserved inward propagation of the ordered phase. At higher temperatures, excessive interdiffusion across the interface changes the stoichiometric ratio, diminishing the atomic ordering, leading to obvious change in morphology. Calculations indicate that the Pd-substitute in (Pt, Pd)-Co system leads to a significantly lower phase transition temperature compared to that of Pt-Co alloy and thus a lower activation energy for atomic diffusion. These insights into atomistic behavior are crucial for future design of multi-component systems.

Fabrication and Mechanism Insight of Multidimensional Coupled Metal-Free van der Waals Heterostructures for Enhanced Photocatalytic Hydrogen Evolution.

It is an arduous issue to significantly improve the charge separation efficiency of polymer photocatalysts due to their inherently high exciton binding energy. Herein, based on an interfacial coupling and atom diffusion strategy, a metal-free 3D/2D van der Waals (VdW) heterojunction is fabricated through the modification of rich-vacancy wrinkle-like S8 (Vs-S8) microspheres on the surface of S-doped polymeric carbon nitride (S-PCN) nanosheets. The insight into the mechanism reveals that the interfacial coupling effect induces a strong built-in electric field from S-PCN to Vs-S8, and the carrier transfer behavior abides by the type-II charge transfer pathway, thereby dramatically improving the separation efficiency and transport kinetics of photogenerated carriers. As a result, the as-prepared metal-free 3D/2D Vs-S8/S-PCN VdW heterojunction is endowed with more superior photocatalytic hydrogen evolution (PHE) performance than PCN. The highest average PHE rate is about 11.3 times higher than that of PCN, and the apparent quantum efficiency reaches 30.1% at 400 nm on the optimal 3%-Vs-S8/S-PCN sample. This work contributes a new design strategy for a metal-free VdW heterojunction and provides a feasible avenue for improving the carrier separation efficiency of polymer photocatalysts.

Unique Applications of para-Hydrogen Matrix Isolation to Spectroscopy and Astrochemistry.

Cryogenic solid para-hydrogen (p-H2) exhibits pronounced quantum effects, enabling unique experiments that are typically not possible in noble-gas matrices. The diminished cage effect facilitates the production of free radicals via in situ photolysis or photoinduced reactions. Electron bombardment during deposition readily produces protonated and hydrogenated species, such as polycyclic aromatic hydrocarbons, that are important in astrochemistry. In addition, quantum diffusion delocalizes hydrogen atoms in solid p-H2, allowing efficient H atom reactions with astrochemical species and introducing new concepts in astrochemical models. Some H atom reactions display anomalous temperature behaviors, highlighting the rich chemistry in p-H2. The investigation on quantum diffusion of heavier atoms and molecules is also important for our understanding of the chemistry in interstellar ice. Additionally, matrix shifts of electronic transitions of polycyclic aromatic hydrocarbons in p-H2 are less divergent than those in solid Ne such that systematic measurements in p-H2 might help in the assignment of diffuse interstellar bands.

Interface Microstructure and Mechanical Properties of Nickel/Steel Bimetal Composite Pipe Fabricated by Explosive Welding

In this paper, the microstructure and mechanical properties at the interface of Incoloy825/X65 bimetallic composite pipe achieved by explosive welding were systematically studied. Results show that a periodic wavy bonding interface was formed between the Incoloy825 and X65 due to the jets caused by the high-impact stresses during explosive welding, which was beneficial for improving the bonding strength of the Incoloy825 and X65. Atomic diffusion and localized melting occurred near the interface during explosive welding. Some fine crystal grains were generated in the vicinity of the interface due to the strong plastic deformation and dynamic recrystallization, whereas some elongated grains growing in the perpendicular direction to the interface were found in the wider localized melted zone. Room temperature nanoindentation test showed that due to the existence of fine grains resulting from the recrystallization at the interface, the hardness of the interface was higher than that of the base metals. Voids and defects were prone to appearing in the vortex regions near the interface, where the weak point in the interface was located.

Oxygen Vacancy-Electron Polarons Featured InSnRuO2 Oxides: Orderly and Concerted In-Ov-Ru-O-Sn Substructures for Acidic Water Oxidation.

Polymetallic oxides with extraordinary electrons/geometry structure ensembles, trimmed electron bands, and way-out coordination environments, built by an isomorphic substitution strategy, may create unique contributing to concertedly catalyze water oxidation, which is of great significance for proton exchange membrane water electrolysis (PEMWE). Herein, well-defined rutile InSnRuO2 oxides with density-controllable oxygen vacancy (Ov)-free electron polarons are firstly fabricated by in situ isomorphic substitution, using trivalent In species as Ov generators and the adjacent metal ions as electron donors to form orderly and concerted In-Ov-Ru-O-Sn substructures in the tetravalent oxides. For acidic water oxidation, the obtained InSnRuO2 displays an ultralow overpotential of 183 mV (versus RHE) and a mass activity (MA) of 103.02 A mgRu -1, respectively. For a long-term stability test of PEMWE, it can run at a low and unchangeable cell potential (1.56 V) for 200 h at 50 mA cm-2, far exceeding current IrO2||Pt/C assembly in 0.5 m H2SO4. Accelerated degradation testing results of PEMWE with pure water as the electrolyte show no significant increase in voltage even when the voltage is gradually increased from 1 to 5 A cm-2. The remarkably improved performance is associated with the concerted In-Ov-Ru-O-Sn substructures stabilized by the dense Ov-electron polarons, which synergistically activates band structure of oxygen species and adjacent Ru sites and then boosting the oxygen evolution kinetics. More importantly, the self-trapped Ov-electron polaron induces a decrease in the entropy and enthalpy, and efficiently hinder Ru atoms leaching by increasing the lattice atom diffusion energy barrier, achieves long-term stability of the oxide. This work may open a door to design next-generation Ru-based catalysts with polarons to create orderly and asymmetric substructures as active sites for efficient electrocatalysis in PEMWE application.

Study of atomic diffusion behavior in diffusion welding of NiTi alloy - based on molecular dynamics

NiTi alloy with nearly equiatomic ratios of Ni and Ti, has a unique shape memory effect and biocompatibility. Atomic diffusion is a determinant factor for the diffusion welding of NiTi alloys joining. In general, the atomic diffusion may be mediated by the temperature, time and pressure and so on. Despite the importance of technology, Ni and Ti atoms’ diffusion mechanism, however, still remains un-elucidated. Few works have investigated the movement rules of atoms from the atomic scale. Molecular dynamics simulations of diffusion welding were performed for 200-800ps to investigate the diffusion process of the NiTi alloy composite plate at temperatures of 1000, 1100, 1200, and 1300K. The results show that the holding temperature had the greatest effect on diffusion, with pressure having the least effect. The diffusion coefficients of NiTi, Ni, and Ti were calculated at temperatures of 1000, 1100, 1200, and 1300K, respectively. The diffusion degree of Ni atoms was higher than that of Ti atoms. The diffusion coefficients of Ni and Ti atoms satisfied the Arrhenius equation, and the diffusion activation energy of Ni atoms was lower than that of Ti atoms. Furthermore, this study demonstrates at the atomic scale that the growth of the diffusion layer at high temperatures follows the parabolic growth kinetics law.

Effects of Scandium doping on the deuterium absorption and desorption behavior of titanium films

Understanding the effects of Scandium (Sc) on the hydrogen absorption and desorption capabilities and the underlying mechanisms within Ti–Sc alloys is crucial for their applications as hydrogen storage materials. In this study, we explore the influence of Sc on deuterium (D) behavior in Titanium (Ti) films through a combination of experimental characterization and theoretical simulations. The Sc-doped Ti films with different Sc ratio were prepared using magnetron sputtering. Our findings indicate that Sc doping raises the D absorption temperature from 350 °C to 500 °C, and the Sc-doped Ti deuteride films exhibit higher apparent activation energies and temperatures for D desorption. Results from both experiments and DFT calculations indicate that these phenomena are attributed to the atomic size effect, in which the larger Sc atoms reduce the Ti–H spacing, thereby strengthening the interaction between the adjacent Ti atoms and H atoms. The enhanced interaction presents a greater challenge for H atom diffusion within α-Ti and complicates the dissociation of TiH2. This study provides a vital theoretical and experimental basis for understanding the effects of Sc doping on the hydrogen absorption and desorption properties in titanium alloys.

Evolution of microstructure and mechanical properties in TiBw/Ti65 composites during vacuum solid-phase diffusion bonding

This paper examines the solid-phase diffusion bonding (DB) of TiBw/Ti65 composites, focusing on the effects of processing parameters such as temperature, time, pressure, and interlayer thickness. The findings show that lower processing conditions resulted in slower atomic diffusion and more defects, whereas higher conditions reduced pores but led to grain growth. Optimal bonding was achieved at 950°C, 10MPa, and 60minutes, yielding a shear strength of 686MPa, which is 81.86% of the base material's strength. The introduction of pure titanium interlayer results in a concentration gradient, which serves as an additional driving force for atomic diffusion, thereby enhancing the quality of diffusion bonding. Shear strength varied with interlayer thickness, peaking at 668MPa for a 5 μm interlayer. Microplastic deformation, dynamic recrystallization (DRX), and grain boundary (GB) migration affected the microstructure and mechanical properties of the bonding interface. TiB whiskers (TiBw) near the bonding interface significantly influenced DRX and GB migration during the DB process.

Radiation Resistivity of Ti-5331 Alloy with Different Microstructures

Titanium alloys have promising potential for applications in marine nuclear power systems owing to their exceptional mechanical and corrosion properties. Nevertheless, their radiation resistivity is a determining factor for their extensive use as structural materials in nuclear energy systems. In this study, the radiation resistivity of Ti-5Al-3V-3Zr-Cr (Ti-5331) alloys with three different microstructures was examined using a combination of characterization techniques including positron annihilation Doppler broadening spectroscopy (DBS), Elastic Recoil Detection Analysis (ERDA), Transmission Electron Microscope (TEM), Small-Angle X-ray scattering (SAXS) and nanoindentation. The results reveal that the equiaxed structure, bimodal structure, and Widmanstatten structure of Ti-5331 alloy obtained through different annealing processes exhibit differences in the number of interfaces and the content of the β phase. The α/β interfaces can significantly enhance the radiation resistance of titanium alloys by inhibiting the diffusion of helium atoms after helium ion irradiation. Notably, the alloy with a bimodal structure exhibited the best overall radiation resistivity, showing small defect size, low hardening effect, and low swelling rate of 0.003%. Moreover, the size of helium bubbles of the bimodal structure is half of that in the equiaxed structure and Widmanstatten structure. Thus, the bimodal structure of the Ti-5331 alloy possesses superior radiation resistivity.

Influence of P and C co-alloying on soft magnetic properties and crystallization behavior of FeSiBPCCu nanocrystalline alloys

In this study, multicomponent synergistic effects were adopted to enhance the glass-forming ability (GFA), processing window (PW), thermal stability, and soft magnetic properties (SMPs) of FeCuSiB nanocrystalline alloys (NAs) with high Fe and Cu contents via P and C co-alloying. The co-addition of P and C is beneficial for enhancing the GFA, expanding the PW, and increasing the crystallization resistance of the compound phases in present FeCuSiBPC alloys. Consequently, the Fe81.5Cu1.7Si3.8B9P3C1 alloy exhibited a large optimum TA window of up to 100 °C and a large tA window of 40 min for nanocrystallization. Crystallization kinetic analysis showed that the co-addition of P and C led to a high-frequency factor (v) in the precipitation of α-Fe crystals, which was related to the high nanocrystal density (Nd) of α-Fe. This result may be attributed to the nucleation of α-Fe by Cu and CuP clusters. Additionally, the co-addition of P and C increased the growth active energy (Ep) of the α-Fe crystals because of their larger atomic diffusion resistance. The high Nd and Ep values led to the formation of fine nanostructures and excellent SMPs in FeCuSiBPC alloys. Therefore, the Fe81.5Cu1.7Si3.8B9P3C1 NA obtained by annealing at 420 °C for 30 min exhibited excellent SMPs with a Bs of up to 1.78 T, a low Hc of 7.5 A/m, and a high μe of 9863 (@1kHz). This study provides technical and theoretical guidance for optimizing the composition and processability of NAs with high Fe and Cu contents, paving the way for mass production of high-performance soft magnetic NAs.

Influence of irradiation wavelength during laser-assisted doping of 4H-silicon carbide in liquid phase

Laser-assisted doping of silicon carbide (SiC) substrates is challenging due to the low diffusion coefficient of dopant atoms and the chemically inert nature of SiC. Single crystal intrinsic 4H-SiC substrate is irradiated with neodymium-doped yttrium aluminium garnet (Nd3+):YAG laser with wavelengths of 1064, 355 and 266 nm, and krypton fluoride (KrF) excimer laser with the wavelength of 248 nm under liquid phase dopant sources. Different liquid solutions were used as dopant sources for aluminium (Al) and phosphorus (P). SiC was transparent to 1064 and 355 nm due to low absorption coefficients, while 266 and 248 nm showed better coupling due to higher absorption coefficients and led to the diffusion of atoms. The electrical resistance of the substrates was measured to be lower than 1000 kΩ after diffusion. Dispersive X-ray spectroscopy (EDS) studies showed that both laser wavelengths of 248 nm and 266 nm resulted in doping of Al and P, with the surface concentrations ranging from 0.5 to 1.5 at.% and from 0.24 to 0.6 at.%, respectively. Two-dimensional thermo-temporal simulation of the laser pulse interaction in the liquid phase revealed that unlike in air, during irradiation with 266 nm laser under liquid, the surface temperature of the substrate was slightly lower. However, the subsurface temperature increased along the depth by a few microns. Similarly, simulation studies with longer pulse irradiation also show that high temperature was maintained for a longer time, indicating improved dopant diffusion into the 4H-SiC substrate.

Single‐Crystalline LiMg Alloy Anode for Deep Cycling All Solid State Lithium Metal Batteries

AbstractAll solid state lithium metal batteries (ASSLMBs) with enhanced energy density has driven the exploration of Li‐alloy anodes such as Li‐Mg alloy owing to its solid‐solution structure and high theoretical specific capacity. But the Li atom diffusion limitation on Li‐Mg electrode surface further leads to sluggish atoms transport dynamics. Herein, single‐crystalline (110)‐oriented Li0.9Mg0.1 (denoted as LiMg(110)) anode is obtained by a tailored melt‐annealing procedure to tackle the above issues. Theoretical analyses and experimental results demonstrate that the crystallographic structural (110) orientation of LiMg anode can facilitate Li atom diffusion and guarantee the electrode stability during deep cycling. As a result, the LiMg(110) electrode exhibits longer cycle life with lower overpotential than polycrystalline LiMg at high current densities and areal capacities in symmetric cells. A critical current density (CCD) at the forefront of 2.5 mA cm−2 is achieved in Li3InCl6 (LIC) solid‐state system. The ASSLMB with high areal capacity (3.8 mAh cm−2), high current density (0.76 mA cm−2), and low negative/positive capacity N/P ratio (2.14) achieves exceptional cyclability over 160 cycles. The outcomes highlight a promising crystallographic regulation strategy toward practical applications of high‐performance lithium metal batteries.

Molecular Dynamics Analysis of Hydrogen Diffusion Behavior in Alpha-Fe Bi-Crystal Under Bending Deformation

The hydrogen embrittlement (HE) phenomenon occurring in drawn pearlitic steel wires sometimes results in dangerous delayed fracture and has been an important issue for a long time. HE is very sensitive to the amount of plastic deformation applied in the drawing process. Hydrogen (H) atom diffusion is affected by ambient thermal and mechanical conditions such as stress, pressure, and temperature. In addition, the influence of stress gradient (SG) on atomic diffusion is supposed to be crucial but is still unclear. Metallic materials undergoing plastic deformation naturally have SG, such as residual stresses, especially in inhomogeneous regions (e.g., surface or grain boundary). In this study, we performed molecular dynamics (MD) simulation using EAM potentials for Fe and H atoms and investigated the behavior of H atoms diffusing in pure iron (α-Fe) with the SG condition. Two types of SG conditions were investigated: an overall gradient established by a bending deformation of the specimen and an atomic-scale local gradient caused by the grain boundary (GB) structure. A bi-crystal model with H atoms and a GB structure was subjected to bending deformation. For a moderate flexure, bending stress is distributed linearly along the thickness of the specimen. The diffusion coefficient of H atoms in the bulk region increased with an increase in the SG value. In addition, it was clearly observed that the direction of diffusion was affected by the existence of the SG. It was found that diffusivity of the H atom is promoted by the reduction in its cohesive energy. From these MD results, we recognize an exponential relationship between the amount of H atom diffusion and the intensity of the SG in nano-sized bending deformation.

Contribution to the Study of the Chemical and Microstructural Quality of Reinforcing Bars in DR. Congo “Case of the City of Lubumbashi”

This research highlights the contribution to the study of the microstructural quality of reinforcing bars on the Lubumbashi market including bars imported from South Africa (FA), Zambia (FZ) and those produced locally ( FC) by the only steel industry, in the former province of Katanga, the iron processing company SOTRAFER, in acronym. The samples of the locally produced reinforcement bars (FC) were collected at SOTRAFER at the end of production, while the samples of the FA and FZ reinforcement bars were taken randomly on the Lushois market in a hardware store specializing in sales to avoid errors.Microstructural analysis of all bars revealed a similar microstructure consisting of a ferrite (light areas) and pearlite (dark areas) matrix and a ferrito-pearlitic structure. This microstructure, as predicted by the Fe-C equilibrium diagram, could be justified by the carbon content (lower than the eutectoid point content); the results prove that all bars are hypoeutectoid steels (%C ≤ 0.77). They can also be assimilated to the category of mild steels (0.1 ≤ %C ≤ 0.25). This also shows that all the bars have not undergone a particular heat treatment and have been cooled very slowly in order to allow the diffusion of atoms and reach equilibrium conditions. The results obtained from the variance analyses of different materials of dimensions of 10, 12 and 16 mm revealed that at the level of chemical and mechanical analyses, there was no significant difference on all the parameters studied and that all the reinforcement bars could perfectly be used in construction. Finally, the survey reveals that FA is reputed to be of better quality among consumers, for several reasons including the psychological one although its price is lower than that produced locally.

Chemically Stable Group IV-V Transition Metal Carbide Thin Films in Hydrogen Radical Environments.

Hydrogen is a crucial element in the green energy transition. However, its tendency to react with and diffuse into surrounding materials poses a significant challenge. Therefore, developing coatings to protect system components in hydrogen environments (molecular, radicals (H*), and plasma) is essential. In this work, we report group IV-V transition metal carbide (TMC) thin films as potential candidates for protective coatings in H* environments at elevated temperatures. We expose TiC, ZrC, HfC, VC, NbC, TaC, and Co2C thin films, with native surface oxycarbides/oxides (TMO x C y /TMO x ), to H* at elevated temperatures. Based on X-ray photoelectron spectroscopy performed on the samples before and after H*-exposure, we identify three classes of TMCs. HfC, ZrC, TiC, TaC, NbC, and VC (class A) are found to have a stable carbidic-C (TM-C) content, with a further subdivision into partial (class A1: HfC, ZrC, and TiC) and strong (class A2: TaC, NbC, and VC) surface deoxidation. In contrast to class A, a strong carbide reduction is observed in Co2C (class B), along with a strong surface deoxidation. The H* interaction with TMC/TMO x C y /TMO x is hypothesized to entail three processes: (i) hydrogenation of surface C/O atoms, (ii) formation of CH x /OH x species, and (iii) subsurface C/O atom diffusion to the surface vacancies. The number of adsorbed H atoms required to form CH x /OH x species (i) and the corresponding thermodynamic energy barriers (ii) are estimated based on the change in the Gibbs free energy (ΔG) for the reduction reactions of TMCs and TMO x . Hydrogenation of surface carbidic-C atoms is proposed to limit the reduction of TMCs, whereas the deoxidation of TMC surfaces is governed by the thermodynamic energy barrier for forming H2O.

Oxygen Vacancy-Mediated Synthesis of Inter-Atomically Ordered Ultrafine Pt-Alloy Nanoparticles for Enhanced Fuel Cell Performance.

Pt-based intermetallics are expected to be the highly active catalysts for oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells but still face great challenges in controllable synthesis of interatomically ordered and ultrafine intermetallic nanoparticles. Here, we propose an oxygen vacancy-mediated atomic diffusion strategy by mechanical alloying to reduce the energy barrier of the transition from interatomic disordering to ordering, and to resist interparticulate sintering via strong M-O-C bonding. This synthesis results in a nanosized core/shell structure featuring an interatomically ordered PtM core and a Pt shell of two to three atomic layers in thickness and can be extended to the multicomponent PtM (M = Co, FeCo, FeCoNi, FeCoNiGa) systems. The electron enrichment in the Pt outer shell induced by the compressive strain leads to the enhanced antibonding orbital occupation below the Fermi level and accelerated OH* desorption kinetics. The optimized PtCo-O/C-6 catalyst presents excellent ORR activity (mass activity = 1.28 A mgPt-1 at 0.9 ViR-free, peak power densities = 2.38/1.25 W cm-2 in H2-O2/-air) and durability (∼1% activity loss in over 50 h in air condition) in fuel cells at a total Pt loading of 0.1 mgPt cm-2. Furthermore, we establish a systematic correlation to elucidate the formation mechanisms of highly ordered intermetallic catalysts underlying oxygen vacancies. This study provides a general approach for the large-scale production of highly ordered and nanosized Pt-dispersed intermetallic catalysts.