Search Results (98)

Low-carbon lath martensite is highly susceptible to hydrogen embrittlement due to the presence of a high density of lath/block boundaries. In this study, I employ a continuum decohesion model to investigate the effects of varying hydrogen concentrations and tensile loads on the cohesive strength of low- and high-angle block boundaries. The thermodynamic properties of the cohesive zone are described using excess variables, which establish a link between atomistic energy calculations and the continuum model for gradual decohesion at a grain boundary. The aim of this study is to develop an in-depth understanding of how hydrogen affects the cohesive strength of block boundaries in a lath martensitic structure by integrating continuum and atomistic computational modeling and to apply the resulting insights to investigate the effects of varying hydrogen concentrations and tensile loads on interface decohesion. I incorporate hydrogen mobility and segregation at low- and high-angle twist boundaries in body-centered cubic (bcc) Fe to quantify the hydrogen-induced effects on progressive decohesion under tensile stress. A constant hydrogen flux through the free surfaces of a bicrystal containing a block boundary is imposed to simulate realistic boundary conditions. The results of the simulations show that, in the presence of hydrogen flux, separation across the block boundaries occurs at a tensile load significantly lower than the critical stress required for rupture in a hydrogen-free lath martensitic structure. Full article

Directed self-assembly (DSA) lithography, a cutting-edge technology based on the self-assembly of block copolymers (BCPs), has received significant attention in recent years. Combining DSA with established lithography technologies, such as extreme ultraviolet (EUV), deep ultraviolet (DUV), electron beam lithography, and nanoimprint lithography, significantly enhances the resolution of target patterns and device density. Currently, there are two commonly used methods in DSA: graphoepitaxy, employing lithographically defined topographic templates to guide BCP assembly, and chemoepitaxy, utilizing chemically patterned surfaces with precisely controlled interfacial energies to direct nanoscale phase segregation. Through novel DSA lithography technology, nanoscale patterns with smaller feature sizes and higher densities can be obtained, realizing the miniaturization of hole and line patterns and pitch multiplication and improving the roughness and local critical dimension uniformity (LCDU). It is gradually becoming one of the most promising and advanced lithography techniques. DSA lithography technology has been applied in logic, memory, and optoelectronic device fabrications. Full article

Adsorbate-induced surface segregation significantly influences the catalytic and electrochemical performance of bimetallic alloys. Using density functional theory (DFT), we investigated Rh segregation in Au–Rh(111) alloys under the influence of adsorbed NO, CO, or O₂. The computational results reveal that these adsorbates can markedly alter Rh segregation trends on the Au–Rh(111) surface. Under vacuum conditions, the Rh atom remains preferentially in the bulk of the alloy; whereas, in the presence of adsorption, it segregates to the topmost layer, where NO has the greatest influence, followed by CO and O₂. Electronic structure analysis and adsorption energy evaluations further reveal that the strength of the surface–adsorbate interactions critically governs the Rh segregation behavior under reactive conditions. These findings establish a theoretical framework for designing Au–Rh alloys as efficient catalysts for CO oxidation. Full article

As an eco-efficient short-process manufacturing technique for aluminum alloys, twin-belt continuous casting and direct rolling (TBCCR) demonstrates significant production advantages. In this study, an Al-Fe-Si alloy system with different Fe-rich intermetallics (α-AlFe(Mn)Si and β-AlFe(Mn)Si) via TBCCR was developed for new energy vehicle batteries, utilizing the Computer Coupling of Phase Diagrams and Thermochemistry (CALPHAD) technique. Comprehensive microstructure and surface segregation analyses of continuous casted ingots and direct-rolled sheets revealed that the Al-Fe-Si alloy with a combined Fe + Si content of 0.7% and an optimal Fe/Si atomic ratio of 3:1 (FS31) presents optimized mechanical properties: ultimate tensile strength of 145.8 MPa, elongation to failure of 5.7%, accompanied by a cupping value of 6.64 mm. Notably, Mn addition further refined the grain structure of casting ingots and enhanced the strength of both ingots and rolled sheets. Among the experimental alloys, FS14 (optimal Fe/Si atomic ratio of 1:4) sheets displayed the least surface segregation upon Mn incorporation. Through systematic optimization, an Al-Fe-Si-Mn alloy composition (Fe + Si = 0.7%, Fe/Si = 1:4 atomic ratio, 0.8 wt.% Mn) was engineered for TBCCR processing, achieving enhanced comprehensive performance: ultimate tensile strength of 189.4 MPa, elongation to failure of 7.32%, and cupping value of 7.71 mm. This composition achieves an optimal balance between grain refinement, mechanical properties (strength–plasticity synergy), formability (cupping value), and corrosion resistance (corrosion current density). The performance optimization strategy integrates synergistic improvements in strength, ductility, and corrosion resistance, providing valuable guidance for developing high-performance aluminum alloys suitable for the TBCCR process. Full article

GeSn alloys are among the most promising materials for the fabrication of high-efficiency silicon-based light sources. However, due to the tendency of Sn to segregate to the surface during growth, it is challenging to achieve a high Sn concentration while maintaining high-quality GeSn alloys. Both theoretical and experimental studies have confirmed that non-substitutional Sn defects (VSnV) are the primary driving factors in Sn surface segregation. However, there is a discrepancy between existing theoretical and experimental findings regarding the variation in VSnV concentration with total Sn concentration. To clarify this issue, we first prepared GeSn materials with varying Sn concentrations using molecular beam epitaxy (MBE) and subjected them to annealing at different temperatures. Subsequently, we characterized the VSnV concentration and Sn surface segregation. The results indicate that a higher total Sn concentration and temperature lead to an increased VSnV concentration, and the proportion of VSnV relative to the total Sn concentration also increases, which is consistent with existing theoretical research. To explain these phenomena, we employed first-principles calculations based on density functional theory (DFT) to investigate the effect of varying the total Sn concentration on the formation of substitutional Sn (Sn_s) and VSnV in GeSn alloys, while simultaneously studying the migration kinetics of Sn atoms. The results demonstrate that as the total Sn concentration increases, the formation of Sn_s becomes more difficult, while the formation of VSnV becomes easier, and Sn atoms exhibit enhanced migration tendencies. The analysis of binding energies and charge density distribution maps reveals that this is due to the weakening of Ge-Sn bond strength with increasing Sn concentration, whereas the binding strength of VSnV exhibits the opposite trend. These findings demonstrate excellent agreement with experimental observations. This study provides both theoretical and experimental references for GeSn material growth and VSnV defect control through a combined theoretical–experimental approach, offering significant guidance for enhancing device performance. Full article

In this study, FeCoNiCrAl high-entropy alloy (HEA) coatings were fabricated on Q235 steel surfaces using laser cladding (LC) to enhance corrosion resistance in harsh environments. The laser processing parameters (laser power, defocus distance, and scanning speed) were optimized using response surface methodology (RSM), establishing a mathematical model to guide the process. The optimized coatings demonstrated strong metallurgical bonding to the substrate, with a microstructure comprising Al-Ni-rich B2 phases and Cr-Fe-rich BCC phases. Elemental segregation was effectively mitigated as energy density decreased, leading to significant improvements in corrosion resistance. Electrochemical tests in 3.5 wt.% NaCl and 0.5 mol/L H₂SO₄ solutions showed that the optimized coating (laser power: 800 W, scanning speed: 450 mm/min, defocus: −15 mm) exhibited exceptionally low corrosion current densities of 1.78 × 10⁻⁷ A/cm² and 1.07 × 10⁻⁵ A/cm², respectively. The passive film on the optimized coating surface consisted of stable oxides, with low oxygen vacancy densities of 1.937 × 10²³ cm⁻³ in NaCl and 4.967 × 10²¹ cm⁻³ in H₂SO₄, significantly enhancing its resistance to localized and uniform corrosion. These results demonstrate the effectiveness of RSM-based optimization in producing HEA coatings with superior corrosion resistance suitable for applications in highly corrosive environments. Full article

A theoretical analysis of the influence of the distribution of the local specific energy dissipation rate on the specific interfacial area, the surface and volumetric mass transfer coefficients in apparatuses with heterophase processes and a liquid continuous phase, as well as the quality of mixing in apparatuses with homophase reactions in the liquid phase, is performed. It is shown that the average value of the specific energy dissipation rate over the volume of the device is not a full-fledged criterion for assessing the useful effect since it does not take into account, on the one hand, the local level of energy dissipation in the active zones and, on the other hand, the features of the flow structure and the local residence time in the active zones, depending on the geometry of the device and the method of energy input into it. Limiting cases are discussed: (1) uneven energy distribution in the presence of a small volume with a high specific dissipation rate and (2) ideally uniform energy distribution throughout the entire volume of the device. In the first case, a significant part of the volume is used inefficiently; in the second case, an excessive amount of energy is spent. In this regard, the concepts of dosed distributed energy input for long-term processes and maximum energy concentration in a microvolume for fast-flowing processes are considered. Full article

Platinum (Pt) and palladium (Pd) are crucial in hydrogen energy technologies, especially in fuel cells, due to their high catalytic activity and chemical stability. Pt-Pd nanoparticles, produced through various methods, enhance catalytic performance based on their size, shape, and composition. These nanocatalysts excel in direct methanol fuel cells (DMFCs) and direct ethanol fuel cells (DEFCs) by promoting alcohol oxidation and reducing CO poisoning. Pt-Pd catalysts are also being explored for their oxygen reduction reaction (ORR) on the cathodic side of fuel cells, showing higher activity and stability than pure platinum. Molecular dynamics (MD) simulations have been conducted to understand the structural and surface energy effects of PdPt nanoparticles, revealing phase separation and chemical ordering, which are critical for optimizing these catalysts. Pd migration to the surface layer in Pt-Pd alloys minimizes the overall potential energy through the formation of Pd surface monolayers and Pt-Pd bonds, leading to a lower surface energy for intermediate compositions compared to that of the pure elements. The potential energy, calculated from MD simulations, increases with a decreasing particle size due to surface creation, indicating higher reactivity for smaller particles. A general contraction of the average distance to the nearest neighbour atoms was determined for the top surface layers within the nanoparticles. This research highlights the significant impact of Pd segregation on the structural and surface energy properties of Pt-Pd nanoparticles. The formation of Pd monolayers and the resulting core–shell structures influence the catalytic activity and stability of these nanoparticles, with smaller particles exhibiting higher surface energy and reactivity. These findings provide insights into the design and optimization of Pt-Pd nanocatalysts for various applications. Full article

Nowadays, the application of protective multicomponent coatings based on hard metal nitrides is increasingly used to increase the resistance of structures and tools to wear, corrosion, and oxidation. In the present work, the multicomponent system Ti-Al-Ta-Si-N is studied, which has high hardness and crack resistance combined with thermal stability and oxidation resistance. The process of formation of the nanocrystalline structure of the coating during its deposition on materials plays a key role in the optimization of these properties. The nanocrystalline structure of the coating is formed due to Si impurity, which is poorly soluble in the Ti_1−x−yAl_xTa_yN system based on B1-TiN and segregates mainly along grain boundaries, forming grain boundary amorphous phases of Si_zN type. In order to find the optimal composition of multicomponent coatings with improved physical and mechanical properties, it is necessary to understand the peculiarities of interaction of Si impurity with the surface of B1-TiN phase in the presence of Al and Ta substitutional impurities. In the present work, with the help of first-principles calculations of electronic and atomic structure of (001) and (111) surfaces of the Ti_1−x−yAl_xTa_yN system with adsorbed Si atom and the interatomic bond study apparatus based on the calculation of a crystal orbital Hamilton population and a crystal orbital bond index, the nature of the bonds between adsorbed Si and the N, Ti, Al, and Ta atoms of the Ti_1−x−yAl_xTa_yN surface system has been studied. It was found that the binding energy of Si with the Ti_1−x−yAl_xTa_yN surface system can be both higher and lower than the binding energy of its bonding with the surface of the binary TiN compound depending on the position of the Al and Ta substitution atoms in the surface layers. The Si bonding with the atoms of the Ti_1−x−yAl_xTa_yN surface is ionic–covalent in nature. It is shown that the Si-Ta interaction has the highest degree of covalency and strength, and the Si-Al interaction is predominantly ionic in most cases considered and is weaker than the Si-Ti and Si-N bonds. Impurity atoms of Al or Ta have very little effect on the Si-Ti and Si-N bonds due to the local nature of the bonds in the Ti_1−x−yAl_xTa_yN surface system with adsorbed silicon atoms. Full article

In this paper, the enhancement of thermochemical energy storage by alkali metal chloride salts-doped Ca-based sorbents is revealed by experiments and DFT calculations. The results indicate that NaCl and KCl doping increases the reaction rate and cycle stability. Compared to CaO, the conversion of NaCl-CaO and KCl-CaO after one cycle is increased by 59.1% and 61.9%, respectively. This enhancement originates from the oxygen vacancies generated by Na₂O and K₂O and the significantly increased surface area by CaCl₂ as well as the sintering delay. The synergistic effect between Na₂O, K₂O, and CaCl₂ increases the reaction rate of calcium-based materials. Meanwhile, the penetration of low-viscosity molten NaCl and KCl into the calcium-based materials successfully segregates the CaO grains and allows the calcium-based material to maintain the porous structure after 80 cycles, thus exhibiting a high effective conversion rate. In addition, the KCl-CaO composites show the best combined performance in terms of effective conversion and averaged thermal energy density. This work paves the way for the application of chloride salts-doped calcium-based materials. Full article

High-nickel ternary LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) is a promising cathode material for lithium-ion batteries due to its high discharge-specific capacity and energy density. However, problems of NCM622 materials, such as unstable surface structure, lithium–nickel co-segregation, and intergranular cracking, led to a decrease in the cycling performance of the material and an inability to fully utilize high specific capacity. Surface coating was the primary approach to address these problems. The effect of TiO₂ coating prepared by the sol–gel method on the performance of LiNi_0.6Co_0.2Mn_0.2O₂ was studied, mainly including the morphology, cell structure, and electrochemical properties. LiNi_0.6Co_0.2Mn_0.2O₂ was coated by TiO₂ with a thickness of about 5 nm. Compared with the pristine NCM622 electrode, the electrochemical performance of the TiO₂-coated NCM622 electrodes is improved. Among all TiO₂-coated NCM622, the NCM622 cathode with TiO₂ coating content of 0.5% demonstrates the highest capacity retention of 89.3% and a discharge capacity of 163.9 mAh g⁻¹, in contrast to 80.9% and145 mAh g⁻¹ for the pristine NCM622 electrode, after 100 cycles at 0.3 C between 3 and 4.3 V. The cycle life of the 5 wt% TiO₂-coated NCM622 electrode is significantly improved at a high cutoff voltage of 4.6 V. The significantly enhanced cycling performance of TiO₂-coated NCM622 materials could be attributed to the TiO₂ coating layer that could block the contact between the material surface and the electrolyte, reducing the interface side reaction and inhibiting the transition metal dissolution. At the same time, the coating layer maintained the stability of layered structures, thus reducing the polarization phenomenon of the electrode and alleviating the irreversible capacity loss in the cycle process. Full article

This study investigates the influence of various heat treatment processes on the microstructure and properties of laser cladding Fe314 coatings. The microstructure, phases, and impact fracture morphology of the cladding layer were observed using X-ray diffraction and scanning electron microscopy, among other methods. The hardness and impact performance of the cladding layer were also tested. The results indicated that there was compositional segregation and non-equilibrium microstructure in the untreated cladding layer, with an average microhardness of 368.67 HV and an impact toughness of 27 J, exhibiting quasi-cleavage fracture. The stress-relief annealing treatment resulted in a uniform distribution of M23C6 carbides inside the cladding layer. The pinning effect generated by M23C6 reduced the microhardness by 16.26% and increased the impact toughness to 54 J. The impact fracture surface exhibited ductile fracture. After secondary normalizing and annealing, the microstructure of the cladding layer transformed into a fine single-phase austenite structure, and fine M7C3 carbides precipitated at the grain boundaries. Under the effects of fine grain strengthening and dispersion strengthening, the microhardness of the cladding layer decreased by 38.14%, and the average impact absorbed energy of the specimen was 64 J, showing complete ductile fracture. Full article

The interface connects the reinforced phase and the matrix of materials, with its microstructure and interfacial configurations directly impacting the overall performance of composites. In this study, utilizing seven atomic layers of Mg(0001) and Ti(0001) surface slab models, four different Mg(0001)/Ti(0001) interfaces with varying atomic stacking configurations were constructed. The calculated interface adhesion energy and electronic bonding information of the Mg(0001)/Ti(0001) interface reveal that the HCP2 interface configuration exhibits the best stability. Moreover, Si, Ca, Sc, V, Cr, Mn, Fe, Cu, Zn, Y, Zr, Nb, Mo, Sn, La, Ce, Nd, and Gd elements are introduced into the Mg/Ti interface layer or interfacial sublayer of the HCP2 configurations, and their interfacial segregation behavior is investigated systematically. The results indicate that Gd atom doping in the Mg(0001)/Ti(0001) interface exhibits the smallest heat of segregation, with a value of −5.83 eV. However, Ca and La atom doping in the Mg(0001)/Ti(0001) interface show larger heat of segregation, with values of 0.84 and 0.63 eV, respectively. This implies that the Gd atom exhibits a higher propensity to segregate at the interface, whereas the Ca and La atoms are less inclined to segregate. Moreover, the electronic density is thoroughly analyzed to elucidate the interfacial segregation behavior. The research findings presented in this paper offer valuable guidance and insights for designing the composition of magnesium-based composites. Full article

The orderings of atoms in bimetallic 1.6–2.1 nm-large CuCo nanoparticles, important as catalytic and magnetic materials, were studied using a combination of DFT calculations with a topological approach. The structure and magnetism of Cu₅₀Co₁₅₁, Cu₁₀₁Co₁₀₀, Cu₁₅₁Co₅₀, and Cu₃₀₃Co₁₀₂ nanoparticles; their resistance to disintegrating into separate Cu and Co species; as well as the exposed surface sites, were quantified and analyzed, showing a clear preference for Cu atoms to occupy surface positions while the Co atoms tended to form a compact cluster in the interior of the nanoparticles. The surface segregation of Co atoms that are encapsulated by less-active Cu atoms, induced by the adsorption of CO molecules, was already enabled at a low coverage of adsorbed CO, providing the energy required to displace the entire compact Co species inside the Cu matrices due to a notable adsorption preference of CO for the Co sites over the Cu ones. The calculated adsorption energies and vibrational frequencies of adsorbed CO should be helpful indicators for experimentally monitoring the nature of the surface sites of CuCo nanoparticles, especially in the case of active Co surface sites emerging in the presence of CO. Full article

Conventional book casting of Sm₂TM₁₇-type alloys (where TM = Co, Fe, Cu, Zr) leads to a coarse, highly segregated microstructure, predominantly due to the slow, variable cooling rate from the mould surface towards the centre of the ingot. These cast alloys require a long homogenisation treatment to remove this segregation and develop a super-saturated, metastable SmTM₇-type hexagonal phase. This SmTM₇ phase is a vital precursor phase required during magnet production to develop the complex cellular structure responsible for high magnetic properties. In this work, strip casting was employed to facilitate rapid solidification to develop thin flakes (<0.5 mm thick) with a columnar grain structure. Rapid cooling has the potential to produce a homogenous microstructure consisting predominantly of the metastable SmTM₇ phase. This could remove or significantly reduce the need for the energy-intensive homogenisation treatment usually required in conventional magnet manufacture. This paper investigates the effect of wheel speed (and hence cooling rate) on flake thickness, microstructure, and phase balance of the cast alloys. It was shown that for wheel speeds between 1.1 and 3.0 m/s, the microstructure showed large variation; however, in all cases, evidence of the columnar SmTM₇ phase was presented. The adhesion between the melt and the wheel was deemed to be critical for the nucleation and subsequent columnar growth of SmTM₇ grains, where the wheel speed controlled both the flow of the alloy onto the wheel and the thickness of the resultant flake. It was determined that in order to achieve a homogenous columnar SmTM₇ structure, the maximum flake thickness should be limited to 270 μm to avoid the formation of equiaxed Sm₂TM₁₇ grains through insufficient cooling. Full article