Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

Electron-deficient ZnO induced by heterointerface engineering as the dominant active component to boost CO_(2)-to-formate conversion

Electrocatalytic CO_(2)-to-formate conversion is considered an economically viable process.In general,Zn-based nanomaterials are well-known to be highly efficient electrocatalysts for the conversion of CO_(2) to CO,but seldom do they exhibit excellent selectivity toward formate.In this article,we demonstrate that a heterointerface catalyst ZnO/ZnSnO3 with nanosheet morphology shows enhanced selectivity with a maximum Faradaic efficiency(FE)of 86%at−0.9 V versus reversible hydrogen electrode and larger current density for the conversion of CO_(2) to formate than pristine ZnO and ZnSnO3.In particular,the FEs of the C1 products(CO+HCOO−)exceed 98%over the potential window.The experimental measurements combined with theoretical calculations revealed that the ZnO in ZnO/ZnSnO3 heterojunction delivers the valence electron depletion and accordingly optimizes Zn d-band center,which results in moderate Zn-O hybridization of HCOO*and weakened Zn-C hybridization of competing COOH*,thus greatly boosting the HCOOH generation.Our study highlights the importance of charge redistribution in catalysts on the selectivity of electrochemical CO_(2) reduction.

Driving inward growth of lithium metal in hollow microcapsule hosts by heteroatom‐controlled nucleation

The application of Li metal anodes in rechargeable batteries is impeded by safety issues arising from the severe volume changes and formation of dendritic Li deposits.Three‐dimensional hollow carbon is receiving increasing attention as a host material capable of accommodating Li metal inside its cavity;however,uncontrollable and nonuniform deposition of Li remains a challenge.In this study,we synthesize metal–organic framework‐derived carbon microcapsules with heteroatom clusters(Zn and Ag)on the capsule walls and it is demonstrated that Ag‐assisted nucleation of Li metal alters the outward‐to‐inward growth in the microcapsule host.Zn‐incorporated microcapsules are prepared via chemical etching of zeolitic imidazole framework‐8 polyhedra and are subsequently decorated with Ag by a galvanic displacement reaction between Ag^(+) and metallic Zn.Galvanically introduced Ag significantly reduces the energy barrier and increases the reaction rate for Li nucleation in the microcapsule host upon Li plating.Through combined electrochemical,microstructural,and computational studies,we verify the beneficial role of Ag‐assisted Li nucleation in facilitating inward growth inside the cavity of the microcapsule host and,in turn,enhancing electrochemical performance.This study provides new insights into the design of reversible host materials for practical Li metal batteries.

Effect of hydro co-extrusion on microstructure of duo-cast Al3003/Al4004 clad materials

The effects of hydro co-extrusion on the microstructure changes of aluminum hybrid duo-cast Al 3003/Al 4004 clad materials were studied. The specimen of duo-cast Al 3003/Al 4004 clad materials was in circle shape, and was composed of Al 3003(outside) and Al 4004(inside) materials. The specimen was extruded by the hydro co-extrusion equipment. The manufacturing conditions of the specimen were 423 K in temperature and 5 in extrusion ratio. The dimensions of the specimen were 80 mm in diameter of the Al 4004 material and 35 mm in thickness of the Al 3003 material before the hydro co-extrusion process, and 30 mm in diameter and about 5 mm in thickness after the extrusion process, respectively. The microstructure and the hardness for two specimens were investigated. The hardness value of cross section in the duo-cast Al 3003/Al 4004 clad materials before the extrusion process was increased in form of the parabola toward the center. However, after the extrusion process, it was almost constant in the portion of Al 4004 material. Lots of big voids above 1 mm in diameter in the specimen existed in the interfacing region of Al 3003 and Al 4004 materials before the extrusion process. These big voids disappeared after the process of hydro co-extrusion.

Effect of bonding interface on delamination behavior of drawn Cu/Al bar clad material

Cu/Al bar clad material was fabricated by a drawing process and a subsequent heat treatment.During these processes,intermetallic compounds have been formed at the interface of Cu/Al and have affected its bonding property.Microstructures of Cu/Al interfaces were observed by OM,SEM and EDX Analyser in order to investigate the bonding properties of the material.According to the microstructure a series of diffusion layers were observed at the interface and the thicknesses of diffusion layers have increased with aging time as a result of the diffusion bonding.The interfaces were composed of 3-ply diffusion layers and their compositions were changed with aging time at 400 °C.These compositional compounds were revealed to be η2,(θ+η2),(α+θ) intermetallic phases.It is evident from V-notch impact tests that the growth of the brittle diffusion layers with the increasing aging time directly influenced delamination distance between the Cu sleeve and the Al core.It is suggested that the proper holding time at 400 °C for aging as post heat treatment of a drawn Cu/Al bar clad material would be within 1 h.

Preparation of TiAlN/ZrN and TiCrN/ZrN multilayers by RF magnetron sputtering

Titanium-based nitride coatings on cutting tools,press molds and dies can be used to prolong their life cycle because of their superior corrosion and oxidation resistance.TiAlN/ZrN and TiCrN/ZrN multilayer coatings were prepared by RF magnetron sputtering,and their microstructural evolution and corrosion resistance during heat treatment were investigated.The TiAlN/ZrN and TiCrN/ZrN multilayer coatings are degraded by heating up to 600 ℃ with the formation of oxides particles on the surface.During the heat treatment,the TiCrN/ZrN and TiAlN/ZrN multilayer coatings show the lowest corrosion current density and the highest polarization resistance at temperature range of 400-500 ℃.Consequently,the TiAlN/ZrN and TiCrN/ZrN multilayer coatings show good corrosion resistance at temperature range of 400-500 ℃ during heating.

Addition of cerium and yttrium to ferritic steel weld metal to improve hydrogen trapping efficiency

The applicability of Ce and Y as promising candidate elements to form irreversible traps in weld metal was investigated by thermal desorption spectroscopy(TDS) with gas chromatography(GC). The precise nature of the precipitate particles newly formed in the weld metal by the addition of Ce and Y to a certain alloy system was characterized. Moreover,the hydrogen trapping efficiency expressed as the reduction of the diffusible hydrogen in the weld metal was analyzed. The results showed that the addition of Ce and/or Y to this alloy system led to the formation of a mixed type of(Ce,Ti)-based oxide,(Y,Ni)-based carbide,or(Ce,Y,Ti)-based oxide particles. Because of the high activation energy of the mixed type of particles(≥ 150 k J/mol),the trapping efficiency for hydrogen was considered to be sufficiently high to effectively reduce the diffusible hydrogen content.

Behavior of CaO and Calcium in pure Magnesium

Mg alloys exhibit a number of good properties such as low density, good castability and high specific strength. However, molten Mg and Mg alloys are ignited without the melt protective gases during melting and casting process due to their high reactivity. The purpose of this study is to investigate effects of Ca and CaO on pure Mg through microstructure observation, ignition test and phase analysis. With increasing Ca and CaO contents, the ignition resistance of Ca or CaO added pure Mg is increased and the grains are refined. As results of XRD and EDS, CaO is reduced to Ca in CaO added pure Mg. Mg2Ca phase is formed even in 0.1 wt.%CaO added pure Mg by reduction mechanism, while Mg2Ca phase is formed over 1.35 wt.% Ca added pure Mg.

Reactive wetting phenomena of MgO-C refractories in contact with CaO-SiO_2 slag

Wetting phenomena between MgO C and CaO SiO2 slags were investigated by varying carbon content.A sessile drop technique was adopted to study the wetting phenomena in conjunction with a high speed camera for the observation of intrinsic wetting phenomena.The results show that the high content of SiO2 and the presence of Al2O3 in slags enhance the diffusion of Mg2+,leading to the promotion of reactive wetting.The carbon in MgO C refractory impedes the penetration of slags by repelling the slag and slowing the diffusion of Mg2+.This accounts for the non-wetting behavior of the slag on MgO C refractory with 17% (mass fraction) carbon similar to that of graphite.

Effect of grain refinement on phase transformation behavior and mechanical properties of Cu-based alloy

A small amount of misch metal was added to Cu-Zn-Al alloy in order to study its effect on grain refinement,mechanical properties,phase transformation behavior and stabilization of martensite.It is found that the addition of misch metal is very effective for reducing the grain size.The coarse grains over 1 000 μm are refined to the size of 30 μm by the addition of 0.43%(mass fraction) misch metal.The grain size of thermo-mechanically treated alloys is barely affected by cold working.The fracture strength and ductility increase significantly with the increase of misch metal content when tensile test is carried out below Mf temperature.Also,the fracture strength is larger in the case of post-quench ageing treatment than that in the case of direct quench ageing treatment.The fracture mode is changed from transgranular brittle fracture to ductile fracture with void formation and coalescence by the addition of misch metal.

Microstructures and Mechanical Properties of Rapidly Solidified Mg-Al-Zn-MM Alloys

Mg-Al-Zn-M M （misch metal） alloy powders were manufactured by inert gas atomization and the characteristics of alloy powders were investigated.In spite of the low fluidity and easy oxidation of the magnesium melt,the spherical powder was made successfully with the improved three piece nozzle systems of gas atomization unit. It was found that most of the solidified powders with particles size of less than 50μm in diameter were single crystal and the solidification structure of rapidly solidified powders showed a typical dendritic morphology because of supercooling prior to nucleation.The spacing of secondary denrite arms was deceasing as the size of powders was decreasing.The rapidly solidified powders were consolidated by vacuum hot extrusion and the effects of misch metal addition to AZ91 on mechanical properties of extruded bars were also examined.During extrusion of the rapidly solidified powders,their dendritic structure was broken into fragments and remained as grains of about 3μm in size.The Mg-Al-Ce intermetallic compounds formed in the interdendritic regions of powders were finely broken,too.The tensile strength and ductility obtained in as-extruded Mg-9 wt pct Al-1 wt pct Zn-3 wt pct MM alloy wereσ-（T.S.） =383 MPa andε=10.6%,respectively.All of these improvements on mechanical properties were resulted from the refined microstructure and second-phase dispersions.

Effect of CaO addition on ignition behavior in molten AZ31 and AZ91D Magnesium alloys

Mg alloys have been widely used in automobile and electronic industries because of high specific strength, good castability, etc. However, molten Mg alloys will burn rapidly in air if not protected. To solve this problem, the molten metal should be protected from oxidation by blanketing the surface with flux or protective gases. SF6 gas is widely used for Mg alloys as a cover gas and has proved to be a successful inhibitor. However, the use of SF6 gas is limited because of its high cost and its significant impact on non-global warming potential. Therefore, SF6 gas is being replaced by alternative protection gases. Recent studies show that there has been another attempt by adding CaO into Mg alloys. The aim of this study is to evaluate the effect of CaO on the minimum amount of protective gas, which is necessary not to make ignition in the molten AZ31 and AZ91 Mg alloys.

Room-temperature sputtered electrocatalyst WSe2 nanomaterials for hydrogen evolution reaction

The low-temperature physical vapor deposition process of atomically thin two-dimensional transition metal dichalcogenide(2D TMD) has been gaining attention owing to the cost-effective production of diverse electrochemical catalysts for hydrogen evolution reaction(HER) applications. We, herein, propose a simple route toward the cost-effective physical vapor deposition process of 2D WSe2 layered nanofilms as HER electrochemical catalysts using RF magnetron sputtering at room temperature(<27℃). By controlling the variable sputtering parameters, such as RF power and deposition time, the loading amount and electrochemical surface area(ECSA) of WSe2 films deposited on carbon paper can be carefully determined. The surface of the sputtered WSe2 films are partially oxidized, which may cause spherical-shaped particles. Regardless of the loading amount of WSe2, Tafel slopes of WSe2 electrodes in the HER test are narrowly distributed to be ~120–138 mV dec-1, which indicates the excellent reproducibility of intrinsic catalytic activity. By considering the trade-off between the loading amount and ECSA, the best HER performance is clearly observed in the 200 W-15 min sample with an overpotential of 220 mV at a current density of 10 mA cm-2. Such a simple sputtering method at low temperature can be easily expanded to other 2D TMD electrochemical catalysts, promising potentially practical electrocatalysts.

Oxidation resistance of Si-coated TZM alloy prepared through combined process of plasma spray and laser surface melting

Plasma thermal spraying ofSi coating layer ontitanium-zirconium-molybdenum （Ti-Zr-Mo）,TZM alloy,was conducted for the surface protection of the Mo substrate that is unstable in air at high temperatures. Although the plasma thermal spraying alone could protect the Mo alloy from oxidation at a high temperature for a short time, the post laser surface melting process further improved the oxidation resistance of Si-coated alloy. In the case of the post laser treated specimen,MoSi compounds, mainly MoSi2 phases, were formed during the additional annealing process, and the oxidation resistance could be even further enhanced. The corrosion behaviors of Si-coated specimens in 3.5%NaCl solution were also investigated;however,nosignificant variations with respect to the post treatment procedure were found.

Plasma Post Oxidation of Plasma Nitrocarburized SKD 61 Steel

Plasma nitrocarburizing and plasma oxidizing treatments were performed to improve the wear and corrosion resistance of SKD 61 steel.Plasma nitrocarburizing was conducted for 12 h at 540℃in the nitrogen, hydrogen and methane atmosphere to produce theε-Fe-（2-3）（N,C） phase.The compound layer produced by plasma nitrocarburising was predominantly composed ofε-phase,with a small proportion ofγ′-Fe-4 （N,C） phase. The thickness of the compound layer and the diffusion layer are about 10μm and about 200μm,respectively. Plasma post oxidation was performed on the nitrocarburized samples with various oxygen/hydrogen ratio at constant temperature of 500℃for 1 h.The very thin magnetite （Fe-3O-4） layer of 1-2μm in thickness on top of the compound layer was obtained.Anodic polarization test revealed that plasma nitrocarburizing process contributed a significant improvement of corrosion resistance of SKD 61 steel.However,the corrosion characteristics of the nitrocarburized compound layer was deteriorated by oxidation treatment.

Effect of knurling shoulder design with polygonal pins on material flow and mechanical properties during friction stir welding of Al-Mg-Si alloy

Understanding the material flow facilitated by tool geometry in friction stir welds is challenging for quality weld production in industrial applications.The optimal tool shoulder and pin design combination,which plays a vital role in material flow was addressed.The flow of plasticized material was analyzed using a marker insert technique.The results show that the knurling shoulder design with square and hexagonal pin design facilitated constant stability force with reference to weld length/time.The uniform mixing and distribution of plasticized material were facilitated by the knurling shoulder design with square tool pin shape(TK)S(sticking length minimum)below which fragmented copper was observed.(TK)S tool facilitated higher mechanical properties for the welds,i.e.strength(182 MPa)and hardness(HV 78)in stir zone.

Evaluation of Alpha-case in Titanium Castings

The alpha-case formation reactions between Ti and investment molds （Al-2O-3,ZrSiO-4,ZrO-2,CaO stabilized ZrO-2） were evaluated in a plasma arc melting furnace.Regardless of thermodynamic approaches,there were distinct alpha-case formations.The reaction products were characterized by electron probe micro-analysis and transmission electron microscopy.Theα-case generation between Ti and Al-2O-3 mold was not able to be explained by the conventionalα-case formation mechanism,which is known to be formed by the interstitials,especially oxygen dissolved from mold materials.However,from our experimental results and thermodynamic calculations,it was confirmed that theα-case is formed not only by an interstitial element but also by substitutional metallic elements dissolved from mold materials.Our newly establishedα-case formation mechanism will surely lead to a variety of significant applications of theα-case controlled Ti casting.

Improving the corrosion properties of magnesium AZ31 alloy GTA weld metal using microarc oxidation process

In this work, the morphology, phase composition, and corrosion properties of microarc oxidized (MAO) gas tungsten arc (GTA) weldments of AZ31 alloy were investigated. Autogenous gas tungsten arc welds were made as full penetration bead-on-plate welding under the alternating-current mode. A uniform oxide layer was developed on the surface of the specimens with MAO treatment in silicate-based alkaline electrolytes for different oxidation times. The corrosion behavior of the samples was evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy. The oxide film improved the corrosion resistance substantially compared to the uncoated specimens. The sample coated for 10 min exhibited better corrosion properties. The corrosion resistance of the coatings was concluded to strongly depend on the morphology, whereas the phase composition and thickness were concluded to only slightly affect the corrosion resistance.

Preparation of Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_2 powders for cathode material in secondary battery by solid-state method

Employing Li2CO3, NiO, Co3O4, and MnCO3 powders as starting materials, Li[Ni1/3Co1/3Mn1/3]O2 was synthesized by solid-state reaction method. Various grinding aids were applied during milling in order to optimize the synthesis process. After successive heat treatments at 650 and 950 ℃, the prepared powders were characterized by X-ray diffraction (XRD) analysis, scanning electron microscopy, and transmission electron microscopy. The powders prepared by adding salt (NaCl) as grinding aid exhibit a clear R3m layer structure. The powders by other grinding aids like heptane show some impurity peaks in the XRD pattern. The former powders show a uniform particle size distribution of less than 1 μm average size while the latter shows a wide distribution ranging from 1 to 10 μm. Energy dispersive X-ray (EDX) analysiss show that the ratio of Ni, Co, and Mn content in the powder is approximately 1/3, 1/3, and 1/3, respecively. The EDX data indicate no incorporation of sodium or chlorine into the powders. Charge-discharge tests gave an initial discharge capacity of 160 mAh·g-1 for the powders with NaCl addition while 70 mAh·g-1 for the powders with heptane.

Effect of aging treatment on irradiation-induced segregation of high Mn-Cr steel

To investigate the effect of aging treatment on irradiation-induced segregation of high Mn-Cr steel, specimens for electron-beam irradiation were prepared from the high Mn-Cr austenitic steel which was solution treated at 1 373 K for 1 h and aging treated at 573 K for 1 000 h, respectively. The electron-beam irradiation was performed at 573 K up to doses of 5.4 dpa in a 1 250 kV HVEM and irradiation-induced segregation analyses were carried out by an EDX in a 200 kV FE-TEM. The results show that void formation is not observed in both solution treated and aging treated ones. The amount of Cr segregation at the grain boundary decreases in the aged one; however, that of Mn is not changed in solution treated one.