Coupling of ultrasmall and small CoxP nanoparticles confined in porous SiO2 matrix for a robust oxygen evolution reaction

Rational design of electrocatalysts is important for a sustainable oxygen evolution reaction(OER).It is still a huge challenge to engineer active sites in multi-sizes and multi-components simultaneously.Here,a series of CoxP nanoparticles(NPs)confined in an SiO2matrix(SiO2/CoxP)is designed and synthesized as OER electrocatalysts.The phosphorization of the hydrolyzed Co-phyllosilicate promotes the formation of ultrasmall and small Co2P and CoP.These are firmly confined in the SiO2matrix.The coupling of multi-size and multi-component CoxP catalysts can regulate reaction kinetics and electron transfer ability,enrich the active sites,and eventually promote the intrinsic OER activity.The SiO2matrix provides abundant porous structure and oxygen vacancies,and these facilitate the exposure of active sites and improve conductivity.Because of the synergy and interplay of multisized/component CoxP NPs and the porous SiO2matrix,the unique SiO2/CoxP heterostructure exhibits low overpotential(293 m V@10 mA cm-2),and robust stability(decay 12 mV after 5000 CV cycles,97.4%of initial current after 100 h chronoamperometric)for the OER process,exceeding many advanced metal phosphide electrocatalysts.This work provides a novel tactic to design low-cost,simple,and highly efficient OER electrocatalysts.

电弧离子镀脉冲电磁频率对CrAlN涂层结构、耐磨和抗冲蚀性的影响

本文利用可控脉冲电磁与永磁体的复合磁场阴极电弧离子镀,在TC11钛合金上制备了氮化铬铝(CrAlN)涂层。采用扫描电子显微镜(SEM)、X射线衍射仪(XRD)和纳米压痕仪研究了电磁频率对涂层形貌、微观结构、纳米硬度和弹性模量的影响。通过摩擦磨损和固体颗粒冲蚀试验,研究了在各种电磁频率下制备的CrAlN涂层对耐磨性和抗冲蚀性的影响。发现随着电磁频率的增加,CrAlN涂层的沉积速率加快。在16.7 Hz时,涂层硬度最高为23.6 GPa,结合力最高为41.5 N。此外,在16.7 Hz和33.3 Hz时沉积的涂层表现出良好的耐磨性和抗固体侵蚀性,摩擦因数约为0.35,在30°下的冲蚀速率约为0.2μm/g,在90°下的冲蚀速率小于1μm/g。这些结果表明,以适当的脉冲电磁频率制备的CrAlN涂层可以获得优异的力学性能,耐磨性和抗固体冲蚀性能。

Mechanism of vertical crack formation in Yb_(2)SiO_(5) coatings deposited via plasma spray-physical vapor deposition

Plasma spray-physical vapor deposition(i.e.,PS-PVD)is a promising method for obtaining advanced environmental barrier coatings(EBCs).The EBCs must meet some requirements in the application,in which the thermal cycle performance affects the service lifetime.The preparation of artificial vertical cracks in Yb_(2)SiO_(5) coatings is an effective approach for meeting the requirements above because vertical cracks provide a strain tolerance.To clarify the formation mechanism of vertical cracks during the PSPVD,the effects of coating thickness and substrate temperature on the formation of vertical cracks were investigated.In addition,the interactions of spray powder and plasma flame during coating deposition were also characterized by optical spectroscopy.It is indicated that vertical cracks are formed due to a thermal expansion mismatch between Yb_(2)SiO_(5) and mullite coating,transient cooling after deposition and the nucleation of evaporated Yb_(2)SiO_(5) as well.

Progress in ceramic materials and structure design toward advanced thermal barrier coatings

Thermal barrier coatings(TBCs)can effectively protect the alloy substrate of hot components in aeroengines or land-based gas turbines by the thermal insulation and corrosion/erosion resistance of the ceramic top coat.However,the continuous pursuit of a higher operating temperature leads to degradation,delamination,and premature failure of the top coat.Both new ceramic materials and new coating structures must be developed to meet the demand for future advanced TBC systems.In this paper,the latest progress of some new ceramic materials is first reviewed.Then,a comprehensive spalling mechanism of the ceramic top coat is summarized to understand the dependence of lifetime on various factors such as oxidation scale growth,ceramic sintering,erosion,and calcium–magnesium–aluminium–silicate(CMAS)molten salt corrosion.Finally,new structural design methods for high-performance TBCs are discussed from the perspectives of lamellar,columnar,and nanostructure inclusions.The latest developments of ceramic top coat will be presented in terms of material selection,structural design,and failure mechanism,and the comprehensive guidance will be provided for the development of next-generation advanced TBCs with higher temperature resistance,better thermal insulation,and longer lifetime.

Pressure infiltration of molten aluminum for densification of environmental barrier coatings

Environmental barrier coatings(EBCs)effectively protect the ceramic matrix composites(CMCs)from harsh engine environments,especially steam and molten salts.However,open pores inevitably formed during the deposition process provide the transport channels for oxidants and corrosives,and lead to premature failure of EBCs.This research work proposed a method of pressure infiltration densification which blocked these open pores in the coatings.These results showed that it was difficult for aluminum to infiltrate spontaneously,but with the increase of external gas pressure and internal vacuum simultaneously,the molten aluminum obviously moved forward,and finally stopped infiltrating at a depth of a specific geometry.Based on the wrinkled zigzag pore model,a mathematical relationship between the critical pressure with the infiltration depth and the pore intrinsic geometry was established.The infiltration results confirmed this relationship,indicating that for a given coating,a dense thick film can be obtained by adjusting the internal and external gas pressures to drive a melt infiltration.

Finished surface morphology, microstructure and magnetic properties of selective laser melted Fe-50wt% Ni permalloy

This work focuses on the structure and magnetic properties of Fe-50wt% Ni permalloy manufactured from the pre-alloyed powder by selective laser melting (SLM). The selective laser melted (SLMed) alloys were characterized by a 3D profilometer,optical microscope, scanning electron microscope, X-ray diffraction, etc. The effects of the volume energy density of laser(LVED) on structure, and magnetic properties with coercivity ( H), remanence ( B), and power losses ( P), were evaluated and discussed systematically. The results show that the relative porosity rate and the surface roughness of the SLMed specimens decreased with the increase in LVED. Only the γ-(FeNi) phase was detected in the X-ray diffraction patterns of the SLMed permalloys fabricated from the different LVEDs. Statistical analysis of optical microscopy images indicated that the grain coarsened at higher LVED. Furthermore, the microstructure of the SLMed parts was a typical columnar structure with an oriented growth of building direction. The highest microhardness reached 198 HV. Besides, the magnetic properties including B, H, and Pof SLMed samples decreased when the LVED ranged from 33.3 to 60.0 J/mm ~3 firstly and then increased while LVED further up to 93.3 J/mm, which is related to the decrease in porosity and the increase in grain size, while the higher residual stress and microcracks presented in the samples manufactured using very high LVED. The observed evolution of magnetic properties and LVED provides a good compromise in terms of reduced porosity and crack formation for the fabrication of SLMed Fe-50 wt% Ni permalloy. The theoretical mechanism in this study can offer guidance to further investigate SLMed soft magnetic alloys.

Selective laser melting(SLM)of CX stainless steel:Theoretical calculation,process optimization and strengthening mechanism

In the present work,selective laser melting(SLM)technology was utilized for manufacturing CX stainless steel samples under a series of laser parameters.The effect of laser linear energy density on the microstructure characteristics,phase distribution,crystallographic orientation and mechanical properties of these CX stainless steel samples were investigated theoretically and experimentally via scanning electron microscope(SEM),X-ray diffraction(XRD),electron backscatter diffraction(EBSD)and transmission electron microscope(TEM).Based on the systematic study,the SLM CX stainless steel sample with best surface roughness(Ra=4.05±1.8μm)and relative density(Rd=99.72%±0.22%)under the optimal linear density(η=245 J/m)can be obtained.SLM CX stainless steel was primarily constituted by a large number of fine martensite(α’phase)structures(i.e.,cell structures,cellular dendrites and blocky grains)and a small quantity of austenite(γphase)structures.The pre ferred crystallographic orientation(i.e.,<111>direction)can be determined in the XZ plane of the SLM CX sample.Furthermore,under the optimal linear energy density,the good combinations with the highest ultimate tensile strength(UTS=1068.0%±5.9%)and the best total elongation(TE=15.70%±0.26%)of the SLM CX sample can be attained.Dislocation strengthening dominates the strengthening mechanism of the SLM CX sample in as-built state.

7YSZ coating prepared by PS-PVD based on heterogeneous nucleation

Plasma spray-physical vapor deposition（PS-PVD） as a novel coating process based on low-pressure plasma spray（LPPS） has been significantly used for thermal barrier coatings（TBCs）.A coating can be deposited from liquid splats, nano-sized clusters, and the vapor phase forming different structured coatings, which shows obvious advantages in contrast to conventional technologies like atmospheric plasma spray（APS） and electron beam-physical vapor deposition（EBPVD）. In addition, it can be used to produce thin, dense, and porous ceramic coatings for special applications because of its special characteristics, such as high power, very low pressure, etc. These provide new opportunities to obtain different advanced microstructures, thus to meet the growing requirements of modern functional coatings. In this work, focusing on exploiting the potential of gas-phase deposition from PS-PVD, a series of 7 YSZ coating experiments with various process conditions was performed in order to better understand the deposition process in PS-PVD, where coatings were deposited on different substrates including graphite and zirconia. Meanwhile, various substrate temperatures were investigated for the same substrate. As a result, a deposition mechanism of heterogeneous nucleation has been presented showing that surface energy is an important influencing factor for coating structures. Besides, undercooling of the interface between substrate and vapor phase plays an important role in coating structures.

Coating deposition regularity depended on orientation difference in PS-PVD plasma jet

The YSZ coatings are prepared by the plasma spray-physical vapor deposition(PS-PVD)technology based on a specific experimental design.The structure,thickness and growth angle of YSZ coatings on the entire circumferential surface of the cylindrical sample are studied.The results indicated that the structure,thickness and deflection growth angle of YSZ coatings are related to the orientation of deposition location.The numerical simulation of the multiphase mixed fluid near the substrate is carried out and the deposition regularity and mechanism of YSZ coatings prepared by PS-PVD is deduced.The growth rate is related to the local characteristics of the plasma flow field,and is directly proportional to the field pressure and inversely proportional to the field velocity.The growth angle of the coating is generally affected by the flow direction of the plasma jet.Especially,the normal component of velocity vector,V_(norm),mainly affects the speed at which the coating grows vertically upwards.The tangential component of velocity vector,V_(tan),determines the degree that the coating growth direction deviates from the vertical direction.When V_(tan)≠0,the coating forms a fine column with a certain deflection angle and finally develops into an oblique columnar structure.

Additive manufacturing of steel–copper functionally graded material with ultrahigh bonding strength

Additive manufacturing enables processing of functionally graded materials(FGMs)with flexible spatial design and high bonding strength.A steel-copper FGM with high interfacial strength was developed using laser powder bed fusion(LPBF).The effect of laser process parameters on interfacial defects was evaluated by X-ray tomography,which indicates a low porosity level of 0.042%therein.Gradient/fine dendritic grains in the interface are incited by high cooling rates,which facilitates interface strengthening.Multiple mechanical tests evaluate the bonding reliability of interface;and the fatigue tests further substantiate the ultrahigh bonding strength in FGMs,which is superior to traditional manufacturing methods.Mechanisms of the high interfacial bond strength were also discussed.

High-temperature oxidation behavior and analysis of impedance spectroscopy of 7YSZ thermal barrier coating prepared by plasma spray-physical vapor deposition

Quasi-columnar structure 7YSZ（yttria stabilized zirconia） thermal barrier coatings（TBCs） are prepared by plasma spray-physical vapor deposition（PS-PVD） onto pretreated and un-pretreated bond coating, respectively. An isothermal oxidation experiment of 7YSZ TBCs is carried out in the atmosphere of 950 °C in order to simulate the high-temperature oxidation process of engine blades. The isothermal oxidation process of 7YSZ thermal barrier coatings is investigated systematically by impedance spectroscopy. The electrochemical physical model and equivalent circuit of columnar 7YSZ coatings are established. Results show that the isothermal oxidation kinetic curve of columnar 7YSZ thermal barrier coatings appears to follow the parabolic law. A pretreatment of bond coating can reduce the growth rate of the thermally grown oxide（TGO） layer, restraining the initiation and propagation of microcracks between YSZ and TGO layers. The oxidation rate constants of 7YSZ coatings with pretreated and un-pretreated bond coating are 0.101×10^（-12） cm^2·s^（-1） and 0.115 × 10^（-13） cm^2 ·s^（-1）, respectively. Impedance analysis shows that the content of oxygen vacancies decreases and the density increases after the TGO layer is oxidized for 150 h. In addition, shrinkage microcracks formed by sintering during the oxidation process is the main reason for an increase of the capacitance and a decrease of the resistance in the grain boundary of YSZ.

Cold spray additive manufacturing of Invar 36 alloy:microstructure,thermal expansion and mechanical properties

In this work,the Invar 36 alloys were manufactured using cold spray(CS)additive manufacturing technique.The systematic investigations were made on the microstructural evolution,thermal expansion and mechanical properties under as-sprayed(AS)and heat-treated(HT)conditions.XRD(X-ray diffraction)and ICP-AES(inductively coupled plasma atomic emission spectroscopy)analyses show that no phase transformation,oxidation,nor element content change have occurred.The X-ray computed tomography(XCT)exhibited a near fully dense structure with a porosity of 0.025%in the helium-produced sample under as-sprayed condition,whereas the nitrogen-produced samples produced at 5 MPa and 800℃show more irregular pore defects.He-AS sample shows a more prominent grain refinement than that of nitrogen samples due to the more extensive plastic deformation.The post heat-treatment exhibited a promoted grain growth,inter-particle diffusion,as well as the formation of annealing twins.Between25℃and 200℃,the nitrogen samples possessed lower CTE(coefficient of thermal expansion)values(1.53×10^(-6)/℃)compared with those produced by casting and laser additive manufacturing.The He-AS samples exhibited a noticeable negative CTE value between 25℃and 200℃,which may due to the significant compressive residual stress(-272 MPa)compensating its displacement with temperature increase during CTE test.The N2-HT and He-HT Invar 36 samples present a notable balance between strength and ductility.In conclusion,the CS technique can be considered as a potential method to produce the Invar36 component with high thermal and mechanical performance.

Effect of Bionic Unit Shapes on Solid Particle Erosion Resistance of ZrO2-7wt%Y2O3 Thermal Barrier Coatings Processed by Laser

Inspired by the coupling phenomena in biological systems, to improve the solid particle erosion resistance of Thermal Barrier Coatings （TBCs）, different kinds of bionic units were made on the coating surfaces using Bionic Coupled Laser Remelting （BCLR） process. The NiCoCrAlYTa/ZrO2-7wt%Y2O3 double-layer structured TBCs were prepared by air plasma spraying. The microstructure, microhardness and phase composition of the as-sprayed and bionic specimens were examined. The solid particle erosion behaviors of bionic specimens as function of bionic unit shape were investigated. The results indicated that the bionic specimens had better erosion resistance than the as-sprayed specimen. The specimen with striation and grid bionic units had the better erosion resistance, while the dot showed the worse. The bionic units were characterized by the dense columnar crystal structure and the high hardness, which are the main reasons for improving the erosion resistance. Under the synergistic action of the shear stress and normal stress on the protrusive coating surface, the erosion failure of the as-sprayed TBCs was proved to be the fracture and spallation of the splats. By contrast, the spallation of segmented bionic unit occurred in the overlapping area between the adjacent laser irradiation, and the erosive unit surface presented the clear and deep furrows, which revealed that the erosion failure mechanism of bionic TBCs was dominated by brittle and some ductile erosion. These results showed more opportunities for bionic application in improving the solid particle erosion resistance of components in the windy and sandy environment.

A comparison between novel Gd_(2)Zr_(2)O_(7)and Gd_(2)Zr_(2)O_(7)/YSZ thermal barrier coatings fabricated by plasma spray-physical vapor deposition

Spherical Gd_(2)Zr_(2)O_(7)hollow powders with a mean size of 8.8μm were fabricated as feedstock for thermal barrier coatings(TBCs)by spray-drying.The single-ceramic-layer(SCL)Gd_(2)Zr_(2)O_(7)TBCs and double-ceramic-layer(DCL)Gd_(2)Zr_(2)O_(7)/YSZ TBCs with quasicolumnar structure were successfully fabricated by plasma spray-physical vapor deposition(PS-PVD).Tensile and water-quenching tests were applied to evaluate TBCs performances.The results show that adhesion strength of SCL Gd_(2)Zr_(2)O_(7)TBCs and DCL Gd_(2)Zr_(2)O_(7)/YSZ TBCs is36.5 MPa and 15.4 MPa,respectively.The delamination of SCL Gd_(2)Zr_(2)O_(7)TBCs and DCL Gd_(2)Zr_(2)O_(7)/YSZ TBCs in the tensile test takes place at the middle and bottom of Gd_(2)Zr_(2)O_(7)layer,respectively,due to relatively lower fracture toughness of Gd_(2)Zr_(2)O_(7)layer.After 40 cycles of water-quenching test,DCL Gd_(2)Zr_(2)O_(7)/YSZ TBC surface keeps relatively intact,while SCL Gd_(2)Zr_(2)O_(7)TBC surface shows 20%visible destroyed regions,which demonstrates that DCL Gd_(2)Zr_(2)O_(7)/YSZ TBCs have a better thermal shock resistance than SCL Gd_(2)Zr_(2)O_(7)TBCs.The cracks in the SCL system propagate near thermally grown oxide(TGO)due to thermal mismatch and TGO growing stress,while cracks in the DCL system propagate in the Gd_(2)Zr_(2)O_(7)layer due to its relatively lower fracture toughness.

A novel laser shock post-processing technique on the laser-induced damage resistance of 1ωHfO_(2)/SiO_(2)

The laser shock processing implemented by a laser-induced high-pressure plasma which propagates into the sample as a shockwave is innovatively applied as a post-processing technique on HfO_(2)/SiO_(2) multilayer coatings for the first time.The pure mechanical post-processing has provided evidence of a considerable promotion effect of the laser-induced damage threshold,which increased by a factor of about 4.6 with appropriate processing parameters.The promotion mechanism is confirmed to be the comprehensive modification of the intrinsic defects and the mechanical properties,which made the applicability of this novel post-processing technique on various types of coatings possible.Based on experiments,an interaction equation for the plasma pressure is established,which clarifies the existence of the critical pressure and provides a theoretical basis for selecting optimal processing parameters.In addition to the further clarification of the underlying damage mechanism,the laser shock post-processing provides a promising technique to realize the comprehensive and effective improvement of the laser-induced damage resistance of coatings.

Structural evolution of plasma sprayed amorphous Li_(4)Ti_(5)O_(12) electrode and ceramic/polymer composite electrolyte during electrochemical cycle of quasi-solid-state lithium battery

A quasi-solid-state lithium battery is assembled by plasma sprayed amorphous Li_(4)Ti_(5)O_(12) to provide the outstanding electrochemical stability and better normal interface contact.Scanning Electron Microscope(SEM),Scanning Transmission Electron Microscopy(STEM),Transmission Electron Microscopy(TEM),and Energy Dispersive Spectrometer(EDS)were used to analyze the structural evolution and performance of plasma sprayed amorphous LTO electrode and ceramic/polymer composite electrolyte before and after electrochemical experiments.By comparing the electrochemical performance of the amorphous LTO electrode and the traditional LTO electrode,the electrochemical behavior of different electrodes is studied.The results show that plasma spraying can prepare an amorphous LTO electrode coating of about 8μm.After 200 electrochemical cycles,the structure of the electrode evolved,and the inside of the electrode fractured and cracks expanded,because of recrystallization at the interface between the rich fluorine compounds and the amorphous LTO electrode.Similarly,the ceramic/polymer composite electrolyte has undergone structural evolution after 200 test cycles.The electrochemical cycle results show that the cycle stability,capacity retention rate,coulomb efficiency,and internal impedance of amorphous LTO electrode are better than traditional LTO electrode.This innovative and facile quasi-solid-state strategy is aimed to promote the intrinsic safety and stability of working lithium battery,shedding light on the development of next-generation high-performance solid-state lithium batteries.

Regional characteristic of 7YSZ coatings prepared by plasma spray-physical vapor deposition technique

7 YSZ coating was prepared by plasma sprayphysical vapor deposition(PS-PVD) technique based on a specific experimental design.The microstructure and deposition properties of 7 YSZ coating along the radius of plasma jet were investigated in detail.Results show that the coating presents regional characteristic in the radial direction,which could be divided into three typical zones:In Zone Ⅰ,the coating is all composed of columnar structures with cauliflower structure,and the coating properties including the surface roughness and deposition efficiency(DE) are almost stable;in Zone Ⅲ,the coating is made up of solid particles,droplet and gas phase mixed without columnar structures;Zone Ⅱ is between Zone Ⅰ and ZoneⅢ, in which there are columns with domed top and small particles.Based on experiment results,a model on the state and distribution of particles in plasma jet was proposed to clarify the regional characteristic.This study is helpful to comprehend and control coatings deposition by PS-PVD technique.

Variation of the band structure in DKDP crystal excited by intense sub-picosecond laser pulses

The nonlinear absorption(NLA) properties of potassium dideuterium phosphate crystals at 515 nm under different excitation laser intensities are investigated with the Z-scan technique. Two critical intensities are highlighted: the critical intensity for exciting the NLA and the critical intensity of the multiphoton absorption mechanism transition.Experimental results indicate the existence of defect states located in the band gap, which can be manipulated by varying laser intensity. A model based on the change of multiphoton absorption mechanism induced by the transformation of defect species is proposed to interpret the experiments. Modeling results are in good agreement with the experiment data.

Absorption modification by laser irradiation in DKDP crystals

Laser-induced modification at 355 nm of deuterated potassium dihydrogen phosphate（DKDP） crystals following exposure to nanosecond（ns） and sub-ns laser irradiation is investigated in order to probe the absorption mechanism in damage initiation. Laser damage resistance is greatly improved by sub-ns laser conditioning,whereas only a little improvement occurred after ns laser conditioning at the same laser fluence. Moreover, scattering and transmittance variations after the two types of laser conditioning indicate similar reduction of linear absorption. However, by contrast, large differences on nonlinear absorption modification are discovered using Z-scan measurement. This characteristic absorption modification by laser irradiation provides evidence that a nonlinear absorption mechanism plays a key role in damage initiation at 355 nm.

Towards high-strength cold spray additive manufactured metals:Methods,mechanisms,and properties

Cold spray,as a solid-state additive manufacturing process,has been attracting increasing attention from both scientific and industrial communities.However,cold-sprayed deposits generally have unfavorable mechanical properties in their as-fabricated state compared to conventionally manufactured and fusion-based additive-manufactured counterparts due to the inherent microstructural defects in the deposits(e.g.,porosity and incomplete interparticle bonding).This downside reduces its competitiveness and limits its wide applications as an additive manufacturing process.In the past years,many strengthening technologies have been developed or introduced to adjust the microstructure and improve the mechanical properties of cold-sprayed deposits.The term“strengthening”in this work specifically refers to improving the mechanical strength,particularly the tensile strength of the cold-sprayed bulk deposits.According to the stage that the strengthening technologies are used in the cold spray process,they can be classified into three categories:pre-process(e.g.,powder heat treatment),in-process(e.g.,powder heating,in-situ micro-forging,laser-assisted cold spray),and post-process(e.g.,post heat treatment,hot isostatic pressing,hot rolling,friction stir processing).Therefore,a comprehensive review of these strengthening technolo-gies is conducted to illuminate the possible correlations between the strengthening mechanisms and the resultant deposit microstructures and mechanical properties.This review paper aims to help researchers and engineers well understand the different strengthening methods and provide guidance for the cold spray community to develop new strengthening strategies for future high-quality mass production.