Chromium plays a vital role in stainless steel due to its ability to improve the corrosion resistance of the latter.However,the re-lease of chromium from stainless steel slag(SSS)during SSS stockpiling causes detrimen...Chromium plays a vital role in stainless steel due to its ability to improve the corrosion resistance of the latter.However,the re-lease of chromium from stainless steel slag(SSS)during SSS stockpiling causes detrimental environmental issues.To prevent chromium pollution,the effects of iron oxide on crystallization behavior and spatial distribution of spinel were investigated in this work.The results revealed that FeO was more conducive to the growth of spinels compared with Fe2O3 and Fe3O4.Spinels were found to be mainly distrib-uted at the top and bottom of slag.The amount of spinel phase at the bottom decreased with the increasing FeO content,while that at the top increased.The average particle size of spinel in the slag with 18wt%FeO content was 12.8μm.Meanwhile,no notable structural changes were observed with a further increase in FeO content.In other words,the spatial distribution of spinel changed when the content of iron oxide varied in the range of 8wt%to 18wt%.Finally,less spinel was found at the bottom of slag with a FeO content of 23wt%.展开更多
Urea holds promise as an alternative water-oxidation substrate in electrolytic cells.High-valence nickelbased spinel,especially after heteroatom doping,excels in urea oxidation reactions(UOR).However,traditional spine...Urea holds promise as an alternative water-oxidation substrate in electrolytic cells.High-valence nickelbased spinel,especially after heteroatom doping,excels in urea oxidation reactions(UOR).However,traditional spinel synthesis methods with prolonged high-temperature reactions lack kinetic precision,hindering the balance between controlled doping and highly active two-dimensional(2D)porous structures design.This significantly impedes the identification of electron configuration-dependent active sites in doped 2D nickel-based spinels.Herein,we present a microwave shock method for the preparation of 2D porous NiCo_(2)O_(4)spinel.Utilizing the transient on-off property of microwave pulses for precise heteroatom doping and 2D porous structural design,non-metal doping(boron,phosphorus,and sulfur)with distinct extranuclear electron disparities serves as straightforward examples for investigation.Precise tuning of lattice parameter reveals the impact of covalent bond strength on NiCo_(2)O_(4)structural stability.The introduced defect levels induce unpaired d-electrons in transition metals,enhancing the adsorption of electron-donating amino groups in urea molecules.Simultaneously,Bode plots confirm the impact mechanism of rapid electron migration caused by reduced band gaps on UOR activity.The prepared phosphorus-doped 2D porous NiCo_(2)O_(4),with optimal electron configuration control,outperforms most reported spinels.This controlled modification strategy advances understanding theoretical structure-activity mechanisms of high-performance 2D spinels in UOR.展开更多
Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catal...Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catalytic contribution of geometric Co site in the electrocatalytic CER plays a pivotal role to precisely modulate electronic configuration of active Co sites to boost CER.Herein,combining density functional theory calculations and experiment results assisted with operando analysis,we found that the Co_(Oh) site acts as the main active site for CER in spinel Co_(3)O_(4),which shows better Cl^(-)adsorption and more moderate intermediate adsorption toward CER than CoTd site,and does not undergo redox transition under CER condition at applied potentials.Guided by above findings,the oxygen vacancies were further introduced into the Co_(3)O_(4) to precisely manipulate the electronic configuration of Co_(Oh) to boost Cl^(-)adsorption and optimize the reaction path of CER and thus to enhance the intrinsic CER activity significantly.Our work figures out the importance of geometric configuration dependent CER activity,shedding light on the rational design of advanced electrocatalysts from geometric configuration optimization at the atomic level.展开更多
The structure of the yttrium modified Co-base alloy layers formed by laser cladding on 2Cr13 and 1Cr18Ni9Ti steel surfaces and its hot corrosion performance have been investigated systematically.The re- sults show tha...The structure of the yttrium modified Co-base alloy layers formed by laser cladding on 2Cr13 and 1Cr18Ni9Ti steel surfaces and its hot corrosion performance have been investigated systematically.The re- sults show that the Y-containing cobalt base clad alloy has a finer microstructure and higher corrosion re- sistance to the salt mixture of 75% Na_2SO_4+25%NaCl at high temperature.The unique properties are ob- tained with addition of 0.875% Y for the formation of a continuous and compact oxide scale.The compact scale may act as a barrier for the inward diffusion of oxygen and sulphur and also for the outward diffusion of alloying elements.展开更多
Fe-based and Co-based cladding layers were prepared on the surface of AISI H13 hot die steel by laser cladding technology.The microstructure,hardness and abrasion resistance of the two cladding layers were studied by ...Fe-based and Co-based cladding layers were prepared on the surface of AISI H13 hot die steel by laser cladding technology.The microstructure,hardness and abrasion resistance of the two cladding layers were studied by means of optical microscope,scanning electron microscope,rockwell hardness tester,and high temperature friction and wear tester.Also,the red hardness of the cladding layers was measured,after holding the layers at 600℃ for 1 hour by muffle furnace and repeated 4 times.The rockwell hardness values of the substrate,the Fe-based and the Co-based alloy coating measured were HRC 47,HRC 52 and HRC 48,respectively.The red hardness values of the substrate and the Fe-based cladding layer were decreased,while that of the Co-based cladding layer was increased.The Co-based cladding layer has the minimal wear loss weight and friction coefficient among them.The wear mechanisms of the substrate,the Fe-based layer and the Cobased layer attribute mainly to abrasive wear,adhesion wear,and both of them,respectively.展开更多
A thermal fatigue behaviour of Co-based alloy coating obtained by laser surface meltcasting on the high temperature alloy GH33 was studied.The results show that after each time of thermal cycling,the final residual st...A thermal fatigue behaviour of Co-based alloy coating obtained by laser surface meltcasting on the high temperature alloy GH33 was studied.The results show that after each time of thermal cycling,the final residual stress was formed in the melt-casting layer which is attributed to the thermal stress and structural stress.Through the first 50 times of thermal cycling,the morphology of coating still inherits the laser casting one,but the dendrites get bigger;After the second 50 times of thermal cycling,corrosion pits emerge from coating,and mostly in the places where coating and substrate meet.The fatigue damage type of coating belongs to stress corrosion.展开更多
The Co-based alloy coatings had been prepared by laser cladding and vacuum fusion sintering. Microstructures of the coatings were investigated and the performance of thermal cycling was also tested using scanning elec...The Co-based alloy coatings had been prepared by laser cladding and vacuum fusion sintering. Microstructures of the coatings were investigated and the performance of thermal cycling was also tested using scanning electron microscopy ( SEM) and X-ray diffraction ( XRD ). The results show that the coatings and substrates combine well. The main phase compositions of laser cladding coating are T-Co, Cr23 C6 and Ni2 9 Cro. 7 Feo. 36, while vacuum fusion sintering coating consists of Co, Cr7 C3, and Ni2.9 Cro. 7 Feo. 36. After thermal cycling, the minimum hot cracking width of laser cladding coating is 14 μm; moreover, laser cladding coating maintains high hardness and hot-cracking susceptibility. Those are beneficial to high temperature wear resistance of hot work dies.展开更多
Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),a 5 V class high voltage cathode,has been regarded as an attractive candidate to further improve the energy density of lithium-ion battery.The issue simultaneously enabling side st...Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),a 5 V class high voltage cathode,has been regarded as an attractive candidate to further improve the energy density of lithium-ion battery.The issue simultaneously enabling side stability and maintaining high interfacial kinetics,however,has not yet been resolved.Herein,we design a coherent Li_(1.3)A_(l0.3)Ti_(1.7)(PO)_(4)(LATP)layer that is crystally connected to the spinel LNMO host lattices,which offers fast lithium ions transportation as well as enhances the mechanical stability that prevents the particle fracture.Furthermore,the inactive Li_(3)BO_(3)(LBO)coating layer inhibits the corrosion of transition metals and continuous side reactions.Consequently,the coherent-engineered LNMO-LATPLBO cathode material exhibits superior electrochemical cycling stability in a window of 3.0–5.0 V,for example a high-capacity retention that is 89.7%after 500 cycles at 200 m A g-1obtained and enhanced rate performance(85.1 m A h g^(-1)at 800 m A g^(-1))when tested with a LiPF6-based carbonate electrolyte.Our work presents a new approach of engineering 5 V class spinel oxide cathode that combines interfacial coherent crystal lattice design and surface coating.展开更多
Augite-based glass ceramics were synthesised using ZnO,FeO,and Fe_(2)O_(3)as additives,and the spinel formation,matrix structure,crystallisation thermodynamics,and physicochemical properties were investigated.The resu...Augite-based glass ceramics were synthesised using ZnO,FeO,and Fe_(2)O_(3)as additives,and the spinel formation,matrix structure,crystallisation thermodynamics,and physicochemical properties were investigated.The results showed that oxides resulted in numerous preliminary spinels in the glass matrix.FeO,ZnO,and Fe_(2)O_(3)influenced the formation of spinel,while FeO simplified the glass network.FeO and ZnO promoted bulk crystallisation of the parent glass.After adding oxides,the grains of augite phase were refined,and the relative quantities of augite crystal planes were also influenced.All samples displayed good mechanical properties and chemical stability.The 2wt%ZnO-doping sample displayed the maximum flexural strength(170.3 MPa).Chromium leaching amount values of all the samples were less than the national standard(1.5 mg/L),confirming the safety of the materials.In conclusion,an appropriate amount of zinc-containing raw material is beneficial for the preparation of augite-based glass ceramics.展开更多
The oxidation behavior of a cast polycrystalline Co-base superalloy was studied at temperatures from 900 to 1050℃ and analyzed by thermogravimetric analysis (TGA), X-ray diffraction (XRD) and scanning electron mi...The oxidation behavior of a cast polycrystalline Co-base superalloy was studied at temperatures from 900 to 1050℃ and analyzed by thermogravimetric analysis (TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results indicate that a cast Co-base superalloy follows the subparabolic oxidation kinetics at 900 and 1000℃, which are controlled by the growth of the inner Cr-rich layer, and that after oxidation at 1050℃ for 200 h, it almost exhibits the linear oxidation kinetics possible due to the volatility of Cr-rich oxide. A mixed scale forms on the alloy after prolonged oxidation. The oxide scale formed at 900 and 1000℃ is composed of an outer layer of spinel and an inner continuous Cr-rich layer and at I050℃ is composed of a very discontinuous Cr-rich layer.展开更多
The effect of La element on the mechanical properties and constitution nearby grain boundary in a Co-base superalloy Co-22Ni-22Cr-14k during 760℃ ageing has been investigated by AES and material testing. Results show...The effect of La element on the mechanical properties and constitution nearby grain boundary in a Co-base superalloy Co-22Ni-22Cr-14k during 760℃ ageing has been investigated by AES and material testing. Results show that element La can be in a state of solid solution and segregates mainly at the vicinity of grain boundaries. The prior segregation of La atoms can affect segregation behaviour of other elements, so that exerts influence on microstructure of the alloy, Particularly increasing of La content can decrease P concentration at the vicinity of grain boundaries but not decrease S concentration. S together with La produce cosegregation effect. The content of La has no obvious effect on high temperature strength. When the content of La comes up to 0.02wt-%, it can obviously improve the high temperature ductility.展开更多
Two novel Co-based clusters with the 2-(hydroxylmethyl)pyridine(hmpH)ligand,formulated as[Co3(hmp)6(hmpH)]×2NO3×3H2O(ZTU-3)and[Co4(hmp)4(CH3CO2)2(H2O)4]×2NO3(ZTU-4),have been successfully synthesized an...Two novel Co-based clusters with the 2-(hydroxylmethyl)pyridine(hmpH)ligand,formulated as[Co3(hmp)6(hmpH)]×2NO3×3H2O(ZTU-3)and[Co4(hmp)4(CH3CO2)2(H2O)4]×2NO3(ZTU-4),have been successfully synthesized and structurally characterized.ZTU-3 features a triangular core geometry,while ZTU-4 exhibits a cuboidal core geometry.In addition,the magnetic properties of ZTU-3 and ZTU-4 are also all investigated.展开更多
Layered Co-based ceramics with a nominal composition Bi2-xLaxSr2Co2O8-δ (x=0.0, 0.4, 0.8, short by BLC-222) were prepared using conventional solid state reaction method. X-ray photoemission spectroscopy (XPS) was use...Layered Co-based ceramics with a nominal composition Bi2-xLaxSr2Co2O8-δ (x=0.0, 0.4, 0.8, short by BLC-222) were prepared using conventional solid state reaction method. X-ray photoemission spectroscopy (XPS) was used to investigate their electronic structures. The cobalt ions are highly mixed valences of Co3+ and Co4+. The fraction of Co4+ almost keeps unchanged with the increase of x. The O-1s photoemission spectra show that there are lattice oxygen and chemical absorbed oxygen in all the samples. The substitution of Bi3+ by La3+ results in a change from metallic-like behavior to semiconductor behavior. This abnormal phenomenon means that La3+ plays a key role in effecting the electrical transport property of BLC-222. The O-Co covalence bond is strengthened by the increase of La3+, which results in the decrease of conductivity.展开更多
The effect of trace element B on microstructure of directionally solidified new type Co-base superalloy is studied systematically in this paper. It is found that the addition of B makes the incipient melting temperatu...The effect of trace element B on microstructure of directionally solidified new type Co-base superalloy is studied systematically in this paper. It is found that the addition of B makes the incipient melting temperature of the alloy decline remarkably. Compared with the alloy having a boron content of 0.05 %, the incipient melting temperature of the alloy with 0.7 % B decreases by 197℃. The primary and secondary dendrite arm spacings increase and the volume fraction of interdendritic carbides with fine microstructure becomes bigger with the enhancement of boron content. When the alloy is with 0.7wt %B, M3B2 precipitates in the interdendrites.展开更多
We investigated the variation of permeability spectra and relaxation frequency in Co-based amorphous ribbon annealed by pulsed Nd:YAG laser at various annealing energy Ea. The complex permeability spectra varies sensi...We investigated the variation of permeability spectra and relaxation frequency in Co-based amorphous ribbon annealed by pulsed Nd:YAG laser at various annealing energy Ea. The complex permeability spectra varies sensitively with the annealing energy, where the spectra could be decomposed into two contributions from domain wall motion,μdw(f) and rotational magnetization μrot(f) by analyzing the measured spectra as a function of driving ac field amplitude. The magnitude of μdw(f) and μrot(f) in dc limit shows maximum at Ea = 176 mJ. The maximum relaxation frequency for rotational magnetization, determined by μ'(f) curve, is about 700 kHz at Ea=62 mJ but that for wall motion is about 26 kHz at 230 mJ. These variations reflect the increase of magnetic softness and microstructural change by the annealing.展开更多
Ammonium dinitramide(ADN)based liquid monopropellants have been identified as environmentally benign substitutes for hydrazine monopropellant.However,new catalysts are to be developed for making ADN monopropellants co...Ammonium dinitramide(ADN)based liquid monopropellants have been identified as environmentally benign substitutes for hydrazine monopropellant.However,new catalysts are to be developed for making ADN monopropellants cold-start capable.In the present study,performance of Co and Ba doped CuCr_2O_4 nanocatalysts prepared by hydrothermal method was evaluated on the decomposition of aqueous ADN solution and ADN liquid monopropellant(LMP103X).The catalysts were characterized by PXRD(Powder X-ray Diffraction),FTIR(Fourier Transform Infrared spectroscopy),SEM(Scanning Electron Microscopy),TEM(Transmission Electron Microscopy),EDS(Energy Dispersive X-ray Spectroscopy),and XPS(X-ray Photoelectron Spectroscopy).The nanosize was confirmed by SEM and TEM,while the nanoflake morphology was confirmed by the SEM analysis.Further,we obtained the elemental composition from the EDS analysis.We investigated the catalytic activity of the catalysts by thermogravimetric(TG)analysis and the developed catalysts lowered the decomposition temperature of ADN monopropellant by about 55℃.The XPS analysis confirmed the presence of metal ions with different chemical states.Apparently,increase in the surface area of the catalysts and the mixed active sites as well as the development of oxygen vacancy on the catalyst surface introduced by metal doping are influencing the decomposition temperature of ADN samples.展开更多
The poor structural stability and capacity retention of the high-voltage spinel-type LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)limits their further application.Herein,Al and Co were doped in LNMO materials for a more stable struct...The poor structural stability and capacity retention of the high-voltage spinel-type LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)limits their further application.Herein,Al and Co were doped in LNMO materials for a more stable structure and capacity.The LNMO,LiNi_(0.45)Al_(0.05)Mn_(1.5)O_(4)(LNAMO)and LiNi_(0.45)Co_(0.05)Mn_(1.5)O_(4)(LNCMO)were synthesized by calcination at 900℃ for 8 h,which was called as solid-phase method and applied universally in industry.XRD,FT-IR and CV test results showed the synthesized samples have cation disordering Fd-3m space group structures.Moreover,the incorporation of Al and Co increased the cation disordering of LNMO,thereby increasing the transfer rate of Li+.The SEM results showed that the doped samples performed more regular and ortho-octahedral.The EDS elemental analysis confirmed the uniform distribution of each metal element in the samples.Moreover,the doped samples showed better electrochemical properties than undoped LNMO.The LNAMO and LNCMO samples were discharged with specific capacities of 116.3 mA·h·g^(-1)and 122.8 mA·h·g^(-1)at 1 C charge/discharge rate with good capacity retention of 95.8% and 94.8% after 200 cycles at room temperature,respectively.The capacity fading phenomenon of the doped samples at 50℃ and 1 C rate was significantly improved.Further,cations doping also enhanced the rate performance,especially for the LNCMO,the discharge specific capacity of 117.9 mA·h·g^(-1)can be obtained at a rate of 5 C.展开更多
Unburned magnesium aluminate spinel refractories were prepared using sintered magnesium aluminate spinel as the main raw material,phenolic resin as the binder,aluminum powder(2%,4%,and 6%by mass)and silicon powder(whe...Unburned magnesium aluminate spinel refractories were prepared using sintered magnesium aluminate spinel as the main raw material,phenolic resin as the binder,aluminum powder(2%,4%,and 6%by mass)and silicon powder(when Al powder addition is 4%,Si powder addition varies:1%and 2%,by mass)as additives.The effects of the Al powder and Si powder additions on the properties and microstructure of the refractories heat treated at different temperatures(1000,1400,and 1600℃for 3 h)were studied.The results show that the Al powder addition can greatly enhance the cold modulus of rupture of the samples fired at 1000 or 1400℃,and meanwhile AlN reinforcement phase forms in the matrix,which greatly improves the hot modulus of rupture of the samples at 1400℃;however,the heat treatment at 1600℃has little influence on the strength;the addition of Al powder and Si powder results in the formation of low melting point phases,greatly reducing the hot modulus of rupture.However,the low melting point phases promote sintering,which enhances the density and the cold modulus of rupture,and decreases the volume change during heating.The samples added with Al and Si all have higher cold modulus of rupture than those added with Al powder only.展开更多
Detailed mineralogical and gemological records were conducted on 340 unheated spinels from the Horana, Eheliyagoda, Ratnapura, and Okkampatiya mining areas in Sri Lanka. The color of Sri Lankan spinel varies greatly: ...Detailed mineralogical and gemological records were conducted on 340 unheated spinels from the Horana, Eheliyagoda, Ratnapura, and Okkampatiya mining areas in Sri Lanka. The color of Sri Lankan spinel varies greatly: in addition to the mainstream pink to purple pink, green and blue can also be seen. Compared with spinel from other regions such as Myanmar, Vietnam, and Tanzania, Sri Lanka's spinel has more abundant inclusions: several mining areas generally have inclusions such as dolomite, apatite, zircon, and chondrodite. Minerals such as graphite and forsterite are also found in spinel produced in the Horana region;graphite and rutile have been found in spinel produced in the Okkamptiya region. Partially healed fissures are most common in spinel in the Okkampatiya mining area;Unlike Vietnamese spinel, dislocations and growth structures are almost absent in Sri Lankan spinel. The LA-ICP-MS analysis results showed that there were no significant differences among the mining areas. LA-ICP-MS analysis of 5 Sri Lankan cobalt blue spinels showed a variation of 11 to 120 ppm in this chromogenic element. The UV visible absorption spectrum results show that Sri Lankan spinel has a combination spectra with variable ratios of the spectral components Cr 3+ , V 3+ and Fe 2+ from pink to red, orange, purple to purple, and blue-green. The results of infrared spectroscopy and laser Raman spectroscopy analysis showed that all samples showed no indications for heat treatment.展开更多
基金the National Natural Science Foundation of China(Nos.52074078 and 52374327)the Applied Fundamental Research Program of Liaoning Province(No.2023JH2/101600002)+2 种基金the Shenyang Young Middle-Aged Scientific and Technological Innovation Talent Support Program(No.RC220491)the Liaoning Province Steel Industry-University-Research Innovation Alliance Cooperation Project of Bensteel Group(No.KJBLM202202)the Fundamental Research Funds for the Central Universities(Nos.N2201023 and N2325009).
文摘Chromium plays a vital role in stainless steel due to its ability to improve the corrosion resistance of the latter.However,the re-lease of chromium from stainless steel slag(SSS)during SSS stockpiling causes detrimental environmental issues.To prevent chromium pollution,the effects of iron oxide on crystallization behavior and spatial distribution of spinel were investigated in this work.The results revealed that FeO was more conducive to the growth of spinels compared with Fe2O3 and Fe3O4.Spinels were found to be mainly distrib-uted at the top and bottom of slag.The amount of spinel phase at the bottom decreased with the increasing FeO content,while that at the top increased.The average particle size of spinel in the slag with 18wt%FeO content was 12.8μm.Meanwhile,no notable structural changes were observed with a further increase in FeO content.In other words,the spatial distribution of spinel changed when the content of iron oxide varied in the range of 8wt%to 18wt%.Finally,less spinel was found at the bottom of slag with a FeO content of 23wt%.
基金financial support from the National Natural Science Foundation of China(52203070)the Open Fund of State Key Laboratory of New Textile Materials and Advanced Processing Technologies(FZ2022005)+2 种基金the Open Fund of Hubei Key Laboratory of Biomass Fiber and Ecological Dyeing and Finishing(STRZ202203)the financial support provided by the China Scholarship Council(CSC)Visiting Scholar Programfinancial support from Institute for Sustainability,Energy and Resources,The University of Adelaide,Future Making Fellowship。
文摘Urea holds promise as an alternative water-oxidation substrate in electrolytic cells.High-valence nickelbased spinel,especially after heteroatom doping,excels in urea oxidation reactions(UOR).However,traditional spinel synthesis methods with prolonged high-temperature reactions lack kinetic precision,hindering the balance between controlled doping and highly active two-dimensional(2D)porous structures design.This significantly impedes the identification of electron configuration-dependent active sites in doped 2D nickel-based spinels.Herein,we present a microwave shock method for the preparation of 2D porous NiCo_(2)O_(4)spinel.Utilizing the transient on-off property of microwave pulses for precise heteroatom doping and 2D porous structural design,non-metal doping(boron,phosphorus,and sulfur)with distinct extranuclear electron disparities serves as straightforward examples for investigation.Precise tuning of lattice parameter reveals the impact of covalent bond strength on NiCo_(2)O_(4)structural stability.The introduced defect levels induce unpaired d-electrons in transition metals,enhancing the adsorption of electron-donating amino groups in urea molecules.Simultaneously,Bode plots confirm the impact mechanism of rapid electron migration caused by reduced band gaps on UOR activity.The prepared phosphorus-doped 2D porous NiCo_(2)O_(4),with optimal electron configuration control,outperforms most reported spinels.This controlled modification strategy advances understanding theoretical structure-activity mechanisms of high-performance 2D spinels in UOR.
基金the National Natural Science Foundation of China(U21A20286,22206054 and 21805069)Natural Science Foundation of Hubei(2021CFB094)the Fundamental Research Funds for the Central China Normal University(CCNU)for financial support。
文摘Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catalytic contribution of geometric Co site in the electrocatalytic CER plays a pivotal role to precisely modulate electronic configuration of active Co sites to boost CER.Herein,combining density functional theory calculations and experiment results assisted with operando analysis,we found that the Co_(Oh) site acts as the main active site for CER in spinel Co_(3)O_(4),which shows better Cl^(-)adsorption and more moderate intermediate adsorption toward CER than CoTd site,and does not undergo redox transition under CER condition at applied potentials.Guided by above findings,the oxygen vacancies were further introduced into the Co_(3)O_(4) to precisely manipulate the electronic configuration of Co_(Oh) to boost Cl^(-)adsorption and optimize the reaction path of CER and thus to enhance the intrinsic CER activity significantly.Our work figures out the importance of geometric configuration dependent CER activity,shedding light on the rational design of advanced electrocatalysts from geometric configuration optimization at the atomic level.
基金Research Project supported by the Corrosion Science Laboratory,Academia Sinica
文摘The structure of the yttrium modified Co-base alloy layers formed by laser cladding on 2Cr13 and 1Cr18Ni9Ti steel surfaces and its hot corrosion performance have been investigated systematically.The re- sults show that the Y-containing cobalt base clad alloy has a finer microstructure and higher corrosion re- sistance to the salt mixture of 75% Na_2SO_4+25%NaCl at high temperature.The unique properties are ob- tained with addition of 0.875% Y for the formation of a continuous and compact oxide scale.The compact scale may act as a barrier for the inward diffusion of oxygen and sulphur and also for the outward diffusion of alloying elements.
文摘Fe-based and Co-based cladding layers were prepared on the surface of AISI H13 hot die steel by laser cladding technology.The microstructure,hardness and abrasion resistance of the two cladding layers were studied by means of optical microscope,scanning electron microscope,rockwell hardness tester,and high temperature friction and wear tester.Also,the red hardness of the cladding layers was measured,after holding the layers at 600℃ for 1 hour by muffle furnace and repeated 4 times.The rockwell hardness values of the substrate,the Fe-based and the Co-based alloy coating measured were HRC 47,HRC 52 and HRC 48,respectively.The red hardness values of the substrate and the Fe-based cladding layer were decreased,while that of the Co-based cladding layer was increased.The Co-based cladding layer has the minimal wear loss weight and friction coefficient among them.The wear mechanisms of the substrate,the Fe-based layer and the Cobased layer attribute mainly to abrasive wear,adhesion wear,and both of them,respectively.
基金Project Sponsored by Committee on Science and Technology of Guizhou Province(943068)
文摘A thermal fatigue behaviour of Co-based alloy coating obtained by laser surface meltcasting on the high temperature alloy GH33 was studied.The results show that after each time of thermal cycling,the final residual stress was formed in the melt-casting layer which is attributed to the thermal stress and structural stress.Through the first 50 times of thermal cycling,the morphology of coating still inherits the laser casting one,but the dendrites get bigger;After the second 50 times of thermal cycling,corrosion pits emerge from coating,and mostly in the places where coating and substrate meet.The fatigue damage type of coating belongs to stress corrosion.
文摘The Co-based alloy coatings had been prepared by laser cladding and vacuum fusion sintering. Microstructures of the coatings were investigated and the performance of thermal cycling was also tested using scanning electron microscopy ( SEM) and X-ray diffraction ( XRD ). The results show that the coatings and substrates combine well. The main phase compositions of laser cladding coating are T-Co, Cr23 C6 and Ni2 9 Cro. 7 Feo. 36, while vacuum fusion sintering coating consists of Co, Cr7 C3, and Ni2.9 Cro. 7 Feo. 36. After thermal cycling, the minimum hot cracking width of laser cladding coating is 14 μm; moreover, laser cladding coating maintains high hardness and hot-cracking susceptibility. Those are beneficial to high temperature wear resistance of hot work dies.
基金supported by the Natural Science Foundation of Jiangsu Province(BK20200800)the National Natural Science Foundation of China(22209075,51902165,12004145)+1 种基金the Natural Science Foundation of Jiangxi Province(20212BAB214032,20192ACBL20048)the Key Science and Technology Plan Project of Ji’an City(20211-015311)。
文摘Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),a 5 V class high voltage cathode,has been regarded as an attractive candidate to further improve the energy density of lithium-ion battery.The issue simultaneously enabling side stability and maintaining high interfacial kinetics,however,has not yet been resolved.Herein,we design a coherent Li_(1.3)A_(l0.3)Ti_(1.7)(PO)_(4)(LATP)layer that is crystally connected to the spinel LNMO host lattices,which offers fast lithium ions transportation as well as enhances the mechanical stability that prevents the particle fracture.Furthermore,the inactive Li_(3)BO_(3)(LBO)coating layer inhibits the corrosion of transition metals and continuous side reactions.Consequently,the coherent-engineered LNMO-LATPLBO cathode material exhibits superior electrochemical cycling stability in a window of 3.0–5.0 V,for example a high-capacity retention that is 89.7%after 500 cycles at 200 m A g-1obtained and enhanced rate performance(85.1 m A h g^(-1)at 800 m A g^(-1))when tested with a LiPF6-based carbonate electrolyte.Our work presents a new approach of engineering 5 V class spinel oxide cathode that combines interfacial coherent crystal lattice design and surface coating.
基金supported by the National Key R&D Program of China(No.2019YFC1905701)the National Natural Science Foundation of China(Nos.U1960201 and 52204336)the China Postdoctoral Science Foundation(No.2022M710359).
文摘Augite-based glass ceramics were synthesised using ZnO,FeO,and Fe_(2)O_(3)as additives,and the spinel formation,matrix structure,crystallisation thermodynamics,and physicochemical properties were investigated.The results showed that oxides resulted in numerous preliminary spinels in the glass matrix.FeO,ZnO,and Fe_(2)O_(3)influenced the formation of spinel,while FeO simplified the glass network.FeO and ZnO promoted bulk crystallisation of the parent glass.After adding oxides,the grains of augite phase were refined,and the relative quantities of augite crystal planes were also influenced.All samples displayed good mechanical properties and chemical stability.The 2wt%ZnO-doping sample displayed the maximum flexural strength(170.3 MPa).Chromium leaching amount values of all the samples were less than the national standard(1.5 mg/L),confirming the safety of the materials.In conclusion,an appropriate amount of zinc-containing raw material is beneficial for the preparation of augite-based glass ceramics.
基金supported by the National Natural Science Foundation of China under Grant No.50501024.
文摘The oxidation behavior of a cast polycrystalline Co-base superalloy was studied at temperatures from 900 to 1050℃ and analyzed by thermogravimetric analysis (TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results indicate that a cast Co-base superalloy follows the subparabolic oxidation kinetics at 900 and 1000℃, which are controlled by the growth of the inner Cr-rich layer, and that after oxidation at 1050℃ for 200 h, it almost exhibits the linear oxidation kinetics possible due to the volatility of Cr-rich oxide. A mixed scale forms on the alloy after prolonged oxidation. The oxide scale formed at 900 and 1000℃ is composed of an outer layer of spinel and an inner continuous Cr-rich layer and at I050℃ is composed of a very discontinuous Cr-rich layer.
文摘The effect of La element on the mechanical properties and constitution nearby grain boundary in a Co-base superalloy Co-22Ni-22Cr-14k during 760℃ ageing has been investigated by AES and material testing. Results show that element La can be in a state of solid solution and segregates mainly at the vicinity of grain boundaries. The prior segregation of La atoms can affect segregation behaviour of other elements, so that exerts influence on microstructure of the alloy, Particularly increasing of La content can decrease P concentration at the vicinity of grain boundaries but not decrease S concentration. S together with La produce cosegregation effect. The content of La has no obvious effect on high temperature strength. When the content of La comes up to 0.02wt-%, it can obviously improve the high temperature ductility.
基金Supported by the National Natural Science Foundation of China(21861044 and 21601137)the Project funded by China Postdoctoral Science Foundation(2018M633426)the Project funded by Yunnan Province Postdoctoral Science Foundation
文摘Two novel Co-based clusters with the 2-(hydroxylmethyl)pyridine(hmpH)ligand,formulated as[Co3(hmp)6(hmpH)]×2NO3×3H2O(ZTU-3)and[Co4(hmp)4(CH3CO2)2(H2O)4]×2NO3(ZTU-4),have been successfully synthesized and structurally characterized.ZTU-3 features a triangular core geometry,while ZTU-4 exhibits a cuboidal core geometry.In addition,the magnetic properties of ZTU-3 and ZTU-4 are also all investigated.
基金the National Nature Science Foundation of China (20571019)the Project-sponsored by SRF for ROCS ,HLJ (LC06C13)+1 种基金Project-Sponsored by Program of Harbin Subject Chief Scientist (2006RFXXG001)Development Programfor Outstanding Young Teachers in Harbin Institute of Technology (HITQNJS.2006.028)
文摘Layered Co-based ceramics with a nominal composition Bi2-xLaxSr2Co2O8-δ (x=0.0, 0.4, 0.8, short by BLC-222) were prepared using conventional solid state reaction method. X-ray photoemission spectroscopy (XPS) was used to investigate their electronic structures. The cobalt ions are highly mixed valences of Co3+ and Co4+. The fraction of Co4+ almost keeps unchanged with the increase of x. The O-1s photoemission spectra show that there are lattice oxygen and chemical absorbed oxygen in all the samples. The substitution of Bi3+ by La3+ results in a change from metallic-like behavior to semiconductor behavior. This abnormal phenomenon means that La3+ plays a key role in effecting the electrical transport property of BLC-222. The O-Co covalence bond is strengthened by the increase of La3+, which results in the decrease of conductivity.
文摘The effect of trace element B on microstructure of directionally solidified new type Co-base superalloy is studied systematically in this paper. It is found that the addition of B makes the incipient melting temperature of the alloy decline remarkably. Compared with the alloy having a boron content of 0.05 %, the incipient melting temperature of the alloy with 0.7 % B decreases by 197℃. The primary and secondary dendrite arm spacings increase and the volume fraction of interdendritic carbides with fine microstructure becomes bigger with the enhancement of boron content. When the alloy is with 0.7wt %B, M3B2 precipitates in the interdendrites.
文摘We investigated the variation of permeability spectra and relaxation frequency in Co-based amorphous ribbon annealed by pulsed Nd:YAG laser at various annealing energy Ea. The complex permeability spectra varies sensitively with the annealing energy, where the spectra could be decomposed into two contributions from domain wall motion,μdw(f) and rotational magnetization μrot(f) by analyzing the measured spectra as a function of driving ac field amplitude. The magnitude of μdw(f) and μrot(f) in dc limit shows maximum at Ea = 176 mJ. The maximum relaxation frequency for rotational magnetization, determined by μ'(f) curve, is about 700 kHz at Ea=62 mJ but that for wall motion is about 26 kHz at 230 mJ. These variations reflect the increase of magnetic softness and microstructural change by the annealing.
基金financial support by DST-SERB (Grant No.SRG/2021/001182)DRDO (Grant No.ARMREB/HEM/2021/241)is gratefully acknowledged。
文摘Ammonium dinitramide(ADN)based liquid monopropellants have been identified as environmentally benign substitutes for hydrazine monopropellant.However,new catalysts are to be developed for making ADN monopropellants cold-start capable.In the present study,performance of Co and Ba doped CuCr_2O_4 nanocatalysts prepared by hydrothermal method was evaluated on the decomposition of aqueous ADN solution and ADN liquid monopropellant(LMP103X).The catalysts were characterized by PXRD(Powder X-ray Diffraction),FTIR(Fourier Transform Infrared spectroscopy),SEM(Scanning Electron Microscopy),TEM(Transmission Electron Microscopy),EDS(Energy Dispersive X-ray Spectroscopy),and XPS(X-ray Photoelectron Spectroscopy).The nanosize was confirmed by SEM and TEM,while the nanoflake morphology was confirmed by the SEM analysis.Further,we obtained the elemental composition from the EDS analysis.We investigated the catalytic activity of the catalysts by thermogravimetric(TG)analysis and the developed catalysts lowered the decomposition temperature of ADN monopropellant by about 55℃.The XPS analysis confirmed the presence of metal ions with different chemical states.Apparently,increase in the surface area of the catalysts and the mixed active sites as well as the development of oxygen vacancy on the catalyst surface introduced by metal doping are influencing the decomposition temperature of ADN samples.
基金supported by the National Natural Science Foundation of China(52022109 and 51834008)Beijing Municipal Natural Science Foundation(2202047)+1 种基金National Key Research and Development Program of China(2021YFC2901100)Science Foundation of China University of Petroleum,Beijing(2462021QNX2010,2462020YXZZ019,2462020YXZZ016,and 2462022QZDX008)。
文摘The poor structural stability and capacity retention of the high-voltage spinel-type LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)limits their further application.Herein,Al and Co were doped in LNMO materials for a more stable structure and capacity.The LNMO,LiNi_(0.45)Al_(0.05)Mn_(1.5)O_(4)(LNAMO)and LiNi_(0.45)Co_(0.05)Mn_(1.5)O_(4)(LNCMO)were synthesized by calcination at 900℃ for 8 h,which was called as solid-phase method and applied universally in industry.XRD,FT-IR and CV test results showed the synthesized samples have cation disordering Fd-3m space group structures.Moreover,the incorporation of Al and Co increased the cation disordering of LNMO,thereby increasing the transfer rate of Li+.The SEM results showed that the doped samples performed more regular and ortho-octahedral.The EDS elemental analysis confirmed the uniform distribution of each metal element in the samples.Moreover,the doped samples showed better electrochemical properties than undoped LNMO.The LNAMO and LNCMO samples were discharged with specific capacities of 116.3 mA·h·g^(-1)and 122.8 mA·h·g^(-1)at 1 C charge/discharge rate with good capacity retention of 95.8% and 94.8% after 200 cycles at room temperature,respectively.The capacity fading phenomenon of the doped samples at 50℃ and 1 C rate was significantly improved.Further,cations doping also enhanced the rate performance,especially for the LNCMO,the discharge specific capacity of 117.9 mA·h·g^(-1)can be obtained at a rate of 5 C.
文摘Unburned magnesium aluminate spinel refractories were prepared using sintered magnesium aluminate spinel as the main raw material,phenolic resin as the binder,aluminum powder(2%,4%,and 6%by mass)and silicon powder(when Al powder addition is 4%,Si powder addition varies:1%and 2%,by mass)as additives.The effects of the Al powder and Si powder additions on the properties and microstructure of the refractories heat treated at different temperatures(1000,1400,and 1600℃for 3 h)were studied.The results show that the Al powder addition can greatly enhance the cold modulus of rupture of the samples fired at 1000 or 1400℃,and meanwhile AlN reinforcement phase forms in the matrix,which greatly improves the hot modulus of rupture of the samples at 1400℃;however,the heat treatment at 1600℃has little influence on the strength;the addition of Al powder and Si powder results in the formation of low melting point phases,greatly reducing the hot modulus of rupture.However,the low melting point phases promote sintering,which enhances the density and the cold modulus of rupture,and decreases the volume change during heating.The samples added with Al and Si all have higher cold modulus of rupture than those added with Al powder only.
文摘Detailed mineralogical and gemological records were conducted on 340 unheated spinels from the Horana, Eheliyagoda, Ratnapura, and Okkampatiya mining areas in Sri Lanka. The color of Sri Lankan spinel varies greatly: in addition to the mainstream pink to purple pink, green and blue can also be seen. Compared with spinel from other regions such as Myanmar, Vietnam, and Tanzania, Sri Lanka's spinel has more abundant inclusions: several mining areas generally have inclusions such as dolomite, apatite, zircon, and chondrodite. Minerals such as graphite and forsterite are also found in spinel produced in the Horana region;graphite and rutile have been found in spinel produced in the Okkamptiya region. Partially healed fissures are most common in spinel in the Okkampatiya mining area;Unlike Vietnamese spinel, dislocations and growth structures are almost absent in Sri Lankan spinel. The LA-ICP-MS analysis results showed that there were no significant differences among the mining areas. LA-ICP-MS analysis of 5 Sri Lankan cobalt blue spinels showed a variation of 11 to 120 ppm in this chromogenic element. The UV visible absorption spectrum results show that Sri Lankan spinel has a combination spectra with variable ratios of the spectral components Cr 3+ , V 3+ and Fe 2+ from pink to red, orange, purple to purple, and blue-green. The results of infrared spectroscopy and laser Raman spectroscopy analysis showed that all samples showed no indications for heat treatment.