Research Progress of High Entropy Carbides

High entropy carbides (HECds) are multi-component carbides consisting of transition metal carbides.HECds are generally composed of five or more metal cations of the equal or near-equal substances,obtaining a single crystal structure.HECds have great potentials for future applications due to excellent mechanical,antioxidant and thermal properties.Due to their complex crystal structures and lattice distortion,computer simulations are widely used to efficiently associate the properties of HECds with the corresponding microstructures.In response to the development of HECds,this article provides an overview of the basic design,preparation process and properties of HECds.

Recent Advances in Interface Modification of Cu/graphite Composites and Layered Ternary Carbides of Modified Layer Candidate

We review the fundamental properties and significant issues related to Cu/graphite composites.In particular,recent research on the interfacial modification of Cu/graphite composites is addressed,including the metal-modified layer,carbide-modified layer,and combined modified layer.Additionally,we propose the use of ternary layered carbide as an interface modification layer for Cu/graphite composites.

Comparative Study on Microstructure and Mechanical Properties of Coarse-grained WC-based Cemented Carbides Sintered with Ultrafine WC or (W+C) as Additives

The effects of ultrafine WC(WC_(UF),0.5μm) or W(1μm) and C(0.3μm)(W+C)_(UF) additives on the densification,microstructure and mechanical properties of coarse-grained cemented carbides were compared systematically.Overall,the cemented carbides with WC_(UF)/(W+C)_(UF) additives are almost fully densification to be higher than 99%,and the average grain size is kept above 2.8μm.The WC_(UF) additive assists grains to(truncated)trigonal prism shape by two dimensional(2D) growth,whereas the(W+C)_(UF) additive assists grains to rounded shape by three dimensional(3D) growth,lowers WC contiguity and increases face-centered-cubic Co.The hardness and bending strength of(75WC_(C)-15WC_(UF))-10Co are 86.6 HRA and 2 272 MPa,respectively,both higher than those of(75WC_(C)-15(W+C)_(UF))-10Co,which could be ascribed to the enhanced densification and unblemished grains.However,the fracture toughness of the(75WC_(C)-15(W+C)_(UF))-10Co is 23.5 MPa·m^(1/2),higher than that of the(75WC_(C)-15WC_(UF))-10Co due to the uniform WC-Co structure and flexible binder phase.

Pulsed laser interference patterning of transition-metal carbides for stable alkaline water electrolysis kinetics

We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed laser ablation of Co,Fe,Ti,and Mo metals in acetone.The interaction between carbon s-p-orbitals and metal d-orbitals causes a redistribution of valence structure through charge transfer,leading to the formation of surface defects as observed by X-ray photoelectron spectroscopy.These defects influence the evolved TMCs,making them effective for hydrogen and oxygen evolution reactions(HER and OER)in an alkaline medium.Co_(3)C with more oxygen affinity promoted CoO(OH)intermediates,and the electrochemical surface oxidation to Co_(3)O_(4)was captured via in situ/operando electrochemical Raman probes,increasing the number of active sites for OER activity.MoC with more d-vacancies exhibits strong hydrogen binding,promoting HER kinetics,whereas Fe_(3)C and TiC with more defect states to trap charge carriers may hinder both OER and HER activities.The results show that the assembled membrane-less electrolyzer with Co_(3)C∥Co_(3)C and MoC∥MoC electrodes requires~2.01 and 1.99 V,respectively,to deliver a 10 mA cm−2 with excellent electrochemical and structural stability.In addition,the ascertained pulsed laser synthesis mechanism and unit-cell packing relations will open up sustainable pathways for obtaining highly stable electrocatalysts for electrolyzers.

Microstructure and formation process of Ni-pool defect in WC-8Ni cemented carbides

The morphologies and formation process of Ni-pool defects in WC?8Ni cemented carbides were studied. The SEM images show that Ni-pool generally has two kinds of morphologies: “island” in isolation and “ring” around a new phase. In the obtained samples with “ring-like Ni-pool”, WC, Ni and Ni2W4C (η phase) phases were detected in XRD patterns. Combined with SEM, EDX and XRD results, it is found that the phase in the center of the “ring-like Ni-pool” is Ni2W4C (η phase) and the main chemical components of Ni-pool are Ni, W and C. In addition, the relationships among large size Ni (agglomerated) particles, volatile impurities, pores and carbon content vs forming process of the Ni-pool defects for WC?8Ni cemented carbides are also presented and discussed.

Effects of cubic carbides and La additions on WC grain morphology,hardness and toughness of WC-Co alloys

Effects of Cr3C2,VC and La2O3 additions on the WC grain morphology,hardness and toughness of WC-10Co alloys were investigated.To intensify the grain growth driving force,nano W and nano C,instead of the conventionally used WC,were used as the starting materials.To obtain a three-dimensional WC grain morphology,the natural sinter skins of the alloys were observed directly by scanning electron microscopy.It is shown that the additions have a strong ability in regulating the WC grain morphological and grain size distribution characteristics and the combinations of hardness and toughness.Due to the formation of regular and homogeneous triangular platelet WC grains,WC-10Co-0.6Cr3C2-0.06La2O3 alloy shows an excellent combination of hardness and toughness.The morphological regulation mechanism,the relationship between the WC grain morphology and the properties were discussed.

Effects of Ta C on microstructure and mechanical properties of coarse grained WC-9Co cemented carbides

Coarse grained WC-9Co cemented carbides with 0-1.0% TaC(mass fraction) were fabricated by HIP-sintering and gas quenching. The effects of TaC on the microstructures and mechanical properties were investigated using scanning electron microscopy(SEM), energy dispersive X-ray analysis(EDS), X-ray diffractometry(XRD) and mechanical properties tests. The results show that the maximum values of hardness and strength are HV 1124 and 2466 MPa respectively when 0.4% TaC is added. When the content of TaC is more than 0.6%, the grain size of WC is no longer affected by the amount of TaC, and(W,Ta)C occurs as well. Moreover, the strength and fracture toughness increase and the(Ta+W) content decreases with the increase of TaC content. The dependence of(Ta+W) content on the mechanical properties indicates that(Ta+W) content in Co should be decreased as low as possible to improve the mechanical properties of coarse grained WC-TaC-9Co cemented carbides with the microstructure of WC+γ two phase regions.

Effects of deep cryogenic treatment on microstructure and properties of WC-11Co cemented carbides with various carbon contents

The effects of deep cryogenic treatment on the microstructure and properties of WC-11 Co cemented carbides with various carbon contents were investigated.The results show that after deep cryogenic treatment,WC grains are refined into triangular prism with sound edges via the process of spheroidization,but WC grain size has no evident change compared with that of untreated alloys.The phase transformation of Co phase from α-Co（FCC） to ε-Co（HCP） is observed in the cryogenically treated alloys,which is attributed to the decrease of W solubility in the binder（Co）.Deep cryogenic treatment enhances the hardness and bending strength of the alloys,while it has no significant effects on the density and cobalt magnetic performance.

Elastoplastic response of functionally graded cemented carbides due to thermal loading

Finite dement formulations are used to simulate the evolution of the elastoplastic response of functionally graded cemented carbides （FGCC） due to thermal loading. The geometry of specimens is an axisymmetric solid cylinder with a two-dimensional gradient. The elastoplastic constitutive relationship is developed by constraint factors. Numerical results show that compressive stresses occur in the surface zone and tensile stresses in the cobalt rich zone when the temperature drops from the initial stress-free temperature of 800 to 0℃. The maximum value of the surface compressive stress is 254 MPa and the maximum value of the tensile stress is 252 MPa in the cobalt rich zones. When the cobalt concentration difference in the specimens is equal to or greater than 0.3, there is pronounced plastic flow in cobalt rich zone. When the temperature heats up from 0 to 800 ℃, the total plastic strain reaches 0.001 4. Plastic flow has a significant effect on the reduction of thermal stress concentration.

Chemical composition and structural identification of primary carbides in as-cast H13 steel

The aim of this study was to characterize the primary carbides formed in as-cast H13 steel. The composition, morphology, type, and size of primary carbides in as-cast H13 steel were investigated by optical microscope (OM), field emission scanning electron microscopy (FE-SEM), electron back-scattered diffraction (EBSD), and X-ray diffraction (XRD) analysis. The number of primary carbides was investigated by ASPEX automated inclusion analysis system. The results indicated that primary carbides in as-cast H13 steel are mainly composed of Cr, Mo, V, and Ti, and there exist four kinds of primary carbides in the interdendritic zones of H13 steel, which are stripy Mo–Cr-rich M2C, eutectic Mo–Cr-rich M2C, V-rich MC, and V-rich MC with Ti and N. Thermodynamic calculation indicated that M2C precipitates in liquid phase at solid fractions larger than 0.99, while MC precipitates in liquid phase at solid fractions larger than 0.96. Statistical results indicated that the number of M2C is much greater than the number of other kinds of primary carbides. Most primary carbides are blocky, with lengths of no more than 10 μm and a length/width ratio of no more than 3. The large primary carbides in as-cast H13 steel are mainly M2C.

Effects of gradient structure on the microstructures and properties of coated cemented carbides

The effects of gradient structure on the microstructure and properties of coated cemented carbides were researched with optical microscopy （OM）, scanning electron microscopy （SEM）, strength measurements, and cutting tests. It shows that vacuum sintering of WC-Ti（C, N）-TaC-Co cemented carbides results in the formation of a surface ductile zone. The ductile zone prevents crack propagation and leads to the increase of transverse rupture strength of the substrate. The impact resistance of coated gradient inserts was obviously improved on the basis of maintaining resistance to abrasion and the forming mechanism of the gradient structure was also analyzed.

Growth kinetics of cubic carbide free layers in graded cemented carbides

In order to reveal the formation mechanism of cubic carbide free layers （CCFL）, graded cemented carbides with CCFL in the surface zone were fabricated by a one-step sintering procedure in vacuum, and the analysis on microstructure and element distribution were performed by scanning electron microscopy （SEM） and electron probe micro-analyzer （EPMA）, respectively. A new physical model and ki- netic equation were established based on experimental results. Being different f^om previous models, this model suggests that nitrogen diffu- sion outward is only considered as an induction factor, and the diffusion of titanium through liquid phase plays a dominative role. The driving force of diffusion is expressed as the differential value between nitrogen partial pressure and nitrogen equilibrium pressure essentially. Simulation results by the kinetic equation are in good agreement with experimental values, and the effect of process parameters on the growth kinetics of CCFL can also be explained reasonably by the current model.

Effects of nano TiN addition on the microstructure and mechanical properties of TiC based steel bonded carbides

TiC based steel bonded carbides with the addition of nano TiN were prepared by vacuum sintering techniques.The microstructure was investigated using scanning electron microscopy（SEM） and transmission electron microscopy（TEM）,and the mechanical properties,such as bending strength,impact toughness,hardness,and density,were measured.The results indicate that the grain size becomes small and there is uniformity in the steel bonded carbide with nano addition;several smaller carbide particles are also found to be inlaid in the rim of the larger carbide grains and prevent the coalescence of TiC grains.The smaller and larger carbide grains joint firmly,and then the reduction of the average size of the grains leads to the increase in the mechanical properties of the steel bonded carbides with nano addition.But the mechanical properties do not increase monotonously with an increase in nano addition.When the nano TiN addition accounts for 6-8 wt.% of the amount of steel bonded carbides,the mechanical properties reach the maximum values and then decrease with further increase in nano TiN addition.

Deposition of tungsten-titanium carbides on surface of diamond by reactive PVD

The coatings of W-Ti carbides on the surface of diamond was obtained by using physical vapor deposition (PVD), during which WO3 powders pre-treated with hydrofluoric acid were reduced by titanium hydride in vacuum at 850 ℃. The resistance of diamond to corrosion at high-temperature was investigated. The formation of W-Ti carbides on the surface of diamond was verified by X-ray diffraction analysis, the interface state between diamond and matrix in metaLbase diamond composite was observed by scanning electron microscope. The results showed that the carbide coating is easy to be formed at low deposition temperature on the surface of diamond, while the resistance of diamond to corrosion at highutemperature and the strength of bonding between diarnond and metal matrix are effectively improved.

Properties and microstructure of VC/Cr_3C_2-doped WC/Co cemented carbides

This paper deals with the effects of codoped VC/Cr3C2 and sintering temperature on the magnetic and mechanical properties of ultra-fine grained WC-12%Co alloys. Results show that the synergistic action of doped VC/Cr3C2 in optimal proportion enhances both the hardness and transverse rupture strength （TRS） of the alloys, with more homogeneous microstructtLre. When the alloy is sintered at 1430℃ and with 0.5% Cr3C2/0.2% VC, the TRS reaches 3786 MPa, the hardness is 91.7 HRA and the grain size smaller than 0.6 μm. The numerical analyses on grain growth during the sintering process show that both VC precipitating on the WC grain boundary and Cr3C2 dissolving in the Co phase decrease the solid/liquid interfacial energy γ, the process of dissolution and reprecipitation is greatly retarded and the coarsening of WC grains is inhibited.

Change in relative density of WC-Co cemented carbides in spark plasma sintering process

The relative density of WC-Co cemented carbides during spark plasma sintering（SPS） was analyzed.Based on the change in displacement of the ram in the SPS system,the relative densities in the sintering process can be achieved at different temperatures.The results indicated that densification of the samples started at near 900°C,the density rapidly reached its maximum at the increasing temperature stage,in which the temperature was lower than the sintering temperature of 1200°C,and most of the densification took place in the stage.Besides,the theoretical values were consistent with the experimental results.

Sintering characteristics and microstructure of WC-Co-VC/Cr_3C_2 ultrafine cemented carbides

The sintering characteristics, microstructure, and mechanical properties of ultrafine WC-12%Co-0.2%VC/0.5%Cr3C2 cemented carbides were investigated. Dilatometric and differential thermal analyses （DTA） indicate that the compacts start to shrink at 600°C, the shrinkage rate peak is at 1190°C, and the liquid formation temperature is lower than the W-C-Co eutectic temperature （1330°C）. Microstructure analysis results show that the cemented carbides with fine and homogeneous microstructure were obtained when sintered at 1430°C. Continuous and discontinuous grain growth was suppressed due to the synergistic action of VC/Cr3C2. The transverse rupture strength （TRS） of the samples reaches 4286 MPa, with the hardness HRA 92.1. The fine and homogeneous microstructure, alloy strengthening, and different phase constitutions of binder in the cemented carbides result in high hardness and TRS. Continuous and discontinuous grain growth was observed in the cemented carbide sintered at 1450°C, which results in significant decreases of hardness and TRS. It indicates that VC/Cr3C2 additions in the cemented carbides can only suppress the grain growth at a certain temperature.

XPS study of potassium-promoted molybdenum carbides for mixed alcohols synthesis via CO hydrogenation

The X-ray photoelectron spectroscopy （XPS） was used to investigate the surface characteristic of potassium-promoted or un-promoted both β-Mo2C and α-MoC1-x pretreated by syngas at different temperatures,and the promotional effect of potassium on the catalytic performance was also studied.XPS results revealed that the content of surface Mo and its valence distribution between β-Mo2C and α-MoC1-x were quite different.Promoted by potassium,the remarkable changes were observed for surface composition and valence of Mo distribution over β-Mo2C.Potassium had strong electronic effect on β-Mo2C,which led to a higher Mo4＋ content.On the contrary,potassium had little electronic effect on α-MoC1-x,and K-Mo interaction was weak.Therefore,Mo0 and Mo2＋ became the dominant species on the catalyst surface,and the Mo4＋ content showed almost no increase as the pretreatment temperature enhanced.In terms of catalytic performance of molybdenum carbides,the increase in Mo0 most likely explained the increase in hydrocarbon selectivity,yet Mo4＋ might be responsible for the alcohols synthesis.

Effect of deep cryogenic treatment on the formation of nano-sized carbides and the wear behavior of D2 tool steel

The effect of deep cryogenic treatment on the microstructure, hardness, and wear behavior of D2 tool steel was studied by scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, X-ray diffraction （XRD）, hardness test, pin-on-disk wear test, and the reciprocating pin-on-fiat wear test. The results show that deep cryogenic treatment eliminates retained austenite, makes a better carbide distribution, and increases the carbide content. Furthermore, some new nano-sized carbides form during the deep cryogenic treatment, thereby increasing the hardness and improving the wear behavior of the samples.

Study on stable and meta-stable carbides in a high speed steel for rollers during tempering processes

A high speed steel （HSS） was studied for rollers in this work. The steel was quenched at 1150℃ and tempered at 520℃. The phase structures of the steel were determined by X-ray diffraction （XRD）, and the hardness of specimens was measured. The volume fraction of carbides was counted by Image-Pro Plus software. The typical microstructures were observed by field emission scanning electron microscope （FESEM）. Stable and meta-stable carbides were deduced by removing the existing phases one by one in the Fe-C equilibrium calculation. It is found that the precipitated carbides are bulk-like MC, long stripe-like M2C, fishbone-like M6C, and daisy-like M7C3 during the tempering process. The stable carbides are MC and M6C, but the meta-stable ones are M2C, M7C3, and M3C.