A fresh class of superconducting and hard pentaborides

On the basis of the current theoretical understanding of boron-based hard superconductors under ambient conditions,numerous studies have been conducted with the aim of developing superconducting materials with favorable mechanical properties using boron-rich compounds.In this paper,first-principles calculations reveal the existence of an unprecedented family of tetragonal pentaborides MB_(5)(M=Na,K,Rb,Ca,Sr,Ba,Sc,and Y),comprising B_(20)cages and centered metal atoms acting as stabilizers and electron donors to the boron sublattice.These compounds exhibit both superconductivity and high hardness,with the maximum superconducting transition temperature T_(c)of 18.6 K being achieved in RbB5 and the peak Vickers hardness Hv of 35.1 GPa being achieved in KB_(5)at 1 atm.The combination of these properties is particularly evident in KB_(5),RbB5,and BaB5,with Tc values of∼14.7,18.6,and 16.3 K and H_(v)values of∼35.1,32.4,and 33.8 GPa,respectively.The results presented here reveal that pentaborides can provide a framework for exploring and designing novel superconducting materials with favorable hardness at achievable pressures and even under ambient conditions.

A first-principle calculation of structural,mechanical and electronic properties of titanium borides

The first-principle calculations are performed to investigate the structural,mechanical and electronic properties of titanium borides （Ti2B,TiB and TiB2）.Those calculated lattice parameters are in good agreement with the experimental data and previous theoretical values.All these borides are found to be mechanically stable at ambient pressure.Compared with parent metal Ti （120 GPa）,the larger bulk modulus of these borides increase successively with the increase of the boron content in three borides,which may be due to direction bonding introduced by the boron atoms in the lattice and the strong covalent Ti-B bonds.Additionally,TiB can be regarded as a candidate of incompressible and hard material besides TiB2.Furthermore,the elastic anisotropy and Debye temperatures are also discussed by investigating the elastic constants and moduli.Electronic density of states and atomic Mulliken charges analysis show that chemical bonding in these titanium borides is a complex mixture of covalent,ionic,and metallic characters.

Development Strategies in Transition Metal Borides for Electrochemical Water Splitting

Electrochemical water splitting is a feasible method for producing environmental benignity energy of hydrogen,while high price and low availability on the earth of noble electrocatalysts constrain their global-scale application.Transition metal borides(TMBs)have displayed unique metalloid characteristic and outstanding performance for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)in the last few decades.Herein,recent developments of the TMBs for HER and OER are summarized.Initially,the impact factors and relevant evaluation of electrocatalytic performance are described,that is,overpotential,Tafel slope and exchange current density,stability,faradaic efficiency,turnover frequency,mass and specific activities.Moreover,the optimization strategies of borides are emphasized,which principally include coupling with effective substrates,elemental doping,phase modification,interfacial engineering,and morphology control.Finally,in order to reach the goal of application,the remaining challenges and perspectives are given to point out a direction for enhancing the performance of borides.

Metal phosphides and borides as the catalytic host of sulfur cathode for lithium–sulfur batteries

Lithium−sulfur batteries are one of the most competitive high-energy batteries due to their high theoretical energy density of _(2)600 W·h·kg^(−1).However,their commercialization is limited by poor cycle stability mainly due to the low intrinsic electrical conductivity of sulfur and its discharged products(Li_(2)S_(2)/Li_(2)S),the sluggish reaction kinetics of sulfur cathode,and the“shuttle effect”of soluble intermediate lithi-um polysulfides in ether-based electrolyte.To address these challenges,catalytic hosts have recently been introduced in sulfur cathodes to en-hance the conversion of soluble polysulfides to the final solid products and thus prevent the dissolution and loss of active-sulfur material.In this review,we summarize the recent progress on the use of metal phosphides and borides of different dimensions as the catalytic host of sulfur cathodes and demonstrate the catalytic conversion mechanism of sulfur cathodes with the help of metal phosphides and borides for high-en-ergy and long-life lithium-sulfur batteries.Finally,future outlooks are proposed on developing advanced catalytic host materials to improve battery performance.

Progress in functional studies of transition metal borides

In recent years,transition metal borides(TMBs)have attracted much attention because they are considered as potential superhard materials and have more abundant crystal structures compared with traditional superhard materials.So far,however,no superhard materials have been found in TMBs.A large number of structures and potential new properties in TMBs are induced by the various hybridization ways of boron atoms and the high valence electrons of transition metals,which provide many possibilities for its application.And most TMBs have layered structures,which make TMBs have the potential to be a two-dimensional(2D)material.The 2D materials have novel properties,but the research on 2D TMBs is still nearly blank.In this paper,the research progress of TMBs is summarized involving structure,mechanical properties,and multifunctional properties.The strong covalent bonds of boron atoms in TMBs can form one-dimensional,twodimensional,and three-dimensional substructures,and the multiple electron transfer between transition metal and boron leads to a variety of chemical bonds in TMBs,which are the keys to obtain high hardness and multifunctional properties of TMBs.Further research on the multifunctional properties of TMBs,such as superconductors,catalysts,and high hardness ferromagnetic materials,is of great significance to the discovery of new multifunctional hard materials.

Ultra-incompressible Ternary Diborides Re_(0.5)Ir_(0.5)B_2,Re_(0.5)Tc_(0.5)B_2,Os_(0.5)W_(0.5)B_2 and Os_(0.5)Ru_(0.5)B_2:Density Functional Calculation

In this paper, density functional computations have been applied to the structural, elastic and electronic properties of ternary transition metal diborides Re0.5Ir0.5B2, Re0.5Tc0.5B2, Os0.5W0.5B2 and Os0.5Ru0.5B2 in hexagonal （P63/mmc） and orthorhombic （Pmmn） structures with both local density approximation and generalized gradient approximation. LDA gives smaller lattice parameters and larger elastic moduli than GGA. Both results show that the hexagonal ones are more stable than orthorhombic ones except Os0.5Ru0.5B2. Moreover, the hexagonal structure has superior elastic property than orthorhombic one. Generally speaking, the calculated elastic moduli of Re0.5Ir0.5B2 and Os0.5Ru0.5B2 are smaller than those values of Re0.5Tc0.5B2 and Os0.5W0.5B2 within the same structure because of the filling of antibonding states. The relativistic effects result in weaker bonds of Tc-B （Ru-B） than those of Re-B （Os-B）. All the diborides are ultra-incompressible. Re0.5Tc0.5B2 has the largest shear modulus and it is a promising superhard diboride like Os0.5W0.5B2. The elastic properties are in high correlation with the bond strength. The shear moduli are more sensitive than the bulk moduli to the bond strength.

Features of the Process of Self-Propagating High-Temperature Synthesis, a Structure and Strong Properties of Borides Iron Layers on the Carbon Steels, Generated Under a Powerful Electron Beam in Vacuum

Conditions of formation, structure and properties of boride iron layers on carbonaceous steels 3 and 45 at electron beam borating are investigated. New process to make layers of iron borides （Fe2B, FeB） using electron beam are reported. The microstructure and microhardness of boride layers are investigated and also are compared to layer properties obtained at solid phase borating. Formed layers were heterogeneous structure combining solid and weak components and resulting in to fragility reduction of boride layer.

Synthesis of Composite Materials Based on Borides of Metals and Aluminum Oxide under the Combustion Conditions

The article presents experimental results on obtaining composites based on the systems TiB2-Al2O3,CrB2-Al2O3 and ZrB2-Al2O3 by a method combining SHS(self-propagating high-temperature synthesis)and MA(mechanical activation).Using the thermodynamic calculation program“THERMO”,the adiabatic temperature and the composition of the equilibrium combustion products are calculated.It is shown that the products of exothermic interaction are refractory compounds of metal borides and alumina,which in the ceramic composite form a dispersed phase and a ceramic binder.The effect of duration of the activated mixing on the morphology of the reaction mixture and formation of the microstructure of the ceramic composite was studied.The realization of solid-state SHS is due to the formation of the initial powder mixture of ultradisperse reagent sizes during mechanochemical activation.The SHS products were examined by X-ray diffraction analysis and a scanning electron microscope.High-temperature phases of borides of chromium,titanium,zirconium,aluminum oxide and their spinel are found in SHS products.The purpose of this work is to investigate the influence of regimes for preparing reaction mixtures on formation of the microstructure of a ceramic SHS composite based on titanium,chromium and zirconium borides.

Morphology and growth mechanism of borides in Ti-48Al+B alloys

The morphology and growth mechanism of borides in Ti 48Al+(0.2%～0.8%)B (mole fraction) alloys were investigated. The results show that TiB 2 phase are all flakes with width <0.5 μm and aspect ratio >100 in alloys containing 0.2% and 0.5%B, respectively, but there are a few hexagonal blocky borides with habit planes of (0001) and {1010} type besides flakes in the alloy containing 0.8%B. Flake borides are the products of irregular eutectic reactions growing coupled with matrix and blocky borides are primary TiB 2 phases growing unconstrained in melt.

Synthesis of niobium borides by powder metallurgy methods using Nb_(2)O_(5), B_(2)O_(3) and Mg blends

Niobium boride powders having NbB, NbB2 and Nb3B4 phases in various amounts and single phase NbB powders were successfully synthesized by using powder metallurgy methods from related metal oxide raw materials in the presence of a strong reducing agent. Nb2O5, B2O3 and Mg powder blends were milled at room temperature by a high-energy ball mill for different time. Subsequently, undesired MgO phase was removed from the milled powders by HCl leaching to constitute NbB?NbB2?Nb3B4 as final products and they were subjected to an annealing process at 1500 °C for 4 h to observe probable boride transformation. Characterization was carried out by XRD, DSC, PSA, SEM/EDX, TEM and VSM. The effects of milling time (up to 9 h) on the formation, microstructure and thermal behavior of the final products were investigated. Reduction reaction took place after milling stoichiometric powder blends for 2 h. Nano-sized NbB?NbB2?Nb3B4 powders in high purity were obtained in the absence of any secondary phase and any impurity via mechanochemistry by milling for 5 h and leaching with 4 mol/L HCl. After annealing, pure and nano-sized NbB?NbB2?Nb3B4 powders transformed to a single NbB phase without leaving behind NbB2 and Nb3B4 phases.

From binary to ternary and back to binary:Transition of electromagnetic wave shielding to absorption among MAB phase Ni_(3)ZnB_(2)and corresponding binary borides Nin+1Bn(n=1,3)

Due to chemical inertness of nickel and boron,the preparation of nickel borides and corresponding layered ternary transition metal borides Ni_(3)ZnB_(2)(MAB phase)has always required high-temperature and/or high-pressure conditions.Yet,an innovative and efficient approach to preparing Ni_(3)ZnB_(2)at only 600℃and without applied pressure is presented in this study.It is discovered that by simply adjusting the temperature,a phase transition from Ni_(3)ZnB_(2)to Ni4B3 with a layered structure could be induced.This transition between the binary-component and the ternary-component brings about significant variation in electromagnetic wave(EMW)shielding/absorption performance of prepared borides.For instance,Ni2B has good EMW shielding performance(42.54 dB in X band)and Ni_(3)ZnB_(2)is of weak EMW shielding(13.43 dB in X band);Ni_(3)ZnB_(2)has poor EMW absorption performance(−5 dB)while Ni4B3 has excellent EMW absorption performance(−45.19 dB)at a thickness of 2.7 mm with effective absorption bandwidth(10.4 GHz).

MBenes:Two-dimensional transition-metal borides with ordered metal vacancies

2D MBenes have been theoretically predicted to possess unique electronic structures and physicochemical properties,and thus shown great promise in various applications.However,the synthesis of individual single-layer MBene remains a grand challenge due to its orthorhombic structure of MAB phases.Recently,scientists from Link?ping University have fabricated 2D monolayer Mo4/3B2-xTzwith ordered metal vacancies.Their results demonstrated the feasibility of top-down approach by chemical exfoliation of laminated compounds and provided the principle for further preparation of a wealth of MBenes.

Theoretical study on hydrogen evolution reaction in transition metal borides

Given increasing energy demands and environmental pollution,it is highly desirable to design new hydrogen evolution reaction(HER)catalysts.In this study,we have performed high throughput screening of transition-metal borides(M2B)and Janus counterparts for appealing catalysts.The simulations showcase that the Pd_(2)B,PdPtB,PdIrB and PdAuB possess favorable HER performance with the different chemical nature and unique asymmetry structure.

A new class of high-entropy M_(3)B_(4) borides

A new class of high-entropy M3B4 borides of the Ta_(3)B_(4)-prototyped orthorhombic structure has been synthesized in the bulk form for the first time.Specimens with compositions of(V0.2Cr0.2Nb0.2Mo0.2Ta0.2)3B4 and(V0.2Cr0.2Nb0.2Ta0.2W0.2)_(3)B_(4) were fabricated via reactive spark plasma sintering of high-energy-ball-milled elemental boron and metal precursors.The sintered specimens were〜98.7%in relative densities with virtually no oxide contamination,albeit the presence of minor(4-5 vol%)secondary high-entropy M5B6 phases.Despite that Mo_(3)B_(4) or W_(3)B_(4) are not stable phase,20%of M03B4 and W3B4 can be stabilized into the high-entropy M3B4 borides.Vickers hardness was measured to be 18.6 and 19.8 GPa at a standard load of 9.8 N.This work has further expanded the family of different structures of high-entropy ceramics reported to date.

Shear anisotropy： Tuning high temperature metal hexaborides from soft to extremely hard

Easy machining into sharp lending edge, nose tip and complex shape components plays a pivotal role in the application of ultrahigh temperature ceramics in hypersonic vehicles, wherein low and controllable hardness is a necessary parameter to ensure the easy machinability. However, the mechanism that driving the hardness of metal hexaborides is not clear. Here, using a combination of the empirical hardness model for polycrystalline materials and density functional theory investigation, the hardness dependence on shear anisotropic factors of high temperature metal hexaborides has been established. It has come to light that through controlling the shear anisotropic factors the hardness of polycrystalline metal hexaborides can be tailored from soft and ductile to extremely hard and brittle, which is underpinned by the degree of chemical bonding anisotropy, i.e., the difference of B-B bond within the B;octahedron and that connecting the B;octahedra.

Microstructure Characteristics and Elevated Temperature Mechanical Properties of a B Containedβ-solidifiedγ-TiAl Alloy

The improved microstructure and enhanced elevated temperature mechanical properties of Ti-44Al-5Nb-(Mo,V,B)alloys were obtained by vacuum arc re-melting(VAR)and primary annealing heat treatment(HT)of 1260℃/6 h/Furnace cooling(FC).The phase transformation,microstructure evolution and tensile properties for as-cast and HTed alloys were investigated.Results indicate that three main phase transformation points are determined,T_(eut)=1164.3℃,T_(γsolv)=1268.3℃and T_(βtrans)=1382.8℃.There are coarse lamellar colonies(300μm in length)and neighbor reticular B2 andγgrain(3-5μm)in as-cast alloy,while lamellar colonies are markedly refined and multi-oriented(20-50μm)as well as the volume fraction and grain sizes of equiaxedγand B2 phases(about 15μm)significantly increase in as-HTed alloy.Phase transformations involvingα+γ→α+γ+β/B2 and discontinuousγcoarsening contribute to the above characteristics.Borides(1-3μm)act as nucleation sites forβ_(eutectic) and produce massiveβgrains with different orientations,thus effectively refining the lamellar colonies and forming homogeneous multi-phase microstructure.Tensile curves show both the alloys exhibit suitable performance at 800℃.As-cast alloy shows a higher ultimate tensile stress of 647 MPa,while a better total elongation of more than 41%is obtained for as-HTed alloy.The mechanical properties improvement is mainly attributed to fine,multi-oriented lamellar colonies,coordinated deformation of homogeneous multi-phase microstructure and borides within lamellar interface preventing crack propagation.

Ballistic performance of titanium-based layered composites made using blended elemental powder metallurgy and hot isostatic pressing

Metal matrix composites tiles based on Ti-6Al-4V(Ti64)alloy,reinforced with 10,20,and 40(vol%)of either TiC or TiB particles were made using press-and-sinter blended elemental powder metallurgy(BEPM)and then bonded together into 3-layer laminated plates using hot isostatic pressing(HIP).The laminates were ballistically tested and demonstrated superior performance.The microstructure and properties of the laminates were analyzed to determine the effect of the BEPM and HIP processing on the ballistic properties of the layered plates.The effect of porosity in sintered composites on further diffusion bonding of the plates during HIP is analyzed to understand the bonding features at the interfaces between different adjacent layers in the laminate.Exceptional ballistic performance of fabricated structures was explained by a significant reduction in the residual porosity of the BEPM products by their additional processing using HIP,which provides an unprecedented increase in the hardness of the layered composites.It is argued that the combination of the used two technologies,BEPM and HIP is principally complimentary for the materials in question with the abilities to solve the essential problems of each used individually.

Preparation and Characterization of Amorphous W–B–C Alloy and Solid Solutions of C in Tungsten Borides

Mixtures of W and B13C2 powders were mechanically milled and subsequently annealed at 900-1200℃.It is found that amorphous W-B-C alloy formed as the mixtures were milled for 20.80 h.After annealing the 80 h-milled mixtures at 900-950℃,solid solutions of C and/or B in tungsten[W（B,C）],C in tungsten boride[W2B（C）or WB（C）]formed by the crystallization of amorphous W-B-C.The formation temperature of W2B（C）and WB（C）is lower than that of W2B and WB reported previously.As the 80 h-milled mixtures were annealed at 1200℃,W reacted with amorphous W-B-C completely to form WB and W2B5 or W2B5 instead of the solid solutions of C in tungsten borides,which is determined by the mole ratio of W to B13C2.The formation mechanisms of the W2B（C）and WB（C）solid solutions as well as phase transition rules of the mixtures at annealing temperature and mole ratio were also investigated using first-principle calculation.

Research Progress of Non-oxide and High Entropy Ceramic Coatings

Ceramic coatings play a keyrole in extending the service life of materials in aerospaceandenergy fields byprotectingmaterials from high temperature,oxidation,corrosion and thermal stress.Non-oxide and high entropy ceramics are new emerging coating materials which have been researched and developed in recent years.Compared with traditional oxide ceramics,non-oxide ceramics have better high temperature stability,oxidation resistance and erosion resistance.These characteristics make non-oxide ceramics perform well in extreme environments.It is particularly noteworthy that the non-oxide high entropy ceramic is a uniform solid solution composed of at least four or fiveatoms.Their unique structure and outstanding propertiesshow great potential application in the field of coating.In this paper,the researches aboutregulating microstructure,preparation technology and properties of nitride and its high entropy system,carbide and its high entropy system and boride and its high entropy system in coating field are summarized,and their future development and prospects are prospected.

Ab initio molecular orbital study of structure on aluminium borides AlB_n (n = 1- 5) series

RECENTLY,great attention has been paid to the physical and chemical properties of atomic andsemiconductor clusters.On the properties of AlB_n atomic cluster,experimental studieshave been reported,yet theoretical studies have not been seen.Aluminium borides(AlB_n)have been widely used to change the fiber strength in mechanical engineering and to adjust