Structural and mechanical stability of rare-earth diborides

Structural and mechanical properties of several rare-earth diborides were systematically investigated by first principles calculations. Specifically, we studied XB2 , where X=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Lu in the hexagonal AlB2 , ReB2 , and orthorhombic OsB2 -type structures. The lattice parameters, bulk modulus, bond distances, second order elastic constants, and related polycrystalline elastic moduli （e.g., shear modulus, Young’s modulus, Poisson’s ratio, Debye temperature, sound velocities） were calculated. Our results indicate that these compounds are mechanically stable in the considered structures, and according to ＂Chen’s method＂, the predicted Vickers hardness shows that they are hard materials in AlB2 - and OsB2 -type structures.

Electronic structures and strengthening mechanisms of superhard high-entropy diborides

High-entropy diborides(HEBs)have attracted extensive research due to their potential ultra-high hardness.In the present work,the effects of transition metals(TM)on lattice parameters,electron work function(EWF),bonding charge density,and hardness of HEBs are comprehensively investigated by the first-principles calculations,including(TiZrHfNbTa)B_(2),(TiZrHfNbMo)B_(2),(TiZrHfTaMo)B_(2),(TiZrNbTaMo)B_(2),and(TiHfNbTaMo)B_(2).It is revealed that the disordered TM atoms result in a severe local lattice distortion and the formation of weak spots.In view of bonding charge density,it is understood that the degree of electron contribution of TM atoms directly affects the bonding strength of the metallic layer,contributing to the optimized hardness of HEBs.Moreover,the proposed power-law-scaled relationship integrating the EWF and the grain size yields an excellent agreement between our predicted results and those reported experimental ones.It is found that the HEBs exhibit relatively high hardness which is higher than those of single transition metal diborides.In particular,the hardness of(TiZrNbTaMo)B_(2)and(TiHfNbTaMo)B_(2)can be as high as29.15 and 28.02 GPa,respectively.This work provides a rapid strategy to discover/design advanced HEBs efficiently,supported by the coupling hardening mechanisms of solid solution and grain refinement based on the atomic and electronic interactions.

General trends in surface stability and oxygen adsorption behavior of transition metal diborides(TMB_2)

The potential applications of transition metal diborides(TMB_2) in extreme environments are particularly attractive but still blocked by some intrinsic properties such as poor resistances to thermal shock and oxidation. Since surface plays a key role during grain growth and oxygen adsorption, an insight into the surface properties of TMB_2 is essential for understanding the materials performance and accelerating the development of ultra-high temperature ceramics. By employing two-region modeling method, the stability and oxygen adsorption behavior of TMB_2 surfaces were investigated by first-principles calculations based on density functional theory. The effects of valance electron concentration on the surface stability and oxygen adsorption were studied and the general trends were summarized. After analyzing the anisotropy in surface stability and oxygen adsorption, the observed grain morphology of TMB_2 were well explained, and it was also predicted that YB_2, HfB_2 and TaB_2 may have better initial oxidation resistance than ZrB_2.

Enabling highly efficient and broadband electromagnetic wave absorption by tuning impedance match in high-entropy transition metal diborides (HETMB_(2))

The advance in communication technology has triggered worldwide concern on electromagnetic wave pollution.To cope with this challenge,exploring high-performance electromagnetic(EM)wave absorbing materials with dielectric and magnetic losses coupling is urgently required.Of the EM wave absorbers,transition metal diborides(TMB2)possess excellent dielectric loss capability.However,akin to other single dielectric materials,poor impedance match leads to inferior performance.High-entropy engineering is expected to be effective in tailoring the balance between dielectric and magnetic losses through compositional design.Herein,three HE TMB2 powders with nominal equimolar TM including HE TMB2-I(TM=Zr,Hf,Nb,Ta),HE TMB2-2(TM=Ti,Zr,Hf,Nb,Ta),and HE TMB2-3(TM=Cr,Zr,Hf,Nb,Ta)have been designed and prepared by one-step boro/carbothermal reduction.As a result of synergistic effects of strong attenuation capability and impedance match,HE TMB2-1 shows much improved performance with the optimal minimum reflection loss(RL_(min))of-59.6 dB(8.48 GHz,2.68 mm)and effective absorption bandwidth(EAB)of 7.6 GHz(2.3 mm).Most impressively,incorporating Cr in HE TMB2-3 greatly improves the impedance match over 1-18 GHz,thus achieving the RLmin of-56.2 dB(8.48 GHz,2.63 mm)and the EAB of 11.0 GHz(2.2 mm),which is superior to most other EM wave absorbing materials.This work reveals that constructing high-entropy compounds,especially by incorporating magnetic elements,is effectual in tailoring the impedance match for highly conductive compounds,i.e.,tuning electrical conductivity and boosting magnetic loss to realize highly efficient and broadband EM wave absorption with dielectric and magnetic coupling in single-phase materials.

Amorphization activated FeB_(2) porous nanosheets enable efficient electrocatalytic N_(2) fixation

Designing active,robust and cost-effective catalysts for the nitrogen reduction reaction(NRR) is of paramount significance for sustainable electrochemical NH3 synthesis.Transition-metal diborides(TMB_2)have been recently theoretically predicted to be a new class of potential NRR catalysts,but direct experimental evidence is still lacking.Herein,we present the first experimental demonstration that amorphous FeB_2 porous nanosheets(a-FeB_2 PNSs) could be a highly efficient NRR catalyst,which exhibited an NH3 yield of 39.8 μg h^(-1) mg^(-1)(-0.3 V) and a Faradaic efficiency of 16.7%(-0.2 V),significantly outperforming their crystalline counterpart and most of existing NRR catalysts.First-principle calculations unveiled that the amorphization could induce the upraised d-band center of a-FeB_2 to boost d-2π~* coupling between the active Fe site and ~*N_2 H intermediate,resulting in enhanced ~*N_2 H stabilization and reduced reaction barrier.Out study may facilitate the development and understanding of earth-abundant TMB_2-based catalysts for electrocatalytic N_2 fixation.

Lattice dynamical and thermodynamical properties of ReB_2,RuB_2,and OsB_2 compounds in the ReB_2 structure

Structural and lattice dynamical properties of ReB2,RuB2,and OsB2 in the ReB2 structure are studied in the framework of density functional theory within the generalized gradient approximation.The present results show that these compounds are dynamically stable for the considered structure.The temperature-dependent behaviors of thermodynamical properties such as internal energy,free energy,entropy,and heat capacity are also presented.The obtained results are in good agreement with the available experimental and theoretical data.

Superconductivity in Mg-Doped Layered Intermetallic Compound NbB2

We have performed low temperature resistivity p（T） and specific heat C（T） measurements on a superconducting polycrystalline Nb0.75Mg0.25B2 sample. The results indicate that the superconducting transition temperature is -4.6 K. The zero temperature upper critical field determined from the resistivity and specific heat is 3123 Oe. The electronic coefficient of specific heat γn=4.51 mJmol^-1K^2 and the Debye temperature θD=419 K are obtained by fitting the zero-field specific heat data in the normal state. At low temperatures, the electronic specific heat in the superconducting state follows Ces/γnTc = 2.84 exp（-1.21Tc/T）. This indicates that the superconducting pairing in Nb0.75Mg0.25B2 has s-wave symmetry.

High-temperature mechanical properties of aluminium alloys reinforced with titanium diboride (TiB_2) particles

The physical and mechanical properties of metal matrix composites were improved by the addition of reinforcements. The mechanical properties of particulate-reinforced metal-matrix composites based on aluminium alloys （6061 and 7015） at high temperatures were studied. Titanium diboride （TiB2） particles were used as the reinforcement. All the composites were produced by hot extrusion. The tensile properties and fracture characteristics of these materials were investigated at room temperature and at high temperatures to determine their ultimate strength and strain to failure. The fracture surface was analysed by scanning electron microscopy. TiB2 particles provide high stability of the alumin- ium alloys （6061 and 7015） in the fabrication process. An improvement in the mechanical behaviour was achieved by adding TiB2 particles as reinforcement in both the aluminium alloys. Adding TiB2 particles reduces the ductility of the aluminium alloys but does not change the microscopic mode of failure, and the fracture surface exhibits a ductile appearance with dimples formed by coalescence.

First principle study on the elastic and thermodynamic properties of TiB_2 crystal under high temperature

This paper predicts the elastic and thermodynamic characteristics of TiB2 crystal through the method of density functional theory within the generalized gradient approximation （GGA）. The five independent elastic constants （Cij）, the bulk modulus （B0）, the dependence of bulk modulus （B0） on temperature T and pressure P and the coefficient of thermal expansion （αL） at various temperatures have been evaluated and discussed. According to calculation, the bulk modulus will increase with increasing pressure while decrease with the increasing temperature. The coefficient of thermal expansion is consistent with the famous Griineisen＇s law when the temperature is not too high. The obtained results agree well with the experimental and other theoretical results.

Influence of B source materials on the synthesis of TiB_2-Al_2O_3 nanocomposite powders by mechanical alloying

An Al2O3-TiB2 nanocomposite was successfully synthesized by ball milling of Al, TiO2 and two B source materials of B2O3 （system （1）） and H3BO3 （system （2））. Phase identification of the milled samples was examined by Xray diffraction. The morphology and microstructure of the milled powders were monitored by scanning electron microscopy and transmission electron microscopy. It was found that the formation of this composite was completed after 15 and 30 h of milling time in systems （1） and （2）, respectively. More milling energy was required for the formation of this composite in system （2） due to the lubricant properties of HaBO3 and also its decomposition to HBO2 and B2O3 during milling. On the basis of X-ray diffraction patterns and thermodynamic calculations, this composite was formed by highly exothermic mechanically induced self-sustaining reactions （MSR） in both systems. The MSR mode took place around 9 h and 25 h of milling in systems （1） and （2）, respectively. At the end of milling （15 h for system （1） and 30 h for system （2）） the grain size of about 35-50 nm was obtained in both systems.

Preparation and Microstructure of Porous ZrB_2 Ceramics Using Reactive Spark Plasma Sintering Method

Zirconium oxide （ZrO：） and boron carbide （B4C） were added to ZrB2 raw powders to prepare ZrB2 porous ceramics by reactive spark plasma sintering （RSPS）. The reactions between ZrO2 and B,C which produce ZrB2 and gas （such as CO and B2O3） result in pore formation. X-Ray Diffraction results indicated that the products phase was ZrB2 and the reaction was completed after the RSPS process. The porosity could be controlled by changing the ratio of synthesized ZrB2 to raw ZrB2 powders. The porosity of porous ceramics with 20 wt% and 40 wt% synthsized ZrB2 are 0.185 and 0.222, respectivly. And dense ZrB：SiC ceramic with a porosity of 0.057 was prepared under the same conditions for comparison. The pores were homogeneously distributed within the microstructure of the porous ceramics. The results indicate a promising method for preparing porous ZrB：based ceramics.

Effect of NaCl on synthesis of ZrB2 by a borothermal reduction reaction of ZrO2

ZrB2 powders were synthesized via a borothermal reduction reaction of ZrO2 with the assistance of NaCl under a flowing Ar atmosphere. The optimal temperature and reaction time were 1223 K and 3 h, respectively. Compared with the reactions conducted without the addition of NaCl, those performed with the addition of an appropriate amount of NaCl finished at substantially lower temperatures. However, the addition of too much NaCl suppressed this effect. With the assistance of NaCl, a special morphology of polyhedral ZrB2 particles covered with ZrB2 nanosheets was obtained. Moreover, the experimental results revealed that the special morphology was the result of the combined effects of B2O3 and NaCl. The formation of the special microstructure is explained on the basis of the “dissolution–recrystallization” mechanism.

Preparation of TiB_2 coatings by electroplating in molten salt

Titanium diboride （TIB2） coatings were prepared by electroplating in fluoride-chloride electrolytes （KF-KC1） containing K2T1F6 and KBF4 as the electrochemically-active components. An attempt was made to correlate the thermodynamic prediction and experimental observations. Thick, adherent, and uniform TtB2 coatings were obtained and the coating microhardness reaches the value of 33 GPa. The effects of the current density on the mechanical properties, structures, and morphologies of the coatings were studied. XRD analysis indicates that the preferred orientation of the coatings is （001）, which is in accordance with the prediction of the two-dimensional crystal nuclei theory. Thermodynamic prediction and experimental results show that some phases such as TixCy and BaCb are absent at the interface, which indicates the substrate and coatings bind mechanically or physically. Some cracks exist at the interface, which is attributed to the difference between the coefficients of thermal expansion of TiB2 and graphite.

Electronic Structure and Chemical Bond of Titanium Diboride

Titanium diboride was calculated by the density function and discrete variational (DFT-DVM) method to study the relation between structure and properties.Titanium and its first-nearest boron atoms form a strong covalent bond,so TiB 2 has high melting point,hardness and chemical stability.Titanium atom releases two electrons to form Ti 2+ ions,and a boron atom gets one electron to come into B- ion.B- takes the sp2 hybrid and forms σ bonds to link other boron atoms in the same layer.The other one 2p z orbital of every B- ion in the same layer interacts each other to form the π molecular orbital,so TiB 2 has fine electrical property.The calculated density of state is close to the result of XPS experiment of TiB 2.Mainly Ti3d and B2p atomic orbitals contribute the total DOS near the Fermi level.

First-principle study on the physical properties of ultra-incompressible ReB_2

The elastic and physical characteristics of ReB2 crystal have been predicted through a method of density functional theory within the generalized gradient approximation （GGA）. Five independent elastic constants are C11=662 GPa, C12=150 GPa, C13=146 GPa, C33=1090 GPa and Caa=263 GPa. The bulk modulus （B）, shear modulus （G）, Young＇s modulus （E）, Poisson＇s ratio （γ） and the ratio of linear com- pressibility coefficient along the a- and c-axis crystal direction （Ka/Kc） are 356 GPa, 305 GPa, 711 GPa, 0.167 and 1.758, respectively. In addition, the dependence of bulk modulus （B） on temperature （T） and pressure （p） as well as the coefficient of thermal expansion （αL） at various temperatures are evaluated and discussed. The coefficient of thermal expansion is consistent with the famous Grüneisen＇s law when the temperature is less than 1500 K. Our results agree well with the other experimental results.

Biomass-derived carbon doping to enhance the current carrying capacity and flux pinning of an isotopic Mg^(11)B_(2)superconductor

Low activation isotopic boron(11B)based magnesium diboride(Mg^(11)B_(2))superconductors doped with biomass-derived activated carbon were synthesized using11B and magnesium powder via solid-state reaction.The effect of carbon doping on the lattice structure and superconducting properties of Mg^(11)B_(2)bulks were evaluated using X-ray powder diffraction,high resolution transmission electron microscopy,scanning electron microscopy and magnetization measurements.Precise refinement of structural parameters indicates successful substitution of carbon in Mg^(11)B_(2)bulks.The critical current density(Jc)of carbon doped Mg^(11)B_(2)synthesized at 650℃was enhanced more than two times compared with the pure Mg^(11)B_(2)bulk.Similar improvement was observed for the Mg^(11)B_(2)bulks heat-treated at 800℃.This enhancement is due to successful substitution of biomass-derived carbon with high surface area into Mg^(11)B_(2)lattice.The flux pinning mechanism of pure and doped Mg^(11)B_(2)bulks were investigated using the Dew-Hughes model.This study provides information regarding enhancement of the Jc of low activation Mg^(11)B_(2)superconductors suitable for next-generation fusion magnets.

Preparation of ZrB_2 Ceramics by Self-propagating High-temperature Synthesis and Hot Pressing Sintering

ZrB2 ceramics were prepared by self-propagating high-temperature synthesis（SHS） and were sintered by hot pressing（HP）.The effects of the granularities and doses of raw materials in Zr-B2O3-Mgon SHS process and product were investigated.XRD and combustion temperature curves prove that the ideal SHS reactants of Zr-B2O3-Mg are 50μm Zr powder,75μm B2O3 powder and 400μm Mg powder with 45% excessive.The particle sizes of SHS product,acid-leached product,sintered product are 2-5μm,0.5-2μm,2-10μm respectively.Chemical analysis indicates that the acid-leached product consists of ZrB2（94.59%）,ZrO2（3.87%）,and H3BO3（1.54%）,The sintered product has a relative density of 95.4%.

STUDY ON THE MICROSTRUCTURE OF LaB_6-ZrB_2 IN-SITU COMPOSITE

LaB 6 ZrB 2 eutectic in situ composite was prepared by use of an electron beam zone heating technique, and oriented ZrB 2 fibers in a LaB 6 matrix was obtained. The range of diameter of the ZrB 2 fibers was 0.2～1.2 μm with fiber lengths up to 100

Wettability and interfacial behaviour of NdF_3-LiF-Nd_2O_3 on TiB_2-based ceramics

Wettability of TiB2-based ceramics by NdF3-LiF-Nd2O3 melt was studied using sessile drop technique in this paper. Wetting experiment was carried out under inert atmosphere at 1050 ℃. Chemical reactions which occurred on the solid-liquid interface and solid-gas interface during wetting process were discussed by thermodynamic calculations combined with X-ray diffraction （XRD） patterns. Micromorphology and element distribution of fracture surface at the interfacial region of solid/liquid system were analyzed by scanning electron microscope （SEM） equipped with energy dispersive spectrometry （EDS）. Contact angles of the drop were determined as a function of time in order to describe the wetting process, and wetting phenomenon was interpreted from a viewpoint of interface structure. The results showed that wetting was a dynamic wetting process with characteristics of reactive wetting. Penetration and oxidization phenomena during the experiment had great effect on wetting process.

Preparation of highly preferred orientation TiB_2 coatings

This paper focuses on the preparation of titanium diboride （TiB2） coatings on the graphite substrate by continuous current plating （CCP） and pulse current plating （PIC） electrochemical techniques in fluoride electrolytes （LiF-NaF-KF） containing K2T1F6 and KBF4 as the electrochemically-active components at 700℃. Thick leveled and uniform coatings were obtained and were composed of relatively pure TiB2. The effect of the experimental parameters on the microstructure of the coatings was studied. The results showed the electrodeposition with PIC produced coatings with better quality, when compared with those obtained by CCP, under the conditions of the current density i = 0.6 A/cm^2, frequency = 100 Hz, and todtofr = 4/1. XRD analysis indicated that the preferred orientation of coatings is （110） plane, which is in accordance with the prediction of the two-dimensional crystal nuclei theory. The effect of a ratio of ton/toff and frequency on the crystal size, textule coefficient and microstress was also investigated.