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.

Interfacial electronic coupling of V-doped Co_(2)P with high-entropy MXene reduces kinetic energy barrier for efficient overall water splitting

Developing efficient,low-cost non-noble metal-based bifunctional catalysts to achieve excellent hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)kinetics in alkaline media is challenging but very meaningful.However,improving the electronic structure of the catalyst to optimize the adsorption of intermediates and reduce the reaction energy barrier is the key to improve the reaction efficiency.Herein,a V-doped Co_(2)P coupled with high-entropy MXene heterostructure catalyst(V-Co_(2)P@HE)was prepared by a two-step electrodeposition and controlled phosphorization process.The analyses of X-ray absorption spectroscopy,X-ray photoelectron spectroscopy and theoretical calculations jointly show that the introduction of V and the strong electron coupling between the two components optimize the adsorption energy of water molecules and reaction intermediates.Benefiting from the abundant active sites and optimizing intermediate adsorption energy and heterogeneous interface electronic structure,V-Co_(2)P@HE has excellent HER and OER activity and long-term stability under alkaline condition.In particular,when assembled as cathode and anode,the bifunctional V-Co_(2)P@HE catalyst can drive a current density of 10 mA cm^(-2)with only 1.53 V.This work provides new strategies for the application of highentropy MXene and the design of novel non-noble metal-based bifunctional electrolytic water catalysts.

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.

高熵过渡金属二硼化物的高温高压合成

高熵过渡金属二硼化物因其优异的力学性能及热物理性能受到了人们的广泛关注。然而,过去通过高温固相反应合成的效率较低。为此,通过高温高压固相反应,在5.5 GPa、2300℃的温压条件下合成了以VB_(2)、NbB_(2)、TaB_(2)为基底的6类高熵过渡金属二硼化物。高压提高了高温下的固相反应效率,促进了高熵过渡金属二硼化物的合成。通过X射线衍射和能量色散X射线光谱仪表征并确认了6类高熵过渡金属二硼化物均由纯相组成,不存在氧化物杂质或第二相,且元素分布均匀,不存在元素偏析,证明了高温高压合成高熵过渡金属二硼化物的有效性和普适性。相,且元素分布均匀,不存在元素偏析,证明了高温高压合成高熵过渡金属二硼化物的有效性和普适性。

Medium and high-entropy transition mental disilicides with improved infrared emissivity for thermal protection applications

Transition metal disilicides are widely used as heating elements and infrared emission coatings.However,the limited intrinsic infrared emissivity and high thermal conductivity are the main limitations to their applications as infrared emission coatings in the thermal protection system.To cope with these prob-lems,four medium and high-entropy transition metal disilicides,i.e.,(V_(0.25)Ta_(0.25)Mo_(0.25)W_(0.25))Si_(2)(ME-1),(Nb_(0.25)Ta_(0.25)Mo_(0.25)W_(0.25))Si_(2)(ME-2),(V_(0.2)Nb_(0.2)Ta_(0.2)Mo_(0.2)W_(0.2))Si_(2)(HE-1),and(Cr_(0.2)Nb_(0.2)Ta_(0.2)Mo_(0.2)W_(0.2))Si_(2)(HE-2),were designed and synthesized by spark plasma sintering method using transition metal binary disilicides as precursors.The introduction of multi-elements into transition metal disilicides not only im-proved the infrared emissivity but also reduced the electrical and thermal conductivity.Among them,(Cr_(0.2)Nb_(0.2)Ta_(0.2)Mo_(0.2)W_(0.2))Si_(2)(HE-2)had the lowest electrical conductivity of 3789 S cm-1,which is over one order of magnitude lower than that of MoSi_(2)(50000 S cm^(-1)),and total infrared emissivity of 0.42 at room temperature,which is nearly double of that of TaSi_(2).Benefiting from low electrical conductivity and phonon scattering due to lattice distortion,the medium and high-entropy transition metal disilicides also demonstrated a significant decline in thermal conductivity compared to their binary counterparts.Of all samples,HE-2 exhibited the lowest thermal conductivity of 6.4 W m^(−1)K^(−1).The high-entropy tran-sition metal disilicides also present excellent oxidation resistance at high temperatures.The improved infrared emissivity,reduced thermal conductivity,excellent oxidation resistance,and lower densities of these medium and high-entropy transition metal disilicides portend that they are promising as infrared emission coating materials for applications in thermal protection systems.

Achieving ultra-broadband electromagnetic wave absorption in high-entropy transition metal carbides (HE TMCs)

Electronic devices pervade everyday life,which has triggered severe electromagnetic(EM)wave pollution.To face this challenge,developing EM wave absorbers with ultra-broadband absorption capacity is critically required.Currently,nano-composite construction has been widely utilized to realize impedance match and broadband absorption.However,complex experimental procedures,limited thermal stability,and interior oxidation resistance are still unneglectable issues.Therefore,it is appealing to realize ultra-broadband EM wave absorption in single-phase materials with good stability.Aiming at this target,two high-entropy transition metal carbides(HE TMCs)including(Zr,Hf,Nb,Ta)C(HE TMC-2)and(Cr,Zr,Hf,Nb,Ta)C(HE TMC-3)are designed and synthesized,of which the microwave absorption performance is investigated in comparison with previously reported(Ti,Zr,Hf,Nb,Ta)C(HE TMC-1).Due to the synergistic effects of dielectric and magnetic losses,HE TMC-2 and HE TMC-3 exhibit better impedance match and wider effective absorption bandwidth(EAB).In specific,the exclusion of Ti element in HE TMC-2 endows it optimal minimum reflection loss(RL_(min))and EAB of−41.7 dB(2.11 mm,10.52 GHz)and 3.5 GHz(at 3.0 mm),respectively.Remarkably,the incorporation of Cr element in HE TMC-3 significantly improves the impedance match,thus realizing EAB of 10.5,9.2,and 13.9 GHz at 2,3,and 4 mm,respectively.The significance of this study lays on realizing ultra-broadband capacity in HE TMC-3(Cr,Zr,Hf,Nb,Ta),demonstrating the effectiveness of high-entropy component design in tailoring the impedance match.

Regulating the formation ability and mechanical properties of high-entropy transition metal carbides by carbon stoichiometry

Tremendous efforts have been dedicated to promote the formation ability of high-entropy transition metal carbides.However,the majority of methods for the synthesis of high-entropy transition metal carbides still face the challenges of high temperature,low efficiency,additional longtime post-treatment and uncontrollable properties.To cope with these challenges,high-entropy transition metal carbides with regulatable carbon stoichiometry(HE TMC)were designed and synthesized,achieving improved ability for single phase solid solutions formation,promoting of sintering and controllable mechanical properties.Two typical composition series,i.e.,easily synthesized(ZrHfTaNb)C(ZHTNC)and difficultly synthesized(Zr_(0.25)Hf_(0.25)Ta_(0.25)Ti_(0.25))C(ZHTTC)are selected to demonstrate the promoting formation ability of single phase solid solutions from carbon stoichiometry deviations.Single phase high-entropy ZHTTC,which has been proven difficult in forming a single phase solid solution,can be prepared with the decrease of C/TM ratio under 2000℃;while the high-entropy ZHTNC,which has been proven easy in forming a single phase solid solution,can be synthesized at lower temperatures with the decrease of C/TM ratio.The synergistic effect of entropy stabilization and reduced chemical bond strength gaining from carbon stoichiometry deviations is responsible for the formation of single phase solid solutions and the promoted sintering of HE TMC.For example,the relative density of bulk(ZrHfTaNb)C(SPS-ZHTNC)increases from 90.98%to 94.25%with decreasing the C/TM atomic ratio from 0.9 to 0.74.More importantly,the room temperature flexural strength,fracture toughness and brittleness index of SPS-ZHTNCcan be tuned in the range of 384 MPa–419 MPa,4.41 MPam–4.73 MPamand 3.679μm–4.083μm,respectively.Thus,the HE TMCprepared by adjusting the ratio of carbon to refractory transition metal oxides have great potential for achieving low temperature synthesis,promoted sintering and tunable properties.

Synthesis and mechanical and elevated temperature tribological properties of a novel high-entropy(TiVNbMoW)C_(4.375) with carbon stoichiometry deviation

High-entropy carbides are a nascent group of ceramics that are promising for high-temperature applications due to the combination of good stability,high hardness(H),high strength,and superior creep resistance that they display.Due to high melting points and low lattice diffusion coefficients,however,the high-entropy carbides are usually difficult to consolidate to a nearly full density.To cope with this challenge,herein,binary carbides including TiC,V_(8)C_(7),NbC,Mo_(2)C,and WC with different carbon stoichiometry were used to prepare dense high-entropy(TiVNbMoW)C_(4.375),and the influence of carbon vacancy on formation ability and mechanical properties of carbon-deficient high-entropy(TiVNbMoW)C_(4.375) were investigated.Intriguingly,although the starting binary carbides have different crystal structures and carbon stoichiometry,the as-prepared high-entropy material showed a rock-salt structure with a relatively high density(98.1%)and good mechanical properties with hardness of 19.4±0.4 GPa and fracture toughness(KIC)of 4.02 MPa·m^(1/2).More importantly,the high-entropy(TiVNbMoW)C_(4.375) exhibited low coefficient of friction(COF)at room temperature(RT)and 800℃.Wear rate(W)gradually increased with the temperature rising,which were attributed to the formation of low-hardness oxidation films at high temperatures to aggravate wear.At 800℃,lubricating films formed from sufficient oxidation products of V_(2)O_(5) and MoO_(3) effectively improved tribological behavior of the high-entropy(TiVNbMoW)C_(4.375).Wear mechanisms were mainly abrasive wear resulting from grain pullout and brittle fracture as well as oxidation wear generated from high-temperature reactions.These results are useful as valuable guidance and reference to the synthesis of high-entropy ceramics(HECs)for sliding parts under high-temperature serving conditions.

(Cr_(0.2)Mn_(0.2)Fe_(0.2)Co_(0.2)Mo_(0.2))B:A novel high-entropy monoboride with good electromagnetic interference shielding performance in K-band

A novel equimolar high-entropy(HE)transition metal monoboride,(Cr_(0.2)Mn_(0.2)Fe_(0.2)Co_(0.2)Mo_(0.2))B,was designed and prepared in powder and bulk form by high temperature elemental reaction method and spark plasma sintering(SPS)method,respectively.XRD analysis shows that HE(Cr_(0.2)Mn_(0.2)Fe_(0.2)Co_(0.2)Mo_(0.2))B possesses orthorhombic structure with Pnma space group.Through Rietveld refinement,the lattice parameters of HE(Cr_(0.2)Mn_(0.2)Fe_(0.2)Co_(0.2)Mo_(0.2))B are a=5.6675,b=2.9714,c=4.2209 and the theoretical density is 6.95 g/cm~3.The Vickers hardness and electrical conductivity of HE(Cr_(0.2)Mn_(0.2)Fe_(0.2)Co_(0.2)Mo_(0.2))B bulk with relative density of 90%is 12.3±0.5 GPa and 0.49±0.04×10~6 S/m,respectively.Due to high electrical conductivity,HE(Cr_(0.2)Mn_(0.2)Fe_(0.2)Co_(0.2)Mo_(0.2))B bulk with 3.0 mm thickness displays superior EMI shielding performance in 18.0–26.5 GHz(K-band),and the average values of SET,SER,and SEAare 23.3 dB,13.9 dB,and 9.4 dB,respectively.The EMI shielding mechanism of HE(Cr_(0.2)Mn_(0.2)Fe_(0.2)Co_(0.2)Mo_(0.2))B mainly results from reflection.

5d过渡金属二硼化物的结构和热、力学性质的第一性原理计算

利用基于密度泛函理论的第一性原理系统地研究了5d过渡金属二硼化物TMB2(TM=Hf—Au)的结构、热学、力学和电学性质.我们考虑了三种结构,分别为AlB2,ReB2和WB2结构.计算得到的晶格常数与先前的理论和实验研究符合得很好.通过计算生成焓预测了化合物的热力学稳定性;从HfB2到AuB2,生成焓的整体趋势是逐渐增加的.在所考虑的结构中,对HfB2和TaB2,AlB2结构是最稳定的;对WB2,ReB2,OsB2,IrB2和AuB2,ReB2结构是最稳定的;对PtB2,WB2结构是最稳定的.在所考虑的化合物中,ReB2结构的ReB2具有最大的剪切模量(295GPa),是最硬的化合物,与先前的理论和实验结果相符.计算得到的总态密度显示所有结构都具有金属特性.讨论了系列化合物的变化趋势.

Porous high entropy(Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)B2: A novel strategy towards making ultrahigh temperature ceramics thermal insulating

Transition metal diborides based ultrahigh temperature ceramics(UHTCs) are characterized by high melting point, high strength and hardness, and high electrical and thermal conductivity. The high thermal conductivity arises from both electronic and phonon contributions. Thus electronic and phonon contributions must be controlled simultaneously in reducing the thermal conductivity of transition metal diborides. In high entropy(HE) materials, both electrons and phonons are scattered such that the thermal conductivity can significantly be reduced, which opens a new window to design novel insulating materials. Inspired by the high entropy effect, porous HE(Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)B2 is designed in this work as a new thermal insulting ultrahigh temperature material and is synthesized by an in-situ thermal borocarbon reduction/partial sintering process. The porous HE(Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)B2 possesses high porosity of 75.67%, pore size of 0.3–1.2 μm, homogeneous microstructure with small grain size of 400–800 nm, which results in low room temperature thermal diffusivity and thermal conductivity of 0.74 mm2 s^-1 and 0.51 W m^-1K^-1, respectively. In addition, it exhibits high compressive strength of3.93 MPa. The combination of these properties indicates that exploring porous high entropy ceramics such as porous HE(Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)B2 is a novel strategy in making UHTCs thermal insulating.

Theoretical predictions and experimental verification on the phase stability of enthalpy-stabilized HE TMREB_(2)s

Transition metal diborides(TMB_(2)s)are the materials of choice in extreme environments due to their excellent thermal and chemical stabilities.However,the degradation of oxidation resistance of TMB_(2)s at elevated temperature still hinders their applications.To cope with this challenge,it is effective to incorporate rare earth elements to form high-entropy transition and rare-earth metal diborides(HE TMREBs).To obtain thermodynamically stable single-phase structures for HE TMREB_(2)s,a“16×16 mixed enthalpy matrix”is constructed using first-principles calculations to predict the single-phase formation ability of120 two-component diborides(TCBs).Through the use of the“16×16 mixed enthalpy matrix”of TCBs,specific combinations of TMB_(2)s and REB_(2)s that are most likely to form single-phase HE TMREB_(2)s are confirmed.Subsequently,based on the energy distribution of the local mixing enthalpies of all possible configurations,the enthalpy and entropy descriptors of HE TMREB_(2)s(RE=Sc,Lu,Tm,Er,Ho and Dy)are investigated.It is found that the mixing enthalpy plays a critical role in the stability of the single-phase HE TMREB_(2)s,i.e.,HE TMREB_(2)s are enthalpy-stabilized materials.The experimental results further confirm that enthalpy dominates the thermodynamic domain and drives the stability of REB_(2)s in HE TMREB_(2)s.This study validates that enthalpy-stabilized HE TMREB_(2)s can further expand the compositional space of ultrahigh temperature ceramics(UHTCs)and is expected to further improve the oxidation resistance and high temperature properties of UHTCs.