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.

Progress in densification and toughening of high entropy carbide ceramics

High entropy carbide ceramics(HECC)are solid solution of inorganic compounds with five or more prin-cipal metal cations.Research interests in HECC are dramatically sparked by the enormous possibilities in composition-microstructure-property tailoring.As widely acknowledged,HECCs enjoy higher hardness and oxidation/corrosion/wear resistance,as well as lower thermal conductivity than conventional engi-neering carbide ceramics,making them the most potential candidates for state-of-the-art structural and functional applications in extreme service conditions.Despite the advantages,however,the poor den-sification coupled with low fracture toughness significantly limited the practical applications of HECC.Adding to the difficulty,the literature available for toughening HECC is woefully limited.In considera-tion of this insufficiency,we apply towards offer a comprehensive,critical review of the mechanical be-havior of HECC,highlighting the densification enhancing strategies(carbon content,sintering techniques,grain size,sintering aids,etc.)as well as toughening methods including particle toughening,whisker/fiber toughening,synergistic toughening,graphene-carbon nanotube toughening,to further the service reliabil-ity of HECC in practical industrial applications.Furthermore,despite some significant successes,important directions for further development of HECC are given as multi-dimensional gradient HECC,additive man-ufacturing of HECC,processing-composition-microstructure-property relationship prediction and genomes of HECC based on machine learning,and high-throughput computing,etc.

High-entropy(Y_(0.2)Gd_(0.2)Dy_(0.2)Er_(0.2)Yb_(0.2))2Hf_(2)O_(7) ceramic: A promising thermal barrier coating material

Thermal barrier coating(TBC)materials perform an increasingly important role in the thermal or chemical protection of hot components in a gas turbine.In this study,a novel high entropy hafnate(Y_(0.2)Gd_(0.2)Dy_(0.2)Er_(0.2)Yb_(0.2))_(2)Hf_(2)O_(7) was synthesized by solution combustion method and investigated as a potential TBC layer.The as-synthesized(Y_(0.2)Gd_(0.2)Dy_(0.2)Er_(0.2)Yb_(0.2))_(2)Hf_(2)O_(7) possesses a pure single disordered fluorite phase with a highly homogeneous distribution of rare earth(RE)cations,exhibiting prominent phase stability and excellent chemical compatibility with Al_(2)O_(3) even at 1300°C.Moreover,(Y_(0.2)Gd_(0.2)Dy_(0.2)Er_(0.2)Yb_(0.2))_(2)Hf_(2)O_(7) demonstrates a more sluggish grain growth rate than Y_(2)Hf_(2)O_(7).The thermal conductivity of(Y_(0.2)Gd_(0.2)Dy_(0.2)Er_(0.2)Yb_(0.2))_(2)Hf_(2)O_(7)(0.73-0.93 W m^(-1)K^(-1))is smaller than those of components RE_(2)Hf_(2)O_(7) and many high entropy TBC materials.Beside,the calculated thermal expansion coefficient(TEC)of(Y_(0.2)Gd_(0.2)Dy_(0.2)Er_(0.2)Yb_(0.2))_(2)Hf_(2)O_(7)(10.68×10^(-6)/K,1100°C)is smaller than that of yttriastabilized zirconia(YSZ).Based on the results of this work,(Y_(0.2)Gd_(0.2)Dy_(0.2)Er_(0.2)Yb_(0.2))_(2)Hf_(2)O_(7) is suitable for the next generation TBC materials with outstanding properties.

High entropy defective fluorite structured rare-earth niobates and tantalates for thermal barrier applications

Rare-earth tantalates and niobates(REjTaO7 and REjNbO7)have been considered as promising candidate thermal barrier coating(TBC)materials in next generation gas-turbine engines due to their ultra-low thermal conductivity and better thermal stability than yttria-stabilized zirconia(YSZ).However,the low Vickers hardness and toughness are the main shortcomings of RE;TaO-and REjNbOr that limit their applications as TBC materials.To increase the hardness,high entropy(Yu3Ybu3Er/3)sTaOr,(Y13YbnErns)NbO,and(Sm1/6Eu1/6Y 1/6Yb1/6Lu1/6Er1/6)3(Nb1/2Ta1/2)O7 are designed and synthesized in this study.These high entropy ceramics exhibit high Vickers hardness(10.912.0 GPa),close thermal expansion coefficients to that of single-principal-component RE3TaO,and RE;NbO,(7.9×10^-6-10.8×10-6 C-1 at room temperature),good phase stability,and good chemical compatibility with thermally grown Al2O3,which make them promising for applications as candidate TBC materials.

Theoretical prediction on thermal and mechanical properties of high entropy(Zr(0.2)Hf(0.2)Ti(0.2)Nb(0.2)Ta(0.2))C by deep learning potential

High entropy materials(HEMs, e.g. high entropy alloys, high entropy ceramics) have gained increasing interests due to the possibility that they can provide challenge properties unattainable by traditional materials. Though a large number of HEMs have emerged, there is still in lack of theoretical predictions and simulations on HEMs, which is probably caused by the chemical complexity of HEMs. In this work,we demonstrate that the machine learning potentials developed in recent years can overcome the complexity of HEMs, and serve as powerful theoretical tools to simulate HEMs. A deep learning potential(DLP) for high entropy(Zr(0.2) Hf(0.2) Ti(0.2) Nb(0.2) Ta(0.2))C is fitted with the prediction error in energy and force being 9.4 me V/atom and 217 me V/?, respectively. The reliability and generality of the DLP are affirmed,since it can accurately predict lattice parameters and elastic constants of mono-phase carbides TMC(TM = Ti, Zr, Hf, Nb and Ta). Lattice constants(increase from 4.5707 ? to 4.6727 ?), thermal expansion coefficients(increase from 7.85×10-6 K^(-1) to 10.58×10-6 K^(-1)), phonon thermal conductivities(decrease from 2.02 W·m-1·K^(-1) to 0.95 W·m-1·K^(-1)), and elastic properties of high entropy(Zr(0.2) Hf(0.2) Ti(0.2) Nb(0.2) Ta(0.2))C in temperature ranging from 0°C to 2400°C are predicted by molecular dynamics simulations. The predicted room temperature properties agree well with experimental measurements, indicating the high accuracy of the DLP. With introducing of machine learning potentials, many problems that are intractable by traditional methods can be handled now. It is hopeful that deep insight into HEMs can be obtained in the future by such powerful methods.

Electromagnetic wave absorbing properties of TMCs(TM=Ti,Zr,Hf,Nb and Ta)and high entropy(Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C

Electromagnetic wave(EMW)absorbing materials play a vital role in modern communication and information processing technologies to inhibit information leakage and prevent possible damages to environment and human bodies.Currently,most of EMW absorbing materials are either composites of two or more phases or in the form of nanosheets,nanowires or nanofibers in order to enhance the EMW absorption performance through dielectric loss,magnetic loss and dielectric/magnetic loss coupling.However,the combination of complex shapes/multi phases and nanosizes may compound the difficulties of materials processing,composition and interfaces control as well as performance maintenance during service.Thus,searching for single phase materials with good stability and superior EMW absorbing properties is appealing.To achieve this goal,the EMW absorbing properties of transition metal carbides TMCs(TM=Ti,Zr,Hf,Nb and Ta)and high entropy(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C which belong to ultrahigh temperature ceramics,were investigated in this work.Due to the good electrical conductivity and splitting of d orbitals into lower energy t2glevel and higher energy eglevel in TMC6octahedral arrangement,TMCs(TM=Ti,Zr,Hf,Nb and Ta)exhibit good EMW absorbing properties.Especially,Hf C and Ta C exhibit superior EMW absorbing properties.The minimum reflection loss(RLmin)value of Hf C is-55.8 d B at 6.0 GHz with the thickness of 3.8 mm and the effective absorption bandwidth(E_(AB))is 6.0 GHz from 12.0 to 18.0 GHz at thickness of 1.9 mm;the RL_(minvalue)of Ta C reaches-41.1 d B at 16.2 GHz with a thickness of 2.0 mm and the EABis 6.1 GHz with a thickness of 2.2 mm.Intriguingly,the electromagnetic parameters,i.e.,complex permittivity and permeability are tunable by forming single phase solid solution or high entropy(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C.The R_(Lminvalue)of high entropy(Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2))C is-38.5 d B at 9.5 GHz with the thickness of 1.9 mm,and the EABis 2.3 GHz(from 11.3 to 13.6 GHz)at thickness of 1.5 mm.The significance of this work is that it opens a new window to design single phase high performance EMW absorbing materials by dielectric/magnetic loss coupling through tuning the conductivity and crystal field splitting energy of d orbitals of transition metals in carbides,nitrides and possibly borides.

High entropy(Y0.2Yb0.2Lu0.2Eu0.2Er0.2)3Al5O12:A novel high temperature stable thermal barrier material

Ytterbium aluminum garnet(Yb3Al5O12)is considered as a promising thermal barrier material.However,the main limitations of Yb3Al5O12 for thermal barrier applications are relative low thermal expansion coefficient and high thermal conductivity.In order to overcome these obstacles,herein,a new high entropy(Y0.2Yb0.2Lu0.2Eu0.2Er0.2)3Al5O12 ceramic was designed,and then powders and bulk were prepared through solid-state reaction method and spark plasma sintering(SPS),respectively.The thermal expansion coefficient of HE(Y0.2Yb0.2Lu0.2Eu0.2Er0.2)3Al5O12 is(8.54±0.29)×10^-6 K^-1 at 673 K–1273 K,which is about 9%higher than that of Yb3Al5O12.The thermal conductivity of HE(Y0.2Yb0.2Lu0.2Eu0.2Er0.2)3Al5O12 ceramic is 3.81 W·m^-1 K^-1 at 300 K,which is about 18%lower than that of Yb3Al5O12.Moreover,there is no reaction between HE(Y0.2Yb0.2Lu0.2Eu0.2Er0.2)3Al5O12 and thermally grown(TG)Al2O3 even at 1600℃.After annealing at 1590℃for 18 h,the average grain size of HE(Y0.2Yb0.2Lu0.2Eu0.2Er0.2)3Al5O12 increases only from 1.56μm to 2.27μm.Close thermal expansion coefficient to TG Al2O3,low thermal conductivity,good phase stability,excellent chemical compatibility with TG Al2O3 and slow grain growth rate make HE(Y0.2Yb0.2Lu0.2Eu0.2Er0.2)3Al5O12 promising for thermal barrier applications.

Achieving strong microwave absorption capability and wide absorption bandwidth through a combination of high entropy rare earth silicide carbides/rare earth oxides

Developing electromagnetic(EM) wave absorbing materials with low reflection coefficient and optimal operating frequency band is urgently needed on account of the increasingly serious EM pollution. However, the applications of common EM absorbing materials are encumbered by poor high-temperature stability, poor oxidation resistance, narrow absorption bandwidth or high density. Herein, the strong EM absorption capability and wide efficient absorption bandwidth of high entropy ceramics are reported for the first time, which are designed by a combination of the novel high entropy(HE) rare earth silicide carbides/rare earth oxides(RE3 Si2 C2/RE2 O3). Three HE powders, i.e., HERSC-1(HE(Tm0.2 Y0.2 Dy0.2 Gd0.2 Tb0.2)3 Si2 C2),HERSC-2 HE(Tm0.2 Y0.2 Dy0.2 Gd0.2 Tb0.2)3 Si2 C2/HE(Tm0.2 Y0.2 Dy0.2 Gd0.2 Tb0.2)2 O3) and HERSC-3(HE(Tm0.2 Y0.2 Dy0.2 Gd0.2 Tb0.2)3 Si2 C2/HE(Tm0.2 Y0.2 Dy0.2 Gd0.2 Tb0.2)2 O3), are synthesized. Although HERSC-1 exhibits a limited absorption effect(the minimum reflection loss(RLmin) is-11.6 d B at 3.4 mm) and a relatively narrow effective absorption bandwidth(EAB) of 1.7 GHz, the optimal absorption RLminvalue and EAB of HERSC-2 and HERSC-3 are-40.7 d B(at 2.9 mm), 3.4 GHz and-50.9 d B(at 2.0 mm), 4.5 GHz,respectively, demonstrating strong microwave absorption capability and wide absorption bandwidth.Considering the better stability, low density and strong EM absorption effect, HE ceramics are promising as a new type of EM absorbing materials.

High entropy rare earth hexaborides/tetraborides(HE REB_(6)/HE REB_(4)) composite powders with enhanced electromagnetic wave absorption performance

The increasing electromagnetic hazards including electromagnetic interference and electromagnetic pollution,which were stemmed from massive usage of electromagnetic technology,have triggered widespread concerns.To cope with this challenge,electromagnetic wave absorbing materials with high performance are greatly needed.Composite construction has been widely applied in electromagnetic(EM)wave absorbing materials to achieve high permittivity,high permeability and impedance matching.However,high-temperature stability,oxidation and corrosion resistance are still unignorable issues.Herein,high entropy hexaborides/tetraborides(HE REB_(6)/HE REB_(4))composites with synergistic dielectric and magnetic losses were designed and successfully synthesized through a one-step boron carbide reduction method.The five as-prepared(Y_(0.2) Nd_(0.2) Sm_(0.2) Eu_(0.2) Er_(0.2))B_(6)/(Y_(0.2) Nd_(0.2) Sm_(0.2) Eu_(0.2) Er_(0.2))B_(4),(Y_(0.2) Nd_(0.2) Sm_(0.2) Er_(0.2) Yb_(0.2))B_(6)/(Y_(0.2) Nd_(0.2) Sm_(0.2) Er_(0.2) Yb_(0.2))B_(4),(Y_(0.2) Nd_(0.2) Eu_(0.2) Er_(0.2) Yb_(0.2))B_(6)/(Y_(0.2) Nd_(0.2) Eu_(0.2) Er_(0.2) Yb_(0.2))B_(4),(Nd_(0.2) Sm_(0.2) Eu_(0.2) Er_(0.2) Yb_(0.2))B_(6)/(Nd_(0.2) Sm_(0.2) Eu_(0.2) Er_(0.2) Yb_(0.2))B_(4) and(Y_(0.2) Sm_(0.2) Eu_(0.2) Er_(0.2) Yb_(0.2))B_(6)/(Y_(0.2) Sm_(0.2) Eu_(0.2) Er_(0.2) Yb_(0.2))B_(4) contain two phases of HE REB_(6) and HE REB_(4).Among them(Y_(0.2) Nd_(0.2) Sm_(0.2) Eu_(0.2) Er_(0.2))B_(6)/(Y_(0.2) Nd_(0.2) Sm_(0.2) Eu_(0.2) Er_(0.2))B_(4)(HE REB_(6)/HE REB_(4)-1)and(Y_(0.2) Nd_(0.2) Sm_(0.2) Er_(0.2) Yb_(0.2))B_(6)/(Y_(0.2) Nd_(0.2) Sm_(0.2) Er_(0.2) Yb_(0.2))B_(4)(HE REB_(6)/HE REB_(4)-2)exhibit excellent EM wave absorption properties.The optimal minimum reflection loss(RL_(m in))and effective absorption bandwidth(E_(AB))of HE REB_(6)/HE REB_(4)-1 and HE REB_(6)/HE REB_(4)-2 are–53.3 dB(at 1.7 mm),4.2 GHz(at 1.5 mm)and–43.5 dB(1.3 mm),4.2 GHz(1.5 mm),respectively.The combination of conducting HE REB_(4) with magnetism into HE REB_(6) as a second phase enhances dielectric and magnetic losses,which lead to enhanced EM wave absorption performance.Considering superior high-temperature stability,oxidation and corrosion resistance of HE REB_(6) and HE REB_(4),HE REB_(6)/HE REB_(4) composite ceramics are promising as a new type of high-performance EM wave absorbing materials.

Grain boundary segregation induced strong UHTCs at elevated temperatures:A universal mechanism from conventional UHTCs to high entropy UHTCs

Ultra-high temperature ceramics(UHTCs)exhibit a unique combination of excellent properties,including ultra-high melting point,excellent chemical stability,and good oxidation resistance,which make them promising candidates for aerospace and nuclear applications.However,the degradation of hightemperature strength is one of the main limitations for their ultra-high temperature applications.Thus,searching for mechanisms that can help to develop high-performance UHTCs with good high-temperature mechanical properties is urgently needed.To achieve this goal,grain boundary segregation of a series of carbides,including conventional,medium entropy,and high entropy transition metal carbides,i.e.,Zr_(0.95)W_(0.05)C,TiZrHfC_(3),ZrHfNbTaC_(4),TiZrHfNbTaC_(5),were studied by atomistic simulations with a fitted Deep Potential(DP),and the effects of segregation on grain boundary strength were emphasized.For all the studied carbides,grain boundary segregations are realized,which are dominated by the atomic size effect.In addition,tensile simulations indicate that grain boundaries(GBs)will usually be strengthened due to segregation.Our simulation results reveal that grain boundary segregation may be a universal mechanism in enhancing the high-temperature strength of both conventional UHTCs and medium/high entropy UHTCs,since GBs play a key role in controlling the fracture of UHTCs at elevated temperatures.