High-entropy fluorite oxides: Atomic stabiliser effects on thermal-mechanical properties

High-entropy oxides Hf_0.25Zr_0.25Ce_0.25Gd_0.125X_0.125O_2-δ (X = Ca, Ti or Si) have been fabricated via solid-state reactions, in which the co-stabiliser X was intentionally chosen for its significant atomic mass and size difference from Gd. The single phase of these cubic fluorite oxides with dense microstructures has been confirmed by XRD, EDS and TEM characterizations. These phases are thermally stable without the appearance of secondary phase and phase separation within the temperature range studied (up to 1200 °C). Compared to yttria-stabilised zirconia (YSZ), which is used in the current commercial thermal barrier coatings, these fluorite oxides have higher coefficients of thermal expansion and lower thermal conductivities. They also exhibit comparable Young’s modulus and hardness with other reported high-entropy fluorite oxides. The fluorite oxides reported in this study are promising to improve the thermal expansion matching between ceramic topcoat and metal substrates for thermal barrier coating applications.     

A five-component entropy-stabilized fluorite oxide

In this paper, we report a new entropy-stabilized fluorite oxide, formed by solid-state reacting the equimolar mixture of CeO₂, ZrO₂, HfO₂, TiO₂ and SnO₂ at 1500?°C. We demonstrated that the oxide is truly entropy-stabilized by showing that the oxide was transferred to a multiphase state when annealed at lower temperatures, and the transition between the low-temperature multiphase and high-temperature single-phase states is reversible. Room-temperature thermal conductivity of the fluorite oxide was measured to be 1.28?Wm^?1?K^?1. The value is only half of that for 7?wt% yttria-stabilized zirconia, suggesting the material could be useful for thermal-insulation applications.     

On the ionic conductivity of some zirconia-derived high-entropy oxides

The reported High Entropy Oxides (HEOs) up to now exhibit lower ionic conductivity values than those of classical SOFC electrolytes. Multi-cations oxides, stabilized with the fluorite-type structure are investigated here in order to examine whether the high entropy is relevant to enhance the anionic conductivity of such HEOs, or not. The two synthesis routes that are used do not show significant impact on material properties. Based on configurational entropy (≥ 1.5 k_B/f.u. for HEOs) and ionic radius difference calculations, new compositions are designed and prepared: i) the (Hf_1/3Ce_1/3Zr_1/3)_1-x(Gd_1/2Y_1/2)_xO_2-x/2 series in which the x ratio is increased so as to promote a high vacancy concentration, ii) the (Hf_xCe_yZr_1-x-y)_0.85Yb_0.15O_1.93 series based on the critical radius concept. The ionic conductivity of these HEOs is slightly improved compared to previously reported data but does not exceed 4 × 10^?4 S.cm^?1 at 600 °C. Possible causes of such a low ionic conductivity value are discussed.     

Formation and properties of Ca2+ substituted (Ce0.2Zr0.2Ti0.2Sn0.2Hf0.2)O2 high-entropy ceramics

Five equimolar multicomponent oxides were synthesized by replacing one of five cations in (Ce_0.2Zr_0.2Ti_0.2Sn_0.2Hf_0.2)O₂ with Ca²⁺. The results reveal that except for the one in which Ce⁴⁺ replaced by Ca²⁺, the other four components can form single-phase high-entropy fluorite oxides (HEFOs) at different temperatures, which indicates that Ce⁴⁺ is very important for the formation of single-phase HEFOs. The sintering behavior, lattice parameter and properties containing density, porosity, flexural strength and thermal conductivity of the four single-phase HEFOs were investigated. With the change of substituted ions, grain size, relative density, flexural strength and thermal conductivity of the materials vary greatly, which are correlated to the size disorder and mass disorder of these materials. The results of this paper provide a reference for the composition designing and performance tailoring of equimolar HEFOs.     

Porous (Ce0.2Zr0.2Ti0.2Sn0.2Ca0.2)O2-δ high-entropy ceramics with both high strength and low thermal conductivity

Single-phase (Ce_0.2Zr_0.2Ti_0.2Sn_0.2Ca_0.2)O_2-δ porous high-entropy ceramics have been in-situ fabricated by foam-gelcasting-freeze drying method at different temperatures. The microstructure, phase composition, and properties of the obtained ceramics were investigated. The results indicate that compared with other porous ceramics reported in the literatures, this type of ceramics exhibits excellent performance. The sample prepared at 1350 °C shows high porosity (88.6 %), low thermal conductivity (0.023 W m^-1 K^-1), and high compressive strength (1.48 MPa). The current study suggests that porous (Ce_0.2Zr_0.2Ti_0.2Sn_0.2Ca_0.2)O_2-δ high entropy ceramics are promising candidates for thermal insulation applications.     

A new class of high-entropy fluorite oxides with tunable expansion coefficients,low thermal conductivity and exceptional sintering resistance

High-temperature thermal barrier coating (TBC) materials are desired for the development of high-efficient gas turbines and diesel engines. Herein, to meet up with this requirement, a new class of high-entropy fluorite-type oxides (HEFOs) has been synthesized via a solid-state reaction method. Comparing to La₂Ce₂O₇, a promising TBC material, the HEFOs exhibit similar high thermal expansion coefficients (TECs) of 11.92×10⁻⁶∼12.11×10⁻⁶ K^-1 at temperatures above 673 K but a better TEC matching performance at the temperature range of 473–673 K. It is also found that through tuning the average A-site cation radius, the TEC of the HEFOs could be tailored efficiently. The HEFOs also possess low thermal conductivities of 1.52-1.55 W∙m^-1∙K^-1 at room temperature, which is much lower than that of La₂Ce₂O₇ and comparable to pyrochlores as Gd₂Zr₂O₇. Moreover, the HEFOs display good sintering resistance and phase stability even at temperatures as high as 1873 K. The combination of these fascinating properties makes the HEFOs good candidates for thermal barrier coating and thermal insulating materials.     

High-entropy stoichiometric perovskite oxides based on valence combinations

The valence-combination strategy was applied to design B-site substitution non-equimolar stoichiometric high-entropy perovskite oxides (HEPOs). 29, 56 and 29 valence combinations with the maximum configurational entropy higher than 1.5R for five-component HEPOs were identified when the average valence of B-site is 3, 4 and 5, respectively. Synthesis experiment was performed on 8 valence combinations with the average valence of B-site equal to 4. Single-phase HEPOs were obtained from 6 of them. It was also found that most of HEPOs have ordered structures. The formation of single-phase HEPO and ordered structure was discussed in terms of structural tolerance factor and valence-difference factor.     

A novel high-entropy monoboride (Mo0.2Ta0.2Ni0.2Cr0.2W0.2)B with superhardness and low thermal conductivity

A new high-entropy monoboride (Mo_0.2Ta_0.2Ni_0.2Cr_0.2W_0.2)B ceramic with a WB-type orthogonal structure was designed and synthesised by in-situ reactive hot pressing at 2000 °C and 30 MPa for 1.5 h under an argon atmosphere. The microstructure of the sintered samples was comprehensively characterised, and the formation of a high-entropy monoboride (Mo_0.2Ta_0.2Ni_0.2Cr_0.2W_0.2)B ceramic was confirmed. Owing to the high density of the dislocations and strengthening metal-boron bonds, the high-entropy (Mo_0.2Ta_0.2Ni_0.2Cr_0.2W_0.2)B ceramic exhibited a hardness of 48.51 ± 4.07 GPa, which enabled it to be classed as a new superhard material. In addition, the thermal conductivity (2.05 ± 0.10 W/(m·K) at 400 °C) and electric conductivity (132.30 S/cm) were determined.     

High-entropy titanate pyrochlore as newly low-thermal conductivity ceramics

Low-thermal conductivity ceramics play an indispensable role in maximizing the efficiency and durability of hot end components. Pyrochlore, particularly zirconate pyrochlore, is currently a highly promising and widely studied candidate for its extremely low thermal conductivity. However, there are still few pyrochlores that offer both stiffness, insulation, and good thermal expansion properties. In this work, the solidification method was innovatively introduced into the preparation of titanate pyrochlore, and combined it with the compositional design of high-entropy. Through careful composition design and solidification control, the high-density and uniform elements distributed high-entropy titanate pyrochlore ceramics were successfully prepared. These samples possess high hardness (15.88 GPa) and Young’s modulus (295.5 GPa), low thermal conductivity (0.947 W·m^?1·K^?1), excellent thermal expansion coefficient (11.6 ×10^?6/K) and an exquisite balance between stiffness and insulation (E/κ, 312.1 GPa·W^?1·m·K), in which the E/κ exhibits the highest value among the current reported works.     

High-entropy carbide ceramics with refined microstructure and enhanced thermal conductivity by the addition of graphite

Aiming at the refined microstructure and enhanced thermal conductivity of high-entropy carbide (HEC) ceramics for high-temperature applications, the addition effect of graphite was comprehensively investigated in this study. HEC ceramics incorporated with different contents of graphite were solidified by spark plasma sintering (SPS) using self-synthesized high-entropy (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C powder and graphite as starting materials. The results demonstrate that the incorporated graphite removed the oxygen impurity in the mixed powders, decreased the oxygen content and increased the lattice parameter of the HEC phase, and improved the densification behavior of HEC ceramics. On the other hand, the addition of graphite brings a refinement of HEC grains and improves the mechanical properties. More importantly, the thermal conductivity of the HEC ceramics was significantly increased owing to the removing effect of oxide impurity by the added graphite. It is considered that the lattice "purified" HEC grains with low oxygen content contribute to the improvement in thermal conductivity of the ceramics.     

Marked reduction in the thermal conductivity of (La0.2Gd0.2Y0.2Yb0.2Er0.2)2Zr2O7 high-entropy ceramics by substituting Zr4+ with Ti4+

The (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ (x = 0–0.5) high-entropy ceramics were successfully prepared by a solid state reaction method and their structures and thermo-physical properties were investigated. It was found that the high-entropy ceramics demonstrate pure pyrochlore phase with the composition of x = 0.1–0.5, while (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂Zr₂O₇ shows the defective fluorite structure. The sintered high-entropy ceramics are dense and the grain boundaries are clean. The grain size of high-entropy ceramics increases with the Ti⁴⁺ content. The average thermal expansion coefficients of the (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ high-entropy ceramics range from 10.65 × 10^?6 K^?1 to 10.84 × 10^?6 K^?1. Importantly, the substitution of Zr⁴⁺ with Ti⁴⁺ resulted in a remarkable decrease in thermal conductivity of (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ high-entropy ceramics. It reduced from 1.66 W m^?1 K^?1 to 1.20 W m^?1 K^?1, which should be ascribed to the synergistic effects of mass disorder, size disorder, mixed configuration entropy value and rattlers.     

High-entropy thermal barrier coating of rare-earth zirconate: A case study on (La0.2Nd0.2Sm0.2Eu0.2Gd0.2)2Zr2O7 prepared by atmospheric plasma spraying

We report a double-ceramic-layer (DCL) thermal barrier coating (TBC) with high-entropy rare-earth zirconate (HE-REZ) as the top layer and yttria stabilized zirconia (YSZ) as the inner layer sprayed on Ni-based superalloy by atmospheric plasma spraying. La₂Zr₂O₇ (LZ) was selected as a reference for the HE-REZ. Thermal cycling test results demonstrate that the HE-REZ/YSZ DCL coating exhibited obviously improved thermal stability when compared to the LZ/YSZ DCL coating. The reasons for the improvement of the thermal shock resistance are considered to be the anti-sinterability of the HE-REZ ceramics during the thermal cycling test attributed to the sluggish diffusion effect and as well as the better match in the coefficient of thermal expansion of HE-REZ coating with the YSZ inner layer. In addition, the HE-REZ coating maintains fluorite structure after thermal cycling test. This study makes one step forward in the development and application of high-entropy rare-earth zirconate ceramic thermal barrier coatings.     

Structural,thermal and mechanical properties of aluminum nitride ceramics with CeO2 as a sintering aid

AlN ceramics have been prepared with CeO₂ as a sintering aid at a sintering temperature of 1900 °C. The effect of CeO₂ contents on the microstructure, density, thermal conductivity and hardness was investigated. Addition of CeO₂ exerted a significant effect on the densification of AlN ceramics and hence on the microstructure. Thermal conductivity of AlN ceramics increased with CeO₂ content and was greater than that of Y₂O₃-doped AlN ceramics at a similar sintering temperature. The resulting AlN ceramics with 1.50 wt% of CeO₂ had the highest relative density of 99.94%, thermal conductivity of 156 W m⁻¹ K⁻¹ and hardness of 72.46 kg/mm².     

From high-entropy ceramics to compositionally-complex ceramics: A case study of fluorite oxides

Using fluorite oxides as an example, this study broadens high-entropy ceramics (HECs) to compositionally-complex ceramics (CCCs) or multi-principal cation ceramics (MPCCs) to include medium-entropy and/or non-equimolar compositions. Nine compositions of compositionally-complex fluorite oxides (CCFOs) with the general formula of (Hf_1/3Zr_1/3Ce_1/3)_1-x(Y_1/2X_1/2)_xO_2-δ (X = Yb, Ca, and Gd; x = 0.4, 0.148, and 0.058) are fabricated. The phase stability, mechanical properties, and thermal conductivities are measured. Compared with yttria-stabilized zirconia, these CCFOs exhibit increased cubic phase stability and reduced thermal conductivity, while retaining high Young’s modulus (∼210 GPa) and nanohardness (∼18 GPa). Moreover, the temperature-dependent thermal conductivity in the non-equimolar CCFOs shows an amorphous-like behavior. In comparison with their equimolar high-entropy counterparts, the medium-entropy non-equimolar CCFOs exhibit even lower thermal conductivity (k) while maintaining high modulus (E), thereby achieving higher E/k ratios. These results suggest a new direction to achieve thermally-insulative yet stiff CCCs (MPCCs) via exploring non-equimolar and/or medium-entropy compositions.     

High-entropy rare earth tetraborides

Six high-entropy rare earth tetraborides of the tetragonal UB₄-prototyped structure have been successfully synthesized for the first time. The specimens are prepared from elemental precursors via high-energy ball mill and in-situ reactive spark plasma sintering. The sintered specimens are >98 % in relative densities without detectable oxide impurities (albeit the presence of minor hexaborides in some compositions). No detectable secondary phase is observed in the composition (Y_0.2Nd_0.2Sm_0.2Gd_0.2Tb_0.2)B₄, which is proven homogeneous at both microscale and nanoscale. The Vickers microhardness are determined to be ～13?15 GPa at a standard indentation load of 9.8 N. A scientifically interesting observation is represented by the anisotropic lattice distortion from the rule-of-mixture averages. This work expands the family of high-entropy ceramics via fabricating a new class of high-entropy borides with a unique tetragonal quasi-layered crystal structure.     

Hard and electrically conductive multicomponent diboride-based films with high thermal stability

We report high-quality, hard (31–41 GPa), crack-resistant (hardness-to-effective Young's modulus ratio of 0.13–0.16) and electrically conductive (2.8–4.2 × 10⁵ S m^?1) HfB₂-based ceramic materials with high thermal stability. The materials were prepared in the form of well adhesive films using a simple deposition process: pulsed magnetron sputtering (B₄C target overlapped by metal stripes) onto floating substrates. We go through a wide range of compositions resulting from incorporating five other metals (Ti, Y, Zr, Ho or Ta) which partially replace Hf, and focus on the effect of the number and characteristics of elements in the metal sublattice. Regardless of the number of incorporated elements, no segregation to more than one AlB₂-type crystalline phase was observed. Growing number of metal elements leads to decreasing crystal size as indicated by the width of diffraction peaks, strongly decreasing compressive stress to less than 2 GPa and slightly decreasing hardness and electrical conductivity. The experimental data are explained by Monte-Carlo calculations of the energy delivered into the growing films. The thermal stability of septenary diboride-based films Hf₈Zr₄Ti₄Ta₄Y₅B₆₀C₉ and Hf₁₀Zr₄Ti₄Ta₄Ho₅B₅₈C₉ was superior to that of quaternary films Hf₂₂Y₅B₅₈C₉ and Hf₂₂Ho₅B₅₈C₉ when annealed to 1300 °C. Both the single solid solution crystalline phase (X-ray diffraction) and the dense and pinhole-free structure (scanning electron microscopy) were observed for the septenary films not only before but also after annealing. The results are important for the design and industry-friendly preparation of thin-film materials combining multiple functional properties for various technological applications.     

An inverse Hall-Petch behavior and improving toughness in translucent nanocrystalline high-entropy zirconate ceramic

Short-range order is a new strengthening effect that can significantly affect the mechanical properties of high-entropy materials. Furthermore, simulation results show that this strengthening effect at a quasi-atomic scale can suppress the grain size softening, leading to the disappearance of inverse Hall-Petch behavior in nanocrystalline high-entropy materials. In this work, the evident inverse Hall-Petch behavior is confirmed in the translucent nanocrystalline high-entropy ceramic (HEC) with an average grain size below 10 nm, fabricated by a high-pressure low-temperature sintering technique. Besides, the as-obtained nanocrystalline HEC also shows an improving fracture toughness compared with the corresponding coarse-crystalline HEC.     

Microstructure and properties of aluminum nitride ceramics prepared by aqueous gelcasting method with nontoxic curdlan as gelling agent

Aluminum nitride ceramics were prepared by aqueous gelcasting method and pressureless sintering technique in N₂ atmosphere using Y₂O₃ as sintering additives with nontoxic curdlan as gel system. The solidification mechanism of curdlan was studied. The effects of curdlan content and solid content on the microstructure, relative density and flexural strength of green bodies were investigated. The influences of Y₂O₃ content and sintering soaking time on the microstructure and properties of sintered bodies were also studied. The results show that, as the temperature increases to 80 °C, the ceramic powders solidify through three-dimensional gel networks of curdlan during gelling process. The green bodies can be successfully fabricated through aqueous gelcasting method with modified powder as original materials. Suitable curdlan content and solid content contribute to fabricating green body with uniform microstructures and high flexural strength. The relative density and flexural strength of sintered bodies enhance as the Y₂O₃ content and soaking time increase. The flexural strength and thermal conductivity are about 107.5∼172.3 MPa and 75.2∼112.5 W/(m·K), respectively. The sintered body with 4 wt% Y₂O₃ soaking for 3 h exhibits the highest thermal conductivity because of appropriate relative density, uniform microstructure and reasonable intergranular phase distribution. The mechanical property and thermal conductivity of sintered bodies can be improved by optimizing the gelcasting process parameter, Y₂O₃ content, and soaking time. The nontoxic gelling system will have wide application for aqueous gelcasting ceramic with complex shape.     

A strategy for fabricating textured silicon nitride with enhanced thermal conductivity

C-axis textured Si₃N₄ with a high thermal conductivity of 176 W m⁻¹ K⁻¹ along the grain alignment direction was fabricated by slip casting raw α-Si₃N₄ powder seeded with near-equiaxed β-Si₃N₄ particles and Y₂O₃–MgSiN₂ as sintering additives in a rotating strong magnetic field of 12 T, followed by gas pressure sintering at 1900 °C for 12 h at a nitrogen pressure of 1 MPa. The green material reached a relative density of 57%, with slip casting and the sintered material exhibited a relative density of 99% and a Lotgering orientation factor of 0.98. The morphology of the β-Si₃N₄ seeds had little effect on the texture development and thermal anisotropy of textured Si₃N₄. The technique developed provides highly conductive Si₃N₄ with conductivity to the thickness direction, which is a major advantage in practical use. The technique is also simple, inexpensive and effective for producing textured Si₃N₄ with high thermal conductivity of over 170 W m⁻¹ K⁻¹.     

Mechanical,electrical and thermal properties of ZrC-ZrB2-SiC ternary eutectic composites prepared by arc melting

ZrC-ZrB₂-SiC composites were prepared by arc-melting in Ar atmosphere using ZrC, ZrB₂ and SiC as starting materials. The ternary eutectic composition of 20ZrC-30ZrB₂-50SiC (mol%) was first identified. SiC about 7?μm in length and 500?nm in diameter, ZrC about 4 μm in length and 1 μm in diameter, in rod-like microstructure, were uniformly dispersed in ZrB₂ matrix of eutectic composite. The eutectic temperature of ZrC-ZrB₂-SiC composite was approximately 2550?K. The Vickers Hardness and fracture toughness of eutectic composite was 23?GPa and 6.2?MPa?m^1/2, respectively. The electrical conductivity decreased from 7.2?×?10⁷ to 1.75?×?10⁶?S?m^?1 with the temperature increasing from 287 to 800?K. The thermal conductivity decreased from 85 to 61?W?K^?1?m^?1 with increasing temperature from 287 to 973?K.