Mechanical properties of directionally solidified Al2O3/Y3Al5O12 eutectic ceramic prepared by optical floating zone technique

Al₂O₃/Y₃Al₅O₁₂(YAG) directionally solidified eutectic (DSE) crystal was prepared by optical floating zone technique. Al₂O₃/YAG DSE consists of continuous entangled Al₂O₃ and the YAG forming a three-dimensional networks structure. The volume fraction of porosity is ultra-low (0.013%) and the average equivalent diameters of most pores (>84%) are smaller than 4?μm. The Al₂O₃/YAG DSE shows excellent high-temperature elastic stiffness. The Young’s modulus at 1500?°C maintains more than 85% of the value at room temperature. Bending strength exhibits excellent retention up to high temperature as well. High-temperature ball indentation testing shows plastic deformation involving dislocations and twinning, which predominantly occur in Al₂O₃ phase, while the YAG phase is stable. Evaluation on H_v/E index predicts Al₂O₃/YAG DSE with moderate capability to accommodate damages. Our results highlight Al₂O₃/YAG DSE as excellent high-temperature structural materials.     

Directionally solidified Al2O3-ME3Al5O12 (ME: Y,Er and Yb) eutectic coatings for thermophotovoltaic systems

Selective emitters for thermophotovoltaic systems consisting of directionally solidified Al₂O₃-ME₃Al₅O₁₂ (ME: Y, Er and Yb) eutectic coatings on Al₂O₃ substrates were produced and characterizated. Coatings were deposited by dip-coating on cylindrical substrates. After sintering, a continuous-wave CO₂ laser was used to produce the surface resolidification. The optimization of the processing parameters yielded dense eutectic coatings with good adhesion to the substrate and with 90–200 µm in thickness. All coatings were free of voids and showed a eutectic microstructure consisting of a three dimensional interpenetrated network of Al₂O₃ and ME₃Al₅O₁₂. The mechanical properties of the coatings (hardness and fracture toughness) were evaluated by indentation techniques. Thermal emission was studied by heating the rods with a CO₂ laser at temperatures between 1000 and 1400 °C. Selective emission was observed in Er³⁺ and Yb³⁺ based coatings and attributed to the electronic transitions of the rare earth ions. Er³⁺-coatings showed the best emission properties as selective emitters for thermophotovoltaic converters.     

On the growth and structure of Al2O3-Y3Al5O12-ZrO2:Y solidified eutectic

Structural features of Al₂O₃-YAG-ZrO₂:Y eutectic plates grown by the EFG process have been studied. X-ray tomography shows that all three phases are continuous along the whole sample, suggesting a fully coupled ternary eutectic growth. However the growth of alumina and YAG is well described by a classical binary coupled growth, in spite of the facetted structure of their growth interface. Colonies are observed at high growth rate and have been related to the chemical rejection of zirconium ions at the solid-liquid interface, possibly due to a slight off-stoechiometry of the raw material.     

Novel (Sm0.2Lu0.2Yb0.2Y0.2Dy0.2)3TaO7 high-entropy ceramic for thermal barrier coatings

A novel (Sm_0.2Lu_0.2Dy_0.2Yb_0.2Y_0.2)₃TaO₇ (SLT-5RE_0.2) oxide with a single-fluorite structure was synthesized via an optimized sol-gel and sintering method, and its crystal structure, mechanical and thermophysical properties were investigated. The results indicate that the calcined nanoscale powder is of high crystallinity, and bulk sample is of a uniform elemental distribution. Compared to YSZ (6–8 wt.% Y₂O₃ partially stabilized by ZrO₂), SLT-5RE_0.2 exhibits lower Young's modulus, less mean acoustic velocity, and higher Vickers microhardness. Owing to the strengthened anharmonic vibration and phonon scattering, SLT-5RE_0.2 exhibits low thermal conductivity (1.107 W K^?1·m^?1, 900 °C). The high thermal expansion coefficient (11.3 × 10^?6 K^?1, 1200 °C) of SLT-5RE_0.2 ceramic can be ascribed to the reduced lattice energy and ionic spacing as well as the cocktail effect of high-entropy ceramics. The excellent mechanical and thermophysical properties, and excellent phase steadiness during the whole testing temperature cope, indicate that SLT-5RE_0.2 high-entropy ceramic can be a candidate material for thermal barrier coatings.     

Microstructure of the directionally solidified ternary eutectic ceramic Al2O3/MgAl2O4/ZrO2

The directionally solidified Al₂O₃/MgAl₂O₄/ZrO₂ ternary eutectic ceramic was prepared via induction heating zone melting. Smooth Al₂O₃/MgAl₂O₄/ZrO₂ eutectic ceramic rods with diameters of 10 mm were successfully obtained. The results demonstrate that the eutectic rods consist of Al₂O₃, MgAl₂O₄ and ZrO₂ phases. In the eutectic microstructure, the MgAl₂O₄ and Al₂O₃ phases form the matrix, the ZrO₂ phase with a fibre or shuttle shape is embedded in the matrix, and a quasi-regular eutectic microstructure formed, presenting a typical in situ composite pattern. During the eutectic growth, the ZrO₂ phase grew on non-faceted phases ahead of the matrix growing on the faceted phase. The hardness and fracture toughness of the eutectic ceramics reached 12 GPa and 6.1 MPa·m ^1/2, respectively, i.e., two times and 1.7 times the values of the pre-sintered ceramic, respectively. In addition, the ZrO₂ phase in the matrix reinforced the matrix, acting as crystal whiskers to reinforce the sintered ceramic.     

Preparation,microstructures, and mechanical properties of directionally solidified Al2O3/Lu3Al5O12 eutectic ceramics

Al₂O₃/Lu₃Al₅O₁₂ (LuAG) directionally solidified eutectic (DSE) ceramics with two solidification rates were prepared utilizing optical floating zone (OFZ) technique. The microstructures (eutectic morphology, preferred growth direction and interface orientation) of Al₂O₃/LuAG were characterized, and the mechanical properties (Vickers hardness and fracture toughness) were compared with those of Al₂O₃/REAG (RE = Y, Er, and Yb). Results show that Al₂O₃/LuAG with solidification rate of 30 mm/h has established preferred growth direction in both Al₂O₃ and LuAG phases with cellular eutectic structures. While Al₂O₃/LuAG with solidification rate of 10 mm/h only shows preferred growth direction in Al₂O₃ phase and presents degenerate irregular eutectic microstructures. Besides, Al₂O₃/LuAG exhibits higher hardness compared with Al₂O₃/REAG (RE = Y, Er, and Yb). In addition, a special attention is focused on the relations among rare earth ionic radius, eutectic microstructures, and mechanical properties of these DSE ceramics. It is demonstrated that a smaller rare earth ionic radius could lead to larger eutectic interspacing as well as higher Vickers hardness of DSE Al₂O₃/REAG, revealing the possibility and feasibility of microstructure control and mechanical properties optimization for DSE Al₂O₃/REAG ceramics by tailoring the rare earth elements.     

Multi-component strategy for remarkable suppression of thermal conductivity in strontium diyttrium oxide: The case of high-entropy Sr(Y0.2Sm0.2Gd0.2Dy0.2Yb0.2)2O4 ceramic

Anti-spinel oxide SrY₂O₄ has attracted extensive attention as a promising host lattice due to its outstanding high-temperature structural stability and large thermal expansion coefficient (TEC). However, the overhigh thermal conductivity limits its application in the field of thermal barrier coatings. To address this issue, a novel high-entropy Sr(Y_0.2Sm_0.2Gd_0.2Dy_0.2Yb_0.2)₂O₄ ceramic was designed and synthesized for the first time via the solid-state method. It is found that the thermal conductivity of Sr(Y_0.2Sm_0.2Gd_0.2Dy_0.2Yb_0.2)₂O₄ is reduced to 1.61 W·m⁻¹·K⁻¹, 53 % lower than that of SrY₂O₄ (3.44 W·m⁻¹·K⁻¹) at 1500 °C. Furthermore, reasonable TEC (11.53 ×10⁻⁶ K⁻¹, 25 °C ∼ 1500 °C), excellent phase stability, and improved fracture toughness (1.92 ± 0.04 MPa·m^1/2) remained for the high-entropy Sr(Y_0.2Sm_0.2Gd_0.2Dy_0.2Yb_0.2)₂O₄ ceramic, making it a promising material for next-generation thermal barrier coatings.     

Effect of an abrupt change in pulling rate on microstructures of directionally solidified Al2O3-Er3Al5O12 eutectic and off-eutectic composite ceramics

Directionally solidified microstructures of Al₂O₃-Er₃Al₅O₁₂ eutectic and off-eutectic in situ composite ceramics were explored under abrupt-change pulling rate conditions. Corresponding temperature distributions and interface locations were studied. In eutectic composition, fluctuation of eutectic spacing occurred when the pulling rate increased abruptly. A gradually increase or abrupt increase in eutectic spacing was observed when the pulling rate decreased abruptly. In hypoeutectic and hypereutectic compositions, formation of the primary phases were suppressed when the pulling rate increased abruptly from 10?µm/s to 100?µm/s, while primary phases precipitated when the pulling rate decreased abruptly from 100?µm/s to 10?µm/s. The interface altitude decreased after the pulling rate increased abruptly, but increased after the pulling rate decreased abruptly. The liquid composition restriction (around the eutectic composition) at the eutectic interface plays an important role in the suppression of the primary dendrite and coupled eutectic oxides can be obtained in off-eutectic compositions even under higher solidification rate conditions.     

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.     

New class of high-entropy defect fluorite oxides RE2(Ce0.2Zr0.2Hf0.2Sn0.2Ti0.2)2O7 (RE = Y,Ho, Er,or Yb) as promising thermal barrier coatings

High-entropy ceramics exhibit great application potential as thermal barrier coating (TBC) materials. Herein, a series of novel high-entropy ceramics with RE₂(Ce_0.2Zr_0.2Hf_0.2Sn_0.2Ti_0.2)₂O₇ (RE₂HE₂O₇, RE = Y, Ho, Er, or Yb) compositions were fabricated via a solid-state reaction. X-ray diffraction (XRD) and energy dispersive spectrometry (EDS) mapping analyses confirmed that RE₂HE₂O₇ formed a single defect fluorite structure with uniform elemental distribution. The thermophysical properties of the RE₂HE₂O₇ ceramics were investigated systematically. The results show that RE₂HE₂O₇ ceramics have excellent high-temperature phase stability, high thermal expansion coefficients (10.3–11.7 × 10^?6 K^-1, 1200 ℃), and low thermal conductivities (1.10-1.37 W m^-1 K^-1, 25 ℃). In addition, RE₂HE₂O₇ ceramics have a high Vickers hardness (13.7–15.0 GPa) and relatively low fracture toughness (1.14-1.27 MPa m^0.5). The outstanding properties of the RE₂HE₂O₇ ceramics indicate that they could be candidates for the next generation of TBC materials.     

A novel high-entropy (Sm0.2Eu0.2Tb0.2Dy0.2Lu0.2)2Zr2O7 ceramic aerogel with ultralow thermal conductivity

Here, we report a novel high-entropy rare earth zirconate (HE-REZ) (Sm_0.2Eu_0.2Tb_0.2Dy_0.2Lu_0.2)₂Zr₂O₇ ceramic aerogel prepared through a sol-gel template method and high-temperature calcination followed by 3-D-structure reconstruction. The structural evolution and crystallisation behaviour of the prepared aerogel were characterised through scanning electron microscopy, X-ray diffraction and transmission electron microscopy. The results indicated that the as-prepared HE-REZ ceramic aerogels had a typical nanoporous structure. The HE-REZ ceramic aerogels thermally treated at 900 °C presented an ultralow room temperature thermal conductivity of 0.031 W/(m·K), high specific surface areas of 443.26 m²/g and a relatively high strength of 12.95 MPa. The effects of different calcination temperatures on the microstructure of the samples were also investigated. Therefore, the excellent insulation performance of these unique HE-REZ ceramic aerogels indicate that they can be used as high-temperature insulators for hypersonic vehicles in the future.     

Dielectric properties of (Y0.2Eu0.2Er0.2Dy0.2Lu0.2)3(AlxFe1-x)5O12 high-entropy garnet ceramics

A new kind of novel high-entropy rare earth garnet ceramics (HEREGCs, (Y_0.2Eu_0.2Er_0.2Dy_0.2Lu_0.2)₃(Al_xFe_1-x)₅O₁₂ (x = 0.4–0.6)) was designed and successfully synthesized by solid state reaction method. With the increase of Al content, the relative dielectric constant (ε_r′) at 100 Hz decreases from 4 × 104 to 1 × 102, while the dielectric loss (tanδ) increases from 0.93 to 2.65. The activation energy of grain boundary electrical conductivity (E_gb) and grain electrical conductivity (E_g) are fitted according to Arrhenius’ law, which indicate that the increase of difference between E_gb and E_g lead to the enhancement of dielectric properties. Our results provide the underlying insights needed to guide the study of colossal dielectric materials.     

Ultrafast high-temperature sintering of (Y0.2Dy0.2Er0.2Tm0.2Yb0.2)4Hf3O12 high-entropy ceramics with defective fluorite structure

An entropy-stabilized rare earth hafnate (Y_0.2Dy_0.2Er_0.2Tm_0.2Yb_0.2)₄Hf₃O₁₂ (5RH) with defective fluorite structure was successfully prepared by the emerging ultrafast high-temperature sintering (UHS) in less than six minutes. The 5RH ceramic possessed a higher thermal expansion coefficient (11.23 ×10^?6/K, 1500 °C) and extremely low thermal conductivity (0.94 W/(m·k), 1300 ℃) owing to the larger lattice distortion of high-entropy materials. After high-temperature annealing at 1500 ℃, the 5RH showed extremely sluggish grain growth characteristics and excellent high-temperature phase stability, mainly attributed to the non-equilibrium sintering characteristic of the UHS and the sluggish diffusion effect of high-entropy materials. Therefore, (Y_0.2Dy_0.2Er_0.2Tm_0.2Yb_0.2)₄Hf₃O₁₂ has excellent potential as a next-generation thermal barrier coating material to replace traditional Y₂O₃ stabilized ZrO₂. Finally, using the UHS to prepare high-entropy ceramics provides a new technique for fast-sintering and developing next-generation thermal barrier coating materials.     

High-entropy (Ho0.2Y0.2Dy0.2Gd0.2Eu0.2)2Ti2O7/TiO2 composites with excellent mechanical and thermal properties

High-performance ceramics with low thermal conductivity, high mechanical properties, and idea thermal expansion coefficients have important applications in fields such as turbine blades and automotive engines. Currently, the thermal conductivity of ceramics has been significantly reduced by local doping/substitution or further high-entropy reconfiguration of the composition, but the mechanical properties, especially the fracture toughness, are insufficient and still need to be improved. In this work, based on the high-entropy titanate pyrochlore, TiO₂ was introduced for composite toughening and the high-entropy (Ho_0.2Y_0.2Dy_0.2Gd_0.2Eu_0.2)₂Ti₂O₇-xTiO₂ (x = 0, 0.2, 0.4, 1.0 and 2.0) composites with high hardness (16.17 GPa), Young's modulus (289.3 GPa) and fracture toughness (3.612 MPa·m^0.5), low thermal conductivity (1.22 W·m⁻¹·K⁻¹), and thermal expansion coefficients close to the substrate material (9.5 ×10⁻⁶/K) were successfully prepared by the solidification method. The fracture toughness of the composite toughened sample is 2.25 times higher than that before toughening, which exceeds most of the current low-thermal conductivity ceramics.     

Novel high entropy (Y0.2Sm0.2Gd0.2Er0.2Ho0.2)3NbO7 nanofibers with ultralow thermal conductivity

Thermal insulation materials can provide thermal protection in extreme environments. Ceramic fibers have played an important role in the thermal protection field at high temperatures due to the advantages of low density, high strength, low thermal conductivity, and excellent thermal stability. In this work, high entropy (Y_0.2Sm_0.2Gd_0.2Er_0.2Ho_0.2)₃NbO₇ (5RE₃NbO₇) nanofibers were fabricated by electrospinning and subsequent calcination. Defective fluorite-structured 5RE₃NbO₇ nanofibers were obtained when heated at 900°C. The research indicates that 5RE₃NbO₇ nanofiber based porous ceramics present an ultralow thermal conductivity (0.0992 W/m·K, porosity of 78.18%), good thermal stability, and high spectral reflectance, which establish the foundation for applications in thermal insulation.     

Fabrication and characterization of highly transparent Er:Y2O3 ceramics with ZrO2 and La2O3 additives

In this study, we report highly transparent Er:Y₂O₃ ceramics (0–10 at% Er) fabricated by a vacuum sintering method using compound sintering additives of ZrO₂ and La₂O₃. The transmittance, microstructure, thermal conductivity and mechanical properties of the Er:Y₂O₃ ceramics were evaluated. The in-line transmittance of all of the Er:Y₂O₃ ceramics (1.2 mm thick) exceeds 83% at 1100 nm and 81% at 600 nm. With an increase in the Er doping concentration from 0 to 10 at%, the average grain size, microhardness and fracture toughness remain nearly unchanged, while the thermal conductivity decreases slightly from 5.55 to 4.89 W/m K. A nearly homogeneous doping level of the laser activator Er up to 10 at% in macro-and nanoscale was measured along the radial direction from the center to the edge of a disk specimen, which is the prominent advantage of polycrystalline over single-crystal materials. Based on the finding of excellent optical and mechanical properties, the compound sintering additives of ZrO₂ and La₂O₃ are demonstrated to be effective for the fabrication of transparent Y₂O₃ ceramics. These results may provide a guideline for the application of transparent Er:Y₂O₃ laser ceramics.     

High-entropy La(Fe0.2Co0.2Ni0.2Cr0.2Mn0.2)O3 ceramic exhibiting high emissivity and low thermal conductivity

A novel, high-entropy, perovskite-structured, solid solution La(Fe_0.2Co_0.2Ni_0.2Cr_0.2Mn_0.2)O₃ ceramic was successfully synthesized via high-temperature solid-state reaction. The crystal structure, microstructure, infrared emissivity, and thermophysical properties were investigated. The experimental results indicated that La(Fe_0.2Co_0.2Ni_0.2Cr_0.2Mn_0.2)O₃ exhibited an infrared emissivity as high as .92 in the near-infrared region of .76–2.50 μm. The thermal conductivity was 1.38–1.72 W m⁻¹ K⁻¹ in the temperature range of 25–1200°C.     

Mechanical properties up to 1900 K of Al2O3/Er3Al5O12/ZrO2 eutectic ceramics grown by the laser floating zone method

Directionally solidified Al₂O₃–Er₃Al₅O₁₂–ZrO₂ eutectic rods were processed using the laser floating zone method at growth rates of 25, 350 and 750 mm/h to obtain microstructures with different domain size. The mechanical properties were investigated as a function of the processing rate. The hardness, ∼15.6 GPa, and the fracture toughness, ∼4 MPa m^1/2, obtained from Vickers indentation at room temperature were practically independent of the size of the eutectic phases. However, the flexural strength increased as the domain size decreased, reaching outstanding strength values close to 3 GPa in the samples grown at 750 mm/h. A high retention of the flexural strength was observed up to 1500 K in the materials processed at 25 and 350 mm/h, while superplastic behaviour was observed at 1700 K in the eutectic rods solidified at the highest rate of 750 mm/h.     

Thermal properties of (Zr0.2Ce0.2Hf0.2Y0.2RE0.2)O1.8 (RE= La,Nd and Sm) high entropy ceramics for thermal barrier materials

The high-entropy ceramic materials (Zr_0.25Ce_0.25Hf_0.25Y_0.25)O_1.875 (H-0) and (Zr_0.2Ce_0.2Hf_0.2Y_0.2RE_0.2)O_1.8 (H-RE) (RE = La, Nd and Sm) with fluorite structure and homogeneous element distribution were prepared. With fluorite structure, fine grain size and high density, the H-0 and H-RE ceramics displayed low thermal conductivity, suitable thermal expansion coefficient, high hardness and fracture toughness. The effect of La, Nd and Sm on the mechanical, heat conductivity and heat expansion properties of high entropy ceramics were discussed. The single-phase high-entropy ceramic materials in this work are very suitable for application as thermal barrier materials.