Sm_2YbTaO_7和La_2AlTaO_7的热物理性能

采用固相反应法制备了Sm_2YbTaO_7和La_2AlTaO_7氧化物,并研究了其热物理性能。Sm_2YbTaO_7和La_2AlTaO_7氧化物在20℃~1200℃范围内的平均热导率分别是0.45 W/(m·K)和1.71 W/(m·K),明显低于现役的氧化钇部分稳定氧化锆陶瓷(YSZ)。与La_2AlTaO_7相比,Sm_2YbTaO_7较低的热导率可以归因于其取代原子与基质原子之间较高的原子质量差别,Sm_2YbTaO_7较高的热膨胀系数则可归因于其A位与B位离子之间较低的电负性差别。Sm_2YbTaO_7和La_2AlTaO_7的热导率和热膨胀系数均满足热障涂层的要求,具有做为新型热障涂层表面陶瓷层材料使用的潜力。     

Synthesis and thermophysical performances of complex Ca3Ln3Ti7Ta2O26.5 (Ln=Dy and Er) oxides

Ca₃Dy₃Ti₇Ta₂O_26.5 and Ca₃Er₃Ti₇Ta₂O_26.5 oxides were synthesized using a high-temperature solid-state fritting technique, and the thermophysical performances of these two oxides were investigated. Both Ca₃Dy₃Ti₇Ta₂O_26.5 and Ca₃Er₃Ti₇Ta₂O_26.5 show a monophasic pyrochlore-type lattice. The thermal conductivity of Ca₃Er₃Ti₇Ta₂O_26.5 is lower than that of Ca₃Dy₃Ti₇Ta₂O_26.5. The oxides exhibit lower thermal conductivities than YSZ owing to their complex elemental compositions, large number of ions, and high oxygen vacancy concentrations. The thermal expansion coefficients of the obtained oxides are similar to that of YSZ.     

Influence of Yb Substitution for La on Thermophysical Property of La2AlTaO7 Ceramics

The (La_1−xYb_x)₂AlTaO₇ ceramics were synthesized by pressureless sintering process at 1600 °C for 10 h in air. The crystal phase, microstructure and thermophysical properties were investigated. Results show that pure (La_1−xYb_x)₂AlTaO₇ cermics with single weberite structure are prepared successfully. Owing to the reduction of crystal-lattice tolerance-factor, the thermal conductivity of (La_1−xYb_x)₂AlTaO₇ (x>0) ceramics increases with increasing Yb₂O₃ fraction at identical temperatures, which is lower than that of La₂AlTaO₇. Due to the relatively high electro-negativity of Yb element, the addition of Yb₂O₃ increases the thermal expansion coefficient of (La_1−xYb_x)₂AlTaO₇ ceramics.     

Improvement on thermophysical and mechanincal properties of LaMgAl11O19 magnetoplumbite by Nd2O3 and Sc2O3 co-doping

LaMgAl₁₁O₁₉-type magnetoplumbite holds great promise to be used above 1300 °C as thermal barrier coatings (TBCs), but its practical application has been restricted because of inferior thermophysical properties. Herein, we focus on optimizing the thermophysical properties of LaMgAl₁₁O₁₉ by simultaneously substituting La³⁺ and Al³⁺ ions with Nd³⁺ and Sc³⁺ ions, respectively. Results show that the effects of co-substitution on reducing thermal conductivity are pronounced. The thermal conductivities of La_1-xNd_xMgAl_11-xSc_xO₁₉ (x = 0, 0.1, 0.2, 0.3) ceramics decrease progressively with dopant concentration and a lowest thermal conductivity of 2.04 W/(m·K) is achieved with x = 0.3 at 1000 °C, which is a value superior to pure LMA and even lower than YSZ. The mechanisms behind the lowered thermal conductivity are investigated. Increase of the thermal expansion coefficient is also realized (8.53 × 10⁻⁶ K⁻¹ for pure LMA, 9.07 × 10⁻⁶ K⁻¹ for x = 0.3, 1300 °C). Most importantly, Nd³⁺ and Sc³⁺ combination doping indeed facilitates mechanical properties of La_1-xNd_xMgAl_11-xSc_xO₁₉ solid solutions as well. It should be noted that Sc³⁺ doping at Al³⁺ site plays more effective role in improving thermal properties than Nd³⁺ does at La³⁺ site. This work provides a path to simultaneously integrate low thermal conductivity, good phase stability, moderate thermal expansion behavior and excellent mechanical properties on LMA for the next generation TBCs.     

Thermal properties of RE2AlTaO7 (RE = Gd and Yb) oxides

In the current paper, the synthesis of RE₂AlTaO₇ (RE = Gd and Yb) oxides was performed through a high-temperature sintering method using Gd₂O₃, Yb₂O₃, Al₂O₃ and Ta₂O₅ as raw chemicals. The phase-structure, micro-morphology and thermal-physical properties of RE₂AlTaO₇ (RE = Gd and Yb) oxides were analyzed. The RE₂AlTaO₇ (RE = Gd and Yb) oxides exhibit single pyrochlore-type crystal-structure. Compared to Yb₂AlTaO₇, the Gd₂AlTaO₇ has greater thermal conductivity owning to relatively weaker phonon scattering. Because of higher electro-negativity of Yb, the Yb₂AlTaO₇ has lower coefficient of thermal expansion than Gd₂AlTaO₇. The RE₂AlTaO₇ (RE = Gd and Yb) oxides also exhibit no phase-transition between ambient and 1473?K.     

Preparation and thermophysical properties of Lu3TaO7

Lu₃TaO₇ was prepared through a modified sol-gel technique and high-temperature sintering method to investigate its lattice type, micro-morphology, phase stability, thermal expansion coefficient, and conductivity. The results indicate that the obtained powder and bulk samples are composed of a single fluorite structure. The obtained bulk sample shows a dense microstructure, and uniform element distribution. The thermal conductivity of the Lu₃TaO₇ oxide slightly increases with temperature due to typical amorphous-like behaviour, which is much lower than those of 7 wt% yttrium oxide–stabilized zirconium oxide (7YSZ) and Sm₂Zr₂O₇ ceramics. Furthermore, the enhanced phonon scattering leads to a lower thermal conductivity of Lu₃TaO₇ than that of Gd₃TaO₇. The thermal expansion coefficient of the Lu₃TaO₇ oxide reaches 10.72 × 10^?6 K^?1 at 1200 °C, which is slightly greater than that of 7YSZ. The outstanding phase stability up to 1200 °C satisfies the requirements for thermal barrier coatings.     

Microstructure and thermal properties of a promising thermal barrier coating: YTaO4

High temperature gas turbine sealing can increase the thermal efficiency of a gas turbine. In this paper, monoclinic phase YTaO₄ ceramics were fabricated via solid-state reaction. Phase composition and microstructures of the high-temperature-sintered YTaO₄ ceramics were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and Raman Spectroscopy. Specific heat capacity rose gradually as temperature increased, due to volumetric expansion and phonon excitations. The thermal diffusivities and conductivities decreased significantly due to the effects of the porosity and phonon scattering. However, the thermal conductivities of the specimens were lower than that of 7–8 wt% yttria-stabilized zirconia (7-8YSZ), and YTaO₄ ceramics have better thermal stability than current (TBCs) material. The Vickers hardnesses of YTaO₄ ceramics as a function of sintering temperature were lower than that of 8YSZ, indicating YTaO₄ has better fracture toughness and thermal tolerance. The results demonstrate that YTaO₄ ceramics would be an excellent candidate for use as a thermal barrier coating material for high temperature gas turbines.     

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.     

Microstructure analyses and thermophysical properties of nanostructured thermal barrier coatings

Nanostructured 8 wt% yttria partially stabilized zirconia coatings were deposited by air plasma spraying. Transmission electron microscopy, scanning electron microscopy, and X-ray diffraction were carried out to analyze the as-sprayed coatings and powders. Mercury intrusion porosimetry was applied to analyze the pore size distribution. Laser flash technique and differential scanning calorimetry were used to examine the thermophysical properties of the nanostructured coatings. The results demonstrate that the as-sprayed nanostructured zirconia coatings consist of the nonequilibrium tetragonal phase. The microstructure of the nanostructured coatings includes the initial nanostructure of powder and columnar grains. Moreover, micron-sized equiaxed grains were also exhibited in the nanostructured coatings. Their evolution mechanisms are discussed. The as-sprayed nanostructured zirconia coating shows a bimodal pore size distribution, and has a lower value of thermal conductivity than the conventional coating.     

The phase stability and thermophysical properties of InFeO3(ZnO)m (m = 2, 3, 4, 5)

The phase stability and thermophysical properties of InFeO₃(ZnO)_m (m = 2, 3, 4, 5) compounds were investigated, which are a general family of homologous layered compounds with general formula InFeO₃(ZnO)_m (m = 1–19). InFeO₃(ZnO)_m (m = 2, 3, 4, 5) ceramics were synthesized using cold pressing followed by solid-state sintering. They revealed an excellent thermal stability after annealing at 1450 °C for 48 h. No phase transformation occurred during heating to 1400 °C. InFeO₃(ZnO)₃ exhibited a thermal conductivity of 1.38 W m⁻¹ K⁻¹ at 1000 °C, which is about 30% lower than that of 8 wt.% yttria stabilized zirconia (8YSZ) thermal barrier coatings. The thermal expansion coefficients (TECs) of InFeO₃(ZnO)m bulk ceramics were in a range of (10.97 ± 0.33) × 10⁻⁶ K⁻¹ to (11.46 ± 0.35) × 10⁻⁶ K⁻¹ at 900 °C, which are comparable to those of 8YSZ ceramics.     

Thermal conductivity and expansion coefficient of Ln2LaTaO7 (Ln=Er and Yb) oxides for thermal barrier coating applications

Two kinds of novel Ln₂LaTaO₇ (Ln=Er and Yb) ceramics were prepared via high-temperature solid reaction method. The phase composition, micro-morphology and thermophysical properties were investigated. Results indicate that pure Ln₂LaTaO₇ ceramics with single fluorite-type structure are synthesized successfully. The thermal conductivities of Er₂LaTaO₇ and Yb₂LaTaO₇ are in the range of 1.22–1.43 W/m K and 1.17–1.51 W/m K, respectively, which are much lower than that of YSZ. The lower thermal conductivity can be attributed to the phonon scattering caused by oxygen vacancies and the substituting atoms. The average thermal expansion coefficients of Yb₂LaTaO₇ and Er₂LaTaO₇ are 9.94×10⁻⁶/K and 9.63×10⁻⁶/K, respectively. As compared with Yb₂LaTaO₇, the higher thermal expansion coefficient of Er₂LaTaO₇ can be ascribed to its lower ionic-bond strength between cations at sites A and B.     

(Sm0.7Yb0.3)2Ce2O7陶瓷的热膨胀系数及热导率

以Sm2O3、Yb2O3和CeO2为原材料,采用固相反应法制备了(Sm0.7Yb0.3)2Ce2O7陶瓷材料,用X射线衍射(XRD分析了其相结构,采用扫描电子显微镜(SEM)和电子能谱(EDS)分析其显微组织和元素组成,用推杆膨胀法和激光脉冲法测试了其热膨胀系数和热导率.结果表明,所制备的(Sm0.7Yb0.3)2Ce2O7具有典型的萤石结构,其微观组织致密,晶界清晰.Yb3+离子较小的离子半径使其热膨胀系数低于Sm2Ce2O7,基质原子与取代原子之间质量及尺寸之间的差别,使其具有比Sm2Ce2O7更低的热导率,该材料有潜力用作新型热障涂层表面陶瓷层材料.     

Electronic structure and thermal properties of Sm3+-doped La2Zr2O7: First-principles calculations and experimental study

By applying the first-principles calculation, the electronic structure, mechanical and thermal properties of Sm³⁺-doped La₂Zr₂O₇ were investigated, and experiments were carried out to verify the theoretical results. As the Sm³⁺ doping rate increases, the lattice parameters decrease while the theoretical density increases. The doping of Sm³⁺ promotes the transformation from pyrochlore structure to defective fluorite structure. The Young's modulus of pure La₂Zr₂O₇ shows obvious anisotropy, while it tends to be isotropy with the doping of Sm³⁺. The calculated theoretical hardness is positively correlated with the doping rate, yet due to the solid solution strengthening effect, the materials with doping rate of 50% get the highest hardness. Based on the calculations and experiments, the optimal Sm³⁺ doping rate of La₂Zr₂O₇ is 50%. LaSmZr₂O₇ has hardness of 11.35 GPa, the thermal conductivity of 1.35 W/(m·K) at 1173 K, and the thermal expansion coefficient of 10.12 × 10⁻⁶/K at 1173 K. The above results indicate that LaSmZr₂O₇ has good mechanical and thermal properties, which provides new ideas for the selection of thermal barrier coating materials.     

Thermo-physical and mechanical properties of Yb2O3 and Sc2O3 co-doped Gd2Zr2O7 ceramics

Ceramic materials for the thermal barrier coating (TBC) application of Gd₂Zr₂O₇ (GZO), (Gd_0.94Yb_0.06)₂Zr₂O₇ (GYb_0.06Z), (Gd_0.925Sc_0.075)₂Zr₂O₇ (GSc_0.075Z), (Gd_0.865Sc_0.075Yb_0.06)₂Zr₂O₇ (GSc_0.075Yb_0.06Z), and (Gd_0.8Sc_0.1Yb_0.1)₂Zr₂O₇ (GSc_0.1Yb_0.1Z) were successfully synthesized by chemical co-precipitation. The effects of the doping of Sc₂O₃ and Yb₂O₃ on the phases, thermo-physical and mechanical properties of the ceramics were investigated. The results show that both Yb₂O₃ and Sc₂O₃ doping promoted the phase transition of GZO from pyrochlore to fluorite. All the Sc₂O₃-doped samples exhibited enhanced fracture toughness, as compared to the undoped sample. Furthermore, the GSc_0.075Yb_0.06Z sample revealed a thermal conductivity of ~0.8 W/mK at 1200 °C, which was nearly 30% lower than that of the undoped sample. The associated mechanisms related to the effects of the doping on the thermophysical and mechanical properties are discussed.     

Synthesis and thermophysical properties of RETa3O9 (RE = Ce,Nd, Sm,Eu, Gd,Dy, Er) as promising thermal barrier coatings

Thermal barrier coatings (TBCs) are one of the most important materials in gas turbine to protect the high temperature components. RETa₃O₉ compounds have a defect‐perovskite structure, indicating that they have low thermal conductivity, which is the critical property of TBCs. Herein, dense RETa₃O₉ bulk ceramics were fabricated via solid‐state reaction. The crystal structure was characterized by X‐ray diffraction (XRD) and Raman Spectroscope. Scanning electron microscope (SEM) was used to observe the microstructure. The thermophysical properties of RETa₃O₉ were studied systematically, including specific heat, thermal diffusivity, thermal conductivity, thermal expansion coefficients, and high‐temperature phase stability. The thermal conductivities of RETa₃O₉ are very low (1.33‐2.37 W/m·K, 373‐1073 K), which are much lower than YSZ and La₂Zr₂O₇; and the thermal expansion coefficients range from 4.0 × 10^?6 K^?1 to 10.2×10^?6 K^?1 (1273 K), which is close to La₂Zr₂O₇ and YSZ. According to the differential scanning calorimetry (DSC) curve there is not phase transition at the test temperature. Due to the high melting point and excellent high‐temperature phase stability with these oxides, RETa₃O₉ ceramics were promising candidate materials for TBCs.     

Determinations of Ce solid solution mechanism and limit thermal conductivity of YTaO4 ceramics

x mol% CeO₂-YTaO₄ (x = 0, 3, 6, 9, 12) ceramics have been synthesized by the spark plasma sintering (SPS) technique. We focus on the changes in lattice distortion, bonding length, thermal conductivity, thermal expansion, and phase stability of the prepared samples. XRD, Raman, and XPS are used to determine the chemical valence and solid solution mechanism of Ce in the lattice of YTaO₄, while its effects on thermal/mechanical properties are elucidated from microstructures. Y³⁺ is substituted via Ce³⁺, and all samples maintain a monoclinic phase. The limit thermal conductivity (1.2 W?m^?1?K^?1, 900 °C) is realized in 9 mol% CeO₂-YTaO₄, and the thermal expansion coefficients are increased to 10.2 × 10^?6 K^?1 at 1200 °C. Furthermore, the exceptional phase stability and mechanical properties of all samples indicate that they can provide good thermal insulation at high temperatures, and have higher working temperatures than the current YSZ thermal barrier coatings.     

Influence of B-site substituent Ce on thermophysical,oxygen diffusion,and mechanical properties of La2Zr2O7

Pyrochlore-type La₂Zr₂O₇ (LZ) is a promising candidate for high-temperature thermal barrier coatings (TBCs). However, its thermal expansion coefficient and low fracture toughness are not optimal for such application and thus, need to be improved. In this study, we systematically report the effect of CeO₂ addition on phase formation, oxygen-ion diffusion, and thermophysical and mechanical properties of full compositions La₂(Zr₁?_xCe_x)₂O₇ (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1). La₂(Zr₁?_xCe_x)₂O₇ exhibits a pyrochlore structure at x ≤ 0.3, while a fluorite structure is observed outside this range. With the increase in CeO₂ content, thermal expansion coefficient and oxygen-ion diffusivity in La₂(Zr₁?_xCe_x)₂O₇ are increased. Oxygen-ion diffusivity of La₂(Zr₁?_xCe_x)₂O₇ is two orders of magnitude less than that of classical 8YSZ. Among La₂(Zr₁?_xCe_x)₂O₇ compounds, La₂(Zr_0.7Ce_0.3)₂O₇ and La₂(Zr_0.5Ce_0.5)₂O₇ exhibit relatively low oxygen diffusivities. The composition La₂(Zr_0.5Ce_0.5)₂O₇ presents the lowest thermal conductivity due to the strongest phonon scattering and also the highest fracture toughness due to the solid-solution toughening. The highest sintering resistance is achieved by the composition La₂(Zr_0.7Ce_0.3)₂O₇ because of its ordered pyrochlore structure and high atomic mass of Ce. Based on these results, the compositions La₂(Zr_0.5Ce_0.5)₂O₇ and La₂(Zr_0.7Ce_0.3)₂O₇ are alternatives for classical 8YSZ for TBC materials operating at ultrahigh temperatures.     

Thermal cycling behavior and bonding strength of single-ceramic-layer Sm2Zr2O7 and double-ceramic-layer Sm2Zr2O7/8YSZ thermal barrier coatings deposited by atmospheric plasma spraying

The single-ceramic-layer (SCL) Sm₂Zr₂O₇ (SZO) and double-ceramic-layer (DCL) Sm₂Zr₂O₇ (SZO)/8YSZ thermal barrier coatings (TBCs) were deposited by atmospheric plasma spraying on nickel-based superalloy substrates with NiCoCrAlY as the bond coat. The mechanical properties of the coatings were evaluated using bonding strength and thermal cycling lifetime tests. The microstructures and phase compositions of the coatings were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The results show that both coatings demonstrate a well compact state. The DCL SZO/8YSZ TBCs exhibits an average bonding strength approximately 1.5 times higher when compared to the SCL SZO TBCs. The thermal cycling lifetime of DCL SZO/8YSZ TBCs is 660 cycles, which is much longer than that of SCL 8YSZ TBCs (150 cycles). After 660 thermal cycling, only a little spot spallation appears on the surface of the DCL SZO/8YSZ coating. The excellent mechanical properties of the DCL LZ/8YSZ TBCs can be attributed to the underlying 8YSZ coating with the combinational structures, which contributes to improve the toughness and relieve the thermal mismatch between the ceramic layer and the metallic bond coat at high temperature.     

Effects of Yb and Sc co-doping on the thermal properties and CMAS corrosion of garnet-type (Y3-xYbx)(Al5-xScx)O12 ceramics

Thermal barrier coatings with excellent thermal performance and corrosion resistance are essential for improving the performance of aero-engines. In this paper, (Y_3-xYb_x)(Al_5-xSc_x)O₁₂ (x = 0, 0.1, 0.2, 0.3) thermal barrier coating materials were synthesized by a combination of sol-gel method and ball milling refinement method. The thermal properties of the (Y_3-xYb_x)(Al_5-xSc_x)O₁₂ ceramics were significantly improved by increasing Yb and Sc doping content. Among designed ceramics, (Y_2.8Yb_0.2)(Al_4.8Sc_0.2)O₁₂ (YS-YAG) showed the lowest thermal conductivity (1.58 Wm^?1K^?1, at 800 °C) and the highest thermal expansion coefficient (10.7 × 10^?6 K^?1, at 1000 °C). In addition, calcium-magnesium- aluminum -silicate (CMAS) corrosion resistance of YS-YAG was further investigated. It was observed that YS-YAG ceramic effectively prevented CMAS corrosion due to its chemical inertness to CMAS as well as its unique and complex structure. Due to the excellent thermal properties and CMAS corrosion resistance, YS-YAG is considered to be prospective material for thermal barrier coatings.