Thermal properties of La2Zr2O7 double-layer thermal barrier coatings

La₂Zr₂O₇ is a promising thermal barrier coating (TBC) material. In this work, La₂Zr₂O₇ and 8YSZ-layered TBC systems were fabricated. Thermal properties such as thermal conductivity and coefficient of thermal expansion were investigated. Furnace heat treatment and jet engine thermal shock (JETS) tests were also conducted. The thermal conductivities of porous La₂Zr₂O₇ single-layer coatings are 0.50–0.66?W?m^?1?°C^?1 at the temperature range from 100 to 900°C, which are 30–40% lower than the 8YSZ coatings. The coefficients of thermal expansion of La₂Zr₂O₇ coatings are about 9–10?×?10^?6?°C^?1 at the temperature range from 200 to 1200°C, which are close to those of 8YSZ at low temperature range and about 10% lower than 8YSZ at high temperature range. Double-layer porous 8YSZ plus La₂Zr₂O₇ coatings show a better performance in thermal cycling experiments. It is likely because porous 8YSZ serves as a buffer layer to release stress.     

Influence of Gd2O3 addition on thermophysical properties of La2Ce2O7 ceramics for thermal barrier coatings

In order to develop new candidate ceramic materials for thermal barrier coatings (La_1?xGd_x)₂Ce₂O₇ ceramics were prepared by pressureless-sintering at 1600 °C for 10 h in air. The phase structure, micro-morphology and thermophysical properties of (La_1?xGd_x)₂Ce₂O₇ ceramics were investigated, respectively. XRD results revealed that pure (La_1?xGd_x)₂Ce₂O₇ ceramics with defect fluorite structure were synthesized and SEM showed that their microstructures were dense and no other phases existed among the particles. With the increasing temperature, their thermal expansion coefficients increased, while the thermal conductivities decreased. The thermophysical results indicated that thermal expansion coefficients of these ceramics were higher than that of 8YSZ, and their thermal conductivities were much lower than that of 8YSZ. The lower thermal conductivities of these ceramics were mainly attributed to more oxygen vacancies and substitution atoms. These results imply that the (La_1?xGd_x)₂Ce₂O₇ ceramics can be explored as candidate materials for the ceramic layer in TBC system.     

Phase structure and thermal conductivities of Er2O3 stabilized ZrO2 toughened Gd2Zr2O7 ceramics for thermal barrier coatings

3.5 mol% Er₂O₃ stabilized ZrO₂ (ErSZ) and Gd₂Zr₂O₇ powders were produced by a chemical co-precipitation and calcination method, and ErSZ was used to toughen Gd₂Zr₂O₇. The phase structure, toughness and thermal conductivities of ErSZ toughened Gd₂Zr₂O₇ ceramics were investigated. When the ErSZ content was below 15 mol%, the compound consisted of pyrochlore phase, the ordering degree of which decreased with the increase of the ErSZ content. High ErSZ doping led to the formation of metastable tetragonal (t′) phase in the compound. The addition of ErSZ in Gd₂Zr₂O₇ benefited its toughness, mainly attributable to the presence of t′ phase in the compound. With the increase of the ErSZ content in the compound, the thermal conductivity first decreased and then showed an upward tendency, and 10 mol% ErSZ toughened Gd₂Zr₂O₇ exhibited the lowest thermal conductivity.     

Characterisation of the microstructure and thermal properties of Nd2Zr2O7 and Nd2Zr2O7/YSZ thermal barrier coatings

The microstructure of following thermal barrier coatings (TBC) was characterised in this paper: monolayer coatings Nd₂Zr₂O₇ and 8YSZ; a double ceramic layered (DCL) coating. Coatings were characterised by thicknesses that did not exceed 300 μm and porosities of approx. 5%. The chemical and phase composition analysis of the DCL layers revealed an external Nd₂Zr₂O₇ ceramic layer approx. 80 μm thick, a transitional zone approx. 120 μm thick and an internal 8YSZ layer 100 μm thick. For the case of the monolayer coating, the Nd₂Zr₂O₇ pyrochlore phase was the only one-phase component. The surface topography of both TBC systems was typical for plasma sprayed coatings, and compressive stress state had a value of approx. 5–10 MPa. Measurements of the thermal parameters, i.e., thermal diffusivity, point to considerably better insulative properties for both new types of layers when compared to the standard 8YSZ layers.     

Thermophysical properties of Yb2O3 doped Gd2Zr2O7 and thermal cycling durability of (Gd0.9Yb0.1)2Zr2O7/YSZ thermal barrier coatings

(Gd_1−xYb_x)₂Zr₂O₇ compounds were synthesized by solid reaction. Yb₂O₃ doped Gd₂Zr₂O₇ exhibited lower thermal conductivities and higher thermal expansion coefficients (TECs) than Gd₂Zr₂O₇. The TECs of (Gd_1−xYb_x)₂Zr₂O₇ ceramics increased with increasing Yb₂O₃ contents. (Gd_0.9Yb_0.1)₂Zr₂O₇ (GYbZ) ceramic exhibited the lowest thermal conductivity among all the ceramics studied, within the range of 0.8–1.1 W/mK (20–1600 °C). The Young's modulus of GYbZ bulk is 265.6 ± 11 GPa. GYbZ/YSZ double-ceramic-layer thermal barrier coatings (TBCs) were prepared by electron beam physical vapor deposition (EB-PVD). The coatings had an average life of more than 3700 cycles during flame shock test with a coating surface temperature of ∼1350 °C. Spallation failure of the TBC occurred by delamination cracking within GYbZ layer, which was a result of high temperature gradient in the GYbZ layer and low fracture toughness of GYbZ material.     

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.     

Characterization of microstructure and thermal properties of Gd2Zr2O7-type thermal barrier coating

We present herein a characterization of the microstructure and thermal properties of thermal barrier coatings (TBCs), which we obtained via plasma spraying of powder Gd₂Zr₂O₇. By using X-ray diffraction (XRD) and electron backscatter diffraction (EBSD), we evaluated the phase composition of a ceramic layer and estimated the ceramic-layer stress state by the sin²ψ method. The tests revealed that the TBC layer consisted of a single-phase structure of Gd₂Zr₂O₇, namely, an Fd3m lattice. The thermal diffusivity of the outer ceramic layer was determined based on a bilayer model and corrected with a factor to account for the presence of pores. The results reveal that the use of the standard parameters in a standard spraying process gives good-quality Gd₂Zr₂O₇ TBCs with a thermal conductivity considerably lower than 8YSZ-type TBCs.     

Phase transformation and grain-boundary segregation in Al-Doped Li7La3Zr2O12 ceramics

Cubic phase garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is a promising solid electrolyte for highly safe Li-ion batteries. Al-doped LLZO (Al-LLZO) has been widely studied due to the low cost of Al₂O₃. The reported ionic conductivities were variable due to the complicated Al³⁺-Li⁺ substitution and Li_xAlO_y segregation in Al-LLZO ceramics. This work prepared Li_7?3xAl_xLa₃Zr₂O₁₂ (x = 0.00~0.40) ceramics via a conventional solid-state reaction method. The AC impedance and corresponding distribution of relaxation times (DRT) were analyzed combined with phase transformation, cross-sectional microstructure evolution, and grain boundary element mapping results for these Al-LLZO ceramics to understand the various ionic transportation levels in LLZO with different Al-doping amounts. The low conductivity in low Al-doped (0.12~0.28) LLZO originates from the slow Li⁺ ion migration (1.4~0.25 μs) in the cubic-tetragonal mixed phase. On the other hand, LiAlO₂ and LaAlO₃ segregation occur at the grain boundaries of high Al-doped (0.40) LLZO, resulting in a gradual Li⁺ ion jump (6.5 μs) over grain boundaries and low ionic conductivity. The Li_6.04Al_0.32La₃Zr₂O₁₂ ceramic delivers the optimum Li⁺ ion conductivity of 1.7 × 10^?4 S cm^?1 at 25 °C.     

Thermal shock behavior of 8YSZ and double-ceramic-layer La2Zr2O7/8YSZ thermal barrier coatings fabricated by atmospheric plasma spraying

The single-ceramic-layer (SCL) 8YSZ (conventional and nanostructured 8YSZ) and double-ceramic-layer (DCL) La₂Zr₂O₇ (LZ)/8YSZ thermal barrier coatings (TBCs) were fabricated by plasma spraying on nickel-based superalloy substrates with NiCrAlY as the bond coat. The thermal shock behavior of the three as-sprayed TBCs at 1000 °C and 1200 °C was investigated. The results indicate that the thermal cycling lifetime of LZ/8YSZ TBCs is longer than that of SCL 8YSZ TBCs due to the fact that the DCL LZ/8YSZ TBCs further enhance the thermal insulation effect, improve the sintering resistance ability and relieve the thermal mismatch between the ceramic layer and the metallic layer at high temperature. The nanostructured 8YSZ has higher thermal shock resistance ability than that of the conventional 8YSZ TBC which is attributed to the lower tensile stress in plane and higher fracture toughness of the nanostructured 8YSZ layer. The pre-existed cracks in the surface propagate toward the interface vertically under the thermal activation. The nucleation and growth of the horizontal crack along the interface eventually lead to the failure of the coating. The crack propagation modes have been established, and the failure patterns of the three as-sprayed coatings during thermal shock have been discussed in detail.     

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.     

Rapid fabrication and phase transition of Nd and Ce co-doped Gd2Zr2O7 ceramics by SPS

A series of Nd and Ce co-doped Gd_2-xNd_xZr_2-yCe_yO₇ (0.0 ≤ x, y ≤ 2.0) ceramics were rapidly fabricated through spark plasma sintering (SPS) within 3?min. The effects of Nd and Ce contents on the phase composition, lattice parameter, active modes, microtopography and microstructure have been investigated in detail. XRD studies reveal that the compositions corresponding to 0.0 ≤ y ≤ 1.0 show a single phase and beyond 1.0 exhibit multiphase. The lattice parameters increase with elevated Nd and Ce content. The grains are densely packed on each other with cube-like shape, and the elements are almost homogeneously distributed in the compound. This synthetic method provides a simple pathway for the preparation of highly densified single phase ceramic at 1600–1700 ℃ for 3?min under pressure of 80?MPa.     

Phase stability and thermo-physical properties of ZrO2-CeO2-TiO2 ceramics for thermal barrier coatings

The properties of ZrO₂ co-stabilized by CeO₂ and TiO₂ ceramic bulks were investigated for potential thermal barrier coating (TBC) applications. Results showed that the (Ce_0.15Ti_x)Zr_0.85-xO7 (x?=?0.05, 0.10, 0.15) compositions with single tetragonal phase were more stable than the traditional 8YSZ at 1573?K. These compositions also showed a large thermal expansion coefficient (TEC) and a high fracture toughness, which were comparable to those of YSZ. However, the phase stability, fracture toughness and sintering resistance of the CeO₂-TiO₂-ZrO₂ system showed a decline tendency with the increase of TiO₂ content. The TEC of the ceramic bulks decreased with increase of TiO₂ content as well because the crystal energy was enhanced with increasing substitution of Zr⁴⁺ by smaller Ti⁴⁺. The (Ce_0.15Ti_0.05)Zr_0.8O₂ had the best comprehensive properties among the (Ce_0.15Ti_x)Zr_0.85-xO₂ compositions as well as a low thermal conductivity. Therefore, it can be explored as a TBC candidate material for high-temperature applications.     

Piezoelectric and dielectric properties of Ce substituted La2Ti2O7 ceramics

The ferroelectric and dielectric properties of cerium (Ce) substituted La₂Ti₂O₇ (LTO) have been investigated. Single phase, dense La_2?xCe_xTi₂O₇ (x = 0.15, 0.25, 0.35) ceramics were prepared by spark plasma sintering. The solubility limit of Ce in La_2?xCe_xTi₂O₇ was found to be between 0.35 and 0.5. The a-, b- and c-axes of the unit cell decrease with increasing Ce substitution. The Curie point (Tc) of La_2?xCe_xTi₂O₇ (x = 0, 0.15, 0.25, 0.35) decreases and dielectric constant and loss increase with increasing Ce substitution. Cerium can increase the d₃₃ of La₂Ti₂O₇. The highest d₃₃ was 3.9 ± 0.1 pC/N for La_1.85Ce_0.15Ti₂O₇ textured ceramic.     

The microstructures and properties of Fe2O3 and TiO2 co-doped corundum ceramics for solar thermal absorbing materials

Solar thermal absorbing materials are the key components of concentrating solar power. In this study, Fe₂O₃ and TiO₂ co-doped corundum ceramics were prepared by pressureless sintering. The effects of different Fe₂O₃/TiO₂ ratios on the phase composition, microstructure, thermal shock resistance and solar absorptance were investigated via XRD and EPMA testing. The results showed that, with the decrease of Fe₂O₃/TiO₂ ratio, the appropriate amount of FeAlTiO₅ would decompose into ferrite particles, which played a bridging role between the corundum grains making the samples have excellent thermal shock resistance. A6 (90% bauxite, 9.5% Fe₂O₃ and 0.5% TiO₂) sintered at 1460 °C had the optimum comprehensive properties, with a bending strength of 154.80 MPa and an absorptance of 89.20% in the spectral range from 0.3 to 2.5 μm. After 30 thermal shock cycles (1000 °C–25 °C, air-cooled), the bending strength of A6 was 222.05 MPa, and the absorptance was 90.40%, which were 43.44% and 1.35% higher than those before thermal shock, respectively. Therefore, it was suitable as an excellent solar thermal absorbing materials.     

有序介孔La_2Zr_2O_7的制备与表征

以F127作为模板剂,通过溶剂蒸发诱导自组装法合成了具有有序孔结构、孔径分布均匀的介孔锆酸镧,系统研究了不同煅烧温度处理后介孔锆酸镧的相组成、比表面积、孔径及其分布以及微观结构。结果表明,经800℃处理后,样品开始晶化,完全晶化的样品中仅含锆酸镧相。经600℃煅烧后样品的比表面积为136 m2/g,孔体积为0.14 cm3/g,800℃煅烧后比表面积仍达90 m2/g,显示出较好的热稳定性。随着煅烧温度进一步升高,样品的比表面积和孔体积急剧减小,表明该方法制备的介孔锆酸镧最高耐热温度为800℃。透射电子显微镜观察发现,400℃去除模板后,样品具有有序介孔结构,预期其具有较好的催化性能。     

Influence of the deposition energy on the composition and thermal cycling behavior of La2(Zr0.7Ce0.3)2O7 coatings

Lanthanum–zirconium–cerium composite oxide (La₂(Zr_0.7Ce_0.3)₂O₇, LZ7C3) coatings were prepared under different conditions by electron beam-physical vapor deposition (EB-PVD). The composition, crystal structure, surface and cross-sectional morphologies, cyclic oxidation behavior of these coatings were studied. Elemental analysis indicates that the coating composition has partially deviated from the stoichiometry of the ingot, and the existence of excess La₂O₃ is also observed. The optimized composition of LZ7C3 coatings could be effectively achieved by the addition of excess CeO₂ into the ingot or by properly controlling the deposition energy. Meanwhile, when the deposition energy is 1.15 × 10⁴–1.30 × 10⁴ J/cm², the coating has a similar X-ray diffraction (XRD) pattern to the ingot, and the thermal cycling life of the coating is also superior to other coatings. The spallation of the coatings occurs either within the ceramic layer approximately 6–10.5 μm above its thermally grown oxide (TGO) layer or at the interface between ceramic layer and bond coat.     

Phase stability and thermal conductivity of RE2O3 (RE=La,Nd, Gd,Yb) and Yb2O3 co-doped Y2O3 stabilized ZrO2 ceramics

Y₂O₃ stabilized ZrO₂ (YSZ) has been considered as the material of choice for thermal barrier coatings (TBCs), but it becomes unstable at high temperatures and its thermal conductivity needs to be further reduced. In this study, 1 mol% RE₂O₃ (RE=La, Nd, Gd, Yb) and 1 mol% Yb₂O₃ co-doped YSZ (1RE1Yb–YSZ) were fabricated to obtain improved phase stability and reduced thermal conductivity. For 1RE1Yb–YSZ ceramics, the phase stability of metastable tetragonal (t′) phase increased with decreasing RE³⁺ size, mainly attributable to the reduced driving force for t′ phase partitioning. The thermal conductivity of 1RE1Yb–YSZ was lower than that of YSZ, with the value decreasing with the increase of the RE³⁺ size mainly due to the increased elastic field in the lattice, but 1La1Yb–YSZ exhibited undesirably high thermal conductivity. By considering the comprehensive properties, 1Gd1Yb–YSZ ceramic could be a good potential material for TBC applications.     

Phase composition,microstructure and thermophysical properties of the Srx(Zr0.9Y0.05Yb0.05)O1.95+x ceramics

Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x (x=1.0, 0.9, 0.8, 0.7) ceramics were prepared by solid state reaction sintering. The sintered Sr_1.0(Zr_0.9Y_0.05Yb_0.05)O_2.95 is a single-phase solid solution while the sintered Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x (x=0.9?0.7) are composites, and a significant grain growth inhibition is observed in the sintered Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x (x=1.0, 0.9). Rare-earth elements distribution in the bulk materials indicates that Yb and Y preferentially substitute Zr-sites in SrZrO₃, and the highest solubility of RE₂O₃ in pure SrZrO₃ is ～0.8 mol%. The sintered Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x have high thermal expansion coefficients up to ～11.0×10^?6 K^-1 (1200°C). Sr_0.8(Zr_0.9Y_0.05Yb_0.05)O_2.75 has the lowest thermal conductivity of 1.38 W·m^-1·K^-1 at 800°C. Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x (x=1.0, 0.9, 0.8) show no phase transition from 600 to 1400°C, whereas Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x (x=0.9, 0.8) have excellent high-temperature phase stability over the whole investigated temperature range. Therefore, Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x (x=1.0, 0.9, 0.8) are considered as promising TBCs materials that might be operated at higher temperatures compared to YSZ.     

The structure and electrical properties of lithium doped pyrochlore Gd2Zr2O7

The lithium-doped phases Gd_1.7Li_0.3Zr₂O_6.7 and Gd₂Zr_1.7Li_0.3O_6.55 with a pyrochlore structure were prepared by the modified Pechini method using citric acid and glycerol. Monitoring of the lithium content by using a nuclear microanalysis showed that a significant loss of lithium occurred after heat treatment above 1200 °C. Dense ceramics with a stoichiometric lithium content can be prepared by a low temperature microwave sintering (1100 °C). The introduction of lithium in the Gd-sublattice was accompanied by a decrease in the unit cell parameter (a = 10.5208 (1) Å vs 10.5346 (2) Å for Gd₂Zr₂O₇) and during doping at the Zr-sites with lithium, the cell parameter increased (10.5720 (1) Å). The doping in both cases led to an increase in the free cell volume. The impedance spectroscopy results showed that the bulk conductivity can be enhanced by the Li⁺-doping at the Gd³⁺-site by almost an order of magnitude. The sample Gd₂Zr_1.7Li_0.3O_6.55 had a conductivity lower than that of Gd_1.7Li_0.3Zr₂O_6.7 due to the possible trapping of oxygen vacancies by a high-charged acceptor defect LiZr???. The conductivity?pO₂ measurements showed that the Li-containing phase was a pure oxide-ion conductor at T < 800 °C.     

Thermal conductivity of plasma sprayed Sm2Zr2O7 coatings

Rare-earth zirconates with a pyrochlore structure have been developed for potential application in thermal barrier coating systems to further improve the performance and durability of gas turbines. The Sm₂Zr₂O₇ (abbreviated as SZ) powder was synthesized by solid state reaction and then deposited by air plasma spraying. The phase stability, microstructure and thermal conductivity of SZ and 8 wt% Y₂O₃ stabilized zirconia (8YSZ) coatings were investigated. The X-ray diffraction results indicated that the crystal structure of the as-sprayed SZ coatings was defect-fluorite, and after heat treating at 1200 °C for 50 h, it started to transform to pyrochlore, and the content of pyrochlore increased with increase in temperature of the heat treatment. The thermal conductivities of SZ coatings were significantly lower than those of 8YSZ coatings before and after heat treatments, which increased considerably after heat treatments compared to the as-sprayed states for both coatings due to sintering effects.