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.     

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.     

Fabrication and evaluation of NiO/Y2O3-stabilized-ZrO2 hollow fibers for anode-supported micro-tubular solid oxide fuel cells

In this work NiO/3 mol% Y₂O₃–ZrO₂ (3YSZ) and NiO/8 mol% Y₂O₃–ZrO₂ (8YSZ) hollow fibers were prepared by phase-inversion. The effect of different kinds of YSZ (3YSZ and 8YSZ) on the porosity, electrical conductivity, shrinkage and flexural strength of the hollow fibers were systematically evaluated. When compared with Ni–8YSZ the porosity and shrinkage of Ni–3YSZ hollow fibers increases while the electrical conductivity decreases, while at the same time also exhibiting enhanced flexural strength. Single cells with Ni–3YSZ and Ni–8YSZ hollow fibers as the supported anode were successfully fabricated showing maximum power densities of 0.53 and 0.67 W cm⁻² at 800 °C, respectively. Furthermore, in order to improve the cell performance, a Ni–8YSZ anode functional layer was added between the electrolyte and Ni–YSZ hollow fiber. Here enhanced peak power densities of 0.79 and 0.73 W cm⁻² were achieved at 800 °C for single cells with Ni–3YSZ and Ni–8YSZ hollow fibers, respectively.     

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.     

Effects of ZrO2-La2O3 co-addition on the microstructural and optical properties of transparent Y2O3 ceramics

Commercial Y₂O₃ powder was used to fabricate Y₂O₃ ceramics sintered at 1600 °C and 1800 °C with concurrent addition of ZrO₂ and La₂O₃ as sintering aids. One group with different contents of La₂O₃ (0–10 mol%) with a fixed amount of 1 mol% ZrO₂ and another group with various contents of ZrO₂ (0–7 mol%) with a fixed amount of 10 mol% La₂O₃ were compared to investigate the effects of co-doping on the microstructural and optical properties of Y₂O₃ ceramics. At low sintering temperature of 1600 °C, the sample single doped with 10 mol% La₂O₃ exhibits much denser microstructure with a few small intragranular pores while the samples with ZrO₂ and La₂O₃ co-doping features a lot of large intergranular pores leading to lower density. When the sintering temperature increases to 1800 °C, samples using composite sintering aids exhibit finer microstructures and better optical properties than those of both ZrO₂ and La₂O₃ single-doped samples. It was proved that the grain growth suppression caused by ZrO₂ overwhelms the acceleration by La₂O₃. Meanwhile, 1 mol% ZrO₂ acts as a very important inflection point with regard to the influence of additive concentration on the transmittance, pore structure and grain size. The highest in-line transmittance of Y₂O₃ ceramic (1.2 mm in thickness) with 3 mol% of ZrO₂ and 10 mol% of La₂O₃ sintered at 1800 °C for 16 h is 81.9% at a wavelength of 1100 nm, with an average grain size of 11.2 µm.     

Effect of TiO2 and Ta2O5 co-doping on phase stability,fracture toughness,and sintering behavior of ZrO2 stabilized by 10mol%(Y0.4Gd0.3Yb0.3)2O3

The effect of TiO₂ and Ta₂O₅ co-doping on the phase structure, fracture toughness, and sintering behavior of 10mol%(Y_0.4Gd_0.3Yb_0.3)₂O₃-stabilized zirconia was investigated using X-ray diffraction, scanning electron microscopy, microindentation, and pressureless sintering. The results showed that 10mol%(Y_0.4Gd_0.3Yb_0.3)₂O₃–ZrO₂ had a single cubic phase structure, and an increase in the Ta₂O₅ (≥6 mol%) and TiO₂ doping concentrations resulted in a simultaneous increase in the content and stability of the tetragonal phase. The fracture toughness of TiO₂ and Ta₂O₅ co-doping 10mol%(Y_0.4Gd_0.3Yb_0.3)₂O₃–ZrO₂ decreased with an increase in the Ta₂O₅ content. On the other hand, the TiO₂ content had no significant effect on the fracture toughness of 10mol%(Y_0.4Gd_0.3Yb_0.3)₂O₃–ZrO₂. The sintering resistance of the specimens increased with an increasing in the Ta₂O₅ content; however, an increase in the TiO₂ content accelerated the densification of the specimens. When the Ta₂O₅ content was 10 mol% and the TiO₂ content was in the range of 4–8 mol%, a single non-transformable tetragonal phase structure with fracture toughness similar to that of 6–8 wt% Y₂O₃ stabilized ZrO₂ and excellent anti-sintering properties could be obtained. This structure can be explored as a thermal barrier coating material for high-temperature applications.     

Low–thermal–conductivity and high–toughness CeO2–Gd2O3 co–stabilized zirconia ceramic for potential thermal barrier coating applications

Yttria partially stabilized zirconia (～4.0?mol% Y₂O₃–ZrO₂, 4YSZ) has been widely employed as thermal barrier coatings (TBCs) to protect the high–temperature components of gas–turbine engines. The phase stability problem existing in the conventional 4YSZ has limited it to application below 1200?°C. Here we report an excellent zirconia system co–doped with 16?mol% CeO₂ and 4?mol% Gd₂O₃ (16Ce–4Gd) presenting nontransformable feature up to 1500?°C, in which no detrimental monoclinic (m) ZrO₂ phase formed on partitioning. It also exhibits a high fracture toughness of ～46?J m^?2 and shows high sintering resistance. Besides, the thermal conductivity and thermal expansion coefficient of 16Ce–4Gd are more competent for TBCs applications as compared to the 4YSZ. The combination of properties suggests that the 16Ce–4Gd system could be of potential use as a thermal barrier coating at 1500?°C.     

Structural parameters and oxygen ion conductivity of Y2O3–ZrO2 and MgO–ZrO2 at high temperature

The oxygen ion conductivity of zirconia-based solid electrolytes doped with 8 mol% Y₂O₃–ZrO₂ (YSZ) and 9 mol% MgO–ZrO₂ (Mg-PSZ) at high temperature was investigated in terms of their thermal behavior and structural changes. At room temperature, YSZ showed a single phase with a fluorite cubic structure, whereas Mg-PSZ had a mixture of cubic, tetragonal and some monoclinic phases. YSZ exhibited higher ionic conductivity than Mg-PSZ at temperatures from 600 °C to 1250 °C because of the existence of the single cubic structure and low activation energy. A considerable increase in the conductivity with increasing temperature was observed in Mg-PSZ, which showed higher ionic conductivity than YSZ within the higher temperature range of 1300–1500 °C. A monoclinic-to-tetragonal phase transformation was found in Mg-PSZ and the lattice parameter of the cubic phase increased at 1200 °C. The phase transformation and the large lattice free volume contributed to the significant enhancement of the ionic conductivity of Mg-PSZ at high temperatures.     

Constrained sintering of 8 mol% Y2O3 stabilised zirconia films

Constrained sintering kinetics of 8 mol% Y₂O₃/92 mol% ZrO₂ (8YSZ) films approximately 10–15 μm thick screen-printed on dense YSZ substrates, and the resulting stress induced in the films, were measured in the temperature range 1100–1350 °C. The results are compared with those reported earlier for 3YSZ films.Both materials behave similarly, although there are differences in detail. The constrained densification rate was greatly retarded compared with the unconstrained densification rate due to the effect of the constraint on the developing anisotropic microstructure (3YSZ) and, in the case of 8YSZ, considerable grain growth. The stress generated during constrained sintering was typically a few MPa. The apparent activation energies for free sintering, constrained sintering, creep and grain growth are found to cover a wide range (135–670 kJ mol^?1) despite all probably being mainly controlled by grain boundary cation diffusion.     

Diffusion of niobium in yttria-stabilized zirconia and in titania-doped yttria-stabilized zirconia polycrystalline materials

Bulk and grain boundary diffusion of Nb⁵⁺ cations in yttria-stabilized zirconia (YSZ, 8 mol% Y₂O₃–92 mol% ZrO₂) and in titania-doped yttria-stabilized zirconia (Ti–YSZ, 5 mol% TiO₂–8 mol% Y₂O₃–87 mol% ZrO₂) was studied in air in the temperature range from 900 to 1300 °C. Experiments were performed in the B-type kinetic region. Diffusion profiles were determined using the secondary ion mass spectrometry (SIMS). The temperature dependencies of the bulk diffusion coefficient D and the grain boundary diffusion parameter D′δs for both the materials were calculated. The activation energies of these transport processes in YSZ amounts to 258 and 226 kJ mol⁻¹, respectively, and 232 and 114 kJ mol⁻¹ in Ti–YSZ. The results were compared to the diffusion data of other cations previously obtained for the same material.     

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.     

Improvement in thermal shock resistance of gadolinium zirconate coating by addition of nanostructured yttria partially-stabilized zirconia

Gadolinium zirconate (Gd₂Zr₂O₇, GZ) as one of the promising thermal barrier coating materials for high-temperature application in gas turbine was toughened by nanostructured 3 mol% yttria partially-stabilized zirconia (YSZ) incorporation. The fracture toughness of the composite of 90 mol% GZ-10 mol% YSZ (GZ–YSZ) was increased by about 60% relative to the monolithic GZ. Both the GZ and GZ–YSZ composite coatings were deposited by atmospheric plasma spraying on Ni-base superalloys and then thermal-shock tested under the same conditions. The thermal-shock lifetime of GZ–YSZ composite coating was improved, which is believed to be mainly attributed to the enhancement of fracture toughness by the addition of YSZ. In addition, the failure mechanisms of the thermal-shock tested GZ–YSZ composite coatings were discussed.     

Evolution of hot corrosion resistance of YSZ,Gd2Zr2O7, and Gd2Zr2O7 + YSZ composite thermal barrier coatings in Na2SO4 + V2O5 at 1050 °C

This paper compares the hot corrosion performance of yttria stabilized zirconia (YSZ), Gd₂Zr₂O₇, and YSZ + Gd₂Zr₂O₇ composite coatings in the presence of molten mixture of Na₂SO₄ + V₂O₅ at 1050 °C. These YSZ and rare earth zirconate coatings were prepared by atmospheric plasma spray (APS). Chemical interaction is found to be the major corrosive mechanism for the deterioration of these coatings. Characterizations using X-ray diffraction (XRD) and scanning electron microscope (SEM) indicate that in the case of YSZ, the reaction between NaVO₃ and Y₂O₃ produces YVO₄ and leads to the transformation of tetragonal ZrO₂ to monoclinic ZrO₂. For the Gd₂Zr₂O₇ + YSZ composite coating, by the formation of GdVO₄, the amount of YVO₄ formed on the YSZ + Gd₂Zr₂O₇ composite coating is significantly reduced. Molten salt also reacts with Gd₂Zr₂O₇ to form GdVO₄. Under a temperature of 1050 °C, Gd₂Zr₂O₇ based coatings are more stable, both thermally and chemically, than YSZ, and exhibit a better hot corrosion resistance.     

ZrO2-doped Y2O3 transparent ceramics via slip casting and vacuum sintering

Commercial Y₂O₃ powder was used to fabricate highly transparent Y₂O₃ ceramics with the addition of ZrO₂ via slip casting and vacuum sintering. The effects of ZrO₂ addition on the transparency, grain size and lattice parameter of Y₂O₃ ceramics were studied. With addition of ZrO₂ the transparency of Y₂O₃ ceramics increased markedly and the grain size of Y₂O₃ ceramics decreased markedly by cation diffusivity mechanism and the lattice parameter of Y₂O₃ ceramics slightly decreased. The highest transmittance (at wavelength 1100 nm) of the 5.0 mol% ZrO₂–Y₂O₃ ceramic (1.0 mm thick) sintered at 1860 °C for 8 h reached 81.7%, very close to the theoretical value of Y₂O₃.     

Yb3+ concentration on emission color,thermal sensing and optical heater behavior of Er3+ doped Y6O5F8 phosphor

Up-conversion phosphor is a potential candidate as non-contact temperature sensor because of its unjammable and unique detection abilities. In this work, we investigate the influence of Yb³⁺ concentration on the emission color, thermal sensing and optical heater behavior of Er³⁺ doped Y₆O₅F₈ phosphor. Our results show that the emission color of Er³⁺ and Yb³⁺ co-doped Y₆O₅F₈ powder changes from green to yellow with the Yb³⁺ concentration increasing. Importantly, the temperature sensing sensitivities of Er³⁺ and Yb³⁺ co-doped Y₆O₅F₈ powder reach 0.008, 0.009, 0.010 and 0.011 K⁻¹ as the sample doped with 2%, 5%, 8% and 11% Yb³⁺ at 476 K, respectively. Moreover, the temperature of high Yb³⁺ concentration sample shows preferable optical heating behavior, whose temperature is ascended by a large value of 94 K when the excitation pump power density changes from 1.0 to 13.1 W cm⁻². These results suggest Er³⁺ and Yb³⁺ co-doped Y₆O₅F₈ powder has great potential in colorful display, temperature sensing and optical heating.     

Tb3+/Yb3+ co-doped Y2O3 upconversion transparent ceramics: Fabrication and characterization for IR excited green emission

Tb³⁺/Yb³⁺ co-doped Y₂O₃ transparent ceramics were fabricated by vacuum sintering of the pellets (prepared from nanopowders by uniaxial pressing) at 1750 °C for 5 h. Zr⁴⁺ and La³⁺ ions were incorporated in Tb³⁺/Yb³⁺ co-doped Y₂O₃ nanoparticle to reduce the formation of pores which limits the transparency of ceramic. An optical transmittance of ∼80% was achieved in ∼450 to 2000 nm range for 1 mm thick pellet which is very close to the theoretical value by taking account of Fresnel’s correction. High intensity luminescence peak at 543 nm (green) was observed in these transparent ceramics under 976 and 929 nm excitations due to Yb–Tb energy transfer upconversion.     

Superplastic deformation of directionally solidified nanofibrillar Al2O3–Y3Al5O12–ZrO2 eutectics

Nanofibrillar Al₂O₃–Y₃Al₅O₁₂–ZrO₂ eutectic rods were manufactured by directional solidification from the melt at high growth rates in an inert atmosphere using the laser-heated floating zone method. Under conditions of cooperative growth, the ternary eutectic presented a homogeneous microstructure, formed by bundles of single-crystal c-oriented Al₂O₃ and Y₃Al₅O₁₂ (YAG) whiskers of ≈100 nm in width with smaller Y₂O₃-doped ZrO₂ (YSZ) whiskers between them. Owing to the anisotropic fibrillar microstructure, Al₂O₃–YAG–YSZ ternary eutectics present high strength and toughness at ambient temperature while they exhibit superplastic behavior at 1600 K and above. Careful examination of the deformed samples by transmission electron microscopy did not show any evidence of dislocation activity and superplastic deformation was attributed to mass-transport by diffusion within the nanometric domains. This combination of high strength and toughness at ambient temperature together with the ability to support large deformations without failure above 1600 K is unique and shows a large potential to develop new structural materials for very high temperature structural applications.     

Microstructure and thermal properties of nanostructured gadolinia doped yttria-stabilized zirconia thermal barrier coatings produced by air plasma spraying

In this article, the nanostructured 2 mol% Gd₂O₃-4.5 mol% Y₂O₃-ZrO₂(2GdYSZ) coating was developed by the atmospheric plasma spraying technique. And the microstructure and thermal properties of plasma-sprayed 2GdYSZ coating were investigated. The result from the investigation indicates that the as-sprayed coating is characterized by typical microstructure consisting of melted zones, nano-zones, splats, nano-pores, high-volume spheroidal pores and micro-cracks. The 2GdYSZ coating shows a lower resistance to destabilization of the metastable tetragonal (t′) phase compared to the yttria stabilized zirconia(YSZ). The thermal diffusivity and thermal conductivity of the nano-2GdYSZ coating at room temperature are 0.431 mm² s⁻¹ and 1.042 W/m K, respectively. Addition of gadolinia to the nano-YSZ can significantly reduce the thermal conductivity compared to the nano-YSZ and the conventional YSZ. The reduction is mainly attributed to the synergetic effect of gadolinia doping along with nanostructure.     

Synthesis and microstructure of Gd2O3-doped HfO2 ceramics

The effect of Gd₂O₃-doping on the crystal structure, surface morphology and chemical composition of the Gd₂O₃–HfO₂ system is reported. Gd₂O₃–HfO₂ ceramics with variable composition were prepared by varying the Gd₂O₃ composition in the range of 0–38 mol% balanced HfO₂. X-ray diffraction (XRD) analysis indicates that the Gd₂O₃ concentration influences the crystal structure of the Gd₂O₃–HfO₂ ceramics. Pure HfO₂ and Gd₂O₃ crystallize in monoclinic and body centered cubic structure, respectively. The Gd₂O₃–HfO₂ ceramics exhibit mixed monoclinic and fluorite structure when the Gd₂O₃ concentration is varied from 4 to 12 mol%. At 20 mol% of Gd₂O₃, existence of only the fluorite phase was found. Increasing the Gd₂O₃ concentration to 38 mol% results in the formation of single-phase pyrochlore Gd₂Hf₂O₇ (a = 5.258 Å).