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.     

Effects of TiO2 doping on the defect chemistry and thermo-physical properties of Yb2O3 stabilized ZrO2

Yb₂O₃ stabilized ZrO₂ (YbSZ) doped with different TiO₂ contents were produced, and their phase structure, thermal conductivities and thermal expansion coefficients were investigated. A new solid-solution model is proposed, i.e. Ti⁴⁺ would take the interstitial sites when its content is below a critical value (≤2.5 mol%) and then substitute for Zr⁴⁺. The abnormal lattice volume and thermo-physical properties of 2.5 mol% TiO₂ doped YbSZ, and the positive effects of TiO₂ doping on the thermal conductivity at moderate doping level are consistent with the new defect model. However, monoclinic phase is formed when the TiO₂ content reaches to 10 mol% and its content increases with doping content, which have negative influence on the thermo-physical properties. Considering the comprehensive properties, 10 mol% TiO₂ doped YbSZ is considered as a promising thermal barrier coating ceramic.     

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.     

Improvement on the phase stability,mechanical properties and thermal insulation of Y2O3-stabilized ZrO2 by Gd2O3 and Yb2O3 co-doping

Gd₂O₃ and Yb₂O₃ co-doped 3.5 mol% Y₂O₃–ZrO₂ and conventional 3.5 mol% Y₂O₃–ZrO₂ (YSZ) powders were synthesized by solid state reaction. The objective of this study was to improve the phase stability, mechanical properties and thermal insulation of YSZ. After heat treatment at 1500 °C for 10 h, 1 mol% Gd₂O₃–1 mol% Yb₂O₃ co-doped YSZ (1Gd1Yb-YSZ) had higher resistance to destabilization of metastable tetragonal phase than YSZ. The hardness of 5 mol% Gd₂O₃–1 mol% Yb₂O₃ co-doped YSZ (5Gd1Yb-YSZ) was higher than that of YSZ. Compared with YSZ, 1Gd1Yb-YSZ and 5Gd1Yb-YSZ exhibited lower thermal conductivity and shorter phonon mean free path. At 1300 °C, the thermal conductivity of 5Gd1Yb-YSZ was 1.23 W/m K, nearly 25% lower than that of YSZ (1.62 W/m K). Gd₂O₃ and Yb₂O₃ co-doped YSZ can be explored as a candidate material for thermal barrier coating applications.     

Synthesis,sintering, and grain growth kinetics of Hf6Ta2O17

A systematic study of the solid-state synthesis, pressureless sintering, and grain growth kinetics of Hf₆Ta₂O₁₇ is presented. The ideal conditions for solids-state synthesis of Hf₆Ta₂O₁₇ powder with minimal particle necking was 1250 °C for 2 h in air. The resultant powder has an average particle size of 210 ± 70 nm. The combined synthesis and ball-milling procedure produces highly sinterable Hf₆Ta₂O₁₇ powder, achieving > 97 % of theoretical density after pressureless sintering at 1600 °C for 2 h in air. The grain growth mechanism was sensitive to processing conditions, appearing to be primarily driven by surface diffusion below 1600 °C and grain boundary diffusion above 1650 °C. The respective activation energies for grain growth were found to be Q_S = 659 ± 79 kJ mol⁻¹ and Q_GB = 478 ± 63 kJ mol⁻¹.     

Phase stability and thermophysical properties of CeO2-Re2O3 (ReEu,Gd, Dy,Y, Er,Yb) co-stabilised zirconia

A series of 16 mol% CeO₂-2 mol% Re₂O₃ co-stabilised zirconia (ZrO₂) (16Ce4ReSZ, ReEu, Gd, Dy, Y, Er, Yb) ceramic materials were synthesised using a chemical coprecipitation– high-temperature roasting method. Their phase structure, high-temperature phase stability, mechanical properties, thermal conductivity and coefficient of thermal expansion (CTE) were investigated. The results show that the ZrO₂ tetragonal phase co-stabilised by CeO₂ and Re³⁺ with a smaller radius has better stability. The 16Ce4ReSZ (ReDy, Y, Er, Yb) materials have high fracture toughnesses, low thermal conductivities, and high CTE values. As the radius of the Re³⁺ ions decreases, the lattice energy increased, while the lattice distortion decreases, the CTE decreases slightly and the thermal conductivity of the material increases slightly. Owing to the high phase stability of 16Ce4YbSZ, its mechanical properties are best after 100 h of sintering at 1400 °C.     

Evaluation of the phase stability,and mechanical and thermal properties of Ba(Sr1/3Ta2/3)O3 as a potential ceramic material for thermal barrier coatings

Ba(Sr_1/3Ta_2/3)O₃ (BST) ceramic was synthesized by a solid-state reaction method. The phase stability, microstructural evolution, and mechanical and thermal properties of the BST ceramic were investigated and characterized to evaluate the potential application of BST as a top coating material for thermal barrier coatings (TBCs). The results show that BST can maintain a stable hexagonal perovskite structure up to 1600 °C. Anisotropic growth of the grains above 1400 °C was observed. Its low elastic modulus and high fracture toughness suggest a high damage tolerance for the BST ceramic. In addition, the moderate coefficient of thermal expansion and superior heat insulation capability of the BST ceramic provide this ceramic the potential to serve as a top coating material of TBCs at higher temperature.     

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.     

Effect of ZnO and TiO2 doping on the sintering behavior of Y2O3 ceramics

Full densification of Y₂O₃ is challenging and requires a very high sintering temperature (above 1700 °C). In this study, the effect of ZnO and TiO₂ dopants on its densification was investigated, showing that both dopants lowered the sintering temperature and improved the process. Moreover, ZnO promoted the grain growth, while TiO₂ inhibited it; hence, the ZnOTiO₂ co-doping and the change in the ZnO/TiO₂ ratio allowed the control of the sintered body microstructure while maintaining high densification. Since Y₂O₃ has a higher plasma erosion resistance than conventional Si-based materials, the plasma dry etching resistance of the sintered Y₂O₃ was also evaluated and found superior due to the improved densification and controlled grain size of the doped samples.     

Effect of Ba concentration on phase stability and mechanical and thermal properties of La2Mo2O9

Ba-substituted La₂Mo₂O₉ ((La_1−xBa_x)₂Mo₂O_9−δ, x = 0–0.12) was prepared and the thermal and mechanical properties were evaluated. The thermal expansion coefficients (TECs) were determined from high-temperature X-ray diffraction (XRD) analysis. Phase transition in La₂Mo₂O₉ was suppressed via substitution of Ba for La, as demonstrated by differential scanning calorimetry (DSC) analysis. The mechanical properties, such as the bulk modulus, shear modulus, Young’s modulus, compressibility, and Debye temperature were evaluated from the measured sound velocities. The thermal conductivity was evaluated from the thermal diffusivity, heat capacity, and density in the temperature range from room temperature to 1073 K. The thermal conductivity decreased with increasing Ba content. Theoretical calculations based on the Klemens–Callaway model were performed to analyze the thermal conductivity, and the results suggest that the reduction of the thermal conductivity was mainly attributed to oxygen defects in the anion sublattice of La₂Mo₂O₉.     

Effect of point defects on the thermal conductivity of Sc2O3-Y2O3 co-stabilized tetragonal ZrO2 ceramic materials

In this paper, the reduction mechanism in thermal conductivity of a series of Sc₂O₃-Y₂O₃ co-stabilized tetragonal ZrO₂ ceramics is systematically discussed. The thermal conductivity is approximately 20–28% lower than that of 6–8 wt.% yttria-stabilized zirconia (YSZ). A phonon scattering model, on account of the influence of oxygen vacancy variation and cation mass fluctuation, is optimized and utilized to depict the thermal conductivity of these materials. For the samples with the same amount of oxygen vacancy, Sc³⁺ is more effective in lowering thermal conductivity than Y³⁺ due to the large mass difference with Zr⁴⁺, as evidenced by the scattering model and phonon vibrational density of states. The experimental and calculation results suggest that this optimized model is proved to be more effective in predicting the thermal conductivity of binary or multiple rare earth oxides co-doped tetragonal ZrO₂ and guiding the compositional design of thermal barrier materials.     

Influence of Yb3+ doping on phase stability and thermophysical properties of (Y1-xYbx)3Al5O12 under high temperature

In this work, Yb³⁺ was selected to replace the Y³⁺ in yttrium aluminum garnet (YAG) in order to reduce its thermal conductivity under high temperature. A series of (Y_1-xYb_x)₃Al₅O₁₂ (x=0, 0.1, 0.2, 0.3, 0.4) ceramics were prepared by solid-state reaction at 1600 °C for 10 h. The microstructure, thermophysical properties and phase stability under high temperature were investigated. The results showed that all the Yb doped (Y_1-xYb_x)₃Al₅O₁₂ ceramics were comprised of a single garnet-type Y₃Al₅O₁₂ phase. The thermal conductivities of (Y_1-xYb_x)₃Al₅O₁₂ ceramics firstly decreased and subsequently increased with Yb ions concentration rising from room temperature to 1200 °C. (Y_0.7Yb_0.3)₃Al₅O₁₂ had the lowest thermal conductivity among investigated specimens, which was about 1.62 W m⁻¹ K⁻¹ at 1000 °C, around 30% lower than that of pure YAG (2.3 W m⁻¹ K⁻¹, 1000 °C). Yb had almost no effect on the coefficients of thermal expansion (CTEs) of (Y_1-xYb_x)₃Al₅O₁₂ ceramics and the CTE was approximate 10.7×10⁻⁶ K⁻¹ at 1200 °C. In addition, (Y_0.7Yb_0.3)₃Al₅O₁₂ ceramic remained good phase stability when heating from room temperature to 1450 °C.     

Effect of direct and alternating current (DC and AC) fields on creep behavior of 8 mol% Y2O3 stabilized cubic ZrO2 polycrystal

The effect of electric field/current on creep deformation was examined in fine-grained 8 mol% Y₂O₃ stabilized cubic ZrO₂ (8Y-CSZ) under direct and alternative current (DC and AC) conditions. Even at similar sample temperature of 1160–1170 °C, although the electric fields/currents accelerate the deformation of 8Y-CSZ, the acceleration effect (athermal effect), which cannot be explained by an increase of the sample temperature due to Joule heating, is much pronounced in AC than in DC. Under the deformation without the electric field/current, the creep behavior can be characterized by diffusional creep processes with a stress exponent of n ≈ 1, whereas under DC and AC, the predominant mechanism changes to grain boundary sliding (GBS) with n ≈ 2. This indicates that the athermal effect under the electric field/current changes the deformation mechanism from diffusional creep to GBS mechanisms by enhancing GBS and its rate controlling process of cation diffusivity, especially in AC.     

Thermo-mechanical properties and CMAS resistance of (Ho0.4Yb0.3Lu0.3)2SiO5 solid solution for environmental barrier coating applications

Rare earth monosilicate (RE₂SiO₅) is one of the most promising candidates as an environmental barrier coating (EBC) for SiC_f/SiC ceramic matrix composites. But single-component RE₂SiO₅ is hard to meet the multiple and harsh performance requirements of EBC which brings a significant challenge to their applications. Based on our previous research on single-component RE₂SiO₅ ceramics, (Ho_0.4Yb_0.3Lu_0.3)₂SiO₅ solid solution was designed and successfully fabricated in this work. Doping of multiple RE elements endows (Ho_0.4Yb_0.3Lu_0.3)₂SiO₅ with excellent thermal insulation properties and matched thermal expansion coefficient with SiC_f/SiC substrates. In addition, it exhibits lower elastic modulus and comparable hardness than that of single-component RE₂SiO₅. (Ho_0.4Yb_0.3Lu_0.3)₂SiO₅ also presents good resistance to calcium-magnesium alumino-silicates (CMAS) corrosion. Rational composition design allows (Ho_0.4Yb_0.3Lu_0.3)₂SiO₅ to retain the merits of single-component RE₂SiO₅ while taking advantage of the solid solution effect. The results of this work suggest (Ho_0.4Yb_0.3Lu_0.3)₂SiO₅ as a promising EBC candidate.     

The influence of Gd doping on thermophysical properties,elasticity modulus and phase stability of garnet-type (Y1-xGdx)3Al5O12 ceramics

In this work, Gd³⁺ was selected to partially substitute the Y³⁺ in yttrium aluminum garnet (YAG) in order to improve the thermophysical properties of YAG. A series of (Y_1-xGd_x)₃Al₅O₁₂ (x = 0, 0.1, 0.2, 0.3, 0.4) ceramics were synthesized through chemical co-precipitation route. The microstructure, thermophysical properties and elasticity modulus of (Y_1-xGd_x)₃Al₅O₁₂ were investigated. The (Y_1-xGd_x)₃Al₅O₁₂ ceramics was comprised of single garnet-type Y₃Al₅O₁₂ phase. The thermal conductivities of (Y_1-xGd_x)₃Al₅O₁₂ bulk samples decreased with increasing doping concentration to 0.2, but increased with furthering increasing the concentration to 0.4. The thermal conductivity of (Y_0.8Gd_0.2)₃Al₅O₁₂ was 1.51 W m⁻¹ K⁻¹ at 1200 °C. The average thermal expansion coefficient of (Y_0.8Gd_0.2)₃Al₅O₁₂ was slightly larger than that of Y₃Al₅O₁₂. (Y_0.8Gd_0.2)₃Al₅O₁₂ bulk sample exhibited the lowest elasticity modulus among the investigated (Y_1-xGd_x)₃Al₅O₁₂. In addition, (Y_0.8Gd_0.2)₃Al₅O₁₂ ceramic remained good phase stability from room temperature to 1600 °C.     

Effect of BaCu(B2O5) on the sintering and microwave dielectric properties of Ca0.4Li0.3Sm0.05Nd0.25TiO3 ceramics

The sintering behaviors and microwave dielectric properties of the Ca_0.4Li_0.3Sm_0.05Nd_0.25TiO₃ (abbreviated CLSNT) ceramics with different amounts of BaCu(B₂O₅) addition were investigated in this paper. Adding BaCu(B₂O₅) to CLSNT lowered its sintering temperature from 1300 °C to 925 °C. No secondary phase was observed in the CLSNT ceramics and complete solid solution of the complex perovskite phase was confirmed. The CLSNT ceramics with small amounts of BaCu(B₂O₅) addition could be well sintered at 925 °C without much degradation in the microwave dielectric properties. Especially, the 1.75 wt.% BaCu(B₂O₅)-doped CLSNT ceramic sample sintered at 925 °C for 3 h had optimum microwave dielectric properties of ε_r = 93.5 ± 3.2, Q × f = 6486 ± 434 GHz, and τ_f = 5 ± 1.5 ppm/°C (at 3–4 GHz), enabling it a promising candidate material for LTCC applications. Obviously, BaCu(B₂O₅) could be a suitable sintering aid to facilitate the densification and microwave dielectric properties of the CLSNT ceramics.     

Phase stability,thermo-physical properties and thermal cycling behavior of plasma-sprayed CTZ,CTZ/YSZ thermal barrier coatings

ZrO₂ co-stabilized by CeO₂ and TiO₂ with stable, nontransformable tetragonal phase has attracted much attention as a potential material for thermal barrier coatings (TBCs) applied at temperatures >?1200?°C. In this study, ZrO₂ co-stabilized by 15?mol% CeO₂ and 5?mol% TiO₂ (CTZ) and CTZ/YSZ (zirconia stabilized by 7.4?wt% Y₂O₃) double-ceramic-layer TBCs were respectively deposited by atmospheric plasma spraying. The microstructures, phase stability and thermo-physical properties of the CTZ coating were examined using scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric-differential scanning calorimeter (TG-DSC), laser pulses and dilatometry. Results showed that the CTZ coating with single tetragonal phase was more stable than the YSZ coating during isothermal heat-treatment at 1300?°C. The CTZ coating had a lower thermal conductivity than that of YSZ coating, decreasing from 0.89?W?m^?1 K^?1 to 0.76?W?m^?1 K^?1 with increasing temperature from room temperature to 1000?°C. The thermal expansion coefficients were in the range of 8.98?×?10^?6 K^?1 – 9.88 ×10^?6 K^?1. Samples were also thermally cycled at 1000?°C and 1100?°C. Failure of the TBCs was mainly a result of the thermal expansion mismatch between CTZ coating and superallloy substrate, the severe coating sintering and the reduction-oxidation of cerium oxide. The thermal durability of the TBCs at 1000?°C can be effectively enhanced by using a YSZ buffer layer, while the thermal cycling life of CTZ/YSZ double-ceramic-layer TBCs at 1100?°C was still unsatisfying. The thermal shock resistance of the CTZ coating should be improved; otherwise the promising properties of CTZ could not be transferred to a well-functioning coating.     

Study on thermal shock resistance of Sc2O3 and Y2O3 co-stabilized ZrO2 thermal barrier coatings

In order to reveal the effect of Sc₂O₃ and Y₂O₃ co-doping system on the thermal shock resistance of ZrO₂ thermal barrier coatings, Y₂O₃ stabilized ZrO₂ thermal barrier coatings (YSZ TBCs) and Sc₂O₃–Y₂O₃ co-stabilized ZrO₂ thermal barrier coatings (ScYSZ TBCs) were prepared by atmospheric plasma spraying technology. The surface and cross-section micromorphologies of YSZ ceramic coating and ScYSZ ceramic coatings were compared, and their phase composition before and after heat treatment at 1200 °C was analyzed. Whereupon, the thermal shock experiment of the two TBCs at 1100 °C was carried out. The results show that the micromorphologies of YSZ ceramic coating and ScYSZ ceramic coating were not much different, but the porosity of the latter was slightly higher. Before heat treatment, the phase composition of both YSZ ceramic coating and ScYSZ ceramic coating was a single T′ phase. After heat treatment, the phase composition of YSZ ceramic coating was a mixture of M phase, T phase, and C phase, while that of ScYSZ ceramic coating was still a single T′ phase, indicating ScYSZ ceramic coating had better T′ phase stability, which could be attributed to the co-doping system of Sc₂O₃ and Y₂O₃ facilitated the formation of defect clusters. In the thermal shock experiment, the thermal shock life of YSZ TBCs was 310 times, while that of ScYSZ TBCs was 370 times, indicating the latter had better thermal shock resistance. The difference in thermal shock resistance could be attributed to the different sintering resistance of ceramic coatings and the different growth rates of thermally grown oxide in the two TBCs. Furthermore, the thermal shock failure modes of YSZ TBCs and ScYSZ TBCs were different, the former was delamination, while the latter was delamination and shallow spallation.     

Effect of sintering temperature on phase transformation behavior and hardness of high-pressure high-temperature sintered 10 mol% Mg-PSZ

The sintering process of zirconia ceramics at high pressures is very different from that under normal pressure. In this paper, 10 mol% MgO partially-stabilized zirconia ceramics (Mg-PSZ) were synthesized under a pressure of 2.5 GPa at temperatures ranging from 1370 to 1610 °C. The effect of sintering temperature on the phase transformation behavior and hardness changes of Mg-PSZ were studied by X-ray diffraction, scanning electron microscopy, Raman spectrometry, and Vickers hardness tests. The optimal sintering conditions of 10 mol% Mg-PSZ were determined. At high pressures, the sintering time was shortened to 60 min, and the sintering temperature was reduced to 1530 °C, which indicates that the high pressure accelerated the sintering rate. Mg-PSZ reached a maximum Vickers hardness of 14.9 GPa at 1530 °C, but when the sintering temperature was further increased to 1610 °C, grain coarsening occurred, and the Vickers hardness decreased to 9.6 GPa.     

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.