Improved properties of scandia and yttria co-doped zirconia as a potential thermal barrier material for high temperature applications

Due to the limited temperature capability of current YSZ thermal barrier coating (TBC) material, considerable effort has been expended world-wide to research new candidates for TBC applications above 1200?°C. Our study suggested that Sc₂O₃ and Y₂O₃ co-doped ZrO₂ (ScYSZ) had excellent t’ phase stability even after annealed at 1500?°C for 336?h. The thermal expansion coefficient of ScYSZ was comparable to the value of YSZ. The thermal conductivity of fully dense ScYSZ was in the range of 2.13–1.91?W?m^?1?K^?1 (25–1300?°C), approximately 25% lower than that of YSZ. Although the fracture toughness of dense ScYSZ was slightly lower than YSZ, an evident decline in elastic modulus was found. Additionally, thermal cycling lifetime of plasma sprayed ScYSZ coating (914 cycles) at 1300?°C was about 2.6 times longer than its YSZ counterpart. The superior comprehensive properties confirm that ScYSZ is a prospective candidate material for high-temperature TBC application.     

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.     

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.     

Corrosion behavior of air plasma spraying zirconia-based thermal barrier coatings subject to Calcium–Magnesium–Aluminum-Silicate (CMAS) via burner rig test

Three different kinds of thermal barrier coatings (TBCs) — 8YSZ, 38YSZ and a dual-layered (DL) TBCs with pure Y₂O₃ on the top of 8YSZ were produced on nickel-based superalloy substrate by air plasma spraying (APS). The Calcium–Magnesium–Aluminum-Silicate (CMAS) corrosion resistance of these three kinds of coatings were researched via burner rig test at 1350 °C for different durations. The microstructures and phase compositions of the coatings were characterized by SEM, EDS and XRD. With the increase of Y content, TBCs exhibit better performance against CMAS corrosion. The corrosion resistance against CMAS of different TBCs in descending was 8YSZ + Y₂O₃, 38YSZ and 8YSZ, respectively. YSZ diffused from TBCs into the CMAS, and formed Y-lean ZrO₂ in TBCs because of the higher diffusion rate and solubility of Y³⁺ in CMAS than Zr⁴⁺. At the same time, 38YSZ/8YSZ + Y₂O₃ reacts with CAMS to form Ca₄Y₆(SiO₄)₆O/Y_4·67(SiO₄)₃O with dense structure, which can prevent further infiltration of CMAS. The failure of 8YSZ coatings occurred at the interface between the ceramic coating and the thermally grown oxide scale (TGO)/bond coating. During the burner rig test, the Y₂O₃ layer of the DL TBCs peeled off progressively and the 8YSZ layer exposed gradually. DL coatings keep roughly intact and did not meet the failure criteria after 3 h test. 38YSZ coating was partially ablated, the overall thickness of the coating is thinned simultaneously after 2 h. Therefore, 8YSZ + Y₂O₃ dual-layered coating is expected to be a CMAS corrosion-resistant TBC with practical properties.     

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.     

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.     

LZC/YSZ DCL TBCs by EB-PVD: Microstructure,low thermal conductivity and high thermal cycling life

Thermal barrier coatings (TBCs) with low thermal conductivity have triggered tremendous attention due to their promising application in the gas turbine engines. Albeit recent studies have investigated double ceramic layers (DCL) with pyrochlore (A₂B₂O₇) phase, it still remains a big challenge for controlling element content and investigating the relationship between the complex hierarchical architectures and their thermal performances. Here we describe a series of DCL La₂O₃-ZrO₂-CeO₂ (LZC)/Y₂O₃-stabilized ZrO₂ (YSZ) coating under different current of electron beam by electron beam-physical vapor deposition (EB-PVD). The formation of hierarchical architecture with feathery microstructure and intra-columnar have been investigated in detail. The DCL coatings achieve a high thermal cycling life and relatively low thermal conductivity at controlling current of electron beam from 1.0 A to 1.3 A. This work may open new opportunities to rationally design other promising TBCs.     

Thermal cycling and hot corrosion behavior of a novel LaPO4/YSZ double-ceramic-layer thermal barrier coating

LaPO₄ powders were produced by a chemical co-precipitation and calcination method. The ceramic exhibited a monazite structure, kept phase stability at 1400?°C for 100?h, and had low thermal conductivity (~ 1.41?W/m?K, 1000?°C). LaPO₄/Y₂O₃ partially stabilized ZrO₂ (LaPO₄/YSZ) double-ceramic-layer (DCL) thermal barrier coatings (TBCs) were fabricated by air plasma spray. The LaPO₄ coating contained many nanozones. Thermal cycling tests indicated that the spallation of LaPO₄/YSZ DCL TBCs initially occurred in the LaPO₄ coating. The failure mode was similar to those of many newly developed TBCs, probably due to the low toughness of the ceramics. LaPO₄/YSZ DCL TBCs were highly resistant to V₂O₅ corrosion. Exposed to V₂O₅ at 700–900?°C for 4?h, La(P,V)O₄ formed as the corrosion product, which had little detrimental effect on the coating microstructure. At 1000?°C for 4?h, a minor amount of LaVO₄ was generated.     

Thermal shock performance and failure behavior of Zr6Ta2O17-8YSZ double-ceramic-layer thermal barrier coatings prepared by atmospheric plasma spraying

Zr₆Ta₂O₁₇ has higher fracture toughness, better phase stability, thermal insulation performance and calcium-magnesium-alumino-silicates (CMAS) attack resistance than yttria-stabilized zirconia (8 YSZ, 7–8 wt%) at temperatures above 1200 °C. However, the thermal expansion coefficients between Zr₆Ta₂O₁₇ coating and bond coating do not match well. A double-ceramic-layer design is applied to alleviate the thermal stress mismatch. The Zr₆Ta₂O₁₇/8 YSZ double-ceramic-layer thermal barrier coatings (TBCs) are prepared by atmospheric plasma spraying (APS). During the thermal shock test, Zr₆Ta₂O₁₇/8 YSZ double-ceramic-layer TBCs exhibit a better thermal shock resistance than 8 YSZ and Zr₆Ta₂O₁₇ single-layer TBCs. The thermal shock performance and failure mechanism of TBCs in the thermal shock test are investigated and discussed in detail.     

Microstructure and thermal shock resistance of Nd2O3-doped YSZ-based thermal barrier coatings

To study the impact of rare earth oxide doping on the thermal failure of thermal barrier coatings, 0.5 mol%, 1.0 mol% and 1.5 mol% Nd₂O₃-doped YSZ coatings were prepared by explosive spraying. SEM, XRD, EDS and microhardness testing were used to analyse the effect of different rare earth oxide doping contents on the morphology, composition and mechanical properties of the coatings. With an increase in the Nd₂O₃ doping content, the porosity of the coatings was reduced. The decrease in the porosity increased the compactness of the coatings and improved the microhardness and fracture toughness. The bonding strength and thermal shock resistance of the coatings were the highest among the samples herein when the rare earth doping content was 1.0 mol%, and the values were 37.6 MPa and 200 times, respectively. The thermal shock failure mode of the coating was mainly due to the exfoliation of the inner layer of the ceramic layer. The luminous intensity of the coating increased with increasing rare earth oxide doping content, and the emission spectrum of the Nd₂O₃-modified YSZ coating after the thermal shock test produced a new emission peak at 594 nm, which decreased at 708 nm.     

CMAS corrosion resistance in high temperature and rainwater environment of double-layer thermal barrier coatings odified by rare earth

In order to explore the difference of CMAS corrosion resistance in high temperature and rainwater environment of single-layer and double-layer thermal barrier coatings (TBCs), and further reveal the mechanism of CMAS corrosion resistance in above environment of double-layer TBCs modified by rare earth, two TBCs were prepared by air plasma spraying, whose ceramic coating were single-layer ZrO₂–Y₂O₃ (YSZ) and double-layer La₂Zr₂O₇(LZ)/YSZ, respectively. Subsequently, CMAS corrosion resistance tests at 1200 °C and rainwater environment of two TBCs were carried out. Results demonstrate that after high temperature CMAS corrosion for the same time, due to phase transformation, the volume of YSZ ceramic coating in single-layer TBCs shrank and surface cracks formed, which would lead to coating failure. When LZ ceramic coating of double-layer TBCs reacted with CMAS, compact apatite phases and fluorite phases formed, the penetration of CMAS into ceramic coating was inhibited effectively. Raman analysis and calculation results show that both of the surface residual stress of ceramic coating in two TBCs were compressive stress, and the residual stress of ceramic coating in double-layer TBCs were smaller than that of single-layer TBCs. Atomic force microscopy of TBCs after CMAS corrosion show that surface of double-layer TBCs was more uniform and compact than that of single-layer TBCs. The electrochemical properties in simulated rainwater of two TBCs after high temperature CMAS corrosion showed that double-layer TBCs possessed higher free corrosion potential, lower corrosion current and higher polarization resistance than those of single-layer TBCs. Consequently, the presence of LZ ceramic coating effectively improved CMAS corrosion resistance in high temperature and rainwater environment of double-layer TBCs.     

Preparation of Pd-doped Y3Al5O12 thermal barrier coatings using cathode plasma electrolytic deposition

Here, noble metal Pd-doped Y₃Al₅O₁₂ thermal barrier coatings (TBCs) were efficaciously prepared by means of cathode plasma electrolytic deposition (CPED). The formation mechanism of the Y₃Al₅O₁₂ coatings and the difference in coating performance before and after doping with Pd were analyzed. The results indicated that the preparation of the Y₃Al₅O₁₂ TBCs by using the CPED method could be divided into three stages, and the phase compositions of the coatings obtained with different deposition times were different. A single-phase Y₃Al₅O₁₂ TBCs with a 115-μm thickness was obtained after a deposition time of 20 min. After Pd doping, the average surface roughness of the TBCs decreased from 27.72 to 13.84 μm, and the high-temperature oxidation resistance and thermal shock resistance at 1050 °C improved significantly.     

Investigating the thermal,mechanical and thermal cyclic properties of plasma-sprayed Al2O3-7YSZ/7YSZ double ceramic layer TBCs

Double ceramic layer (DCL) TBCs consisting of a top 20 wt.% Al₂O₃-7YSZ layer and a bottom 7YSZ layer were desirably designed to achieve preferable performance while the thermal, mechanical and thermal cyclic properties were comprehensively investigated. Compared to the conventional 7YSZ TBCs, the thermal insulation properties of the DCL coating were significantly improved due to the increased oxygen vacancy concentration induced by Al₂O₃ addition while the thickness of the thermally grown oxides was diminished by the decreased oxygen diffusion rate. Furthermore, the improved fracture toughness of the DCL coating also prolonged the thermal cyclic life.     

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.     

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.     

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.     

Preparation and properties of LaMgAl11O19 thermal barrier coatings doped with Gd2O3

As a rare earth hexaaluminate, LaMgAl₁₁O₁₉ (LMA) has been one of the most promising materials used as thermal barrier coatings (TBCs). A large amount of amorphous phase, however, often exists in the plasma-sprayed LMA coating and significantly reduces the service lifetime of TBCs. In this study, La_1-xGd_xMgAl₁₁O₁₉ (x = 0, 0.2, 0.4, 0.6, and 0.8) ceramic powders are synthesised by solid-state reaction, and all of these powders are employed to prepare the corresponding coatings. The phase compositions and microstructures of samples are examined by X-ray diffraction and scanning electron microscopy, respectively. The linear thermal expansion behaviour and thermal cycling behaviour of the coatings are also analysed. The results show that the amorphous phase content is decreased and the thermal expansion behaviour is improved by doping the coatings with Gd₂O₃. The thermal cycling lifetime of the coating, however, basically remains unchanged.     

Mechanical properties and thermal shock in thin ZrO2–Y2O3–Al2O3 films obtained by the sol-gel method

Thin multilayer coatings of ZrO₂–Y₂O₃–Al₂O₃ were prepared using the sol-gel method and dip-coating technique in order to advance in the study of what influence the incorporation of Al₂O₃ has on films of Y₂O₃-doped ZrO₂, investigating its role in the synthesis of the solutions and in the characteristics and properties of the coatings. After the characterization of the solutions used in the process, the microstructure of the films was studied and their mechanical behaviour and resistance to thermal shock were determined so as to optimize the characteristics and functionality of these coatings. With increased alumina content, 3YSZ-Al₂O₃ (20 mol%), the cubic phase of the zirconia disappeared completely at the sintering temperature used (700 °C), resulting in the tetragonal phase with Al in solution. There was also a decrease in the coatings' hardness and Young's modulus, and an increase in toughness and resistance to thermal shock. These results allow guidelines to be established for the design of multilayer structures that are, tougher, more resistant, and have improved surface properties.     

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.     

Structure evolution,thermal properties and sintering resistance of promising thermal barrier coating material La2(Zr0.75Ce0.25)2O7

Rare-earth doped zirconates are promising candidate materials for high-performance thermal barrier coatings (TBCs). The phase and microstructure stability is an important issue for the materials that must be clarified, which is related to the long-term stable work of TBCs at high temperatures. In this work, La₂(Zr_0.75Ce_0.25)₂O₇ (LCZ) ceramic coatings prepared by atmospheric plasma spraying present a metastable fluorite phase, which can transform into stable pyrochlore under high-temperature annealing. The detailed structure evolution of the ceramic coatings is characterized systematically by SEM, XRD and Raman. The associated thermal properties of LCZ ceramics were also reported. Results show that LCZ ceramic has an ultralow thermal conductivity (0.65 W/m·K, 1200 °C), which is only 1/3 of that of yttria-stabilized zirconia (YSZ). The thermal expansion coefficients of LCZ ceramic increase from 9.68 × 10^-6 K^-1 to 10.7 × 10^-6 K^-1 (300 - 1500 °C), which are relatively larger than those of La₂Zr₂O₇. Besides, Long-term sintering demonstrates that LCZ ceramic coating has preferable sintering resistance at 1500 °C, which is desirable for TBC applications.