Feasibility research of Yb3Al5O12 garnet as environmental barrier coating materials

In this work, Yb₃Al₅O₁₂ (YbAG) garnet, as a new material for environment barrier coating (EBC) application, was synthesized and prepared by atmospheric plasma spraying (APS). The phases and microstructures of the coatings were characterized by XRD, EDS and SEM, respectively. The thermal stability was measured by TG-DSC. The mechanical and thermal-physical properties, including Vickers hardness (H_v), fracture toughness (K_IC), Young's modulus (E), thermal conductivity (κ) and coefficient of thermal expansion (CTE) were also measured. The results showed that the as-sprayed coating was mainly composed of crystalline Yb₃Al₅O₁₂ and amorphous phase which crystallized at around 917 °C. Moreover, it has a hardness of 6.81 ± 0.23 GPa, fracture toughness of 1.61 ± 0.18 MPa m^1/2, as well as low thermal conductivity (0.82–1.37 W/m·K from RT-1000 °C) and an average coefficient of thermal expansion (CTE) (∼6.3 × 10⁻⁶ K⁻¹ from RT to 660 °C). In addition, the thermal shock and water-vapor corrosion behaviors of the Yb₃Al₅O₁₂-EBC systems on the SiC_f/SiC substrates were investigated and their failure mechanisms were analyzed in details. The Yb₃Al₅O₁₂ coating has an average thermal shock lifetime of 72 ± 10 cycles as well as an excellent resistance to steam. These combined properties indicated that the Yb₃Al₅O₁₂ coating might be a potential EBC material. Both the thermal shock failure and the steam recession of the Yb₃Al₅O₁₂-EBC systems are primarily associated with the CTE mismatch stress.     

Constrained sintering and thermal ageing behaviour of electrophoretically deposited Yb2Si2O7 environmental barrier coating

The oxidation of SiC and the formation of a thermally grown oxide layer (TGO) limit the lifetime of environmental barrier coatings. Thus, this paper focuses on the deposition of denser Yb₂Si₂O₇ coatings using electrophoretic deposition to reduce the TGO growth rate. The findings showed densification for Yb₂Si₂O₇ can be achieved with an optimized sintering profile (heating/cooling rate, temperature, and time). However, the addition of 1.5 wt% of Al₂O₃ to Yb₂Si₂O₇ promoted densification and lowered the required sintering temperature, 1380 °C using 2 °C/min heating/cooling rate for 10 h provided efficient coating density. Moreover, adding Al₂O₃ reduced the TGO growth rate by more than 70 % compared to the Al₂O₃-free coatings, without cracking in TGO after 150 h of thermal ageing at 1350 °C. Results within this study suggest electrophoretic deposition with Al₂O₃ addition produces promising Yb₂Si₂O₇ environmental barrier coatings on SiC substrate with low oxidation rates and increased lifetime.     

Interaction of Yb2Si2O7 environmental barrier coating material with Calcium-Ferrum-Alumina-Silicate (CFAS) at high temperature

Experimental investigations of Yb₂Si₂O₇ pellet exposed to Calcium-Ferrum-Alumina-Silicate (CFAS) at 1400 °C in ambient air were carried out to reveal corrosion reaction between molten silicate deposit and Yb₂Si₂O₇. Phase transformation, microstructure evolution and reaction mechanism were evaluated. Results indicated that the corrosion process was accompanied by the infiltration of CFAS melt, the dissolution of Yb₂Si₂O₇ and the reprecipitation of Yb₂Si₂O₇ and Ca₂Yb₈(SiO₄)₆O₂ apatite as reaction product. The formation of apatite decreased the concentration of Ca²⁺ in the melt. After CFAS exposure at 1400 °C for 30 h, the thickness of the apatite layer stopped increasing due to insufficient Ca²⁺ content, and remained at about 115.4 μm. However, the infiltration depth of CFAS melt increased with the extending corrosion duration and increasing deposit content. And the infiltration rate was preliminarily found to first decrease and then increase with time. Most of the residual CFAS were crystallized into garnet (Ca₃Fe₂(SiO₄)₃ and Yb₃Fe₅O₁₂) and mayerite (Ca₁₂Al₁₄O₃₃), while a small volume of amorphous glass was dispersed among the garnet and mayerite grains.     

High-Temperature thermochemical interactions of molten silicates with Yb2Si2O7 and Y2Si2O7 environmental barrier coating materials

The thermochemical behavior of EBC candidate materials yttrium disilicate (Y₂Si₂O₇) and ytterbium disilicate (Yb₂Si₂O₇) was evaluated with three calcium-magnesium-aluminosilicate (CMAS) glasses possessing CaO:SiO₂ ratios relevant to gas turbine systems. Pellet mixtures of 50 mol% EBC powder to 50 mol% CMAS glass powder were heat treated at 1200°C, 1300°C, and 1400°C. The products of these interactions were evaluated using X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy. Above glass melting temperatures, exposure of the disilicates primarily resulted in dissolution into the molten glass followed by precipitation of a Ca₂RE₈(SiO₄)₆O₂ (RE = Yb³⁺, Y³⁺) apatite-type silicate and/or rare earth disilicate. In glasses with high CaO concentrations, apatite readily forms while the disilicate material is consumed by the reaction. As CaO content decreases, the disilicate phase becomes the main reaction product. Overall, reactions with yttrium disilicate favored more apatite crystallization than ytterbium disilicate. The viability of using these disilicates in various operating environments is discussed.     

High-temperature performances of Si-HfO2-based environmental barrier coatings via atmospheric plasma spraying

To improve high-temperature bearing capability of coatings, novel agglomerated Si-HfO₂ powders were prepared by adding HfO₂ powders into original Si powders by spray drying method. Three-layer environmental barrier coatings (EBCs) with Si-HfO₂ bond layer, Yb₂Si₂O₇ intermediate layer and Yb₂SiO₅ surface layer were prepared on SiC ceramic substrates by atmospheric plasma spraying (APS). The high temperature properties of coatings were systematically investigated. The results indicated that the coatings had good high temperature oxidation resistance, and remained intact after being oxidized or steam corrosion at 1400 °C for 500 h, so the addition of HfO₂ improved the thermal cycling performances of the coating. The HfO₂ in Si bond coating could effectively inhibit the growth of thermal grown oxide at high temperatures. This work indicates that the high temperature properties of the coatings are improved by this novel EBCs using the novel agglomerated Si-HfO₂ powders.     

Failure mechanisms in model thermal and environmental barrier coating systems

The durability of environmental barrier coating (EBC) systems in gas turbine engine environments depends upon their temperature dependent rates of degradation by processes such as steam volatilization and bond coat oxidation. While addition of a thermal barrier coating (TBC) reduces the temperature within the EBC system, it introduces new failure mechanisms. Deposition of a segmented HfO₂ TBC with a reduced in-plane Young’s modulus is essential to avoid bifurcated TBC channel cracking into a Yb₂Si₂O₇ EBC, and delamination, as a result of an approximately 50% difference in coefficients of thermal expansion (CTE) of the coating layers. During prolonged high temperature steam cycling, a thin fluorite phase reaction layer is observed to develop at the HfO₂-YbDS interface consistent with recent thermochemical assessments. The CTE of the fluorite phase is shown to be substantially higher than that of either of the layers to which it is bonded, resulting in tunnel cracking of the fluorite, and eventual coating delamination of the TBC at either the fluorite-HfO₂ or YbDS-fluorite interfaces upon cooling. The study highlights the importance of matching the CTEs of the TBC and EBC layers during coating system design, and those of the reaction products that may form between them.     

Investigation on behavior and mechanism of enhanced water vapor corrosion resistance for (Lu0.25Yb0.25Er0.25Y0.25)2SiO5 environmental barrier coating

Rare-earth monosilicate (RE₂SiO₅) have been considered to be a promising material for the environmental barrier coating because of their superior thermal and mechanical properties. However, the water vapor corrosion resistance of single-component RE-silicate materials, such as Y₂SiO₅, should be further improved. The high-entropy design is one of the most suitable methods to enhance the corrosion resistance for single-component RE-silicate materials. In this work, the multicomponent RE-silicate ((Lu_0.25Yb_0.25Er_0.25Y_0.25)₂SiO₅, (4HES)) and single-component RE-silicate (Y₂SiO₅) coatings were investigated with regard to its water vapor corrosion behaviors at 1350 °C for 300 h. A thinner and denser corrosion layer was generated in the 4HES coating, indicating that the 4HES coating possessed better corrosion resistance than the Y₂SiO₅ coating. The improved corrosion resistance is attributed to the better hydrophobic property as well as the more stable crystal structure of the rare-earth oxide and 4HES phase which was resulted from the high-entropy design.     

Thermal shock resistance and bonding strength of tri-layer Yb2SiO5/mullite/Si coating on SiCf/SiC composites

A Yb₂SiO₅/mullite/Si tri-layer environmental-barrier-coating (EBC) were coated on SiC_f/SiC substrates via Air Plasma Spraying (APS). The thermal cycle tests (TCT) were conducted under thermal corrosive condition of vapor-oxygen (50 vol% H₂O and 50 vol% O₂) with thermal shock from 1200 °C to 200 °C. Microstructures, weight loss and bonding strength of the samples were systemically investigated after 101, 396, 606 and 700 TCT cycles respectively. The results show that the corner of the tri-layer coating peel off from the sample with weight loss of 1.3% after 700 TCT cycles. The bonding strength between substrate and tri-layer coatings gradually decreases to 6.79 MPa (approximately 55.2% of virgin specimens) after 700 cycles due to thermal shock induced cracks distributed horizontally within Si layers and between Si layer and outer layers.     

Crack-healing behaviour of MoSi2 dispersed Yb2Si2O7 environmental barrier coatings

MoSi₂ doped Yb₂Si₂O₇ composites were designed to extend the lifetime of Yb₂Si₂O₇ environmental barrier coatings (EBCs) via self-healing cracks during high-temperature applications. Yb₂Si₂O₇–Yb₂SiO₅–MoSi₂ composites with different mass fractions were prepared by applying spark plasma sintering. X-ray diffraction results confirmed that the composites consisted of Yb₂Si₂O₇, Yb₂SiO₅, and MoSi₂. The thermal expansion coefficients (CTEs) of the composites increased with an increase in the MoSi₂ content. The average CTE of the 15 wt% MoSi₂ doped Yb₂Si₂O₇ composite was 5.24 × 10^?6 K^?1, indicating that it still meets the CTE requirement of EBC materials. After being pre-cracked by using the Vickers indentation technique, the samples were annealed for 0.5 h at 1100 or 1300 °C to evaluate the crack-healing ability. Microstructural studies showed that cracks in 15 wt% MoSi₂ doped Yb₂Si₂O₇ composites were fully healed during annealing at 1300 °C. Two mechanisms may be responsible for crack healing. First, the cracks were filled with SiO₂ glass formed by MoSi₂ oxidation. Second, the formed SiO₂ continued to react with Yb₂SiO₅ to form Yb₂Si₂O₇, which can cause cracks to heal owing to volumetric expansion. The Yb₂Si₂O₇ formation with smaller volume expansion is more beneficial.     

High-entropy rare-earth disilicate (Lu0.2Yb0.2Er0.2Tm0.2Sc0.2)2Si2O7: A potential environmental barrier coating material

A new high-entropy ceramic (Lu_0.2Yb_0.2Er_0.2Tm_0.2Sc_0.2)₂Si₂O₇ ((5RE_0.2)₂Si₂O₇) was proposed as a potential environmental barrier coating (EBC) material for ceramics matrix composites in this work. Experimental results showed that the (5RE_0.2)₂Si₂O₇ synthesized by solid-phase sintering was a monoclinic solid solution and had good phase stability proved by no obvious absorption/exothermic peak in the DSC curve from room temperature to 1400 °C. It performed a lower coefficient of thermal expansion (2.08 ×10^?6-4.03 ×10^?6 °C^?1) and thermal conductivity (1.76–2.99 W?m^?1?°C^?1) compared with the five single principal RE₂Si₂O₇. In water vapor corrosion tests, (5RE_0.2)₂Si₂O₇ also exhibited better water vapor corrosion resistance attributed to the multiple doping effects. The weight loss was only 3.1831 × 10^?5 g?cm^?2 after 200 h corrosion at 1500 °C, which was lower than that of each single principal RE₂Si₂O₇. Therefore, (5RE_0.2)₂Si₂O₇ could be regarded as a remarkable candidate for EBCs.     

Thermal shock resistance of tri‐layer Yb2SiO5/Yb2Si2O7/Si coating for SiC and SiC‐matrix composites

A new tri‐layer Yb₂SiO₅/Yb₂Si₂O₇/Si coating was fabricated on SiC, C/SiC, and SiC/SiC substrates, respectively, using atmospheric plasma spray (APS) technique. All coated samples were subjected to thermal shock test at 1350°C. The evolution of phase composition and microstructure and thermo‐mechanical properties of those samples before and after thermal shock test were characterized. Results showed that adhesion between all the 3 layers and substrates appeared good. After thermal shock tests, through microcracks which penetrated the Yb₂SiO₅ top layer were mostly halted at the Yb₂SiO₅‐Yb₂Si₂O₇ interface and no thermal growth oxide (TGO) was formed after 40‐50 quenching cycles, implying the excellent crack propagation resistance of the environmental barrier coating (EBC) system. Transmission electron microscopy analysis confirmed that twinnings and dislocations were the main mechanisms of plastic deformation of the Yb₂Si₂O₇ coating, which might have positive effects on crack propagation resistance. The thermal shock behaviors were clarified based on thermal stresses combined with thermal expansion behaviors and elastic modulus analysis. This study provides a strategy for designing EBC systems with excellent crack propagation resistance.     

Effect of environmental pressure on the microstructure of YSZ thermal barrier coating via suspension plasma spraying

Suspension plasma spraying (SPS) as a potential technique to prepare thermal barrier coatings (TBCs) has been attracting more and more attention. However, most reports on SPS were carried out in the atmosphere. Given the unique features of in-flight particles and plasma jets under low pressure, the resulting coatings are expected to be different from those under atmospheric pressure. In this article, yttria-stabilized zirconia (YSZ) thermal barrier coatings were prepared using suspension plasma spraying under different environmental pressures. The results show that as the environmental pressure decreased, the column-like structural coating turned into a vertical crack segmented structure, as well as a dramatic decrease in surface roughness. More nanoparticle agglomerates were formed in the coating under lower environmental pressures. The real porosity of the coating increased with a decrease in environmental pressure.     

Corrosion of RE2Si2O7 (RE=Y,Yb, and Lu) environmental barrier coating materials by molten calcium-magnesium-alumino-silicate glass at high temperatures

With the increased demand for high operating temperature of gas turbine engines, corrosion by molten calcium-magnesium-alumino-silicate (CMAS) exhibits a significant challenge to the development of durable environmental barrier coatings (EBCs). EBC candidates, γ-Y₂Si₂O₇, β-Yb₂Si₂O₇, and β-Lu₂Si₂O₇ were explored on their corrosion resistance to CMAS melts at 1300 °C and 1500 °C for 50 h. Interaction and degradation mechanisms were investigated and the corrosion behaviors showed different trends at high temperatures. At 1300 °C, RE₂Si₂O₇ dissolves into CMAS melts and apatite phases reprecipitate forming a thick recession layer. However, when the temperature increases to 1500 °C, CMAS melts vigorously penetrate through the grain boundary of RE₂Si₂O₇ and ‘blister’ cracks form throughout the samples. The reduced grain boundary stability at 1500 °C promotes the penetration of CMAS melts in RE₂Si₂O₇. Grain boundary engineering is critically demanded to optimize CMAS corrosion at high temperatures.     

Crystallization and phase evolution in novel (Gd1/6Tb1/6Dy1/6Tm1/6Yb1/6Lu1/6)2Si2O7 environmental barrier coating

Design of multiple rare-earth (RE) principal elements is a practical strategy to optimize key property of RE disilicate environmental barrier coating (EBC). However, multi-RE component in the feedstocks may also introduce critical fabrication problems due to the different evaporating and crystallizing behaviors of the EBC containing various RE composition. We herein report the preparation of a novel multi-RE disilicate (Gd_1/6Tb_1/6Dy_1/6Tm_1/6Yb_1/6Lu_1/6)₂Si₂O₇ EBC by atmospheric plasma spraying (APS). The crystallization behavior of the as-deposited coating annealed at 1100°C–1300°C with different durations (5 and 20 h) in air and argon atmospheres were investigated through comprehensive characterization techniques. RE disilicate, RE mono-silicate, and RE apatite were detected in the as-sprayed coatings, and mono-silicate and apatite transform to RE₂Si₂O₇ with the increment of temperature and extension of annealing duration. Furthermore, the contribution of multiple RE to the formation of apatite phase is discussed. The results provide a fundamental understanding and may guide the controllable preparation of multi-RE disilicate EBC via APS method.     

Phase and microstructure evolution in plasma sprayed Yb2Si2O7 coatings

Yb₂Si₂O₇ coatings were deposited on Si/SiC substrates by atmospheric plasma spray (APS). The different power and plasma chemistries used in this work produced mainly amorphous crack-free coatings with compositions shifted to lower SiO₂ content with higher power and H₂ flow. Differences in microstructure and thermomechanical properties (crystallization behavior, thermal expansion coefficient and thermal conductivity) of as-deposited and thermally treated coatings were directly related to the evolution from amorphous to crystalline phases. A Yb₂SiO₅ metastable phase was identified after thermal treatments at temperatures ～ 1000 °C that transformed to its stable isomorph at 1220 °C. This transformation, followed by the growth of the crystal cell volume, promoted the coating expansion and the “healing” of microcracks present in the amorphous as-sprayed coating.     

High-entropy thermal barrier coating of rare-earth zirconate: A case study on (La0.2Nd0.2Sm0.2Eu0.2Gd0.2)2Zr2O7 prepared by atmospheric plasma spraying

We report a double-ceramic-layer (DCL) thermal barrier coating (TBC) with high-entropy rare-earth zirconate (HE-REZ) as the top layer and yttria stabilized zirconia (YSZ) as the inner layer sprayed on Ni-based superalloy by atmospheric plasma spraying. La₂Zr₂O₇ (LZ) was selected as a reference for the HE-REZ. Thermal cycling test results demonstrate that the HE-REZ/YSZ DCL coating exhibited obviously improved thermal stability when compared to the LZ/YSZ DCL coating. The reasons for the improvement of the thermal shock resistance are considered to be the anti-sinterability of the HE-REZ ceramics during the thermal cycling test attributed to the sluggish diffusion effect and as well as the better match in the coefficient of thermal expansion of HE-REZ coating with the YSZ inner layer. In addition, the HE-REZ coating maintains fluorite structure after thermal cycling test. This study makes one step forward in the development and application of high-entropy rare-earth zirconate ceramic thermal barrier coatings.     

Mechanical properties and microstructure of Yb2SiO5 environmental barrier coatings under isothermal heat treatment

Yb₂SiO₅ (ytterbium monosilicate) top coatings and Si bond coat layer were deposited by air plasma spray method as a protection layer on SiC substrates for environmental barrier coatings (EBCs) application. The Yb₂SiO₅-coated specimens were subjected to isothermal heat treatment at 1400 °C on air for 0, 1, 10, and 50 h. The Yb₂SiO₅ phase of the top coat layer reacted with Si from the bonding layer and O₂ from atmosphere formed to the Yb₂Si₂O₇ phase upon heat treatment at 1400 °C. The oxygen penetrated into the cracks to form SiO₂ phase of thermally grown oxide (TGO) in the bond coat and the interface of specimens during heat treatment. Horizontal cracks were also observed, due to a mismatch of the coefficient of thermal expansion (CTE) between the top coat and bond coat. The isothermal heat treatment improves the hardness and elastic modulus of Yb₂SiO₅ coatings; however, these properties in the Si bond coat were a little bit decreased.     

Heat treatment effect on coating shock resistance of thermal barrier coating system with different types of bond coat

The effect of heat treatment, growth of the TGO layer, oxidation of bond coat, and the impact of the presence of two bond coats on the TBC's thermal shock resistance has been investigated experimentally. TGO oxide layers were created with two-time heat treatment of 12 and 24 h at 1000. Then the thermal shock test was performed on the APS/APS and HVOF/APS/APS samples. The results show that the use of two BCs and the presence of a thin TGO layer has a good effect on TBC performance. The presence of two BC layers increased the shock resistance by an average of 37.2%. 12 h heat treatment caused a 14.0% and 17.4% shock resistance increase in samples with the HVOF/APS/APS layer and APS/APS layer, respectively. 24 h heat treatment decreased the samples' performance by 6.7% and 10.2% for samples with two BC and one BC, respectively.     

Effect of SiC whiskers on the anti-oxidation properties of Yb2Si2O7/mullite/SiC tri-layer environmental barrier coating for CMCs

The mullite and ytterbium disilicate (β-Yb₂Si₂O₇) powders as starting materials for the Yb₂Si₂O₇/mullite/SiC tri-layer coating are synthesized by a sol–gel method. The effect of SiC whiskers on the anti-oxidation properties of Yb₂Si₂O₇/mullite/SiC tri-layer coating for C/SiC composites in the air environment is deeply studied. Results show that the formation temperature and complete transition temperature of mullite were 800–1000 and 1300°C, respectively. Yb₂SiO₅, α-Yb₂Si₂O₇, and β-Yb₂Si₂O₇ were gradually formed between 800 and 1000°C, and Yb₂SiO₅ and α-Yb₂Si₂O₇ were completely transformed into β-Yb₂Si₂O₇ at a temperature above 1200°C. The weight loss of Yb₂Si₂O₇/(SiC_w–mullite)/SiC tri-layer coating coated specimens was 0.15 × 10⁻³ g cm⁻² after 200 h oxidation at 1400°C, which is lower than that of Yb₂Si₂O₇/mullite/SiC tri-layer coating (2.84 × 10⁻³ g cm⁻²). The SiC whiskers in mullite middle coating can not only alleviate the coefficient of thermal expansion difference between mullite middle coating and β-Yb₂Si₂O₇ outer coating, but also improve the self-healing performance of the mullite middle coating owing to the self-healing aluminosilicate glass phase formed by the reaction between SiO₂ (oxidation of SiC whiskers) and mullite particles.     

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.