Hot corrosion behavior of Yb2Si2O7 ceramic under NaVO3 salt attack

Hot corrosion behavior of Yb₂Si₂O₇ bulk exposed to NaVO₃ molten salt was investigated at 1000–1500 °C for 2 h. Results showed that YbVO₄ was produced on the bulk surface at 1000–1200 °C because of the acidity of the corrosion medium. The corrosion product of Yb₂SiO₅ was yielded at 1300–1500 °C due to the transformation of the corrosion medium from acidity to alkalinity. The content of YbVO₄ in the products decreased as the temperature increased, while that of Yb₂SiO₅ increased with an increase in temperature. In this paper, various hot corrosion mechanisms of Yb₂Si₂O₇ bulk exposed to NaVO₃ molten salt are discussed based on the formation of YbVO₄ and Yb₂SiO₅.     

Thermochemical stability and microstructural evolution of Yb2Si2O7 in high-velocity high-temperature water vapor

Thermochemical stability and microstructural evolution of Yb₂Si₂O₇ was studied in high-temperature high-velocity water vapor at temperatures between 1200–1400 °C. Two reactions were shown to occur in the steam environment: Yb₂Si₂O₇ reaction to form Yb₂SiO₅, and further Yb₂SiO₅ reaction to form Yb₂O₃. Parabolic rates of both reactions were observed, and similar reaction enthalpies were determined for each reaction; 207 kJ/mol and 205 kJ/mol, respectively. Densification of the product phase Yb₂SiO₅ shut off pore connectivity for gas transport to the reaction interface at gas velocities exceeding 115?125 m/s and for temperatures of 1300 °C and 1400 °C, resulting in reduced reaction rates at higher velocities. Outward gas diffusion by a silicon hydroxide species is predicted to govern ytterbium silicate reactions with high temperature water vapor. Microstructure changes at high temperatures and velocities were shown to greatly impact the long-term stability of Yb₂Si₂O₇.     

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.     

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.     

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.     

Property evolutions of Si/mixed Yb2Si2O7 and Yb2SiO5 environmental barrier coatings completely wrapping up SiCf/SiC composites under 1300 °C water vapor corrosion

A bi-layer environmental barrier coating (EBC) consisting of silicon(Si) bond coat/mixed ytterbium disilicate (Yb₂Si₂O₇) and ytterbium monosilicate (Yb₂SiO₅) topcoats has been successfully prepared to completely wrap up the SiC_f/SiC composites and the protective effects of such EBC have been evaluated by soaking them in a mixed 50% O₂ and 50% H₂O corrosive gases at 1300 °C for various times. In topcoats, Yb₂Si₂O₇ is the major phase, providing good thermal expansion coefficient (CTE) matching with composite substrate and thus excellent thermal shock resistance, whereas Yb₂SiO₅ is the dispersing minor phase, providing improved water vapor corrosion resistance. The completely wrapping up of SiC_f/SiC composites by above EBC system is employed to avoid direct exposure to the corrosive conditions, making it possible to evaluate the genuine protection effects of current EBCs. Under 1300 °C water vapor corrosion, the mass change, the phase composition and the evolution of microstructure are investigated, which suggest that the bi-layer EBC has excellent performance on protecting SiC_f/SiC composites from water vapor corrosion at 1300 °C.     

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.     

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.     

Autonomous crack healing ability of SiC dispersed Yb2Si2O7 by oxidations in air and water vapor

Yb₂Si₂O₇ is a popular environmental barrier coating; however, it decomposes into Yb₂SiO₅ in high-temperature steam environments. The thermal mismatch between Yb₂Si₂O₇ and Yb₂SiO₅ leads to the cracking and failure of the disilicate coating via oxidation. Dispersing SiC nanofillers into the Yb₂Si₂O₇ matrix is suggested to maintain the Yb₂Si₂O₇ matrix and promote crack self-healing. This study is aimed at clarifying the effect of water vapor on the self-healing ability of such composites. X-ray diffraction analysis and scanning electron microscopy were used to monitor the surface composition and the crack formation, respectively, in 10 vol% SiC-dispersed Yb₂Si₂O₇ composites. Annealing at temperatures higher than 750 °C in air or in a water vapor rich atmosphere led to strength recovery and the self-healing of indentation-induced surface cracks owing to volume expansion during the oxidation of SiC. The self-healing effect was influenced by the oxidation time and temperature. Rapid diffusion of H₂O as an oxidizer into the SiO₂ layer promoted self-healing in a water vapor rich atmosphere. However, accelerated oxidation at temperatures higher than 1150 °C formed bubbles on the surface. Fabricating composites with a small amount of Yb₂SiO₅ will be a solution to these problems.     

Strength improvement and purification of Yb2Si2O7‐SiC nanocomposites by surface oxidation treatment

A two‐step processing was developed to prepare Yb₂Si₂O₇‐SiC nanocomposites. Yb₂Si₂O₇‐Yb₂SiO₅‐SiC composites were first fabricated by a solid‐state reaction/hot‐pressing method. The composites were then annealed at 1250°C in air for 2 hours to activate the oxidation of SiC, which effectively transformed the Yb₂SiO₅ into Yb₂Si₂O₇. The surface cracks purposely induced can be fully healed during the oxidation treatment. The treated composites have improved flexural strength compared to their pristine composites. The mechanism for crack healing and silicate transformation have been proposed and discussed in detail.     

Environmental barrier coatings using low pressure plasma spray process

Yb₂Si₂O₇/Si bilayer environmental barrier coatings (EBCs) on SiC ceramic substrate were produced by low pressure plasma spray (LPPS) process. Phase composition, microstructure, and thermal durability of LPPS Yb₂Si₂O₇/Si coating were investigated. XRD analysis indicated that the coating is mainly composed of Yb₂Si₂O₇ with ~15.5v% Yb₂SiO₅ phases. The LPPS EBCs have a dense microstructure with porosity less than 4%. Adhesion strength measurement indicated the LPPS EBCs have an average adhesion strength of 29.1 ± 0.8 MPa. Furnace cycle test (FCT) on the coatings in air at 1316°C was performed and the test ran for 900 cycles and there was no coating spallation/failure for LPPS Yb₂Si₂O₇/Si EBCs. The FCT results demonstrated the excellent thermal cycle durability of LPPS EBCs. Oxidation kinetics investigation of LPPS EBCs in flowing 90% H₂O (g)+10% air at 1316°C showed that the thermally grown oxide (TGO) growth rate is close to the oxidation rate of pure Si in dry air and is significantly lower than that in water vapor environment. The LPPS process is promising in making highly durable Yb2Si2O7-based dense EBCs by impeding diffusion and ingression of water vapor/O₂.     

Interactions of Na2SO4 and yttrium-silicate environmental barrier coatings at 825°C

Yttrium-silicates (Y₂Si₂O₇ and Y₂SiO₅) are candidate environmental barrier coating (EBC) materials for silicon carbide ceramic matrix composites (SiC-CMCs). These materials’ high-temperature, high-velocity steam, and siliceous debris resistance are well studied. However, Na₂SO₄-induced hot corrosion mechanisms are less understood. Free-standing atmospheric plasma sprayed Y₂Si₂O₇ and Y₂SiO₅ coupons were exposed to 2.5 mg/cm² of Na₂SO₄ at 825°C in 0.1% SO₂-O₂ (g). Scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and inductively coupled plasma-optical emission spectrometry were used to identify a previously unknown damage mechanism. Water-soluble Y and Na-Y sulfates and oxysulfates formed in reaction with Na₂SO₄, causing significant damage to the yttrium-silicate EBCs materials.     

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.     

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.     

Synthesis and characterization of yttrium and ytterbium silicates from their oxides and an oligosilazane by the PDC route for coating applications to protect Si3N4 in hot gas environments

Environmental barrier coatings are required to protect Si₃N₄ against hot gas corrosion and enable its application in gas turbines, among which yttrium and ytterbium silicate-coatings stand out. Thus, the polymer-derived ceramic route was used to synthesize these silicates for basic investigations regarding their intrinsic properties from a mixture of Y₂O₃ or Yb₂O₃ powders and the oligosilazane Durazane 1800. After pyrolysis above 1200 °C in air, the silicates are predominant phases. The corrosion behaviour of the resulting composites was tested at 1400 °C for 80 h in moist environments. The material containing x₂-Yb₂SiO₅ and Yb₂Si₂O₇ undergoes the lowest corrosion rate (−1.8 μg cm⁻² h⁻¹). Finally, the processing of Y₂O₃/Durazane 1800 as well-adherent, crack-free and thick (40 μm) coatings for Si₃N₄ was achieved after pyrolysis at 1400 °C in air. The coating consisted of an Y₂O₃/Y₂SiO₅ top-layer and an Y₂O₃/Y₂Si₂O₇ interlayer due to the interaction of the coating system with the substrate.     

Hot corrosion behaviors of SrZrO3 ceramic co-doped with Y2O3 and Yb2O3 in molten Na2SO4, V2O5, and Na2SO4 + V2O5 salts mixture

The hot corrosion behaviors of Sr(Y_0.05Yb_0.05Zr_0.9)O_2.95 (SYYZ) ceramic were investigated in Na₂SO₄, V₂O₅, and Na₂SO₄ + V₂O₅ salts mixture, respectively. Na₂SO₄ did not react with SYYZ ceramic at 900, 950 and 1000 °C. m-ZrO₂, YVO₄ and YbVO₄ were the main corrosion products on the SYYZ ceramic surface in V₂O₅ at 800 and 900 °C, whereas Sr₃V₂O₈ and t-ZrO₂ appeared at 1000 °C. In Na₂SO₄ + V₂O₅ salts mixture, the corrosion products were Sr₃V₂O₈ and t-ZrO₂ at 800 and 900 °C on the SYYZ ceramic surface, however, a new phase of SrZrO₃ developed at 1000 °C. The phase transformation and chemical interaction are the primary corrosion mechanisms for degradation of SYYZ ceramic.     

Damage Tolerance and Extensive Plastic Deformation of β‐Yb2Si2O7 from Room to High Temperatures

β‐Yb₂Si₂O₇ is a promising environmental barrier coating (EBC) material and recently attracted attention for its damage tolerance. To investigate the mechanisms of its damage tolerance and possible plasticity, dense β‐Yb₂Si₂O₇ sample was synthesized by in situ reaction/hot‐pressing method, and its mechanical properties were measured from room to high temperatures. The low magnitudes of hardness to Young's modulus ratio H_V/E, shear modulus to bulk modulus ratio G/B, and high fracture toughness to strength ratio K_IC/σ provide evidences of damage tolerance of β‐Yb₂Si₂O₇. β‐Yb₂Si₂O₇ exhibits extensive plastic deformation in Hertzian contact tests at both room and high temperatures. Transmission electron microscopy (TEM) observations show that the deformation mechanisms are different at low and high temperatures. Deformation twinning and parallel dislocation arrangement occur in plastic deformation at room temperature. Above the brittle‐to‐ductile transition temperature (between 1200°C and 1300°C), plastic deformation brings out extensive slip and climb of dislocations, while twinning is seldom observed. Measurement of temperature‐dependent dynamic Young's modulus demonstrates excellent elastic stiffness retention up to 1300°C.     

Mechanisms of Ytterbium Monosilicate/Mullite/Silicon Coating Failure During Thermal Cycling in Water Vapor

An air plasma spray process has been used to apply a model tri‐layer Yb₂SiO₅/Al₆Si₂O₁₃/Si environmental barrier coating system on SiC test coupons. Significant differences in the thermal expansion of the component layers resulted in periodically spaced mud cracks in the Yb₂SiO₅ and Al₆Si₂O₁₃ layers. Upon thermal cycling between 1316°C and 110°C in a 90% H₂O/10% O₂ environment flowing at 4.4 cm/s, it was found that partial delamination occurred with the fracture plane located within a thermally grown oxide (TGO) at the Al₆Si₂O₁₃–Si interface. Delamination initiated at test coupon edges where the gaseous environment preferentially oxidized the exposed Si bond coat to form β‐cristobalite. Simultaneous ingress of the gaseous environment through mud cracks initiated local formation of β‐cristobalite (SiO₂), the thickness of which was greatest directly below mud cracks. Upon cooling, cristobalite transformed from the β to α phase with a large, constrained volume contraction that resulted in severe microfracture of the TGO. Continued thermal cycling eventually propagated delamination cracks and caused partial spallation of the coatings. Formation of the cristobalite TGO appears to be the delamination life‐determining factor in protective coating systems utilizing a Si bond coat.     

High temperature abradable sealing coating for SiCf/SiC ceramic matrix composites

A study of porous YSZ abradable sealing coating (ASC) plasma-sprayed onto SiC_f/SiC ceramic matrix composites (CMC) through the compatibility of intermediate layers is reported. The multilayer Si/Yb₂Si₂O₇/LaMgAl₁₁O₁₉ thermal-environmental barrier coating (T-EBC) is served as intermediate layers in consideration of its ability to protect the CMC from recession and ease the misfit of the thermal expansivity. Isothermal exposure and thermal shock tests were conducted at 1200°C and led to the decomposition of t'-ZrO₂ phase to t-ZrO₂ and c-ZrO₂ phases in YSZ topcoat, the formation of mud-cracks throughout the entire coating structure and thermally grown oxide (SiO₂), with following an Yb₂Si₂O₇ reaction layer. The measured bond strength of the coated samples was 5.47 ± 0.85 MPa, and the fracture position mainly happened inside the CMC substrate. The Superficial Rockwell Hardness (HR15Y) considered to be an important factor in abradability increased by only 1.34% after 1200°C isothermal exposure for 100 h, showing excellent high temperature hardness stability. The abradability of the ASC was investigated by a sliding wear test, the fatigue wear mainly occurred in worn scar when encountering Si₃N₄ ceramic ball with high hardness and low thermal conductivity, while adhesive wear occurred when GCr15 steel ball with low hardness and high thermal conductivity are encountered.     

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.