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.     

Characterization of Yb2Si2O7–Yb2SiO5 composite environmental barrier coatings resultant from in situ plasma spray processing

Plasma spraying of multicomponent materials produces shifts in coating composition associated with differential vaporization of constituent elements within the strong thermal gradients of the process. This effect is quite noticeable in rare-earth silicates which are now widely being employed as Environmental Barrier Coatings (EBCs) for SiC based ceramic components of turbine engines. Of particular interest is the preferential volatilization of SiO₂ during thermal plasma spraying Yb₂Si₂O₇ (ytterbium disilicate) coatings which leads to the deviation from stoichiometry of the desired disilicate composition resulting in a mixed phase coating consisting of Yb₂Si₂O₇ plus Yb₂SiO₅ (ytterbium monosilicate). Recent work has shown that presence of monosilicate can be beneficial as its evolution from amorphous, metastable to stable crystalline phase can lead to crack healing during high temperature exposure, however, careful control of the chemistry and architecture may be needed. In this work a 50/50 mol% Yb₂Si₂O₇–Yb₂SiO₅ composite coating has been targeted through in situ decomposition during plasma spray from stoichiometric Yb₂Si₂O₇ powder. The as sprayed amorphous coating reverts to crystalline upon thermal treatment passing through a metastable state identified by XRD and Raman spectroscopy. The transition to the final stable phases results in a mixed phase coating comprising of 46/54 mol% Yb₂Si₂O₇–Yb₂SiO₅ composite that is thermo-mechanically stable with the underlying bond coated silicon coated SiC substrate.     

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.     

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.     

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.     

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.     

Enhancing CMAS corrosion resistance of PS-PVD Si/Yb2Si2O7 EBCs via Al-modification

Enhancing the resistance to molten silicate corrosion is crucial for the long service life of environmental barrier coatings (EBCs). In this study, we used the Al-modification technique to enhance the CMAS corrosion resistance of Si/Yb₂Si₂O₇ coatings prepared by plasma spray-physical vapor deposition. The results show that the Al-modified Yb₂Si₂O₇ coating had higher resistance to CMAS corrosion than the Yb₂Si₂O₇ coating annealed at 1300 ℃ for 100 h, which is related to the refractory mullite and Yb₂Mg(AlO₂)₂O₃ generated during the CMAS exposure of Al-modified Yb₂Si₂O₇ coating. The Al-modified Yb₂Si₂O₇ coating also exhibited excellent resistance to oxygen penetration. The Al-modification technology provides the direction for the corrosion resistance of Yb₂Si₂O₇ system to CMAS.     

Interfacial reactions between B2O3 and spark plasma sintered Yb2Si2O7

Reactions between boria (B₂O₃) and Yb₂Si₂O₇ were studied via a series of idealized interfacial “well” tests. Boria oxidizes out of SiC/SiC ceramic matrix composites (CMCs) where BN is used as a fiber/matrix interphase and boron-rich inclusions often serve as aids in the melt infiltration process. Borate phases are highly reactive and can react with the rare earth silicates currently being utilized as environmental barrier coatings (EBCs) for these CMC systems. Ytterbium disilicate substrates for these well tests are prepared via spark plasma sintering. The well is then drilled into the substrates and filled with a boria glass plug. Exposures in a stagnant-air box furnace show that the boria is reacting with the disilicate via a substitution reaction leaving YbBO₃ and amorphous silica glass as the product phases. This phase was characterized with scanning electron microscopy and elemental dispersive spectroscopy (SEM/EDS), micro-focus X-ray diffraction, and selected-area electron diffraction (SAED). Inductively coupled plasma optical emission spectroscopy (ICP-OES) was also used to analyze water-soluble glassy phases left on the surface of the substrates post-exposure, indicating that the boron content of the glass was decreasing with both increasing exposure times and temperatures. There are few data on the borate product phase properties, however the results of this study suggest that the boria formed via oxidation from the SiC/BN/SiC composites could be detrimental to the performance of Yb₂Si₂O₇ environmental barrier coatings via formation of the borate phase and silica.     

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.     

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.     

Phase composition and property evolution of (Yb1−xHox)2Si2O7 solid solution as environmental/thermal barrier coating candidates

RE disilicates are good candidates as environmental/thermal barrier coating for SiC_f/SiC composite in harsh gas turbine engines. We designed (Yb_1?xHo_x)₂Si₂O₇ solid solutions and studied mechanical properties, thermal properties, and water vapor resistance. Powders with different compositions were synthesized by pressureless sintering, and bulk samples were prepared by Spark Plasma Sintering (SPS). Polymorphic changes with temperature and composition of the solid solutions were examined. Through doping Ho into Yb₂Si₂O₇, water vapor corrosion resistance is significantly promoted, and thermal expansion coefficient is maintained close to that of Si-based ceramics. Compared with host disilicates, thermal conductivity of solid solutions are decreased, and mechanical properties, including Vickers hardness and fracture toughness, are increased. A two-phase domain is found at (Yb_1/2Ho_1/2)₂Si₂O₇, and the γ to δ phase transition of Ho₂Si₂O₇ is observed during SPS. Among all samples, γ-(Yb_1/3Ho_2/3)₂Si₂O₇ possesses superior high temperature stability, and excellent water vapor resistance, indicating its performance as environmental/thermal barrier coating.     

Self-healing behavior and strength recovery of ytterbium disilicate ceramic reinforced with silicon carbide nanofillers

Environmental barrier coatings (EBCs) are necessary to protect SiC/SiC ceramic components against oxidation and hot corrosion in high-temperature applications. The volatilization of SiO₂ in SiC-reinforced materials is a major obstacle for the implementation of these self-crack-healing ceramics. The Yb₂Si₂O₇-Yb₂SiO₅-SiC composite is known as a self-healing material that can help to avoid this SiC recession. In this research, the crack-healing behavior of this composite is investigated by using pre-cracking followed by annealing in an oxidizing environment. The crack-healing mechanism is explored and elucidated as a function of the filler morphology, crack size, annealing time, and annealing temperature. The two main crack-healing mechanisms are the filling of cracks with SiO₂ glass and the volume expansion of Yb₂Si₂O₇ induced by the reaction between SiO₂ and Yb₂SiO₅. Full crack recovery is achieved with only 10 vol% SiC, with evidence from XRD and EDS analyses. SiC nanoparticulates are more efficient fillers than nanofibers and nanowhiskers.     

Cyclic oxidation performances of new environmental barrier coatings of HfO2-SiO2/Yb2Si2O7 coated SiC at 1375 °C and 1475 °C in the air environment

The objective of this work is to study the cyclic oxidation performances of the environmental barrier coatings (EBCs) containing the novel HfO₂-SiO₂ bond coats in the air environment. Bi-layer HfO₂-SiO₂/Yb₂Si₂O₇ (50HfO₂-50SiO₂, 70HfO₂-30SiO₂ bond coats) and conventional Si/Yb₂Si₂O₇ EBCs were deposited on SiC substrate using atmospheric plasma spray. The effect of the pre-mixing ratios of HfO₂/SiO₂ on the cyclic oxidation behavior of HfO₂-SiO₂/Yb₂Si₂O₇ EBCs was examined. The results showed that the higher content of the HfSiO₄ formed from the 50HfO₂-50SiO₂ bond coats, and it remained intact. A thermally grown oxide (TGO) SiO₂ layer was formed at the bond coat/SiC interface. The parabolic oxidation rate constant (k_p, μm²/h) of the TGO has been reduced 2 orders of magnitude in 50HfO₂-50SiO₂/Yb₂Si₂O₇ EBCs coated SiC compared to the bare SiC at 1475 °C, indicating that the 50HfO₂-50SiO₂/Yb₂Si₂O₇ EBCs effectively protected the SiC substrate at 1475 °C.     

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 environmental barrier coating for the ceramic matrix composites

A novel high-entropy material, (Yb_0.2Y_0.2Lu_0.2Sc_0.2Gd_0.2)₂Si₂O₇ ((5RE_0.2)₂Si₂O₇) was prepared by the sol-gel method and investigated as a promising environmental barrier coating (EBC) for SiC-based composites. The results of X-ray diffraction and transmission electron microscopy indicated that rare-earth elements were distributed homogeneously in the single monoclinic phase. Moreover, it was found that the new material (5RE_0.2)₂Si₂O₇ had good phase stability, well-matched coefficient of thermal expansion with SiC-based composite, and excellent resistance to water-vapor corrosion. The water-vapor corrosion test of (5RE_0.2)₂Si₂O₇ coated C_f/SiC composites further confirmed that (5RE_0.2)₂Si₂O₇ was suitable for application as EBC material and could provide effective protection to C_f/SiC composites from water-vapor damage.     

An Investigation of Environment Barrier Coating on 2D C/SiC Composites Prepared by Liquid Phase Process

Sc₂Si₂O₇-based environmental barrier coating (EBC) was prepared on 2D C/SiC composites by different liquid phase processes. Single Sc₂Si₂O₇ coating was brushed with sol and slurry. The multi-layer coating, which consisted of BSAS (Ba_0.25Sr_0.75Al₂Si₂O₈, B) as bond coat, BSAS?+?Sc₂Si₂O₇ (BS) as interlayer and Sc₂Si₂O₇ (S) as top coat, was painted with slurry and modified slurry. The slurry process was modified using amorphous instead of crystallized powders as raw materials derived from the sol–gel method. Modification mechanisms were proposed and characterized by weight losses of BSAS and Sc₂Si₂O₇ dry gel from thermogravimetric analysis and their sintering shrinkage ratios from coefficient of thermal expansion tests. The microstructure of the prepared coating was observed using scanning electron microscopy. The phase composition was detected by X-ray diffraction. The results showed that the S/BS/B coating with 30?μm thickness, which was prepared by the modified slurry, possessed excellent adhesion to the substrate and the best compactness among the above coatings. Higher activity, lower sintering energy barrier and tiny sintering shrinkage of S and B amorphous powders are mainly responsible for the performance enhancement.     

Fabrication and characterization of Yb2Si2O7-based composites as novel abradable sealing coatings

Ceramic matrix composites (CMCs) have gradually replaced superalloys for use in hot sections of aero-engines to meet the requirements for increasingly high engine temperatures. However, the abradable sealing coatings (ASCs) commonly applied to superalloys are not suitable for CMCs owing to factors such as the difference in the coefficient of thermal expansion, therefore it is necessary to develop a new system suitable for CMCs. Yb₂Si₂O₇ exhibits good high-temperature phase stability and relatively low hardness and may be a suitable material for ASCs. In the present study, Yb₂Si₂O₇-based composite coatings with different hexagonal boron nitride (hBN) contents (0, 5, 10, and 15 wt%) were deposited by air plasma spray (APS), and the microstructure, mechanical properties, and abradability of the coatings were characterized. The results showed that the system of Yb₂Si₂O₇ combined with hBN exhibits lower hardness, lower friction coefficient, higher wear rate, and smaller IDR value than the pure Yb₂Si₂O₇ coating and is appropriate for use in ASCs. However, excessive hBN caused severe wear of the coatings. The relevant wear mechanisms of the coatings were analysed, and this study may provide guidelines for the development of ASCs suitable for CMCs.     

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.     

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.     

Preparation and characterization of a novel nanostructured Yb2Si2O7 feedstock used for plasma-sprayed environmental barrier coatings

In this work, the preparation process of a novel nanostructured Yb₂Si₂O₇ feedstock for plasma-sprayed environmental barrier coatings (EBCs) was explored. Results show that sintering parameter and mass ratio between Yb₂O₃ and SiO₂ significantly affect the solid-state reaction process for the synthesis of Yb₂Si₂O₇ feedstocks. The increase of SiO₂/Yb₂O₃ ratio in the spray-dried granules can reduce the average grain size of β-Yb₂Si₂O₇ phase and the second phase content of the sintered powder. Nanostructured Yb₂Si₂O₇ feedstocks with high content of β-Yb₂Si₂O₇ phase and good sprayability were successfully obtained after plasma treatment. The nanostructured Yb₂Si₂O₇ coatings can be gained using as-synthesized feedstocks via plasma spraying, which verifies the applicability of nanostructured Yb₂Si₂O₇ feedstocks.