In situ Y2Si2O7 coatings on Hi-Nicalon-S SiC fibers: Phase formation and fiber strength

Y₂Si₂O₇ coatings were formed on Hi-Nicalon-S SiC fibers by reaction of solution-derived YPO₄ coatings with glass SiO₂ scales formed by fiber oxidation. Two oxidation methods were used: pre-oxidation, where fibers were oxidized prior to YPO₄ coating, or post-oxidation, where fibers were first coated with YPO₄ and then oxidized. Fibers with YPO₄/SiO₂ films were heat-treated in argon at 1200°C for 20 hours to react YPO₄ and SiO₂ to Y₂Si₂O₇. The effects of SiO₂ to YPO₄ film thicknesses on fiber strength and on the Y₂Si₂O₇formation kinetics were investigated. An optimized process to obtain single-phase continuous Y₂Si₂O₇ coatings on Hi-Nicalon-S fibers with low loss in fiber strength is suggested.     

Almost seamless joining of SiC using an in-situ reaction transition phase of Y3Si2C2

A new design of seamless joining was proposed to join SiC using electric field-assisted sintering technology. A 500 nm Y coating on SiC was used as the initial joining filler to obtain a desired transition phase of Y₃Si₂C₂ layer via the appropriate interface reactions with the SiC matrix. The phase transformation and decomposition of the transition phase of Y₃Si₂C₂ was designed to achieve almost seamless joining of SiC. The decomposition of the joining layer to SiC, followed up by the inter-diffusion and complete densification with the initial SiC matrix, resulted in the formation of an almost seamless joint at the temperature of 1900 °C. The bending strength of the seamless joint was 134.8 ± 2.1 MPa, which was comparable to the strength of the SiC matrix. The proposed design of seamless joining could potentially be applied for joining of SiC-based ceramic matrix composites with RE₃Si₂C₂ as the joining layer.     

Microstructure and corrosion behavior of in-situ grown Y3Si2C2 coated SiC fibers exposed to air and wet-oxygen at 1400 ℃

Y₃Si₂C₂ ternary ceramics were in-situ grown on the third-generation Chinese commercial SiC fiber (KD-SA SiC fiber) surface via molten salt method. Microstructures and oxidation/corrosion behavior of in-situ grown Y₃Si₂C₂ coated SiC fibers exposed to air and wet-oxygen at 1400 ℃ were investigated. Results indicated that the layered Y₃Si₂C₂ slices with thickness of approximately 15 nm can be successfully in-situ grown on SiC fibers. The product on the fibers surface after oxidation/corrosion at 1400 ℃ for 1 h in both ambient air and wet-oxygen are Y₂Si₂O₇ and SiO₂. Moreover, microstructural characterization indicates that the immigration and expansion of gaseous bubbles induced by oxidation product, mainly CO, result in microstructural differences of SiC fiber specimens, and finally oxidation mechanism based on the microstructural difference were proposed.     

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.     

Enhanced wet-oxidation resistance of Y2O3 modified SiC ceramics by the formation of Y2Si2O7 protective layer

The poor wet-oxidation resistance limits the long-life service of SiC_f/SiC composites as the hot end components of aero-engines. The stability of SiC_f/SiC composites under high-temperature wet oxygen environment can be promoted by more robust SiC matrix. In this work, the effect of Y₂O₃ on the corrosion behaviors of SiC ceramics in flowing O₂/H₂O atmosphere at 1400 ℃ was studied. Duo to the continuous Y₂Si₂O₇ layer formed on the surface, SiC-Y₂O₃ ceramics exhibit much better wet-oxidation resistance than original SiC ceramics. During the oxidation process, Y₂O₃ dispersed in the ceramics migrates to the surface and reacts with SiO₂ to form β-Y₂Si₂O₇. Subsequently, the β-Y₂Si₂O₇ aggregates and grows to form a continuous Y₂Si₂O₇ layer, inhibiting the corrosion from oxidizing medium to the inner SiC matrix. This study is expected to provide important ideas for the design and structure regulation of wet-oxidation resistant SiC_f/SiC composites.     

Nano-SiC-decorated Y2Si2O7 ceramic for enhancing electromagnetic waves absorption performance

To improve the electromagnetic (EM) wave absorption performance of rare earth silicate in harsh environments, this work synthesized dense SiC–Y₂Si₂O₇ composite ceramics with excellent EM wave absorption properties by using the polymer permeation pyrolysis (PIP) process, which introduced carbon and SiC into a porous Y₂Si₂O₇ matrix to form novel composite ceramics. SiC–Y₂Si₂O₇ composite ceramics with different numbers of PIP cycles were tested and analysed. The results show that the as-prepared composites exhibit different microstructures, porosities, dielectric properties and EM wave absorption properties. On the whole, the SiC–Y₂Si₂O₇ composite ceramics (with a SiC/C content of 29.88 wt%) show superior microwave absorption properties. The minimum reflection loss (RL_min) reaches ?16.1 dB when the thickness is 3.9 mm at 9.8 GHz. Moreover, the effective absorption bandwidth (EAB) included a broad frequency from 8.2 GHz to 12.4 GHz as the absorbent thickness varied from 3.15 mm to 4.6 mm. In addition, the EM wave absorption mechanism was analysed profoundly, which ascribed to the multiple mediums of nanocrystalline, amorphous phases and turbostratic carbon distributed in the Y₂Si₂O₇ matrix. Therefore, SiC–Y₂Si₂O₇ composite ceramics with high-efficiency EM wave absorption performance promise to be a novel wave absorbing material for applications in harsh environments.     

Low-temperature Pr3Si2C2-assisted liquid-phase sintering of SiC with improved thermal conductivity

A novel Pr₃Si₂C₂ additive was uniformly coated on SiC particles using a molten-salt method to fabricate a high-density SiC ceramics via liquid-phase spark plasma sintering at a relatively low temperature (1400°C). According to the calculated Pr–Si–C-phase diagram, the liquid phase was formed at ∼1217°C, which effectively improved the sintering rate of SiC by the solution–reprecipitation process. When the sintering temperature increased from 1400 to 1600°C, the thermal conductivity of SiC increased from 84 to 126 W/(m K), as a consequence of the grain growth. However, an increasing amount of the sintering additive increased the interfacial thermal resistance, resulting in a decrease of thermal conductivity of the materials. The highest thermal conductivity of 141 W/(m K) was obtained for the material having the largest SiC grains and an optimized amount of the additive at the grain boundaries and triple junctions. The proposed Pr₃Si₂C₂-assisted liquid-phase sintering of SiC can be potentially used for the fabrication of SiC-based ceramic composites, where a low sintering temperature would inhibit the grain growth of SiC fibers.     

SiC/SiC mini-composites with yttrium disilicate fiber coatings: Oxidation in steam

Solutions of YPO₄ were used to precipitate YPO₄ on pre-oxidized Hi-Nicalon-S SiC fibers. Tows of the coated fibers were then infiltrated with a preceramic polymer loaded with SiC particles to form mini-composites. During pyrolysis of the matrix, SiO₂ and YPO₄ on the fibers reacted and formed a Y₂Si₂O₇ fiber matrix interphase. Mini-composites were exposed to steam at 1000 °C for 10, 50, and 100 h, tensile tested, and the effect of oxidation in steam on the functionality of the Y₂Si₂O₇ fiber coating was investigated. The minicomposites oxidized at 1000 °C for 10 h retained 100 % of their unoxidized strength, and those oxidized for 50 and 100 h retained 92 % and 90 % of unoxidized strength, respectively. Strength retention and fiber pullout in both unoxidized and oxidized minicomposites suggests that the Y₂Si₂O₇ interphase was effective in maintaining a weak fiber-matrix interface.     

Evaluation of SiC/SiC minicomposites with yttrium disilicate fiber coating

Hi‐Nicalon‐S/α‐Y₂Si₂O₇/SiC minicomposites were formed by polymer infiltration pyrolysis (PIP) and characterized by TEM, SEM fractography, tensile testing, and fiber push‐in testing. All minicomposites with α‐Y₂Si₂O₇ fiber coatings had strengths significantly higher than the control samples without fiber coatings. Extensive fiber pullout with debonding at the coating‐fiber interface or within the coating itself was observed in minicomposites with Y₂Si₂O₇ fiber coatings, but no debonding was observed in minicomposites without fiber coatings. Debond energies of 4.5 ± 3, 4.6 ± 3 J/m² and average sliding stresses of 91 ± 40, 94 ± 40 MPa were measured by fiber push‐in tests.     

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.     

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.     

Fabrication of SiCN-Sc2Si2O7 coatings on C/SiC composites at low temperatures

SiCN-Sc₂Si₂O₇ environmental barrier coatings were fabricated on the surface of C/SiC composites at low temperatures by adding Li₂CO₃ as sintering aids. With this addition, the fabrication temperature could be lowered about 100-200 °C. The shrinkage of the polysilazane-Sc₂Si₂O₇ bars with and without Li₂CO₃ was tested by dilatometer. The results indicate that the shrinkage speed of the polysilazane-Sc₂Si₂O₇ bar with Li₂CO₃ is faster than the one without Li₂CO₃, indicating that the Li₂CO₃ greatly promotes the sintering of polysilazane-Sc₂Si₂O₇. Water-vapor corrosion behavior of the SiCN-Sc₂Si₂O₇ coated C/SiC composites was carried out at 1250 °C. The results reveal that the SiCN-Sc₂Si₂O₇ coatings can effectively protect the C/SiC composites. The corrosion resistance of SiCN-Sc₂Si₂O₇ coatings is not degraded by adding Li₂CO₃.     

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.     

The influence of Y2O3-containing sintering additives on the oxidation of Si3N4-based ceramics and the interfacial interactions with liquid Al-alloys

Sintering additives containing Y₂O₃ influence the microstructure and the crystalline-state of Si₃N₄-ceramics produced via pressureless sintering, and determine their response towards oxidation. Y₂SiO₅ and Y₂Si₂O₇ were formed after sintering and oxidation, respectively. The superficial layers formed after oxidation are thinner and formed faster on the surface of the compositions 90Si₃N₄–5Y₂O₃–5Al₂O₃ and 90Si₃N₄–5Y₂O₃–5AlN than on 90Si₃N₄–5Y₂O₃–2.5Al₂O₃–2.5AlN (in wt.%). The 90Si₃N₄–5Y₂O₃–5Al₂O₃/liquid Al interface features strong interfacial adhesion while mild diffusion should govern the interfacial interactions. Compounds, whose formation results from the yttria-containing sintering aids, such as yttrium aluminates, should act as diffusion barriers at the ceramic/liquid metal interface. The experimental results indicate attractive features for applications in both Al-foundry industry and production of Si₃N₄–Al composites.     

In situ growth of one-dimensional carbon-rich SiC nanowires in porous Sc2Si2O7 ceramics with excellent microwave absorption properties

For enhancing the absorption ability of dielectric and electromagnetic wave (EMW), C-rich SiC NWs /Sc₂Si₂O₇ ceramics are successfully fabricated through in-situ growth of SiC nanowires (NWs) into porous Sc₂Si₂O₇ ceramics by precursor infiltration and pyrolysis (PIP) at 1400?°C in Ar. SiC NWs are in-situ formed in the pore channels via a vapor-liquid-solid (VLS) mechanism, the relative complex permittivity increases notably with the content of absorber (C-rich SiC NWs), which tune the microstructure and dielectric property of C-rich SiC NWs/Sc₂Si₂O₇ ceramics. Meanwhile, the minimum reflection coefficient (RC) of C-rich SiC NWs/Sc₂Si₂O₇ ceramic decreases from ?9.5?dB to ??35.5?dB at 11?GHz with a thickness of 2.75?mm, and the effective absorption bandwidth (EAB) covers the whole X band (8.2–12.4?GHz) when the content of absorber is 24.5?wt%. The results indicate that Sc₂Si₂O₇ ceramics decorated with SiC NWs and nanosized carbon have a superior microwave-absorbing ability, which can be contributed to the Debye relaxation, interfacial polarization and conductivity loss enhanced by in-situ formed SiC NWs and nanosized carbon phases. The C-rich SiC NWs /Sc₂Si₂O₇ ceramics can be a promising microwave absorbing materials within a broad bandwidth.     

Processing and Testing of RE2Si2O7 Fiber–Matrix Interphases for SiC–SiC Composites

Rare‐earth disilicates (RE₂Si₂O₇) are investigated for use as oxidation‐resistant alternatives to carbon or BN fiber–matrix interphases in ceramic matrix composites (CMC). Dense α, β, γ‐Y₂Si₂O₇, and γ‐Ho₂Si₂O₇ pellets were formed at 64 MPa and 1050°C–1200°C for 1 h using the field‐assisted sintering technique (FAST). Pellet modulus was measured using nanoindentation, and Vickers hardness was measured at loads of 100, 500, and 1000 g. The sliding stress of SCS‐0 SiC fibers incorporated in α‐, β‐, and γ‐RE₂Si₂O₇ matrices were measured by fiber push‐out. Deformation of RE₂Si₂O₇ after indentation and after fiber push‐out was characterized by TEM. Implications of the results for use of RE₂Si₂O₇ as a fiber–matrix interphase in CMCs are discussed.     

Effect of the Y2O3 amount on the oxidation behavior of ZrB2-SiC-based coatings for carbon/carbon composites

In this paper, the effect of Y₂O₃ addition on the oxidation resistance of ZrB₂-SiC-Y₂O₃ coating for the SiC coated carbon/carbon composites was investigated. Results confirmed the great benefits of adding Y₂O₃ to the oxidation-resistant properties of the original coating from different aspects. The dense structure of surface and cross-section and formation of yttria stabilized zirconia, Y₂Si₂O₇, t-ZrO₂ phases were observed after adding Y₂O₃. Additionally, according to the TEM results, yttrium silicate existed in the form of nanoparticles, while yttria stabilized zirconia existed in the form of agglomeration within the SiO₂ liquid phase. This superior oxidation resistance was attributed to the following reasons: (i) the formed Zr-Si-Y-O glass barrier layer blocked the oxygen diffusion and healed the cracks; (ii) the reduced m-ZrO₂ content weakened the volume expansion of the coating and avoided spallation; (iii) Y₂Si₂O₇ served as a pinning phase which modified the stability of liquid SiO₂ at elevated temperatures.     

Investigation of Native Point Defects and Nonstoichiometry Mechanisms of Two Yttrium Silicates by First‐Principles Calculations

First‐principles method is used to study the native point defects in Y₂SiO₅ and Y₂Si₂O₇ silicates. The calculated defect formulation energies show similar native point defect behaviors in Y₂SiO₅ and Y₂Si₂O₇: the oxygen Frenkel defect is predominant; and it is followed by the cation antisite and Schottky defects. The possible chemical potential range of each constituent is further considered in the calculation of defect formation energy. Oxygen interstitial (O_i) and oxygen vacancy (V_O) are the predominant native point defects under O‐rich and O‐poor condition, respectively. In addition, the mechanisms of accommodating composition deviations from stoichiometric Y₂SiO₅ and Y₂Si₂O₇ are investigated. For Y₂SiO₅, Y₂Si₂O₇ impurity may appear, together with the defects of Si_Y antisite, O_i interstitial, and/or V_Y vacancy when SiO₂ is excess; while Y_Si antisite appears together with Y_i interstitial and/or V_O vacancy in Y₂SiO₅ when Y₂O₃ is excess. For Y₂Si₂O₇, the main process is the formation of Si_Y antisite accompanied by O_i interstitial and/or V_Y vacancy when SiO₂ is excess; but Y₂SiO₅ impurity forms, together with Y_Si antisite, V_O vacancy, and/or Y_i interstitial in Y₂Si₂O₇ when Y₂O₃ is excess. We expect that the results are useful to control of processing conditions and further to optimization of performance of the two silicates.     

Effect of Y2O3 on the oxidation properties of ZrSi2/SiC coating prepared by SAPS on the carbon-carbon composites

In order to improve the oxidation resistance of carbon-carbon (C/C) composites at high temperature, different content of Y₂O₃ modified ZrSi₂/SiC coating for C/C composites were prepared by pack cementation and supersonic atmosphere plasma spraying (SAPS). Microstructure observation and phase identification of the coatings were analyzed by SEM, XRD, DSC/TG and EDS. Experimental results shown that the coating with 10?wt% Y₂O₃ effectively protected C/C composites from oxidation at 1500?°C in air for 301?h with a mass loss of 0.13% and experienced 18 thermal shock times from room temperature (RT) to 1500?°C. First, Y₂O₃ could restrain the phase transition of ZrO₂ to reduce the formation of thermal stresses of the coating; second, the random distribution of ZrO₂ ceramic particles and the formation of ZrSiO₄ enhanced the stability of the SiO₂; third, the formation of Y₂Si₂O₇ and Y₂SiO₅ could relieve the thermal mismatch between ZrSi₂-Y₂O₃ outer layer and the inner layer.     

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.