High temperature oxidation resistance of Y2O3 modified ZrB2-SiC coating for carbon/carbon composites

To protect carbon/carbon (C/C) composites from oxidation at high temperature, Y₂O₃ modified ZrB₂-SiC coating was fabricated on C/C composites by atmospheric plasma spraying. The microstructure and chemical composition of the coatings were characterized by SEM, EDS, and XRD. Experiment results showed that the coating with 10 wt% Y₂O₃ presented a relatively compact surface without evident holes and cracks. No peeling off occurred on the interface between the coating and substrate. The ZSY10 coating underwent oxidation at 1450 °C for 10 h with a mass loss of 5.77%, while that of ZS coating was as high as 16.79%. The existence of Y₂O₃ played an important role in inhibiting the phase transition of ZrO₂, thus avoiding the cracks caused by the volume expansion of the coating. Meanwhile, Y₂SiO₅ and ZrSiO₄ had a similar coefficient of thermal expansion (CTE), which could relieve the thermal stress inside the coating. The ceramic phases Y₂SiO₅, Y₂Si₂O₇ and ZrSiO₄ with high thermal stability and low oxygen permeability reduced the volatilization of SiO₂.     

Degradation behavior of SiO2f/Al2O3-SiO2 composites: Anti-oxidation behavior and high-temperature flexural strength

2.5-Dimensional SiO₂ fiber-reinforced Al₂O₃-SiO₂ (SiO_2f/Al₂O₃-SiO₂) composites were prepared by the sol-gel method, using diphasic SiO₂ sol as the precursor into which Al₂O₃ powders were added. Their antioxidative behaviors and flexural strengths at high temperature were tested and compared. In an oxidation atmosphere, the composites showed high oxidation resistance, with a flexural strength retention ratio of over 90.00% at 1200?°C. After oxidation at 1500?°C, the mass retention ratio and flexural strength were 97.49% and 65.0?MPa respectively. The oxidation resistance of SiO_2f/Al₂O₃-SiO₂ composites was higher than that of SiO_2f/SiO₂ composites. After high-temperature test, the flexural strength retention ratios of SiO_2f/SiO₂ and SiO_2f/Al₂O₃-SiO₂ composites were 86.18% and 94.80% respectively, and the latter had a flexural strength of 134.9?MPa. SiO_2?f/Al₂O₃-SiO₂ composites worked better than SiO_2f/SiO₂ composites did in the flexural strength test at 1200?°C. The mechanical performance degradation and mass variations of the composites during tests were closely associated with their microstructural evolutions.     

Influence of Y2O3 addition on the mechanical and oxidation behaviour of carbon fibre reinforced ZrB2/SiC composites

The influence of Y₂O₃ addition on the microstructure, thermo-mechanical properties and oxidation resistance of carbon fibre reinforced ZrB₂/SiC composites was investigated. Y₂O₃ reacted with oxide impurities present on the surface of ZrB₂ and SiC grains and formed a liquid phase, effectively lowering the sintering temperature and allowing to reach full density at 1900 °C. The presence of a carbon source (fibres) led to additional reactions which resulted in the formation of new secondary phases such as yttrium boro-carbides. Mechanical properties were significantly enhanced compared to the un-doped composite. Further tests at high temperatures resulted in strength increase up to 700 MPa at 1500 °C which was attributed to stress relaxation. Oxidation tests carried out at 1500 °C and 1650 °C in air showed that the presence of the Y-based secondary phases enhanced the growth of ZrO₂ grains, but offered limited protection to oxygen due to the lower availability of surficial SiO₂ formed from SiC.     

Oxidation resistance and thermal shock properties of self-healing SiCN/borosilicate glass-B4C-Al2O3 coatings for C/C aircraft brake materials

SiCN/borosilicate glass-B₄C-Al₂O₃ coating was deposited on carbon fiber-reinforced carbon matrix (C/C) brake materials to protect them from oxidation. Microstructural analysis revealed that the coating was dense and uniform. Fabricated coating showed excellent oxidation resistance and significantly low weight losses after oxidation in dry air for 10?h than SiCN/borosilicate glass-B₄C coated samples (ca. 0.12%, 0.51%, and 0.29% at 700, 800, and 900?°C, respectively). B₄C is believed to react with the oxygen diffused into the coating to produce B₂O₃, which could heal cracks of the coating and improve its self-sealing ability and oxidation resistance. The Al₂O₃ present in the outer glass layer is believed to inhibit volatilization of B₂O₃, thereby reducing weight losses in air. Fabricated coating also possessed excellent oxidation resistance under fresh and sea water conditions, with cracks and pores generated during oxidization process being effectively healed. Prepared coating materials showed excellent thermal shock resistances after 50 thermal shock cycles, with weight losses being as low as 0.23%.     

Microstructures and oxidation behaviors of Al-modified and Al2O3-modified SiC coatings on carbon/carbon composites via pack cementation

Al₂O₃-modified SiC (AOSC) and Al-modified SiC (ASC) coatings were prepared on carbon/carbon (C/C) composites by one-time pack cementation (PC). Their microstructures and anti-oxidation performances were studied. Compared with ASC coating, AOSC coating shows more conspicuous defects (micro-cracks and holes) and lower densification. ASC coating can offer better oxidation resistance and thermal shock resistance to C/C composites than AOSC coating. Al additive can more efficiently improve the sinterability of SiC, which causes the above results. Besides, Al₂O₃ oxidation product is more stable than SiO₂ (l) of oxidized SiC at 1500 °C based on the thermodynamic analysis.     

Research on microstructure and oxidation resistant property of ZrSi2-SiC/SiC coating on HTR graphite spheres

ZrSi₂-SiC/SiC coating was prepared on the surface of high temperature gas-cooled reactor (HTR) matrix graphite spheres by two-step pack cementation and sintering process. The microstructure, oxidation resistance and thermal shock resistance properties of the as-prepared coatings with different original powder mixtures were investigated. Results show that dense microstructure of the ZrSi₂-SiC/SiC coating and continuous ZrSiO₄-SiO₂-ZrO₂ glass phase generated during the oxidation process were the key factors for the outstanding thermal properties. When the mole ratio of Zr:Si:C reaches 1:7:3 in the second pack cementation powders, the coated graphite spheres have optimum oxidation resistant ability. The weight gain is only 0.6 wt% after 15 times thermal shock tests and 0.12 wt% after isothermal oxidation test at 1500 °C for 20 h in air. The oxidation resistant mechanism of the coating was also discussed. The dense inner SiC layer and the outer glass layer generated during the oxidation process could protect the ZrSi₂-SiC/SiC coating from further oxidation.     

Protective properties of SiO2 with SiO2 and Al2O3 nanoparticles sol-gel coatings deposited on FeCrAl alloys

Five layer SiO₂ coatings containing SiO₂ or Al₂O₃ nanopowders were deposited on FeCrAl alloy support by sol-gel method. Studies of protective properties of the coatings were carried out during high temperature cyclic oxidation. Changes in surface topography, structure and chemical composition of the surface layer of FeCrAl alloy were investigated. It has been shown that the type of nanofillers present in the SiO₂ coating (about 2.5?wt%) affects morphology of Al₂O₃ growing scale and determines the heat resistance of FeCrAl alloy. The lowest relative mass change (approx. 1.3%) after 10 oxidation cycles in air at 900?°C (one cycle = 12?h) was measured for the samples with coatings containing hydrophilic nanosilica (Aerosil 380) as filler. The protective efficiency of the coatings in the process of high-temperature oxidation is from 66% to 85%. The thickness of the formed scale and the value of the parabolic rate constant depend on the type of nanopowder in the coating.     

Experimental and first-principles simulation study on oxidation behavior at 1700 °C of Lu2O3–SiC-HfB2 ternary coating for SiC coated carbon/carbon composites

The oxidation behavior and microstructure evolution of Lu₂O₃–SiC-HfB₂ ceramic coating specimen at 1700 °C were investigated systematically by experimental study and first-principles simulation. The prepared ternary coating possesses a compact morphology, which effectively defends C/C substrate against oxidation at 1700 °C for 130 h, showing a good antioxidant property. The formed HfSiO₄, Lu₂Si₂O₇, and HfO₂ with high melting points play an active role in developing the thermal stability of the oxidized scale. Besides, Lu and Hf atoms incline to diffuse into SiO₂, which enhances its structural stability. The improved thermal property of the oxidized scale for the Lu₂O₃–SiC-HfB₂/SiC ceramic coating can delay the effective delivery of oxygen inwardly and thus prolong its oxidation protection time. The quick volatilization of SiO₂ at 1700 °C induces that some glass phase evaporates with being not completely stabilized, which causes the formation of holes and the consumption of the inner coating.     

Resistance of 2ZrO2·Y2O3 top coat in thermal/environmental barrier coatings to calcia‐magnesia‐aluminosilicate attack at 1500°C

Internally cooled, hollow SiC‐based ceramic matrix composites (CMCs) components that may replace metallic components in the hot section of future high‐efficiency gas‐turbine engines will require multilayered thermal/environmental barrier coatings (T/EBCs) for insulation and protection. In the T/EBC system, the thermally insulating outermost (top coat) ceramic layer must also provide resistance to attack by molten calcia‐magnesia‐aluminosilicate (CMAS) deposits. The interactions between a potential candidate for top coat made of air‐plasma‐sprayed (APS) 2ZrO₂·Y₂O₃ solid‐solution (ss) ceramic and two different CMASs (sand and fly ash) are investigated at a relevant high temperature of 1500°C. APS 2ZrO₂·Y₂O₃(ss) top coat was found to resist CMAS penetration at 1500°C for 24 hours via reaction products that block CMAS penetration pathways. In situ X‐ray diffraction (XRD) studies have identified the main reaction product to be an Ca‐Y‐Si apatite, and have helped elucidate the proposed mechanism for CMAS attack mitigation. Ex situ electron microscopy and analytical spectroscopy studies have identified the advantageous characteristics of the reaction products in helping the CMAS attack mitigation in the APS 2ZrO₂·Y₂O₃(ss) coating at 1500°C. Finally, the Y³⁺ solubility limit and transport behavior are identified as potential comparative tools for assessing the CMAS resistance ability of top‐coat ceramics.     

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

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

Evaluation of Yttria Coated High Density Graphite with Silicon Carbide Interlayer for Uranium Melting Applications

Yttrium Oxide (Y₂O₃) deposited over High Density Graphite (HDG) by Atmospheric Plasma Spray (APS) process is highly desirable as a chemical barrier coating for reusable Uranium (U) melting crucibles in the pyrochemical reprocessing of spent metallic fuels. In the present study, an oxidation protective Silicon Carbide (SiC) interlayer coating over HDG has been achieved by pack cementation process. The high-temperature oxidation resistance and resistance to thermal fatigue failure of Y₂O₃ coating with and without SiC interlayer were evaluated by performing repeated thermal cycling studies at 1450, 1500 and 1550?°C. The durability performance of Y₂O₃ coating with SiC interlayer in the actual working environment was simulated by performing U melting studies using miniature size HDG coated crucibles. The microstructural, chemical and phase characterization of coatings prior and post thermal cycle failure were carried out by SEM/EDS and XRD techniques. It is observed that the SiC interlayer developed by novel pack cementation technique for the Y₂O₃ top coat extended the thermal cycling and life of the coating with U melting in inert argon gas environment significantly. The occurrence of micro-cracking over Y₂O₃ top coat with SiC interlayer perceived after 33, 30 and 25 thermal cycles at 1450, 1500 and 1550?°C, respectively.     

Low–thermal–conductivity and high–toughness CeO2–Gd2O3 co–stabilized zirconia ceramic for potential thermal barrier coating applications

Yttria partially stabilized zirconia (～4.0?mol% Y₂O₃–ZrO₂, 4YSZ) has been widely employed as thermal barrier coatings (TBCs) to protect the high–temperature components of gas–turbine engines. The phase stability problem existing in the conventional 4YSZ has limited it to application below 1200?°C. Here we report an excellent zirconia system co–doped with 16?mol% CeO₂ and 4?mol% Gd₂O₃ (16Ce–4Gd) presenting nontransformable feature up to 1500?°C, in which no detrimental monoclinic (m) ZrO₂ phase formed on partitioning. It also exhibits a high fracture toughness of ～46?J m^?2 and shows high sintering resistance. Besides, the thermal conductivity and thermal expansion coefficient of 16Ce–4Gd are more competent for TBCs applications as compared to the 4YSZ. The combination of properties suggests that the 16Ce–4Gd system could be of potential use as a thermal barrier coating at 1500?°C.     

Matrix–filler interactions in polysilazane-derived ceramics with Al2O3 and ZrO2 fillers

Interactions between a poly(vinyl)silazane and Al₂O₃ or Y₂O₃-stabilised ZrO₂ fillers were studied during the fabrication of polysilazane-derived bulk ceramics in order to investigate the influence of oxide fillers on resulting properties. Specimens were produced by coating of the filler powders with the polysilazane, warm-pressing of the resulting composite powders, and pyrolytic conversion in flowing N₂ at various temperatures between 1000 °C and 1400 °C. Significant differences in densification were observed, depending on the filler used. Reactions between the polysilazane-derived matrix and Al₂O₃ or ZrO₂ at temperatures ≥1300 °C resulted in the formation of Si₅AlON₇ or ZrSiO₄, respectively. Reactivity in the polysilazane-derived component was a result of SiO₂ contamination caused primarily by adsorbed species on the filler particle surface. Knowledge of polysilazane/filler interface processes is found to be decisive for the prediction of properties such as shrinkage and porosity, which heavily influence performance of a material.     

Bimodal microstructure ZrB2-MoSi2 coating prepared by atmospheric plasma spraying for carbon/carbon composites against long-term ablation

To protect carbon/carbon composites against long-term ablation, a bimodal microstructure ZrB₂-MoSi₂ coating, consisting of an outer ZrB₂-MoSi₂ layer modified by Y₂O₃ and an inner basal ZrB₂-MoSi₂ layer, was prepared by atmospheric plasma spraying. The microstructure, phase composition and ablation resistance of the proposed coating were investigated in detail. Results showed that the bimodal coating maintained integrity in structure except for phase composition. There was no visible interlayer between the inner ZrB₂-MiSi₂ layer and the outer modified one. Mass ablation rate of the bimodal microstructure ZrB₂-MoSi₂ coated C/C composites was −2.02 × 10⁻³ g/s under an oxyacetylene flame ablation at 1873 K for 600 s, which exhibited better ablation resistance than a single ZrB₂-MoSi₂ coating. The excellent ablation resistance was ascribed to the positive effect of Y₂O₃, which not only pined in the glassy phase and alleviated the volatilization of SiO₂ glass phase by reacting with SiO₂ to form high viscosity of Y₂SiO₅, but also stabilized ZrO₂ and promoted its recrystallization and growth.     

Rapid solidification in the Al2O3ZrO2 system

Eutectic compositions of Al₂O₃ and ZrO₂ have been melted and rapidly solidified by shock-wave quenching, flame-pressure atomization and high-pressure water atomization. Quenching rates > 10⁴ K/s resulted in amorphous particles which, on annealing, crystallized at 1310°C. Microcrystalline particles with tetragonal ZrO₂ distributed in an ?-Al₂O₃ matrix formed at lower quenching rates. ?-Al₂O₃ transformed into α-Al₂O₃ on annealing at 953°C.     

New anti-ablation candidate for carbon/carbon composites: Preparation,composition and ablation behavior of Y2Hf2O7 coating under an oxyacetylene torch

Y₂Hf₂O₇ possesses low thermal conductivity and high melting point, which make it promising for a new anti-ablation material. For evaluating the thermal stability and the potential applications of Y₂Hf₂O₇ on anti-ablation protection of C/C composites, Y₂Hf₂O₇ ceramic powder was synthesized by solution combustion method and Y₂Hf₂O₇ coating was prepared on the surface of SiC coated C/C composites using SAPS. Results shown that the coating exhibits good ablation resistance under the heat flux of 2.4?MW/m² with the linear and mass ablation rates are 0.16?μm?s^?1 and ?0.028?mg?s^?1, respectively, after ablation for 40?s. With the prolonging of the ablation time, the increasing thermal stress causes the increase of cracks. Moreover, the chemical erosion from SiO₂ and the physical volatilization of low temperature molten products aggravate failure of the Y₂Hf₂O₇ coating.     

Oxidation and recession of plain weave carbon fiber reinforced ZrB2-SiC-ZrC in oxygen–hydrogen torch environment

The oxidation and recession of four plain weave carbon fiber reinforced ZrB₂-SiC-ZrC composites with different matrix compositions were compared with those of a plain weave carbon fiber reinforced ZrB₂-SiC matrix composite. These composites were fabricated using a silicon melt infiltration method. The composite with the higher ZrC content also formed ZrSi₂ in the matrix instead of residual silicon. The composites were oxidized at 1700 and 1800 °C in an oxygen–hydrogen torch environment. The oxides consisted of ZrO₂ and SiO₂, which formed on the surface of all samples. Carbon fiber at the surface was lost due to oxidation. The recession resistance of ZrB₂-SiC-ZrC matrix composites remained constant at 1700 °C, even if the matrix composition varied, while the resistance at 1800 °C increased with the matrix of ZrC and ZrSi₂. The ZrB₂-SiC-ZrC matrix composite with the higher ZrC and ZrSi₂ compositions formed a sintered ZrO₂-rich layer, which was denser than the ZrO₂-SiO₂ and improved the recession resistance.     

Thermal shock resistance of Al2O3/SiO2 composites by sol-gel

In this paper, the SiO₂ ceramic matrix composites were reinforced by the two-dimensional (2D) braided Al₂O₃ fibers by sol-gel. To develop the high performance aeroengine with excellent resistance to thermal shock for advanced aerospace application, two different thermal shock temperatures (1100?°C and 1300?°C) and three different thermal shock cycles (10, 20 and 30 cycles) were tested and compared in this paper; besides, the thermal shock resistance of Al₂O₃/SiO₂ composites was investigated in air. Our results suggested that, the flexural strength of the untreated composites was 78.157?MPa, while the residual strength of Al₂O₃/SiO₂ composites under diverse thermal shock cycles and temperatures had accounted for about 95% and 50% of the untreated composites, respectively. Meanwhile, the density and porosity of the composites were gradually increased with the increase in test temperature. Moreover, the changes in fracture morphology and micro-structural evolution of the composites were also observed. Our observations indicated that, the fracture morphology of the composites mainly exhibited ductile fracture at the thermal shock temperature of 1100?°C, whereas brittle fracture at the thermal shock temperature of 1300?°C. Additionally, Al₂O₃/SiO₂ composites belonged to the Oxide/Oxide CMCs, so no new phase was formed after thermal shock tests. Above all, findings of this paper showed that Al₂O₃/SiO₂ composites had displayed outstanding thermal shock resistance.     

Microstructure,phase structure,and electrical properties of nitrided 3 mol% Y2O3 stabilized ZrO2 (3YSZ)

3?mol% Y₂O₃ stabilized monoclinic and tetragonal ZrO₂ (3YSZ) was prepared by a co-precipitation method. When the sintered 3YSZ samples were embedded into ZrN powder and heat-treated at different temperatures (1300–1500?°C) in flowing nitrogen gas, nitrided 3YSZ (3YSZ-N) was formed. The microstructure, phase structure, ionic conductivity, and electronic conductivity were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and Hebb-Wagner method, respectively. The results showed that the grain-boundary of tetragonal phase 3YSZ-N was difficult to be observed. Above 700?°C, the conductivity of 3YSZ-N was higher than that of 3YSZ, and increased with the increase in nitrogen content. The electronic conductivity of 3YSZ-N decreased and then increased with the increase of nitrogen content. The thermogravimetric and differential scanning calorimeter analyses (TG-DSC) showed that 3YSZ-N was oxidized in air above 600?°C.     

Rate of formation of C3S in the system CaOSiO2Al2O3Fe2O3MgO with addition of CaF2

The influence of CaF₂ on the kinetics of the reaction C+C₂S → C₃S in five-component diffusion sandwiches (CaOSiO₂Al₂O₃Fe₂O₃MgO) was determined in the temperature interval 1350°C to 1500°C. With the addition of 0.5% CaF₂ to the reacting system the rate of reaction increased by a factor of 2.4 at a reaction temperature of 1350°C, and a factor of 1.2 at 1500°C. Addition of 1% CaF₂ raised the reaction rate 2.8 times at 1350°C and 1.7 times at 1500°C. The effect of CaF₂ on the rate of C₃S formation may be attributed to the fact that the C₃S primary field is much wider in the CSCaF₂ system than in the CSAF system.