Design of an inlaid interface structure to improve the oxidation protective ability of SiC–MoSi2–ZrB2 coating for C/C composites

To improve the oxidation protective ability of SiC–MoSi₂–ZrB₂ coating for carbon/carbon (C/C) composites, pre-oxidation treatment and pack cementation were applied to construct a buffer interface layer between C/C substrate and SiC–MoSi₂–ZrB₂ coating. The tensile strength increased from 2.29 to 3.35 MPa after pre-oxidation treatment, and the mass loss was only 1.91% after oxidation at 1500 °C for 30 h. Compared with the coated C/C composites without pre-oxidation treatment, after 18 thermal cycles from 1500 °C and room temperature, the mass loss was decreased by 30.6%. The improvements of oxidation resistance and mechanical property are primarily attributed to the formation of inlaid interface between the C/C substrate and SiC–MoSi₂–ZrB₂ coating.     

Oxidation behavior of Al2O3 reinforced MoSi2 composite coatings fabricated by vacuum plasma spraying

MoSi₂, MoSi₂–10 vol.% Al₂O₃, MoSi₂–30 vol.% Al₂O₃ (denoted as MA0, MA1, MA3, respectively) coatings were fabricated by vacuum plasma spraying (VPS), and their oxidation behavior was examined at low temperature (500 °C) and high temperature (1500 °C). The test at 500 °C showed that the addition of Al₂O₃ effectively restrained the pest oxidation of MoSi₂. The MA1 coating had satisfactory fluid surface and presented good oxidation resistance at 1500 °C. However, the MA3 coating showed worse oxidation resistant behavior compared with the MA0 coating because of mullite formation.     

Effect of temperature gradient on the erosion behavior of SiC coating for carbon/carbon composites in a combustion environment

SiC coating with a thickness of 50–70 µm was prepared on the surface of C/C composites by in-situ reaction method. The SiC coated C/C composites were then tested in a wind tunnel where a temperature gradient from 200 to 1600 °C could be obtained to investigate their erosion behavior. The results of wind tunnel test indicated that the service life of C/C composites was prolonged from 0.5 to 44 h after applying the SiC coating. After the wind tunnel test, three typical oxidation morphologies, including glassy SiO₂ layer, porous SiO₂ layer and clusters of honeycomb-like SiO₂ grains, were found on the SiC coated C/C composites. With the decrease of oxidation temperature, the amount of glassy SiO₂ declined and the thermal stress increased, which induced the cracking followed by the degradation of the SiC coating.     

SiC nanowire-toughened MoSi2-WSi2-SiC-Si multiphase coating for improved oxidation resistance of C/C composites

To improve the oxidation resistance of carbon/carbon (C/C) composites at high temperature, a SiC nanowire-toughened MoSi₂-WSi₂-SiC-Si multiphase coating was prepared by chemical vapor deposition (CVD) and pack cementation. The microstructure, mechanical properties and oxidation resistance of the coating were investigated. After the introduction of SiC nanowires, the elastic modulus, hardness, and fracture toughness of the MoSi₂-WSi₂-SiC-Si coating were increased by 25.48%, 4.09% and 45.03%, respectively. The weight loss of the coated sample with SiC nanowires was deceased from 4.83–2.08% after thermal shock between 1773 K and room temperature for 30 cycles and the weight loss is only 3.24% after isothermal oxidation at 1773 K in air for 82 h. The good oxidation resistance of the coating is mainly attributed to that SiC nanowires can effectively inhibit the propagation of cracks in the coating by the toughening mechanisms including bridging and pull-out.     

Fabrication of a SiC/Si/MoSi2 multi-coating on graphite materials by a two-step technique

A SiC/Si/MoSi₂ multi-coating for graphite materials was prepared by a two-step technique. SiC whisker reinforcement coating was produced by pyrolysis of hydrogen silicone oil (H-PSO) at 1600 °C, and then the dense coating was formed by embedding with the powder mixture of Si, graphite and MoSi₂ at 1600 °C in argon atmosphere. The microstructure, thickness, phase and oxidation resistance of the coating were investigated. Research results showed that, the phase of multi-coating was composed of SiC, Si and MoSi₂. The thickness of the coating was about 300 μm. In addition, the coating combined with matrix well, and surface was continuous and dense. The oxidation pretreatment experiment was carried out in the static air at 1400 °C for 4 h before thermal failure tests and the specimens had 0.045% weight gain. Subsequent thermal failure tests showed that, the SiC/Si/MoSi₂ multi-coating had excellent anti-oxidation property, which could protect graphite materials from oxidation at 1000 °C in air for 12 h and the corresponding weight loss was below 1 wt%. Based on the surface morphology changes, oxidation pretreatment experiment and thermal failure tests enhanced densification of multi-coating and the coating had a certain self-healing ability.     

Dynamic oxidation and protection of the PAN pre-oxidized fiber C/C composites

Pre-oxidized fibers as reinforcement are candidates for reducing the overall cost of C/C composites with superior properties. This study investigated the dynamic oxidation and protection of the pre-oxidized fiber C/C composites (Pr-Ox-C-C). According to the Arrhenius equation, the oxidation kinetics of the Pr-Ox-C-C consisted of two different oxidation mechanism with the transition point was at about 700 °C. Scanning electron microscopy investigation showed that oxidation initiated from the fiber/matrix interface of composites, whereas the matrix carbon was easily oxidized. To improve the anti-oxidant properties of Pr-Ox-C-C, a ceramic powder-modified organic silicone resin/ZrB₂-SiC coating was prepared by the slurry method. The coated samples were subjected to isothermal oxidation for 320 h at 700 °C, 800 °C, 900 °C, 1000 °C and 1100 °C with incurred weight losses of ? 1.6%, 0.77%, ? 1.28%, 0.68% and 1.19%, respectively. After 110 cycles of thermal shock between 1100 °C and room temperature, a weight loss of 1.30% was obtained. The Arrhenius curve presented four different phases and mechanisms for coating oxidation kinetics. The excellent oxidation resistance properties of the prepared coating could be attributed to the inner layer which was able to form B₂O₃-Cr₂O₃-SiO₂ glass to cure cracks, and the ZrB₂-SiC outer layer that could provide protective oxides to reduce oxygen infiltration and to seal bubbles.     

Solid-state synthesis of mullite from spent catalysts for manufacturing refractory brick coatings

This paper shows the results of the solid-state synthesis of mullite from spent catalysts discarded from fluid catalytic cracking (FCC); the catalysts are mainly composed of silica and alumina but are polluted with SO_X, forming a non-crystalline network. The synthesized mullite was used as a feedstock to thermally spray a coating onto a silica-alumina refractory brick, and its chemical resistance at high temperature was subsequently evaluated by contact with K₂CO₃ at 950 °C. Initially, the spent catalyst was thermally treated for 2 h at 600, 900, and 1200 °C to eliminate the SO_X pollutant. The heat treatment at 1200 °C completely removed the SO_X in the sample. Additionally, four thermal processes were performed by heating the spent FCC catalyst in an electrical furnace to 1500 and 1600 °C and by using an oxyacetylene flame to synthesize mullite. Thermal treatments at 1500 °C were performed with and without alumina added to the spent FCC catalyst, whereas those conducted at 1600 °C and using a flame were performed using only added alumina. In the powders thermally treated at 1500 °C, silica-rich mullite (3Al₂O₃.2SiO₂) accompanied by an excess of alumina or silica was obtained with or without alumina added, respectively. In contrast, the materials treated at 1600 °C formed alumina-rich mullite (2Al₂O₃.SiO₂), which was accompanied by an excess of alumina. Mullite was not synthesized in the flame-heated powder. The silica-rich mullite accompanied by an excess of alumina was used as feedstock powder to modify the surface of a refractory brick, improving its resistance to chemical attack by K₂CO₃ at high temperature.     

Synthesis and oxidation behavior of (Mo0.97Nb0.03)(Si0.97Al0.03)2 ceramic

(Mo_0.97Nb_0.03)(Si_0.97Al_0.03)₂ ceramic was synthesized by self-propagating high-temperature synthesis using commercial elemental powders, and then dense monolithic ceramic was prepared via vacuum hot pressing. The oxidation behavior of the bulk ceramic was investigated at 500 °C and 1200 °C. At 500 °C, due to the preferential oxidation of Nb-rich phase and the formation of uniform oxidation layer, the oxidation rate of (Mo_0.97Nb_0.03)(Si_0.97Al_0.03)₂ is lower than pure MoSi₂. At 1200 °C, (Mo_0.97Nb_0.03)(Si_0.97Al_0.03)₂ shows better oxidation resistance than MoSi₂, owing to the uniform complex oxide layer with SiO₂, Al₂O₃ and Nb₂O₅ formed on the surface of the prepared ceramic.     

Microstructure and oxidation behavior of Si–MoSi2 functionally graded coating on Mo substrate

The Si–MoSi₂ functionally graded coating on Mo substrate consisting of a Si–MoSi₂ layer (2.5 µm), a MoSi₂ layer (18 µm) and a Mo–Mo₅Si₃–Mo₃Si layer (2–4 µm) was prepared by a liquid phase siliconizing method. The siliconized coating has a dense layered structure and no micro-cracks and holes. The Si element mainly enriches on the surface with the highest content of about 50 wt%, and inhibits the formation of Mo₅Si₃ and volatile MoO₃ and improves the high-temperature oxidation resistance of the coating. The mass gain of Si-MoSi₂ coating is only 0.17 wt% after oxidized at 1600 ℃ for 70 h. The Si–MoSi₂ functionally graded coating exhibits better high temperature oxidation resistance than pure MoSi₂ coating.     

Microstructural evolution of multi-walled carbon nanotubes in the presence of mixture of silicon and silica powders at high temperatures

Microstructural evolution of multi-walled carbon nanotubes (MWCNTs) in the presence of mixture of silicon and silica powders in a coke bed is studied in the temperature range of 1000–1500 °C by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and thermogravimetry–differential scanning calorimetry (TG–DSC). The results showed that a thin amorphous SiO₂ coating was formed on the surface of MWCNTs at the temperature below 1300 °C. With the increase of the treated temperature, the coating became thicker, 3–7 nm in thickness at 1400 °C and a maximum of 10 nm at 1500 °C. Meanwhile, SiC nanowires and SiC nanocrystals around Ni catalyst at the tip of MWCNTs were formed at 1400 °C and 1500 °C, which were related to the vapor–vapor (V–V) and vapor–liquid–solid (V–L–S) reactions between SiO (g) and CO (g) or C (s), respectively. The oxidation resistance of all the treated MWCNTs was better than that of as-received ones. The oxidation peak temperature reached 804.2 °C for the treated MWCNTs, much higher than 652.2 °C for as-received ones.     

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.     

High temperature oxidation behavior of MoSi2–Al2O3 composite coating on TZM alloy

A novel MoSi₂–Al₂O₃ composite coating was prepared on Mo-based TZM alloy by slurry sintering method. The oxidation behavior of the coating was evaluated at 1600 °C in static air. Microstructure and phase composition of the as-prepared and oxidized coatings were characterized, and the antioxidant mechanism of the coating at high temperature was discussed. A three-layer structure was observed in the as-prepared coating, consisting of a ～2 μm thick Mo₅Si₃ diffusion layer, a ～65 μm thick MoSi₂ inner layer and a ～36 μm thick outer layer of mixture of MoSi₂ and Al₂O₃. After oxidation at 1600 °C for 5 h, all MoSi₂ phases were completely converted to intermediate silicide Mo₅Si₃ by solid-state diffusion, and the formed Mo₅Si₃ phase would be transformed into Mo₃Si phase with further extending the oxidation time. Furthermore, a dense oxide layer of SiO₂-mullite was formed on the specimen surface, which can effectively protect the material to further oxidation. The MoSi₂–Al₂O₃ coating could protect the substrate effectively at 1600 °C for 20 h without failure. The enhanced oxidation resistance of MoSi₂–Al₂O₃ coating is due to the formation of multi-layer structure containing a SiO₂-mullite composite oxide outer layer with high thermal stability and low oxygen permeability.     

A novel combination of precursor pyrolysis assisted sintering and rapid sintering for construction of multi-composition coatings to improve ablation resistance of SiOC ceramic modified carbon fiber needled felt preform composites

A double-layer coating composed of MoSi₂–SiO₂–SiC/ZrB₂–MoSi₂–SiC was designed and successfully constructed by a novel combination of precursor pyrolysis assisted sintering and rapid sintering to improve the ablation resistance of SiOC ceramic modified carbon fiber needled felt preform composites (CSs). The ZrB₂–MoSi₂–SiC inner layer coating was in relatively uniform distribution in the zone of 0–3 mm from the surface of CSs through the slurry/precursor infiltration in vacuum and SiOC precursor pyrolysis assisted sintering, which played a predominant role in improving oxidation and ablation resistance and maintaining the morphology of CSs. The MoSi₂–SiO₂–SiC outer layer coating was prepared by the spray and rapid sintering to further protect CSs from high-temperature oxidation. The ablation resistance of CSs coated with double-layer coating was evaluated by an oxygen-acetylene ablation test under the temperature of 1600–1800 °C with different ablation time of 1000 and 1500 s. The results revealed that the mass recession rates increased with the rise of ablation temperature and extension of ablation time, ranging from 0.47 g/(m²·s) to 0.98 g/(m²·s) at 1600–1800 °C for 1000 s and from 0.72 g/(m²·s) to 0.86 g/(m²·s) for 1000–1500 s at 1700 °C, while the linear recession rates showed negative values at 1700 °C due to the formation of oxides, such as SiO₂ and ZrO₂. The ablation mechanism of the double-layer coating was analyzed and found that a SiO₂–ZrO₂–Mo_4.8Si₃C_0.6 oxidation protection barrier would be formed during the ablation process to prevent the oxygen diffusion into the interior CSs, and this study provided a novel and effective way to fabricate high-temperature oxidation protective and ablation resistant coating.     

High-temperature erosion resistance and aerodynamic oxidation mechanism of multi-layer MoSi2–CrSi2–Si/SiC coated carbon/carbon composites in a wind tunnel at 1873 K

The high-temperature erosion resistance of multi-layer MoSi₂–CrSi₂–Si/SiC coated carbon/carbon (C/C) composites was investigated in a wind tunnel. To study the aerodynamic oxidation mechanism and analyze the failure of the coated C/C composites, the shear force and bending moment distribution of the tested specimens in a wind tunnel were calculated. Flexural strengths and thermogravimetric analysis of the coated specimens were measured. These results show that the multi-layer MoSi₂–CrSi₂–Si/SiC antioxidation coating can protect the C/C composites from high-temperature erosion in a wind tunnel at 1873 K for more than 86 h. Due to the high viscosity of SiO₂, the multi-layer coating lacked effective oxidation resistance from 900 to 1500 K, resulting in extensive mechanical damage and the fracture of the tested specimens.     

Dynamic oxidation resistance and residual mechanical strength of ZrB2-CrSi2-SiC-Si/SiC coated C/C composites

To improve oxidation resistance of carbon/carbon (C/C) composites, a multiphase double-layer ZrB₂-CrSi₂-SiC-Si/SiC coating was prepared on the surface of C/C composites by pack cementation. Thermogravimetry analysis showed that the as-prepared coating could provide effective oxidative protection for C/C composites from room temperature to 1490 °C. After thermal cycling between 1500 °C and room temperature, the fracture behaviors of the as-prepared specimens changed and their residual flexural strengths decreased as thermal cycles increased. The specimen after 20 thermal cycles presented pseudo-plastic fracture characteristics and relatively high residual flexural strength (83.1%), while the specimen after 30 thermal cycles failed catastrophically without fiber pullout due to the severe oxidation damage of C/C substrate especially the brittleness of the reinforcement fibers.     

Evaluation of oxidation behavior of laser clad CoWSi–WSi2 coating on pure Ni substrate at different temperatures

Microstructural aspects of CoWSi–WSi₂ coating on pure Ni and its oxidation performance under cyclic heating and cooling conditions in air at 900, 1100 and 1300 °C have been studied. The coating was applied by laser cladding process. The microstructure evaluations demonstrated that a uniform free cracks coating formed which was metallurgically bonded to the substrate. XRD and EDS analysis results showed that the coating consisted of CoWSi, WSi₂ and γ-Co. The mass gain/unit area versus oxidation time plot for all the samples was parabolic indicating that the oxidation process was diffusion-controlled. The structure of scales depended on oxidation temperatures; at 900 °C, a dense scale layer consisting of SiO₂ and small amounts of WO₃ and CoO, at 1100 °C, a characteristic scale structure, namely a mixed layer structure and at 1300 °C, the dense oxide scale enrichment of SiO₂ and porous interdiffusion layer with low oxygen concentration was formed.     

Design and optimization of oxidation resistant coating for C/C aircraft brake materials

A SiCN/borosilicate glass anti-oxidation coating with double-layer structure was designed for C/C aircraft brake materials. The SiCN layer was introduced as transition layer to improve the wettability between borosilicate glass and C/C composites, and the microstructure results indicated that the coating with SiCN inner layer was dense and uniform. The oxidation resistance evaluation of the coated samples was conducted at 800 °C in air for 10 h. The weight loss of SiCN/borosilicate glass coated samples valued ~ 5.66% indicated that the oxidation resistant property of the simple SiCN/borosilicate glass coating was not good, which was mainly due to the relative large viscosity of borosilicate glass at 800 °C. B₄C was introduced to add into the outer glass coating to improve the self-healing ability of the coating. After oxidized at 800 °C in air for 10 h, the weight loss of the SiCN/borosilicate glass-B₄C coated samples was ~ 2.48%. B₄C could consume the oxygen diffused into the coating and the reacted product B₂O₃ with a better fluidity at 800 °C could effectively heal cracks and pores in the coating to improve the oxidation resistance property. The reaction of B₄C oxidized to B₂O₃ was accompanied with ~ 1.5 times volume expansion, which was also beneficial for the healing of defects.     

Sintering,microstructure and hardness of Y-TZP- 64S bioglass ceramics

3 mol% yttria-partially stabilized zirconia (Y-TZP) powder and a sol-gel derived CaO- P₂O₅- SiO₂ (64S) bioglass, were used to produce Y-TZP- 64S slip cast compacts. The compacts with 10.5 and 19.9 vol% 64S were sintered at different temperatures up to 1500 °C using 5 and 10 °C/min heating/cooling rates. The densification behaviour, crystalline phase formation and zirconia grain growth were investigated as a function of sintering temperature and 64S glass content. Ca₃(PO₄)₂ along with SiO₂ as a major phase were obtained from thermal decomposition of the 64S glass at 950–1500 °C. Both 64S additions, 10.5 and 19.9 vol%, promoted the sintering process at a lower temperature with respect to Y-TZP (1500 °C); the SiO₂ phase markedly increased the Y-TZP solid state sintering rate at the intermediate stage. The rapidly cooling at 10 °C/min inhibited the t-m transformation of Y-TZP and markedly reduced that of Y-TZP- 64S at 1300–1500 °C. Sintered Y-TZP with 10.5 vol% 64S, nearly fully densified at 1300–1400 °C, was constituted by polygonal ZrSiO₄ particles and elongated Ca₂P₂O₇ particles uniformly distributed in the tetragonal zirconia fine grain matrix. This ceramic exhibited similar hardness to that of Y-TZP sintered at 1500 °C; the in situ formation of calcium phosphate will have the potential to improve the Y-TZP biological properties without significantly affecting its hardness.     

Oxidation protection of graphite materials by single-phase ultra-high temperature boride modified monolayer Si-SiC coating

To improve the oxidation resistance of Si-SiC coating, single-phase ultra-high temperature boride (ZrB₂ or TaB₂) modified Si-SiC coating was designed and established on graphite substrates by combination of dipping and reactive infiltration process. ZrB₂ or TaB₂ phase was introduced in Si-SiC coating by directly mixing raw materials and phenol formaldehyde resin in the slurry, and then the ZrB₂-SiC-Si and TaB₂-SiC-Si coatings were fabricated on the graphite samples by dipping-curing, pyrolysis, and siliconizing. The crystalline phases and microstructure of the as-obtained multiphase coatings were investigated by X-ray diffraction analysis and scanning electron microscopy. The interrupted oxidation tests from room-temperature to 1500?°C were conducted to assess the anti-oxidation property of the prepared coatings. After 1200?h of oxidation at 1500?°C in air (30 times thermal cycles), the mass losses of the graphite substrates coated with ZrB₂-SiC-Si and TaB₂-SiC-Si coatings were 0.086% and 0.537%, respectively, and the high-temperature stability of the modified coatings was greatly improved compared to the Si-SiC coating. The excellent anti-oxidation performances of the compound coatings were attributed to the compact structure of the coatings and the formation of compound oxide layers covering on the surfaces. The compound Zr-Si-O and Ta-Si-O films possessed low oxygen diffusion rate and appropriate viscosity, which can provide appreciable oxidation protection for the internal coatings, thus obtaining the excellent oxidation and spallation resistance property.     

MoSi2-based oxidation protective coatings for SiC-coated carbon/carbon composites prepared by supersonic plasma spraying

To protect carbon/carbon (C/C) composites against oxidation, MoSi₂-based oxidation protective coatings for SiC-coated carbon/carbon composites were prepared on them by supersonic plasma spraying. The MoSi₂-based coatings primarily consist of MoSi₂, Mo₅Si₃ and glassy SiO₂. Only a few pinholes and some microcracks are observed on the surface and no through-thickness cracks penetrate the cross-section. Weight loss of the MoSi₂-based coated specimens is only 1.14% after 400 h oxidation in air at 1773 K and the coated C/C composites remain intact after 11 thermal cycles between 1773 K and room temperature. The outstanding anti-oxidation ability is mainly attributable to the formation of SiO₂-based layer on the surface of MoSi₂-based coatings.