Oxidation behavior of 3D Hi–Nicalon/SiC composite

Oxidation behavior of a three dimensional (3D) Hi–Nicalon/SiC composite with CVD SiC coating was investigated in the simulated air using a thermogravimetric analysis (TGA) device. Below 1100 °C, the oxidation kinetics was controlled by gas diffusion through the defects in the SiC matrix and coating and resulted in the consumption of PyC interphase. The residual flexural strength did have not a remarkable fluctuation and the relationship between the residual strength to temperature and weight change to temperature of the 3D Hi–Nicalon/PyC/SiC composite indicated the same regularity. Above 1200 °C, the oxidation kinetics was controlled by oxygen diffusion through the SiO₂ scale formed on the SiC coating and matrix. And the residual flexural strength of the composites was governed by the strength degradation of the Hi–Nicalon fiber. After oxidation, the fracture displacement in flexural tests increased with the weight loss increasing and the fracture mode showed a non-brittle pattern.     

Microstructure and oxidation behaviour of Fe–Cr–silicide coating on a niobium alloy

The cyclic oxidation performance of a Fe–Cr-modified silicide coating on Nb-alloy C-103 was evaluated in air at temperatures between 1100 and 1500°C and the microstructural changes examined. The coating was oxidation resistant and the duration of protection increased from 60 minutes at 1100°C to 255 minutes at 1500°C. The formation of the surface glassy silica layer and its ability to heal the cracks in the coating enhanced the oxidation performance at high temperatures. The outer NbSi₂ layer served as a reservoir of Si and sustained the formation of the protective silica scale. Spallation of the silica scale and the concomitant depletion of the NbSi₂ layer towards the regeneration of the silica scale limit the oxidation life of the coating.     

Oxidation behavior and mechanical properties of C/SiC composites with Si-MoSi2 oxidation protection coating

A new kind of oxidation protection coating of Si-MoSi₂ was developed for three dimensional carbon fiber reinforced silicon carbide composites which could be serviced upto 1550 °C. The overall oxidation behavior could be divided into three stages: (i) 500 °C < T < 800 °C, the oxidation mechanism was considered to be controlled by the chemical reaction between carbon and oxygen; (ii) 800 °C < T < 1100 °C, the oxidation of the composite was controlled by the diffusion of oxygen through the micro-cracks, and; (iii) T > 1100 °C, the oxidation of SiC became significant and was controlled by oxygen diffusion through the SiC layer. Microstructural analysis revealed that the oxidation protection coating had a three-layer structure: the out layer is oxidation layer of silica glass, the media layer is Si + MoSi₂ layer, and the inside layer is SiC layer. The coated C/SiC composites exhibited excellent oxidation resistance and thermal shock resistance. After the composites annealed at 1550 °C for 50 h in air and 1550 °C 100 °C thermal shock for 50 times, the flexural strength was maintained by 85% and 80% respectively. The relationship between oxidation weight change and flexural strength revealed the criteria for protection coating was that the maximum point of oxidation weight gain was the failure starting point for oxidation protection coating.     

Fabrication and oxidation resistance of silicon nitride fiber reinforced silica matrix wave-transparent composites

Wave-transparent ceramic matrix composites for the high temperature use should possess excellent oxidation resistance. In this work, Si_3N_(4f)/SiO_2 composites with different fiber content were fabricated by filament winding and sol gel method. The oxidation resistance was investigated by tracking the response of flexural strength to the testing temperature. The results show that the flexural strength and toughness of the composites with fiber content of over 37% can reach high levels at around 175.0 MPa and 6.2 MPa m1/2, respectively. After 1 h oxidation at 1100?C, the flexural strength drops a lot but can still reach 114.4 MPa, which is high enough to ensure the safety of structures. However, when the oxidation temperature rises to 1200–1400?C, the flexural strengths continue to fall to a relatively low level at 50.0–66.4 MPa. The degradation at high temperatures is caused by the combination of over strong interfacial bonding, the damage of fiber and the crystallization of silica matrix.     

The Degradation Behavior of SiC<Subscript>f</Subscript>/SiO<Subscript>2</Subscript> Composites in High-Temperature Environment

SiC_f/SiO₂ composites had been fabricated efficiently by Sol-Gel method. The oxidation behavior, thermal shock property and ablation behavior of SiC_f/SiO₂ composites was investigated. SiC_f/SiO₂ composites showed higher oxidation resistance in oxidation atmosphere, the flexural strength retention ratio was larger than 90.00%. After 1300 °C thermal shock, the mass retention ratio was 97.00%, and the flexural strength retention ratio was 92.60%, while after 1500 °C thermal shock, the mass retention ratio was 95.37%, and the flexural strength retention ratio was 83.34%. After 15 s ablation, the mass loss rate was 0.049 g/s and recession loss rate was 0.067 mm/s. The SiO₂ matrix was melted in priority and becomes loosen and porous. With the ablation going on, the oxides were washed away by the shearing action of the oxyacetylene flame. The evaporation of SiO₂ took away large amount of heat, which is also beneficial to the protection for SiC_f/SiO₂ composites.     

Phase transformation and mechanical properties of B2O3-doped cordierite derived from complex-alkoxide

Cordierite gel powders doped with up to 3 mol % B₂O₃ were prepared by the hydrolysis of an alkoxide complex. The effects of B₂O₃-doping on phase transformation were investigated for the purpose of preventing micro-cracking due to μ-α cordierite transformation. B₂O₃-doping retarded the crystallization from amorphous to μ-cordierite, and accelerated the crystallization of α-cordierite. High doping concentrations (e.g. 1.5 mol %) appeared to promote the direct formation of α-cordierite from the amorphous state. The development of microcracks due to the μ-α cordierite transformation was prevented by the modified crystallization characteristics. The flexural strengths of the sintered bodies reached 190 MPa. B₂O₃-doping also lowered the temperatures of densification and crystallization of α-cordierite to 850 and 950 °C, respectively. At the sintering temperatures of 1100 °C or above, however, glassy phase oozed out on to the surfaces and internal pores were formed in the sintered bodies, resulting in decreased flexural strength.     

Oxidation behavior of silicide coating on Ti3SiC2-based ceramic

A silicide coating was prepared on Ti₃SiC₂-based ceramic by pack cementation to improve the oxidation resistance of Ti₃SiC₂, which is a technologically important material for high temperature applications. The microstructure, phase composition and oxidation resistance of the coated sample were investigated. The results demonstrated that the silicide coating was mainly composed of TiSi₂ and SiC. A single layer of a mixture of SiO₂ and TiO₂ was formed on the surface of the coated sample during isothermal oxidation at 1100 °C and 1200 °C for 20h. Compared to Ti₃SiC₂, the parabolic rate constant of silicide coated Ti₃SiC₂ decreased by 2~3 orders of magnitude. Furthermore, the coated sample showed much better cyclic oxidation resistance than Ti₃SiC₂ during the cyclic oxidation at 1100 °C for 400 times. However, during the preparation of the coating, a number of fine cracks formed in the outer layer of the coating. When these cracks penetrated the whole coating during the cyclic oxidation, the oxidation rate was accelerated, which degraded the oxidation resistance. Electronic Publication     

Oxidation behaviour of SiC-platelets and particulates-reinforced Al2O3/ZrO2 matrix composites

The oxidation behavior of hot-pressed SiC-platelets and particulates-reinforced Al₂O₃/ZrO₂ composites has been studied in an electric furnace at atmospheric pressure at different temperatures. The mass gain as a result of transformation of SiC into SiO₂ is described as a function of oxidation temperature, time and type of SiC. The mass gain up to 1100°C was low, but increased strongly at 1350°C. The oxidation process follows a parabolic rate at all oxidation temperatures. Oxidation of composites containing SiC-particulates is higher than the corresponding one containing SiC-platelets. The activation energy, obtained in the present investigation, was 297–333 kj/mol. Diffusion of oxygen and carbon monoxide through the matrix and oxide products appeared to be the rate controlling process. The reaction products were aluminosilicate glass phase and mullite as indicated by SEM and EDX.     

Pressureless sintering of Si3N4 with Y2O2 and Al2O3

Pressureless sintering of Si₃N₄ with Y₂O₃ and Al₂O₃ as additives was carried out at 1750°C in N₂ atmosphere. Si₃N₄ materials which had more than 92% relative density were obtained with 20wt% addition of additives. The flexural strength of as-sintered materials containing 5 to 8.6wt% Al₂O₃ and 15 to 11.4wt% Y₂O₃ was in the range of 480 to 560 MPa at room temperature. The glassy grain-boundary phase of as-sintered materials crystallized to 3Y₂O₃ · 5Al₂O₃ (YAG), Y₂O₃ · SiO₂ (YS), Y₂O₃ · 2SiO₂ (Y2S) and 10Y₂O₃ · 9SiO₂ sd Si₃N₄ (NA) by heat-treatment at 1250° C for 3 days. A specimen containing 15wt% Y₂O₃ and 5wt% Al₂O₃ sintered at 1750° C for 4 h was heat-treated at 1250° C for 3 days to precipitate YAG and YS. The nitrogen concentration of the grain-boundary glassy phase of the specimen was found to be very high, and therefore the flexural strength of the crystallized specimen scarcely decreased at elevated temperatures (the flexural strength of this specimen is 390 MPa at room temperature and 360 MPa at 1300° C). Resistance to oxidation at 1200° C of the specimen was good as well as the flexural strength, compared with that of as-sintered materials.     

Effects of water vapor on corrosion behaviors of C/SiC in oxidizing atmosphere containing Na2SO4 vapor

Corrosion of a C/SiC composite has been investigated in the atmosphere containing oxygen, water vapor and sodium sulfate vapor at the temperatures range from 1000 to 1500 °C. The effect of water vapor on the corrosion mechanism of C/SiC were discussed based on the weight change, the residual strength change, the microstructure and calculated results from FactSage. The corrosion of C/SiC is attributed to (i) the permeation of gas through the SiO₂ film below 1300 °C, (ii) the diffusion of oxidant through pores caused by bubbles broken in the SiO₂ film above 1300 °C. The water vapor does not change the corrosion mechanism of C/SiC composite but the temperature range in which the corrosion mechanism works by accelerating the oxidation of SiC and the corrosion of SiO₂.     

Effects of water vapor on corrosion behaviors of C/SiC in oxidizing atmosphere containing Na2SO4 vapor

Corrosion of a C/SiC composite has been investigated in the atmosphere containing oxygen, water vapor and sodium sulfate vapor at the temperatures range from 1000 to 1500 °C. The effect of water vapor on the corrosion mechanism of C/SiC were discussed based on the weight change, the residual strength change, the microstructure and calculated results from FactSage. The corrosion of C/SiC is attributed to (i) the permeation of gas through the SiO₂ film below 1300 °C, (ii) the diffusion of oxidant through pores caused by bubbles broken in the SiO₂ film above 1300 °C. The water vapor does not change the corrosion mechanism of C/SiC composite but the temperature range in which the corrosion mechanism works by accelerating the oxidation of SiC and the corrosion of SiO₂.     

Preparation of mullite bonded porous SiC ceramics by an infiltration method

A powder compact of α-SiC and α-Al₂O₃ was infiltrated with a liquid precursor of SiO₂, which on subsequent heat treatment at 1500 °C produced a mullite bonded porous SiC ceramics. Results showed that infiltration rate could be estimated by using weight gain measurements and theoretical analysis. The bond phase was composed of needle-shaped mullite which was observed to be grown from a siliceous melt formed during the process of oxide bonding. The porous SiC ceramics exhibited a density and porosity of 2 g cm⁻³ and 30 vol%, respectively, and also a pore size distribution in a range of 2–15 μm with an average pore size of 5 μm. No appreciable degradation of room temperature flexural strength (51 MPa) was observed at high temperatures (1100 °C).     

Oxidation barriers on SiC particles for use in aluminium matrix composites manufactured by casting route: Mechanisms of interfacial protection

This paper is centred on a study of the interface reaction mechanisms which participate in the fabrication of an aluminium-SiC composite by a casting route, when reinforcements (particles, in this case) have been previously coated by oxidation with a SiO₂ layer. The studies, which were carried out using transmission electron microscopy and differential scanning calorimetry, made it possible to propose a model of action of the SiO₂ barrier in relation to the coating thickness and the reaction time. The first reaction that occurred in this SiC-SiO₂-molten Al system was the formation of an Al-Si-O glassy phase which progressively consumed the SiO₂ barrier, reducing the matrix-particle interface energy and favouring wetting of the SiC surfaces. When the oxidation coating was completely consumed, the SiC was preferentially dissolved by the glassy phase, inside which the formation of amorphous carbon was detected. These studies also show that carbon enrichment of the reaction layer activated the precipitation of metallic impurities (such as Fe or Cu) in the reaction. Longer reaction times (8 h) could also favour crystallization of the glassy phase to form mullite and the formation of microcrystalline alumina at the reaction interface.     

Oxidation Protective Multilayer CVD SiC Coatings Modified by a Graphitic B-C Interlayer for 3D C/SiC Composite

A layered graphitic CVD B-C coating was introduced between two CVD SiC coating layers. Microstructure and chemical characterization of the CVD B-C and the hybrid SiC/B-C/SiC multilayer coating was performed using SEM, EDS, XPS and XRD. Oxidation protection ability of the coating for the C/SiC composite was studied using a thermogravimetric analyzer (TGA) in the isothermal mode and by measuring residual flexural strength. The layered graphitic CVD B-C coating middle layer reduced the maximum crack width in the CVD SiC coating. The hybrid SiC/B-C/SiC multilayer coating provided a better oxidation protection for C/SiC composite than a three layer CVD SiC coating due to coating crack control and sealing effects at temperatures up to 1,300°C for 900 min.     

Oxidation of SiC-ZrO2 composites

Planar silicon carbide-zirconium oxide composites were oxidized at temperatures between 910 and 1050 °C in oxygen, argon and CO-CO₂ atmospheres. In addition, bare SiC substrates were oxidized in oxygen. The bare substrates showed parabolic oxidation kinetics. The oxidation kinetics of the composites were more difficult to interpret because of the solid state reaction between the ZrO₂ and the SiO₂, but were approximately parabolic.     

涂敷含硼硅玻璃SiC涂层的C/SiC复合材料空气氧化行为

以2D C/SiC复合材料为基底, 采用聚合物裂解工艺(Polymer plyen)制备了含硼硅玻璃SiC自愈合涂层。利用扫描电镜对含硼硅玻璃SiC涂层的2D C/SiC复合材料氧化前后的微结构形貌进行了分析。研究了含硼硅玻璃SiC涂层的C/SiC复合材料在静态空气中700℃、 1000℃和1200℃下的氧化行为, 并分析了涂层层数对C/SiC复合材料氧化行为的影响。结果表明: 含硼硅玻璃SiC涂层在该温度下形成的玻璃相可以较好地封填表面缺陷(裂纹和孔洞); 并且随温度升高及涂层层数增加, 试样在氧化过程中质量减少率降低, 氧化后的强度保持率提高。      

Effect of the La<Subscript>2</Subscript>O<Subscript>3</Subscript> sol–gel coating on the alumina scale adherence on a model Fe–20Cr–5Al alloy at 1100 °C

The effect of lanthanum sol–gel coatings was studied in order to improve the alumina scale adherence during the model Fe–20Cr–5Al alloy oxidation, at 1100 °C, in air. Various sol–gel coating procedures were applied. Argon annealing of the lanthanum sol–gel coating was tested at temperatures ranging between 600 and 1000 °C. The coating crystallographic nature was characterized by X-ray diffraction (XRD) depending on the annealing temperature. The oxidation process has been examined at 1100 °C by in situ XRD on blank Fe–20Cr–5Al, sol–gel coated and argon-annealed specimens. This study shows that the coating argon annealing at 1000 °C leads to the preferential formation of LaAlO₃ instead of La₂O₃. This coating procedure leads to an alumina scale formation showing the best adherence under thermal cycling conditions at 1100 °C.     

The effect of high-temperature heat-treatment on the strength of C/C–SiC joints

Joining of carbon fiber reinforced C–SiC dual matrix composite (denoted by C/C–SiC) is critical for its aeronautical and astronautical applications. Joining of C/C–SiC has been realized through a reaction joining process using boron-modified phenolic resin with micro-size B₄C and nano-size SiO₂ powder additives. The effect of the heat-treatment temperature on the retained strength of the joints, calculated by dividing the strength of the heat-treated joints by the strength of the joints before heat-treatment, was studied. The maximum retained strength of the joints is as high as 96.0% after the heat-treatment at 1200 °C for 30 min in vacuum, indicating good heat resistance of the joints. The thickness of the interlayer of the joint after the heat-treatment is about 18 μm and it is uniform and densified. There are no obvious cracks or pores at the interfaces. During the heat-treatment, carbon, oxygen, silicon, and boron diffuse at the interfacial area. The interlayer is composed of B₄C, SiO₂, glassy carbon, amorphous B₂O₃, and borosilicate glass. SiC appears in the interlayer of the joint heat-treated at 1400 °C for 30 min in vacuum. The addition of B₄C and SiO₂ powders contributes to the densification of the interlayer, the bonding at the interfaces and the heat resistance of the joints.     

The anti-oxidation behavior and infrared emissivity property of SiC/ZrSiO4–SiO2 coating

In order to improve the oxidation resistance and decrease the infrared emissivity of carbon/carbon(C/C) composites, the SiC and SiC/ZrSiO₄–SiO₂ (SZS) coating were prepared by pack cementation and slurry painting method. The phase compositions and microstructures of the as-prepared coatings were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive spectrometer. The anti-oxidation property, failure and infrared emissivity of single SiC coating and SZS coating were investigated. The results show that the weight loss of single SiC coated sample reached 2.1 ± 0.025 % after 58 h isothermal oxidation at 1,500 °C. While the SZS coating exhibits superior oxidation resistance and can protect C/C matrix from oxidation for more than 198 h with a weight-gain of 3.67 ± 0.025 %. The failure mechanisms of single SiC coating are mainly resulting from unself-healing defects caused by the CO₂ gas which generated during the oxidation process of SiC. The investigation of infrared emissivity property reveals that, the infrared emissivity of SZS coating increases gradually from 0.45 to 0.72 between 3 and 14 μm. The infrared emissivity at 500 °C increases gradually from 0.2 to 0.65 between 3 and 14 μm. The coupled effect between dipole moments and lattice vibration in higher temperature becomes weaker, which in turn lead to the reducing of infrared emissivity in turn. From the anti-oxidation and infrared emissivity property point of view, the SZS coating may be one of the most promising candidates for the anti-oxidation at high temperature and low infrared emissivity of C/C composite.     

XPS Studies on the Oxidation Behavior of SiC Particles

An X-ray photoelectron spectroscopic study has been carried out on both oxidized and as-received SiC specimens. Oxidation of SiC was performed in the temperature range 900-1100°C. It has been observed that a native oxide layer of silicon (SiO₂) exists on the surface of as-received SiC particles and that static oxidation of SiC increases the thickness of this oxide layer. It has also been observed that at a given temperature SiC particle surfaces are oxidized to a greater extent as the time of oxidation is increased. Chemical states are identified from the measured values of Auger parameters. Specimens studied were found to contain extraneous carbon in addition to carbide carbon.