Oxidation behavior of silicon carbide at 1200 °C in both air and water–vapor-rich environments

Oxidation of SiC in both air and water–vapor–rich environments was carried out at 1200 °C to examine the effects of different oxidation conditions on the early-stage oxidation behavior of SiC. Two different types of SiC oxidation behavior were found, passive or active, depending on the oxidation environment. All the samples possessed amorphous oxide layers, regardless of the oxidation environment. Three Si oxidation states (SiO, Si₂O₃, and SiO₂) were observed in this layer. The amorphous Si₂O₃ state was dominant, and the ratio of the three different states changed with the test conditions.     

Active Oxidation of SiC

Silicon carbide (SiC) forms a protective condensed-phase oxide (SiO₂) in passive oxidation and a volatile sub-oxide (SiO(g)) in active oxidation. The transition between these two modes of oxidation and the rates of active oxidation are critical issues. A literature review indicates that impurity effects, the difference between active-to-passive and passive-to-active transitions, and the effect of total pressure on these transitions remain unexplored for SiC. Measurements were made in a thermogravimetric apparatus (TGA) by changing oxygen potentials either by blending O₂/Ar mixtures or changing total pressures in a pure oxygen gas stream to the point where a transition occurs. Specimens were examined with standard optical and electron-optical techniques. Active-to-passive and passive-to-active transitions were measured and found to be similar for SiC, which is in contrast to pure Si. The similarity in SiC is attributed to SiC/SiO₂ interfacial reactions producing the necessary conditions for passive scale formation (active-to-passive) or passive scale breakdown (passive-to-active). Comparable results were obtained in both the O₂/Ar and reduced total O₂ pressure cases for SiC.     

ZrB2–SiC(Al) ceramics with high resistance to oxidation at 1500 °C

In this paper, we study the oxidation behaviour of a ZrB₂/Al-doped SiC composite at 1500 °C. The composite was prepared by hot-pressing the mixture of ZrB₂ and polymer-derived SiC(Al). The oxidation behaviour was studied by measuring the weight change as a function of oxidation time and by observing the structure of the oxide layer. It is shown that the ZrB₂–SiC(Al) exhibits different oxidation behaviour and improved oxidation resistance as compared to the conventional ZrB₂–SiC without Al-doping. The improvement in oxidation resistance is attributed to that Al-doping could increase the bond strength of the Si–O and suppress the active oxidation of SiC.     

ZrSiO4 Oxidation Protective Coating for SiC-Coated Carbon/Carbon Composites Prepared by Supersonic Plasma Spraying

To protect carbon/carbon (C/C) composites against oxidation, ZrSiO₄ oxidation protective coating was prepared on SiC-coated C/C composites by supersonic plasma spraying. X-ray diffraction and scanning electron microscopy were used to analyze the phase and microstructure of the coating. The results show that the as-prepared ZrSiO₄ coating is continuous and well bonded with the SiC inner layer without penetrating crack, which exhibits good oxidation-resistant properties. After oxidation at 1773 K in air for 97 h and nine thermal shock cycles between 1773 K and room temperature, the weight loss of the coated C/C composites was only 0.08%. The excellent oxidation-resistant properties of the coating were attributed to its dense structure and the formation of the stable ZrO₂-SiO₂ glassy mixture on the surface of ZrSiO₄ coating.     

Air oxidation of SiC fibers prepared from carbon fibers and SiO vapor

Activated carbon fiber composite (ACFC) was reacted with SiO vapor to prepare SiC fibers containing nanopores. The SiC fibers obtained were not oxidation resistant, showing nearly complete oxidation at 1000°C after about 25 hr in air, though the oxidation product was amorphous silica which was generally considered to be oxidation resistant. The poor oxidation resistance was attributed to highly porous, amorphous SiO₂ formation on the inherently highly porous SiC fibers. Interconnected micropores inside the fibers rendered the fibers easily oxidizable.     

C/SiC/MoSi2–SiC–Si multilayer coating for oxidation protection of carbon/carbon composites

C/SiC/MoSi₂–SiC–Si oxidation protective multilayer coating for carbon/carbon (C/C) composites was prepared by pack cementation and slurry method. The microstructure, element distribution and phase composition of the as-received coating were analyzed by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The results show that the multilayer coating was composed of MoSi₂, SiC and Si. It could effectively protect C/C composites against oxidation for 200 h with the mass loss of 3.25% at 1873 K in static air. The mass loss of the coated C/C composites results from the volatilization of SiO₂ and the formation of cracks and bubble holes in the coating.     

Self-diffusion and impurity diffusion in silicon dioxide

We present experimental and simulation results of silicon (Si) self-diffusion and boron (B) diffusion in silicon dioxide (SiO₂), and examine the effect of nitrogen (N) on diffusion in SiO₂. To elucidate the point defect that mainly governs the diffusion in SiO₂, the diffusion of implanted ³⁰Si in thermally grown ²⁸SiO₂ is investigated. The experimental results show that Si self-diffusivity increases with decreasing distance between the ³⁰Si and Si-SiO₂ interface. We propose a model in which SiO molecules generated at the interface and diffusing into SiO₂ enhance Si self-diffusion, and the simulation results fit the experimental results. The B diffusivity also increases with decreasing the distance, which indicates that B diffusion is enhanced by SiO. In addition, we investigate the effects of B and N on SiO diffusion in SiO₂. We show that the existence of B increases SiO diffusivity and hence decreases the viscosity of SiO₂. On the other hand, the incorporation of N decreases SiO diffusivity, which reduces B diffusion in SiO₂ and increases the viscosity.     

A MoSi2/SiC oxidation protective coating for carbon/carbon composites

To protect carbon/carbon (C/C) composites against oxidation, a MoSi₂ outer coating was prepared on pack-cementation SiC coated C/C composites by a hydrothermal electrophoretic deposition. The phase composition, microstructure and oxidation resistance of the prepared MoSi₂/SiC coatings were investigated. Results show that hydrothermal electrophoretic deposition is an effective route to achieve crack-free MoSi₂ outer coatings. The MoSi₂/SiC coating can protect C/C composites from oxidation at 1773 K for 346 h with a weight loss of 2.49 mg cm⁻² and at 1903 K for 88 h with a weight loss of 5.68 mg cm⁻².     

Isothermal oxidation of Zr2[Al(Si)]4C5–SiC composites at 1000–1300 °C in air

The effect of SiC on the oxidation performance of Zr₂[Al(Si)]₄C₅–SiC composites at 1000–1300 °C was explored. The present results demonstrated that scale growth on Zr₂[Al(Si)]₄C₅ ceramics obeyed a nearly linear rate law during oxidation, while the oxidation rate of Zr₂[Al(Si)]₄C₅–20SiC ceramics obeyed a nearly parabolic law, increasing rapidly during the initial stages of the reaction and then becoming slower. The oxidation resistance of Zr₂[Al(Si)]₄C₅–20SiC was improved remarkably; this was likely due to the formation of more protective oxide scales on the ceramic consisting of viscid aluminosilicate glass.     

Oxidation protection of C/SiC coated carbon/carbon composites with Si–Mo coating at high temperature

To protect carbon/carbon (C/C) composites against oxidation, a Si–Mo coating was prepared on C/SiC-coated C/C composites by a simple slurry method. The microstructure of the coating was characterized by X-ray diffraction, scanning electron microscopy and Raman spectra. Results showed that the coating was mainly composed of SiC, MoSi₂ and Si. It could protect C/C composites from oxidation at 1873 K in air for 300 h and withstand 13 thermal cycles between room temperature and 1873 K. The excellent oxidation and thermal shock resistance of the coating was attributed to the formation of dense SiO₂ glass at high temperature. The volatilization of MoO₃ and SiO₂ at 1873 K was the main reason of the weight loss of the coated C/C composites.     

钼合金Si-Cr-Ti-SiC-MnO2涂层的制备与组织性能

目的提高钼合金表面红外辐射性能与高温抗氧化性能。方法将40%Si、20%Cr、5%Ti、5%SiC、30%Mn O_2五种粉末与酒精、粘结剂按比例混合,经高能球磨6 h后制得均匀悬浮的料浆。采用浸涂工艺对预处理的钼合金试样进行料浆涂覆,在1450℃真空烧结0.5 h后制得黑色涂层试样。通过1550℃高温静态氧化试验和高温粒子薄片红外光谱综合实验系统,分别评价涂层抗氧化性能和红外辐射性能,并通过扫描电镜(SEM)、能谱分析(EDS)、X射线衍射仪(XRD)对涂层氧化前后的形貌与组织结构进行分析。结果钼合金Si-Cr-Ti-SiC-Mn O_2涂层在700、900℃的法向发射率分别达0.85、0.88,在1550℃高温有氧环境下的静态抗氧化寿命达7 h。原始涂层呈四层复合梯度结构,由外到内分别为SiO_2+Mn3O_4+M5Si3(M指Mo、Cr、Ti)、M5Si3+Mo Si2+SiC+Mn3O_4、Mo Si2、Mo5Si3。高温氧化后,涂层四层复合结构由外到内转变为SiO_2+(Cr,Ti)5Si3+Mn Cr2O_4+Mn3O_4、M5Si3+SiC+Mn Cr2O_4+Mn3O_4、Mo Si2、M5Si3。高温氧化过程中,MSi2高硅化物层逐渐转变为M5Si3低硅化物层,涂层表面形成含Mn Cr2O_4尖晶石相和复合硅化物的致密SiO_2玻璃膜。结论 Si-Cr-Ti-SiC-Mn O_2涂层可有效提高钼合金基体的红外辐射性能和高温抗氧化性能,复合硅化物与硅锰复杂氧化物具有良好的抗氧化性能、高辐射性能和自愈合性能。     

A MoSi2-SiC-Si oxidation protective coating for carbon/carbon composites

To protect carbon/carbon (C/C) composites from oxidation, a dense coating has been produced by a two-step pack cementation technique. XRD and SEM analysis shows that the as-obtained coating was composed of MoSi₂, SiC and Si with a thickness of 80-100 μm. The MoSi₂-SiC-Si coating has excellent anti-oxidation property, which can protect C/C composites from oxidation at 1773 K in air for 200 h and the corresponding weight loss is only 1.04%. The weight loss of the coated C/C composites is primarily due to the reaction of C/C substrate and oxygen diffusing through the penetration cracks in the coating.     

Microstructure and mechanical properties of ZrB2–SiC ultrahigh temperature ceramic composite joint using TiZrNiCu filler metal

Abstract

ZrB₂–SiC ceramic composite was brazed by using TiZrNiCu active filler metal. The microstructure and interfacial phenomena of the joints were analysed by means of SEM, energy dispersive X-ray spectroscopy and X-ray diffraction. The joining effect was evaluated by shear strength. The results showed that the reaction products of the ZrB₂–SiC ceramic composite joint were TiC, ZrC, Ti₅Si₃, Zr₂Si, Zr(s,s) and (Ti, Zr)₂ (Ni, Cu), and the microstructure was separately ZrB₂–SiC/Zr(s,s)/Ti₅Si₃+Zr₂Si+TiC+ZrC+(Ti,Zr)₂(Ni,Cu)/Zr(s,s)/ZrB₂–SiC. A conceptual interface evolution model was established to explain the interface evolution mechanism. The maximum shear strength of the brazed joints was 143·5 MPa at the brazing temperature T of 920°C and the holding time t of 10 min.     

金属钼表面Mo-C-N-Si涂层的制备及其高温氧化特性

在金属钼表面制备了Mo-C-N-Si涂层,研究了涂层在1600℃大气环境下的氧化特性,采用SEM和XRD分析了涂层的微观结构和物相组成。结果表明:Mo-C-N-Si涂层以MoSi2为主相,SiC和Si3N4为次相,存在Mo2C+MoxN中间层;由于扩散和氧化反应,涂层在氧化初期形成SiO2氧化膜层、MoSi2主体层、Mo5Si3层和Mo2C+MoxN层等四层结构,氧化后期转变为Mo2C+MoxN层和Mo3Si+Mo5Si3层的双层结构,导致涂层失效。由于C、N的引入,涂层抗热震性能良好。     

Si-W-Mo coating for SiC coated carbon/carbon composites against oxidation

In order to prevent carbon/carbon (C/C) composites from oxidation at 1773 K, a Si-W-Mo coating was prepared on the surface of SiC coated C/C composites by a simple pack cementation technique. The microstructures and phase composition of the as-received multi-coating were examined by SEM, XRD and EDS. It was seen that the compact multi-coating was composed of α-SiC, Si and (W_xMo_1 − x)Si_2. Oxidation behaviour of the SiC/Si-W-Mo coated C/C composites was also studied. After 315 h oxidation in air at 1773 K and thermal cycling between 1773 K and room temperature for 17times, no weight loss of the as-coated C/C composites was measured. The excellent anti-oxidation ability of the multi-coating is attributed to its dense structure and the formation of the stable glassy SiO₂ film on the coating surface during oxidation.     

Oxidation behavior of magnetron sputtered double layer coatings containing molybdenum,silicon and boron

Protective coating systems were applied to Mo–9Si–8B (at.%) alloys to prevent oxidation at elevated temperatures. The coatings produced by magnetron sputtering and subsequent annealing consisted of an outer oxidation protection layer and an interlayer between this and the substrate. Three amorphous outer layers with different compositions were deposited: Mo–45Si–25B, Mo–55Si–10B and Mo–29Si–15B (all in at.%). The interlayer was selected to give a diffusion barrier with the composition of the Mo₅SiB₂ (T2) phase. All coatings were dense and well-adherent. During vacuum annealing the amorphous as-deposited coatings became crystalline exhibiting mainly the intermetallic Mo₅SiB₂ compound as interlayer and the MoSi₂, Mo₅Si₃ and MoB phases in the top layers. The samples were exposed to dry laboratory air in the pesting regime at 800 °C and above, i.e. at 1000 and 1300 °C for up to 100 h under cyclic conditions. All coatings were protective at 800 and 1000 °C for at least 100 h and showed a marked improvement in mass change compared to the uncoated substrate. For protection at 800 °C higher boron content is preferential, while at higher oxidation temperatures a lower boron content provides improved oxidation protection. At 1300 °C stress induced failures like cracking, spallation and buckling occurred due to the relatively high CTE mismatch between PVD coating and substrate. Even though, the mass change was still markedly reduced as compared to the bare substrate.     

The individual effects of niobium and silicon on the oxidation behaviour of Ti3Al based alloys

The oxidation kinetics of the Ti₃Al based alloys with Nb (0 to 20 at%) or Si (0 to 15 at%) addition was carefully measured at 800 and 900°C, respectively. The oxide scale was characterised by high temperature in-situ XRD, SEM, EPMA and conventional XRD. The weight gains of the alloys were greatly reduced by Nb or Si addition. The improvement of the oxidation resistance in the Ti₃Al alloys by Nb addition is attributed to the formation of a compact scale. The formation of a compact scale is favoured not only by doping effect but also by the TiN layer which barriers the outward Al diffusion into the scale to form porous intermixed titania/alumina. Si addition promotes the formation of a compact TiO₂ layer in the oxide scale and the formation of SiO₂, thus the oxidation resistance of the Ti₃Al based alloys is improved. The oxidation behaviour of the alloys with Si addition is a combinative function of the α₂-Ti₃Al matrix and the Ti₅Si₃ silicide phase.     

The thermal stability in air of hot-pressed diboride matrix composites for uses at ultra-high temperatures

The resistance to oxidation in ambient air at a temperature up to 1600 °C of two hot-pressed diborides matrix composites, both containing 19.5% v/o SiC and 3 v/o HfN (as sintering aid), was investigated. The diboride matrix was based on HfB₂ or a ZrB₂/HfB₂ mixture (volume ratio ≈ 1). Both the materials were subjected to repeated heating-cooling cycles at 1600 °C, and a 20 h exposure at 1450 °C in flowing dry air. Modest weight gains and limited corrosion depths highlighted a rather good thermal stability. In accordance with the thermo-gravimetric test at 1450 °C, the oxidation kinetics for both the composites superbly fit a para-linear law. The introduction of the SiC particles provided tangible benefits for the resistance to oxidation. One of the oxidation products, a borosilicate glass, sealed pores and coated the exposed faces, greatly limiting the inward transport of oxygen towards the internal oxide/diboride interfaces.     

Direct bonding of silicon paris with heterogeneous insulator using different annealing methods

We prepared SOI (silicon-on-insulator) wafer pairs of 2000 Å-SiO₂/Si(100) and 560 å-Si₃N₄/Si(100) by CFA (Conventional electric Fumace Annealing), RTA (Rapid Thermal Annealing), and FLA (Fast Linear Annealing) at different annealing temperatures for each annealing process. We measured the bonding area and the bonding strength for the respective processes. It was demonstrated that the measured bonding area was close to 100% above 450°C for RTA, and 400°C for CFA. The maximum bond strength of the SiO₂/Si₃N₄ wafer pair was 2344, 2300, and 195 mJ/m² for CFA, FLA, and RTA, respectively. We clearly demonstrated that the FLA method is far superior in producing high-quality directly bonded Si wafer pairs with SiO₂ and Si₃N₄films compared to the CFA and RTA methods.     

Fabrication of Y2Si2O7 coating and its oxidation protection for C/SiC composites

Yttrium silicate (Y₂Si₂O₇) coating was fabricated on C/SiC composites through dip-coating with silicone resin + Y₂O₃ powder slurry as raw materials. The synthesis, microstructure and oxidation resistance and the anti-oxidation mechanism of Y₂Si₂O₇ coating were in–estigated. Y₂Si₂O₇ can be synthesized by the pyrolysis of Y₂O₃ powder filled silicone resin at mass ratio of 54.2:45.8 and 800 °C in air and then heat treated at 1400 °C under Ar. The as-fabricated coating shows high density and fa–orable bonding to C/SiC composites. After oxidation in air at 1400, 1500 and 1600 °C for 30 min, the coating-containing composites possess 130%–140% of original flexural strength. The desirable thermal stability and the further densification of coating during oxidation are responsible for the excellent oxidation resistance. In addition, the formation of eutectic Y–Si–Al–O glassy phase between Y₂Si₂O₇ and Al₂O₃ sample bracket at 1500 °C is disco–ered.