Oxidation protection of C/C composites with a multilayer coating of SiC and Si + SiC + SiC nanowires

An oxidation protective Si–SiC coating with randomly oriented SiC nanowires was prepared on the SiC-coated carbon/carbon (C/C) composites by a two-step technique. First, a porous network of SiC nanowires was produced using chemical vapor deposition. This material was subjected to pack cementation to infiltrate the porous layer with a mixture of Si and SiC. The nanowires in the coating could efficiently suppress the cracking of the coating by various toughening mechanisms including nanowire pullout, nanowire bridging, microcrack deflection and good interaction between nanowire/matrix interface. The results of thermogravimetric analysis and thermal shock showed that the coating had excellent oxidation protection for C/C composites between room temperature and 1500 °C. These results were confirmed by two additional oxidation experiments conducted at temperature of 900 and 1400 °C, which demonstrated that the coating could efficiently protect C/C composites from oxidation at 900 °C for more than 313 h or at 1400 °C for more than 112 h.     

The resistance to oxidation of an HfB2–SiC composite

The oxidation resistance of an hot-pressed HfB₂–SiC composite was studied through non-isothermal and isothermal treatments at temperatures up to 1600 °C in air. The most severe oxidation conditions consisted of repeated heating-cooling cycles at 1600 °C for up to 80 min of exposure. A thermogravimetric test for over 20 h at 1450 °C provided evidence that, at this temperature, the oxidation kinetics fits a paralinear law until 10 h, when a partial rupture of external oxide scale occurs (i.e. a break-away reaction). Afterwards, the weight gain data fit a linear law. The main secondary phases formed in the composite during hot-pressing, namely BN, Hf(C,N) and a Si-based compound, although in limited amounts, influenced the oxidation resistance at temperatures below 1350 °C. At temperatures higher than about 1400 °C, the presence of SiC particles markedly improved the oxidation resistance due to the formation of a protective borosilicate glassy coating on the exposed surfaces.     

Processing and properties of glass-bonded silicon carbide membrane supports

Porous SiC membrane supports were fabricated from SiC and glass frit at a temperature as low as 850 °C in air by a simple pressing and heat-treatment process. The effects of the initial SiC particle size and frit content on the porosity, flexural strength, and air permeation of the membrane supports were investigated. During heat-treatment, the glass frit transformed to a viscous glass phase, which acted as a bonding material between SiC particles and as a protecting layer for severe oxidation of SiC particles. The porosity of the porous SiC membrane supports could be controlled within a range of 37–46% with the present set of processing conditions. The typical flexural strength, permeability, and specific air flow rate of the porous membrane supports fabricated using 23 μm SiC particles with 15 wt% glass frit were 75 MPa, 4.2 × 10⁻¹³ m², and 32.4 L/min/cm², respectively.     

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.     

TaB2–SiC–Si multiphase oxidation protective coating for SiC-coated carbon/carbon composites

To improve the oxidation resistance of the carbon/carbon (C/C) composites, a TaB₂–SiC–Si multiphase oxidation protective ceramic coating was prepared on the surface of SiC coated C/C composites by pack cementation. Results showed that the outer multiphase coating was mainly composed of TaB₂, SiC and Si. The multilayer coating is about 200 μm in thickness, which has no penetration crack or big hole. The coating could protect C/C from oxidation for 300 h with only 0.26 × 10^?2 g²/cm² mass loss at 1773 K in air. The formed silicate glass layer containing SiO₂ and tantalum oxides can not only seal the defects in the coating, but also reduce oxygen diffusion rates, thus improving the oxidation resistance.     

Preparation of antireflective SiO2 nanometric films

Antireflective nanometric SiO₂ films were formed on glass substrates by dip coating from a colloidal SiO₂ sol having an average particle size of 9 nm. Withdrawal speed of dip coating was varied between 100 and 200 mm/min with 25 mm increments, and baking temperature of the films was altered between 300 and 550 °C with 50 °C increments. Obtained SiO₂ films were in 80–200 nm thickness range. Film thickness was seen to increase with increasing withdrawal speed and to decrease with increasing baking temperature. A maximum light transmittance of 95% was obtained with 4.5% points increase, from the films which were withdrawn at 100 mm/min and baked at 450 or 500 °C. It was seen from SEM observations that the films exhibited full coverage on glass surface and contained no voids or cracks. Size of SiO₂ particles in the film was seen in the AFM analyses to increase with baking temperature. Sintering of SiO₂ particles appeared to accelerate at temperatures over 450 °C.     

Development of microstructure during creep of polycrystalline mullite and a nanocomposite mullite/5 vol.% SiC

The microstructures of as-sintered and creep tested polycrystalline mullite and mullite reinforced with 5 vol.% nano-sized SiC particles have been characterized by scanning and transmission electron microscopy. The dislocation densities after tensile creep testing at 1300 and 1400 °C were virtually unchanged as compared to the as-sintered materials which indicates diffusion-controlled deformation. Mullite matrix grain boundaries bending around intergranular SiC particles suggest that grain boundary pinning, in addition to a reduced mullite grain size, contributed to the increased creep resistance of the mullite/5 vol.% SiC nanocomposite. Both materials showed pronounced cavitation at multi-grain junctions after creep testing at 1400 °C which suggests that unaccommodated grain boundary sliding, facilitated by softening of the intergranular glass, occurred at this temperature. This is consistent with the higher stress exponents at 1400 °C.     

Oxidation protection of carbon/carbon composites with SiC/indialite coating for intermediate temperatures

In order to improve the oxidation resistance of carbon/carbon composites at intermediate temperatures, a novel double-layer SiC/indialite coating was prepared by a simple and low-cost method. The internal SiC transition layer was prepared by pack cementation and the external indialite glass–ceramic coating was produced by in situ crystallization of ternary MgO–Al₂O₃–SiO₂ glass. The microstructures and morphologies of coating were determined by scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS). Oxidation resistance of the as-coated C/C composites was evaluated in ambient air at temperature from 800 °C to 1200 °C. Nearly neglectable mass loss was measured after 100 h isothermal oxidation test, indicating that SiC/indialite coating possesses excellent oxidation protection ability. The as-coated samples have a good thermal shock resistance and no obvious damage was found in the coating even after suffered more than 11 thermal cycles between test temperature and room temperature. The oxidation protection mechanism of this coating was also discussed.     

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.     

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

To protect carbon/carbon (C/C) composites against oxidation, a mullite coating was prepared on SiC precoated C/C composites by a hydrothermal electrophoretic deposition process. The phase composition, microstructure and oxidation resistance of the prepared mullite/SiC coatings were investigated. Results show that hydrothermal electrophoretic deposition is an effective route to achieve crack-free mullite coatings. The mullite/SiC coating displays excellent oxidation resistance and can protect C/C composites from oxidation at 1773 K for 322 h with a weight loss rate of only 4.89 × 10^?4 g/cm² h. The failure of the multi-layer coatings is considered to be caused by the volatilization of silicate glass layer, the formation of microholes and microcracks on the coating surface and the formation of penetrative holes between the SiC bonding layer and the C/C matrix at 1773 K. The corresponding high temperature oxidation activation energy of the coated C/C composites at 1573–1773 K is calculated to be 111.11 kJ/mol.     

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.     

Structural characterization of plasma sprayed basalt–SiC glass–ceramic coatings

In the present study, the effect of SiC addition on properties of basalt base glass–ceramic coating was investigated. SiC reinforced glass–ceramic coating was realized by atmospheric air plasma spray coating technique on AISI 1040 steel pre-coated with Ni + 5 wt.%Al bond coat. Composite powder mixture consisted of 10%, 20% and 30% SiC by weight were used for coating treatment. Controlled heat treatment for crystallization was realized on pre-coated samples in argon atmosphere at 800 °C, 900 °C and 1000 °C which determined by differential thermal analysis for 1–4 h in order to obtain to the glass–ceramic structure. Microstructural examination showed that the coating performed by plasma spray coating treatment and crystallized was crack free, homogeneous in macro-scale and good bonded. The hardness of the coated samples changed between 666 ± 27 and 873 ± 32 HV_0.01 depending on SiC addition and crystallization temperature. The more the SiC addition and the higher the treatment temperature, the harder the basalt base SiC reinforced glass–ceramic coating became. X-ray diffraction analysis showed that the coatings include augeite [(CaFeMg)–SiO₃], diopside [Ca(Mg_0.15Fe_0.85)(SiO₃)₂], albite [(Na,Ca)Al(Si,Al)₃O₈], andesine [Na_0.499Ca_0.492(Al_1.488Si_2.506O₈] and moissanite (SiC) phases. EDX analyses support the X-ray diffraction analysis.     

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.     

Influence of silicon carbide particle size on the microstructure and mechanical properties of zirconium diboride–silicon carbide ceramics

The influence of silicon carbide (SiC) particle size on the microstructure and mechanical properties of zirconium diboride–silicon carbide (ZrB₂–SiC) ceramics was investigated. ZrB₂-based ceramics containing 30 vol.% SiC particles were prepared from four different α-SiC precursor powders with average particle sizes ranging from 0.45 to 10 μm. Examination of the dense ceramics showed that smaller starting SiC particle sizes led to improved densification, finer grain sizes, and higher strength. For example, ceramics prepared from SiC with the particle size of 10 μm had a strength of 389 MPa, but the strength increased to 909 MPa for ceramics prepared from SiC with a starting particle size of 0.45 μm. Analysis indicates that SiC particle size controls the strength of ZrB₂–SiC.     

Oxidation behavior of CVD star-shaped TiN coating in ambient air

Star-shaped 800-TiN and 850-TiN coatings were deposited on the surface of 310S stainless steel foils by CVD and their oxidation behavior was investigated in ambient air, from 300 °C to 800 °C for 1800 s by XRD, SEM, EDX and Raman spectroscopy. Initial oxidation of 850-TiN coating with a partial color change occurs at 350 °C, remarkable oxidation of 850-TiN coating occurring between 400 °C and 450 °C. The EDX results show that obvious oxidation of 850-TiN starts at 400 °C with about 9 at% oxygen detected; no N atoms could be detected while the O content reaching a maximum of ca. 70% at oxidation temperature above 700 °C. The XRD and Raman results show that only rutile-TiO₂ formed on the surface of oxidized TiN coating. The oxidation of star-shaped TiN coating can be divided into three stages. In the case of mild oxidation (below 500 °C), TiN coating can maintain the star-shaped microstructure although oxygen diffuses into the TiN lattice resulting in replacement of N by O atoms. For moderate oxidation (550–600 °C), the star-shaped microstructures start to crack along the (111) twin planes, and the boundary of particles remains clear with oxide and oxynitride layer coexisting on the surface of 850-TiN coating. For severe oxidation (650–750 °C), the cracks of the star-shaped microstructures start to expand and become apparent, meanwhile the boundary of particles become uncertain. After oxidizing at 800 °C, the 850-TiN coating will lose efficacy due to the bad spalling resistance.     

A SiC–Si–ZrB2 multiphase oxidation protective ceramic coating for SiC-coated carbon/carbon composites

In order to improve the oxidation protective ability of SiC-coated carbon/carbon (C/C) composites, a SiC–Si–ZrB₂ multiphase ceramic coating was prepared on the surface of SiC-coated C/C composite by the process of pack cementation. The microstructures of the coating were characterized using X-ray diffraction and scanning electron microscopy. The coating was found to be composed of SiC, Si and ZrB₂. The oxidation resistance of the coated specimens was investigated at 1773 K. The results show that the SiC–Si–ZrB₂ can protect C/C against oxidation at 1773 K for more than 386 h. The excellent oxidation protective performance is attributed to the integrity and stability of SiO₂ glass improved by the formation of ZrSiO₄ phase during oxidation. The coated specimens were given thermal shocks between 1773 K and room temperature for 20 times. After thermal shocks, the residual flexural strength of the coated C/C composites was decreased by 16.3%.     

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.     

Mechanical behavior of zirconium diboride–silicon carbide ceramics at elevated temperature in air

The mechanical properties of zirconium diboride–silicon carbide (ZrB₂–SiC) ceramics were characterized from room temperature up to 1600 °C in air. ZrB₂ containing nominally 30 vol% SiC was hot pressed to full density at 1950 °C using B₄C as a sintering aid. After hot pressing, the composition was determined to be 68.5 vol% ZrB₂, 29.5 vol% SiC, and 2.0 vol% B₄C using image analysis. The average ZrB₂ grain size was 1.9 μm. The average SiC particles size was 1.2 μm, but the SiC particles formed larger clusters. The room temperature flexural strength was 680 MPa and strength increased to 750 MPa at 800 °C. Strength decreased to ～360 MPa at 1500 °C and 1600 °C. The elastic modulus at room temperature was 510 GPa. Modulus decreased nearly linearly with temperature to 210 GPa at 1500 °C, with a more rapid decrease to 110 GPa at 1600 °C. The fracture toughness was 3.6 MPa·m^½ at room temperature, increased to 4.8 MPa·m^½ at 800 °C, and then decreased linearly to 3.3 MPa·m^½ at 1600 °C. The strength was controlled by the SiC cluster size up to 1000 °C, and oxidation damage above 1200 °C.     

Synthesis and characterization of titanium oxide nanotubes and its performance in epoxy nanocomposite coating

Titanium oxide nanotubes (TiO₂ nanotube, TNT) were prepared from hydrothermal treatment of TiO₂ particles in NaOH at 140 °C, followed by neutralization with HCl. The structure of the nanotubes was characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). TNT synthesized under the optimal conditions with approximately 10–20 nm wide, and several (100–200) of nanometers long. TNT is used as white pigment for two component epoxy-based coating. Ultrasonication followed by mechanical stirring has been applied for dispersion of TNT powder in an epoxy matrix. The resulting perfect dispersion of TNT particles in epoxy coating revealed by scanning electron microscopy (SEM) ensured white particles embedded in the epoxy matrix. The effects of TNT particle concentrations on thermal, mechanical and corrosion resistance of epoxy coatings composite were studied and compared to that of submicron particles. It was found that the TNT significantly enhances the heat resistance, the thermal stability and the glass transition temperature of epoxy resin. Epoxy/TNT nanocomposite with 5.0 wt.% TNT shows the highest thermal stability, the temperature of 50% weight loss increased from 365 to 378 °C, the amount of char yields or residues at 600 °C increased from 7.13 to 13.50 wt.%, respectively to 1.0 and 5.0 wt.% TNT. The glass transition temperature (Tg) increased from 182 to 220 °C too. The mechanical properties and corrosion resistance of epoxy resin greatly improved by using reinforcing TNT and this improvement increases with increase TNT wt.%.     

Processing and properties of cordierite-silica bonded porous SiC ceramics

Cordierite-silica bonded porous SiC ceramics were fabricated by infiltrating a porous powder compact of SiC with cordierite sol followed by sintering at 1300–1400 °C in air. The porosity, average pore diameter and flexural strength of the ceramics varied 30–36 vol%, ~ 4–22 µm and ~ 13–38 MPa respectively with variation of sintering temperature and SiC particle sizes. In the final ceramics SiC particles were bonded by the oxidation-derived SiO₂ and sol-gel derived cordierite. The corrosion behaviour of sintered SiC ceramics was studied in acidic and alkaline medium. The porous SiC ceramics were observed to exhibit better corrosion resistance in acid solution.