SiC nanowire-toughened MoSi2-SiC coating to protect carbon/carbon composites against oxidation

To protect carbon/carbon (C/C) composites against oxidation, a SiC nanowire-toughened MoSi₂-SiC coating was prepared on them using a two-step technique of chemical vapor deposition and pack cementation. SiC nanowires obtained by chemical vapor deposition were distributed random-orientedly on C/C substrates and MoSi₂-SiC was filled in the holes of SiC nanowire layer to form a dense coating. After introduction of SiC nanowires, the size of the cracks in MoSi₂-SiC coating decreased from 18 ± 2.3 to 6 ± 1.7 μm, and the weight loss of the coated C/C samples decreased from 4.53% to 1.78% after oxidation in air at 1500 °C for 110 h.     

Microstructural evolution of coating-modified 3D C/SiC composites after annealing in wet oxygen at different temperatures

Two types of coating-modified 3D C/SiC, coated with CVD SiC/SiC/SiC (type I) and CVD SiC/amorphous-BC/SiC (type II), are subjected to a 14 vol.% H₂O/8 vol.% O₂/78 vol.% Ar atmosphere at 700, 1000 and 1200 °C up to 100 h. Microstructure and corrosion behaviour are investigated using a variety of characterization techniques. The type II shows a better oxidation resistance than type I during annealing at relatively low temperatures. Nevertheless, residual strength of the type I annealed above 1000 °C is enhanced by healing of many micron-sized defects. Interfacial bond strength of the composites is reasonably improved after annealing.     

A ZrSiO4/SiC oxidation protective coating for carbon/carbon composites

In order to improve the oxidation resistance of carbon/carbon (C/C) composites, a ZrSiO₄ coating on SiC pre-coated C/C composites was prepared by a hydrothermal electrophoretic deposition process. Phase compositions and microstructures of the as-prepared ZrSiO₄/SiC coating were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The anti-oxidation property and failure mechanism of the multi-layer coating were investigated. Results show that hydrothermal electrophoretic deposition is an effective route to prepare crack-free ZrSiO₄ outer coatings. The multi-layer coating obviously exhibits two-layer structure. The inner layer is composed of SiC phase and the outer layer is composed of ZrSiO₄ phase. The bonding strength between the outer layer coatings and C/C–SiC substrate are 30.38 MPa. The ZrSiO₄/SiC coating displays excellent oxidation resistance and can protect C/C composites from oxidation at 1773 K for 332 h with a mass loss rate of only 0.48 × 10^− 4 g/cm²·h. The mechanical properties of the specimens are 84.36 MPa before oxidation and 68.29 MPa after oxidation. The corresponding high temperature oxidation activation energy of the coated C/C composites at 1573–1773 K is calculated to be 119.8 kJ/mol. The oxidation process is predominantly controlled by the diffusion rate of oxygen through the ZrSiO₄/SiC multi-coating. The failure of the coating is due to the formation of penetrative holes between the SiC bonding layer and the C/C matrix at 1773 K.     

Preparation and oxidation protection of CVD SiC/a-BC/SiC coatings for 3D C/SiC composites

An amorphous boron carbide (a-BC) coating was prepared by LPCVD process from BCl₃-CH₄-H₂-Ar system. XPS result showed that the boron concentration was 15.0 at.%, and carbon was 82.0 at.%. One third of boron was distributed to a bonding with carbon and 37.0 at.% was dissolved in graphite lattice. A multiple-layered structure of CVD SiC/a-BC/SiC was coated on 3D C/SiC composites. Oxidation tests were conducted at 700, 1000, and 1200 °C in 14 vol.% H₂O/8 vol.% O₂/78 vol.% Ar atmosphere up to 100 h. The 3D C/SiC composites with the modified coating system had a good oxidation resistance. This resulted in the high strength retained ratio of the composites even after the oxidation.     

Effect of ozone adsorption on the oxidation behaviour of ZrB2–SiC ceramic composites

Ceramics of ZrB₂–20 vol.% SiC were prepared by hot pressing method, and ozone (O₃) was adsorbed on the surface of the ceramics. Then the as-adsorbed ceramics were oxidized in air and the effect of ozone adsorption on the oxidation behaviour of the ceramic composites was analyzed. The experimental results indicate that adsorption of ozone promotes the oxidation of the ceramic composites, especially for the SiC. In addition, more silica glass formed promotes the formation and crystal growth of zircon.     

Mullite-gadolinium silicate environmental barrier coatings for melt infiltrated SiC/SiC composites

Slurry based mullite/gadolinium silicate (Gd₂SiO₅) environmental barrier coatings (EBCs) were developed for melt infiltrated (MI) SiC/SiC composites. The coating chemically adhered well on the substrates. Thermal cycling of uncoated MI-SiC/SiC composites conducted between 1350 °C and 90 °C (one hour hot and 15 min cold) in a 96.5% H₂O-3.5% O₂ environment caused severe oxidation damage after 100 cycles resulting in the formation of dense silica layer of about 25 μm maximum thickness. Mullite/Gd₂SiO₅ EBCs provided excellent protection to MI-SiC/SiC against moisture damage with significantly less oxidation of the substrate; only about a 2 μm thick oxide layer formed even after 400 similar thermal cycles. The hair-line cracks formed at the coating/substrate interface after 400 cycles causing partial coating de-lamination.     

SiC nanowire-toughened SiC-MoSi2-CrSi2 oxidation protective coating for carbon/carbon composites

To prevent carbon/carbon (C/C) composites from oxidation, a dense SiC nanowire-toughened SiC-MoSi₂-CrSi₂ multiphase coating was prepared by the two-step technique composed of chemical vapor deposition (CVD) and pack cementation. The coatings were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). SiC nanowires could decrease the dimension of cracks and improve the oxidation and thermal shock resistance of SiC-MoSi₂-CrSi₂ multiphase coating. Oxidation test shows that, after introducing SiC nanowires, the weight loss of the coated sample can be reduced from 1.06% to 0.64% after oxidation at 1773 K for 155 h and decreased from 6.92% to 3.42% after thermal cycling between 1773 K and room temperature for 30 times.     

(S)TEM study of different stages of Ti-45Al-8Nb-0.2W-0.2B-0.02Y alloy oxidation at 900 °C

The oxidation process of Ti-45Al-8Nb-0.2W-0.2B-0.02Y (at%) can be divided into three stages during 100 h at 900 °C. The change of ion diffusion path leads to the discontinuity of the oxidation curve between the second and third stage. Different stages of oxidation morphology have been investigated combined with TEM and STEM. AlNb₂ phase forms at the interface of oxide scale/base alloy. Contrary to a continuous formation of ‘x’ phase in γ-TiAl with Nb free at the interface of oxide scale/base alloy. AlNb₂ phase hinder continuous ‘x’ phase formation, which can promote TiAl oxidation protection.     

Oxidation mechanism and resistance of ZrB2–SiC composites

The oxidation mechanism of ZrB₂–SiC composites was investigated based on a combination of theory and experiments. The oxidation reactions, microstructure evolution, scale stability and temperature limit were examined in our research and a good correspondence was obtained between theoretical predictions and experimental results. Microstructure evolution and stability are significantly dependent on both temperature and composition. SiO₂ is thermochemically stable below 1800 °C and will lose its protective properties at temperatures above 2300 °C. The temperature limit for ZrB₂–SiC composites is strongly dependent on the vapor pressure of the gaseous products and volume content of ZrB₂.     

Microstructure and oxidation of multi-layer MoSi2-CrSi2-Si coatings for SiC coated carbon/carbon composites

Multi-layer MoSi₂-CrSi₂-Si anti-oxidation coatings with different compositional ratios were prepared on the surface of SiC coated carbon/carbon (C/C) composites by a two-step pack cementation method. The microstructure and anti-oxidation performance of the coating were studied. The results show that the multi-layered coatings could protect the C/C composites from oxidation in air at 1773 K for 1000 h or 1873 K for 750 h, respectively. The anti-oxidation performance of the multi-layer MoSi₂-CrSi₂-Si coating is mainly attributed to their dense and microcrack-free structure, appropriate thermal expansion coefficient and the well dispersed MoSi₂ and CrSi₂ in the coating.     

Thermodynamic and kinetic consideration on the corrosion of Fe, Ni and Cr beneath a molten KCl-ZnCl2 mixture

Thermogravimetric (TG) experiments have been carried out to study the kinetics of hot corrosion of Fe, Cr and Ni, covered by a molten KCl-ZnCl₂ mixture of a composition close to the eutectic (50 mol% KCl-50 mol% ZnCl₂). Furthermore binary and ternary phase diagrams were calculated in order to describe the corrosion process. The tests were conducted at a temperature of 320 °C in an atmosphere consisting of argon and oxygen. For iron different stages are observed in a TG curve. They can be attributed to the different reaction steps of iron chloride formation (incubation phase), oxide precipitation (linear stage) and scale formation (parabolic or logarithmic stage). Based on these observations a model, described by Spiegel [A. Spiegel, Molten Salt Forum 7 (2003) 253], is confirmed. For Cr and Ni these stages are not observed. At 8 vol% O₂ only slight oxidation of Cr and Ni was observed accompanied by evaporation of the salt deposit. At 16 vol% O₂ the rate of oxidation increases and the experiments yield a curve that is either parabolic or logarithmic for both Ni and Cr. As a result it is shown that the solubility of iron chloride in the KCl-ZnCl₂ melt is higher than the solubility of nickel chloride and chromium (III) chloride in the KCl-ZnCl₂ melt. This enables a higher diffusibility of iron chloride to the upper region of the melt where a higher oxygen partial pressure (p(O₂)) is present leading to a higher oxidation rate of iron.     

Effect of lamellar microstructure on oxidation kinetics of Fe3Al sintered by hot isostatic pressing

The present paper focuses on the investigation of the relationship between microstructure of Fe₃Al prepared by hot isostatic pressing (HIP) and kinetics of alumina layer formation during oxidation at 900 °C, 1000 °C and 1100 °C. As prepared HIPed Fe₃Al sample reveals lamellar microstructure with inhomogeneous Al distribution which originates from the preliminary mechanical activation of Fe-Al mixture. At 900 °C, Fe₃Al oxidation is characterized by selective growth of very rough alumina layer containing only transient aluminium oxides. In addition to these transient oxides, α-Al₂O₃ stable phase is formed at 1000 °C. At the highest temperature (1100 °C), continuous and relatively smooth alumina layer mainly contains fine crystallites of α-Al₂O₃. The initial lamellar structure and phase inhomogeneity in as-HIPed Fe₃Al samples are supposed to be the main factors that determine observed peculiarities after Fe₃Al oxidation at 900 °C and 1000 °C.     

KCl-induced high temperature corrosion of the austenitic Fe-Cr-Ni alloys 304L and Sanicro 28 at 600 °C

The influence of KCl(s) on the high temperature oxidation of the austenitic alloys 304L and Sanicro 28 at 600 °C in O₂ + H₂O environment is reported. 0.10 mg/cm² KCl(s) was added before exposure. The samples are investigated by grazing angle XRD, SEM/EDX, and AES. In the absence of KCl, both alloys show protective behaviour in dry O₂. In O₂ + H₂O environment, alloy 304L suffers local breakaway corrosion while Sanicro 28 still shows protective behaviour. The oxidation of both alloys is strongly accelerated by KCl. KCl reacts with chromium in the normally protective corundum-type oxide, forming K₂CrO₄. This depletes the scale in chromia and leads to the formation of a non-protective, iron-rich scale. The significance of KCl-induced corrosion in real applications is discussed and the oxidation behaviour of the two steels is compared.     

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.     

Influence of reinforcement proportion and matrix composition on pitting corrosion behaviour of cast aluminium matrix composites (A3xx.x/SiCp)

The influence of silicon carbide (SiCp) proportion and matrix composition on four aluminium metal matrix composites (A360/SiC/10p, A360/SiC/20p, A380/SiC/10p, A380/SiC/20p) immersed in 1-3.5 wt% NaCl at 22 °C was investigated by potentiodynamic polarization. The kinetics of the corrosion process was studied on the basis of gravimetric measurements. The nature of corrosion products was analysed by scanning electron microscopy (SEM) and low angle X-ray diffraction (XRD). The corrosion damage in Al/SiCp composites was caused by pitting attack and by nucleation and growth of Al₂O₃ · 3H₂O on the material surface. The main attack nucleation sites were the interface region between the matrix and the reinforcement particles. The corrosion process was influenced more by the concentration of alloy elements in the matrix than by the proportion of SiCp reinforcement and saline concentration.     

Multilayer oxidation protective coating for C/C composites from room temperature to 1500 °C

To prevent carbon/carbon (C/C) composites from oxidation, a multilayer oxidation resistant coating was prepared. The inner SiC coating was prepared by pack cementation, and the outer SiC-MoSi₂ three-layer coating was obtained by slurry coating using silicon-sol as the caking agent. X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy were used to analyze the phase, microstructure and element distribution of the as-prepared coating. The results show that, the as-received multilayer coating has a crack-free structure with the thickness of about 300 μm. It is provided with excellent oxidation resistance from room temperature to 1500 °C in air and can protect C/C composites from oxidation for more than 120 h at 900 °C and more than 110 h at 1500 °C in air. The weight loss of the coated samples during oxidation tests mainly resulted from the oxidation of Mo₅Si₃ and the volatilization of SiO₂ in the coating.     

Electrochemical stability of anodic titanium oxide films grown at potentials higher than 3 V in a simulated physiological solution

The cathodic behaviour of oxides formed on titanium electrodes in physiological solutions at potentials between 3 and 5 V (vs. SCE) was studied by cyclic voltammetry. In case of anodic polarization at potentials higher than 3 V (vs. SCE), a cathodic peak at ∼0.4 V (vs. SCE) appears in the cathodic scan, which could be due to the reduction of unstable peroxides. The results show that this peak depends on the anodic potential and the oxidation time. This behaviour supposedly is due to the formation of unstable titanium peroxides like TiO₃ during anodization. Based on repetitive oxidation-reduction processes can be concluded that the created amount of TiO₃ inside of the TiO₂ surface layer seems to be constant.     

Development and oxidation resistance of air plasma sprayed Mo-Si-Al coating on an Nbss/Nb5Si3 in situ composite

A Mo-Si-Al coating, which is mainly composed of Mo(Si,Al)₂ and Mo₅(Si,Al)₃, was developed to protect a Nb_ss/Nb₅Si₃ in situ composite by air plasma spraying. After oxidation at 1250 °C, the oxidation curve followed parabolic law and even after oxidation for 100 h, the weight gain of Mo-Si-Al coating was 8.24 mg/cm². The surface of the oxidized samples became flatter and smoother as time increased due to the formation of SiO₂ glass. Moreover, the microstructure of Mo-Si-Al coating changed and a layer structured interdiffusion zone was formed at the substrate-coating interface after oxidation.     

Cyclic oxidation behaviour of electrodeposited Ni3Al-CeO2 base coatings at 1050 °C

This paper presents the cyclic oxidation behaviour of electrodeposited pure, nano CeO₂ (9-15 nm)- and micron CeO₂ (5 μm)-modified Ni₃Al coatings on Fe-Ni-Cr substrate at 1050 °C for periods up to 500 h. The pure Ni₃Al coating had a marginal resistance to cyclic oxidation at 1050 °C, while the CeO₂-dispersed Ni₃Al coatings showed much better cyclic oxidation resistance. This difference was attributed to many beneficial effects of CeO₂ including changing the growth mechanism of α-Al₂O₃ scale, reducing the growth rate of the scale, improving mechanical properties of the scale, and reducing void formation at the scale/coating interface and at the scale-grain boundaries.     

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.