Effect of silicon/graphite ratio and temperature on oxidation protective properties of SiC/ZrB2–SiC coatings prepared by pack cementation

To investigate the silicon/graphite ratio and temperature on preparation and properties of ZrB₂–SiC coatings, ZrB₂, silicon, and graphite powders were used as pack powders to prepare ZrB₂–SiC coatings on SiC coated graphite samples at different temperatures by pack cementation method. The composition, microstructure, thermal shock, and oxidation resistance of these coatings were characterized and assessed. High silicon/graphite ratio (in this case, 2) did not guarantee higher coating density, instead could be harmful to coating formation and led to the lump of pack powders, especially at temperatures of 2100 and 2200 °C. But residual silicon in the coating is beneficial for high density and oxidation protection ability. The SiC/ZrB₂–SiC (ZS50-2) coating prepared at 2000 °C showed excellent oxidation protective ability, owing to the residual silicon in the coating and dense coating structure. The weight loss of ZS50-2 after 15 thermal shocks between 1500 °C and room temperature, and oxidation for 19 h at 1500 °C are 6.5% and 2.9%, respectively.     

High-temperature oxidation behavior and oxidation mechanism of C/SiBCN composites in static air

On account of the excellent oxidation resistance of precursor-derived SiBCN ceramics, carbon-fiber-reinforced SiBCN (C/SiBCN) composites are increasingly being used in high-temperature aerospace applications. However, very few studies have investigated the high-temperature oxidation behavior of C/SiBCN composites for their application to high-heat engines. Herein, C/SiBCN composites prepared by precursor infiltration and pyrolysis were tested in static air up to an oxidation temperature of 1700 °C. The composites’ structural evolution after oxidation and their potential oxidation mechanisms were investigated in detail. The carbon fibers were preferentially oxidized at temperatures in the range of 1200–1500 °C and completely oxidized at 1500 °C. The oxidation of the fibers at 1500 °C resulted in the formation of abundant oxygen channels and consequently a high oxide scale growth rate of 5–7 μm² h⁻¹ and a large mass loss of 54.6 wt%. At elevated temperatures in the range of 1600–1700 °C, a dense SiO₂ oxide layer was formed by the sacrificial oxidation of the SiBCN matrix. The oxidation rate of the composites was therefore controlled by the diffusion rate of oxygen through the protective SiO₂ oxide layer and the weight loss of the composites decreased to 28.6% after oxidation at 1600 °C for 60 min. The structural integrity of the composites was maintained after long-term oxidation at 1600 °C.     

Adhesion properties and fracture mechanism of plasma sprayed NiCrAl/Al2O3–13wt.%TiO2 coatings by post annealing

Plasma-sprayed NiCrAl/Al₂O₃–13wt.%TiO₂ coatings (AT13) deposited on mild steel substrate were annealed with varying temperatures in air. The adhesion of the coating was evaluated by tensile adhesive strength test. The microstructure and the fracture mechanism were studied using optical microscopy, X-ray diffraction, and scanning electron spectroscopy/energy dispersive spectroscopy. It was found that the tensile bond strength of the coatings increased with increasing of annealing temperature at first and then decreased with increasing of annealing temperature further. The as-sprayed coating fractured at the interfaces of substrate/bond layer and bond layer/ceramic coating with a brittle–ductile mixed fracture. The measured strength expressed the adhesive strength and internal adhesive strength of the coating. The failure of the coating annealed at 300, 400, and 500 °C took place at the interface of substrate/bond layer and had a mixed fracture surface of transgranular cleavage fracture and localized ductile fracture. The strength obtained is the adhesive strength between the coating and the steel substrate. The coating annealed at 400 °C had a maximum strength of 42.9 MPa. When the temperature is above 600 °C, the bonding strength would be damaged. Therefore, there is a proper annealing temperature which can significantly improve the bond strength of the coating.     

Thermostability,oxidation, and high-temperature tribological properties of nano-multilayered AlCrSiN/VN coatings

In this study, monolithic AlCrSiN, VN, and nano-multilayered AlCrSiN/VN coatings were deposited using a hybrid deposition system combining arc ion plating and pulsed direct current magnetron sputtering. The microstructure, thermostability, mechanical, oxidation and tribological properties of the coatings were comparably investigated. The multilayered AlCrSiN/VN coating exhibited a face-centered cubic (fcc) structure with (200) preferred orientation and showed the highest hardness (30.7 ± 0.5 GPa) among these three coatings due to the multilayer interface enhancement mechanism and higher compressive stress. The AlCrSiN sublayers effectively prevented the V element from rapid outward diffusion to the surface of AlCrSiN/VN coating at elevated temperatures, which improved the oxidation resistance of the coating. Decomposition of V (Cr)–N bonds occurred at annealing temperatures from 800 °C to 1000 °C and V₂N phase appeared at 1100 °C. The AlCrSiN/VN coating showed excellent tribological performance at high temperatures by combining the merits of VN layers for low friction coefficient and AlCrSiN layers for superior oxidation resistance. Compared to VN and AlCrSiN coatings, AlCrSiN/VN coating showed the lowest wear rate of 2.6×10^-15 m³/N·m at 600 °C and lowest friction coefficient of 0.26 at 800 °C with a relativity low wear rate of 39.4×10^-15 m³/N·m.     

Preparation and high-temperature oxidation resistance of multilayer MoSi2/MoB coating by spent MoSi2-based materials

Spent MoSi₂ and MoB were used as raw materials to prepare multilayer MoSi₂/MoB coating on molybdenum by the two-step method of slurry deposition and spark plasma sintering. The results showed dense MoSi₂/MoB coating after sintering while penetrated cracks appeared in MoSi₂ coating due to coefficient of thermal expansion mismatch between the Mo substrate and coating. After the sintering of MoSi₂/MoB coatings, MoB and Mo₂B diffusion layers were formed between MoB transition layer and Mo substrate without defects, exhibiting good metallurgical bonding. The high-temperature oxidation behavior of coatings (1500°C) was also explored. After oxidation of 50 h at 1500°C, lowest mass gain (0.035 mg/cm²) was obtained for MoSi₂/MoB coating, and the oxide scale was dense and complete without voids, making the oxygen diffusion at elevated temperature inhibited. Compared with MoSi₂ coating under the same oxidation conditions, relatively thinner silica oxide scale was acquired by MoSi₂/MoB coating because of the reduction of cracks, and the multilayer coating exhibits better anti-oxidation properties at high temperature.     

Fabrication and properties of dense α-cordierite glass-ceramic coating on porous BN/Si2N2O ceramic

α-Cordierite glass-ceramic coating was fabricated on the porous BN/Si₂N₂O ceramic by glass-ceramic method. The effect of the heating temperature on the phase composition, microstructure, mechanical properties, water resistance and dielectric properties of the coatings was investigated. A large amount of α-cordierite precipitated from the glass phase when the heating temperature was 1050?°C and the content of α-cordierite in the coating increased with increasing the heating temperature. The resulting α-cordierite glass-ceramic coatings had a good wettability and adhesion with the porous ceramic substrate. The coating/substrate interface was continuous without defects. When the heating temperature was 1050–1200?°C, the resulting coatings possessed positive mechanical properties and good water resistance due to the high densification. And the dielectric constant and loss tangent of the coated samples prepared at 1050–1200?°C were 4.1–4.3 and 0.005–0.01 respectively in the frequency of 21–36?GHz.     

Low–thermal–conductivity and high–toughness CeO2–Gd2O3 co–stabilized zirconia ceramic for potential thermal barrier coating applications

Yttria partially stabilized zirconia (～4.0?mol% Y₂O₃–ZrO₂, 4YSZ) has been widely employed as thermal barrier coatings (TBCs) to protect the high–temperature components of gas–turbine engines. The phase stability problem existing in the conventional 4YSZ has limited it to application below 1200?°C. Here we report an excellent zirconia system co–doped with 16?mol% CeO₂ and 4?mol% Gd₂O₃ (16Ce–4Gd) presenting nontransformable feature up to 1500?°C, in which no detrimental monoclinic (m) ZrO₂ phase formed on partitioning. It also exhibits a high fracture toughness of ～46?J m^?2 and shows high sintering resistance. Besides, the thermal conductivity and thermal expansion coefficient of 16Ce–4Gd are more competent for TBCs applications as compared to the 4YSZ. The combination of properties suggests that the 16Ce–4Gd system could be of potential use as a thermal barrier coating at 1500?°C.     

Microstructure and high-temperature sintering properties of APS coatings prepared from spherical thin-walled hollow-shell powders

High-performance thermal barrier coatings (TBCs) made of 4 mol.% Y₂O₃–stabilized ZrO₂ (4YSZ) powder with a spherical thin-walled hollow-shell (STHS) structure exhibited a special microstructure different from the conventional lamellar structure of air plasma-sprayed (APS) coatings. The as-sprayed STHS APS coatings had a completely tetragonal prime (t′) structure and non-lamellated closed-cell structure with high porosity, which resulted in relatively low thermal conductivity (～1.0 W m^?1 K^?1) and high Vicker's hardness (～6 GPa). The influences of high-temperature aging on the microstructure stability, phase stability, and sintering capability were investigated after long-time heat treatment at different temperatures. The characterization results indicated that the pore content was basically constant, and it was less than 0.5% for sintered linear shrinkage of the STHS coatings after heat treatment at 1500 °C for 100 h. Furthermore, no spalling appeared in the STHS APS coating with the t′ phase structure after 101 thermal cycles of the water-quenching method at 1050 °C, and no monoclinic ZrO₂ (m-ZrO₂) phase was present in all of the STHS coatings after aging at 1200 °C for 1–1100 h. The excellent anti-sintering properties and phase stability of the STHS coatings are attributed to the closed-pore microstructure and the highly pure t′ phase composition with uniform distribution of ions, respectively. The results suggested that the non-lamellated closed-cell microstructure is beneficial for improving the coating properties, and the results also provide guidelines for microstructure design of TBCs using a feedstock powder.     

TaSi2–SiC high-emissivity coating modified by SiB6 on flexible alumina fibre fabric with enhanced oxidation resistance and high interfacial bonding strength

To improve the oxidation inhibition of TaSi₂-based high-emissivity coatings at high temperatures, TaSi₂–SiC coating modified by SiB₆ was prepared on the surface of alumina fibre fabrics. The effects of the SiB₆ content on the surface appearance and emissivity of the coating were investigated, and the mechanical properties of the coated fabrics were compared. When the SiB₆ content in the coating was 2.5%, the borosilicate glass liquid phase generated by SiB₆ oxidation effectively prevented the oxidation of TaSi₂. The bond strength between the coatings and fibre fabric was 207 kPa after calcination at 1200 °C, which was 39% higher than that of the coated fabric without SiB₆. The emissivity of the TaSi₂–SiC coating, modified by a SiB₆ content of 2.5%, reached above 0.92 after calcination at 1200 °C for 5 h. Therefore, the TaSi₂–SiC high-emissivity coating modified by SiB₆ has good application prospects in the field of thermal protection.     

Fabrication of ceramic composite coatings using electrophoretic deposition,reaction bonding and low temperature sintering

We have developed a novel combination of electrophoretic deposition (EPD), reaction bonding and low temperature sintering techniques for the fabrication of yttria stablised zirconia (YSZ)/alumina composite coatings on Fecralloys. A mixture of ethanol and acetylacetone solvent was found to be an effective medium for YSZ and aluminium particle suspension. With the particle size of YSZ and aluminium being significantly reduced during ball milling. By using the EPD process, uniform green form coatings containing YSZ and aluminium particles were produced on Fecralloys. After oxidation of aluminium at 500°C and sintering at 1200°C, a dense and adherent YSZ/Al₂O₃ coating was produced. The presence of aluminium in the green form coatings not only contribute to the bonding between the coating and the metal substrate, but also compensate for the volume shrinkage of the coatings during sintering by the volume expansion arising from oxidation of aluminium to alumina.     

Influence of LaMgAl11O19 On Solid Particle Impact Erosion Wear Behavior of 3YSZ Ceramic at Elevated Temperatures

To study the improvement in solid particle impact erosion wear resistances of 3 mol% yttria‐stabilized zirconia (3YSZ) ceramic at elevated temperatures up to 1400°C, 2 wt% LaMgA1₁₁O₁₉ was added into 3YSZ to prepare LaMgA1₁₁O₁₉‐3YSZ ceramic for erosion resistance tests with angular corundum abrasive particles. The testing results show that the volume erosion rates of 3YSZ and LaMgA1₁₁O₁₉‐3YSZ ceramic were similar in the temperature range from room temperature to 600°C, then exhibited a sharp increase from 600°C to 1200°C, and dropped again at 1400°C. It was mainly caused by the change in material removal mechanisms from plastic deformation below 600°C to the interaction of transverse cracks in the temperature range from 600°C to 1400°C. The solid particle impact erosion wear properties of 3YSZ ceramic in the temperature range from 600°C to 1400°C were successfully improved by the addition 2 wt% LaMgA1₁₁O₁₉ platelets. Comparing with the volume erosion rate of pure 3YSZ ceramic (0.687 mm³/g) at 1200°C, the value of LaMgA1₁₁O₁₉‐3YSZ ceramic (0.551 mm³/g) has been decreased by 20%.     

Generation of meso- and microporous structures by pyrolysis of polysiloxane microspheres and by HF etching of SiOC microspheres

The porosity of polysiloxane microspheres obtained by emulsion processing of variably modified polyhydromethylsiloxane (PHMS) and subjected to pyrolysis in an Ar atmosphere at 450–650 °C was studied. Materials having micro- and mesopores with specific surface areas (SSAs) of up to 786 m²/g and pore volumes of up to 0.35 cm³/g were obtained. A high porosity was displayed by the microspheres heated at 600 °C that underwent deep depolymerization processes. Some polysiloxane microspheres were ceramized at temperatures of 1200–1500 °C and were subjected to etching by 35% aqueous HF. The microspheres heated to 1200–1400 °C were free of microcracks, whereas those ceramized at 1500 °C showed microcracks and macropores, although they preserved their spherical structure well. All of the microspheres ceramized at temperatures of 1200–1400 °C had low porosity. HF etching granted high micro- and mesoporosity to the materials ceramized at 1300–1500 °C. Microspheres heated at 1500 °C showed specific surface areas above 1000 m²/g after etching. These microspheres had low oxygen contents and were mostly composed of silicon carbide. Since they also showed macroporosity, HF etching of the polysiloxane microspheres ceramized at 1500 °C could be used to obtain hierarchically mesoporous-macroporous ceramic microspheres.     

Deposition Rate,Texture, and Mechanical Properties of SiC Coatings Produced by Chemical Vapor Deposition at Different Temperatures

Silicon carbide (SiC) coatings were produced on carbon/carbon (C/C) composites substrates using chemical vapor deposition (CVD) at different temperatures (1100°C, 1200°C, and 1300°C). The deposition rate was found to increase with deposition temperature from 1100°C to 1200°C. From 1200°C to 1300°C, the deposition rate decreased. SiC coating produced at 1200°C exhibited a strong (111) texture compared with the coatings produced at other temperatures. Both hardness and Young's modulus were also found to be higher in the coating produced at 1200°C. The variation in mechanical properties with the increase in temperature from 1100°C to 1300°C showed a direct correlation with the change in deposition rate and (111) texture. Microstructure analysis shows that the change in CVD temperature leads to the change in grain size, crystallinity, and density of stacking faults of SiC coatings, which appears to have no significant effect on mechanical properties of SiC compared with the texture observed in SiC coating. For the coating deposited at 1200°C, both the hardness and Young's modulus increased gradually from the substrate/coating interface to the top surface. The nonuniformity of mechanical properties along the cross‐section of the coating is attributed to the nonuniform microstructure.     

TiO2–ZnO/Ni–5wt.%Al composite coatings on GH4169 superalloys by atmospheric plasma spray techniques and theirs elevated-temperature tribological behavior

Ni–based composite coatings with different amounts of TiO₂–ZnO were fabricated by atmospheric plasma spraying (APS) to protect GH4169 superalloy substrates against excess wear and friction at elevated temperatures. In addition, the influence of the simultaneous addition of the oxides on the microstructure, microhardness, and wear behaviour was investigated. According to the results, the simultaneous addition of TiO₂/ZnO provides anti-friction and wear inhibition over 600 °C. In particular at 800 °C, the TiO₂–ZnO/Ni–5wt.%Al composite coating (10 wt% TiO₂ and 10 wt% ZnO were incorporated within Ni–5wt.%Al matrix) exhibits a superior lubricity and wear resistance compared to the Ni–5wt.%Al based coatings. The XRD, Raman, and TEM characterisations reveal the formation of a glaze oxide layer consisting of NiO, TiO₂, ZnO and the in-situ production of ternary oxide (Zn₂TiO₄), which was primarily responsible for the tribological performance of the sliding wear contacts at the specific temperature.     

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.     

Effect of temperature on the growth of boron nitride interfacial coatings on SiC fibers by chemical vapor infiltration

In order to improve bonding property between SiC fibers and matrix of SiC_f/SiC composites, boron nitride (BN) interfacial coatings were synthesized by chemical vapor infiltration. BN coatings were fabricated from BCl₃–NH₃ gaseous mixtures at four different temperatures (843 °C, 900 °C, 950 °C and 1050 °C) with different deposition times. Growth kinetics, nucleation and growth processes, microstructure and chemical composition of boron nitride coatings were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Raman spectrometry. Results showed that deposition rate increased as the temperature increased from 843 °C to 950 °C. However, deposition rate decreased slightly from 23.10 ± 0.85 nm/min (950 °C) to 21.39 ± 0.67 nm/min when the temperature was increased further to 1050 °C. It could be due to the nucleation occurring in the gas and the consumption of a large amount of BCl₃ and NH₃. When deposition temperature was 843 °C, BN grains deposited on top layer of the coating could not completely cross Ehrlich-Schwoebel barrier and grew in island growth mode. On the other hand, the deposition pattern followed a layer-by-layer growth mode when deposition temperature was 1050 °C. Deposition temperature significantly affected the microstructure of as-deposited BN coatings. At 843 °C, 950 °C and 1050 °C, the coatings presented amorphous, polycrystalline and hexagonal structures, respectively.     

Kinetics and mechanisms for the densification and grain growth of the α-alumina fibers isothermally sintered at elevated temperatures

Understanding the densification and grain growth processes is essential for preparing dense alumina fibers with nanograins. In this study, the alumina fibers were prepared via isothermal sintering at 1200, 1300, 1400, and 1500 °C for 1–30 min. The phase, microstructure, and density of the sintered fibers were investigated using XRD, SEM, and Archimedes methods. It was found that the phase transformation during the isothermal sintering enhances the densification of Al₂O₃ fibers in the initial stage, while the pores generated during the phase transformation retard the densification in the later period. The kinetics and mechanisms for the densification and grain growth of the fibers were discussed based on the sintering and grain growth models. It was revealed that the densification process of the fibers sintered at 1500 °C is dominated by the lattice diffusion mechanism, while the samples sintered at 1200–1400 °C are dominated by the grain boundary diffusion mechanism. The grain growth of the Al₂O₃ fibers sintered at 1200–1300 °C is governed by surface-diffusion-controlled pore drag, and that sintered at 1400 °C is dominated by lattice-diffusion-controlled pore drag.     

Structural and phase transitions in TiN-AlN and TiN-AlN-(Ni-Cr-Al) composites produced by focused solar radiation

Results are given on the effects of concentrated solar radiation on the structure and phase transitions of composite materials (CM) based on TiN-AlN. Oxidation in the TiN-AlN system leads to the formation of β-Al₂TiO₅, which prevents the diffusion of titanium and aluminum to the surface of the specimen and correspondingly is a protective barrier for the CM in air up to temperatures above 1500°C. A CM based on TiN-AlN with Ni-Cr-Al bonding has high resistance to oxidation above 1500°C. The introduction of this metal alloy into the CM favors the formation of the spinel NiCr₂O₄, which reacts with titanium and aluminum oxides to form a dense oxide film providing protection of the CM from oxidation. Then CM with compositions TiN-AlN and TiN-AlN-30% (Ni-Cr-Al) have elevated corrosion resistance above 1500°C and can be used as corrosion-resistant CM and as coatings. Translated from Novye Ogneupory, No. 9, pp. 51–53, September, 2008.     

Structure evolution,thermal properties and sintering resistance of promising thermal barrier coating material La2(Zr0.75Ce0.25)2O7

Rare-earth doped zirconates are promising candidate materials for high-performance thermal barrier coatings (TBCs). The phase and microstructure stability is an important issue for the materials that must be clarified, which is related to the long-term stable work of TBCs at high temperatures. In this work, La₂(Zr_0.75Ce_0.25)₂O₇ (LCZ) ceramic coatings prepared by atmospheric plasma spraying present a metastable fluorite phase, which can transform into stable pyrochlore under high-temperature annealing. The detailed structure evolution of the ceramic coatings is characterized systematically by SEM, XRD and Raman. The associated thermal properties of LCZ ceramics were also reported. Results show that LCZ ceramic has an ultralow thermal conductivity (0.65 W/m·K, 1200 °C), which is only 1/3 of that of yttria-stabilized zirconia (YSZ). The thermal expansion coefficients of LCZ ceramic increase from 9.68 × 10^-6 K^-1 to 10.7 × 10^-6 K^-1 (300 - 1500 °C), which are relatively larger than those of La₂Zr₂O₇. Besides, Long-term sintering demonstrates that LCZ ceramic coating has preferable sintering resistance at 1500 °C, which is desirable for TBC applications.     

Sintering characteristics of Chinese bauxites

The sintering behaviour of Chinese bauxites of the diaspore-kaolinite type proceeds in three stages, viz: decomposition stage (400–1200°C), secondary mullitization stage (1200–1400 or 1500°C) and recrystallization sintering stage (above 1400 or 1500°C). The sinterability of different grades of bauxites is dependent on the Al₂O₃ content. The closer is the composition of calcined bauxite to that of mullite, the more difficult is it to sinter. It is postulated that secondary mullitization and liquid phase action are the two principal factors influencing the sintering of these bauxites. Grade II bauxites characterised by maximum secondary mullite formation and relatively low glass content are found to be most difficult to sinter.