Microstructure and ablation mechanism of graphite/SiC composites under oxy-acetylene flame

Graphite/SiC composites were prepared by reactive metal infiltration (RMI). The microstructure and the ablation mechanism under oxy-acetylene flame were investigated. The ablation surface was composed of a central zone, an intermediate zone and an outer zone. The surface of the intermediate zone was covered by a SiO₂ layer due to the oxidation of Si and SiC. A particle layer, which consisted of SiC particles and graphite particles, was found beneath the SiO₂ layer due to the large inner stress. In the central zone, an extra SiO layer was detected owing to the high temperature and the few oxygen in the particle layer. Due to the good wettability with graphite, the SiO₂ layer exhibited excellent ablation resistance by inhibiting oxygen diffusion and lowering the mechanical erosion of the flame. Besides, the evolution of the gases formed inside the composite helped to improve the ablation resistance.     

Oxidation behaviour of nano-sized SiC particulate reinforced Alon composites

Silicon carbide (SiC)-aluminium oxynitride (Alon) ceramic composites exhibited improved mechanical properties, but the high temperature oxidation behaviour was unknown. The aim of this investigation was to identify oxidation characteristics and kinetics of 8 wt% SiC-Alon composites over a temperature range between 700 °C and 1200 °C in air. The Alon matrix and SiC particles near the surface were oxidized to form Al₂O₃ and SiO₂, respectively. The starting oxidation temperature of Alon was observed to be about 1000 °C. While the addition of nano-sized SiC particles resulted in a reduced starting oxidation temperature due to the large cumulative surface area and high total surface energy, the oxidation resistance at higher temperatures of 1100 °C and 1200 °C was remarkably enhanced. The oxidation kinetics changed from a linear weight gain for pure Alon into a logarithmic weight gain for the composites due to the formation of a dense protective oxidation layer arising from the presence of SiO₂.     

Formation of Ni(CO)4 during the Interaction between CO and Silica-Supported Nickel Catalyst: an FTIR Spectroscopic Study

The formation of Ni(CO)₄ during interaction of CO with silica-supported highly dispersed nickel metal (d _av4 nm) was investigated by FTIR spectroscopy. At temperatures below 145 K, in addition to linear and bridged nickel carbonyls, CO adsorption on Ni⁰/SiO₂ leads to the formation of Ni(CO) _x (x=2, 3) subcarbonyls (band at ca. 2090 cm^–1) and negligible amounts of Ni(CO)₄ adsorbed on SiO₂ (band at 2048 cm^–1). Up to this temperature CO causes no detectable erosion of the metal surface. Above 145 K the rate of interaction between CO and the nickel particles significantly increases. Until 235 K Ni(CO)₄ mainly remains in the adsorbed state, while at still higher temperatures the equilibrium between adsorbed and gaseous Ni(CO)₄ (band at 2058 cm^–1) is shifted towards the latter. It is assumed that subcarbonyls formed on defect sites of the metal surface are precursors of the nickel tetracarbonyl. Successive adsorption–evacuation cycles of CO at room temperature result in a decrease in the amount of the Ni(CO)₄ formed, probably due to a reduction of the number of defect metal sites. On the basis of ¹²CO and ¹³CO coadsorption, an alternative interpretation of the band at 2048 cm^–1 to species containing isolated Ni(CO)₃ groups is proposed.     

Catalytic roughening of surface layers of BDD for various applications

The surface layers of BDD electrodes have been roughened through excavation by small Ni, Co and Pt particles in a flowing gas mixture of H₂(10%) and N₂(90%) between 800 °C and 1000 °C. The specific surface area of the BDD evaluated with the double layer capacitance was enhanced by the excavation of up to nearly 15 times as much pristine BDD electrode. The following potential applications for the surface-roughened BDD were proposed: (1) interlayer of the porous oxide catalyst layer and metal substrate of IrO₂-Ta₂O₅/(Ti or Nb) electrode, for instance, and (2) supporting material with large surface area for catalyst metal particles.     

Improved antioxidative and mechanical properties of SiC coated C/C composites via a SiO2-SiC reticulated layer

To improve the oxidation resistances of SiC coated C/C composites by a pack cementation (PC) method at high temperature and alleviate the siliconization erosion of molten silicon on C/C substrate during the preparation of SiC coating, a SiO₂-SiC reticulated layer with SiC nanowires was pre-prepared on C/C composites through combined slurry painting and thermal treatment before the fabrication of SiC coating. The presence of porous SiO₂-SiC layer with SiC nanowires was beneficial to fabricate a compact and homogeneous SiC coating resulting from synergistic effect of further reaction between SiO₂ and pack powders and the reinforcement of SiC nanowires. Therefore, the results of thermal shock and isothermal oxidation tests showed that the mass loss of modified SiC coating was only 0.02 % after suffering 50-time thermal cycles between room temperature and 1773 K and decreased from 5.95 % to 1.08 % after static oxidation for 49.5 h in air at 1773 K. Moreover, due to the blocking effect of SiO₂-SiC reticulated layer on siliconization erosion during PC, the flexural strength of SiC coated C/C composites with SiO₂-SiC reticulated layer increased by 64.8 % compared with the untreated specimen.     

High-temperature oxidation behavior of the SiC layer of TRISO particles in low-pressure oxygen

Surrogate tristructural-isotropic (TRISO)-coated fuel particles were oxidized in 0.2 kPa O₂ at 1200–1600°C to examine the behavior of the SiC layer and understand the mechanisms. The thickness and microstructure of the resultant SiO₂ layers were analyzed using scanning electron microscopy, focused ion beam, and transmission electron microscopy. The majority of the surface comprised smooth, amorphous SiO₂ with a constant thickness indicative of passive oxidation. The apparent activation energy for oxide growth was 188 ± 8 kJ/mol and consistent across all temperatures in 0.2 kPa O₂. The relationship between activation energy and oxidation mechanism is discussed. Raised nodules of porous, crystalline SiO₂ were dispersed across the surface, suggesting that active oxidation and redeposition occurred in those locations. These nodules were correlated with clusters of nanocrystalline SiC grains, which may facilitate active oxidation. These findings suggest that microstructural inhomogeneities such as irregular grain size influence the oxidation response of the SiC layer of TRISO particles and may influence their accident tolerance.     

Machine learning-assisted characterization of electroless deposited Ni–P particles on nano/micro SiC particles

In this experiment, Ni–P nanoparticles were deposited (ED) on SiC micro- and nanoparticles with different parameters. Our goal was to successfully prepare metal deposits and develop an effective method for comparing and evaluating the various procedures.During the experimental work, a three-step electroless Ni–P coating process was applied with different concentrations. The coated SiC particles were examined by scanning electron microscopy (SEM). The mass-specific surface area (SSA) of the coated SiC was measured by the Brunauer‒Emmett‒Teller (BET) method, while the volumetric-specific surface area (VSSA) was also calculated. The adhesion between the metal and the ceramic particle was analyzed by X-ray photoelectron spectroscopy (XPS).An image processing macroprogram was created (with a machine learning-based Trainable Weka Segmentation algorithm) to segment the SEM images of the ED metal particles to calculate the specific surface area (S_V).     

Effect of hydrothermal corrosion on the fracture strength of SiC layer in tristructural-isotropic fuel particles

The hydrothermal corrosion behavior of SiC layer in tristructural-isotropic (TRISO) fuel particles and its effect on the fracture strength were investigated. The corrosion test was performed using the static autoclave at 400°C/10.3 MPa. The SiC layer exhibited a thickness loss and the corrosion rate followed a linear law. During corrosion, carbon was formed on the SiC surface due to the loss of Si. The corrosion was found preferentially occurred at the grain boundary of SiC, leading to the grain detachment and pit formation. The rate determining step of the corrosion was SiO₂ formation rather than SiO₂ dissolution in the hydrothermal environment. The fracture strength of SiC shell after corrosion was evaluated using the crush test. It showed a slight decrease with an increase in corrosion time, due to the thickness reduction in SiC layer. The results of this study demonstrated that the SiC in TRISO particles has good corrosion resistance in the hydrothermal environment.     

Laser ablation behavior of flake graphite and SiO2 particle-filled hyperbranched polycarbosilane matrix composite coatings

Composite coatings consisting of flake graphite and SiO₂ fillers in a hyperbranched polycarbosilane (HBPCS) matrix were designed and prepared to meet the requirements of laser protection. The laser ablation behavior of the composite coatings were investigated. Control experiments were designed to study the performance of SiO₂ during laser irradiation. The results show that the introduction of SiO₂ changes the anti-laser protective mechanism and can improve the anti-laser property of the coating. High power laser irradiation results in pyrolysis of HBPCS and the formation of SiC particles. Chemical reactions between SiO₂, graphite, and SiC play an important role in consuming energy, and provide an excellent cooling effect to the substrate, leading to decreased temperature. SiC particles formed on the surface of the laser ablation area act as a shield to prevent the laser from irradiating deeper layers of the coating. Due to the cooling effect and thermal stability of SiC, the proposed coating shows a good anti-laser property.     

In situ observation of the dissolution phenomena of SiC particle in CaO–SiO2–MnO slag

The dissolution of SiC particle at 1600 °C in the CaO–SiO₂–MnO slag was observed in situ by means of confocal scanning laser microscopy in order to make the determination of dissolution mechanism. The SiC particle is initially wetted by molten slag from the outer surface and the wetting between SiC and slag phase is more dominant in the composition of higher CaO/SiO₂ ratio. When the SiC particle is wetted by molten slag, the gas bubbles that are mainly CO gas is generated by the reaction between SiC and MnO in slag phase and are continuously evolved at the wetted area, which is pronounced as the CaO/SiO₂ ratio increases. The dissolution of SiC particle in the slag through the reaction with MnO is enhanced in the composition of higher CaO/SiO₂ ratio not only due to greater thermodynamic driving force but also due to accelerated mass transport kinetics.     

Synthesis of metal–cadmium sulfide nanocomposites using jingle-bell-shaped core-shell photocatalyst particles

Photocatalytic deposition of gold (Au) and silver (Ag) nanoparticles was investigated using jingle-bell-shaped silica (SiO₂)-coated cadmium sulfide (CdS) nanoparticles (SiO₂/CdS), which each had a void space between the CdS core and SiO₂ shell, as a photocatalyst. A size-selective photoetching technique was used to prepare the jingle bell nanostructure of SiO₂/CdS. Nanoparticles of Au and Ag were deposited by irradiation of the photoetched SiO₂/CdS in the presence of the corresponding metal complexes under deaerated conditions. Chemical etching of Au-deposited particles enabled the selective removal of CdS without any influence on the surface-plasmon absorption of Au. TEM analyses of the resulting particles suggested that some particles were encapsulated in hollow SiO₂ particles, while other Au particles were deposited on the outer surface of the SiO₂ shell. Emission spectra of the photoetched SiO₂/CdS showed that the metal deposition developed a broad emission with a peak around 650 nm originating from surface defect sites, the degree being dependent on the kind of metal nanoparticles and their amount of deposition. This fact can be explained by the formation of metal–CdS binary nanoparticles having defect sites at the interface between metal and CdS.     

Production of Carbon Nanotube by Ethylene Decomposition over Silica-Coated Metal Catalysts

Formation of carbon nanofibers (CNFs) and carbon nanotubes (CNTs) through the decomposition of ethylene at 973 K was achieved using various metal catalysts covered with silica layers. CNFs of various diameters were formed by ethylene decomposition over a Co metal catalyst supported on the outer surface of the silica. In contrast, silica-coated Co catalysts formed CNTs with uniform diameters by ethylene decomposition. Silica-coated Ni/SiO₂ and Pt/carbon black also formed CNTs with uniform diameters, while CNFs and CNTs with various diameters were formed over Ni/SiO₂ and Pt/carbon black without a silica coating. These results indicate that silica layers that envelop metal particles prevent sintering of the metal particles during ethylene decomposition. This results in the preferential formation of CNTs with a uniform diameter.     

Silicon carbide fiber oxidation behavior in the presence of boron nitride

The oxidation behavior of Sylramic SiC fibers without a boron nitride surface layer was compared to Sylramic iBN SiC fibers with a boron nitride surface layer by conducting thermogravimetric analysis in dry O₂ at temperatures ranging from 800 to 1300°C for times up to 100 hours. Sylramic fibers followed the Deal and Grove oxidation kinetic model. A transient period of accelerated oxidation kinetics was observed with Sylramic iBN fibers. Raman spectroscopic analysis of oxidized fibers provided evidence for a borosilicate glass structure. The boron concentrations in the oxides, quantified by inductively coupled plasma‐optical emission spectrometry, were correlated with the weight change behavior, oxide thickness, and fiber recession of the oxidized fibers. Oxides formed from Sylramic iBN fibers were typically higher in boron concentration, which led to initial rapid oxidation rates that were 3‐10 times faster than observed for pure SiC. Slower oxidation rates followed as the oxide surface became increasingly enriched with SiO₂ due to boria volatilization, thus limiting boria effects on SiC fiber oxidation kinetics. The accelerated high‐temperature oxidation of SiC fibers due to the presence of BN are discussed in terms of the borosilicate glass structure and composition.     

Fabrication of mullite-bonded porous silicon carbide ceramics by in situ reaction bonding

An in situ reaction bonding technique was developed to fabricate mullite-bonded porous silicon carbide (SiC) ceramics in air from SiC and α-Al₂O₃, using graphite as the pore-former. Graphite is burned out to produce pores and the surface of SiC is oxidized to SiO₂ at high temperature. With further increasing the temperature, the amorphous SiO₂ converts into cristobalite and reacts with α-Al₂O₃ to form mullite (3Al₂O₃·2SiO₂). SiC particles are bonded by the mullite and oxidation-derived SiO₂ to obtain porous SiC ceramics. The reaction bonding behavior, open porosity, pore size distribution and mechanical strength of porous SiC ceramics were investigated as a function of the sintering temperature, forming pressure and graphite content. In addition, the phase composition and microstructure were also studied.     

Synthesis and Growth Mechanism of SiC/SiO2 Nanochains Heterostructure by Catalyst‐Free Chemical Vapor Deposition

The SiC/SiO₂ nanochains heterostructure with double amorphous layers was successfully synthesized by a catalyst‐free chemical vapor deposition process at 1280°C. The SiC/SiO₂ nanochains experience an apparent regular periodic structure, whose SiO₂ beads with diameters of about 160 nm are positioned on the SiC strings beside one another. Their growth mechanism could be mainly ascribed to Rayleigh instability and vapor‐solid mechanism. The double layers structure of amorphous silica on the surface of the strings results from the different silica deposition stages. SiC nanowires with diameters of 20–50 nm were also found accompanied with the SiC/SiO₂ nanochains and not changed into the chains‐shaped morphology because of their small diameters and much higher additive surface pressure of bending silica melt layer on the nanowires.     

Wet-oxygen corrosion resistance and mechanism of bi-layer Mullite/SiC coating for Cf/SiC composites

A bi-layer oxidation-resistant coating consisting of a mullite outer coating, and a SiC inner coating on the surface of C_f/SiC composites was prepared by the chemical vapour deposition and an air spray sol-gel process, and its corrosion behavior was evaluated in a wet-oxygen coupling environment. Results show that the formation of SiO₂ glass layer and its reaction with mullite particles to form aluminosilicate glass layer, leading to an increase in the density of the mullite outer coating, so that the weight loss of bi-layer Mullite/SiC coating coated C/SiC sample was only 1.11 × 10^?3 g·cm^?2 in the first 100 h of oxidation. However, the weight loss of the coated sample reached 26.82 × 10^?3 g·cm^?2 after 200 h of oxidation due to a part of the mullite outer coating was detached. The SiO₂ glass phase reacted with water vapour to generate gaseous Si(OH)_x, which created distinct holes on the surface of the SiO₂ glass layer or inside the molten aluminosilicate glass layer. Eventually, the mullite outer coating was blistered and detached from the surface of the sample due to the combination and growth of holes.     

Kinetic Analysis of Nonisothermal Reduction of Silica-Supported Nickel Catalyst Precursors in a Hydrogen Atmosphere

A series of silica-supported nickel catalyst precursors was synthesized with different SiO₂/Ni molar ratios. Reduction of Ni catalyst precursors with different SiO₂/Ni molar ratios under a hydrogen atmosphere was investigated at different heating rates. Kinetic parameters were determined using Kissinger–Akahira–Sunose isoconversional and invariant kinetic parameter methods. It was found that for all molar ratios, the apparent activation energy (E_a) is practically constant in the conversion range of 0.20 ≤ α ≤ 0.80. In the considered conversion range, following values of E_a were found: 134.5 kJ mol^?1 (SiO₂/Ni = 0.20), 139.6 kJ mol^?1 (SiO₂/Ni = 0.80), and 128.3 kJ mol^?1 (SiO₂/Ni = 1.15). It was established that the reduction of Ni catalyst precursors with different SiO₂/Ni molar ratios is a complex process and can be described by the ?esták–Berggren autocatalytic model. It was found that the reaction is more Langmuir–Hinshelwood type, as hydrogen dissociates rapidly on surface nuclei and the dissociated hydrogen reacts with the Ni–O active system. It was concluded that the reduction process proceeds through bulk nucleation, which is a dominant mechanism, where three-dimensional growth of crystals with polyhedron-like morphology exists. It was found that the Ni/Si ratio decreases after the reduction process. This has been explained by low Ni and higher Si surface concentrations. It has been disclosed that Ni dispersion decreases.     

In situ production of nickel/graphitic carbon nanofiber composites and application in catalytic hydrodechlorination

The action of Ni/SiO₂ in the gas phase hydrodechlorination (at 573 K) of chlorobenzene, 1,3-dichlorobenzene and 1,3,5-trichlorobenzene is compared with that of a Ni/SiO₂ + C composite. The latter was prepared in situ by the decomposition of chlorobenzene at 873 K to generate graphitic carbon nanofibers bearing Ni particles at the fiber tips. The Ni/SiO₂ and Ni/SiO₂ + C (with varying C content) catalysts have been characterized by TEM, SEM, XRD and H₂ chemisorption. While the Ni/SiO₂ + C system delivered a lower initial fractional dechlorination, the composite outperformed the starting Ni/SiO₂ in terms of long-term activity, an effect that is linked to the structural characteristics.     

Effect of Ni loading and calcination temperature on catalyst performance and catalyst deactivation of Ni/SiO2 in the hydrodechlorination of 1,2‐dichloropropane into propylene

The hydrodechlorination of 1,2‐dichloropropane (DCPA), a chlorinated organic waste which is produced in the epichlorohydrin process, to propylene was carried out over Ni/SiO₂ catalysts. The effects of Ni loading and calcination temperature on catalyst performance and catalyst deactivation of Ni/SiO₂ were systematically investigated. The Ni/SiO₂ catalysts efficiently converted DCPA into propylene in 95% selectivity or higher. The particle size of Ni on SiO₂ was strongly related to the catalyst stability. In terms of the effect of Ni loading, the largest Ni particles on SiO₂ showed the best durability against deactivation. A series of TPR and UV‐DRS measurements revealed that nickel hydrosilicate was formed as the result of the interaction between Ni and SiO₂. Nickel hydrosilicate was found to be responsible for the catalyst stability leading to low catalyst deactivation. HCl adsorption on Ni/SiO₂ was the main reason for catalyst deactivation. HCl modified the crystal structure of metallic Ni to NiCl₂ and led to irreversible deactivation and metal sintering. This revised version was published online in July 2006 with corrections to the Cover Date.     

Suppression of carbon deposition in CO2-reforming of methane on metal sulfide catalysts

The catalytic performance of metal sulfides of Mo and W was studied for the CO₂-reforming of methane by comparing with that of Ni/SiO₂. The sulfide catalysts have lower activity than the Ni/SiO₂ catalyst for this reaction, however, no deactivation due to carbon deposition was observed on the sulfide catalysts. The activity for direct decomposition of CH₄ was much smaller on the sulfides than on supported Ni. The rate equation suggested that, during steady-state reaction, the surface was abundant in adsorbed CO₂ on sulfides, by which direct decomposition of CH₄ should be retarded in addition to their lower activity for this reaction.