The influence of reaction parameters on the free Si and C contents in the synthesis of nano-sized SiC

Uniform nano-sized beta-silicon carbide (β-SiC) powder was synthesized from the reaction of silicon (Si) and carbon black (C). Mixed Si and C-black powder were pressed into pellets and the influence of four parameters, temperature (1250, 1300 and 1350 °C), heating rate (20 and 50 °C/min), soaking time (1 and 3 h) and atmosphere (vacuum and argon), were tested. It was found that higher temperatures, higher heating rates and longer soaking times in a vacuum system lead to lower free Si content in the SiC powder created. Temperature was the parameter with the greatest influence on the Si content of the SiC powder. This study also found that the Si–C reaction occurs through gas–solid (SiO–C) and solid–solid (Si–C) reactions that occur simultaneously.     

Sintering characteristics of in situ formed low expansion ceramics from a powder precursor in the form of hydroxy hydrogel

Lithium aluminosilicate powder precursors of compositions Li₂O:Al₂O₃:SiO₂ as 1:1:2; 1:1:2.5 and 1:1:3 were prepared in the hydroxy hydrogel form by wet interaction technique in aqueous medium followed by sintering for ultimate synthesis of low expansion ceramics. Phases formed in the sintered specimens were analyzed by XRD technique. Thermal expansion of the specimens sintered at 1100, 1200 and 1300 °C were also measured. It was found that β-spodumene, lithium aluminum oxide and silica were the predominat phases in all the specimens. Sintering was optimum up to 1200 °C beyond which no further noticeable shrinkage was observed. The sintered specimens remained highly porous even after firing at 1300 °C, whose bulk density and apparent porosity were in the range of 1.25–1.42 g/cm³ and 43–48%, respectively. Thermal expansion characteristics and density of the sintered specimens were found to be primarily related to the composition of the phases formed during sintering. A porous low expansion ceramic monolith could be prepared using the present technique.     

High surface area silicon carbide doped with zirconium for use as catalyst support. Preparation, characterization and catalytic application

Zirconium doped SiC with a surface area from 88 to 200 m² g⁻¹ was synthesized using the shape memory concept method followed by calcination in air at a temperature of ≤480°C. The material obtained was composed of β-SiC and small ZrO₂ particles dispersed throughout the material matrix and a significant amount of an amorphous phase containing Si, Zr and O. Molybdenum oxycarbide, the active isomerization phase, supported on such a material displayed a similar behavior to that obtained on pure SiC for the n-heptane isomerization reaction. A comparison made with the molybdenum oxycarbide catalyst supported on pure ZrO₂ showed that the Zr doped SiC was not simply made of silicon carbide coated with a layer of ZrO₂ on the surface but probably an amorphous phase containing Si, Zr and O which displays a similar behavior as pure SiC.     

Influence of temperature on the structure of SiC coatings prepared by dynamic ion mixing

We deposited silicon carbide films, 0.5 μm and 0.86 μm thick at room temperature (RT) and 750 °C on (100) silicon wafers and TA6V substrates. An SiC target was sputtered with a 1.2 keV Ar⁺ ion beam delivered by a Kaufman-type ion source, and the growing films were continuously bombarded with a beam of 160 keV Ar⁺ ions. The microstructural state of the films was investigated by complementary techniques: transmission electron microscopy (TEM), high-resolution TEM, glancing X-ray diffraction (GXRD) and Fourier transform infrared spectroscopy (FTIR). All these characterization methods show that the bombardment of the growing films induces important structural changes. The SiC films prepared at RT without mixing are amorphous, whereas those deposited by dynamic ion mixing (DIM) at RT exhibit the beginning of crystallization of the β-SiC phase. At 750 °C the films prepared by DIM are formed of nanocrystallized grains of the cubic β-SiC phase.     

Characterization of nanocrystalline porous SiC powder by electrospinning and carbothermal reduction

Nanocrystalline porous silicon carbide (SiC) powder was prepared from various ratios with SiO₂ as silicon source and carbon black as carbon source by electrospinning method and subsequent carbothermal reduction. Their microstructure, thermal stability and porosity of prepared porous silicon carbide (SiC) powder were evaluated as function of Si to C ratios in precursor. 3C/Si could not often maintain the spherical form against oxygen–carbon reaction during calcination owing to relatively low carbon content. On the other hand, the uniformed spherical forms were presented with deep wrinkles in the other prepared samples. They were believed that the wrinkled surfaces were formed by vaporization of carbonaceous gas made from carbon and oxygen. When the carbon ratio to silicon (C/Si) was 5, the β-SiC was observed without remained silica and silicon metal. Further increase in the carbon content in the precursor led to sharp and high intensity of SiC peak. Initial decomposition temperature of prepared sample was increased with decreasing C/Si ratio. We confirmed that whereas 3C/Si and 4C/Si had higher big macropore, 5C/Si and 6C/Si had much large pore volume in the range of mesopore diameter (2–50 nm) and small macropore (50–100 nm).     

Porous Silicon Carbide Ceramics Produced by a Carbon Foam Derived from Mixtures of Mesophase Pitch and Si Particles

Carbon foam templates were prepared from a mixture of mesophase pitch (MP) and Si particles, followed by foaming and carbonization. Subsequent molten Si infiltrated into the carbon foam at 1500°C for 4 h in an inert atmosphere resulted in the formation of porous SiC ceramics. Micrographs were investigated by a scanning electron microscope (SEM), and phase identification of porous SiC ceramics was performed by X-ray diffraction (XRD). The flexural strength and bulk density of porous SiC ceramics were also measured and calculated. The results revealed that the flexural strength of porous SiC ceramics increases with increasing Si content and decreasing porosity. The addition of Si in MP results in an increased densification of porous SiC struts. With 50 wt% Si, porous SiC ceramics with a high flexural strength of 23.9 MPa and a porosity of 55% were obtained.     

Preparation and properties of C/SiC/ZrO2 porous composites by hot isostatic pressing the pyrolyzed preforms

Three phase mixture of C/SiC/ZrO₂ porous composites were prepared from commercially available phenolic resin, Si and ZrO₂ powders. In the first step, mixed powders were pyrolyzed at 850 °C in vacuum to obtain a carbonized microporous material and then hot isostatically pressed at 1200, 1300 and 1350 °C for 10 min in an argon pressure of 50 MPa to prepare C/SiC/ZrO₂ porous composites, in second step. The hot isostatic pressing led to the increase in density from 3.28 to 3.48 g/cm³ and reduction in porosity (from 32 to 20%) of the composites. X-ray diffraction analyses revealed the existence of β-SiC and carbon might be amorphous in the composites. According to the results of scanning electron microscopy, the crystal growth of β-SiC with facets was observed at 1350 °C. In addition, the energy dispersive spectroscopy showed that carbon/silicon atomic ratio was 1:1 in the crystals. X-ray photoelectron spectroscopy of the composites suggested that evolved gaseous molecules, due to the decomposition of phenolic resin, reacted with molecules containing Si to form β-SiC. The formation and growth of β-SiC in addition to the densification of matrix by hot isostatic pressing led to the increase in hardness (max.: 13.99 GPa) at higher temperatures.     

SiC-Si coating with micro-pores to protect carbon/carbon composites against oxidation

To improve the oxidation resistance of carbon/carbon (C/C) composites at high temperatures, a SiC-Si coating with micro-pores was prepared by slurry and heat-treatment on the surface of C/C composites with SiC-Si inner coating acquired by pack cementation (PC). The microstructure, phase composition, element distribution, and anti-oxidation properties of the dual-layer SiC-Si coating were investigated. The results show that a SiO₂-SiC inlay structure was formed during the oxidation process, due to a large amount of SiO₂ rapidly generated by the oxidation of SiC particles in the porous coating. The coating with this structure could inhibit the cracking of SiO₂ glass and had a good resistance to oxygen diffusion. Moreover, the crack propagation was blocked by the remaining micro-pores of the coating. The coating could protect C/C composites against oxidation for 846 h only with the mass loss of 0.16 % at 1773 K in air.     

Low temperature synthesis of β-SiC by a metal vapor vacuum arc ion source

β-SiC surface layers were synthesized by implantation of C⁺ into Si substrates at a comparatively low temperature of 400°C with a metal vapour vacuum arc ion source. X-ray diffraction patterns showed that these layers had a strong (111) preferred orientation. The amount of β-SiC formed increased significantly with the rise of the implantation dose, but the crystallinity of the layers formed relied little on the implantation dose. Both the broad X-ray diffraction peaks and the scanning electron microscopy photograph showed that the grain size of the sample with a dose of 7×10¹⁷ cm⁻² is relatively small.     

Phase transitions of antiferroelectric lead zirconate thin films in high electric field

Phase transitions in antiferroelectric lead zirconate thin films were studied at room temperature and at 77 K. The lead zirconate films were prepared on Pt coated Si substrates by a reactive magnetron co-sputtering mthod followed by a rapid thermal annealing process at 700 °C. An electric field induced antiferroelectric — ferroelectric phase transition was observed at room temperature with a maximum polarization value of 70 μC/cm². The average field required to induce the ferroelectric state and that for the reversion to the antiferroelectric state were 294 kV/cm and 179 kV/cm respectively. At 77 K a metastable ferroelectric — ferroelectric transition was observed with a maximum polarization of 58 μC/cm². These transitions were found to be coincident with those of lead zirconate single crystals.     

Facile synthesis of SiOx spheres or dumbbell-shaped β-SiC whiskers on expanded graphite by silicon vapor deposition

A facile method was developed to synthesize SiO_x spheres or dumbbell-shaped β-SiC whiskers on expanded graphite (SiO_x/EG or β-SiC/EG) by silicon vapor deposition without catalyst. With the carbon black atmosphere, the above hybrids were synthesized above 1100 °C in a graphite crucible where silicon powder was placed under the expanded graphite (EG). The growth of SiO_x spheres is controlled by vapor-solid mechanism at 1100 °C and 1200 °C. Namely, the active carbon atoms absorbed SiO (g) and Si (g) to form SiC nuclei. Then, the SiO₂, residual SiO (g) and Si (g) deposited on SiC nuclei to form SiO_x spheres. At 1300 °C and 1400 °C, the same SiO_x spheres formed on EG as well as many dumbbell-shaped β-SiC whiskers. The growth of dumbbell-shaped β-SiC whiskers is controlled by vapor-vapor and vapor-solid mechanism successively. In a word, firstly, the β-SiC whiskers with defects formed via the reaction between Si (g) and CO (g). After that, the SiO₂, residual SiO (g) and residual Si (g) preferentially deposited on defects, then deposited on other parts of β-SiC whiskers to form dumbbell-shaped SiC whiskers.     

Preparation of three-dimensional ordered macroporous SiCN ceramic using sacrificing template method

Three-dimensional (3D) long range well ordered macroporous SiCN ceramics were prepared by infiltrating sacrificial colloidal silica templates with the low molecular weight preceramic polymer, polysilazane. This was followed by a thermal curing step, pyrolysis at 1250 °C in a N₂ atmosphere, and finally the removal of the templates by etching with dilute HF. The produced macroporous SiCN ceramics showed high BET surface areas (pore volume) in the range 455 m²/g (0.31 cm³/g)–250 m²/g (0.16 cm³/g) with the pore sizes of 98–578 nm, which could be tailored by controlling the sizes of the sacrificial silica spheres in the range 112–650 nm. The sphere-inversed macropores were interconnected by 50 ± 30 nm windows and 3–5 nm mesopores embedded in the porous SiCN ceramic frameworks, which resulted in a trimodal pore size distribution. The surface of the achieved porous SiCN ceramic was then modified by Pt–Ru nanoparticle depositing under mild chemical conditions.     

The thermal,electrical and mechanical properties of porous α-SiC ceramics bonded with Ti3SiC2 and β-SiC via low temperature in-situ reaction sintering

Porous SiC ceramics have recently attracted wide attention for their applications in the electrically heatable filter. Further improvement of the thermal and electrical conductivity without sacrificing permeability is a critical parameter for such applications. In the present work, porous SiC/Ti₃SiC₂ ceramic composites with Ti₃SiC₂ and micro/nano SiC have been prepared from TiC/Si/α-SiC mixtures at a low sintering temperature (1400 °C). Nano-laminated Ti₃SiC₂ enhanced the electrical conductivity, while the good thermal conductivity was achieved through in-situ formed nano β-SiC and raw coarse α-SiC in the porous ceramics. Along with the increase of initial α-SiC particle size from 0.76 to 16.13 μm, the permeability, thermal and electrical conductivity improved due to the decreased porosity and increased pore size in porous SiC/Ti₃SiC₂ ceramics. The results suggested that the decoupling of the electrical conductivity from the thermal conductivity could be tuned by adjusting the initial α-SiC particle size.     

Synthesis, densification and electrical properties of strontium cerate ceramics

Powders of pure and 5% ytterbium substituted strontium cerate (SrCeO₃/SrCe_0.95Yb_0.05O_3−δ) were prepared by spray pyrolysis of nitrate salt solutions. The powders were single phase after calcination in nitrogen atmosphere at 1100 °C (SrCeO₃) and 1200 °C (SrCe_0.95Yb_0.05O_3−δ). Dense SrCeO₃ and SrCe_0.95Yb_0.05O_3−δ materials were obtained by sintering at 1350–1400 °C in air. Heat treatment at 850 and 1000 °C, respectively, was necessary prior to sintering to obtain high density. The dense materials had homogenous microstructures with grain size in the range 6–10 μm for SrCeO₃ and 1–2 μm for SrCe_0.95Yb_0.05O_3−δ. The electrical conductivity of SrCe_0.95Yb_0.05O_3−δ was in good agreement with reported data, showing mixed ionic–electronic conduction. The ionic contribution was dominated by protons below 1000 °C and the proton conductivity reached a maximum of 0.005 S/cm above 900 °C. In oxidizing atmosphere the p-type electronic conduction was dominating above 700 °C, while the contribution from n-type electronic conduction only was significant above 1000 °C in reducing atmosphere.     

Development of SiC–Si composites with fine-grained SiC microstructures

This work summarises the influence of the original particle-size of the SiC powder on the mechanical properties of silicon infiltrated SiC (SiC-Si) composite. These composites are based on a defined SiC particle-size structure. Using α-SiC powders with a mean particle-size of 12·8, 6·4, 4·5 and 3 μm, a clear linear enhancement of the bending strength with decrease of SiC-particle-size was observed. However, a further decrease of the SiC particle-size (from 3 to 0·5 μm) brought no increase of the strength and toughness, respectively. ©     

光伏废料制备Si3N4-SiC材料的抗氧化性和抗侵蚀性

将光伏废料经酸洗除杂后,与硅粉按85∶15的质量比配料,以聚乙二醇做结合剂,成型为10 mm×10 mm×20 mm的生坯后,在1380℃保温2 h氮化制成Si3N4-SiC材料,然后研究了该Si3N4-SiC材料的抗氧化性和抗侵蚀性。结果表明:1)制备的Si3N4-SiC材料在空气气氛中抗氧化性较好,主要是由于其氧化产物Si2N2O和SiO2填充气孔,促进烧结,提高了试样的致密度。2)在静态熔盐(Na3AlF6)中的抗侵蚀性能较好,主要是由于Na3AlF6渗入气孔中,使其显气孔率降低。3)在动态熔盐中的抗侵蚀性相对变差,主要是由于CO2气体的搅拌和对Si3N4、SiC的氧化二者共同作用的结果。     

Pressure‐less joining of C/SiC and SiC/SiC by a MoSi2/Si composite

A MoSi₂/Si composite obtained in situ by reaction of silicon and molybdenum at 1450°C in Ar flow is proposed as pressure‐less joining material for C/SiC and SiC/SiC composites. A new “Mo‐wrap” technique was developed to form the joining material and to control silicon infiltration in porous composites. MoSi₂/Si composite joining material infiltration inside coated and uncoated C/SiC and SiC/SiC composites, as well as its microstructure and interfacial reactions were studied. Preliminary mechanical strength of joints was tested at room temperature and after aging at service temperatures, resulting in interlaminar failure of the composites in most cases.     

The preparation and properties of PZT thin film by sputering method

The ferroelectric PZT thin films were prepared on Pt/Ti/SiO₂/Si substrate by RF sputtering method followed by the rapid thermal annealing. The preparation of the Pt and Ti thin films as bottom electrode, and their influences on the PZT thin films were studied in details. The substrate temperature during sputtering was room temperature; the rapid thermal annealing temperature was 500°C-750°C and the annealing time was 30-70s. The influences of different preparation parameters on the structure and electric properties were studied with X-ray diffraction technique and RT66A Standardized Ferroelectric Test System. The electric properties of the prepared PZT thin film was: P_a=39μc/cm₂, P_r = 9.3 μc/cm², E_c=28KV/mm, ε=300, p=10⁹ω⋅cm.     

Nitridation of silicon powder studied by XRD, Si MAS NMR and surface analysis techniques

The nitridation of elemental silicon powder at 900–1475 °C was studied by X-ray photoelectron spectroscopy (XPS), X-ray excited Auger electron spectroscopy (XAES), XRD, thermal analysis and ²⁹Si MAS NMR. An initial mass gain of about 12% at 1250–1300 °C corresponds to the formation of a product layer about 0·2 μm thick (assuming spherical particles). XPS and XAES show that in this temperature range, the surface atomic ratio of N/Si increases and the ratio O/Si decreases as the surface layer is converted to Si₂N₂O. XRD shows that above 1300 °C the Si is rapidly converted to a mixture of - and β-Si₃N₄, the latter predominating >1400 °C. In this temperature range there are only slight changes in the composition of the surface material, which at the higher temperatures regains a small amount of an oxidised surface layer. By contrast, in the interval 1400–1475 °C, the ²⁹Si MAS NMR chemical shift of the elemental Si changes progressively from about −80 ppm to −70 ppm, in tandem with the growth of the Si₃N₄ resonance at about −48 ppm. Possible reasons for this previously unreported change in the Si chemical shift are discussed. ©     

A Si–SiC oxidation protective coating for carbon/carbon composites prepared by a two-step pack cementation

To prevent carbon/carbon (C/C) composites from oxidation, a Si–SiC coating has been prepared by a two-step pack cementation technique. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis show that the coating obtained by the first step pack cementation is a porous β-SiC structure, and a dense structure consisting α-SiC, β-SiC and Si is obtained after heat-treatment by the second step pack cementation. By energy dispersive spectroscopy (EDS) analysis, a gradient C–SiC transition layer can be formed at the C/C-coating interface. The as-received coating has excellent oxidation protection ability and can protect C/C composites from oxidation for 166 h at 1773 K in air. The weigh loss of the coated C/C is due to the formation of bubble holes on the coating surface and through-coating cracks in the coating.