Computations on Metallofullerenes Derivatized during Extraction: La@C80-C6H3Cl2 and La@C82-C6H3Cl2

Recently, an extraction of la metallofullerenes from soot using 1,2,4-trichlorobenzene has been reported for La@C₈₀ and La@C₈₂. In both cases, the cages were derivatized by the solvent (forming La@C₈₀-C₆H₃Cl₂ and La@C₈₂-C₆H₃Cl₂) and the following X-ray analysis disclosed rather unexpected cages: C₈₀(C _2v ;3) and C₈₂(C _3v ;7). In order to explain the challenging observations, a two-step computational treatment is presented. The first step deals with the high-temperature gas-phase formation of the underivatized endohedrals while the second step models the reaction with the solvent. The Gibbs free energies were evaluated for representative temperatures and the computational scheme was able to confirm high relative populations for the observed derivatized cages.     

Thermal plasma chemical vapour deposition for SiC powders from SiCH3Cl3-H2

Ultrafine -SiC powders were synthesized by introducing trichloromethylsilane and hydrogen into the high temperature RF thermal plasma argon gas. Powders were characterized by XRD, TEM, TGA, FT-IR and wet chemical analysis. Two different positions of reactant gas injection, i.e., upstream and downstream of the plasma flame, were compared in terms of the powder characteristics. The optimum concentration of hydrogen was found out to be about 3 to 4 mol % for the upstream injection. Amorphous SiC with free carbon was formed when the hydrogen concentration was lower than optimum and -SiC with free silicon was formed when it was higher than the optimum. For the downstream injection, free silicon formation was not significant and free carbon formation was suppressed when the hydrogen concentration was higher than 7 mol %. Chemical reaction pathways were suggested which could explain these observations.     

Chemical vapour deposition of Si3N4 from a gas mixture of Si2Cl6, NH3 and H2

Si₃N₄ layers were obtained on a quartz substrate from a gas mixture of Si₂Cl₆, NH₃ and H₂ under a reduced pressure in a temperature range of 800 to 1300‡ C. Amorphous Si₃N₄ layers that were dense and adherent to the substrate were obtained in a temperature range of 800 to 1100‡ C. On the other hand,α-Si₃N₄ layers were obtained at 1200‡ C and a source-gas ratio (N/Si) of 1.33 to 1.77. The lowest deposition temperature of amorphous Si₃N₄ was considered to be about 700‡ C. The microhardness of amorphous Si₃N₄ obtained in a temperature range of 800 to 1100‡ C was 2400 to 2600 kg mm⁻² (load: 50 g), and that ofα-Si₃N₄ obtained at 1200‡ C was 3400 kg mm⁻². Chlorine contents in the Si₃N₄ layer decreased with increasing deposition temperature and source-gas ratio (N/Si), and with decreasing total pressure.     

Deposition rate and structural properties of microcrystalline glow discharge Si:H,Cl films

The deposition rate and the structural properties of Si:H, Cl films produced in SiCl₄H₂ glow discharges were studied as functions of the substrate temperature, the gas feed composition and the operating pressure. The experimental results were interpreted on the basis of a discharge equilibrium involving both deposition and etching of the film. A close relationship between the deposition rate and the crystallite size is shown.     

Deposition, evaluation and control of 4H and 6H SiC epitaxial layers for device applications

We report an experimental investigation of the deposition, optical characterization and electrical properties of 6H and 4H-SiC epitaxial layers grown by atmospheric pressure chemical vapor deposition in a home made ‘cold wall’ reactor. From a growth kinetic study performed using our deposition conditions (1 atm, 1700 K) we show that our results can be very well explained using a stagnant layer model. We also underline that the decrease of the growth efficiency for high molar fractions of silane comes from the occurrence of a gaseous phase nucleation. The electronic properties of the resulting layers have been studied by Hall effect measurements. The values of electrons mobility (900 cm² Vs⁻¹ for a low doped layer) compare well with those of other groups. Finally, Schottky diodes have been processed with good forward characteristics.     

BCl3-NH3-H2-N2前驱体化学气相沉积法制备氮化硼涂层

以BCl₃-NH₃-H₂-N₂为前驱体系统, 在垂直放置的热壁反应器中利用化学气相沉积工艺制备氮化硼(BN)涂层, 分析了工艺参数对沉积速率的影响, 通过扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和X射线衍射技术(XRD)分析了碳化硅纤维表面BN涂层的形貌和微观结构, 提出了BN沉积过程中主要的气相和表面反应, 以及关键气相组分。研究结果显示：在600~850℃的范围内, 随着沉积温度的升高, BN沉积速率逐渐加快, 同一温度下, 沉积区域内BN沉积速率沿气流方向逐渐减缓, 表明气相组分在气流方向逐渐消耗; 随着系统压力的提高, BN沉积速率先加快后减缓, 表明沉积过程由表面反应控制转变为质量传输控制; 随滞留时间延长, 距气体入口1~3 cm处, BN的沉积速率逐渐增大, 而距气体入口4~5 cm处, 沉积速率先增大后逐渐变小。SEM照片显示碳化硅纤维表面BN涂层光滑致密, XPS结果表明主要成分为BN及氧化产物B₂O₃, XRD图谱表明热处理前BN为无定形态, 1200℃热处理后BN的结晶度提高, 并向六方形态转变。BN的沉积是由BCl₃和NH₃反应所生成的中间气相组分Cl₂BNH₂、ClB(NH₂)₂和B(NH₂)₃来实现的。     

Preparation of SiO2 films from Si(OC2H5)4-C2H5OH-H2O solutions without catalysts

Thin and homogeneous SiO₂ films were prepared on aluminium plates from Si(OC₂H₅)₄-C₂H₅OH-H₂O solutions which had controlled compositions and did not contain any acid as a catalyst. Aluminium with the coatings showed good corrosion resistance. However, SiO₂ films prepared from alkoxide solutions with HCI contained Cl^– ions. Aluminium with coatings including Cl^– ions corroded in a corrosion test. Alkoxide solutions without acids were necessary for use in the coating of aluminium. The transformation of gels prepared from solutions without acids to amorphous SiO₂ was investigated.     

Preparation of SiC ultrafine particles from SiH2Cl2 and C2H4 gas mixtures by a CO2 laser

Preparation of SiC ultrafine particles from SiH₂Cl₂-C₂H₄ mixtures by a CO₂ laser was investigated. The powders with specific surface area in the 8–150 m² g^–1 range were obtained by irradiating SiH₂Cl₂-C₂H₄ gas mixtures with a CO₂ laser at atmospheric pressure. X-ray diffraction of the products showed that silicon, SiC and free carbon were produced and the composition of the powders depended on the C₂H₄/SiH₂Cl₂ ratio. The reaction flame temperature changed from less than 1273 K to more than 3073 K with the laser power density and C₂H₄/SiH₂Cl₂ ratio. When SiH₂Cl₂ was irradiated with the CO₂ laser, the reaction temperature was less than 1273 K and silicon particles were formed. When the SiH₂Cl₂-C₂H₄ mixture was irradiated with a CO₂ laser, the reaction temperature was low (<1273 K) at low power density and low C₂H₄/SiH₂Cl₂ ratio, but it increased rapidly to around 3000 K at high laser power density and high C₂H₄/SiH₂Cl₂ ratio (>0.3). SiC was formed at both high and low reaction flame temperatures. It was considered that the rapid increase in the reaction flame temperature was caused by the initiation of exothermic reactions and the increase in laser absorption which was caused mainly by carbon particle formation. Hysteresis was observed between the reaction flame temperature and the power density of the laser beam. It was found that SiH₂Cl₂ underwent a disproportionation reaction on irradiation with the CO₂ laser, and silicon and SiC particles were formed through the various products of the disproportionation reaction. In particular, at low reaction flame temperature, the reactive species, such as SiH₄ and SiH₃Cl, produced by the disproportionation of SiH₂Cl₂ were considered to play an important role in the formation of silicon and SiC particles.     

Effect of gas phase on SiC and Si3N4 formations from SiO2

During the synthesis of SiC, Si₃N₄ and sialon whiskers by carbothermal reduction of SiO₂, a localized formation of amorphous phases or Si₂N₂O powders was observed beneath these whiskers. Because these whiskers were formed by the vapour/solid mechanism, the controlling gas phase was of primary importance to obtain whiskers of tailored morphology and chemistry. To elucidate the effect of the gas phase composition on the reaction mechanisms of SiC and Si₃N₄, the oxygen partial pressure was measured during the synthesis with a ZrO₂ solid electrolyte. The carbothermal reduction of SiO₂, as well as evolution of gases, were accelerated by a formation of a molten fluorosilicate with an auxiliary halide bath. The oxygen partial pressure steadily increased with increasing temperature and reached a maximum level of 10^–1110^–12 atm in the early stage of reaction at 1623 K, then decreased again towards the end of reaction in both cases. Effects of the gas phase on the SiC and Si₃N₄ formations were not the same: p _CO and and their ratio were important factors in the SiC formation, while the higher formed an oxynitride phase in the Si₃N₄ formation.     

温度对BCl3-CH4-H2化学气相沉积掺硼碳沉积过程的影响

以三氯化硼、甲烷和氢气的混合气体为前驱体,利用磁悬浮天平热重系统研究了850～1200℃区间内化学气相沉积掺硼碳的原位动力学.探索了温度对沉积速率的影响,计算了该温度区间内沉积过程的表观活化能,同时借助SEM和EDS技术.测试了不同温度点(900℃、1000℃、1100℃和1200℃)沉积产物的微观结构和成分.结果表明,化学气相沉积掺硼碳属于典型的热激活反应过程;在所研究的温度区间内存在5种不同的反应控制机制;随着温度的升高,沉积产物的n(B)/n(C)和堆积密度都显著变小,说明高n(B)/n(C)和高致密度的掺硼碳涂层应在较低的温度下制备.     

Hydration kinetics and microstructural development in the 3 CaO. Al2O3-CaSO4.2H2O-CaCO3-H2O system

Hydration and microstructural characteristics of mixtures containing C₃A and CaSO₄.2H₂O (0, 12.5, 25%) with or without addition of CaCO₃ (0, 12.5, 25%) are followed by X-ray diffraction, differential scanning calorimetry, differential thermogravimetry, scanning electron microscopy and conduction calorimetry. Depending on the length of hydration, products formed at different periods from 5 min to 3 days consisted of hexagonal calcium aluminate hydrate, cubic calcium aluminate hydrate, calcium monocarboaluminate hydrate, etrringite, calcium monosulfoaluminate hydrate and possibly a solid solution of hexagonal calcium aluminate hydrate with monocarbo-and sulfo-aluminate hydrates. Calcium carbonate retards or suppresses the formation of the cubic aluminate hydrate in the hydration of C₃A. It accelerates formation of ettringite and its conversion to the monosulfoaluminate phase when added to the C₃A+gypsum+H₂O mixture.

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Résumé On étudie l’hydratation et les caractéristiques de la microstructure de mélanges renfermant du C₃A et du CaSO₄.2H₂O (0, 12,5 et 25% avec ou sans addition de CaCO₃ (0, 12,5 et 25%) à l’aide de la diffraction X, de la calorimétrie par balayage différentiel, la thermogra-vimétrie différentielle, la microscopie électronique à balayage et la calorimétrie par conduction. Selon la durée de l’hydration, il se forme à différents intervalles allant de 5 minutes à 3 jours de l’hydrate d’aluminate de calcium hexagonal, de l’hydrate d’aluminate de calcium cubique, de l’hydrate de monocarboaluminate de calcium, de l’ettringite, de l’hydrate de monosulfoaluminate de calcium et parfois une solution solide d’hydrate d’aluminate de calcium hexagonal avec hydrate de monocarbo et sulfoaluminate. Le carbonate de calcium retarde ou empêche la formation d’hydrate d’aluminate cubique dans l’hydratation de C₃A. Il accélère la formation d’ettringite et sa conversion en phase monosulfoaluminate lorsqu’il s’ajoute au mélange C₃A+platre+H₂O.

     

Synthesis of SiO2 glass fibres from Si(OC2H5)4-H2O-C2H5OH-HCl solutions through sol-gel method

Various factors affecting the spinnability of the Si(OC₂H₅)₄-H₂O-C₂H₅OH-HCl solutions have been investigated in order to find appropriate experimental conditions for making gel-derived SiO₂ glass fibres. The molar ratios of H₂O, C₂H₅OH and HCl to Si(OC₂H₅)₄ were changed in the range from 0.5 to 10.0, 0.5 to 7.0 and 0.001 to 0.1, respectively. The solutions were reacted at 30 and 80° C. It has been reconfirmed that the most important factor determining the spinnability of the solution in the course of the hydrolysis reaction is the molar ratio of water to Si(OC₂H₅)₄ in the solution. The rise of the reaction temperature led to the remarkable shortening of the time required for drawing fibres. The increase of the amount of HCl decreased the upper limit of the H₂O/Si(OC₂H₅)₄ molar ratio range where the spinnability is found as well as reaction temperature. The solutions with a H₂O/Si(OC₂H₅)₄ ratio larger than 2.0 gave often fibres having a circular cross-section, while other solutions gave fibres with a non-circular one. The tensile strength of the gel-derived SiO₂ glass fibres was also reported.     

Siliconizing of molybdenum plate using Si2Cl6 and some of its properties

Molybdenum plate was siliconized using Si₂Cl₆ as a silicon source, and the siliconizing conditions and some of its properties were examined. The siliconizing of the molybdenum plate began by the deposition here and there of island-like MoSi₂ deposits 4 to 6m thick in the initial stage (after 10 min induction time), and then coalescence of the deposits proceeded to form a uniform MoSi₂ layer all over the molybdenum plate after 30 min siliconizing time. The weight decrease of the siliconized plate by anodic dissolution in 0.2 M sulphuric acid reduced exponentially with increasing thickness of the MOSi₂ layer, and no weight decrease was observed at all above 16m thickness. The sea water corrosion and sea sand abrasion resistivities of the siliconized molybdenum plate increased with increasing siliconizing temperature and Si₂Cl₆ flow rate.     

On the chemical vapour deposition of Ti3SiC2 from TiCl4-SiCl4-CH4-H2 gas mixtures

In the ternary system Ti-Si-C, the ternary compound Ti₃SiC₂ seems to exhibit promising thermal and mechanical properties. Its synthesis as a thin film from the vapour phase is very difficult owing to the complexity of the system. A contribution to the knowledge of the CVD of Ti₃SiC₂ from a TiCl₄-SiCl₄-CH₄-H₂ gas mixture is proposed on the basis of a thermodynamic approach. This approach is based on a reliable estimation of Ti₃SiC₂ thermodynamic data in good accordance with recent experimental results on its thermal stability. A first equilibrium calculation for the deposition on an inert substrate shows the influence of the experimental parameters on the composition of both the deposit and the gas phase. As a result, the deposition of Ti₃SiC₂ can be favoured by an excess of TiCl₄ ( 45%), a rather low pressure (10–20 kPa), high temperature ( 1273 K) and low H₂ dilution ratio. On the basis of equilibrium calculations for various reactive substrates, complex mechanisms of Ti₃SiC₂ deposition are pointed out, with intermediate steps of substrate consumption, e.g. the formation of TiC from a carbon substrate or TiSi₂ from a silicon substrate.     

On the chemical vapour deposition of Ti3SiC2 from TiCl4-SiCl4-CH4-H2 gas mixtures

An experimental study of the deposition of Ti₃SiC₂-based ceramics from TiCI₄-SiCI₄-CH₄-H₂ gaseous precursors is carried out under conditions chosen on the basis of a previous thermodynamic approach, i.e. a temperature of 1100°C, a total pressure of 1 7 kPa, various initial compositions and substrates of silicon or carbon. Ti₃SiC₂ is deposited within a narrow composition range and never as a pure phase. A two-step deposition process is observed, in agreement with the thermodynamic calculations. For a silicon substrate, TiSi₂ is formed as an intermediate phase from consumption of Si by TiCI₄ and then is carburized by CH₄ into Ti₃SiC₂. For a carbon substrate, the first step is the formation of TiC_x either from consumption of carbon by TiCI₄ or by reaction between TiCI₄ and CH₄ and then TiC_x reacts with the gaseous mixture to give rise to Ti₃SiC₂. In most cases, Ti₃SiC₂ is obtained as small hexagonal plates oriented perpendicular to the substrate surface. These nano- or micro-crystals are usually co-deposited with TiC_x and to a lesser extent SiC, and their size is increased by increasing the dilution of the gaseous mixture in hydrogen.     

Mechanism of the chemical vapour deposition of Si3N4 films from SiH2Cl2 and NH3 under diffusion-controlled conditions

At medium carrier gas flow rates the rate of chemical vapour deposition of Si₃N₄ films is limited by diffusion in the gaseous phase. The mechanism of Si₃N₄ deposition from, for example, the SiH₂Cl₂-NH₃ system in the diffusion regime is explained on the basis of the stagnant gas layer model. The applicability of the general stagnant gas layer model is based on the following simplifying assumptions: the limitation of the deposition rate by the diffusion of the single silicon-containing species, i.e. SiH₂Cl₂, and the insignificant contribution of the homogeneous reaction in the gaseous phase. The experimental results are in reasonable agreement with the theoretical predictions of the model.     

蒸发速率对Si衬底上SSMBE外延SiC薄膜的影响

采用固源分子束外延（SSMBE）生长技术,用不同的蒸发速率,在Si（111）衬底上生长SiC薄膜。利用反射式高能电子衍射（RHEED）、X射线衍射（XRD）、原子力显微镜（AFM）等实验技术,对生长的样品的形貌和结构进行研究。结果表明,在优化的蒸发速率（1.0 nm&#183;min^-1）下,所生长的薄膜质量最好。低的蒸发速率（0.25 nm&#183;min^-1）难以抑制孔洞的形成,衬底的Si原子可通过这些孔洞扩散到样品表面,导致结晶质量变差。在高的蒸发速率（1.8 nm&#183;min^-1）下,以岛状方式生长甚至以团簇聚集,表面的原子难以迁移到最佳取向的平衡位置,导致样品表面粗糙度变大,薄膜的结晶质量变差,甚至出现多晶。     

熔盐辅助合成Dy3Si2C2包裹SiC粉体及其陶瓷的烧结行为

碳化硅陶瓷因自身优良的物理化学性能而具有广泛的应用前景.碳化硅的化学键结合特性决定了其难以烧结成型,因此如何制备高质量碳化硅陶瓷是领域内的难点之一.本研究以三元稀土碳化物Dy3Si2C2作为新型SiC陶瓷的烧结助剂,依据Dy-Si-C体系的高温相转变原位促进碳化硅的烧结致密化.采用放电等离子烧结技术,利用金属Dy与Si...     

Oxidation kinetics of SiC deposited from CH3SiCl3/H2 under CVI conditions

Oxidation tests were performed on SiC deposits prepared from CH₃SiCl₃/H₂ under chemical vapour infiltration conditions, at temperatures ranging from 900–1500 °C under a flow of pure oxygen at 100 kPa (passive oxidation regime). The kinetics of growth of the silica layer were established from thickness measurements performed by spectroreflectometry. They obey classical parabolic laws from which rate constants are calculated. Within 1000–1400 °C, the oxidation process is thermally activated with an apparent activation energy of 128 kJ mol^–1. Above 1400 °C and below 1000 °C, an increase in the activation energy is observed which is thought to be related to a change in the mechanism of the oxygen transport across the silica layer forT>1400 °C and tentatively to stress effects forT<1000 °C. The kinetics data are compared to those measured on silicon single crystals (used as a standard) and to other reported data on SiC.