Silica to Silicon: Key Carbothermic Reactions and Kinetics

The primary carbothermic reactions for the reduction of silica to produce silicon were defined and the reaction kinetics were determined. Most possible reactions between silicon oxide and carbon or carbon compounds were studied by a series of thermogravimetric analyses at temperatures up to 2000°C. Four key sequential reactions occur with SiC and SiO as intermediate reactants; two reactions involve SiO₂ and two involve SiO. Reaction rate versus temperature, activation energy, and preexponential factors were determined for each of six reactions involving SiO₂ or SiO. These kinetic studies show that SiO, when combined with either carbon or Sic, reacts in the gaseous state, and the sublimation of SiO is not the rate-limiting reaction for forming silicon.     

The use of a mixing-sensitive chemical reaction for the study of pulp fibre suspension mixing

The competitive, consecutive chemical reactions between 1-naphthol and diazotized sulfanilic acid were utilized to study the mixing of a pulp fibre suspension in a 22 L stirred tank reactor. Mixing quality was determined from the distribution between the mono and bis substituted reaction products once a correlation was made for the adsorption of the product dyes onto the suspended fibres. The technique was found to be adequate for assessing micromixing and turbulence intensity within a fibre suspension provided the measured product distribution, Xs, was between 0.4 and 0.01. Thus the mixing conditions that could be assessed depended on both the energy dissipation within the mixer and the amount of the fibre present. For the experimental conditions chosen for this study energy dissipation rates would typically have to be less than 80 W/kg and the suspension mass concentration less than 2.5%. When compared with water, a reduction in turbulence levels at both the impeller zone and a remote zone in the stirred vessel was observed for fibre mass concentrations as low as 0.5%. The turbulence decreased as the suspension mass concentration was increased. This decrease is attributed to energy dissipation by friction at fibre-fibre contact points as the fibres move relative to one another in the flow. This sink removes energy from the turbulence cascade which never shows up as small-scale fluid deformations leading to better mixing.     

Ractions of SiC with H2/H2O/Ar Mixtures at 1300°C

The reactions of a sintered α-SiC with 5% H₂/H₂O/Ar at 1300°C were studied. Thermomchemical modeling indicates that three reaction regions are expected, depending on the initial water vapor or equivalently oxygen content of the gas stream. A high oxygen content ( P (O₂) > 10⁻²² atm) leads to a SiO₂ formation. This generally forms as a protective film and limits consumption of the SiC (passive oxidation). An intermediate oxygen content (10⁻²² atm > P (O₂) > 10⁻²⁶ atm) leads to SiO and CO formation. These gaseous products can lead to rapid consumption of the SiC (active oxidation). Thermogravimetric studies in this intermediate region gave reaction rates which appear to be controlled by H₂O gas-phase transport to the sample and reacted microstructures showed extensive grain-boundary attack in this region. Finally, a very low oxygen content ( P (O₂) < 10⁻²⁶ atm) is thermochemically predicted to lead to selective removal of carbon and formation of free silicon. Experimentally low weight losses and iron silicides are observed in this region. The iron silicides are attributed to reaction of free silicon and iron impurities in the system.     

Two-variable periodic perturbation of kinetic oscillations

Using one of the generic models (CO oxidation on Pt with surface-oxide formation) predicting kinetic oscillations in heterogeneous catalytic reactions, we show that the efficiency of two-variable periodic perturbations with respect to converting natural period-1 oscillations to period-l oscillations at the forcing frequency is remarkably sensitive to the kind of perturbations used. Counter-phase perturbations are much more effective compared to in-phase perturbations. The physics underlying these findings is suggestive of their applicability to many other models and/or real systems exhibiting kinetic oscillations.     

基于正交试验设计的岩坡力学参数反演

对某岩坡Ⅲ区现场勘察后认为,该区为断层破碎带,属碎裂结构,岩体分级为Ⅳ级.由于地质情况复杂、岩体破碎以及边坡开挖引起的应力释放等原因,致使边坡岩体加固的力学参数用常规方法较难确定.运用正交试验设计的方法借助有限差分程序FLAC进行分析,以安全系数作为评价指标,模拟各参数不同水平的各种组合,对影响边坡稳定性的各因素进行了敏感性分析,并对边坡力学参数进行了反演,得出较为合理的力学参数,为边坡治理提供依据.     

From surface science to catalysis: Surface “explosions” observed on Rh crystals and supported catalysts

Phenomena called surface explosions have been reported for decomposition reactions on single crystals, and have been identified by the use of desorption methods. In particular, in TPD, they are manifested by extremely narrow peaks (as little as 3 K in width) and a desorption rate which increases with time in isothermal experiments. In this paper we report such observations for acetate species on Rh single crystals, but extend this to show for the first time that such effects are not restricted to single crystal/UHV experiments, but can also be found on a Rh/Al₂O₃ catalyst under ambient pressure conditions. These reactions can be classified as second order autocatalytic surface processes, where free surface Rh sites are an essential component of the reaction. It is shown that coadsorbed adatoms are also essential for such explosions to be seen and their role is proposed to be that of a template layer acting to order the acetate in self-poisoning configurations.     

Measurement of intrinsic rates for homogeneous gas‐phase reactions at high temperatures

A coiled quartz tubular reactor has been designed to measure the intrinsic reaction kinetics for homogeneous reactions at high temperatures up to 1100°C. Actual gas residence times were less than 100 ms. A simple and well‐studied test reaction (i.e., the decomposition of nitrous oxide, N₂O), with published intrinsic kinetics, was used to verify the operation of the experimental reactor. For this system, Peclet numbers (Pe = uL/DL) computed from experimental conversion data were greater than 1000, indicating that the plug flow assumption could be used with this reactor system to determine intrinsic rate expressions with errors of less than 5% for the conditions studied.     

Poly(styrene-b-isobutylene-b-styrene) block copolymer ionomers (BCPI) and BCPI/silicate nanocomposites. 2. NaBCPI sol-gel polymerization templates

Polystyrene (PS) blocks in poly(styrene-b-isobutylene-b-styrene) (PS-PIB-PS) block copolymers were partially sulfonated and the acid groups converted to Na⁺SO₃⁻ groups to create ionomers. Then, dimethylacetamide was used to selectively swell the ionic PS domains and the swollen films were exposed to sol-gel reactive tetraethylorthosilicate solutions. (EtO)_4−xSi(OH)_x monomers then permeated films so that sol-gel reactions occurred within/around the ionic PS domains. Environmental scanning electron microscopy/energy dispersive X-ray spectroscopy investigations showed that silicate structures can be incorporated within the interior of the ionomer films. Differential scanning calorimetry studies indicated that there is no variance in the PIB block T_g with respect to ionomer formation, or with respect to silicate loading of the ionomer at low levels, which suggests that the silicate component does not reside in the PIB phase. ²³Na solid state NMR spectroscopy detected isolated Na⁺SO₃⁻ groups as well as aggregated SO₃⁻Na⁺ ion pairs for ‘as cast’ and ‘dry’ non-silicate containing ionomer samples. In a hydrated sample, almost all Na⁺ ions were solvent-separated. AFM analysis showed that phase separation exists, but that the degree of order is significantly less than that for hybrids based on the corresponding benzyltrimethylammonium ionomer. This frustrated morphology was also seen in the results of small angle X-ray scattering experiments. Given the scale of organic/inorganic heterogeneity, these hybrids are properly classified as nanocomposites.     

高能量密度水溶性有机液流电池的开发策略

水溶性有机液流电池自2014年出现后发展迅猛,特别是近些年来有机电活性物质的降解和二聚导致的容量衰减问题得到初步解决后,该类液流电池有望作为大规模储能系统的候选者。然而能量密度较低的问题限制了其商业化的进程。对此,主要从增大溶解度、提高电化学窗口和电子的得失数这3个方面详细介绍了5种提高水溶性有机液流电池能量密度的方法——分子结构剪裁、“interaction-mediating”策略的应用、采用聚合物电活性物质、“氧化还原靶向”原理和电极表面的改性,同时对进一步提高水溶性有机液流电池能量密度的策略进行了简要展望。     

A transient method for characterizing flow regimes in a circulating fluid bed

In recent years, although an increasing number of literature have been devoted to circulating fluidized bed (CFB), the prediction of velocities over which different fluidization regimes exist is still difficult. In this study, a transient method was applied which readily allows one to identify operational features and critical transitions. The method is based on stopping the solids flow rate into the riser when riser is operating in fully dense transport regime. The analysis of transient pressure drop data across the riser during a solids flow cut-off experiment against its time derivative demonstrate the three distinct operating regimes that exist as the gas deplete the solid out of the riser. The transient was compared to data taken under steady state operations using statistically designed experiments. Results indicated that although there were significant differences when comparing operations in dilute conditions, there were no significant differences between the two methods in the fast fluidized and dense transport regimes. The transient method was capable of reproducing the solids circulation dependence on riser solids holdup and on the axial pressure profile. This transient method offers an accurate, easy, rapid, and reproducible means of characterizing CFB operations over a wide range of flow conditions. The lack of accuracy in the dilute regime is conjectured to be due to the wide particle size distribution that resulted in segregation during the transient testing.