Mechanistic Studies of the Solvolyses of Carbamoyl Chlorides and Related Reactions

Carbamoyl chlorides are important intermediates, both in the research laboratory and in industrial scale syntheses. The most studied and used are the disubstituted derivatives, incorporating either aryl or alkyl groups (Ar₂NCOCl or R₂NCOCl). Sometimes, the groups are tied back to give a ring and piperidino- and morpholino-derivatives are commonly encountered. Some studies have been made with two different groups attached. Solvolyses tend to occur at the carbonyl carbon, with replacement of the chloride ion. Studies of both rate and products are reviewed and the solvolysis reactions are usually S_N1, although addition of an amine leads to a superimposable bimolecular component. Many of the studies under solvolytic conditions include the application of the extended Grunwald–Winstein equation. The monosubstituted derivatives (ArNHCOCl or RNHCOCl) are less studied. They are readily prepared by the addition of HCl to an isocyanate. In acetonitrile, they decompose to set up and reach equilibrium with the isocyanate (ArNCO or RNCO) and HCl. Considering that the structurally related formyl chloride (HOCOCl) is highly unstable (with formation of HCl + CO₂), the unsubstituted carbamoyl chloride (H₂NCOCl) is remarkably stable. Recommended synthetic procedures require it to survive reaction temperatures in the 300–400 °C range. There has been very little study of its reactions.     

How Different Characterization Techniques Elucidate the Nature of the Gold Species in a Polycrystalline Au/TiO2 Catalyst

TiO₂‐supported gold species were prepared via the deposition‐precipitation route, with conservation of the initial speciation by freeze‐drying. The structural and electronic properties of the Au species were investigated by X‐ray absorption spectroscopy, electron microscopy, and IR spectroscopy of adsorbed CO in four states. Exclusively Au^III was deposited on the TiO₂ surface in patches ranging from isolated Au ions to three‐dimensional clusters. This paper illustrates in detail the unique contributions of all characterization techniques to this structural model.     

An Innovative Submerged Entry Nozzle Design for Billet and Bloom Casting

Fluid flow in the mold has a significant impact on the quality of continuously cast steel products.Since it is strongly influenced by the SEN design,attention h...     

A Reliable Method for Recycling (RE)‐Ba‐Cu‐O (RE: Sm,Gd, Y) Bulk Superconductors

Single grain (RE)‐Ba‐Cu‐O (RE: Sm, Gd, Y) high‐temperature superconductors are able to generate high magnetic fields. However, the relatively high cost of the raw materials and the low yield of the manufacturing process have impeded the development of practical applications of these materials to date. This article describes a simple, reliable, and economical method of recycling failed bulk (RE)‐Ba‐Cu‐O (RE: Sm, Gd, Y) samples. Sixty‐four failed bulk samples, with diameters up to 31 mm, were recycled with a yield of 90%. The key innovation in this recycling process involves reintroducing the liquid phase into the melt process, which is normally lost during the primary peritectic processing of these materials. This enables the direct re‐growth of failed samples from solid form without the need for re‐grinding into powder. We also demonstrate that the superconducting performance and microstructure of the recycled samples is similar to that of the primary grown samples.     

Soil-washing design methodology for a lead-contaminated sandy-soil

Soils located near high traffic roadways, particularly where renovations have taken place, typically exhibit elevated levels of trace metals in the upper soil horizon. Regulators are currently seeking an efficient method of site characterization and treatment system design which will lend itself to timely and environmentally efficacious clean-up. The soil investigated in this study was a silty sand collected near a bridge abutment for a major interstate highway. The soil had a total lead content of 1392 mg/kg. In addition, the soil contained a considerable fraction of organic carbon (approximately 6.3%). A sequential chemical extraction indicated that a fraction of contaminants were in labile soil phases and thus amenable to chemical extraction (soil-washing). A soil washing design methodology is presented based on surface chemistry and equilibrium stage operation. In this work, a double layer surface complexation model was used to describe equilibrium sorption behavior and a preliminary design of an ex-situ counter-current equilibrium stage extraction process is presented. Model calibration was conducted using sorption data obtained from a 1:40 solid to liquid ratio (s/l), adsorption edge. Model validation was accomplished with batch titration data and a 1:20 s/l, adsorption edge. The model accurately predicted leachable lead concentrations over a wide pH range. The required number of ideal equilibrium stages was highly sensitive to pH.     

外包混凝土组合钢柱的偏心受压分析

给出了偏心受压下外包混凝土组合钢柱的3维非线性模型。该组合柱两端铰接,沿主要轴线方向施加一个偏心力。此偏心率的范围在柱截面总高度的0.125～0.375之间。该模型考虑钢、混凝土、纵向和横向钢筋的非弹性性能,以及组合柱中混凝土的约束作用。考虑了钢与混凝土之间、纵向与横向钢筋之间、钢筋与混凝土之间交界面粘结力,以及不同材料对组合柱抵抗变形所起的作用。该模型考虑了初始几何缺陷。已有的试验数据证明了模型的有效性。混凝土强度等级为30～110MPa。钢截面的屈服应力为275～690MPa。通过改变偏心率、柱的尺寸、结构钢尺寸与屈服应力值和混凝土强度,以确定其对偏心受压下组合柱性能的影响。结果显示,结构钢屈服应力的增加对组合柱强度的影响较大,尤其当柱的偏心率为0.125D时。当柱的偏心率为0.375D且混凝强度低于70MPa时,结构钢屈服强度的变化对柱强度影响较大。将数值分析所得组合柱的强度与设计规范Eurocode4的计算结果进行比较。结果表明,Eurocode4准确地计算出偏心组合柱强度,但是估算的弯矩过大。     

Comparative study of arsenic removal by iron using electrocoagulation and chemical coagulation

This research studied As(III) and As(V) removal during electrocoagulation (EC) in comparison with FeCl₃ chemical coagulation (CC). The study also attempted to verify chlorine production and the reported oxidation of As(III) during EC. Results showed that As(V) removal during batch EC was erratic at pH 6.5 and the removal was higher-than-expected based on the generation of ferrous iron (Fe²⁺) during EC. As(V) removal by batch EC was equal to or better than CC at pH 7.5 and 8.5, however soluble Fe²⁺ was observed in the 0.2-μm membrane filtrate at pH 7.5 (10-45%), and is a cause for concern. Continuous steady-state operation of the EC unit confirmed the deleterious presence of soluble Fe²⁺ in the treated water. The higher-than-expected As(V) removals during batch mode were presumed due to As(V) adsorption onto the iron rod oxyhydroxides surfaces prior to the attainment of steady-state operation. As(V) removal increased with decreasing pH during both CC and EC, however EC at pH 6.5 was anomalous because of erratic Fe²⁺ oxidation. The best adsorption capacity was observed with CC at pH 6.5, while lower but similar adsorption capacities were observed at pH 7.5 and 8.5 with CC and EC. A comparison of As(III) adsorption showed better removals during EC compared with CC possibly due to a temporary pH increase during EC. In contrast to literature reports, As(III) oxidation was not observed during EC, and As(III) adsorption onto iron hydroxides during EC was only 5-30% that of As(V) adsorption. Also in contrast to literature, significant Cl₂ was not generated during EC, in fact, the rods actually produced a significant chlorine demand due to reduced iron oxides on the rod. Although Cl₂ generation and As(III) oxidation are possible using a graphite anode, a combination of graphite and iron rods in the same EC unit did not produce As(III) oxidation. However, a two-stage process (graphite anode followed by iron anode in separate chambers) was effective in As(III) oxidation and removal. The competing ions, silica and phosphate interfered with As(V) adsorption during both CC and EC. However, the degree of interference depends on the concentration and presence of other competing ions. In particular, the presence of silica lowered the effect of phosphate with increasing pH due to silica’s own significant effect at high pHs.     

Mathematical modeling of ammonia-fed solid oxide fuel cells with different electrolytes

An electrochemical model was developed to study the ammonia (NH₃)-fed solid oxide fuel cells with proton-conducting electrolyte (SOFC-H) and oxygen ion-conducting electrolyte (SOFC-O). Different from previous thermodynamic analysis, the present study reveals that the actual performance of the NH₃-fed SOFC-H is considerably lower than the SOFC-O, mainly due to higher ohmic overpotential of the SOFC-H electrolyte. More analyses have been performed to study the separate overpotentials of the NH₃-fed SOFC-H and SOFC-O. Compared with the NH₃-fed SOFC-H, the SOFC-O has higher anode concentration overpotential and lower cathode concentration overpotential. The effects of temperature and electrode porosity on concentration overpotentials have also been studied in order to identify possible methods for improvement of SOFC performance. This study reveals that the use of different electrolytes not only causes different ion conduction characteristics at the electrolyte, but also significantly influences the concentration overpotentials at the electrodes. The model developed in this article can be extended to 2D and 3D models for further design optimization.     

Atomic Insights into the Enhanced Surface Stability in High Voltage Cathode Materials by Ultrathin Coating

Surface properties of electrode materials play a critical role in the function of batteries. Therefore, surface modifications, such as coatings, have been widely used to improve battery performance. Understanding how these coatings function to improve battery performance is crucial for both scientific research and applications. In this study the electrochemical performance of coated and uncoated LiNi_0.5Mn_1.5O₄ (LNMO) electrodes is correlated with ensemble‐averaged soft X‐ray absorption spectroscopy (XAS) and spatially resolved scanning transmission electron microscopy‐electron energy loss spectroscopy (STEM‐EELS) to illustrate the mechanism of how ultrathin layer Al₂O₃ coatings improve the cycle life of LiNi_0.5Mn_1.5O₄. Mn²⁺ evolution on the surface is clearly observed in the uncoated sample, which results from the reaction between the electrolytic solution and the surfaces of LiNi_0.5Mn_1.5O₄ particles, and also possibly atomic structure reconstructions and oxygen loss from the surface region in LiNi_0.5Mn_1.5O₄. The coating effectively suppresses Mn²⁺ evolution and improves the battery performance by decelerating the impedance buildup from the surface passivation. This study demonstrates the importance of combining ensemble‐averaged techniques (e.g., XAS) with localized techniques (e.g., STEM‐EELS), as the latter may yield unrepresentative information due to the limited number of studied particles, and sheds light on the design of future coating processes and materials.     

具有壁面Weis-Fogh机构流体动力多重网格并行计算

应用多重网格区域分裂并行计算方法研究具有壁面Weis-Fogh机构绕流，将二维物理平面流动区域变换为矩形区域，推导出流函数的多重网格差分计算格式，编制出并行计算程序。全部计算在英国London大学ITL并行计算中心完成。结果表明，多重网格并行计算具有较高的加速比，绕机翼的环量计算值与理论吻合。