基于波动模态耦合的铝电解槽磁流体稳定性傅立叶级数法分析

铝电解槽内磁流体稳定性对铝电解生产有重要影响。本文结合铝电解槽实体仿真的电磁场计算结果,应用傅立叶级数法对槽内磁流体波动稳定性进行数值计算,并对波动的模态耦合问题进行了重点分析。在此基础上,本文以某320kA铝电解槽为研究载体分析了槽长宽比设计对磁流体稳定性的影响,结果表明:波动的不稳定分量集中分布在频谱图中重力波模态密集的低频区域;不考虑母线对体系的影响,增大槽的长宽比,有利于提高磁流体的稳定性。     

Research Progress on Typical Quaternary Ammonium Salt Polymers

Quaternary ammonium salt polymers, a kind of polyelectrolyte with a quaternary ammonium group, are widely used in traditional and emerging industries due to their good water-solubility, adjustable cationicity and molecular weight, high efficiency and nontoxicity. In this paper, firstly, the properties and several synthesis methods of typical quaternary ammonium salt monomers were introduced. Secondly, the research progress on the synthesis of polymers was summarized from the perspective of obtaining products with high molecular weight, narrow molecular weight distribution and high monomer conversion, and special functional polymers. Thirdly, the relationships between the structures and properties of the polymer were analyzed from the perspectives of molecular weight, charge density, structural stability, and microstructural regulation of the polymer chain unit. Fourthly, typical examples of quaternary ammonium salt polymers in the application fields of water treatment, daily chemicals, petroleum exploitation, papermaking, and textile printing and dyeing were listed. Finally, constructive suggestions were put forward on developing quaternary ammonium salt polymers with high molecular weights, strengthening the research on the relationships between the structures and their properties and pinpointing relevant application fields.     

Reaction kinetics and thermochemistry of the chemically activated and stabilized primary ethyl radical of methyl ethyl sulfide,CH3SCH2CH2•, with O2 to CH3SCH2CH2OO•

Oxidation of methyl ethyl sulfide (CH₃SCH₂CH₃, methylthioethane, MES) under atmospheric and combustion conditions is initiated by hydroxyl radicals, MES radicals, generated after loss of a H atom via OH abstraction, will further react with O₂ to form chemically activated and stabilized peroxyl radical adducts. The kinetics of the chemically activated reaction between the CH₃SCH₂CH₂• radical and molecular oxygen are analyzed using quantum Rice-Ramsperger-Kassel theory for k(E) with master equation analysis and a modified strong-collision approach to account for further reactions and collisional deactivation. Thermodynamic properties of reactants, products, and transition states are determined by the B3LYP/6-31+G(2d,p), M062X/6-311+G(2d,p), ωB97XD/6-311+G(2d,p) density functional theory, and CBS-QB3, G3MP2B3, and G4 composite methods. The reaction of CH₃SCH₂CH₂• with O₂ forms an energized peroxy adduct CH₃SCH₂CH₂OO• with a calculated well depth of 34.1 kcal mol⁻¹ at the CBS-QB3 level of theory. Thermochemical properties of reactants, transition states, and products obtained under CBS-QB3 level are used for calculation of kinetic parameters. Reaction enthalpies are compared between the methods. The temperature and pressure-dependent rate coefficients for both the chemically activated reactions of the energized adduct and the thermally activated reactions of the stabilized adducts are presented. Stabilization and isomerization of the CH₃SCH₂CH₂OO• adduct are important under high pressure and low temperature. At higher temperatures and atmospheric pressure, the chemically activated peroxy adduct reacts to new products before stabilization. Addition of the peroxyl oxygen radical to the sulfur atom followed by sulfur-oxygen double bond formation and elimination of the methyl radical to form S(= O)CCO• + CH₃ (branching) is a potentially important new pathway for other alkyl-sulfide peroxy radical systems under thermal or combustion conditions.     

Asymmetric reduction of ketones with sodium aluminum hydride modified by various chiral diols

New stereoselective reducing reagents were preparedin situ by modification of NaAlH₄ with various chiral diols. The efficiency of 1,4- and 1,3-diols as chiral auxiliaries in the reactions of alkyl aryl ketones with modified NaAlH₄ was considerably higher than that of 1,2-diols. The effect of the nature of the achiral ligand additionally introduced into the chiral hydride reagent on the enantioselectivity of ketone reduction was studied. It was proposed that the sodium cation does not necessarily participate at the stage governing the reaction stereochemistry. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp 459–464, March, 2000.     

纳米复合固体超强酸SO42-/CoFe2O4的制备和表征

采用纳米化学制备技术合成了新型的纳米复合团体超强酸催化剂ＳＯ４２－／ＣｏＦｅ２Ｏ４。用ＸＲＤ、ＴＥＭ、ＸＰＳ、红 外光谱和比表面测定等技术研究了该催化剂的结构形态,结果表明：所研制的ＳＯ４２－／ＣｏＦｅ２Ｏ４催化剂为晶态纳 米粒子（＜ ５０ｎｍ）,比表面积很大（１５７ｍ２· ｇ－１）,ＳＯ４２－与氧化物的金属离子呈无机双齿螯合状配位化合物的结 合形式。以乙酸乙酯合成为模型反应考察了该催化剂的催化活性,比较了酸性和酸强度,推断出该催化剂的酸 强度Ｈ０＜－１４．５。     

Effect of the nature of the support for copper-cerium oxide catalysts on selective oxidation of CO in hydrogen-rich mixtures

We have studied the catalytic properties of copper-cerium oxide catalysts, supported on zirconium, aluminum, titanium, and manganese oxides, in the reaction of selective oxidation of CO in hydrogen-rich mixtures. We have shown that the high activity and selectivity of catalysts supported on zirconium and aluminum oxides is connected with the presence of (in addition to divalent copper) higher amounts of copper in the (+1) oxidation state in the catalysts. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 2, pp. 119–124, March–April, 2006.     

Ultra‐wideline 27Al NMR Investigation of Three‐ and Five‐Coordinate Aluminum Environments

Ultra‐wideline ²⁷Al NMR experiments are conducted on coordination compounds with ²⁷Al nuclei possessing immense quadrupolar interactions that result from exceptionally nonspherical coordination environments. NMR spectra are acquired using a methodology involving frequency‐stepped, piecewise acquisition of NMR spectra with Hahn‐echo or quadrupolar Carr–Purcell Meiboom–Gill (QCPMG) pulse sequences, which is applicable to any half‐integer quadrupolar nucleus with extremely broad NMR powder patterns. Despite the large breadth of these central transition powder patterns, ranging from 250 to 700 kHz, the total experimental times are an order of magnitude less than previously reported experiments on analogous complexes with smaller quadrupolar interactions. The complexes examined feature three‐ or five‐coordinate aluminum sites: trismesitylaluminum (AlMes₃), tris(bis(trimethylsilyl)amino)aluminum (Al(NTMS₂)₃), bis[dimethyl tetrahydrofurfuryloxide aluminum] ([Me₂‐Al(μ‐OTHF)]₂), and bis[diethyl tetrahydrofurfuryloxide aluminum] ([Et₂‐Al(μ‐OTHF)]₂). We report some of the largest ²⁷Al quadrupolar coupling constants measured to date, with values of C_Q(²⁷Al) of 48.2(1), 36.3(1), 19.9(1), and 19.6(2) MHz for AlMes₃ , Al(NTMS₂)₃ , [Me₂‐Al(μ‐OTHF)]₂ , and [Et₂‐Al(μ‐OTHF)]₂ , respectively. X‐ray crystallographic data and theoretical (Hartree–Fock and DFT) calculations of ²⁷Al electric field gradient (EFG) tensors are utilized to examine the relationships between the quadrupolar interactions and molecular structure; in particular, the origin of the immense quadrupolar interaction in the three‐coordinate species is studied via analyses of molecular orbitals.     

Dynamic mechanical properties of aluminum nitride/cyanate ester composites for high performance electronic packaging

Viscoelastic ature is one of the key features of polymeric composites. A series of cyanate ester (CE)‐based composites with different aluminum nitride (AlN) contents for high performance electronic packaging, coded as AlN/CE, were developed; the viscoelastic nature of AlN/CE composites was intensively investigated by employing dynamic mechanical analysis (DMA). Results show that the AlN content has a great effect on dynamic mechanical properties of AlN/CE composites. The storage modulus in the glassy region increases linearly with the addition of AlN as well as the increase of AlN content. Meanwhile, all composites also exhibit notably higher loss modulus than cured CE resin due to the appearance of new energy dissipation forms. In addition, the incorporation of AlN has a significant effect on damping factor peak. All reasons leading to these phenomena are analyzed from the view of structure–property relationship. Copyright © 2009 John Wiley & Sons, Ltd.