A RESIDUAL-BASED UNRESOLVED-SCALE FINITE ELEMENT MODELLING FOR IMPLICT LARGE EDDY SIMULATION 1)

对应于湍流的大尺度与小尺度流场信息, 本文在有限元的框架下, 假设Navier-Stokes方程的解的形函数由大尺度和不可解尺度形函数叠加组成, 引入对应的权函数, 将Navier-Stokes方程的有限元变分形式分解为大尺度和不可解尺度系统. 根据不可解尺度系统, 构建基于Navier-Stokes大尺度方程残差的不可解尺度模型, 将其代入Navier-Stokes方程的大尺度系统, 进而数值求解大尺度系统得到Navier-Stokes方程的大尺度解. 该方法无需像传统的大涡模拟方法那样对方程的解进行过滤, 通过对形函数进行尺度分解实现解的尺度分解. 本文使用该方法的自编程序代码开展了槽道湍流的数值模拟. 通过与有限差分大涡模拟、DNS计算结果的比较, 发现在使用较少网格情况下该方法预测的平均流向速度在近壁区与DNS数据吻合, 在黏性外层略偏高; 该方法对雷诺应力预测偏低导致从流向向垂向方向上湍动能输运略偏低. 流向速度等值面图显示该方法有效捕捉到了大尺度旋涡结构; 同时在近壁区可以观察到明显的低速条带结构.     

Studies on adsorption and separation characteristics of americium and lanthanides using a silica-based macroporous bi(2-ethylhexyl) phosphoric acid (HDEHP) adsorbent

Activity concentrations of ⁹⁰Sr in samples of wild boar bones hunted in different regions of Slovakia were determined. Molecular recognition technology product IBC´s AnaLig^®Sr-01 and tributyl phosphate were used for strontium determination. From 7 to 10 g of bone ash was used for ⁹⁰Sr analysis. Both separation methods were statistical tested and compared. The presented results were evaluated as correct for all experimental data for ⁹⁰Sr determination in ash bone samples. Activity concentrations of ⁹⁰Sr in bones were in the range of (4.5–69.0) Bq kg^?1.     

Comprehensive utilization of dairy manure to produce glucose and hierarchical porous carbon for supercapacitors

Dairy manure, one of the most abundant agricultural wastes generated in livestock farming, was pretreated with KOH aqueous solution to relieve the constraint of lignin, thus facilitating cellulose hydrolysis. The generated black liquor waste was used to prepare porous carbon. Glucose yield of 261 g/kg was obtained from dairy manure pretreated in 0.73 wt% HCl aqueous solution, much higher than that obtained from crude dairy manure (116 g/kg). The generated black liquor, mainly containing lignin and KOH, was employed to prepare porous carbon via a self-templating method. The obtained material had a three-dimensional (3D) hierarchical structure and was applied for supercapacitors. Good capacitance of 202 F/g was obtained in a two-electrode system with 6 M KOH electrolyte. The porous carbon-based electrode showed excellent cycling stability with retention of 100% after 3000 galvanostatic charge–discharge (GCD) cycles. This work provides a scalable strategy for comprehensive utilization of lignocellulosic biomass resources.     

Tetrakis(tetramethylammonium) tricarbonatodioxidouranate octahydrate

The environment of the U atom in the title compound, (C₄H₁₂N)₄[UO₂(CO₃)₃]·8H₂O, presents a typical hexagonal bipyramidal geometry found in many actinide complexes. It is a model for actinide species and consists of common environmental moieties (carbonate, water and ammonia species). The structure displays a sheet‐like hydrogen‐bonding network formed from crystallization water molecules and carbonate ligands. The compound is isomorphous with a previously described Np isolog [Grigorev et al. (1997). Radiokhimiya (Russ. Radiochem.), 39 , 325–329].     

Kinetic enolate formation by lithium arylamide: effects of basicity on selectivity

Five ketones R1COCH2R2 (1a-e) were enolized in tetrahydrofuran solvent employing lithium arylamides with different electron-withdrawing and -donating substituents on the phenyl ring (4a-e). Enolate selectivity is unaffected by a moderate electron-releasing or -withdrawing group, but significantly enhanced by strong electron-withdrawing substituents to yield predominantly Z-enolate. Outstanding selectivity was achieved with lithium trichloroanilide (5) and lithium diphenylamide (6). The results are rationalized in terms of electronic effects on the tightness of the transition states.     

Thermodynamic Studies of the Complexation between Neodymium and Acetate at Elevated Temperatures

Complexation of neodymium (III) with acetate in 2.2 mol-kg^-1 NaClO₄ solution was studied at elevated temperatures (45 and 70°C) by potentiometry, calorimetry, and optical spectroscopy. The formation constants of the consecutive complexes, Nd(OOCCH₃),²⁺ Nd(OOCCH₃) ₂ ⁺ , and Nd(OOCCH₃)₃, and the molar enthalpies of complexation at these temperatures were determined. The stability of the three complexes increases with increased temperatures, because of increased positive entropy change at higher temperatures, which exceeds the increased values of the positive (endothermic) enthalpy. The molar heat capacity changes of complexation C_p,m(MLj) (J-K^-1-mol^-1) for Nd(OOCCH₃) _j ^(3-j)+ in the temperature range from 25 to 70°C were calculated to be: 102 ± 13 (j = 1); 122 ± 19 (j = 2); and 239 ± 27 (j = 3). The effect of temperature on the complexation is discussed in terms of the electrostatic model.     

Clusters containing ynamine ligands. 4. The synthesis and characterizations of ReMn(CO)8 [μ-MeC2NMe2] and ReMn(CO)7 [μ-MeCC(NMe2)C(NMe2)CMe] and the development of a bonding model for the coordination of ynamines to M2(CO)8 clusters

The compound ReMn(CO)₈ (-MeC₂NMe₂),2 was obtained in 11% yield by the decarbonylation of ReMn(CO)₁₀ with Me₃NO followed by reaction MeC₂NMe₂. Compound2 will add one equivalent of MeC₂NMe₂ at 25°C to yield the mixed metal complex ReMn(CO)₇ [-C(Me) C(NMe₂) C(NMe₂) C(Me)],3 in 7% yield. Compounds2 and3 were characterized by IR,¹H NMR, and single crystal x-ray diffraction analyses. Compound2 exists as two isomers. Each isomer contains an asymmetric bridging ynamine ligand. The principal isomer has the amine-substituted carbon atom coordinated to the manganese atom. The minor isomer has the amine-substituted carbon atom coordinated to the rhenium atom. In compound3 the two ynamines have been coupled in a head-to-head fashion to produce a ferrole-like structure in which the coupled ligands are -bonded to the manganese atom. Extended Hückel molecular orbital calculations were performed on the parent complex Re₂(CO)₈ (-MeC₂NMe₂),1 to try to understand the reasons for the preferred asymmetric coordination of the ynamine ligand in1 and2. It was found that the asymmetric coordination permits a strong stabilizing interaction between the one of the * orbitals of the ligand and the metallic orbital that is principally responsible for the formation of the metal-metal bond. Crystal Data: for2: space group=P2₁/c,a=9.740(1)Å,b=11.293(2)Å,c=15.483(3)Å, =97.46(1)°,Z=4, 1876 reflections,R=0.026; for3: space group=Pca2₁,a=17.541(2)Å,b=8.441(1)Å,c=14.033(3)Å,Z=4, 1335 reflections,R=0.022.     

Complexation of uranium(VI) and samarium(III) with oxydiacetic acid: temperature effect and coordination modes

The complexation of uranium(VI) and samarium(III) with oxydiacetate (ODA) in 1.05 mol kg(-1) NaClO(4) is studied at variable temperatures (25-70 degrees C). Three U(VI)/ODA complexes (UO(2)L, UO(2)L(2)(2-), and UO(2)HL(2)(-)) and three Sm(III)/ODA complexes (SmL(j)((3-2)(j)+) with j = 1, 2, 3) are identified in this temperature range. The formation constants and the molar enthalpies of complexation are determined by potentiometry and calorimetry. The complexation of uranium(VI) and samarium(III) with oxydiacetate becomes more endothermic at higher temperatures. However, the complexes become stronger due to increasingly more positive entropy of complexation at higher temperatures that exceeds the increase in the enthalpy of complexation. The values of the heat capacity of complexation (Delta C(p) degrees in J K(-1) mol(-1)) are 95 +/- 6, 297 +/- 14, and 162 +/- 19 for UO(2)L, UO(2)L(2)(2-), and UO(2)HL(2)(-), and 142 +/- 6, 198 +/- 14, and 157 +/- 19 for SmL(+), SmL(2)(-), and SmL(3)(3-), respectively. The thermodynamic parameters, in conjunction with the structural information from spectroscopy, help to identify the coordination modes in the uranium oxydiacetate complexes. The effect of temperature on the thermodynamics of the complexation is discussed in terms of the electrostatic model and the change in the solvent structure.     

甲烷/石松子两相混合体系爆炸强度参数

基于改进的20 L球形粉尘爆炸装置,在相同初始条件下分别测量了甲烷、石松子粉尘和甲烷/石松子两相混合体系的爆炸压力、爆炸压力上升速率和爆炸指数等参数,系统研究了甲烷/石松子粉尘两相混合体系爆炸特性变化规律。结果表明:甲烷的添加能显著提高低质量浓度石松子粉尘爆炸压力而降低高质量浓度石松子粉尘爆炸压力;甲烷对石松子粉尘最大爆炸压力没有显著影响,但能显著提高石松子粉尘最大爆炸压力上升速率。甲烷/石松子粉尘混合体系爆炸指数高于单相石松子粉尘爆炸指数,但甲烷/石松子粉尘混合体系和单相石松子粉尘爆炸指数均低于单相甲烷爆炸指数。工业生产过程中应避免粉尘混入可燃气体以降低粉尘爆炸危险性。