Electronic structures and chemical bonding in 4d transition metal monohalides

Bond distances, vibrational frequencies, dipole moments, dissociation energies, electron affinities, and ionization potentials of NIX (XM = Y-Cd, X = F, Cl, Br, I) molecules in neutral, positively, and negatively charged ions were studied by density functional method, B3LYP. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides ionic component, covalent bonds are formed between the 4d transition metal s, d orbitals, and the p orbital of halogen. For both neutral and charged molecules, the fluorides have the shortest bond distance, iodides the longest. Although the opposite situation is observed for vibrational frequency, that is, fluorides have the largest value, iodides the smallest. For neutral and anionic species, the dissociation energy tends to decrease with the increasing atomic number from Y to Cd, suggesting the decreasing or weakening of the bond strength. For cationic species, the trend is observed from Y to Ag.

Analysis of interfacial phenomena of aqueous solutions of polyethylene oxide and polyethylene glycol flowing in hydrophilic and hydrophobic capillary viscometers

Viscosities of aqueous solutions of five polyethylene oxide (PEO) samples with molar masses from 1.5 x 10(5) to 1.0 x 10(6) were carefully measured in a polytetrafluoroethylene (PTFE) capillary Ubbelohde viscometer in the concentration range from dilute down to extremely dilute concentration regions and compared with those of the same sample obtained from a glass capillary viscometer. At the same time, viscosities of aqueous solutions of three PEG samples in glass and paraffin-coated capillary viscosity were measured. The wall effects occurred in viscosity measurements for PEO and PEG aqueous solutions in different capillary viscometers were theoretically analyzed and discussed. It was found that different interfacial behaviors occurred in both hydrophobic and hydrophilic capillary viscometers respectively and the interfacial behaviors also exhibit molar mass dependence.

Electronic structures of 3d-metal mononitrides

Bond distances, vibrational frequencies, electron affinities, ionization potentials, and dissociation energies of the title molecules in neutral, positively, and negatively charged ions were studied by use of density functional methods B3LYP, BLYP, BHLYP, BPW91, and B3PW91. The calculated results are compared with experiments and previous theoretical studies. It was found that the calculated properties are highly dependent on the functionals employed, in particular for the dissociation energy and vibrational frequency. For neutral species, pure density functional methods BLYP and BPW91 have relatively good performance in reproducing the experimental bond distance and vibrational frequency. For cations, hybrid exchange functional methods B3LYP and B3PW91 are good in predicting the dissociation energy. For both neutral and charged species, BHLYP tends to give smaller dissociation energy.

Functionalization of an ethylene-propylene copolymer with allyl (3-isocyanate-4-tolyl) carbamate

An ethylene-propylene copolymer (EPM) was functionalized with an iso cyanate-bearing unsaturated monomer, allyl(3-isocyanate-4-tolyl) carbamate (TAI), with dicumyl peroxide as an initiator in a xylene solution. Fourier transform infrared (FTIR) was used to confirm the formation of EPM-g-TAI. The peak at 2273 cm(-1), characteristic of -NCO groups in EPM-g-TAI, revealed evidence of grafting. The grafting degree was determined with both chemical titration and FTIR. The grafting degree could be adjusted, and the maximum was over 6 wt % without any gelation. The molar mass distribution of EPM-g-TAI was narrower than that of EPM. The rheological behavior of both EPM-g-TAI and EPM was investigated with a rotational rheometer. The apparent viscosity of EPM-g-TAI was higher than that of EPM and increased with an increasing grafting degree of TAI. Surface analysis by contact-angle measurements showed that contact angles of EPM-g-TAI samples to a given polar liquid decreased with an increasing grafting degree of TAI. We also obtained the dispersion component of the surface free energy (gamma(S)(d)), the polar component of the surface free energy (gamma(S)(d)), and the total surface free energy (gamma(S) = gamma(S)(d) + gamma(S)(p)) of the grafted EPM. These parameters increased with the enhancement of the grafting degree, which gave us a quantitative estimation of the polar contribution of the grafted TAI to the total surface free energy of EPM-g-TAI.

Conformational and orientational analyses of 2,2 '-bithiophene under interaction of external electric field constructed by point charges

The fully relaxed single-bond torsional potentials and orientation-related rotational potentials of 2,2'-bithiophene (BT) under the interaction of an external electric field (EF) constructed by point charges have been evaluated with semi-empirical AMI and PM3 calculations. The torsional potentials are sensitive to both EF strength and direction. While the EF is parallel to the molecular long axis, the torsional barrier around C-x-C-x' bond obviously rises with increasing the EF strength, whereas the relative energies of syn and anti minima show a slight change. The interaction between the EF and the induced dipole moment has been proposed to elucidate this observation. On the other hand, the relative energy difference between the syn and anti minima shows an obvious change, while the EF is perpendicular to the molecular long axis. This feature has been ascribed to the interaction between the EF and the permanent dipole moment of BT. Furthermore, conformational and orientational analyses in two dimensions have been carried out by changing the torsional and rotational angles in the different EF. The conformation and orientation of a gas-phase BT in the EF are governed by both the above factors.

NMR studies of Gd(DTPA-BIN) in human serum albumin solution

Stable gadolinium complexes, such as Gd(DTPA) and Gd(DOTA), are usually used as the contrast agents for magnetic resonance imaging(MRI). Reported here are the enhanced relaxation properties of a novel gadolinium complex, diethylene-triaminopentaacetate Lis (isoniazid) [Gd(DTPA-BIN)], in aqueous and in human serum albumin(HSA) solution, which indicates that (1) two Gd(DTPA-BIN) can integrate non-covalently with one HSA with an equilibrium constant of 0. 02 mmol(-2) . L-2 ; (2) the relaxivities are 3. 28 and 4. 92 mmol(-1) . L . s(-1) for the free Gd(DTPA-BIN) and the [Gd(DTPA-BIN)](2), HSA conjugator, respectively; (3) the rotational correlation time of protein conjugator is notably higher than that of the free complex, The above results may imply that Gd(DTPA-BIN) has a higher tissue selectivity than that of its parent Gd(DTPA).

Rheological properties of phenophthalein poly(ether ether ketone)

The rheological properties of the novel engineering thermoplastic phenophthalein poly(ether ether ketone) (PEK-C) have been investigated using both a rotational and a capillary rheometer. The dependence of the viscosity on the shear rate and temperature was obtained. The activation energy was evaluated both from the Arrhenius and the Williams-Landel-Ferry (WLF) equation. An estimate for the proper E(eta) (dependent only on the chemical structure of the polymer) has been found from the WLF equation at temperatures about T-g + 200 degrees C. Measurements of the die swell have been performed. The first normal stress differences were evaluated from the die swell results and compared with the values obtained from the rotational rheometer at low shear rates.

Rheological properties and crystallization behavior of yttrium oxide filled low ethylene content polypropylene copolymer

The rheological properties and crystallization characteristics of low ethylene content poly propylene (EPM) with and without Yittrium oxide (Y2O3) as a filler was investigated by cone-plate viscometer and differential scanning calorimetry. Yittrium oxide had a profound effect on the viscosities of the systems. To determine the nonisothermal crystallization rate of the materials, a new estimation method was used. From the results, we can conclude that Y2O3 acts as a nucleating agent, which increased the crystallization rate of the EPM. (C) 1996 John Wiley & Sons, Inc.

Effects of cell density, light intensity and mixing on Undaria pinnatifida gametophyte activity in a photobioreactor

An on-line controlled 7 1 sterilizable photobioreactor was used for the optimisation of a culture of gametophytes of Undaria pinnatifida. The gametophytes, which had been stored for three years in a culture cabinet at 16 degreesC, could rapidly grow in the photobioreactor under controlled conditions. The rate of increase of dissolved oxygen and pH were used to monitor the photosynthetic activity. Optimal gametophytes density changed varying the light intensity. The optimal cell densities were 3.24 and 3.45 g FW l(-1) when the cultures were exposed to 61.7 and 82.3 muE m(-2) s(-1), respectively. The optimal cell density was higher under a high photon flux density (PFD) than under low PFD. On the other hand, the optimal light intensities were different for different cell density cultures. The light saturation point was higher at high cell density cultures than at low cell density cultures. The optimal rotational speed was 150 rpm for high cell density culture in the photobioreactor. (C) 2003 Elsevier B.V. All rights reserved.

五轴磨抛机器人补偿算法研究与实现

通过分析基于模型的补偿方法和非模型补偿方法的优缺点,结合一个五轴磨抛机器人的结构特点,提出了两种补偿方法相结合的混合补偿算法.针对平移关节误差的主要来源难于建模的特点,采用非模型的方法进行补偿;针对转动关节误差主要来源为几何参数误差,能够建模,但有些参数随机器人末端位置不同而变化的特点,采用二者相结合的混合方法进行补偿.通过对该机器人系统的实验,验证了方法的有效性和可行性.

一种适用于多指灵巧手的机电一体化驱动器概念

本文提出了一种机电一体化驱动器的概念,这种驱动器能够将电机的旋转运动转换为直线运动,并在不外加力和力矩传感器的基础上利用运动转换副上产生的微应变来估算电机的输出力矩和驱动器末端的牵引力信息。利用高精度、高灵敏度并带有温度和噪声补偿电路的应变片来测量微应变,以取得稳定而可靠的测量结果。应变片直接贴在驱动器的主体结构表面可以最小化尺寸,而且可以实现机电一体化而不是机械-电子集成系统。仿真实验表明,这种方法和传统的电流估算法相比,可以减少由于噪音和波动带来的电流信号误差,得到更加精确的信息,并且(与加入力或者力矩传感器相比)能够有效缩小外型尺寸,同时去除不必要的机械与电子接口,因此增加了系统的鲁棒性。

水下机器人粘性类水动力数值计算方法研究

通过对通用流体动力学仿真软件CFX的研究,提出了一套水下机器人粘性类水动力的数值计算方法.该方法采用标准k-ε湍流模型计算位置力系数,采用标准k-ω湍流模型计算旋转力系数及其它耦合水动力系数.对“CR-02”6000 m自治水下机器人的计算表明,通过这种方法获得的水动力系数具有较高的精度,可以满足水下机器人方案设计阶段的操纵性设计、运动预报和仿真等需求.

遥控作业移动机器人环境建模方法研究

本文介绍了用于遥控机器人作业虚拟环境生成的建模方法．重点研究了基于人机交互的双目立体视觉和多视点建模方法，以克服视觉自动建模方法计算复杂、鲁棒性差的缺点．给出了环境建模的实验系统和实验结果。

边坡工程的极限分析上限法

Theory of limit analysis include upper bound theorem and lower bound theorem. To deal with slope stability analysis by limit analysis is to approximate the real solution from upper limit and lower limit. The most used method of limit analysis is upper bound theorem, therefore it is often applied to slope engineering in many cases. Although upper bound approach of limit analysis can keep away from vague constitutive relation and complex stress analyses, it also can obtain rigorous result. Assuming the critical surface is circular slip surface, two kinematically admissible velocity fields for perpendicular slice method and radial slice method can be established according to the limit analysis of upper bound theorem. By means of virtual work rate equation and strength reduction method, the upper-bound solution of limit analysis for homogeneous soil slope can be obtained. A log-spiral rotational failure mechanism for homogeneous slope is discussed from two different conditions which represent the position of shear crack passing the toe and below the toe. In the dissertition, the author also establishes a rotational failure mechanics with combination of different logarithmic spiral arcs. Furthermore, the calculation formula of upper bound solution for inhomogeneous soil slope stability problem can be deduced based on the upper bound approach of rigid elements. Through calculating the external work rate caused by soil nail, anti-slide pile, geotechnological grid and retaining wall, the upper bound solution of safety factor of soil nail structure slope, slip resistance of anti-slide pile, critical height of reinforced soil slope and active earth pressure of retaining wall can be obtained by upper bound limit analysis method. Taking accumulated body slope as subject investigated, with study on the limit analysis method to calculate slope safety factor, the kinematically admissible velocity fields of perpendicular slice method for slope with broken slip surface is proposed. Through calculating not only the energy dissipation rate produced in the broken slip surfaces and the vertical velocity discontinuity, but also the work rate produced by self-weight and external load, the upper bound solution of slope with broken slip surface is deduced. As a case study, the slope stability of the Sanmashan landslide in the area of the Three Gorges reservoir is analyzed. Based on the theory of limit analysis, the upper bound solution for rock slope with planar failure surface is obtained. By means of virtual work-rate equation, energy dissipation caused by dislocation of thin-layer and terrane can be calculated; furthermore, the formulas of safety factor for upper bound approach of limit analysis can be deduced. In the end, a new computational model of stability analysis for anchored rock slope is presented after taking into consideration the supporting effect of rock-bolts, the action of seismic force and fissure water pressure. By using the model, not only the external woke-rate done by self-weight, seismic force, fissure water pressure and anchorage force but also the internal energy dissipation produced in the slip surface and structural planes can be totally calculated. According to the condition of virtual work rate equation in limit state, the formula of safety factor for upper bound limit analysis can be deduced.