Study of viscosity of mono-, di-, and trialkylamines

Viscosities of several mono-, di-, and trialkylamines have been measured in the temperature range 298 to 333 K. It is observed that viscosities are highly dependent on shape, size, and association through H-bond or through dipole. Following the transition state theory, energy, Gibbs free energy, and entropy of activation of viscous flow have been calculated. The values of expansion energy for these liquids have also been calculated using free volume theory, and subsequently amines have been classified as volume-restrained or energy-restrained liquids. The group contribution method of Van Velzen, Cardozo, and Langenkamp for estimating viscosity has been examined with the present and literature data, and the new group contribution increments N _i and B _i for amines have been evaluated.     

An experimental study of the thermodynamic properties of 1,1-difluoroethane

Experimental vapor pressures andP--T data of an important alternative refrigerant, 1, 1-difluoroethane (HFC-152a), have been measured by means of a constant-volume method coupled with expansion procedures. SixtyP--T data were measured along eight isochores in a range of temperaturesT from 330 to 440 K, at pressuresP from 1.6 to 9.3 MPa, and at densities from 51 to 811 kg·m^–3. Forty-six vapor pressures were also measured at temperatures from 320 K to the critical temperature. The uncertainties of the temperature and pressure measurements are within ±7mK and ±2kPa, respectively, while the uncertainty of the density values is within ±0.1%. The purity of the sample used is 99.9 wt%. On the basis of the measurements along each isochore, five saturation points were determined and the critical pressure was determined by correlating the vapor-pressure measurements. The second and third virial coefficients for temperatures from 360 to 440 K have also been determined.     

遥感图像理想均衡化及图像质量定量评价

大多数原始的遥感影像由于其灰度分布集中在较窄的范围内,影像的细节不够清晰,对比度较低。为了使影像的灰度范围拉开或使灰度均匀分布,从而增大反差,增强影像细节信息,通常采用的方法为直方图均衡化。通过对信息熵定义的阐述,引出直方图均衡化的图像增强算法。通过分析传统直方图均衡化算法中存在的缺陷,进而基于分段映射思想提出一种改进的理想直方图均衡化算法。同时,为了对传统算法和改进算法进行定量化地分析比较,基于同时对比度以及人类视觉对比度分辨率限制和模糊数学的相关思想,分别提出基于加权几何平均数法的合成平均对比度和细节评价参数的定义。最后,采用同时对比度、基于加权几何平均数法的合成平均对比度以及细节评价参数作为定量评价的指标,对所提出的改进算法进行了定量评价。评价结果表明,该改进算法的图像增强效果优于传统的直方图均衡化算法。     

The statistical modeling of surface roughness in high-speed flat end milling

Surface roughness is one of the most important requirements in machining process. The surface roughness value is a result of the tool wear. When tool wear increase, the surface roughness also increases. The determination of the sufficient cutting parameters is a very important process obtained by means of both minimum surface roughness values and long tool life. The statistical models were developed to predict the surface roughness.This paper presents the development of a statistical model for surface roughness estimation in a high-speed flat end milling process under wet cutting conditions, using machining variables such as spindle speed, feed rate, depth of cut, and step over. First- and second-order models were developed using experimental results of a rotatable central composite design, and assessed by means of various statistical tests. The highest coefficient of correlation (R_adj²) (88%) was obtained with a 10-parameter second-order model. Meanwhile, a time trend was observed in residual values between model predictions and experimental data, reflecting the probable effect of the tool wear on surface roughness. Thus, in order to enhance the estimation capability of the model, another independent variable was included into the model to account for the effect of the tool wear, and the total operating time of the tool was selected as the most suitable variable for this purpose. By inserting this new variable as a linear term into the model, R_adj² was increased to 94% and a good fit was observed between the model predictions and supplementary experimental data.In this study, it was observed that, the order of significance of the main variables is as X₅>X₃>X₄>X₁>X₂ (total machining time, depth of cut, step over, spindle speed and feed rate, respectively).     

Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked Systems

The study of the L- and D-amino acid properties in proteins and peptides has attracted considerable attention in recent years, as the replacement of even one L-amino acid by its D-analogue due to aging of the body is resulted in a number of pathological conditions, including Alzheimer’s and Parkinson’s diseases. A recent trend is using short model systems to study the peculiarities of proteins with D-amino acids. In this report, the comparison of the excited states quenching of L- and D-tryptophan (Trp) in a model donor–acceptor dyad with (R)- and (S)-ketoprofen (KP-Trp) was carried out by photochemically induced dynamic nuclear polarization (CIDNP) and fluorescence spectroscopy. Quenching of the Trp excited states, which occurs via two mechanisms: prevailing resonance energy transfer (RET) and electron transfer (ET), indeed demonstrates some peculiarities for all three studied configurations of the dyad: (R,S)-, (S,R)-, and (S,S)-. Thus, the ET efficiency is identical for (S,R)- and (R,S)-enantiomers, while RET differs by 1.6 times. For (S,S)-, the CIDNP coefficient is almost an order of magnitude greater than for (R,S)- and (S,R)-. To understand the source of this difference, hyperpolarization of (S,S)-and (R,S)- has been calculated using theory involving the electron dipole–dipole interaction in the secular equation.     

A Methionine Chemical Shift Based Order Parameter Characterizing Global Protein Dynamics

Coupling of side chain dynamics over long distances is an important component of allostery. Methionine side chains show the largest intrinsic flexibility among methyl-containing residues but the actual degree of conformational averaging depends on the proximity and mobility of neighboring residues. The ¹³C NMR chemical shifts of the methyl groups of methionine residues located at long distances in the same protein show a similar scaling with respect to the values predicted from the static X-ray structure by quantum methods. This results in a good linear correlation between calculated and observed chemical shifts. The slope is protein dependent and ranges from zero for the highly flexible calmodulin to 0.7 for the much more rigid calcineurin catalytic domain. The linear correlation is indicative of a similar level of side-chain conformational averaging over long distances, and the slope of the correlation line can be interpreted as an order parameter of the global side-chain flexibility.     

Effect of deposition conditions on the properties and annealing behavior of cold-sprayed copper

The deposition of copper by cold gas dynamic spraying has attracted much interest in recent years due to the capability to deposit low-porosity oxide-free coatings. However, it is generally found that as-deposited copper has a signicantly greater hardness, and potentially lower ductility, than bulk material. In this article, copper was deposited by cold spraying using helium as the driving gas at both 298 and 523 K. Evidence is presented indicating that the material sprayed at the lower temperature exhibits a lower dislocation density throughout the grain structure than the material sprayed at the higher temperature. The low stacking fault energy of copper restricts recovery during annealing, and thus microstructural changes during annealing only proceed once recrystallization begins. The material sprayed at low temperature (with the low dislocation density) exhibited recrystallization at annealing temperatures as low as 373 K with a corresponding reduction in hardness. However, the copper sprayed with helium at 523 K was resistant to annealing at temperatures up to 473 K where the dislocations in the structure prevented recrystallization. However, at higher temperatures, recrystallization did proceed (with corresponding reductions in hardness). The fracture behavior of the copper that was cold sprayed with helium at 523 K, both in the as-sprayed condition and following annealing, was measured and explained in terms of the annealing mechanisms proposed. The original version of this paper was published in the CD ROM Thermal Spray Connects: Explore Its Surfacing Potential, International Thermal Spray Conference, sponsored by DVS, ASM International, and HW International Institute of Welding, Basel, Switzerland, May 2–4, 2005, DVS-Verlag GmbH, Düsseldorf, Germany.     

解析参数对活性焦再生过程及再生效果的影响

 活性焦的热解析参数对再生活性焦的脱硫脱硝性能和机械强度至关重要。为了明确解析参数对活性焦再生过程和再生效果的影响规律,通过热解析试验探究活性焦硫残余比例、CO₂和CO生成量及再生活性焦脱硫脱硝性能随解析温度和解析时间的变化规律,继而明确适宜的活性焦热解析参数。结果表明,活性焦升温解析过程中,脱硫产物在317 ℃左右迅速分解,随后分解速率下降;在进入恒温解析阶段后脱硫产物分解速率先快速下降,而后进入缓慢解析状态。硫残余比例随恒温解析温度的升高而下降,在530 ℃下解析3 h可使脱硫产物完全解析;解析温度高于430 ℃后,活性焦表面的酚基、醌基、内酯基等含氧官能团分解量明显增加,并随恒温解析温度的升高而持续增加,分解所生成的CO和CO₂也随之大幅增加,这将使活性焦的孔隙结构进一步发展,继而不利于活性焦机械强度的保持;解析温度低于530 ℃时,硫残余比例随解析温度的升高而持续降低,使再生活性焦的脱硫脱硝性能持续提高;解析温度高于530 ℃后,含氧官能团分解量随解析温度的升高而持续增加,这将有利于提高活性焦表面SO₂氧化反应速率,继而使再生活性焦的脱硫性能持续升高,但酚基、内酯基等酸性含氧官能团的分解使再生活性焦对NH₃的吸附性能降低,进而使其脱硝性能降低。在兼顾再生活性焦脱硫脱硝性能、机械强度和生产效率等多方面因素时,430 ℃恒温解析3 h是相对较优的解析参数。在此解析条件下,再生活性焦的硫残余比例仅为1.8%,含氧官能团尚未发生大量分解,脱硫脱硝性能相对较为优良。     

Enhanced oxidation of the 9%Cr steel P91 in water vapour containing environments

The short term (∼100 h) oxidation behaviour of the 9%Cr steel P91 was studied at 650 °C in N₂-O₂-H₂O gas mixtures containing a relatively low oxygen level of 1%. The oxidation kinetics were measured thermogravimetrically and the oxide scale growth mechanisms were studied using H₂¹⁸O-tracer with subsequent analyses of oxide scale composition and tracer distribution by MCs⁺-SIMS depth profiling. The corrosion products were additionally characterised by light optical microscopy, SEM-EDX and XRD. It was found that the transition from protective, Cr-rich oxide formation into non-protective mixed oxide scales is governed by the ratio H₂O^(g)/O₂ ratio rather than the absolute level of H₂O^(g). The results of the tracer studies in combination with the data obtained from experiments involving in situ gas changes clearly illustrated that under the prevailing conditions the penetration of water vapour molecules triggers the enhanced oxidation and sustains the high growth rates of the poorly protective Fe-rich oxide scale formed in atmospheres with high H₂O^(g)/O₂ ratios. The experimental observations can be explained if one assumes the scale growth to be governed by a competitive adsorption of oxygen and water vapour molecules on external and internal surfaces of the oxide scales in combination with the formation of a volatile Fe-hydroxide during transient oxidation. The formation of the non-protective Fe-rich oxide scales is suppressed in atmospheres with low H₂O^(g)/O₂ -ratios, and the healing of any such scale is promoted.     

工艺参数对微区沉淀法制备纳米MgAl2O4粉体的影响

采用高分子网络微区沉淀法制备纳米镁铝尖晶石（MgAl2O4）粉体，并采用TGA／DTA、XRD和TEM等分析测试技术对前驱体的热分解和所制得粉体的物相组成、形貌及颗粒尺寸进行表征，结果表明所制得的MgAl2O4粉体颗粒粒径小，结晶良好，成分单一且粒径大小均匀。而实验过程中工艺参数的改变会对生成粉体的粒径和形貌产生一定的影响，进而即研究了各种工艺参数的改变对该方法制备纳米MgAl2O4粉体的影响。