Mechanism of Hetero-nuclear β-type Chelates Formed by Rare Earths with p-sulphoaminobromophosphonazo

The reaction behavior of forming the hetero-nuclear β-type chelates of rare earth ions (RE 3+) with p-sulphoaminobromophosphonazo(BPA-pSN) in ClCH_2COOH-CH_3COONa buffer solutions were studied by a spectrophotometric method. The interaction of RE 3+ with BPA-pSN, which can forms hetero-nuclear β-type chelates having composition ratio of RE_1 (light rare earth):BPA-pSN:RE_2(heavy rare earth ion)=1∶3∶1, is a first-order reaction. Meanwhile, BPA-pSN can only forms homo-nuclear β-type chelates with heavy rare earth ions, having a composition ratio of RE∶BPA-pSN=1∶2 and being a second-order reaction. The rate constants of forming homo-and hetero-nuclear β-type chelates were obtained and the mechanism of forming hetero-nuclear β-type chelates was proposed.

The Mechanism of Critical Strain of Serrated Yielding in Strain Rate Domain

The mechanism of the critical strain of serrated yielding is studied via tension tests at various strain rates. Betore the critical strain, it is deduced that dislocations are not pinned at high strain rates, and dislocations at low strain rates are pinned but cannot escape. The critical strain depends on the first pinning process at high strain rates and on the first unpinning process at low strain rates. The calculated results based on the two criteria are in good consistency with the experiment.

Hydrogen Abstraction Reaction Mechanisms and Rate Constants for Isoflurane with a Cl Atom at 200～2000 K:A Theoretical Investigation

The kinetics and mechanisms of H abstraction reaction between isoflurane and a CI atom have been investigated using DFT and G3（MP2） methods of theory. The geometrical structures of all species were optimized by the wB97XD/6-311＋＋G＊＊ method. Intrinsic reaction coordinate （IRC） analysis has been carried out for the reaction channels. Thermochemistry data have been obtained by utilizing the high accurate model chemistry method G3（MP2） combined with the standard statistical thermodynamic calculations. Gibbs free energies were used for reaction channels analysis. Two channels were obtained, which correspond to P（1） and P（2）. The rate constants for the two channels over a wide temperature range of 200-2000 K were also obtained. The results show that the barriers of P（1） and P（2） reaction channels are 50.36 and 50.34 kJ/mol, respectively, predicting that it exists two competitive channels. The calculated rate constant is in good agreement with the experiment value. Additionally, the results also show that the rate constants also increase from 1.85x10^-16 to 2.16x 10^12 cm3.moleculel.s-1 from 200 to 2000 K

Theoretical Research on the Multi-channel Reaction Mechanism of CHF Radical with HNCO by Density Functional Theory

The reaction mechanism of CHF radical with HNCO was investigated by the B3LYP method of density functional theory （DFT）, while the geometries and harmonic vibration frequencies of reactants, intermediates, transition states and products were calculated at the B3LYP/6-311＋＋G＊＊ level. In the temperature range of 100-2600 K, the statistical thermody- namics and Eyring transition state theory with Winger correction were used to study the thermodynamic and kinetic characters of the channel with low energy barrier. In addition, the analysis on the combining interaction between CHF radical and HNCO was performed by atom-in-molecules theory （AIM） and natural bond orbitals （NBO） analysis. The calculation results indicated that the reaction of CHF radical with HNCO had ten channels, and the channel of NH direct extraction （CHF ＋ HNCO→IM6→TS7→IM7→CHFNH ＋ CO） in singlet state was the main channel with low potential energy and high equilibrium constant and reaction rate constant. CHFNH and CO were the main products.

Anti-plane analysis of semi-infinite crack in piezoelectric strip

Using the complex variable function method and the technique of the conformal mapping, the fracture problem of a semi-infinite crack in a piezoelectric strip is studied under the anti-plane shear stress and the in-plane electric load. The analytic solutions of the field intensity factors and the mechanical strain energy release rate are presented under the assumption that the surface of the crack is electrically impermeable. When the height of the strip tends to infinity, the analytic solutions of an infinitely large piezoelectric solid with a semi-infinite crack are obtained. Moreover, the present results can be reduced to the well-known solutions for a purely elastic material in the absence of the electric loading. In addition, numerical examples are given to show the influences of the loaded crack length, the height of the strip, and the applied mechanical/electric loads on the mechanical strain energy release rate.

Effects of cooling rate and Al on MnS formation in medium-carbon non-quenched and tempered steels

The effect of Al on the morphology of MnS in medium-carbon non-quenched and tempered steel was investigated at three different cooling rates of 0.24, 0.43, and 200°C·s^-1. The formation mechanisms of three types of MnS were elucidated based on phase diagram information combined with crystal growth models. The morphology of MnS is governed by the precipitation mode and the growth conditions. A monotectic reaction and subsequent fast solidification lead to globular Type I MnS. Type II MnS inclusions with different morphological characteristics form as a result of a eutectic reaction followed by the growth in the Fe matrix. Type III MnS presents a divorced eutectic morphology. At the cooling rate of 0.24°C·s^-1, the precipitation of dispersed Type III MnS is significantly enhanced by the addition of 0.044wt% acid-soluble Al（Als）, while Type II MnS clusters prefer to form in steels with either 0.034wt% or 0.052wt% Als. At the relatively higher cooling rates of 200°C·s^-1 and 0.43°C·s^-1, the formation of Type I and Type II MnS inclusions is promoted, and the influence of Al is negligible. The results of this work are expected to be employed in practice to improve the mechanical properties of non-quenched and tempered steels.

Exact solutions of two semi-infinite collinear cracks in piezoelectric strip

Using the complex variable function method and the conformal mapping technique, the fracture problem of two semi-infinite collinear cracks in a piezoelectric strip is studied under the anti-plane shear stress and the in-plane electric load on the partial crack surface. Analytic solutions of the field intensity factors and the mechanical strain energy release rate are derived under the assumption that the surfaces of the crack are electrically impermeable. The results can be reduced to the well-known solutions for a purely elastic material in the absence of an electric load. Moreover, when the distance between the two crack tips tends to infinity, analytic solutions of a semi-infinite crack in a piezoelectric strip can be obtained. Numerical examples are given to show the influence of the loaded crack length, the height of the strip, the distance between the two crack tips, and the applied mechanical/electric loads on the mechanical strain energy release rate. It is shown that the material is easier to fail when the distance between two crack tips becomes shorter, and the mechanical/electric loads have greater influence on the propagation of the left crack than those of the right one.

CHARACTERISTCS OF FLUID FILM IN OPTIMIZED SPIRAL GROOVE MECHANICAL SEAL

In order to investigate the sealing performance variation resulted from the thermal deformation of the end faces, the equations to calculate the fluid film pressure distribution, the bearing force and the leakage rate are derived, for the fluid film both in parallel gap and in wedgy gap. The geometrical parameters of the sealing members are optimized by means of heat transfer analysis and complex method. The analysis results indicate that the shallow spiral grooves can generate hydrodynamic pressure while the rotating ring rotates and the bearing force of the fluid film in spiral groove end faces is much larger than that in the flat end faces. The deformation increases the bearing force of the fluid film in flat end faces, but it decreases the hydrodynamic pressure of the fluid film in spiral groove end faces. The gap dimensions which determine the characteristics of the fluid film is obtained by coupling analysis of the frictional heat and the thermal deformation in consideration of the equilibrium condition of the bearing force and the closing force. For different gap dimensions, the relation- ship between the closing force and the leakage rate is also investigated, based on which the leakage rate can be controlled by adjusting the closing force.

Trends in gravity changes from 2009 to 2013 derived from ground-based gravimetry and GRACE data in North China

North China is a key region for studying geophysical progress. In this study, ground-based and Gravity Recovery and Climate Experiment（GRACE） gravity data from 2009 to 2013 are used to calculate the gravity change rate（GCR） using the polynomial fitting method. In general, the study area was divided into the Shanxi rift, Jing-Jin-Ji（Beijing-Tianjin-Hebei Province）, and Bohai Bay Basin（BBB） regions. Results of the distribution of the GCR determined from ground-based gravimetry show that the GCR appears to be ＂negativepositive-negative＂ from west to east, which indicates that different geophysical mechanisms are involved in the tectonic activities of these regions. However, GRACE solutions are conducted over a larger spatial scale and are able to show a difference between southern and northern areas and a mass redistribution of land water storage.

Exploring the methane combustion reaction: A theoretical contribution

This paper represents an attempt to extend the mechanisms of reactions and kinetics of a methane combustion reaction.Three saddle points（SPs） are identified in the reaction CH_4＋ O（~3P） → OH ＋ CH_3 using the complete active space selfconsistent field and the multireference configuration interaction methods with a proper active space. Our calculations give a fairly accurate description of the regions around the twin first-order SPs（~3A＇ and ~3A〞） along the direction of O（~3P） attacking a near-collinear H–CH_3. One second-order SP^（2nd）（~3E） between the above twin SPs is the result of the C_（3v） symmetry Jahn–Teller coupling within the branching space. Further kinetic calculations are performed with the canonical unified statistical theory method with the temperature ranging from 298 K to 1000 K. The rate constants are also reported. The present work reveals the reaction mechanism of hydrogen-abstraction by the O（~3P） from methane, and develops a better understanding for the role of SPs. In addition, a comparison of the reactions of O（~3P） with methane through different channels allows a molecule-level discussion of the reactivity and mechanism of the title reaction.

Mechanism and kinetics study on the ozonolysis reaction of 2,3,7,8-TCDD in the atmosphere

The ozonolysis of 2,3,7,8-tetra-chlorodibenzo-p-dioxin （2,3,7,8-TCDD） is an efficient degradation way in the atmosphere. The ozonolysis process and possible reactions path of Criegee Intermediates with NO and H2O are introduced in detail at the method of MPWB1K/6-31＋G（d,p）//MPWB1K/6- 311＋G（3df,2p） level. In ozonolysis, H2O is an important source of OH radical formation and initiated the subsequent degradation reaction. The Rice-Ramsperger-Kassel-Marcus （RRKM） theory was applied to calculate rate constants with the temperature ranging from 200 to 600 K. The rate constant of reaction between 2,3,7,8-TCDD and 03 is 4.80 × 10^-20 cm3/（mole.sec） at 298 K and 760 Tort. The atmospheric lifetime of the reaction species was estimated according to rate constants, which is helpful for the atmospheric model study on the degradation and risk assessment of dioxin.

Mechanism and rate constants for complete series reactions of 19 fluorophenols with atomic H

Fluorine-containing halogenated fluorophenol may have effect as intermediate species involved in the formation of polyfluorinated dibenzo-p-dioxin/dibenzofurans （PFDDs/Fs）. The mechanism for the atomic H initiated reactions with complete series of nineteen fluorophenol congeners was studies using the density functional theory. At the MPWB1K,/6-31＋G（d,p） level, the geometries and frequencies of reactants, transition states, and products were obtained, and the accurate energetic values were acquired at the MPWB 1K/6-311 ＋G（3df,2p） level. The rate constants were evaluated by the canonical variational transition-state theory with the small curvature tunneling contribution over a wide temperature range of 600-1000 K. The study shows that the intramolecular hydrogen-bond in the ortho-substituted FPs as well as the inductive effect of the electron-withdrawing fluorine and steric repulsion of multiple substitutions may ultimately be responsible for the relative strength of the O-H bonds in FPs. The results can be used for further studies on PFDD/Fs formation mechanism.

Mechanism and kinetic properties of NO_3-initiated atmospheric degradation of DDT

In this article, the NO3 radical-initiated atmospheric oxidation degradation of DDT was theoretically investigated using molecular orbital theory calculations. All the calculations of intermediates, transition states and products were performed at the MPWB1K/6-311＋G（3df,2p）//MPWB1K/6- 31＋G（d,p） level of theory. Several energetically favorable reaction pathways were revealed. The formation mechanisms of secondary pollutants were presented and discussed. The rate constants were deduced over the temperature range of 273-333 K using canonical variational transition-state （CVT） theory with the small curvature tunneling （SCT） method. Our study shows that H abstraction from the alkyl group and NO3 addition to the Ca atom of the benzene ring are the dominant reaction pathways. The rate-temperature formula of the overall rate constants is k（T）（DDT＋NO3） = （7.21 ~ 10-15）exp（-153.81/T） cm3/（mol.sec） over the possible atmospheric temperature range of 273-333 K. The atmospheric lifetime of DDT determined by NO3 radical is about 52.5 days, which indicates that it can be degraded in the gas phase within several months.

Coarsening Behavior of Gamma Prime Precipitates in a Nickel Based Single Crystal Superalloy

The γ/γ＇ microstructural evolution in a nickel based single crystal superalloy during load-free thermal exposure at 900 ℃ has been further investigated in this paper. The growth characteristics of γ＇ precipitates were discussed in detail. The generation of interfacial dislocations would accelerate the rate of coalescence in the dendrite arms. The average sizes of precipitates were used to compare interface with diffusion controlled growth mechanism and no mechanism seems obviously dominant, although the square rate law gives slightly better fit. The coarsening behavior may be controlled by diffusion through the ragged interface between the γ＇ precipitate and the y matrix.

Effect of polishing parameters on abrasive free chemical mechanical planarization of semi-polar(1122) aluminum nitride surface

An abrasive free chemical mechanical planarization（AFCMP） of semi-polar（1122） Al N surface has been demonstrated. The effect of slurry p H, polishing pressure, and platen velocity on the material removal rate（MRR） and surface quality（RMS roughness） have been studied. The effect of polishing pressure on the AFCMP of the（1122） Al N surface has been compared with that of the（1122） Al Ga N surface. The maximum MRR has been found to be 562 nm/h for the semi-polar（1122） Al N surface, under the experimental conditions of 38 k Pa pressure,90 rpm platen velocity, 30 rpm carrier velocity, slurry p H 3 and 0.4 M oxidizer concentration. The best root mean square（RMS） surface roughness of 1.2 nm and 0.7 nm, over a large scanning area of 0.70×0.96 mm^2, has been achieved on AFCMP processed semi-polar（1122） AlN and（AlGaN） surfaces using optimized slurry chemistry and processing parameters.