Addition reactions of nitrones on the reconstructed C(100)-2 x 1 surfaces

In this paper, the reactions of nitrone, N-methyl nitrone, N-phenyl nitrone and their hydroxylamine tautomers (vinyl-hydroxylamine, N-methyl-vinyl-hydroxylamine and N-phenyl-vinyl-hydroxylamine) on the reconstructed C(100)-2 x 1 surface have been investigated using hybrid density functional theory (B3LYP), Moller-Plesset second-order perturbation (MP2) and multi-configuration complete-active-space self-consistent-field (CASSCF) methods. The calculations showed that all the nitrones can react with the surface "dimer" via facile 1.3-dipolar cycloaddition with small activation barriers (less than 12.0 kJ/mol at B3LYP/6-31g(d) level). The [2+2] cycloaddition of hydroxylamine tautomers on the C(100) surface follows a diradical mechanism. Hydroxylamine tautomers first form diradical intermediates with the reconstructed C(I 00)-2 x I surface by overcoming a large activation barrier of 50-60 kJ/mol (B3LYP), then generate [2+2] cycloaddition products via diradical transition states with negligible activation barriers. The surface reactions result in hydroxyl or amino-terminated diamond surfaces, which offers new opportunity for further modifications. (C) 2007 Elsevier B.V. All rights reserved.

Addition reaction of nitrones on the reconstructed Si(100)-2 x 1 surface

The reaction of nitrone, N-methyl nitrone, and their hydroxylamine tautomers (vinyl-hydroxylamine and N-methyl vinyl-hydroxylamine) on the reconstructed Si(100)-2 x 1 surface has been investigated by means of hybrid density functional theory (B3LYP) and Moller-Plesset second-order perturbation (MP2) methods. The calculations predicted that both of the nitrones should react with the surface dimer via facile concerted 1,3-dipolar cycloaddition leading to 5-member-ring compounds. The reaction of hydroxylamine tautomers on the Si(100) surface follows pi-complex (intermediate) mechanism. For the reaction of N-methyl vinyl-hydroxylamine, the pi-complex intermediate undergoes [2+2] cycloaddition leading to a 4-member-ring compound. But in the reaction of vinyl-hydroxylamine, the intermediate undergoes H-migration reaction ("ene" reaction) resulting in the oxime-terminated Si surface. All the surface reactions result in the hydroxyl-terminated silicon surfaces, which are very useful for the further modification of the semiconductor.

Theoretical study on adsorption of Na+ and Na+(H2O)(n) (n=1-6) on a clean Si(111) surface

To model the adsorption of Na+ in aqueous solution on the semiconductor surface, the interactions of Na+ and Na+(H2O)(n) (n = 1-6) with a clean Si(111) surface were investigated by using hybrid density functional theory (B3LYP) and Moller-Plesset second-order perturbation (MP2) methods. The Si(111) surface was described with Si8H12, Si16H20, and Si22H21 Cluster models. The effect of the basis set superposition error (BSSE) was taken into account by applying the counterpoise (CP) correction. The calculated results indicated that the interactions between the Na+ cation and the dangling bonds of the Si(111) surface are primarily electrostatic with partial orbital interactions. The magnitude of the binding energies depends weakly on the adsorption sites and the size of the clusters. When water molecules are present, the interaction between the Nal and Si(I 11) surfaces weakens and the binding energy has the tendency to saturate. On a Si22H21 cluster described surface, the optimized Na+-surface distance for Na+(H2O)(5) adsorbed at on-top site is 4.16 angstrom and the CP-corrected binding energy (MP2) is -35.4 kJ/mol, implying a weakly adsorption of hydrated Na+ cation on clean Si(111) surface.

基于IGES的卷曲类工件结构光测量路径规划研究

本文通过对卷曲类工件IGES文件的分析,本文提出了一种新的基于IGES文件的测量路径规划策略。根据张量积曲面的性质,提出了一种曲面组合算法,运用了张量积曲面的性质,将曲面操作转化为多次曲线操作,将IGES文件中存储的多片曲面片组合为一整片曲面,从而为自由曲面测量路径的提取提供了数学模型。运用二次逼近原理,提出了一种B样条曲线上的等距采样算法。通过在实际系统进行实验,上述策略及算法得到了验证,并在自主开发的智能测量建模加工一体化装备中得到了应用。

二氧化碳在孔隙咸水层中多相流动数值模拟研究

There has been a growing concern about the use of fossil fuels and its adverse effects on the atmospheric greenhouse and ecological environment. A reduction in the release rate of CO2 into the atmosphere poses a major challenge to the land ecology of China. The most promising way of achieving CO2 reduction is to dispose of CO2 in deep saline aquifers. Deep aquifers have a large potential for CO2 sequestration in geological medium in terms of volume and duration. Through the numerical simulation of multiphase flow in a porous media, the transformation and motion of CO2 in saline aquifers has been implemented under various temperature and hydrostatic pressure conditions, which plays an important role to the assessment of the reliability and safety of CO2 geological storage. As expected, the calculated results can provide meaningful and scientific information for management purposes. The key problem to the numerical simulation of multiphase flow in a porous media is to accurately capture the mass interface and to deal with the geological heterogeneity. In this study, the updated CE/SE (Space and time conservation element and solution element) method has been proposed, and the Hybrid Particle Level Set method (HPLS) has extended for multiphase flows in porous medium, which can accurately trace the transformation of the mass interface. The benchmark problems have been applied to evaluate and validate the proposed method. In this study, the reliability of CO2 storage in saline aquifers in Daqingzi oil field in Sunlong basin has been discussed. The simulation code developed in this study takes into account the state for CO2 covering the triple point temperature and pressure to the supercritical region. The geological heterogeneity has been implemented, using the well known geostatistical model (GSLIB) on the base of the hard data. The 2D and 3D model have been set up to simulate the CO2 multiphase flow in the porous saline aquifer, applying the CE/SE method and the HPLS method .The main contents and results are summarized as followings. (1) The 2D CE/SE method with first and second –order accuracy has been extended to simulate the multiphase flow in porous medium, which takes into account the contribution of source and sink in the momentum equation. The 3D CE/SE method with the first accuracy has been deduced. The accuracy and efficiency of the proposed CE/SE method have been investigated, using the benchmark problems. (2) The hybrid particle level set method has been made appropriate and extended for capturing the mass interface of multiphase flows in porous media, and the numerical method for level set function calculated has been formulated. (3) The closed equations for multiphase flow in porous medium has been developed, adept to both the Darcy flow and non-Darcy flow, getting over the limitation of Reynolds number to the calculation. It is found that Darcy number has a decisive influence on pressure as well as velocity given the Darcy number. (4) The new Euler scheme for numerical simulations of multiphase flows in porous medium has been proposed, which is efficient and can accurately capture the mass interface. The artificial compressibility method has been used to couple the velocities and pressure. It is found that the Darcy number has determinant effects on the numerical convergence and stability. In terms of the different Darcy numbers, the coefficient of artificial compressibility and the time step have been obtained. (5) The time scale of the critical instability for critical CO2 in the saline aquifer has been found, which is comparable with that of completely CO2 dissolved saline aquifer. (6) The concept model for CO2 multiphase flows in the saline aquifer has been configured, based on the temperature, pressure, porosity as well as permeability of the field site .Numerical simulation of CO2 hydrodynamic trapping in saline aquifers has been performed, applying the proposed CE/SE method. The state for CO2 has been employed to take into account realistic reservoir conditions for CO2 geological sequestration. The geological heterogeneity has been sufficiently treated , using the geostatistical model. (7) It is found that the Rayleigh-Taylor instability phenomenon, which is associated with the penetration of saline fluid into CO2 fluid in the direction of gravity, has been observed in CO2 multiphase flows in the saline aquifer. Development of a mushroom-type spike is a strong indication of the formation of Kelvin-Helmholtz instability due to the developed short wavelength perturbations present along the interface and parallel to the bulk flow. Additional key findings: the geological heterogeneity can distort the flow convection. The ascending of CO2 can induce the persistent flow cycling effects. The results show that boundary conditions of the field site have determinant effects on the transformation and motion of CO2 in saline aquifers. It is confirmed that the proposed method and numerical model has the reliability to simulate the process of the hydrodynamic trapping, which is the controlling mechanism for the initial period of CO2 storage at time scale of 100 years.

东营凹陷下第三系岩性油气藏形成条件与预测

The Dongying depression, located in the northern part of the jiyang Sag in the Buohaiwan Basin, comprises one of the major oil-producing bases of the Shengli oil-field. The prediction and exploration of subtle or litho1ogical oil traps in the oil-field has become the major confronted target. This is also one of the frontier study areas in the highly-explored oil-bearing basins in East China and abroad. Based on the integrated analysis of the geological, seismic and logging data and the theories of sequence stratigraphy, tectono-stratigraphy and petroleum system, the paper has attempted to document the characteristics of the sequence stratigraphic and structural frameworks of the low Tertiary, the syndepositional faults and their control on deposition, and then to investigate the forming conditions and distribution of the tithological oil traps in the depression. The study has set up a set of analysis methods, which can be used to effectively analysis the sequence stratigraphy of inland basins and predict the distribution of sandstone reservoirs in the basins. The major achievements of the study are as follows: 1. The low Tertiary can be divided into 4 second-order sequences and 13 third-order sequences, and the systems tracts in the third-order sequences have been also identified based on the examination and correction of well logging data and seismic profiles. At the same time, the parasequences and their stacking pattern in the deltaic systems of the third member of the Shahejie Formation have been recognized in the key study area. It has been documented that the genetic relation of different order sequences to tectonic, climatic and sediment supply changes. The study suggested that the formation of the second-order sequences was related to multiple rifting, while the activity of the syndepositional faults controlled the stacking pattern of parasequences of the axial deltaic system in the depression. 2. A number of depositional facies have been recognized in the low Tertiary on the basis of seismic facies and well logging analysis. They include alluvial fan, fan delta or braided delta, axial delta, lowstand fan, lacustrine and gravity flow deposits. The lacustrine lowstand fan deposits are firstly recognized in the depression, and their facies architecture and distribution have been investigated. The study has shown that the lowstand fan deposits are the important sandstone reservoirs as lithological oil traps in the depression. 3. The mapping of depositional systems within sequences has revealed the time and special distrbution of depositional systems developed in the basin. It is pointed out that major elastic systems comprise the northern marginal depositional systems consisting of alluvial fan, fan delta and offshore lowstand fan deposits, the southern gentle slope elastic deposits composed of shallow lacustrine, braided delta and lowstand fan deposits and the axial deltaic systems including those from eastern and western ends of the depression. 4. The genetic relationship between the syndepositional faults and the distribution of sandstones has been studied in the paper, upper on the analysis of structural framework and syndepositional fault systems in the depression. The concept of structural slope-break has been firstly introduced into the study and the role of syndepositional faults controlling the development of sequence architecture and distribution of sandstones along the hinged and faulted margins have been widely investigated. It is suggested that structural styles of the structural slope-break controlled the distribution of lowstand fan deposits and formed a favorable zone for the formation of lithological or structure-lithological oil traps in the basin. 5. The paper has made a deep investigation into the forming condition and processes of the lithological traps in the depression, based the analysis of composition of reservoir, seal and resource rocks. It is pointed out that there were two major oil pool-forming periods, namely the end of the Dongying and Guangtao periods, and the later one is the most important. 6. The study has finally predicted a number of favorable targets for exploration of lithologieal traps in the depression. Most of them have been drilled and made great succeed with new discovered thousands tons of raw oil reserves.