STUDIES ON ORGANOLANTHANIDE COMPLEXES .40. SYNTHESIS AND X-RAY STRUCTURE OF BIS (2-METHOXYETHYLCYCLOPENTADIENYL) YTTRIUM AND YTTERBIUM TETRAHYDROBORATES

New bis (2-methoxyethylcyclopentadienyl) yttrium and ytterbium tetrahydroborates (Ln = Y, 1; Yb, 2) have been synthesized in good yield by the reaction of bis (2-methoxyethylcyclopentadienyl) lanthanide chlorides (Ln = Y, Yb) with sodium borohydride in THF at room temperature. The title complexes were characterized by elemental analyses, MS, H-1 NMR and IR spectra. The crystal structures of 1 and 2 have been determined by X-ray diffraction. 1 crystallizes from THF-n-Hexane in space group Pna2(1) with unit cell parametert: a = 1.2390(3), b = 1.1339(2), c = 1.1919 (2) nm and V = 1.6745(6) nm3 with z = 4 for D(c) = 1.39 g.cm-3.The structure was solved by direct method and refined to final R = 0.061 (for 1730 observed reflections). The Space group of 2 is Pna2(1) with unit cell parameters: a = 1.2399(6), b = 1.1371(5), c = 1.1897(2) nm and V = 1.6773(1) nm3 with z = 4 for D(c) = 1.72 g.cm-3, R = 0.038 (for 2157 observed reflections). The X ray structures and IR reveal the bidentate yttrium and ytterbium tetrahydroborate complexes with the intramolecular coordination bonds between lanthanide metal and ligand oxygen atoms.

Preparation of porous chitosan/agarose microsphere and its R-phycoerythrin release properties

The chitosan microspheres (CS-CL) were prepared by suspension crosslinking method and used as carriers of R-phycoerythrin (R-PE). In this study, R-PE was loaded in the microspheres and released in vitro. The effects of pH value, temperature, ionic strength, and R-PE concentration on loading efficiency and release behavior were discussed. A novel microsphere that contained agarose (CS-AR MP) was prepared and the basic loading and releasing behavior for R-PE of this kind of new micro-spheres were also investigated. The results showed that all these chitosan microspheres have the ability to control-release R-PE. The addition of agarose may somewhat accelerate the release rate of R-PE from microspheres and reduce the capacity of adsorption for R-PE. (c) 2006 Wiley Periodicals, Inc.

Ship-board measurements and estimations of air-sea fluxes in the western tropical Pacific during TOGA COARE

Direct air-sea flux measurements were made on RN Kexue #1 at 40 degrees S, 156 degrees E during the Tropical Ocean Global Atmosphere (TOGA) Coupled Ocean-Atmospheric Response Experiment (COARE) Intensive Observation Period (IOP). An array of six accelerometers was used to measure the motion of the anchored ship, and a sonic anemometer and Lyman-alpha hygrometer were used to measure the turbulent wind vector and specific humidity. The contamination of the turbulent wind components by ship motion was largely removed by an improvement of a procedure due to Shao based on the acceleration signals. The scheme of the wind correction for ship motion is briefly outlined. Results are presented from data for the best wind direction relative to the ship to minimize flow distortion effects. Both the time series and the power spectra of the sonic-measured wind components show swell-induced ship motion contamination, which is largely removed by the accelerometer correction scheme, There was less contamination in the longitudinal wind component than in the vertical and transverse components. The spectral characteristics of the surface-layer turbulence properties are compared with those from previous land and ocean results, Momentum and latent heat fluxes were calculated by eddy correlation and compared to those estimated by the inertial dissipation method and the TOGA COARE bulk formula. The estimations of wind stress determined by eddy correlation are smaller than those from the TOGA COARE bulk formula, especially for higher wind speeds, while those from the bulk formula and inertial dissipation technique are generally in agreement. The estimations of latent heal flux from the three different methods are in reasonable agreement. The effect of the correction for ship motion on latent heat fluxes is not as large as on momentum fluxes.

Simultaneous enumeration of diatom, protozoa and meiobenthos from marine sediments using Ludox-QPS method

The Ludox-QPS method is a newly developed technique, which combines the Ludox HS 40 density centrifugation and quantitative protargol stain, to enumerate marine ciliates with good taxonomic resolution. We tested the method for simultaneous enumeration of diatoms, protozoa and meiobenthos and compared its extraction efficiency for meiobenthos with that of the routine Ludox-TM centrifugation and a modified protocol using Ludox HS 40. We conducted the evaluation with a sample size of 8.3 ml each from sandy, muddy-sand and muddy sediments collected from the intertidal area of the Yellow Sea in summer 2006 and spring 2007. The Ludox-QPS method not only produced high extraction efficiencies of 97 +/- 1.3% for diatoms and 97.6 +/- 0.8% for ciliates, indicating a reliable enumeration for eukaryotic microbenthos, but also produced excellent extraction efficiencies of on average 97.3% for total meiobenthos, 97.9% for nematodes and 97.8% for copepods from sands, muddy sands and mud. By contrast, the routine Ludox-TM centrifugation obtained only about 74% of total meiobenthos abundance with one extraction cycle, and the modified Ludox HS 40 centrifugation yielded on average 93% of total meiobenthos: 89.4 +/- 2.0% from sands, 93 +/- 4.1% from muddy sands and 97.1 +/- 3.0% from mud. Apart from the sediment type, sample volume was another important factor affecting the extraction efficiency for meiobenthos. The extraction rate was increased to about 96.4% when using the same modified Ludox centrifugation for a 4 ml sediment sample. Besides the excellent extraction efficiency, the Ludox-QPS method obtained higher abundances of meiobenthos, in particular nematodes, than the routine Ludox centrifugation, which frequently resulted in an uncertain loss of small meiobenthos during the sieving process. Statistical analyses demonstrated that there were no significant differences between the meiobenthos communities revealed by the Ludox-QPS method and the modified Ludox HS 40 centrifugation, showing the high efficiency of the Ludox-QPS method for simultaneous enumeration of diatom, protozoa and meiobenthos. Moreover, the comparatively high taxonomic resolution of the method, especially for diatoms and ciliates, makes it feasible to investigate microbial ecology at community level.

2,3,5-triphenyl-2H-tetrazolium chloride and 2,4,6-tri(2-pyridyl)-s-triazine on the corrosion of mild steel in HCl

Electrochemical measurement, quantum chemical method, and scanning electron microscopy (SEM) were performed to investigate the inhibitive effect of 2,3,5-triphenyl-2H-tetrazolium chloride (TTC) and 2,4,6-tri(2-pyridyl)-s-triazine(TPT) on the corrosion of mild steel in 1mol.L-1 HCl at room temperature. Impedance spectroscopy measurement showed that the polarization resistance increased and that double layer capacitance decreased with the increase in the inhibitive concentration, and the results of potentiodynamic polarization showed that the inhibitors suppressed both cathodic and anodic processes of steel corrosion without change in the mechanism. Higher the orbital density distribution strength of the lowest unoccupied molecular orbital, higher is the molecule dipole, and lower energy gap between the energy of the highest occupied molecular orbital and the energy of the lowest unoccupied molecular orbital resulted in higher inhibitory efficiency. The results of SEM analysis showed that the metal was protected from aggressive corrosion by the addition of TTC and TPT.

Analysis of primary aromatic amines using precolumn derivatization by HPLC fluorescence detection and online MS identification

2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and 2-(9-acridone)-acetic acid (AAA), two novel precolumn fluorescent derivatization reagents, have been developed and compared for analysis of primary aromatic amines by high performance liquid chromatographic fluorescence detection coupled with online mass spectrometric identification. PPIA and AAA react rapidly and smoothly with the aromatic amines on the basis of a condensation reaction using 1-ethyl-3-(3dimethylaminopropyl)-carbodiimide (EDC) as dehydrating catalyst to form stable derivatives with emission wavelengths at 380 and 440 nm, respectively. Taking six primary aromatic amines (aniline, 2-methylaniline, 2-methoxyaniline, 4-methylaniline, 4-chloroaniline, and 4-bromoaniline) as testing compounds, derivatization conditions such as coupling reagent, basic catalyst, reaction temperature and time, reaction solvent, and fluorescent labeling reagent concentration have also been investigated. With the better PPIA method, chromatographic separation of derivatized aromatic amines exhibited a good baseline resolution on an RP column. At the same time, by online mass spectrometric identification with atmospheric pressure chemical ionization (APCI) source in positive ion mode, the PPIA-labeled derivatives were characterized by easy-to-interpret mass spectra due to the prominent protonated molecular ion m/z [M + H](+) and specific fragment ions (MS/MS) m/z 335 and 295. The linear range is 24.41 fmol-200.0 pmol with correlation coefficients in the range of 0.9996-0.9999, and detection limits of PPIA-labeled aromatic amines are 0.12-0.21 nmol/L (S/N = 3). Method repeatability, precision, and recovery were evaluated and the results were excellent for the efficient HPLC analysis. The most important argument, however, was the high sensitivity and ease-of-handling of the PPIA method. Preliminary experiments with wastewater samples collected from the waterspout of a paper mill and its nearby soil where pollution with aromatic amines may be expected show that the method is highly validated with little interference in the chromatogram.

Global negative vegetation feedback to climate warming responses of leaf litter decomposition rates in cold biomes

Whether climate change will turn cold biomes from large long-term carbon sinks into sources is hotly debated because of the great potential for ecosystem-mediated feedbacks to global climate. Critical are the direction, magnitude and generality of climate responses of plant litter decomposition. Here, we present the first quantitative analysis of the major climate-change-related drivers of litter decomposition rates in cold northern biomes worldwide. Leaf litters collected from the predominant species in 33 global change manipulation experiments in circum-arctic-alpine ecosystems were incubated simultaneously in two contrasting arctic life zones. We demonstrate that longer-term, large-scale changes to leaf litter decomposition will be driven primarily by both direct warming effects and concomitant shifts in plant growth form composition, with a much smaller role for changes in litter quality within species. Specifically, the ongoing warming-induced expansion of shrubs with recalcitrant leaf litter across cold biomes would constitute a negative feedback to global warming. Depending on the strength of other (previously reported) positive feedbacks of shrub expansion on soil carbon turnover, this may partly counteract direct warming enhancement of litter decomposition.

一种新的角加速度估计方法及其应用

首先提出了一种新的基于卡尔曼滤波及牛顿预测的角加速度估计方法,在已知电机驱动系统位置信息的情况下,利用卡尔曼滤波实时估计系统的角加速度;同时采用牛顿预测方法解决估计算法的滞后问题,进一步提高了估计加速度的响应频带．以此为基础,本文进一步分析了利用估计加速度进行反馈控制以增强系统对外扰动的鲁棒性问题,提出了加速度反馈控制策略的设计准则并分析了稳定性．在一个直接驱动机器人关节上针对上述加速度估计及控制方法进行了实验研究:将估计加速度的实验结果与实测加速度(利用加速度计)的实验结果进行了比较分析,从而定量地揭示出估计加速度及其反馈控制在实际系统中的可行性及有效性．

典型人类活动对边坡变形及稳定性的影响研究

China is a mountainous country in which geological hazards occurred frequently, especially in the east of China. Except the geology, topography and extreme climate, the large scale human activities have become a major factor to landslides. Typical human activities which induced landslides are fill, cut and underground mining. On the topic of the deformation mechanism and slope stability, taking three different man-made slopes as examples, deformation mechanism and slope stability were studied by several methods, such as field work, numerical modeling and monitor. The details are as following: (1) The numerical modeling approach advantages over other conventional methods such as limit methods, so the numerical modeling is the major tool in this thesis. So far, there is no uniform failure criterion for numerical simulation. The failure criterion were summarized and analyzed firstly, subsequently the appropriate criterion was determinated. (2) Taking 220kV Yanjin transformation substation fill slope as example, the deformable characteristic, unstable mode and laboratory tests were studied systematically. The results show: the slope deformation was probably caused by a combination effect of unfavorable topographic, geological and hydro geological conditions, and external loading due to filling. It was concluded that the creep deformation of the slope was triggered by external loading applied at the back of the slope. In order to define the calculating parameters, a set of consolidated drained (CD) tests, consolidated undrained (CU) tests, repeated direct shear tests and UCS tests were carried out. The stability of the slope before and after reinforcement was assessed using 3D numerical modeling and shear strength reduction technique. The numerical modeling results showed: the factor of safety (FOS) of the slope was 1.10 in the natural state, and reduced to 1.03 after fill, which was close to the critical state and it caused creeping slip or deformation under rainfall. The failure surface in the slope is in active shear failure, whereas tensile failure occurs at the slope crest. After the site was reinforced with piles, the FOS was 1.27. Therefore, the slope is stable after reinforcement measures were taken. (3) The cut slope stability is a complex problem. Taking the left cut slope of Xiangjiaba as example in this thesis, the deformation and slope stability were studied systematically by numerical modeling and monitor methods. The numerical results show: the displacement is gradually increasing along with the cutting, and the largest displacement is 27.5mm which located at the bench between the elevation 340 and 380. Some failure state units distribute near the undermining part and there is no linked failure state occurred from crest to bottom during cutting. After cutting, some failure units appeared at the ground surface between elevation 340 and 360. The increasing tense stress made the disturbed rock failed. The slope is stable after cutting by the monitor method, such as surface monitor, multipoint displacement meter, inclinometer and anchor cable tensometer. (4) The interaction between underground mining and slope stability is a common situation in mountainous. The slope deformation mechanism induced by underground mining may contributed significantly to slope destabilization. The Mabukan slope in xiangjiaba was analyzed to illustrate this. Failure mechanism and the slope stability were presented by numerical modeling and residual deformation monitor. The results show: the roof deformed to the free face and the floor uplift lightly to the free face. The subsidence basin is formed, but the subsidence and the horizontal movement is small, and there is no failure zone occurred. When the underground mining is going on, the roof deformation, subsidence and the horizontal movements begin increasing. The rock deformation near the free face is larger than the ground surface, and the interaction between these coal seams appeared. There are some tensile failures and shear failures occurred on the roof and floor, and a majority of failure is tensile failure. The roof deformation, subsidence and the horizontal movements increased obviously along with the underground mining. The failure characteristic is shear failure which means the tensile stress transformed to the compressive stress. So the underground mining will induced tensile stress first which lead to structure crack, subsequently the compressive stress appeared which result in slippage. The crest was subjected to horizontal tension which made the rock crack along with the joint. The long term residual deformation monitor demonstrates that the slope is stable after the underground mining stopped.

基于精细结构描述及数值试验的断续节理岩体力学参数智能选取

Evaluating the mechanical properties of rock masses is the base of rock engineering design and construction. It has great influence on the safety and cost of rock project. The recognition is inevitable consequence of new engineering activities in rock, including high-rise building, super bridge, complex underground installations, hydraulic project and etc. During the constructions, lots of engineering accidents happened, which bring great damage to people. According to the investigation, many failures are due to choosing improper mechanical properties. ‘Can’t give the proper properties’ becomes one of big problems for theoretic analysis and numerical simulation. Selecting the properties reasonably and effectively is very significant for the planning, design and construction of rock engineering works. A multiple method based on site investigation, theoretic analysis, model test, numerical test and back analysis by artificial neural network is conducted to determine and optimize the mechanical properties for engineering design. The following outcomes are obtained: (1) Mapping of the rock mass structure Detailed geological investigation is the soul of the fine structure description. Based on statistical window，geological sketch and digital photography，a new method for rock mass fine structure in-situ mapping is developed. It has already been taken into practice and received good comments in Baihetan Hydropower Station. (2) Theoretic analysis of rock mass containing intermittent joints The shear strength mechanisms of joint and rock bridge are analyzed respectively. And the multiple modes of failure on different stress condition are summarized and supplied. Then, through introducing deformation compatibility equation in normal direction, the direct shear strength formulation and compression shear strength formulation for coplanar intermittent joints, as well as compression shear strength formulation for ladderlike intermittent joints are deducted respectively. In order to apply the deducted formulation conveniently in the real projects, a relationship between these formulations and Mohr-Coulomb hypothesis is built up. (3) Model test of rock mass containing intermittent joints Model tests are adopted to study the mechanical mechanism of joints to rock masses. The failure modes of rock mass containing intermittent joints are summarized from the model test. Six typical failure modes are found in the test, and brittle failures are the main failure mode. The evolvement processes of shear stress, shear displacement, normal stress and normal displacement are monitored by using rigid servo test machine. And the deformation and failure character during the loading process is analyzed. According to the model test, the failure modes quite depend on the joint distribution, connectivity and stress states. According to the contrastive analysis of complete stress strain curve, different failure developing stages are found in the intact rock, across jointed rock mass and intermittent jointed rock mass. There are four typical stages in the stress strain curve of intact rock, namely shear contraction stage, linear elastic stage, failure stage and residual strength stage. There are three typical stages in the across jointed rock mass, namely linear elastic stage, transition zone and sliding failure stage. Correspondingly, five typical stages are found in the intermittent jointed rock mass, namely linear elastic stage, sliding of joint, steady growth of post-crack, joint coalescence failure, and residual strength. According to strength analysis, the failure envelopes of intact rock and across jointed rock mass are the upper bound and lower bound separately. The strength of intermittent jointed rock mass can be evaluated by reducing the bandwidth of the failure envelope with geo-mechanics analysis. (4) Numerical test of rock mass Two sets of methods, i.e. the distinct element method (DEC) based on in-situ geology mapping and the realistic failure process analysis (RFPA) based on high-definition digital imaging, are developed and introduced. The operation process and analysis results are demonstrated detailedly from the research on parameters of rock mass based on numerical test in the Jinping First Stage Hydropower Station and Baihetan Hydropower Station. By comparison，the advantages and disadvantages are discussed. Then the applicable fields are figured out respectively. (5) Intelligent evaluation based on artificial neural network (ANN) The characters of both ANN and parameter evaluation of rock mass are discussed and summarized. According to the investigations, ANN has a bright application future in the field of parameter evaluation of rock mass. Intelligent evaluation of mechanical parameters in the Jinping First Stage Hydropower Station is taken as an example to demonstrate the analysis process. The problems in five aspects, i. e. sample selection, network design, initial value selection, learning rate and expected error, are discussed detailedly.

土石混合体细观结构力学及其边坡稳定性研究

Soil-rock mixture (S-RM) refers to one extremely uneven loose rock and soil materials system with certain stone content. Its formation has started since Quaternary and it is composed of block stone, fine grained soil and pore with certain project scale and high strength. S-RM has extensive distribution in nature, especially in southwest China where the geotectonic background is complicated, the fracture activity is developed and the geomorphological characteristics of high mountain and steep gorge area are protuberant. This kind of complicated geologic body has developed wider in these areas. S-RM has obvious difference with the general soil or rock (rock mass) in physical and mechanical properties because its two components-“soil” and “rock-block” has extreme differences in physical and mechanical properties. The proposition of S-RM and its deep research are needed in the modern engineering construction. It is also the necessity in the modern development of rock and soil mechanics. The dissertation starts from the meso-structural characteristics of soil-rock and takes a systematic research on its meso-structural mechanics, deformation and failure mechanism and the stability of S-RM slope. In summary, it achieves the following innovative results and conclusions. There are various views on the conception of S-RM and its classification system. Based on the large number of field tests, the dissertation makes the conception and classification of S-RM more systematic. It systematically proposed the conception of meso-structural mechanics of S-RM. Thus the dissertation has laid a foundation for its deep study. With the fast development of the computer technology and digital image processing theory, digital image processing technology has been successfully applied in many fields and provided reliable technology support for the quantitative description of the structural characteristics of S-RM. Based on the digital image processing technology, the dissertation systematically proposes and developed the quantitative analysis method and quantitative index for the meso-structure of S-RM. The results indicate that the meso-structure such as its internal soil-rock granularity composition, the soil-rock shape and the orientability has obvious self-organization in the macro statistical level. The dissertation makes a systematic research on the physical mechanical properties, deformation and failure mechanism of S-RM based on large field test. It proposes the field test for the underwater S-RM and deduces the 3D data analysis method of in-situ horizontal push-shear test. The result indicates that S-RM has significant phenomenon of shear dilatancy in the shearing process, and its dilatancy will be more obvious with the increased proportion of rock or the decreased confining pressure. The proportion of rock has great effect on the strength of S-RM and rock-block, especially the spatial position of particles with comparatively big size has great effect on the shape and spatial position of the sample shear zone. The dissertation makes some improvements in the single ring infiltration test equipment and its application on the permeability of S-RM. The results indicate that the increasing of rock-block would make it more difficult for the soil to fill in the vacuity between the rock-block and the proportion would increase which would result in the increased permeability coefficient. The dissertation builds the real meso-structural model of S-RM based on the digital image processing technology. By using geometric reconstruction technology, it transfers the structural mode represented by Binary image into CAD format, which makes it possible to introduce the present finite element analysis software to take research on numerical experimental investigation. It systematically realizes leaping research from the image，geometric mode, to meso-structural mechanics numerical experiment. By using this method, the dissertation takes large scale numerical direct-shear test on the section of S-RM. From the mesoscopic perspective, it reveals three extended modes about the shear failure plane of S-RM. Based on the real meso-structural model and by using the numerical simulation test, the character and mechanics of seepage failure of S-RM are studied. At the same time, it builds the real structural mode of the slope based on the analysis about the slope crosssection of S-RM. By using the strength reduction method, it takes the research on the stability of S-RM and gets great achievements. The three dimensional geometric reconstruction technology of rock block is proposed, which provides technical support for the reconstruction of the 3D meso-structural model of S-RM. For the first time, the dissertation builds the stochastic structure model of two-dimensional and three-dimensional polygons or polyhedron based on the stochastic simulation technique of monte carlo method. It breaks the traditional research which restricted to the random generation method of regular polygon and develops the relevant software system (R-SRM2D/3D) which has great effect on meso-structural mechanics of S-RM. Based on the R-SRM software system which randomly generates the meso-structural mode of S-RM according to the different meso-structural characteristics, the dissertation takes a series of research on numerical test of dual axis and real three-axis, systematically analyses the meso destroy system, the effects of meso-structural characteristics such as on the stone content, size composition and block directionality on the macro mechanical behavior and macro-permeability. Then it proposes the expression of the upper and lower limit for the macro-permeability coefficient of the inhomogeneous geomaterials, such as S-RM. By using the strength reduction FEM, the dissertation takes the research on the stability of the slope structural mode of the randomly formed S-RM. The results indicate that generally, the stability coefficient of S-RM slope increases with the increasing of stone content; on the condition of the same stone content, the stability coefficient of slope will be different with different size composition and the space position of large block at the internal slop has great effect on the stability. It suggests that meso-structural characteristics, especially the space position of large block should be considered when analyzing the stability of this kind of slope and strengthening design. Taking Xiazanri S-RM slope as an example, the dissertation proposes the fine modeling of complicated geologic body based on reverse engineering and the generation method of FLAC3D mode. It resolves the bottleneck problem about building the fine structural mode of three-dimensional geological body. By using FLAC3D, the dissertation takes research on the seepage field and the displacement field of Xiazanri S-RM slope in the process of reservoir water level rising and decreasing. By using strength reduction method, it analyses the three-dimension stability in the process of reservoir water level rising and decreasing. The results indicate that the slope stability firstly show downward trend in the process of reservoir water level rising and then rebound to increase; the sudden drawdown of reservoir water level has great effect on the slope stability and this effect will increase with the sudden drawdown amplitude rising. Based on the result of the rock block size analysis of S-RM, and using R-SRM2D the stochastic structure model of Xiazanri S-RM slope is built. By using strength reduction method, the stability of the stochastic structure model is analysis, the results shows that the stability factor increases significantly after considering the block.

水-岩土反应的力学与环境效应研究

The research on mechanical effects of water-rock and soil interaction on deformation and failure of rocks and soils involves three aspects of mechanics, physics and chemistry. It is the cross between geochemistry and rock mechanics and soil mechanics. To sum up, the mechanical effects of water-rock and soil interaction is related to many complex processes. Research in this respect has been being an important forward field and has broad prospects. In connection with the mechanism of the effects of the chemical action of water-rock on deformation and failure of rocks and soils, the research significance, the present state, the developments in this research domain are summarized. Author prospects the future of this research. The research of the subject should be possessed of important position in studying engineering geology and will lead directly to a new understand on geological hazard and control research. In order to investigation the macroscopic mechanics effects of chemical kinetics of water-rock interaction on the deformation and failure, calcic rock, red sandstone and grey granite reacting chemically with different aqueous solution at atmospheric temperature and atmospheric pressure are uniaxially compressed. The quantitative results concerning the changes of uniaxially compressive strength and elastic modulus under different conditions are obtained. It is found that the mechanical effects of water on rock is closely related to the chemical action of water-rock or the chemical damage in rock, and the intensity of chemical damage is direct ratio to the intensity of chemical action in water-rock system. It is also found that the hydrochemical action on rock is time-dependent through the test. The mechanism of permeation and hydrochemical action resulting in failure of loaded rock mass or propagation of fractures in rocks would be a key question in rock fracture mechanics. In this paper, the fracture mechanical effects of chemical action of water-rock and their time- and chemical environment-dependent behavior in grey granite, green granite, grey sandstone and red sandstone are analyzed by testing K_(IC) and COD of rock under different conditions. It is found that: ①the fracture mechanical effect of chemical action of water-rock is outstanding and time-dependent, and high differences exist in the influence of different aqueous solution, different rocks, different immersion ways and different velocity of cycle flow on the fracture mechanical effects in rock. ②the mechanical effects of water-rock interaction on propagation of fractures is consistent with the mechanical effects on the peak strength of rock. ③the intensity of the mechanical fracture effects increases as the intensity of chemical action of water-rock increases. ④iron and calcium ion bearing mineral or cement in rock are some key ion or chemical composition, and especially iron ion-bearing mineral resulting in chemical action of water-rock to be provided with both positive and negative mechanical effects on rock. Through the above two tests, we suggest that primary factors influencing chemical damage in rock consist of the chemical property of rock and aqueous solution, the structure or homogeneity of rocks, the flow velocity of aqueous solution passing through rock, and cause of formation or evolution of rock. The paper explores the mechanism on the mechanical effects of water-rock interaction on rock by using the theory of chemistry and rock fracture mechanics with chemical damage proposed by author, the modeling method and the energy point of view. In this paper, the concept of absorbed suction between soil grains caused by capillary response is given and expounded, and the relation and basic distinction among this absorbed suction, surface tension and capillary pressure of the soil are analyzed and established. The law of absorbed suction change and the primary factors affecting it are approached. We hold that the structure suction are changeable along with the change of the saturation state in unsaturated soils. In view of this, the concept of intrinsic structure suction and variable structure suction are given and expounded, and this paper points out: What we should study is variable structure suction when studying the effective stress. By IIIy κHH's theory of structure strength of soils, the computer method for variable structure suction is analyzed, the measure method for variable structure suction is discussed, and it reach the conclusions: ①Besides saturation state, variable structure suction is affected by grain composition and packing patter of grains. ②The internal relations are present between structure parameter N in computing structure suction and structure parameter D in computing absorbed suction. We think that some problems exit in available principle of effective stress and shear strength theory for unsaturated soil. Based on the variable structure suction and absorbed suction, the classification of saturation in soil and a principle of narrow sense effective stress are proposed for unsaturated soils. Based on generalized suction, the generalized effective stress formula and a principle of generalized effective stress are proposed for unsaturated soils. The experience parameter χ in Bishop's effective stress formula is defined, and the principal factors influencing effective stress or χ. The primary factor affecting the effective stress in unsaturated soils, and the principle classifying unsaturated soils and its mechanics methods analyzing unsaturated soils are discussed, and this paper points out: The theory on studying unsaturated soil mechanics should adopt the micromechanics method, then raise it to macromechanics and to applying. Researching the mechanical effects of chemical action of water-soil on soil is of great importance to geoenvironmental hazard control. The texture of soil and the fabric of soil mass are set forth. The tests on physical and mechanical property are performed to investigate the mechanism of the positive and negative mechanical effects of different chemical property of aqueous solution. The test results make clear that the plastic limit, liquid limit and plasticity index are changed, and there exists both positive and negative effects on specimens in this test. Based on analyzing the mechanism of the mechanical effects of water-soil interaction on soil, author thinks that hydrochemical actions being provided with mechanical effects on soil comprise three kinds of dissolution, sedimentation or crystallization. The significance of these tests lie in which it is recognized for us that we may improve, adjust and control the quality of soils, and may achieve the goal geological hazard control and prevention.The present and the significance of the research on environmental effects of water-rock and soil interaction. Various living example on geoenvironmental hazard in this field are enumerated. Following above thinking, we have approached such ideals that: ①changing the intensity and distribution of source and sink in groundwater flow system can be used to control the water-rock and soil interaction. ②the chemical action of water-rock and soil can be used to ameliorate the physical and mechanical property of rocks and soils. Lastly, the research thinking and the research methods on mechanical effects and environmental effects of water-rock and soil interaction are put forward and detailed.

基于工程地质力学的岩土工程加固理论、技术与实践

In the engineering reinforcement of-rock and soil mass, engineers must consider how to obtain better reinforcing effect at the cost of less reinforcing expense, which, in fact, is the aim of reinforcement design. In order to accomplish the purpose, they require not only researching the material used to reinforce and its structure, but also taking into account of several important geological factors, such as the structure and property of rock and soil mass. How to improve the reinforcing effect according to engineering geomechanical principle at the respect of the reinforcement of engineering soil and rock mass is studied and discussed in this paper. The author studies the theory, technology and practice of geotechnical reinforcement based on engineering geomechanics, taking example for the soil treatment of Zhengzhou Airport, the effect analysis of reinforcement to the slope on the left bank of Wuqiangxi Hydropower Station and the reinforcing design of the No. 102 Landslide and unique sand-slide slope on the Sichuan-Tibet Highway. The paper is comprised of two parts for the convenience of discussion. In the first part, from the first chapter to the fifth chapter, trying to perform the relevant research and application at the viewpoint of soil mass engineering geomechanics, the author mainly discusses the study of reinforcing soft ground soil through dynamical consolidation and its application. Then, in the second part, from the sixth chapter to the eleventh chapter, the study of new technologies in the rock slope reinforcement and their application are discussed. The author finds that not only better reinforcing effect can be gained in the research where the principle and method of rock mass engineering geomechanics is adopted, but also new reinforcing technologies can be put forward. Zhengzhou Airport is an important one in central plains. It lies on Yellow River alluvial deposit and the structure of stratum is complex and heterogeneous. The area of airport is very large, which can result in differential settlement easily, damage of airport and aircraft accident, whereas, there are no similar experiences to dispose the foundation, so the foundation treatment become a principal problem. During the process of treatment, the method of dynamic compaction was adopted after compared with other methods using the theory of synthetic integration. Dynamic compaction is an important method to consolidate foundation, which was successfully used in the foundation of Zhengzhou Airport. For fill foundation, controlling the thickness of fill so as to make the foundation treatment can reach the design demand and optimum thickness of the fill is a difficult problem. Considering this problem, the author proposed a calculation method to evaluate the thickness of fill. The method can consider not only the self-settlement of fill but also the settlement of the ground surface under applied load so as to ensure the settlement occurred during the using period can satisfy the design demand. It is proved that the method is correct after using it to choose reasonable energy of dynamic compaction to treat foundation. At the same time, in order to examine the effect of dynamic compaction, many monitor methods were adopted in the test such as static loading test, modulus of resilience test, deep pore pressure -test, static cone penetration test and the variation of the pore volume measurement. Through the tests, the author summarized the discipline of the accumulation and dissipation of pore pressure in Yellow River alluvial deposit under the action of dynamic compaction, gave a correct division of the property change of silt and clay under dynamic compaction, determined the bearing capacity of foundation after treatment and weighted the reinforcing effect of dynamic consolidation from the variation of the soil particle in microcosmic and the parameter of soil mass' density. It can be considered that the compactness of soil is in proportion to the energy of dynamic compaction. This conclusion provided a reference to the research of the "Problem of Soil Structure-the Central Problem of Soil Mechanics in 21 Century ". It is also important to strengthen rock mass for water conservancy and electric power engineering. Slip-resistance pile and anchoring adit full of reinforced concrete are usually adopted in engineering experience to strengthen rock mass and very important for engineering. But there also some deficiency such as the weakest section can't be highlighted, the monitor is inconvenient and the diameter of pile and adit is very large etc. The author and his supervisor professor Yangzhifa invented prestressed slip-resistance pile and prestressed anchoring adit full of reinforced concrete, utilizing the advantage that the prestressed structure has better anti-tensile characteristic (this invention is to be published). These inventions overcome the disadvantages of general slip-resistance pile and anchoring adit full of reinforced concrete and have the functions of engineering prospecting, strengthening, drainage and monitor simultaneous, so they have better strengthened effect and be more convenient for monitor and more economical than traditional methods. Drainage is an important factor in treatments of rock mass and slop. In view of the traditional drainage method that drainage pore often be clogged so as to resulted in incident, professor Yangzhifa invented the method and setting of guide penetration by fiber bundle. It would take good effect to use it in prestressed slip-resistance pile and anchoring adit full of reinforced concrete. In this paper, the author took example for anchoring adit full of reinforced concrete used to strengthen Wuqiangxi left bank to simulate the strengthened effect after consolidated by prestressed slip-resistance pile, took example for 102 landslide occurred along Sichuan-Tibet highway to simulate the application of slip-resistance pile and the new technology of drainage. At the same time the author proposed the treatment method of flowing sand in Sichuan-Tibet highway, which will benefit the study on strengthening similar engineering. There are five novelties in the paper with the author's theoretical study and engineering practice: 1. Summarizing the role of pore water pressure accumulation and dissipation of the Yellow River alluvial and diluvial soil under the action of dynamical consolidation, which has instructive significance in the engineering construction under the analogical engineering geological conditions in the future. It has not been researched by the predecessors. 2. Putting forward the concept of density D in microcosmic based on the microcosmical structure study of the soil sample. Adopting D to weight the reinforcing effect of dynamic consolidation is considered to be appropriate by the means of comparing the D values of Zhengzhou Airport's ground soil before with after dynamically consolidating reinforcement, so a more convenient balancing method can be provided for engineering practice. 3. According to the deep research into the soil mass engineering geology, engineering rock and soil science, soil mechanics, as well as considerable field experiments, improving the consolidating method in airport construction, from the conventional method, which is dynamically compactmg original ground surface firstly, then filling soil and dynamically layer-consolidating or layer-compacting at last to the upgraded method, which is performing dynamical consolidation after filling soil to place totally at the extent of the certain earth-filling depth. The result of the dynamical consolidation not only complies with the specifications, but also reduces the soil treatment investment by 10 million RMB. 4. Proposing the method for calculating the height of the filled soil by the means of estimating the potential displacement produced in the original ground surface and the filled earth soil under the possible load, selecting the appropriate dynamically-compacting power and determining the virtual height of the filled earth soil. The method is proved to be effective and scientific. 5. According to the thought of Engineering Geomechanics Metal-Synthetic Methodology (EGMS), patenting two inventions (to the stage of roclamation, with Professor Yang Zhi-fa, the cooperative tutor, and etc.) in which multi-functions, engineering geological investigation, reinforcement, drainage and strength remedy, are integrated all over in one body at the viewpoint of the breakage mechanism of the rock slope.

Synthesis and characterization of gallium-based perovskite-type dense membrane with oxygen semipermeability

La0.15Sr0.85Ga0.3Fe0.7O3-delta (LSGFO) and La0.15Sr0.85Co0.3Fe0.7O3-delta (LSCFO) mixed oxygen-ion and electron conducting oxides were synthesized by using a combined EDTA and citrate complexing method, and the corresponding dense membranes were fabricated. The properties of the oxide powders and membranes were characterized with combined SEM, XRD, H-2-TPR, O-2-TPD techniques, mechanical strength and oxygen permeation measurement. The results showed that LSGFO had much higher thermochemical stability than LSCFO due to the higher valence stability of Ga3+. After the temperature-programmed reduction by 5% H-2 in Ar from 20 degreesC to 1020 degreesC, the basic perovskite structure of LSGFO was successfully preserved. LSGFO also favors the oxygen vacancy formation better than LSCFO. Oxygen permeation measurement demonstrated that LSGFO had higher oxygen permeation flux than LSCFO, but they had similar activation energy for oxygen transportation, with a value of 110 and 117 kJ . mol(-1), respectively The difference in oxygen permeation fluxes was correlated with the difference in oxygen vacancy concentrations for the two materials.

New method for analysis of Chinese herbal complex prescription and its application

Traditional Chinese medicine (TCM) is a great treasure of China, the analysis of which is an arduous task. The viewpoint that all chemical constituents of Chinese herbal complex prescription should be analyzed as a black box is elucidated for the first time. Intelligent multi-mode multi-column chromatographic system (IMMCC) with its hybrids is the basic method and HPLC Unified Method is the breakthrough for the black box analysis. Dang-Gui-Bu-Xue-Tang was selected as a typical TCM and a systematic separation method from non-aqueous mobile phase to pure water mobile phase was put forward in order to convert unknown sample to known sample. The a, c values and UV spectra of 66 components of Astragalus, 78 components of Angelica and 71 components of Dang-Gui-Bu-Xue-Tang were obtained. Intelligent optimization and peak identification method and software for complex samples were developed and the optimum multi-step multi-binary gradient curve of mobile phase for Astragalus was ascertained. The maximum error and minimum error of predicted retention time for all components of Astragalus are 8.62% and 0.05% respectively. All components of Astragalus were compared with those of Angelica and it is found that many components of Astragalus are the same as those of Angelica, while the contents of these components are different. Many components of Dang-Gui-Bu-Xue-Tang are also the same as those of Astragalus and Angelica with different contents.