Preparation and luminescence properties of in situ formed lanthanide complexes covalently grafted to a silica network

Lanthanide-doped sol-gel-derived materials are an attractive type of luminescent materials that can be processed at ambient temperatures. However, the solubility of the lanthanide complexes in the matrix is a problem and it is difficult to obtain a uniform distribution of the complexes. Fortunately, these problems can be solved by covalently linking the lanthanide complex to the sol-gel-derived matrix. In this study, luminescent Eu3+ and Tb3+ bipyridine complexes were immobilized on sol-gel-derived silica. FT-IR, DTA-TG and luminescence spectra, as well as luminescence decay analysis, were used to characterize the obtained hybrid materials. The organic groups from the bipyridine-Si moiety were mostly destroyed between 220 and 600 degreesC. The luminescence properties of lanthanide bipyridine complexes anchored to the backbone of the silica network and the corresponding pure complexes were comparatively investigated, which indicates that the lanthanide bipyridine complex was formed during the hydrolysis and co-condensation of TEOS and modified bipyridine. Excitation at the ligand absorption wavelength (336 nm for the hybrid materials and 350 nm for the pure complexes) resulted in strong emission of the lanthanide ions: Eu3+ D-5(0)-F-7(J) (J = 0, 1, 2, 3, 4) and Tb3+ D-5(4)-F-7(J) (J = 6, 5, 4, 3) emission lines due to efficient energy transfer from the ligands to the lanthanide ions.

Mesoscopic simulation of the impregnating process of unidirectional fibrous preform in resin transfer molding

The resin transfer molding has gained popularity in the preparation of fiber-reinforced polymer-matrix composites because of its high efficiency and low pollution. The non-uniform inter-tow and intra-tow flows are regarded as the reason of void formation in RTM. According to the process characteristics, the axisymmetric model was developed to study the interaction between the flow in the inter-tow space and that in the intra-tow space. The flow behavior inside the fiber tows was formulated using Brinkman's equation, while that in the open space around the fiber tows was formulated by Stokes' equation. The volume of fluid (VOF) method was applied to track the flow front, and the effects of filling velocity, resin viscosity, inter-tow dimension and intra-tow permeability on fluid pressure and flow front were analyzed. The results show that the flow front difference between the inter-tow and intra-tow becomes larger with the decrease of intra-tow permeability, as well as the increase of filling velocity and inter-tow dimension.

南海北部陆缘深水区构造－热演化与烃源岩成熟度史研究

Abstract In order to provide basic data for evaluation of the petroleum potential in the deep water area of the northern margin of the South China Sea (SCS), present-day thermal regime and basin tectonothermal evolution are reconstructed and the maturation history of the Cenozoic major source rocks in the study area is derived. The present-day geothermal regime in the deep water area of the northern margin of SCS is defined according to the geothermal gradient, thermal properties and heat flow data. Tectonic subsidence history is reconstructed based on borehole and seismic data, and accordingly the stretching episodes are determined from the subsidence pattern. Heat flow history in the deep water area of the northern margin of SCS is estimated on a finite time, laterally non-uniform and multi-episode stretching model. Maturation history of the main source rocks in the study area is estimated through EASYRo% kinetic model and thermal history, and the potential of petroleum in the deep water area of the northern margin of SCS is evaluated based on the data above. The results show that the present-day geothermal regime in the deep water area of the northern margin of SCS is characterized by “hot basin” with high geothermal gradient (39.1±7.4℃/km) and high heat flow (77.5±14.8 mW/m2), and that the Qiongdongnan Basin (QDNB) underwent three stretching episodes and consequently suffered three heating episodes (Eocene, Oligocene and Pliocene time) with highest paleo-heat flow of 65～90 mW/m2 at the end of the Pliocene, that the Pearl River Mouth Basin (PRMB) two stretching and two heating episodes (Eocene, Oligocene time) with highest paleo-heat flow of 60～70 mW/m2 at the end of the Oligocene, and that the source rocks matured drastically responding to the heating episodes. There are four hydrocarbon generation kitchens in the deep water area of the northern margin of SCS which are favor of its bright petroleum perspective. Tectonothermal analysis indicates that the present-day geothermal regime which is characterized with “hot basin” in the deep water area of the PRMB resulted mainly from the Cenozoic stretching as well as faulting and magmatic activities during the Neotectonic period, and that the Pliocene heating episode of the QDNB is coupled with the transition from sinistral to dextral gliding of the Red Rive fault, and that the deep water basins in the northern margin of SCS are typical of multiple rifting which caused multi-episode heating process.

南海张裂大陆边缘数值模拟研究

The South China Sea (SCS) is one of the largest marginal seas in the western Pacific, which is located at the junction of Eurasian plate, Pacific plate and Indian-Australian plate. It was formed by continent breakup and sea-floor spreading in Cenozoic. The complicated interaction among the three major plates made tectonic movement complex and geological phenomena very rich in this area. The SCS is an ideal place to study the formation and evolution of rifted continental margin and sea-floor spreading since it is old enough to have experienced the major stages of the basin evolution but still young enough to have preserved its original nature. As the demand for energy grows day by day in our country, the deep water region of the northern continental margin in the SCS has become a focus of oil and gas exploration because of its huge hydrocarbon potential. Therefore, to study the rifted continental margin of the SCS not only can improve our understanding of the formation and evolution processes of rifted continental margin, but also can provide theoretical support for hydrocarbon exploration in rifted continental margin. This dissertation mainly includes five topics as follows: (1) Various classic lithosphere stretching models are reviewed, and the continuous non-uniform stretching model is modified to make it suitable for the case where the extension of lithopheric mantle exceeds that of the crust. Then simple/pure shear flexural cantilever model is applied to model the basement geometries of SO49-18 profile in the northern continental margin of the SCS. By fitting the basements obtained by using 2DMove software with modeling results, it is found that the reasonable effective elastic thickness is less than 5km in this region. According to this result, it is assumed that there is weak lower crust in the northern continental margin in the SCS. (2) We research on the methods for stretching factor estimation based on various lithosphere stretching models, and apply the method based on multiple finite rifting model to estimate the stretching factors of several wells and profiles in the northern continental margin of the SCS. (3) We improve one-dimension strain rate inversion method with conjugate gradient method, and apply it to invert the strain rate of several wells in the northern continental margin of the SCS. Two-dimension strain rate forward modeling is carried out, and the modeling results show that effective elastic thickness is a key parameter to control basin’s geometry. (4) We simulate divergent upwelling mantle flow model using finite difference method, and apply this newly developed model to examine the formation mechanism of the northwest and central sub-basin in the SCS. (5) We inverse plate thickness and basal temperature of oceanic lithosphere using sea-floor ages and bathymetries of the North Pacific and the North Atlantic based on varied-parameters plate model, in which the heat conductivity, heat capacity and coefficient of thermal expansion depend on temperature or depth. A new empirical formula is put forward based the inversed parameters, which depicts the relation among sea-floor age, bathymetry and heat flow. Then various similar empirical formulae, including the newly developed one, are applied to examine the sea-floor spread issue in the SCS based on the heat flow and bathymetry data of the abyssal sub-basin.

接收函数方法与中国及邻区上地幔间断面的研究

The receiver function method applied in researching the discontinuities in upper mantle was systematically studied in this paper. Using the theoretical receiver functions, the characteristics of P410S and P660S phases were analyzed, and the influencing factors for detection of these phases were discussed. The stability of receiver function was studied, and a new computational method of receiver function, RFSSMS (Receiver Function of Stack and Smooth of Multi seismic-records at a Single station), was put forward. We built initial reference velocity model for the media beneath each of 18 seismic stations respectively; then estimated the buried depths of 410-km and 660-km discontinuities(simply marked as '410' and '660') under the stations by using the arrive time differences of P410S and P660S with P. We developed a new receiver function inversion method -PGARFI (Peeling-Genetic Algorithm of Receiver Function Inversion), to obtain the whole crust and upper mantle velocity structure and the depths of discontinuities beneath a station. The major works and results could be summarized as follows: (1) By analysis of the theoretical receiver functions with different velocity models and different ray parameters, we obtain the knowledge: The amplitudes of P410S and P660S phases are decreasing with the increasing of epicentral distance A , and the arrival time differences of these phases with P are shorter as A is longer. The multiple refracted and/or reflected waves yielded on Moho and the discontinuities in the crust interfere the identification of P410S. If existing LVZ under the lithosphere, some multiple waves caused by LVZ will interfere the identification of P410S. The multiple waves produced by discontinuity lied near 120km depth will mix with P410s phase in some range of epicentral distance; and the multiple waves concerned with the discontinuity lied near 210km depth will interfere the identification of P660S. The epicentral distance for P4i0s identification is limited, the upper limit is 80° . The identification of P660S is not restricted by the epicenter distance obviously. The identification of P410S and P6gos in the theoretical receiver functions is interfered weakly from the seismic wave attenuation caused by the media absorption if the Q value in a reasonable range. (2) The stability of receiver function was studied by using synthetic seismograms with different kind of noise. The results show that on the condition of high signal-noise-ratio of seismic records, the high frequency background noise and the low frequency microseism noise do not influence the calculating result of receiver function. But the media "scattering noise" influence the stability of receiver function. When the scattering effect reach some level, the identification of P4iOs and P66os is difficult in single receiver function which is yielded from only one seismic record. We provided a new method to calculate receiver function, that is, with a group of earthquake records, stacking the R and Z components respectively in the frequency domain, and weighted smooth the stacked Z component, then compute the complex spectrum ratio of R to Z. This method can improve the stability of receiver function and protrude the P4i0s and P66os in the receiver function curves. (3) 263 receiver functions were provided from 1364 three component broadband seismograms recorded at 18 stations in China and adjacent areas for the tele-earthquakes. The observed arrival time differences of P410S and P660S with P were obtained in these receiver functions. The initial velocity model for every station was built according to the prior research results. The buried depths of '410' and '660' under a station were acquired by the way of adjusting the depths of these two discontinuities in the initial velocity model until the theoretical arrival time differences of P410S and P660S with P well conformed to the observed. The results show an obvious lateral heterogeneity of buried depths of ' 410' and (660' . The depth of '410' is shallower beneath BJI, XAN, LZH and ENH, but deeper under QIZ and CHTO, and the average is 403km . The average depth of '660' is 663km, deeper under MDJ and MAJO, but shallower under QIZ and HYB. (4) For inversing the whole crust and upper mantle velocity structure, a new inversion method -PGARFI (Peeling-Genetic Algorithm of Receiver Function Inversion) has- been developed here. The media beneath a station is divided into segments, then the velocity structure is inversed from receiver function from surface to deep successively. Using PGARFI, the multi reflection / refraction phases of shallower discontinuities are isolated from the first order refraction transform phase of deep discontinuity. The genetic algorithm with floating-point coding was used hi the inversion of every segment, and arithmetical crossover and non-uniform mutation technologies were employed in the genetic optimization. 10 independent inversions are completed for every segment, and 50 most excellent velocity models are selected according to the priority of fitness from all models produced in the inversion process. The final velocity structure of every segment is obtained from the weighted average of these 50 models. Before inversion, a wide range of velocity variation with depth and depth range of the main discontinuities are given according to priori knowledge. PGARFI was verified with numerical test and applied in the inversion of the velocity structure beneath HIA station down to 700km depth.

Distribution, stability, bifurcations and catastrophe of steady rotation of a symmetrical heavy gyroscope with viscous-liquid-filled cavity

The number, the angles of orientation and the stability in Rumyantsev Movchan's sense of oblique steady rotations of a symmetric heavy gyroscope with a cavity completely filled with a uniform viscous liquid, possessing a fixed point 0 on its symmetric axis. are given for various values of the parameters. By taking the square of the upright component of the angular momentum M2 as a control parameter, three types of bifurcation diagrams of the steady rotations, two types of jumps and two kinds of local catastrophes, one being the symmetric reduced cusp type and the other being of the symmetric reduced butterfly type, are obtained. By taking account of the M2-damping owing to the moment of unavoidable faint friction, two different modes for the gyroscope, initially in a stable quasi-steady upright rotation with a nutation angle theta(s) equal to zero, to topple over are found.

Rotating wheel filter design and optimization for a uniform depth dose distribution in heavy ion therapy

Treatment planning of heavy-ion radiotherapy involves predictive calculation of not only the physical dose but also the biological dose in a patient body. The goal in designing beam-modulating devices for heavy ion therapy is to achieve uniform biological effects across the spread-out Bragg peak (SOBP). To achieve this, a mathematical model of Bragg peak movement is presented. The parameters of this model have been resolved with Monte Carlo method. And a rotating wheel filter is designed basing on the velocity of the Bragg peak movement.

Sulfonated poly(ether ether ketone)/aminopropyltriethoxysilane/phosphotungstic acid hybrid membranes with non-covalent bond: Characterization, thermal stability, and proton conductivity

Sulfonated poly(ether ether ketone) (SPEEK) and aminopropyltriethoxysilane (KH550) hybrid membranes doped with different weight ratio of phosphotungstic acid (PWA) were prepared by the casting procedure, as well as PWA as a catalyst for sol-gel process of KH550. The chemical structures of hybrid membranes were characterized by energy dispersive X-ray spectrometry (EDX) and Fourier transform infrared spectroscopy (FTIR). The morphology of hybrid membranes was investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results had proved the uniform and homogeneous distribution of KH550 and PWA in these hybrid membranes.

First-passage time distribution and non-Markovian diffusion dynamics of protein folding

We study the kinetics of protein folding via statistical energy landscape theory. We concentrate on the local-connectivity case, where the configurational changes can only occur among neighboring states, with the folding progress described in terms of an order parameter given by the fraction of native conformations. The non-Markovian diffusion dynamics is analyzed in detail and an expression for the mean first-passage time (MFPT) from non-native unfolded states to native folded state is obtained. It was found that the MFPT has a V-shaped dependence on the temperature. We also find that the MFPT is shortened as one increases the gap between the energy of the native and average non-native folded states relative to the fluctuations of the energy landscape. The second- and higher-order moments are studied to infer the first-passage time distribution. At high temperature, the distribution becomes close to a Poisson distribution, while at low temperatures the distribution becomes a Levy-type distribution with power-law tails, indicating a nonself-averaging intermittent behavior of folding dynamics. We note the likely relevance of this result to single-molecule dynamics experiments, where a power law (Levy) distribution of the relaxation time of the underlined protein energy landscape is observed.