THE EFFECT OF DOPING WITH TANTALUM ON THE PROPERTIES OF YBA2CU3O7-Y

YBa2Cu3-xTaxO7-y (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) superconductors have been prepared, X-ray diffraction shows that the system remains orthorhombic for all compositions studied but. for x > 0.2, Ta2O5 was detected as an impurity phase. Substitution of Ta5+ for Cu2+ occurs in the Cu(2) sites on the Cu(2)O planes. The introduction of the high-valence element tantalum produces extra free electrons. These electrons recombine with the positive carrier of the system, which causes the mobility and the Hall number of YBa2Cu3-xTaxO7-y to decrease and also results in a depression in T(c).

COORDINATION CHEMISTRY AND SUPERCONDUCTIVITY

Analysing the coordination state of copper ions in cuprate superconductors, it is found that the larger the energy splitting between d(x2-y2) and d(z2) orbitals of Cu or the higher the energy of the d(x2-y2) orbital, the higher the Tc. Thus, appropriate coordination structures and strong-field ligands must be chosen for expanding the energy splitting and increasing the energy of the d(x2-y2) orbital when searching for new high-Tc superconductors. Summarizing the experimental results of ESR and XPS, it is considered that the [Cu2+ - O open-square-box 2- - Cu3+] resonance exists in cuprate superconductors and the electron field breathing mode is present. Analysing the mechanism and the relationship between the coordination state of Cu and Tc, we consider that the two dimensional Cu-O planes are responsible for the superconductivity of YBa2Cu3O7-y.

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.

内蒙古乌拉特中旗北部宝音图群研究

The Baoyintu Group, lies in Wulate-zhongqi, Inner Mongolia, is a set of medium-grade metamorphic rock series which undergoes complex deformations. It consists of pelite schist, greenschist, plagioclase amphibolite quartzite and marble. The pelite schist is the main rock type and contains the classic medium pressure metamorphic minerals. The author divided Baoyintu group into five assemblages, investigated the rock association and plotted geological section of each assemblage in this area. Based on the systemically study of structural geology, petrology, geochemistry and mineralogy, the author reconstructs the protolith, sedimentary environment and tectonic evolution, discusses the mesoscopic and microscopic structure, metamorphism, geochemistry characters and the correlation between porphyroblast growth and deformation-metamorphism. There are three phase deformations in the research area: the earliest one occurred as the Baoyintu group deformed and metamorphosed and the main structure pattern is tight fold within layers during the Dl, large scale reversed fold and two phase faults (Fl fault and F2 fault) during the D2, and superimposed fold and F3 fault during D3. The F3 trancate the Wenduermian group of Silurian. The second and third phase deformation are relate to the orogenic event of late period of early Paleozoic. According to the rock association ,characteristics of the rocks and research of geochemistry, we get some information of the sedimentary environment and tectonic evolution of Baoyintu group. The source rocks are a set of terrigenous deposits-volcanic formation which reflect the history of the tectonic setting: stable- active-restable. And there are two sedimentary cycle from first assemblage to fifth assemblage: from first assemblage to fourth assemblage is a course of progression and the fifth assemblage is a start of regression. We also get the information of the P-T-t path by studying petrographies and calculating temperature and pressure. The path is not similiat to any classic type. And the interpretation is different from the traditional opinion. The P-T-t path reflects the dynamic course of convergence and uplift, magma underplating, back-arc extension and convergence of continental margin. Applying the theory of deformation partitioning to this area, the author discuss the relationship between deformation and porphyroblast growth, and get the conclusion of the sequence of deformation and metamorphism. At the first time we measure the distribution of chemical composition within the porphyroblast by XRF, confirm the theory of deformation partitioning quantitative and get new understanding about growth phase of porphyroblast and growth mode of porphyroblast: porphyroblast grow in the manner as "rose flower", the growth is controlled by the deformation. The elements distribution in porphyroblast reflects the growth manner and indicate history of metamorphism and deformation. So, we can deduce the metmorphism and deformation from the elements distribution in porphyroblast.

Direct observation of subsurface oxygen on the defects of Pd(100)

Oxygen adsorption and desorption on a Pd(100) surface with a mesoscopic defect were studied by photoemission electron microscopy (PEEM). The defect surface, with an area of approximately 200 x 60 mu m(2), behaved differently from the perfect Pd(100) surface towards the adsorption of oxygen. When saturated, both surface oxygen and subsurface oxygen coexisted on the defect surface, whereas only surface oxygen was present on the Pd(100) surface. Upon heating, subsurface oxygen diffused back to the surface and desorbed with surface oxygen at the same time. The difference in oxygen adsorption ability between the defect surface and the perfect Pd(100) surface can be attributed to different structures of these two surfaces. (C) 1999 Elsevier Science B.V. All rights reserved.

Acid catalyzed synthesis of ordered bifunctionalized mesoporous organosilicas with large pore

Thiol-functionalized mesoporous ethane-silicas with large pore were synthesized by co-condensation of 1,2-bis(trimethoxy-sily)ethane (BTME) with 3-mercaptopropyltrimethoxysilane (MPTMS) using nonionic oligomeric polymer C1H (OCH(2)-CH(2))(10)OH (Brij-76) or poly(alkylene oxide) block copolymer (P123) as surfactant in acidic medium. The results of powder X-ray diffraction (XRD), nitrogen gas adsorption, and transmission electron microscopy (TEM) show that the resultant materials have well-ordered hexagonal mesoscopic structure with uniform pore size distributions. (29)Si MAS NNR, (13)C CP-MAS NMR. FT-IR, and UV Raman spectroscopies confirm the attachment of thiol functionalities in the mesoporous ethane-sificas. The maximum content of the attached thiol group (-SH) in the mesoporous framework is 2.48mmol/g. The ordered mesoporous materials are efficient Hg(2+) adsorbents with almost every -SH site accessible to Hg(2+). In the presence of various kinds of heavy metal ions such as Hg(2+), Cd(2+), Zn(2+), Cu(2+) and Cr(3+), the materials synthesized using poly(alkylene oxide) block cooollxmier (Pluronic 123) g(2+), as surfactant show almost similar affinity to Hg(2+), Cd(2+), and Cr(3+), while the materials synthesized using ofigomeric polymer C(18)H(37)(OCH(2)CH(2))(10)OH (Brij-76) as surfactant exhibit high selectivity to Hg(2+). (C) 2004 Elsevier Inc. All rights reserved.

Structural relation properties of hydrothermally stable functionalized mesoporous organosilicas and catalysis

The surfactant assistant syntheses of sulfonic acid functionalized periodic mesoporous organosilicas with large pores are reported. A one-step condensation of tetramethoxysilane (TMOS) with 1,2-bis(trimethoxysilyi)ethane (BTME) and 3-mercaptopropyltrimethoxysilane (MPTMS) in highly acidic medium was performed in the presence of triblock copolymer Pluronic P123 and inorganic salt as additive. During the condensation process, thiol (-SH) group was in situ oxidized to sulfonic acid (-SO3H) by hydrogen peroxide (30 wt % H2O2). X-ray diffraction studies along with nitrogen and water sorption analyses reveal the formation of stable, highly hydrophobic, and well-ordered hexagonal mesoscopic structures in a wide range of -CH2CH2-concentrations in the mesoporous framework. The resultant materials were also investigated by Si-29 MAS and C-13 CP MAS NMR, thermogravimetric analyses, UV-Raman spectroscopy, and FT-IR spectroscopy. The role of the bridged organic group on the hydrothermal stability of the mesoporous materials was established, which revealed an enhancement in hydrothermal stability of the materials with incorporation of the bridged organic groups in the network. The catalytic performance of -SO3H functionalized mesoporous materials was investigated in the esterification of ethanol with acetic acid, and the results demonstrate that the ethane groups incorporated in the mesoporous framework have a positive influence on the catalytic behavior of the materials.

Computational modeling of defects in nanoscale device materials

This PhD thesis concerns the computational modeling of the electronic and atomic structure of point defects in technologically relevant materials. Identifying the atomistic origin of defects observed in the electrical characteristics of electronic devices has been a long-term goal of first-principles methods. First principles simulations are performed in this thesis, consisting of density functional theory (DFT) supplemented with many body perturbation theory (MBPT) methods, of native defects in bulk and slab models of In0.53Ga0.47As. The latter consist of (100) - oriented surfaces passivated with A12O3. Our results indicate that the experimentally extracted midgap interface state density (Dit) peaks are not the result of defects directly at the semiconductor/oxide interface, but originate from defects in a more bulk-like chemical environment. This conclusion is reached by considering the energy of charge transition levels for defects at the interface as a function of distance from the oxide. Our work provides insight into the types of defects responsible for the observed departure from ideal electrical behaviour in III-V metal-oxidesemiconductor (MOS) capacitors. In addition, the formation energetics and electron scattering properties of point defects in carbon nanotubes (CNTs) are studied using DFT in conjunction with Green’s function based techniques. The latter are applied to evaluate the low-temperature, low-bias Landauer conductance spectrum from which mesoscopic transport properties such as the elastic mean free path and localization length of technologically relevant CNT sizes can be estimated from computationally tractable CNT models. Our calculations show that at CNT diameters pertinent to interconnect applications, the 555777 divacancy defect results in increased scattering and hence higher electrical resistance for electron transport near the Fermi level.

Nanoscopic modelling of the adhesion, indentation and fracture characteristics of metallic systems via molecular dynamics simulations

Large-scale molecular dynamics simulations have been performed on canonical ensembles to model the adhesion and indentation characteristics of 3-D metallic nano-scale junctions in tip-substrate geometries, and the crack propagation in 2-D metallic lattices. It is shown that irreversible flows in nano-volumes of materials control the behaviour of the 3-D nano-contacts, and that local diffusional flow constitutes the atomistic mechanism underlying these plastic flows. These simulations show that the force of adhesion in metallic nano-contacts is reduced when adsorbate monolayers are present at the metal—metal junctions. Our results are in agreement with the conclusions of very accurate point-contact experiments carried out in this field. Our fracture simulations reveal that at low temperatures cleavage fractures can occur in both an elemental metal and an alloy. At elevated temperatures, the nucleation of dislocations is shown to cause a brittle-to-ductile transition. Limiting crack propagation velocities are computed for different strain rates and a dynamic instability is shown to control the crack movement beyond this limiting velocity, in line with the recent experimental results.

Probing warm dense lithium by inelastic X-ray scattering

One of the grand challenges of contemporary physics is understanding strongly interacting quantum systems comprising such diverse examples as ultracold atoms in traps, electrons in high-temperature superconductors and nuclear matter. Warm dense matter, defined by temperatures of a few electron volts and densities comparable with solids, is a complex state of such interacting matter. Moreover, the study of warm dense matter states has practical applications for controlled thermonuclear fusion, where it is encountered during the implosion phase, and it also represents laboratory analogues of astrophysical environments found in the core of planets and the crusts of old stars, Here we demonstrate how warm dense matter states can be diagnosed and structural properties can be obtained by inelastic X-ray scattering measurements on a compressed lithium sample. Combining experiments and ab initio simulations enables us to determine its microscopic state and to evaluate more approximate theoretical models for the ionic structure.

Cold-Atom-Induced Control of an Optomechanical Device

We consider a cavity with a vibrating end mirror and coupled to a Bose-Einstein condensate. The cavity field mediates the interplay between mirror and collective oscillations of the atomic density. We study the implications of this dynamics and the possibility of an indirect diagnostic. Our predictions can be observed in a realistic setup that is central to the current quest for mesoscopic quantumness.

Hybridization of a class of "second order" models of traffic flow

Despite the simultaneous progress of traffic modelling both on the macroscopic and microscopic front, recent works [E. Bourrel, J.B. Lessort, Mixing micro and macro representation of traffic flow: a hybrid model based on the LWR theory, Transport. Res. Rec. 1852 (2003) 193–200; D. Helbing, M. Treiber, Critical discussion of “synchronized flow”, Coop. Transport. Dyn. 1 (2002) 2.1–2.24; A. Hennecke, M. Treiber, D. Helbing, Macroscopic simulations of open systems and micro–macro link, in: D. Helbing, H.J. Herrmann, M. Schreckenberg, D.E. Wolf (Eds.), Traffic and Granular Flow ’99, Springer, Berlin, 2000, pp. 383–388] highlighted that one of the most promising way to simulate efficiently traffic flow on large road networks is a clever combination of both traffic representations: the hybrid modelling. Our focus in this paper is to propose two hybrid models for which the macroscopic (resp. mesoscopic) part is based on a class of second order model [A. Aw, M. Rascle, Resurection of second order models of traffic flow?, SIAM J. Appl. Math. 60 (2000) 916–938] whereas the microscopic part is a Follow-the Leader type model [D.C. Gazis, R. Herman, R.W. Rothery, Nonlinear follow-the-leader models of traffic flow, Oper. Res. 9 (1961) 545–567; R. Herman, I. Prigogine, Kinetic Theory of Vehicular Traffic, American Elsevier, New York, 1971]. For the first hybrid model, we define precisely the translation of boundary conditions at interfaces and for the second one we explain the synchronization processes. Furthermore, through some numerical simulations we show that the waves propagation is not disturbed and the mass is accurately conserved when passing from one traffic representation to another.

Small angle neutron scattering from 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids ([C(n)mim][PF6], n=4, 6, and 8)

The presence of local anisotropy in the bulk, isotropic, and ionic liquid phases-leading to local mesoscopic inhomogeneity-with nanoscale segregation and expanding nonpolar domains on increasing the length of the cation alkyl-substituents has been proposed on the basis of molecular dynamics (MD) simulations. However, there has been little conclusive experimental evidence for the existence of intermediate mesoscopic structure between the first/second shell correlations shown by neutron scattering on short chain length based materials and the mesophase structure of the long chain length ionic liquid crystals. Herein, small angle neutron scattering measurements have been performed on selectively H/D-isotopically substituted 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids with butyl, hexyl, and octyl substituents. The data show the unambiguous existence of a diffraction peak in the low-Q region for all three liquids which moves to longer distances (lower Q), sharpens, and increases in intensity with increasing length of the alkyl substituent. It is notable, however, that this peak occurs at lower values of Q (longer length scale) than predicted in any of the previously published MD simulations of ionic liquids, and that the magnitude of the scattering from this peak is comparable with that from the remainder of the amorphous ionic liquid. This strongly suggests that the peak arises from the second coordination shells of the ions along the vector of alkyl-chain substituents as a consequence of increasing the anisotropy of the cation, and that there is little or no long-range correlated nanostructure in these ionic liquids.