Low temperature preparation and fuel cell properties of rare earth doped barium cerate solid electrolytes

The solid electrolytes, BaCe(0.8)Ln(0.2)O(2.9) (Ln: Gd, Sm, Eu), were prepared by the sol-gel method. XRD indicated that a pure orthorhombic phase was formed at 900 degrees C. The synthesis temperature by the sol-gel method was about 600 degrees C: lower than the high temperature solid phase reaction method. The electrical conductivity and impedance spectra were measured and the conduction mechanism was studied. The grain-boundary resistance of the solid electrolyte could be reduced or eliminated by the sol-gel method. The conductivity of BaCe0.8Gd0.2O2.9 is 7.87 x 10(-2) S.cm(-1) at 800 degrees C. The open-circuit voltage of hydrogen-oxygen fuel cell using BaCe0.8Gd0.2O2.9 as electrolyte was near to 1 V and its maximum power density was 30 mW.cm(-2).

大别山硬玉石英岩带中的水

The Dabie Mountains is a collisional orogenic belt between the North China and Yantze Continental plates. It is the eastern elongation of the Tongbai and Qingling orogen, and is truncated at its east end by the Tan-Lu fault. Jadeite-quartzite belt occurs in the eastern margin of UHPMB from the Dabie Mountains. Geochemical features indicate that the protoliths of the jadeite-quartzite and associated eclogite to be supracrustal rocks. The occurrence of micro-inclusions of coesite in jadeite and garnet confirmed that the continental crust can be subducted to great depth (8 0-100km) and then exhumed rapidly with its UHP mineral signature fairly preserved. Therefore, study of UHP jadeite-quartzite provides important information on subduction of continental crustal rocks and their exhumation histories, as well as the dynamics of plate tectonic processes at convergent margins. The purpose of this paper is to investigate the presence of hydrous component in the jadeite-quartzite belt, significant natural variations in the hydrous component content of UHP minerals and to discuss the role of water in petrology, geochemistry and micro-tectonic. On the basis of our previous studies, some new geological evidences have been found in the jadeite-quartzite belt by researches on petrography, mineralogy, micro-tectonic, hydrous component content of UHP minerals and combined with the study on rheology of materials using microprob, ER, TEM. By research and analysis of these phenomenona, the results obtained are as follows: 1. The existence of fluid during ultra-high pressure metamorphic process. Jadeites, omphacite, garnet, rutile, coesite and quartz from the jadeite-quartzite belt have been investigated by Fourier transform infrared spectrometer and TEM. Results show that all of these minerals contain trace amount of water which occur as hydroxyl and free-water in these minerals. The two-type hydrous components in UHP minerals are indicated stable in the mantle-depth. The results demonstrated that these ultra-high pressure metamorphic minerals, which were derived from continental crust protoliths, they could bring water into the mantle depth during the ultra-high pressure metamorphism. The clusters of water molecules within garnet are very important evidence of the existence of fluid during ultra-high pressure metamorphic process. It indicated that the metamorphic system was not "dry"during the ultra-high pressure stage. 2.The distribution of hydrous component in UHP minerals of jadeite-quartzite. The systematic distribution of hydrous components in UHP minerals are a strong indication that water in these minerals, are controlled by some factors and that the observed variations are not of a random nature. The distribution and concentration of hydrous component is not only correlated with composition of minerals, but also a function of geological environment. Therefore, the hydrous component in the minerals can not only take important part in the UHP metamorphic fluid during subduction of continental crustal rocks, but also their hydroxyl transported water molecules with decreasing pressure during their exhumation. And these water molecules can not only promote the deformation of jadeite through hydrolytic weakening, but also may be the part of the retrograde metamorphic fluid. 3.The role of water in the deformed UHP minerals. The jadeite, omphacite, garnet are strong elongated deformation in the jadeite-quartzite from the Dabie Mountains. They are (1) they are developed strong plastic deformation; (2) developed dislocation loop, dislocation wall; (3) the existence of clusters of water molecular in the garnet; and (4) the evolution of micero-tectonic from clusters of water molecular-dislocation loop in omphacite. That indicated that the water weakening controlled the mechanism of deformed minerals. Because the data presented here are not only the existence of clusters of water molecular in the garnet, but also developed strong elongation, high density of dislocation and high aspect ratios, adding microprobe data demonstrate the studied garnet crystals no compositional zoning. Therefore, this indicates that the diffusion process of the grain boundary mobility did not take place in these garnets. On the basis of above features, we consider that it can only be explained by plastic deformation of the garnets. The clusters of water molecules present in garnet was directly associated with mechanical weakening and inducing in plastic deformation of garnet by glissile dislocations. Investigate of LPO, strain analysis, TEM indicated that these clinopyroxenes developed strong elongation, high aspect ratios, and developed dislocation loop, dislocation wall and free dislocations. These indicated that the deformation mechanism of the clinopyroxenes plastically from the Dabie Mountains is dominant dislocation creep under the condition of the UHP metamorphic conditions. There are some bubbles with dislocation loops attached to them in the omphacite crystal. The bubbles attached to the dislocation loops sometimes form a string of bubble beads and some loops are often connected to one another via a common bubble. The water present in omphacite was directly associated with hydrolitic weakening and inducing in plastic deformation of omphacite by dislocations. The role of water in brittle deformation. Using microscopy, deformation has been identified as plastic deformation and brittle deformation in UHP minerals from the Dabie Mountains. The study of micro-tectonic on these minerals shows that the brittle deformation within UHP minerals was related to local stresses. The brittle deformation is interpreted as being caused by an interaction of high fluid pressure, volume changes. The hydroxyl within UHP minerals transported water molecules with decreasing pressure due to their exhumation. However, under eclogite facies conditions, the litho-static pressure is extreme, but a high fluid pressure will reduce the effective stress and make brittle deformation possible. The role of water in prograde metamorphism. Geochemical research on jadeite-quartzite and associated eclogite show that the protoliths of these rocks are supracrustal rocks. With increasing of temperature and pressure, the chlorite, biotite, muscovite was dehydrous reaction and released hydrous component during the subduction of continental lithosphere. The supracrustal rocks were transformed UHP rocks and formed UHP facies assemblage promotely by water introduction, and was retained in UHP minerals as hydrous component. The water within UHP minerals may be one of the retrograde metamorphic fluids. Petrological research on UHP rocks of jadeite-quartzite belt shows that there was existence of local fluids during early retrograde metamorphism. That are: (1) coronal textures and symplectite around relict UHP minerls crystals formed from UHP minerls by hydration reactions; (2) coronal textures of albite around ruitle; and (3) micro-fractures in jadeite or garnet were filled symplectite of Amp + PI + Mt. That indicated that the reactions of early retrograde metamorphism dependent on fluid introduction. These fluids not only promoted retrograde reaction of UHP minerals, but also were facilitate to diffuse intergranular and promote growth in minerals. Therefore, the hydrous component in the UHP minerals can not only take important part in the UHP metamorphic fluid during subduction of continental crustal rocks, but also their hydroxyl transport water molecules with decreasing pressure and may take part in the retrograde metamorphic fluid during their exhumation. 7. The role of water in geochemistry of UHP jadeite-quartzite. Geochemical research show that there are major, trace and rare earth element geochemical variations in the jadeite-quartzite from the Changpu district of Dabie Mountains, during retrograde metamorphic processes from the jadeite-quartzite--gneiss. The elements such as SiO_2、FeO、Ba、Zr、Ga、La、Ce、PTN Nd% Sm and Eu increase gradually from the jadeite-quartzite to retrograded jadeite-quartzite and to gneiss, whilst TiO_2. Na_2CK Fe2O_3、Rb、Y、Nb、Gd、Tb、Dy、Ho、Er、Tm、Yb decrease gradually. And its fO_2 keep nearly unchanged during early retrograde metamorphism, but decreased obviously during later retrograde metamorphism. These indicate that such changes are not only controlled by element transformation between mineralogical phases, but also closely relative to fluid-rock interaction in the decompression retrograde metamorphic processes.

Structure and impedance of ZrO2 doped with SC2O3 and CeO2

Scandia and ceria doped zirconia samples, with 10 mol% SC2O3 and different content of CeO2, were synthesized and characterized. The XRD results depict that the sintered samples have a cubic phase structure. However, Raman spectra show that besides the main cubic phase, a secondary phase is also present in the sintered samples. The addition of CeO2 can raise the content of the cubic phase, but the minor metastable tetragonal phase (t'-phase) exists even at the CeO2 content as high as 10 mol%. The near-UV Raman spectra indicate that the deformed tetragonal structure predominates at the grain boundary. The addition of CeO2 can reduce the impurity at grain boundary, and no impurity can be found by near-UV Raman spectroscopy at the grain boundary of the samples with high CeO2 content. The impedance measurements show that with the increase of CeO2 content, the impedance of grain boundary decreases and the bulk impedance increases. The low impedance of grain boundary can be attributed to the formation of a clean grain boundary upon CeO2 doping, and the increase of the bulk impedance is due to the blocking effect of the large Ce(IV) ions. (c) 2005 Elsevier B.V All rights reserved.

Damage analysis of tetragonal perovskite structure ceramics implicated by asymptotic field solutions and boundary conditions

Cracking of ceramics with tetragonal perovskite grain structure is known to appear at different sites and scale level. The multiscale character of damage depends on the combined effects of electromechanical coupling, prevailing physical parameters and boundary conditions. These detail features are exhibited by application of the energy density criterion with judicious use of the mode I asymptotic and full field solution in the range of r/a = 10(-4) to 10(-2) where r and a are, respectively, the distance to the crack tip and half crack length. Very close to the stationary crack tip, bifurcation is predicted resembling the dislocation emission behavior invoked in the molecular dynamics model. At the macroscopic scale, crack growth is predicted to occur straight ahead with two yield zones to the sides. A multiscale feature of crack tip damage is provided for the first time. Numerical values of the relative distances and bifurcation angles are reported for the PZT-4 ceramic subjected to different electric field to applied stress ratio and boundary conditions that consist of the specification of electric field/mechanical stress, electric displacement/mechanical strain, and mixed conditions. To be emphasized is that the multiscale character of damage in piezoceramics does not appear in general. It occurs only for specific combinations of the external and internal field parameters, elastic/piezoelectric/dielectric constants and specified boundary conditions. (C) 2002 Published by Elsevier Science Ltd.

Direct Numerical Simulation of a Spatially Evolving Supersonic Turbulent Boundary Layer at Ma=6

Direct numerical simulation is carried out for a spatially evolving supersonic turbulent boundary layer at free-stream Mach number 6. To overcome numerical instability, the seventh-order WENO scheme is used for the convection terms of Navier-Stokes equations, and fine mesh is adopted to minimize numerical dissipation. Compressibilty effects on the near-wall turbulent kinetic energy budget are studied. The cross-stream extended self-similarity and scaling exponents including the near-wall region are studied. In high Mach number flows, the coherence vortex structures are arranged to be smoother and streamwised, and the hair-pin vortices are less likely to occur.

Microstructure and Evolution of Mechanically-Induced Ultrafine Grain in Surface Layer of Al-Alloy Subjected to USSP

Experiments were conducted to investigate the ultrafine-grained (UFG) microstructures in the surface layer of an aluminum alloy 7075 heavily worked by ultrasonic shot peening. Conventional and high-resolution electron microscopy was performed at various depths of the deformed layer. Results showed that UFG structures were introdued into the surface layer of 62 μm thick. With increasing strain, the various microstructural features, e.g., the dislocation emission source, elongated microbands, dislocation cells, dislocation cell blocks, equiaxed submicro-, and nano-crystal grains etc., were successively produced. The grain subdivision into the subgrains was found to be the main mechanism responsible for grain refinement. The simultaneous evolution of high boundary misorientations was ascribed to the subgrain boundary rotation for accommodating further strains. Formed microstructures were highly nonequilibratory.  2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Dns Of Compressible Turbulent Boundary Layer Around A Sharp Cone

Direct numerical simulation of the turbulent boundary layer over a sharp cone with 20 degrees cone angle (or 10 degrees half-cone angle) is performed by using the mixed seventh-order up-wind biased finite difference scheme and sixth-order central difference scheme. The free stream Mach number is 0.7 and free stream unit Reynolds number is 250000/inch. The characteristics of transition and turbulence of the sharp cone boundary layer are compared with those of the flat plate boundary layer. Statistics of fully developed turbulent flow agree well with the experimental and theoretical data for the turbulent flat-plate boundary layer flow. The near wall streak-like structure is shown and the average space between streaks (normalized by the local wall unit) keeps approximately invariable at different streamwise locations. The turbulent energy equation in the cylindrical coordinate is given and turbulent energy budget is studied. The computed results show that the effect of circumferential curvature on turbulence characteristics is not obvious.

A field model interpretation of crack initiation and growth behavior in ferroelectric ceramics: change of poling direction and boundary condition

Strain energy density expressions are obtained from a field model that can qualitatively exhibit how the electrical and mechanical disturbances would affect the crack growth behavior in ferroelectric ceramics. Simplification is achieved by considering only three material constants to account for elastic, piezoelectric and dielectric effects. Cross interaction of electric field (or displacement) with mechanical stress (or strain) is identified with the piezoelectric effect; it occurs only when the pole is aligned normal to the crack. Switching of the pole axis by 90degrees and 180degrees is examined for possible connection with domain switching. Opposing crack growth behavior can be obtained when the specification of mechanical stress sigma(infinity) and electric field E-infinity or (sigma(infinity), E-infinity) is replaced by strain e and electric displacement D-infinity or (epsilon(infinity), D-infinity). Mixed conditions (sigma(infinity),D-infinity) and (epsilon(infinity),E-infinity) are also considered. In general, crack growth is found to be larger when compared to that without the application of electric disturbances. This includes both the electric field and displacement. For the eight possible boundary conditions, crack growth retardation is identified only with (E-y(infinity),sigma(y)(infinity)) for negative E-y(infinity) and (D-y(infinity), epsilon(y)(infinity)) for positive D-y(infinity) while the mechanical conditions sigma(y)(infinity) or epsilon(y)infinity are not changed. Suitable combinations of the elastic, piezoelectric and dielectric material constants could also be made to suppress crack growth. (C) 2002 Published by Elsevier Science Ltd.

Additional response: Additional discussion of “Mixed mode ductile fracture using the strain energy density criterion”

boundary-layer flows, the skin friction and wall heat-transfer are higher and the

Acoustic Calculation for Supersonic Turbulent Boundary Layer Flow

An approach which combines direct numerical simulation (DNS) with the Lighthill acoustic analogy theory is used to study the potential noise sources during the transition process of a Mach 2.25 flat plate boundary layer. The quadrupole sound sources due to the flow fluctuations and the dipole sound sources due to the fluctuating surface stress are obtained. Numerical results suggest that formation of the high shear layers leads to a dramatic amplification of amplitude of the fluctuating quadrupole sound sources. Compared with the quadrupole sound source, the energy of dipole sound source is concentrated in the relatively low frequency range.

Effect of microstructure of TiO2 thin films on optical band gap energy

TiO2 coatings are prepared on fused silica with conventional electron beam evaporation deposition. After annealed at different temperatures for four hours, the spectra and XRD patterns of TiO2 thin film are obtained. XRD patterns reveal that only anatase phase can be observed in TiO2 coatings regardless of the different annealing temperatures, and with the increasing annealing temperature, the grain size gradually increases. The relationship between the energy gap and microstructure of anatase is determined and discussed. The quantum confinement effect is observed that with the increasing grain size of TiO2 thin film, the band gap energy shifts from 3.4 eV to 3.21 eV. Moreover, other possible influence of the TiO2 thin-film microstructure, such as surface roughness and thin film absorption, on band gap energy is also expected.

The effects of oxygen partial pressure on the optical absorption edge and the UV emission energy of ZnO films

The optical absorption edge and ultraviolet (UV) emission energy of ZnO films deposited by direct current (DC) reactive magnetron sputtering at room temperature have been investigated. With the oxygen ratio increasing, the structure of films changes from zinc and zinc oxide coexisting phase to single-phase ZnO and finally to the highly (002) orientation. Both the grain size and the stress of ZnO film vary with the oxygen partial pressure. Upon increasing the oxygen partial pressure in the growing ambient, the visible emission in the room-temperature photoluminescence spectra was suppressed without sacrificing the band-edge emission intensity in the ultraviolet region. The peaks of photoluminescence spectra were located at 3.06---3.15 eV. From optical transmittance spectra of ZnO films, the optical band gap edge was observed to shift towards shorter wavelength with the increase of oxygen partial pressure.

Effects of crystalline quality on the phase stability of cubic boron nitride thin films under medium-energy ion irradiation

To investigate the effect of radiation damage on the stability and the compressive stress of cubic boron nitride (c-BN) thin films, c-BN films with various crystalline qualities prepared by dual beam ion assisted deposition were irradiated at room temperature with 300 keV Ar+ ions over a large fluence range up to 2 x 10(16) cm(-2). Fourier transform infrared spectroscopy (FTIR) data were taken before and after each irradiation step. The results show that the c-BN films with high crystallinity are significantly more resistant against medium-energy bombardment than those of lower crystalline quality. However, even for pure c-BN films without any sp(2)-bonded BN, there is a mechanism present, which causes the transformation from pure c-BN to h-BN or to an amorphous BN phase. Additional high resolution transmission electron microscopy (HRTEM) results support the conclusion from the FTIR data. For c-BN films with thickness smaller than the projected range of the bombarding Ar ions, complete stress relaxation was found for ion fluences approaching 4 x 10(15) cm(-2). This relaxation is accompanied, however, by a significant increase of the width of c-BN FTIR TO-line. This observation points to a build-up of disorder and/or a decreasing average grain size due to the bombardment. (c) 2005 Elsevier B.V. All rights reserved.

A New Criterion Number for the Boundary Conditions at the Solid/Liquid Interface in Nanoscale

A simple, but important three-atom model was proposed at the solid/liquid interface, leading to a new criterion number, lambda, governing the boundary conditions (BCs) in nanoscale. The solid wall is considered as the face-centered-cubic (fcc) structure. The fluid is the liquid argon with the well-known LJ potential. Based on the concept, the two micro-systems have the same BCs if they have The same criterion number. The degree of the locking BCs is enhanced when lambda equals to 0.757. Such critical criterion number results in the substantial epitaxial ordering and one, two, or even three liquid layers are locked by the solid wall, depending on the coupling energy scale ratio of the solid and liquid atoms. With deviation from the critical criterion number, the flow approaches the slip BCs and there are little ordering structures within the liquid. Always at the same criterion number, the degree of the slip is decreased or the locking is enhanced with increasing the coupling energy scale ratio of the solid and liquid atoms. The above analysis is well confirmed by the molecular dynamics (MD) simulation. The slip length is well correlated in terms of the new criterion number. The future work is suggested to extend the present theory for other microstructures of the solid wall atoms and quasi-LJ potentials.

1ST PRINCIPLES PSEUDOPOTENTIAL CALCULATIONS OF ZONE BOUNDARY PHONON FREQUENCIES OF III-V-ZINCBLENDE SEMICONDUCTORS

Longitudinal zone boundary X phonon frequencies have been calculated by a first principles pseudopotential method for III-V zincblende semiconductors AlP, AlAs, AlSb, GaP, GaAs, GaSb, InP, InAs and InSb. The phonon frequencies have been evaluated from total energy calculations in the frozen phonon approximation. The calculated phonon frequencies agree very well with the experimental values.