Sol-gel synthesis and properties of Ce1-xGdxO2-x/2 solid solutions

A series of solid electrolytes Ce1-xGdxO2-x/2(x=0 similar to0.6) was prepared by sol-gel method. The structure, thermal expansion coefficient and electrical properties of the solid solutions were systematically studied. XRD data showed that a complete cubic fluorite structure was formed at 160 degreesC. The purity of the product prepared by the sol-gel method is higher, the grain size is uniformly smaller. They were easily sintered into highly dense ceramic pellets at 1 300 degreesC. The sintering temperature was significantly lower than that by traditionally high temperature solid phase reaction method. The thermal expansion coefficient of Ce0.8Gd0.2O1.9, determined from high- temperature XRD data, is 8. 125 X 10(-6) K-1. Impedance spectra analyses showed that the grain-boundary resistance of the solid electrolyte prepared by sol-gel method was reduced or even eliminated. The conductivity of Ce0.8Gd0.2O1.9 is 5.26 X 10(-3) S/cm at 600 degreesC. The activation energy (E-a) is 0.82 eV.

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).

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.

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.

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.

东海榴辉岩向斜长角闪岩的转化过程

The Ultrahigh Pressure Metamorphic (UHPM) eclogite, which was resulted from deep subduction of crustal continent, is very significant due to its continental dynamic implications. Further more, this kind of rocks experienced great P-T, fluid and stresses changes during its forming and exhumation, causing mineral reactions occur intensively, which resulted in a lot of fantastic micro-texture. The micro-texture was preserved duo to a rapid exhumation of the eclogite. This PhD dissertation takes such micro-textures in 10 Donghai eclogite samples South Sulu UHPM terrene, as research object to reveal the transformation of the eclogite to amphibolite. Microscope and Scanning Electron Microscope were employed to observe the micro-texture. Basing on microprobe analysis of minerals, the ACF projections and iso-con analysis were used to uncover the mineral reactions during the transformation. Micro-texture observation (both of Microcopy and Electron Scanning Microscope), demonstrated: l.The peak mineral assemblage of the researched Donghai eclogites is garnet + omphacite + rutile (+ kyanite + aptite +coesite). 2.The transformation of the Donghai eclogite to amphibolite can be divided into two stages: The earlier one is Symplectization, resulting in the forming of diopside + albite (+magnetite) symplectite that occurred only along the boundary between two adjacent omphacite grains. Other minerals were not involved in such reaction. The latter stage is Fluid-Infiltration of the eclogite, which was caused by fluid-intrusion. The infiltration is demonstrated by amphibolization of the symplectite, decomposition of garnet and the forming of some hydrous minerals such as phengite and epidote, and resulted in an amphibole + plagioclase + phengite + epidote or ziosite assemblage. Basing on microprobe analysis of the minerals, ACF projections indicated: In the ACF diagrams, the two joint lines of peak Grt + Omp and Dio + Ab crossed at Omp projection-point, indicating that the garnet had not taken part in the forming reaction of the Dio + Ab symplectite, just like that had been pointed out by micro-texture observation. In the ACF diagrams, the hornblende + plagioclase + epidote + phengite quadrilateral intersected with Dio + Ab + Grt triangle, demonstrating that the hydrous mineral assemblage was formed by fluid infiltration through garnet, diopside and albite. Iso-con (mass-balance) analysis of the symplectization and infiltration reveals: 1.The symplectization of the omphacite has a very complex mass exchange: Some symplectite gained only silicon from its surroundings; and some one requires Ca, but provides Na to its surroundings; while other symplectite provides Ca, Mg and Fe to its surroundings. 2.The infiltration cause variable mass exchanges occurring among the garnet, diopside and albite: In some eclogite sample, no mass, except H2O, exchange occurred during the infiltration. Meanwhile, there was not any hydrous mineral except hornblende formed in the sample accordingly. In some samples, the mass exchange among the three minerals is complex: amphibolization of the diopside in a symplectite gained Al from garnet, and provided Si and Ca to its surrounding, resulting in a Si, Ca and Al-rich fluid. Correspondingly, there was a lot of phengite and ziosite occurred in the sample. In other samples, the amphibolization of a symplectite provided Fe and Mg besides Si and Ca to its surrounding while gained Al. In such kind of sample, epidote occurred within the hydrous mineral assemblage. Synthesizing the micro-texture observation, ACF analysis and iso-con analysis, we deduced the transformation procedure as following: 1. A symplectite after an omphacite was resulted by one, or two, or all of following mineral reactions together: Jd (Ca-Tsch) +SiO2=Ab (An) (1) 4NaA IS i.A+CaO=2NaAlS i308+Na20+CaAl2S 1208 (2) 2NaAlSi2OB (Jd in Omp)+CaMgSi;,0B(Dio in Omp)-2NaAlSi:,O"(Ab)+Ca0+Mg0 (3) 2(CaAl2Si0fi) (Ca-tsch in Omp)+CaFeSi2O6(Hed in 0mp)-H>2CaAl2Si208(An)+Ca0 + FeO (4) A CO2-rich fluid is suggested as cataclysm for the above reactions, which largely increased the mobility of Ca, Mg and Na resulted from reaction (2), (3) and (4). The immobile product Fe2* combined with rutile to form ilmenite, resulting in rutile + ilmenite symplectite. Or, the Fe was precipitated as hematite locally. A procedure of the fluid infiltration as following is suggested: I .A hydrous fluid intruded into the eclogite, and reacted first with garnet to form hornblende and extra Al, resulting in a hornblende film around the garnet grain and an Al-rich fluid. 2.The Al-rich fluid infiltrated through the symplectite, OH" and part of the Al in the fluid combined with Dio while some Si and Ca in the Dio were dissolved made the Dio transferred to amphibole. Meanwhile, plagioclase-type cation exchange occurred between the fluid and plagioclase in the symplectite, making the plagioclase have a higher An-content. 3.Above infiltration and cation exchange resulted in an Al, Si, Ca (and K, providing the primary hydrous fluid contain K)-rich fluid. 4.Under suitable conditions, the solute in the fluid precipitated to form phengite firstly. After the K element in the fluid was consumed up, ziosite or epidote was formed. If the fluid did not contain any K. element, only ziosite or epidote was precipitated. For those eclogites, where all omphacite had been replaced by symplectite before infiltration, neither element exchange occurred, nor did phengite or epidote form during the infiltration. At the last stage, the garnet was oxidized and breakdown: garnet + H2O = epidote + hornblende + hematite, due to more and more fluid intruding into the eclogite. At this time, all the peak minerals were replaced by amphibolite-phase ones, and the eclogite transformed to an amphibolite completely. Tentative pressure calculation indicates that the infiltration occurred at 3-6kbar (about 10-20km depth), where the deformation mechanics transformed from brittle to ductile yield. At such depth, the surface water can permeate the rocks through fault system, causing a rapid cooling.