PHYSICAL VAPOR TRANSPORT AND CRYSTAL-GROWTH OF GESEXTE1-X SOLID-SOLUTIONS

Physical vapor transport studies of GeSe(x)Te1 - x (x = 0.1, 0.2, 0.3, and 0.4) solid solutions demonstrated, that individual, large single crystals of these materials can be grown in closed ampoules. A compositional analysis of the grown crystals revealed, that the mass transport (crystal growth) process under steady-state conditions is pseudo-congruent and controlled by diffusion processes in the source material. From these experiments, the degree of non-stoichiometry (Ge-vacancy concentrations) of GeSe(x)Te1 - x single crystals could be estimated. The effects of the cubic to rhombohedral phase transformation during cooling on the microstructure and morphology of the grown mixed crystals are observed. This work provides the basis for subsequent defect studies and electrical measurements on these crystals.

Structural characteristics and redox behaviors of Ce1-xCuxOy solid solutions

Nanosized Ce1-xCuxOy materials were prepared by complexation-combustion method. The structural characteristics and redox behaviors were investigated using X-ray diffraction (XRD), temperature programmed reduction (H-2-TPR), UV-Vis, and Raman spectroscopies. In XRD patterns, no evidence of CuO diffraction peaks are observed for the Ce1-xCuxOy samples calcinated at 650 degreesC for 5 h, until the Cu/(Ce + Cu) ratio is higher than 0.4. The stepwise decrease of the 2theta value of CeO2 in Ce1-xCuxOy with the increasing of Cu concentration suggests that the CU2+ ions incorporate into the CeO2 lattice to form Ce1-xCuxOy solid solutions for low Cu/(Ce + Cu) ratios (x less than or equal to 0.1). The CuO phase begins to segregate from the solid solutions with the further increasing of Cu/(Ce+Cu) ratio. The Raman mode at 1176 cm(-1) ascribed to the enhanced defects appears for CeO2 and the Ce0.9Cu0.1Oy solid solution. Compared with CeO2 alone, the Raman mode of cubic CeO2 shifts from 462 to 443 cm(-1) for the Ce0.9Cu0.1Oy solid solution. The H-2 consumption of the fresh Ce0.95Cu0.05Oy is 1.65 times higher than that needed to reduce CuO to Cu, and it increases to 2.4 after a reoxidation of the partially reduced Ce0.95Cu0.05Oy at 300 degreesC, which indicates that the CeO2 phase is also extensively reduced. Compared with the high Cu/(Ce+Cu) ratio sample Ce0.7Cu0.3Oy, the Ce0.9Cu0.1Oy solid solution shows high and stable redox property even after different reoxidation temperatures. When the reoxidation temperature exceeds 200 degreesC, the a peak (similar to170 degreesC) ascribed to the reduction of surface oxygen disappears, and the P peak (similar to190 degreesC) ascribed to the reduction of Cu2+ species and the partial reduction of bulk CeO2 shifts to higher temperatures with the H-2 consumption 1.16 times higher than that for fresh sample. The result demonstrates that the redox property of the CeO2 is Significantly improved by forming the Ce1-xCuxOy solid solutions.

Preparation, structure and oxide ion conductivity in Ce6-xYxMoO15-delta (x=0.1-1.4) solid solutions

The Ce6-xYxMoO15-delta solid solution with fluorite-related structure have been characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), IR, Raman, scanning electric microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) methods. The electric conductivity of samples is investigated by Ac impedance spectroscopy. An essentially pure oxide-ion conductivity of the oxygen-deficiency was observed in pure argon, oxygen and air. The highest oxygen-ion conductivity was found in Ce5.5Y0.5MoO15-delta ranging from 5.9 X 10(-5)(S cm(-1)) at 300 degrees C to 1.3 X 10(-2)(S cm(-1)) at 650 degrees C, respectively. The oxide-ion conductivities remained stable over 80 h-long test at 800 degrees C. These properties suggested that significant oxide-ionic conductivity exists in these materials at moderately elevated temperatures.

On improving the phase stability and thermal expansion coefficients of lanthanum cerium oxide solid solutions

The phase stability of lanthanum cerium oxide (La2Ce2O7), which is stable up to 1400 degrees C, and the thermal expansion coefficient of La2Ce2O7 doped with Ta2O5 or WO3 were studied. The thermal expansion coefficient of La2Ce2O7 below 400 degrees C was increased by adding more CeO2 or doping with either Ta2O5 or WO3.

Nitrate-citrate combustion synthesis and properties of Ce1-xSmxO2-x/2 solid solutions

A nitrate-citrate combustion route to synthesize nanocrystalline samarium-doped ceria powders for solid electrolyte ceramics is presented. This route is based on the gelling of nitrate solutions by the addition of citric acid and ammonium hydroxide, followed by an intense combustion process due to an exothermic redox reaction between nitrate and citrate ions. The influence of ignition temperature on the characteristics of the powders was studied. The change of the crystal structure with the content of doped Sm was investigated. High temperature X-ray, and Raman scattering were used to characterize the sample. The lattice constant and unit volume increase with doping level and increasing temperature. Dense ceramic samples prepared by uniaxial pressing and sintering in air were also studied.

Synthesis of new solid solutions on neodymium-stabilized La2Mo2O9

A new ionic conductor La2-xNdxMo2O9 (x=0.0-2.0) has been synthesized by wet-chemistry method. The precursors and the resultant oxide powders were characterized by DTA/TG, DSC, XRD and XPS techniques. Effect of substituting Nd for La reveals that the phase transition which occurs in La2Mo2O9 around 565degreesC disappears when x>0.2. And the maximum amount of Nd stabilized the high temperature phase of beta-La2Mo2O9 from cubic to tetragonal is about x=1.6. The measurements of impedance spectroscopy indicate that the ionic conductivity becomes considerably higher in comparison to that of La2Mo2O9.

Low temperature preparation of ceria solid solutions doubly doped with rare-earth and alkali-earth and their properties as solid oxide fuel cells

A series of solid electrolytes, (Ce(0.8)Ln(0.2))(1 - x)MxO2 - delta(Ln = La, Nd, Sm, Gd, M:Alkali-earth), were prepared by amorphous citrate gel method. XRD patterns indicate that a pure fluorite phase is formed at 800 degreesC. The electrical conductivity and the AC impedance spectra were measured. XPS spectra show that the oxygen vacancies increase owing to the MO doping, which results in the increase of the oxygen ionic transport number and conductivity. The performance of ceria-based solid electrolyte is improved. The effects of rare-earth and alkali-earth ions on the electricity were discussed. The open-circuit voltages and maximum power density of planar solid oxide fuel cell using (Ce0.8Sm0.2)(1 - 0.05)Ca0.05O2 - delta as electrolyte are 0.86 V and 33 mW . cm(-2), respectively.

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.

THE CRYSTALLIZATION BEHAVIOUR OF BLOCK COPOLYMER/HOMOPOLYMER BLENDS I. INFLUENCE OF NONSPHERICAL MICELLE ON CRYSTALLIZATION BEHAVIOUR IN DILUTE SOLID SOLUTIONS

The effect of micelle on crystallization behaviour of dilute poly(methyl methacrylate-b-tetrahydrofuran) diblock copolymer/tetrahydrofuran homopolymer, dilute poly (ethylene-b-styrene-b-ethylene) triblock copolymer/ethylene homopolymer solutions has been studied. The results show that with the structural teansitions from spherical to nonspherical micelle in the blends, great changes in the nucleation and spherulite morphologies take place.

Crystallization of micelles and matrix in dilute diblock copolymer/homopolymer solutions

The crystallization, morphology, and crystalline structure of dilute solid solutions of tetrahydrofuran-methyl methacrylate diblock copolymer (PTHF-b-PMMA) in poly(ethylene oxide) (PEO) and PTHF have been studied with differential scanning calorimetry (DSC), X-ray, and optical microscopy. This study provides a new insight into the crystallization behavior of block copolymers. For the dilute PTHF-b-PMMA/PEO system containing only 2 to 7 wt % of PTHF content, crystallization of the PTHF micellar core was detected both on cooling and on heating. Compared the crystallization of the PTHF in the dilute solutions with that in the pure copolymer, it was found that the crystallizability of the PTHF micellar core in the solution is much greater than that of the dispersed PTHF microdomain in the pure copolymer. The stronger crystallizability in the solution was presumably due to a softened PMMA corona formed in the solution of the copolymer with PEG. However, the "soft" micelles formed in the solution (meaning that the glass transition temperatures (T-g) of the micelle is lower than the T-m of the matrix phase) showed almost no effects on the spherulitic morphology of the PEO component, compared with that of the pure PEO sample. In contrast, significant effects of the micelles with a "hard" PMMA core (meaning that the T-g of the core is higher than the T-m of the PTHF homopolymer) on the nucleation, crystalline structure, and spherulitic morphology were observed for the dilute PTHF-b-PMMA/PTHF system. (C) 1998 John Wiley & Sons, Inc.

Effects of heat-treatment processes on the electroless Ni-B coating and its natural aging mechanism

A Ni-B coating was prepared with EN using potassium borohydride reducing agent. The as-plated micro-structure of the coating was confirmed from XRD to be a mixture of amorphous and supersaturated solid solution. Three kinds of phase transformation were observed from the DSC curve. Different from the previous works, the formation of Ni4B3 and Ni2B was found during some transformation processes. The key factors which influence the variation of micro-hardness and micro-structure in deposits are the formation, the size and amount of Ni3B, Ni4B3 and Ni2B. Aging of the deposits treated under some heat treatment conditions occurred at room temperature. Changes of the micro-hardness indicated aging phenomena evidently. the natural aging phenomena are concerned with various kinds of decomposition of borides, especially with Ni4B3 phase. The extent of natural aging depends on the formation and the quantity of Ni(4)B3 and Ni2B.

Microstructural evolution and formation of nanocrystalline intermetallic compound during surface mechanical attrition treatment of cobalt

Nanocrystalline intermetallic Co3Fe7 was produced on the surface of cobalt via surface mechanical attrition (SMA). Deformationinduced diffusion entailed the formation of a series of solid solutions. Phase transitions occurred depending on the atomic fraction of Fe in the surface solid solutions: from hexagonal close-packed (<4% Fe) to face-centered cubic (fcc) (4-11% Fe), and from fcc to body-centered cubic (>11% Fe). Nanoscale compositional probing suggested significantly higher Fe contents at grain boundaries and triple junctions than grain interiors. Short-circuit diffusion along grain boundaries and triple junctions dominate in the nanocrystalline intermetallic compound. Stacking faults contribute significantly to diffusion. Diffusion enhancement due to high-rate deformation in SMA was analyzed by regarding dislocations as solute-pumping channels, and the creation of excess vacancies. Non-equilibrium, atomic level alloying can then be ascribed to deformation-induced intermixing of constituent species. The formation mechanism of nanocrystalline intermetallic grains on the SMA surface can be thought of as a consequence of numerous nucleation events and limited growth. (C) 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Enhanced luminescence from transparent Ni2+-doped MgO-Al2O3-SiO2 glass ceramics by Ga2O3 addition

Transparent Ni2+-doped MgO-Al2O3-SiO2 glass ceramics without and with Ga2O3 were synthetized. The precipitation of spinel nanocrystals, which was identified as solid solutions in the glass ceramics, could be favored by Ga2O3 addition and their sizes were about 7.6 nm in diameter. The luminescent intensity of the Ni2+-doped glass ceramics was largely enhanced by Ga2O3 addition which could mainly be caused by increasing of Ni2+ in the octahedral sites and the reduction of the mean frequency of phonon density of states in the spinel nanocrystals of solid solutions. The full width at half maximum (FWHM) of emissions for the glass ceramics with different Ga2O3 content was all more than 200 nm. The emission lifetime increased with the Ga2O3 content and the longest lifetime is about 250 mu s. The Ni2+-doped transparent glass ceramics with Ga2O3 addition have potential application as broadband optical amplifier and laser materials. (C) 2007 Elsevier Ltd. All rights reserved.