Coprecipitation synthesis and characterization of La0.8Sr0.2Ga(0.8-x)Mg0.2Co(x)O2.8 for intermediate temperature solid oxide fuel cell electrolytes

La0.8Sr0.2Ga(0.8-x)Mg0.2CO(x)O2.8 (LSGMC) electrolyte powders containing different amount of Co (0 < or = x < or = 0.15) were prepared by ammonium carbonate coprecipitation method. The precursors, the calcined powders, and the sintered pellets were characterized by thermogravimetry/differential thermal analysis, X-ray diffractometry, scanning electron microscopy, and an impedance analyzer. The thermal decomposition of the LSGMC precursors was completed at around 900 degrees C with the total weight loss of approximately 35%. The LSGMC samples sintered at 1350 degrees C consisted of the pure perovskite structure. The ionic conductivity was significantly improved by Co doping for the Ga-site of the La0.8Sr0.2Ga0.8Mg0.2O2.8 (LSGM) electrolytes. The ionic conductivity of LSGMC (x = 0.1) exhibited the highest values of 1.6 x 10(-1) S cm(-1) at 700 degrees C with an activation energy for the oxide-ion conduction of 0.29 eV. The results of this study indicated that the Co-doped LSGM electrolytes had excellent properties for use as an electrolyte in an IT-SOFC and the ammonium carbonate coprecipitation process could be employed as the efficient method for the preparation of the Co-doped LSGM electrolytes.     

Thermoelectric properties of nanocrystalline Ca(3-x)Cu(x)Co4O9 (0 < or = x < or = 0.32) for power generation

We successfully synthesized nano-sized Ca(3-x)Cu(x)Co4O9 (0 < or = x < or = 0.32) powders by solution combustion process. Plate-like grains and porous structure were observed in the sintered Ca(3-x)Cu(x)Co4O9 ceramics. The sintered Ca(3-x)Cu(x)Co4O9 showed a monoclinic symmetry. The electrical conductivity of the Ca(3-x)Cu(x)Co4O9 increased with increasing temperature, indicative of a semiconducting behavior. The added Cu led to a significant increase in the electrical conductivity. The Seebeck coefficient of the Cu-added Ca(3-x)Cu(x)Co4O9 was much higher than that of the Cu-free Ca3Co4O9. The highest power factor (9.99 x 10(-4) Wm(-1)K-2) was obtained for Ca2.76Cu0.24Co4O9 at 800 degrees C.     

Fabrication of (Nd(0.01)La(x)Y(0.99-x))2O3 nanoparticles and transparent ceramics by combustion synthesis

Y2O3 acts as the matrix material when doped with different content of La2O3 for reducing sintering temperature and refining grains. The (Nd(0.01)La(x)Y(0.99-x))2O3 nanoparticles and transparent ceramics are fabricated by a combustion synthesis. The powder feature is characterized by TEM. The microstructure, mechanical properties and transmittance of the samples are examined by SEM, HV-1000 hardness tester and fluorescence analyzer respectively. The results show that the (Nd(0.01)La(x)Y(0.99-x))2O3 nanoparticles are homogeneous in size and nearly spherical with average diameter in the range of 40-60 nm. There are no other phases except the Y2O3 cubic phase in the (Nd(0.01)La(x)Y(0.99-x))2O3 nanoparticles. The grains of the samples significantly reduce with increasing La2O3 content. The hardness and fracture toughness increase rapidly first and then gradually tend to plateau with increasing La2O3 content. The transmittance of sample also increases gradually with increasing La2O3, the largest transmittance exceeds 77% when the La2O3 content is x = 0.12.     

Electrical properties of nanocrystalline Ce(0.8)Sm(0.2)O(2-delta) and Ce(1-x)Gd(x)O(2-delta) (0.1 < or = x < or = 0.3) ceramics for IT-SOFC

Ce(0.8)Sm(0.2)O(2-delta) and Ce(1-x)Gd(x)O(2-delta) (0.1 < or = x < or = 0.3) nano-sized powders were successfully synthesized by the solution combustion synthesis process. The calcined nanopowders showed a ceria-based single phase with a cubic fluorite structure. In this study, we discussed the structural and electrical characteristics of the sintered Ce(0.8)Sm(0.2)O(2-delta) and Ce(1-x)Gd(x)O(2-delta). We obtained high-quality Ce(0.8)Sm(0.2)O(2-delta) and Ce(1-x)Gd(x)O(2-delta) ceramics with a high density, ultra-fine grain size, and high electrical conductivity even at low sintering temperature using the nanosized powders. The electrical conductivities at 800 degrees C for the Ce(0.8)Sm(0.2)O(2-delta) sintered at 1400 degrees C and the Ce(0.8)Gd(0.2)O(2-delta) sintered at 1350 degrees C were 0.110 and 0.104 Scm(-1), respectively.     

Hydrothermal synthesis and photoluminescence of Eu(2-x)Sm(x)Sn2O7 (x = 0-2.0) nanophosphors

Eu(2-x)Sm(x)Sn2O7 (x = 0, 0.1, 0.5, 1.0, 1.5, and 2.0) solid solutions were successfully synthesized by a simple, mild hydrothermal process. The crystal structure, particle size, and chemical composition of the solid solutions were characterized by X-ray diffraction, transmission electron microscopy, and energy dispersive X-ray spectroscopy. X-ray diffraction patterns and transmission electron microscopy images reveal that all the products were cubic pyrochlore-type Eu(2-x)Sm(x)Sn2O7 nanocrystals with the diameter of approximately 20 nm. Due to efficient energy transfer from Sm3+ to Eu3+, the Eu(2-x)Sm(x)Sn2O7 (x = 0.1, 0.5, 1.0, and 1.5) nanocrystals exhibited strong 5D0 --> 7F1 photoluminescence emission of Eu3+. The dominant 5D0 --> 7F1 transition revealed good monochromaticity and low distortion of the Eu(2-x)Sm(x)Sn2O7 nanophosphors.     

Cooperative mechanisms of fast-ion conduction in gallium-based oxides with tetrahedral moieties

The need for greater energy efficiency has garnered increasing support for the use of fuel-cell technology, a prime example being the solid-oxide fuel cell. A crucial requirement for such devices is a good ionic (O(2-) or H+) conductor as the electrolyte. Traditionally, fluorite- and perovskite-type oxides have been targeted, although there is growing interest in alternative structure types for intermediate-temperature (400-700 ( composite function)C) solid-oxide fuel cells. In particular, structures containing tetrahedral moieties, such as La(1-x)Ca(x)MO(4-x/2)(M=Ta,Nb,P) (refs 7,8), La(1-x)Ba(1+x)GaO(4-x/2) (refs 9,10) and La(9.33+x)Si(6)O(26+3x/2) (ref. 11), have been attracting considerable attention recently. However, an atomic-scale understanding of the conduction mechanisms in these systems is still lacking; such mechanistic detail is important for developing strategies for optimizing the conductivity, as well as identifying next-generation materials. In this context, we report a combined experimental and computational modelling study of the La(1-x)Ba(1+x)GaO(4-x/2) system, which exhibits both proton and oxide-ion conduction. Here we show that oxide-ion conduction proceeds via a cooperative 'cog-wheel'-type process involving the breaking and re-forming of Ga(2)O(7) units, whereas the rate-limiting step for proton conduction is intra-tetrahedron proton transfer. Both mechanisms are unusual for ceramic oxide materials, and similar cooperative processes may be important in related systems containing tetrahedral moieties.     

Fabrication and magnetic property of BaSm(x)Fe(12-x)O19 (x < or = 0.4) nanofibers

BaSm(x)Fe(12-x)O19 (x < or = 0.4) ferrite nanofibers were prepared by sol-gel method from starting reagents of metal salts and citric acid. These nanofibers were characterized by TG-DTA, FTIR, SEM, XRD and VSM. These results show that the BaSm(x)Fe(12-x)O19 (x < or = 0.4) ferrite nanofibers were obtained subsequently from calcination at 750 degrees C for 1 h. The BaSm(x)Fe(12-x)O19 (x < or = 0.4) microstructure and magnetic property are mainly influenced by chemical composition and heat-treatment temperature. The grain sizes of BaSm0.3Fe11.7O19 ferrite nanofibers are in a nanoscale from 40 nm to 62 nm corresponding to the calcination temperature from 750 degrees C to 1050 derees C. The saturation magnetization of BaSm(x)Fe(12-x)O19 ferrite nanofiber calcined at 950 degrees C for 1 h initially decreases with the Sm content from 0 to 0.3 and then increases with a further Sm content, while the coercivity exhibits a continuous increase from 348 kA x m(-1) (x = 0) to 427 kA x m(-1) (x = 0.4). The differences of magnetic properties are attributed to lattice distortion and enhancement for the anisotropy energy.     

Terahertz dielectric response of ferroelectric Ba(x)Sr(1-x)TiO3 thin films

Terahertz time-domain spectroscopy has been used to investigate the dielectric and optical properties of ferroelectric Ba(x)Sr(1-x)TiO(3) thin films for nominal x-values of 0.4, 0.6, and 0.8 in the frequency range of 0.3 to 2.5 THz. The ferroelectric thin films were deposited at approximately 700 nm thickness on [001] MgO substrate by pulsed laser deposition. The measured complex dielectric and optical constants were compared with the Cole-Cole relaxation model. The results show that the Cole-Cole relaxation model fits well with the data throughout the frequency range and the dielectric relaxation behavior of ferroelectric Ba(x)Sr(1-x)TiO(3) thin films varies with the films compositions. Among the compositions of Ba(x)Sr(1-x)TiO(3) films with different Ba/Sr ratios, Ba(0.6)Sr(0.4)TiO(3) has the highest dielectric constants and the shortest dielectric relaxation time.     

Photoluminescence of CaxSr(1-x) (NbO3)2:Pr3+ (0 < or = x < or = 1) nanophosphors

Nanoparticles of CaxSr(1-x) (NbO3)2 doped with Pr3+ have been synthesized by sol-gel method. Particles have sizes in the range of 50-70 nm. The CaxSr(1-x) (NbO3)2:Pr3+ phosphors showed a white emission under the near-ultraviolet excitation (254 nm). There is a large photoluminescence enhancement of the CaxSr(1-x) (NbO3)2:Pr3+ phosphor samples when added with 0.5% KCl. X-ray diffraction (XRD), transmission electron microscope (TEM), photo luminescent (PL) analysis were utilized to characterize the CaxSr(1-x) (NbO3)2:Pr+ particles. The concentration quenching of the samples was discussed as well. The optical concentration and the calcination temperature were 0.8 mol% of Ca2+ and 900 degrees C for these phosphors, respectively, the possible mechanism was discussed. CaxSr(1-x) (NbO3)2:Pr3+ is a promising white phosphor under near-ultraviolet excitation for various applications.     

Synthesis and microstructural characterization of Ce1-xTb(x)O2-delta (0 < or = x < or = 1) nano-powders

Ce1-xTb(x)O2-delta nano-powders have been successfully synthesized by using the ammonium carbonate coprecipitation method in an entire compositional range of 0 < or = x < or = 1 by adjusting the preparation conditions. Studies of X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that the powders with different compositions mainly consist of fluorite structure. In addition, a small amount of secondary phase was observed in the powders with x > or = 0.7. TEM observation indicated that the secondary phase could have a superstructure formed by a structural modulation of the fluorite structure.     

Electrochemical and thermal behaviour of Li[Li(x)(Ni0.3Co0.1Mn0.6)1 - x]O2 (x = 0.09, 0.11) cathode Materials for lithium rechargeable batteries

High rate capable Mn-rich layered Li[Li(x)(Ni0.3Co0.1Mn0.6)1-x]O2 (x = 0.09, 0.11) cathode materials that are fully charged are investigated with respect to stability. Differential scanning calorimetry is used to determine the thermal stability of cathode material compositions together with PVdF binder and a conductive agent by heating from 30 degrees C to 400 degrees C at 10 degrees C/min. In the Li[Li(x)(Ni0.3Co0.1Mn0.6)1-x]O2 (x = 0.09, x = 0.11) cathode materials, the exothermic reaction started at 100 degrees C. Due to thermal runway, a sharp peak was observed at 279.25 degrees C for the material of x = 0.09 with exothermic heat generation of 168.4 J/g. For the Mn-rich cathode material, where x = 0.11, two relatively smaller peaks appeared at 250.72 degrees C and 268.60 degrees C with heat evolution of 71.49 J/g and 93.67 J/g, respectively. These layered cathode materials are thermally stable. The x = 0.09 composition shows huge heat flow occurrence when compared to the x = 0.11. It is concluded from a heat generation analysis that the two Mn-rich cathode materials are thermally stable for lithium rechargeable batteries.     

The role of dopants in tailoring the microwave properties of Ba6-xR8+2/3x Ti18O54 R = (La–Gd) Ceramics

Microwave dielectric ceramics with a high dielectric constant need to satisfy very high technical demands. They should possess extremely low losses to achieve high Q-values (Quality factor) a small temperature coefficient of resonant frequency (τf), and a relative permittivity (εr) higher than 80. Industrial applications require very stringent electrical and dimensional tolerances, typically ± 0.5–1.0 ppm K-1 for a specified τf and ± 0.25% for a specified εr. To meet such requirements ceramics based on BaO–R2O3 – TiO2 (R = La–Gd) are used. The investigation of this type of ceramic was stimulated by the observation that ceramics based on compositions in the TiO2-rich region of the system exhibit highly temperature stable electrical properties. Especially interesting are compositions within the solid solubility region with the general formula Ba6-xR8+2/3x Ti18O54. As the ionic radius of the rare earth decreases the extent of the solid solubility region becomes narrower, i.e., 0<x<3 for La and x = 0.5 for Gd. Further improvements in the dielectric microwave properties can be achieved by combining different rare earth oxides, and by partial replacement of Ba2+ with other alkaline earth atoms such as Ca2+ and Sr2+. Typically such ceramics meet the requirements for Q and εr; however, τf must be additionally adjusted by the use of dopants. Most commonly bismuth and lead oxides or titanates are used. In the present contribution the role of different dopants and their influence on the resulting microwave dielectric properties of Ba6-xR8+2/3x Ti18O54 based ceramics are discussed. This revised version was published online in November 2006 with corrections to the Cover Date.     

Device optimization of CO2 gas sensor using planar technology

A planar type Li+ ion based potentiometric CO2 micro gas sensor of size 2 x 3 mm has been fabricated on alumina substrate by combining thin and thick film technology. The heater, electrodes and electrolyte were deposited by thin film deposition technique and the sensing and reference electrodes were printed by silk screen printing technology. The optimal thickness and sintering temperature of electrolyte are 1.2 microm and 775 degrees C. The sensor with Li2CO3 and 20 mol% BaCO3 not only exhibits a good Nernstian behavior but also consistent results over a long time at 450 degrees C in dry as well as 70% RH humidity condition between 160-5000 ppm CO2 concentrations. The spreading effect of the sensing and reference materials was controlled by the addition of Al2O3:B2O3 (1:2 mol%) glass.     

Nanocrystalline sensor-grade Sn1-xInxO2 (0 < or = x < or = 0.2)

Nanocrystalline Sn1-xInxO2 (0 < or = x < or = 0.2) has been successfully prepared by a solution chemical route. High-resolution transmission electron microscopy studies show that the average grain size of Sn0.8In0.2O2 heated at 310 degrees C, 500 degrees C, and 800 degrees C for 12 h is about 3-4 nm, 5-6 nm, and 7-10 nm, respectively. The corresponding values for pure SnO2 are 3-4 nm, 7-10 nm, and 50-90 nm, respectively. Powder X-ray diffraction and electron diffraction studies confirm the existence of solid solution only in the nanocrystalline state (the average particle size is in the range of 5-10 nm) with the solubility limited to 20% of In2O3. Indium ions stabilize the nanocrystalline nature of Sn1-xInxO2 (0 < or = x < or = 0.2) and prevent the grain growth by entering the SnO2 lattice. The thermal characteristics of nanocrystalline Sn1-xInxO2 (0 < or = x < or = 0.2) investigated by thermogravimetric (TG) and differential thermal analysis (DTA) show that the solid solution decomposes at 820 degrees C into SnO2 and In2O3, which is accompanied by a rapid crystal growth. The electrical conductivity and activation energy of Sn1-xInxO2 (0 < or = x < or = 0.2) undergo significant changes when the average grain size is less than or equal to 2 x the Debye length, LD.     

Gas sensing property of perovskite SrTi(1-x)Fe(x)O3_delta fabricated by thick film planar technology

Planar sensor of SrTi(1-x)Fe(x)O3-delta, x = 0.4 and 0.6, with perovskite structure was fabricated on alumina substrate using thick film technology. Electrical resistance was measured as a function of thermal treatment conditions, atmosphere, time and temperature. Sensing property was also measured as a function of temperature and the gases of O2, CH4, CO, CO2, NO and NO2. The resistance of SrTi(1-x)Fe(x)O3-delta is lower than those of SrTiO3 or SrFeO3. TCR (temperature coefficient of resistance) of zero over 550 degrees C was measured for the composition of SrTi(1-x)Fe(x)O3-delta after thermal treatment at 1100 degrees C in air atmosphere only. The perovskite SrTi(1-x)Fe(x)O3-delta didn't show any response to CH4, CO, CO2, NO and NO2, but an excellent response and recovery characteristics with oxygen concentration.     

Electronic structure and magnetic properties of the Ni0.2Cd0.3Fe(2.5-x)A1(x)O4 (0 < or = x < or = 0.4) ferrite nanoparticles

The structural, magnetic, and electronic structural properties of Ni0.2Cd0.3Fe(2.5-x)Al(x)O4 ferrite nanoparticles were studied via X-ray diffraction (XRD), transmission electron microscopy (TEM), DC magnetization, and near-edge X-ray absorption fine-structure spectroscopy (NEXAFS) measurements. Nanoparticles of Ni0.2Cd0.3Fe(2.5x)Al(x)O4 (0 < or = x < or = 0.4) ferrite were synthesized using the sol-gel method. The XRD and TEM measurements showed that all the samples had a single-phase nature with a cubic structure, and had nanocrystalline behavior. From the XRD and TEM analysis, it was found that the particle size increases with Al doping. The DC magnetization measurements revealed that the blocking temperature increases with increased Al doping. It was observed that the magnetic moment decreases with Al doping, which may be due to the dilution of the sublattice by the doping of the Al ions. The NEXAFS measurements performed at room temperature indicated that Fe exists in a mixed-valence state.     

Enhanced thermoelectric properties of solution grown Bi2Te(3-x)Se(x) nanoplatelet composites

We report on the enhanced thermoelectric properties of selenium (Se) doped bismuth telluride (Bi(2)Te(3-x)Se(x)) nanoplatelet (NP) composites synthesized by the polyol method. Variation of the Se composition within NPs is demonstrated by X-ray diffraction and Raman spectroscopy. While the calculated lattice parameters closely follow the Vegard's law, a discontinuity in the shifting of the high frequency (E(g)(2) and A(1g)(2)) phonon modes illustrates a two mode behavior for Bi(2)Te(3-x)Se(x) NPs. The electrical resistivity (ρ) of spark plasma sintered pellet composites shows metallic conduction for pure Bi(2)Te(3) NP composites and semiconducting behavior for intermediate Se compositions. The thermal conductivity (κ) for all NP composites is much smaller than the bulk values and is dominated by microstructural grain boundary scattering. With temperature dependent electrical and thermal transport measurements, we show that both the thermoelectric power S (-259 μV/K) and the figure of merit ZT (0.54) are enhanced by nearly a factor of 4 for SPS pellets of Bi(2)Te(2.7)Se(0.3) in comparison to Bi(2)Te(3) NP composites. Tentatively, such an enhancement of the thermoelectric performance in nanoplatelet composites is attributed to the energy filtering of low energy electrons by abundant grain boundaries in aligned nanocomposites.     

Ni(2+) and H(2)PO(4)(-) uptake properties of compounds in the CaTiO(3)-CaFeO(2.5) system

A batch method was used to investigate the uptake of heavy metal cations and anions by the compounds in the CaTiO(3)-CaFeO(2.5) system, in which a series of oxygen vacancies was systematically introduced into a perovskite structure as the x-value of Ca(Fe(x)Ti(1-x))O(3-x/2) was increased. Samples of CaTiO(3), CaFe(0.1)Ti(0.9)O(2.95), CaFe(0.5)Ti(0.5)O(2.75), CaFe(0.67)Ti(0.33)O(2.67) and CaFeO(2.5) were prepared by solid mixing (SM), co-precipitation (CP) and gel evaporation (GE) methods. The resulting samples were calcined at temperatures between 400 and 1000 °C. The target crystalline phases differed according to the preparation method, but in most cases were formed at 700-800 °C. The Ni(2+) sorption isotherms of all the samples were fitted better by the Langmuir model than by the Freundlich model, while in the case of H(2)PO(4)(-) sorption isotherms, these were better fitted by the latter model. The uptake ability increased with increasing x value of the samples. The maximum values for the saturated sorption of Ni(2+) (Q(0)(Ni(2+)) = 2.83 mmol/g) and H(2)PO(4)(-) (K(F)(H(2)PO(4)(-)) = 2.95 mmol/g) were achieved for x = 1 (i.e. CaFeO(2.5)) sample.     

Composition and temperature dependence of the optical properties of Zn(1-x) Cd(x)Se (0 < or = x < or = 0.34) below the fundamental bandgap

The II-VI ternary semiconductor alloy system Zn(1-x) Cd(x) Se with 0 < or = x < or = 0.2 has important applications as the active material in blue-green light-emitting diodes and lasers. For the wavelength and temperature ranges over which these devices are designed to operate, a knowledge of the optical properties of the alloys is important. We report the results of spectroscopic ellipsometry measurements of the real part of the dielectric function epsilon1 for Zn-rich Zn(1-x) Cd(x) Se layers deposited epitaxially on (100) GaAs. We derive compact expressions that allow one to calculate accurate epsilon1 spectra from 1.5 eV, the low-energy limit of our ellipsometer, to E0-0.05 eV, where E0 is the fundamental bandgap energy, for any composition and temperature within the ranges 0 < or = x < or = 0.34 and 25 < or = T < 260 degrees C. Furthermore, we expect that the results can also be extrapolated to cover the substrate temperature range typically used for the growth of these films (250-300 degrees C). Hence the results presented here are also useful in future real-time spectroscopic ellipsometry studies of Zn(1-x) Cd(x) Se film growth.     

Magnetic and magnetocaloric properties of nanocrystalline Pr(1-x)A(x)Mn(1-y)Co(y)O3 (A = Ca, Sr) (x = 0.3; y = 0.5) manganites

Structural, magnetic and magnetocaloric properties of sol-gel prepared, nanocrystalline oxides Pr(1-x)A(x)Mn(1-y)Co(y)O3 (A = Ca, Sr) (x = 0.3; y = 0.5) (cubic, space group Fm3m) have been studied. From the X-ray data, the crystallite size of Pro.7Ca0.3Mn0.5Co0,503 and Pr0.7Sr0.3Mn0.5Co0.5O3 samples is found to be approximately 24 nm and approximately15 nm respectively. High resolution transmission electron microscopy image shows average particle size of approximately 34 nm and approximately 20 nm. Magnetization measurements indicate a Curie temperature of approximately 153 K and approximately172 K in applied magnetic field of 100 Oe for Pr0.7Ca0.3Mn0.5Co0.5O3 and Pr0.7Sr0.3Mn0.5Co0.O3 compounds. The magnetization versus applied magnetic field curves obtained at temperatures below 150 K show significant hysteresis and magnetization is not saturated even in a field of 7 T. The magnetocaloric effect is calculated from M versus H data obtained at various temperatures. Magnetic entropy change shows a maximum near T(c) for both the samples and is of the order approximately 2.5 J/kg/K.