Electrochemical removal of NOx with porous cell stacks

In this study porous cell stacks were investigated for their ability to remove NO_x electrochemically. The cell stacks were made from laminated tapes of porous electrolyte Ce_0.9Gd_0.1O_1.95 and composite electrodes of La_1−xSr_xMnO₃ (x = 0.15, and 0.5) and ceria doped with Gd or Pr. The cell stacks were infiltrated with nano-particles of pure ceria, Ce_0.9Gd_0.1O_1.95 and Ce_0.8Pr_0.2O_2−δ after sintering. A gas stream containing NO were sent through the cell stack. When the cell stacks were polarised with 0.75 V per cell then it was possible to remove some of the NO_x in the temperature interval of 250-400 °C. The cell stacks infiltrated with ceria showed the highest activity, while the ones infiltrated with Ce_0.9Gd_0.1O_1.95 had the highest selectivity towards NO compared to O₂. When the cell stack was polarised with 1.5 V for each cell it was possible to remove up to 35% of NO present.     

High performance Gd and Y co-doped ceria-based electrolytes for intermediate temperature solid oxide fuel cells

Co-doped ceria of Ce_1−xGd_x−yY_yO_2−0.5x, wherein x = 0.15 and 0.2, 0 ≤ y ≤ x, were prepared by glycine-nitrate method. Their structures and ionic conductivities were characterized by X-ray diffraction (XRD) and AC impedance spectroscopy (IS). All the electrolytes were found to be ceria-based solid solutions of fluorite type structures. Co-doping was found to effectively enhance the conductivity. In comparison to the singly doped ceria, the co-doped ceria showed much higher ionic conductivities at 673-973 K. At 773 K, the ionic conductivity of Ce_0.8Gd_0.05Y_0.15O_1.9 is 0.013 S cm⁻¹ which is three times as high as that of Ce_0.8Gd_0.2O_1.9. These Gd³⁺and Y³⁺ co-doped ceria are ideal electrolyte materials of intermediate temperature solid oxide fuel cells (SOFCs).     

Effects of gallia additions on sintering behavior of Ce<Subscript>0.8</Subscript>Gd<Subscript>0.2</Subscript>O<Subscript>1.9</Subscript> ceramics prepared by commercial powders

The densification behavior and grain growth of Ce_0.8Gd_0.2O_1.9 ceramics were investigated with the gallia concentration ranging from 0 to 10 mol%. Both the sintered density and grain size were found to increase rapidly up to 0.5 mol% Ga₂O₃, and then to decrease with further additions. Under the same sintering conditions, the samples with 3 mol% Ga₂O₃ and less exhibited a higher sintered density, as compared to the one without Ga₂O₃ addition. However, a pinning effect on grain growth was found at 2 mol% Ga₂O₃. In the dopant content range of 0 to 10 mol%, 0.5 mol% Ga₂O₃ was the optimum doping level in promoting densification and grain growth of commercially available powders of Ce_0.8Gd_0.2O_1.9.     

The synthesis and optical property of solid-state-prepared YAG:Ce phosphor by a spray-drying method

Ce³⁺-activated yttrium aluminum garnet (Y₃Al₅O₁₂:Ce, YAG:Ce) powder as luminescent phosphor was synthesized by the solid-state reaction method. The phase identification, microstructure and photoluminescent properties of the products were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), absorption spectrum and photoluminescence (PL) analysis. Spherical phosphor particle is considered better than irregular-shaped particle to improve PL property and application, so this phosphor was granulated into a sphere-like shape by a spray-drying device. After calcinating at 1500 °C for 0, 4, and 8 h, the product was identified as YAG and CeO₂ phases. The CeO₂ phase content is decreased by increasing the calcination time or decreasing the Ce³⁺ doping content. The product showed higher emission intensity resulted from more Ce³⁺ content and larger grain size. The product with CeO₂ was found to have lower emission intensity. This paper presents the crystal structures of Rietveld refinement results of powder XRD data.     

Crystal growth and characterization of Yb-doped Gd3Ga5O12

Single crystals of (Yb_xGd_1−x)₃Ga₅O₁₂ (0.0 ≤ x ≤ 1.0) have been grown by the micro-pulling-down method. Formation of continuous solid solutions with a garnet structure was confirmed. Composition dependence of the lattice constant, thermal diffusivity, specific heat capacity and thermal conductivity was investigated. Assignment of the Yb³⁺-energy levels in Gd₃Ga₅O₁₂-host lattice has been performed by using absorption, emission and Raman spectroscopy measurements at both, room temperature and at 12 K.     

Phase relations, lattice thermal expansion in CeO2-Gd2O3 system, and stabilization of cubic gadolinia

The phase relation in CeO₂-Gd₂O₃ system has been established under slow cooled conditions from 1400 °C. Two phase regions, namely F-type cubic and C-type cubic, were observed in this system. A striking observation of this investigation is the stabilization of C-type gadolinia after Ce⁴⁺ substitution, which is attributed to decrease in average cationic size on Ce⁴⁺ substitution at Gd³⁺ site. The lattice thermal expansion behaviour of C-type gadolinia samples was investigated by High temperature-XRD. The lattice thermal expansion coefficient was found to gradually increase on increasing the Ce⁴⁺ content, within the C-type homogeneity range, in Ce_1−xGd_xO_2−x/2 series.     

Luminescence of SrGdGa3O7:RE(RE = Eu, Tb) phosphors and energy transfer from Gd to RE

Eu³⁺- and Tb³⁺-activated SrGdGa₃O₇ phosphors were synthesized by the solid-state reaction and their luminescence properties were investigated. Sr(Gd_1 − xEu_x)Ga₃O₇ and Sr(Gd_1 − xTb_x)Ga₃O₇ formed continuous solid solution in the range of x = 0-1.0. Unactivated SrGdGa₃O₇ exhibited a typical characteristic excitation and emission of Gd ion. The SrGdGa₃O₇:xEu³⁺ and SrGdGa₃O₇:xTb³⁺ phosphors also showed the well-known Eu³⁺ and Tb³⁺ excitation and emission. The energy transfer from Gd³⁺ to Eu³⁺ and Tb³⁺ were verified by photoluminescence spectra. The dependence of photoluminescence intensity on Eu³⁺ and Tb³⁺ concentration were also studied in detail and the photoluminescence (PL) intensity of SrGdGa₃O₇:Eu and SrGdGa₃O₇:Tb were compared with commercial phosphors, Y₂O₃:Eu and LaPO₄:Ce,Tb. The luminescence decay measurements showed that the lifetimes of Eu³⁺ and Tb³⁺ were in the range of microsecond. The energy transfer from Gd³⁺ to Tb³⁺ was also observed in decay curve.     

Thermal expansion studies of Gd2Mo3O12 and Gd2W3O12

Simultaneous thermogravimetric/differential thermal analysis of Gd₂Mo₃O₁₂ showed an irreversible phase transition at 1178 K where as Gd₂W₃O₁₂ showed reversible phase transition at 1433 K, which were confirmed by powder X-ray diffraction. The thermal expansion behavior of α-Gd₂Mo₃O₁₂ (room temperature phase), β-Gd₂Mo₃O₁₂ (phase obtained by heating Gd₂Mo₃O₁₂ at 1223 K) and Gd₂W₃O₁₂ have been investigated using high temperature X-ray diffractometer. The cell volume of α-Gd₂Mo₃O₁₂, β-Gd₂Mo₃O₁₂ and Gd₂W₃O₁₂, fit into polynomial expression with respect to temperature, showed positive thermal expansion up to 1073, 1173 and 1173 K, respectively. The average volume expansion coefficients for α-Gd₂Mo₃O₁₂, β-Gd₂Mo₃O₁₂ and Gd₂W₃O₁₂ are 39.52 × 10⁻⁶, 21.23 × 10⁻⁶ and 37.96 × 10⁻⁶ K⁻¹, respectively.     

Novel composite interconnecting ceramics La0.7Ca0.3CrO3−δ/Ce0.8Sm0.2O1.9 for solid oxide fuel cells

In this paper, an interconnecting ceramic for solid oxide fuel cells was developed, based on the modification from La_0.7Ca_0.3CrO_3−δ by addition of Ce_0.8Sm_0.2O_1.9. It is found that addition of small amount Ce_0.8Sm_0.2O_1.9 into La_0.7Ca_0.3CrO_3−δ dramatically increased the electrical conductivity. For the best system, La_0.7Ca_0.3CrO_3−δ + 5 wt.% Ce_0.8Sm_0.2O_1.9, the electrical conductivity reached 687.8 S cm⁻¹ at 800 °C in air. In H₂ at 800 °C, the specimen with 3 wt.% Ce_0.8Sm_0.2O_1.9 had the maximal electrical conductivity of 7.1 S cm⁻¹. With the increase of Ce_0.8Sm_0.2O_1.9 content the relative density increased, reaching 98.7% when the Ce_0.8Sm_0.2O_1.9 content was 10 wt.%. The average coefficient of thermal expansion at 30-1000 °C in air increased with Ce_0.8Sm_0.2O_1.9 content, ranging from 11.12 × 10⁻⁶ to 12.46 × 10⁻⁶ K⁻¹. The oxygen permeation measurement illustrated a negligible oxygen ionic conduction, indicating it is still an electronically conducting ceramic. Therefore, this material system will be a very promising interconnect for solid oxide fuel cells.     

Silicon dioxide coating of CeO2 nanoparticles by solid state reaction at room temperature

The synthesis of SiO₂ coated CeO₂ nanoparticles by humid solid state reaction at room temperature is described. Transmission electron microscope results show that CeO₂ particles were coated with a layer of SiO₂. Binding energy of Ce 3d_5/2 was shifted from 883.8 to 882.8 eV after coating in the XPS Ce 3d spectra. This confirms the chemical bond formation between SiO₃²⁻ and Ce⁴⁺. Because the surface photovoltage property of CeO₂ nanoparticles that were used as core materials in the experiment approaches to that of CeO₂ macroparticles, peak P2 (electron transition from O 2p on surface to Ce 4f) disappeared in the surface photovoltage spectrum of CeO₂ nanoparticles. Also, the effect of SiO₂ on the electron transition from O 2p to Ce 4f results in the lowering of surface photovoltage response intensity of P1 peak (electron transition from O 2p in bulk to Ce 4f).     

Aluminium doped ceria–zirconia supported palladium-alumina catalyst with high oxygen storage capacity and CO oxidation activity

The Ce_0.5Zr_0.3Al_0.2O_1.9/Pd-γ-Al₂O₃ catalyst prepared by a mechanochemical route and calcined at 1000 °C for 20 h in air atmosphere to evaluate the thermal stability. The prepared Ce_0.5Zr_0.3Al_0.2O_1.9/Pd-γ-Al₂O₃ catalyst was characterized for the oxygen storage capacity (OSC) and CO oxidation activity in automotive catalysis. For the characterization, X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique were employed. The OSC values of all samples were measured at 600 °C using thermogravimetric-differential thermal analysis. Ce_0.5Zr_0.3Al_0.2O_1.9/Pd-γ-Al₂O₃ catalyst calcined at 1000 °C for 20 h with a BET surface area of 41 m² g⁻¹ exhibited the considerably high OSC of 583 μmol-O g⁻¹ and good OSC performance stability. The same synthesis route was employed for the preparation of the CeO₂/Pd-γ-Al₂O₃ and Ce_0.5Zr_0.5O₂/Pd-γ-Al₂O₃ for comparison.     

Study of Ln0.6Sr0.4Co0.8Mn0.2O3-δ (Ln=La, Gd, Sm or Nd) as the cathode materials for intermediate temperature SOFC

Perovskite type oxides Ln_0.6Sr_0.4Co_0.8Mn_0.2O_3−δ (Ln=La, Gd, Sm, or Nd) have been prepared by the solid state reaction of corresponding oxides. The crystal parameters of the compositions were determined by XRD powder diffraction, which revealed that all the compositions have orthorhombic structure. The reaction test of all samples with Ce_0.8Gd_0.2O_1.9 was carried out at 1200 °C for 48 h, and no reaction product was detected by XRD. The change in mass of La_0.6Sr_0.4Co_0.8Mn_0.2O_3−δ as a function of temperature was determined by thermogravimetric analysis (TGA). The electrical conductivity of the sintered samples were measured as a function of temperature from 200 to 1000 °C. The highest conductivity of about 1400 S cm⁻¹ was found in La_0.6Sr_0.4Co_0.8Mn_0.2O_3−δ. The cathodic polarization of these oxides electrodes deposited on Ce_0.8Gd_0.2O_1.9 tablet was studied at 500-800 °C in air.     

Performance of Ni/ScSZ cermet anode modified by coating with Gd0.2Ce0.8O2 for a SOFC

A Ni/scandia-stabilized zirconia (ScSZ) cermet anode was modified by coating with nano-sized gadolinium-doped ceria (GDC, Gd_0.2Ce_0.8O₂) within the pores of the anode for a solid oxide fuel cell (SOFC). X-ray diffraction (XRD) and scanning electron microscopy (SEM) were employed in the anode characterizations. Open circuit voltages (OCVs) increased from 1.027 to 1.078 V, and the maximum power densities increased from 238 to 825 mW/cm², as the operating temperature of a SOFC with 2.0 wt.%GDC-coated Ni/ScSZ anode was increased from 700 to 850 °C in humidified hydrogen. The coating of nano-sized Gd_0.2Ce_0.8O₂ particle within the pores of the porous Ni/ScSZ anode significantly improved the performance of anode supported cell. Electrochemical impedance spectra (EIS) illustrated that the cell with Ni/ScSZ anode exhibited far greater impedances than the cell with 2.0 wt.%GDC-coated Ni/ScSZ anode. Consequently, 2.0 wt.%GDC-coated Ni/ScSZ anode could be used as a novel anode material for a SOFC due to better electrochemical performance.     

Synthesis of CuCr and CuCrAg alloy with nano-ceramic dispersion by mechanical alloying and consolidation by laser assisted sintering

Cu-4.5Cr and Cu-4.5Cr-3Ag (in wt%) alloys without or with 10 wt% nanocrystalline Al₂O₃ and ZrO₂ dispersion have been synthesized by mechanical alloying or milling and consolidated by laser assisted sintering in Ar atmosphere. Microstructural characterization by scanning and transmission electron microscopy and phase analysis by X-ray diffraction suggest that the alloyed matrix undergoes significant grain growth after sintering while the dispersoids retain their ultrafine size and uniform distribution in the matrix. The dispersion of nano-Al₂O₃ is more effective than that of nano-ZrO₂ in enhancing the mechanical properties due to the smaller initial particle size of Al₂O₃ than that of ZrO₂. In general, laser sintering of mechanically alloyed Cu-4.5Cr and Cu-4.5Cr-3Ag alloys with 10 wt% nanocrystalline Al₂O₃ at 100 W laser power and 1-2 mm s⁻¹ scan speed yields the optimum combination of high density (7.1-7.5 mg m⁻³), hardness (165-225 VHN), wear resistance and electrical conductivity (13-20% IACS).     

Structural and electrical properties of Ce0.75(Gd0.95−xSrxCa0.05)0.25O2−δ thick film electrolyte

The effects of Sr doping on the electrical properties of Ce_0.75(Gd_0.95−xSr_xCa_0.05)_0.25O_2−δ (x = 0, 0.01, 0.02, 0.03, 0.04, 0.05 mol%) electrolytes thick films were investigated. The samples sintered at 1400 °C for 8 h. X-ray diffraction (XRD) showed typical XRD patterns of a cubic fluorite structure, and the ionic conductivity was examined by AC impedance spectroscopy. From the experimental results, it was observed that Ce_0.75(Gd_0.95−xSr_xCa_0.05)_0.25O_2−δ (x = 0.04 mol%) electrolytes thick film have higher conductivity and minimum activation energy at 600 °C. This is explained in terms of the increased in the oxygen vacancy concentration at the grain boundary.     

Synthesis and characterisation of chromium lutetium gallium garnet solid solution

The chromium lutetium gallium garnet system has been studied. Samples with 2xCaOxCr₂O₃(3 − 2x)Lu₂O₃5Ga₂O₃ (x = 0.025, 0.05, 0.075, 0.1, 0.2 and 0.3,) and xCr₂O₃(3 − x)Lu₂O₃5Ga₂O₃ (x = 0, 0.05, 0.075 and 0.3) compositions have been prepared in Ca,Cr:LGG and Cr:LGG systems, respectively. Samples were prepared by ceramic method, fired at 1250 °C/6 h and characterised by XRD, lattice parameters, UV-vis-NIR spectroscopy, CIE L^*a^*b^* measurements and SEM/EDX. Results indicate that Ca,Cr:LGG and Cr:LGG solid solutions are obtained. In Cr:LGG system only Cr(III) is stabilised in octahedral positions substituting for Lu(III) and Ga(III). Both Cr(III) and Cr(IV) are present in Ca,Cr:LGG. The calcium is a charge compensator to stabilise Cr(IV) and this is the predominant oxidation state up to x = 0.075 composition. From this composition, Cr(III) becomes more stabilised in garnet lattice. Cr(IV) occupies generally tetrahedral and dodecahedral sites substituting for Ga(III) and Lu(III), while Cr(III) is in octahedral site substituting for Ga(III).     

Hydrothermal synthesis and luminescent properties of Y2O3:Tb and Gd2O3:Tb microrods

One-dimensional (1D) Y₂O₃:Tb³⁺ and Gd₂O₃:Tb³⁺ microrods have been successfully prepared through a large-scale and facile hydrothermal method followed by a subsequent calcination process in N₂/H₂ mixed atmosphere. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (IR), thermogravimetric analysis (TGA), energy-dispersive X-ray spectra (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL) and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The as-formed products via the hydrothermal process could transform to cubic Y₂O₃:Tb³⁺ and Gd₂O₃:Tb³⁺ with the same morphology and slight shrinking in size after a postannealing process. Both Y₂O₃:Tb³⁺ and Gd₂O₃:Tb³⁺ microrods exhibit strong green emission corresponding to ⁵D₄ → ⁷F₅ transition (542 nm) of Tb³⁺ under UV light excitation (307 and 258 nm, respectively), and low-voltage electron beam excitation (1.5 → 3.5 kV), which have potential applications in fluorescent lamps and field emission displays.     

Luminescent properties of Gd2Ti2O7: Eu phosphor films prepared by sol-gel process

Gd₂Ti₂O₇: Eu³⁺ thin film phosphors were fabricated by a sol-gel process. X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 800 °C and the crystallinity increased with the elevation of annealing temperatures. Uniform and crack free phosphor films were obtained, which mainly consisted of grains with an average size of 70 nm. The doped Eu³⁺ showed orange-red emission in crystalline Gd₂Ti₂O₇ phosphor films due to an energy transfer from Gd₂Ti₂O₇ host to them. Both the lifetimes and PL intensity of the Eu³⁺ increased with increasing the annealing temperature from 800 to 1000 °C, and the optimum concentrations for Eu³⁺ were determined to be 9 at.%. of Gd³⁺ in Gd₂Ti₂O₇ film host.     

Pechini sol-gel deposition and luminescent properties of SrLa1−xRExGa3O7 (RE = Eu, Tb) phosphor films

SrLa_1−xRE_xGa₃O₇ (RE = Eu³⁺, Tb³⁺) phosphor films were deposited on quartz glass substrates by a simple Pechini sol-gel method. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy, field-emission scanning electron microscopy, photoluminescence spectra, and lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 700 °C and crystallized fully at 900 °C. The results of FT-IR spectra were in agreement with those of XRD. Uniform and crack-free films annealed at 900 °C were obtained with average grain size of 80 nm, root mean square roughness of 46 nm and thickness of 130 nm. The RE ions showed their characteristic emission in crystalline SrLa_1−xRE_xGa₃O₇ films, i.e., Eu³⁺⁵D₀-⁷F_J (J = 0, 1, 2, 3, 4), Tb³⁺⁵D₄-⁷F_J (J = 6, 5, 4, 3) emissions, respectively. The optimum concentrations (x) of Eu³⁺ and Tb³⁺ were determined to be 50, and 80 mol% in SrLa_1−xRE_xGa₃O₇ films, respectively.