Structural,electrical and catalytic properties of ion-implanted oxides

The potential application of ion implantation to modify the surfaces of ceramic materials is discussed. Changes in the chemical composition and microstructure result in important variations of the electrical and catalytic properties of oxides.     

On the magnetic properties of mechanosynthesized Co-Fe-Ni ternary alloys

X-ray diffraction, Mössbauer spectroscopy and magnetization measurements were used as complementary methods to obtain structural data and to determine magnetic properties of the mechanically synthesized and subsequently thermally treated Co-Fe-Ni alloys. New, however approximate, phase diagrams were established on the basis of X-ray diffraction investigations. Mössbauer spectroscopy and magnetization measurements allowed to reveal practically linear correlation between the average values of the hyperfine magnetic field induction, 〈B_hf〉, and the effective magnetic moments, μ_eff, of the alloys. The decrease in 〈B_hf〉 with the number of electrons per atom, e/a, was observed. Moreover, the dependence of μ_eff on the valence 3d and 4s electrons per atom follows the Slater-Pauling curve. Thermal treatment of mechanosynthesized Co-Fe-Ni alloys led to some changes in the phase diagrams, increase in the grain size and decrease of the level of internal strains in alloys. Dependencies of lattice constants, average hyperfine magnetic fields, effective magnetic moments and Curie temperatures on the number of electrons per atom have the same trends for mechanically synthesized as well as for thermally treated alloys.     

Relationship between optical and structural properties of hydrogenated amorphous silicon

A series of experimental studies has been made on the relationship between optical and structural properties of hydrogenated amorphous silicon (a-Si:H) prepared under various conditions. It has been clarified by analysing the results that the shape of the energy spectrum near the band edge and the distribution of the valence-band tail states depend primarily on the structural disorder of the Si network in a-Si:H. On the other hand, the total content and the bonding mode of bonded hydrogen have little effects on these electronic properties of a-Si:H. It has also been found that the distribution of the valenceband tail states might be related to other unidentified factor(s) besides the structural disorder. The present results have been compared with those of the previous experimental and theoretical studies.     

The structural and spectroscopic properties for uranium oxides

The equilibrium structures, the charge population, and the spectroscopic properties of UO, UO 2 , UO 3 , and U 2 O 3 molecules are systematically investigated using the density functional theory (DFT) with the method of generalized gradient approximation (GGA). The bond lengths and the vibrational frequencies of the ground states of UO, UO 2 , and UO 3 molecules are all in agreement with available experimental data. For U 2 O 3 molecules, our calculations indicate that the ground state of the U 2 O 3 molecule is an X 7 A ′ 1 state with D 3h (trigonal bipyramid) symmetry (R 1 (U–O)=0.2113 nm, R 2 (U 1 –U 2 )=0.2921 nm, ∠U 1 OU 2 = 87.5 , dihedral angle Θ(U,O 1 ,O 2 ,O 3 )=62.40 ). The harmonic frequency, the IR intensity and the spin density of the U 2 O 3 molecule are all obtained for the first time in theory. For the ground state of U 2 O 3 molecules, the vibrational frequencies are 178.46 (A ′ 1 ), 276.79 (E ′′ 1 ), 310.77 (E ′ 1 ), 396.63 (A ′′ 2 ), 579.15 (E ′ 1 ), and 614.98 (A ′ 1 ) cm 1 . The vibrational modes corresponding to the IR maximum peaks are worked out for UO 3 and U 2 O 3 molecules. Besides, the results of Gophinatan–Jug bond order indicate that UO, UO 2 , and UO 3 molecules possess U=O double bonds and that the U 2 O 3 molecule possesses U–O single bonds and a U–U single bond.     

Influence of cobalt ions on the electrochemical properties of lamellar manganese oxides

Evaluation of Co-doping on the electrochemical properties of the sol-gel birnessite and the new lithiated manganese oxide Li_0.45MnO_2+δ is reported. For both compounds the synthesis of Co-doped materials via a solution technique is described. We demonstrate the interest of Co-doped structures with the selected content of 0.15 Co per mole of oxide as the optimum composition. In the case of Li_0.45Mn_1−yCo_yO_2+δ. prepared at 300 °C, a mixture of a lamellar phase and a cubic one is identified while the Co-doped birnessite appears as a single phase. A probable substitution of Mn by Co ions explains the better specific capacity of 185 mAh/g found and the excellent stability observed over 40 cycles in the voltage range 4.2−2.0 V. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Synthesis, characterization and catalytic properties of sol-gel derived mixed oxides

Alumina and 1:1 mixed oxides of Al₂O₃-ZrO₂, Al₂O₃-TiO₂, SiO₂-TiO₂ and ZrO₂-TiO₂ were synthesized via a sol-gel process by the so-called neutral amine route, followed by calcination at 600 °C. The mixed oxides were characterized before calcination by X-ray diffraction, revealing ordered hexagonal (Al₂O₃, Al₂O₃-ZrO₂, ZrO₂-TiO₂) and lamellar (SiO₂-TiO₂, Al₂O₃-TiO₂) structures. After calcination, all samples exhibited amorphous structures. Surface areas and pore characteristics of all materials were determined by nitrogen adsorption isotherms. The calcined oxides are active catalysts in the epoxidation of cyclooctene with tert-butyl hydroperoxide as oxidant. Epoxide yields from 14 to 45% were found for reaction times of 24 h. The titanium oxide containing catalysts are the most active and selective ones. On the other hand, the poisoning of acidic centers yields a decreasing activity while increasing selectivity.     

Binding properties between ferroic oxides and metals

Using first principles calculations the binding characteristics of a metallic film covering a piezo-electric oxide is studied. The band structures and the charge densities of interfaces and single compounds are calculated. Comparing the overlaps of the densities of states and the differences in the charge densities, it is found that the interface stabilitydepends on the thickness of the metallic film. The bonding is shown to be a result of charge transfer.     

Synthesis and characterization of cobalt–manganese oxides

Cobalt doped/un-doped manganese oxides materials were synthesized at various doping rates by soft chemical reactions, oxidation-reduction method, which allows generating a metal-mixed oxide. The synthesized materials were characterized using several techniques including chemical analysis, X-rays diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The chemical analysis confirmed the presence of cobalt in the samples. XRD patterns reveal mainly a spinel-like structure and SEM micrographs exhibited morphology with fine aggregate of particles. TGA profiles showed weight loss due to loss of water in a first step, followed by a loss of oxygen from the lattice associated with partial reduction of Mn⁴⁺ to Mn³⁺. VSM was used to measure the magnetization as a function of the applied magnetic field at temperatures T=50 and 300 K. Different magnetic behaviors were observed when cobalt percentage changed in the samples. These behaviors are considered to be related to the size of the particles and composition of the materials. Higher coercive field and lesser magnetization were observed for the sample with higher cobalt content.     

Relationship between local structure and relaxor behavior in perovskite oxides

Despite intensive investigations over the past five decades, the microscopic origins of the fascinating dielectric properties of ABO3 relaxor ferroelectrics are currently poorly understood. Here, we show that the frequency dispersion that is the hallmark of relaxor behavior is quantitatively related to the crystal chemical characteristics of the solid solution. Density functional theory is used in conjunction with experimental determination of cation arrangement to identify the 0 K structural motifs. These are then used to parametrize a simple phenomenological Landau theory that predicts the universal dependence of frequency dispersion on the solid solution cation arrangement and off-center cation displacements.     

Enhanced electrochemical properties of Al-doped bulk manganese oxides synthesized by a facile liquid-phase method

Aluminum doped MnO₂ nanoparticles were synthesized by a simple liquid-phase process using potassium permanganate as oxidation agent, glycol as reducing agent. Specific capacitance of the optimal sample electrode can reach 290 F g^?1 after 10 cycles. The electrode also exhibits excellent cycle stability, retaining 86.6 % after 1,000 cycles. The infrared absorption bands of aluminum doped manganese oxide shift to high wave number for the reason that aluminum ion has smaller nuclear charge. The doping of aluminum strengthens the Mn–O bond and decreases the aggregation degree, thus the electrochemical properties are enhanced.     

Near-surface structural study of transition metal oxides to understand their electronic properties

The atomic arrangement in a solid contains a great amount of information, and observation of its structure is essential for understanding the electronic and magnetic properties of transition metal oxides at a microscopic level. Increasing interest in the surfaces and interfaces of oxide systems, which is partly driven by the anticipation of device applications, enhances the importance of structural studies of the near-surface region. We review various types of structural studies with x-ray scattering on the near-surface region of metal oxides-from thick films to surfaces-in order to clarify the structural effects on their electronic properties.     

Electrical properties of lithiated boron oxide fast-ion conducting glasses

Lithiated boron oxide glasses of the family xLi₂O-B₂O₃, with x ranging from 1.0 to 4.5, were prepared by melting at high temperatures and shaped in the form of slabs. The glasses’ properties were evaluated by Complex Impedance Spectroscopy and Scanning Electron Microscopy techniques. The variation of lithium-ion conductivity at room temperature as a function of the glasses’ lithium content is found to exhibit a maximum at a molar ratio of x=3.5. This maximum in the ionic conductivity is correlated to the formation of crystalline regions in the vitreous structure of the material as the lithium concentration is increased. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15–21, 2002.     

Influence of Fe-doping on the microstructure and electromagnetic performance of manganese oxides

A simple wet chemical method was used to synthesize Fe-doped MnO₂ composites with iron amount ranging from 0 to 90 M percent. X-ray diffraction, electron probe micro-analyzer, scanning electron microscopy and vector network analyzer were employed to investigate the effect of iron doping on the microstructure and electromagnetic performance of the as-synthesized samples. Results indicate that relative small content of Fe-doping cannot change the α-MnO₂ structure but can promote the formation of hollow-structural morphology. The as-obtained products are transformed into a novel compound (Fe_0.67Mn_0.33)OOH with the increase of Fe-doping to 30 mol%. The possible formation mechanism was proposed in detail. Compared with the pure MnO₂, the Fe-doped samples exhibit decreased dielectric loss but increased magnetic loss with increasing the iron content below 20 mol% while relatively poor electromagnetic properties with the iron content above 30 mol%.     

Phase diagrams and ranges of cation homogeneity for systems composed of oxides of manganese and 4f rare earth elements (La57-Lu71), oxides of manganese and Sc21, and oxides of manganese and Y39

P-T-x phase diagrams are constructed for rare earth element (La⁵⁷-Lu⁷¹)-manganese-oxygen and Sc²¹ (or Y³⁹)-manganese-oxygen systems in the temperature range of 1123–1673 K and at oxygen pressures from atmospheric to 10^?20. In addition, diagrams for the ranges cation homogeneity in air are constructed on the basis of experimental data.     

Effects of silver and gold catalytic activities on the structural and optical properties of silicon nanowires

The metal-assisted chemical etching of silicon in an aqueous solution of hydrofluoric acid and hydrogen peroxide is established for the fabrication of large area, uniform silicon nanowire (SiNW) arrays. In this study, silver (Ag) and gold (Au) are considered as catalysts and the effect of different catalysts with various thicknesses on the structural and optical properties of the fabricated SiNWs is investigated. The morphology of deposited catalysts on the silicon wafer is characterized by atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM). It is shown that the morphology of the fabricated silicon nanostructures remarkably depends upon the catalyst layer thickness, and the catalyst etching time directly affects the structural and optical properties of the synthesized SiNWs. FESEM images show a linear increment of the nanowire length versus time, whereas the etching rate for the Au-etched SiNWs was lower than the Ag-etched ones. Strong light scattering in SiNWs caused the total reflection to decrease in the range of visible light, and this decrement was higher for the Ag-etched SiNW sample, with a longer length than the Au-etched one. A broadband visible photoluminescence (PL) with different peak positions is observed for the Au- and Ag-etched samples. The synthesized optically active SiNWs can be considered as a promising candidate for a new generation of nano-scale opto-electronic devices.     

Differences in catalytic properties between mesoporous and nanoparticulate platinum

Conventional Pt/Al₂O₃ catalysts prepared by wet-impregnation are composed of Pt nanoparticles exposing convex and facetted surfaces deposited on high-surface area γ-Al₂O₃ supports. A hexagonal phase mesoporous Pt material (denoted H₁-Pt) prepared by chemical reduction in the aqueous domains of a lyotropic liquid crystalline template exposes however mainly a concave surface with expected different catalytic properties. A series of Pt/Al₂O₃ catalysts were prepared using H₁-Pt, Pt-black or wet-impregnated Pt, and the samples were characterized by SEM-EDX and TEM, and finally evaluated for CO oxidation. The H₁-Pt/Al₂O₃ catalyst showed an ignition profile for CO oxidation at lower temperatures and thus appeared less sensitive to CO poisoning than the two other types of samples. This difference may be related to the differences in surface curvature.     

Relationships between surface compositions and properties of surfaces of mixed fumed oxides

Fumed oxides SiO₂/Al₂O₃ (SA), SiO₂/TiO₂ (ST) and Al₂O₃/SiO₂/TiO₂ (AST) at different content of alumina and titania were investigated by one-pass temperature-programmed desorption (OPTPD) time-of-flight mass-spectrometry (TOFMS), Auger electron spectroscopy (AES), NMR, FTIR, thermally stimulated depolarization current (TSDC), microcalorimetry, adsorption of nitrogen, water, (dimethylamino)azobenzene (DMAAB) and metal ions (Pb(II) and Ni(II)). It was shown that all the studied adsorption/desorption and energetic properties of mixed fumed oxides depend strongly on the surface content of alumina (shown as a surface content of aluminum, ) in SA and AST and titania (shown as a surface content of titanium, ) in ST and AST. Many of these properties demonstrate clear correlations with the and values over the total range of alumina and titania content in the materials.