Characteristics of Fe2O3 Nanoparticles from Doped Low-pressure H2/O2/Ar Flames

A burner stabilized premixed low-pressure flame has been used to generate iron-oxide (Fe₂O₃) nanoparticles with sizes in the range 7–20nm. The H₂/O₂/Ar flames were doped with different amounts of iron-pentacarbonyl (Fe(CO)₅) with concentrations in the range 524–2096ppm. The influence of precursor concentration on composition, structure, morphology, and size have been studied utilizing transmission electron microscopy (TEM), X-ray powder diffraction (XRD), measurements of the specific surface area (BET), and infrared spectroscopy (FT-IR). The product particles consist of both, the - and the -phase of Fe₂O₃. Average particle sizes were measured in the range 7.4–16nm depending on precursor concentration and flame conditions.     

Interfacial segregation in Ag-Au,Au-Pd,and Cu-Ni alloys: I. (100) surfaces

Atomistic simulations of segregation to (100) free surface in Ag–Au, Au–Pd, and Cu–Ni alloy systems have been performed for a wide range of temperatures and compositions within the solid solution region of these alloy phase diagrams. In addition to the surface segregation profiles, surface free energies, enthalpies, and entropies were determined. These simulations were performed within the framework of the free energy simulation method, in which an approximate free energy functional is minimized with respect to atomic coordinates and atomic site occupation. The effects of the relaxation with respect to either the atomic positions or the atomic concentrations are discussed. For all alloy bulk compositions (0.05 C 0.95) and temperatures (400 T(K) 1,100) examined, Ag, Au, and Cu segregates to the surface in the Ag–Au, Au–Pd, and Cu–Ni alloy systems, respectively. The present results are compared with several theories for segregation. The resultant segregation profiles in Au–Pd and Ag–Au alloys are shown to be in good agreement with an empirical segregation theory, while in Cu–Ni alloys the disagreement in Ni-rich alloys is substantial. The width of the segregation profile is limited to approximately three to four atomic planes. The surface thermodynamic properties depend sensitively on the magnitude of the surface segregation, and some of them are shown to vary linearly with the magnitude of the surface segregation.     

Preparation of ZnO–Al2O3 Particles in a Premixed Flame

Zinc oxide (ZnO) and alumina (Al₂O₃) particles are synthesized by the combustion of their volatilized acetylacetonate precursors in a premixed air–methane flame reactor. The particles are characterized by XRD, transmission electron microscopy, scanning mobility particle sizing and by measurement of the BET specific surface area. Pure (-)alumina particles appear as dendritic aggregates with average mobile diameter 43–93 nm consisting of partly sintered, crystalline primary particles with diameter 7.1–8.8 nm and specific surface area 184–229 m²/g. Pure zinc oxide yields compact, crystalline particles with diameter 25–40 nm and specific surface area 27–43 m²/g. The crystallite size for both oxides, estimated from the XRD line broadening, is comparable to or slightly smaller than the primary particle diameter. The specific surface area increases and the primary particle size decreases with a decreasing flame temperature and a decreasing precursor vapour pressure. The combustion of precursor mixtures leads to composite particles consisting of zinc aluminate ZnAl₂O₄ intermixed with either ZnO or Al₂O₃ phases. The zinc aluminate particles are dendritic aggregates, resembling the alumina particles, and are evidently synthesized to the full extent allowed by the overall precursor composition. The addition of even small amounts of alumina to ZnO increases the specific surface area of the composites significantly, for example, zinc aluminate particles increases to approximately 150 m²/g. The gas-to-particle conversion is initiated by the fast nucleation of Al₂O₃ or ZnAl₂O₃, succeeded by a more gradual condensation of the excess ZnO with a rate probably controlled by the cooling rate for the flame.     

Structure of grain boundaries in YBa2Cu3O7 thin-film step-edge junctions

The atomic structure of 90° [100] (or [010]) tilt grain boundaries in YBa₂Cu₃O₇ thin-film step-edge junctions and, for comparison, in the interface between a-axis and c-axis oriented YBa₂Cu₃O₇ grains is investigated by means of high-resolution transmission electron microscopy. For (100)(001)-type boundaries two different structures are found. In the first a (001) CuO₂ plane of one grain faces a (100) Y–Ba–O plane of the other grain, in the second a (001) BaO plane faces a (100) Cu–O plane. In the former structure an incomplete unit cell of YBa₂Cu₃O₇ terminates at the boundary and a smaller strain in the adjacent CuO₂ planes is detected in comparison with the latter. It is found that a combination of a partial dislocation with a 124 stacking fault is a way to accommodate the lattice mismatch between c and 3a of YBa₂Cu₃O₇ in the boundary. For a symmetric (103)(103)-type boundary a displacement of the Cu-atoms of the CuO₂ planes is found near the boundary plane. From this a redistribution of the oxygen atoms around the Y-atoms located right in the boundary plane is inferred. The possible effect of the boundary structure on the superconducting properties of YBa₂Cu₃O₇ films is discussed.     

Optically pumped submillimeter laser lines from CH2F2 and CD2Cl2 using a12C18O2 CW laser

Thirty-nine new submillimetre laser lines in CH₂F₂ and twelve in CD₂Cl₂ have been obtained in a Fabry-Perot FIR resonator by optically pumping with a CW¹²C¹⁸O₂ laser. The wavelength range obtained for CH₂F₂ is 126m to 1091m and for CD₂Cl₂ 212m to 774m. The wavelength measurements are accurate to within 5.10^–3. The relative polarisations of the pump laser and the FIR laser output were also determined. Tentative assignments of the IR and FIR transitions were made using existing microwave data.     

Manipulating Bonding at a Cu/(0001)Al2O3 Interface by Different Substrate Cleaning Processes

Growth of Cu films on (0001)Al₂O₃ substrates can result in metallic Cu—Al or ionic-covalent Cu—O bonds at atomically abrupt interfaces. The type of bonding depends on the substrate cleaning procedure prior to film growth. Cu films deposited on Ar⁺-ion sputter-cleaned substrates exhibit interfacial Cu-L_2,3, Al-L_2,3 and O-K energy-loss near-edge structures that indicate the formation of metallic Cu—Al bonds at the Cu/Al₂O₃ interface. In contrast, growth on chemically cleaned -Al₂O₃ substrates results in interfacial energy-loss near-edge structures that suggest Cu—O bonding at the interface. The experimental electron energy-loss spectroscopic results are compared to calculated spectra, and the mechanisms causing the changes in the atomic and electronic structure are addressed.     

Conversion of egg shell membrane to inorganic porous CexZr1−xO2 fibrous network

The binary system CeO₂–ZrO₂ is thermally stable and has superior reduction–oxidation properties. It has been commonly used in the three-way catalytic converters for automobiles. In this work, an inorganic biomorphic porous Ce_xZr_1−xO₂ fibrous network was successfully synthesized by using the egg shell membrane (ESM) as templates, and its morphology was a perfect replica of the original ESM. The synthesis involved a simple infiltration and calcination process. A fresh ESM was peeled from a chicken egg shell. It was soaked in a Ce(NO₃)₃ and Zr(NO₃)₄ mixture before it was calcined at 700 °C in ambient environment. The fibers in the biomorphic network had diameter ranged from 1 to 4 μm, and they were composed of Ce_xZr_1−xO₂ nanocrystallites having an average grain size of 10 nm.     

Microwave dielectric properties of (1 − x)(Mg0.95Co0.05)TiO3–x(Na0.5La0.5)TiO3 ceramic system

The microstructures and the microwave dielectric properties of the (1 − x)(Mg_0.95Co_0.05)TiO₃–x(Na_0.5La_0.5)TiO₃ ceramic system were investigated. Two-phase system was confirmed by the XRD patterns and the EDX analysis. A co-existed second phase (Mg_0.95Co_0.05)Ti₂O₅ was also detected. The microwave dielectric properties are strongly related to the density and the matrix of the specimen. A new microwave dielectric material 0.88(Mg_0.95Co_0.05)TiO₃–0.12(Na_0.5La_0.5)TiO₃, possessing an excellent combination of dielectric properties: ε_r  22.36, Q × f  110,000 GHz (at 9 GHz), τ_f  2.9 ppm/°C), is proposed as a candidate dielectric for GPS patch antennas.     

Interfacial segregation in Ag-Au,Au-Pd,and Cu-Ni alloys: II. [001] Σ5 twist grain boundaries

Atomistic simulations of segregation to [001] 5 twist boundaries in Cu–Ni, Au–Pd, and Ag–Au alloy systems have been performed for a wide range of temperatures and compositions within the solid solution region of these alloy phase diagrams. In addition to the grain boundary segregation profiles, grain boundary free energies, enthalpies, and entropies were determined. These simulations were performed within the framework of the free energy simulation method, in which an approximate free energy functional is minimized with respect to atomic coordinates and atomic site occupation. For all alloy bulk compositions (0.05 C 0.95) and temperatures (400 T (K) 1,100) examined, Cu and Au segregates to the boundary in the Cu–Ni and Au–Pd alloy systems, respectively; although in the Ag–Au alloys, the majority element segregates to the boundary. The width of the segregation profile is limited to approximately three to four (002) atomic planes. The classical theories for the segregation, and the effects of the relaxation with respect to either the atomic positions or the atomic concentrations, are discussed. The boundary thermodynamic properties depend sensitively on the magnitude of the boundary segregation, and some of them are shown to vary linearly with the magnitude of the grain boundary segregation.     

Reduced anti-ferromagnetism promoted by Zn 3d substitution at CuO2 planar sites of Cu0.5Tl0.5Ba2Ca3Cu4O12−δ superconductors

The role of charge carriers in ZnO₂/CuO₂ planes of Cu_0.5Tl_0.5Ba₂Ca₃Cu_4−yZn_yO_12−δ material in bringing about superconductivity has been explained. Due to suppression of anti-ferromagnetic order with Zn 3d¹⁰ (S=0) substitution at Cu 3d⁹ sites in the inner CuO₂ planes of Cu_0.5Tl_0.5Ba₂Ca₃Cu₄O_12−δ superconductor, the distribution of charge carriers becomes homogeneous and optimum, which is evident from the enhanced superconductivity parameters. The decreased c-axis length with the increase of Zn doping improves interlayer coupling and hence the three dimensional (3D) conductivity in the unit cell is enhanced. Also the softening of phonon modes with the increased Zn doping indicates that the electron–phonon interaction has an essential role in the mechanism of high-T_c superconductivity in these compounds.     

Hollow nanoparticles of <Emphasis Type="Italic">β</Emphasis>-iron oxide synthesized by chemical vapor condensation

Hollow nanoparticles of -Fe₂O₃ were synthesized by chemical vapor condensation (CVC). A structural study revealed that the nanoparticles, 10–20 nm in diameter, consisted of hollow structures with several shells 3–5 nm in thickness. TEM observation indicated that the shells of the -Fe₂O₃ nanoparticles consist of several grain structures having different crystal orientations. This feature of the crystallinity enables us to infer the formation mechanism of the hollow structure of the -Fe₂O₃ nanoparticles during CVC process.     

Oxygen content of superconducting Ba2YCu3O6.5+x

Single-phase non-stoichiometric Ba₂YCu₃O_6.5+x with –0.248x0.300 can be obtained by annealing prereacted samples at 0.01–1 bar oxygen partial pressure. Samples withx=–0.248 are semiconducting, samples at 0.239x0.300 are metallic withT _c increasing from 92.2 to 94.0 K for annealing in 0.02–1 bar O₂.     

Percolation and electrical resistivity in the YBa2Cu3O7−Ag composite system

We have measured the resistivity of the YBa₂Cu₃O₇–Ag composite system with Ag volume fraction,p _Ag ranging from 0–100%. The percolation behavior and the normal-state resistivity are studied. We find a three-dimensional threshold for the Ag matrix occurring atp _Ag 20% and a threshold for the superconducting matrix occurring at 1–p _Ag30%. The electrical resistivity is interpreted in terms of a resistivity model for granular YBa₂Cu₃O₇ proposed by Halbritter et al. [Z. Phys. B —Condensed Matter71, 411 (1988)]. Based on this model, we show that the resistivities between the YBa₂Cu₃O₇ grains and flaws in the grains are greatly diminished in the samples, indicating significantly improved grain growth behavior of the YBa₂Cu₃O₇ phase resulting from the addition of Ag. With the diminishing of the grain boundary resistivities, an intrinsic value for the temperature coefficient of resistivity, (1/gr)(d/dT), can be inferred, which is 3.3×10^–3/K at 300 K. This value is very close to that observed in the Cu–O₂ planes in single crystals and epitaxial films of YBa₂Cu₃O₇.     

Pitfalls in the Use of Common Luminescent Probes for Oxidative and Nitrosative Stress

Lucigenin (LC²⁺, bis-N-methylacridinium) and 2,7-dichlorofluorescin (DCFH₂) are widely used as chemiluminescent or fluorescent probes for cellular oxidative stress, to reflect levels of superoxide (O₂ ^·–) and hydrogen peroxide, respectively. We report mechanistic studies that add to the growing evidence for the unsuitability of either probe except in very well-defined circumstances. The ability for lucigenin to generate superoxide via reduction of LC²⁺ to LC^·+ and redox cycling with oxygen depends on the reduction potential of the LC²⁺/LC^·+ couple. Redox equilibrium between LC^·+ and the redox indicator benzyl viologen is established in microseconds after generation of the radicals by pulse radiolysis and indicated E(LC²⁺/LC^·+) –0.28 V vs. NHE. Reaction of LC^·+ with O₂ to generate O₂ ^·– was also observed directly similarly, occurring in milliseconds, with a rate constant k 3 × 10⁶ M ^–1 s^–1. Quinones act as redox mediators in LC^·+/O₂ redox cycling. Oxidation of DCFH₂ to fluorescent DCF is not achieved by O₂ ^·– or H₂O₂, but NO₂ ^·) reacts rapidly: k 1 × 10⁷ M ^–1 s^–1. Oxidation by H₂O₂ requires a catalyst: cytochrome c (released into the cytosol in apoptosis) is very effective (even 10 nM). Fluorescence reflects catalyst level as much as O₂ ^·–) production.     

New observation of the , 1Δg, and 2Πg states and molecular constants with all Li2, Li2, and LiLi data

This paper reports our new observation of the , 1³Δ_g (v = 2–4), and 2³Π_g (v = 2–8) states of ⁶Li⁷Li by continuous wave perturbation facilitated optical–optical double resonance spectroscopy. Combining our new experimental term values of ⁶Li⁷Li with the available experimental data of ⁶Li₂ and ⁷Li₂, molecular constants and potential energy curves by Rydberg–Klein–Rees and direct-potential-fit techniques have been determined. Born-Oppenheimer breakdown parameters of the Li₂ 1³Δ_g and 2³Π_g states are calculated.     

Lithium ion conductive glass–ceramics with Li3Fe2(PO4)3 and YAG laser-induced local crystallization in lithium iron phosphate glasses

The glasses with the composition of 37.5Li₂O–(25 − x)Fe₂O₃–xNb₂O₅–37.5P₂O₅ (mol%) (x = 5,10,15) are prepared, and it is found that the addition of Nb₂O₅ is effective for the glass formation in the lithium iron phosphate system. The glass–ceramics consisting of Nasicon-type Li₃Fe₂(PO₄)₃ crystals with an orthorhombic structure are developed through conventional crystallization in an electric furnace, showing electrical conductivities of 3 × 10^− 6 Scm^− 1 at room temperature and the activation energies of 0.48 eV (x = 5) and 0.51 eV (x = 10) for Li⁺ ion conduction in the temperature range of 30–200 °C. A continuous wave Nd:YAG laser (wavelength: 1064 nm) with powers of 0.14–0.30 W and a scanning speed of 10 μm/s is irradiated onto the surface of the glasses, and the formation of Li₃Fe₂(PO₄)₃ crystals is confirmed from XRD analyses and micro-Raman scattering spectra. The crystallization of the precursor glasses is considered as new route for the fabrication of Li₃Fe₂(PO₄)₃ crystals being candidates for use as electrolyte materials in lithium ion secondary batteries.     

Scanning tunneling microscopy/spectroscopy on multi-layered cuprate superconductor Ba2Ca5Cu6O12 (O1−x Fx)2

Scanning tunneling microscopy/spectroscopy (STM/STS) measurements on multi-layered cuprate superconductor Ba₂Ca₅Cu₆O₁₂ (O_1−x F_x)₂ are carried out. STM topographies show randomly distributed bright spot structures with a typical spot size of 0.8 nm. These bright spots are occupied about 28% per one unit cell of c-plane, which is comparable to the regular amount of apical oxygen of 20% obtained from element analysis. Tunneling spectra simultaneously show both the small and the large gap structures. These gap sizes at 4.9 K are about Δ 15 meV and 90 meV, respectively. The small gap structure disappears at the temperature close to T_C, while the large gap persists up to 200 K. Therefore, these features correspond to the superconducting gap and pseudogap, respectively. These facts give evidence for some ordered state with large energy scale even in the superconducting state. For the superconducting gap, the ratio of 2Δ/K_BT_C = 4.9 is obtained with T_C = 70 K, which is determined from temperature dependence of the tunneling spectra.     

Theoretical study of CO and Pb adsorption on the Ni(1 1 1) and Ni3Al(1 1 1) surfaces

Adsorption of CO molecules and Pb atoms on the Ni(1 1 1) and Ni₃Al(1 1 1) substrates is studied theoretically within an ab initio density-functional-theory approach. Stable adsorption sites and the corresponding adsorption energies are first determined for stoichiometric surfaces. The three-fold hollow sites (fcc for Pb and hcp for CO) are found most favourable on both substrates. Next, the effect of surface alloying by a substitution of selected topmost substrate atoms by Pb or Ni atoms on the adsorption characteristics is investigated. When the surface Al atoms of the Ni₃Al(1 1 1) substrate are replaced by Ni atoms, the Pb and CO adsorption energies approach those for a pure Ni(1 1 1) substrate. The Pb alloying has a more substantial effect. On the Ni₃Al(1 1 1) substrate, it reduces considerably adsorption energy of CO. On the Ni(1 1 1) substrate, CO binding strengthens slightly upon the formation of the Ni(1 1 1)p(2×2)-Pb surface alloy, whereas it weakens drastically when the Ni(1 1 1)-Pb surface alloy is formed.     

Negative muon precession in nuclei with spin

Polarized negative muons were stopped in various materials containing nuclei with nonzero spin. The TF-SR precession signal of theF ⁺ hyperfine state (frequencyv ₊ > 0) was pronounced for ^–Li and ^–Be, faint for ^–Cl (in NiCl₂), and undetectable for ^–F (in CaF₂ or NiF₂) and ^–P. TheF ^– signal (frequencyv _– < 0) was observed clearly for ^–Be, ^–Al and ^–Na, marginally for ^–K, ^–V and ^–Nb, and not at all for ^–Ga (at 4 kOe) or ^–Co (ferrromagnetic, zero field). In the heavier elements theF ^– signal is fed by transitions from theF ⁺ to theF ^– state at a rateR, as long asR(v ₊ –v _–). [See separate paper on ^–Al in these Proceedings, p. 879.]I am grateful to Alex Schenck and Bruce Patterson for the loan of equipment and samples, to Fred Gygax for helping set up the apparatus, to Jun Imazato for help with the experiment, and to Toshi Yamazaki and Tak Suzuki for valuable comments. I am also indebted to SIN for several weeks of free ^– beam time and to SIN, BOOM, and the University of Tokyo for free time on their VAX computers, which were kept busy for several months in the analysis.     

Microwave–assisted synthesis of <Emphasis Type="Italic">submicrometer</Emphasis> GaO(OH) and Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> rods

Submicrometer sized gallium oxide hydroxide (GaO(OH)) and gallium oxide (Ga₂O₃) rods have been successfully fabricated on a large scale by refluxing an aqueous solution of Ga(NO₃)₃ and NH₄OH in a simple domestic microwave oven (DMO). The structures, morphologies, compositions and physical properties of the as–synthesized and calcined products have been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), selected area energy dispersive X-ray spectroscopy (SAEDS), thermo gravimetric analysis (TGA), differential scanning calorimetry (DSC), and energy dispersive X-ray (EDX) analysis. TEM images show that submicrometer sized as–synthesized Ga O(OH) rods have diameters of 0.3–0.5 m and lengths of 3.2–3.5 m. The calcined product consists of submicrometer rods with diameters of 0.4–0.5 m and lengths of 5–5.5 m. XRD, EDX and SAED analysis together indicate that the as–synthesized product has an orthorhombic gallium oxide hydroxide (GaO(OH)) crystal structure, and that the calcined product is rhombohedral Ga₂O₃. A possible mechanism for the formation of submicrometer sized GaO(OH) rods is discussed briefly.