Transport properties of strongly correlated metals: A dynamical mean-field approach

The temperature dependence of the transport properties of the metallic phase of a frustrated Hubbard model on the hypercubic lattice at half-filling is calculated. Dynamical mean-held theory, which maps the Hubbard model onto a single impurity,Anderson model that is solved self-consistently, and becomes exact in the limit of large dimensionality, is used. As the temperature increases there is a smooth crossover from coherent Fermi liquid excitations at low temperatures to incoherent excitations at high temperatures. This crossover leads to a nonmonotonic temperature dependence for the resistance, thermopower, and Hall coefficient, unlike in conventional metals. The resistance smoothly increases from a quadratic temperature dependence at low temperatures to large values which can exceed the Mott-Ioffe-Regel value ha/e(2) (where a is a lattice constant) associated with mean free paths less than a lattice constant. Further signatures of the thermal destruction of quasiparticle excitations are a peak in the thermopower and the absence of a Drude peak in the optical conductivity. The results presented here are relevant to a wide range of strongly correlated metals, including transition metal oxides, strontium ruthenates, and organic metals.

Effects of promoters on catalytic activity and carbon deposition of Ni/gamma-Al2O3 catalysts in CO2 reforming of CH4

Catalytic reforming of methane with carbon dioxide was studied in a fixed-bed reactor using unpromoted and promoted Ni/gamma-Al2O3 catalysts. The effects of promoters, such as alkali metal oxide (Na2O), alkaline-earth metal oxides (MgO, CaO) and rare-earth metal oxides (La2O3, CeO2), on the catalytic activity and stability in terms of coking resistance and coke reactivity were systematically examined. CaO-, La2O3- and CeO2-promoted Ni/gamma-Al2O3 catalysts exhibited higher stability whereas MgO- and Na2O-promoted catalysts demonstrated lower activity and significant deactivation. Metal-oxide promoters (Na2O, MgO, La2O3, and CeO2) suppressed the carbon deposition, primarily due to the enhanced basicities of the supports and highly reactive carbon species formed during the reaction. In contrast, CaO increased the carbon deposition; however, it promoted the carbon reactivity. (C) 2000 Society of Chemical Industry.

Initial results of ultrasound screening for aneurysm of the abdominal aorta in Western Australia: relevance for endoluminal treatment of aneurysm disease

Background. Increased life expectancy in men during the last thirty years is largely due to the decrease in mortality from cardiovascular disease in the age group 29-69 yr. This change has resulted in a change in the disease profile of the population with conditions such as aneurysm of the abdominal aorta (AAA) becoming more prevalent. The advent of endoluminal treatment for AAA has encouraged prophylactic intervention and fuelled the argument to screen for the disease. The feasibility of inserting an endoluminal graft is dependent on the morphology and growth characteristics of the aneurysm. This study used data from a randomized controlled trial of ultrasound screening for AAA in men aged 65-83 yr in Western Australia for the purpose of determining the norms of the living anatomy in the pressurized infrarenal aorta. Aims. To examine (1) the diameters of the infra-renal aorta in aneurysmal and non-aneurysmal cases, (2) the implications for treatment modalities, with particular reference to endoluminal grafting, which is most dependent on normal and aneurysmal morphology, and (3) any evidence to support the notion that northern Europeans are predisposed to aneurysmal disease. Methods. Using ultrasound, a randomized control trial was established in Western Australia to assess the value of a screening program in males aged 65-83 yr, The infra-renal aorta was defined as aneurysmal if the maximum diameter was 30 mm or more. Aortic diameter was modelled both as a continuous tin mm) and as a binary outcome variable, for those men who had an infra-renal diameter of 30 mm or more. ANOVA and linear regression were used for modelling aortic diameter as a continuum, while chi-square analysis and logistic regression were used in comparing men with and without the diagnosis of AAA. Findings. By December 1998, of 19.583 men had been invited to undergo ultrasound screening for AAA, 12.203 accepted the invitation (corrected response fraction 70.8%). The prevalence of AAA increased with age from 4.8% at 65 yr to 10.8% at 80 yr (chi (2) = 77.9, df = 3, P<0.001). The median (IQR) diameter for the non-aneurysmal group was 21.4 mm (3.3 mm) and there was an increase (<chi>(2) = 76.0, df = 1, P<0.001) in the diameter of the infra-renal aorta with age. Since 27 mm is the 95th centile for the non-aneurysmal infra-renal aorta, a diameter of 30 mm or more is justified as defining an aneurysm. The risk of AAA was higher in men of Australian (OR = 1.0) and northern European origin (OR = 1.0, 95%CL: 0.9. 1.2) compared with those of Mediterranean origin (OR = 0.5, 99%CL: 0.4, 0.7). Conclusion. Although screening has not yet been shown to reduce mortality from AAA. these population-based data assist the understanding of aneurysmal disease and the further development and use of endoluminal grafts for this condition. (C) 2001 Published by Elsevier Science Ltd on behalf of The International Society for Cardiovascular Surgery.

Porous clays and pillared clays-based catalysts. Part 2: A review of the catalytic and molecular sieve applications

Metal oxide pillared clay (PILC) possesses several interesting properties, such as large surface area, high pore volume and tunable pore size (from micropore to mesopore), high thermal stability, strong surface acidity and catalytic active substrates/metal oxide pillars. These unique characteristics make PILC an attractive material in catalytic reactions. It can be made either as catalyst support or directly used as catalyst. This paper is a continuous work from Kloprogge's review (J.T. Kloprogge, J. Porous Mater. 5, 5 1998) on the synthesis and properties of smectites and related PILCs and will focus on the diverse applications of clay pillared with different types of metal oxides in the heterogeneous catalysis area and adsorption area. The relation between the performance of the PILC and its physico-chemical features will be addressed.

Preface - Special issue on environmental toxicology of metals and metalloids

Following the Ninth International Congress of Toxicology (ICT-IX) and its satellite meeting ‘The International Conference on the Environmental Toxicology of Metals and Metalloids’ held in 2001 in Australia, a special issue on Arsenic was published in July 2002 (Toxicology Letters, 133(1), 1–120, 2002). We felt that it was timely to follow up with a special issue covering a wider range of metals and metalloids. Participants from the above conferences were invited to contribute to this special issue on ‘Environmental Toxicology of Metals and Metalloids’. This special issue consists of 11 manuscripts, representing up to date studies on a number of important harmful elements including aluminium, arsenic, cadmium, selenium, tin (tributyltin) and zinc. It illustrates the multidisciplinary nature of modern research in environmental toxicology involving chemical, biological and molecular technological approaches. It has been our great pleasure to produce this special issue. We would like to thank the authors for their contributions. We greatly appreciate the guidance and assistance provided by Dr J.P. Kehrer (Managing Editor), Dr Lulu Stader (Senior Publishing Editor) and their colleagues at Elsevier Science.

Combined in-fermenter extraction and cross-flow microfiltration for improved inclusion body processing

In this study we demonstrate a new in-fermenter chemical extraction procedure that degrades the cell wall of Escherichia coli and releases inclusion bodies (IBs) into the fermentation medium. We then prove that cross-flow microfiltration can be used to remove 91% of soluble contaminants from the released IBs. The extraction protocol, based on a combination of Triton X-100, EDTA, and intracellular T7 lysozyme, effectively released most of the intracellular soluble content without solubilising the IBs. Cross-flow microfiltration using a 0.2 mum ceramic membrane successfully recovered the granulocyte macrophagecolony stimulating factor (GM-CSF) IBs with removal of 91% of the soluble contaminants and virtually no loss of IBs to the permeate. The filtration efficiency, in terms of both flux and transmission, was significantly enhanced by infermenter Benzonase(R) digestion of nucleic acids following chemical extraction. Both the extraction and filtration methods exerted their efficacy directly on a crude fermentation broth, eliminating the need for cell recovery and re-suspension in buffer. The processes demonstrated here can all be performed using just a fermenter and a single cross-flow filtration unit, demonstrating a high level of process intensification. Furthermore, there is considerable scope to also use the microfiltration system to subsequently solubilise the IBs, to separate the denatured protein from cell debris, and to refold the protein using diafiltration. In this way refolded protein can potentially be obtained, in a relatively pure state, using only two unit operations. (C) 2004 Wiley Periodicals Inc.

An investigation of the microstructure/electrical conductivity relationship in In2O3-substituted LSGM

The effect of controlled In3+ substitution on to the B-site in the perovskite oxygen ion conductor La0.9Sr0.1Ga0.8Mg0.2O2.85 (LSGM) has been examined with a view to exploring the influence on oxygen ion conductivity. In combination with the electrical conductivity study, detailed microstructural analysis was used to verify the location of the substituting cation and to determine the nature of secondary phase formation. The indium species clearly substituted for Ga3+ on the B-site of the lattice and the electrical conductivity showed a gradual decrease as the In+3 content increased. The interpretation of this data was complicated by the formation of the secondary phases LaInO3 and LaSrGaO4. (C) 2001 Elsevier Science Ltd. All rights reserved.

The strain-driven pyrochlore to "defect fluorite" phase transition in rare earth sesquioxide stabilized cubic zirconias

The relationship between the ordering characteristic of the pyrochlore structure type and that characteristic of the defect fluorite structure type (immediately on either side of two phase regions separating the two structure types) in a range of rare eath sesquioxide stabilized cubic zirconias is investigated via electron diffraction and imaging. Systematic structural change as a function of composition and relative size of the constituent metal ions is highlighted and a multi-q to single-q = 1/2 [111]* model proposed for the observed pyrochlore to defect fluorite phase transition. Strain introduced into the close-packed {111} metal ion planes of the defect fluorite average structure by the local cation and oxygen vacancy distribution is pointed to as the likely origin of the observed behavior. (C) 2001 Academic Press

Can increasing the viscosity of formulations be used to reduce the human skin penetration of the sunscreen oxybenzone?

The effect of adding thickening agents on the penetration of a sunscreen benzophenone-3 through epidermal and a high-density polyethylene membrane was studied using both very thick (infinite dose) and thin tin use) applications. Contradictory results were obtained. Thickening agents retard skin penetration, in a manner consistent with a diffusional resistance in the formulation, when applied as an infinite dose. In contrast, when applied as in thin (in use) doses, thickening agents promote penetration, most likely through greater stratum corneum diffusivity arising from an enhanced hydration by the thicker formulations. The two key implications from this work are (i) a recognition of the danger in the potential extrapolation of infinite dosing to in use situations, and (ii) to recognize that thicker formulations may sometimes enhance the penetration of other topical agents when applied in use.

Quaternary continental weathering geochronology by laser-heating Ar-40/Ar-39 analysis of supergene cryptomelane

Incremental laser-heating analyses of supergene cryptomelane clusters extracted from three distinct weathering profiles from the Mary Valley region, southeast Queensland, Australia, yield reproducible and well-defined plateau ages ranging from 346 +/- 15 to 291 +/- 14 ka (2 a). Precipitation of supergene cryptomelane in this period implies that relative humid climate prevailed in southeast Queensland from 340 to 290 ha, a result consistent with oxygen isotope analyses of marine sediments from Ocean Drilling Program Site 820 and with regional pollen and spore records. These results, the first report on the precise Ar-40/Ar-39 dating of Quaternary supergene cryptomelane, indicate that Ar-40/Ar-39 analysis of pedogenic minerals provides a reliable geochronometer for the study of Quaternary surficial processes useful in the study of soil formation rates, continental paleoclimates, and archaeological sites devoid of datable volcanic minerals.

The effect of trace elements on the sintering of an Al-Zn-Mg-Cu alloy

Trace elements can have a significant effect on the processing and properties of aluminium alloys, including sintered alloys. As little as 0.07 wt% (100 ppm) lead, tin or indium promotes sintering in an Al-Zn-Mg-Cu alloy produced from mixed elemental powders. This is a liquid phase sintering system and thin liquid films form uniformly throughout the alloy in the presence of the trace elements, but liquid pools develop in their absence. Analytical transmission electron microscopy indicates that the trace elements are confined to the interparticle and grain boundary regions. The sintering enhancement is attributed to the segregation of the microalloying addition to the liquid-vapour interface. Because the microalloying elements have a low surface tension, they lower the effective surface tension of the liquid. This reduces the wetting angle and extends the spreading of the liquid through the matrix. An improvement in sintering results. (C) 2001 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

An XPS study of an isomorphous trivalent lanthanoid series

X-ray photoelectron spectroscopy has been used to investigate the core electron binding energies within an isomorphous series of lanthanoid complexes; [LnL(1)] where Ln=La-Lu (except Pm) and H3L is the heptadentate ligand 2,2',2-tris(salicylideneimino)triethylamine. This study also examines spin-orbit coupling of the trivalent lanthanoids bound to this organic ligand and addresses the issue of satellite peaks in the spectra. (C) 2002 Elsevier Science B.V. All rights reserved.

Investigations of growth processes in Y-Ba-Cu-O materials by microstructural examination of quenched samples

Y-Ba-Cu-O samples with additions of Y2O3 and CeO2 were quenched during seeded isothermal melt processing and examined by optical microscopy and scanning electron microscopy. Large YBa2Cu3O7-y (Y123) particles in the starting powder were found to form a distinct type of melt during heating, which was unaffected by the Y2O3 or CeO2 additives. This type of melt later formed regions with a low concentration of Y2BaCuO5 (Y211) particles in the Y123 matrix. The maximum growth rate of Y123 that could be sustained in the sample was found to be lower in the melt formed from large Y123 particles, and this may lead to growth accidents and subgrains in some samples.

Investigation of electrical conductivity as a function of dopant-ion radius in the systems Zr0.75Ce0.08M0.17O1.92 (M=Nd, Sm, Gd, Dy, Ho, Y, Er, Yb, Sc)

Electrical conductivity versus dopant ionic radius studies in zirconia- and ceria-based, solid oxide fuel cell (SOFC) electrolyte systems have shown that oxygen-ion conductivity is highest when the host and dopant ions are similar in size [J. Am. Ceram. Soc. 48 (1965) 286; Solid State Ionics 37 (1989) 67; Solid State Ionics 5 (1981) 547]. Under these conditions, it is thought that the conduction paths within the crystal lattice become less distorted [Solid State Ionics 8 (1983) 201]. In this study, binary ZrO2-M2O3 unit cells were expanded, via the partial substitution of Ce+4 for Zr+4 into the lattice, in an attempt to identify new, ternary, zirconia/ceria-based electrolyte systems with enhanced electrical conductivity. The compositions Zr0.75Ce0.08M0.17O1.92 (M = Nd, Sm, Gd, Dy, Ho, Y, Yb, Sc) were prepared using traditional solid state techniques. Bulk phase characterisation and precise lattice parameter measurements were performed with X-ray diffraction techniques. Four-probe DC conductivity measurements between 400 and 900 degreesC showed that the dopant-ion radius influenced electrical conductivity. The conductivity versus dopant-ion radius trends previously observed in zirconia-based, binary systems are clearly apparent in the ternary systems investigated in this study. The addition of ceria was found to have a negative influence on the electrical conductivity over the temperature range 400-900 degreesC. It is suggested that distortion of the oxygen-ion conduction path by the presence of the larger M+3 and Ce+4 species (relative to Zr+4) is the reason for the decreasing electrical conductivity as a function of increasing dopant size and ceria addition, respectively. (C) 2002 Elsevier Science B.V. All rights reserved.