Coherent tunnelling in Cu2+- and Ag2+-doped MgO and CaO: Cu2+ explored through ab initio calculations

The observation of coherent tunnelling in Cu2+ - and Ag2+ -doped MgO and CaO:Cu2+ was a crucial discovery in the realm of the Jahn-Teller (JT) effect. The main reasons favoring this dynamic behavior are now clarified through ab initio calculations on Cu2+ - and Ag2+ -doped cubic oxides. Small JT distortions and an unexpected low anharmonicity of the eg JT mode are behind energy barriers smaller than 25 cm-1 derived through CASPT2 calculations for Cu2+ - and Ag2+ -doped MgO and CaO:Cu2+ . The low anharmonicity is shown to come from a strong vibrational coupling of MO610- units (M=Cu,Ag) to the host lattice. The average distance between the d9 impurity and ligands is found to vary significantly on passing from MgO to SrO following to a good extent the lattice parameter.

Ion-beam induced oxidation of GaAs and AlGaAs

The oxidation of GaAs and AlxGa1−xAs targets by oxygen irradiation has been studied in detail. It was found that the oxidation process is characterized by the strong preferential oxidation of Al as compared to Ga, and of Ga as compared to As. This experimental observation, which has been accurately quantified by using x‐ray photoelectron spectroscopy, is connected to the different heats of formation of the corresponding oxides. The oxide grown by ion beam oxidation shows a strong depletion in As and relatively low oxidation of As as well. The depletion can be associated with the preferential sputtering of the As oxide in respect to other compounds whereas the low oxidation is due to the low heat of formation. In contrast Al is rapidly and fully oxidized, turning the outermost layer of the altered layer to a single Al2O3 overlayer, as observed by transmission electron microscopy. The radiation enhanced diffusion of oxygen and aluminum in the altered layer explains the large thickness of these altered layers and the formation of Al oxides on top of the layers. For the case of ion‐beam oxidation of GaAs a simulation program has been developed which describes adequately the various growth mechanisms experimentally observed

The use of heterogeneous chemistry for the characterization of functional groups at the gas/particle interface of soot and TiO(2) nanoparticles

Six gases (N((CH3)3), NH2OH, CF3COOH, HCl, NO2, O3) were selected to probe the surface of seven combustion aerosol (amorphous carbon, flame soot) and three types of TiO2 nanoparticles using heterogeneous, that is gas-surface reactions. The gas uptake to saturation of the probes was measured under molecular flow conditions in a Knudsen flow reactor and expressed as a density of surface functional groups on a particular aerosol, namely acidic (carboxylic) and basic (conjugated oxides such as pyrones, N-heterocycles) sites, carbonyl (R1-C(O)-R2) and oxidizable (olefinic, -OH) groups. The limit of detection was generally well below 1% of a formal monolayer of adsorbed probe gas. With few exceptions most investigated aerosol samples interacted with all probe gases which points to the coexistence of different functional groups on the same aerosol surface such as acidic and basic groups. Generally, the carbonaceous particles displayed significant differences in surface group density: Printex 60 amorphous carbon had the lowest density of surface functional groups throughout, whereas Diesel soot recovered from a Diesel particulate filter had the largest. The presence of basic oxides on carbonaceous aerosol particles was inferred from the ratio of uptakes of CF3COOH and HCl owing to the larger stability of the acetate compared to the chloride counterion in the resulting pyrylium salt. Both soots generated from a rich and a lean hexane diffusion flame had a large density of oxidizable groups similar to amorphous carbon FS 101. TiO2 15 had the lowest density of functional groups among the three studied TiO2 nanoparticles for all probe gases despite the smallest size of its primary particles. The used technique enabled the measurement of the uptake probability of the probe gases on the various supported aerosol samples. The initial uptake probability, g0, of the probe gas onto the supported nanoparticles differed significantly among the various investigated aerosol samples but was roughly correlated with the density of surface groups, as expected. [Authors]

Boron adsorption in soils from the State of São Paulo, Brazil

Boron adsorption was studied in five representative soils (Rhodic Hapludox, Arenic Paleudalf and three Typic Hapludox) from the State of São Paulo, Brazil. Adsorption was higher in the clayey Oxisols, followed by the Alfisol and the coarser Oxisols. Calcium carbonate promoted an increase in the amount of adsorbed boron in all soils, with the most pronounced effect in the coarser-textured Oxisols. High correlation coefficients were found between adsorbed boron and clay and amorphous aluminum oxide contents and specific surface area (r = 0.79, 0.76 and 0.73, respectively, p < 0.01). Clay content, free aluminum oxide, and hot CaCl2 (0.01 mol L-1)-extracted boron explained 93% of the variation of adsorbed boron. Langmuir and Freundlich isotherms fitted well to the adsorbed data, and highest values for maximum boron adsorption were found in clayey soils, which were significantly correlated with contents of total, free and amorphous iron and aluminum oxides, as well with the physical attributes. Ninety four percent of the variation in the maximum adsorption could be related to the free iron content.

Differentiated chemical reactivity of nanoparticles toward DTT

RATIONALE: Induction of oxidative stress and impairment of the antioxidant defense are considered important biological responses following nanoparticle (NP) exposure. The acellular in vitro dithiothreitol (DTT) assay is proposed to measure the oxidative potential of NP. In addition, DTT can be considered as a model compound of sulfur containing antioxidants. The objective of this work is to evaluate the surface reactivity in solution of a NP panel toward DTT. METHOD: The NP panel was composed of four carbonaceous particles, six types of metal oxides and silver with primary size ranged from 7 to 300 nm. Suspensions were prepared in surfactant solution with 30 min sonication. DTT was used as reductant to evaluate the oxidative properties of the different NP. The determination of the NP ability to catalyze electron transfer from DTT to oxygen was carried out as described in Sauvain et al., Nanotoxicology, 2008, 2:3, 121−129. RESULTS: All the carbonaceous NP catalyzed the oxidation of DTT by oxygen following the mass based order: carbon black > diesel exhaust particle > nanotubes > fullerene. A contrasting reactivity was observed for the metallic NP. Except for nickel oxide and metallic silver, which reacted similarly to the carbonaceous NP, all other metal oxides hindered the oxidation of DTT by oxygen, with ZnO being the most effective one. CONCLUSIONS : DTT was stabilized against oxidation in the presence of metal oxide NP in the solution. This suggests that different chemical interactions take place compared with carbonaceous NP. To explain these differences, we hypothesize that DTT could form complexes with the metal oxide surface (or dissolved metal ions), rendering it less susceptible to oxidation. By analogy, such a process could be thought to apply in biological systems with sulfur−containing antioxidants, reducing their buffer capacity. Such NP could thus contribute to oxidative stress by an alternative mechanism.

High Molecular Weight Methacrylate Sealing of a Bridge Deck, HR-2031, 1988

The Iowa Department of Transportation used a high molecular weight methacrylate (HMWM) resin to seal a 3,340 ft. x 64 ft. bridge deck in October 1986. The sealing was necessary to prevent deicing salt brine from entering a substantial number of transverse cracks that coincided with the epoxy coated top steel and unprotected bottom steel. HMWM resin is a three component product composed of a monomer, a cumene hydroperoxide initiator and a cobalt naphthenate promoter. The HMWM was applied with a dual spray bar system and flat-fan nozzles. Initiated monomer delivered through one spray bar was mixed in the air with promoted monomer from the other spray bar. The application rate averaged 0.956 gallons per 100 square feet for the tined textured driving lanes. Dry sand was broadcast on the surface at an average coverage of 0.58 lbs. per square yard to maintain friction. Coring showed that the HMWM resin penetrated the cracks more than two inches deep. Testing of the treated deck yielded Friction Numbers averaging 33 with a treaded tire compared to 36 prior to treatment. An inspection soon after treatment found five leaky cracks in one of the 15 spans. One inspection during a steady rain showed no leakage, but leakage from numerous cracks occurred during a subsequent rain. A second HMWM application was made on two spans. Leakage through the double application occurred during a rain. Neither the single or double application were successful in preventing leakage through the cracks.

Igneous layering, fractional crystallization and growth of granitic plutons: The Dolbel batholith in SW Niger

This study reassesses the development of compositional layering during the growth of granitic plutons, with emphasis on fractional crystallization and its interaction with both injection and inflation-related deformation. The Dolbel batholith (SW Niger) consists of 14, kilometre-sized plutons emplaced by pulsed magma inputs. Each pluton has a coarse-grained core and a peripheral layered series. Rocks consist of albite (An(<= 11)), K-feldspar (Or(96 99), Ab(1) (4)), quartz, edenite (X(Mg)=0337-0.55), augite (X(Mg)=0.65-0.72) and accessories (apatite, titanite and Fe-Ti-oxides). Whole-rock compositions are metaluminous, sodic (K(2)O/Na(2)O=0.49-0.62) and iron-rich [FeO(tot)/(FeO(tot)+MgO)=0.65-0.82]. The layering is present as size-graded and modally graded, sub-vertical, rhythmic units. Each unit is composed of three layers, which are, towards the interior: edenite +/- plagioclase (C(a/p)), edenite+plagioclase+augite+quartz (C(q)), and edenite+plagioclase+augite+quartz+K-feldspar (C(k)). All phases except quartz show zoned microstructures consisting of external intercumulus overgrowths, a central section showing oscillatory zoning and, in the case of amphibole and titanite, complexly zoned cores. Ba and Sr contents of feldspars decrease towards the rims. Plagioclase crystal size distributions are similar in all units, suggesting that each unit experienced a similar thermal history. Edenite, characteristic of the basal C(a/p) layer, is the earliest phase to crystallize. Microtextures and phase diagrams suggest that edenite cores may have been brought up with magma batches at the site of emplacement and mechanically segregated along the crystallized wall, whereas outer zones of the same crystals formed in situ. The subsequent C(q) layers correspond to cotectic compositions in the Qz-Ab-Or phase diagram at P(H2O)=5 kbar. Each rhythmic unit may therefore correspond to a magma batch and their repetition to crystallization of recurrent magma recharges. Microtextures and chemical variations in major phases allow four main crystallization stages to be distinguished: (1) open-system crystallization in a stirred magma during magma emplacement, involving dissolution and overgrowth (core of edenite and titanite crystals); (2) in situ fractional crystallization in boundary layers (C(a/p) and C(q) layers); (3) equilibrium `en masse' eutectic crystallization (C(k) layers); (4) compaction and crystallization of the interstitial liquid in a highly crystallized mush (e. g. feldspar intercumulus overgrowths). It is concluded that the formation of the layered series in the Dolbel plutons corresponds principally to in situ differentiation of successive magma batches. The variable thickness of the Ck layers and the microtextures show that crystallization of a rhythmic unit stops and it is compacted when a new magma batch is injected into the chamber. Therefore, assembly of pulsed magma injections and fractional crystallization are independent, but complementary, processes during pluton construction.

The use of micro-XRD for the study of glaze color decorations

The compounds responsible for the colours and decorations in glass and glazed ceramics include: colouring agents (transition metal ions), pigments (micro-and nano-precipitates of compounds that either do not dissolve or recrystallize in the glassy matrix) and opacifiers (microcrystalline compounds with high light scattering capability). Their composition, structure and range of stability are highly dependent not only on the composition but also on the procedures followed to obtain them. Chemical composition of the colorants and crystallites may be obtained by means of SEM-EDX and WDX. Synchrotron Radiation micro-X-ray Diffraction has a small beam size adequate (10 to 50 microns footprint size) to obtain the structural information of crystalline compounds and high brilliance, optimal for determining the crystallites even when present in low amounts. In addition, in glass decorations the crystallites often appear forming thin layers (from 10 to 100 micrometers thick) and they show a depth dependent composition and crystal structure. Their nature and distribution across the glass/glazes decorations gives direct information on the technology of production and stability and may be related to the color and appearance. A selection of glass and glaze coloring agents and decorations are studied by means of SR-micro- XRD and SEM-EDX including: manganese brown, antimony yellow, red copper lusters and cobalt blue. The selection includes Medieval (Islamic, and Hispano Moresque) and renaissance tin glazed ceramics from the 10th to the 17th century AD.

Human inhalation exposure to iron oxide particles

In the past decade, many studies have been conducted to determine the health effects induced by exposure to engineered nanomaterials (NMs). Specifically for exposure via inhalation, numerous in vitro and animal in vivo inhalation toxicity studies on several types of NMs have been published. However, these results are not easily extrapolated to judge the effects of inhaling NMs in humans, and few published studies on the human response to inhalation of NMs exist. Given the emergence of more industries utilizing iron oxide nanoparticles as well as more nanomedicine applications of superparamagnetic iron oxide nanoparticles (SPIONs), this review presents an overview of the inhalation studies that have been conducted in humans on iron oxides. Both occupational exposure studies on complex iron oxide dusts and fumes, as well as human clinical studies on aerosolized, micron-size iron oxide particles are discussed. Iron oxide particles have not been described to elicit acute inhalation response nor promote lung disease after chronic exposure. The few human clinical studies comparing inhalation of fine and ultrafine metal oxide particles report no acute changes in the health parameters measured. Taken together existing evidence suggests that controlled human exposure to iron oxide nanoparticles, such as SPIONs, could be conducted safely.

The fixation of the cemented femoral component. Effects of stem stiffness, cement thickness and roughness of the cement-bone surface.

After cemented total hip arthroplasty (THA) there may be failure at either the cement-stem or the cement-bone interface. This results from the occurrence of abnormally high shear and compressive stresses within the cement and excessive relative micromovement. We therefore evaluated micromovement and stress at the cement-bone and cement-stem interfaces for a titanium and a chromium-cobalt stem. The behaviour of both implants was similar and no substantial differences were found in the size and distribution of micromovement on either interface with respect to the stiffness of the stem. Micromovement was minimal with a cement mantle 3 to 4 mm thick but then increased with greater thickness of the cement. Abnormally high micromovement occurred when the cement was thinner than 2 mm and the stem was made of titanium. The relative decrease in surface roughness augmented slipping but decreased debonding at the cement-bone interface. Shear stress at this site did not vary significantly for the different coefficients of cement-bone friction while compressive and hoop stresses within the cement increased slightly.

The Role of Magnesium in Concrete Deterioration, HR-355, Appendix, 1994

In the main report concerning the role that magnesium may have in highway concrete aggregate, over 20,000 electron microprobe data were obtained, primarily from automated scans, or traverses, across dolomite aggregate grains and the adjacent cement paste. Representative traverses were shown in figures and averages of the data were presented in Table II. In this Appendix, detailed representative and selected analyses of carbonate aggregate only are presented. These analyses were not presented in the main report because they would be interesting to only a few specialists in dolomite· rocks. In this Appendix, individual point analyses of mineral compositions in the paste have been omitted along with dolomite compositions at grain boundaries and cracks. Clay minerals and quartz inclusions in the aggregate are also not included. In the analyses, the first three column headings from left to right show line number, x-axis, and y-axis (Line number is an artifact of the computer print-out for each new traverse. Consecutive line numbers indicate a continuous traverse with distances between each point of 1.5 to a few μ-m. X-axis and y-axis are coordinates on the electron microscope stage). The next columns present weight percent oxide content of FeO, K20, CaO, Si02, Al203, MgO, SrO, BaO, MnO, Na20, and C02 (calculated assuming the number of moles of C02 is equal to the sum of moles of oxides, chiefly CaO and MgO), TOTAL (the sum of all oxides), and total (sum of all oxides excluding COi). In many of the analyses total is omitted.

Compositional influence on the electrical performance of zinc indium tin oxide transparent thin-film transistors

In this work, zinc indium tin oxide layers with different compositions are used as the active layer of thin film transistors. This multicomponent transparent conductive oxide is gaining great interest due to its reduced content of the scarce indium element. Experimental data indicate that the incorporation of zinc promotes the creation of oxygen vacancies. In thin-film transistors this effect leads to a higher threshold voltage values. The field-effect mobility is also strongly degraded, probably due to coulomb scattering by ionized defects. A post deposition annealing in air reduces the density of oxygen vacancies and improves the fieldeffect mobility by orders of magnitude. Finally, the electrical characteristics of the fabricated thin-film transistors have been analyzed to estimate the density of states in the gap of the active layers. These measurements reveal a clear peak located at 0.3 eV from the conduction band edge that could be attributed to oxygen vacancies.

Selective ablation of photovoltaic materials with UV laser sources for monolithic interconnection of devices based on a-Si:H

Lasers are essential tools for cell isolation and monolithic interconnection in thin-film-silicon photovoltaic technologies. Laser ablation of transparent conductive oxides (TCOs), amorphous silicon structures and back contact removal are standard processes in industry for monolithic device interconnection. However, material ablation with minimum debris and small heat affected zone is one of the main difficulty is to achieve, to reduce costs and to improve device efficiency. In this paper we present recent results in laser ablation of photovoltaic materials using excimer and UV wavelengths of diode-pumped solid-state (DPSS) laser sources. We discuss results concerning UV ablation of different TCO and thin-film silicon (a-Si:H and nc-Si:H), focussing our study on ablation threshold measurements and process-quality assessment using advanced optical microscopy techniques. In that way we show the advantages of using UV wavelengths for minimizing the characteristic material thermal affection of laser irradiation in the ns regime at higher wavelengths. Additionally we include preliminary results of selective ablation of film on film structures irradiating from the film side (direct writing configuration) including the problem of selective ablation of ZnO films on a-Si:H layers. In that way we demonstrate the potential use of UV wavelengths of fully commercial laser sources as an alternative to standard backscribing process in device fabrication.