Perturbed angular correlation study of Ta-181-doped PbTi1-xHfxO3 compounds

In this work, the hyperfine quadrupole interaction at Ta-doped PbTi1-xHfxO3 polycrystalline samples is studied for the first time. Powders with x=0.25, 0.50 and 0.75 were prepared and characterized by X-ray diffraction analysis. Perturbed Angular Correlation (PAC) analyses were done as a function of temperature, using low concentration Ta-181 nuclei as probes. In the ferroelectric and paraelectric phases of these compounds two sites were occupied by the probes. For each site the quadrupole frequency, asymmetry and relative distribution width parameters were obtained as a function of temperature above and below the Curie temperature (T-C). One of these sites was assigned to the regular Ti-Hf site, while the other one was assigned to some kind of defect. The behavior of the hyperfine parameters as a function of temperature was analyzed in terms of a recent published phase diagram and the presence of disorder below and above T-C. For the three compositions measured, the obtained hyperfine parameters present discontinuities which correspond to the ferroelectric-paraelectric phase transition. In both phases it was found broad frequency distributed interactions. The disorder in the electronic distribution would be responsible for the broad line width of the hyperfine interaction. (C) 2012 Elsevier B.V. All rights reserved.

Mapping strain exerted on blood vessel walls using deuterium double-quantum-filtered MRI

A technique is described for displaying distinct tissue layers of large blood vessel walls as well as measuring their mechanical strain. The technique is based on deuterium double-quantum-filtered (DQF) spectroscopic imaging. The effectiveness of the double-quantum filtration in suppressing the signal of bulk water is demonstrated on a phantom consisting of rat tail tendon fibers. Only intrafibrillar water is displayed, excluding all other signals of water molecules that reorient isotropically. One- and two-dimensional spectroscopic imaging of bovine aorta and coronary arteries show the characteristic DQF spectrum of each of the tissue layers. This property is used to obtain separate images of the outer layer, the tunica adventitia, or the intermediate layer, the tunica media, or both. To visualize the effect of elongation, the average residual quadrupole splitting <Δνq> is calculated for each pixel. Two-dimensional deuterium quadrupolar splitting images are obtained for a fully relaxed and a 55% elongated sample of bovine coronary artery. These images indicate that the strong effect of strain is associated with water molecules in the tunica adventitia whereas the DQF NMR signal of water in the tunica media is apparently strain-insensitive. After appropriate calibration, these average quadrupolar splitting images can be interpreted as strain maps.

Solid and liquid phase 59Co NMR studies of cobalamins and their derivatives

We describe the application of 59Co NMR to the study of naturally occurring cobalamins. Targets of these investigations included vitamin B12, the B12 coenzyme, methylcobalamin, and dicyanocobyrinic acid heptamethylester. These measurements were carried out on solutions and powders of different origins, and repeated at a variety of magnetic field strengths. Particularly informative were the solid-state central transition NMR spectra, which when combined with numerical line shape analyses provided a clear description of the cobalt coupling parameters. These parameters showed a high sensitivity to the type of ligands attached to the metal and to the crystallization history of the sample. 59Co NMR determinations also were carried out on synthetic cobaloximes possessing alkyl, cyanide, aquo, and nitrogenated axial groups, substituents that paralleled the coordination of the natural compounds. These analogs displayed coupling anisotropies comparable to those of the cobalamins, as well as systematic up-field shifts that can be rationalized in terms of their stronger binding affinity to the cobalt atom. Cobaloximes also displayed a higher regularity in the relative orientations of their quadrupole and shielding coupling tensors, reflecting a higher symmetry in their in-plane coordination. For the cobalamines, poor correlations were observed between the values measured for the quadrupole couplings in the solid and the line widths observed in the corresponding solution 59Co NMR resonances.

Collective effects in light scattering from cold strontium clouds

A cold atomic cloud is a versatile object, because it offers many handles to control and tune its properties. This facilitates studies of its behavior in various circumstances, such as sample temperature, size and density, composition, dimensionality and coherence time. The range of possible experiments is constrained by the specifications of the atomic species used. In this thesis presents the work done in the experiment for laser cooling of strontium atoms, focusing on its stability, which should provide cold and ultracold samples for the study of collective effects in light scattering. From the initial apparatus, innumerous changes were performed. The vacuum system got improved and now reached lower ultra high vacuum due to the pre-baking done to its parts and adding a titanium-sublimation stage. The quadrupole trap were improved by the design and construction of a new pair of coils. The stability of the blue, green and red laser systems and the loss prevention of laser light were improved, giving rise to a robust apparatus. Another important point is the development of homemade devices to reduce the costs and to be used as a monitor of different parts of an cold atoms experiment. From this homemade devices, we could demonstrate a dramatic linewidth narrowing by injection lock of an low cost 461 nm diode laser and its application to our strontium experiment. In the end, this improved experimental apparatus made possible the study of a new scattering effect, the mirror assisted coherent back-scattering (mCBS).

Excitations in Bose-Einstein condensates: collective modes, quantum turbulence and matter wave statistics

In this thesis, we present the generation and studies of a 87Rb Bose-Einstein condensate (BEC) perturbed by an oscillatory excitation. The atoms are trapped in a harmonic magnetic trap where, after an evaporative cooling process, we produce the BEC. In order to study the effect caused by oscillatory excitations, a quadrupole magnetic field time oscillatory is superimposed to the trapping potential. Through this perturbation, collective modes were observed. The dipole mode is excited even for low excitation amplitudes. However, a minimum excitation energy is needed to excite the condensate quadrupole mode. Observing the excited cloud in TOF expansion, we note that for excitation amplitude in which the quadrupole mode is excited, the cloud expands without invert its aspect ratio. By looking these clouds, after long time-of-flight, it was possible to see vortices and, sometimes, a turbulent state in the condensed cloud. We calculated the momentum distribution of the perturbed BECs and a power law behavior, like the law to Kolmogorov turbulence, was observed. Furthermore, we show that using the method that we have developed to calculate the momentum distribution, the distribution curve (including the power law exponent) exhibits a dependence on the quadrupole mode oscillation of the cloud. The randomness distribution of peaks and depletions in density distribution image of an expanded turbulent BEC, remind us to the intensity profile of a speckle light beam. The analogy between matter-wave speckle and light speckle is justified by showing the similarities in the spatial propagation (or time expansion) of the waves. In addition, the second order correlation function is evaluated and the same dependence with distance was observed for the both waves. This creates the possibility to understand the properties of quantum matter in a disordered state. The propagation of a three-dimensional speckle field (as the matter-wave speckle described here) creates an opportunity to investigate the speckle phenomenon existing in dimensions higher than 2D (the case of light speckle).

A systematic study on the influence of carbon on the behavior of hard-to-ionize elements in inductively coupled plasma–mass spectrometry

A systematic study on the influence of carbon on the signal of a large number of hard-to-ionize elements (i.e. B, Be, P, S, Zn, As, Se, Pd, Cd, Sb, I, Te, Os, Ir, Pt, Au, and Hg) in inductively coupled plasma–mass spectrometry has been carried out. To this end, carbon matrix effects have been evaluated considering different plasma parameters (i.e. nebulizer gas flow rate, r.f. power and sample uptake rate), sample introduction systems, concentration and type of carbon matrix (i.e. glycerol, citric acid, potassium citrate and ammonium carbonate) and type of mass spectrometer (i.e. quadrupole filter vs. double-focusing sector field mass spectrometer). Experimental results show that P, As, Se, Sb, Te, I, Au and Hg sensitivities are always higher for carbon-containing solutions than those obtained without carbon. The other hard-to-ionize elements (Be, B, S, Zn, Pd, Cd, Os, Ir and Pt) show no matrix effect, signal enhancement or signal suppression depending on the experimental conditions selected. The matrix effects caused by the presence of carbon are explained by changes in the plasma characteristics and the corresponding changes in ion distribution in the plasma (as reflected in the signal behavior plot, i.e. the signal intensity as a function of the nebulizer gas flow rate). However, the matrix effects for P, As, Se, Sb, Te, I, Au and Hg are also related to an increase in analyte ion population caused as a result of charge transfer reactions involving carbon-containing charged species in the plasma. The predominant specie is C+, but other species such as CO+, CO2+, C2+ and ArC+ could also play a role. Theoretical data suggest that B, Be, S, Pd, Cd, Os, Ir and Pt could also be involved in carbon based charge transfer reactions, but no experimental evidence substantiating this view has been found.

Chemical composition of glauconite and montmorillonite group minerals from sediments and rocks of the Norwegian Sea

Two quadrupole splitting doublets with delta E_q = 0.74 and 1.62 mm/s were found in the montmorillonite spectra. The more intense doublet corresponds to iron in a somewhat distorted tetrahedral coordination, while the less intense corresponds to quadri-coordinated iron. The EPR spectrum also exhibits two lines with a q-factor of 3 and 4.3, which corresponds to transformed minerals.

Chemical and isotopic compositions of hydrothermal manifestations and minerals from the Broken Spur hydrothermal field

A representative collection of hydrothermal manifestations was sampled practically from all hydrothermal mounds of the Broken Spur hydrothermal vent field with use of the Mir manned submersibles during three cruises of R/V Akademik Mstislav Keldysh. Mineral associations characteristic for different morphological types of sulfide ores from hydrothermal pipes, plates, and diffusers are assessed. Particular attention is paid to distribution of minor elements and their distribution patterns determined by mineralogical zonation. Measured isotopic composition of sulfur in sulfide minerals varies from 0.4 to 5.2 per mil that indicates their similarity with ores from the Snake Pit vent field and is related to dilution of hot ore-bearing solutions by seawater and reduction of water sulfate ions to H2S with heavy isotopic composition.

Mössbauer study at DSDP Hole 95-612

57Fe Mössbauer spectra of 15 oceanic sediment samples collected from Site 612 (Deep Sea Drilling Project Leg 95) were recorded. These spectra showed that most of the iron in the sediments was present as high-spin, paramagnetic Fe2+ and Fe3+. The ferrous iron was mainly distributed in terrigenous clays and biogenic carbonates. The variation of the Mössbauer parameters for Fe2+ with sub-bottom depth suggests that the main Fe2+-bearing component changed with geologic time. The amount of iron in each iron-bearing phase as estimated from the corresponding peak areas in the spectra also changed with depth. These variations in the Mössbauer parameters and peak areas are correlated with lithologic changes in the sediment column.

Application of density functional theory to equilibrium adsorption of argon and nitrogen on amorphous silica surface

We present a new version of non-local density functional theory (NL-DFT) adapted to description of vapor adsorption isotherms on amorphous materials like non-porous silica. The novel feature of this approach is that it accounts for the roughness of adsorbent surface. The solid–fluid interaction is described in the same framework as in the case of fluid–fluid interactions, using the Weeks–Chandler–Andersen (WCA) scheme and the Carnahan–Starling (CS) equation for attractive and repulsive parts of the Helmholtz free energy, respectively. Application to nitrogen and argon adsorption isotherms on non-porous silica LiChrospher Si-1000 at their boiling points, recently published by Jaroniec and co-workers, has shown an excellent correlative ability of our approach over the complete range of pressures, which suggests that the surface roughness is mostly the reason for the observed behavior of adsorption isotherms. From the analysis of these data, we found that in the case of nitrogen adsorption short-range interactions between oxygen atoms on the silica surface and quadrupole of nitrogen molecules play an important role. The approach presented in this paper may be further used in quantitative analysis of adsorption and desorption isotherms in cylindrical pores such as MCM-41 and carbon nanotubes.

Kinetics of reduction of FeO from slag by graphite and coal chars

The rates of reduction of FeO from iron-saturated FeO-CaO-Al2O3-SiO2 slags by graphite, coke, bituminous coal and anthracitic coal chars at temperatures in the range 1 673-1873 K have been measured using a sessile drop technique. The extents of reaction were determined using EPMA analysis of quenched samples, and on line gas analysis using a quadrupole mass spectrometer. The reaction rates have been shown to be dependent critically on carbon type. For the reaction geometry used in this investigation the reduction rates of graphite and coke are observed to be faster than with coal chars. This unexpected finding is shown to be associated with differences in the dominant chemical and mass transfer mechanisms occurring at the reaction interface. High reaction rates are observed to occur with the formation of liquid Fe-C alloy product and the associated gasification of carbon from the alloy. The rates of reduction by coal chars are determined principally by the chemical reaction at the carbon/gas interface and slag phase mass transfer.

Direct quantification of rare earth element concentrations in natural waters by ICP-MS

A direct quadrupole ICP-MS technique has been developed for the analysis of the rare earth elements and yttrium in natural waters. The method has been validated by comparison of the results obtained for the river water reference material SLRS-4 with literature values. The detection limit of the technique was investigated by analysis of serial dilutions of SLRS-4 and revealed that single elements can be quantified at single-digit fg/g concentrations. A coherent normalised rare earth pattern was retained at concentrations two orders of magnitude below natural concentrations for SLRS-4, demonstrating the excellent inter-element accuracy and precision of the method. The technique was applied to the analysis of a diluted mid-salinity estuarine sample, which also displayed a coherent normalised rare earth element pattern, yielding the expected distinctive marine characteristics. (c) 2006 Published by Elsevier Ltd.

The behaviour of the rare earth elements during estuarine mixing-revisited

Complete rare earth element (except Eu) and Y concentrations from the estuarine mixing zone (salinity =0.2 to 33) of Elimbah Creek, Queensland, Australia, were measured by quadrupole ICP-MS without preconcentration. High sampling density in the low salinity regime along with high quality data allow accurate tracing of the development of the typical marine rare earth element anomalies as well as Y/Ho fractionation. Over the entire estuary, the rare earth elements are strongly removed relative to a freshwater endmember (60-80% removal). This large overall removal occurs despite a strong remineralisation peak (190% for La, 130% for Y relative to the freshwater endmember) in the mid-salinity zone. Removal and remineralisation are accompanied by fractionation of the original (freshwater) rare earth element pattern, resulting in light rare earth element depletion. Estuarine fractionation generates a large positive La anomaly and a superchondritic Y/Ho ratio. Conversely, we observe no evidence to support the generation of the negative Ce anomaly in the estuary. With the exception of Ce, the typical marine rare earth element features can thus be attributed to estuarine mixing processes. The persistence of these features in hydrogenous sediments for at least 3.71 Ga highlights the importance of estuarine processes for marine chemistry on geological timescales. (c) 2005 Elsevier B.V. All rights reserved.

Surface studies in ultra high vacuum

An ultra high vacuum system capable of attaining pressures of 10-12 mm Hg was used for thermal desorption experiments. The metal chosen for these experiments was tantalum because of its suitability for thermal desorption experiments and because relatively little work has been done using this metal. The gases investigated were carbon monoxide, hydrogen and ethylene. The kinetic and thermodynamic parameters relating to the desorption reaction were calculated and the values obtained related to the reaction on the surface. The thermal desorption reaction was not capable of supplying all the information necessary to form a complete picture of the desorption reaction. Further information was obtained by using a quadrupole mass spectrometer to analyse the desorbed species. The identification of the desorbed species combined with the value of the desorption parameters meant that possible adatom structures could be postulated. A combination of these two techniques proved to be a very powerful tool when investigating gas-metal surface reactions and gave realistic values for the measured parameters such as the surface coverage, order of reaction, the activation energy and pre-exponential function for desorption. Electron microscopy and X-ray diffraction were also used to investigate the effect of the gases on the metal surface.