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Temperature Dependence of the Absolute Third-order Rate Constant for the Reaction between Na + O₂ + N₂ over the Range 571 - 1016 K Studied by Time-resolved Atomic Resonance Absorption Spectroscopy

Description: Article on temperature dependence of the absolute third-order rate constant for the reaction between Na + O₂ + N₂ over the range 571-1016 K studied by time-resolved atomic resonance absorption spectroscopy.
Date: 1985
Creator: Husain, David; Marshall, Paul & Plane, John M. C.
Partner: UNT College of Arts and Sciences

In situ X-ray absorption fine structure studies of a manganese dioxide electrode in a rechargeable MnO{sub 2}/Zn alkaline battery environment

Description: Electronic and structural aspects of a MnO{sub 2} electrode in a rechargeable MnO{sub 2}/Zn battery environment have been investigated by in situ Mn K-edge X-ray absorption fine structure (XAFS). The relative amplitudes of the three major Fourier transform shells of the EXAFS (extended XAFS) function of the rechargeable MnO{sub 2} electrode in the undischarged state were found to be similar to those found for ramsdellite, a MnO{sub 2} polymorph with substantial corner-sharing linkages among the basic MnO{sub 6} octahedral units. The analyses of the background-subtracted pre-edge peaks and absorption edge regions for the nominally 1-e{sup {minus}} discharged electrode were consistent with Mn{sup 3+} as being the predominant constituent species, rather than a mixture of Mn{sup 4+} and Mn{sup 2+} sites. Furthermore, careful inspection of both the XANES (X-ray absorption near edge structure) and EXAFS indicated that the full recharge of MnO, which had been previously discharged either by a 1- or 2-equivalent corner-sharing linkages compared to the original undischarged MnO{sub 2}.
Date: December 31, 1996
Creator: Mo, Y.; Hu, Y.; Bae, I.T.; Miller, B.; Scherson, D.A. & Antonio, M.R.
Partner: UNT Libraries Government Documents Department

Remote detection of chemicals by millimeter-wave spectroscopy

Description: This paper discusses the development and field testing of a remote chemical detection system that is based on millimeter-wave (mm-wave) spectroscopy. The mm-wave system is a monostatic swept-frequency radar that consists of a mm-wave sweeper, a hot-electron-bolometer detector, and a trihedral reflector. The chemical plume to be detected is situated between the transmitter/detector and the reflector. Millimeter-wave absorption spectra of chemicals in the plume are determined by measuring the swept-frequency radar return signals with and without the plume in the beam path. The problem of pressure broadening, which hampered open-path spectroscopy in the past, has been mitigated in this work by designing a fast sweeping source over a broad frequency range. The heart of the system is a Russian backward-wave oscillator (BWO) tube that can be tuned over 225--315 GHz. A mm-wave sweeper that includes the BWO tube was built to sweep the entire frequency range within 10 ms. The radar system was field-tested at the DOE Nevada Test Site at a standoff distance of 60 m. Methyl chloride was released from a wind tunnel that produced a 2-m diameter plume at its exit point. The mm-wave system detected methyl chloride plumes down to a concentration of 12 ppm. The measurement results agree well with model-fitted data. Remote or standoff sensing of airborne chemicals is gaining importance for arms control and treaty verification, intelligence collection, and environmental monitoring.
Date: September 1, 1998
Creator: Gopalsami, N. & Raptis, A.C.
Partner: UNT Libraries Government Documents Department

Plasma-surface interactions with ICRF antennas and lower hybrid grills in Tore Supra

Description: The edge plasma interactions of the actively cooled radio-frequency heating launchers in Tore Supra- ion-cyclotron range-of-frequencies (ICRF) antennas and lower-hybrid (LH) grills-are studied using infrared video imaging. On the two-strap ICRF antennas, operated in fast-wave electron heating or current drive mode, hot spots with temperatures of 500-900{degrees} C are observed by the end of 2-s power pulses of 2 MW per antenna. The distribution and maximum values of temperature are determined principally by the relative phase of the two antenna straps: dipole (heating) phasing results in significantly less antenna heating than does 90` (current drive) phasing. Transient heat fluxes of 1-20 MW/m{sup 2} are measured on the lateral protection bumpers at ICRF turn-on; these fluxes are primarily a function of plasma and radio frequency (rf) control, and are not simply correlated with the strap phasing or the final surface temperature distributions. The remarkable feature of the lower hybrid edge interaction is the production of beams of heat flux in front of the grills; these beams propagate along the helical magnetic field lines and can deliver fluxes of 5-10 MW/m{sup 2} over areas of several cm{sup 2} to plasma-facing components such as the grill or antenna lateral bumpers. Both the ICRF and LH phenomena appear to result from the acceleration of particles by the near fields of the launchers. Modeling of the heat flux deposition on components and its relation to sputtering processes is presented, and possibilities for controlling these interactions are discussed.
Date: October 1, 1996
Creator: Harris, J.H.; Hutter, T. & Hogan, J.T.
Partner: UNT Libraries Government Documents Department

Calcium EXAFS establishes the Mn-Ca cluster in the oxygen-evolving complex of Photosystem II

Description: The proximity of Ca to the Mn cluster of the photosynthetic water-oxidation complex is demonstrated by X-ray absorption spectroscopy. We have collected EXAFS data at the Ca K-edge using active PS II membrane samples that contain approximately 2 Ca per 4 Mn. These samples are much less perturbed than previously investigated Sr-substituted samples, which were prepared subsequent to Ca depletion. The new Ca EXAFS clearly shows backscattering from Mn at 3.4 angstroms, a distance that agrees with that surmised from previously recorded Mn EXAFS. This result is also consistent with earlier related experiments at the Sr K-edge, using samples that contained functional Sr, that show Mn is {approx}; 3.5 angstroms distant from Sr. The totality of the evidence clearly advances the notion that the catalytic center of oxygen evolution is a Mn-Ca heteronuclear cluster.
Date: August 2, 2002
Creator: Cinco, Roehl M.; McFarlane Holman, Karen L.; Robblee, John H.; Yano, Junko; Pizarro, Shelly A.; Bellacchio, Emanuele et al.
Partner: UNT Libraries Government Documents Department

Target induced, turbulence-modulated speckle noise

Description: Many papers on DIAL for remote sensing have been devoted to the averaging properties of speckle noise from diffuse-target returns; i.e., how many (N) return pulses can be averaged before the I/N reduction in signal variance expected from uncorrelated noise fails. An apparent limit of about 100 pulses or fewer has been the most important factor in determining the accuracy of DIAL measurements using diffusely-scattering targets in the field. The relevant literature is briefly reviewed, and various explanations for the apparent limit are summarized. Recent speckle experiments at LLNL`s Site 300 may suggest that the limit of {approximately}100 pulses is not fundamental. The speckle experiments very clearly show that the limit on signal averaging in this data was the result of long-term ({approximately}1 minute) drifts in the signal returns rather than of any more subtle statistical properties. The long-term drifts are completely removed to the useful limits of the data sets by working with the log-ratio of adjacent pulses. This procedure is analogous (but not identical) to processing the log-ratios of the powers at different wavelengths in a multi-line DIAL system. We think the Site 300 data therefore suggests that as long as the laser system is constructed to ensure that any long-term drifts are identical among the transmitted wavelengths, the log-ratio of the individual returns will provide a data set that does usefully average over a large number of pulses.
Date: July 1, 1994
Creator: Scharlemann, E.T.
Partner: UNT Libraries Government Documents Department

Ceramic catalyst materials

Description: This project focuses on the modification of silica and alumina surfaces by titania and hydrous titanium oxide ion-exchange films, and the use of these modified materials as supports for MoS{sub 2} catalysts. FTIR studies of molybdena interaction with {gamma}-Al{sub 2}O{sub 3} demonstrate that at low loadings Mo interacts with the most basic hydroxyl groups, and that these hydroxyls are associated with tetrahedrally coordinated Al. Furthermore, hydrodesulfurization (HDS) activity as a function of Mo loading shows a maximum in specific activity with loading. The Mo species bound to tetrahedrally coordinated Al sites are therefore believed to be inactive for the HDS reaction. Only after the tetrahedral Al sites have completely consumed does molybdena adsorb on the alumina in a manner that leads to an active catalyst. According to this scheme, the activity of alumina supported MoS{sub 2} catalysts could be greatly improved by either titrating the tetrahedral Al sites with a modifier, or by using {alpha}-Al{sub 2}O{sub 3} which contains no tetrahedrally coordinated Al. HDS tests over MoS{sub 2} supported on both {alpha}-Al{sub 2}O{sub 3} and {gamma}-Al{sub 2}O{sub 3} modified by a titania film confirm this hypothesis. Neither support material gives rise to a maximum in activity with Mo loading, but rather exhibits a smooth decrease in activity with loading. Furthermore, for equivalent Mo loadings the activity of both of these support materials exceeds that of unmodified {gamma}-Al{sub 2}O{sub 3} due to the fact that no Mo is tied up in the inactive form. FTIR, XPS, and TEM are currently being used to determine whether the model can indeed account for the observed activity trends. Although the surface area of {alpha}-Al{sub 2}O{sub 3} is too low for use as a commercial catalyst, the titania coated {gamma}-Al{sub 2}O{sub 3} represents an important, practical improvement in support materials for hydrotreating catalysts.
Date: July 1, 1996
Creator: Sault, A.G.; Reardon, J. & Datye, A.K.
Partner: UNT Libraries Government Documents Department

Spectroscopic temperature measurements of non-equilibrium plasmas

Description: The characterization of laser-produced plasmas has required the application of spectroscopic techniques to non-standard conditions where kinetics models have not been extensively tested. The plasmas are produced by the Nova laser for the study of inertial confinement fusion, can be mm in size, and evolve on sub-nanosecond time scales. These targets typically achieve electron temperatures from 2-4 keV and electron densities of 10{sup 20}-10{sup 22} cm{sup {minus}3}. The authors have measured the electron temperature of two types of targets: bags of gas and hohlraums, Au cylinders with laser entrance holes in the flat ends. By comparing data from different targets, they examine the time-dependence of spectroscopic plasma diagnostics.
Date: April 24, 1996
Creator: Back, C.A.; Glenzer, S.H.; Lee, R.W. & MacGowan, B.J.
Partner: UNT Libraries Government Documents Department

An acousto-optic tunable filter enhanced CO{sub 2} lidar atmospheric monitor

Description: The atmospheric monitor conceptual design is based on a pulsed CO{sub 2} laser. The narrow laser lines provide high spectral selectivity in the 9-11 {mu}m region, within the 8-14 {mu}m ``fingerprint`` region where most large molecules have unique spectral absorption signatures. Laser power has been chosen so that topological objects, e.g., trees or buildings, as far as 4 km can be used as backreflectors, but the laser intensity is sufficiently low that the laser beam is eye-safe. Time-of-flight measurements give the distance to the topological reflector. The lidar system is augmented with an acousto-optic tunable filter (AOTF) which measures the thermal emission spectra from 3 to 14 {mu}m with a 3 cm{sup -1} passband. Sensitivity to narrow emission lines is enhanced by derivative spectroscopy in which the passband of the AOTF is dithered via the rf drive. Path-averaged concentrations are determined from the emission intensity and laser- determined range.
Date: December 31, 1996
Creator: Taylor, L.H.; Suhre, D.R. & Mani, S.S.
Partner: UNT Libraries Government Documents Department

Actinide speciation in glass leach-layers: An EXAFS study

Description: Uranium L{sub 3} X-ray absorption data were obtained from two borosilicate glasses, which are considered as models for radioactive wasteforms, both before and after leaching. Surface sensitivity to uranium speciation was attained by a novel application of simultaneous fluorescence and electron-yield detection. Changes in speciation are clearly discernible, from U(VI) in the bulk to (UO{sub 2}){sup 2+}-uranyl in the leach layer. The leach-layer uranium concentration variations with leaching times are also determined from the data.
Date: December 1996
Creator: Biwer, B. M.; Soderholm, L.; Greegor, R. B. & Lytle, F. W.
Partner: UNT Libraries Government Documents Department

Soft x-ray optics for spectromicroscopy at the Advanced Light Source

Description: A variety of systems for performing spectromicroscopy, spatially resolved spectroscopy, are in operation or under construction at the Advanced Light Source (ALS). For example, part of the program is centered around the surface analysis problems of local semiconductor industries, and this has required the construction of a microscope with wafer handling, fiducialization, optical microscopy, coordinated ion beam etching, and X-ray Photoelectron Spectroscopy (XPS) integrated in this case with Kirkpatrick-Baez (K-B) grazing incidence micro-focusing optics. The microscope is to be used in conjunction with a highly efficient entrance slitless Spherical Grating Monochromator (SGM). The design and expected performance of this instrument will be described, with emphasis on the production of the elliptically curved surfaces of the K-B mirrors by elastic bending of flat mirror substrates. For higher resolution, zone-plate (Z-P) focusing optics are used and one instrument, a Scanning Transmission X-ray Microscope (STXM) is in routine operation on undulator beamline 7.0. A second Z-P based system is being commissioned on the same beamline, and differs from the STXM in that it will operate at Ultra-High Vacuum (UHV) and will be able to perform XPS at 0.1 {micro}m spatial resolution. Spatially resolved X-ray Absorption Spectroscopy (XAS) can be performed by imaging electrons photoemitted from a material with a Photo-Emission Electron Microscope (PEEM). The optical requirements of a beamline designed for PEEM are very different to those of micro-focus systems and they give examples of bending magnet and undulator based instruments.
Date: September 1996
Creator: Padmore, H.A.
Partner: UNT Libraries Government Documents Department

The analysis of mixtures: Application of principal component analysis to XAS spectra

Description: Many samples which are subjected to XAS analysis contain the element of interest in more than one chemical form. The interpretation of the spectras from such samples is often not straightforward, particularly if appropriate model systems are not available. We have applied principal component analysis (PCA) to real and simulated systems which contain mixtures of several species for a given element PCA has been extensively used for the analysis of other types of spectra, including MS, IR and UV-VIS. The application of PCA to XAS is illustrated by examining the speciation of iron within coals. PCA can determine how many different species that contain a particular element are present in a series of spectra. In tandem with model compounds, principal component analysis can suggest which of the models may contribute to the observed XAS spectra.
Date: October 1996
Creator: Wasserman, S. R.
Partner: UNT Libraries Government Documents Department

Diffuse reflectance FTIR of stains on grit blasted metals

Description: Diffuse reflectance mid-infrared Fourier transform (DRIFT) spectroscopy has been applied to the detection of oil contamination on grit-blasted metals. The object of this application is to detect and discriminate between silicone and hydrocarbon oil contamination at levels approaching 10 mg/m{sup 2}. A portable FTIR spectrometer with dedicated diffuse reflectance optics was developed for this purpose. Using translation devices positioned by instructions from the spectrometer operating system, images of macroscopic substrates were produced with millimeter spatial resolution. The pixels that comprise an image are each a full mid-infrared spectrum with excellent signal-to-noise, each determined as individual files and uniquely saved to disc. Reduced spectra amplitudes, based on peak height, area, or other chemometric techniques, mapped as a function of the spatial coordinates of the pixel are used to display the image. This paper demonstrates the application of the technique to the analysis of stains on grit-blasted metals, including the calibration of the method, the inspection of substrates, and the migration of oil contamination.
Date: August 9, 1997
Creator: Powell, G.L.; Hallman, R.L. Jr. & Cox, R.L.
Partner: UNT Libraries Government Documents Department

Soft x-ray spectromicroscopy development for materials science at the Advanced Light Source

Description: Several third generation synchrotron radiation facilities are now operational and the high brightness of these photon sources offers new opportunities for x-ray microscopy. Well developed synchrotron radiation spectroscopy techniques are being applied in new instruments capable of imaging the surface of a material with a spatial resolution smaller than one micron. There are two aspects to this. One is to further the field of surface science by exploring the effects of spatial variations across a surface on a scale not previously accessible to x-ray measurements. The other is to open up new analytical techniques in materials science using x-rays, on a spatial scale comparable to that of the processes or devices to be studied. The development of the spectromicroscopy program at the Advanced Light Source will employ a variety of instruments, some are already operational. Their development and use will be discussed, and recent results will be presented to illustrate their capabilities.
Date: August 1, 1996
Creator: Warwick, T.; Padmore, H.; Ade, H.; Hitchcock, A.P.; Rightor, E.G. & Tonner, B.P.
Partner: UNT Libraries Government Documents Department

Oxidation states of the ``unusual`` rare earths (R=Ce, Pr and Tb) in double layer high-T{sub c} superconductors

Description: X-ray absorption and magnetization experiments are used to describe the oxidation states of the rare earths R= Ce, Pr, and Tb in the double layer high-Tc superconducting series RBa{sub 2}Cu{sub 3}O{sub 7} and Pb{sub 2}Sr{sub 2}R{sub 1-x}Ca{sub x}Cu{sub 3}O{sub 8}. We obtained the same oxidation states for the rare earths in these two classes of compounds, namely, R=Ce tetravalent and R=Pr and Tb trivalent.
Date: July 1, 1996
Creator: Staub, U.; Soderholm, L.; Skanthakumar, S. & Antonio, M.R.
Partner: UNT Libraries Government Documents Department

NMR spectroscopic investigations of surface and interlayer species on minerals, clays and other oxides

Description: The behavior of chemical species adsorbed on solid surfaces and exchanged into clay interlayers plays a significant role in controlling many natural and technologically important processes, including rheological behavior, catalysis, plant growth, transport in natural pore fluids and those near anthropogenic hazardous waste sites, and water-mineral interaction. Adsorption and exchange reactions have been the focus of intense study for many decades. Only more recently, however, have there been extensive spectroscopic studies of surface species. Among the spectroscopic methods useful for studying surface and exchanged species (e.g., infrared, X-ray photoelectron spectroscopy [XPS] and X-ray absorption spectroscopy [XAS]), nuclear magnetic resonance spectroscopy (NMR) has the considerable advantage of providing not only structural information via the chemical shift and quadrupole coupling constant but dynamical information in the Hz-mHz range via lineshape analysis and relaxation rate measurements. It is also possible to obtain data in the presence of a separate fluid phase, which is essential for many applications. This paper illustrates the range of applications of NMR methods to surface and exchanged species through review of recent work from our laboratory on Cs in clay interlayers and Cs, Na and phosphate adsorbed on oxide surfaces. The substrate materials used for these experiments and our long-term objectives are related to problems of geochemical interest, but the principals and techniques are of fundamental interest and applicable to a wide range of technological problems.
Date: July 1, 1996
Creator: Kirkpatrick, R. J.; Yeongkyoo Kim; Weiss, C. A. & Cygan, R. T.
Partner: UNT Libraries Government Documents Department

Frequency agile OPO-based transmitters for multiwavelength DIAL

Description: We describe a first generation mid-infrared transmitter with pulse to pulse frequency agility and both wide and narrow band capability. This transmitter was used to make multicomponent Differential Absorption LIDAR (DIAL) measurements in the field.
Date: September 1, 1996
Creator: Velsko, S.P.; Ruggiero, A. & Herman, M.
Partner: UNT Libraries Government Documents Department

Hybrid KED/XRF measurement of minor actinides in reprocessing plants

Description: Minor actinides have received considerable attention recently in the nuclear power industry. Because of their potential value as recycle fuels in thermal and breeder reactors, reprocessing plants may have an economic incentive to extract Np, Am, and Cm from their waste streams. This report discusses the technique of hybrid densitometry and its potential to measure Np and Am in reprocessing plants. Precision estimates are made for the hybrid analysis of Np and Am in two types of dissolver solutions.
Date: December 31, 1996
Creator: Hsue, S.T. & Collins, M.L.
Partner: UNT Libraries Government Documents Department

Chemometrics applied to vibrational spectroscopy: overview, challenges and pitfalls

Description: Chemometric multivariate calibration methods are rapidly impacting quantitative infrared spectroscopy in many positive ways. The combination of vibrational spectroscopy and chemometrics has been used by industry for quality control and process monitoring. The growth of these methods has been phenomenal in the past decade. Yet, as with any new technology, there are growing pains. The methods are so powerful at finding correlations in the data, that when used without great care they can readily yield results that are not valid for the analysis of future unknown samples. In this paper, the power of the multivariate calibration methods is discussed while pointing out common pitfalls and some remaining challenges that may slow the implementation of chemometrics in research and industry.
Date: October 1, 1996
Creator: Haaland, D.M.
Partner: UNT Libraries Government Documents Department

Coordination and valence of europium in [Eu({alpha}-2-As{sub 2}W{sub 17}O{sub 61}){sub 2}]{sup 17{minus}} and [Eu(W{sub 5}O{sub 18}){sub 2}]{sup 9{minus}}

Description: Europium L{sub 3}-edge X-ray absorption fine structure (XAFS) spectroelectrochemistry was used to determine the valence of europium in [Eu({alpha}-2-As{sub 2}W{sub 17}O{sub 61}){sub 2}]{sup 17{minus}} and [Eu(w{sub 5}O{sub 18}){sub 2}]{sup 9{minus}}. Dilute solutions of these anions in aqueous supporting electrolytes were examined at ambient temperature and at extreme potentials. In situ XANES (X-ray absorption near edge structure) data revealed that Eu is trivalent in both [Eu({alpha}-2-As{sub 2}W{sub 17}O{sub 61}){sub 2}]{sup 17{minus}} and [Eu(W{sub 5}O{sub 18}){sub 2}]{sup 9{minus}} at rest potential. Furthermore, it was not reduced to Eu{sup 2+} by constant-potential bulk electrolysis at significantly reducing potentials under the electrochemical conditions used herein. These results stand in obvious contrast to the redox behavior of [EuP{sub 5}W{sub 30}O{sub 110}]{sup 12{minus}}, in which Eu{sup 3+} is reduced to Eu{sup 2+} under similar electrochemical conditions.
Date: September 1, 1997
Creator: Antonio, M.R.; Soderholm, L.; Jennings, G.; Francesconi, L.C.; Dankova, M. & Bartis, J.
Partner: UNT Libraries Government Documents Department

In situ Fe K-edge X-ray absorption fine structure of a pyrite electrode in a Li/polyethylene oxide (LiClO{sub 4})/FeS{sub 2} battery environment

Description: Electronic and structural properties of materials generated by the reduction and subsequent oxidation of pyrite in a lithium-based solid polymer electrolyte have been examined by in situ fluorescence Fe K-edge X-ray absorption fine structure (XAFS) in a FeS{sub 2}/Li battery environment. The XAFS results obtained are consistent with the formation of metallic iron as one of the products of the full (4-electron) discharge, in agreement with information reported in other laboratories. Extended X-ray absorption fine structure (EXAFS) data reveal that a subsequent 2-electron or 4-electron recharge generates a species with a Fe-S bond distance identical to that of pyrite, d(Fe-S) = 2.259 {angstrom}, with no other clearly detectable interactions due to more distant atoms. Based on the similarities between the metrical parameters and other features in the X-ray absorption near edge structure (XANES), the ferrous sites in these species appear to be tetrahedrally coordinated, as in chalcopyrite (CuFeS{sub 2}), for which d(Fe-S) is 2.257 {angstrom}, and, thus, different than in Li{sub 2} FeS{sub 2}, a material that exhibits longer Fe-S distances.
Date: December 31, 1996
Creator: Totir, D.; Bae, I.T.; Hu, Y.; Scherson, D.A. & Antonio, M.R.
Partner: UNT Libraries Government Documents Department