RESUMEN

We describe a fixture that allows electrochemical devices to be studied under electrical bias in the type of vacuum systems commonly used in surface science. Three spring-loaded probes provide independent contacts for device operation and the characterization in vacuum or under in situ conditions with reactive gases. We document the robustness of the electrical contacts over large temperature changes and their reliability for conventional electrochemical measurements such as impedance spectroscopy. The optical access provided to the device enables the analysis by many techniques, as we demonstrate using x-ray photoelectron spectroscopy to measure local electrical potentials on a solid-oxide electrolyte device operating at high temperature in near-ambient pressure.

RESUMEN

Photoelectron spectroscopic measurements have the potential to provide detailed mechanistic insight by resolving chemical states, electrochemically active regions and local potentials or potential losses in operating solid oxide electrochemical cells (SOCs), such as fuel cells. However, high-vacuum requirements have limited X-ray photoelectron spectroscopy (XPS) analysis of electrochemical cells to ex situ investigations. Using a combination of ambient-pressure XPS and CeO(2-x)/YSZ/Pt single-chamber cells, we carry out in situ spectroscopy to probe oxidation states of all exposed surfaces in operational SOCs at 750 °C in 1 mbar reactant gases H(2) and H(2)O. Kinetic energy shifts of core-level photoelectron spectra provide a direct measure of the local surface potentials and a basis for calculating local overpotentials across exposed interfaces. The mixed ionic/electronic conducting CeO(2-x) electrodes undergo Ce(3+)/Ce(4+) oxidation-reduction changes with applied bias. The simultaneous measurements of local surface Ce oxidation states and electric potentials reveal the active ceria regions during H(2) electro-oxidation and H(2)O electrolysis. The active regions extend ~150 µm from the current collectors and are not limited by the three-phase-boundary interfaces associated with other SOC materials. The persistence of the Ce(3+)/Ce(4+) shifts in the ~150 µm active region suggests that the surface reaction kinetics and lateral electron transport on the thin ceria electrodes are co-limiting processes.

RESUMEN

We use photo-electrons as a non-contact probe to measure local electrical potentials in a solid-oxide electrochemical cell. We characterize the cell in operando at near-ambient pressure using spatially-resolved X-ray photoemission spectroscopy. The overpotentials at the interfaces between the Ni and Pt electrodes and the yttria-stabilized zirconia (YSZ) electrolyte are directly measured. The method is validated using electrochemical impedance spectroscopy. Using the overpotentials, which characterize the cell's inefficiencies, we compare without ambiguity the electro-catalytic efficiencies of Ni and Pt, finding that on Ni H(2)O splitting proceeds more rapidly than H(2) oxidation, while on Pt, H(2) oxidation proceeds more rapidly than H(2)O splitting.

RESUMEN

In Part I of this study [1], good agreement between experimental measurements and results from Monte Carlo simulations were obtained for the spatial intensity distribution of a laser beam propagating within a turbid environment. In this second part, the validated Monte Carlo model is used to investigate spatial and temporal effects from distinct scattering orders on image formation. The contribution of ballistic photons and the first twelve scattering orders are analyzed individually by filtering the appropriate data from simulation results. Side-scattering and forward-scattering detection geometries are investigated and compared. We demonstrate that the distribution of positions for the final scattering events is independent of particle concentration when considering a given scattering order in forward detection. From this observation, it follows that the normalized intensity distribution of each order, in both space and time, is independent of the number density of particles. As a result, the amount of transmitted information is constant for a given scattering order and is directly related to the phase function in association with the detection acceptance angle. Finally, a contrast analysis is performed in order to quantify this information at the image plane.

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RESUMEN

Temporal behavior of pulses from a Q-switched Nd:YAG laser with an unstable resonator can vary significantly with radial position in the beam. Our laser provides pulses with position-dependent durations spanning 8-11.5 ns at 1064 nm and 7-10 ns at 532 nm. Pulses emerge first and have the longest duration at the center of the beam; they are shorter (by up to 4 ns) and increasingly delayed (by up to 10 ns) with increasing radial distance from the center. This behavior can have a dramatic effect on time-sensitive experiments, such as laser-induced incandescence of soot, if not taken into account.

RESUMEN

The diagnostic techniques for simultaneous velocity and relative OH distribution, simultaneous temperature and relative OH distribution, and three component velocity mapping are described. The data extracted from the measurements include statistical moments for inflow fluid dynamics, temperature, conditional velocities, and scalar flux. The work is a first step in the development of a detailed large eddy simulation (LES) validation database for a turbulent, premixed flame. The low-swirl burner used in this investigation has many of the necessary attributes for LES model validation, including a simplified interior geometry; it operates well into the thin reaction zone for turbulent premixed flames, and flame stabilization is based entirely on the flow field and not on hardware or pilot flames.

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RESUMEN

We investigate the scattering and multiple scattering of a typical laser beam (lambda = 800 nm) in the intermediate scattering regime. The turbid media used in this work are homogeneous solutions of monodisperse polystyrene spheres in distilled water. The two-dimensional distribution of light intensity is recorded experimentally, and calculated via Monte Carlo simulation for both forward and side scattering. The contribution of each scattering order to the total detected light intensity is quantified for a range of different scattering phase functions, optical depths, and detection acceptance angles. The Lorentz-Mie scattering phase function for individual particles is varied by using different sphere diameters (D = 1 and 5 mum). The optical depth of the turbid medium is varied (OD = 2, 5, and 10) by employing different concentrations of polystyrene spheres. Detection angles of theta(a) = 1.5 degrees and 8.5 degrees are considered. A novel approach which realistically models the experimental laser source is employed in this paper, and very good agreement between the experimental and simulated results is demonstrated. The data presented here can be of use to validate any other modern Monte Carlo models which generate spatially resolved light intensity distributions. Finally, an effective correction procedure to the Beer-Lambert law is proposed based on the Monte Carlo calculation of the ballistic photon contribution to the total detected light intensity.

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We describe adaptation of ballistic imaging for the liquid core of an atomizing spray. To describe unambiguously the forces that act to break apart the liquid core in a spray, one must directly measure the force vectors themselves. It would be invaluable, therefore, to obtain velocity and acceleration data at the liquid-gas interface. We employ double-image ballistic imaging to extract velocity information through the application of image analysis algorithms. This method is shown to be effective for liquid phase droplet features within the resolution limit of the imaging system. In light of these results, it is clear that a three- or four-image implementation of this technique would allow the determination of acceleration, and by extension, information about the forces active in spray breakup.

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A time-gated ballistic imaging instrument is used to obtain high-spatial-resolution, single-shot images of the liquid core in a water spray issuing into a gaseous crossflow. We describe further development of the diagnostic technique to improve spatial resolution and present images and statistics for various jets under crossflow experimental conditions (different Weber numbers). Series of these images reveal a near-nozzle flow field undergoing breakup and subsequent droplet formation by stripping. One can also detect signatures of spatially periodic behavior in the liquid core and formation of small voids during breakup.

RESUMEN

Picosecond pump-probe absorption spectroscopy is a spatially resolved technique that is capable of measuring species concentrations in an absolute sense without the need for calibrations. When laser pulses are used that are shorter than the collision time in a sample, this pump-probe technique exhibits reduced sensitivity to collisional effects such as electronic quenching. We describe modeling and experimental characterization of this technique. The model is developed from rate equations that describe the interactions of the pump and probe pulses with the sample. Calculations based on the density-matrix equations are used to identify limits of applicability for the model. Excellent agreement between the model and the experimental data is observed when both 1.3- and 65-ps pulses are used to detect potassium in a flame and in an atomic vapor cell.