Mark Linne

Measuring fundamental properties in operating solid oxide electrochemical cells by using in situ X-ray photoelectron spectroscopy

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.

Application of structured illumination for multiple scattering suppression in planar laser imaging of dense sprays

A novel approach to reduce the multiple light scattering contribution in planar laser images of atomizing sprays is reported. This new technique, named Structured Laser Illumination Planar Imaging (SLIPI), has been demonstrated in the dense region of a hollow-cone water spray generated in ambient air at 50 bars injection pressure. The idea is based on using an incident laser sheet which is spatially modulated along the vertical direction. By properly shifting the spatial phase of the modulation and using post-processing of the successive recorded images, the blurring effects from multiple light scattering can be mitigated. Since hollow-cone sprays have a known inner structure in the central region, the efficiency of the method could be evaluated. We demonstrate, for the case of averaged images, that an unwanted contribution of 44% of the detected light intensity can be removed. The suppression of this diffuse light enables an increase from 55% to 80% in image contrast. Such an improvement allows a more accurate description of the near-field region and of the spray interior. The possibility of extracting instantaneous flow motion is also shown, here, for a dilute flow of water droplets. These results indicate promising applications of the technique to denser two-phase flows such as air-blast atomizer and diesel sprays.

Simultaneous PIV/PH-PLIF, Rayleigh thermometry/OH-PLIF and stereo PIV measurements in a low-swirl-flame

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.

Laser light scattering in turbid media Part I: Experimental and simulated results for the spatial intensity distribution

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.

Fixed-frequency cavity ringdown diagnostic for atmospheric particulate matter

A nonresonant cavity ringdown diagnostic to measure light attenuation from atmospheric particulate matter at 532- and 355-nm wavelengths is described. The presence of atmospheric particulate is clearly detectable with this technique, as demonstrated by experimental results. The extinction cross section is higher at 355 than at 532 nm, although we were able to purchase significantly higher-reflectivity optics at 532 nm. The expected advantage at 355 nm is thus lost. This new technique is compared with a commercially available instrument, and sensitivity limitations are discussed.

Ballistic imaging of the liquid core for a steady jet in crossflow

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.

Note: Fixture for characterizing electrochemical devices in-operando in traditional vacuum systems

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.

Development of a cavity ringdown laser absorption spectrometer for detection of trace levels of mercury

A potential new laser-based air pollution measurement technique, capable of measuring ultralow concentrations of urban air toxins in the field and in real time, is examined. Cavity ringdown laser absorption spectroscopy (CRLAS) holds promise as an air pollution monitor because it is a highly sensitive species detection technique that uses either pulsed or continuous tunable laser sources. The sensitivity results from an extremely long absorption path length and the fact that the quantity measured, the cavity decay time, is unaffected by fluctuations in the laser source. In laboratory experiments, we reach detection limits for mercury of the order of 0.50 parts per trillion. We developed a CRLAS system in our laboratory and measured Hg with the system, investigating issues such as background interference. We report experimental results for mercury detection limits, the dynamic range of the sensor, detection of Hg in an absorbing background of ozone and SO(2), and detection of a mercury-containing compound (HgCl(2) in this case).

Laser light scattering in turbid media Part II: Spatial and temporal analysis of individual scattering orders via Monte Carlo simulation.

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.

Fast-framing ballistic imaging of velocity in an aerated spray

We describe further development of ballistic imaging adapted for the liquid core of an atomizing spray. To fully understand spray breakup dynamics, one must measure the velocity and acceleration vectors that describe the forces active in primary breakup. This information is inaccessible to most optical diagnostics, as the signal is occluded by strong scattering in the medium. Ballistic imaging mitigates this scattering noise, resolving clean shadowgram-type images of structures within the dense spray region. We demonstrate that velocity data can be extracted from ballistic images of a spray relevant to fuel-injection applications, by implementing a simple, targeted correlation method for determining velocity from pairs of spray images. This work presents the first ballistic images of a liquid-fuel injector for scramjet combustion, and the first velocity information from ballistic images relevant to breakup in the near-field of a spray.