Quantitative one-dimensional imaging using picosecond dual-broadband pure-rotational coherent anti-Stokes Raman spectroscopy.

We employ picosecond dual-broadband pure-rotational coherent anti-Stokes Raman spectroscopy (CARS) in a one-dimensional (1D) imaging configuration. Temperature and O(2):N(2) concentration ratios are measured along a 1D line of up to 12 mm in length. The images consist of up to 330 individual rotational CARS (RCARS) spectra, corresponding to 330 spatially resolved volume elements in the probe volume. Signal levels are sufficient for the collection of single-laser-pulse images at temperatures of up to approximately 1200 K and shot-averaged images at flame temperatures, demonstrated at 2100 K. The precision of picosecond pure-rotational 1D imaging CARS is assessed by acquiring a series of 100 single-laser-pulse images in a heated flow of N(2) from 410 K-1200 K and evaluating a single volume element for temperature in each image. Accuracy is demonstrated by comparing temperatures from the evaluated averaged spectra to thermocouple readings in the heated flow. Deviations from the thermocouple of <30 K in the evaluated temperature were found at up to 1205 K. Accuracy and single-shot precision are compared to those reported for single-point nanosecond dual-broadband pure-RCARS and nanosecond 1D vibrational CARS.

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.

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.

Measuring individual overpotentials in an operating solid-oxide electrochemical cell.

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.

Four-wave mixing in nanosecond pulsed fiber amplifiers.

We present an experimental and theoretical analysis of four-wave mixing in nanosecond pulsed amplifiers based on double-clad ytterbium-doped fibers. This process leads to saturation of the amplified pulse energy at 1064 nm and to distortion of the spectral and temporal profiles. These behaviours are well described by a simple model considering both Raman and four-wave-mixing contributions. The role of seed laser polarization in birefringent fibers is also presented. These results point out the critical parameters and possible tradeoffs for optimization.

Peak-power limits on fiber amplifiers imposed by self-focusing.

We have numerically investigated the behavior of the fundamental mode of a step-index, multimode (MM) fiber as the optical power approaches the self-focusing limit (P(crit)). The analysis includes the effects of gain and bending (applicable to coiled fiber amplifiers). We find power-dependent, stationary solutions that propagate essentially without change at beam powers approaching P(crit) in straight and bent fibers. We show that in a MM fiber amplifier seeded with its fundamental eigenmode at powers <

High-Power fiber amplifier with widely tunable repetition rate, fixed pulse duration, and multiple output wavelengths.

We report a pulsed, fiber-amplified microchip laser providing widely tunable repetition rate (7.1 - 27 kHz) with constant pulse duration (1.0 ns), pulse energy up to 0.41 mJ, linear output polarization, diffraction-limited beam quality (M(2) < 1.2), and < 1% pulse-energy fluctuations. The pulse duration was shown to minimize nonlinear effects that cause temporal and spectral distortion of the amplified pulses. This source employs passive Q-switching, single-stage single-pass amplification, and cw pumping, thus offering high efficiency, simplicity, and compact, rugged packaging for use in practical applications. The high peak power and high beam quality make this system an ideal pump source for nonlinear frequency conversion, and we demonstrated efficient harmonic generation and optical parametric generation of wavelengths from 213 nm to 4.4 mum with Watt-level output powers.