We have developed and built a small porous-plug burner based on the original McKenna burner design. The new burner generates a laminar premixed flat flame for use in studies of combustion chemistry and soot formation. The size is particularly relevant for space-constrained, synchrotron-based X-ray diagnostics. In this paper, we present details of the design, construction, operation, and supporting infrastructure for this burner, including engineering attributes that enable its small size. We also present data for charactering the flames produced by this burner. These data include temperature profiles for three premixed sooting ethylene/air flames (equivalence ratios of 1.5, 1.8, and 2.1); temperatures were recorded using direct one-dimensional coherent Raman imaging. We include calculated temperature profiles, and, for one of these ethylene/air flames, we show the carbon and hydrogen content of heavy hydrocarbon species measured using an aerosol mass spectrometer coupled with vacuum ultraviolet photoionization (VUV-AMS) and soot-volume-fraction measurements obtained using laser-induced incandescence. In addition, we provide calculated mole-fraction profiles of selected gas-phase species and characteristic profiles for seven mass peaks from AMS measurements. Using these experimental and calculated results, we discuss the differences between standard McKenna burners and the new miniature porous-plug burner introduced here.
In many fields of study, from coherent Raman microscopy on living cells to time-resolved coherent Raman spectroscopy of gas-phase turbulence and combustion reaction dynamics, the need for the capability to time-resolve fast dynamical and nonrepetitive processes has led to the continued development of high-speed coherent Raman methods and new high-repetition rate laser sources, such as pulse-burst laser systems. However, much less emphasis has been placed on our ability to detect shot to shot coherent Raman spectra at equivalently high scan rates, across the kilohertz to megahertz regime. This is beyond the capability of modern scientific charge coupled device (CCD) cameras, for instance, as would be employed with a Czerny-Turner type spectrograph. As an alternative detection strategy with megahertz spectral detection rate, we demonstrate dispersive Fourier transformation detection of pulsed (~90 ps) coherent Raman signals in the time-domain. Instead of reading the frequency domain signal out using a spectrometer and CCD, the signal is transformed into a time-domain waveform through dispersive Fourier transformation in a long single-mode fiber and read-out with a fast sampling photodiode and oscilloscope. Molecular O- and S-branch rotational sideband spectra from both N2 and H2 were acquired employing this scheme, and the waveform is fitted to show highly quantitative agreement with a molecular model. The total detection time for the rotational spectrum was 20 ns, indicating an upper limit to the detection frequency of ~50 MHz, significantly faster than any other reported spectrally-resolved coherent anti-Stokes Raman detection strategy to date.
Coherent anti-Stokes Raman spectroscopy (CARS) is a sensitive technique for probing highly luminous flames in combustion applications to determine temperatures and species concentrations. CARS thermometry has been demonstrated for the vibrational Q-branch and pure-rotational S-branch of several small molecules. Practical advantages of pure-rotational CARS, such as multi-species detection, reduction of coherent line mixing and collisional narrowing even at high pressures, and the potential for more precise thermometry, have motivated experimental and theoretical advances in S-branch CARS of nitrogen (N2), for example, which is a dominant species in air-fed combustion processes. Although hydrogen (H2) is of interest given its prevalence as a reactant and product in many gas-phase reactions, laser bandwidth limitations have precluded the extension of CARS thermometry to the H2 S-branch. We demonstrate H2 thermometry using hybrid femtosecond/picosecond pure-rotational CARS, in which a broadband pump/Stokes pulse enables simultaneous excitation of the set of H2 S-branch transitions populated at flame temperatures over the spectral region of 0-2200 cm-1. We present a pure-rotational H2 CARS spectral model for data fitting and compare extracted temperatures to those from simultaneously collected N2 spectra in two systems of study: a heated flow and a diffusion flame on a Wolfhard-Parker slot burner. From 300 to 650 K in the heated flow, the H2 and N2 CARS extracted temperatures are, on average, within 2% of the set temperature. For flame measurements, the fitted H2 and N2 temperatures are, on average, within 5% of each other from 300 to 1600 K. Our results confirm the viability of pure-rotational H2 CARS thermometry for probing combustion reactions.
Ultrabroadband coherent anti-Stokes Ra man spectroscopy (CARS) has been developed for one -dimensional imaging of temperature and major species distributions simultaneously in the near-wall region of a methane/air flame supported on a side-wall-quenching (SWQ) burner. Automatic temporal and spatial overlap of the ~7 femtosecond pump and Stokes pulses is achieved utilizing a two-beam CARS phase-matching scheme, and the crossed ~75 picosecond probe beam provide s excellent spatial sectioning of the probed location. Concurrent detection of N2, O2, H2, CO, CO2, and CH4 is demonstrated while high-fidelity flame thermometry is assessed from the N2 pure rotational S-branch in a one-dimensional -CARS imaging configuration. A methane/air premixed flame at lean, stoichiometric, and rich conditions ( Φ = 0.83, 1.0 , and 1.2) and Reynolds number = 5,000 is probed as it quenches against a cooled steel side- wall parallel to the flow providing a persistent flame-wall interaction. Here, an imaging resolution of better than 40 μm is achieved across the field -of-view, thus allowing thermochemical states (temperature and major species) of the thermal boundary layer to be resolved to within ~30 μm of the interface.
We report measurements of temperature and O2/N2 mole-fraction ratio in the vicinity of a burning and decomposing carbon-epoxy composite aircraft material samples exposed to uniform heat fluxes of 48 and 69 kW/m2. Controlled laboratory experiments were conducted with the samples suspended above a cone-type heater and enclosed in an optically accessible chimney. Noninvasive coherent anti-Stokes Raman scattering (CARS) measurements we performed on a single-laser-shot basis. The CARS data were performed with both a traditional point measurement system and with a one-dimensional line imaging scheme that provides single-shot temperature and O2/N2 profiles to reveal the quantitative structure of the temperature and oxygen concentration profiles over the duration of the 30-40 minute duration events. The measured near-surface temperature and oxygen transport are an important factor for exothermic chemistry and oxidation of char materials and the carbon fibers themselves in a fire scenario. These unique laser-diagnostic experiments provide new information on physical/chemical processes in a well-controlled environment which may be useful for the development of heat-and mass-transfer models for the composite fire scenario.
This report documents work that was performed under the Laboratory Directed Research and Development project, Science of Battery Degradation. The focus of this work was on the creation of new experimental and theoretical approaches to understand atomistic mechanisms of degradation in battery electrodes that result in loss of electrical energy storage capacity. Several unique approaches were developed during the course of the project, including the invention of a technique based on ultramicrotoming to cross-section commercial scale battery electrodes, the demonstration of scanning transmission x-ray microscopy (STXM) to probe lithium transport mechanisms within Li-ion battery electrodes, the creation of in-situ liquid cells to observe electrochemical reactions in real-time using both transmission electron microscopy (TEM) and STXM, the creation of an in-situ optical cell utilizing Raman spectroscopy and the application of the cell for analyzing redox flow batteries, the invention of an approach for performing ab initio simulation of electrochemical reactions under potential control and its application for the study of electrolyte degradation, and the development of an electrochemical entropy technique combined with x-ray based structural measurements for understanding origins of battery degradation. These approaches led to a number of scientific discoveries. Using STXM we learned that lithium iron phosphate battery cathodes display unexpected behavior during lithiation wherein lithium transport is controlled by nucleation of a lithiated phase, leading to high heterogeneity in lithium content at each particle and a surprising invariance of local current density with the overall electrode charging current. We discovered using in-situ transmission electron microscopy that there is a size limit to lithiation of silicon anode particles above which particle fracture controls electrode degradation. From electrochemical entropy measurements, we discovered that entropy changes little with degradation but the origin of degradation in cathodes is kinetic in nature, i.e. lower rate cycling recovers lost capacity. Finally, our modeling of electrode-electrolyte interfaces revealed that electrolyte degradation may occur by either a single or double electron transfer process depending on thickness of the solid-electrolyte-interphase layer, and this cross-over can be modeled and predicted.
Hybrid femtosecond/picosecond rotational coherent anti-Stokes Raman spectroscopy (CARS) is developed utilizing a two-beam phase-matching approach for one-dimensional (1D) measurements demonstrated in an impinging jet burner to probe time-resolved head on quenching (HOQ) of a methane/air premixed flame at Φ = 1.0 and Reynolds number = 5000. Single-laser-shot 1D temperature profiles are obtained over a distance of at least 4 mm by fitting the pure-rotational N2 CARS spectra to a spectral library calculated from a time-domain CARS code. An imaging resolution of ∼61 μm is obtained in the 1D-CARS measurements. The acquisition of single-shot 1D CARS measurements, as opposed to traditional point-wise CARS techniques, enables new spatially correlated conditional statistics to be determined, such as the position, magnitude, and fluctuations of the instantaneous temperature gradient. The temperature gradient increases as the flame approaches the metal surface, and decreases during quenching. The standard deviation of the temperature gradient follows the same trend as the temperature gradient, increasing as the flame front approaches the surface, and decreasing after quenching.
Advances in technology for electrochemical energy storage require increased understanding of electrolyte/electrode interfaces, including the electric double layer structure, and processes involved in charging of the interface, and the incorporation of this understanding into quantitative models. Simplified models such as Helmholtz's electric double-layer (EDL) concept don't account for the molecular nature of ion distributions, solvents, and electrode surfaces and therefore cannot be used in predictive, high-fidelity simulations for device design. This report presents theoretical results from models that explicitly include the molecular nature of the electrical double layer and predict critical electrochemical quantities such as interfacial capacitance. It also describes development of experimental tools for probing molecular properties of electrochemical interfaces through optical spectroscopy. These optical experimental methods are designed to test our new theoretical models that provide descriptions of the electric double layer in unprecedented detail.