Measurements of hydroxyl concentrations and lifetimes in laminar flames using picosecond time-resolved laser-induced fluorescence

Picosecond time-resolved laser-induced fluorescence (PITLIF) can potentially be used to obtain measurements of minor species concentrations in rapidly fluctuating flames. Previous studies demonstrated this potential for atomic sodium by monitoring the temporal fluorescence signal with both an equivalent-time and a real-time sampling method. In this developmental study, PITLIF is used to determine hydroxyl concentrations in laminar CH(4)-O(2)-N(2) flames by the measurement of both the integrated fluorescence signal and the fluorescence lifetime. The quenching environment can be monitored with real-time sampling, and thus the necessary quenching rate coefficient is obtained in 348 us, which is fast enough for use in many turbulent flows. Fluorescence lifetimes of OH are also measured at different equivalence ratios in laminar flames by the use of the equivalent-time sampling technique. These results compare favorably with predicted lifetimes based on relevant quenching cross sections and calculated species concentrations.     

Strategies for laser-induced fluorescence detection of nitric oxide in high-pressure flames. III. Comparison of A-X excitation schemes

Laser-induced fluorescence (LIF) has proven a reliable technique for nitric oxide (NO) diagnostics in practical combustion systems. However, a wide variety of different excitation and detection strategies are proposed in the literature without giving clear guidelines of which strategies to use for a particular diagnostic situation. We give a brief review of the high-pressure NO LIF diagnostics literature and compare strategies for exciting selected transitions in the A-X(0, 0), (0, 1), and (0, 2) bands using a different detection bandpass. The strategies are compared in terms of NO LIF signal strength, attenuation of laser and signal light in the hot combustion gases, signal selectivity against LIF interference from O2 and CO2, and temperature and pressure sensitivity of the LIF signal. The discussion is based on spectroscopic measurements in laminar premixed methane-air flames at pressures between 1 and 60 bars and on NO and O2 LIF spectral simulations.     

Strategies for laser-induced fluorescence detection of nitric oxide in high-pressure flames. II. A-X(0,1) excitation

A-X(0,1) excitation is a promising new approach for NO laser-induced fluorescence (LIF) diagnostics at elevated pressures and temperatures. We present what to our knowledge are the first detailed spectroscopic investigations within this excitation band using wavelength-resolved LIF measurements in premixed methane/air flames at pressures between 1 and 60 bar and a range of fuel/air ratios. Interference from O2 LIF is a significant problem in lean flames for NO LIF measurements, and pressure broadening and quenching lead to increased interference with increased pressure. Three different excitation schemes are identified that maximize NO/O2 LIF signal ratios, thereby minimizing the O2 interference. The NO LIF signal strength, interference by hot molecular oxygen, and temperature dependence of the three schemes are investigated.     

Strategies for laser-induced fluorescence detection of nitric oxide in high-pressure flames. I. A-X(0,0) excitation

Three different high-pressure flame measurement strategies for NO laser-induced fluorescence (LIF) with A-X(0,0) excitation have been studied previously with computational simulations and experiments in flames up to 15 bars. Interference from O2 LIF is a significant problem in lean flames for NO LIF measurements, and pressure broadening and quenching lead to increased interference with increased pressure. We investigate the NO LIF signal strength, interference by hot molecular oxygen, and temperature dependence of the three previous schemes and for two newly chosen excitation schemes with wavelength-resolved LIF measurements in premixed methane and air flames at pressures between 1 and 60 bars and a range of fuel/air ratios. In slightly lean flames with an equivalence ratio of 0.83 at 60 bars, the contribution of O2 LIF to the NO LIF signal varies between 8% and 29% for the previous schemes. The O2 interference is best suppressed with excitation at 226.03 nm.     

Two-photon nitric oxide laser-induced fluorescence measurements in a diesel engine

A two-photon nitric oxide (NO) laser-induced fluorescence (LIF) technique was developed and applied to study in-cylinder diesel combustion. The technique prevents many problems associated with in-cylinder, single-photon NO planar-laser-induced fluorescence measurements, including fluorescence interference from the Schumann-Runge bands of hot O2, absorption of a UV excitation beam by in-cylinder gases, and difficulty in rejecting scattered laser light while simultaneously attempting to maximize fluorescence signal collection. Verification that the signal resulted from NO was provided by tuning of the laser to a vibrational off-resonance wavelength that showed near-zero signal levels, which resulted from either fluorescence or interference at in-cylinder pressures of as much as 20 bar. The two-photon NO LIF signal showed good qualitative agreement with NO exhaust-gas measurements obtained over a wide range of engine loads.     

Measurements of absolute CH concentrations by cavity ring-down spectroscopy and linear laser-induced fluorescence in laminar, counterflow partially premixed and nonpremixed flames at atmospheric pressure

We report quantitative, spatially resolved measurements of methylidyne concentration ([CH]) in laminar, counterflow partially premixed and nonpremixed flames at atmospheric pressure by using both cavity ring-down spectroscopy (CRDS) and linear laser-induced fluorescence (LIF) in the A-X (0, 0) band. Three partially premixed (phiB = 1.45, 1.6, 2.0) flames plus a single nonpremixed methane-air flame are investigated at a global strain rate of 20 s(-1). These quantitative measurements are compared with predictions from an opposed-flow flame code when utilizing two GRI chemical kinetic mechanisms (versions 2.11 and 3.0). The LIF measurements of [CH] are corrected for variations in the electronic quenching rate coefficient by using predicted major species concentrations and temperatures along with quenching cross sections for CH that are available in the literature. The peak CH concentration obtained by CRDS is used to calibrate the quenching-corrected LIF measurements. Excellent agreement is obtained between CH concentration profiles measured by using the CRDS and LIF techniques. The spatial location of the CH layer is very well predicted by GRI 3.0; moreover, the measured and predicted CH concentrations are in good agreement for all the flames of this study.     

Use of laser-induced ionization to detect soot inception in premixed flames

Experimental measurements of laser-induced ionization were performed for ethene-air premixed flames operated near the soot inception point. Soot was ionized with a pulsed laser operated at 532 nm. The ionization signal was collected with a tungsten electrode located in the postflame region. Ionization signals were collected by use of both single-electrode and dual-electrode configurations. Earlier laser-induced-ionization studies focused on the use of a single biased electrode to generate the electric field, with the burner head serving as the path to ground. In many practical combustion systems, a path to ground is not readily available. To apply the laser-induced-ionization diagnostic to these geometries, a dual-electrode geometry must be employed. The influence of electrode configuration, flame equivalence ratio, and flame height on ionization signal detection was determined. The efficacy of the laser-induced-ionization diagnostic in detecting soot inception in the postflame region of a premixed flame by use of a dual-electrode configuration was investigated. Of the dual-electrode configurations tested, the dual-electrode geometry oriented parallel to the laser beam was observed to be most sensitive for detecting the soot inception point in a premixed flame.     

Background corrections for laser-induced-fluorescence measurements of nitric oxide in lean, high-pressure, premixed methane flames

An experimental technique is presented that both minimizes and accounts for the interference background when laser-induced-fluorescence (LIF) measurements are made of NO in lean, high-pressure, premixed, CH(4)/O(2)/N(2) flames. Measurement interferences such as fluorescence and Raman scattering from secondary species become increasingly important for high-pressure LIF studies. O(2) fluorescence interferences are particularly troublesome in lean premixed flames. An excitation-detection scheme that minimizes the effects of these interferences is identified. A procedure that corrects the resulting LIF signal so as to account for any remaining interference signal is then developed. This correction is found to vary from less than 10% of the overall NO signal at atmospheric pressure to over 40% of the overall signal at 14.6 atm for LIF measurements of NO in a series of worst-case flames (phi = 0.6, dilution ratio 2.2). The correction technique is further demonstrated to be portable over a useful range of flame conditions at each pressure.     

Synthesis of germanium oxide nanoparticles in low-pressure premixed flames

Germanium oxide (GeOx) nanoparticles in the size range from 1 nm to 5 nm were synthesized in a low-pressure premixed H2/O2/Ar flat flame of 30 mbar. The premixed flame was doped with different amounts of tetramethyl germanium (Ge(CH3)4) ranging from 250 ppm to 2000 ppm. The influence of process parameters such as the amount of oxygen in the reaction gas, the condensation and reaction time, standoff, and precursor concentration with respect to growth of germanium oxide particles were investigated. The particles formed were analyzed in situ according to their mass and charge with a particle mass spectrometer. The specific surface area was determined ex situ by the BET method. The crystal form and chemical composition of produced nanopowders were characterized by EDX analysis and X-ray diffraction measurements.     

Confocal, two-photon laser-induced fluorescence technique for the detection of nitric oxide

We describe a confocal two-photon laser-induced fluorescence scheme for the detection of gaseous NO. Excitation from a simple YAG-pumped Coumarin 450 dye system near 452.6 nm was used to promote the two-photon NO(A (2)?(+), nu? = 0 ? X (2)?, nu? = 0) transition in the gamma(0, 0) band. Subsequent fluorescence detection in the range 200-300 nm permitted almost total rejection of elastic and geometric scatter of laser radiation for excellent signal/noise ratio characteristics. The goal of the research was to apply NO fluorescence to a relatively realistic limited optical access combustion environment. A confocal optical arrangement was demonstrated for single-point measurements of NO concentration in gas samples and in atmospheric-pressure flames. The technique is suitable for applications that offer only a single direction for optical access and when significant elastic scatter is present.     

MHz-rate nitric oxide planar laser-induced fluorescence imaging in a Mach 10 hypersonic wind tunnel

Nitric oxide planar laser-induced fluorescence (NO PLIF) imaging at repetition rates as high as 1 MHz is demonstrated in the NASA Langley 31 in. Mach 10 hypersonic wind tunnel. Approximately 200 time-correlated image sequences of between 10 and 20 individual frames were obtained over eight days of wind tunnel testing spanning two entries in March and September of 2009. The image sequences presented were obtained from the boundary layer of a 20° flat plate model, in which transition was induced using a variety of different shaped protuberances, including a cylinder and a triangle. The high-speed image sequences captured a variety of laminar and transitional flow phenomena, ranging from mostly laminar flow, typically at a lower Reynolds number and/or in the near wall region of the model, to highly transitional flow in which the temporal evolution and progression of characteristic streak instabilities and/or corkscrew-shaped vortices could be clearly identified.     

Pressure dependence of laser-induced fluorescence from acetone

The use of laser-induced fluorescence (LIF) from acetone is becoming increasingly widespread as a diagnostic of mixing processes in both reacting and nonreacting flows. One of the major reasons for its increasing use is that the acetone LIF signal is believed to be nearly independent of pressure because of fast intersystem crossing from the first excited singlet state, from which the fluorescence signal originates, to the first excited triplet state, which does not fluoresce. To evaluate the use of acetone LIF at pressures higher than atmospheric, we have performed a study of acetone LIF in a flowing gas cell at pressures up to 8 atm. We used four different buffer gases: air, nitrogen, methane, and helium. Surprisingly, we find that the acetone fluorescence quantum efficiency increases slightly (~30%-50%) as the buffer-gas pressure increases from 0.6 to 5 atm for all four buffer gases. When the buffer gas is air, we observe a decrease in the acetone fluorescence quantum efficiency as the buffer-gas pressure is increased from 5 to 8 atm; for the other three buffer gases the quantum efficiency is constant to within experimental error in this pressure regime. The observed pressure dependence of the acetone fluorescence signal is explained by use of a four-level model. The increase in the fluorescence quantum efficiency with pressure is probably the result of incomplete vibrational relaxation coupled with an increase in the intersystem crossing rate with increasing vibrational excitation in the first excited singlet manifold.     

Comparisons of laser-saturated, laser-induced, and planar laser-induced fluorescence measurements of nitric oxide in a lean direct-injection spray flame

We report quantitative, spatially resolved laser-saturated fluorescence (LSF), linear laser-induced fluorescence (LIF), and planar laser-induced fluorescence (PLIF) measurements of nitric oxide (NO) concentration in a preheated, lean direct-injection spray flame at atmospheric pressure. The spray is produced by a hollow-cone, pressure-atomized nozzle supplied with liquid heptane, and the overall equivalence ratio is unity. NO is excited by means of the Q(2)(26.5) transition of the gamma(0, 0) band. LSF and LIF detection are performed in a 2-nm region centered on the gamma(0, 1) band. PLIF detection is performed in a broad ~70-nm region with a peak transmission at 270 nm. Quantitative radial NO profiles obtained by LSF are presented and analyzed so as to correct similar LIF and PLIF profiles. Excellent agreement is achieved among the three fluorescence methodologies.     

Photochemical effect in two-photon laser-induced fluorescence detection of carbon monoxide in hydrocarbon flames

The CO formation as a result of the CO(2) photodissociation at 230.08 nm was observed by using the two-photon laser-induced fluorescence (LIF) method. The measurements were performed in a propane-air combustion product flow and in mixtures of CO(2) and O(2). The temperature dependence of the fluorescence signal caused by CO molecules, produced in the photodissociation of CO(2) molecules under the action of laser radiation at a wavelength of 230.08 nm, was measured at temperatures ranging from 1300 to 2000 K. It is shown that consideration of CO(2) photodissociation under the action of the probing radiation is necessary when one applies the two-photon LIF method for the measurement of small CO concentrations in high-temperature gas mixtures containing CO(2). As an example, a correction is given of the CO concentration profiles measured by the LIF method in the combustion product flow around a cooled metallic plate.     

Simultaneous planar laser-induced incandescence, OH planar laser-induced fluorescence, and droplet Mie scattering in swirl-stabilized spray flames

Simultaneous planar laser-induced incandescence, hydroxyl radical planar laser-induced fluorescence, and droplet Mie scattering are used to study the instantaneous flame structure and soot formation process in an atmospheric pressure, swirl-stabilized, liquid-fueled, model gas-turbine combustor. Optimal excitation and detection schemes to maximize single-shot signals and avoid interferences from soot-laden flame emission are discussed. The data indicate that rich pockets of premixed fuel and air along the interface between the spray flame and the recirculation zone serve as primary sites for soot inception. Intermittent large-scale structures and local equivalence ratio are also found to play an important role in soot formation.     

Temperature measurements in steady axisymmetric partially premixed flames by use of rainbow schlieren deflectometry

We focus on the utility of rainbow schlieren as a tool for measuring the temperature of axisymmetric partially premixed flames (PPFs). Methane-air PPFs are established on a coannular burner. The flames involve two spatially distinct reaction zones, one in an inner premixed region that has a curved tip and a spatially planar wing portion and another that involves an outer nonpremixed zone in which intermediate species burn in air. Schlieren images are found to visualize clearly these PPF characteristics through light deflection by steep refractive-index gradients in the two reaction zone fronts. The temperature distributions of two flames established at fuel-rich mixture equivalence ratios of phi(r) = 1.5 and 2.0, with bulk-averaged velocities, Vreac = 60 cm s(-1) and Vair = 50 cm s(-1), are inferred from color schlieren images, and a measurement error analysis is performed. Errors arise from two sources. One lies in the process of inferring the temperature from the refractive-index measurement by making assumptions regarding the local composition of the flame. We have shown through simulations that the average temperature deviations due to these assumptions are 1.7% for the phi(r) = 1.5 flame and 2.3% for the phi(r) = 2.0 flame. Another source involves the local uncertainty in the measurement of the transverse ray displacement at the filter plane that is used to determine the refractive index and thereafter the flame temperature. We have ascertained that a maximum error of 4.3% in the temperature determination can be attributed to this local measurement uncertainty. This investigation demonstrates the capability of the schlieren technique for providing not only qualitative displays of the PPFs but also full-field-of-view temperature measurements that are accurate, spatially resolved, and nonintrusive.     

Experimental assessment of O(2) interferences on laser-induced fluorescence measurements of NO in high-pressure, lean premixed flames by use of narrow-band and broadband detection

We experimentally investigate the influence of O(2) interferences on laser-induced fluorescence measurements of NO in lean methane-fueled flames at a range of pressures for both narrow-band and broadband fluorescence detection. We identify NO excitation schemes that minimize O(2) interferences. From detection scans we obtain interference spectra for the different NO excitation schemes. We then identify optimum excitation-detection schemes for narrow-band detection measurements of NO. To simulate broadband detection experiments, we numerically apply five different filter combinations to the experimentally obtained detection scans. We develop filter-assessment parameters to judge the effectiveness of the different filtering schemes, and we establish a methodology for evaluating broadband excitation-detection strategies. From this research we identify optimum excitation-detection schemes for broadband detection measurements of NO.     

Measuring nitric oxide in single neurons by capillary electrophoresis with laser-induced fluorescence: use of ascorbate oxidase in diaminofluorescein measurements

As a family of novel fluorescent indicators for nitric oxide (NO), the diaminofluoresceins (DAFs) have allowed real-time measurement of neuronal NO, an important gaseous neurotransmitter. However, the measurement of NO by the most commonly used NO sensor, 4,5-diaminofluorescein (DAF-2), is altered by two processes: the interaction of DAF-2 with intracellular dehydroascorbic acid (DHA) and the impact of ascorbic acid (AA) on the levels of N2O3, the intermediate product of the oxidation of NO that reacts with DAF-2. Similar AA/DHA effects are observed with other DAF probes, including DAF-FM and DAR-4M. To overcome these limitations, we use a specific enzymatic reaction to eliminate the confounding effect of AA on DAF quantitation of NO and then use capillary electrophoresis (CE) with laser-induced fluorescence (LIF) detection to distinguish the various reaction products. First, the enzyme ascorbate oxidase (AO) is used to catalyze the oxidation of AA to DHA. Next, CE-LIF separates the fluorescent products of the reaction of DAF-2 with NO and DHA. Control experiments, including standard mixtures and single neurons with added NO donor, successfully demonstrate the utility of this approach. This protocol is further tested with homogenates of the mouth area from the sea slug Aplysia californica, previously shown to be NO-positive, and individual nitric oxide synthase-containing buccal neurons from the freshwater snail, Lymnaea stagnalis. In each case, significant amounts of NO are detected. This AO DAF methodology is specific, effective, simple, and allows NO to be measured in single cells without detectable interference from other compounds.     

Temperature and pressure imaging using infrared planar laser-induced fluorescence

A new diagnostic technique for measurements of temperature and pressure distribution in gaseous flows has been developed. The technique, based on infrared planar laser-induced fluorescence (IR-PLIF), is applicable to all IR-active species. A simple two-line excitation approach is used for measurements of temperature, while pressure measurements utilize online excitation on one rotational line and offline excitation on another. A demonstration of the technique in a supersonic underexpanded jet of 30% CO2 and 70% N2 was performed, and the results are, to the best of our knowledge, the first demonstration of temperature and pressure imaging using IR-PLIF. The developed diagnostic shows potential for single-shot two-dimensional measurements of temperature and pressure in gaseous flows.     

Comparison of nanosecond and picosecond excitation for two-photon laser-induced fluorescence imaging of atomic oxygen in flames

Two-photon laser-induced fluorescence (LIF) imaging of atomic oxygen is investigated in premixed hydrogen and methane flames with nanosecond and picosecond pulsed lasers at 226 nm. In the hydrogen flame, the interference from photolysis is negligible compared with the LIF signal from native atomic oxygen, and the major limitations on quantitative measurements are stimulated emission and photoionization. Excitation with a nanosecond laser is advantageous in the hydrogen flames, because it reduces the effects of stimulated emission and photoionization. In the methane flames, however, photolytic interference is the major complication for quantitative O-atom measurements. A comparison of methane and hydrogen flames indicates that vibrationally excited CO2 is the dominant precursor for laser-generated atomic oxygen. In the methane flames, picosecond excitation offers a significant advantage by dramatically reducing the photolytic interference. The prospects for improved O-atom imaging in hydrogen and hydrocarbon flames are presented.