Laser-induced Fluorescence Measurements Of OH Research Articles

Flame features and oscillation characteristics in near-blowout swirl-stabilized flames using high-speed OH-PLIF and mode decomposition methods

Flame features and dynamics are important to the explanation and prediction of a lean blowout (LBO) phenomenon. In this paper, recognition of near-LBO flame features and oscillation characterization methods were proposed based on flame spectroscopic images. High-speed planar laser-induced fluorescence measurements of OH were used to capture unique dynamic features such as the local extinction and reignition feature and entrained reactant pockets. The Zernike moment demonstrated a good performance in recognition of stability and near-LBO conditions, though the geometric moment had more advantages to characterize frequency characteristics. Low-frequency oscillations, especially at the obvious self-excited oscillation frequency around 200 Hz, were found when approaching an LBO condition, which can be expected to be used as a novel prediction characteristic parameter of the flameout limit. Proper orthogonal decomposition (POD) and dynamic mode decomposition (DMD) were used to conduct dynamic analysis of near-LBO flames. POD modes spectra showed the unique frequency characteristics of stable and near-LBO flames, which were basically in line with those at the heat-release frequency. The primary POD modes demonstrated that the radial vibration mode dominated in a stable flame, while the rotation mode was found to exist in a near-LBO flame. Analysis of modal decomposition showed that flame shedding and agminated entrained reactant pockets were responsible for generating self-excited flame oscillations.

Stabilization Mechanisms of Swirling Premixed Flames With an Axial-Plus-Tangential Swirler

The stabilization of premixed flames within a swirling flow produced by an axial-plus-tangential swirler is investigated in an atmospheric test rig. In this system, flames are stabilized aerodynamically away from the solid components of the combustor without the help of any solid anchoring device. Experiments are reported for lean CH4/air mixtures, eventually also diluted with N2, with injection Reynolds numbers varying from 8500 to 25,000. Changes of the flame shape are examined with OH* chemiluminescence and OH laser-induced fluorescence measurements as a function of the operating conditions. Particle image velocimetry (PIV) measurements are used to reveal the structure of the velocity field in nonreacting and reacting conditions. It is shown that the axial-plus-tangential swirler allows to easily control the flame shape and the position of the flame leading edge with respect to the injector outlet. The ratio of the bulk injection velocity over the laminar burning velocity Ub/SL, the adiabatic flame temperature Tad, and the swirl number S0 are shown to control the flame shape and its position inside the combustion chamber. It is then shown that the axial velocity field produced by the axial-plus-tangential swirler is different from those produced by purely axial or radial devices. It takes here a W-shape profile with three local maxima and two minima. The mean turbulent flame front also takes this W-shape in an axial plane, with two lower positions located slightly off-axis and corresponding to the positions where the axial flow velocity is the lowest. It is finally shown that these positions can be inferred from axial flow velocity profiles under nonreacting conditions.

Interaction of turbulent premixed flames with combustion products: Role of stoichiometry

Stabilization methods of turbulent flames often involve mixing of reactants with hot products of combustion. The stabilizing effect of combustion product enthalpy has been long recognized, but the role played by the chemical composition of the product gases is typically overlooked. We employ a counterflow system to pinpoint the effects of the combustion product stoichiometry on the structure of turbulent premixed flames under conditions of both stable burning and local extinction. To that end, a turbulent jet of lean-to-rich, CH4/O2/N2-premixed reactants at a turbulent Reynolds number of 1050 was opposed to a stream of hot products of combustion that were generated in a preburner. While the combustion product stream temperature was kept constant, its stoichiometry was varied independently from that of the reactant stream, leading to reactant-to-product stratification of relevance to practical combustion systems. The detailed structure of the turbulent flame front was analyzed in two series of experiments using laser-induced fluorescence (LIF): joint CH2O LIF and OH LIF measurements and joint CO LIF and OH LIF measurements. Results revealed that a decrease in local CH2O+OH and CO+OH reaction rates coincide with the depletion of OH radicals in the vicinity of the combustion product stream. These critical combustion reaction rates were more readily quenched in the presence of products of combustion from a stoichiometric flame, whereas they were favored by lean combustion products. As a result, stoichiometric combustion products contributed to a greater occurrence of local extinction. Furthermore, they limited the capacity of premixed reactants to ignite and of the turbulent premixed flames to stabilize. In contrast, lean and rich combustion products facilitated flame ignition and stability and reduced the rate of local extinction. The influence of the combustion product stream on the turbulent flame front was limited to a zone of approximately two millimeters from the gas mixing layer interface (GMLI) of the product stream. Flame fronts that were separated from the GMLI by larger distances were unaffected by the product stream stoichiometry.

Imaging measurements and LES-CMC modeling of a partially-premixed turbulent dimethyl ether/air jet flame

Turbulent dimethyl ether (DME) jet flames provide a canonical flame geometry for studying turbulence–flame interactions in oxygenated fuels and for developing predictive models of these interactions. The development of accurate models for DME/air flames would establish a foundation for studies of more complex oxygenated fuels. We present a joint experimental and computational investigation of the velocity field and OH and CH2O distributions in a piloted, partially-premixed turbulent DME/air jet flame with a jet exit Reynolds number, ReD, of 29,300. The turbulent DME/air flame is analogous to the well-studied, partially-premixed methane/air jet flame, Sandia Flame D, with identical stoichiometric mixture fraction, ξst=0.35, and bulk jet exit velocity, Vbulk=45.9m/s. Measurements include particle image velocimetry (PIV) and simultaneous CH2O and OH laser-induced fluorescence (LIF) imaging. Simulations are performed using a large eddy simulation combined with conditional moment closure (LES-CMC) on an intermediate size grid of 1.3million cells. Overall, the downstream evolution of the mean and RMS profiles of velocity, OH, and CH2O are well predicted, with the largest discrepancies occurring for CH2O at x/D=20–25. LES-CMC simulations employing two different chemical reaction mechanisms (Kaiser et al., 2000 [20] and Zhao et al., 2008 [21]) show approximately a factor of two difference in the peak CH2O mole fractions, whereas OH mole fractions are in good agreement between the two mechanisms. The single-shot LIF measurements of OH and CH2O show a wide range of separation distances between the spatial distributions of these intermediate species with gaps on the order of millimeters. The intermittency in the overlap between these species indicates that the consumption rates of formaldehyde by OH in the turbulent DME/air jet flame may be highly intermittent with significant departures from flamelet models.

Optical spectroscopy diagnostics of discharges at atmospheric pressure

In this paper we review the application of classical optical spectroscopy techniques, optical emission spectroscopy, laser-induced fluorescence (LIF) and absorption, to atmospheric-pressure discharges, with special emphasis on the importance of collision-induced transformations in electronic excited states. Collision processes will be reviewed that are relevant to the main atomic and molecular radicals of interest in the actual application framework. A critical discussion will be devoted to the available rate constant data for collision quenching and vibrational relaxation of N2(C 3Πu, v = 0–4) and , whose emissions are used for the spectroscopic determination of the reduced electric field by the nitrogen band ratio method. A further detailed discussion will address LIF measurements of OH in unknown He(Ar) + humid air mixtures.

Airborne intercomparison of HO<sub>x</sub> measurements using laser-induced fluorescence and chemical ionization mass spectrometry during ARCTAS

Abstract. The hydroxyl (OH) and hydroperoxyl (HO2) radicals, collectively called HOx, play central roles in tropospheric chemistry. Accurate measurements of OH and HO2 are critical to examine our understanding of atmospheric chemistry. Intercomparisons of different techniques for detecting OH and HO2 are vital to evaluate their measurement capabilities. Three instruments that measured OH and/or HO2 radicals were deployed on the NASA DC-8 aircraft throughout Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) in the spring and summer of 2008. One instrument was the Penn State Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) for OH and HO2 measurements based on Laser-Induced Fluorescence (LIF) spectroscopy. A second instrument was the NCAR Selected-Ion Chemical Ionization Mass Spectrometer (SI-CIMS) for OH measurement. A third instrument was the NCAR Peroxy Radical Chemical Ionization Mass Spectrometer (PeRCIMS) for HO2 measurement. Formal intercomparison of LIF and CIMS was conducted for the first time on a same aircraft platform. The three instruments were calibrated by quantitative photolysis of water vapor by ultraviolet (UV) light at 184.9 nm with three different calibration systems. The absolute accuracies were ±32% (2σ) for the LIF instrument, ±65% (2σ) for the SI-CIMS instrument, and ±50% (2σ) for the PeRCIMS instrument. In general, good agreement was obtained between the CIMS and LIF measurements of both OH and HO2 measurements. Linear regression of the entire data set yields [OH]CIMS = 0.89 × [OH]LIF + 2.8 × 104 cm−3 with a correlation coefficient r2 = 0.72 for OH, and [HO2]CIMS = 0.86 × [HO2]LIF + 3.9 parts per trillion by volume (pptv, equivalent to pmol mol−1) with a correlation coefficient r2 = 0.72 for HO2. In general, the difference between CIMS and LIF instruments for OH and HO2 measurements can be explained by their combined measurement uncertainties. Comparison with box model results shows some similarities for both the CIMS and LIF measurements. First, the observed-to-modeled HO2 ratio increases greatly for higher NO mixing ratios, indicating that the model may not properly account for HOx sources that correlate with NO. Second, the observed-to-modeled OH ratio increases with increasing isoprene mixing ratios, suggesting either incomplete understanding of isoprene chemistry in the model or interferences in the measurements in environments where biogenic emissions dominate ambient volatile organic compounds.

Uncertainty assessment of species measurements in acetone counterflow diffusion flames

To quantitatively understand the uncertainty of intrusive species sampling measurements using a microprobe, velocity and speciation profiles of acetone counterflow diffusion flames have been experimentally investigated with cross validations using non-intrusive particle image velocimetry (PIV) and laser induced fluorescence (LIF) measurements. It is shown that the separation distance between the fuel and oxidizer nozzles needs to be sufficiently large to achieve uniform radial velocity profiles at the nozzle exit and accurate measurements of fuel concentration distributions in flames. The impacts of the diffusion flame location relative to the stagnation plane and the diffusion flame thickness on quantitative species sampling are investigated by varying the fuel to oxygen ratio as well as nitrogen and helium as fuel diluents. The results show that the diffusion flame needs to be located on the fuel side far from the stagnation plane in order to obtain reliable speciation measurements of fuel oxidation-related species. For helium dilution in the fuel side, a significant deviation from the model prediction is found due to the excessively fast diffusion velocity of helium. The impact of the intrusive probe on the flow field and the structure of the counterflow diffusion flame are identified by acetone and OH LIF measurements. The uncertainty in the speciation measurement associated with flow perturbations by the probe is quantified and found to be comparable to the outer diameter of the probe, ±0.3mm. A simple Reynolds number analysis shows that the flow near the probe is just on the outskirts of the Stokes regime. Finally, the structure of the acetone diffusion flame is measured quantitatively with species measurements of ethane, ethylene, and acetylene. The comparison between predictions and measurements indicate that the current C2 kinetic mechanism needs to be improved for quantitative prediction of the acetone flame structures.

The role of in situ reforming in plasma enhanced ultra lean premixed methane/air flames

This paper describes a mechanism for the stabilization of ultra lean premixed methane/air flames by pulsed nonequilibrium plasma enhancement. It is shown that the pulsed discharge plasma produces a cool (∼500–600 K) stream of relatively stable intermediate species including hydrogen (H 2) and carbon monoxide (CO), which play a central role in enhancing flame stability. This stream is readily visualized by ultraviolet emission from electronically excited hydroxyl (OH) radicals. The rotational and vibrational temperature of this “preflame” are determined from its emission spectrum. Qualitative imaging of the overall flame structure is obtained by planar laser-induced fluorescence measurements of OH. Preflame nitric oxide (NO) concentrations are determined by gas sampling chromatography. A simple numerical model of this plasma enhanced premixed flame is proposed that includes the generation of the preflame through plasma activation, and predicts the formation of a dual flame structure that arises when the preflame serves to pilot the combustion of the surrounding non-activated premixed flow. The calculation represents the plasma through its ability to produce an initial radical yield, which serves as a boundary condition for conventional flame simulations. The simulations also capture the presence of the preflame and the dual flame structure, and predict preflame levels of NO comparable to those measured. A subsequent pseudo-sensitivity analysis of the preflame shows that flame stability is most sensitive to the concentrations of H 2 and CO in the preflame. As a consequence of the role of H 2 and CO in enhancing the flame stability, the blowout limit extensions of methane/air and hydrogen/air mixtures in the absence/presence of a discharge are investigated experimentally. For methane/air mixtures, the blowout limit of the current burner is extended by ∼10% in the presence of a discharge while comparable studies carried out in lean hydrogen/air flames fail to extend this limit.

Influence of ferrocene addition to a laminar premixed propene flame: Laser diagnostics, mass spectrometry and numerical simulations

The detailed influence of ferrocene in a low-pressure, fuel-rich, laminar, premixed propene/oxygen/argon flat flame was investigated experimentally using molecular beam sampling mass spectrometry (MBMS), laser-induced fluorescence (LIF), and compared to numerical simulations. MBMS was applied to analyze the species profiles of important intermediates in the flames with and without ferrocene doping. The concentration profile of iron atoms was measured with absorption sensitive LIF, which provides absolute number densities without additional calibrations. The flame temperature was obtained by two-line OH LIF measurements. One dimensional numerical simulations of the flames using detailed models from the literature were performed and the modeling results are compared with the experimental measurements. The iron measurements show reasonable agreement with the numerical simulation, while some discrepancies were found at larger heights. The MBMS measurements show a decrease in flame velocity when ferrocene was added, which was not provided by the model.

Laser-induced fluorescence measurements of NCN in low-pressure CH 4/O 2/N 2 flames and its role in prompt NO formation

NCN profiles were measured for five rich and lean premixed, low-pressure methane flames using laser-induced fluorescence (LIF). A semiquantitative determination of the NCN mole fractions as a function of spatial height above the burner is made by calibrating the NCN LIF signals using highly accurate OH LIF measurements in an adjacent spectral region. The resulting calibration yields an uncertainty estimate of a factor of 3 for the absolute values, but only ±25% for the relative NCN profiles. For all flame conditions, the NCN profiles occur immediately downstream of previously measured CH profiles. In addition, high correlations are found between the peak CH and peak NCN concentrations and the peak NCN and postflame NO concentrations over all equivalence ratios. These observations are consistent with NCN being the primary product channel from the CH + N 2 reaction and the initial intermediate in the prompt NO formation. This is the first mechanistic study in hydrocarbon flames that provides such experimental evidence. The experimental profiles are compared to numerical calculations using modified versions of two well-established hydrocarbon kinetic mechanisms. Reasonable agreement between the calculations and experiment is found for NCN profile shape, location of peak NCN concentrations, and absolute mole fractions. However, the dependence on stoichiometry of the peak NCN concentration is overestimated. Further work is required on NCN kinetics for modeling prompt NO in laminar premixed flames.

Hydroxyl radical concentration measurements near the deposition substrate in low-pressure diamond-forming flames

OH radical profiles were measured in the near-deposition-surface region in low-pressure, stagnation-flow diamond-forming flames using laser-induced fluorescence (LIF). The objective of these measurements was to explore the chemistry of the diamond chemical-vapor deposition (CVD) process by resolving the OH profile near the deposition substrate. Detailed OH LIF measurements were performed in stagnation-flow diamond-forming C 2H 2/O 2 flames with equivalence ratios of 1.80, 2.10, and 2.32. The flame with an equivalence ratio of 1.80 exhibited no diamond film growth, while the flame with an equivalence ratio of 2.32 exhibited significant diamond film growth. The LIF measurements were performed in the linear LIF regime and the laser frequency was scanned across the spectral profile of the P 1(3) line in the (1,0) band of the A 2 Σ +– X 2 Π electronic transition at each spatial location. In earlier H 2 CARS measurements, the temperature gradients near the deposition substrate were resolved and good agreement between the measured temperature profiles and the numerical modeling results was demonstrated. The measured LIF profiles were corrected for electronic quenching and the variation of the Boltzmann fraction with temperature. Major species profiles were calculated using the results of the numerical flame code. The laser beam spatial profile was accounted for by convolving the theoretical OH profiles from the numerical model with the measured laser beam profile. The experimental OH profiles for all three cases are compared with theoretical results calculated using a stagnation-flame model that includes the diamond-formation surface chemistry. The measured OH concentrations near the deposition surface are substantially lower than theoretical results from a flame model that does not include the surface chemistry, but somewhat higher than for the model that does include the diamond-formation surface chemistry, especially for the flames with equivalence ratios of 1.80 and 2.10. The measured OH profile for the flame with an equivalence ratio of 2.32 is in good agreement with the profile calculated using a theoretical model with diamond-formation surface chemistry.

Laser imaging system for determination of three-dimensional scalar gradients in turbulent flames.

An imaging system for the measurement of three-dimensional (3D) scalar gradients in turbulent hydrocarbon flames is described. Combined line imaging of Raman scattering, Rayleigh scattering, and CO laser-induced fluorescence (LIF) allows for simultaneous single-shot line measurements of major species, temperature, mixture fraction, and a one-dimensional surrogate of scalar dissipation rate in hydrocarbon flames, while simultaneous use of two crossed, planar LIF measurements of OH allows for determination of instantaneous flame orientation. In this manner the full 3D scalar dissipation can be estimated in some regions of a turbulent flame on a single-shot basis.

Photochemical effects of KrF excimer excitation in laser-induced fluorescence measurements of OH in combustion environments

This paper presents experimental evidence that using the KrF excimer laser for quantitative laser-induced fluorescence (LIF) studies of the OH A-X (3,0) system is highly problematic if the effects of both photobleaching and photochemistry are not included for laser spectral irradiances greater than 20 MW/cm2 cm-1. Pump-probe and time-resolved measurements of the OH LIF signal in an atmospheric pressure, premixed CH4-air flame at low- and high-laser-spectral-irradiance conditions show that a significant amount of OH is produced from photofragments resulting from the simultaneous 2-photon predissociation of H2O molecules in the C-X system. A 5+2-level rate-equation model that includes the effects of both photobleaching and photochemical OH production is shown to satisfactorily predict the data using a single adjustable parameter given by the effective, spectrally integrated 2-photon cross-section of H2O near 248 nm. The time-integrated OH LIF signal was found to depend on both the laser spectral irradiance and the local concentration of H2O. Additionally, use of the KrF excimer laser for 2-line rotational thermometry can produce temperature errors as great as +550 K at high laser-pulse energies.

Picosecond planar laser-induced fluorescence measurements of OH A^2 Σ^+ (ν′ = 2) lifetime and energy transfer in atmospheric pressure flames

A picosecond, excimer-Raman laser (268 nm, 400 ps FWHM) was used for laser sheet excitation of OH in the (2, 0) band. The fluorescence was detected with a fast-gated, intensified camera (400-ps gate width). The effective collisional lifetime of the spectrally integrated fluorescence was measured in two dimensions by shifting the intensifier gate across the decay curve. The average lifetime is ~2.0 ns for a stoichiometric methane -air flame with spatial variations of +/-10 %. Shorter collisional lifetimes were measured for rich flame conditions that are due to a higher number density of the quenchers. Vibrational energy transfer (VET) was observed in premixed methane -air and methane -oxygen flames by putting the fast-gated camera behind a spectrometer. The spectrum of the methane -air flame shows strong VET in contrast with the methane -oxygen flame. This is because N2 is a weak electronic quencher but a strong VET agent. By fitting the measured time dependence of the different vibrational populations ( ' = 2, 1, 0) to a four-level model, rate constants for quenching and VET were determined. For the lower states ( ' = 0, 1) our results are in good agreement with literature values. For a prediction of a spectrally integrated, collisional lifetime in a known collisional environment it is important to consider not only the quenching but also the amount of energy transfer in the excited state as well as the spectral detection sensitivity.

The oxidation of soot and carbon monoxide in hydrocarbon diffusion flames

Quantitative OH · concentrations and primary soot particle sizes have been determined in the soot oxidation regions of axisymmetric diffusion flames burning methane, methane/butane, and methane/1-butene in air at atmospheric pressure. The total carbon flow rate was held constant in these flames while the maximum amount of soot varied by a factor of seven along the centerline. Laser-induced fluorescence measurements of OH · were placed on an absolute basis by calibration against earlier absorption results. The primary size measurements of the soot particles were made using thermophoretic sampling and transmission electron microscopy. OH · concentrations are greatly reduced in the presence of soot particles. Whereas large super-equilibrium ratios are observed in the high-temperature reaction zones in the absence of soot, the OH · concentrations approach equilibrium values when the soot loading is high. The diminished OH · concentrations are found to arise from reactions with the soot particles and only to a minor degree from lower temperatures due to soot radiation losses. Analysis of the soot oxidation rates computed from the primary particle size profiles as a function of time along the flame centerlines shows that OH · is the dominant oxidizer of soot, with O 2 making only a small contribution. Higher collision efficiencies of OH · reactions with soot particles are found for the flames containing larger soot concentrations at lower temperatures. A comparison of the soot and CO oxidation rates shows that although CO is inherently more reactive than soot, the soot successfully competes with CO for OH · and hence suppresses CO oxidation for large soot concentrations.

Laser-induced fluorescence measurements of oh· concentrations in the oxidation region of laminar, hydrocarbon diffusion flames

Quantitative OH· concentrations have been measured in four coannular diffusion flames, burning, methane at a single fuel, flow rate and ethene at fuel flow rates which produce nonsmoking incipient smoking, and smoking conditions. Laser-induced fluorescence has been used to make point profile, line image, and two-dimensional image measurements. These data have been placed on an absolute basis by reference to earlier absorption results. Particular emphasis has been placed, on the investigation of the soot oxidation region in these laminar flames, since current soot models must utilize either assumed or estimated OH· concentrations. As the soot concentration increases, both the OH· concentration and the flame temperature are found to decrease. Estimates of the superequilibrium levels of OH· increase as the measured concentrations decrease, which makes accurate a priori prediction of OH· concentrations problematic in diffusion flames containing significant soot concentrations.

A complete treatment of a steady-state four-level model for the interpretation of OH laser-induced fluorescence measurements in atmospheric pressure flames

In order to obtain OH concentration measurements in atmospheric pressure flames from saturated fluorescence signal, we have developed a stationary four-level model. A general relationship between the measured upper state population and the total number density has been derived. The effects of the imbalance between the rotational transfer rates in the upper and ground states is analyzed. We show that in the case of comparable rotational rates, the results of our treatment are similar to the ones obtained with the balanced cross rate model. A set of complementary data which should facilitate absolute OH concentration measurements is also pointed out.

Laser-Induced Fluorescence Measurements of OH in Laminar C2H6/O2/N2Flames at High Pressure

Abstract Using the laser-induced fluorescence method, we have measured relative OH concentration profiles in flat laminar, lean premixed C2H6/O2/N2, flames at 3.2, 6.3, 9.5, and 12.6 atm. By employing a range of flow rates of the combustible mixture, we demonstrate that the reaction zone can be probed at these pressures. In comparison to atmospheric flames, the reaction zone was small and accordingly the [OH] gradient was large; we also observed large gradients in the OH recombination zone. A result of the large gradients is an increase in the noise of the fluorescence signal compared to that at atmospheric pressure. Another impediment to making measurements was beam steering resulting from flame instability, which increased with pressure. We therefore limited our measurements to 12.6 atm.

Influence of Rotational Relaxation on Tropospheric OH Laser Induced Fluorescence Measurements

Abstract Rotational relaxation of OH molecules in the 2II electronic ground state has been observed to occur in collisions with water molecules with gas kinetic probability. It causes an additional contribution to the already well known sources of interference when LIF is used to monitor tropospheric OH. As the laser generated OH is originally produced mostly in high rotational states, the fast relaxation phenomenon leads to a further population of OH in low rotational states. These states are used to monitor tropospheric OH by spectroscopic methods. The observed effect therefore increases the interference. A mathematical analysis is presented, revealing the effect of all relevant parameters.

Single-pulse laser-induced OH fluorescence in an atmospheric flame, spatially resolved with a diode array detector

Laser-induced fluorescence measurements of OH have been performed in an atmospheric stoichiometric CH(4)/air flame and in a highly sooting propane flame. The measurements were realized with a single 6-nsec pulse from a frequency-doubled dye laser pumped by a Nd:YAG laser and with a spatial resolution of ~25 microm. This was achieved by imaging through a suitably chosen filter set a section of the laser beam onto a gated and intensified diode array.