Laser-induced fluorescence determination of flame temperatures in comparison with CARS measurements

Temperature profiles in several premixed low pressure H₂/O₂/N₂ flames and in an atmospheric pressure CH₄/air flame were determined by laser-induced fluorescence (LIF) and by CARS experiments. In the LIF study, temperatures were derived from OH excitation spectra, CARS temperatures were deduced from N₂ Q-branch spectra. The present study is the first quantitative comparison of these two methods for temperature determination in flames burning at pressures up to 1 bar. The resulting temperatures showed good agreement.     

Laser-induced fluorescence detection of acetylene in low-pressure propane and methane flames

Laser-induced fluorescence is used to detect and record profiles of acetylene formed as an intermediate species in 10-Torr premixed propane and methane flames. In low-temperature regions of the flames, excitation spectra confirm acetylene as the spectral carrier. The spectra of acetylene overlap those of O₂ and NO in terms of both excitation and detection wavelengths, however, acetylene can be detected with relatively little interference in the vicinity of 228 nm, using a detection wavelength of 260 nm. The fluorescence lifetime of acetylene in the flame conditions studied is approximately 20 ns, much shorter than the radiative lifetime, due to a high quenching rate for all the colliders investigated. This can be exploited in low-pressure flames to avoid interference from acetylene in monitoring nitric oxide. The acetylene mole fraction in propane flames reaches its peak value at nearly the same location as that of HCO, slightly closer to the burner than the peak CH mole fraction. The acetylene fluorescence signal is easily detected in propane flames over equivalence ratios from 0.6 to 1.2, although it increases under fuel-rich conditions. In methane flames, the acetylene signal is much weaker and is undetectable for fuel-lean conditions. Received: 5 August 2002 / Revised version: 30 September 2002 / Published online: 20 December 2002 RID="*" ID="*"Corresponding author. Fax: +1-202/767-1716, E-mail: brad@code6185.nrl.navy.mil     

Quantitative laser-induced fluorescence: Some recent developments in combustion diagnostics

This report summarizes several recent applications of quantitative laser-induced fluorescence techniques for the determination of species concentrations and temperature in combustion processes. Several lines of further development are discussed.     

Laser-induced fluorescence detection of singlet CH2 in low-pressure methane/oxygen flames

Methylene, CH₂, is a chemically important intermediate in hydrocarbon combustion but has previously eluded optical detection in a combustion environment. The CH₂ signal as a function of height above the burner surface in a premixed, laminar, methane/oxygen flame (5.6 Torr and fuel equivalence ratio 1.05) is measured by laser-induced fluorescence (LIF) in the B ₁ – ã¹ A ₁ electronic system. The ã state which lies 3165 cm^–1 above the ground state is populated at the high temperatures of the flame (800–1800 K). Although less than one photon for each laser pulse is detected, we can unambiguously attribute the LIF features in the region 450 to 650 nm to CH₂ by both scanning the excitation laser and dispersing fluorescence. LIF temperatures and CH and OH LIF concentration profiles are also obtained for the flame. The CH₂ radical concentration maximum occurs closer to the burner than that of either OH or CH, as expected from models of methane combustion chemistry.     

Time-, wavelength-, and polarization-resolved measurements of OH (A 2Σ+ ) picosecond laser-induced fluorescence in atmospheric- pressure flames

Laser-induced fluorescence of OH (A ²Σ⁺, v’=1) was measured in hydrogen/oxygen and hydrogen/air/nitrogen flames using laser pulses of 80 psec duration. A 2D signal acquisition scheme simultaneously employed wavelength, temporal, and polarization resolution. The signals emitted in different rotational branches exhibit polarization-dependent intensities, depending on the rotational branch of the absorption line used. It is possible to select experimental conditions such that rotational and vibrational relaxation as well as electronic quenching can be monitored simultaneously. Advantages and limitations of the experimental approach are discussed. Numerical simulations are presented of the LIF spectra affected by energy transfer. Received: 29 March 1999 / Revised version: 14 June 1999 / Published online: 27 October 1999     

Spatially resolved absolute concentration and fluorescence-lifetime determination of H2CO in atmospheric-pressure CH4/air flames

Using laser-induced fluorescence (LIF), spatially resolved concentration profiles of formaldehyde (H₂CO) were obtained in the preheating zone of atmospheric-pressure premixed CH₄/air flames stabilized on the central slot of a multiple-slot burner similar in construction to domestic boilers. The isolated pQ₁(6) rotational line (339.23 nm) in the 2¹ ₀4¹ ₀ vibronic combination transition in the ?¹A₂- ¹A₁ electronic band system around 339 nm was excited in the linear LIF intensity regime. For a quantification of quenching effects on the measured LIF signal intensities, relative fluorescence quantum yields were determined from direct fluorescence lifetime as a function of height above the slot exit. Absolute H₂CO number densities in the flames were evaluated from a calibration of measured LIF signal intensities versus those obtained in a low-pressure sample with a known H₂CO vapor pressure. Peak concentrations in the slightly lean and rich flames reached (994±298) and (174±52) ppm, respectively. Received: 25 September 2000 / Published online: 30 November 2000     

Two-photon predissociative fluorescence of H2O by a KrF laser for concentration and temperature measurement in flames

Two-photon laser-induced predissociative fluorescence (LIPF) of H₂O is examined as a potential measurement technique of H₂O concentration and temperature in flames. Two-photons of 248 nm light from a narrowband KrF laser excite H₂O to the highly predissociative state in a hydrogen-air flame. The subsequent bound-free emission is observed from 400–500 nm in the flame at temperatures of 1000–2000 K and is found to be free of fluorescence interference from other flame species. This LIPF signal is not affected by collisional quenching due to the short lifetime of the predissociative state (2.5 ps). Broadband laser dispersion spectra, narrowband laser dispersion spectra, laser excitation spectra and probability density functions of the H₂O fluorescence are obtained in the hydrogen flame. The H₂O LIPF signal is found to be temperature sensitive and a two-line LIPF technique is needed for concentration and temperature measurement. The accuracy of a two-line LIPF technique for H₂O concentration and temperature measurement is determined.     

Sensitive detection of H2 molecules by two-photon excited laser-induced fluorescence

The sensitive detection of H₂ molecules was demonstrated by means of twophoton excited laser-induces fluorescence spectroscopy with a narrow-band ArF excimer laser. A detection limit of 2×10¹⁴ cm^–3 was obtained with an excitation power of 150 kW. This is already comparable with that obtained by the coherent anti-Stokes Raman scattering (CARS). This technique was successfully applied to measure a spatial distribution of H₂ in a town-gas burner.     

Measurement of vibrational energy transfer of OH (A2Σ+,v′=1→0) in low-pressure flames

2 Σ⁺) was measured in a low-pressure H₂/O₂ flame for three rotational levels of OH (v^′=1). Rate coefficients for collisions with H₂O and N₂ were determined. At 1600 K, k_VET (N₂) is (in 10^-11 cm³s^-1) 10.1±2, 6.1±1.8, and 3.8±1.3 for N^′=0, 5, and 13, respectively. The k_VET (H₂O) is <1.1±1.8. The k_Q (N₂) is <2.4±8 for both vibrational levels. The k_Q (H₂O) in v^′=1 is 59.1±6.5, 54.7±6.4, and 54.9±6.6 for N^′=0, 5, and 13, respectively, and, determined indirectly, 74.6±10.4, 70.6±10.3, and 63.4±7.3 for N^′=0, 5, and 13 in v^′=0. A multi-level model of OH population dynamics, which is being developed for the quantitative simulation of experimental LIF spectra, was extended to include VET. It was attempted to simulate state-to-state-specific VET coefficients for N₂ collisions. From these simulations it appears that angular momentum conservation does not determine the N dependence of the vibrational relaxation step. Received: 9 September 1996/Revised version: 6 January 1997     

C2 creation,emission, and laser-induced fluorescence in flames and cold gases

We describe photochemical production of C₂ in the upper (d ³_g) and the lower (a ³_u) levels of the Swan-band transitions by 266 and 292-nm laser irradiation of flames and room-temperature flows of acetylene and ethylene. Topics treated include the spectroscopy of the Swan bands, lifetimes and quenching of the Swan-band emission, intensity dependences of the Swan-band emission in several environments, profiles of C₂ in low-pressure hydrocarbon flames, and the affect of Swan-band emission on three-photon-excited fluorescence detection of atomic hydrogen in hydrocarbon flames.This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences     

Carbon atom fluorescence and C2 emission detected in fuel-rich flames using a UV laser

Laser-induced fluorescence from carbon atoms, excited at the two-photon resonances around 280 nm, has been detected in fuel-rich hydrocarbon flames together with Swan band emission from the C₂ radical, which was non-resonantly excited at the same wavelengths. The emission from the C atom and from the C₂ molecule exhibited several similarities, indicating a possible common photo-chemical origin.     

Wide- and narrow-band saturated fluorescence measurements of hydroxyl concentration in premixed flames from 1 bar to 10 bar

We have studied the use of wide-band detection in conjunction with saturation of a rovibronic transition of OH within itsA ^{2 +}–X ²(0,0) band. For wide-band detection, in which fluorescence is detected from the entire excited rotational manifold, the fluorescence yield is sensitive to collisions in two ways. First, it is sensitive to the ratio of rate coefficients describing rotational energy transfer and electronic quenching; this ratio determines the number of neighboring rotational levels that are populated during the laser pulse. Second, the fluorescence yield can vary with the total collisional rate coefficient; only after a sufficient number of collisions, corresponding to 2.5 ns in an atmospheric flame, does the rotational manifold reach steady state. We also compare measurements employing wide-band (detecting theR ₁ andR ₂ branches) and narrow-band (detecting a single transition) saturated fluorescence of OH. Over a wide range of conditions — obtained by varying the equivalence ratio, temperature, N₂ dilution, and pressure — the wide- and narrow-band fluorescence techniques compare well. Given this good agreement, wide-band saturated fluorescence could be especially useful for analyzing atmospheric flames with XeCl-excimer lasers; one can potentially obtain 2—D images of OH which have a high signal-to-noise ratio and a reduced sensitivity to laser irradiance and quenching.     

Laser diagnostics of NO reburning in fuel-rich propene flames

Absolute NO concentrations were measured by laser-induced fluorescence (LIF) in three different fuel-rich non-sooting propene flames (φ=1.5, 1.8 and 2.3). The experiments were performed in low-pressure premixed propene flames with 0.2%-1% NO added. Laser diagnostics was applied as a tool for investigating reburn chemistry. The Q₂(25.5) line in the A-X(0,0) band was excited because of the small temperature dependence of its ground state population. The NO fluorescence lifetimes were measured directly and compared to theoretical values. The initial NO levels are strongly reduced in all three flames. According to modeling results, the HCN mole fraction increases strongly with stoichiometry. As guidelines for laser diagnostics applications in such systems, the modeling results were analyzed with respect to the main reaction channels and reaction partners in fuel-rich flames. Received: 1 March 2000 / Revised version: 20 April 2000 / Published online: 20 September 2000     

Laser-induced fluorescence imaging in a 100 kW natural gas flame

A tunable excimer laser at 248 nm (KrF) and 193 nm (ArF) has been used to monitor two-dimensional OH and NO distributions in the turbulent flame of a 100 kW natural gas burner. Spatially resolved fluorescence (spatial resolution better than 1.0 mm) from a 20 cm×20 cm area is collected under single shot conditions. We describe the problems encountered when laser-induced fluorescence imaging techniques are applied to large scale flames. Special experimental arrangements, imposed by the turbulent behavior of the flame we used, are also described.     

Calibration of imaging laser-induced fluorescence measurements in highly absorbing flames

It has been described earlier that imaging measurements of laser-induced fluorescence (LIF) in flames can be calibrated to number densities with an integrated absorption measurement provided the integrated absorption is small. In this paper a method is presented that extends the technique to flames with substantial absorption, improves the number density determination and allows the experimental parameters to be chosen more freely. The method is based on an iterative computer procedure that reconstructs the 1-D spatially resolved absorption profile from laser measurements of the 1-D spatially resolved LIF and the integrated absorption of the laser beam. The technique is experimentally demonstrated by measurements of OH number densities in atmospheric flames. It is potentially a single-pulse method. Other applications of the iterative procedure are mentioned.     

Degenerate four-wave mixing diagnostics on OH and NH radicals in flames

Degenerate four wave mixing (DFWM) is applied as a diagnostic to study OH and NH radicals in flames. DFWM is a coherent technique which offers the advantages of a highly collimated signal beam permitting efficient rejection of interfering radiation and requiring minimal optical access. Rotational temperatures have been determined from the DFWM spectra and are in close agreement with the temperatures measured using coherent anti-Stokes Raman scattering of nitrogen.Work performed at the Combustion Research Facility, Sandia National Laboratories, supported by the U.S. Department of Energy, Energy Conversion and Utilization Technologies Program and Office of Basic Energy Sciences, Division of Chemical Sciences     

ps-LIF measurements of minor species concentration in a counterflow diffusion flame interacting with a vortex

Interactions of vortices and flame fronts may be considered as the basic structural elements of turbulent combustion. Additionally, they play an important role in flame instabilities as well as extinction and ignition processes. An ideal geometry to study these interactions is the counterflow diffusion burner with an additional actuator-driven nozzle for the generation of a vortex ring. This burner has already been well-characterized by other methods including CARS, LDA and PLIF. We present first quantitative measurements of minor species concentration in this flame using a short-pulse laser and time- and spatially resolved fluorescence detection with a streak camera. Quench-free OH concentrations are obtained by analysis of the time-resolved profiles. The high power density of the laser pulses allowed linewise detection of hydrogen using a three-photon excitation scheme. Simultaneously, shape and position of the vortex was monitored using two-dimensional detection of flame emissions. Spatially resolved concentration profiles of H and OH are presented for different interaction heights and times in the vortex. For steady flames, comparisons with model calculations are shown. Received: 19 July 2000 / Revised version: 13 December 2000 / Published online: 21 February 2001     

Laser-diagnostic multi-species imaging in strongly swirling natural gas flames

Within the TECFLAM group a standard swirl burner is investigated, both experimentally using optical and probe measurements and by simulations using different modeling attempts. The present study is focused on the laser-based investigation of the NO distribution within the reacting flow field of a strongly swirling, confined 150-kW natural gas flame. Simultaneous quantitative measurements of NO- and OH-concentration fields by laser-induced fluorescence imaging (LIF) and temperature distribution (Rayleigh scattering) are performed. Mixing properties of the unburned gases are investigated for the isothermal and the combusting flow using tetrahydrothiophene (THT) as a new fluorescing tracer. These measurements show which areas are sufficiently mixed allowing for the application of planar Rayleigh thermometry. Areas where THT-LIF interferes with OH-LIF detection are localized and omitted from data evaluation. The data is analyzed yielding global scalar fields for comparison with model simulations and correlations between the different measured scalars are investigated showing an almost linear correlation of NO concentration and temperature within the swirl flame whereas no apparent correlation between NO and OH concentration was found. Received: 20 April 2000 / Revised version: 16 May 2000 / Published online: 20 September 2000