Quantitative NO-LIF imaging in high-pressure flames

Planar laser-induced fluorescence (PLIF) images of NO concentration are reported in premixed laminar flames from 1–60 bar exciting the A-X(0,0) band. The influence of O₂ interference and gas composition, the variation with local temperature, and the effect of laser and signal attenuation by UV light absorption are investigated. Despite choosing a NO excitation and detection scheme with minimum O₂-LIF contribution, this interference produces errors of up to 25% in a slightly lean 60 bar flame. The overall dependence of the inferred NO number density with temperature in the relevant (1200–2500 K) range is low (<±15%) because different effects cancel. The attenuation of laser and signal light by combustion products CO₂ and H₂O is frequently neglected, yet such absorption yields errors of up to 40% in our experiment despite the small scale (8 mm flame diameter). Understanding the dynamic range for each of these corrections provides guidance to minimize errors in single shot imaging experiments at high pressure. Received: 13 May 2002 / Published online: 8 August 2002     

Absolute radical concentration measurements in low-pressure H2/O2 flames during the combustion of graphite

Absolute CN and CH radical concentrations were determined in situ during the combustion of a graphite substrate in premixed, laminar, low-pressure, H₂/O₂ flames for two different equivalence ratios, = 1.0 and = 1.5. For CN measurements, a small amount of NO (1.8%) was added. The concentration of CN was measured by cavity ring-down spectroscopy (CRDS) probing the absorption of the P_1,2 (13) in the B–X (0, 0) band at 388.1 nm, and the concentration of CH was measured by linear unsaturated laser-induced fluorescence (LIF) exciting the fluorescence of the R₁ (4) in the B–X (0, 0) band at 387.4 nm. Temperature measurements were done based on LIF excitation spectra of OH in the A–X (0, 0) band. It was found that the graphite substrate reduces the flame temperature in the vicinity of its surface. The CN concentrations were found to be three times higher for the rich flame than for the stoichiometric flame. CH concentrations were slightly higher for the stoichiometric flame than for the rich flame. The observed CH/CN concentration ratio is substantially lower compared to NO-doped low-pressure CH₄/O₂ flames. The obtained quantitative information can serve as a first calibration point for detailed numerical simulations of the burning solid graphite, which are based on the concept of surface elementary reactions.     

Quantitative measurement of CN radical in a low-pressure methane/air flame by cavity ring-down spectroscopy

The ultrasensitivity of the cavity ring down spectroscopy technique has been used to detect the minor CN species in a premixed rich (φ=1.2) methane/air flame stabilized at 53 hPa. The CN radical has been probed around 387 nm on the B–X (0–0) band. A peak concentration of 4.7·10⁹ cm⁻³ has been measured which corresponds to a mole fraction of 0.022 ppm. A detection limit of a few ppb has been reached despite the presence of an important off-resonance background due to the flame.     

Quantitative measurements of the CH radical in sooting diffusion flames at atmospheric pressure

The potential of Laser Induced Fluorescence detection of the CH radical using C–X (0–0) excitation is investigated in a sooting methane/air diffusion flame at atmospheric pressure. Fluorescence is detected using the very narrow (<0.4 nm) Q-branch of the C–X (0–0) band, which enables the measurement of CH in sooting flames without interference from PAH fluorescence and soot emissions. Absolute concentrations are obtained using Cavity Ring Down Spectroscopy. 1D CH profiles in the sooting zone are recorded using a CCD camera with an excellent signal-to-noise ratio. The C–X (0–0) excitation associated with Q-branch detection is shown to be three times more efficient than the B–X scheme. Received: 4 March 2002 / Revised version: 5 November 2002 / Published online: 5 May 2003 RID="*" ID="*"Corresponding author. Fax: +33-3/2033-6463, E-mail: eric.therssen@univ-lille1.fr     

Temperature and excitation wavelength dependencies of 3-pentanone absorption and fluorescence for PLIF applications

The temperature and excitation wavelength dependencies of 3-pentanone absorption and fluorescence were studied in support of planar laser-induced fluorescence (PLIF) imaging of temperature and mixture fraction in flows of practical interest. The temperature dependencies (300–875 K) of absorption and fluorescence were measured for gaseous 3-pentanoneat atmospheric pressure in a nitrogen bath gas using 248, 266, and 308 nm excitation. The results indicate that the fluorescence signal per unit mole fraction using 248 nm excitation is highly temperature-sensitive below 600 K, while the signal from 308 nm excitation is not temperature sensitive below 500 K. For quantitative measurements over a broad range of temperatures, one must choose excitation schemes carefully to balance the trade-off between measurement sensitivity and the amount of signal at the expected conditions. As an example of such a choice and to show the capabilities of ketone PLIF techniques, we include temperature and mixture fraction images of a 300–650 K heated air jet using near-simultaneous 308 and 266 nm excitation. Received: 29 May 2002 / Revised version: 5 November 2002 / Published online: 26 February 2003 RID="*" ID="*"Corresponding author. Fax: +1-650/723-1748, E-mail: jkoch@stanford.edu RID="**" ID="**"E-mail: hanson@me.stanford.edu     

Application of mid-infrared cavity-ringdown spectroscopy to trace explosives vapor detection using a broadly tunable (6–8 μm) optical parametric oscillator

A novel instrument, based on cavity-ringdown spectroscopy (CRDS), has been developed for trace gas detection. The new instrument utilizes a widely tunable optical parametric oscillator (OPO), which incorporates a zinc–germanium–phosphide (ZGP) crystal that is pumped at 2.8 μm by a 25-Hz Er,Cr:YSGG laser. The resultant mid-IR beam profile is nearly Gaussian, with energies exceeding 200 μJ/pulse between 6 and 8 μm, corresponding to a quantum conversion efficiency of approximately 35%. Vapor-phase mid-infrared spectra of common explosives (TNT, TATP, RDX, PETN and Tetryl) were acquired using the CRDS technique. Parts-per-billion concentration levels were readily detected with no sample preconcentration. A collection/flash-heating sequence was implemented in order to enhance detection limits for ambient air sampling. Detection limits as low as 75 ppt for TNT are expected, with similar concentration levels for the other explosives. Received: 1 April 2002 / Revised version: 13 June 2002 / Published online: 12 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-408/524-0551, E-mail: mtodd@picarro.com     

Mid-infrared laser-absorption diagnostic for vapor-phase fuel mole fraction and liquid fuel film thickness

A novel two-wavelength mid-infrared laser-absorption diagnostic has been developed for simultaneous measurements of vapor-phase fuel mole fraction and liquid fuel film thickness. The diagnostic was demonstrated for time-resolved measurements of n-dodecane liquid films in the absence and presence of n-decane vapor at 25°C and 1 atm. Laser wavelengths were selected from FTIR measurements of the C–H stretching band of vapor n-decane and liquid n-dodecane near 3.4 μm (3000 cm⁻¹). n-Dodecane film thicknesses <20 μm were accurately measured in the absence of vapor, and simultaneous measurements of n-dodecane liquid film thickness and n-decane vapor mole fraction (300 ppm) were measured with <10% uncertainty for film thicknesses <10 μm. A potential application of the measurement technique is to provide accurate values of vapor mole fraction in combustion environments where strong absorption by liquid fuel or oil films on windows make conventional direct absorption measurements of the gas problematic.     

The effects of burner stabilization on Fenimore NO formation in low-pressure, fuel-rich premixed CH4/O2/N2 flames

We investigate the effects of varying the degree of burner stabilization on Fenimore NO formation in fuel-rich low-pressure flat CH₄/O₂/N₂ flames. Towards this end, axial profiles of flame temperature and OH, NO and CH mole fractions are measured using laser-induced fluorescence (LIF). The experiments are performed at equivalence ratios between 1.3 and 1.5. The flame temperature is seen to decrease by 200-300 K, with a concomitant decrease in OH mole fraction, upon reducing the total flow rate from 5 to 3 L/min, thus increasing stabilization. At equivalence ratios between 1.3 and 1.5, this decrease in flow rate lowers the maximum CH mole fraction by a factor of 2, and the NO mole fraction by ∼40% in all flames studied. Integrating the reaction rate for CH + N₂ to estimate Fenimore NO formation, using the rate coefficient in GRI-Mech 3.0, and the measured temperatures and CH profiles show very good agreement with the measured NO mole fraction for ? = 1.3 and 1.4, supporting the current choice for this rate. This agreement also shows that the increase in residence time caused by increased stabilization is an important factor in the ultimate impact of the changes in CH mole fraction on NO formation. The results at ? = 1.5 suggest that substantial quantities of fixed nitrogen species, e.g., HCN, are only slowly oxidized in the post-flame zone under these conditions, leading to a significant discrepancy between the measured NO mole fraction and that obtained by integrating over the CH profile. Detailed calculations using GRI-Mech 3.0 predict the experimental results at ? = 1.3 nearly quantitatively, but show increasing differences with the measurements for both CH and NO profiles with increasing equivalence ratio.     

Experimental study of signal trapping of OH laser induced fluorescence and chemiluminescence in flames

The absorption of OH^∗ chemiluminescence and laser-induced fluorescence (LIF) in the exhaust gas of confined premixed laminar CH₄/air flames at atmospheric pressure was investigated. One flame was used as source and a second as absorber. OH LIF was excited in the ν″=0→ν′=1 band of the A–X electronic system around ≈283 nm and spectrally resolved detected in the (0,0) and (1,1) vibrational bands around 305–320 nm. For OH^∗ chemiluminescence, spectrally resolved detection was performed in the wavelength range 280–340 nm. For an absorption path of 54 mm and at T≈2000 K, signal trapping on the order of 10–40% was observed. Signal trapping was most pronounced in the (0,0) band, as expected from the thermal population distribution of OH in the electronic ground state. The spectral distribution of the signals and the wavelength dependence of the signal trapping are addressed in this paper. Implications from the results with respect to detection strategies and chemiluminescence-based equivalence ratio measurements are discussed.     

Cavity ring-down measurements of seeded NO in premixed atmospheric-pressure H2/air and CH4/air flames

Quantitative aspects of using cavity ring-down absorption spectroscopy near 226 nm for measurements of NO mole fractions in premixed atmospheric-pressure flames are discussed. Measurements in methane–air flames showed strong broadband absorption near 226 nm by hot CO₂ molecules, precluding using the cavity ring-down method in these flames at atmospheric pressure. In hydrogen–air flames, the broadband absorption at this wavelength was substantially lower. Absorption cross sections derived from non-seeded cavity ring-down spectra suggest that absorption by water is the major contribution to the background in these flames. The detectability limit for NO by cavity ring-down measurements in hydrogen–air flames using the current setup is estimated to be 10 ppm. Effects of the cold boundary layer on the measured NO mole fraction were accounted for by measuring the radial distributions of temperature and NO mole fraction using coherent anti-Stokes Raman scattering and laser-induced fluorescence (LIF), respectively. Measurements performed in seeded stoichiometric and lean hydrogen–air flames showed no reburning at temperatures above 1750 K, demonstrating the adequacy of using these flames for calibration of LIF measurements. At lower temperatures, the mole fraction of NO in the hot gases was up to 30% lower than that expected from the degree of seeding in the cold gases. PACS 42.62.Fi; 42.68.Ca; 82.33.Vx     

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     

Vapor phase synthesis and characterization of bimetallic alloy and supported nanoparticle catalysts

The laser vaporization controlled condensation (LVCC) technique coupled with a differential mobility analyzer (DMA) is used to synthesize size-selected alloy nanoparticles and nanoparticle catalyst systems. The formation of Au–Ag alloy nanoparticles is concluded from the observation of only one plasmon band. The maximum of the plasmon absorption is found to vary linearly with the gold mole fraction. For the Au–Pd system, the XRD data confirms the formation of the alloy nanoparticles with no evidence of any of the pure components. The Au/CeO₂ nanoparticle catalyst prepared by the LVCC method is a promising catalyst for low temperature CO oxidation due to its high activity and stability.     

Thermal emission spectrum of MgI

Thermally excited emission spectrum of MgI, hitherto known only in flame and absorption sources, has been recorded in the spectral region λλ3668–4220, using a high temperature vacuum graphite tube furnace. The bands were classified into three new band systems in the wavelength regions λλ3905–4002, λλ3834–4079 and λλ3668–3888 along with a number of additional bands in the previously known system A, λλ3955–4220. The constants for the various systems are as follows:      

Optimization of the mode matching in pulsed cavity ringdown spectroscopy by monitoring non-degenerate transverse mode beating

A simple and reliable method is presented for optimizing the mode matching of a laser beam to the high-finesse cavity used in pulsed cavity ringdown spectroscopy (CRDS). The method is based on minimizing the excitation of higher-order transverse cavity modes through monitoring the non-degenerate transverse mode beating which becomes visible with induced cavity asymmetry caused by slight misalignment. No additional instrument is required other than a pinhole aperture, thus this method can be applied for CRDS experiments in the whole wavelength range. Measurements of the CRDS absorption spectrum of acetylene (C₂H₂) near 571 nm demonstrate that the mode-matching optimization improves the sensitivity of pulsed CRDS. Received: 22 October 2001 / Revised version: 16 January 2002 / Published online: 14 March 2002     

Numerical investigation of the effect of signal trapping on soot measurements using LII in laminar coflow diffusion flames

Laser-induced incandescence has been rapidly developed into a powerful diagnostic technique for measurements of soot in many applications. The incandescence intensity generated by laser-heated soot particles at the measurement location suffers the signal trapping effect caused by absorption and scattering by soot particles present between the measurement location and the detector. The signal trapping effect was numerically investigated in soot measurements using both a 2D LII setup and the corresponding point LII setup at detection wavelengths of 400 and 780 nm in a laminar coflow ethylene/air flame. The radiative properties of aggregated soot particles were calculated using the Rayleigh–Debye–Gans polydisperse fractal aggregate theory. The radiative transfer equation in emitting, absorbing, and scattering media was solved using the discrete-ordinates method. The radiation intensity along an arbitrary direction was obtained using the infinitely small weight technique. The contribution of scattering to signal trapping was found to be negligible in atmospheric laminar diffusion flames. When uncorrected LII intensities are used to determine soot particle temperature and the soot volume fraction, the errors are smaller in 2D LII setup where soot particles are excited by a laser sheet. The simple Beer–Lambert exponential attenuation relationship holds in LII applications to axisymmetric flames as long as the effective extinction coefficient is adequately defined.     

Nitric oxide concentration measurements in atmospheric pressure flames using electronic-resonance-enhanced coherent anti-Stokes Raman scattering

We report the application of electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) for measurements of nitric oxide concentration ([NO]) in three different atmospheric pressure flames. Visible pump (532 nm) and Stokes (591 nm) beams are used to probe the Q-branch of the Raman transition. A significant resonance enhancement is obtained by tuning an ultraviolet probe beam (236 nm) into resonance with specific rotational transitions in the (v’=0, v”=1) vibrational band of the A²Σ⁺–X²Π electronic system of NO. ERE-CARS spectra are recorded at various heights within a hydrogen-air flame producing relatively low concentrations of NO over a Hencken burner. Good agreement is obtained between NO ERE-CARS measurements and the results of flame computations using UNICORN, a two-dimensional flame code. Excellent agreement between measured and calculated NO spectra is also obtained when using a modified version of the Sandia CARSFT code for heavily sooting acetylene-air flames (φ=0.8 to φ=1.6) on the same Hencken burner. Finally, NO concentration profiles are measured using ERE-CARS in a laminar, counter-flow, non-premixed hydrogen-air flame. Spectral scans are recorded by probing the Q₁ (9.5), Q₁ (13.5) and Q₁ (17.5) Raman transitions. The measured shape of the [NO] profile is in good agreement with that predicted using the OPPDIF code, even without correcting for collisional effects. These comparisons between [NO] measurements and predictions establish the utility of ERE-CARS for detection of NO in flames with large temperature and concentration gradients as well as in sooting environments. PACS 07.88.+y; 42.62.Fi; 42.65.Dr     

Thermal grating and broadband degenerate four-wave mixing spectroscopy of OH in high-pressure flames

2 ∑–X²Π(0,0) band of OH has been studied in premixed methane/air flames using a cw Ar⁺ laser probe. Measurements of flame temperature and pressure were derived from fits of theoretical simulations to the observed time variation of signals over a pressure range of 10 to 40 bar and for different stoichiometry that were in agreement with independent measurements using N₂ CARS and predictions of a one-dimensional flame calculation. Broadband DFWM spectra in the same band of OH were observed up to a pressure of 9 bar, above which signals were obtained only from scattering from thermal gratings. Received: 10 November 1997/Revised version: 28 May 1998     

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     

Pulsed cavity ring-down spectroscopy of NO and NO2 in the exhaust of a diesel engine

The application of pulsed cavity ring-down spectroscopy has been demonstrated for the in situ quantitative determination of NO and NO₂ in the exhaust of a diesel engine. NO absorption has been monitored at the transition from the Χ²Π ground state to the A²Σ⁺ state at 226 nm. For NO₂, absorption bands in the spectral region from 438 nm to 450 nm were used. At the selected engine conditions, concentrations of 212±22 ppm and 29±4 ppm have been measured for NO and NO₂, respectively, in good agreement with separate chemical exhaust gas analysis. The method is sensitive enough to meet the European Euro V standard directive on NO_x emissions. This communication discusses the relatively simple setup needed for this type of measurement, the problems encountered, as well as the prospects for single-stroke, simultaneous measurements of both NO and NO₂ at the sub-ppm level. Received: 30 November 2001 / Revised version: 18 February 2002 / Published online: 14 March 2002