LIF measurements and chemical kinetic analysis of methylidyne formation in high-pressure counter-flow partially premixed and non-premixed flames

We report quantitative, spatially resolved, linear laser-induced fluorescence (LIF) measurements of methylidyne concentration ([CH]) in laminar, methane–air, counter-flow partially premixed and non-premixed flames using excitation near 431.5 nm in the A–X (0,0) band. For partially premixed flames, fuel-side equivalence ratios (_B) of 1.45, 1.6 and 2.0 are studied at pressures of 1, 3, 6, 9 and 12 atm. For non-premixed flames, the fuel-side mixture consists of 25% CH₄ and 75% N₂; measurements are obtained at pressures of 1, 2, 3, 4, 5, 6, 9 and 12 atm. The quantitative CH measurements are compared with predictions from an opposed-flow flame code utilizing two GRI chemical kinetic mechanisms (versions 2.11 and 3.0). LIF measurements of [CH] are corrected for variations in the quenching rate coefficient by using major species concentrations and temperatures generated by the code along with suitable quenching cross sections for CH available from the literature. A pathway analysis provides relative contributions from important elementary reactions to the total amount of CH produced at various pressures. Key reactions controlling peak CH concentrations are also identified by using a sensitivity analysis. For the partially premixed flames, measured CH profiles are reproduced reasonably well by GRI 3.0, although some quantitative disagreement exists at all pressures. Two CH radical peaks are observed for _B=1.45 and _B=1.6 at pressures above 3 atm. Peak CH concentrations for the non-premixed flames are significantly underpredicted by GRI 3.0. The latter agrees with previously reported NO concentrations, which are also underpredicted in these same high-pressure counter-flow diffusion flames. PACS 07.35.+k; 42.62.Fi; 82.33.Vx     

Laser-induced fluorescence thermometry and concentration measurements on NOA–X (0-0) transitions in the exhaust gas of high pressure CH4/air flames

Laser-Induced Fluorescence (LIF) excitation spectra in the NOA–X (0-0) band were used for temperature measurements in the postflame region of high-pressure CH₄/air flames. To improve the quality of the measured spectra and to perform reliable line-shape measurements, the initial mixture was doped with approximately 400 ppm NO. At pressures up to 18 bar, excellent agreement was obtained between NO LIF temperatures and NARS/rotational Raman temperatures. Effective broadening coefficients were also determined in these flames. Problems with quantitative concentration measurements of NO and single-pulse temperature measurements at high pressures are discussed.     

Comparison of laser-induced and planar laser-induced fluorescence measurements of nitric oxide in a high-pressure, swirl-stabilized, spray flame

We report spatially resolved linear laser-induced fluorescence (LIF) and planar laser-induced fluorescence (PLIF) measurements of nitric oxide (NO) in a pre-heated, high-pressure (4.27 atm), lean direct-injection (LDI) spray flame. The feasibility of using PLIF in lieu of LIF is assessed with respect to measuring NO concentrations in high-pressure LDI spray flames. NO is excited via the resonant Q₂(26.5) transition of the γ(0,0) band while a non-resonant wavelength is employed to subtract background interferences. LIF detection is performed in a 2-nm region centered on the γ(0,1) band. PLIF detection is performed in a 68-nm window that captures fluorescence from several vibrational bands. An in situ NO doping scheme for fluorescence calibration is successfully employed to quantify the LIF signals. However, a similar calibration scheme for the reduction of PLIF images to quantitative field measurements is plagued by the laser-excited background. Excitation scans and calibration comparisons have been performed to assess the background contribution for PLIF detection. Quantitative radial NO profiles measured by LIF are presented and analyzed so as to correct the PLIF measurements to within the accuracy bars of the LIF measurements via a single-point scaling of the PLIF image. Received: 23 November 1999 / Revised version: 17 January 2000 / Published online: 27 April 2000     

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     

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     

Detection of trace nitric oxide concentrations using 1-D laser-induced fluorescence imaging

Spectrally resolved laser-induced fluorescence (LIF) with one-dimensional spatial imaging was investigated as a technique for detection of trace concentrations of nitric oxide (NO) in high-pressure flames. Experiments were performed in the burnt gases of premixed methane/argon/oxygen flames with seeded NO (15 to 50 ppm), pressures of 10 to 60 bar, and an equivalence ratio of 0.9. LIF signals were dispersed with a spectrometer and recorded on a 2-D intensified CCD array yielding both spectral resolution and 1-D spatial resolution. This method allows isolation of NO-LIF from interference signals due to alternative species (mainly hot O₂ and CO₂) while providing spatial resolution along the line of the excitation laser. A fast data analysis strategy was developed to enable pulse-by-pulse NO concentration measurements from these images. Statistical analyses as a function of laser energy of these single-shot data were used to determine the detection limits for NO concentration as well as the measurement precision. Extrapolating these results to pulse energies of ～?16 mJ/pulse yielded a predicted detection limit of ～?10 ppm for pressures up to 60 bar. Quantitative 1-D LIF measurements were performed in CH₄/air flames to validate capability for detection of nascent NO in flames at 10–60 bar.     

Raman-Rayleigh-LIF measurements of temperature and species concentrations in the Delft piloted turbulent jet diffusion flame

We report a series of Raman-Rayleigh-LIF measurements in two turbulent natural-gas jet diffusion flames produced by the Delft piloted jet diffusion flame burner. The main objective of the Raman-Rayleigh-LIF measurements was to obtain detailed information on the major species concentrations in the flames. The measurements provide simultaneous data on temperature, the concentrations of the major species and the radicals OH and NO and mixture fraction. The application of the Raman technique in the undiluted natural-gas flames proves to be very challenging because of the high fluorescence interference levels. The interference contributions to the recorded Raman signals are identified and subtracted using empirical correlations between the Raman signals and the signals on fluorescence interference monitor channels. The calibration and data reduction of the Raman-Rayleigh and LIF signals are discussed in detail. The resulting dataset compares excellently with data from previous experiments. Because the Raman-Rayleigh-LIF data provide quantitative concentrations and accordingly quantitative mixture fractions, they form a valuable and useful extension of the existing database for the Delft piloted jet diffusion flame burner. Received: 19 October 1999 / Revised version: 31 January 2000 / Published online: 7 June 2000     

Experimental evaluation of strategies for quantitative laser-induced-fluorescence imaging of nitric oxide in high-pressure flames (1-60 bar)

Nitric oxide laser-induced-fluorescence (NO-LIF) 2-D imaging measurements using a new multi-spectral detection strategy are reported for high-pressure flames (1-60 bar). This work builds on previous research that identified interference LIF from O₂ and CO₂ in high-pressure flames and optimized the choice of excitation strategies as a function of application conditions. In this study, design rules are presented to optimize the LIF detection wavelengths for quantitative 2-D NO-LIF measurements over a wide range of pressures (1-60 bar) and temperatures. Simultaneous detection of LIF in multiple wavelength regions enables correction of the NO signal for interference from O₂ and CO₂ and allows simultaneous imaging of all three species. New experiments of wavelength-resolved 1-D LIF in slightly lean (? = 0.9) and slightly rich (? = 1.1) methane/air flames are used to evaluate the design rules and estimate the NO detection limits for a wide range of flame conditions. The quantitative 2-D measurements of NO in the burnt gas are compared with model calculations (using GRI-Mech 3.0) versus pressure for slightly lean and slightly rich flames. The discussions and demonstrations reported in this study provide a practical guideline for application of instantaneous 1-D or 2-D NO-LIF imaging strategies in high-pressure combustion systems.     

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     

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.     

Measurements of burning velocities of dimethyl ether and air premixed flames at elevated pressures

Laminar burning velocities of dimethyl ether (DME) and air premixed flames at elevated pressures up to 10 atm were measured by using a newly developed pressure-release type spherical bomb. The measurement system was validated using laminar burning velocities of methane–air flames. A comparison with the previous experimental data shows an excellent agreement and demonstrates the accuracy and reliability of the present experimental system. The measured flame speeds of DME–air flames were compared with the previous experimental data and the predictions using the full and reduced mechanisms. At atmospheric pressure, the measured laminar burning velocities of DME–air flames are in reasonable agreement with the previous data from spherical bomb method, but are much lower than both predictions and the experimental data of the PIV based counterflow flame measurements. The laminar burning velocities of DME–air flames at 2, 6, and 10 atm were also measured. It was found that flame speed decreases considerably with the increase of pressure. Moreover, the measured flame speeds are also lower than the predictions at high pressures. In addition, experiments showed that at high pressures the rich DME–air flames are strongly affected by the hydrodynamic and thermal-diffusive instabilities. Markstein lengths and the overall reaction order at different equivalence ratios were extracted from the flame speed data at elevated pressures. Sensitivity analysis showed that reactions involving methyl and formyl radicals play an important role in DME–air flame propagation and suggested that systematic modification of the reactions rates associated with methyl and formyl formations are necessary to reduce the discrepancies between predictions and measurements.     

A pulse-pileup correction procedure for rapid measurements of hydroxyl concentrations using picosecond time-resolved laser-induced fluorescence

The measurement of fluorescence lifetimes is important for determining minor-species concentrations in flames when using linear laser-induced fluorescence (LIF). Applications of LIF to turbulent flames require that the quenching rate coefficient be determined in less than ∼100 μs. Moreover, the measurement technique must be insensitive to the existence of relatively large backgrounds, such as occur from flame emission. To meet these goals, we have recently developed a rapid, gated photon-counting technique, termed LIFTIME. However, for ultimate application to turbulent time-series measurements, LIFTIME must be extended to photon count rates which unfortunately result in nonlinear discriminator operation. In this paper, a correction technique is derived to permit quantitative measurements of fluorescence lifetimes and concentrations at sampling rates up to 4 kHz. The technique was tested against liquid samples having a known lifetime and is further shown to reproduce previous hydroxyl concentration measurements in a series of laminar flames with total photon count rates of up to ∼35 million detected photoelectrons per second. The fluorescence lifetimes and hydroxyl concentrations are shown to be measured with ∼10% accuracy (68% confidence interval) for sampling times as low as 250 μs. Received: 9 October 1998 / Revised version: 30 December 1998 / Published online: 28 April 1999     

Nitrous oxide conversion in laminar premixed flames of CH4 + O2 + Ar

Experimental measurements of the adiabatic burning velocity in neat and NO formation in CH₄ + O₂ + Ar flames doped with small amounts of N₂O are presented. The oxygen content in the oxidizer was varied from 15 to 17%. Non-stretched flames were stabilized on a perforated plate burner at 1 atm. The Heat Flux method was used to determine burning velocities under conditions when the net heat loss of the flame is zero. Adiabatic burning velocities of methane + oxygen + argon mixtures were found in satisfactory agreement with the modeling. The NO concentrations in the flames doped with N₂O (100 ppm in the argon stream before mixing) were measured in the burnt gases at a fixed distance from the burner using probe sampling. Axial profiles of [NO] were found insensitive to the downstream heat losses. Experimental dependencies of [NO] versus equivalence ratio had a maximum between φ = 1.1 and 1.2. Calculated concentrations of NO were in good agreement with the measurements. In lean flames calculated concentrations of NO strongly depends on the rate constant of reaction N₂O + O=NO + NO if too high values proposed in the literature are employed. These new experimental data thus allowed for validation of the key reactions of the nitrous oxide mechanism of NO formation in flames.     

The diffusion flame structure of an ammonium perchlorate based composite propellant at elevated pressures

Examination of the surface behavior and flame structure of a bimodal ammonium perchlorate (AP) composite propellant at elevated pressure was performed using high speed (5 kHz) planar laser-induced fluorescence (PLIF) from 1 to 12 atm and visible surface imaging spanning 1–20 atm. The dynamics of the combustion of single, coarse AP crystals were resolved using these techniques. It was found that the ignition delay time for individual AP crystals contributed significant to the particle lifetime only at pressures below about 6 atm. In situ AP crystal burning rates were found to be higher than rates reported for pure AP deflagration studies. The flame structure was studied by exciting OH molecules in the gas phase. Two types of diffusion flames were observed above the composite propellant: jet-like flames and v-shaped, inverted, overventilated, flames (IOF) lifted off the surface. While jet-like diffusion flames have been imaged at low pressures and simulated by models, the lifted IOFs have not been previously reported or predicted. The causes for the observed flame structures are explained by drawing on an understanding of the surface topography and disparities in the burning rates of the fuel and oxidizer.     

Temperature measurement in fuel-rich non-sooting low-pressure hydrocarbon flames

Several temperature measurement techniques were compared for the investigation of fuel-rich, premixed, flat, low-pressure flames of propene, acetylene, and cyclopentene with maximum temperatures around 2400 K. Vibrational Stokes/anti-Stokes Raman measurements with a KrF excimer laser using CO, H₂, and H₂O as temperature indicators were examined at 50 and 200 mbar for different flame stoichiometries. Also, laser-induced fluorescence (LIF) of OH in the A-X band was used, and complementary lifetime measurements were performed to account for a variation of fluorescence quantum yield with rotational quantum number. LIF using seeded NO (0.2-1.0%) was applied both in point-wise and 1D temperature measurement in spite of the anticipated interaction of NO with the fuel-rich flame chemistry. Furthermore, thermocouple measurements were performed in the preheat zone. These techniques were compared with respect to accuracy and the potential for routine applications under fuel-rich low-pressure conditions.     

Simultaneous high-speed measurement of temperature and lifetime-corrected OH laser-induced fluorescence in unsteady flames

A means of performing simultaneous, high-speed measurements of temperature and OH lifetime-corrected laser-induced fluorescence (LIF) for tracking unsteady flames has been developed and demonstrated. The system uses the frequency-doubled and frequency-tripled output beams of an 80 MHz mode-locked Ti:sapphire laser to achieve ultrashort laser pulses (order 2 ps) for Rayleigh-scattering thermometry at 460 nm and lifetime-corrected OH LIF at 306.5 nm, respectively. Simultaneous, high-speed measurements of temperature and OH number density enable studies of flame chemistry, heat release, and flame extinction in unsteady, strained flames where the local fluorescence-quenching environment is unknown.     

On the tunable infrared gas lasers

The high-pressure (≈ 10 atm) electrically excited molecular gas lasers with full overlapping of the rotational lines caused by high-pressure broadening are considered as a possible new type of the powerful infrared lasers with tunable frequency. For CO₂ - laser the overlapping occurs at pressures 10 ≈ 15 atm. It is experimentally shown that the transverse-excitation multiple-arc technique allows laser action at gas pressures up to 1.8 atm for CO₂ and ≈ 0.9 atm for HF-lasers.     

Simultaneous Raman/LIF measurements of major species and NO in turbulent H2/air diffusion flames

A single-pulse spontaneous Raman scattering apparatus, based on a flashlamp-pumped dye laser, was used to determine the concentrations of the major species and the temperature in turbulent H₂/N₂/air jet diffusion flames. The concentrations of nitric oxide were simultaneously measured by Laser-Induced Fluorescence (LIF) after excitation of theA ^{2 +}–X ² transition with a Nd: YAG-pumped dye laser. Some fundamentals of the employed methods, including the calibration procedure, quenching corrections, and accuracy are discussed. Besides a detailed study of the experimental technique, a main goal of the presented investigations was the generation of comprehensive data sets of high accuracy from well-defined turbulent flames which allow for a quantitative comparison with model calculations. Two flames with different fuel dilution and Reynolds numbers were investigated in a pattern of typically 100 measuring locations each comprising 300 single shots. In addition, four flames with different flow velocities but same fuel composition were compared with respect to their temperature and NO concentration profiles. The results show that differential diffusion plays an important role in these flames, especially near the flame base, where the temperature is increased above the adiabatic flame temperature and deviations from adiabatic equilibrium are large. The correlations between NO and mixture fraction and NO and temperature reveal characteristic features of the different flames.     

Gas-phase temperature imaging in spray systems using multi-line NO-LIF thermometry

Two-dimensional gas-phase temperature fields were measured in spray flames and evaporating spray systems using laser-induced fluorescence (LIF) of nitric oxide (NO). The recently developed multi-line technique yields absolute temperature without calibration. It is successfully applied to temperature measurements in the presence of droplets. The method is based on the temperature dependence of the NO-LIF signal. Measurements have been carried out in heated nitrogen flows at room temperature to validate the accuracy (<±1%) and precision (1%) of the technique by comparing results to thermocouple readings. Temperature measurements in a dilute evaporating acetone spray at room temperature showed cooling of the entrained air of 15±6 K. Temperature imaging in an ethanol spray flame at various conditions yields the entire temperature range from the coflow temperature at 300±4 K (1%) to the flame temperature at 1900±40 K (2%). PACS 07.20.Dt; 32.50.+d; 42.62.Fi     

Effects of benzene,cyclo-hexane and n-hexane addition to methane on soot yields in high-pressure laminar diffusion flames

Effects of doping high pressure methane diffusion flames with benzene, cyclo-hexane and n-hexane were investigated to assess the sooting propensity of three hydrocarbons with six carbons at elevated pressures. Amount of liquid hydrocarbons added to methane constituted 7.5% of the total carbon content of the fuel stream. The pressure range investigated extended up to 10 bar and the experiments were carried out in a high pressure combustion chamber capable of establishing stable laminar diffusion flames with various fuels at elevated pressures and was used in similar experiments previously. Temperatures and soot volume fractions were measured using the spectral soot emission technique capturing spectrally-resolved line-of-sight intensities which were subsequently inverted using an Abel type algorithm to obtain radial distributions assuming that the flames are axisymmetric. The total mass carbon flow of the fuel stream was kept constant at 0.524 mg/s in neat methane, benzene-doped methane, cyclo-hexane-doped methane, and n-hexane-doped methane flames to have tractable measurements at all pressures. Measured maximum soot volume fractions and evaluated maximum soot yields showed that benzene-doped methane flame had the higher values than cyclo-hexane doped methane flames which in turn had higher values than n-hexane doped methane flames at all pressures. Sooting propensity dependence of the three hydrocarbons on pressure can be ranked as, in descending order, n-hexane, cyclo-hexane, and benzene; however, the difference between pressure dependencies of n-hexane and cyclo-hexane was within the measurement error margins. Ratio of soot yields of benzene to n-hexane doped flames changed from about 2 at 2 bar to 1.2 at 10 bar; the ratio of benzene to cyclo-hexane doped flames showed similar trends.