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     

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     

Effective A-state fluorescence lifetime of formaldehyde in atmospheric pressure CH4/air flames

Using excitation pulses of ∼30-ps duration and a fast photomultiplier detector, effective fluorescence lifetimes of the A-stateof formaldehyde after excitation at 355 and 339 nm have been measured in the preheating zone of an atmospheric pressure, premixed methane/air flame. The fluorescence lifetimes were determined as a function of height above the exit of a slot burner and were thus probed in regions of varying gas temperature and composition. The fluorescence lifetimes were independent of the intensity of the excitation pulse and decreased as a function of height in the burner from ∼18±8 ns at 1.2 mm down to 7±1 ns at 3.8 mm. This trend of the effective fluorescence lifetime with composition and temperature in the flame can qualitatively be reproduced using calculated major species mole fractions and species-specific quenching cross sections for CH from the literature. Received: 13 June 2001 / Revised version: 27 September 2001 / Published online: 29 November 2001     

Fluorescence-lifetime measurements in atmospheric-pressure flames using nanosecond-pulsed lasers

Measurements of fluorescence lifetimes are needed to quantify concentration measurements when using linear laser-induced fluorescence. However, lifetimes are only a few nanoseconds for many important species at atmospheric pressure. When using a typical Q-switched laser with a pulse width of about 10 ns, the fluorescence follows the shape of the laser pulse and the lifetime cannot be easily measured. In this paper, a technique is described for experimentally determining the fluorescence lifetime in atmospheric-pressure flames using a nanosecond-pulsed laser; that is, measurement of a lifetime an order-of-magnitude faster than the laser pulse itself. This technique relies on an observable temporal shift in the fluorescence signal as a function of the lifetime. Simulations show the efficacy of this approach, and data in liquid samples and in an atmospheric-pressure flame show excellent agreement with prior picosecond measurements. This technique is successful because only the temporal shift is examined and details of the fluorescence profile are ignored. Received: 23 August 2001 / Revised version: 19 November 2001 / Published online: 17 January 2002     

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     

A UV–Visible–NIR fluorescence lifetime imaging microscope for laser-based biological sensing with picosecond resolution

This article describes the design and characterization of a wide-field, time-domain fluorescence lifetime imaging microscopy (FLIM) system developed for picosecond time-resolved biological imaging. The system consists of a nitrogen-pumped dye laser for UV–visible–NIR excitation (337.1–960 nm), an epi-illuminated microscope with UV compatible optics, and a time-gated intensified CCD camera with an adjustable gate width (200 ps-10^-3 s) for temporally resolved, single-photon detection of fluorescence decays with 9.6-bit intensity resolution and 1.4-μm spatial resolution. Intensity measurements used for fluorescence decay calculations are reproducible to within 2%, achieved by synchronizing the ICCD gate delay to the excitation laser pulse via a constant fraction optical discriminator and picosecond delay card. A self-consistent FLIM system response model is presented, allowing for fluorescence lifetimes (0.6 ns) significantly smaller than the FLIM system response (1.14 ns) to be determined to 3% of independently determined values. The FLIM system was able to discriminate fluorescence lifetime differences of at least 50 ps. The spectral tunability and large temporal dynamic range of the system are demonstrated by imaging in living human cells: UV-excited endogenous fluorescence from metabolic cofactors (lifetime ∼1.4 ns); and 460-nm excited fluorescence from an exogenous oxygen-quenched ruthenium dye (lifetime ∼400 ns). Received: 23 February 2003 / Published online: 22 May 2003 RID="*" ID="*"Corresponding author. Fax: +1-734/9361-905, E-mail: mycek@umich.edu     

Fluorescence quantum yield of carbon dioxide for quantitative UV laser-induced fluorescence in high-pressure flames

The fluorescence quantum yield for ultraviolet laser-induced fluorescence of CO₂ is determined for selected excitation wavelengths in the range 215–250 nm. Wavelength-resolved laser-induced fluorescence (LIF) spectra of CO₂, NO, and O₂ are measured in the burned gases of a laminar CH₄/air flame (φ=0.9 and 1.1) at 20 bar with additional NO seeded into the flow. The fluorescence spectra are fit to determine the relative contribution of the three species to infer an estimate of fluorescence quantum yield for CO₂ that ranges from 2–8×10^?6 depending on temperature and excitation wavelength with an estimated uncertainty of ±0.5×10^?6. The CO₂ fluorescence signal increases linearly with gas pressure for flames with constant CO₂ mole fraction for the 10 to 60 bar range, indicating that collisional quenching is not an important contributor to the CO₂ fluorescence quantum yield. Spectral simulation calculations are used to choose two wavelengths for excitation of CO₂, 239.34 and 242.14 nm, which minimize interference from LIF of NO and O₂. Quantitative LIF images of CO₂ are demonstrated using these two excitation wavelengths and the measured fluorescence quantum yield.     

Study of energy transfer processes in CH as prerequisite for quantitative minor species concentration measurements

Energy transfer effects on CH A-X (0,0) laser-induced fluorescence spectra have been studied for the first time in rich methane and acetylene atmospheric-pressure flames using a picosecond laser system in conjunction with a streak camera. Results allowed determination of typical fluorescence lifetimes of levels in the A state populated by rotational energy transfer (RET), and of state-dependent quenching. These values are used to extend the LASKIN simulation program that has originally been developed to study energy transfer processes in OH, for modelling of spectra of the CH A-X (0,0) transition. Results show good agreement between experiment and simulation both in the spectrally as well as in the temporally-resolved regime.Additionally, a novel strategy for quantitative CH measurements relying on time-resolved broadband detection after excitation in the A-X (0,0) band is presented . This method allows determination of both the fluorescence lifetime and the quench-free amplitude of the fluorescence, which is directly proportional to the CH number density. Results obtained in acetylene flames show significantly higher quenching than expected from extrapolations using published coefficients. This discrepancy is most likely due to an incorrect value for the quenching of CH by collisions with CO. PACS 06.60.Jn; 33.50.-j; 34.50.Ez     

Two-dimensional imaging of glyoxal (C2H2O2) in acetylene flames using laser-induced fluorescence

2 H₂O₂). Laser-induced fluorescence spectra from glyoxal vapor using the same excitation wavelength of 428 nm showed the same strongest lines as the signal from the flame. Glyoxal was visualized in two different modes; two-dimensional imaging and a spatial-spectral mode where spectra were obtained at different spatial positions in the flame simultaneously. For the premixed laminar rich flame it is shown that glyoxal is produced early in the flame, before the signals for C₂ and CH appear. For the turbulent non-premixed flames it is shown that glyoxal is produced in a layer on the fuel rich side of the flames. Here the fuel is premixed with ambient air. This layer is thin and has a high spatial resolution. The general trend was that the glyoxal signal appeared in regions with a lower temperature compared with the emission from C₂ and CH. The imaging of glyoxal in turbulent acetylene flames is a promising tool for achieving new insight into flame phenomena, as it gives very good structural information on the flame front. Tests so far do not indicate that the detected glyoxal is a result of photo-production. To our knowledge, this is the first detection of glyoxal in flames using laser-induced fluorescence. Received: 19 December 1996/Revised version: 26 May 1997     

Dilution effects on laminar jet diffusion flame lengths

Many studies have examined the stoichiometric lengths of laminar gas jet diffusion flames. However, these have emphasized normal flames of undiluted fuel burning in air. Many questions remain about the effects of fuel dilution, oxygen-enhanced combustion, and inverse flames. Thus, the stoichiometric lengths of 287 normal and inverse gas jet flames are measured for a broad range of nitrogen dilution. The fuels are methane and propane and the ambient pressure is atmospheric. Nitrogen addition to the fuel and/or oxidizer is found to increase the stoichiometric lengths of both normal and inverse diffusion flames, but this effect is small at high reactant mole fraction. This counters previous assertions that inert addition to the fuel stream has a negligible effect on the lengths of normal diffusion flames. The analytical model of Roper is extended to these conditions by specifying the characteristic diffusivity to be the mean diffusivity of the fuel and oxidizer into stoichiometric products and a characteristic temperature that scales with the adiabatic flame temperature and the ambient temperature. The extended model correlates the measured lengths of normal and inverse flames with coefficients of determination of 0.87 for methane and 0.97 for propane.     

Nitrogen atom detection in low-pressure flames by two-photon laser-excited fluorescence

Nitrogen atoms have been detected in stoichiometric flat premixed H₂/O₂/N₂ flames at 33 and 96 mbar doped with small amounts of NH₃, HCN, and (CN)₂ using two-photon laser excitation at 211 nm and fluorescence detection around 870 nm. The shape of the fluorescence intensity profiles versus height above the burner surface is markedly different for the different additives. Using measured quenching rate coefficients and calibrating with the aid of known N-atom concentrations in a discharge flow reactor, peak N-atom concentrations in these flames are estimated to be on the order of 10¹²–5×10¹³ cm^–3; the detection limit is about 1×10¹¹ cm^–3.     

Quantitative laser-induced fluorescence of CH in atmospheric pressure flames

Absolute number densities of the CH radical were determined in a partially premixed methane/air flame (equivalence ratio was 1.36) at atmospheric pressure by exciting a predissociating level via the CH B–X(1,0) transition using a quasi-linear laser-induced fluorescence scheme. The peak number density was (1.0±0.4)×10¹³ cm^-3 or 2.4±1 ppm at 1900 K, with a flame-front width of 250 μm (FWHM). Rotational energy transfer must be considered for correct laser-induced fluorescence signal interpretation. Competition between optical pumping and rotational relaxation in both excited and ground states produces a signal that varies almost linearly with laser pulse energy even for large pumping rates. For these conditions, the population of the initial ground-state rotational level is depleted by optical pumping, and rotational energy transfer collisions rapidly repopulate the level during the laser pulse. Deviations from linear behavior are less than 20%. The effects of spatial resolution and polarization of the fluorescence on the absolute measurements are also discussed. Received: 27 March 2002 / Revised version: 22 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Present address: Lam Research Corporation, Fremont, CA 94538, USA RID="**" ID="**"Present address: Mechanical Engineering, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands RID="***" ID="***"Present address: Mechanical Engineering Dept., Stanford University, Stanford CA 94305, USA RID="****" ID="****"Corresponding author. Fax: +1-650/859-6196, E-mail: smith@mplvax.sri.com     

Quantification of stable minor species in confined flames by cavity ring-down spectroscopy: application to NO

Cavity ring-down spectroscopy (CRDS) is used to measure the NO mole fraction formed in the burnt gases of low-pressure premixed flames. It is shown that the line-of-sight absorption is greatly increased by the contribution of the NO molecules surrounding the burner. This contribution has been quantified by developing a mathematical procedure taking into account the spatial and spectral features of the CRDS measurement. Calculations have been undertaken in the general case of a stable species not consumed in the flame. The most sensitive parameter is the temperature both in the flame and outside the flame. Simulations allow the selection of the best spectroscopic transitions for a given flame (i.e. a given temperature profile), ensuring the weakest influence of the inaccuracy affecting the temperature determination. High quantum states belonging to the A–X (0–1) band of NO have been found to be the most valuable and have led to a NO mole fraction determination with an accuracy of ±13%. NO absorption in the flame was completely masked using the A–X (0–0) band. Finally, the prompt-NO mole fraction formed in a methane/air flame stabilized at 33 Torr is obtained by combining CRDS and laser induced fluorescence techniques. Received: 12 October / Revised version: 1 February 2002 / Published online: 14 March 2002     

Coherence gating in optical heterodyne detection measurements of scattering and absorption in highly scattering media

Laser-Induced Fluorescence (LIF) from the S₁ state of acetone and 3-pentanone was studied as a function of temperature and pressure using excitation at 248 nm. Additionally, LIF of 3-pentanone was investigated using 277 and 312 nm excitation. Added gases were synthetic air, O₂, and N₂ respectively, in the range 0–50 bar. At 383 K and for excitation at 248 nm, all the chosen collision partners gave an initial enhancement in fluorescence intensity with added gas pressure. Thereafter, the signal intensity remained constant for N₂ but decreased markedly for O₂. For synthetic air, only a small decrease occurred beyond 25 bar. At longer excitation wavelengths (277 and 312 nm), the corresponding initial rise in signal with synthetic air pressure was less than that for 248 nm. The temperature dependence of the fluorescence intensity was determined in the range 383–640 K at a constant pressure of 1 bar synthetic air. For 248 nm excitation, a marked fall in the fluorescence signal was observed, whereas for 277 nm excitation the corresponding decrease was only half as strong. By contrast, exciting 3-pentanone at 312 nm, the signal intensity increased markedly in the same temperature range. These results are consistent with the observation of a red shift of the absorption spectra (9 nm) over this temperature range. Essentially, the same temperature dependence was obtained at 10 and 20 bar pressure of synthetic air. It is demonstrated that temperatures can be determined from the relative fluorescence intensities following excitation of 3-pentanone at 248 and 312 nm, respectively. This new approach could be of interest as a non-intrusive thermometry method, e.g., for the compression phase in combustion engines.     

Exhaust-gas imaging via planar laser- induced fluorescence of sulfur dioxide

The potential use of planar laser-induced fluorescence (PLIF) of sulfur dioxide (SO₂) for visualization of exhaust-gas distributions is outlined and demonstrated. Strong absorption features in the UV spectral range allow excitation of SO₂ with the fourth harmonic of a Nd:YAG laser at 266 nm. Fluorescence emissions are mostly red-shifted and can be easily detected in single-shot imaging arrangements with a good signal-to-noise ratio. This study uses a premixed methane/air flame that is doped with SO₂ to demonstrate the technique. The signal strength has a pronounced temperature dependence for excitation at 266 nm. Received: 14 January 2002 / Revised version: 30 January 2002 / Published online: 14 March 2002     

Picosecond laser-induced fluorescence from gas-phase polycyclic aromatic hydrocarbons at elevated temperatures. II. Flame-seeding measurements

Picosecond laser-induced radiative emission from flames injected with aromatic substances has been measured spectrally and temporally resolved. The measurements were performed in various seeded regions and for different stoichiometric ratios of the surrounding gas. The wavelength of the excitation radiation was 266 nm. Changes in the lifetime and the spectral composition of the emission were observed with changes in the equivalence ratio and the position in the flame. Considerable agreement with previously reported cell measurements was obtained for those regions close to the injection zone. Temperatures were determined from spectrally and temporally resolved measurements. The comparison with elastic scattering gave reasonable results at low seeding rates for naphthalene, and is hoped to be improved even further in future experiments by increasing the time resolution and the signal-to-noise ratio of the measurements. Downstream and towards the surrounding gas, the lifetimes increased and the spectral profiles shifted and broadened towards the red. This effect increased when the equivalence ratio for the surrounding gas decreased and the oxygen concentration increased. The study was also directed towards characterizing features in the emission that could be indicative of a transition from the seeded aromatic substance to the formation of soot. An indicator for molecular or particle growth was the composition of the spectral emission in terms of UV, blue and green–yellow bands and the ratio between elastic-scattering signal and total emission signal. Spatially resolved measurements across the seeding region using a gated intensified CCD camera allowed a closer study of the molecular-growth region from the parent aromatic substance seeded to the soot formed. The fluorescence properties of dimers and their cyclodehydrogenated compounds and polymers containing aryl units are also discussed. Received: 11 July 2000 / Revised version: 30 October 2000 / Published online: 21 February 2001     

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.     

Photolytic interference affecting two-photon laser-induced fluorescence detection of atomic oxygen in hydrocarbon flames

This study reports on photochemical interferences affecting atomic oxygen detection using two-photon laser-induced fluorescence at 226 nm. In contrast to previous studies in which molecular oxygen was proven to be the relevant photochemical precursor molecule in a hydrogen-fueled flame, the present investigations were carried out in a laminar diffusion flame of methane and air. The most significant interferences were found at the fuel side of the flame in the absence of molecular oxygen, and vibrationally excited carbon dioxide was identified as the most probable precursor molecule for the photochemical production of oxygen atoms. Received: 11 December 2002 / Revised version: 10 March 2003 / Published online: 16 April 2003 RID="*" ID="*"Corresponding author. Fax: +1-925/294-2595, E-mail: tbsette@sandia.gov     

Excitation of Tm<Superscript>+3</Superscript> at a wavelength of 1064 nm

We report on the experimental study of the excitation mechanism of fluorescence in a 10000-ppm wt. Tm⁺³-doped ZBLAN fiber. Visible (at 453 nm and 480 nm) and near-infrared (∼800 nm) radiations were studied under excitation at 1.064 μm. The up-conversion mechanisms responsible are investigated, based on experimental data. The results show that the³ H ₄ and the ¹ D ₂ levels are predominantly excited by ion-ion cross-relaxation processes. Received: 19 August 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +41/31-631-3765, E-mail: Reda.El-Agmy@iap.unibe.ch