Quasi-simultaneous detection of CH2O and CH by cavity ring-down absorption and laser-induced fluorescence in a methane/air low-pressure flame

The combination of two-dimensional, planar laser-induced fluorescence (PLIF) and cavity ring-down (CRD) absorption spectroscopy is applied to map quantitatively the spatial distributions of CH₂O and CH in a methane/air flame at 25 Torr. Both species are detected in the same spectral region using the overlapping CH₂O A ¹ A ₂ -X ¹ A ₁ 4₁ ⁰ and CH B-X(1,0 )bands. The combination of diagnostic techniques exploits the spatial resolution of LIF and the quantitative CRD absorption measure of column density. The spatially resolved PLIF provides the distribution of absorbers and line-of-sight CRD absorption the absolute number density needed for quantitative concentration images. The peak CH₂O concentration is (3.5±1.4 )×10¹⁴ cm^-3, or 1450±550 ppm at 1000 K. The lack of precise absorption cross-section data produces these large error limits. Although a flame model predicts lower amounts, these large uncertainties limit this measurement’susefulness as a test of the flame chemistry. Received: 24 April 2001 / Revised version: 10 July 2001 / Published online: 10 October 2001     

Quantitative K-Cl-S chemistry in thermochemical conversion processes using in situ optical diagnostics

The sulfation of gas-phase KOH and KCl was investigated in both oxidizing and reducing atmospheres at temperatures of 1120 K, 1260 K, 1390 K, and 1550 K. Well-defined gas environments were generated in a laminar flame burner fuelled with CH₄/air/O₂/N₂. Atomized K₂CO₃ and KCl water solution fog and SO₂ were introduced into the hot gas as sources of potassium, chlorine, and sulfur, respectively. The in situ concentrations of KOH, KCl, and OH radicals were measured using broadband UV absorption spectroscopy, and the concentration of K atom was measured using TDLAS at 769.9 nm and 404.4 nm. The nucleated and condensed K₂SO₄ aerosols were visualized as illuminated by a green laser sheet. With SO₂ addition, reduced concentrations of KOH, KCl, and K atom were measured in the hot gas. The sulfation was more significant for the low temperature cases. KOH was sulfated more rapidly than KCl. K₂SO₄ aerosols, formed by homogeneous nucleation, were observed at temperatures below 1260 K. At 1390 K, no aerosols were formed, indicating that the consumed KOH was transformed into gaseous KHSO₄ or K₂SO₄. K atoms formed in the hot flue gas with KOH addition enhanced the consumption of OH radicals except at the high-temperature case at 1550 K. At 1120 K and 1260 K, the sulfation of KOH with SO₂ seeding reduced the concentration of K atom, resulting in less OH radical consumption. Studies were also conducted in a hot reducing environment at 1140 K, with the flame at an equivalence ratio of 1.31. Similar to the observation in the oxidizing atmosphere, the concentrations of KOH and K atom decreased dramatically with SO₂ seeding. An unknown absorption spectrum observed was attributed to UV absorption by KOSO. The experimental results were used to evaluate a detailed K-Cl-S reaction mechanism, and a reasonable agreement was obtained.     

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     

Fiber laser intracavity absorption spectroscopy for in situ multicomponent gas analysis in the atmosphere and combustion environments

Intracavity absorption spectroscopy with a broadband Er³⁺-doped fiber laser is applied for the measurements of several molecular species revealing quantitative information about the gas concentration, temperature and chemical reactions in flames. The spectral range of measurements extends from 6200 cm⁻¹ to 6550 cm⁻¹ with the proper choice of the fiber length and by moving an intracavity lens. With a pulsed laser applied in this experiment, the sensitivity to absorption corresponds to an effective absorption path length of 3 km assuming the cavity is completely filled with the sample. For a cw laser, the effective absorption path length is estimated to be 50 km. Absorption spectra of various molecules such as CO₂, CO, H₂O, H₂S, C₂H₂ and OH were recorded separately in the cell and/or in low-pressure methane and propane flames. The presented measurements demonstrate simultaneous in situ detection of three molecular products of chemical reactions at different flame locations. Variation of the relative strengths of OH absorption lines with the temperature enables the estimation of the local flame temperature. The sensitivity of this laser does not depend on the broadband cavity losses and it can be used for in situ measurements of absorption spectra in hostile environments such as contaminated samples, flames or combustion engines. The presented technique can be applied for various diagnostic purposes, such as in environmental, combustion and plasma research, in medicine and in the determination of stable isotope ratios.     

CH4/air/SO2 premixed flame spectroscopy with a 7.5-μm diode laser

As sulfur dioxide (SO₂) is often involved in combustion processes, we present here SO₂-concentration measurements in the post-flame region of a CH₄/air/SO₂ premixed flame. SO₂ concentrations were deduced from high-resolution absorption spectra recorded with a mid-infrared tunable diode-laser (TDL) source operating at liquid nitrogen temperature. Single-mode, continuous frequency tuning around 1384.5 cm^-1 (or 7.5 μm) is achieved by a fine TDL temperature ramp. These experiments lead us to develop in situ combustion-pollutant measurements with compact apparatus. We show that this non-intrusive method is efficient for detection and allows the retrieval of SO₂ concentration and temperature. Received: 19 February 2001 / Revised version: 18 April 2001 / Published online: 7 June 2001     

基于差分光学吸收光谱方法的OH自由基定标系统研究

介绍了一种基于差分光学吸收光谱(DOAS)方法的OH自由基定标系统, 该系统可产生一定浓度的OH自由基并同时进行精确测量. 系统采用紫外灯185 nm光线分解水汽产生OH自由基, 利用500 W氙灯准直光作为光源; 使用基长1.25 m、反射次数60次、总光程75.0 m的多次反射池来增加OH自由基的吸收光程; 以超高分辨率中阶梯光栅光谱仪(最高分辨率3.3 pm)作为光谱采集系统对光谱信号进行采集, 采用DOAS测量方法获得OH自由基的浓度. 通过改变腔内水汽的浓度, 系统准确测量了5×10⁸-1.8×10¹⁰ molecules/cm³浓度范围的OH自由基. 分析了OH自由基测量过程中受到的吸收截面偏差、气压等因素影响, 得到系统总测量误差小于7.3%. 在实验的浓度范围内, 系统可用于大气OH自由基气体扩张激光诱导荧光测量技术的定标.     

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     

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     

Electromagnetic interaction of fluorophores with designed two-dimensional silver nanoparticle arrays

We study the fluorescence enhancement of dye molecules adsorbed on regular two-dimensional arrays of designed silver nanoparticles. The silver particles show two orthogonal optical resonances at different wavelengths because of their elongated shape. The short-wavelength resonance was designed to fit to the absorption maximum of the fluorophore. When the excitation light drives the short-wavelength resonance, the measured fluorescence intensity is strongly enhanced compared to that for the orthogonal particle orientation. This shows directly a strong electromagnetic coupling between the nanoparticles and the fluorophore. Additionally enhanced photochemical bleaching is observed due to the interaction of fluorophores with the particles. Using a rate model describing the fluorescence enhancement and the bleaching enhancement, an average value for the particle-induced increase in the radiative fluorescence rate is obtained, together with a lower limit for the averaged particle-induced field intensity enhancement factor. Received: 3 July 2001 / Revised version: 3 September 2001 / Published online: 15 October 2001     

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

This paper presents experimental evidence that using the KrF excimer laser for quantitative laser-induced fluorescence (LIF) studies of the OH A-X (3,0) system is highly problematic if the effects of both photobleaching and photochemistry are not included for laser spectral irradiances greater than 20 MW/cm² cm^-1. Pump-probe and time-resolved measurements of the OH LIF signal in an atmospheric pressure, premixed CH₄-air flame at low- and high-laser-spectral-irradiance conditions show that a significant amount of OH is produced from photofragments resulting from the simultaneous 2-photon predissociation of H₂O molecules in the C-X system. A 5+2-level rate-equation model that includes the effects of both photobleaching and photochemical OH production is shown to satisfactorily predict the data using a single adjustable parameter given by the effective, spectrally integrated 2-photon cross-section of H₂O near 248 nm. The time-integrated OH LIF signal was found to depend on both the laser spectral irradiance and the local concentration of H₂O. Additionally, use of the KrF excimer laser for 2-line rotational thermometry can produce temperature errors as great as +550 K at high laser-pulse energies. Received: 21 August 2000 / Revised version: 30 October 2000 / Published online: 21 February 2001     

Intracavity laser absorption spectroscopy and cavity ring-down spectroscopy in low-pressure flames

Intracavity laser absorption spectroscopy (ICLAS) and cavity ring-down spectroscopy (CRDS) have been used for measurement of the NH₂-radical spectrum near 643 nm. NH₂ was obtained in low-pressure methane/air flat flames doped with minor amounts of ammonia (as low as 0.023%). The NH₂ concentration was measured both by CRDS and ICLAS in the same conditions. This enables us to compare the practical sensitivity of the two methods. Both methods were also used for measurements in a sooting acetylene/air flame (ϕ = 2.6). The comparative advantages of the methods and their complementarities are discussed.     

Hydroxyl tagging velocimetry (HTV) in experimental air flows

 The new nonintrusive instantaneous molecular flow tagging method, hydroxyl tagging velocimetry (HTV), previously demonstrated only for high-temperature reacting flows, is now demonstrated in low-temperature (300 K) ambient air flowfields. Single-photon photodissociation of ground-state H₂O by a ∼193-nm ArF excimer laser ‘writes’ very long grid lines (>50 mm) of superequilibrium OH and H photoproducts in a room air flowfield due to the presence of ambient H₂O vapor. After displacement, the positions of the OH tag lines are revealed through fluorescence caused by A²Σ⁺ (ν^′=0)?X²Π_i (ν^′′=0) OH excitation using a pulsed frequency-doubled dye laser with an operating output wavelength of ∼308 nm. The dye ‘read’ laser accesses the strong Q₁(1) line, compensating for the relatively weak 193-nm absorption of room-temperature H₂O. The weak absorption of ground vibrational state H₂O has previously precluded the use of HTV at low temperatures, since previous HTV systems relied on a KrF excimer ‘read’ laser that could only access a weak (3?0) OH transition. The instantaneous velocity field is determined by time-of-flight analysis. HTV tag lifetime comparisons between experimental results and theoretical predictions are discussed. Multiple-line tag grids are shown displaced due to an experimental air flowfield, thus providing 2-D multipoint velocity information. Due to the instantaneous nature of the HTV tag formation, HTV is particularly suitable for, but not limited to, a variety of fast flowfield applications including nonreacting base flows for high-speed projectiles and low-temperature hypersonic external or internal flows. Received: 3 July 2001 / Revised version: 6 November 2001 / Published online: 17 January 2002     

The Raman spectra and cross-sections of H2O, D2O, and HDO in the OH/OD stretching regions

We report the OH and OD stretching regions of the vapor phase Raman spectra of H₂O, and of a D₂O/HDO mixture, at room temperature. Also, the corresponding spectrum of H₂O at ∼2000 K in a methane/air flame is reported. These spectra are interpreted in terms of transition moments of the molecular polarizability, based on high-level ab initio calculations of the polarizability surface, and on variational wavefunctions considering the rotational-vibrational coupling in full. As a byproduct of this analysis several tables have been compiled including scattering strengths and assignments for individual rotational transitions of the three species. From these tables the Raman spectra in the OH/OD stretching regions can be simulated over the range of temperatures up to 2000 K for H₂O, and up to 300 K for D₂O and HDO.     

Effect of hydroxyl groups on Er doped Bi2O3-B2O3-SiO2 glasses

A series of Er³⁺-doped Bi₂O₃-B₂O₃-SiO₂-Na₂O glasses with different hydroxyl groups were prepared and the interaction between the Er³⁺ ions and OH groups was investigated. Infrared spectra were measured in order to calculate the exact content of OH groups in samples. The observed increase of the fluorescence lifetime with the oxygen bubbling time has been related to the reduction in the OH content concentration evidenced by infrared (IR) absorption spectra, which confirmed that the OH groups were dominant quenching centers of excited Er³⁺ and a cause of concentration quenching of 1.5 μm band emission. Various nonradiative decay rates from ⁴I_13/2 of Er³⁺ with the change of OH content were determined from the fluorescence lifetimes and radiative decay rates, which were calculated on the basis of Judd-Ofelt theory.     

Evaluation of heat release indicators in lean premixed H2/Air cellular tubular flames

Heat release rate in combustion systems must be understood in order to control thermoacoustic instabilities, flame extinction, and heat losses. Traditionally OH chemiluminescence (OH*) is used to trace heat release rate (HRR) in H₂/air flames, but its accuracy as a tracer has not been assessed. Lean premixed H₂/air cellular tubular flames are a good test case to evaluate HRR tracers due to the presence of highly reactive flame cells surrounded by regions of near extinction. Comparing the calculated heat release rate to OH* concentration, one finds that [OH*] profiles correlate with the regions of high reactivity (flame cells) but the correlation fails in the low reactivity regions where the HRR is much higher than the [OH*] value indicates. Alternate HRR tracers including [H] and pixel-by-pixel products of [O₂]x[H], [OH]x[H₂], and [O]x[H₂] are analyzed with detailed numerical simulations. The chosen products derive from the main chain reaction steps that contribute to overall HRR in lean, premixed H₂/air flames. Findings suggest that [H] is an accurate yet simple way of tracking HRR. Planar measurements of HRR are possible if LIF measurements of [H] are improved.     

Oxygen measurements at high pressures with vertical cavity surface-emitting lasers

Measurements of oxygen concentration at high pressures (to 10.9 bar) were made using diode-laser absorption of oxygen A-band transitions near 760 nm. The wide current-tuning frequency range (>30 cm^-1) of vertical cavity surface-emitting lasers (VCSELs) was exploited to enable the first scanned-wavelength demonstration of diode-laser absorption at high pressures; this strategy is more robust than fixed-wavelength strategies, particularly in hostile environments. The wide tuning range and rapid frequency response of the current tuning were further exploited to demonstrate wavelength-modulation absorption spectroscopy in a high-pressure environment. The minimum detectable absorbance demonstrated, ∼1×10^-4, corresponds to ∼800 ppm-m oxygen detectivity at room temperature and is limited by etalon noise. The rapid- and wide-frequency tunability of VCSELs should significantly expand the application domain of absorption-based sensors limited in the past by the small current-tuning frequency range (typically <2 cm^-1) of conventional edge-emitting diode lasers. Received: 26 July 2000 / Revised version: 2 January 2001 / Published online: 20 April 2001     

Degenerate four-wave mixing in nitrogen dioxide: Application to combustion diagnostics

Single shot degenerate four wave mixing (DFWM) images of the distribution of nitrogen dioxide (NO₂) doped into a propane/air flame at concentrations of the order of 7000 ppm have been obtained. These images indicate the relative concentration of NO₂ in different parts of the flame with an estimated spatial resolution of 150 m.Initial experiments were performed using NO₂ in a glass cell with nitrogen buffer gas. DFWM signals were generated using both the frequency doubled output of a pulsed ND:YAG laser and the tunable blue output of an excimer pumped dye laser. The signal was investigated as a function of laser power, NO₂ concentration and buffer gas pressure. In addition, spectra of NO₂ in the region 450 to 480 nm were obtained.Signals were then sought in both a cold air/NO₂ gas flow and an ignited mixture of propane and air seeded with NO₂, using a DFWM imaging geometry. The resulting images from the flame demonstrate the disappearance of the NO₂ molecules in the flame interaction zone.This work was done when previously employed by AEA Technology at Harwell     

碳氢扩散火焰实验研究：燃烧气氛对火焰光谱与温度的影响

辐射是各种燃烧过程中热传递的主要方式。在不同的火焰中,辐射光谱分布十分复杂。在这项工作中,利用光谱仪测量了可见光(200～900 nm),近红外(900～1 700 nm)和中红外(2 500～5 000 nm)波段火焰的光谱强度,分析了空气和富氧气氛下扩散火焰的光谱特征。并基于光谱分析,定量得到了火焰中碳烟以及气体发射的辐射力,计算了火焰的温度分布。结果表明,空气燃烧中的火焰温度低于富氧燃烧中的火焰温度。在空气气氛下,火焰中的碳烟和气体均对中的热辐射起着重要作用。而在富氧气氛下,气体对于火焰热辐射更为重要。在可见光和近红外波段,由于在空气气氛下火焰中碳烟的大量形成,光谱曲线显示出了良好连续性。而富氧气氛下火焰的辐射光谱降低。在中红外波段,空气气氛下火焰的气体辐射明显弱于富氧气氛下火焰的气体辐射。     

Characterisation of a spark ignition system by planar laser-induced fluorescence of OH at high repetition rates and comparison with chemical kinetic calculations

This study reports the application of a novel, high speed laser-detector system for the time-resolved study of flame propagation in a well-controlled spark ignition system. The ignition system allowed full and reproducible control over the energy deposited during breakdown and the ensuing arc discharge of the spark plasma. Ignition was performed in a closed vessel which was filled with stoichiometric mixtures of methane and air. Four sequential snapshots of two-dimensional OH distributions were recorded during single ignition events by the use of planar laser-induced fluorescence (PLIF). From these OH distributions flame front velocities have been extracted with an accuracy of better than 2%. One-dimensional numerical simulations of the ignition event including detailed chemistry and transport processes have been performed. Experimental results and results from the simulations have been compared to each other with respect to flame front velocities as well as spatial concentration profiles of OH radicals. In general a good agreement was obtained. In this way the ignition system was carefully characterised. Received: 6 April 1999 / Published online: 27 October 1999