Measurements of absolute CH concentrations by cavity ring-down spectroscopy and linear laser-induced fluorescence in laminar, counterflow partially premixed and nonpremixed flames at atmospheric pressure

We report quantitative, spatially resolved measurements of methylidyne concentration ([CH]) in laminar, counterflow partially premixed and nonpremixed flames at atmospheric pressure by using both cavity ring-down spectroscopy (CRDS) and linear laser-induced fluorescence (LIF) in the A-X (0, 0) band. Three partially premixed (phiB = 1.45, 1.6, 2.0) flames plus a single nonpremixed methane-air flame are investigated at a global strain rate of 20 s(-1). These quantitative measurements are compared with predictions from an opposed-flow flame code when utilizing two GRI chemical kinetic mechanisms (versions 2.11 and 3.0). The LIF measurements of [CH] are corrected for variations in the electronic quenching rate coefficient by using predicted major species concentrations and temperatures along with quenching cross sections for CH that are available in the literature. The peak CH concentration obtained by CRDS is used to calibrate the quenching-corrected LIF measurements. Excellent agreement is obtained between CH concentration profiles measured by using the CRDS and LIF techniques. The spatial location of the CH layer is very well predicted by GRI 3.0; moreover, the measured and predicted CH concentrations are in good agreement for all the flames of this study.     

Numerical analysis of beam propagation in pulsed cavity ring-down spectroscopy

A numerical simulation of pulsed cavity ring-down spectroscopy (CRDS) is developed with the commercially available software package GENERAL LASER ANALYSIS AND DESIGN. The model is verified through a series of numerical experiments. Several issues of concern in CRDS are investigated, including spatial resolution, misalignment, non-Gaussian beam input, and the effect of flames inside a ring-down cavity. Suggestions for the design of pulsed CRDS instruments are provided.     

Off-axis cavity ringdown spectroscopy: application to atmospheric nitrate radical detection

Atmospheric nitrate radicals (NO3) are detected using off-axis cavity ringdown spectroscopy (CRDS) for the first time to our knowledge with a room-temperature continuous-wave (cw) diode laser operating near 662 nm. A prototype instrument was constructed that achieved a 1sigma absorption sensitivity of 5 x 10(-10) cm(-1) Hz(-1/2), corresponding to a 1.4 part per trillion by volume 2sigma detection limit in 4.6 s at 80 degrees C. This sensitivity is a significant improvement over a recent implementation of off-axis cavity-enhanced absorption spectroscopy and comparable to that of the most advanced cw CRDS and pulsed CRDS applications for atmospheric detection of NO3. A comparison of measurements of ambient air in Fairbanks, Alaska, recorded with the off-axis CRDS instrument and a previously characterized conventional cw CRDS instrument showed good agreement (R2 = 0.97).     

Comparison of nanosecond and picosecond excitation for interference-free two-photon laser-induced fluorescence detection of atomic hydrogen in flames

Two-photon laser-induced fluorescence (TP-LIF) line imaging of atomic hydrogen was investigated in a series of premixed CH4/O2/N2, H2/O2, and H2/O2/N2 flames using excitation with either picosecond or nanosecond pulsed lasers operating at 205 nm. Radial TP-LIF profiles were measured for a range of pulse fluences to determine the maximum interference-free signal levels and the corresponding picosecond and nanosecond laser fluences in each of 12 flames. For an interference-free measurement, the shape of the TP-LIF profile is independent of laser fluence. For larger fluences, distortions in the profile are attributed to photodissociation of H2O, CH3, and/or other combustion intermediates, and stimulated emission. In comparison with the nanosecond laser, excitation with the picosecond laser can effectively reduce the photolytic interference and produces approximately an order of magnitude larger interference-free signal in CH4/O2/N2 flames with equivalence ratios in the range of 0.5< or =Phi< or =1.4, and in H2/O2 flames with 0.3< or =Phi< or =1.2. Although photolytic interference limits the nanosecond laser fluence in all flames, stimulated emission, occurring between the laser-excited level, H(n=3), and H(n=2), is the limiting factor for picosecond excitation in the flames with the highest H atom concentration. Nanosecond excitation is advantageous in the richest (Phi=1.64) CH4/O2/N2 flame and in H2/O2/N2 flames. The optimal excitation pulse width for interference-free H atom detection depends on the relative concentrations of hydrogen atoms and photolytic precursors, the flame temperature, and the laser path length within the flame.     

光腔衰荡光谱技术及其在痕量气体分析中的应用

光腔衰荡光谱(CRDS)技术是一种新兴的高灵敏度吸收光谱检测技术.在介绍光腔衰荡光谱检测原理和痕量气体浓度检测公式的基础上,总结了CRDS技术在痕量气体分析方面的优势.综述了CRDS技术在气体污染物、超纯气杂质和水分检测方面的应用.     

Simultaneous vibrational and pure rotational coherent anti-stokes Raman spectroscopy for temperature and multispecies concentration measurements demonstrated in sooting flames

The potential of measuring temperature and multiple species concentrations (N2, O2, CO) by use of combined vibrational coherent anti-Stokes Raman spectroscopy (CARS) and pure rotational CARS has been investigated. This was achieved with only one Nd:YAG laser and one dye laser together with a single spectrograph and CCD camera. From measurements in premixed sooting C2H4-air flames it was possible to evaluate temperatures from both vibrational CARS and rotational CARS spectra, O2 concentration from the rotational CARS spectra, and CO concentration from the vibrational CARS spectra. Quantitative results from premixed sooting C2H4-air flames are presented, and the uncertainties in the results as well as the possibility of extending the combined CARS technique for probing of additional species are discussed.     

Diode-Laser Wavelength-Modulation Absorption Spectroscopy for Quantitative in situ Measurements of Temperature and OH Radical Concentration in Combustion Gases

The in situ quantitative profiles of temperature and OH radical concentration in a postflame region of methane-air premixed counterflow flames were measured by wavelength modulation spectroscopy with a 1.5-mum external cavity diode laser. The second harmonic (2f) signal was generated from absorption by overtone vibrational-rotational transitions of OH: the ?(3/2) (v?, v?) = (2, 0) P11.5e (nu(0) = 6421.35 cm(-1)) or the ?(3/2) (v?, v?) = (3, 1) P5.5f (nu(0) = 6434.61 cm(-1)) transitions. The absorption occurred in the postflame region between methane-air premixed twin flames stabilized in a two-dimensional laminar counterflow burner (Tsuji burner) with a 60-mm line-of-sight path length. The temperature and OH concentration profiles at an equivalence ratio of phi = 0.85 were determined by least-squares fitting of theoretical 2f line shapes to the experimental counterparts and by calculation of the ratio of the line intensities of the two different OH transitions (two-line thermometry). The measured temperature and OH concentration profiles were cross checked by Rayleigh scattering thermometry, thermocouple measurements, and two-dimensional numerical prediction of premixed combustion by use of a detailed chemical kinetic mechanism. The measurements and the prediction showed reasonable agreement.     

Effect of Oxygen Enrichment in Propane Laminar Diffusion Flames under Microgravity and Earth Gravity Conditions

Diffusion flames are the most common type of flame which we see in our daily life such as candle flame and match-stick flame. Also, they are the most used flames in practical combustion system such as industrial burner (coal fired, gas fired or oil fired), diesel engines, gas turbines, and solid fuel rockets. In the present study, steady-state global chemistry calculations for 24 different flames were performed using an axisymmetric computational fluid dynamics code (UNICORN). Computation involved simulations of inverse and normal diffusion flames of propane in earth and microgravity condition with varying oxidizer compositions (21, 30, 50, 100 % O₂, by mole, in N₂). 2 cases were compared with the experimental result for validating the computational model. These flames were stabilized on a 5.5 mm diameter burner with 10 mm of burner length. The effect of oxygen enrichment and variation in gravity (earth gravity and microgravity) on shape and size of diffusion flames, flame temperature, flame velocity have been studied from the computational result obtained. Oxygen enrichment resulted in significant increase in flame temperature for both types of diffusion flames. Also, oxygen enrichment and gravity variation have significant effect on the flame configuration of normal diffusion flames in comparison with inverse diffusion flames. Microgravity normal diffusion flames are spherical in shape and much wider in comparison to earth gravity normal diffusion flames. In inverse diffusion flames, microgravity flames were wider than earth gravity flames. However, microgravity inverse flames were not spherical in shape.     

Quantitative imaging of temperature and OH in turbulent diffusion flames by using a single laser source

We describe a diagnostic technique for obtaining quantitative, simultaneous, and instantaneous images of temperature and the concentration of the hydroxyl radical OH in turbulent flames. The technique uses a single laser source and a single intensified CCD camera. A stoichiometric premixed flame is used for calibration. We use detailed calculations of laminar flames of similar fuels to estimate the effects of quenching and ground-state population on the OH signal. A factor combining both effects is generated as a function of temperature. We validate the technique by comparing measured temperature and OH number density with calculated values in laminar diffusion flames. Absolute errors of 10-20% and 20-30% are estimated on the measured temperature and OH number density, respectively. The technique is applicable to regions of the flames where the Rayleigh cross section is close to that of air.     

Line Raman, Rayleigh, and laser-induced predissociation fluorescence technique for combustion with a tunable KrF excimer laser

We have applied a line UV Raman, Rayleigh, and laser-induced predissociation fluorescence technique for measurement of turbulent hydrocarbon flames. The species concentration of CO(2), O(2), CO, N(2), CH(4), H(2)O, OH, and H(2) and the temperature are measured instantaneously and simultaneously along a line of 11.4 mm, from which the gradients with respect to mixture fraction and spatial direction are obtained. The technique has been successfully tested in a laminar premixed stoichiometric methane flame and a laminar hydrogen diffusion flame. In addition the technique has been tested in a highly turbulent rich premixed methane flame. The data show that the technique can be used to provide instantaneous measurements of local profiles that describe the local flame structure in highly turbulent flames.     

N2 and CO vibrational CARS and H2 rotational CARS spectroscopy of CH4/N2O flames

Broadband CARS spectra of N2 and CO have been obtained from the postflame gases of rich CH4/N2O flames using the nonplanar BOXCARS technique. The temperature and concentration of both N2 and CO in these flames were estimated from CARS spectra with the aid of model calculations and agreed with standard thermochemical predictions. In addition, several pure rotational H2 CARS transitions, certain of which had been previously unobserved, were seen in several spectral regions, most notably in both the CO and NO CARS regions. These observations are important in future modeling of CARS data.     

Correcting for methane interferences on δ2H and δ18O measurements in pore water using H2Oliquid-H2Ovapor equilibration laser spectroscopy

Cavity ring-down spectroscopy (CRDS) is a new and evolving technology that shows great promise for isotopic δ(18)O and δ(2)H analyses of pore water from equilibrated headspace H(2)O vapor from environmental and geologic cores. We show that naturally occurring levels of CH(4) can seriously interfere with CRDS spectra, leading to erroneous δ(18)O and δ(2)H results for water. We created a new CRDS correction algorithm to account for CH(4) concentrations typically observed in subsurface and anaerobic environments, such as ground waters or lake bottom sediments. We subsequently applied the correction method to a series of geologic cores that contain CH(4). The correction overcomes the spectral interference and provides accurate pore water δ(18)O and δ(2)H values with acceptable precision levels as well as accurate concentrations of CH(4).     

H2O absorption spectroscopy for determination of temperature and H2O mole fraction in high-temperature particle synthesis systems

Water absorption spectroscopy has been successfully demonstrated as a sensitive and accurate means for in situ determination of temperature and H2O mole fraction in silica (SiO2) particle-forming flames. Frequency modulation of near-infrared emission from a semiconductor diode laser was used to obtain multiple line-shape profiles of H2O rovibrational (v1 + v3) transitions in the 7170-7185-cm(-1) region. Temperature was determined by the relative peak height ratios, and XH2O was determined by use of the line-shape profiles. Measurements were made in the multiphase regions of silane/hydrogen/oxygen/ argon flames to verify the applicability of the diagnostic approach to combustion synthesis systems with high particle loadings. A range of equivalence ratios was studied (phi = 0.47 - 2.15). The results were compared with flames where no silane was present and with adiabatic equilibrium calculations. The spectroscopic results for temperature were in good agreement with thermocouple measurements, and the qualitative trends as a function of the equivalence ratio were in good agreement with the equilibrium predictions. The determinations for water mole fraction were in good agreement with theoretical predictions but were sensitive to the spectroscopic model parameters used to describe collisional broadening. Water absorption spectroscopy has substantial potential as a valuable and practical technology for both research and production combustion synthesis facilities.     

Quantitative technique for imaging mixture fraction, temperature, and the hydroxyl radical in turbulent diffusion flames

A technique for obtaining simultaneous quantitative images of the hydroxyl radical, OH, temperature, mixture fraction, and scalar dissipation rates in turbulent diffusion flames is described. Mixture fraction is obtained from images of Rayleigh and fuel Raman scattering. We quantified the OH laser-induced fluorescence (LIF) images using detailed calibration and a correction for quenching and population distribution effects based on the simultaneous mixture fraction and temperature images. This correction was derived from calculations of laminar counterflow diffusion flames for identical fuel mixtures. These laminar flame computations are further used to estimate the errors in the measured OH concentrations. The technique is applied to piloted, nonpremixed flames over a range of jet velocities. The measured mixture fraction, temperature, and OH concentrations are in good agreement with those obtained earlier in similar flames using the single-point Raman/Rayleigh/LIF technique.     

Strategies for laser-induced fluorescence detection of nitric oxide in high-pressure flames. II. A-X(0,1) excitation

A-X(0,1) excitation is a promising new approach for NO laser-induced fluorescence (LIF) diagnostics at elevated pressures and temperatures. We present what to our knowledge are the first detailed spectroscopic investigations within this excitation band using wavelength-resolved LIF measurements in premixed methane/air flames at pressures between 1 and 60 bar and a range of fuel/air ratios. Interference from O2 LIF is a significant problem in lean flames for NO LIF measurements, and pressure broadening and quenching lead to increased interference with increased pressure. Three different excitation schemes are identified that maximize NO/O2 LIF signal ratios, thereby minimizing the O2 interference. The NO LIF signal strength, interference by hot molecular oxygen, and temperature dependence of the three schemes are investigated.     

Optical diagnostics on sooting laminar diffusion flames in microgravity

Laser-induced incandescence was successfully applied to the investigation of soot formation in both buoyant and non-buoyant laminar jet diffusion flames. Microgravity experiments were conducted in the Drop Tower Bremen, Germany. By the use of imaging laser-induced incandescence (LII) it was possible for the first time to obtain simultaneously two-dimensional information on soot concentration and primary particle size under microgravity. Additionally, temperature fields were measured by 2-color emission pyrometry. Results for the fuels propane and ethene show that soot formation and oxidation is drastically altered under microgravity. Maximum temperatures are reduced by roughly 220 K and 120 K, respectively, which in the case of ethene results in a termination of oxidation processes and the emission of soot. The distribution of soot within the non-buoyant flames is always concentrated in relatively small bands. For all non-buoyant flames investigated the maximum primary particle size roughly doubles compared to the buoyant ones.     

Development of alternative plasma sources for cavity ring-down measurements of mercury

We have been exploring innovative technologies for elemental and hyperfine structure measurements using cavity ring-down spectroscopy (CRDS) combined with various plasma sources. A laboratory CRDS system utilizing a tunable dye laser is employed in this work to demonstrate the feasibility of the technology. An in-house fabricated sampling system is used to generate aerosols from solution samples and introduce the aerosols into the plasma source. The ring-down signals are monitored using a photomultiplier tube and recorded using a digital oscilloscope interfaced to a computer. Several microwave plasma discharge devices are tested for mercury CRDS measurement. Various discharge tubes have been designed and tested to reduce background interference and increase the sample path length while still controlling turbulence generated from the plasma gas flow. Significant background reduction has been achieved with the implementation of the newly designed tube-shaped plasma devices, which has resulted in a detection limit of 0.4 ng/mL for mercury with the plasma source CRDS. The calibration curves obtained in this work readily show that linearity over 2 orders of magnitude can be obtained with plasma-CRDS for mercury detection. In this work, the hyperfine structure of mercury at the experimental plasma temperatures is clearly identified. We expect that plasma source cavity ring-down spectroscopy will provide enhanced capabilities for elemental and isotopic measurements.     

温室气体浓度监测的光腔衰荡光谱研究进展

全球气候变化给人类生活带来的影响受到世界各国的普遍关注,温室气体是影响和改变全球气候的关键因素之一,限制和降低温室气体排放量成为人类发展的重要议题.温室气体大多都在10"(每百万个气体分子中所含该种气体分子的个数)级别,且气体分子结构差异大,因此传统方法很难获得较高的精度,而光腔衰荡光谱法是能解决该难题的关键技术之一....     

Concurrent measurement of temperature and soot concentration of pulverized coal flames

This paper presents a novel instrumentation system for the concurrent measurement of temperature and soot concentration of pulverized coal flames. The system operates on the two-color principle, combining CCD camera optical sensing and digital image processing techniques. The temperature and its distribution in a flame are calculated from the ratio between the grey-levels of corresponding pixels within two images captured at two carefully selected wavelengths. The soot concentration distribution of the flame is represented and estimated using the KL factor that is derived from intermediate information obtained during the temperature measurement. The system is calibrated using a tungsten lamp as a standard temperature source. The maximum relative error in the temperature measurement is 1.83%. Experimental results obtained on a 0.5 MW/sub th/ combustion test facility show that the temperature distribution of a coal-fired flame ranged from 1380 to 1700/spl deg/C, while the KL factor ranged from 0.18 to 0.33.     

Exploration of microwave plasma source cavity ring-down spectroscopy for elemental measurements

We are exploring sensitive techniques for elemental measurements using cavity ring-down spectroscopy (CRDS) combined with a compact microwave plasma source as an atomic absorption cell. The research work marries the high sensitivity of CRDS with a low-power microwave plasma source to develop a new instrument that yields high sensitivity and capability for elemental measurements. CRDS can provide orders of magnitude improvement in sensitivity over conventional absorption techniques. Additional benefit is gained from a compact microwave plasma source that possesses the advantages of low power and low-plasma gas flow rate, which are of benefit for atomic absorption measurements. A laboratory CRDS system consisting of a tunable dye laser is used in this work for developing a scientific base and demonstrating the feasibility of the technique. A laboratory-designed and -built sampling system for solution sample introduction is used for testing. The ring-down signals are monitored using a photomultiplier tube and recorded using a digital oscilloscope interfaced to a computer. Lead is chosen as a typical element for the system optimization and characterization. The effects of baseline noise from the plasma source are reported. A detection limit of 0.8 ppb (10(-)(10)) is obtained with such a device.