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.     

In situ measurements of H2O from a stratospheric balloon by diode laser direct-differential absorption spectroscopy at 1.39 microm

A distributed-feedback InGaAs laser diode emitting near 1.393 mum is used in conjunction with an optical multipass cell that is open to the atmosphere to yield ambient water-vapor measurements by infrared absorption spectroscopy. To obtain the high dynamic range for the measurements that is required for continuous water-vapor monitoring in the upper troposphere and the lower stratosphere, we used a simple circuit that combined differential and direct detection. Furthermore, the laser emission wavelength was tuned to balance the steep decrease in H(2)O concentration with altitude by sweeping molecular transitions of stronger line strengths. The technique was implemented by use of the Spectromètre à Diodes Laser Accordables (SDLA), a tunable diode laser spectrometer operated from a stratospheric balloon. Absorption spectra of H(2)O in the 5-30-km altitude range obtained at 1-s intervals during recent balloon flights are reported. Water-vapor mixing ratios were retrieved from the absorption spectra by a fit to the full molecular line shape in conjunction with in situ pressure and temperature measurements, with a precision error ranging from 5% to 10%.     

Absorption line shift with temperature and pressure: impact on laser-diode-based H2O sensing at 1.393 microm

High-resolution absorption measurements of the H2O line in the v1 + v3 band at 1.3928 microm were made in the temperature range of 296-1100 K by use of an InGaAsP distributed-feedback laser diode operating at 1.39 microm. Spectral line shift, line strength, and N2 broadening on the water-vapor line and their impact on the accuracy of optical-absorption-based gas sensing have been investigated. The results obtained were compared with values obtained from the HITRAN database and values reported in the literature, facilitating H2O sensing in a nonstandard temperature and pressure environment.     

Simultaneous measurements of CO2 and CO using a single distributed-feedback (DFB) diode laser near 1.57 μm at elevated temperatures

A sensor using a single distributed-feedback (DFB) diode laser at 1.57 μm for the simultaneous measurement of CO(2) and CO concentration at elevated temperatures is developed. A proper line pair near 6361.250 and 6361.344 cm(-1) is chosen based on absorption strength, separation of the two lines, and isolation from interference of neighboring transitions of the major combustion gases. The concentrations of CO(2) and CO are inferred from their wavelength modulation spectroscopy (WMS) 1?-normalized absorption-based WMS-2? signal peak heights. The CO(2) and CO concentration measurements are within 3.3% and 5% of the expected values over the full temperature range.     

Detection of high-temperature water vapor at 940 nm with vertical-cavity surface-emitting lasers

A vertical-cavity surface-emitting laser was used to study the absorption of water vapor in the 940 nm region. Measurements for several absorption lines within the 2 v1 + V3 vibrational band were performed. Line strengths at room temperature and in a heated absorption cell over the temperature range of 420-970 K were obtained. The line strength values were in good agreement with simulations based on the values of the HITRAN 2004 database. The measurements also showed that water vapor transitions near 940 nm are suitable for sensitive temperature determination.     

In Situ Combustion Measurements of CO(2) by Use of a Distributed-Feedback Diode-Laser Sensor Near 2.0 mum

High-resolution absorption measurements of CO(2) were made in a heated static cell and in the combustion region above a flat-flame burner for the development of an in situ CO(2) combustion diagnostic based on a distributed-feedback diode laser operating near 2.0 mum. Calculated absorption spectra of high-temperature H(2)O and CO(2) were used to find candidate transitions for CO(2) detection, and the R(50) transition at 1.997 mum (the nu(1) + 2nu(2) + nu(3) band) was selected on the basis of its line strength and its isolation from interfering high-temperature water absorption. Measurements of spectroscopic parameters such as the line strength, the self-broadening coefficient, and the line position were made for the R(50) transition, and an improved value for the line strength is reported. The combustion-product populations of CO(2) in the combustion region above a flat-flame burner were determined in situ to verify the measured spectroscopic parameters and to demonstrate the feasibility of the diode-laser sensor.     

Observation of CO and CO(2) absorption near 1.57 microm with an external-cavity diode laser

Near-IR and visible room-temperature diode lasers in broadly tunable external-cavity configurations are becoming commercially available for gas-sensing applications. Near 1.57 mum, a coincidence of overtone and combination-band transitions from CO, CO(2), OH, and H(2)O is particularly interesting for combustion and combustor emissions monitoring. We report initial observations of the room-temperature absorption of CO and CO(2) made with a commercial external-cavity diode laser.     

Application of a diode-laser absorption technique with the d(2) transition of atomic rb for hypersonic flow-field measurements

With a first application of semiconductor lasers to absorption measurements of seeded atomic Rb in high-enthalpy flow fields, a diagnostic technique for time-resolved determination of flow velocity and gas temperature with a line-shape analysis was developed. In our measurements a GaAlAs diode laser was used to scan repetitively at 15 kHz over 1.3 cm(-1) across the D(2) resonance transition (5S(1/2) ? 5P(3/2), 780.2 nm) of seeded atomic Rb to obtain multiple absorption line shapes. The time-dependent signal contains highly resolved spectral line-shape information, which we interpret by fitting the spectrally resolved line shapes to Voigt profiles. Kinetic temperatures in the range 900-1400 K and gas velocities in the range 3900-6200 ms(-1) were obtained from the Doppler-broadened component of the line shape and from the Doppler shift, respectively, of the absorption frequency.     

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.     

Ultrasensitive dual-beam absorption and gain spectroscopy: applications for near-infrared and visible diode laser sensors

A dual-beam detection strategy with automatic balancing is described for ultrasensitive spectroscopy. Absorbances of 2 × 10(-7) Hz(-?) in free-space configurations and 5 × 10(-6) Hz(-?) in fiber-coupled configurations are demonstrated. With the dual-beam technique, atmospherically broadened absorption transitions may be resolved with InGaAsP, AlGaAs, and AlGaInP single-longitudinal-mode diode lasers. Applications to trace measurements of NO(2), O(2), and H(2)O are described by the use of simple, inexpensive laser and detector systems. Small signal gain measurements on optically pumped I(2) with a sensitivity of 10(-5) are also reported.     

Diode-Laser Absorption Sensor for Line-of-Sight Gas Temperature Distributions

Line-of-sight diode-laser absorption techniques have been extended to enable temperature measurements in nonuniform-property flows. The sensing strategy for such flows exploits the broad wavelength-scanning abilities (>1.7 nm approximately 30 cm(-1)) of a vertical cavity surface-emitting laser (VCSEL) to interrogate multiple absorption transitions along a single line of sight. To demonstrate the strategy, a VCSEL-based sensor for oxygen gas temperature distributions was developed. A VCSEL beam was directed through paths containing atmospheric-pressure air with known (and relatively simple) temperature distributions in the 200-700 K range. The VCSEL was scanned over ten transitions in the R branch of the oxygen A band near 760 nm and optionally over six transitions in the P branch. Temperature distribution information can be inferred from these scans because the line strength of each probed transition has a unique temperature dependence; the measurement accuracy and resolution depend on the details of this temperature dependence and on the total number of lines scanned. The performance of the sensing strategy can be optimized and predicted theoretically. Because the sensor exhibits a fast time response (~30 ms) and can be adapted to probe a variety of species over a range of temperatures and pressures, it shows promise for industrial application.     

In situ combustion measurements of CO with diode-laser absorption near 2.3 microm

In situ measurements of CO concentration were recorded with tunable diode-laser absorption spectroscopy techniques in both the exhaust and the immediate post-flame regions of an atmospheric-pressure flat-flame burner operating on ethylene air. Two room-temperature cw single-mode InGaAsSb/AlGaAsSb diode lasers operating near 2.3 microm were tuned over individual transitions in the CO first overtone band (v' = 2 <-- v" = 0) to record high-resolution absorption line shapes in the exhaust duct [79 cm above the burner, approximately 470 K; R(15) transition at 4311.96 cm(-1)] and the immediate postflame zone [1.5 cm above the burner, 1820-1975 K; R(30) transition at 4343.81 cm(-1)]. The CO concentration was determined from the measured absorption and the gas temperature, which was monitored with type-S thermocouples. For measurements in the exhaust duct, the noise-equivalent absorbance was approximately 3 x 10(-5) (50-kHz detection bandwidth, 50-sweep average, 0.1-s total measurement time), which corresponds to a CO detection limit of 1.5 ppm m at 470 K. Wavelength modulation spectroscopy techniques were used to improve the detection limit in the exhaust to approximately 0.1 ppm m (approximately 500-Hz detection bandwidth, 20-sweep average, 0.4-s total measurement time). For measurements in the immediate postflame zone, the measured CO concentrations in the fuel-rich flames were in good agreement with chemical equilibrium predictions. These experiments demonstrate the utility of diode-laser absorption sensors operating near 2.3 microm for in situ combustion emission monitoring and combustion diagnostics.     

Extension of wavelength-modulation spectroscopy to large modulation depth for diode laser absorption measurements in high-pressure gases

Tunable diode laser absorption measurements at high pressures by use of wavelength-modulation spectroscopy (WMS) require large modulation depths for optimum detection of molecular absorption spectra blended by collisional broadening or dense spacing of the rovibrational transitions. Diode lasers have a large and nonlinear intensity modulation when the wavelength is modulated over a large range by injection-current tuning. In addition to this intensity modulation, other laser performance parameters are measured, including the phase shift between the frequency modulation and the intensity modulation. Following published theory, these parameters are incorporated into an improved model of the WMS signal. The influence of these nonideal laser effects is investigated by means of wavelength-scanned WMS measurements as a function of bath gas pressure on rovibrational transitions of water vapor near 1388 nm. Lock-in detection of the magnitude of the 2f signal is performed to remove the dependence on detection phase. We find good agreement between measurements and the improved model developed for the 2f component of the WMS signal. The effects of the nonideal performance parameters of commercial diode lasers are especially important away from the line center of discrete spectra, and these contributions become more pronounced for 2f signals with the large modulation depths needed for WMS at elevated pressures.     

Diode laser sensor for measurements of CO, CO(2), and CH(4) in combustion flows

A diode laser sensor has been applied to monitor CO, CO(2), and CH(4) in combustion gases with absorption spectroscopy and fast extraction-sampling techniques. Survey spectra of the CO 3nu band (R branch) and the 2nu(1) + 2nu(2)(0) + nu(3) CO(2) band (R branch) near 6350 cm(-1) and H(2)O lines from the nu(1) + 2nu(2) and 2nu(2) + nu(3) bands in the spectral region from 6345 to 6660 cm(-1) were recorded and compared with calculated spectra (from the HITRAN 96 database) to select optimum transitions for species detection. Species concentrations above a laminar, premixed, methane-air flame were determined from measured absorption in a fast-flow multipass absorption cell containing probe-sampled combustion gases; good agreement was found with calculated chemical equilibrium values.     

Shock-tube study of high-pressure H2O spectroscopy

Water-vapor absorption features near 7117, 7185, and 7462 cm(-1) were probed at pressures to 65 atm (1 atm = 760 Torr) and temperatures to 1800 K in shock-heated mixtures of H(2)O in N(2) and Ar with a diode-laser source. Calculated absorbances based on Voigt line shapes and measured line parameters were in good agreement, within 10%, with measured absorbances at 7185.4 and 7117.4 cm(-1). We obtained temperature-dependent N(2) and Ar shift parameters for H(2)O absorption features by shifting the calculated spectra to match the recorded absorption scan. Absorbance simulations based on line parameters from HITRAN and HITEMP were found to be similar over the range of temperatures 600-1800 K and were within 25% of the measurements. The combined use of Toth's [Appl. Opt. 36, 4851 (1994)] line positions and strengths and HITRAN broadening parameters resulted in calculated absorption coefficients that were within 15% of the measurements at all three probed wavelengths.     

Simultaneous in situ measurement of CO,H2O,and gas temperatures in a full-sized coal-fired power plant by near-infrared diode lasers

We present what is to our knowledge the first near-infrared diode-laser-based absorption spectrometer that is suitable for simultaneous in situ measurement of carbon monoxide, water vapor, and temperature in the combustion chamber (20-m diameter, 13-m path length) of a 600-MW lignite-fired power plant. A fiber-coupled distributed-feedback diode-laser module at 1.56 microm served for CO detection, and a Fabry-Perot diode laser at 813 nm was used to determine H2O concentrations and temperature from multiline water spectra. Despite severe light losses (transmission, <10(-8)) and strong background radiation we achieved a resolution of 1.9 x 10(-4) (1sigma) fractional absorption, equivalent to 200 parts in 10(6) by volume of CO (at 1450 K, 10(5) Pa) with 30-s averaging time.     

Two-Line Laser-Induced Fluorescence Imaging of Vibrational Temperatures in a NO-Seeded Flame

Two-dimensional temperature fields are measured in lean and sooting flames by means of two-color laser-induced fluorescence (LIF) imaging that uses seeded NO. Vibrational thermometry is performed by the probing of different vibrational ground-state levels. Spectral properties of the excited transitions within the A (2)?(+)-X (2)? system are well known from previous studies. The energy difference of 1974 cm(-1) between the (0, 0)Q(1) + P(21)(33.5) and the (0, 2)O(12)(5.5) lines offers great sensitivity in the temperature range that is relevant for combustion processes. Excitation is possible by use of a tunable KrF excimer laser on its fundamental (248-nm) and Raman shifted (in H(2), 225-nm) wavelengths. An excitation scheme for instantaneous two-line measurements by use of a single laser is developed. The possibility of single-shot measurements is discussed.     

Measurements of OH radical concentration in combustion environments by wavelength-modulation spectroscopy with a 1.55-microm distributed-feedback diode laser

Wavelength-modulation spectroscopy with a standard commercial 1.55-microm distributed-feedback diode laser was applied to in situ quantitative measurements of OH radical concentration in combustion environments. The second-harmonic (2f) signal was generated from absorption by the P11.5 (nu', nu") = (2, 0) overtone vibrational transition of OH at 6421.354 cm(-1). The absorption occurred in the postflame region of a two-dimensional laminar counterflow burner (Tsuji burner) with a 60-mm line-of-sight path length. The postflame region lies between propane-air premixed twin flames stabilized in the Tsuji burner at various equivalence ratios (phi = 0.65-1.0). The OH concentrations were determined by least-squares fitting of theoretical f line shapes to the experimental counterparts. The measured OH concentrations were in general agreement with adiabatic chemical equilibrium predictions. The lower limit of OH detectivity by multiline deconvolution was limited by ubiquitous unidentified high-temperature H(2)O transitions.     

Diode-Laser Absorption Measurements of CO(2) Near 2.0 mum at Elevated Temperatures

A diode-laser sensor system based on absorption spectroscopy techniques has been developed for nonintrusive measurements of CO(2) in high-temperature environments. Survey spectra of the CO(2) (20 degrees 1,04 degrees 1)(I)-00 degrees 0 and (20 degrees 1,04 degrees 1)(II)-00 degrees 0 bands between 1.966 and 2.035 mum (4915-5085 cm(-1)) were recorded at temperatures between 296 and 1425 K in a heated static cell and compared with calculated spectra (by using the HITRAN 96/HITEMP database) to find candidate transitions for CO(2) detection. High-resolution measurements of the CO(2) R(56) line shape [(20 degrees 1,04 degrees 1)(II)-00 degrees 0 band] were used to determine the transition line strength, the self-broadening half-width, and the coefficient of temperature dependence of the self-broadening half-width. The results represent what are believed to be the first measurements of CO(2) absorption near 2.0 mum with room-temperature diode lasers. Potential applications of the diode-laser sensor system include in situ combustion measurements and environmental monitoring.     

Quantitative Analysis of Trace Moisture in N(2) and NH(3) Gases with Dual-Cell Near-Infrared Diode Laser Absorption Spectroscopy

This paper demonstrates our optical measurement system based on near-infrared tunable diode laser absorption spectrometry and reports the results of trace moisture determination in nitrogen and ammonia gases. A near-infrared InGaAsP distributed feedback diode laser operating at room temperature was employed as the optical source. We used a dual-cell detection strategy to cancel common mode noise from the diode laser and remove the effect of the residual moisture absorption in the beam path outside the sample cell. We also used this method to successfully eliminate the interfering absorption of matrix gas molecules such as NH(3). The detection limit of H(2)O absorption of 4 ppb in nitrogen and 12 ppb in ammonia was obtained using a single-pass absorption cell of only 92 cm in length and the average results of 10 scan measurements. This system has characteristics of both the high sensitivity and capability of in situ and real-time measurement.