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.     

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.     

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 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.     

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.     

Measurements of benzene concentration by difference-frequency laser absorption spectroscopy

Measurements of benzene concentration based on high-resolution laser absorption spectroscopy by use of the R(6) transition in the nu(4) fundamental vibrational band near 14.8 mum (676.6 cm(-1)) are reported. These measurements were performed with a tunable continuous-wave, mid-infrared spectroscopic light source that employs difference-frequency mixing of two Ti:sapphire lasers in a GaSe nonlinear optical crystal. A minimum benzene concentration detection of ~11.5 parts in 10(6) was realized at a reduced pressure of 40 mbars.     

Ammonia Monitoring Near 1.5 mum with Diode-Laser Absorption Sensors

We investigated ammonia spectroscopy near 1.5 mum to select transitions appropriate for trace ammonia detection in air-quality and combustion emissions-monitoring applications using diode lasers. Six ammonia features were selected for these trace-gas detection applications based on their transition strengths and isolation from interfering species. The strengths, positions, and lower-state energies for the lines in each of these features were measured and compared with values published in the literature. Ammonia slip was measured in the exhaust above an atmospheric pressure premixed ethylene-air burner to demonstrate the feasibility of the in situ diode-laser sensor.     

Tunable diode-laser absorption measurements of methane at elevated temperatures

A diode-laser sensor system based on absorption spectroscopy techniques has been developed to monitor CH(4) nonintrusively in high-temperature environments. Fundamental spectroscopic parameters, including the line strengths of the transitions in the R(6) manifold of the 2ν(3) band near 1.646 μm, havebeen determined from high-resolution absorption measurements in a heated static cell. In addition, acorrected expression for the CH(4) partition function has been validated experimentally over thetemperature range from 400 to 915 K. Potential applications of the diode-laser sensor system includeprocess control, combustion measurements, and atmospheric monitoring.     

Frequency-resolved absorption tomography with tunable diode lasers

A tunable diode laser was used for absorption tomography in an axisymmetric atmospheric pressure flat-flame burner. A rapid tomographic inversion algorithm was used to facilitate the many reconstructions at a relatively sparse set of projections typical of laser absorption tomography. Profiles of temperature and CO2 mole fraction were measured simultaneously in methane-air flames. Absorption measurements were made near the R-branch bandhead at 4.17 microm to minimize interferences with other species, while providing good temperature and concentration sensitivity at flame conditions. The procedure showed the advantage of reconstructing detailed spectra at each radial node.     

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.     

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.     

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.     

Measurements of NH(3) and CO(2) with Distributed-Feedback Diode Lasers Near 2.0 mum in Bioreactor Vent Gases

Measurements of NH(3) and CO(2) were made in bioreactor vent gases with distributed-feedback diode-laser sensors operating near 2 mum. Calculated spectra of NH(3) and CO(2) were used to determine the optimum transitions for interrogating with an absorption sensor. For ammonia, a strong and isolated absorption transition at 5016.977 cm(-1) was selected for trace gas monitoring. For CO(2), an isolated transition at 5007.787 cm(-1) was selected to measure widely varying concentrations [500 parts per million (ppm) to 10%], with sufficient signal for low mole fractions and without being optically thick for high mole fractions. Using direct absorption and a 36-m total path-length multipass flow-through cell, we achieved a minimum detectivity of 0.25 ppm for NH(3) and 40 ppm for CO(2). We report on the quasi-continuous field measurements of NH(3) and CO(2) concentration in bioreactor vent gases that were recorded at NASA Johnson Space Center with a portable and automated sensor system over a 45-h data collection window.     

In situ combustion measurements of CO, H2O, and temperature with a 1.58-microm diode laser and two-tone frequency modulation

An optical near-infrared process sensor for electric arc furnace pollution control and energy efficiency is proposed. A near-IR tunable diode laser has performed simultaneous in situ measurements of CO (1577.96 nm), H(2)O (1577.8 and 1578.1 nm), and temperature in the exhaust gas region above a laboratory burner fueled with methane and propane. The applicable range of conditions tested is representative of those found in a commercial electric arc furnace and includes temperatures from 1250 to 1750 K, CO concentrations from 0 to 10%, and H(2)O concentrations from 3 to 27%. Two-tone frequency modulation was used to increase the detection sensitivity. An analysis of the method's accuracy has been conducted with 209 calibration and 105 unique test burner setpoints. Based on the standard deviation of differences between optical predictions and independently measured values, the minimum accuracy of the technique has been estimated as 36 K for temperature, 0.5% for CO, and 3% for H(2)O for all 105 test data points. This accuracy is sufficient for electric arc furnace control. The sensor's ability to nonintrusively measure CO and temperature in real time will allow for improved process control in this application.     

Diode laser absorption measurements of CH(3)Cl and CH(4) near 1.65 microm

Two distributed-feedback (InGaAsP) diode lasers were used to record high-resolution absorption spectra of the parallel and the perpendicular components of the 2nu(4) band of methyl chloride (CH(3)Cl) and the 2nu(3) band of methane (CH(4)) near 1.65 mum. The room-temperature absorption measurements, which were conducted in a multipass cell with a variable path length (878-1020 cm), were used to determine the mole fractions of the constituent gases and thus demonstrate species-specific, nonintrusive concentration measurements of species with overlapping spectra.     

In situ high-temperature visible microspectroscopy for volcanic materials

In situ high-temperature visible microspectroscopy has been developed in order to study color change kinetics of volcanic materials. Olivine thin sections put on a synthetic alumina plate are heated on a heating stage at 600-800 degrees C under a visible microspectroscope. Changes in visible absorption spectra are monitored every 60 s for 5 hours. The obtained high-temperature visible spectra showed a gradual increase with time in absorbance in the shorter wavelength region (400-600 nm). The 430 nm absorbance (ligand field transition of Fe3+ increased more with time at higher temperatures. Assuming diffusional transport in plane sheets, apparent diffusion coefficients were determined at temperatures of 600-800 degrees C. The activation energy for this diffusion in olivine is 208 +/- 17 kJ/mol. This activation energy value is similar to those for the metal vacancy diffusion in olivine. This newly developed in situ high-temperature visible microspectroscopy can provide kinetic measurements of visible spectral change of materials at high temperatures such as volcanic materials.     

Coupled electrooxidation and electrical conduction in a single gold nanowire

The resistance, R, of single gold nanowires was measured in situ during electrooxidation in aqueous 0.10 M sulfuric acid. Electrooxidation caused the formation of a gold oxide that is approximately 0.8 monolayers (ML) in thickness at +1.1 V vs saturated mercurous sulfate reference electrode (MSE) based upon coulometry and ex situ X-ray photoelectron spectroscopic analysis. As the gold nanowires were electrooxidized, R increased by an amount that depended on the wire thickness, ranging from Delta R/ R 0.10V = 14% for a 63 nm (h) x 200 nm (w) wire to 57% for an 18 nm (h) x 95 nm (w) wire at +1.1 V. These nanowires were millimeters in total length, but just 46 mum lengths were exposed to the electrolyte solution. The oxidation process and the accompanying increase in R were reversible: Reduction of the oxide at +0.10 V resulted in recovery of the reduced wire R except for a small resistance offset caused by the dissolution of approximately 0.4 ML of gold during each oxidation/reduction cycle. The measured increase in R during oxidation exceeds by a factor of 4 the predicted increases in R associated with the reduction in cross-sectional area of the nanowire and the expected decrease in the specular scattering parameter, p, at the gold-oxide interface at wire surfaces. We propose that this anomalous increase in R is caused by infiltration of the oxide into the nanowire at grain boundaries.     

Scanning infrared radiometer for measuring the air-sea temperature difference

We describe a vertically scanning infrared radiometer for measuring the air-sea temperature difference without disturbing the water skin layer. The radiometer operates with a single wavelength channel that is 1.1 mum wide, centered on 14.2 mum, on the short-wavelength edge of a CO(2) atmospheric absorption band. The resulting high atmospheric absorption enables calibration of the horizontal-viewing signal with an in situ air-temperature sensor. The signal at all other scan angles is measured relative to that at the horizontal, providing a differential air-sea temperature measurement that is nearly independent of calibration offsets that can be a problem with independent air- and water-temperature sensors. We show data measured on a ship in the Tropical Western Pacific Ocean during July 1999, which exhibit important discrepancies from in situ data using bulk air-and water-temperature sensors. These discrepancies illustrate important differences between bulk versus skin water temperature.     

Absorption measurement of nu2 + 2nu3 band of CH4 at 1.33 microm using an InGaAsP light emitting diode

The combination band of nu2 + 2nu3 of CH4 at 1.33 microm (7512 cm(-1)) was observed at 0.3-cm(-1) resolution by a simple experimental arrangement using a near-infrared high-radiant InGaAsP light emitting diode (LED) and a Ge detector. Forty-six line centers were measured with accuracies of 0.03 cm(-1). The assignment of these manifolds was made by inspection of the P, Q, and R branches. The experimental result indicates that the nu2 + 2nu3 band can be used for fully optical remote monitoring of methane using InGaAsP optical sources in conjunction with an ultralow-loss optical fiber network.     

Measurement of absolute minority species concentration and temperature in a flame by the photothermal deflection spectroscopy technique

It is experimentally demonstrated that absolute concentrations of minority species in flames can be measured by the photothermal deflection spectroscopy (PTDS) technique. In addition, the PTDS signal simultaneously yields the flame temperature the measurement point. Absolute concentration profiles of OH have been measured in a flat-flame burner with methane as fuel. The PTDS measurements agree well with those obtained independently by the absorption technique. The flame temperature measurements by PTDS are also in good agreement with those obtained by the Boltzmann distribution among the rotational levels of OH.