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.     

Strategies for laser-induced fluorescence detection of nitric oxide in high-pressure flames. III. Comparison of A-X excitation schemes

Laser-induced fluorescence (LIF) has proven a reliable technique for nitric oxide (NO) diagnostics in practical combustion systems. However, a wide variety of different excitation and detection strategies are proposed in the literature without giving clear guidelines of which strategies to use for a particular diagnostic situation. We give a brief review of the high-pressure NO LIF diagnostics literature and compare strategies for exciting selected transitions in the A-X(0, 0), (0, 1), and (0, 2) bands using a different detection bandpass. The strategies are compared in terms of NO LIF signal strength, attenuation of laser and signal light in the hot combustion gases, signal selectivity against LIF interference from O2 and CO2, and temperature and pressure sensitivity of the LIF signal. The discussion is based on spectroscopic measurements in laminar premixed methane-air flames at pressures between 1 and 60 bars and on NO and O2 LIF spectral simulations.     

Laser-induced-fluorescence detection of nitric oxide in high-pressure flames with A-X(0, 2) excitation

Laser-induced fluorescence techniques have been used successfully for quantitative two-dimensional measurements of nitric oxide. The commonly applied D-X(0, 1) or A-X(0, 0) schemes are restricted to atmospheric-pressure flames and engines driven with gaseous fuels because of strong attenuation of the exciting laser beam by combustion intermediates. The properties of a detection scheme for which excitation in the nitric oxide A-X(0, 2) band was used were investigated. We discuss the advantages of the A-X(0, 2) system (excited at 247.95 nm) based on measurements in laminar premixed methane/air flames at 1-40 bars.     

Quantification of NO A-X (0, 2) laser-induced fluorescence: investigation of calibration and collisional influences in high-pressure flames

Laser-induced-fluorescence techniques have been used successfully for quantitative two-dimensional measurements of nitric oxide. NO A-X(0, 2) excitation at 248 nm recently found applications in internal-combustion engines. We assess the collisional processes that influence quantification of signal intensities in terms of saturation, rotational energy transfer, and line broadening, using laminar high-pressure methane/air and n-heptane/air flames at pressures as high as 80 bars (8 x 10(6) Pa). A calibration method that is applicable in technical combustion systems based on addition of NO to the burning flame is investigated for various air/fuel ratios and pressures and yields information about the influence of NO reburn processes.     

Temperature dependence of laser-induced fluorescence of nitric oxide in laminar premixed atmospheric-pressure flames

The temperature dependence of laser-induced NO A (2)?(+)-X (2)? fluorescence in the hot gases of natural gas-air flames, seeded with known quantities of NO, has been determined experimentally by means of a difference method. The flame temperature at three fixed equivalence ratios was changed when the mixture velocity was varied through a water-cooled, flat-flame burner and was measured by coherent anti-Stokes Raman spectroscopy. When the possible reburning of part of the seeded NO is allowed for, the results in the range 1700-2150 K are best described by the temperature dependence obtained from a model in which quenching corrections are neglected, as in the case of a saturated two-level system, when millijoule pulse energies are used. Measurements of the fluorescence intensity at constant seed concentration as a function of equivalence ratio between 0.75 and 1.3 also indicate that quenching corrections are unnecessary under these excitation conditions. Using the measured intensities of the seeded flame as a calibration factor, we determined the absolute NO concentrations as functions of the equivalence ratio at 1 cm above the burner. The results indicate that, with the calibration method presented here, a relative accuracy of 5% should be obtainable.     

Confocal, two-photon laser-induced fluorescence technique for the detection of nitric oxide

We describe a confocal two-photon laser-induced fluorescence scheme for the detection of gaseous NO. Excitation from a simple YAG-pumped Coumarin 450 dye system near 452.6 nm was used to promote the two-photon NO(A (2)?(+), nu? = 0 ? X (2)?, nu? = 0) transition in the gamma(0, 0) band. Subsequent fluorescence detection in the range 200-300 nm permitted almost total rejection of elastic and geometric scatter of laser radiation for excellent signal/noise ratio characteristics. The goal of the research was to apply NO fluorescence to a relatively realistic limited optical access combustion environment. A confocal optical arrangement was demonstrated for single-point measurements of NO concentration in gas samples and in atmospheric-pressure flames. The technique is suitable for applications that offer only a single direction for optical access and when significant elastic scatter is present.     

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.     

Comparison of nanosecond and picosecond excitation for two-photon laser-induced fluorescence imaging of atomic oxygen in flames

Two-photon laser-induced fluorescence (LIF) imaging of atomic oxygen is investigated in premixed hydrogen and methane flames with nanosecond and picosecond pulsed lasers at 226 nm. In the hydrogen flame, the interference from photolysis is negligible compared with the LIF signal from native atomic oxygen, and the major limitations on quantitative measurements are stimulated emission and photoionization. Excitation with a nanosecond laser is advantageous in the hydrogen flames, because it reduces the effects of stimulated emission and photoionization. In the methane flames, however, photolytic interference is the major complication for quantitative O-atom measurements. A comparison of methane and hydrogen flames indicates that vibrationally excited CO2 is the dominant precursor for laser-generated atomic oxygen. In the methane flames, picosecond excitation offers a significant advantage by dramatically reducing the photolytic interference. The prospects for improved O-atom imaging in hydrogen and hydrocarbon flames are presented.     

Two-photon nitric oxide laser-induced fluorescence measurements in a diesel engine

A two-photon nitric oxide (NO) laser-induced fluorescence (LIF) technique was developed and applied to study in-cylinder diesel combustion. The technique prevents many problems associated with in-cylinder, single-photon NO planar-laser-induced fluorescence measurements, including fluorescence interference from the Schumann-Runge bands of hot O2, absorption of a UV excitation beam by in-cylinder gases, and difficulty in rejecting scattered laser light while simultaneously attempting to maximize fluorescence signal collection. Verification that the signal resulted from NO was provided by tuning of the laser to a vibrational off-resonance wavelength that showed near-zero signal levels, which resulted from either fluorescence or interference at in-cylinder pressures of as much as 20 bar. The two-photon NO LIF signal showed good qualitative agreement with NO exhaust-gas measurements obtained over a wide range of engine loads.     

Experimental assessment of O(2) interferences on laser-induced fluorescence measurements of NO in high-pressure, lean premixed flames by use of narrow-band and broadband detection

We experimentally investigate the influence of O(2) interferences on laser-induced fluorescence measurements of NO in lean methane-fueled flames at a range of pressures for both narrow-band and broadband fluorescence detection. We identify NO excitation schemes that minimize O(2) interferences. From detection scans we obtain interference spectra for the different NO excitation schemes. We then identify optimum excitation-detection schemes for narrow-band detection measurements of NO. To simulate broadband detection experiments, we numerically apply five different filter combinations to the experimentally obtained detection scans. We develop filter-assessment parameters to judge the effectiveness of the different filtering schemes, and we establish a methodology for evaluating broadband excitation-detection strategies. From this research we identify optimum excitation-detection schemes for broadband detection measurements of NO.     

Photochemical effect in two-photon laser-induced fluorescence detection of carbon monoxide in hydrocarbon flames

The CO formation as a result of the CO(2) photodissociation at 230.08 nm was observed by using the two-photon laser-induced fluorescence (LIF) method. The measurements were performed in a propane-air combustion product flow and in mixtures of CO(2) and O(2). The temperature dependence of the fluorescence signal caused by CO molecules, produced in the photodissociation of CO(2) molecules under the action of laser radiation at a wavelength of 230.08 nm, was measured at temperatures ranging from 1300 to 2000 K. It is shown that consideration of CO(2) photodissociation under the action of the probing radiation is necessary when one applies the two-photon LIF method for the measurement of small CO concentrations in high-temperature gas mixtures containing CO(2). As an example, a correction is given of the CO concentration profiles measured by the LIF method in the combustion product flow around a cooled metallic plate.     

Background corrections for laser-induced-fluorescence measurements of nitric oxide in lean, high-pressure, premixed methane flames

An experimental technique is presented that both minimizes and accounts for the interference background when laser-induced-fluorescence (LIF) measurements are made of NO in lean, high-pressure, premixed, CH(4)/O(2)/N(2) flames. Measurement interferences such as fluorescence and Raman scattering from secondary species become increasingly important for high-pressure LIF studies. O(2) fluorescence interferences are particularly troublesome in lean premixed flames. An excitation-detection scheme that minimizes the effects of these interferences is identified. A procedure that corrects the resulting LIF signal so as to account for any remaining interference signal is then developed. This correction is found to vary from less than 10% of the overall NO signal at atmospheric pressure to over 40% of the overall signal at 14.6 atm for LIF measurements of NO in a series of worst-case flames (phi = 0.6, dilution ratio 2.2). The correction technique is further demonstrated to be portable over a useful range of flame conditions at each pressure.     

MHz-rate nitric oxide planar laser-induced fluorescence imaging in a Mach 10 hypersonic wind tunnel

Nitric oxide planar laser-induced fluorescence (NO PLIF) imaging at repetition rates as high as 1 MHz is demonstrated in the NASA Langley 31 in. Mach 10 hypersonic wind tunnel. Approximately 200 time-correlated image sequences of between 10 and 20 individual frames were obtained over eight days of wind tunnel testing spanning two entries in March and September of 2009. The image sequences presented were obtained from the boundary layer of a 20° flat plate model, in which transition was induced using a variety of different shaped protuberances, including a cylinder and a triangle. The high-speed image sequences captured a variety of laminar and transitional flow phenomena, ranging from mostly laminar flow, typically at a lower Reynolds number and/or in the near wall region of the model, to highly transitional flow in which the temporal evolution and progression of characteristic streak instabilities and/or corkscrew-shaped vortices could be clearly identified.     

Comparisons of laser-saturated, laser-induced, and planar laser-induced fluorescence measurements of nitric oxide in a lean direct-injection spray flame

We report quantitative, spatially resolved laser-saturated fluorescence (LSF), linear laser-induced fluorescence (LIF), and planar laser-induced fluorescence (PLIF) measurements of nitric oxide (NO) concentration in a preheated, lean direct-injection spray flame at atmospheric pressure. The spray is produced by a hollow-cone, pressure-atomized nozzle supplied with liquid heptane, and the overall equivalence ratio is unity. NO is excited by means of the Q(2)(26.5) transition of the gamma(0, 0) band. LSF and LIF detection are performed in a 2-nm region centered on the gamma(0, 1) band. PLIF detection is performed in a broad ~70-nm region with a peak transmission at 270 nm. Quantitative radial NO profiles obtained by LSF are presented and analyzed so as to correct similar LIF and PLIF profiles. Excellent agreement is achieved among the three fluorescence methodologies.     

Time-delayed detection of laser-induced incandescence for the two-dimensional visualization of soot in flames

The time-delayed detection of soot incandescence is demonstrated to discriminate against other laser-induced signals that have shorter decay times. This technique exhibits high sensitivity and no need for any verification of the spectral content of the signal; it is promising for two-dimensional imaging applications in hostile environments, such as in practical flame and combustion chambers, in which it permits an easy visualization of sooty regions.     

Sheath-flow cuvette for high-sensitivity laser-induced fluorescence detection in capillary electrophoresis

The sheath-flow cuvette is a key component in a high-sensitivity post-column laser-induced fluorescence detector for capillary electrophoresis. Most designs are based on commercial cuvettes originally manufactured for use in a flow cytometer. In these devices, a quartz flow chamber is held in a stainless-steel fixture that is difficult to machine and subjects the cuvette to a torque when sealed, which frequently leads to damage of the flow chamber. In this report we present a design for a cuvette that may easily be constructed. This design uses compression to hold and seal the quartz flow chamber without applying torque. The system produces detection limits (3sigma) of 115 yoctomoles (70 copies) for FQ-labeled carbonic anhydrase.     

Competitive quenching fluorescence immunoassay for chlorophenols based on laser-induced fluorescence detection in microdroplets

An improved biomonitoring system for the analysis of 2,4,6-trichlorophenol (TCP) in urine samples has been developed. The principle of the biosensor device is the detection of laser-induced fluorescence (LIF) in single microdroplets by a homogeneous quenching fluorescence immunoassay (QFIA). The competitive immunoassay occurs in microdroplets (d = 58,4 microm) produced by a piezoelectric generator system with 10-microm-diameter orifice. A continuous Ar ion laser (488 nm) excites the fluorescent tracer; its fluorescence is detected by a spectrometer attached to a 512 x 512 cooled, charge-coupled device camera. Fluorescence is quenched by specific binding of TCP polyclonal antibodies to the fluorescent tracer (hapten A-fluorescein); the quenching effect is diminished by the presence of the analyte. Thus, an increase in the signal is produced in a positive dose-dependent manner when TCP is present in the sample. In 10 mM PBS buffer, the IC50 of the LIF-microdroplet QFIA is 0.45 microg L(-1) reaching a LOD of 0.04 microg L(-1). The QFIA with the same reagents performed in microtiter plate format achieved a LOD of 0.36 microg L(-1) in buffer solution. Performance in human urine was similar to that observed in the buffer. A LOD of 1.6 ,g L(-1), with a dynamic range between 4 and 149.5 microg L(-1) in urine, was obtained without any sample treatment other than dilution with the assay buffer. The detectability achieved is sufficient for occupational exposure risk assessment.     

Fiber-optic laser-induced fluorescence probe for the detection of environmental pollutants

Laser-induced fluorescence (LIF) spectroscopy in combination with fiber optics is shown to be a powerful tool for qualitative and quantitative diagnostics of environmental pollutants in water and soil. Timeintegrated data accumulation of the LIF signals in early and late time windows with respect to the excitation pulse simplifies the method so that it becomes attractive for practical applications. Results from field measurements are reported, as oil contaminations under a gas station and in an industrial sewer system are investigated. A KrF-excimer laser and a hydrogen Raman shifter can be applied for multiwavelength excitation. This allows a discrimination between benzene, toluene, xylene, and ethylbenzene aromatics and polycyclic aromatic hydrocarbon molecules in the samples under investigation. For a rough theoretical approach, a computer simulation is developed to describe the experimental results.     

Measurements of hydroxyl concentrations and lifetimes in laminar flames using picosecond time-resolved laser-induced fluorescence

Picosecond time-resolved laser-induced fluorescence (PITLIF) can potentially be used to obtain measurements of minor species concentrations in rapidly fluctuating flames. Previous studies demonstrated this potential for atomic sodium by monitoring the temporal fluorescence signal with both an equivalent-time and a real-time sampling method. In this developmental study, PITLIF is used to determine hydroxyl concentrations in laminar CH(4)-O(2)-N(2) flames by the measurement of both the integrated fluorescence signal and the fluorescence lifetime. The quenching environment can be monitored with real-time sampling, and thus the necessary quenching rate coefficient is obtained in 348 us, which is fast enough for use in many turbulent flows. Fluorescence lifetimes of OH are also measured at different equivalence ratios in laminar flames by the use of the equivalent-time sampling technique. These results compare favorably with predicted lifetimes based on relevant quenching cross sections and calculated species concentrations.