OH Laser-induced Fluorescence Research Articles

Effect of water content in ethanol on flame front wrinkling and curvature in a spark-ignition engine using OH PLIF imaging

The production of ethanol fuel involves separating water and ethanol by distillation and dehydration in an energy intensive process. To reduce the carbon footprint, hydrous ethanol is seen as a promising alternative. This study focused on the effect of water content in ethanol on flame development in a single-cylinder optical spark-ignition engine. Ethanol with 0%, 4% and 10% water content per volume was used with Port Fuel Injection (PFI) and Direct Injection (DI) for homogeneous and heterogeneous mixture preparation. Tests were also conducted with iso-octane for comparison. Flames captured by Planar Laser Induced Fluorescence (PLIF) of OH were spatially filtered to remove scales larger than the flame size, then the flame brush was quantified in terms of thickness, crossing frequency between instantaneous and filtered contours, and curvature. Increasing water content resulted in slower flame growth, with 10% hydrous exhibiting marginally higher flame speed than iso-octane. PFI led to faster flame growth and thicker flame brushes than DI at the same timing after ignition. When the brush thickness was normalised by flame radius, all hydrous fuels and iso-octane exhibited similar values with PFI, whilst anhydrous ethanol exhibited the thickest normalised brush. The alcohols maintained similar normalised thicknesses with DI and iso-octane exhibited the thickest normalised brush. When flames of the same radii were considered with PFI at the same timing, the fuels with sequentially lower laminar burning velocity were associated with larger crossing frequency. For PFI, increasing water content resulted in decreased flame roundness irrespective of size, with the 4% hydrous and iso-octane exhibiting similar values. With DI, anhydrous ethanol flames were rounder than the 4% hydrous when averaged over all cycles, but marginally rounder than the 10% hydrous and iso-octane. Increasing water content widened the curvature distribution and increased the mean with PFI. Flame roundness decreased with increase in mean curvature and Lewis number for both PFI and DI.

Development of thermally assisted OH PLIF temperature measurement method based on a single femtosecond laser

Recently, OH planar laser-induced fluorescence (PLIF) using the broadband, ultrashort femtosecond-duration (fs-duration) and the thermally assisted vibrational transfer in excited state has been investigated in flames. In this present work, we first measured temperature by thermally assisted OH laser-induced fluorescence (TALF) method with a single ultrashort broadband fs laser. In the experiment, the fs excitation of OH at ultraviolet wavelength is followed by fluorescence detection from two different vibrational bands. The ratio of two measured (1–0) and (0–0) band fluorescence is calibrated with calculated temperature using Chemkin PRO PRIMIX. The calibrated results are used in measuring temperature distributions in different laminar flames. It is found that TALF method using the fs laser can detect 2D temperature distribution in the burnt area with high OH fluorescence signal. However, OH chemiluminescence brings inevitable noise at the flame front that the TALF method does not perform well. And because (1–0) band fluorescence is so weak, the noise from the camera sensor and imaging intensifier (I.I.) remains at the measured temperature imaging. In conclusion, quantitative temperature measurement based on OH TALF based on a single broadband, ultrashort fs laser can be applied in laminar flames with high frequency by a simple experiment setup.

Kinetics of the reaction of OH with methyl nitrate (223-343 K).

Rate coefficients (k4) for the reaction of hydroxyl radicals (OH) with methyl nitrate (CH3ONO2) were measured over the temperature range 232-343 K using pulsed laser photolysis to generate OH and pulsed laser-induced fluorescence to detect it in real-time and under pseudo-first-order conditions. In order to optimize the accuracy of the rate coefficients obtained, the concentration of CH3ONO2 (the reactant in excess) was measured on-line by absorption spectroscopy at 213.86 nm for which the absorption cross-section was also measured (σ213.86 = 1.65 ± 0.09 × 10-18 cm2 molecule-1). The temperature-dependent rate coefficient is described by k4(T) = 7.5 × 10-13 exp[(-1034 ± 40)/T] cm3 molecule-1 s-1 with a room temperature rate coefficient of k4(296 ± 2 K) = (2.32 ± 0.12) × 10-14 cm3 molecule-1 s-1 where the uncertainty includes the statistical error of 2σ and an estimation of the potential systematic bias of 5%. This new dataset helps to consolidate the database for this rate coefficient and to reduce uncertainty in the atmospheric lifetime of CH3ONO2. As part of this study, an approximate rate coefficient for the reaction of H-atoms with CH3ONO2 (k9) was also derived at room temperature: k9(298 K) = (1.68 ± 0.45) × 10-13 cm3 molecule-1 s-1.

Multi-line OH-LIF for gas-phase temperature and concentration imaging in the SpraySyn burner

Gas-phase temperature and OH concentration images are measured in the SpraySyn nanoparticle-synthesis standard burner using multi-line OH laser-induced fluorescence (LIF) thermometry. In this burner, a spray flame fed by a combustible nanoparticle precursor solution is stabilized by a surrounding axisymmetric lean premixed laminar methane/oxygen pilot flame. For measuring OH rotational temperature, the laser is scanned across the 282.05–282.17 nm range and LIF excitation spectra are fitted for each image pixel by simulated spectra. Temperature maps are determined for the pilot flame and the ethanol spray flame with variable dispersion gas flow rates of oxygen used in the two-fluid nozzle. The addition of 2-EHA (2-ethylhexanoic acid) to the solution was found to increase the flame temperature. Laser attenuation across the flame was measured using simultaneous recordings of the fluorescence of uranine/water solution from two dye cuvettes illuminated with the laser sheet before and after the flame and the effect of attenuation was quantified. Absolute OH concentration distributions are determined by combining the LIF images, laser attenuation measurements, and derived temperature distributions. The temporal stability of the flame is investigated for various operating conditions by statistical evaluation of recorded instantaneous OH-LIF images.

Kinetic study of C1 criegee intermediate with diethylamine and ethylamine and their atmospheric implications

This paper investigates the pressure and temperature-dependent kinetics of CH2OO reacting with diethylamine (DEA) and ethylamine (EA) using the OH laser-induced fluorescence method. Pressure independence was observed within the range of 5.4–75 Torr. The rate coefficients for these reactions at 298 K are (2.49 ± 0.39) × 10−11 and (8.14 ± 1.25) × 10−12 cm3 molecule−1 s−1. The activation energies, determined from experiments conducted between 283 and 328 K, are (−2.01 ± 0.08) and (−1.35 ± 0.02) kcal mol−1. These reactions may contribute to the degradation of DEA and EA under specific environmental conditions.

Characteristics of ammonia-hydrogen nonpremixed bluff-body-stabilized flames

The combustion of ammonia (NH3) has received much attention over the last few years due to challenges associated with its low reactivity and the emission of nitric oxides. One way to improve the reactivity of NH3 is to blend it with (H2/N2) mixture as the product of its dissociation, before introducing it into energy systems. In this study, experimental measurements were carried out on nonpremixed bluff-body stabilized flames to better understand the flame and emission characteristics of NH3/H2/N2 flames. Four fuel mixtures at different NH3 and (H2/N2) ratios were investigated to represent different levels of ammonia cracking. Photography, planar laser-induced fluorescence of OH, thermocouples, and gas analysis techniques were used to understand flame features, reaction zone characteristics, NO, and NH3 concentration within the flame and at the exhaust. It was observed that a decrease in NH3 ratio in the mixtures resulted in longer and more stable flame with reduced thermal radiation as compared to NH3-rich fuel blends. For the highest NH3 blend studied, the flames exhibit extinction and re-ignition in the neck zone, as evidenced by OH-planar images and temperature profiles. As the H2/N2 ratio in the fuel mixture is increased, while keeping the Re constant, the momentum flux ratio (jet/co-flow) also increased resulting in a fuel-lean recirculation zone (RZ), and a shift in the maximum temperature and OH region from the outer shear layer to the inner layer next to the central jet. At levels of NH3 in the fuel mixture above 50% by volume, unburned ammonia slips through the flame and into the exhaust, and the subsequent reburn mechanism resulted in reduced NO emission. CFD simulations using Reynolds-averaged Navier-Stokes (RANS) and the flamelet–progress-variable submodel were conducted and compared with the experimental results. The CFD results helped to qualitatively describe and further explain what was observed in the experiment including the flame appearance, mixing field, and the reaction zone location in the tested flames.

LIF-imaging of temperature and iron-atom concentration in iron nitrate doped low-pressure aerosol flat flames

To enable the investigation of the flame chemistry of precursor-laden nanoparticle forming spray flames in quasi-one-dimensional geometry, a matrix burner was developed in which a laminar flat flame is uniformly supplied with liquid aerosol. In the present work, the burner was used to study the interaction of iron(III) nitrate as precursor dissolved in 1-butanol with the flame. Distributions of temperature and relative iron-atom concentrations were measured via OH and Fe laser-induced fluorescence imaging, respectively. Elastic laser light scattering was used to determine the spatial distribution of particles and droplets to characterize the burner and to obtain insight into the particle formation process. The matrix burner was operated with hydrogen or methane. The measured flame temperatures were compared with one- and three-dimensional CFD simulations supporting the development of reaction mechanisms for precursor-laden flames.

Kinetics for the reaction of Criegee intermediate CH2OO with n-butyraldehyde and its atmospheric implications

The Criegee intermediates (CIs), formed through ozone oxidation of unsaturated hydrocarbons, can undergo reactions with various carbonyl compounds in the atmosphere. In this study, we have investigated the 1,3-cycloaddition reaction of n-butyraldehyde with the simplest Criegee intermediate, CH2OO, using the OH laser-induced fluorescence (LIF) method. The experiments were conducted over a temperature and pressure range of 283–318 K and 5–100 Torr, respectively. Our results reveal that the bimolecular rate constant of the reaction is dependent on both temperature and pressure. Specifically, the measured rate constants at 100 Torr are (3.51 ± 0.63), (2.97 ± 0.53), (2.70 ± 0.49), and (2.52 ± 0.45) × 10−12 cm3 molecule−1 s−1 at temperatures of 283, 298, 308, and 318 K, respectively, with a total error of 18%. By fitting the pressure-dependent rate constants according to the Lindemann mechanism, we obtained a high-pressure limit rate constant of (3.05 ± 0.55) × 10−12 cm3 molecule−1 s−1 at 298 K. The Arrhenius plot of the temperature-dependent rate constants yields an activation energy of (−1.71 ± 0.30) kcal mol−1 and a pre-exponential factor of (1.66 ± 0.24) × 10−13 cm−3 s−1 (total error). Furthermore, our findings indicate that the title reaction exhibits a more pronounced temperature-dependent effect compared to that of CH2OO with water dimer and SO2, as well as that of OH with n-butyraldehyde. This observation suggests that the significance of title reaction in the atmosphere increases at lower temperature.

Characterizing the SpraySyn burners with MMC-LES

This paper presents a detailed validation of a modeling framework and its implementation for the simulation of flame spray pyrolysis (FSP) using different nozzle geometries of the so-called SpraySyn burner. Gas, liquid and particulate dynamics are compared against experimental data from literature as well as our own laser-Doppler anemometry, phase-Doppler anemometry and multi-line OH laser-induced fluorescence thermometry imaging measurements. The modeling framework consists of large eddy simulations (LES) coupled to the sparse-Lagrangian multiple mapping conditioning (MMC) model, a Lagrangian spray solver and a sectional description of the population balance equation. Simulations start downstream of the burner exit planes where turbulent inlet data for the gas and liquid phases are generated by independent LES that use a 1-Fluid method to capture the dynamics of the liquid jet break-up. The gas and liquid dynamics are validated and analyzed for an ethanol spray flame in the SpraySyn1 and SpraySyn2 burners. In these burners iron(III) oxide particulates are synthesized from iron pentacarbonyl (IPC)-ethanol solutions with varying IPC concentrations. The results demonstrate the very good predictive capabilities of the MMC modeling framework for the gas and liquid phases. The predictions of the particulate formation are validated by comparison of elastic light scattering (ELS) signals from experiments against synthetic ELS signals calculated from the simulations. Results are of reasonable accuracy for the SpraySyn1 FSP series but indicate an imbalance between particulate growth and dilution with the surrounding gas. Predictions for the SpraySyn2 FSP series are consistent with SpraySyn1 results and indicate an increased product particulate size due to an increased residence time downstream of the heat release zone.

Investigation on the Effect of Charge Injection from Non-Thermal Plasma on Soot Formation in Laminar Coflow Diffusion Flame

ABSTRACT A novel, modified coflow burner was developed to study the effect of charge injection from a non-thermal plasma into three helium-diluted laminar coflow diffusion ethylene flames. The frequency of the high voltage (HV) signal was varied to control the ion concentration (charge) injected into the flames. Optical emission spectroscopy was used to characterize the non-thermal plasma while a bias plate methodology was used to gauge the relative amount of charge generated. For different HV signal frequencies, the laser-induced fluorescence of OH, chemiluminescence of CH*, and laser-induced incandescence of soot in flames were measured. The OH and CH* measurements showed that the flames retained the classic flame shape with charge injection. Significant soot reduction was observed at low HV signal frequencies, corresponding to an increase in charge injection. Notably, at low HV signal frequency, soot reduction in highly concentrated (60%) ethylene flame is three times lower than the less concentrated (32%) ethylene flame. This can be attributed to the decrease in the injected charge to soot precursor concentration ratio when the concentration of ethylene in the flame is increased. These results demonstrate that the current system is a promising candidate for studying the charge effect from non-thermal plasma on soot formation in laminar coflow diffusion flames.

Kinetics of the Simplest Criegee Intermediate CH2OO Reaction with tert-Butylamine

The kinetics of the simplest Criegee intermediate (CH2OO) reaction with tert-butylamine ((CH3)3CNH2) was studied under pseudo-first-order conditions with the OH laser-induced fluorescence (LIF) method at the temperature range of 283-318 K and the pressure range of 5-75 Torr. Our pressure-dependent measurement showed that at 5 Torr─the lowest pressure measured in the current experiment─this reaction was under the high-pressure limit condition. At 298 K, the reaction rate coefficient was measured to be (4.95 ± 0.64) × 10-12 cm3 molecule-1 s-1. The title reaction was observed to be negative temperature-dependent; the activation energy of (-2.82 ± 0.37) kcal mol-1 and the pre-exponential factor of (4.21 ± 0.55) × 10-14 cm3 molecule-1 s-1 were derived from the Arrhenius equation. The rate coefficient of the title reaction is slightly larger than (4.3 ± 0.5) × 10-12 cm3 molecule-1 s-1 of the CH2OO reaction with methylamine; the electron inductive effect and the steric hindrance effect might play a role in contributing to such difference.

The simplest Criegee intermediate CH2OO reaction with dimethylamine and trimethylamine: kinetics and atmospheric implications.

We have used the OH laser-induced fluorescence (LIF) method to measure the kinetics of the simplest Criegee intermediate (CH2OO) reacting with two abundant amines in the atmosphere: dimethylamine ((CH3)2NH) and trimethylamine ((CH3)3N). Our experiments were conducted under pseudo-first-order approximation conditions. The rate coefficients we report are (2.15 ± 0.28) × 10-11 cm3 molecule-1 s-1 for (CH3)2NH at 298 K and 10 Torr, and (1.56 ± 0.23) × 10-12 cm3 molecule-1 s-1 for (CH3)3N at 298 K and 25 Torr with Ar as the bath gas. Both reactions exhibit a negative temperature dependence. The activation energy and pre-exponential factors derived from the Arrhenius equation were (-2.03 ± 0.26) kcal mol-1 and (6.89 ± 0.90) × 10-13 cm3 molecule-1 s-1 for (CH3)2NH, and (-1.60 ± 0.24) kcal mol-1 and (1.06 ± 0.16) × 10-13 cm3 molecule-1 s-1 for (CH3)3N. We propose that the electronegativity of the atom in the co-reactant attached to the C atom of CH2OO, in addition to the dissociation energy of the fragile covalent bonds with H atoms (H-X bond), plays an important role in the 1,2-insertion reactions. Under certain circumstances, the title reactions can contribute to the sink of amines and Criegee intermediates and to the formation of secondary organic aerosol (SOA).

Investigation of reacting fuel jets in hot vitiated crossflow

Near-wall reacting jets can occur in different engineering applications, such as rocket combustion chambers and in gas turbine combustors and turbines. This work presents results of experimental investigations of reacting gaseous fuel jets (hydrogen, methane, propane) injected normally into a hot oxygen-rich cross-flow using OH laser-induced fluorescence and OH* chemiluminescence diagnostics. RANS CFD simulations with EDC combustion model are performed for comparison. To determine the surface heat fluxes, the inverse heat conduction method was applied using measured wall temperature data as input. It was observed, that hydrogen jets ignite directly at the injection location and caused a higher surface heat flux than the hydrocarbon jets, where jet-like diffusion flames emerged. With the latter fuels, a significant ignition delay length was observed. Operation with methane fuel showed the least stability, least reactivity and the lowest surface heat flux. Increasing the jet momentum ratio led to a reduced ignition delay length due to enhanced jet-crossflow interaction, and to a reduction of surface heat flux as the reacting jet detached more from the surface. CFD results using the Eddy-Dissipation Concept (EDC) combustion model predicted ignition delay lengths and reaction zone shapes in qualitative agreement with the experiment but with a trend of overestimating combustion temperatures.

Planar Laser Induced Fluorescence of OH for Thermometry in a Flow Field Based on Two Temperature Point Calibration Method

In view of the uncertainty in the calibration process of two-color plane laser-induced fluorescence (PLIF) temperature measurement, a new calibration method is proposed, in which the influence of fluorescence yield is considered. The calibration process was carried out at high and low temperature region, respectively. Then, the bias of thermometry results origin from quenching is restrained. This new calibration method is validated in a jet flame with temperature range of 1300–1800 K. Here, the temperature results from Coherent Anti-Stokes Raman scattering (CARS), single-point calibrated PLIF, and two-point calibrated PLIF are all acquired with the maximum standard errors of 13 K, 36 K, and 37 K, respectively. The temperature deviation between the average results from PLIF and Coherent Anti-Stokes Raman scattering (CARS) is 120 K and 10 K, when the two-point and one-point calibration methods are used. Therefore, the two-point calibrated PLIF is preferred in the combustion field, especially with a large temperature range and strong quenching coefficient.

Absolute OH density measurements in a CO2–H2O glow discharge by laser-induced fluorescence spectroscopy

Time-resolved absolute OH density measurements in a millisecond-pulsed DC glow discharge from carbon dioxide with water admixture, by laser-induced fluorescence (LIF) spectroscopy, are presented. For this purpose, a novel technique is suggested to calibrate the OH LIF setup by means of two-photon absorption LIF spectroscopy measurements on a CO-filled gas cell. OH densities in the order of 1 × 1018 m−3 are reported at a pressure of 6.67 mbar with a water admixture of 20% and a discharge current of 50 mA. Furthermore, the time evolution of the CO2 conversion is determined from collision energy transfer LIF and validated against the literature. The time-dependent rotational temperature of OH is obtained with LIF thermometry.

Crosstalk-Free Excitation Scheme for Quantitative OH Laser-Induced Fluorescence in Environments Containing Excited CO

Spectral overlap in the single-photon laser-induced fluorescence between the 3064 Å system of OH and the third positive system of CO is detected in a highly-excited environment, namely, a CO2-H2O plasma. The overlap is distorting excitation and fluorescence spectra as well as fluorescence time decays of commonly used excitation transitions of OH. As a consequence, systematic errors are introduced into the determination of temperatures, gas compositions, and absolute number densities. The P1(2) transition is proposed to circumvent the distortion while still allowing for quantitative measurements due to the availability of non-radiative rate coefficients.

Experimental and Computational Studies of Criegee Intermediate syn-CH3CHOO Reaction with Hydrogen Chloride.

Hydrogen chloride (HCl) contributes substantially to the atmospheric Cl; both species could affect the composition of Earth's atmosphere and the fate of pollutants. Here, we present the kinetics study for syn-CH3CHOO reaction with HCl using experimental measurement and theoretical calculations. The experiment was conducted in a flow tube reactor at a pressure of 10 Torr and temperatures ranging from 283 to 318 K by using the OH laser-induced fluorescence (LIF) method. Transition-state theory and quantum chemistry calculations with QCISD(T) were used to calculate the rate coefficients. Weak negative temperature dependence was observed with a measured activation energy of -(2.98 ± 0.12) kcal mol-1 and a calculated zero-point-corrected barrier energy of -3.29 kcal mol-1. At 298 K, the rate coefficient was measured to be (4.77 ± 0.95) × 10-11 cm3 s-1, which was in reasonable agreement with 2.2 × 10-11 cm3 s-1 from the theoretical calculation.

Experimental study of vorticity-strain interactions in turbulent premixed counterflow flames

The effects of heat release on interactions between vorticity (ω) and strain rate (s) in turbulent premixed CH4/O2/N2 counterflow flames are investigated using simultaneous OH laser-induced fluorescence (LIF) and tomographic particle image velocimetry (TPIV) measurements. A comparison between the flames and a corresponding turbulent non-reacting variable density N2-vs-products counterflow reveals the impact of heat release on vorticity-strain rate alignment statistics. Vorticity and strain rate statistics in the flames and non-reacting flow are conditioned on distance from the local flame front and gas mixing layer interface (GMLI) contours, respectively. The magnitude, alignment, and spatial distribution of the vorticity and principal strain rates (s1,s2,s3) are rather different when heat release is present. Density variations without heat release enhance the ω-s2 alignment while significantly reducing the ω-s3 alignment and modestly reducing the ω-s1 alignment. In contrast, heat release at the flame front further reduces the ω-s1 alignment but increases the ω-s3 alignment and suppresses the preferential ω-s2 alignment. Furthermore, increasing turbulence diminishes the effect of heat release on this preferential alignment. In regions with the largest vorticities, both the reacting and non-reacting counterflows show an increase in the probability of ω-s2 alignment. All counterflow cases have a net positive vortex-stretching contribution to the enstrophy production with a peak production rate at the flame front or GMLI, but the peak values depend on the density variation, heat release, and turbulence level. Elucidation of the complex interplay between these factors contributes to the understanding of the dynamics of turbulence-flame interactions.

Experimental and numerical investigation of iron-doped flames: FeO formation and impact on flame temperature

Gas-phase iron compounds strongly affect the flame structure already at very low concentrations, which implies the control of combustion efficiency, pollution formation, and materials synthesis in flames. The impact of iron pentacarbonyl on low-pressure premixed flames was investigated experimentally and numerically for a broad range of equivalence ratios. The burner was operated in top-to-bottom orientation, causing a strong effect of buoyancy on the flow field, a configuration, also known as buoyancy-opposed flame. The application of ultra-sensitive broadband intracavity laser absorption diagnostics enabled path-integrated measurements of gas-phase FeO in the particle-laden flow. Spatially-resolved temperature distributions were measured via OH laser-induced fluorescence. The measurements were complemented by detailed simulations of the down-firing flame to determine the (one-dimensional) flow field on the centerline of the burner. The experimental findings were the basis for extension of existing reaction schemes for iron-doped flames and a new skeletal scheme was proposed. Measured temperatures and normalized FeO concentrations were used to validate both the detailed and the skeletal scheme. The results of the optimization and reduction procedure helped to improve the understanding of the structure of the iron-doped flame and the role of iron-cluster formation in the interaction mechanisms which cause the flame inhibition or promotion by iron-compounds.

Velocimetry and thermometry in intermediate temperature flow using planar laser-induced fluorescence of OH from photo-dissociation of H2O

A technique for simultaneous velocimetry and thermometry in intermediate temperature flow is developed by combining hydroxyl-tagging velocimetry (HTV) and two-line OH planar laser-induced fluorescence (OH-PLIF). The OH tagging particles generated in HTV from the dissociation of water vapor are then used in two-line PLIF for thermometry. Using fragmentary OH expands PLIF to thermometry in regions that lack original OH, such as low temperature or unreactive ones. Meanwhile, using the PLIF system for both velocimetry and thermometry makes for a more efficient experimental system. As a proof of concept, the temperature and velocity are measured of a heated gas mixture comprising helium and water vapor. The temperature results agree well with the thermocouple results.