Effect of H-atom concentration on soot formation in premixed ethylene/air flames

Soot formation is a major challenge in the development of clean and efficient combustion systems based on hydrocarbon fuels. Fundamental understanding of the reaction mechanism leading to soot formation can be obtained by investigating the role of key reactive species such as atomic hydrogen taking part in soot formation pathways. In this study, two-dimensional laser induced incandescence (LII) measurements using λ?=?1064?nm laser have been used to measure soot volume fraction (f_V) in a series of rich ethylene (C₂H₄)/air flames, stabilized over a McKenna burner fitted with a flame stabilizing metal disc. Moreover, a comparison of UV (λ?=?283?nm), visible (λ?=?532?nm) and IR (λ?=?1064?nm) laser excited LII measurements of soot is discussed. Recently developed, femtosecond two-photon laser-induced fluorescence (fs-TPLIF) technique has been applied for obtaining spatially resolved H-atom concentration ([H]) profiles under the same flame conditions. The structure of the flames has also been determined using hydroxyl radical (OH) planar laser induced fluorescence (PLIF) imaging. The results indicate an inverse dependence of f_V on [H] for a range of C₂H₄/air rich flames up to an equivalence ratio, Φ?=?3.0. Although an absolute relationship between [H] and f_V cannot be easily derived owing to the multiple steps involving H and other intermediate species in soot formation pathways, the present study demonstrates the feasibility to couple [H] and f_V obtained using advanced optical techniques for soot formation studies.     

In situ soft X-ray absorption spectroscopy of flames

The feasibility of in situ soft X-ray absorption spectroscopy for imaging carbonaceous species in hydrocarbon flames is demonstrated using synchrotron radiation. Soft X-rays are absorbed by core level electrons in all carbon atoms regardless of their molecular structure. Core electron spectroscopy affords distinct advantages over valence spectroscopy, which forms the basis of traditional laser diagnostic techniques for combustion. In core level spectroscopy, the transition linewidths are predominantly determined by the instrument response function and the decay time of the core–hole, which is on the order of a femtosecond. As a result, soft X-ray absorption measurements can be performed in flames with negligible Doppler and collisional broadening. Core level spectroscopy has the further advantage of measuring all carbonaceous species regardless of molecular structure in the far-edge region, whereas near-edge features are molecule specific. Interferences from non-carbon flame species are unstructured and can be subtracted. In the present study, absorption measurements in the carbon K-edge region are demonstrated in low-pressure (P _total = 20–30 Torr) methane jet flames. Two-dimensional imaging of the major carbonaceous species, CH₄, CO₂, and CO, is accomplished by tuning the synchrotron radiation to the respective carbon K-edge, near-edge X-ray absorption fine structure (NEXAFS) transitions and scanning the burner.     

Fiber laser intracavity absorption spectroscopy for in situ multicomponent gas analysis in the atmosphere and combustion environments

Intracavity absorption spectroscopy with a broadband Er³⁺-doped fiber laser is applied for the measurements of several molecular species revealing quantitative information about the gas concentration, temperature and chemical reactions in flames. The spectral range of measurements extends from 6200 cm⁻¹ to 6550 cm⁻¹ with the proper choice of the fiber length and by moving an intracavity lens. With a pulsed laser applied in this experiment, the sensitivity to absorption corresponds to an effective absorption path length of 3 km assuming the cavity is completely filled with the sample. For a cw laser, the effective absorption path length is estimated to be 50 km. Absorption spectra of various molecules such as CO₂, CO, H₂O, H₂S, C₂H₂ and OH were recorded separately in the cell and/or in low-pressure methane and propane flames. The presented measurements demonstrate simultaneous in situ detection of three molecular products of chemical reactions at different flame locations. Variation of the relative strengths of OH absorption lines with the temperature enables the estimation of the local flame temperature. The sensitivity of this laser does not depend on the broadband cavity losses and it can be used for in situ measurements of absorption spectra in hostile environments such as contaminated samples, flames or combustion engines. The presented technique can be applied for various diagnostic purposes, such as in environmental, combustion and plasma research, in medicine and in the determination of stable isotope ratios.     

Experimental evaluation of strategies for quantitative laser-induced-fluorescence imaging of nitric oxide in high-pressure flames (1-60 bar)

Nitric oxide laser-induced-fluorescence (NO-LIF) 2-D imaging measurements using a new multi-spectral detection strategy are reported for high-pressure flames (1-60 bar). This work builds on previous research that identified interference LIF from O₂ and CO₂ in high-pressure flames and optimized the choice of excitation strategies as a function of application conditions. In this study, design rules are presented to optimize the LIF detection wavelengths for quantitative 2-D NO-LIF measurements over a wide range of pressures (1-60 bar) and temperatures. Simultaneous detection of LIF in multiple wavelength regions enables correction of the NO signal for interference from O₂ and CO₂ and allows simultaneous imaging of all three species. New experiments of wavelength-resolved 1-D LIF in slightly lean (? = 0.9) and slightly rich (? = 1.1) methane/air flames are used to evaluate the design rules and estimate the NO detection limits for a wide range of flame conditions. The quantitative 2-D measurements of NO in the burnt gas are compared with model calculations (using GRI-Mech 3.0) versus pressure for slightly lean and slightly rich flames. The discussions and demonstrations reported in this study provide a practical guideline for application of instantaneous 1-D or 2-D NO-LIF imaging strategies in high-pressure combustion systems.     

Pulverized coal swirl flames in oxy-fuel conditions: Effects of oxidizer O2 concentration on flow field and local gas composition

In an experimental study the effects of varied oxygen concentrations in the oxidizer gas on resulting flow fields, combustion products and general behavior of pulverized coal swirl flames under oxy-fuel conditions have been investigated. Experiments were carried out in a small scale down-fired cylindrical combustion chamber equipped with an annular swirl burner. Studied flames had a constant power output of 40 kW_th and O₂/CO₂ oxidizer gas mixtures with O₂ concentrations ranging from 23 to 33 vol%. Detailed two-dimensional flow field measurements are obtained from laser Doppler anemometry (LDA). Velocity profiles (Mean and RMS) have been obtained for all conditions investigated and serve as basis for identification of flow field characteristics. Velocity RMS values are provided as supplementary material. To complement flow field measurements, in-flame gas composition measurements were also conducted using a sampling probe combined with infrared gas absorption analysis via Fourier-transform infrared (FTIR) spectrometry. The results obtained show increased velocities, particularly along the main vortex for flames with increased oxygen contents, while lower velocities are found to occur inside the recirculation regions. The opposite occurs with lower O₂ concentrations, showing significantly reduced velocities in the main vortex, but stronger recirculation than the high oxygen counterparts. This effect is attributed to a modification of the swirl level introduced by the expansion of product gases. Measured NO and CO in-flame concentrations showed significant variations under different O₂ concentrations in the oxidizer.     

Quantitative C2H2 measurements in sooty flames using mid-infrared polarization spectroscopy

Quantitative measurements of acetylene (C₂H₂) molecules as a combustion intermediate species in a series of rich premixed C₂H₄/air flames were non-intrusively performed, spatially resolved, using mid-infrared polarization spectroscopy (IRPS), by probing its fundamental ro-vibrational transitions. The flat sooty C₂H₄/air premixed flames with different equivalence ratios varying from 1.25 to 2.50 were produced on a 6 cm diameter porous-plug McKenna type burner at atmospheric pressure, and all measurements were performed at a height of 8.5 mm above the burner surface. IRPS excitation scans in different flame conditions were performed and rotational line-resolved spectra were recorded. Spectral features of acetylene molecules were readily recognized in the spectral ranges selected, with special attention to avoid the spectral interference from the large amount of coexisting hot water and other hydrocarbon molecules. On-line calibration of the optical system was performed in a laminar C₂H₂/N₂ gas flow at ambient conditions. Using the flame temperatures measured by coherent anti-Stokes Raman spectroscopy in a previous work, C₂H₂ mole fractions in different flames were evaluated with collision effects and spectral overlap between molecular line and laser source being analyzed and taken into account. C₂H₂ IRPS signals in two different buffering gases, N₂ and CO₂, had been investigated in a tube furnace in order to estimate the spectral overlap coefficients and collision effects at different temperatures. The soot-volume fractions (SVF) in the studied flames were measured using a He–Ne laser-extinction method, and no obvious degrading of the IRPS technique due to the sooty environment has been observed in the flame with SVF up to ～2×10^?7. With the increase of flame equivalence ratios not only the SVF but also the C₂H₂ mole fractions increased.     

Formation and dispersion of CO<Subscript>2</Subscript> after combustion in closed area

This study deals with the formation of carbon dioxide (CO₂) after combustion process and dispersion in a closed area. The formation and dispersion of CO₂ were numerically simulated and validated by experiment. Ethanol (C₂H₅OH) was chosen as a fuel for the combustion process. Numerical simulations were carried out by using Reynolds averaged Navier–Stokes (RANS) approach with k-ε and k-ω turbulent models. The combustion process was simulated using two methods. Species transport with chemical reactions was the first method, and the second method was the nonpremix combustion model based on the mixture fraction theory. There were done some sensitivity studies on the influence of the time step size and a resolution of computational grid. Results from numerical simulations were validated by experimental measurements, where the CO₂ concentration was measured by the non-dispersive infrared (NDIR) sensor at four points.     

Heterodyne spectrometer for the 10 micron region

We first consider the interest of infrared heterodyne spectroscopy to study the vertical distribution of atmospheric constituents such O₃. Then an heterodyne spectrometer is described. It operates in the 10 micron region with a CO₂ laser and gives a resolution of 5 MHz. A laboratory spectrum of C₂H₄ is presented as a preliminary result.     

Two-photon spectroscopy of 15NH3 with isotopic CO2 lasers and double resonance studies with a new coincidence

Eleven transitions of the ν₂ band of ¹⁵NH₃ were measured by the technique of infrared-microwave two-photon spectroscopy using an isotopic CO₂ laser and 20-mW microwave power. By combining these results with those of previous two-photon measurements and with Stark laser spectroscopy results, the spectroscopic constants of this band were calculated. Using the previously unknown coincidence between the R(18) ¹³CO₂ laser line and the _asQ(5,4) infrared transition, velocity tuned multiple-photon Lamb-dip signals were observed. Very intense double resonance signals were observed on the (5,4), (6,4), and (4,4) microwave transitions and the magnitude of these effects was compared to those observed previously in ¹⁴NH₃.     

A mid-infrared scanned-wavelength laser absorption sensor for carbon monoxide and temperature measurements from 900 to 4000 K

Mid-infrared laser absorption sensors based on quantum cascade laser (QCL) technology offer the potential for high-sensitivity, selective, and high-speed measurements of temperature and concentration for species of interest in high-temperature environments, such as those found in combustion devices. A new mid-infrared QCL absorption sensor for carbon monoxide and temperature measurements has been developed near the intensity peak of the CO fundamental band at 4.6 μm, providing orders-of-magnitude greater sensitivity than the overtone bands accessible with telecommunications lasers. The sensor is capable of probing the R(9), R(10), R(17), and R(18) transitions of the CO fundamental ro-vibrational band which are located at frequencies where H₂O and CO₂ spectral interference is minimal. Temperature measurements are made via scanned-wavelength two-line ratio techniques using either the R(9) and R(17) or the R(10) and R(18) line pairs. The high-speed (1–2 kHz) scanned-wavelength sensor is demonstrated in room-temperature gas cell measurements of CO and, to demonstrate the potential of the sensor for high-temperature thermometry, in shock-heated gases containing CO for a very wide range of temperature (950–3500 K) near 1 atm. To our knowledge, these measurements represent the first use of QCL-based absorption sensor for thermometry at elevated combustion-like temperatures. The high-temperature measurements of CO mole fraction and temperature agree with the post-reflected-shock conditions within ±1.5% and ±1.2% (1σ deviation), respectively.     

Laser spectroscopic monitoring of gas emission and measurements of the C/C isotope ratio in CO2 from a wood-based combustion

We report on the application of a compact and field-deployable instrument, based on a continuous-wave fiber-coupled Telecom external cavity diode laser, to measure the ¹³C/¹²C isotope ratio in CO₂ from a wood-based combustion. Carbon dioxide, the most important greenhouse gas, is a major product of combustion. The measurements of the ¹³C/¹²C isotopic ratio in CO₂ from combustion emission permit one to identify the CO₂ source and to study the temporal and spatial variations of pollution in the atmosphere. The average value of the ¹³CO₂/¹²CO₂ ratio is found to be (1.1011±0.0024)%. The corresponding δ-value relative to PDB standard is (−20.17±2.14)‰, which is in good agreement with the typical value of (−25±2)‰ for wood. Simultaneous monitoring of multiple species from gas emission has been performed using direct-absorption spectroscopy. The concentrations of C₂H₂, CO, CO₂ and H₂O were determined on the basis of integrated absorbance measured by least-squares fitting a Voigt lineshape to experimental absorption spectra.     

Miniaturized laser heterodyne radiometer for measurements of CO2 in the atmospheric column

We have developed a low-cost, miniaturized laser heterodyne radiometer for highly sensitive measurements of carbon dioxide (CO₂) in the atmospheric column. In this passive design, sunlight that has undergone absorption by CO₂ in the atmosphere is collected and mixed with continuous wave laser light that is step-scanned across the absorption feature centered at 1,573.6 nm. The resulting radio frequency beat signal is collected as a function of laser wavelength, from which the total column mole fraction can be de-convolved. We are expanding this technique to include methane (CH₄) and carbon monoxide (CO), and with minor modifications, this technique can be expanded to include species such as water vapor (H₂O) and nitrous oxide (N₂O).     

Gas temperature measurements using widely tunable long-wavelength VCSEL

A method for gas temperature measurements with a widely tunable laser diode is presented. The method involves rapidly switching the laser frequency between two distantly spaced absorption lines chosen for optical thermometry. Direct absorption spectroscopy using a single-mode VCSEL was employed to probe the R10 and R22 lines of the 2ν₁+2ν₂ ⁰+ν₃ combination band of CO₂ near 6355.9 and 6363.7 cm^-1 sequentially. A specially designed 0.5-m cryogenic gas cell was filled with 10 mbar CO₂ at room temperature and cooled to 150 K with liquid N₂. The VCSEL was modulated with a 10-kHz ramp superimposed on a 1-kHz square waveform to scan two 0.04 cm^-1 intervals sequentially. The gas temperatures obtained with the VCSEL in the 150–300 K range are in a good agreement with those derived from gas pressure ratios. The maximum relative error of temperature measurements using the VCSEL was ± 3%. A compact VCSEL-based sensor can be developed for gas temperature and concentration measurements in the Martian atmosphere. The method proposed can be used for many applications including in situ monitoring of combustion processes. PACS 42.62.Fi; 42.55.Px; 39.30.+w     

Relaxation oscillations in cw optically pumped CD3OD and15NH3 lasers

We report the results of heterodyne measurements of the mode quality and tuning range of a cw CO₂ laser designed for optically pumping a far-infrared (FIR) molecular laser, and describe the implications of multi-mode operation. In particular we report the observation of relaxation oscillations in the output of a FIR waveguide laser.     

Attenuation of combustion instability in a fuel-staged dual-nozzle gas turbine combustor with asymmetric hydrogen composition

The instability attenuation mechanism of fuel staging was investigated in a CH₄/H₂ fueled dual-nozzle gas turbine combustor. Fuel staging was implemented using an asymmetry in fuel composition between the two nozzles. The fuel composition of the upper nozzle was varied while keeping that of the lower nozzle constant. Under these conditions, the self-excited and forced responses of fuel-staged flames were analyzed using OH* chemiluminescence imaging, OH planar laser-induced fluorescence, and particle image velocimetry. In the self-excited measurements, although strong combustion instability was exhibited in the symmetric condition, it weakened gradually with increasing asymmetry in fuel composition. The symmetric flame exhibited significant fluctuations in the heat release rate around the flame tip, which acted as the primary cause of driving combustion instability. However, in asymmetric flames, the H₂ addition induced phase leads in heat release rate fluctuations at the upper region, which damped combustion instability. Thus, our observations revealed a high correlation between the phase leads and the attenuation of combustion instability. Analyses of the forced responses showed that the heat release rate fluctuations were induced by interactions between the flame and the shedding vortex released from the nozzle tip into the downstream. Although these characteristics of shedding vortices did not depend on the H₂ addition, the change in the axial position of the flame caused by the H₂ addition induced the relocation of the site, at which the flame interacted with the vortex. Subsequently, it induced phase leads in the heat release rate fluctuations. The phase difference of heat release rate fluctuations between the two flames due to this phase leads enlarged progressively with increasing asymmetry in fuel composition, leading to the attenuation of combustion instability in asymmetric conditions.     

A phase-sensitive technique to measure small changes in laser frequency: application to measure the shift and broadening of a saturated absorption line of OsO4

A phase-sensitive technique was used to measure the sensitivity to operating conditions of the output frequency of a highly stable carbon dioxide laser, which operated on the 10-μmm R(0) transition (28.8 THz) and was locked to the saturated absorption of the Q(15) transition of OsO₄. Periodic changes in the operating conditions were imposed on the laser and the resulting changes in the output frequency were measured through phase-sensitive demodulation of the heterodyne beat with a second CO₂ laser of much lower stability. Shifts as small as 50Hz could be detected by this technique. The results are in good agreement with previous measurements which employed an infrared frequency chain.     

Combustion characteristics of Mg vapor jet flames in CO2 atmospheres

An experimental study was performed on the combustion characteristics of a jet diffusion flame of Mg vapor injected through a small nozzle into CO₂ atmospheres at low pressures from 8 to 48 kPa with a view to using Mg as fuel for a CO₂-breathing turbojet engine in the Mars atmosphere. The Mg vapor jet produced three types of the flame. At lower pressures and higher injection velocities, a red-heated jet flame formed, in which the injected Mg vapor was heated by spontaneous reactions, turning red. At medium pressures and injection velocities, a stable luminous lifted-like flame developed above the rim of the chimney, a tube-like combustion product for the Mg vapor passage that grew on the nozzle during combustion. The flame had similar flame length properties to laminar jet diffusion flames of gaseous fuels. At higher pressures and lower injection velocities, a stable luminous attached flame developed at the rim of the chimney. The same reactions, producing MgO(g), CO and MgO(c), proceeded preferentially for all flames and chimneys. Carbon was only subordinately generated. Burning behavior of Mg vapor jets in a CO₂ atmosphere has been represented, including the homogeneous reaction of Mg vapor with CO₂, the diffusion of CO₂, and the condensation and deposit of MgO. The injection velocity of Mg vapor at the rim of the chimney and the exothermic reactions with diffused CO₂ that occur there play a crucial role in the attachment and development of the flames. The flame structure may be explained in terms of the relatively low gas-phase reaction rate of Mg with CO₂.     

Experimental study of a confined premixed metal combustor: Metal flame stabilization dynamics and nitrogen oxides production

This work presents a study of a magnesium/air combustion process in the context of innovative zero carbon dioxide (CO₂) energy carriers for reducing global warming effects. In order to analyze more deeply the confined combustion of magnesium under fluctuating overpressure conditions (0 to 24 hPa) and the generated gaseous by-products, magnesium/air flames have been realized in a combustion chamber with a conical bluff-body as flame holder and different contraction ratios diaphragms at the exit duct. Sieved magnesium samples with two size-fractions were tested: 20–50?µm and 50–70?µm. The gaseous emissions of nitrogen oxides (NO_x) and dioxygen (O₂) were analyzed with on-line infrared, ultraviolet and paramagnetic analyzers. A flame pulsating behavior was clearly observed from light emission intensity (monitored by a photodiode) and pressure fluctuations (monitored by a pressure sensor); the frequencies obtained ranged between 3 and 10?Hz. The frequency of the pulsation exhibited strong dependence on the geometric configuration of the chamber: a contraction diaphragm divided by two the frequency level of the fluctuations in the studied range of maximum overpressure. Such fluctuations may probably be the consequence of periodic perturbations of the recirculation zone behind the bluff-body. These periodic perturbations are themselves caused by strong periodic overpressure variations due to stiff contraction downstream responding to gas velocity fluctuations. This feed-back-loop mechanism was considered in this study. NO_x emissions produced through the thermal pathway were analyzed for equivalence ratios ranging from 0.29 to 1. The representation of NO_x versus equivalence ratio exhibited a parabolic shape with a maximum for an equivalence ratio of 0.4. Moreover, NO_x emissions of this metal combustor have shown a similar order of magnitude than current internal combustion engines.     

Simultaneous CO concentration and temperature measurements using tunable diode laser absorption spectroscopy near 2.3 μm

Simultaneous measurements of carbon monoxide (CO) mole fraction and temperature using tunable diode laser absorption spectroscopy (TDLAS) near 2.3 μm are reported. The measurement method uses ro-vibrational transitions [R(27): v″ = 1 → v′ = 3] and [R(6): v″ = 0 → v′ = 2] in the first overtone band of CO near 2.3 μm (~4,278 cm^?1). The measurements were performed in the post flame environment of fuel rich premixed ethylene–air flames with a N₂ co-flow, stabilized over a water cooled McKenna burner. Non-uniformity in the temperature and CO mole fraction, along the absorption line of sight, in the mixing layer of the co-flow, was considered during data analysis. The TDLAS based temperature measurements (±80 K) were in good agreement with those obtained using N₂ vibrational coherent anti-Stokes Raman scattering (±20 K), and the CO mole fraction measurements were in good agreement with the equilibrium values, for equivalence ratios lower than 1.8. A signal to noise ratio of 45 was achieved at an equivalence ratio of 1 for a CO concentration of 0.8 % at 1,854 K.     

Laser frequency measurements and spectroscopic assignments of optically pumped 13CH3OH

A three-laser heterodyne system was used to measure the frequencies of twelve optically pumped laser emissions from ¹³CH₃OH in the far-infrared (FIR) region. These emissions, ranging from 54 to 142 μm, are reported with fractional uncertainties up to ±2×10^-7 along with their polarization relative to the CO₂ pump. Using the 9P32 and 10R14 CO₂ lines, complete spectroscopic assignments for two laser systems were confirmed. Received: 31 May 2001 / Published online: 19 September 2001