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.     

A thermogravimetric method for the measurement of CO/CO2 ratio at the surface of carbon during combustion

This work presents a new method of measuring the CO/CO₂ ratio at the surface of carbon particles during combustion. This thermogravimetric method deduces the ratio of CO to CO₂ by comparing the rate of consumption of carbon with the rate of oxidation of an external reference material with fast oxidation kinetics, in this case Cu. The method is useful when combustion is controlled by external mass transfer, commonly encountered in large-scale processes. The viability of this method has been demonstrated experimentally with graphite and a lignite char. It was found that in an atmosphere of ～ 1% O₂, the graphite produced CO₂ between 700 and 900 °C whilst the lignite char produced a mixture of CO and CO₂ between 700 and 800 °C with the proportion of CO increasing with temperature, and above 850 °C, only CO was produced. It was also found that for this particular lignite char, the ratio of CO/CO₂ increased with decreasing pO₂ in the environment.     

CO concentration and temperature sensor for combustion gases using quantum-cascade laser absorption near 4.7 μm

A sensor for sensitive in situ measurements of carbon monoxide and temperature in combustion gases has been developed using absorption transitions in the (v′=1←v″=0) and (v′=2←v″=1) fundamental bands of CO. Recent availability of mid-infrared quantum-cascade (QC) lasers provides convenient access to the CO fundamental band near 4.7 μm, having approximately 10⁴ and 10² times stronger absorption line-strengths compared to the overtone bands near 1.55 μm and 2.3 μm used previously to sense CO in combustion gases. Spectroscopic parameters of the selected transitions were determined via laboratory measurements in a shock tube over the 1100–2000 K range and also at room temperature. A single-laser absorption sensor was developed for accurate CO measurements in shock-heated gases by scanning the line pair v″=0, R(12) and v″=1, R(21) at 2.5 kHz. To capture the rapidly varying CO time-histories in chemical reactions, two different QC lasers were then used to probe the line-center absorbance of transitions v″=0, P(20) and v″=1, R(21) with a bandwidth of 1 MHz using fixed-wavelength direct absorption. The sensor was applied in successful shock tube measurements of temperature and CO time-histories during the pyrolysis and oxidation of methyl formate, illustrating the capability of this sensor for chemical kinetic studies.     

Application of a difference-frequency-mixing based diode-laser sensor for carbon monoxide detection in the 4.4–4.8 μm spectral region

An all-solid-state continuous-wave (cw) laser system for mid-infrared absorption measurements of the carbon monoxide (CO) molecule has been developed and demonstrated. The single-mode, tunable output of an external-cavity diode laser (ECDL) is difference-frequency mixed with the output of a 550-mW diode-pumped cw Nd:YAG laser in a periodically poled lithium niobate (PPLN) crystal to generate tunable cw radiation in the mid-infrared region. The wavelength of the 860-nm ECDL can be coarse tuned from 860.782 to 872.826 nm, allowing the sensor to be operated in the spectral region 4.4–4.8 μm. CO-concentration measurements were performed in CO/CO₂/N₂ mixtures in a room-temperature gas cell, in the exhaust stream of a well-stirred reactor (WSR) at Wright-Patterson Air Force Base and in a near-adiabatic hydrogen/air CO₂-doped flame. The noise equivalent detection limits were estimated to be 1.1 and 2.5 ppm per meter for the gas cell and flame experiments, respectively. These limits were computed for combustion gas at 1000 K and atmospheric pressure assuming a signal-to-noise ratio of 1. The sensor uncertainty was estimated to be 2% for the gas-cell measurements and 10% for the flame measurements based on the repeatability of the peak absorption. PACS 07.07.Df; 42.62.Fi; 42.65.Ky; 42.72.Ai     

On-line monitoring of cyclotron target-gas output by means of tunable lead salt diode laser absorption spectroscopy

We demonstrate what is, to our knowledge, the first use of mid-infrared laser absorption spectroscopy for trace-gas measurements of cyclotron target outputs used for the generation of radioactive carbon-11 in positron emission tomography (PET). The spectrometer was based upon a liquid-nitrogen-cooled lead salt diode laser generating single-mode radiation in the wavenumber range of 2230–2240 cm^?1. The sample flowed to a multiple-pass optical cell with a total path length of 15.23 m and the laser radiation was detected by two liquid-nitrogen-cooled InSb photodetectors. We present the results of CO, N₂O and CO₂ measurements on PET trace cyclotron output and discuss future work on ¹¹CO and ¹¹CO₂ detection.     

The absorption cross sections of N2, O2, CO,NO, CO2, N2O,CH4, C2H4, C2H6 and C4H10 from 180 to 700Å

The absorption cross sections of N₂, O₂, CO, NO, CO₂, N₂O, CH₄, C₂H₄, C₂H₆, C₄H₁₀ have been measured photoelectrically in the 180–700 Å region using synchrotron radiation. The absorption cross sections in the region λ ≥ 500 Å was found to be structureless and to increase monotonically with wavelength for all gases. The positions of the structure observed in the 520–720 Å region for N₂, O₂, CO₂ and N₂O are consistent with the various Rydberg series reported by previous authors.     

Line parameter measurements and calculations of CO broadened by H2O and CO2 at elevated temperatures

Measurements of collisional broadening of four fundamental CO lines in atmospheres of CO₂ and H₂O at 300–600 K were made. The Voigt line-shape model was fitted parametrically to the absorption spectra line-shapes. The results are compared with other experimental studies and with theoretical calculations for CO₂ broadening. Absorption spectra of the exhaust gases of a flat flame were recorded and analyzed to yield CO concentration, temperature, and line half-widths. The flame spectra half-widths were compared with extrapolations of lower temperature data using the simple power law approximation $\text{γ(T)=γ(T}{}_0\text{) (}\text{T}{}_0\text{T}\text{)}{}^{\mathrm{n}}$. The utility of this approximation in the development of combustion diagnostic techniques is discussed.     

A mechanistic char oxidation model consistent with observed CO2/CO production ratios

Reliable prediction of char conversion, heat release, and particle temperature during heterogeneous char oxidation relies upon quantitative calculation of the CO₂/CO production ratio. This ratio depends strongly on the surface temperature, but also on the local partial pressure of oxygen and thus becomes more important in simulations of oxy-fuel or pressurized combustion systems. Existing semi-empirical intrinsic kinetic models of char combustion have been calibrated against the temperature-dependence of the CO₂/CO production ratio, but have neglected the effect of the local oxygen concentration. In this study we employ steady-state analysis to demonstrate the limitations of the existing 3-step semi-global kinetics models and to show the necessity of using a 5-step model to adequately capture the temperature- and oxygen-dependence of the CO₂/CO production ratio. A suitable 5-step heterogeneous reaction mechanism is developed and its rate parameters fit to match CO₂/CO production data, global reaction orders, and activation energies reported in the literature. The model predictions are interrogated for a broad range of conditions characteristic of pressurized, oxy-fuel, and conventional high-temperature char combustion, for which essentially no experimental information on the CO₂/CO production ratio is available. The results suggest that the CO₂/CO production ratio may be considerably lower than that estimated with existing power-law correlations for oxygen partial pressures less than 10 kPa and surface temperatures higher than 1600 K. To assist with implementation of the mechanistic CO₂/CO production ratio results, an analytical procedure for calculating the CO₂/CO production ratio is presented.     

Mid-infrared heterodyne phase-sensitive dispersion spectroscopy in flame measurements

We present the first demonstration of heterodyne phase-sensitive dispersion spectroscopy (HPSDS) for in situ, non-intrusive and quantitative CO₂ concentration measurements in flames. Dispersion spectroscopy retrieves gas properties by measuring the refractive index in the vicinity of a molecular resonance. The HPSDS scheme features a significant diagnostic advantage of the intrinsic immunity to laser power fluctuations caused by beam steering, thermal radiation and soot scattering in combustion environments, and thus no extra calibration process is required. In this work, we described the spectroscopic fundamentals for measuring heterodyne phase signals in flames. As a proof of principle, we used a mid-infrared interband cascade laser (ICL) near 4183?nm to exploit the strong CO₂ transitions in the R-branch of the v₃ fundamental band. The HPSDS signals of four CO₂ lines, R(76), R(78), R(80) and R(82), were measured in CH₄/air flames to obtain CO₂ concentrations at different equivalence ratios (Φ?=?0.8–1.2), yielding a good agreement with the simultaneous laser absorption measurements using the same ICL. With its immunity to laser power fluctuations verified experimentally, the HPSDS sensor was successfully implemented to measure CO₂ concentrations in C₂H₄/air sooting flames (Φ?=?1.78–2.38). Laser dispersion spectroscopy proves to be a promising and alternative diagnostic tool for combustion measurements.     

Simultaneous detection of trace gases using multiplexed tunable diode lasers and a photoacoustic cell containing a cantilever microphone

We report what we believe to be a novel demonstration of simultaneous detection of multiple trace gases by near-IR tunable diode laser photoacoustic spectroscopy using a cell containing a cantilever microphone. Simultaneous detection of carbon monoxide (CO), ethyne (C₂H₂), methane (CH₄) and combined carbon monoxide/carbon dioxide (CO+CO₂) in nitrogen-based gas mixtures was achieved by modulation frequency division multiplexing the outputs of four near-IR tunable diode lasers. Normalized noise-equivalent absorption coefficients of 3.4×10^?9, 3.6×10^?9 and 1.4×10^?9 cm^?1?W?Hz^?1/2 were obtained for the simultaneous detection of CO, C₂H₂ and CH₄ at atmospheric pressure. These corresponded to noise-equivalent detection limits of 249.6 ppmv (CO), 1.5 ppmv (C₂H₂) and 293.7 ppmv (CH₄) respectively over a measurement period of 2.6 s at the relevant laser power. The performance of the system was not influenced by the number of lasers deployed, the main source of noise arising from ambient acoustic effects. The results confirm that small-volume photoacoustic cells can be used with low optical power tunable diode lasers for rapid simultaneous detection of trace gases with high sensitivity and specificity.     

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.     

Multi-band infrared CO2 absorption sensor for sensitive temperature and species measurements in high-temperature gases

A continuous-wave laser absorption diagnostic, based on the infrared CO₂ bands near 4.2 and 2.7 μm, was developed for sensitive temperature and concentration measurements in high-temperature gas systems using fixed-wavelength methods. Transitions in the respective R-branches of both the fundamental υ ₃ band (~2,350 cm^?1) and combination υ ₁ + υ ₃ band (~3,610 cm^?1) were chosen based on absorption line-strength, spectral isolation, and temperature sensitivity. The R(76) line near 2,390.52 cm^?1 was selected for sensitive CO₂ concentration measurements, and a detection limit of <5 ppm was achieved in shock tube kinetics experiments (~1,300 K). A cross-band, two-line thermometry technique was also established utilizing the R(96) line near 2,395.14 cm^?1, paired with the R(28) line near 3,633.08 cm^?1. This combination yields high temperature sensitivity (ΔE” = 3,305 cm^-1) and expanded range compared with previous intra-band CO₂ sensors. Thermometry performance was validated in a shock tube over a range of temperatures (600–1,800 K) important for combustion. Measured temperature accuracy was demonstrated to be better than 1 % over the entire range of conditions, with a standard error of ~0.5 % and µs temporal resolution.     

CO concentration and temperature measurements in a shock tube for Martian mixtures by coupling OES and TDLAS

CO concentration and gas temperature distribution are diagnosed behind a strong shock wave simulating the Martian atmosphere entry processes by coupling optical emission spectroscopy (OES) and tunable diode laser absorption spectroscopy (TDLAS). The strong shock wave (6.31 ± 0.11 km/s) is established in a shock tube driven by combustion of hydrogen and oxygen. Temperature of the shock-heated gas is inferred through a precise analysis of the high temporal and spatial resolution experimental spectral of CN violet system (B ² Σ ⁺ →X ² Σ ⁺, Δv = 0 sequence) using OES. A CO absorption line near 2,335.778 nm is utilized for detecting the CO concentration using scanned-wavelength direct absorption mode with 50 kHz repetition rate. Combined with temperature results from OES, CO concentration in the thermal equilibrium region is derived. The current experimental results are complementary for determining an accurate rate coefficient of CO₂ dissociation and validation relevant chemical kinetics models in Mars atmosphere entry processes.     

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).     

Multi-species laser absorption sensors for in situ monitoring of syngas composition

Tunable diode laser absorption spectroscopy sensors for detection of CO, CO₂, CH₄ and H₂O at elevated pressures in mixtures of synthesis gas (syngas: products of coal and/or biomass gasification) were developed and tested. Wavelength modulation spectroscopy (WMS) with 1f-normalized 2f detection was employed. Fiber-coupled DFB diode lasers operating at 2325, 2017, 2290 and 1352 nm were used for simultaneously measuring CO, CO₂, CH₄ and H₂O, respectively. Criteria for the selection of transitions were developed, and transitions were selected to optimize the signal and minimize interference from other species. For quantitative WMS measurements, the collision-broadening coefficients of the selected transitions were determined for collisions with possible syngas components, namely CO, CO₂, CH₄, H₂O, N₂ and H₂. Sample measurements were performed for each species in gas cells at a temperature of 25 °C up to pressures of 20 atm. To validate the sensor performance, the composition of synthetic syngas was determined by the absorption sensor and compared with the known values. A method of estimating the lower heating value and Wobbe index of the syngas mixture from these measurements was also demonstrated.     

Absorption of CO laser radiation by NO

Absorption of CO i.r. laser radiation by NO has been studied over the temperature range 300°–4000°K using a grating-tunable CO laser in conjunction with a room-temperature absorption cell and a shock tube. The CO laser line with strongest absorption at elevated temperatures was determined to be the V = 7 → 6, J = 12 → 13 line at 1935.4817 cm^-1, which is nearly coincident with the ²Π_{$\text{3}\text{2}$}V = 0 → 1, J = 37/2 → 39/2 transition in NO. The absorption cell measurements (300°K) were used to infer the position of the NO absorption line (a Λ-doublet at 1935.492 and 1935.497 cm^-1) as well as collision-broadening parameters in pure NO and NO dilute in foreign gases: 2γ° (collision-broadened full width at half maximum in cm^-1 atm^-1 at 300°K) = 0.110, NO-NO; 0.072, NO in Ar; 0.069, NO in Kr; 0.109, NO in N₂. Calculations of the NO absorption coefficient at 1935.4817 cm^-1 are presented for a range of conditions applicable to current studies in combustion and NO_x kinetics. Shock tube measurements (630°–4000°K) supporting these calculations are also reported.     

Mid-IR difference frequency laser-based sensors for ambient CH4, CO, and N2O monitoring

A new mid-infrared sensor platform is described, which combines difference frequency generation (DFG)-based tunable laser sources with simple direct absorption spectroscopy. DFG lasers operating in the 3–5 micron window are tuned to access a variety of species in the C–H, N–O, and C–O stretch regions. The sensors are capable of sub-ppb detection of key greenhouse gas species as well as common pollutants and tracer species. Specific examples of sensor data obtained for methane, nitrous oxide, and carbon monoxide are presented, including relevant time series data and associated Allan Variances. The platform provides a cost-effective alternative to other laser-based approaches in some cases, performing at similar or superior levels. Emphasis on achieving key performance metrics driven by World Meteorological Organization guidelines for Global Air Watch program and other applications is highlighted.     

Shock-tube study on high-temperature CO formation during dry methane reforming

The use of natural-gas-fueled combustion engines at unusual operating conditions to provide electrical and/or chemical energy on demand emphasizes the need for fundamental research on decomposition and formation of base chemicals at these conditions. In this work, the CO formation behind reflected shock waves from the pyrolysis of CO₂/CH₄ mixtures was investigated for the first time in the context of engine-based dry methane reforming, to understand the interaction of CO₂ and CH₄ at high temperatures and to test the validity of literature reaction mechanisms. Different CO₂/CH₄ mixtures at atmospheric pressure and temperatures between 1900 K and 2700 K were investigated. Time-resolved CO measurements were performed by laser absorption using a quantum cascade laser.With increasing CO₂ addition later reaction onset was observed, showing a reduction in the overall reactivity. Rate of production and sensitivity analyses highlight competing reactions in the pyrolysis and oxidation pathways and that the number of available H radicals is limited, which is attributed to the reduced reactivity. However, the analysis shows that CO₂ is also a source for OH radicals (via CO₂ + H ⇌ CO + OH), which enhance methane decomposition. The comparison with literature reaction mechanisms showed that none of the tested mechanisms can perfectly predict the time-resolved CO formation, highlighting the need for the validation of detailed kinetics models under nontypical conditions.     

High pressure ignition delay times of H2/CO mixture in carbon dioxide and argon diluent

Ignition Delay Time (IDT) plays a significant role in combustion process of advanced power cycles such as direct-fired supercritical carbon dioxide (sCO₂) cycle. In this cycle, fuel and oxidizer are heavily diluted with carbon dioxide (CO₂) and autoignite at a combustor inlet pressure range of 10–30 MPa and a temperature range of 900–1500 K. A fuel candidate for sCO₂ power cycle applications is syngas (H₂/CO mixture); however, its ignition properties at these conditions are not studied. Moreover, the existing chemical kinetics models have not been evaluated for H₂/CO mixtures applications relevant to elevated pressure conditions and under large dilution levels of CO₂. Therefore, two tasks are performed in this study. First, IDTs of a H₂/CO=95:5 mixture at stoichiometric and rich (Φ=2) conditions are measured in a high-pressure shock tube under 95.5% CO₂ dilution level and at 10 MPa and 20 MPa for a temperature range of 1161–1365 K. For the experimental conditions considered in this work, Aramco 2.0, FFCM-1, HP-Mech and USC Mech II kinetic models are capable of capturing IDT data. Second, similar experiments are conducted by replacing the CO₂ dilute gas with Argon (Ar) to understand the chemical effect of CO₂ on IDT globally. Sensitivity analysis results reveal that for both diluents, reaction H + O₂(+M)=HO₂(+M) is the most important reaction in controlling ignition. Further, a rate of production analysis shows that CO₂ has a competing effect on OH radical production. On one hand, CO₂ accelerates the consumption of H radicals through H + O₂+CO₂→HO₂+CO₂ therefore hindering HO₂+HOH+OH reaction for OH production. On the other hand, CO₂ is shown to enhance OH production through H₂O₂+M=OH+OH+M. These kinetic effects from CO₂ cancel out, therefore CO₂ does not significantly alter the IDT globally when compared to the Ar bath case. This is confirmed by both experimental results and simulation.     

On the opto-voltaic measurements in CO and CO2 lasers

We observed and compared the opto-voltaic signals in CO and CO₂ lasers. The signals are obtained capacitively from the water cooling jacket as a low voltage source not influencing the current circuit. We observed from measurement that the output power and the so-called optovoltaic input power have a distinct relationship depending on laser current and cavity parameters. It will be shown that opto-voltaic detection is a very sensitive method especially for CO lasers.