Two-color polarization spectroscopy measurements of Zeeman state-to-state collision induced transitions of nitric oxide in binary gas mixtures.

We investigated collision induced transitions in the (0, 0) band of the A2Σ+-X2Π electronic transition of nitric oxide (NO) using two-color polarization spectroscopy (TCPS). Two sets of TCPS spectra for 1% NO, diluted in different buffer gases at 295 K and 1 atm, were obtained with the pump beam tuned to the R11(11.5) and OP12(1.5) transitions. The buffer gases were He, Ar, and N2. The probe was scanned while the pump beam was tuned to the line center. Theoretical TCPS spectra, calculated by solving the density matrix formulation of the time-dependent Schrödinger wave equation, were compared with the experimental spectra. A collision model based on the modified exponential-gap law was used to model the rotational level-to-rotational level collision dynamics. A model for collisional transfer from an initial to a final Zeeman state was developed based on the difference in cosine of the rotational quantum number J projection angle with the z-axis for the two Zeeman states. Rotational energy transfer rates and Zeeman state collisional dynamics were varied to obtain good agreement between theory and experiment for the two different TCPS pump transitions and for the three different buffer gases. One key finding, in agreement with quasi-classical trajectory calculations, is that the spin-rotation changing transition rate in the A2Σ+ level of NO is almost zero for rotational quantum numbers ≥8. It was necessary to set this rate to near zero to obtain agreement with the TCPS spectra.

Broadband ultrafast-laser-absorption spectroscopy for multi-hydrocarbon measurements near 3.3 µm in flames.

This paper presents the development and application of a broadband ultrafast-laser-absorption-spectroscopy (ULAS) technique operating in the mid-infrared for simultaneous measurements of temperature, methane (C H 4), and propane (C 3 H 8) mole fractions. Single-shot measurements targeting the C-H stretch fundamental vibration bands of C H 4 and C 3 H 8 near 3.3 µm were acquired in both a heated gas cell up to ≈650K and laminar diffusion flames at 5 kHz. The average temperature error is 0.6%. The average species mole fraction errors are 5.4% for C H 4 and 9.9% for C 3 H 8. This demonstrates that ULAS is capable of providing high-fidelity hydrocarbon-based thermometry and simultaneous measurements of both large and small hydrocarbons in combustion gases.

Background suppression for CARS thermometry in highly luminous flames using an electro-optical shutter.

An electro-optical shutter (EOS), comprising a Pockels cell located between crossed-axis polarizers, is integrated into a nanosecond coherent anti-Stokes Raman scattering (CARS) system. The use of the EOS enables thermometry measurements in high-luminosity flames through significant reduction of the background resulting from broadband flame emission. A temporal gating ≤100 ns along with an extinction ratio >10,000:1 are achieved using the EOS. Integration of the EOS enables the use of an unintensified CCD camera for signal detection, improving upon the signal-to-noise ratio achievable with inherently noisy microchannel plate intensification processes previously employed for short temporal gating. The reduction in background luminescence afforded by the EOS in these measurements allows the camera sensor to capture CARS spectra at a broad range of signal intensities and corresponding temperatures, without saturation of the sensor, thus enhancing the dynamic range of these measurements.

0.1-5 MHz ultrahigh-speed gas density distributions using digital holographic interferometry.

Gas density distributions for an underexpanded jet at several different pressure ratios were measured at ultrahigh speeds in this work using digital holographic interferometry (DHI). DHI measurements have generally been performed on the order of several Hz in the literature, although some recent groups report measurements at 10 and 100 kHz. We demonstrate 2D imaging of gas density distributions at imaging rates up to 5 MHz, which is an increase by a factor of 50 compared to the previous DHI literature. A narrow-linewidth, continuous-wave laser was used in a Mach-Zehnder configuration, and the holograms were recorded using one of two different CMOS cameras. The interferograms were analyzed using the Fourier method, and a phase unwrapping was performed. Axisymmetric flow was assumed for the region near the nozzle exit, and an Abel inversion was performed to generate a planar-slice gas density distribution from the line-of-sight unwrapped phase. The challenges and opportunities associated with performing DHI measurements at ultrahigh speeds are discussed.

Simultaneous Temperature and Pressure Measurements in Compressible Flow Using Nanosecond O2 Coherent Anti-Stokes Raman Spectroscopy.

Simultaneous pure-rotational coherent anti-Stokes Raman spectroscopy (PRCARS) and vibrational O2 CARS spectroscopy (VCARS) were performed at elevated pressure and lowered temperature conditions in non-reacting compressible flow. We applied dual-pump CARS in a three-laser, three-color configuration to simultaneously acquire the PRCARS and VCARS spectra of O2. PRCARS spectra provide excellent sensitivity to temperature at relatively low temperatures. Pressure was extracted using the differential response of collisional effects in the PRCARS and the VCARS spectra. We used an under-expanded jet outside a choked converging nozzle as the compressible flow-field. We numerically analyze the pressure sensitivity of the combined CARS technique. Finally, we compare the collisional narrowing lineshape models of rotational diffusion narrowing and modified-exponential-gap model, for fitting the experimental spectrum.

Effects of self-phase modulation (SPM) on femtosecond coherent anti-Stokes Raman scattering spectroscopy.

The effects of self-phase modulation (SPM) on the power spectra of femtosecond (fs) pulses and the consequent impact on N2 chirped-probe-pulse (CPP) fs coherent anti-Stokes Raman scattering (CARS) spectra are discussed in this paper. We investigated the pressure dependence of CPP fs CARS for N2 in a room-temperature gas cell at pressures ranging from 1 to 10 bar, and in our initial experiments the CPP fs CARS spectrum changed drastically as the pressure increased. We found that the spectra of the near-Fourier-transform-limited, 60-fs pump and Stokes pulses at the exit of the gas cell changed drastically as the pressure increased due to self-phase-modulation (SPM). This effect was examined in detail in further experiments where the pulse energies of the pump and Stokes pulses were controlled using a combination of a half-wave plate and a linear polarizer. Along with the generated CARS spectrum, the spectra of pump and Stokes pulses were measured at the entrance and exit of the gas cell. The extent of SPM effects for a particular spectrum was characterized by the least squares difference between that spectrum and a spectrum recorded at low enough pressure and laser intensities that SPM was negligible. SPM effects were investigated for N2, O2, CO2, and CH4, for pressures ranging from 1 to 10 bar, and for pump and Stokes pulse energies ranging from 10 to 60 µJ. We found that SPM effects in N2 were much weaker than for O2, CO2 and CH4.

The development and performance of a perforated plate burner to produce vitiated flow with negligible swirl under engine-relevant gas turbine conditions.

The development and performance of a perforated plate burner (PPB) operating using premixed natural gas and air at engine-relevant inlet temperatures and combustor pressures with thermal powers up to 1 MW is discussed. A significant benefit of using burners with simplified flow fields, such as the PPB, for experimental studies in the laboratory is the potential for decoupling the complex fluid dynamics in typical combustors from the chemical kinetics. The primary motivation for developing this burner was to use it as a source of vitiated flow with negligible swirl for reacting jet in vitiated crossflow experiments. The design methodology for the PPB is described, including plate geometry selection and flashback mitigation features. The stable operation of the PPB within a high-pressure test rig was validated: successful ignition, effective use of red-lines for flashback mitigation, and long duration steady-state operation in both piloted and nonpiloted modes were all observed. Exhaust gas emissions measured using a Fourier-transform infrared (FTIR) spectrometer showed very good performance of the PPB in terms of the combustion efficiency (based on measured CO and UHC), and a stability diagram of the PPB was developed as a function of the equivalence ratio and the PPB hole velocity. FTIR measurements also showed very low levels of NOX in nonpiloted operation that were generally within 3 ppm (reported dry and referenced to 15% O2). The capability for steady-state operation, high combustion efficiency, and low levels of NOX makes this PPB an excellent burner candidate for combustion experiments in the laboratory.

Dynamic imaging of the temperature field within an energetic composite using phosphor thermography.

An improved understanding of energy localization ("hot spots") is needed to improve the safety and performance of explosives. We propose a technique to visualize and quantify the properties of a dynamic hot spot from within an energetic composite subjected to ultrasonic mechanical excitation. The composite is composed of an optically transparent binder and a countable number of octahydro 1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystals. The evolving temperature field is measured by observing the luminescence from embedded phosphor particles and subsequent application of the intensity ratio method. The spatial temperature precision is less than 2% of the measured absolute temperature in the temperature regime of interest (23°C-220°C). The temperature field is mapped from within an HMX-binder composite under periodic mechanical excitation.

Innovative scheme for high-repetition-rate imaging of CN radical.

We have employed, to the best of our knowledge, a novel excitation scheme to perform the first high-repetition-rate planar laser-induced fluorescence (PLIF) measurements of a CN radical in combustion. The third harmonic of a Nd:YVO4 laser at 355 nm due to its relatively large linewidth overlaps with several R branch transitions in a CN ground electronic state. Therefore, the 355 nm beam was employed to directly excite the CN transitions with good efficiency. The CN measurements were performed in premixed CH4-N2O flames with varying equivalence ratios. A detailed characterization of the high-speed CN PLIF imaging system is presented via its ability to capture statistical and dynamical information in these premixed flames. Single-shot CN PLIF images obtained over a HMX pellet undergoing self-supported deflagration are presented as an example of the imaging system being applied towards characterizing the flame structure of energetic materials.

Technique developments and performance analysis of chirped-probe-pulse femtosecond coherent anti-Stokes Raman scattering combustion thermometry.

This work characterizes the state of the art in the analysis of high-repetition-rate, ultrafast combustion thermometry using chirped-probe-pulse femtosecond coherent anti-Stokes Raman scattering (CPP fs-CARS). Several key aspects of the CARS spectroscopy system are described, including: (1) the ultrafast laser source, (2) use of the frequency-doubled idler versus signal from the optical parametric amplifier, (3) the geometry constraints for phase matching, and (4) spectral fitting for single-shot temperature measurements. A frequency-dependent instrument response function (IRF) for the detection system was modeled as a variable-width Gaussian and implemented through a frequency convolution of synthetic spectra. Proper accounting of the IRF increased spectral fitting performance in the high-frequency region where signal oscillations are weaker and narrower. Aggregated data from 25 system performance assessments taken over four months yielded accuracy and precision of 2.7% and ±3.5% for flame temperatures, and 9.9% and ±6.1% at room temperature, using the commonly reported method. A new processing technique, based on the statistical method of maximum likelihood, was implemented for turbulent flames where strong fluctuations in expected temperatures necessitate use of multiple temperature calibrations. Results from multiple sets of laser parameters are combined to generate an error-weighted temperature from the top-performing calibrations. A testing procedure was designed to characterize system performance when the range of expected temperatures is unknown, simulating the random temperature field of a highly turbulent flame. Accuracy error of the CPP fs-CARS system increased in this more-stressing test at all temperatures, but precision was significantly affected only at room temperature. System stability is characterized, and the contribution from shot-to-shot laser fluctuations on measurement precision is quantified. Finally, the near-adiabatic and steady assumptions for the Hencken burner calibration flame are examined in an axial scan; significant deviations from ideal behavior were observed only at heights of more than four diameters above the burner surface.

A model combustor for studying a reacting jet in an oscillating crossflow.

This paper discusses a novel model combustion experiment that was built for studying the structure and dynamics of a reacting jet in an unsteady crossflow. A natural-gas-fired dump combustor is used to generate and sustain an acoustically oscillating vitiated flow that serves as the crossflow for transverse jet injection. Unlike most other techniques that are limited in operating pressure or acoustic amplitude, this method of generating an unsteady flow field is demonstrated at a pressure of 10 atm with peak-to-peak oscillation amplitudes approaching 20% of the mean pressure. An optically accessible test section designed for these conditions provides access for advanced laser and optical diagnostic measurements. Detailed measurements provide insight into the complex acoustic-hydrodynamic-combustion coupling processes and offer high-quality, high-resolution validation data for numerical simulations. Careful instrumentation port design considerations for the higher amplitude acoustics are detailed. As a whole, this paper focuses on select representative segments of the experiment operational space that highlight our strategy of providing an oscillatory flowfield. This includes presenting the acoustic operational space such as acoustic amplitudes, frequencies, and mode shapes. Select imaging results are then reported to support our strategies capability to produce high-fidelity measurements.

Two-photon-absorption line strengths for nitric oxide: Comparison of theory and sub-Doppler, laser-induced fluorescence measurements.

We discuss the results of high-resolution, sub-Doppler two-photon-absorption laser-induced fluorescence (TPALIF) spectroscopy of nitric oxide at low pressure and room temperature. The measurements were performed using the single-longitudinal mode output of a diode-laser-seeded optical parametric generator (OPG) system with a measured frequency bandwidth of 220 MHz. The measurements were performed using a counter-propagating pump beam geometry, resulting in sub-Doppler TPALIF spectra of NO for various rotational transitions in the (0,0) vibrational band of the A2Σ+ - X2Π electronic transition. The experimental results are compared with the results of a perturbative treatment of the rotational line strengths for the 20 different rotational branches of the X2Π(v″ = 0) → A2Σ+(v' = 0) two-photon absorption band. In the derivation of the expressions for the two-photon transition absorption strength, the closure relation is used for rotational states in the intermediate levels of the two-photon transition in analogy with the Placzek treatment of Raman transitions. The theoretical treatment of the effect of angular momentum coupling on the two-photon rotational line strengths features the use of irreducible spherical tensors and 3j symbols. The final results are expressed in terms of the Hund's case (a) coupling coefficients aJ and bJ for the X2Π(v″ = 0) rotational level wavefunctions, which are intermediate between Hund's case (a) and case (b). Considerable physical insight is provided by this final form of the equations for the rotational line strengths. Corrections to the two-photon absorption rotational line strength for higher order effects such as centrifugal stretching can be included in a straightforward fashion in the analysis by incorporating higher order terms in these coupling coefficients aJ and bJ, although these corrections are essentially negligible for J < 50. The theoretical calculations of relative line intensities are in good agreement both with our experiment and with published experimental results. In addition, the calculated line shapes and relative intensities for closely spaced main branch and satellite transitions are in excellent agreement with our experimental measurements.

Simultaneous high-speed gas property measurements at the exhaust gas recirculation cooler exit and at the turbocharger inlet of a multicylinder diesel engine using diode-laser-absorption spectroscopy.

A diode-laser-absorption-spectroscopy-based sensor system was used to perform high-speed (100 Hz to 5 kHz) measurements of gas properties (temperature, pressure, and H(2)O vapor concentration) at the turbocharger inlet and at the exhaust gas recirculation (EGR) cooler exit of a diesel engine. An earlier version of this system was previously used for high-speed measurements of gas temperature and H(2)O vapor concentration in the intake manifold of the diesel engine. A 1387.2 N m tunable distributed feedback diode laser was used to scan across multiple H(2)O absorption transitions, and the direct absorption signal was recorded using a high-speed data acquisition system. Compact optical connectors were designed to conduct simultaneous measurements in the intake manifold, the EGR cooler exit, and the turbocharger inlet of the engine. For measurements at the turbocharger inlet, these custom optical connectors survived gas temperatures as high as 800 K using a simple and passive arrangement in which the temperature-sensitive components were protected from high temperatures using ceramic insulators. This arrangement reduced system cost and complexity by eliminating the need for any active water or oil cooling. Diode-laser measurements performed during steady-state engine operation were within 5% of the thermocouple and pressure sensor measurements, and within 10% of the H(2)O concentration values derived from the CO(2) gas analyzer measurements. Measurements were also performed in the engine during transient events. In one such transient event, where a step change in fueling was introduced, the diode-laser sensor was able to capture the 30 ms change in the gas properties; the thermocouple, on the other hand, required 7.4 s to accurately reflect the change in gas conditions, while the gas analyzer required nearly 600 ms. To the best of our knowledge, this is the first implementation of such a simple and passive arrangement of high-temperature optical connectors as well as the first documented application of diode-laser absorption for high-speed gas dynamics measurements in the turbocharger inlet and EGR cooler exit of a diesel engine.

The development of an optically accessible, high-power combustion test rig.

This work summarizes the development of a gas turbine combustion experiment which will allow advanced optical measurements to be made at realistic engine conditions. Facility requirements are addressed, including instrumentation and control needs for remote operation when working with high energy flows. The methodology employed in the design of the optically accessible combustion chamber is elucidated, including window considerations and thermal management of the experimental hardware under extremely high heat loads. Experimental uncertainties are also quantified. The stable operation of the experiment is validated using multiple techniques and the boundary conditions are verified. The successful prediction of operating conditions by the design analysis is documented and preliminary data are shown to demonstrate the capability of the experiment to produce high-fidelity datasets for advanced combustion research.

High-repetition-rate three-dimensional OH imaging using scanned planar laser-induced fluorescence system for multiphase combustion.

Imaging dynamic multiphase combusting events is challenging. Conventional techniques can image only a single plane of an event, capturing limited details. Here, we report on a three-dimensional, time-resolved, OH planar laser-induced fluorescence (3D OH PLIF) technique that was developed to measure the relative OH concentration in multiphase combustion flow fields. To the best of our knowledge, this is the first time a 3D OH PLIF technique has been reported in the open literature. The technique involves rapidly scanning a laser sheet across a flow field of interest. The overall experimental system consists of a 5 kHz OH PLIF system, a high-speed detection system (image intensifier and CMOS camera), and a galvanometric scanning mirror. The scanning mirror was synchronized with a 500 Hz triangular sweep pattern generated using Labview. Images were acquired at 5 kHz corresponding to six images per mirror scan, and 1000 scans per second. The six images obtained in a scan were reconstructed into a volumetric representation. The resulting spatial resolution was 500×500×6 voxels mapped to a field of interest covering 30 mm×30 mm×8 mm. The novel 3D OH PLIF system was applied toward imaging droplet combustion of methanol gelled with hydroxypropyl cellulose (HPC) (3 wt. %, 6 wt. %), as well as solid propellant combustion, and impinging jet spray combustion. The resulting 3D dataset shows a comprehensive view of jetting events in gelled droplet combustion that was not observed with high-speed imaging or 2D OH PLIF. Although the scan is noninstantaneous, the temporal and spatial resolution was sufficient to view the dynamic events in the multiphase combustion flow fields of interest. The system is limited by the repetition rate of the pulsed laser and the step response time of the galvanometric mirror; however, the repetition rates are sufficient to resolve events in the order of 100 Hz. Future upgrade includes 40 kHz pulsed UV laser system, which can reduce the scan time to 125 µs, while keeping the high repetition rate of 1000 Hz.

Development of a combined pure rotational and vibrational coherent anti-Stokes Raman scattering system.

A combined pure rotational coherent anti-Stokes Raman scattering (PRCARS) and vibrational CARS (VCARS) system has been developed. In this system two beams, a broadband beam centered at 607 nm and the frequency-doubled Nd:YAG output at 532 nm is used to generate the PRCARS signal. A second 532 nm beam is used along with the other two beams to simultaneously generate the N(2) VCARS signal using a standard phase-matching scheme.

Polarization suppression of the nonresonant background in femtosecond coherent anti-Stokes Raman scattering for flame thermometry at 5 kHz.

Coherent anti-Stokes Raman scattering (CARS) spectra are acquired at 5 kHz in steady and unsteady flames while suppressing the nonresonant background by polarization techniques. Broadband femtosecond (fs) pump and Stokes pulses efficiently excite many Raman transitions in diatomic nitrogen which subsequently interfere and decay. Single-laser-shot measurements are performed as the decay of the Raman coherence is mapped to the frequency of the CARS signal by a chirped-probe pulse (CPP). As temperature increases, more Raman transitions contribute to the Raman coherence which leads to faster decay of the Raman coherence. Experimental fs CARS spectra are compared to a theoretical model to extract temperature measurements. The effects of probe time delay and temperature on nonresonant background suppressed CPP fs CARS spectra are examined. By suppressing the nonresonant background the evolution of the Raman coherence near zero probe time delay is more clearly revealed. The structure of the CPP fs CARS spectra with and without nonresonant background suppression is compared. The utility of polarization suppression of the nonresonant background for CPP fs CARS measurements is discussed.

Electronic-resonance-enhanced coherent anti-Stokes Raman scattering of nitric oxide: saturation and Stark effects.

A theoretical analysis of electronic-resonance-enhanced (ERE) coherent anti-Stokes Raman scattering (CARS) of NO is described. The time-dependent density-matrix equations for the nonlinear ERE-CARS process are derived and manipulated into a form suitable for direct numerical integration. In the ERE-CARS configuration considered in this paper, the pump and Stokes beams are far from electronic-resonance. The visible 532 and 591 nm laser beams are used to excite Q-branch Raman resonances in the vibrational bands of the X (2)Pi electronic state of NO. An ultraviolet probe beam at 236 nm is used to excite P-, Q-, or R-branch transitions in the (v'=0, v"=1) band of the A (2)Sigma(+)-X (2)Pi electronic system of NO molecule. Experimental spectra are obtained either by scanning the ultraviolet probe beam while keeping the Stokes frequency fixed (probe scans) or by scanning the Stokes frequency while keeping the probe frequency fixed (Stokes scans). The calculated NO ERE-CARS spectra are compared with experimental spectra, and good agreement is observed between theory and experiment in terms of spectral peak locations and relative intensities. The effects of saturation of the two-photon Raman-resonant Q-branch transitions, the saturation of a one-photon electronic-resonant P-, Q-, or R-branch transitions in the A (2)Sigma(+)-X (2)Pi electronic system, and the coupling of these saturation processes are investigated. The coupling of the saturation processes for the probe and Raman transitions is complex and exhibits behavior similar to that observed in the electromagnetic induced transparency process. The probe scan spectra are significantly affected by Stark broadening due to the interaction of the pump and Stokes radiation with single-photon resonances between the upper vibration-rotation probe level in the A (2)Sigma(+) electronic levels and vibration-rotation levels in higher lying electronic levels. The ERE-CARS signal intensity is found to be much less sensitive to variations in the collisional dephasing rates under saturation conditions.

Gas-phase single-shot thermometry at 1 kHz using fs-CARS spectroscopy.

Single-laser-shot temperature measurements at a data rate of 1 kHz employing femtosecond coherent anti-Stokes Raman scattering (fs-CARS) spectroscopy of N(2) are demonstrated. The measurements are performed using a chirped-probe pulse to map the time-dependent frequency-spread dephasing of the Raman coherence, which is created by approximately 80-fs pump and Stokes beams, into the spectrum of the coherent anti-Stokes Raman scattering signal pulse. Temperature is determined from the spectral shape of the fs-CARS signal for probe delays of approximately 2 ps with respect to the pump-Stokes excitation. The accuracy and precision of the measurements for the 300-2400 K range are found to be approximately 1%-6% and approximately 1.5%-3%, respectively.

Effects of collisions on electronic-resonance-enhanced coherent anti-Stokes Raman scattering of nitric oxide.

A six-level model is developed and used to study the effects of collisional energy transfer and dephasing on electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) in nitric oxide. The model includes the three levels that are coherently coupled by the three applied lasers as well as three additional bath levels that enable inclusion of the effects of electronic quenching and rotational energy transfer. The density-matrix equations that describe the evolution of the relevant populations and coherences are presented. The parametric dependencies of the ERE-CARS signal on collisional energy transfer and dephasing processes are described in terms of both a steady-state analytical solution and the numerical solutions to the governing equations. In the weak-field limit, the ERE-CARS signal scales inversely with the square of the dephasing rates for the electronic and Raman coherences. In accord with published experimental observations [Roy et al., Appl. Phys. Lett. 89, 104105 (2006)], the ERE-CARS signal is shown to be insensitive to the collisional quenching rate. Parametric dependencies on quenching, rotational energy transfer, and pure electronic dephasing are presented, demonstrating reduced collisional dependence for saturating laser fields.