Wide- and narrow-band saturated fluorescence measurements of hydroxyl concentration in premixed flames from 1 bar to 10 bar

We have studied the use of wide-band detection in conjunction with saturation of a rovibronic transition of OH within itsA ^{2 +}–X ²(0,0) band. For wide-band detection, in which fluorescence is detected from the entire excited rotational manifold, the fluorescence yield is sensitive to collisions in two ways. First, it is sensitive to the ratio of rate coefficients describing rotational energy transfer and electronic quenching; this ratio determines the number of neighboring rotational levels that are populated during the laser pulse. Second, the fluorescence yield can vary with the total collisional rate coefficient; only after a sufficient number of collisions, corresponding to 2.5 ns in an atmospheric flame, does the rotational manifold reach steady state. We also compare measurements employing wide-band (detecting theR ₁ andR ₂ branches) and narrow-band (detecting a single transition) saturated fluorescence of OH. Over a wide range of conditions — obtained by varying the equivalence ratio, temperature, N₂ dilution, and pressure — the wide- and narrow-band fluorescence techniques compare well. Given this good agreement, wide-band saturated fluorescence could be especially useful for analyzing atmospheric flames with XeCl-excimer lasers; one can potentially obtain 2—D images of OH which have a high signal-to-noise ratio and a reduced sensitivity to laser irradiance and quenching.     

Rotational temperature measurement in high-temperature air using KrF laser-induced O2 fluorescence

Rotational temperature of O₂ has been measured in an atmospheric-air furnace using KrF laser-induced fluorescence. Average measurement errors of 10.7% and 5.1% over a temperature range of 1325–1725K were observed using two- and four-line excitation techniques, respectively. Ground-state depletion was observed for a spectral laser irradiance greater than approximately 7.5×10⁶ W/cm² cm^–1. This technique is suitable for temperature measurements when the O₂ vibrational population is not in thermal equilibrium.     

Characterization of an ethylene free jet

The rotational population distribution in a free molecular jet of ethylene, C₂H₄, is found to be thermal over a range of distances below the nozzle (z/d=0.5–13.2, nozzle diameter d=0.50 mm). Results for on-axis rotational temperature, number density and flow velocity are presented. The average number of gas-kinetic collisions experienced by any molecule in travelling some distance along the jet axis is calculated.     

Two Dimensional Rotational Temperature Measurement by Multiline Laser Induced Fluorescence of Nitric Oxide in Combustion Flame

Two-dimensional rotational temperature measurement was performed in a stable combustion flame of premixed butane and oxygen using multiline laser induced fluorescence (LIF) of nitric oxide molecules. Multiple rotational absorption lines of A²∑⁺Π;X²II(0,0) Q₁ and Q₂ lines were excited by laser light around 226 nm, and the LIF signal was observed by an image-intensified digital camera. Temperature was determined through least squares fitting correlation between LIF intensity and excitation rotational quantum number for the Boltzmann distribution function. The measured LIF intensity was approximated by the Boltzmann distribution with good accuracy, and the temperature obtained was between 500 K and 1800 K for the test flame. The measuring error of the temperature was evaluated and found to be 80 K, which corresponded to 8% of the measured fluorescence intensity. The two-line LIF scheme was evaluated by different pairs of excitation lines (Q₁(31.5)/Q₁(16.5) and Q₁(18.5)/Q₁(16.5)) for comparison with the multiline LIF approach. Temperature which was obtained by two-line LIF scheme corresponded well with multiline LIF results for Q₁(31.5)/Q₁(16.5) excitation. However, for Q₁(18.5)/Q₁(16.5) excitation, the obtained temperature did not agree with the multiline LIF result because the population of rotational states J=18.5 and J=16.5 is similar at high temperatures. We found that two-line LIF temperature measurement was reliable when excitation lines were suitably selected.     

Mapping the surface temperature of ceramic and superalloy turbine engine components using laser-induced fluorescence of thermographic phosphor

An excimer laser-based system for mapping the surface temperature of turbine engine parts coated with thermographic phosphors has been developed. The intensities measured for Y₂O₃:Eu over the temperature range 500–750°C are presented. In addition, the data correction and error analysis algorithm is discussed. The overall accuracy of this intensity-based surface temperature measurement technique was estimated to be ±5%. Furthermore, surface temperature measurements obtained from a ceramic matrix composite and superalloy components are presented.     

Two-photon predissociative fluorescence of H2O by a KrF laser for concentration and temperature measurement in flames

Two-photon laser-induced predissociative fluorescence (LIPF) of H₂O is examined as a potential measurement technique of H₂O concentration and temperature in flames. Two-photons of 248 nm light from a narrowband KrF laser excite H₂O to the highly predissociative state in a hydrogen-air flame. The subsequent bound-free emission is observed from 400–500 nm in the flame at temperatures of 1000–2000 K and is found to be free of fluorescence interference from other flame species. This LIPF signal is not affected by collisional quenching due to the short lifetime of the predissociative state (2.5 ps). Broadband laser dispersion spectra, narrowband laser dispersion spectra, laser excitation spectra and probability density functions of the H₂O fluorescence are obtained in the hydrogen flame. The H₂O LIPF signal is found to be temperature sensitive and a two-line LIPF technique is needed for concentration and temperature measurement. The accuracy of a two-line LIPF technique for H₂O concentration and temperature measurement is determined.     

Parameter studies in practical nitrogen CARS thermometry using standard and advanced fitting codes

A systematic study of the influence of the collisional narrowing and the cross coherence effect on the temperature analysis of N₂-Q branch-CARS spectra at atmospheric pressure is presented. A comparison of calculated spectra over a temperature range 300–2000 K reveals that the standard theory neglecting these effects leads to temperature errors of +1.7% under flame conditions, when the nonresonant background is suppressed. This result is supported by the analysis of experimental CARS temperature measurements on a standard laminar diffusion flame. Furthermore, the temperature misreadings originating from erroneous slit function parameters and laser linewidth were investigated.     

Dynamic properties of P4O6S and P4O7: P spin–echo and P MAS–NMR investigations

The rotational dynamics of P₄O₆S and P₄O₇ in the solid state were studied by means of ³¹P NMR spectra of spinning and static powder samples in the temperature range of 153–295 K and 295–388 K, respectively. All spectra were simulated to confirm the type of the motion and to extract the time scales as a function of the temperature. Good agreement between experimental and theoretical data was obtained on the basis of a three-site jump model. For P₄O₆S, the activation energy and the pre-exponential factor derived from the lineshape simulations amount to 51(2) kJ/mol and 6(3)·10¹⁵ s⁻¹. For P₄O₇, the spectral analysis yields an activation energy of 67(1) kJ/mol and a pre-exponential factor of 6(2)·10¹⁴ s⁻¹. The dynamic behavior was checked independently by lineshape analyses under both MAS and static conditions. Activation energies are consistent within the errors for the lineshape analyses. Additionally, we have analyzed spin–lattice relaxation measurements, which show the correct trends for the activation energies.     

Autoignition of propane–air mixtures behind reflected shock waves

Ignition times and autoignition modes for propane–air mixtures have been studied behind reflected shock waves. Experiments were performed over temperatures between 1000 and 1750 K, pressures between 2 and 20 atm, and equivalence ratios of = 0.5, 1.0, and 2.0. Ignition delay times were determined using pressure measurements, C₂ emission profiles, and luminosity measurements in the visible spectrum (380–680 nm). Empirical correlations for ignition time for low temperature (1000–1300 K) and high temperature (1300–1800 K) ranges have been deduced from the experimental data. Different autoignition modes of the mixture (strong, transient, and weak) were identified by comparing velocities of reflected shock wave at different distances from the reflecting wall.     

Sensitive detection of temperature behind reflected shock waves using wavelength modulation spectroscopy of CO2 near 2.7?μm

Tunable diode-laser absorption of CO₂ near 2.7 μm incorporating wavelength modulation spectroscopy with second-harmonic detection (WMS-2f) is used to provide a new sensor for sensitive and accurate measurement of the temperature behind reflected shock waves in a shock-tube. The temperature is inferred from the ratio of 2f signals for two selected absorption transitions, at 3633.08 and 3645.56 cm⁻¹, belonging to the ν ₁+ν ₃ combination vibrational band of CO₂ near 2.7 μm. The modulation depths of 0.078 and 0.063 cm⁻¹ are optimized for the target conditions of the shock-heated gases (P∼1–2 atm, T∼800–1600 K). The sensor is designed to achieve a high sensitivity to the temperature and a low sensitivity to cold boundary-layer effects and any changes in gas pressure or composition. The fixed-wavelength WMS-2f sensor is tested for temperature and CO₂ concentration measurements in a heated static cell (600–1200 K) and in non-reactive shock-tube experiments (900–1700 K) using CO₂–Ar mixtures. The relatively large CO₂ absorption strength near 2.7 μm and the use of a WMS-2f strategy minimizes noise and enables measurements with lower concentration, higher accuracy, better sensitivity and improved signal-to-noise ratio (SNR) relative to earlier work, using transitions in the 1.5 and 2.0 μm CO₂ combination bands. The standard deviation of the measured temperature histories behind reflected shock waves is less than 0.5%. The temperature sensor is also demonstrated in reactive shock-tube experiments of n-heptane oxidation. Seeding of relatively inert CO₂ in the initial fuel-oxidizer mixture is utilized to enable measurements of the pre-ignition temperature profiles. To our knowledge, this work represents the first application of wavelength modulation spectroscopy to this new class of diode lasers near 2.7 μm.     

Fluorescence measurements in a Low-pressure Kr/F2 medium

The time-resolved measurement of the sidelight fluorescence of KrF* formed by a short electron-beam pumping pulse (20 ns FWHM, 19 kA, 860 kV) was performed as a function of both the total pressure ranging from 100 Torr to 400 Torr and the partial F₂ concentration (0.1–1.0%). We have estimated the fluorescence yields (FY) for various laser-gas conditions experimentally and the results were compared with numerical predictions. This study indicates a superior amplification performance for a single ultrashort pulse in a low-pressure medium because of the higher FY for KrF*.     

Environmental influence on the IR fluorescence of Xe<Subscript>2</Subscript><Superscript>*</Superscript> molecules in electron beam excited Ar–Xe mixture at high density

We report new measurements of the near infrared (NIR) Xe₂^* excimer fluorescence in an electron–beam–excited Ar (90%)–Xe (10 %) mixture at room temperature. Previous measurements up to a density N≈2×10²⁶ m^-3 discovered a broad excimer fluorescence band at ≈7800 cm^-1, whose center is red–shifted by increasing N [A.F. Borghesani, G. Bressi, G. Carugno, E. Conti, D. Iannuzzi, J. Chem. Phys. 115, 6042 (2001)]. The shift has been explained by assuming that the energy of the optical active electron in the molecule is shifted by the density–dependent Fermi shift and by accounting for the solvation effect due to the environment. We have extended the density range up to N≈6×10²⁶ m^-3, confirming the previous measurements and extending the validity of the interpretative model. A detailed analysis of the width of the fluorescence band gives a value of 2.85 nm for the size of the investigated excimer state. Such a large value lends credibility to the validity of the proposed explanation of the experimental findings.     

Pressure broadening coefficients of induced by for Venus atmosphere

Carbon dioxide (CO₂) induced pressure broadening coefficients of water vapor (H₂O) lines have been determined using a terahertz time-domain spectrometer (TDS). Thirty-two rotational transitions of H₂O were observed in the spectral range of 18– (550–3050 GHz) for the first time. Using TDS allows one to measure absorption spectra with one order of magnitude better precision than Fourier transform spectrometer in this frequency region. The precision of our broadening coefficient measurements was 2.4% in average. The measured CO₂ induced pressure broadening coefficients are compared to those calculated by the complex Robert–Bonamy formalism. The difference between the measurement and the theoretical estimation was in the range of -10.7% to +19.0% confirming the credibility of the theoretical approach. The impact on retrieval of water vapor abundance was examined by performing inversion analysis on H₂O spectra of Venus atmosphere obtained with the Submillimeter Wave Astronomy Satellite. In this example case, the retrieved water vapor mixing ratio reduces by half at the altitude region of 70–85 km when applying the newly measured broadening coefficient compared to the air-broadening coefficient, and changes by 5% compared to that estimated by the complex Robert–Bonamy formalism.     

Multi-line fluorescence imaging of the rotational temperature field in a shock-tunnel free jet

A quasi-steady, highly underexpanded free jet of argon seeded with nitric oxide (NO) was generated at the exit of a converging, axisymmetric nozzle supplied by a shock-tunnel reservoir at 4200 K and 3.0 atm. During each run of the facility, an isolated transition in theA ² X ² (0, 0) band of NO at 226 nm was pumped with a pulse of frequency-doubled dye laser light formed into a thin sheet and directed perpendicularly through the axis of the jet. The red-shifted components of the resulting fluorescence at 90° with respect to the laser were imaged onto an intensified, charge-coupled device array. A ratio of images obtained by exciting lines originating from two different rotational states could be used to infer the mean rotational temperature field. However, because of the extreme variations in temperature and density present in the free jet, no single pair of lines simultaneously provided adequate signal levels and temperature sensitivity over the flow's entire temperature range (i.e., 100–3100 K). Instead, a combination of images obtained with four different transitions was used. Excellent agreement was observed between multi-line temperature evaluations from single-shot and frame-averaged images and a numerical simulation of the flow performed by the method of characteristics.     

Quantitative NO-LIF imaging in high-pressure flames

Planar laser-induced fluorescence (PLIF) images of NO concentration are reported in premixed laminar flames from 1–60 bar exciting the A-X(0,0) band. The influence of O₂ interference and gas composition, the variation with local temperature, and the effect of laser and signal attenuation by UV light absorption are investigated. Despite choosing a NO excitation and detection scheme with minimum O₂-LIF contribution, this interference produces errors of up to 25% in a slightly lean 60 bar flame. The overall dependence of the inferred NO number density with temperature in the relevant (1200–2500 K) range is low (<±15%) because different effects cancel. The attenuation of laser and signal light by combustion products CO₂ and H₂O is frequently neglected, yet such absorption yields errors of up to 40% in our experiment despite the small scale (8 mm flame diameter). Understanding the dynamic range for each of these corrections provides guidance to minimize errors in single shot imaging experiments at high pressure. Received: 13 May 2002 / Published online: 8 August 2002     

Parametric fluorescence in A D P and K D P excited by a 2573 Å CW Pump

Temperature tunable, 90° phase matchable, parametric fluorescence has been observed in ADP and KDP crystals. The fluorescence was pumped by 2573 Å CW radiation obtained from a second harmonic argon-ion laser. Fluorescence was observed in ADP over the complete visible spectrum by temperature tuning through the range —12 to+40° C. The measurements demonstrate the usefulness of these materials for visible parametric oscillators. The values of d(n _2v ^e –n _v ^o )/dT deduced from these and other measurements are found to disagree with values in the literature.     

Determination of the gap distribution in YBa2Cu3O7 using a far-infrared reflection-Fabry-Pérot device

This paper reports on far-infrared measurements of YBa₂Cu₃O₇ films oriented with the c-axis perpendicular to the surface, by using a silicon reflection Fabry-Pérot interferometer as a multireflection device. From these we could derive the dielectric function, the refractive index, the field penetration depth and the surface impedance of the material. The one order of magnitude higher sensitivity of the method compared to a direct reflectance measurement allowed to find an almost continuous gap distribution in the 70–215 cm^–1 region together with a separate gap at about 330 cm^–1. A quasizero gap absorption is found down to 20 cm^–1 even at low temperatures (10 K).     

Water Vapor Measurements between 590 and 2582 cm: Line Positions and Strengths

This study involves measurements of H₂¹⁶O, H₂¹⁷O, and H₂¹⁸O vapor spectra for the region between 590 and 2582 cm⁻¹. The parameters derived from the data include line positions, energy levels, and linestrengths. The study involves high-resolution line-position measurements with samples at room temperature in the (000)–(000), (010)–(010), and (010)–(000) bands. The experimental frequencies were used along with microwave, far-infrared, and hot water emission measurements in an analysis to obtain high-accuracy rotational energy level values in the (000), and (010) vibrational states of H₂¹⁶O forJ≤ 20. The experimental linestrengths were fitted by least squares to a model in which the dipole moment was represented as a series expansion containing up to 19 dipole moment matrix elements. The measurements in this work were more extensive than reported in prior studies by this author for the (010)–(000) band.     

High-Resolution Laser Spectroscopy of YbCl: The AΠ–XΣ Transition

The A²Π–X²Σ⁺ transition of ¹⁷⁴Yb³⁵Cl and ¹⁷²Yb³⁵Cl has been rotationally analyzed for the first time. Doppler-limited laser excitation spectroscopy with selective detection of fluorescence was used to obtain spectra of the 0–0 and 1–0 bands with a measurement accuracy of approximately 0.0035 cm⁻¹. Resolved fluorescence was used to record the 0–1, 0–2, and 0–3 bands and to unequivocally assign the rotational numbering, N, to the laser excitation spectra. In total, over 1300 line positions have been measured and assigned for each of the two isotopomers and employed in least-squares fits of molecular parameters. The principal results for the A²Π state are A_e = 1491.494(2) cm⁻¹ and R_e = 2.4433(1) Å, and for the X²Σ⁺ state, R_e = 2.4883(2) Å and γ_e = 4.59(2) × 10⁻³ cm⁻¹. The interaction between the X²Σ⁺ and A²Π states has been investigated and is shown to be the main contributor to the spin–rotation splitting in the ground state.     

Hydrogen sensitive gas sensor based on porous silicon/TiO2−x structure

Porous silicon (PS) layer was formed by electrochemical anodization on a p-type Si surface. Thereafter, n-type TiO_2−x thin film was deposited onto the PS surface by electron-beam evaporation. Pt catalytic layer and Au electrical contacts for further measurements were deposited onto the PS/TiO_2−x structure by ion-beam sputtering. Current–voltage characteristic, sensitivity to different concentration of hydrogen and resistance change of obtained structures versus time were examined. Results of measurements have shown that the current–voltage characteristics of structures are similar to that of diode. High sensitivity to hydrogen of obtained structures was also detected. Note that all measurements were carried out at room temperature.