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

Measurements of the line strengths and collisional broadening widths of CO in a N₂ atmosphere were made from 300 to 600 K. The lines studied were the P(2), P(3), P(7), P(12), P(18), and P(22) lines of the fundamental band at 2100 cm^?1. The absorption spectra were parametrically fit to a Voigt lineshape model. The band strength was determined to be 250±8 cm^?2atm^?1. The broadening results are compared to Anderson-Tsao-Curnutte calculations and to other experimental studies. The possibility of using an equation of the form $\text{γ(T)=γ(T}{}_0\text{(}\text{T}{}_0\text{T}\text{)}{}^{\mathrm{n}}$ to extrapolate the temperature dependence of the half-widths to flame temperatures is discussed.     

Collision widths of CO lines broadened by water vapor at elevated temperatures

The collisional broadening by water vapor of the P(2), P(3), and P(7) absorption lines of the fundamental band of CO was studied at 7 temperatures ranging from 400 to 1000 K. The Lorentz halfwidth was determined by a parametric fit of the measured lineshape to the Voigt profile. The halfwidth at standard temperature was found by fitting the data for each line to $\text{γ(T}{}_0\text{)=γ(T)(}\text{T}\text{T}{}_0\text{)}{}^{\mathrm{-N}}$. The value of N for the P(2) line was found to be 0.7343±0.0067, for the P(3) line 0.70168±0.00073, and for the P(7) line 0.76686±0.00006.     

Layer formation on silicon steel by processing in H2/H2O at elevated temperatures

Silicon steel (Fe-3wt%Si), as used for transformers and generators, has been annealed in wet hydrogen at elevated temperatures. The composition, sequence, and thicknesses of the layers found by conversion electron Mössbauer spectroscopy (CEMS) and Auger electron spectroscopy (AES) depth profiling for a 10 minutes anneal in different atmospheres are reported. In the range from 500°C to 720°C we observed carbide formation, indicating that the decarburization is hindered. Above 800°C, the layers consist of fayalite or of fayalite and iron oxides, depending on the oxygen potentiala _O . At 843°C, the onset of iron oxide formation was found ata _O=0.33.     

Simplified models for the temperature dependence of linewidths at elevated temperatures and applications to CO broadened by Ar and N2

The broadening coefficients for i.r. lines of CO perturbed by Ar are calculated in the temperature range 300–3500 K using the formalism previously developed by two of us (D.R. and J.B.). The results are compared with high-resolution spectroscopic measurements of shock-heated CO-Ar gas mixtures. A simplified model is proposed to describe the temperature dependence of the linewidths. The resulting model is applied to CO broadened by N₂ and the results are critically discussed.     

Half-width calculations for CO lines broadened by CO2

Half-widths of CO lines, in the fundamental and first overtone bands, broadened by CO₂ have been computed using the Anderson-Tsao-Curnutte theory. Comparison with the high-resolution measurements of Varanasi at 295°K shows excellent prediction of line widths by the theory. Comparison is also made between calculations including dipole-quadrupole and quadrupole-quadrupole interactions with those taking only the dominant quadrupole-quadrupole forces into account. Line widthd at 295°K range from 0.126417 cm^-1 atm^-1 fom m = 1 to 0.04397 cm^-1atm^-1 for m = 32, which corresponds to the asymptonic kinetic-theory value. Half-width computations are also presented at 200°K and 250°K appropriate for Martian and Venusian atmospheres, respectively.     

R-branch head of the ν3 band of CO2 at elevated temperatures

The R-branch head of the 00⁰1 ← 00⁰0 band of ¹²C¹⁶O₂ has been recorded with Doppler-limited resolution using a tunable laser difference-frequency spectrometer. J values to 140 were measured at temperatures to 985 K. The data have been combined with extremely precise transition frequencies for 0 ≤ J ≤ 76 measured with a Fourier transform interferometer to obtain an improved set of spectral constants for this ν₃ band of CO₂.     

High-resolution transmission measurements of CO2 at high temperatures for industrial applications

High-resolution transmission spectra of CO₂ in the 2.7, 4.3 and 15 μm regions at temperatures up to 1773 K and at approximately atmospheric pressure (1.00±0.01 atm) are measured and compared with line-by-line calculations based on the HITEMP-1995, HITEMP-2010, CDSD-HITEMP and CDSD-4000 databases. The spectra have been recorded in a high-temperature flow gas cell and using a Fourier transform infrared (FTIR) spectrometer at a nominal resolution of 0.125 cm^?1. The volume fractions of CO₂ in the measurements were 1, 10 and 100%. The measurements have been validated by comparison with medium-resolution data obtained by Bharadwaj and Modest [6]. The deviations between the experimental spectra and the calculations at 1773 K and the vibrational energy exchange and thermal dissociation of CO₂ at high temperatures are discussed.     

Measurements of the CO first overtone bandstrength at elevated temperatures

The spectrally resolved emission from the CO first overtone vibration-rotation band has been studied over the temperature range of 1100-2600 K in a shock-tube experiment. First overtone bandstrengths have been deduced from the data. These compare favorably with theoretical expectations.     

Non-contact sound velocities and attenuation measurements of several ceramics at elevated temperatures

Laser ultrasonic technique has been employed to carry out the sound velocities and attenuation measurements as a function of temperature in alumina, two kinds of silicon nitride and partially stabilized zirconia (PSZ) samples. Accuracy of the laser technique used has been checked in terms of the diffraction effect and reproducibility of the results. Results of attenuation at room temperature have been compared with quartz transducer technique. In PSZ, velocity behavior has become non-linear and also, a peak in attenuation has been observed around 500 degrees C. In one of the silicon nitride sample, which uses glassy sintering agent, attenuation has shown a sharp peak around 950 degrees C. Interestingly, when the experiment was repeated from 800 to 1000 degrees C, this anomalous attenuation peak has disappeared, leaving a background increasing towards higher temperatures.     

Simultaneous detection of CO and CO2 at elevated temperatures using tunable diode laser absorption spectroscopy near 1570 nm

Simultaneous measurements of CO and CO₂ at elevated temperatures are demonstrated using a single semiconductor distributed-feedback (DFB) laser near 1570 nm. Wavelength modulation spectroscopy with second-harmonic detection is used to improve the detection sensitivity and accuracy. A proper line pair near 6368.086 and 6368.330 cm^?1 is selected using some line-selection criterions for the target temperature range of 300–1000 K. Normalization of the 2f signal with the 1f signal magnitude is used to remove the need for calibration and correct for transmission variation due to beam steering, mechanical misalignments, soot, and windows fouling. The CO and CO₂ concentrations measurements are within 2.21% and 2.55% of the expected values over the tested temperature range of 300–1000 K. The minimum detectable concentrations of CO and CO₂ at 1000 K are 80 ppm m and 153 ppm m, respectively.     

3-Pentanone LIF at elevated temperatures and pressures: measurements and modeling

The objective of this study is to investigate 3-pentanone fluorescence experiments in a constant volume vessel at high temperature and high pressure to underline the influent parameters in conditions close to those encountered in internal combustion engines. To obtain quantitative analysis, measured fluorescence signals must be corrected by considering the influence of preponderant parameters such as temperature, pressure and gas composition. Quantitative dependences of fluorescence on thermodynamic parameters are measured and compared with the predictions of a photophysical model, which combines the effects of temperature, pressure, excitation wavelength on fluorescence quantum yield. The increase of 3-pentanone fluorescence with pressure is due to the vibrational relaxation of energy levels. The fluorescence decreases with increasing temperature, except at low temperature where the fluorescence increase is due to an activation of intersystem crossing between triplet toward singlet levels. The influences of thermodynamic parameters are based on an increase of the non-radiative decay rate with the vibrational energy level of excited electronic state and the important collisions to remove the excess vibrational energy. Experimental and calculated results show a satisfactory agreement. PACS 33.20; 33.50; 34.90     

3-pentanone fluorescence yield measurements and modeling at elevated temperatures and pressures

Measurements of 3-pentanone fluorescence quantum yield (FQY) over a wide range of temperatures and pressures in air and nitrogen bath gases are reported and a comprehensive FQY model in support of quantitative planar laser-induced fluorescence diagnostics at elevated pressures and temperatures is presented. Measurements were made of the FQY for 20 mbar of 3-pentanone in nitrogen and air for pressures between 1 and 25 bar in a high-pressure and high-temperature cell for excitation wavelengths of 248, 266, 277, and 308 nm. The measurements were performed in nitrogen from 298 to 745 K and in air from 298 to 567 K. The 3-pentanone FQY data were used to optimize FQY model parameters, including the oxygen and nitrogen quenching rates and vibrational relaxation cascade parameters for nitrogen and oxygen. This work introduces vibrational energy dependence for cascade parameters, as well as a nitrogen quenching rate. The new 3-pentanone FQY model agrees with the measurements within 10%, as well as with fluorescence signal measurements from optical internal combustion engines at pressures and temperatures up to 28 bar and 1100 K.     

Thermal infrared lines of methane broadened by nitrogen at low temperatures

Measurements of spectral transmittance in the v₄-fundamental band of ¹²CH₄ have been performed at low temperatures using a Fourier transform spectrometer with apodized spectral resolution of 0.06 cm^-1. With applications to lines formed in the atmospheres of Titan and Earth in mind, N₂ has been used as the broadening gas. Comparisons of observed and computed spectral transmittances on a line-by-line basis have yielded line strengths, N₂-broadened half-widths and their variation with temperature. Best agreement between measured and computed spectra was obtained when the absolute intensity of the band was taken as 128 cm^-2-atm^-1 at 296 K. Line widths were found to vary as Tⁿ with n = -1.0 for lines of the F-species and 0.63 for the A-species. Our measured line widths are considerably larger than those used in the AFGL compilation.     

Emissivity of CO2-H2O mixtures at temperatures up to 1000° K

The emissivity in the 2.7 m range is examined with a spectrometer having 25 cm^–1 for 2.5, ,7.5 cm·atm,4 8cm·atm, 400T1000° K; 150P730 mm Hg. It is found that relation (1) is obeyed to within /0.1, though the calculated transmission is usually less than the measured value. It is shown that the relation is obeyed on account of the mutual position of the CO₂ and H₂O lines in the band, i.e., one gas may be considered as unselective relative to the other.     

Absorption measurements of H2O at high temperatures using a CO laser

Absorption of CO laser radiation (v = 8→7, J = 14→15 transition at 1901.762 cm^-1) by H₂O has been studied in shock-heated H₂/O₂/Ar mixtures over the temperature range 1300–2300 K. This laser transition is nearly coincident with the v₂-band 12_3,10←11_2,9 transition of H₂O at 1901.760 cm^-1, thereby providing a convenient and sensitive absorption-based H₂O diagnostic useful for studies of combustion. The collision-broadening parameter for this H₂O line, due to broadening by Ar, was determined to be 2γ (cm^-1atm^-1) = 0.027 (T/1300)^-0.9 in the temperature range 1300–2300 K. Calculations of the H₂O absorption coefficient (at 1901.762 cm^-1) based on this expression for 2γ are presented for the temperature range 300–2500 K and pressure range 0.3–1 atm.     

Strengthening sapphire at elevated temperatures by SiO2 films

SiO₂ films have been prepared on sapphire by radio frequency magnetron reactive sputtering in order to increase the optical and mechanical properties of infrared windows and domes of sapphire at elevated temperatures. Infrared transmission and flexural strength of uncoated and coated sapphires have been investigated at different temperatures. SiO₂ films were shown to have apparent antireflective effect on sapphire substrate at room temperature. With increasing temperature, the coated sapphires have larger average transmission than the uncoated ones. The temperature was proven to only weakly affect the absorption coefficient and antireflection capability of the deposited films. It is also indicated that the flexural strengths of the c-axis sapphire samples coated with SiO₂ films are increased by 1.2 and 1.5 times than those of uncoated at 600 and 800 °C, respectively.     

Linewidths of HCl broadened by CO2 and N2 and CO broadened by CO2

High resolution measurement of the linewidths of HCl broadened by CO₂ and N₂ and CO broadened by CO₂ have been performed in both the 1-0 and 2-0 bands of HCl and the 2-0 band of CO. The data were analyzed by the direct and the peak absorption methods. Values of the linewidths obtained by the two methods are in good agreement. For |m| ≤ 3, for the case of HCl + CO₂, the agreement is good for the values obtained in both bands of HCl. However for |m| > 3, the HCl + CO₂ linewidths in the 1-0 band are smaller than the corresponding lines in the 2-0 band by as much as 11% for |m| = 9. Lines (|m| ≤ 3) of the 1-0 and 2-0 bands of HCl broadened by CO₂ were also analyzed in terms of the super-Lorentzian line profile proposed by Varanasi, S. K. Sarangi, and G. D. T. Tejwani (J. Quan. Spectr. Radiative Transfer12, 857 (1972)) and the Lorentzian profile. The results indicate that near the line center (within 3γ), the shape of HCl + CO₂ lines are Lorentzian.     

Intensity and transmission measurements in the ν3-fundamental of N2O at low temperatures

Spectral transmission of i.r. radiation through the nitrogen-broadened lines of the υ₃-fundamental of N₂O has been measured at 154°, 202° and 300°K. A value of S⁰_v = 1411±54 cm^-2atm^-1 at S.T.P. has been obtained for the combined strength of the ν₃ and ν₂¹+ν₃?ν₂¹ bands using the Wilson-Wells-Penner-Weber method. This value for S_v, the relative intensity calculations of Gray Young, the room-temperature data of Toth for nitrogen-broadened half-widths in the ν₁+ν₃ and 2ν₂⁰+ν₃ bands and the T^-0.75 variation of line width with temperature proposed by Varanasi and Sarangi are shown to yield excellent agreement between the measured and computed spectral transmittance throughout the band.     

Tritium isotope separation by CO2-laser irradiation at low temperatures

Tritium isotope separation by CO₂-laser induced multiphoton dissociation of CTF₃ is investigated. For the optimization of the performance of this working substance, trifluoromethane, the conditions to yield high-selectivity at high-operating pressure and low-critical fluence for complete dissociation are studied using our deconvolution procedure. The irradiation conditions are varied over the following ranges; wavenumber: 1052–1087 cm^–1, gas temperature: 25°C to –78°C, CHF₃ pressure: 5–205 Torr. The selectivities exceeding 10⁴ are observed for 85–205 Torr CHF₃ at –78°C by the irradiation at 1057 cm^–1.