Temperature prediction for CO2 laser heating of moving glass rods

This paper presents a heat transfer model to calculate the temperature field in moving glass rods heated by a CO₂ laser. Conduction and radiation heat transfer in radial and axial directions are taken into account in the current model. The Rosseland diffusion approximation is incorporated to analyze the radiation heat transfer in the glass rod. A two-band model is used to simulate the spectral property of the glass. Results of the simulation show that glass rods of sufficiently large optical thickness should be treated as a semitransparent medium for radiative transfer, and it is reasonably accurate to assume it to be opaque to CO₂ laser irradiation. It has been shown that the resulting temperature profile is strongly dependent on the laser parameters, i.e., the size of laser beam and the power of the laser. The diameter and speed of the moving glass rod are also important in determining the temperature field although the convective heat transfer coefficient between the glass rod and the environment has little effect.     

Rotational CARS for simultaneous measurements of temperature and concentrations of N2, O2, CO, and CO2 demonstrated in a CO/air diffusion flame

Rotational coherent anti-Stokes Raman spectroscopy (CARS) has over the years demonstrated its strong potential to measure temperature and relative concentrations of major species in combustion. A recent work is the development and experimental validation of a CO₂ model for thermometry, in addition to our previous rotational CARS models for other molecules. In the present work, additional calibration measurements for relative CO₂/N₂ concentrations have been made in the temperature range 294-1246 K in standardized CO₂/N₂ mixtures. Following these calibration measurements, rotational CARS measurements were performed in a laminar CO/air diffusion flame stabilized on a Wolfhard-Parker burner. High-quality spectra were recorded from the fuel-rich region to the surrounding hot air in a lateral cross section of the flame. The spectra were evaluated to obtain simultaneous profiles of temperature and concentrations of all major species; N₂, O₂, CO, and CO₂. The potential for rotational CARS as a multi-species detection technique is discussed in relation to corresponding strategies for vibrational CARS.     

Infrared radiative transfer in planetary atmospheres—I. Effects of computational and spectroscopic economies on thermal heating/cooling rates

The availability of accurate spectroscopic data and improved knowledge of continuum absorption characteristics has required a further detailed study of i.r. radiative transfer. A sophisticated radiative transfer scheme based upon the Mayer-Goody random band model is developed and the derived transmissivities for H₂O, CO₂ and O₃ are calibrated against laboratory measurements. This calibrated scheme is used to assess the effects on calculated heating/cooling rate profiles of introducing computational and spectroscopic economies.     

Intrinsic ultraviolet luminescence from Lu2O3, Lu2SiO5 and Lu2SiO5:Ce

Radioluminescence and thermally stimulated luminescence measurements on Lu₂O₃, Lu₂SiO₅ (LSO) and Lu₂SiO₅:Ce³⁺ (LSO:Ce) reveal the presence of intrinsic ultraviolet luminescence bands. Characteristic emission with maximum at 256 nm occurs in each specimen and is attributed to radiative recombination of self-trapped excitons. Thermal quenching of this band obeys the Mott-Seitz relation yielding quenching energies 24, 38 and 13 meV for Lu₂O₃, LSO and LSO:Ce, respectively. A second intrinsic band appears at 315 nm in LSO and LSO:Ce, and at 368 nm in Lu₂O₃. Quenching curves for these bands show an initial increase in peak intensity followed by a decrease. Similarity in spectral peak position and quenching behavior indicate that this band has a common origin in each of the samples and is attributed to radiative recombination of self-trapped holes, in agreement with previous work on similar specimens. Comparison of glow curves and emission spectra show that the lowest temperature glow peaks in each specimen are associated with thermal decay of self-trapped excitons and self-trapped holes. Interplay between the intrinsic defects and extrinsic Ce³⁺ emission in LSO:Ce is strongly indicated.     

UV-laser-light-controlled photoluminescence of metal oxide nanoparticles in different gas atmospheres: BaTiO3, SrTiO3 and HfO2

The photoluminescence (PL) enhancement has been studied at room temperature using various specimen atmospheres (O₂ gas, CO₂ gas, CO₂–H₂ mixture gas, Ar–H₂ mixture gas and vacuum) under 325 nm laser light irradiation on various metal oxides. Of them, the results obtained for BaTiO₃ nanocrystals, SrTiO₃ ones and HfO₂ powder crystal are given in the present paper. Their PL were considerably increased in intensity by irradiation of 325 nm laser light in CO₂ gas and CO₂–H₂ mixture gas. The cause of the PL intensity enhancements is discussed in the light of the exciton theory, the defect chemistry and the photocatalytic theory. The results may be applied for the utilization of greenhouse gas (CO₂) and the optical sensor for CO₂ gas.     

Evaluation of errors from neglecting polarization in the forward modeling of O2A band measurements from space, with relevance to CO2 column retrieval from polarization-sensitive instruments

Sensitivity studies have been performed to evaluate the errors resulting from ignoring polarization in analyzing spectroscopic measurements of the O₂A band from space, using the Orbiting Carbon Observatory (OCO) as a test case. An 11-layer atmosphere, with both gas and aerosol loading, and bounded from below by a lambertian reflecting surface, was used for the study. The numerical computations were performed with a plane-parallel vectorized discrete ordinate radiative transfer code. Beam and viewing geometry, surface reflectance and aerosol loading were varied one at a time to evaluate and understand the individual errors. Different behavior was observed in the line cores and the continuum because of the different paths taken by the photons in the two cases. The errors were largest when the solar zenith angle was high, and the aerosol loading and surface reflectance low. To understand the effect of neglecting polarization on CO₂ column retrievals, a linear error analysis study was performed on simulated measurements from the OCO spectral regions, viz. the 1.61 and 2.06 μm CO₂ bands and the O₂A band. It was seen that neglecting polarization could introduce errors as high as 10 ppm, which is substantially larger than the required retrieval precision of ∼2 ppm. A variety of approaches, including orders of scattering, spectral binning and the use of lookup tables are being explored to reduce the errors.     

Measurements and modelling of high pressure pure CO2 spectra from 750 to 8500 cm. I—central and wing regions of the allowed vibrational bands

Precise modelling of infrared absorption by carbon dioxide is of primary importance for radiative transfer calculations in CO₂-rich atmospheres like those of Venus and Mars. Despite various measurements and theoretical models dedicated to this subject, accurate data at different temperatures and pressures are still lacking in numerous spectral regions. In this work, using two Fourier Transform Spectrometers, we have measured spectra of pure CO₂ in a large spectral region range, from 750 to 8500 cm⁻¹ at various densities (3-57 amagat) and temperatures (230-473 K). Comparisons between measured dipolar absorption bands and spectra calculated with the widely used Lorentz line shape show very large discrepancies. This result is expected since the Lorentz approach neglects line-coupling effects due to intermolecular collisions which transfer absorption from the wings to the band center. In order to account for this effect, a theoretical approach based on the impact and Energy Corrected Sudden approximations has been developed. Comparisons of this model with numerous laboratory spectra in a wide range of pressure, temperature and spectral domain show satisfactory agreements for band centers and near wing regions where the impact approximation is valid. However, as expected, due to the breakdown of the impact approximation, the model fails when considering far wing regions. In the absence of precise models accounting for line-mixing and finite collision duration (non impact) effects, empirical approximations are proposed in order to model the far wings.     

Model, software and database for line-mixing effects in the ν3 and ν4 bands of CH4 and tests using laboratory and planetary measurements—I: N2 (and air) broadenings and the earth atmosphere

Absorption spectra of the infrared ν₃ and ν₄ bands of CH₄ perturbed by N₂ over large ranges of pressure and temperature have been measured in the laboratory. A theoretical approach accounting for line mixing is proposed to (successfully) model these experiments. It is similar to that of Pieroni et al. [J Chem Phys 1999;110:7717-32] and is based on state-to-state rotational cross-sections calculated with a semi-classical approach and a few empirical parameters. The latter, which enable switching from the state space to the line space, are deduced from a fit of a single room temperature spectrum of the ν₃ band at 50 atm. The comparisons between numerous measured and calculated spectra under a vast variety of conditions (ν₃ and ν₄, 0-500 atm, 170-300 K) then demonstrate the quality and consistency of the proposed model. This success is a first validation of a database and associated software built in order to model the shape of CH₄ absorption in air, that are available and suitable for the updating of atmospheric radiative transfer codes. The accuracy of these tools is then further demonstrated using transmission measurements of the Earth atmosphere in the ν₃ region (3 μm) recorded in solar absorption with ground and balloon based Fourier transform instruments. Similar tests in the ν₄ region using satellite based emission spectra and ground-based transmission measurements confirm the model quality although they show very small line-mixing effects and their masking by strong contributions of other species.     

A new software suite for NO2 vertical profile retrieval from ground-based zenith-sky spectrometers

Here we present an operational method to improve accuracy and information content of ground-based measurements of stratospheric NO₂. The motive is to improve the investigation of trends in NO₂, and is important because the current trend in NO₂ appears to contradict the trend in its source, suggesting that the stratospheric circulation has changed. To do so, a new software package for retrieving NO₂ vertical profiles from slant columns measured by zenith-sky spectrometers has been created. It uses a Rodgers optimal linear inverse method coupled with a radiative transfer model for calculations of transfer functions between profiles and columns, and a chemical box model for taking into account the NO₂ variations during twilight and during the day. Each model has parameters that vary according to season and location. Forerunners of each model have been previously validated. The scheme maps random errors in the measurements and systematic errors in the models and their parameters on to the retrieved profiles. Initialisation for models is derived from well-established climatologies. The software has been tested by comparing retrieved profiles to simultaneous balloon-borne profiles at mid-latitudes in spring.     

Emission features of Ho ion in Nb2O5, Ta2O5 and La2O3 mixed Li2O-ZrO2-SiO2 glasses

Li₂O-ZrO₂-SiO₂: Ho³⁺ glasses mixed with three interesting d-block elemental oxides, viz., Nb₂O₅, Ta₂O₅ and La₂O₃, were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature. The luminescence spectra of Nb₂O₅ and Ta₂O₅ mixed Li₂O-ZrO₂-SiO₂ glasses (free of Ho³⁺ ions) have also exhibited broad emission band in the blue region. This band is attributed to radiative recombination of self-trapped excitons (STEs) localized on substitutionally positioned octahedral Ta⁵⁺ and Nb⁵⁺ ions in the glass network. The Judd-Ofelt theory was successfully applied to characterize Ho³⁺ spectra of all the three glasses. From this theory various radiative properties, like transition probability A, branching ratio β_r and the radiative lifetime τ_r, for ⁵S₂ emission levels in the spectra of these glasses have been evaluated. The radiative lifetime for ⁵S₂ level of Ho³⁺ ions has also been measured and quantum efficiencies were estimated. Among the three glasses studied the La₂O₃ mixed glass exhibited the highest quantum efficiency. The reasons for such higher value have been discussed based on the relationship between the structural modifications taking place around the Ho³⁺ ions.     

A line-by-line calculation of low-resolution radiative properties of CO2-CO-transparent nonisothermal gases mixtures up to 3000 K

Low-resolution radiative properties (absorptivities, transmissivities, intensities) of nonisothermal or inhomogeneous gas mixtures at high temperatures, suitable for radiative heat transfer applications (e.g., in combustion) are obtained from a line-by-line calculation, using recently published high-resolution spectroscopic data at 296 K given by AFGL. It is shown that absorptivities obtained for isothermal mixtures of CO₂, CO, N₂ (and sometimes H₂O) agree with the corresponding measured spectra.     

Radiative and radiationless processes of Er3+ in MnF2

We have designed a method for the measurement of radiative and radiationless transition rates of fluorescent systems with several metastable levels. This method applies to systems with adjacent metastable levels connected by multiphonon relaxation processes. The measurements required are those of the integrated fluorescence intensities and decay times at different temperatures; no absorption or excitation measurements are required. We have applied this method to the study of the fluorescence of Er³⁺ in MnF₂. The knowledge of both radiative and non- radiative decays has allowed us to reconstruct the kinetics of the excitation and de-excitation processes and to find the dependence on temperature and energy gap of multiphonon relaxation processes in this system.     

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.     

The chemisorption of CO,CO2, C2H2, C2H4, H2 and NH3 on the clean Fe(100) and (111) crystal surfaces

The chemisorption of small molecules (CO, CO₂, C₂H₂, C₂H₄, H₂ and NH₃) has been studied on the clean Fe(110) and (111) crystal faces by low-energy electron diffraction (LEED) and thermal desorption. C₂H₄ and C₂H₂ yield the same sequence of surface structures that change with temperature and crystal orientation. CO and CO₂ chemisorption similarly results in the formation of the same types of surface structures that change with surface temperature and crystal orientation. Ammonia forms several ordered surface structures on both iron crystal faces. All of the molecules decompose as a function of temperature on the iron surfaces as indicated by the Auger and thermal desorption spectra.     

CO2/CO2 isotopic ratio measurements with a continuous-wave quantum cascade laser in exhaled breath

A laser spectrometer based on a continuous-wave thermoelectrically-cooled distributed feedback quantum cascade laser at ∼2308 cm⁻¹ has been evaluated for measurement of ¹³CO₂/¹²CO₂ isotopic ratio (δ¹³C) changes in exhaled breath samples and in CO₂ gas flows in the concentration range 1-5%. Mid-infrared CO₂ absorption spectra were measured in a 54.2-cm long optical cell using balanced detection whereby the beam passing through the cell was ratioed against a reference beam split-off from the main beam before the cell. Signal-to-noise ratios (SNR) were estimated for CO₂ concentration measurements determined from either absorption peak amplitude or absorption peak area. The highest SNR were achieved in the measurements based upon a fitted absorption peak area. Typical short-term δ¹³C precisions of 1.1⁰/₀₀ (1-s integration time) and 0.5⁰/₀₀ (8-12-s integration time) were estimated from the two-sample (Allan) variance plots of data recorded in the optical cell at a pressure of 20 Torr and with no active temperature stabilization of the cell and gas flow. The best precision of 0.12⁰/₀₀ was achieved for averaging 80 successive 1-s integration time measurements.     

Thermochemical studies on RE2O2CO3 (RE=Gd, Nd) decomposition

Thermochemistry in the decomposition of gadolinium di-oxycarbonate, Gd₂O₂CO₃(s) and neodymium di-oxycarbonate, Nd₂O₂CO₃(s) was studied over the temperature region of 774-952 K and 775-1105 K, respectively. The equilibrium properties of the decomposition reactions were obtained by tensimetric measurement of the CO₂(g) pressure over the biphasic mixture of RE₂O₂CO₃(s) and RE₂O₃(s) at different temperatures (RE=Gd, Nd) and also by thermogravimetric analysis of the decomposition temperature at different CO₂ pressures. The temperature dependence of the equilibrium pressure of CO₂ thus measured could be given by

ln p_CO2/Pa (±0.13)=−22599.1/T+35.21 (774≤T (K)≤952) for Gd₂O₂CO₃ decomposition and

ln p_CO2/Pa (±0.19)=−23824.7/T+33.14 (775≤T (K)≤1105) for Nd₂O₂CO₃ decomposition.

From the above vapor pressure expressions, the median enthalpy and entropy of the decomposition of the oxycarbonates were calculated by the second law analysis and their thermodynamic stabilities were derived. The results are discussed in the light of available thermochemical data of the compounds.     

Channel selection using information content analysis: A case study of CO2 retrieval from near infrared measurements

A major challenge in retrieving CO₂ concentrations from thermal infrared remote sensing comes from the fact that measurements in the 4.3 and 15 μm absorption bands (AIRS or TES) are sensitive to both temperature and CO₂ variations. This complicates the selection of absorption channels with maximum CO₂ concentration information content. In contrast, retrievals using near infrared (NIR) CO₂ absorption bands are relatively insensitive to temperature and are most sensitive to changes of CO₂ near the surface, where the sources and sinks are located. The Orbiting Carbon Observatory (OCO) was built to measure reflected sunlight in three NIR spectral regions (the 0.76 μm O₂ A-band and two CO₂ bands at 1.61 and 2.06 μm). In an effort to significantly increase the speed of accurate CO₂ retrieval algorithms for OCO, we performed an information content analysis to identify the 20 best channels from each CO₂ spectral region to use in OCO retrievals. Retrievals using these 40 channels provide as much as 75% of the total CO₂ information content compared to retrievals using all 1016 channels in each spectral region. The CO₂ retrievals using our selected channels have a precision better than 0.1 ppm. This technique can be applied to the retrieval of other geophysical variables (e.g., temperature or CH₄), or modified for other instruments, such as AIRS or TES.     

Interaction of O2, CO2, CO,C2H4 and C2H4O with Ag(110)

The interaction of O₂, CO₂, CO, C₂H₄ AND C₂H₄O with Ag(110) has been studied by low energy electron diffraction (LEED), temperature programmed desorption (TPD) and electron energy loss spectroscopy (EELS). For adsorbed oxygen the EELS and TPD signals are measured as a function of coverage (θ). Up to θ = 0.25 the EELS signal is proportional to coverage; above 0.25 evidence is found for dipole-dipole interaction as the EELS signal is no longer proportional to coverage. The TPD signal is not directly proportional to the oxygen coverage, which is explained by diffusion of part of the adsorbed oxygen into the bulk. Oxygen has been adsorbed both at pressures of less than 10^-4 Pa in an ultrahigh vacuum chamber and at pressures up to 10³ Pa in a preparation chamber. After desorption at 10³ Pa a new type of weakly bound subsurface oxygen is identified, which can be transferred to the surface by heating the crystal to 470 K. CO₂ is not adsorbed as such on clean silver at 300 K. However, it is adsorbed in the form of a carbonate ion if the surface is first exposed to oxygen. If the crystal is heated this complex decomposes into O_ad and CO₂ with an activation energy of 27 kcal/mol(1 kcal = 4.187 kJ). Up to an oxygen coverage of 0.25 one CO₂ molecule is adsorbed per two oxygen atoms on the surface. At higher oxygen coverages the amount of CO₂ adsorbed becomes smaller. CO readily reacts with O_ad at room temperature to form CO₂. This reaction has been used to measure the number of O atoms present on the surface at 300 K relative to the amount of CO₂ that is adsorbed at 300 K by the formation of a carbonate ion. Weakly bound subsurface oxygen does not react with CO at 300 K. Adsorption of C₂H₄O at 110 K is promoted by the presence of atomic oxygen. The activation energy for desorption of C₂H₄O from clean silver is ～ 9 kcal/mol, whereas on the oxygen-precovered surface two states are found with activation energies of 8.5 and 12.5 kcal/mol. The results are discussed in terms of the mechanism of ethylene epoxidation over unpromoted and unmoderated silver.     

Optical and electronic properties of NiFe2O4 and CoFe2O4 thin films

We report the optical and electronic properties of the inverse spinel ferrite NiFe₂O₄ and CoFe₂O₄ thin films deposited on single crystal sapphire by electron beam deposition. We carried out variable temperature (78–500 K) transmittance measurements on the thin films to investigate the optical properties and electronic structures of these ferrites. The absorption spectra of both NiFe₂O₄ and CoFe₂O₄ thin films show insulating characters with Ni (Co) d to d on-site transitions below 3 eV. The energy bands above 3 eV are mainly due to the O 2p to Fe 3d charge transfer transitions. The observed electronic transitions have been assigned based on the first principles calculations and comparisons with structurally similar Ni and Co-containing compounds. The Co²⁺ d to d transition in the CoFe₂O₄ thin film shows a strong temperature dependence, likely due to the spin-charge coupling effect.     

Ni2+:BeAl2O4晶体发光性质的研究

用时间分辨的激光诱导荧光光谱方法测量了10—300K温度范围内Ni²⁺:BeAl₂O₄晶体的红外荧光光谱和荧光寿命。通过荧光寿命的温度变化特性分析,得出³T_2g态的内禀辐射衰减寿命为123±7.2μs。无辐射弛豫的Mott激活能为1147cm^-1,并导出了此晶体发光量子效率随温度的变化关系式。Ni²⁺:BeAl₂O_{4关键词：}