The high temperature absorption of CO2 laser radiation by SF6, NF3, and NH3

The absorption coefficients of SF₆, NF₃ and NH₃ at CO₂ laser wavelengths have been evaluated at elevated temperatures in a shock tube study. Measurements were performed in the pressure range of P = 10−70 atm for temperatures between 500 and 2900 K. The effects of finite rate chemical decomposition on the absorption observations are discussed.     

Stmmry talk on evaluation and theory

Abstract

Single crystal samples of Ce³⁺-doped fluorides CaNaYF₆ and BaMgF₄ have been grown in a reducing atmosphere, with the intent of studying the effects of symmetry and ligand coordination on the dopant energy levels. The optical absorption spectra of Ce³⁺ in these crystals consist, at most, of five overlapping bands. The luminescence is also a broad band due to strong electron—phonon interaction in the 5d excited state. The energies of the lowest absorption band and the luminescence band are shifted to low energy compared to those in LiCaAlF₆ and LiYF₄. This trend may be explained by lowering symmetry of the anion-coordinate polyhedra of Ce³⁺ in these crystals.     

Anomalies in resonant absorption line profiles of atoms with large hyperfine splitting

We examine a monochromatic absorption line in the velocity-nonselective excitation of atoms when the components of the hyperfine stricture of the electronic ground states are optically pumped. We show that the absorption lines possess unusual substructures for some values of the hyperfine splitting of the ground state (which exceed the Doppler absorption linewidth severalfold). These substructures in the absorption spectrum are most apparent if the hyperfine structure of the excited electronic state is taken into account. We calculate the absorption spectra of monochromatic light near the D ₁ and D ₂ lines of atomic rubidium ^85,87Rb. With real hyperfine splitting taken into account, the D ₁ and D ₂ lines are modeled by 4-and 6-level diagrams, respectively. Finally, we show that atomic rubidium vapor can be successfully used to observe the spectral features experimentally. Zh. éksp. Teor. Fiz. 111, 93–106 (January 1997)     

Spectroscopic manifestations of phase changes in CaAr n clusters: finite size effects

The finite temperature optical spectroscopy of CaAr_n clusters in the range 6 n 146 is investigated using a Diatomics-In-Molecule (DIM) Hamiltonian and classical parallel tempering Monte Carlo simulations. The absorption spectrum is calculated in the vertical approximation at various temperatures between 2 K and 50 K. Several typical situations are reported. CaAr₆ shows a strong thermal broadening and shift of the spectral lines, possibly associated with isomerization. CaAr₁₃ only shows some broadening. CaAr₃₇ exhibits features corresponding to coexisting isomers at low temperature. Finally, the abrupt changes in the absorption spectrum in CaAr₁₄₆ at about 20 K are indicative of surface diffusion.     

Electrooptical effect in YBa2Cu3O6+x films

Optical absorption in YBa₂Cu₃O_6+x metal films carrying a direct current up to 100 mA is investigated. For films with a highly nonlinear I-V curve the current is observed to have a strong influence on interband absorption. The effect is not observed in the region of optical transitions at local levels. The results are analyzed from the standpoint of carrier localization and delocalization processes. Fiz. Tverd. Tela (St. Petersburg) 39, 1747–1749 (October 1997)     

Energy absorption buildup factors of some potential bioactive compounds in the energy region 0.015–15 MeV

Kinetic energy released per unit mass relative to air and energy absorption buildup factors has been calculated for some potential bioactive compounds in the energy region of 0.015–15?MeV. The bioactive compounds of 1-aryl-3-dibenzylamino-propane-1-on hydrochloride type Mannich bases were used in this work. Aryl part was changed as C₆H₅ (1), 4-CH₃C₆H₄ (2), C₄H₃S-2-yl (3), 4-FC₆H₄ (4), 4-BrC₆H₄ (5), 4-ClC₆H₄ (6), and 4-NO₂C₆H₄ (7). The energy absorption buildup factors have been calculated for penetration depth of 40 mean free paths. It is observed that kinetic energy released per unit mass relative to air depends on the photon energy and chemical content of compounds. The compounds with least mean atomic number possess the maximum value of energy absorption buildup factors. Also, the energy absorption buildup factors are found the highest in intermediate energy, whereas the lowest in low as well as high energies.     

Electronic excitations of Sc3+ impurity in α-Al2O3 crystals

Optical properties, including luminescence, of scandium-doped α-Al₂O₃ crystals have been studied in the VUV range. An absorption band associated with the scandium impurity was observed at the fundamental-absorption edge of crystalline corundum. A strong luminescence band peaking at 5.6 eV, which is most effectively excited within the 7.7–8.8-eV interval, was found. The kinetic and polarization characteristics of this luminescence were studied within the temperature range 6–500 K. An excitation model of the impurity complex and the mechanism of its relaxation are discussed. Fiz. Tverd. Tela (St. Petersburg) 40, 653–654 (April 1998)     

High-temperature measurements of the rates of the reactions CH2O + Ar → Products and CH2O + O2 → Products

The two-channel thermal decomposition of formaldehyde [CH₂O], (1a) CH₂O + Ar → HCO + H + Ar, and (1b) CH₂O + Ar → H₂ + CO + Ar, was studied in shock tube experiments in the 2258-2687 K temperature range, at an average total pressure of 1.6 atm. OH radicals, generated on shock heating trioxane-O₂-Ar mixtures, were monitored behind the reflected shock front using narrow-linewidth laser absorption. 1,3,5 trioxane [C₃H₆O₃] was used as the CH₂O precursor in the current experiments. H-atoms formed upon CH₂O and HCO decomposition rapidly react with O₂ to produce OH via H + O₂ → O + OH. The recorded OH time-histories show dominant sensitivity to the formaldehyde decomposition pathways. The second-order reaction rate coefficients were inferred by matching measured and modeled OH profiles behind the reflected shock. Two-parameter fits for k_1a and k_1b, applicable in this temperature range, are:

     

Methyl concentration time-histories during iso-octane and n-heptane oxidation and pyrolysis

Methyl radical concentration time-histories were measured during the oxidation and pyrolysis of iso-octane and n-heptane behind reflected shock waves. Initial reflected shock conditions covered temperatures of 1100-1560 K, pressures of 1.6-2.0 atm and initial fuel concentrations of 100-500 ppm. Methyl radicals were detected using cw UV laser absorption near 216 nm; three wavelengths were used to compensate for time- and wavelength-dependent interference absorption. Methyl time-histories were compared to the predictions of several current oxidation models. While some agreement was found between modeling and measurement in the early rise, peak and plateau values of methyl, and in the ignition time, none of the current mechanisms accurately recover all of these features. Sensitivity analysis of the ignition times for both iso-octane and n-heptane showed a strong dependence on the reaction C₃H₅ + H = C₃H₄ + H₂, and a recommended rate was found for this reaction. Sensitivity analysis of the initial rate of CH₃ production during pyrolysis indicated that for both iso-octane and n-heptane, reaction rates for the initial decomposition channels are well isolated, and overall values for these rates were obtained. The present concentration time-history data provide strong constraints on the reaction mechanisms of both iso-octane and n-heptane oxidation, and in conjunction with OH concentration time-histories and ignition delay times, recently measured in our laboratory, should provide a self-consistent set of kinetic targets for the validation and refinement of iso-octane and n-heptane reaction mechanisms.     

Spectroscopic Studies of Chemical Reactions in Strong Shock Waves

Shock tube provides a promising tool of studying high temperature chemical reaction in gases. The heating by shock wave is uniform, extremely fast and intense. So that the temperature may rise thousands of degrees in a fraction of a second. Observations of the effects of this heating on C₆H₆ has shown extensive decomposition into C₂ and CN.     

Adsorption behaviour of SO2 and SOF2 gas on Rh-doped BNNT: a DFT study

Abstract

As the insulating medium, SF₆ is widely used in gas insulation equipment. Partial discharge and local overheating can cause the decomposition of SF₆, resulting in a decrease in insulation strength of the equipment. The detection of SF₆ decomposition gas can be used for on-line insulation detection of gas insulation equipment in electric power industry. In order to develop a new sensor gas sensing material for gas detecting. In this work, based on the first-principles density functional calculation (DFT) method of DMol³, the adsorption of SF₆ decomposition gas on (5,0) Z-type Rh-BNNT in different ways was explored. The adsorption energy, adsorption distance, charge transfer as well as density of states were discussed. The results show that the adsorption strength between SO₂ molecule with Rh-BNNT is larger than with SOF₂ molecule, combined with desorption time, theoretically predicts Rh -BNNT have the potential to be a material for SO₂ gas sensors.     

Microwave absorption in the Kondo lattice of CeB6 in strong magnetic fields

The characteristic features of microwave (30–120 GHz) magnetoabsorption in the magnetic Kondo lattice of CeB₆ at liquid-helium temperatures in strong magnetic fields are investigated. It is discovered that the absorption structure is the result of the superposition of the ESR of the cerium 4 f electrons, which has a pronounced doublet structure, and features whose position does not depend on the radiation frequency and which are associated with transitions in the magnetic phase diagram of CeB₆. The character of the absorption in the vicinity of the ESR can be linked to the splitting of the ² F _5/2 state in the crystal field; here the g factor is substantially renormalized from g=2.06±0.03 to g=1.83±0.03 as the temperature decreases from 4.2 K to 1.8 K, respectively. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 6, 431–435 (25 March 1996)     

First-principle study on the structural and electronic properties of H2S and SO2 adsorption on Pd-doped MoS2 monolayer

The partial discharge in SF₆-insulated equipment produces characteristic decomposition products: SO₂ and H₂S. The characteristic decomposition products vastly speed up the process of discharge faults. Based on density functional theory (DFT) calculation, single layer Pd-doped MoS₂ (Pd-MoS₂) is adopted as the adsorbent to adsorb SO₂ and H₂S to ensure the operational stability of SF₆-insulated equipment. The adsorption energy, charge transfer and structure parameters of SF₆, H₂S, and SO₂ adsorption on the Pd-MoS₂ monolayer are analysed to find the most stable adsorption structure. The molecular orbital theory, total density of states and partial density of states are studied to analyse the adsorption mechanism. The results show that Pd-MoS₂ adsorbent possesses high catalytic activity and excellent adsorption performance to H₂S and SO₂ by strong chemical adsorption. This study is of great significance to ensure the operational stability of SF6-insulated equipment by removing these characteristic decomposition products.     

Spectral-kinetic characteristics of transient absorption in calcium fluoride crystals

The method of absorption spectroscopy with nanosecond resolution is used to study transient absorption in nominally pure crystals of CaF₂ irradiated by a pulse of fast electrons. Optical absorption caused by self-trapped excitons appears in the form of a superposition of bands with half-widths of no more than 0.2 eV in both the electron and hole components. These groups of bands are assigned to absorption of F, H pairs in various configurations. We observe a regular change in the spectral-kinetic characteristics depending on the distance between the components of the pair. Fiz. Tverd. Tela (St. Petersburg) 39, 1197–1201 (July 1997)     

An experimental and computational study of methyl ester decomposition pathways using shock tubes

The high-temperature decomposition of three simple methyl esters: methyl acetate, methyl propionate and methyl butanoate, were studied behind reflected shock waves using tunable diode laser absorption of CO₂ near 2.7 μm. CO₂ yield measurements were made over the range of temperatures 1260-1653 K, pressures of 1.4-1.7 atm and reactant concentrations of 2-3%, with the balance Ar. The CO₂ absorption strengths near 2.7 μm are approximately 50 to 1000 times stronger than the bands near 2.0 and 1.55 μm, respectively, and offer opportunities for significantly more sensitive and accurate combustion measurements than previous absorption work using CO₂ bands at shorter wavelength. The experiments provide the first laser-based time-history measurements of the CO₂ yields during pyrolysis of these bio-diesel surrogate fuels in a shock tube. Model predictions for CO₂ yields during methyl butanoate pyrolysis at high temperatures, using the detailed reaction mechanisms of [E. M. Fisher, W. J. Pitz, H. J. Curran, C. K. Westbrook, Proc. Combust. Inst. 28 (2000) 1579-1586.] and others, are significantly lower than those measured in this study. However, an improved methyl butanoate model which extends the recent theoretical work of [L.K. Huynh, A. Violi, J. Org. Chem. 73 (2008) 94-101.] provides substantially improved predictions of CO₂ yields during methyl butanoate pyrolysis. As earlier mechanisms predicted low yields of CO₂ from methyl butanoate decomposition, these new findings imply that existing bio-diesel fuel models, which rely on the rapid formation of two oxygenate radicals from methyl esters (rather than a single non-reactive CO₂ molecule) to account for the tendency for soot reduction, may have to be revisited.     

An equation of state of a carbon-fibre epoxy composite under shock loading

An anisotropic equation of state (EOS) is proposed for the accurate extrapolation of high-pressure shock Hugoniot (anisotropic and isotropic) states to other thermodynamic (anisotropic and isotropic) states for a shocked carbon-fibre epoxy composite (CFC) of any symmetry. The proposed EOS, using a generalised decomposition of a stress tensor [A.A. Lukyanov, Int. J. Plasticity 24, 140 (2008)], represents a mathematical and physical generalisation of the Mie-Grüneisen EOS for isotropic material and reduces to this equation in the limit of isotropy. Although a linear relation between the generalised anisotropic bulk shock velocity U_s ^A and particle velocity u_p was adequate in the through-thickness orientation, damage softening process produces discontinuities both in value and slope in the U_s ^A-u_p relation. Therefore, the two-wave structure (non-linear anisotropic and isotropic elastic waves) that accompanies damage softening process was proposed for describing CFC behaviour under shock loading. The linear relationship U_s ^A-u_p over the range of measurements corresponding to non-linear anisotropic elastic wave shows a value of c₀ ^A (the intercept of the U_s ^A-u_p curve) that is in the range between first and second generalised anisotropic bulk speed of sound [A.A. Lukyanov, Eur. Phys. J. B 64, 159 (2008)]. An analytical calculation showed that Hugoniot Stress Levels (HSLs) in different directions for a CFC composite subject to the two-wave structure (non-linear anisotropic elastic and isotropic elastic waves) agree with experimental measurements at low and at high shock intensities. The results are presented, discussed and future studies are outlined.     

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.     

Decomposition of nitromethane in shock waves: The primary stage and the kinetics of decomposition at pressures of about 40 atm

The kinetics of nitromethane (NM) decomposition and the observed rate constant of the process were measured behind reflected shock wave using absorption spectroscopy at λ = 230 nm, temperatures of 1060 to 1350 K, pressure of ∼40 atm, and initial reactant concentration within 30–100 ppm. It was observed that, at the initial stage, nitromethane decomposes exponentially, without autoacceleration. The results of numerical simulations with the help of three most known kinetic schemes of nitromethane decomposition proved to be in close to agreement with our experimental data over the entire temperature range covered. It was demonstrated that the measured rate constant is identical to the rate constant of the dissociation CH₃NO₂ → CH₃ + NO₂. The temperature dependence of k ₁ was approximated by the Arrhenius formula k ₁ = 2.57 × 10¹⁴ exp(−52.85/RT) s⁻¹ (activation energy in kcal/mol), which suggests that the nitromethane dissociation proceeds in the falloff pressure region.     

Nitromethane pyrolysis in shock tubes and a micro flow reactor with a controlled temperature profile

Nitromethane has many applications, such as in racing, as a gasoline fuel additive, and as a monopropellant. Despite a large number of studies and the small size of the molecule, the combustion chemistry of nitromethane is still not well understood. To improve models, the pyrolysis of nitromethane (CH₃NO₂) was investigated experimentally in shock tubes and in a micro flow reactor with a controlled temperature profile (MFR), under dilute conditions. Several spectroscopic diagnostics were used in the shock tubes to follow the concentration time histories of CO, H₂O (both using IR laser absorption), and CH₃NO₂ (UV light absorption). A quadrupole mass spectrometer was used to measure CH₃NO₂, NO₂, CH₄, C₂H₄, and C₂H₂ at various temperatures with the MFR. These unique experimental results were compared to modern, detailed kinetics models from the literature, and no mechanism was able to reproduce these data over the wide range of conditions investigated. Predictions for the CO and H₂O levels were generally inaccurate, and the CH₄, C₂H₄, and C₂H₂ predictions were poor in most cases for the MFR data. Importantly, all models largely differ in their predictions. A numerical analysis was performed to identify ways to improve the next generation of nitromethane models. Results indicate that nitromethane decomposition needs to be improved below 1050 K, and that hydrocarbon-NOx interactions still need to be further investigated.     

Microstructural, optical and photocatalytic properties of CdS doped TiO2 thin films

CdS doped TiO₂ thin films (with CdS content=0, 3, 6, 9 and 12 at%) were grown on glass substrates. The X-ray diffraction analysis revealed that the films are polycrystalline of monoclinic TiO₂ structure. The microstructure parameters of the films such as crystallite size (D_ν) and microstrain (e) are calculated. Both the crystallites size and the microstrain are decreased with increasing CdS content. The optical constants have been determined in terms of Murmann's exact equations. The refractive index and extinction coefficient are increased with increasing CdS content. The optical band gap is calculated in the strong absorption region. The possible optical transition in these films is found to be an allowed direct transition. The values of E_g^opt are found to decrease as the CdS content increased. The films with 3 at% CdS content have better decomposition efficiency than undoped TiO₂. The films with 6 at% and 9 at% CdS content have decomposition efficiency comparable to that of undoped TiO₂, although they have lower band gap. The CdS doped TiO₂ could have a better impact on the decomposing of organic wastes.