Nikolay N. Yuryshev

Physics and engineering of singlet delta oxygen production in low-temperature plasma

An overview is presented of experimental and theoretical research in the field of physics and engineering of singlet delta oxygen (SDO) production in low-temperature plasma of various electric discharges. Attention is paid mainly to the SDO production with SDO yield adequate for the development of an electric discharge oxygen–iodine laser (DOIL). The review comprises a historical sketch describing the main experimental results on SDO physics in low-temperature plasma obtained since the first detection of SDO in electric discharge in the 1950s and the first attempt to launch a DOIL in the 1970s up to the mid-1980s when several research groups started their activity aimed at DOIL development, stimulated by success in the development of a chemical oxygen–iodine laser (COIL). A detailed analysis of theoretical and experimental research on SDO production in electric discharge from the mid-1980s to the present, when the first DOIL has been launched, is given. Different kinetic models of oxygen low-temperature plasma are compared with the model developed by the authors. The latter comprises electron kinetics based on the accompanying solution of the electron Boltzmann equation, plasma chemistry including reactions of excited molecules and numerous ion–molecular reactions, thermal energy balance and electric circuit equation. The experimental part of the overview is focused on the experimental methods of SDO detection including experiments on the measurements of the Einstein coefficient for SDO transition and experimental procedures of SDO production in self-sustained and non-self-sustained discharges and analysis of different plasma-chemical processes occurring in oxygen low-temperature plasma which brings limitation to the maximum SDO yield and to the lifetime of the SDO in an electric discharge and its afterglow. Quite recently obtained results on gain and output characteristics of DOIL and some projects aimed at the development of high-power DOIL are discussed.

Mechanism of pulse discharge production of iodine atoms from CF3I molecules for a chemical oxygen?iodine laser

The pulsed chemical oxygen–iodine laser (COIL) development is aimed at many new applications. Pulsed electric discharge is most effective in turning COIL operation into the pulse mode by instant production of iodine atoms. A numerical model is developed for simulations of the pulsed COIL initiated by an electric discharge. The model comprises a system of kinetic equations for neutral and charged species, electric circuit equation, gas thermal balance equation and the photon balance equation. Reaction rate coefficients for processes involving electrons are found by solving the electron Boltzmann equation, which is re-calculated in a course of computations when plasma parameters changed. The processes accounted for in the Boltzmann equation include excitation and ionization of atoms and molecules, dissociation of molecules, electron attachment processes, electron–ion recombination, electron–electron collisions, second-kind collisions and stepwise excitation of molecules. The last processes are particularly important because of a high singlet oxygen concentration in gas flow from the singlet oxygen chemical generator. Results of numerical simulations are compared with experimental laser pulse waveforms. It is concluded that there is satisfactory agreement between theory and the experiment. The prevailing mechanism of iodine atom formation from the CF3I donor in a very complex kinetic system of the COIL medium under pulse discharge conditions, based on their detailed numerical modelling and by comparing these results both with experimental results of other authors and their own experiments, is established. The dominant iodine atom production mechanism for conditions under study is the electron-impact dissociation of CF3I molecules. It was proved that in the conditions of the experiment the secondary chemical reactions with O atoms play an insignificant role.

Influence of nitrogen oxides NO and NO2 on singlet delta oxygen production in pulsed discharge

The influence of nitrogen oxides NO and NO2 on the specific input energy (SIE) and the time behaviour of singlet delta oxygen (SDO) luminescence excited by a pulsed e-beam sustained discharge in oxygen were experimentally and theoretically studied. NO and NO2 addition into oxygen results in a small increase and decrease in the SIE, respectively, the latter being connected with a large energy of electron affinity to NO2. The addition of 0.1–0.3% nitrogen oxides was experimentally and theoretically demonstrated to result in a notable enhancement of the SDO lifetime, which is related to a decrease in the atomic oxygen concentration in afterglow. It was experimentally demonstrated that to get a high SDO concentration at the gas pressure 30–60 Torr for a time interval of less than ~0.5 s one needs to add not less than 0.2% nitrogen oxides into oxygen. The temperature dependence of the relaxation constant for SDO quenching by unexcited oxygen was estimated by using experimental data on the time behaviour of SDO luminescence.

The methods of singlet oxygen detection for DOIL program

The problem of development of a singlet delta oxygen O2(1Δg) (SDO) generators alternative to chemical one needs application of the accurate methods of measuring the SDO concentration. A chemical SDO generator providing efficient operation of a chemical oxygen-iodine laser (COIL) is proposed to be used as a reference source for absolute calibration of the system measuring the SDO concentration. The principle of the COIL operation results in the threshold and output COIL parameters make it possible to evaluate the SDO yield with a satisfactory accuracy. A convenient sparger chemical SDO generator was applied as a reference source for absolute calibration of detectors of dimole (λ=634nm) and b→X (λ=762 nm) radiations. The values of b-state concentration formed in a longitudinal electric discharge were evaluated. The intracavity laser spectroscopy (ICLS) was absolutely calibrated for measuring the SDO concentration. ICLS method has a very high sensitivity and makes it possible to monitor the absorption corresponding to the O2(1Δg)→O2(1Σg+) (λ = 1.91 μm) transition. The cross-sections of lines of the Q - branch of the vibrational 0-0 band of the a1Δg → b1Σg+ transition of molecular oxygen were measured. The method developed was applied to measure the concentration of singlet oxygen produced in the microwave discharge. He - Ne laser (λ = 633 nm) was used for absolute calibration of a system monitoring the dimole radiation. The rate constant of the process responsible for dimole emission was measured. The value obtained kd=7.34•10-23 cm3/s is in agreement with literature.

Role of N2 molecules in pulse discharge production of I atoms for a pulsed chemical oxygen–iodine laser

A pulsed electric discharge is the most effective means to turn chemical oxygen–iodine laser (COIL) operation into the pulse mode by fast production of iodine atoms. Experimental studies and numerical simulations are performed on a pulsed COIL initiated by an electric discharge in a mixture CF3I : N2 : O2(3X) : O2(a 1Δg) flowing out of a chemical singlet oxygen generator. A transverse pulsed discharge is realized at various iodide pressures. The model comprises a system of kinetic equations for neutral and charged species, the electric circuit equation, the gas thermal balance equation and the photon balance equation. Reaction rate coefficients for processes involving electrons are repeatedly re-calculated by the electron Boltzmann equation solver when the plasma parameters are changed. The processes accounted for in the Boltzmann equation include direct and stepwise excitation and ionization of atoms and molecules, dissociation of molecules, electron attachment processes, electron–ion recombination, electron–electron collisions and second-kind collisions. The last processes are particularly important because of a high singlet oxygen concentration in gas flow from the singlet oxygen chemical generator. A conclusion is drawn about satisfactory agreement between the theory and the experiment.

Singlet delta oxygen production in e-beam sustained discharge: theory and experiment

Singlet delta oxygen (SDO) production in a pulsed e-beam sustained discharge (EBSD) ignited in molecular oxygen with carbon monoxide stabilizing this discharge is theoretically and experimentally studied. Temporal behavior of SDO concentration and yield in the EBSD afterglow is analyzed. Experimentally measured SDO yield for oxygen mixture O2:Ar:CO=1:1:0.05 at total gas pressure 30 Torr comes up to 7% at specific input energy (SIE) of ~3.0 kJ/(1 atm(O2+CO)), whereas its theoretical value riches ~ 17.5%. The efficiency of SDO production is theoretically analyzed as function of the SIE.

Theoretical studies on kinetics of singlet oxygen in nonthermal plasma

An idea to replace singlet delta oxygen (SDO) generator working with wet chemistry by electric discharge generator has got much attention last years. Different kinds of discharge were examined for this purpose, but without a great success. The existing theoretical models are not validated by well-characterized experimental data. To describe complicated kinetics in gas discharge with oxygen one needs to know in detail processes involving numerous electronic excited oxygen molecules and atoms. To gain new knowledge about these processes experimental studies were made on electric discharge properties in gas mixture flow with independent control of inlet SDO concentration. The theoretical model extended to include minor additives like oxygen atoms, water molecules, ozone was developed. Comparison with careful experimental measurements of electric characteristics along with gas composition allows us to verify the model and make theoretical predictions more reliable. Results of numerical simulations using this model for an electron-beam sustained discharge are reported and compared with the experimental data.

Electron-beam sustained discharge in oxygen gas mixtures: singlet delta oxygen production for oxygen-iodine laser

Electric properties and spectroscopy of an e-beam sustained discharge (EBSD) in oxygen and oxygen gas mixtures at gas pressure up to 100 Torr were experimentally studied. The pulsed discharge in pure oxygen and its mixtures with noble gases was shown to be very unstable and characterized by low input energy. When adding small amount of carbon monoxide or hydrogen, the electric stability of the discharge increases, specific input energy (SIE) per molecular component being more than order of magnitude higher and coming up to 6.5 kJ/(l atm) for gas mixture O2:Ar:CO = 1:1:0.1. The results of experiments on spectroscopy of the singlet delta oxygen O2(a1Δg)(SDO) and O2(b1Σg+) states in the EBSD are presented. The calibration of the optical scheme for measuring the SDO absolute concentration and yield using the detection of luminescence of the SDO going from a chemical SDO generator was done. The preliminary measurement of the SDO yield demonstrated that it was ~3% for the SIE of ~1 kJ/(l atm), which is close to the results of theoretical calculations for such a SIE. Theoretical calculations demonstrated that for the SIE of 6.5 kJ/(l atm) the SDO yield may reach ~20% exceeding its threshold value needed for oxygen-iodine laser operation at room temperature, although a part of the energy loaded into the EBSD goes into the vibrational energy of the molecular admixture, (which was experimentally demonstrated by launching a CO laser operating on an oxygen-rich mixture O2:Ar:CO = 1:1:0.1 and measuring its small-signal gain).

Iodine atom production rates by electron impact versus post discharge reactions for pulsed COIL

Pulsed discharge is effective means to achieve high-peak lasing in COIL. Numerical model is developed for simulation of pulsed discharge in gas stream from the singlet oxygen generator mixed with CF3I. The model comprises a system of kinetic equations for neutral and charged species, electric circuit equation, and gas thermal balance equation. Sources of iodine atoms under discharge and post-discharge conditions are analyzed. The dominant source in the discharge is electron-impact dissociation of CF3I molecules. In post-discharge phase chemical reactions are identified giving notable input into I production. Deformation of laser pulse waveform observed experimentally is explained by influence of these reactions.

Influence of nitrogen oxides on singlet delta oxygen production in pulsed electric discharge for oxygen-iodine laser

Experimental and theoretical study of influence of nitrogen oxides NO and NO2 admixtures in oxygen containing gas mixture excited by pulsed electron-beam sustained discharge on input energy and time behavior of singlet delta oxygen (SDO) luminescence was carried out. Temperature dependence of the constant of SDO relaxation by unexcited molecular oxygen was estimated.