A scalable high pressure centrifugal spray generator of singlet oxygen for chemical oxygen-iodine laser (COIL) was
developed. This generator uses nitrogen as chlorine diluting gas. Different spray nozzles were tested which could be
assembled together and so enable a high chlorine flow rates for a high-power COIL. The designed generator can produce
singlet oxygen, O2(1Δg), with reasonable chlorine utilization and O2(1Δg) yield even at very high generator pressures,
which cannot be attained by other O2(1Δg) generators. This high-pressure operation is beneficial for a pressure recovery
system of the laser. Another advantage of this generator is a very high BHP utilization. The problem of heating of exit
gas was solved by introducing additional nitrogen between the separator rotor and stator.
The COIL operation using a new method of I2 generation is demonstrated. The method is based on the gas-phase
chemical reaction between Cl2 and HI in a separate reactor. This process is easily scalable and can simplify the COIL
operation by providing better control of I2 flow rate. A yield of I2 in the generation reaction up to 85% was achieved in a
reasonable volume of the reactor. A small-signal gain up to 0.75 %-cm-1 at temperature of 150 K in the center of
supersonic cavity was measured. A comparison with the established evaporation way of I2 delivery confirmed that the
chemical method has little or no impact on the COIL kinetics. The COIL output power measured with the chemical and
evaporation methods was nearly identical at comparable conditions.
A chemical oxygen-iodine laser driven by the centrifugal spray generator of singlet oxygen was developed and
experimentally studied. Modeling and experimental studies showed that the designed generator can produce singlet
oxygen, O2(1Δg), with a high efficiency (chlorine utilization 0.68 - 0.87 and O2(1Δg) yield 0.35 - 0.7) even at very high
generator pressures (25 - 70 kPa), which cannot be attained by other O2(1Δg) generators. This high-pressure operation
should be beneficial for a pressure recovery system of the laser. Another specific feature of the generator is a very high
BHP utilization (0.24-0.6). The developed separator can effectively remove even small droplets (> 1 μm) from gas at the
generator exit. Preliminary experiments on the COIL driven the centrifugal spray generator provided the small signal
gain up to 0.5 % cm-1.
KEYWORDS: Iodine, Chemical species, Fluorine, Chemical oxygen iodine lasers, Gases, Temperature metrology, Laser resonators, Chemical lasers, Chlorine, Throat
A generation of atomic iodine via F atoms with their immediate injection to the supersonic COIL nozzle has been
studied. Very high concentrations of I atoms were obtained in the laser cavity in the absence of O2(1Δg). Low values of
small signal gain measured in the O2(1Δg) flow did not correspond to high efficiency of I generation. This was ascribed to
O2(1Δg) quenching by DO2· radical.
A new spray-type generator of singlet oxygen, O2(1Δ), with a following centrifugal separation of depleted liquid was
studied. This generator was developed to fulfill following requirements suitable for an advanced Chemical Oxygen-
Iodine Laser (COIL): (i) a high-pressure operation, (ii) a single pass of reaction liquid, (iii) an efficient disengagement of
gas/liquid mixture, and (iv) a scalability for airborne and mobile application. The generator design takes advantage of
very high g/l interfacial surface area of a fine spray produced by a two-phase nozzle and a very fast liquid separation by
applying a high centrifugal force.
Generation of singlet oxygen and atomic iodine for operation of the chemical or discharge oxygen-iodine laser
(COIL/DOIL) is described, employing novel methods and device configurations proposed in our laboratory. A
centrifugal spray generator of singlet oxygen was developed, based on the conventional reaction between chlorine and
basic hydrogen peroxide. Recent results of theoretical and experimental investigation of the generator parameters are
presented. A new conception of the discharge generator of singlet oxygen was initiated, based on a combined DC arc jet
and RF discharge techniques. Principle of the generator currently developed and constructed is described. A new device
configuration was designed for the alternative method of atomic iodine generation using a radiofrequency discharge
decomposition of iodine compounds like CH3I or CF3I. Some recent experimental results of this research are also
presented.
A chemical method of atomic iodine generation for the chemical oxygen-iodine laser (COIL) was studied. This method
is based on fast reaction of gaseous hydrogen iodide with chemically produced fluorine atoms formed by a preceding
reaction of molecular fluorine with nitrogen oxide. Iodine atoms were generated in special reactors and injected into the
supersonic flow of nitrogen in the COIL cavity. Concentration profiles of atomic iodine both along and perpendicular to
the primary gas flow were measured in dependence on flow rates of the reaction gases. Very high concentration of
atomic iodine (up to 3.2x1015 cm-3) was measured in the laser cavity with a good yield related to both F2 (up to nearly
100 %) and HI (up to 60%). An important advantage of this method is using of commercially available reactive gases.
Some drawback of this method for its application in the COIL is a rather high gas temperature (250 - 400 K).
A spray type singlet oxygen generator (SOG) for chemical oxygen-iodine laser (COIL) was studied. Mathematical modeling has shown that a high O2(1&Dgr;) yield can be attained with BHP (basic hydrogen peroxide) spray in the Cl2-He atmosphere. It was found experimentally that O2(1&Dgr;) was produced with a ≥50% yield at a total pressure up to 50 kPa (375 Torr). A rotating separator was developed that can segregate even very small droplets (≥0.5 &mgr;m) from O2(1&Dgr;) flow.
The alternative method of atomic iodine generation by chemical process from gaseous reactants for a chemical oxygen
iodine laser (COIL) was experimentally investigated. Research on efficiency of the atomic iodine generation, suitable
configuration of iodine atom injection into the laser cavity and small signal gain measurements was performed, and some
results were included in this contribution.
KEYWORDS: Iodine, Chlorine, Laser resonators, Chemical species, Chemical oxygen iodine lasers, Oxygen, Chemical lasers, Throat, Helium, Temperature metrology
An advanced Chemical Oxygen-Iodine Laser (COIL) using the chemical generation of atomic iodine was studied. Atomic iodine is produced by the reaction of atomic chlorine with hydrogen iodide (HI) in two separated reactors tightly attached to the supersonic laser cavity. The iodine-contained mixture is injected to the flow of singlet oxygen by means of the supersonic orifices located 5 mm downstream the nozzle throat. The atomic iodine number density in the laser cavity up to 1.2 x 1015 cm-3 and a small-signal gain up to 0.35 %/cm were achieved. An rather high quenching of singlet oxygen by HI caused that the attained laser power was low. The results of small signal gain and the laser power are compared with the previous system including the mixing of reactants upstream the nozzle throat.
An alternative method of atomic iodine production for a Chemical Oxygen-Iodine Laser (COIL) was studied. The proposed all-gas process include reaction of chlorine dioxide (C1O2) with nitrogen oxide (NO) followed by subsequent reaction of atomic chlorine with hydrogen iodide (HI). In difference to our previous experiments, atomic iodine was produced separately from the primary flow. The generated atomic iodine was injected through two rows of sonic orifices into the supersonic part of the converging-diverging nozzle, 2 mm downstream the nozzle throat. A penetration of atomic iodine to the primary flow was substantially improved by introducing additional nitrogen downstream the iodine injector. This led to an increasing I number density and static temperature. Inversed order of reactants injection (HI-NO instead of NO-HI) substantially increased the production efficiency. Some results were explained by 2-D modelling. Number density of atomic iodine up to 1.6 × 1015 cm-3 was attained in laser cavity with nearly 100% efficiency.
The chemical oxygen-iodine laser (COIL) with a chemical method of atomic iodine generation was studied. Two
methods of atomic iodine generation were proposed and developed. They are based on fast reactions of gaseous
hydrogen iodide with chemically produced chlorine or fluorine atoms. Atomic iodine formation via Cl atoms we studied
earlier by mixing of reaction gases directly in the primary O2(1Δg) flow in COIL. A revealed oxidation of HI by singlet
oxygen and the O2(1Δg) quenching by some reaction product, however, reduced the attainable laser gain. This problem
could be avoided by atomic iodine generation in separate reactors with following injection of atomic iodine into the
primary O2(1Δg) flow. Gain measurements using this arrangement are presented in this paper. New experimental results
on atomic iodine production via F atoms are also summarized. Using of reactive gases commercially available in
pressure cylinders is the main advantage of this method.
The generator of singlet oxygen (SOG) remains still a challenge for a chemical oxygen-iodine laser (COIL). Hitherto,
only chemical generators based on the gas-liquid reaction system (chlorine-basic hydrogen peroxide) can supply singlet
oxygen, O2(1Δ), in enough high yields and at pressures to maintain operation of the high power supersonic COIL
facilities. Employing conventional generators of jet-type or rotating disc-type makes often problems resulting mainly
from liquid droplets entrained by an O2 (1Δ) stream into the laser cavity, and a limited scalability of these generators.
Advanced generator concepts investigated currently are based on two different approaches: (i)O2(1Δ) generation by the
electrical discharge in various configurations, eliminating thus a liquid chemistry, and (ii) O2(1Δ) generation by the
conventional chemistry in novel configurations offering the SOG efficiency increase and eliminating drawbacks of
existing devices. One of the advanced concepts of chemical generator - a spray SOG with centrifugal separation of gasliquid
phases - has been proposed and investigated in our laboratory. In this paper we present a description of the
generator principle, some essential results of theoretical estimations, and interim experimental results obtained with the
spray SOG.
Recent experimental results on new all gas-phase chemical generation of atomic iodine via atomic fluorine for a Chemical Oxygen-Iodine Laser (COIL) are presented. Advantages of this method are emphasized in comparison with the conventional use of molecular iodine as a precursor of atomic iodine for lasing. Fluorine atoms are produced by fast reaction of molecular fluorine with nitrogen oxide and then react with hydrogen iodide to atomic iodine. Reaction conditions and the most convenient experimental arrangements were searched for their application in the supersonic COIL. An inevitable instrument used in this investigation was the optical Iodine Scan Diagnostics (ISD) of generated atomic iodine, based on the tunable diode probe laser. Concentration of atomic iodine was mapped by this method in the reactor at different experimental configurations, pressure and concentration of reactants. This research supported by mathematical modeling revealed that, the best arrangement would be generating atomic iodine in a separate reactor and injecting it into the singlet oxygen flow in the COIL.
Two alternative chemical methods of atomic iodine generation for a chemical oxygen-iodine laser (COIL) were studied. These methods are based on fast reactions of gaseous hydrogen iodide with chemically produced chlorine and fluorine atoms. Both processes were studied first in small-scale reactors. A yield of atomic iodine in the Cl system and nitrogen (non-reactive) atmosphere exceeded 80%, while in the F system it was only up to 27% related to F2 or 50% related to HI. The process of atomic iodine generation via Cl atoms was employed in operation of the supersonic COIL. A laser power of 430 W at 40 mmol Cl2/s, and the small signal gain up to 0.4%/cm were attained. The proposed methods promise an increase in laser power, easier control of laser operation, and simpler iodine management in comparison with the conventional source of atomic iodine using I2. The experimental results obtained so far with this experimental arrangement did not proved yet increasing COIL chemical efficiency because some process quenching a part of singlet oxygen was indicated. Therefore a modified experimental set-up has been designed and prepared for further investigation.
New results of experimental investigation of the chemical generation of atomic iodine for a Chemical Oxygen-Iodine Laser (COIL) are presented. Atomic fluorine was produced at first step by the reaction of molecular fluorine with nitrogen oxide. At second step atomic fluorine reacted with hydrogen iodide producing atomic iodine. It follows from obtained results that two experimental arrangements may be used in COIL. First, atomic F generated in a separate reactor may be injected into singlet oxygen stream with a subsequent HI injection. Second, atomic I may be produced in a separate reactor and then injected into a singlet oxygen stream. It was found that yield of the atomic iodine in the second arrangement may be higher, but a higher loss of I atoms at I atoms injection is anticipated due to wall recombination. The processes of I atoms and F atoms injection will be investigated in a near future.
KEYWORDS: Iodine, Fluorine, Chemical species, Gases, Chemical oxygen iodine lasers, Chemical lasers, Temperature metrology, Chlorine, Molecules, Laser beam diagnostics
Chemical generation of atomic iodine for a Chemical Oxygen-Iodine Laser (COIL) was investigated experimentally. This all-gas process includes atomic fluorine as an intermediate species. In the two-step reaction mechanism, F atoms are produced in reaction of molecular fluorine with NO and react further with hydrogen iodide to iodine atoms. The efficiency of this process was studied in dependence on mixing conditions, flow rate of reacting gases and pressure in the reactor. The maximum concentration of atomic iodine was obtained at approximately equimolar ratio of reacting gases (F2, NO and HI), which agrees with the stoichiometry of the production reactions. A shortage of any of the reacting gases limits the rate of atomic iodine formation. A considerable excess of F2 against NO at a simultaneous deficit of HI had a most detrimental effect on atomic iodine production. Sufficiently high concentrations of atomic iodine (5 to 8 x 1015 cm-3) can be achieved by this method even at pressure 4 - 9 kPa that enable to inject the gas with iodine atoms into the singlet oxygen flow upstream the nozzle throat in the chemical oxygen-iodine laser.
Development of a Chemical Oxygen-Iodine Laser (COIL) with alternative ways of atomic iodine generation is aimed at power increase and simplified laser operation. Advantages of chemical generation of atomic iodine using gaseous reactants directly in the laser medium are confronted with disadvantages of using molecular iodine as a source of atomic iodine in conventional COIL devices. Some recent results on COIL operation with chemically generated atomic iodine supported with computational modeling are presented.
KEYWORDS: Fluorine, Iodine, Chemical species, Chemical oxygen iodine lasers, Gases, Temperature metrology, Chemical lasers, Molecules, Laser beam diagnostics, Industrial chemicals
Results of experimental investigation of the chemical generation of atomic iodine for a Chemical Oxygen-Iodine Laser (COIL) are presented. The work was focused on the reaction system with atomic fluorine as an intermediate species produced by the chemical way from gaseous reactants. At the first step, atomic fluorine is produced in reaction of molecular fluorine with nitrogen oxide. Then F atoms react with gaseous hydrogen iodide producing atomic iodine. The efficiency of this two-step process was studied thoroughly in dependence on mixing conditions, flow rate of reacting gases and pressure in the reactor. The results obtained on the small-scale device under experimental conditions simulating pressure and flow conditions in a COIL show that atomic iodine is generated by this alternative, advantageous method with rather high concentrations sufficient for operation of the supersonic COIL.
Two-dimensional CFD model was applied for the study of mixing and reaction between gaseous chlorine dioxide and nitrogen monoxide diluted with nitrogen during atomic iodine generation. The influence of molecular diffusion on the production of atomic chlorine as a precursor of atomic iodine was predominantly studied. The results were compared with one-dimensional modeling of the system.
An alternative chemical way of atomic iodine generation for the chemical oxygen-iodine laser (COIL) was studied. This development was aimed at the laser power increase and simplification of the laser operation control. The method is based on the fast reaction of hydrogen iodide with chemically produced chlorine atoms. Kinetics of the process was studied in two types of the small-scale reactor and verified in the cavity of the supersonic COIL. The optimum yield of atomic iodine formation in the nitrogen atmosphere was very high (up to 100%) even in the COIL cavity and declined slightly with the distance from the supersonic nozzle throat. In the first experiments of atomic iodine generation in the flow of singlet oxygen in COIL, the gain of 0.18%.cm-1 was attained at rather low flow rate of atomic iodine (0.9 mmol.s-1). In earlier investigation of COIL in the conventional arrangement with molecular iodine, no gain was achieved at the corresponding I2 flow rate (0.45 mmol.s-1). In the COIL with the new method of chemical generation of atomic iodine, a nearly constant gain along the flow axis was measured. It gives evidence that there is no strong quencher of excited atomic iodine in the reaction mixture. The published data represent the first results on gain measurement in the COIL with chemically generated atomic iodine. They promise an improvement of the COIL operation using the chemically generated atomic iodine.
A study of recently proposed chemical method of atomic iodine production in the Chemical Oxygen-Iodine Laser (COIL) was performed. The process using gaseous reactants is based on the fast reaction of hydrogen iodide with chemically produced atomic chlorine. In the absence of singlet oxygen, the high yield of atomic iodine was attained (80 to 100 %). In the flow of singlet oxygen, the gain of 0.32 % cm-1 on 3-4 transition in iodine atom was achieved. It was found that both the rate of atomic iodine generation and gain depend substantially on mixing conditions of reacting gases. In laser experiments, effects of ratio of reactants, and their dilution by nitrogen on the laser output power were studied. The output power of 285 W was attained at chlorine flow rate of 27 mmol s-1 corresponding to chemical efficiency of 11.7 %. It was the first time when gain and laser output power were achieved in the COIL with atomic iodine generated by the proposed method.
The results of theoretical and experimental investigation of gas phase chemical generation of atomic iodine, I(2P3/2), for stimulated emission in chemical oxygen-iodine laser (COIL) are presented. The method of I atoms generation employs a principal reaction X+HI implies I(2P3/2)+HX, where X equals F or Cl. A computational modeling was based on the 1D flow development exploring the chemical processes within the reaction systems, and was aimed at the theoretical understanding of the two complex reaction systems and finding out which is better applicable for conditions in COIL. The results of modeling were further used for a design of the device and conditions during the experimental investigation, and for an interpretation of the experimental results. The experimental work has been done, for the present, on the atomic iodine generation via Cl atoms. A high yield of atomic iodine of 70% to 100% (related to the initial HI flow rate) was attained in a flow of nitrogen. Gain was observed in preliminary experiments on the chemical generation of atomic iodine in a flow of singlet oxygen.
The mathematical modeling of reaction systems for chemical generation of atomic iodine is presented. This process can be applied in the chemical oxygen-iodine laser (COIL), where it can save a substantial part of energy of singlet oxygen and so increase the laser output power. The parametric study of the production of atomic fluorine and subsequently atomic iodine in dependence on the pressure and dilution with inert gas was made. The calculation of the interaction between produced atomic iodine and singlet oxygen was made with four different mixing/reacting schemes.
The key results gathered in the COIL Laboratory of the Institute of Physics AS in the Czech Republic since 1985 to date on the experimental and theoretical investigation of Chemical Oxygen-Iodine Laser (COIL), and related problems are reviewed in a certain context of historical perspectives of the COIL research and development.
A method of the chemical production of atomic iodine aimed for application in COIL was studied experimentally. The method is based on chemical generation of chlorine atoms and their subsequent reaction with hydrogen iodide. Effects of initial ratio of reactants and the way of their mixing were investigated and interpreted by means of the developed model of the reaction system. In optimum conditions, the yield of iodine atoms, related to HI, attained 70 - 100 percent.
A purely chemical method was suggested for generation of atomic iodine from gaseous reactants for the use in a COIL. In this method, fluorine or chlorine atoms are produced and subsequently react with hydrogen iodide forming atomic iodine. Both reaction systems were modeled for different reaction conditions. A yield of atomic iodine up to 80 % was achieved in the optimum case for the system leading via chlorine.
A chemical method of atomic iodine generation with a potential application in chemical oxygen-iodine laser (COIL) was investigated experimentally. The process consists in a fast reaction of gaseous hydrogen iodide with chlorine atoms produced in reaction of gaseous chlorine dioxide with nitrogen oxide. In conditions characteristic for a subsonic mixing region of COIL, atomic iodine was produced with a yield of 20-50 %. This is in a fair agreement with results ofmathematical modeling ofthis complex reaction system.
This paper deals with an estimation of the Einstein A-coefficient for spontaneous emission of singlet delta oxygen, 02(1?g), fld contributes to a current discussion that was launched recently about the conventionally used value of 2.58 x 10-4 s-1 by Badger et al.1 (a half-lifetime of O2(1?g) corresponding to 45 min).The A-value is used in a Chemical Oxygen- Iodine Laser (COIL) for an evaluation of O2(1?g) concentration determined from its fundamental emission. The published values of the A-coefficient substantially differ, corresponding to a radiative lifetime of O2(1?g), ??rad from ~53 min to ~151 min. This fact can make questionable an evaluation of COIL performance. In this paper, the Einstein A-coefficient was computed from the comparison of O2(1?g) concentrations obtained by two independent experimental methods - the electron paramagnetic resonance (EPR), and the emission spectroscopy at which a proposed mathematical model for calculation of O2(1?g) concentration was used. Singlet oxygen was generated chemically by the reaction used in a COIL, in contrast to other papers concerned in this fundamental phenomena. A great effort in our work was devoted to the EPR spectra evaluation as it was shown that it affects crucially the resulting value of the A-coefficient. The average value of the Einstein A-coefficient following from our investigation is equal to (2.24 ± 0.40) x 10-4 s-1 that corresponds to ??rad of~ 74 min (a half-lifetime of 51 min)
This paper is a contribution to the current discussion on radiative lifetime, or the Einstein coefficient for spontaneous emission of singlet delta oxygen [O2(1(Delta) g)]. A verification of widely-used the A-coefficient by Badger et al. (2.58 X 10-4 s-1) in emission spectroscopy for determination of O2(1(Delta) g) concentration in Chemical Oxygen-Iodine Laser (COIL) was examined. Two independent comparative techniques, the EPR and emission spectroscopy, completed by a proposed mathematical model for calculation of O2(1(Delta) g) concentration from emission measurements, were employed. Singlet oxygen was generated chemically by a conventional way used in COIL. Within the accuracy of the both experimental techniques, the value of the Einstein A-coefficient estimated by this investigation is equal to (2.31 plus or minus 0.51) X 10-4 s-1, that is slightly less than the Badger et al. value.
A 1D kinetic model of COIL performance based on the concept of mixing length is described. The results of calculations are compared with the experimental data measured on the COIL device in the Institute of Physics, Prague.
Experimental investigation of a jet singlet oxygen generator for a supersonic chemical oxygen-iodine laser was performed aimed to evaluation of the effects of BHP temperature and composition on the water content and other output generator parameters. Laser experiments on a small-scale system were realized to prove the obtained results.
A jet singlet oxygen generator for a supersonic chemical oxygen-iodine laser was studied including singlet delta oxygen, O2(1(Delta) g), and residual chlorine concentration measurements. The investigation was intended mainly for a water vapor measurement in gas effluent of generator in dependence on properties of liquid jets: a chemical composition and temperature of the input liquid (alkaline solution of hydrogen peroxide), a liquid jets diameter and their geometrical arrangement. Effects of these parameters on output power of a small-scale supersonic laser were studied as well. Possible approaches to a chemical fuels management in a chemical oxygen-iodine laser for industrial applications are considered. An 'open loop' cycle with a possible use of sodium hydroxide, and a 'closed loop' cycle with a regeneration of both potassium hydroxide and hydrogen peroxide are discussed.
This presentation is an historical overview of the activities related to the Chemical Oxygen- Iodine Laser conducted in the Czech Republic. It includes small scale basic research, both the experimental and the theoretical, with a view to particular topics of this laser system in the cw and the pulsed regime of generation.
An effect of various arrangement of liquid jets and jet diameters on singlet oxygen yield, residual chlorine and water vapor content has been studied experimentally in a jet singlet oxygen generator for a chemical oxygen-iodine laser.
A new concept of singlet oxygen generator with respect to a chemical oxygen-iodine laser has been investigated experimentally. The idea is based on the photodynamic effect (a photo- assisted transfer of energy) in the system of solid photosensitizer -- dioxygen -- source of UV/VIS radiation for singlet oxygen production in gaseous phase. Preliminary experiments on fullerenes C60/C70, methylene dye and phtalocyanine like substance, respectively, used as solid photosensitizers have been attempted.
This paper brings experimental results on a repetitively pulsed Chemical Oxygen-Iodine Laser (COIL) using a gain modulation or switching by means of an externally applied magnetic field, based on the Zeeman effect. A peak-to-average laser power enhancement factor and a power conservation factor were evaluated from these experiments in dependence on a magnetic field intensity and a length of magnetic pulses, as well as their shape. A critical view on the pulsed method used is presented.
KEYWORDS: Magnetism, Iodine, Chemical oxygen iodine lasers, Chemical lasers, Resonators, Laser damage threshold, Modulation, Laser resonators, Zeeman effect, Chemical species
A magnetic quenching of generation in a chemical oxygen-iodine laser (COIL) has been studied experimentally. This work gives experimental data on a quenching threshold magnetic field in dependence on a resonator output coupling and an iodine concentration in the laser active zone, respectively.
A magnetic quenching of generation in a chemical oxygen-iodine laser (COIL) has been studied experimentally. This work gives data on a quenching threshold magnetic field in dependence on a resonator output coupling and an iodine concentration in the laser active zone, respectively. It was found that the threshold value of magnetic field was a decreasing function of the output coupling and an increasing function of the iodine molar flow rate. The normalized gain ((alpha) th/(alpha) ) is a decreasing function of the threshold field.
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