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NASA NTRS1995

Spectroscopic Evidence Against Nitric Acid Trihydrate in Polar Stratospheric Clouds

Heterogeneous reactions on polar stratospheric clouds (PSC's) play a key role in the photochemical mechanism thought to be responsible for ozone depletion in the Antarctic and Arctic. Reactions of PSC particles activate chlorine to forms that are capable of photochemical ozone destruction, and sequester nitrogen oxides (NOx) that would otherwise deactivate the chlorine. Although the heterogeneous chemistry is now well established, the composition of the clouds themselves is uncertain. It is commonly thought that they are composed of nitric acid trihydrate, although observations have left this question unresolved. Here we reanalyse infrared spectra of type 1 PSCs obtained in Antarctica in September 1987, using recently measured optical constants of the various compounds that might be present in PSCs. We find these PSCs were not composed of nitric acid trihydrate but instead had a more complex compositon, perhaps that of a ternary solution. Because cloud formation is sensitive to their composition, this finding will alter our understanding of the locations and conditions in which PSCs form. In addition, the extent of ozone loss depends on the ability of the PSCs to remove NOx permanently through sedimentation, The sedimentation rates depend on PSC particle size which in turn is controlled by the composition and formation mechanism.

Toon, Owen B.↗
NASA NTRS1995

Spectroscopic Evidence Against Nitric Acid Trihydrate in Polar Stratospheric Clouds

Heterogeneous reactions on polar stratospheric clouds (PSC's) play a key role in the photochemical mechanisms thought to be responsible for ozone depletion in the Antarctic and the Arctic. Reactions on PSC particles activate chlorine to forms that are capable of photochemical ozone destruction, and sequester nitrogen oxides (NOx) that would otherwise deactivate the chlorine. Although the heterogeneous chemistry is now well established, the composition of the clouds themselves is uncertain. It is commonly thought that they are composed of nitric acid trihydrate, although observations have left this question unresolved. Here we reanalyse infrared spectra of type I PCS's obtained in Antarctica in September 1987, using recently measured optical constraints of the various compounds that might be present in PSC's. We find that these PSC's were not composed of nitric acid trihydrate but instead had a more complex composition perhaps that of a ternary solution. Because cloud formation is sensitive to their composition, this finding will alter our understanding of the locations and conditions in which PSCs form. In addition, the extent of ozone loss depends on the ability of the PSC's to remove NOx permanently through sedimentation. The sedimentation rates depend on PSC particle size which in turn is controlled by the composition and formation mechanism.

Toon, Owen B.↗
NASA NTRS1996

Atomization and Dispersion of a Liquid Jet Injected Into a Crossflow of Air

In recent years, environmental regulations have become more stringent, requiring lower emissions of mainly nitrogen oxides (NOx), as well as carbon monoxide (CO) and unburned hydrocarbons (UHC). These regulations have forced the gas turbine industry to examine non-conventional combustion strategies, such as the lean burn approach. The reasoning behind operating under lean conditions is to maintain the temperature of combustion near and below temperatures required for the formation of thermal nitric oxide (NO). To be successful, however, the lean processes require careful preparation of the fuel/air mixture to preclude formation of either locally rich reaction zones, which may give rise to NO formation, or locally lean reaction zones, which may give rise to inefficient fuel processing. As a result fuel preparation is crucial to the development and success of new aeroengine combustor technologies. A key element of the fuel preparation process is the fuel nozzle. As nozzle technologies have developed, airblast atomization has been adopted for both industrial and aircraft gas turbine applications. However, the majority of the work to date has focused on prefilming nozzles, which despite their complexity and high cost have become an industry standard for conventional combustion strategies. It is likely that the new strategies required to meet future emissions goals will utilize novel fuel injector approaches, such as radial injection. This thesis proposes and demonstrates an experiment to examine, on a mechanistic level (i.e., the physics of the action), the processes associated with the atomization, evaporation, and dispersion of a liquid jet introduced, from a radial, plain-jet airblast injector, into a crossflow of air. This understanding requires the knowledge not only of what factors influence atomization, but also the underlying mechanism associated with liquid breakup and dispersion. The experimental data acquired identify conditions and geometries for improved performance of radial airblast injectors.

Seay, J. E.↗
NASA NTRS1997

A Pilot-Scale Evaluation of a New Technology to Control NO(x) Emissions from Boilers at KSC: Hydrogen Peroxide Injection into Boiler Flue Gases Followed by Wet Scrubbing of Acid Gases

Emissions of nitrogen oxides NO(x) are a significant problem in the United States. NO(x) are formed in any combustion process, therefore it is not surprising that NO(x) are emitted from the boilers at KSC. Research at UCF has shown (in the laboratory) that injecting H2O2 into hot simulated flue gases can oxidize the NO and NO2 to their acid gas forms, HNO2 and HNO3, respectively. These acid gases are much more water soluble than their counterparts, and theoretically can be removed easily by wet scrubbing. This technology was of interest to NASA, both for their boilers at KSC, and for their combustion sources elsewhere. However, it was necessary to field test the technology and to provide pilot-scale data to aid in design of full-scale facilities. Hence this project was initiated in May of 1996.

Cooper, C. David↗
NASA NTRS1997

Development of High Temperature Gas Sensor Technology

The measurement of engine emissions is important for their monitoring and control. However, the ability to measure these emissions in-situ is limited. We are developing a family of high temperature gas sensors which are intended to operate in harsh environments such as those in an engine. The development of these sensors is based on progress in two types of technology: (1) The development of SiC-based semiconductor technology; and (2) Improvements in micromachining and microfabrication technology. These technologies are being used to develop point-contact sensors to measure gases which are important in emission control especially hydrogen, hydrocarbons, nitrogen oxides, and oxygen. The purpose of this paper is to discuss the development of this point-contact sensor technology. The detection of each type of gas involves its own challenges in the fields of materials science and fabrication technology. Of particular importance is sensor sensitivity, selectivity, and stability in long-term, high temperature operation. An overview is presented of each sensor type with an evaluation of its stage of development. It is concluded that this technology has significant potential for use in engine applications but further development is necessary.

Hunter, Gary W.↗
NASA NTRS1997

Chemical Gas Sensors for Aeronautic and Space Applications

Aeronautic and space applications require the development of chemical sensors with capabilities beyond those of commercially available sensors. Two areas of particular interest are safety monitoring and emission monitoring. In safety monitoring, detection of low concentrations of hydrogen at potentially low temperatures is important while for emission monitoring the detection of nitrogen oxides, hydrogen, hydrocarbons and oxygen is of interest. This paper discusses the needs of aeronautic and space applications and the point-contact sensor technology being developed to address these needs. The development of these sensors is based on progress in two types of technology: (1) Micromachining and microfabrication technology to fabricate miniaturized sensors. (2) The development of high temperature semiconductors, especially silicon carbide. The detection of each type of gas involves its own challenges in the fields of materials science and fabrication technology. The number of dual-use commercial applications of this microfabricated gas sensor technology make this general area of sensor development a field of significant interest.

Hunter, Gary W.↗
NASA NTRS1997

Characteristic of Nitron for Use as a Chemical Sensor in Studies of the Upper Atmosphere

We are investigating the use of nitron as a potential chemical sensor for nitric acid and other electron deficient nitrogen oxides. Solutions of nitron in 1-propanol, toluene, and chloroform have been tested for use on a piezoelectric quartz crystal microbalance. We are testing various solvents and metal cations which can maximize the lifetime and reaction specificity of nitron so that they may be used as chemical coatings for stratospheric measurement of trace gases. Results of the work to date will be shown, and future direction discussed.

Meadows, Kapres↗
NASA NTRS1997

SiC-Based Gas Sensors

Electronic grade Silicon Carbide (SiC) is a ceramic material which can operate as a semiconductor at temperatures above 600 C. Recently, SiC semiconductors have been used in Schottky diode gas sensor structures. These sensors have been shown to be functional at temperatures significantly above the normal operating range of Si-based devices. SiC sensor operation at these higher temperatures allows detection of gases such as hydrocarbons which are not detectable at lower temperatures. This paper discusses the development of SiC-based Schottky diode gas sensors for the detection of hydrogen, hydrocarbons, and nitrogen oxides (NO(x)). Sensor designs for these applications are discussed. High sensitivity is observed for the hydrogen and hydrocarbon sensors using Pd on SiC Schottky diodes while the NO(x) sensors are still under development. A prototype sensor package has been fabricated which allows high temperature operation in a room temperature ambient by minimizing heat loss to that ambient. It is concluded that SiC-based gas sensors have considerable potential in a variety of gas sensing applications.

Chen, Liang-Yu↗
NASA NTRS1997

The Kinetic Nonequilibrium Processes in the Internal Flow and in the Plume of Subsonic and Supersonic Aircrafts

(1) Our results show that under combustion of thermal destruction products of n-C8H18, and other hydrocarbon fuels with air at the equivalent ratio -0.5 and less the chemical equilibrium is not realized at the exit plane of combustion chamber and in the gas turbine and nozzle for most of small components such as NO2, NO3, HNO, HNO2, HNO3, N(x)H(y), HO2, OH. The chemical equilibrium is not realized in the internal flow of ramjet hydrogen combustion engine too. So at the nozzle exit plane both of gas-turbine hydrocarbon combustion engine and of ramjet hydrogen combustion engine the relatively large values of concentration of such small components as NO3, HNO2, N2O, HNO3, HNO, NH, N2H, HO2, H2O2 may be realized. The exact definition of these component concentration as well as concentration of NO(x), OH, SO2, O, H, H2, H2O at the nozzle exit plane is very important for plume chemistry. (2) The results which were obtained for subsonic and hypersonic aircrafts indicate on the considerable change of the composition of the gas mixture along the plume. This change can be caused not only by the mixture of combustion products with the atmosphere air but by proceeding of whole complex of nonequilibrium photochemical reactions. The photodissociation processes begin to influence on the formation of the free atoms and radicals at flight altitude H greater than or equal to 18 km. Neglect of these processes can result in essential (up to 10(exp 4) times) mistakes of values gamma(sub OH), gamma(sub O), gamma(sub H), gamma(sub HSO3) and some products of CFC's disintegration. It was found that penetration of Cl-containing species from the atmosphere into the exhaust flow and its interaction with nitrogen oxides leads to essential increasing of the concentration of Cl, Cl2, ClO2, ClNO3, CH3Cl and sometimes HCl and the decreasing of ClO concentration by comparison with background values. The results of our analysis show that the plume aircraft with both hydrocarbon and hydrogen combustion engine may be source of various pollutant components such as HNO, HNO4,ClO2, CH3NO2, CH3NO3, CH2O, Cl, H2O2, but not only NO, NO2, HNO2, HNO3, N2O5, SO2, SO3, H2SO4 as it was supposed before.

Starik, Alexander M.↗
NASA NTRS1994

The Distribution of Hydrogen, Nitrogen, and Chlorine Radicals in the Lower Stratosphere: Implications for Changes in O3 due to Emission of NO(y) from Supersonic Aircraft

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained in the lower stratosphere during the Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE) are compared to results from a photochemical model that assimilates measurements of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N2O5 agree well with measured concentrations of NO and ClO, but concentrations of HO2 and OH are underestimated by 10 to 25%, concentrations of NO2 are overestimated by 10 to 30%, and concentrations of HCl are overestimated by a factor of 2. Discrepancies for [OH] and [HO2] are reduced if we allow for higher yields of O(sup 1)D) from 03 photolysis and for heterogeneous production of HNO2. The data suggest more efficient catalytic removal of O3 by hydrogen and halogen radicals relative to nitrogen oxide radicals than predicted by models using recommended rates and cross sections. Increases in [O3] in the lower stratosphere may be larger in response to inputs of NO(sub y) from supersonic aircraft than estimated by current assessment models.

Salawitch, R. J.↗
NASA NTRS1998

Year 2015 Aircraft Emission Scenario for Scheduled Air Traffic

This report describes the development of a three-dimensional scenario of aircraft fuel burn and emissions (fuel burned, NOx, CO, and hydrocarbons)for projected year 2015 scheduled air traffic. These emission inventories are available for use by atmospheric scientists conducting the Atmospheric Effects of Aviation Project (AEAP) modeling studies. Fuel burned and emissions of nitrogen oxides (NOx as NO2), carbon monoxides, and hydrocarbons have been calculated on a 1 degree latitude x 1 degree longitude x 1 kilometer altitude grid and delivered to NASA as electronic files.

Baughcum, Steven L.↗
NASA NTRS1998

Aircraft Emission Scenarios Projected in Year 2015 for the NASA Technology Concept Aircraft (TCA) High Speed Civil Transport

This report describes the development of a three-dimensional database of aircraft fuel burn and emissions (fuel burned, NOx, CO, and hydrocarbons) from projected fleets of high speed civil transports (HSCTs) on a universal airline network. Inventories for 500 and 1000 HSCT fleets, as well as the concurrent subsonic fleets, were calculated. The HSCT scenarios are calculated using the NASA technology concept airplane (TCA) and update an earlier report. These emissions inventories are available for use by atmospheric scientists conducting the Atmospheric Effects of Stratospheric Aircraft (AESA) modeling studies. Fuel burned and emissions of nitrogen oxides (NOx as NO2), carbon monoxide, and hydrocarbons have been calculated on a 1 degree latitude x 1 degree longitude x 1 kilometer pressure altitude grid and delivered to NASA as electronic files.

Baughcum, Steven L.↗
NASA NTRS1995

Fuel-Air Mixing Effect on Nox Emissions for a Lean Premixed-Prevaporized Combustion System

The lean premixed-prevaporized (LPP) concept effectively meets low nitrogen oxides (NOx) emission requirements for combustors with the high inlet temperature and pressure typical of the High-Speed Civil Transport (HSCT). For the LPP system fuel-air mixture uniformity is probably the most important factor for low NOx emissions. Previous studies have suggested that the fuel-air mixture uniformity can be severely affected by changing the number and configuration of fuel injection points. Therefore, an experimental study was performed to determine how the number of fuel injection points and their arrangement affect NOx emissions from an LPP system. The NOx emissions were measured by a gas-sampling probe in a flame-tube rig at the following conditions: inlet temperature of 810 K (1000 F), rig pressure of 10 atm, reference velocity of 150 ft/s, and residence time near 0.005 s. Additionally, a focused Schlieren diagnostic technique coupled with a high speed camera was used to provide a qualitative description of the spatial flow field.

Lee, Chi-Ming↗
NASA NTRS1993

Chemical Loss of Ozone in the Arctic Polar Vortex in the Winter of 1991-1992

In situ measurements of chlorine monoxide, bromine monoxide, and ozone are extrapolated globally, with the use of meteorological tracers, to infer the loss rates for ozone in the Arctic lower stratosphere during the Airborne Arctic Stratospheric Expedition II (AASE II) in the winter of 1991-1992. The analysis indicates removal of 15 to 20 percent of ambient ozone because of elevated concentrations of chlorine monoxide and bromine monoxide. Observations during AASE II define rates of removal of chlorine monoxide attributable to reaction with nitrogen dioxide (produced by photolysis of nitric acid) and to production of hydrochloric acid. Ozone loss ceased in March as concentrations of chlorine monoxide declined. Ozone losses could approach 50 percent if regeneration of nitrogen dioxide were inhibited by irreversible removal of nitrogen oxides (denitrification), as presently observed in the Antarctic, or without denitrification if inorganic chlorine concentrations were to double.

Salawitch, R. J.↗
NASA NTRS1998

Chemistry and dynamics of the lower troposphere over North America and the North Atlantic Ocean in fall 1997 observed using an airborne UV DIAL system

The NASA Langley Research Center's airborne UV Differential Absorption Lidar (DIAL) system participated in the Subsonic Assessment, Ozone and Nitrogen Oxide Experiment (SONEX) mission from October 13 to November 12, 1997. The purpose of the mission was to study the upper troposphere/lower stratosphere in and near the North Atlantic flight corridor to better understand this region of the atmosphere and how civilian air travel in the corridor might be affecting the atmospheric chemistry. Bases of operations included NASA Ames, California (37.4 deg N, 122.1 deg W); Bangor, Maine (44.8 deg N, 68.8 deg W); Shannon, Ireland (52.7 deg N, 8.9 deg W); and Lajes, Terceira Island, Azores (38.8 deg N, 27.1 deg W). Since the UV DIAL system observes in the nadir as well as the zenith, aerosol and ozone data were obtained from near the Earth's surface to the lower stratosphere. A number of interesting features were noted relating to both chemistry and dynamics of the troposphere, which are reported here.

Grant, William B.↗
NASA NTRS1996

NOx Emissions from a Lobed Fuel Injector/Burner

The present experimental study examines the performance of a novel fuel injector/burner configuration with respect to reduction in nitrogen oxide NOx emissions. The lobed injector/burner is a device in which very rapid initial mixing of reactants can occur through strong streamwise vorticity generation, producing high fluid mechanical strain rates which can delay ignition and thus prevent the formation of stoichiometric diffusion flames. Further downstream of the rapid mixing region. this flowfield produces a reduced effective strain rate, thus allowing ignition to occur in a premixed mode, where it is possible for combustion to take place under locally lean conditions. potentially reducing NOx emissions from the burner. The present experiments compare NO/NO2/NOx emissions from a lobed fuel injector configuration with emissions from a straight fuel injector to determine the net effect of streamwise vorticity generation. Preliminary results show that the lobed injector geometry can produce lean premixed flame structures. while for comparable flow conditions, a straight fuel injector geometry produces much longer. sooting diffusion flames or slightly rich pre-mixed flames. NO measurements show that emissions from a lobed fuel injector/burner can be made significantly lower than from a straight fuel injector under comparable flow conditions.

Mitchell, M. G.↗
NASA NTRS1998

Microfabricated Chemical Sensors for Safety and Emission Control Applications

Chemical sensor technology is being developed for leak detection, emission monitoring, and fire safety applications. The development of these sensors is based on progress in two types of technology: 1) Micromachining and microfabrication (MicroElectroMechanical Systems (MEMS)-based) technology to fabricate miniaturized sensors. 2) The development of high temperature semiconductors, especially silicon carbide. Using these technologies, sensors to measure hydrogen, hydrocarbons, nitrogen oxides, carbon monoxide, oxygen, and carbon dioxide are being developed. A description is given of each sensor type and its present stage of development. It is concluded that microfabricated sensor technology has significant potential for use in a range of aerospace applications.

Hunter, G. W.↗
NASA NTRS1998

Tropospheric- Stratospheric Measurement Studies Summary

The two high altitude aircraft, ER-2 NASA #706 and 709 and the DC-8 NASA #717 are in active use in several programs of upper atmospheric research to study polar ozone changes, stratospheric-tropospheric exchange processes and atmospheric effects of aviation aircraft. The ER-2 has participated in seven major missions which mainly concentrated on vortex dynamics and the large losses of Ozone in the Polar regions (Ozone hole) observed in the spring. One mission verified the complex dynamical chemical and physical processes that occur during sunrise and sunset. Stratospheric Tracers of Atmospheric Transport (STRAT) obtained background measurements using the full ER-2 suite of instruments. Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) in 1997 assisted in understanding the mid-latitude and Arctic Ozone losses during the Northern Summer. The DC-8 with the Meteorological Measurement System (MMS) has participated in the Subsonic Aircraft: Cloud and Contrail Effects Special Study (SUCCESS), in 1996 and the Subsonic assessment Ozone and Nitrogen oxide experiment (SONEX) in 1997 missions. The MMS with its sophisticated software accurately measures ground speed and attitude, in-situ static and dynamic pressure total temperature, which are used to calculate the three dimensional wind fields, static pressure, temperature and turbulence values to meteorological accuracy. The meteorological data is not only of interest for its own sake in atmospheric dynamical processes such as mountain waves and flux measurements; but is also required by other ER-2 experiments that simultaneously measure water vapor, O3, aerosols, NO, HCl, CH4, N2O, ClO, BrO, CO2, NOy, HOx and temperature gradients. MMS products are extensively used to assist in the interpretation of their results in understanding the importance of convective effects relative to in-situ chemical changes, as may be noted by examining the list of references attached. The MMS consists of three subsystems: (a) aircraft instrumentation, inertial navigation system (INS), static and dynamic pressure taps, (b) additional dedicated instrumentation measuring angle of attack, yaw, total temperature, and a GPS which on the DC-8 measures position, velocity and attitude (c) an on board data, storage and computing acquisition system. This instrumentation and the associated software requires both an on-going laboratory ground calibration procedure for the total air temperature, static and total pressure inputs, verification of the INS dynamic response and also extensive air measurements and intercomparisons which ultimately verify and calibrate the complete system and its software. More than the usual accuracy is required because of the near cancellation occurring in the difference between the ground speed and true airspeed vectors used to give the wind vector. In the past year we have redesigned, recalibrated and used the MMS system on the NASA DC-8 that was previously used in the SUCCESS mission for the SONEX mission. Two papers were co-authored based on SUCCESS flights. Several reports and handouts were written for SONEX. Calibrations of the DC-8 pressure transducer temperature measuring thermistors was completed and an extensive analysis spanning several years of data files of the DC-8 Rosemount pressure transducer calibrations was done.

Browen, Stuart W.↗