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Cold plasma processing of local planetary ores for oxygen and metallurgically important metals

The utilization of a cold or nonequilibrium plasma in chlorination processing is discussed. Titanium dioxide (TiO2) was successfully chlorinated at temperatures between 700 and 900 C without the aid of carbon. In addition to these initial experiments, a technique was developed for determining the temperature of a specimen in a plasma. Development of that technique has required evaluating the emissivity of TiO2, ZrO2, and FeOTiO2 and analyzing the specimen temperature in a plasma as a function of both power absorbed by the plasma and the pressure of the plasma. The mass spectrometer was also calibrated with TiCl4 and CCl4 vapor.

Lynch, D. C.

Plastic deformation and wear process at a surface during unlubricated sliding

The plastic deformation and wear of a 304 stainless steel surface sliding against an aluminum oxide rider with a spherical surface (the radius of curvature: 1.3 cm) were observed by using scanning electron and optical microscopes. Experiments were conducted in a vacuum of one million Pa and in an environment of fifty thousandth Pa of chlorine gas at 25 C. The load was 500 grams and the sliding velocity was 0.5 centimeter per second. The deformed surface layer which accumulates and develops successively is left behind the rider, and step shaped proturbances are developed even after single pass sliding under both environmental conditions. A fully developed surface layer is gradually torn off leaving a characteristic pattern. The mechanism for tearing away of the surface layer from the contact area and sliding track contour is explained assuming the simplified process of material removal based on the adhesion theory for the wear of materials.

Yamamoto, T.

Plastic deformation and wear process at a surface during unlubricated sliding

The plastic deformation and wear of a 304 stainless steel surface sliding against an aluminum oxide rider with a spherical surface (the radius of curvature: 1.3 cm) were observed by using scanning electron and optical microscopes. Experiments were conducted in a vacuum of one million Pa and in an environment of fifty thousandth Pa of chlorine gas at 25 C. The load was 500 grams and the sliding velocity was 0.5 centimeter per second. The deformed surface layer which accumulates and develops successively is left behind the rider, and step shaped proturbances are developed even after single pass sliding under both environmental conditions. A fully developed surface layer is gradually torn off leaving a characteristic pattern. The mechanism for tearing away of the surface layer from the contact area and sliding track contour is explained assuming the simplified process of material removal based on the adhesion theory for the wear of materials. Previously announced in STAR as N82-32735

Yamamoto, T.

Introduction and data summary, chapter 5

A subset of data representing most of the participating model groups was discussed and reviewed. The results are presented for intercomparisons of that subset of data. Subsequent to the workshop, the various modeling groups had the opportunity to either update or add to the data sets discussed at the workshop. The overall revised data sets as of December 1988 are presented. Data from all the models (where available) are grouped according to: (1) photochemistry and radiation (photodissociation coefficients, and ultraviolet heating and infrared cooling); (2) transport (net radiative heating, tropospheric source tracer experiment, time-dependent source conserved tracer experiment, stratospheric source tracer experiment, and O3 column); (3) current atmosphere (integrated columns of trace gases, Cl(y) and NO(y), nitrogen gases, chlorine gases, O(x) and HO(x) gases, and source gases); and (4) perturbed circulations and temperatures. The data presented provide a detailed summary of the two-dimensional picture of the atmosphere as seen by current atmospheric models.

Source record

Work Done For the Safety and Assurance Directorate

The Safety and Assurance Directorate (SAAD) has a vision. The vision is to be an essential part of NASA Glenn's journey to excellence. SAAD is in charge of leading safety, security, and quality and is important to our customers. When it comes to programmatic and technical decision making and implementation, SAAD provides clear safety, reliability, maintainable, quality assurance and security. I worked on a couple different things during my internship with Sandra Hardy. I did a lot of logistics for meeting and trips. I helped run the budget for the SAAD directorate. I also worked with Rich Miller for one week and we took water samples and ran tests. We also calibrated the different equipment. There is a lot more to meetings than people see. I did one for a retirement party. I had to get work orders and set up the facilities where the event is going to take place. I also set up a trip to Plum Brook Station. I had to order vans and talk with the people up there to see when a good time was. I also had to make invitations and coordinate everything. I also help Sandy run the numbers in the budget. We use excel to do this, which makes it a lot easier. things. He is in the environmental safety office. I learned how to collaborate the equipment using alpha and beta sources. I went out with him and we took water samples and tested them for conductivity and chlorine. I have learned a lot in the short time I've been here. It has been a great experience and I have has the pleasure of meeting and working with great people.

Struhar, Paul T., Jr.

Shock-tube pyrolysis of chlorinated hydrocarbons - Formation of soot

Soot formation in pyrolysis of chlorinated methanes, their mixtures with methane, and chlorinated ethylenes were studied behind reflected shock waves by monitoring the attenuation of an He-Ne laser beam. An additional single-pulse shock-tube study was conducted for the pyrolysis of methane, methyl chloride, and dichloromethane. The experiments were performed at temperatures 1300-3000 K, pressures of 0.4-3.6 bar, and total carbon atom concentrations of 1-5 x 10 to the 17th atoms cu cm. The amounts of soot produced in the pyrolysis of chlorinated hydrocarbons are larger than that of their nonchlorinated counterparts. The sooting behavior and product distribution can be generally explained in terms of chlorine-catalyzed chemical reaction mechanisms. The pathway to soot from chlorinated methanes and ethylenes with high H:Cl ratio proceeds via the formation of C2H, C2H2, and C2H3 species. For chlorinated hydrocarbons with low H:Cl ratio, the formation of C2 and its contribution to soot formation at high temperatures becomes significant. There is evidence for the importance of CHCl radical and its reactions in the pyrolysis of dichloromethane.

Frenklach, M.

Quasi-Liquid Layer Formation on Ice under Stratospheric Conditions

Characterization of the interaction of hydrogen chloride (HCl) with ice is essential to understanding at a molecular level the processes responsible for ozone depletion involving polar stratospheric cloud (PSC) particles. To explain the catalytic role PSC particle surfaces play during chlorine activation, we proposed previously that HCl induces the formation of a disordered region on the ice surface, a quasi-liquid layer (QLL), at stratospheric conditions. The QLL is known to exist in pure ice crystals at temperatures near the melting point, but its existence at stratospheric temperatures (-85 C to -70 C) had not been reported yet. We studied the interaction of HCl with ice under stratospheric conditions using the complementary approach of a) ellipsometry to directly monitor the ice surface, using chemical ionization mass spectrometry (CIMS) to monitor the gas phase species present in the ellipsometry experiments, and b) flow-tube experiments with CIMS detection. Here we show that trace amounts of HCl induce QLL formation at stratospheric temperatures, and that the QLL enhances the chlorine-activation reaction of HCl with chlorine nitrate (ClONO2), and also enhances acetic acid (CH3COOH) adsorption.

McNeill, V. Faye

Electrochemical Oxidation of Seawater for Renewable Energy Generation and Storage in Coastal Areas

In this work, we demonstrated how the Clean Sustainable Electrochemical Treatment process can be used to process seawater while simultaneously generating molecular hydrogen. The specific goal of this project is to (1) demonstrate selective removal of chemical oxygen demand over the oxygen and chlorine evolution reactions, (2) optimize electrode composition to improve electrochemical performance, and (3) demonstrate long-term (>100 h) stability experiments.

08 HYDROGEN

Airborne Arctic Stratospheric Expedition 2: An overview

The sudden onset of ozone depletion in the antarctic vortex set a precedent for both the time scale and the severity of global change. The Airborne Antarctic Ozone Experiment (AAOE), stages from Punta Arenas, Chile, in 1987, established that CFCs, halons, and methyl bromide, the dominant sources of chlorine and bromide radicals in the stratosphere, control the rate of ozone destruction over the Antarctic; that the vortex is depleted in reactive nitrogen and water vapor; and that diabatic cooling during the antarctic winter leads to subsidence within the vortex core, importing air from higher altitudes and lower latitudes. This last conclusion is based on observed dramatic distortion in the tracer fields, most notably N2O. In 1989, the first Airborne Arctic Stratospheric Expedition (AASE-1), staged from Stavanger, Norway, and using the same aircraft employed for AAOE (the NASA ER-2 and the NASA DC-8), discovered that while NO(x) and to some degree NO(y) were perturbed within the arctic vortex, there was little evidence for desiccation. Under these (in contrast to the antarctic) marginally perturbed conditions, however, ClO was found to be dramatically enhanced such that a large fraction of the available (inorganic) chlorine resided in the form of ClO and its dimer ClOOCl. This leaves two abiding issues for the northern hemisphere and the mission of the second Airborne Arctic Stratospheric Expedition (AASE-2): (1) Will significant ozone erosion occur within the arctic vortex in the next ten years as chlorine loading in the stratosphere exceeds four parts per billion by volume? (2) Which mechanisms are responsible for the observed ozone erosion poleward of 30 deg N in the winter/spring northern hemisphere reported in satellite observations?

Anderson, James G.

Airborne Arctic Stratospheric Expedition 2: An Overview

The sudden onset of ozone depletion in the antarctic vortex set a precedent for both the time scale and the severity of global change. The Airborne Antarctic Ozone Experiment (AAOE), staged from Punta Arenas, Chile, in 1987, established that CFCs, halons, and methyl bromide, the dominant sources of chlorine and bromine radicals in the stratosphere, control the rate of ozone destruction over the Antarctic; that the vortex is depleted in reactive nitrogen and water vapor; and that diabatic cooling during the antarctic winter leads to subsidence within the vortex core, importing air from higher altitudes and lower latitudes. This last conclusion is based on observed dramatic distortion in the tracer fields, most notably N2O. In 1989, the first Airborne Arctic Stratospheric Expedition (AASE-I), staged from Stavanger, Norway, and using the same aircraft employed for AAOE (the NASA ER-2 and the NASA DC-8), discovered that while NO(x) and to some degree NO(y) were perturbed within the arctic vortex, there was little evidence for desiccation. Under these (in contrast to the antarctic) marginally perturbed conditions, however, Cl0 was found to be dramatically enhanced such that a large fraction of the available (inorganic) chlorine resided in the form of Cl0 and its dimer ClOOCl. This leaves two abiding issues for the northern hemisphere and the mission of the second Airborne Arctic Stratospheric Expedition (AASE-II): (1) Will significant ozone erosion occur within the arctic vortex in the next ten years as chlorine loading in the stratosphere exceeds four parts per billion by volume? and (2) Which mechanisms are responsible for the observed ozone erosion poleward of 30 deg N in the winter/spring northern hemisphere reported in satellite observations?

Anderson, James G.

Toxic Hazards Research Unit annual technical report, 1972

The activities of the Toxic Hazards Research Unit (THRU) for the period of June 1971 through May 1972 are reviewed in this report. Acute inhalation toxicity experiments were conducted on hydrogen chloride (HCl) gas and aerosol, ethyl bromide (C2H5Br), hydrogen bromide (HBr), hydrogen sulfide (H2S), ammonia (NH3), chlorine (CL2), and silane (SiH4). Subacute toxicity studies were conducted on chlorine pentafluoride (ClF5), dichloromethane (CH2Cl2) and coal tar volatiles. Further toxicity studies of subacute and chronic responses to inhaled monomethylhydrazine (MMH) are also described.

Macewen, J. D.

Heterogeneous processes: Laboratory, field, and modeling studies

The efficiencies of chemical families such as ClO(x) and NO(x) for altering the total abundance and distribution of stratospheric ozone are controlled by a partitioning between reactive (active) and nonreactive (reservoir) compounds within each family. Gas phase thermodynamics, photochemistry, and kinetics would dictate, for example, that only about 1 percent of the chlorine resident in the lower stratosphere would be in the form of active Cl or ClO, the remainder existing in the reservoir compounds HCl and ClONO2. The consistency of this picture was recently challenged by the recognition that important chemical transformations take place on polar regions: the Airborne Antarctic Ozone Experiment (AAOE) and the Airborne Arctic Stratospheric Expedition (AASA). Following the discovery of the Antarctic ozone hole, Solomon et al. suggested that the heterogeneous chemical reaction: ClONO2(g)+HCl(s) yields Cl2(g)+HNO3(s) could play a key role in converting chlorine from inactive forms into a species (Cl2) that would rapidly dissociate in sunlight to liberate atomic chlorine and initiate ozone depletion. The symbols (s) and (g) denote solid phase, or adsorbed onto a solid surface, and gas phase, respectively, and represent the approach by which such a reaction is modeled rather than the microscopic details of the reaction. The reaction was expected to be most important at altitudes where PSC's were most prevalent (10 to 25 km), thereby extending the altitude range over which chlorine compounds can efficiently destroy ozone from the 35 to 45 km region (where concentrations of active chlorine are usually highest) to lower altitudes where the ozone concentration is at its peak. This chapter will briefly review the current state of knowledge of heterogeneous processes in the stratosphere, emphasizing those results obtained since the World Meteorological Organization (WMO) conference. Sections are included on laboratory investigations of heterogeneous reactions, the characteristics and climatology of PSC's, stratospheric sulfate aerosols, and evidence of heterogeneous chemical processing.

Poole, Lamont R.

Chlorine Nuclear Data Evaluation Aided Through New LANSCE Measurements

The collaboration between the Los Alamos National Laboratory Neutron Science Center (LANSCE) and TerraPower LLC enables the enhanced understanding of fast spectrum critical systems consisting of chlorine. Specifically, TerraPower is interested in updating the nuclear data for the stable isotopes of chlorine, 35 Cl and 37 Cl, because these nuclides are the primary constituents of the chloride fuel salt in the Molten Chloride Reactor Experiment (MCRE), for which TerraPower is leading the design. The Cooperative Research and Development Agreement (CRADA) between the parties is funded by DOE’s Office of Nuclear Energy’s Gateway for Accelerated Innovation in Nuclear (GAIN) initiative to provide the nuclear community with access to the technical, regulatory, and financial support necessary to motivate innovative nuclear reactor technologies toward commercialization. New measurements of 35 Cl(n,p total ) and 35 Cl(n,α total ) were completed at LANSCE to constrain the reaction theory models that are used to generate the updated evaluations. The updated evaluations were then tested across the sensitivities of the MCRE by TerraPower to provide direct feedback to the evaluation for application specific sensitivities.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA

Kinetics of the reactions of ClO with O and with NO

The rate constants k1, k2, and k3 for the reactions Cl + O3 yields ClO + O2 (1), ClO + O yields Cl + O2 (2), and ClO + NO yields Cl + NO2 (3), respectively, were measured by the discharge-flow technique, in which chlorine atoms are added to a flow of O3 and either O or NO in a helium carrier gas. The conditions of the experiment were such that the steady-state concentration ratios of Cl to ClO are simply interpretable in terms of the rate constant ratios k2/k3 or k3/k1. These rate constant ratios were measured over the range 220 to 298 K and combined with the directly determined k1 value to yield k2 and k3. The results are: k1 = 2.12 x 10 to the -11th exp(-157/T); k2 = 3.38 x 10 to -11th exp(75 plus or minus 40/T); and k3 = 1.13 x 10 to the -11th exp(200 plus or minus 30/T) cu cm/sec.

Zahniser, M. S.

Spectroscopic Detection of COClF in the Tropical and Mid-Latitude Lower Stratosphere

We report retrievals of COClF (carbonyl chlorofluoride) based on atmospheric chemistry experiment (ACE) solar occultation spectra recorded at tropical and mid-latitudes during 2004-2005. The COClF molecule is a temporary reservoir of both chlorine and fluorine and has not been measured previously by remote sensing. A maximum COClF mixing ratio of 99.7+/-48.0 pptv (10(exp -12) per unit volume, 1 sigma) is measured at 28km for tropical and subtropical occultations (latitudes below 20deg in both hemispheres) with lower mixing ratios at both higher and lower altitudes. Northern hemisphere mid-latitude mixing ratios (30-50degN) resulted in an average profile with a peak mixing ratio of 51.7+/-32.1 pptv, 1 sigma, at 27 km, also decreasing above and below that altitude. We compare the measured average profiles with the one reported set of in situ lower stratospheric mid-latitude measurements from 1986 and 1987, a previous two-dimensional (2-D) model calculation for 1987 and 1993, and a 2-D-model prediction for 2004. The measured average tropical profile is in close agreement with the model prediction; the northern mid-latitude profile is also consistent, although the peak in the measured profile occurs at a higher altitude (2.5-4.5km offset) than in the model prediction. Seasonal average 2-D-model predictions of the COClF stratospheric distribution for 2004 are also reported.

Rinsland, Curtis P.

Remediation Technologies Eliminate Contaminants

All research and development has a story behind it, says Jacqueline Quinn, environmental engineer at Kennedy Space Center. For Quinn, one such story begins with the Saturn 1B launch stand at Kennedy and ends with a unique solution to a challenging environmental problem. Used in a number of Apollo missions and during the Skylab program, the Saturn 1B launch stand was dismantled following the transition to the Space Shuttle Program and stored in an open field at Kennedy. Decades later, the Center s Environmental Program Office discovered evidence of chemicals called polychlorinated biphenyls (PCBs) in the field s soil. The findings were puzzling since PCBs a toxin classified as a probable carcinogen by the Environmental Protection Agency (EPA) have been banned in the United States since 1979. Before the ban, PCBs were commonly used in transformer oils that leached into the ground when the oils were changed out and dumped near transformer sites, but there were no electrical transformers near the dismantled stand. It soon became apparent that the source of the PCBs was the launch stand itself. Prior to the ban, PCBs were used extensively in paints to add elasticity and other desirable characteristics. The PCB-laden paint on the Saturn 1B launch stand was flaking off into the field s soil. Nobody knew there were PCBs in the paint, says Quinn, noting that the ingredient was not monitored carefully when it was in use in 1960s. In fact, she says, the U.S. EPA was not even established until 1970, a year after Neil Armstrong first set foot on the Moon. Nobody knew any better at the time, Quinn says, but today, we have the responsibility to return any natural environmental media to as close to pristine a condition as possible. Quinn, fellow engineer Kathleen Loftin, and other Kennedy colleagues already had experience developing unprecedented solutions for environmental contamination; the team invented the emulsified zero-valent iron (EZVI) technology to safely treat groundwater tainted by chlorinated solvents once used to clean rocket engine components. The award-winning innovation (Spinoff 2010) is now NASA s most licensed technology to date. PCBs in paint presented a new challenge. Removing the launch stand for recycling proved a difficult operation; the toxic paint had to be fully stripped from the steel structure, a lengthy and costly process that required the stripped paint to be treated before disposal. Noting the lack of efficient, environmentally friendly options for dealing with PCBs, Quinn and her colleagues developed the Activated Metal Treatment System (AMTS). AMTS is a paste consisting of a solvent solution containing microscale particles of activated zero-valent metal. When applied to a painted surface, the paste extracts and degrades the PCBs into benign byproducts while leaving the paint on the structure. This provides a superior alternative to other methods for PCB remediation, such as stripping the paint or incinerating the structure, which prevents reuse and can release volatized PCBs into the air. Since its development, AMTS has proven to be a valuable solution for removing PCBs from paint, caulking, and various insulation and filler materials in older buildings, naval ships, and former munitions facilities where the presence of PCBs interferes with methods for removing trace explosive materials. Miles of potentially toxic caulking join sections of runways at airports. Any of these materials installed before 1979 potentially contain PCBs, Quinn says. "This is not just a NASA problem," she says. "It s a global problem."

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Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

Molina, M. J.

Lagrangian photochemical modeling studies of the 1987 Antarctic spring vortex. II - Seasonal trends in ozone

A photochemical model consisting of 40 species and 107 reactions is integrated along 80-day air parcel trajectories calculated in the lower stratosphere for the springtime Antarctic. For the trajectory starting at 58 deg S, which may be regarded as outside the circumpolar vortex, only a small change in O3 occurs in the model. In contrast, for the air parcel starting in the vortex at 74 deg S, the O3 concentration is reduced by 93 percent during the 80 days from the beginning of August to late October. The model results for several species are compared with measurements from the Airborne Antarctic Ozone Experiment and, in general, good agreement is obtained. In the model, the dentrification of the air parcels in polar stratospheric clouds increases the amount of chlorine present in active form. Heterogeneous reactions maintain high active chlorine which destroys O3 via the formation of the ClO dimer. Results of calculations with reduced concentrations of inorganic chlorine show considerably reduced O3 destruction rates and compare favorably with the behavior of total O3 since the late 1970s. The remaining major uncertainties in the photochemical aspects of the Antarctic ozone hole are highlighted.

Austin, J.