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NASA NTRS1997

Combustibility Tests of 1,1,1,2-tetrafluoroethane in a Simulated Compressor Cylinder

The advantages of high-molecular-weight gas (heavy gas) as a wind-tunnel medium have been recognized for some time. The current heavy gas of choice chlorofluorocarbon-12(CFC-12) (refrigerant R12) for the Transonic Dynamics Tunnel(TDT) must be replaced because manufacture of this gas ceased in 1995. An attractive replacement is 1,1,1,2-tetrafluoroethane (refrigerant R134a). Acceptable properties of this gas include molecular weight and speed of sound. Its vapor pressure allows simplified reclamation from mixtures with air. However, it is recognized that R134a is combustible under certain conditions of temperature, pressure, and concentration. A comprehensive study was conducted to identify those conditions and the influence of various parameters on the combustibility of the gas-air mixture.

Babcock, Dale A.↗

NASA NTRS1997

Replacement Technologies for Precision Cleaning of Aerospace Hardware for Propellant Service

The NASA White Sands Test Facility (WSTF) is developing cleaning and verification processes to replace currently used chlorofluorocarbon-l13- (CFC-113-) based processes. The processes being evaluated include both aqueous- and solvent-based techniques. Replacement technologies are being investigated for aerospace hardware and for gauges and instrumentation. This paper includes the findings of investigations of aqueous cleaning and verification of aerospace hardware using known contaminants, such as hydraulic fluid and commonly used oils. The results correlate nonvolatile residue with CFC 113. The studies also include enhancements to aqueous sampling for organic and particulate contamination. Although aqueous alternatives have been identified for several processes, a need still exists for nonaqueous solvent cleaning, such as the cleaning and cleanliness verification of gauges used for oxygen service. The cleaning effectiveness of tetrachloroethylene (PCE), trichloroethylene (TCE), ethanol, hydrochlorofluorocarbon 225 (HCFC 225), HCFC 141b, HFE 7100(R), and Vertrel MCA(R) was evaluated using aerospace gauges and precision instruments and then compared to the cleaning effectiveness of CFC 113. Solvents considered for use in oxygen systems were also tested for oxygen compatibility using high-pressure oxygen autogenous ignition and liquid oxygen mechanical impact testing.

Harold Beeson↗

NASA NTRS1997

Comparison of Environmentally Friendly Space Compatible Grease to its Predecessor in a Space Mechanism Bearing Test Rig

Perfluoroakylpolyether (PFPE) greases are used extensively in critical flight hardware in a space environment. In the past, these greases have been processed using chlorofluorocarbon (CFC) based solvents. In response to the recent ban of CFC's, new formulations of environmentally friendly PFPE greases that are not processed with CFC based solvents were developed. The purpose of this study was to compare the performance of a new environmentally friendly formulation PFPE grease to a previously proven space compatible formulation PFPE grease. A one year test using 20 small electrical motors (two bearings per motor) was conducted in a high vacuum environment(2.0 x 10(exp 4)) Torr at a temperature of 90 C. Twenty bearings were lubricated with a new environmentally friendly formulation, and twenty bearings were lubricated with an old formulation. The mass of each lubricated bearing was measured both pre and post test. Along with mass loss measurements a profilometer trace was taken to measure post test wear of the bearings. In addition the bearings were visually examined and analyzed using an optical microscope.

T R Jett↗

NASA NTRS1996

Chemical Characteristics of Continental Outflow Over the Tropical South Atlantic Ocean from Brazil and Africa

The chemical characteristics of air parcels over the tropical South Atlantic during September - October 1992 are summarized by analysis of aged marine and continental outflow classifications. Positive correlations between CO and CH3CL and minimal enhancements of C2CL40, and various ChloroFluoroCarbon (CFC) species in air parcels recently advected over the South Atlantic basin strongly suggest an impact on tropospheric chemistry from biomass burning on adjacent continental areas of Brazil and Africa. Comparison of the composition of aged Pacific air with aged marine air over the South Atlantic basin from 0.3 to 12.5 km altitude indicates potential accumulation of long-lived species during the local dry season. This may amount to enhancements of up to two-fold for C2H6, 30% for CO, and 10% for CH3Cl. Nitric oxide and NO(x) were significantly enhanced (up to approx. 1 part per billion by volume (ppbv)) above 10 km altitude and poorly correlated with CO and CH3Cl. In addition, median mixing ratios of NO and NO(x) were essentially identical in aged marine and continental outflow air masses. It appears that in addition to biomass burning, lightning or recycled reactive nitrogen may be an important source of NO(x) to the upper troposphere. Methane exhibited a monotonic increase with altitude from approx. 1690 to 1720 ppbv in both aged marine and continental outflow air masses. The largest mixing ratios in the upper troposphere were often anticorrelated with CO, CH3Cl, and CO2, suggesting CH, contributions from natural sources. We also argue, based on CH4/CO ratios and relationships with various hydrocarbon and CFC species, that inputs from biomass burning and the northern hemisphere are unlikely to be the dominant sources of CO, CH4 and C2H6 in aged marine air. Emissions from urban areas would seem to be necessary to account for the distribution of at least CH4 and C2H6. Over the African and South American continents an efficient mechanism of convective vertical transport coupled with large-scale circulations conveys biomass burning, urban, and natural emissions to the upper troposphere over the South Atlantic basin. Slow subsidence over the eastern South Atlantic basin may play an important role in establishing and maintaining the rather uniform vertical distribution of long-lived species over this region. The common occurrence of values greater than 1 for the ratio CH3OOH/H2O2 in the upper troposphere suggests that precipitation scavenging effectively removed highly water soluble gases (H2O2, HNO3, HCOOH, and CH3COOH) and aerosols during vertical convective transport over the continents. However, horizontal injection of biomass burning products over the South Atlantic, particularly water soluble species and aerosol particles, was frequent below 6 km altitude.

Talbot, R. W.↗

NASA NTRS1996

Biodegradation of Trihalomethanes and Other Halogenated Aliphatic Compounds

The biological dehalogenation of common water pollutants such as trichloromethane (chloroform) and other halogenated aliphatic compounds was the subject of this project. Samples from diverse water environments such as from groundwater contaminated with halogenated compounds and wastewaters from regional treatment plants were studied to identify conditions that favor certain dehalogenation reactions over others. Gene probe analyses of DNA extracted from the dichlormethane-degrading wastewater indicated the presence of the gene coding for dichloromethane dehalogenase, indicating the genetic basis for the dechlorination activity observed. These studies indicate that methanogenic bacteria are the organisms responsible for the chloroform dechlorination. Dechlorination of a common chlorofluorocarbon (CFC-11) was identified in samples taken from a regional aquifer contaminated with halogenated aliphatic compounds.

HALOGENATED ALIPHATC HYDROCARBONS↗

NASA NTRS1998

Fiber-Optic Coupled Lidar Receiver System to Measure Stratospheric Ozone

The measurement of ozone in the atmosphere has become increasingly important over the past two decades. Significant increases of ozone concentrations in the lower atmosphere, or troposphere, and decreases in the upper atmosphere, or stratosphere, have been attributed to man-made causes. High ozone concentrations in the troposphere pose a health hazard to plants and animals and can add to global warming. On the other hand, ozone in the stratosphere serves as a protective barrier against strong ultraviolet (UV) radiation from the sun. Man-made CFC's (chlorofluorocarbons) act as a catalyst with a free oxygen atom and an ozone molecule to produce two oxygen molecules therefore depleting the protective layer of ozone in the stratosphere. The beneficial and harmful effects of ozone require the study of ozone creation and destruction processes in the atmosphere. Therefore, to provide an accurate model of these processes, an ozone lidar system must be able to be used frequently with as large a measurement range as possible. Various methods can be used to measure atmospheric ozone concentrations. These include different airborne and balloon measurements, solar occulation satellite techniques, and the use of lasers in lidar (high detection and ranging,) systems to probe the atmosphere. Typical devices such as weather balloons can only measure within the direct vicinity of the instrument and are therefore used infrequently. Satellites use solar occulation techniques that yield low horizontal and vertical resolution column densities of ozone.

Harper, David Brent↗

NASA NTRS1998

Analysis of the UV-B Regime and Potential Effects on Alfalfa

Life at the surface of the Earth, over the last 400 m.y., evolved under conditions of decreased short-wave radiation (i.e., ultraviolet) relative to solar output due to absorption and scattering by constituents (e.g., ozone, water vapor, aerosols) in the upper atmosphere. However, a significant amount of ultraviolet radiation in the range from 280-320 nm, known as ultraviolet-B radiation, reaches the Earth's surface and has sufficient energy to be damaging to biologic tissue. Natural fluctuations in atmospheric constituents (seasonal variation, volcanic eruptions, etc.), changes in the orbital attitude of the Earth (precession, axial tilt, orbital eccentricity), and long-term solar variability contribute to changes in the total amount of ultraviolet radiation reaching the surface of the Earth, and thus, the biosphere. More recently, the atmospheric release of commercial propellants and refrigerants, known as chlorofluorocarbons (CFCs), has contributed to a significant depletion in naturally occurring ozone in the stratosphere. Thus, decreased stratospheric ozone has resulted in an increased UV-B flux at the Earth's surface which may have profound effects on terrestrial and marine organisms. In this study, we are investigating the effects of differing solar UV-B fluxes on alfalfa (Medicago sativa L.), an important agricultural crop. A long-term goal of this research is to develop spectral signatures to detect plant response to increased UV-B radiation from remote sensor platforms.

Seitz, Jeffery C.↗

NASA NTRS1999

Effect of Bearing Cleaning on Long Term Bearing Life

For many years chlorofluorocarbon (CFC) based solvents, such as CFC-113 and 1,1,1, trichloroethane (TCA), were used as bearing cleaning solvents for space mechanism bearings. The 1995 ban on the production of ozone depleting chemicals (ODC) such as CFCs caused a change requiring the use of ODC-free cleaners for precision bearing cleaning. With this change the question arises; what effect if any do these new cleaners have on long term bearing life? The purpose of this study was to evaluate this effect. A one year test using 60 small electrical motors (two bearings per motor) was conducted in a high vacuum environment (2.0 x 10(exp -6) torr) at a temperature of 90 C. Prior to testing the bearings were cleaned with one of four cleaners. These cleaners included two aqueous based cleaners, a CFC based cleaner and supercritical carbon dioxide. Three space compatible greases were tested. After testing, the mass of each lubricated bearing was measured both pre and post test. Along with mass loss measurements a profilometer trace of each bearing was taken to measure post test wear of the bearings. In addition, the bearings were visually examined and analyzed using an optical microscope.

Jett, Tim↗

NASA NTRS1999

Aqueous Cleaning and Validation for Space Shuttle Propulsion Hardware at the White Sands Test Facility

The NASA White Sands Test Facility (WSTF) has developed an entirely aqueous final cleaning and verification process to replace the current chlorofluorocarbon (CFC) 113 based process. This process has been accepted for final cleaning and cleanliness verification of WSTF ground support equipment. The aqueous process relies on ultrapure water at 50 C (323 K) and ultrasonic agitation for removal of organic compounds and particulate. The cleanliness is verified bv determining the total organic carbon (TOC) content and filtration with particulate counting. The effectiveness of the aqueous methods for detecting hydrocarbon contamination and particulate was compared to the accepted CFC 113 sampling procedures. Testing with known contaminants, such as hydraulic fluid and cutting and lubricating oils, to establish a correlation between aqueous TOC and CFC 113 nonvolatile residue (NVR) was performed. Particulate sampling on cleaned batches of hardware that were randomly separated and sampled by the two methods was performed. This paper presents the approach and results, and discusses the issues in establishing the equivalence of aqueous sampling to CFC 113 sampling, while describing the approach for implementing aqueous techniques on Space Shuttle Propulsion hardware.

Hornung, Steven D.↗

NASA NTRS1999

Evaluation of Solvent Alternatives for Cleaning of Oxygen Systems

The NASA White Sands Test Facility (WSTF) in a joint program with the Naval Sea Systems Command has evaluated a number of solvents as alternatives to the use of chlorofluorocarbons currently utilized for cleaning of oxygen systems. Particular attention has been given to the cleaning of gauges and instrumentation used in oxygen service, since there have been no identified aqueous alternatives. The requirements identified as selection criteria, include toxicity, physical properties consistent with application, flammability, oxygen compatibility, and cleaning ability. This paper provides a summary of results and recommendations for solvents evaluated to date.

Beeson, Harold↗

NASA NTRS1998

Effect of Bearing Cleaning on Long Term Bearing Life

For many years chlorofluorocarbon (CFC ) based solvents, such as Freon and 1,1,1, Trichloroethane (TCA), were used as bearing cleaning solvents for space mechanisms. The 1995 ban on the production of ozone depleting chemicals (ODC) such as CFCs caused a change to new ODC-free cleaners for the precision bearing cleaning. With this change the question arises what effect if any do these new cleaners have on long term bearing life. The purpose of this study was to evaluate this effect. A one year test using 60 small electrical motors (two bearings per motor) was conducted in a high vacuum environment (2.0* 10(exp -6) torr) at a temperature of 90C. Prior to testing the bearings were cleaned with one of four cleaners. These cleaners included two aqueous based cleaners, a CFC based cleaner and supercritical carbon dioxide. Three space compatible greases were tested. After testing the mass of each lubricated bearing was measured both pre and post test. Along with mass loss measurements a profilometer trace of each bearing was taken to measure post test wear of the bearings. In addition the bearings were visually examined and analyzed using an optical microscope.

Jett, Timothy Raymond↗

NASA NTRS1999

History of Ozone Research: From Schonbein to the Present

In 1840, C.F. Schonbein recognized that the smell generated in several different electrical and chemical processes was a single substance. He named this substance "ozein" from the Greek for "to smell". This substance we know today as ozone. Several periods can be distinguished in the continued development of our understanding of ozone. Throughout the late 19th century, the identity and properties of ozone were established and described. Ozone was recognized to be a constituent of normal air and tests were established to measure its concentration. Its disinfectant properties were recognized. New methods were developed for making ozone in the laboratory. In 1879, ultraviolet spectroscopic techniques were applied to the measurement of the solar spectrum and it was discovered by Comu that the spectrum was cut off at about 300 nm wavelength. Hartley suggested, based on laboratory measurements, that this cutoff was due to ozone in the atmosphere which he correctly asserted was somewhere in the upper atmosphere. This began the period of development of the amount and distribution of ozone throughout the atmosphere. In 1930, Chapman put forward the first theory of the formation and destruction of ozone. By the mid-1960s it was becoming obvious that the description of the chemical loss term was inadequate. By the early 1970s the chemical destruction of ozone by the oxides of hydrogen, nitrogen, chlorine, and bromine was recognized as an essential element in the chemical balance determining the ozone concentration. Today, ozone is a broad research project which crosses the boundaries of traditional disciplines. Stratospheric ozone loss due to chlorofluorocarbons is a newsworthy item. The Antarctic ozone hole opens up every spring. The provisions of the Montreal Protocol were agreed upon by countries around the world and promise to reduce the future levels of ozone-destroying chlorine in the stratosphere. Ozone concentrations in polluted cities are a subject of local and national regulations to limit its potential for causing health problems and corrosive effects on materials. A lot is known about ozone but many new questions are still being developed.

Stolarski, Richard S.↗

NASA NTRS1999

Model Experiments and Model Descriptions

The Second Workshop on Stratospheric Models and Measurements Workshop (M&M II) is the continuation of the effort previously started in the first Workshop (M&M I, Prather and Remsberg [1993]) held in 1992. As originally stated, the aim of M&M is to provide a foundation for establishing the credibility of stratospheric models used in environmental assessments of the ozone response to chlorofluorocarbons, aircraft emissions, and other climate-chemistry interactions. To accomplish this, a set of measurements of the present day atmosphere was selected. The intent was that successful simulations of the set of measurements should become the prerequisite for the acceptance of these models as having a reliable prediction for future ozone behavior. This section is divided into two: model experiment and model descriptions. In the model experiment, participant were given the charge to design a number of experiments that would use observations to test whether models are using the correct mechanisms to simulate the distributions of ozone and other trace gases in the atmosphere. The purpose is closely tied to the needs to reduce the uncertainties in the model predicted responses of stratospheric ozone to perturbations. The specifications for the experiments were sent out to the modeling community in June 1997. Twenty eight modeling groups responded to the requests for input. The first part of this section discusses the different modeling group, along with the experiments performed. Part two of this section, gives brief descriptions of each model as provided by the individual modeling groups.

Jackman, Charles H.↗

NASA NTRS2000

Global Warming in the Twenty-First Century: An Alternative Scenario

A common view is that the current global warming rate will continue or accelerate. But we argue that rapid warming in recent decades has been driven mainly by non-CO2 greenhouse gases (GHGs), such as chlorofluorocarbons, CH4, and N2O, not by the products of fossil fuel burning, CO2 and aerosols, the positive and negative climate forcings of which are partially offsetting. The growth rate of non-CO2 GHGs has declined in the past decade. If sources of CH4 and O3 precursors were reduced in the future, the change in climate forcing by non-CO2 GHGs in the next 50 years could be near zero. Combined with a reduction of black carbon emissions and plausible success in slowing CO2 emissions, this reduction of non-CO2 GHGs could lead to a decline in the rate of global warming, reducing the danger of dramatic climate change. Such a focus on air pollution has practical benefits that unite the interests of developed and developing countries. However, assessment of ongoing and future climate change requires composition specific long-term global monitoring of aerosol properties.

Hansen, James↗

NASA NTRS2001

Nonflammable, Nonaqueous, Low Atmospheric Impact, High Performance Cleaning Solvents

For many years, chlorofluorocarbon (CFC) and chlorocarbon solvents have played an important part in aerospace operations. These solvents found extensive use as cleaning and analysis (EPA) solvents in precision and critical cleaning. However, CFCs and chlorocarbon solvents have deleterious effects on the ozone layer, are relatively strong greenhouse gases, and some are suspect or known carcinogens. Because of their ozone-depletion potential (ODP), the Montreal Protocol and its amendments, as well as other environmental regulations, have resulted in the phaseout of CFC-113 and 1,1,1-trichloroethane (TCA). Although alternatives have been recommended, they do not perform as well as the original solvents. In addition, some analyses, such as the infrared analysis of extracted hydrocarbons, cannot be performed with the substitute solvents that contain C-H bonds. CFC-113 solvent has been used for many critical aerospace applications. CFC-113, also known as Freon (registered) TF, has been used extensively in NASA's cleaning facilities for precision and critical cleaning, in particular the final rinsing in Class 100 areas, with gas chromatography analysis of rinse residue. While some cleaning can be accomplished by other processes, there are certain critical applications where CFC-113 or a similar solvent is highly cost-effective and ensures safety. Oxygen system components are one example where a solvent compatible with oxygen and capable of removing fluorocarbon grease is needed. Electronic components and precision mechanical components can also be damaged by aggressive cleaning solvents.

Dhooge, P. M.↗

NASA NTRS2001

Update: HFC 245fa Blown Foam Development with External Tank Spray Foams

The Marshall Space Flight Center (MSFC) Thermal Protection Systems (TPS) Materials Research Laboratory is currently investigating environmentally friendly blowing agents for use in the insulations of the Space Shuttle's External Tank. The original TPS foam materials of the External Tank were blown with chlorofluorocarbon 11, which is now regulated because of its high Ozone Depletion Potential (ODP). Hydrochlorofluorocarbons (HCFCs), with an ODP that is one tenth that of CFCs, have been widely adopted as an interim blowing agent in urethane insulations. In FY96, Lockheed Martin completed the production qualification and validation of HCFC 141b blown insulations. Because of the expected limited commercial lifetime of HCFC 141b, research efforts are underway to identify and develop alternatives with zero ODP. HFC245fa (1,1,1,3,3-pentaflouropropane) has been chosen by the manufacturer as a third-generation blowing agent to be marketed commercially. Preliminary work evaluating this third-generation candidate has demonstrated promising material mechanical property data. Favorable results from small-scale spray activities have justified evaluations using production foam processing spray parameters. With the scale-up of the spray equipment, however, additional processing issues have been identified. This paper will present data collected to date regarding the use of this blowing agent in External Tank spray foams.

Davis, S.↗

NASA NTRS2000

Global Warming in the Twenty-First Century: An Alternative Scenario

Hansen, James↗

NASA NTRS1995

Monitoring Trace Contaminants in Air Via Ion Trap Mass Spectrometry

Recent passage of the Clean Air Act with its stricter regulation of toxic gas emissions, and the ever-growing number of applications which require faster turnaround times between sampling and analysis are two major factors which are helping to drive the development of new instrument technologies for in-situ, on-line, real-time monitoring. The ion trap, with its small size, excellent sensitivity, and tandem mass spectrometry capability is a rapidly evolving technology which is well-suited for these applications. In this paper, we describe the use of a commercial ion trap instrument for monitoring trace levels of chlorofluorocarbons (CFCs) and volatile organic compounds (VOCs) in air. A number of sample introduction devices including a direct transfer line interface, short column GC, and a cryotrapping interface are employed to achieve increasing levels of sensitivity. MS, MS/MS, and MS/MS/MS methods are compared to illustrate trade-offs between sensitivity and selectivity. Filtered Noise Field (FNF) technology is found to be an excellent means for achieving lower detection limits through selective storage of the ion(s) of interest during ionization. Figures of merit including typical sample sizes, detection limits, and response times are provided. The results indicate the potential of these techniques for atmospheric assessments, the High Speed Research Program, and advanced life support monitoring applications for NASA.

Palmer, Peter T.↗