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Fischer-Tropsch Cobalt Catalyst Improvements with the Presence of TiO2, La2O3, and ZrO2 on an Alumina Support

The objective of this study was to evaluate the effect of titanium oxide, lanthanum oxide, and zirconium oxide on alumina supported cobalt catalysts. The hypothesis was that the presence of lanthanum oxide, titanium oxide, and zirconium oxide would reduce the interaction between cobalt and the alumina support. This was of interest because an optimized weakened interaction could lead to the most advantageous cobalt dispersion, particle size, and reducibility. The presence of these oxides on the support were investigated using a wide range of characterization techniques such as SEM, nitrogen adsorption, x-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed reduction after reduction (TPR-AR), and hydrogen chemisorptions/pulse reoxidation. Results indicated that both La2O3 and TiO2 doped supports facilitated the reduction of cobalt oxide species in reference to pure alumina supported cobalt catalysts, however further investigation is needed to determine the effect of ZrO2 on the reduction profile. Results showed an increased corrected cluster size for all three doped supported catalysts in comparison to their reference catalysts. The increase in reduction and an increase in the cluster size led to the conclusion that the support-metal interaction weakened by the addition of TiO2 and La2O3. It is also likely that the interaction decreased upon presence of ZrO2 on the alumina, but further research is necessary. Preliminary results have indicated that the alumina-supported catalysts with titanium oxide and lanthanum oxide present are of interest because of the weakened cobalt support interaction. These catalysts showed an increased extent of reduction, therefore more metallic cobalt is present on the support. However, whether or not there is more cobalt available to participate in the Fischer-Tropsch synthesis reaction (cobalt surface atoms) depends also on the cluster size. On one hand, increasing cluster size alone tends to decrease the active site density; on the other hand, by increasing the size of the cobalt clusters, there is less likelihood of forming oxidized cobalt complexes (cobalt aluminate) during Fischer-Tropsch synthesis. Thus, from the standpoint of stability, improving the extent of reduction while increasing the particle size slightly may be beneficial for maintaining the sites, even if there is a slight decrease in overall initial active site density.

Klettlinger, Jennifer Lindsey Suder↗

Life's Requirements

Life on Earth is molecular in nature, with its lifelike attributes- e.g., information processing and catalysis- emerging as a result of both the specific properties of those molecules and the interactions among them. If this is a general model for life, then life must require (i) a source of energy, with which to build and sustain molecular complexity and information processing; (ii) elemental raw materials, from which to construct molecules having specific properties and reactivity; (iii)a solvent that supports the synthesis of the full range of molecules required by life and properly mediates the full range of necessary interactions among those molecules; and (iv) physicochemical conditions in which life's molecules can be synthesized, are appropriately stable, and can interact as needed for lifelike function. For life on Earth, these general requirements, respectively, take the specific form: (i) light energy in visible-to-near-infrared wavelengths or chemical energy as provided by oxidation–reduction disequilibrium, (ii) the "biogenic "elements (carbon, hydrogen, oxygen, nitrogen, phosphorus, and sulfur) (iii)liquid water, and (iv) specific ranges in temperature, pH, salinity, pressure, and other environmental factors. Our knowledge of these factors relates to cellula rlife as we observe it now or can infer from the fossil or molecular records. Life's origin may be constrained by a more stringent set of requirements that are, as yet,not fully understood.

Habitability↗

Status of Technological Advancements for Reducing Aircraft Gas Turbine Engine Pollutant Emissions

Combustor test rig results indicate that substantial reductions from current emission levels of carbon monoxide (CO), total unburned hydrocarbons (THC), oxides of nitrogen (NOx), and smoke are achievable by employing varying degrees of technological advancements in combustion systems. Minor to moderate modifications to existing conventional combustors produced significant reductions in CO and THC emissions at engine low power (idle/taxi) operating conditions but did not effectively reduce NOx at engine full power (takeoff) operating conditions. Staged combusiton techniques were needed to simultaneously reduce the levels of all the emissions over the entire engine operating range (from idle to takeoff). Emission levels that approached or were below the requirements of the 1979 EPA standards were achieved with the staged combustion systems and in some cases with the minor to moderate modifications to existing conventional combustion systems. Results from research programs indicate that an entire new generation of combustor technology with extremely low emission levels may be possible in the future.

Rudey, R. A.↗

Friction wear and auger analysis of iron implanted with 1.5-MeV nitrogen ions

The effect of implantation of 1.5-MeV nitrogen ions on the friction and wear characteristics of pure iron sliding against steel was studied in a pin-on disk apparatus. An implantation dose of 5 x 10 to the 17th power ions/sq cm was used. Small reductions in initial and steady-state wear rates were observed for nitrogen-implanted iron riders as compared with unimplanted controls. Auger electron spectroscopy revealed a subsurface Gaussian nitrogen distribution with a maximum concentration of 15 at. % at a depth of 8 x 10 to the -7th m. A similar analysis within the wear scar of an implanted rider after 20 microns of wear yielded only background nitrogen concentration, thus giving no evidence for diffusion of nitrogen beyond the implanted range.

Ferrante, J.↗

Stratospheric cruise emission reduction program

A recently implemented NASA effort specifically aimed at reducing cruise oxides of nitrogen from high-altitude aircraft is discussed. The desired emission levels and the combustor technology required to achieve them are discussed. A brief overview of the SCERP operating plan is given. Lean premixed-prevaporized combustion and some of the potential difficulties that are associated with applying this technique to gas turbine combustors are examined. Base technology was developed in several key areas. These fundamental studies are viewed as a requirement for successful implementation of the lean premixed combustion technique.

Diehl, L. A.↗

Plasma Activated Water for Crewed Transit and Planetary Habitation: A Study of Gas Type, Electrode Material, and Power Supply Selection and the Impact on the Final Frontier - FY21 CIF

An in-depth study of plasma activated water (PAW) generation was conducted to link changes in power supply, electrode material, input gas, and treatment time to the resulting reaction chemistry. These changes in chemistry can help tailor PAW for different space applications. An AC, DC, and nanosecond (ns) pulsed power supply were each used to generate PAW with stainless steel, copper, tungsten, or platinum (Pt) electrodes while utilizing air, nitrogen (N2), carbon dioxide (CO2), helium (He), or argon (Ar) as the feed gas. Tap or deionized (DI) water was treated for 1 to 15 minutes, and the generated PAW was tested for changes in pH, conductivity, oxidation reduction potential, nitrates (NO3-), ammonium (NH4+), and peroxide. Calculations showed that the production of reactive nitrogen species was the leading cause of pH and conductivity changes. The DC generated air plasma was able to reduce the pH of DI water and generate NO3‑. The pulsed supply, operating at 20% of the input power of the DC supply, lowered the pH generated NO3‑. When a simulated Martian gas mixture of 95% CO2 and 5% N2 was used as the feed gas, NO3‑ was generated with the DC and pulsed supplies, respectively. Mixing PAW with plasma generated ash from inedible biomass allowed pH control, thus enhancing PAW’s potential use for sanitation applications. The large shift in pH was used to study sanitation effects of Escherichia coli (E. coli) reduction and Staphylococcus aureus (S. aureus), in which log reductions were found to be negligible. Additionally, the plasma generated ash in combination with PAW was also implemented in 10-day microgreen growth trials, in which PAW and ash resulted in quicker emergence of the microgreens compared to the standard growth conditions and comparable dry masses to Hoagland’s nutrient solution treated samples.

plasma activated water (PAW)↗

Tribological characteristics of nitrogen (N+) implanted iron

The effect of implantation of nitrogen ions (1.5 MeV) on the friction and wear characteristics of pure ion sliding against M-50 steel (unimplanted) was studied in a pin-on-disk sliding friction apparatus. Test conditions included room temperature (25 C), a dry air atmosphere, a load of 1/2 kg (4.9 N), sliding velocities of 0.043 to 0.078 m/sec (15 to 25 rpm), a pure hydrocarbon lubricant (n-hexadecane), or a U.S.P. mineral oil and nitrogen ion implantation doses of 5x10 to the 15th power and 5x10 to the 17th power ions/sq cm. No differences in wear rates were observed in the low dose experiments. In the high dose experiments, small reductions in initial (40 percent) and steady state (20 percent) wear rates were observed for nitrogen implanted iron riders as compared with unimplanted controls. No differences in average friction coefficients were noted for either dose. Auger electron spectroscopy combined with argon ion bombardment revealed a subsurface Gaussian nitrogen distribution with a maximum concentration of 6 atomic percent at a depth of 0.8 microns. Similar analysis within the wear scar of an implanted rider after 20 microns of wear yielded only background nitrogen concentration. No inward migration of nitrogen ions was observed.

Jones, W. R.↗

Tribological characteristics of nitrogen (N+) implanted iron

The effect of implantation of nitrogen ions (1.5 MeV) on the friction and wear characteristics of pure ion sliding against M-50 steel (unimplanted) was studied in a pin-on-disk sliding friction apparatus. Test conditions included room temperature (25 C), a dry air atmosphere, a load of 1/2 kg (4.9 N), sliding velocities of 0.043 to 0.078 m/sec (15 to 25 rpm), a pure hydrocarbon lubricant (n-hexadecane), or a U.S.P. mineral oil and nitrogen ion implantation doses of 5x10 to the 15th power and 5x10 to the 17th power ions/sq cm. No differences in wear rates were observed in the low dose experiments. In the high dose experiments, small reductions in initial (40 percent) and steady state (20 percent) wear rates were observed for nitrogen implanted iron riders as compared with unimplanted controls. No differences in average friction coefficients were noted for either dose. Auger electron spectroscopy combined with argon ion bombardment revealed a subsurface Gaussian nitrogen distribution with a maximum concentration of 6 atomic percent at a depth of 0.8 microns. Similar analysis within the wear scar of an implanted rider after 20 microns of wear yielded only background nitrogen concentration. No inward migration of nitrogen ions was observed. Previously announced in STAR as N82-24322

Jones, W. R., Jr.↗

Controlling Microbial Byproducts using Model-Based Substrate Monitoring and Control Strategies

We have developed a computer-controlled bioreactor system to study various aspects of microbially-mediated nitrogen cycling. The system has been used to investigate methods for controlling microbial denitrification (the dissimilatory reduction of nitrate to N2O and N2) in hydroponic plant growth chambers. Such chambers are key elements of advanced life support systems being designed for use on long duration space missions, but nitrogen use efficiency in them is reduced by denitrification. Control software architecture was designed which permits the heterogeneous control of system hardware using traditional feedback control, and quantitative and qualitative models of various system features. Model-based feed forward control entails prediction of future systems in states and automated regulation of system parameters to achieve desired and avoid undesirable system states. A bacterial growth rate model based on the classic Monod model of saturation kinetics was used to evaluate the response of several individual denitrifying species to varying environmental conditions. The system and models are now being applied to mixed microbial communities harvested from the root zone of a hydroponic growth chamber. The use of a modified Monod organism interaction model was evaluated as a means of achieving more accurate description of the dynamic behavior of the communities. A minimum variance parameter estimation routine was also' used to calibrate the constant parameters in the model by iterative evaluation of substrate (nitrate) uptake and growth kinetics. This representation of processes and interactions aids in the formulation of control laws. The feed forward control strategy being developed will increase system autonomy, reduce crew intervention and limit the accumulation of undesirable waste products (NOx).

Smernoff, David T.↗

Measurements of Nitric Acid and Aerosol Species Aboard the NASA DC-8 Aircraft During the SASS Ozone and Nitrogen Oxide Experiment (SONEX)

The SASS Ozone and Nitrogen Oxides Experiment (SONEX) over the North Atlantic during October/November 1997 offered an excellent opportunity to examine the budget of total reactive nitrogen (NO(sub y)) in the upper troposphere (8 - 12 km altitude). The median measured NO(sub y) mixing ratio was 425 parts per trillion by volume (pptv). Two different methods were used to measure HNO3: (1) the mist chamber technique and, (2) chemical ionization mass spectrometry. Two merged data sets using these HNO3 measurements were used to calculate NO(sub y) by summing the reactive nitrogen species (a combination of measured plus modeled results) and comparing the resultant values to measured NO(sub y) (gold catalytic reduction method). Both comparisons showed good agreement in the two quantities (slope > 0.9 and r(exp 2) > 0.9). Thus, the total reactive nitrogen budget in the upper troposphere over the North Atlantic can be explained in a general manner as a simple mixture of NO(sub x). (NO + NO2), HNO3, and PAN. Median values of NO(sub x)/NO(sub y) were approximately equal to 0.25, HNO3/NO(sub y) were approximately equal to 0.35 and Peroxyacetyl Nitrate (PAN)/NO(sub y) were approximately equal to 0. 17. Particulate NO3 and alkyl nitrates together composed <10 % of NO(sub y), while model estimated HNO4 averaged 12%.

Talbot, Robert W.↗

The experimental clean combustor program - Description and status

The experimental clean combustor program is a contract effort with primary objectives including the generation and demonstration of technology for development of advanced commercial CTOL aircraft engines with lower exhaust emissions than current aircraft, and the demonstration of this technology in full scale engines in 1976. The program is being conducted in three phases. These consist of screening of low pollutant combustors, refinement of the best combustors, and engine demonstration of the best combustors. Pollution goals are emission index values of 20 and 4 for carbon monoxide and unburned hydrocarbons respectively at engine idle conditions, and an oxides of nitrogen emission index level of 10 at engine takeoff conditions. Pollution reduction approaches which are being investigated include multiple burning zone combustors, investigations of improved fuel distribution, and preparation and the staging of combustor airflow.

Niedzwiecki, R. W.↗

Lean, premixed, prevaporized combustion for aircraft gas turbine engines

The application of lean, premixed, prevaporized combustion to aircraft turbine engine systems can result in benefits in terms of superior combustion performance, improved combustor and turbine durability, and environmentally acceptable pollutant emissions. Lean, premixed prevaporized combustion is particularly attractive for reducing the oxides of nitrogen emissions during high altitude cruise. The NASA stratospheric cruise emission reduction program will evolve and demonstrate lean, premixed, prevaporized combustion technology for aircraft engines. This multiphased program is described. In addition, the various elements of the fundamental studies phase of the program are reviewed, and results to date of many of these studies are summarized.

Mularz, E. J.↗

Lean, premixed, prevaporized combustion for aircraft gas turbine engines

The application of lean, premixed, prevaporized combustion to aircraft gas turbine engine systems can result in benefits in terms of superior combustion performance, improved combustor and turbine durability, and environmentally acceptable pollutant emissions. Lean, premixed, prevaporized combustion is particularly attractive for reducing the oxides of nitrogen emissions during high altitude cruise. The NASA Stratospheric Cruise Emission Reduction Program will evolve and demonstrate lean, premixed, prevaporized combustion technology for aircraft engines. This multiphased program is described. In addition, the various elements of the Fundamental Studies Phase of the program are reviewed, and results to date of many of these studies are summarized.

Mularz, E. J.↗

Multifuel evaluation of rich/quench/lean combustor

The fuel flexible combustor technology was developed for application to the Model 570-K industrial gas turbine engine. The technology, to achieve emission goals, emphasizes dry NOx reduction methods. Due to the high levels of fuel-bound nitrogen (FBN), control of NOx can be effected through a staged combustor with a rich initial combustion zone. A rich/quench/lean variable geometry combustor utilizes the technology presented to achieve low NOx from alternate fuels containing FBN. The results focus on emissions and durability for multifuel operation.

Notardonato, J. J.↗

A Self-Perpetuating Catalyst for the Production of Complex Organic Molecules in Protostellar Nebulae

The formation of abundant carbonaceous material in meteorites is a long standing problem and an important factor in the debate on the potential for the origin of life in other stellar systems. Many mechanisms may contribute to the total organic content in protostellar nebulae, ranging from organics formed via ion-molecule and atom-molecule reactions in the cold dark clouds from which such nebulae collapse, to similar ion-molecule and atom-molecule reactions in the dark regions of the nebula far from the proto star, to gas phase reactions in sub-nebulae around growing giant planets and in the nebulae themselves. The Fischer-Tropsch-type (FTT) catalytic reduction of CO by hydrogen was once the preferred model for production of organic materials in the primitive solar nebula. The Haber-Bosch catalytic reduction of N2 by hydrogen was thought to produce the reduced nitrogen found in meteorites. However, the clean iron metal surfaces that catalyze these reactions are easily poisoned via reaction with any number of molecules, including the very same complex organics that they produce and both reactions work more efficiently in the hot regions of the nebula. We have demonstrated that many grain surfaces can catalyze both FTT and HB-type reactions, including amorphous iron and magnesium silicates, pure silica smokes as well as several minerals. Although none work as well as pure iron grains, and all produce a wide range of organic products rather than just pure methane, these materials are not truly catalysts.

Nuth, Joseph A.↗

Measurements of Nitric Acid and Aerosol Species Aboard the NASA DC-8 Aircraft During the SASS OZone and Nitrogen Oxide Experiment (SONEX)

The SASS Ozone and Nitrogen Oxides Experiment (SONEX) over the north Atlantic during October/November 1997 offered an excellent opportunity to examine the budget of total reactive nitrogen (NO(y)) in the upper troposphere (8 - 12 km altitude). The median measured NO(y) mixing ratio was 425 parts per trillion by volume (pptv). Two different methods were used to measure HNO3: (1) the mist chamber technique and, (2) chemical ionization mass spectrometry. Two merged data sets using these HNO3 measurements were used to calculate NO(y) by summing the reactive nitrogen species (a combination of measured plus modeled results) and comparing the resultant values to measured NO(y) (gold catalytic reduction method). Both comparisons showed good agreement in the two quantities (slope greater than 0.9 and r(sup 2) greater than 0.9). Thus, the total reactive nitrogen budget in the upper troposphere over the North Atlantic can be explained in a general manner as a simple mixture of NO(x). (NO + NO2), HNO3, and PAN. Median values of NO(x)/NO(y) were approx. = 0.25, HNO3/NO(y) approx. = 0.35 and PAN/NO(y) approx. = 0.17. Particulate NO3 and alkyl nitrates together composed less than 10% of NO(y), while model estimated HNO4 averaged 12%.

Talbot, Robert W.↗

Lightweight spacecraft propulsion system selection

Various methods of significantly reducing the mass of planetary spacecraft propulsion systems were addressed. Because of the Space Shuttle Challenger accident, the availability of the Space Transportation System for planetary missions may be limited. Mounting a future planetary mission with lower-energy launch vehicles will require a significant reduction in the spacecraft mass. Smaller launch vehicles for planetary missions were considered. In this study, the assumed payload capability for the planetary missions were considered. In this study, the assumed payload capability for the planetary missions was restricted to the Delta and the Atlas-Centaur launch vehicles. Several propulsion and propulsion-related technologies for spacecraft mass reduction were investigated; ion, arcjet, resistojet, and Magneto-Plasma-Dynamic propulsion and earth-storable high-energy propulsion system thrusters were candidates. The propulsion-related technologies included a start-basket Propellant Management Device, a nitrogen tetroxide diaphragm, and a solid-cryogen cooler. Xenon-ion propulsion allowed the greatest mass reduction.

Palaszewski, B.↗

Inhomogeneity of pulmonary ventilation during sustained microgravity as determined by single-breath washouts

Gravity is known to cause inhomogeneity of ventilation. Nongravitational factors are also recognized, but their relative contribution is not understood. We therefore studied ventilatory inhomogeneity during sustained microgravity during the 9-day flight of Spacelab SLS-1. All seven crew members performed single-breath nitrogen washouts. They inspired a vital capacity breath of 100% oxygen with a bolus of argon at the start of inspiration, and the inspiratory and expiratory flow rates were controlled at 0.5 l/s. Control measurements in normal gravity (1 G) were made pre- and postflight in the standing and supine position. Compared with the standing 1-G measurements, there was a marked decrease in ventilatory inhomogeneity during microgravity, as evidenced by the significant reductions in cardiogenic oscillations, slope of phase III, and height of phase IV for nitrogen and argon. However, argon phase IV volume was not reduced, and considerable ventilatory inhomogeneity remained. For example, the heights of the cardiogenic oscillations during microgravity for nitrogen and argon were 44 and 24%, respectively, of their values at 1 G, whereas the slopes of phase III for nitrogen and argon were 78 and 29%, respectively, of those at 1 G. The presence of a phase IV in microgravity is strong evidence that airway closure still occurs in the absence of gravity. The results were qualitatively similar to those found previously during short periods of 0 G in parabolic flight.

Guy, Harold J. B.↗