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Novel Materials, Processing and Device Technologies for Space Exploration with Potential Dual-Use Applications

We highlight results of a broad spectrum of efforts on lower-temperature processing of nanomaterials, novel approaches to energy conversion, and environmentally rugged devices. Solution-processed quantum dots of copper indium chalcogenide semiconductors and multiwalled carbon nanotubes from lower-temperature spray pyrolysis are enabled by novel (precursor) chemistry. Metal-doped zinc oxide (ZnO) nanostructured components of photovoltaic cells have been grown in solution at low temperature on a conductive indium tin oxide substrate. Arrays of ZnO nanorods can be templated and decorated with various semiconductor and metallic nanoparticles. Utilizing ZnO in a more broadly defined energy conversion sense as photocatalysts, unwanted organic waste materials can potentially be repurposed. Current efforts on charge carrier dynamics in nanoscale electrode architectures used in photoelectrochemical cells for generating solar electricity and fuels are described. The objective is to develop oxide nanowire-based electrode architectures that exhibit improved charge separation, charge collection and allow for efficient light absorption. Investigation of the charge carrier transport and recombination properties of the electrodes will aid in the understanding of how nanowire architectures improve performance of electrodes for dye-sensitized solar cells. Nanomaterials can be incorporated in a number of advanced higher-performance (i.e. mass specific power) photovoltaic arrays. Advanced technologies for the deposition of 4H-silicon carbide are described. The use of novel precursors, advanced processing, and process studies, including modeling are discussed from the perspective of enhancing the performance of this promising material for enabling technologies such as solar electric propulsion. Potential impact(s) of these technologies for a variety of aerospace applications are highlighted throughout. Finally, examples are given of technologies with potential spin-offs for dual-use or terrestrial applications.

solid state devices↗

Novel Materials, Processing, and Device Technologies for Space Exploration with Potential Dual-Use Applications

We highlight results of a broad spectrum of efforts on lower-temperature processing of nanomaterials, novel approaches to energy conversion, and environmentally rugged devices. Solution-processed quantum dots of copper indium chalcogenide semiconductors and multi-walled carbon nanotubes from lower-temperature spray pyrolysis are enabled by novel (precursor) chemistry. Metal-doped zinc oxide (ZnO) nanostructured components of photovoltaic cells have been grown in solution at low temperature on a conductive indium tin oxide substrate. Arrays of ZnO nanorods can be templated and decorated with various semiconductor and metallic nanoparticles. Utilizing ZnO in a more broadly defined energy conversion sense as photocatalysts, unwanted organic waste materials can potentially be re-purposed. Current efforts on charge carrier dynamics in nanoscale electrode architectures used in photoelectrochemical cells for generating solar electricity and fuels are described. The objective is to develop oxide nanowire-based electrode architectures that exhibit improved charge separation, charge collection and allow for efficient light absorption. Investigation of the charge carrier transport and recombination properties of the electrodes will aid in the understanding of how nanowire architectures improve performance of electrodes for dye-sensitized solar cells. Nanomaterials can be incorporated in a number of advanced higher-performance (i.e. mass specific power) photovoltaic arrays. Advanced technologies for the deposition of 4H-silicon carbide are described. The use of novel precursors, advanced processing, and process studies, including modeling are discussed from the perspective of enhancing the performance of this promising material for enabling technologies such as solar electric propulsion. Potential impact(s) of these technologies for a variety of aerospace applications are highlighted throughout. Finally, examples are given of technologies with potential spin-offs for dual-use or terrestrial applications.

thin films↗

The photophysics of monomeric bacteriochlorophylls c and d and their derivatives: properties of the triplet state and singlet oxygen photogeneration and quenching

Measurements of pigment triplet-triplet absorption, pigment phosphorescence and photosensitized singlet oxygen luminescence were carried out on solutions containing monomeric bacteriochlorophylls (Bchl) c and d, isolated from green photosynthetic bacteria, and their magnesium-free and farnesyl-free analogs. The energies of the pigment triplet states fell in the range 1.29-1.34 eV. The triplet lifetimes in aerobic solutions were 200-250 ns; they increased to 280 +/- 70 microseconds after nitrogen purging in liquid solutions and to 0.7-2.1 ms in a solid matrix at ambient or liquid nitrogen temperatures. Rate constants for quenching of the pigment triplet state by oxygen were (2.0-2.5) x 10(9) M-1 s-1, which is close to 1/9 of the rate constant for diffusion-controlled reactions. This quenching was accompanied by singlet oxygen formation. The quantum yields for the triplet state formation and singlet oxygen production were 55-75% in air-saturated solutions. Singlet oxygen quenching by ground-state pigment molecules was observed. Quenching was the most efficient for magnesium-containing pigments, kq = (0.31-1.2) x 10(9) M-1 s-1. It is caused mainly by a physical process of singlet oxygen (1O2) deactivation. Thus, Bchl c and d and their derivatives, as well as chlorophyll and Bchl a, combine a high efficiency of singlet oxygen production with the ability to protect photochemical and photobiological systems against damage by singlet oxygen.

NASA Discipline Number 52-30↗

HgCdTe Photoconductive Mixers for 2-8 THz

Heterodyne spectroscopy has been taken to wavelengths as short as 63 micrometers with Schottky-diode mixers. Schottkys, however, are relatively insensitive compared to superconducting mixers such as the hot-electron microbolometer (HEB), which has an effective quantum efficiency of 3% at 120 micrometers (2.5 THz). Although HEB sensitivities are bound to improve, there will always be losses associated with antenna coupling of radiation into sub-micron size devices. Another approach to far infrared (FIR) mixer design is to use a photoconductive device which can be made much larger than a wavelength, and thus act as its own antenna. For example, HgCdTe photodiodes have been used as mixers in the lambda = 10 micrometers band for over 25 years, with sensitivities now only a factor of 2 from the quantum-noise-limit. HgCdTe can also be applied at FIR wavelengths, but surprisingly little work has been done to date. The exception is the pioneering work of Spears and Kostiuk and Spears, who developed HgCdTe photomixers for the 20-120 micrometer region. The spectral versatility of the HgCdTe alloy is well recognized for wavelengths as long as 8-20 micrometers. What is not so recognized, however, is that theoretically there is no long wavelength limit for appropriately composited HgCdTe. Although Spears successfully demonstrated a photoconductive response from HgCdTe at 120 micrometers, this initial effort was apparently never followed up, in part because of the difficulty of controlling the HgCdTe alloy composition with liquid-phase-epitaxy (LPE) techniques. With the availability of precise molecular-beam-epitaxy (MBE) since the early 1990's, it is now appropriate to reconsider HgCdTe for detector applications longward of lambda = 20 micrometers. We recently initiated an effort to fabricate detectors and mixers using II-VI materials for FIR wavelengths. Of particular interest are device structures called superlattices, which offer a number of advantages for high sensitivity direct detectors and very long wavelength heterodyne mixers.

Betz, A. L.↗

Nuclear model calculations and their role in space radiation research

Proper assessments of spacecraft shielding requirements and concomitant estimates of risk to spacecraft crews from energetic space radiation requires accurate, quantitative methods of characterizing the compositional changes in these radiation fields as they pass through thick absorbers. These quantitative methods are also needed for characterizing accelerator beams used in space radiobiology studies. Because of the impracticality/impossibility of measuring these altered radiation fields inside critical internal body organs of biological test specimens and humans, computational methods rather than direct measurements must be used. Since composition changes in the fields arise from nuclear interaction processes (elastic, inelastic and breakup), knowledge of the appropriate cross sections and spectra must be available. Experiments alone cannot provide the necessary cross section and secondary particle (neutron and charged particle) spectral data because of the large number of nuclear species and wide range of energies involved in space radiation research. Hence, nuclear models are needed. In this paper current methods of predicting total and absorption cross sections and secondary particle (neutrons and ions) yields and spectra for space radiation protection analyses are reviewed. Model shortcomings are discussed and future needs presented. c2002 COSPAR. Published by Elsevier Science Ltd. All right reserved.

NASA Center JSC↗

Laboratory Apparatus Generates Dual-Species Cold Atomic Beam

A laser cooling apparatus that generates a cold beam of rubidium and cesium atoms at low pressure has been constructed as one of several intermediate products of a continuing program of research on laser cooling and atomic physics. Laser-cooled atomic beams, which can have temperatures as low as a microkelvin, have been used in diverse applications that include measurements of fundamental constants, atomic clocks that realize the international standard unit of time, atom-wave interferometers, and experiments on Bose-Einstein condensation. The present apparatus is a prototype of one being evaluated for use in a proposed microgravitational experiment called the Quantum Interferometric Test of Equivalence (QuITE). In this experiment, interferometric measurements of cesium and rubidium atoms in free fall would be part of a test of Einstein s equivalence principle. The present apparatus and its anticipated successors may also be useful in other experiments, in both microgravity and normal Earth gravity, in which there are requirements for dual-species atomic beams, low temperatures, and low pressures. The apparatus includes a pyramidal magneto-optical trap in which the illumination is provided by multiple lasers tuned to frequencies characteristic of the two atomic species. The inlet to the apparatus is located in a vacuum chamber that contains rubidium and cesium atoms at a low pressure; the beam leaving through the outlet of the apparatus is used to transfer the atoms to a higher-vacuum (lower-pressure) chamber in which measurements are performed. The pyramidal magneto-optical trap is designed so that the laser cooling forces in one direction are unbalanced, resulting in a continuous cold beam of atoms that leak out of the trap (see figure). The radiant intensity (number of atoms per unit time per unit solid angle) of the apparatus is the greatest of any other source of the same type reported to date. In addition, this is the first such apparatus capable of producing a slow, collimated beam that contains two atomic species at the same time.

Thompson, Robert↗

The components of crop productivity: measuring and modeling plant metabolism

Several investigators in the CELSS program have demonstrated that crop plants can be remarkably productive in optimal environments where plants are limited only by incident radiation. Radiation use efficiencies of 0.4 to 0.7 g biomass per mol of incident photons have been measured for crops in several laboratories. Some early published values for radiation use efficiency (1 g mol-1) were inflated due to the effect of side lighting. Sealed chambers are the basic research module for crop studies for space. Such chambers allow the measurement of radiation and CO2 fluxes, thus providing values for three determinants of plant growth: radiation absorption, photosynthetic efficiency (quantum yield), and respiration efficiency (carbon use efficiency). Continuous measurement of each of these parameters over the plant life cycle has provided a blueprint for daily growth rates, and is the basis for modeling crop productivity based on component metabolic processes. Much of what has been interpreted as low photosynthetic efficiency is really the result of reduced leaf expansion and poor radiation absorption. Measurements and models of short-term (minutes to hours) and long-term (days to weeks) plant metabolic rates have enormously improved our understanding of plant environment interactions in ground-based growth chambers and are critical to understanding plant responses to the space environment.

NASA Discipline Life Support Systems↗

A Step Beyond Simple Keyword Searches: Services Enabled by a Full Content Digital Journal Archive

The problems of managing and searching large archives of scientific journal articles can potentially be addressed through data mining and statistical techniques matured primarily for quantitative scientific data analysis. A journal paper could be represented by a multivariate descriptor, e.g., the occurrence counts of a number key technical terms or phrases (keywords), perhaps derived from a controlled vocabulary ( e . g . , the American Meteorological Society's Glossary of Meteorology) or bootstrapped from the journal archive itself. With this technique, conventional statistical classification tools can be leveraged to address challenges faced by both scientists and professional societies in knowledge management. For example, cluster analyses can be used to find bundles of "most-related" papers, and address the issue of journal bifurcation (when is a new journal necessary, and what topics should it encompass). Similarly, neural networks can be trained to predict the optimal journal (within a society's collection) in which a newly submitted paper should be published. Comparable techniques could enable very powerful end-user tools for journal searches, all premised on the view of a paper as a data point in a multidimensional descriptor space, e.g.: "find papers most similar to the one I am reading", "build a personalized subscription service, based on the content of the papers I am interested in, rather than preselected keywords", "find suitable reviewers, based on the content of their own published works", etc. Such services may represent the next "quantum leap" beyond the rudimentary search interfaces currently provided to end-users, as well as a compelling value-added component needed to bridge the print-to-digital-medium gap, and help stabilize professional societies' revenue stream during the print-to-digital transition.

Boccippio, Dennis J.↗

Impact of Emerging Computing Architectures and Opportunities for Process Systems Engineering Applications

Moore’s “law” was the observation that the number of transistors in an integrated circuit doubled approximately every two years. This trend has distinctly failed to hold in recent years. The death of Moore’s law has left researchers and practitioners in the computational sciences searching for technologies to provide the speedups formerly supported by Moore’s law. Previously overlooked chip architectures and other computing technologies are now receiving more development resources. Critically, these technologies are gaining more mature software support, opening their adoption by researchers in algorithms and applications. In this article, we review some of these computing technologies, their relationship with various algorithms and applications, and their potential benefits (or pitfalls). We close with recommendations for future work by the process systems engineering community specifically.

Emerging hardware↗

Probabilistic Aeroelastic Analysis Developed for Turbomachinery Components

Aeroelastic analyses for advanced turbomachines are being developed for use at the NASA Glenn Research Center and industry. However, these analyses at present are used for turbomachinery design with uncertainties accounted for by using safety factors. This approach may lead to overly conservative designs, thereby reducing the potential of designing higher efficiency engines. An integration of the deterministic aeroelastic analysis methods with probabilistic analysis methods offers the potential to design efficient engines with fewer aeroelastic problems and to make a quantum leap toward designing safe reliable engines. In this research, probabilistic analysis is integrated with aeroelastic analysis: (1) to determine the parameters that most affect the aeroelastic characteristics (forced response and stability) of a turbomachine component such as a fan, compressor, or turbine and (2) to give the acceptable standard deviation on the design parameters for an aeroelastically stable system. The approach taken is to combine the aeroelastic analysis of the MISER (MIStuned Engine Response) code with the FPI (fast probability integration) code. The role of MISER is to provide the functional relationships that tie the structural and aerodynamic parameters (the primitive variables) to the forced response amplitudes and stability eigenvalues (the response properties). The role of FPI is to perform probabilistic analyses by utilizing the response properties generated by MISER. The results are a probability density function for the response properties. The probabilistic sensitivities of the response variables to uncertainty in primitive variables are obtained as a byproduct of the FPI technique. The combined analysis of aeroelastic and probabilistic analysis is applied to a 12-bladed cascade vibrating in bending and torsion. Out of the total 11 design parameters, 6 are considered as having probabilistic variation. The six parameters are space-to-chord ratio (SBYC), stagger angle (GAMA), elastic axis (ELAXS), Mach number (MACH), mass ratio (MASSR), and frequency ratio (WHWB). The cascade is considered to be in subsonic flow with Mach 0.7. The results of the probabilistic aeroelastic analysis are the probability density function of predicted aerodynamic damping and frequency for flutter and the response amplitudes for forced response.

Reddy, T. S. R.↗

22” ADP Fan Rig Liners Design Report

A liner design study was conducted as part of a cooperative effort between five (5) government/industry teams that together seek to demonstrate the technology for designing and manufacturing acoustic liners that are twenty five percent (25%) more efficient than 1992 technology liners. The study emphasized teaming collaboration. The improved liners were designed by Pratt & Whitney and Boeing Airplane Company and built by Rohr Inc, and will be tested in the NASA/P& W 22-inch ADP fan rig at NASA Lewis Research Center's 9' x 15' wind tunnel. Design guidelines and decisions were made collectively during monthly design review telecons and at the formal final design review. The tools that were used to design the new improved liners were not new, but the process that was developed as part of this study that led into the evaluation and selection of the final and best liner designs is new. Until now, the liner design process as practiced by different industry teams varied greatly. Some procedures were based on empirical liner attenuation databases which could not adequately account for engine-to-engine hardwall fan noise spectral differences, while others were entirely theoretical. And regardless of which method one chose, the major difficulty was still the lack of understanding and knowledge of the actual hardwall fan source noise modal structure and farfield SPL spectra. The NASA-led effort to attempt actual measurements of the fan source noise modal structure by means of the rotating microphone array is expected to contribute significantly to the understanding of the nature of the fan tone noise modes, but the application to broadband noise is still a long way off. The new design process included consideration of the measured fan tone modes, but for the majority of the spectra a separate, systematic process was used. It is a common practice in the engine/nacelle industry that acoustic liners for new products are designed before actual measured hardwall engine far-field noise spectra are available. Target noise spectra are normally derived from existing engine noise databases with some adjustments to absolute SPLs and frequencies. This practice has been acceptable as long as the new engine was a derivative of the base engine. However, in the case of the ADP, the transition from a current engine base is too - great, and the adjustments could not adequately account for the quantum changes in SPL spectral differences. Examples were the 1992 single degree of freedom (SDOF) inlet and aft liners (designed by P&W) that would be used as the baseline liners against which the new improved liners' efficien¬cies would -be measured. As will be shown, these baseline liners have been found to be deeper than the desire optimum depths. The new liner design process begins with the selection of the target hard wall fan noise spectra. These spectra were obtained by scaling up (5.91 scale factor) the measured hardwall fan spectral data from the 22” ADP fan rig. Next, the modal energy contents for each 1/3-octave band center frequency of these hardwall fan noise spectra are estimated. (Within each 1/3-octave band center frequency, the model energy distribution approximation is for both tone and broadband noise). For the inlet noise, P&W uses a derivative of the NASA Lewis (Ed Rice's) method of classifying; and grouping propagating modes by their cutoff ratios. The next step is to assign energy level to each group of modes having the same cutoff ratio. In Ed Rice's model, the modes were grouped according to ten (10) cutoff ratio intervals with center values located at 1.026, 1.085, 1.155, 1.24, 1.35, 1.49, 1.69, 2.0, and 4.47 (with equal number of modes in each interval). The modes were assumed to have equal energy. P&W’s model expands the cutoff ratio-mode grouping into two hundred (200) smaller cutoff ratio intervals with center values located f1".'m 1.003 to 11.5 in 199 increasing incremental intervals. Next, P&W's model uses a "2-parameter" normal distribution as a template to assign energy levels to these 200 pre-determined cutoff ratio values (for each 1/3-octave band center frequency). In the past, P&W had conducted an extensive study to determine what "2-parameter" values are appropriate for fullscale inlet liners, and had developed a set of twenty-four (24) "2-pararneter" values (i.e. one for each 1/3-octave frequency band) that when used in Ed Rice's Inlet Attenuation Prediction Method produced predicted liner attenuations that closely matched measured liner attenuations from several P&W's engines. In the absence of actual measured tone and broadband modal data from the 22" ADP rig, the process will use P&W's proprietary set of "2-parameter" values for this liner design study. For the aft noise, Boeing uses a modal energy approximation that the "transport energy" of each propagating mode is equal. This approximation is almost the same as the equal energy per mode approximation, except for modes that are near cutoff. Boeing's model forces these modes to have lower energy levels. Both P&W and Boeing agreed that the "transport energy" approximation should work well for the ADP aft fan noise which appears to be dominated by broadband noise. The design process then proceeds to calculate the optimum liner impedances for each frequency in both the inlet and the aft. These optimum impedances represent the target impedances that the designed liners should have. Liners with impedances matching the optimum impedances at all frequencies are "ideal" liners. These ideal liners are theoretically the best liners. Unfortunately, it has been showed that it is impossible to design and build such ideal liners. The next best liners are ones that have impedances matching the optimum impedances over some frequency range (not all frequencies as for the ideal). This is accomplished by the use of "frequency weightings". Several of P&W's and Boeing's existing computer decks were used for optimizing and matching the designed liner impedances to the target optimum values (with the various frequency weightings specified). The optimization produces liner candidates with predicted liner impedances and descriptions of their physical liner characteristics. These candidate liner impedances are then used to predict their spectral attenuation characteristics which are then used together with the target hardwall fan noise spectra to determine the resulting treated noise spectra and PNLT values. Further optimization around the selected candidate designs yield final designs that are best in PNLT attenuations. Use of the optimization decks allowed a large number of liner candidates to be screened in a relatively short period of time. This design process is systematic and is efficient. The new inlet SDOF liner design obtained from the improved process was predicted to be 34% more effective (per unit area) than the 1992 baseline inlet liner. This inlet liner design is a 112 rayl wovenwiremesh facesheet over a 0.312-inch deep honeycomb core. The new aft SDOF liner design was predicted to be 52% more efficient than the aft baseline liner. The new aft SDOF liner is "segmented" with a shallower liner on the core cowl (inner duct wall) and a deeper liner on the fan cowl (outer duct wall). The shallower liner is a 70.6 rayl woven-wiremesh facesheet over a 0.141-inch deep honeycomb core. The deeper liner is a 68 rayl woven-wiremesh facesheet over a 0.309-inch deep honeycomb core. All liner dimensions are for the 22-inch model-scale ADP fan rig liners. The selected advanced liners are "segmented" double-layer (DDOF) liners for the inlet and aft locations. Also, for the inlet, a bulk liner with ceramic foam for wider broadband noise absorption was also selected. Triple-layer liner designs were not considered since the model scaled liners ( 1/5. 91) were dimensionally too small to be built correctly, and irrin earlier concept study, Boeing found a triple-layer to have only very small benefits over a double-layer. The inlet DDOF liner was predicted to be 83% more effective than the baseline. The inlet DDOF design is a 78 rayl facesheet over a 0.080 top cavity depth, a 68 rayl septum and a 0.227-inch bottom cavity depth. The inlet bulk liner is a 60 rayl facesheet over a 0.33-inch deep honeycomb filled with high temperature (HTP) ceramic foam with a density of 4.8 lb/cu.ft and a flow resistivity of 167 rayl/cm. The inlet bulk liner was predicted to be 83% more effective than the baseline liner. The aft DDOF liners are segmented with a shallower liner on the core cowl and a deeper liner on the fan cowl. The shallow DDOF liner is a 49.8 rayl facesheet over a 0.093-inch top cavity depth, a septum of 88.2 rayls over a 0.181-inch bottom cavity depth. The deep DDOF liner is a 12.9 rayl facesheet over a 0.140-inch top cavity depth, a septum of 53.1 ray ls over a 0.258-inch botom cavity depth. The segmented aft DDOF liners were predicted to be 86% more efficient than the baseline liner.

turbofan acoustic treatment↗

Multiple-Event, Single-Photon Counting Imaging Sensor

The single-photon counting imaging sensor is typically an array of silicon Geiger-mode avalanche photodiodes that are monolithically integrated with CMOS (complementary metal oxide semiconductor) readout, signal processing, and addressing circuits located in each pixel and the peripheral area of the chip. The major problem is its single-event method for photon count number registration. A single-event single-photon counting imaging array only allows registration of up to one photon count in each of its pixels during a frame time, i.e., the interval between two successive pixel reset operations. Since the frame time can t be too short, this will lead to very low dynamic range and make the sensor merely useful for very low flux environments. The second problem of the prior technique is a limited fill factor resulting from consumption of chip area by the monolithically integrated CMOS readout in pixels. The resulting low photon collection efficiency will substantially ruin any benefit gained from the very sensitive single-photon counting detection. The single-photon counting imaging sensor developed in this work has a novel multiple-event architecture, which allows each of its pixels to register as more than one million (or more) photon-counting events during a frame time. Because of a consequently boosted dynamic range, the imaging array of the invention is capable of performing single-photon counting under ultra-low light through high-flux environments. On the other hand, since the multiple-event architecture is implemented in a hybrid structure, back-illumination and close-to-unity fill factor can be realized, and maximized quantum efficiency can also be achieved in the detector array.

Zheng, Xinyu↗

Accuracy of quantum sensors measuring yield photon flux and photosynthetic photon flux

Photosynthesis is fundamentally driven by photon flux rather than energy flux, but not all absorbed photons yield equal amounts of photosynthesis. Thus, two measures of photosynthetically active radiation have emerged: photosynthetic photon flux (PPF), which values all photons from 400 to 700 nm equally, and yield photon flux (YPF), which weights photons in the range from 360 to 760 nm according to plant photosynthetic response. We selected seven common radiation sources and measured YPF and PPF from each source with a spectroradiometer. We then compared these measurements with measurements from three quantum sensors designed to measure YPF, and from six quantum sensors designed to measure PPF. There were few differences among sensors within a group (usually <5%), but YPF values from sensors were consistently lower (3% to 20%) than YPF values calculated from spectroradiometric measurements. Quantum sensor measurements of PPF also were consistently lower than PPF values calculated from spectroradiometric measurements, but the differences were <7% for all sources, except red-light-emitting diodes. The sensors were most accurate for broad-band sources and least accurate for narrow-band sources. According to spectroradiometric measurements, YPF sensors were significantly less accurate (>9% difference) than PPF sensors under metal halide, high-pressure sodium, and low-pressure sodium lamps. Both sensor types were inaccurate (>18% error) under red-light-emitting diodes. Because both YPF and PPF sensors are imperfect integrators, and because spectroradiometers can measure photosynthetically active radiation much more accurately, researchers should consider developing calibration factors from spectroradiometric data for some specific radiation sources to improve the accuracy of integrating sensors.

NASA Center KSC↗

Trace Chemistry

The goals of the trace chemistry group were to identify the processes relevant to aerosol and aerosol precursor formation occurring within aircraft gas turbine engines; that is, within the combustor, turbine, and nozzle. The topics of discussion focused on whether the chemistry of aerosol formation is homogeneous or heterogeneous; what species are important for aerosol and aerosol precursor formation; what modeling/theoretical activities to pursue; what experiments to carry out that both support modeling activities and elucidate fundamental processes; and the role of particulates in aerosol and aerosol precursor formation. The consensus of the group was that attention should be focused on SO2, SO3, and aerosols. Of immediate concern is the measurement of the concentration of the species SO3, SO2, H2SO4 OH, HO2, H2O2, O, NO, NO2, HONO, HNO3, CO, and CO2 and particulates in various engines, both those currently in use and those in development. The recommendation was that concentration measurements should be made at both the combustor exit and the engine exit. At each location the above species were classified into one of four categories of decreasing importance, Priority I through IV, as follows: Combustor exit: Priority I species - SO3:SO2 ratio, SO3, SO2, and particulates; Priority II species: OH and O; Priority III species - NO and NO2; and Priority IV species - CO and CO2. For the Engine exit: Priority I species - SO3:SO2 ratio, SO3, SO2,H2SO4, and particulates; Priority II species: OH,HO2, H2O2, and O; Priority III species - NO, NO2, HONO, and HNO3; and Priority IV species - CO and CO2. Table I summarizes the anticipated concentration range of each of these species. For particulate matter, the quantities of interest are the number density, size distribution, and composition. In order to provide data for validating multidimensional reacting flow models, it would be desirable to make 2-D, time-resolved measurements of the concentrations of the above species and, in addition, of the pressure, temperature, and velocity. A near term goal of the experimental program should be to confirm the nonlinear effects of sulfur speciation, and if present, to provide an explanation for them. It is also desirable to examine if the particulate matter retains any sulfur. The recommendation is to examine the effects on SOx production of variations in fuel-bound sulfur and aromatic content (which may affect the amount of particulates formed). These experiments should help us to understand if there is a coupling between particulate formation and SO, concentration. Similarly, any coupling with NOx can be examined either by introducing NOx into the combustion air or by using fuel-bound nitrogen. Also of immediate urgency is the need to establish and validate a detailed mechanism for sulfur oxidation/aerosol formation, whose chemistry is concluded to be homogeneous, because there is not enough surface area for heterogeneous effects. It is envisaged that this work will involve both experimental and theoretical programs. The experimental work will require, in addition to the measurements described above, fundamental studies in devices such as flow reactors and shock tubes. Complementing this effort should be modeling and theoretical activities. One impediment to the successful modeling of sulfur oxidation is the lack of reliable data for thermodynamic and transport properties for several species, such as aqueous nitric acid, sulfur oxides, and sulfuric acid. Quantum mechanical calculations are recommended as a convenient means of deriving values for these properties. Such calculations would also help establish rate constants for several important reactions for which experimental measurements are inherently fraught with uncertainty. Efforts to implement sufficiently detailed chemistry into computational fluid dynamic codes should be continued. Zero- and one-dimensional flow models are also useful vehicles for elucidating the minimal set of species and reactions that must be included in two- and three-dimensional modeling studies.

Radhakrishnan, Krishnan↗

Fluorescence Studies of Protein Crystallization Interactions

We are investigating protein-protein interactions in under- and over-saturated crystallization solution conditions using fluorescence methods. The use of fluorescence requires fluorescent derivatives where the probe does not markedly affect the crystal packing. A number of chicken egg white lysozyme (CEWL) derivatives have been prepared, with the probes covalently attached to one of two different sites on the protein molecule; the side chain carboxyl of ASP 101, within the active site cleft, and the N-terminal amine. The ASP 101 derivatives crystallize while the N-terminal amine derivatives do not. However, the N-terminal amine is part of the contact region between adjacent 43 helix chains, and blocking this site does would not interfere with formation of these structures in solution. Preliminary FRET data have been obtained at pH 4.6, 0.1M NaAc buffer, at 5 and 7% NaCl, 4 C, using the N-terminal bound pyrene acetic acid (PAA, Ex 340 nm, Em 376 nm) and ASP 101 bound Lucifer Yellow (LY, Ex 425 nm, Em 525 nm) probe combination. The corresponding Csat values are 0.471 and 0.362 mg/ml (approximately 3.3 and approximately 2.5 x 10 (exp 5) M respectively), and all experiments were carried out at approximately Csat or lower total protein concentration. The data at both salt concentrations show a consistent trend of decreasing fluorescence yield of the donor species (PAA) with increasing total protein concentration. This decrease is apparently more pronounced at 7% NaCl, consistent with the expected increased intermolecular interactions at higher salt concentrations (reflected in the lower solubility). The estimated average distance between protein molecules at 5 x 10 (exp 6) M is approximately 70 nm, well beyond the range where any FRET can be expected. The calculated RO, where 50% of the donor energy is transferred to the acceptor, for the PAA-CEWL * LY-CEWL system is 3.28 nm, based upon a PAA-CEWL quantum efficiency of 0.41.

Pusey, Marc L.↗

Exploration Architecture with Quantum Inertial Gravimetry and In-Situ ChipSat Sensors

The Dual Exploration Architecture is a mission concept that combines remote sensing and in-situ observations into a single mission to answer planetary science questions that can only be answered with both types of data. Adoption of dual exploration architectures may short circuit the long, slow cycle of missions to inaccessible bodies by eliminating the need for separate precursor and follow-up missions. Additionally, the dual architecture possesses inherent flexibility that enables the design of adaptive, event-driven missions that are very different from traditional, largely pre-planned missions. Five key observations about the state and trends of planetary science exploration lead us to the dual architecture: increasing complexity of observations; scarcity of future mission opportunities; desire to capture transitory events; continued miniaturization of spacecraft components; and the Mars exploration cycle. Our goal in this study is to explore missions that can only happen using the dual architecture concept and find technology development needs that must be filled for those missions to compete. A survey of historical and current missions finds that opportunities for exploration are becoming less frequent, causing the flexibility and dual-nature elements of each mission to become more common. The dual exploration architecture takes these trends to their far conclusion, attempting to eliminate precursor and follow-up missions while still returning more scientific payoff. A study of the future of planetary science goals through the decadal survey reveals broad applicability of dual missions to solve mysteries that cannot be answered with a traditional mission architecture. These missions fall into three broad classes: choosing a local target from a global survey; dynamic/reactive science; and global in-situ networks. Two example missions of each class are notionally described. A deeper look at these dual architecture classes reveals four technology development needs that must be addressed for wide adoption of dual missions: passive landers; guided atmospheric probes; robust sensing packages; and small, precise orbital instruments. This study pursues a specific focus on two examples of such enabling technologies: the ChipSat and cold atom gravimetry. The ChipSat is a fully functional spacecraft-on-a-chip system that has broad versatility in the dual architecture mission space. Initial studies show that ChipSats could survive as passive impactor landers on bodies up to the size of Europa. Furthermore, COTS (Commercial Off-The-Shelf) components could provide an in-situ sensor suite that readily answers a number of pressing planetary science questions. Cold atom gravimetry uses inertial sensors based on light-pulse atom interferometry in a small form factor to map the gravity field of a body to precision equaling what would normally require two full spacecraft to achieve. The cold atom gravimeter provides an example of how advanced remote sensing capability can enable dual missions by providing greater returns in a significantly smaller package. Using the above two technologies, we study an example dual-architecture mission to both characterize and sample the subsurface oceans at Europa. The greatest scientific return in terms of detecting extraterrestrial life is in those regions where Europa’s ice crust is thin. The identification of regions with thin ice should therefore precede the selection of surface targets and dispatch of probes to those targets. This two-step process, if accomplished by separate flagship-scale missions, might take decades. As a result, a combined mission to both identify thin areas of Europa’s ice and follow up with surface observations at those regions is a good candidate for the dual-exploration architecture. This example mission consists of an orbiter spacecraft carrying a cold atom gravimeter capable of sensing or inferring the ice thickness on regional to local scales, along with a number of ChipSat probes capable of landing on the moon. The small size and weight of the ChipSats allows large numbers of them to be carried, ensuring that enough can be dropped to ensure survival of a minimum number of probes and potentially allowing for the in-situ sampling of multiple locations on the moon. The example missions and Europa case study show that amazing scientific return can obtained from dual-exploration architecture missions with a single launch by breaking the long timescales of planetary exploration and providing the flexibility to capturing transitory events and collect data across the local, regional, and global scales.

Exploration↗

Sensor for Monitoring Nanodevice-Fabrication Plasmas

The term plasma process diagnostics (PPD) refers to a spectroscopic technique and sensing hardware that have been proposed for monitoring plasma processes used to fabricate electronic devices that feature sizes as small as several nanometers. Nanometer dimensions are characteristic of the quantum level of miniaturization, where single impurity atoms or molecules can drastically change the local properties of the nanostructures. Such changes may be purposely used in nanoscale design but may also be extremely damaging or cause improper operation of the fabricated devices. Determination of temperature and densities of reactants near the developing features is important, since the structural synthesis is affected by characteristics of the local microenvironment. Consequently, sensors capable of nonintrusive monitoring with high sensitivity and high resolution are essential for real-time atomistic control of reaction kinetics and minimizing trace contamination in plasma processes used to fabricate electronic nanodevices. Such process-monitoring sensors are required to be compact, multiparametric, and immune to the harsh environments of processing plasmas. PPD is intended to satisfy these requirements. The specific technique used to implement plasma diagnostics with a PPD sensor would be an advanced version of continuous-wave cavity-ringdown spectroscopy (CW-CRDS) capable of profiling spectral line broadenings in order to derive both Doppler and Stark components. CRDS is based on measurements of the rate of absorption of laser light in an optical resonator. The ultimate sensitivity results from a very long absorption path length within the cavity and immunity to variations in incident laser intensity. The proposed version of this technique would involve the use of multiplexing tunable laser diodes and an actively modulated high-reflectivity optical resonator, thus offering a synergistic combination of simplicity, compactness, high sensitivity, and high resolution. The multiplexing capabilities of diode lasers could be utilized to make the PPD sensor a single, simple, compact, and inexpensive tool for the acquisition of multiparametric data. A PPD sensor would be capable of continuous measurement of such physical parameters as gas temperature, gas velocity, electron number density, and absolute densities of reacting chemical species. A laser beam can be easily adjusted to analyze the immediate vicinity of the growing nanostructures (or features etched down) in real time. The absorption enhancement in an optical cavity would afford the sensitivity needed for measurement of the temperature and densities of species at concentrations significantly lower than measurable by other nonintrusive techniques. It is anticipated that fully developed PPD sensors would enable simultaneous measurement of local temperature and determination of plasma species responsible for the synthesis and functionalization of nanodevices. These sensors would also enable tracking the pathways and origins of damaging contaminants, thereby providing feedback for adjustment of processes to optimize them and reduce contamination. The PPD sensors should also be useful for optimization of conventional microelectronics manufacturing plasma processes. Going beyond plasma processes for fabrication of electronic devices, PPD sensors could be used for monitoring of atoms, molecules, ions, radicals, clusters, and particles in a variety of other settings, including outer space. Because of their high sensitivity, such sensors could also prove useful for detecting traces of illegal drugs and explosives.

Bolshakov, Alexander↗

Analytic Theory and Control of the Motion of Spinning Rigid Bodies

Numerical simulations are often resorted to, in order to understand the attitude response and control characteristics of a rigid body. However, this approach in performing sensitivity and/or error analyses may be prohibitively expensive and time consuming, especially when a large number of problem parameters are involved. Thus, there is an important role for analytical models in obtaining an understanding of the complex dynamical behavior. In this dissertation, new analytic solutions are derived for the complete attitude motion of spinning rigid bodies, under minimal assumptions. Hence, we obtain the most general solutions reported in the literature so far. Specifically, large external torques and large asymmetries are included in the problem statement. Moreover, problems involving large angular excursions are treated in detail. A new tractable formulation of the kinematics is introduced which proves to be extremely helpful in the search for analytic solutions of the attitude history of such kinds of problems. The main utility of the new formulation becomes apparent however, when searching for feedback control laws for stabilization and/or reorientation of spinning spacecraft. This is an inherently nonlinear problem, where standard linear control techniques fail. We derive a class of control laws for spin axis stabilization of symmetric spacecraft using only two pairs of gas jet actuators. Practically, this could correspond to a spacecraft operating in failure mode, for example. Theoretically, it is also an important control problem which, because of its difficulty, has received little, if any, attention in the literature. The proposed control laws are especially simple and elegant. A feedback control law that achieves arbitrary reorientation of the spacecraft is also derived, using ideas from invariant manifold theory. The significance of this research is twofold. First, it provides a deeper understanding of the fundamental behavior of rigid bodies subject to body-fixed torques. Assessment of the analytic solutions reveals that they are very accurate; for symmetric bodies the solutions of Euler's equations of motion are, in fact, exact. Second, the results of this research have a fundamental impact on practical scientific and mechanical applications in terms of the analysis and control of all finite-sized rigid bodies ranging from nanomachines to very large bodies, both man made and natural. After all, Euler's equations of motion apply to all physical bodies, barring only the extreme limits of quantum mechanics and relativity.

Tsiotras, Panagiotis↗