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NASA NTRS1995

The growth of low band-gap InAs on (111)B GaAs substrates

The use of low band-gap materials is of interest for a number of photovoltaic and optoelectronic applications, such as bottom cells of optimized multijunction solar cell designs, long wavelength light sources, detectors, and thermophotovoltaics. However, low band-gap materials are generally mismatched with respect to lattice constant, thermal expansion coefficient, and chemical bonding to the most appropriate commercially available substrates (Si, Ge, and GaAs). For the specific case of III-V semiconductor heteroepitaxy, one must contend with the strain induced by both lattice constant mismatch at the growth temperature and differences in the rates of mechanical deformation during the cool down cycle. Several experimental techniques have been developed to minimize the impact of these phenomena (i.e., compositional grading, strained layer superlattices, and high-temperature annealing). However, in highly strained systems such as InAs-on-GaAs, three-dimensional island formation and large defect densities (greater than or equal to 10(exp 8)/ cm(exp -2)) tend to limit their applicability. In these particular cases, the surface morphology and defect density must be controlled during the initial stages of nucleation and growth. At the last SPRAT conference, we reported on a study of the evolution of InAs islands on (100) and (111)B GaAs substrates. Growth on the (111)B orientation exhibits a number of advantageous properties as compared to the (100) during these early stages of strained-layer epitaxy. In accordance with a developing model of nucleation and growth, we have deposited thin (60 A - 2500 A), fully relaxed InAs films on (111)B GaAs substrates. Although thicker InAs films are subject to the formation of twin defects common to epitaxy on the (111)B orientation, appropriate control of the growth parameters can greatly minimize their density. Using this knowledge base, InAs films up to 2 microns in thickness with improved morphology and structural quality have been grown on (111)B GaAs substrates, thereby enabling the measurement of electronic and optical properties.

Welser, R. E.↗
NASA NTRS1999

Thermophysical Property Measurements of Molten Semiconductors in 1-g and Reduced-g Condition

Understanding and controlling the formation kinetics of varieties of crystal imperfections such as point defects, non uniform distribution of doping atoms, and impurity atoms in growing crystals are very important. Theoretical (numerical) modeling of the crystal growth process is an essential step to achieving these objectives. In order to obtain reliable modeling results, input parameters, i.e. various thermophysical parameters, must be accurate. The importance of accurate thermophysical properties of semiconductors in crystal growth cannot be overly emphasized. The total hemispherical emissivity, for instance, has a dramatic impact on the thermal environment. It determines the radiative emission from the surface of the melt which determines to a large extent the profile of the solidified crystal. In order to understand the convection and the turbulence in a melt, viscosity becomes an important parameter. The liquid surface tension determines the shape of the liquid-atmosphere interface near the solid-liquid-atmosphere triple point. Currently used values for these parameters are rather inaccurate, and this program intends to provide more reliable measurements of these thermophysical properties. Thus, the objective of this program is in the accurate measurements of various thermophysical properties which can be reliably used in the modeling of various crystal growth processes. In this program, thermophysical properties of molten semiconductors, such as Si, Ge, Si-Ge, and InSb will be measured as a function of temperature using the High Temperature Electrostatic Levitator at JPL. Each material will be doped by different kinds of impurities at various doping levels. Thermophysical properties which will be measured include: density, thermal expansion coefficient, surface tension, viscosity, specific heat, hemispherical total emissivity, and perhaps electrical and thermal conductivities. Many molten semiconductors are chemically reactive with crucibles. As a result, these dispersed impurities in the melts tend to substantially modify the properties of pure semiconductors. Sample levitation done in a vacuum clearly helps maintain the sample purity. However, in the 1-g environment, all gravity caused effects such as convection, sedimentation and buoyancy are still present in the sample. In addition, large forces needed to levitate a sample in the presence of the gravity can cause additional flows in the melt. The use of the High Temperature Electrostatic Levitator (HTESL) for the present research is a recent development and little is known about the flows induced by the electrostatic forces. In this ground base program, we will define the limits of HTESL technology as various thermophysical properties of molten semiconductors are measured.

Rhim, Won-Kyu↗
NASA NTRS2000

Silicon-Based Ceramic-Matrix Composites for Advanced Turbine Engines: Some Degradation Issues

SiC/BN/SiC composites are designed to take advantage of the high specific strengths and moduli of non-oxide ceramics, and their excellent resistance to creep, chemical attack, and oxidation, while circumventing the brittleness inherent in ceramics. Hence, these composites have the potential to take turbine engines of the future to higher operating temperatures than is achievable with metal alloys. However, these composites remain developmental and more work needs to be done to optimize processing techniques. This paper highlights the lingering issue of pest degradation in these materials and shows that it results from vestiges of processing steps and can thus be minimized or eliminated.

Thomas-Ogbuji, Linus U. J.↗
NASA NTRS2014

Nuclear Thermal Rocket (NTR) Development Risk Communication

There are clear advantages of development of a Nuclear Thermal Rocket (NTR) for a crewed mission to Mars. NTR for in-space propulsion enables more ambitious space missions by providing high thrust at high specific impulse (approximately 900 sec) that is 2 times the best theoretical performance possible for chemical rockets. Missions can be optimized for maximum payload capability to take more payload with reduced total mass to orbit; saving cost on reduction of the number of launch vehicles needed. Or missions can be optimized to minimize trip time significantly to reduce the deep space radiation exposure to the crew. NTR propulsion technology is a game changer for space exploration. However, "NUCLEAR" is a word that is feared and vilified by some groups and the hostility towards development of any nuclear systems can meet great opposition by the public as well as from national leaders and people in authority. Communication of nuclear safety will be critical to the success of the development of the NTR. Why is there a fear of nuclear? A bomb that can level a city is a scary weapon. The first and only times the Nuclear Bomb was used in a war was on Hiroshima and Nagasaki during World War 2. The "Little Boy" atomic bomb was dropped on Hiroshima on August 6, 1945 and the "Fat Man" on Nagasaki 3 days later on August 9th. Within the first 4 months of bombings, 90- 166 thousand people died in Hiroshima and 60-80 thousand died in Nagasaki. It is important to note for comparison that over 500 thousand people died and 5 million made homeless due to strategic bombing (approximately 150 thousand tons) of Japanese cities and war assets with conventional non-nuclear weapons between 1942- 1945. A major bombing campaign of "firebombing" of Tokyo called "Operation Meetinghouse" on March 9 and 10 consisting of 334 B-29's dropped approximately1,700 tons of bombs around 16 square mile area and over 100 thousand people have been estimated to have died. The declaration of death is very clear for conventional weapons and then the declaration of death due to radiation becomes vague and unclear. This may have been due to people mis-understanding the dangers and effects of radiation when assessing the damage and harm to people initially, but it is also become insidious when expressing opposition to nuclear energy. A nuclear radiation accident can be scary due to the power involved and the fear of radiation release. The International Atomic Energy Agency defines a nuclear and radiation accident a "an event that has led to significant consequences to people, the environment or the facility." There have been 3 commercial nuclear reactor accidents (Chernobyl, Three Mile Island, and Fukushima) that stand out to the public and much of the information about the result and impact to workers, environment, and public can be misleading. Often information is presented without clear correlation with radiation and other pertinent information is left out presenting a very scary situation to affect the emotions of the reader. A very boring but "critically acclaimed" movie was made in 1979 called "The China Syndrome" starring Jane Fonda and Jack Lemmon. The film was released on March 16, 1979, 12 days before the 3-Mile Island nuclear accident in Pennsylvania. The basis from the movie was from a few nuclear plant incidents and in particular, the Brown's Ferry Alabama Power Plant fire. In one scene from the movie, a physicist Dr. Elliott Lowell played by Donald Hotton states that a China Syndrome event would make "an area the size of Pennsylvania" permanently uninhabitable. Real serious nuclear incidents like Chernobyl and Fukushima are often sited to make people fear the consequences of using nuclear power. However, the consequences are at best poorly communicated and at worst fictitiously inflated to instigate social unrest against nuclear power. There is an article being circulated on Facebook with a title "28 Signs that the (US) West Coast is being absolutely fried with nuclear radiation from Fukushima" which focus on mis-information and fear mongering. Nuclear power and NTR are powerful resources that can open many doors for future prosperity and capability. With great power comes great responsibility. Radiation and its effects need to be better understood, quantified, and communicated. A human mission to mars has its own risks of deep space radiation and is considered a considerable risk at 400 milli-Sieverts per year in deep space and 245 milli-Sieverts per year on the surface of Mars as measured by the Mars Curiosity mission. Although these quantities of ionizing radiation are within the astronaut career limit, it exceeds the yearly average amounts of ionizing radiation. Astronaut crews have experienced these levels of radiation before, but for durations shorter than a year, and a mission to Mars could possibly be 3 years in length. There is also evidence that people can comfortably handle higher levels of ionizing radiation where the radiation occurs naturally like Ramsar, Iran when people can experience 270 milli-Sieverts per year. A risk posture that the development, test, and flight of an NTR will meet opposition from groups who oppose nuclear energy must be likely and the impact can be sever to the effort. Active risk mitigation must be taken for an NTR full-scale development project. The NTR design must take into account safety for transport and off nominal conditions. Nuclear fuel element must consider containment of fission products and Low Enriched Uranium (LEU) that may meet less opposition should be considered for safety and security reasons. Even though testing was conducted on Rover/NERVA safely and successfully in the 60's with exhaust sent heavenward in to open air, modern testing of NTR must consider full containment and no release of ionizing radiation to the public and must meet the current requirement of no more than 0.1 milli-Sieverts per year to the public. 0.1 milli-Sieverts is equivalent to eating one banana or a 20 hour plane flight. Good communication with the public and regulatory agencies will be essential to show that all effort is applied toward protection to the public and astronauts. The inspiring endeavor to put humans on Mars to study the planet, search for life, and learn more about this Solar System will be full of risks but it will be worth it. NTR will be worth the development effort if it allows humans to explore our Solar System.

Kim, Tony↗
NASA NTRS2016

Conventional and Bimodal Nuclear Thermal Rocket (NTR) Artificial Gravity Mars Transfer Vehicle Concepts

A variety of countermeasures have been developed to address the debilitating physiological effects of zero-gravity (0-g) experienced by cosmonauts and astronauts during their approximately 0.5 to 1.2 year long stays in low Earth orbit (LEO). Longer interplanetary flights, combined with possible prolonged stays in Mars orbit, could subject crewmembers to up to approximately 2.5 years of weightlessness. In view of known and recently diagnosed problems associated with 0-g, an artificial gravity (AG) spacecraft offers many advantages and may indeed be an enabling technology for human flights to Mars. A number of important human factors must be taken into account in selecting the rotation radius, rotation rate, and orientation of the habitation module or modules. These factors include the gravity gradient effect, radial and tangential Coriolis forces, along with cross-coupled acceleration effects. Artificial gravity Mars transfer vehicle (MTV) concepts are presented that utilize both conventional NTR, as well as, enhanced bimodal nuclear thermal rocket (BNTR) propulsion. The NTR is a proven technology that generates high thrust and has a specific impulse (Isp) capability of approximately 900 s-twice that of today's best chemical rockets. The AG/MTV concepts using conventional Nuclear Thermal Propulsion (NTP) carry twin cylindrical International Space Station (ISS)- type habitation modules with their long axes oriented either perpendicular or parallel to the longitudinal spin axis of the MTV and utilize photovoltaic arrays (PVAs) for spacecraft power. The twin habitat modules are connected to a central operations hub located at the front of the MTV via two pressurized tunnels that provide the rotation radius for the habitat modules. For the BNTR AG/MTV option, each engine has its own closed secondary helium(He)-xenon (Xe) gas loop and Brayton Rotating Unit (BRU) that can generate 10s of kilowatts (kWe) of spacecraft electrical power during the mission coast phase eliminating the need for large PVAs. A single inflatable TransHab-type habitation module is also used with multiple vertical floors oriented radial to the MTV spin axis. The BNTR MTV's geometry-long and linear-is naturally compatible with AG operation. By rotating the vehicle about its center-of-mass (CM) and perpendicular to its flight vector at approximately 3.0 to 5.2 rpm, a centrifugal force and AG environment corresponding to approximately 0.38 to 1.0 g can be established to help maintain crew fitness out to Mars and back. Vehicles using NTP/ Bimodal Nuclear Thermal Propulsion (BNTP) can more readily accommodate the heavier payload mass and increased RCS propellant loading associated with AG operation, and can travel faster to and from Mars thereby reducing the crew's exposure to galactic cosmic radiation and solar flares. Mission scenario descriptions, key vehicle features and operational characteristics for each propulsion option are presented using the lift capability and payload volumes estimated for the Space Launch System (SLS)-1B and followon Heavy Lift Vehicle (HLV).

Nuclear Propulsion↗
NASA NTRS2017

Evaluation of CVI SiC/SiC Composites for High Temperature Applications

Silicon carbide fiber reinforced silicon carbide (SiC/SiC) composites are candidate materials for various high temperature turbine engine applications because of their high specific strength and good creep resistance at temperatures of 1400 C (2552 F) and higher. Chemical vapor infiltration (CVI) SiC/SiC ceramic matrix composites (CMC) incorporating Sylramic-iBN SiC fiber were evaluated via fast fracture tensile tests (acoustic emission damage characterization to assess cracking behavior), tensile creep testing, and microscopy. The results of this testing and observed material behavior degradation mechanisms are reviewed.

testing↗
NASA NTRSDate not supplied

Strategy for Developing Technologies for Megawatt-class Nuclear Electric Propulsion Systems

In late fiscal year 2020, the Space Nuclear Propulsion (SNP) project began the process of formulating an investment strategy to support development of the technologies required for a high-power (megawatt-class) nuclear electric propulsion (NEP) system capable of performing human-scale missions. This activity was initiated concurrent with several high-level studies and assessments were either under way or had just concluded. Studies of human-scale Mars missions have been performed several times over the past two decades. One of the most recent studies examined opposition-class human Mars missions to occur in the late 2030s timeframe [1,2]. The mission architecture assumed a hybrid NEP/chem-propelled vehicle that used a high specific impulse (Isp) NEP-system and a liquid oxygen (LOx)-liquid methane high thrust chemical stage (two 110 kN (25 klbf) thrust, 365 s Isp engines) for maneuvers performed to enter and exit gravity wells. Trajectory analyses performed in this study showed that such a mission could be performed with 2-4 MWe directed into the electric propulsion system (operating for 20,000+ hours), with the large range representing different opposition-class Mars mission opportunities and permutations on the trajectory design, concept of operations, and technology choices. In 2020, the NASA Engineering and Safety Center (NESC) performed a study to evaluate the maturity of the different technologies required for nuclear propulsion systems [3]. The executive summary of this report provided the following top-level conclusions: • “The majority of critical technologies for… NEP/Chem… systems are relatively immature” • “TRLs [technology readiness levels] in the literature are often overestimated” • “The majority of critical technologies… for NEP/Chem… systems are at a relatively high level of advancement degree of difficulty (AD2 > 4) for maturation, requiring a dual development approach” • “The proper assessment of baseline TRL and AD2 values and the estimation of requirements and resources required for advancement have been consistent issues for NEP,” • “Non-advocate reviews should occur at the start of a technology program and at all key milestones.” In 2021, the National Academies of Science, Engineering, and Medicine (NASEM) issued a separate report [4] identifying the “primary technical and programmatic challenges, merits, and risks for maturing space nuclear propulsion technologies of interest to a future human Mars exploration mission.” That work contained several important findings, including: • “Developing a MWe-class NEP system for the baseline mission would require increasing power by orders of magnitude relative to NEP system flight- or ground-based technology demonstrations completed to date.” • “Subscale in-space flight testing of NEP systems cannot address many of the risks and potential failure modes associated with the baseline mission NEP system. With sufficient M&S [modeling & simulation] and ground testing, including modular subsystem tests at full scale and power, flight qualification requirements can be met by the cargo missions that will precede the first crewed mission to Mars. Fully integrated ground testing may not be required.” • “As a result of low and intermittent investment over the past several decades, it is unclear if even an aggressive program would be able to develop an NEP system capable of executing the baseline mission in 2039.” These efforts motivated the SNP project to investigate the technologies available for a megawatt-class high power nuclear electric propulsion system. That system is illustrated schematically in Figure 1 and is comprised of five separate top-level critical technology elements (CTEs). 1. Nuclear Reactor – Thermal power source for the system, utilizing high-assay low enriched uranium (HALEU) as the nuclear fuel. Reactor radiation shielding is also included in this CTE. 2. Power Conversion – Operates as a thermodynamic cycle, accepting nuclear reactor thermal power as an input and converting it to mechanical power. 3. Power Management and Distribution (PMAD) – Accepts as an input mechanical power from the power conversion system, which is used to generate electrical power. The PMAD system also distributes the generated electrical power to all other parts of the spacecraft, including the high-power EP system. The PMAD system may also perform duties such as isolation, fault detection, and power transformation/rectification for different spacecraft systems, including the thrusters. 4. Electric Propulsion (EP) – Accepts as an input electrical power, which is used to accelerate a propellant to high speeds to produce thrust. This system includes the power processing unit (PPU), which converts the power it receives to the correct current and voltage required by the thrusters, and the propellant storage and feed systems, which contain and meter the flow of propellant to the thrusters. 5. Thermal Management (Radiators/Heat Rejection) – The cold side of the thermodynamic power conversion cycle, accepts thermal power from the power conversion system and radiatively rejects that heat to space. In this paper, we describe the SNP project formulation and investment strategy that aims to accomplish the research and development required to advance the technology readiness for each CTE. The strategy relies heavily upon experimental testing supported by modeling and simulation to yield realistic assessments of the technologies, which in turn will be used to inform future NEP system-level design decisions and any potential technology downselects.

Kurt A Polzin↗
NASA NTRS2022

A Closer Look at Non-Random Patterns Within Chemistry Space for a Smaller, Earlier Amino Acid Alphabet

Recent findings, in vitro and in silico, are strengthening the idea of a simpler, earlier stage of genetically encoded proteins which used amino acids produced by prebiotic chemistry. These findings motivate a re-examination of prior work which has identified unusual properties of the set of twenty amino acids found within the full genetic code, while leaving it unclear whether similar patterns also characterize the subset of prebiotically plausible amino acids. We have suggested previously that this ambiguity may result from the low number of amino acids recognized by the definition of prebiotic plausibility used for the analysis. Here, we test this hypothesis using significantly updated data for organic material detected within meteorites, which contain several coded and non-coded amino acids absent from prior studies. In addition to confirming the well-established idea that “late” arriving amino acids expanded the chemistry space encoded by genetic material, we find that a prebiotically plausible subset of coded amino acids generally emulates the patterns found in the full set of 20, namely an exceptionally broad and even distribution of volumes and an exceptionally even distribution of hydrophobicities (quantified as logP) over a narrow range. However, the strength of this pattern varies depending on both the size and composition the library used to create a background (null model) for a random alphabet, and the precise definition of exactly which amino acids were present in a simpler, earlier code. Findings support the idea that a small sample size of amino acids caused previous ambiguous results, and further improvements in meteorite analysis, and/or prebiotic simulations will further clarify the nature and extent of unusual properties. We discuss the case of sulfur-containing amino acids as a specific and clear example and conclude by reviewing the potential impact of better understanding the chemical “logic” of a smaller forerunner to the standard amino acid alphabet.

Amino acids↗
DOE OSTI2024

Understanding the Chemical Complexity of Multicomponent Systems: Uranium Polyoxometalates as Nanosorbents

The overarching objective of this project was to develop a molecular-scale understanding of chemical interactions of the transuranic (TRU) elements with uranyl-based polyoxometalate nanoclusters (UPOMs). The specific goals that supported this overarching objective were to: (i) quantify TRU interactions with UPOMs as a function of TRU, carbonate, and UPOM concentration, pH, and temperature; (ii) examine the molecular-level bonding environment of TRU-UPOM complexes; and (iii) develop a rate expression capable of describing the sorption and reduction of TRU by UPOMs. The published literature suggests several potential interactions can occur in TRU-UPOM systems: (i) encapsulation of TRU and coordination with the internal ‘-yl’ oxygens of the UPOM, (ii) coordination of TRU with the external ‘-yl’ oxygens of the UPOM, and (iii) coordination of TRU with the bridging ligands (e.g., peroxo, hydroxo, oxalate) of the UPOM. The latter two may induce aggregation of the UPOMs. The concept of encapsulation is demonstrated by the X-ray diffraction structure of crystallized U 20 , which reveals a Na + cation under each pentagonal face (Sigmon et al., 2009). Computational modeling shows that, while the negative charge of U 20 is spread among all the oxygen atoms, the internal ‘-yl’ oxygens host the most negative charge (Miro and Bo, 2012). This negative charge is reduced through the complexation of the templating sodium ions in the interior of the UPOM. Furthermore, Nyman et al. (2011) shows that cesium can exit through the pentagonal window of U 28 in the aqueous phase, suggesting that the TRU elements, which are smaller than cesium, may be capable of entering a UPOM through these windows in an exchange reaction. Under this project, we focused on hafnium, neptunium, and plutonium interactions with UPOMs.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Organic amendments change soil organic C structure and microbial community but not total organic matter on sub-decadal scales

Organic C has many benefits for soil, but it is depleted by tillage and crop harvest, and especially so for biofuel crops. Accordingly, strategies such as partially retaining stover or planting a cover crop can help ameliorate the negative effect of C removal. We used a long-term field experiment to study the impacts of stover retention and planting cover crop on soil organic matter (SOM), its extractable components and the soil microbial community. SOM chemical composition characterization was determined by electrospray ionization (ESI) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) in sequential water, methanol (MeOH), and chloroform (CHCl3) extracts. The characteristics of the soil bacterial community were measured by phospholipid fatty acid (PLFA), real-time quantitative PCR, and 16S rRNA gene sequence. The variations in total SOM content, total microbial biomass, and bacterial population were slight among treatments, but SOM chemical compounds, arbuscular mycorrhizal fungi (AMF) biomass, and bacterial structure changed significantly, and especially so in the coupled application of stover retention and cover crop. Specifically, stover retention enriched more lignin-like compounds in soil, whereas cover crop enriched more condensed hydrocarbons, and had more compounds with an aromaticity index (AI) >0.5. The bacterial community was not altered by the cover crop, but the corn stover retention increased the relative abundances of Myxococcales (Deltaproteobacteria) and decreased that of Actinobacteria. Redundancy analysis (RDA) further unveiled that the bacterial community in the stover treatments had significantly positive association with CHCl3-extracted chemical classes, i.e. unsaturated hydrocarbon and lipid with the coupled application (stover and cover crop), and lignin and protein with the single corn stover treatment. Taken together, our study shows how different C addition practices influence the molecular composition of SOM and the structure of soil microbial communities.

Xu, Jiangbin↗
DOE OSTI2020

Deep level defects and cation sublattice disorder in ZnGeN 2

The III-nitrides have revolutionized lighting technology and power electronics. Expanding the nitride semiconductor family to include the heterovalent ternary nitrides opens up new and exciting opportunities for device design that may help overcome some of the limitations of the binary nitrides as well as new applications. However, the more complex cation sublattice also gives rise to new complexities with both native and extrinsic defects, such as disorder on the cation sublattice. Here, depth-resolved cathodoluminescence spectroscopy and surface photovoltage spectroscopy measurements of defect energy levels in ZnGeN 2 combined with transmission microscopy and crystal lattice diffraction reveal optical signatures of mid-gap states that can be associated with cation sublattice disorder. The energies of these characteristic optical signatures in ZnGeN 2 thin films grown by metal-organic chemical vapor deposition are in good agreement with energy levels predicted by density functional theory for specific thermodynamically stable native point defects. To test the dependence of these defect signatures on crystal atomic composition, we correlated spatially-resolved optical and atomic composition measurements using spatially resolved x-ray photoelectron spectroscopy with systematically varied growth conditions on the same ZnGeN 2 films. The resultant elemental maps versus defect spectral energies and intensities suggest that cation antisite complexes (Zn Ge -Ge Zn ) versus isolated native point defects form preferentially and introduce mid-gap states that dominate electron-hole pair recombination. Complexing of Zn Ge and Ge Zn antisites manifests as disorder in the cation sub-lattice and leads to the formation of wurtzitic ZnGeN 2 as indicated by transmission electron microscopy diffraction patterns and x-ray diffraction (XRD) reciprocal space maps. Furthermore, these findings emphasize the importance of growth conditions to control cation place exchange.

42 ENGINEERING↗
NASA NTRS2021

Validation of the aerosol optical property products derived by the GRASP/Component approach from multi-angular polarimetric observations

The multi-angle polarimetric satellite observations are helpful for improving the retrievals of aerosol parameters. However, practical applications of polarization technology are still limited because of complexity of measurement and interpretation of polarimetric observations. In this study, we analyze the performance of a new component approach developed in the frame of the Generalized Retrieval of Atmosphere and Surface Properties (GRASP) algorithm. In addition to aerosol optical properties including particle size distribution, non-sphericity and index of refraction that are commonly derived from multi-angle radiance and polarization measurements, the GRASP/Component approach also provides some information about aerosol composition. Specifically, in this approach aerosol is modeled as an internal mixture of several components with distinctly different chemical compositions and known refractive indices. The approach is intended not only to provide additional insight on aerosol composition but also to improve retrieval of basic aerosol optical properties. This study presents comprehensive validation and evaluation of Aerosol Optical Depth (AOD), Ångstrom exponent (AE), fine mode AOD (AODF), coarse mode AOD (AODC), and single scattering albedo (SSA) as retrieved by the GRASP/Component approach. The GRASP/Component products include aerosol retrievals using two different aerosol component mixing rules, i.e., Maxwell-Garnett (MG) effective medium approximation and a simple Volume- Weighted averaging (VW). The differences between the results obtained using these two assumptions are also discussed. The obtained results show that the aerosol optical property products of GRASP/Component approach have good agreement with the ground-based AERONET measurements, which is comparable to other PARASOL/ GRASP approaches. Specifically, the AOD retrieved by GRASP/Component approach show high correlation and nearly no bias both over land and ocean, as compared with AERONET. The more detailed aerosol properties such as AE, AODF, AODC and SSA also show one of the best comparisons with AERONET. These improvements can probably be attributed to the use of the additional physical constraints on spectral dependence of the complex refractive index and the reduction of total number of aerosol parameters directly retrieved in the GRASP/Component approach. In addition, the choice of mixing rules had no significant effect on optical retrievals. With the exception of SSA, the results obtained based on the MG mixing rule were found to be slightly better over those obtained using VW mixing rule, especially for bias.

Brent N Holben↗
NASA NTRS1993

Space propulsion

Lewis Research Center is developing broad-based new technologies for space chemical engines to satisfy long-term needs of ETO launch vehicles and other vehicles operating in and beyond Earth orbit. Specific objectives are focused on high performance LO2/LH2 engines providing moderate thrusts of 7,5-200 klb. This effort encompasses research related to design analysis and manufacturing processes needed to apply advanced materials to subcomponents, components, and subsystems of space-based systems and related ground-support equipment. High-performance space-based chemical engines face a number of technical challenges. Liquid hydrogen turbopump impellers are often so large that they cannot be machined from a single piece, yet high stress at the vane/shroud interface makes bonding extremely difficult. Tolerances on fillets are critical on large impellers. Advanced materials and fabricating techniques are needed to address these and other issues of interest. Turbopump bearings are needed which can provide reliable, long life operation at high speed and high load with low friction losses. Hydrostatic bearings provide good performance, but transients during pump starts and stops may be an issue because no pressurized fluid is available unless a separate bearing pressurization system is included. Durable materials and/or coatings are needed that can demonstrate low wear in the harsh LO2/LH2 environment. Advanced materials are also needed to improve the lifetime, reliability and performance of other propulsion system elements such as seals and chambers.

Kazaroff, John M.↗
NASA NTRS1986

Process for preparing essentially colorless polyimide film containing phenoxy-linked diamines

A polyimide film that is approximately 90% transparent at 500 nm, useful for thermal protective coatings and solar cells, and the processes for preparing the same by thermal and chemical conversion are disclosed. An essential feature for achieving maximum optical transparency films requires utilizing recrystallized and/or sublimated specific aromatic diamines and dianhydride monomers and introducing phenoxy or thiophenyl separator groups and isomeric m,m' or o,p'-oriented diamines into the polymer molecular structure. The incorporation of these groups in the polymer structure serves to separate the chromaphoric centers and reduce the formation of inter-chain and intra-chain charge transfer complexes which normally cause absorptions in the UV-visible range. The films may be obtained by hand, brushing, casting, or spraying a layer of polyamic acid solutions onto a surface and thermally converting the applied layer to the polyimide, or the polyamic acid solution can be chemically converted to the polyimide, subsequentially dissolved in an organic solvent, and applied as a polyimide film layer with the solvent therein thermally removed.

Stclair, A. K.↗
DOE OSTI2024

Intrinsic Bonding and Reactivity of Actinide Clusters Poster

The effect of electronic structure on chemical bonding and reactivity is one of the most important questions in the field of chemistry. Insight into chemical bond formation involving elements that contain f electrons (i.e., the lanthanides and actinides) is critical for solving specific technical challenges, such as development of advanced nuclear fuel cycles and efficient rare earth separations, as well as a broader understanding of bonding across the entire periodic table. The primary technique for studying the fundamentals of lanthanide and actinide bonding is crystallization of metal-ligand compounds followed by structural determination with X-rays and comparison to theory with computational chemistry. While this procedure has yielded significant insights for a wide variety of elements, it is challenging to apply to the heavier trans-uranic actinides such as berkelium and californium because of limited material availability, significant radioactivity, and poorly understood chemical reactivity of these elements. We hypothesize that by forming actinide-ligand clusters in a mass spectrometer and probing their reactivity in the gas-phase, many of the challenges associated with studying the heavier trans-uranic elements can be circumvented. This project will develop a capability to address a wide range of actinide bonding and reactivity phenomena, increasing Idaho National Laboratory’s capability to address fundamental questions at the forefront of heavy element chemical and molecular science.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Overcoming the Conductance versus Crossover Trade-off in State-of-the-Art Proton Exchange Fuel-Cell Membranes by Incorporating Atomically Thin Chemical Vapor Deposition Graphene

Permeance–selectivity trade-offs are inherent to polymeric membranes. In fuel cells, thinner proton exchange membranes (PEMs) could enable higher proton conductance and increased power density with lower area-specific resistance (ASR), smaller ohmic losses, and lower ionomer cost. However, reducing thickness is accompanied by an increase in undesired species crossover harming performance and long-term efficiency. Here, we show that incorporating atomically thin monolayer graphene synthesized via scalable chemical vapor deposition (CVD) and tunable defect density into PEMs (Nafion, ~5–25 μm thick) can allow for reduced H 2 crossover (~34–78% of Nafion of a similar thickness) while maintaining adequate areal proton conductance for applications (>4 S cm –2 ). In contrast to most prior work using >50 μm symmetric Nafion sandwich structures, we elucidate the interplay of graphene defect density and Nafion proton transport resistance on the performance of Nafion|graphene composite membranes and find high-quality low-defect density CVD graphene (G) supported on Nafion 211 (~25 μm); i.e., N211|G has a high areal proton conductance (~6.1 S cm –2 ) and the lowest H 2 crossover (~0.7 mA cm –2 ). Fully functional centimeter-scale N211|G fuel-cell membranes demonstrate performance comparable to that of state-of-the-art Nafion N211 at room temperature as well as standard operating conditions (~80 °C, ~150–250 kPa-abs) with H 2 /air (power density ~0.57–0.63 W cm –2 ) and H 2 /O 2 feed (power density ~1.4–1.62 W cm –2 ) and markedly reduced H 2 crossover (~53–57%).

25 ENERGY STORAGE↗
NASA NTRS1971

Thermodynamic properties and theoretical rocket performance of hydrogen to 100,000 K and 1.01325 x 10 to the 8th power N/sq m

The composition and thermodynamic properties were calculated for 100 to 110,000 K and 1.01325 x 10 to the 2nd power to 1.01325 x 10 to the 8th power N/sq m for chemical equilibrium in the Debye-Huckel and ideal-gas approximations. Quantities obtained were the concentrations of hydrogen atoms, protons, free electrons, hydrogen molecules, negative hydrogen ions, hydrogen diatomic molecular ions, and hydrogen triatomic molecular ions, and the enthalpy, entropy, average molecular weight, specific heat at constant pressure, density, and isentropic exponent. Electronically excited states of H and H2 were included. Choked, isentropic, one-dimensional nozzle flow with shifting chemical equilibrium was calculated to the Debye-Huckel and ideal-gas approximations for stagnation temperatures from 2500 to 100,000 K. The mass flow per unit throat area and the sonic flow factor were obtained. The pressure ratio, temperature, velocity, and ideal and vacuum specific impulses at the throat and for pressure ratios as low as 0.000001 downstream were found. For high temperatures at pressures approaching 1.01325 x 10 to the 8th power N/sq m, the ideal-gas approximation was found to be inadequate for calculations of composition, precise thermodynamic properties, and precise nozzle flow. The greatest discrepancy in nozzle flow occurred in the exit temperature, which was as much as 21 percent higher when the Debye-Huckel approximation was used.

Patch, R. W.↗
DOE OSTI2020

Modular Electrochemical Synthesis Using a Redox Reservoir Paired with Independent Half-Reactions

Electrochemical synthesis of high-value chemicals using renewable electricity could lead to sustainability advantages over conventional chemical manufacturing. The tight coupling between paired anodic and cathodic reactions in conventional electrochemical processes, however, constrains the products and their efficiencies. Here, we demonstrate a strategy to achieve modular electrochemical synthesis (ModES) of different chemicals by decoupling and pairing the oxidative and reductive half-reactions with a heterogeneous redox reservoir (RR). Specifically, sodium nickel hexacyanoferrate (NaNiHCF) can serve as a robust and reversible RR that enables the modular production of several strong oxidants, hydrogen peroxide (H 2 O2) and sodium persulfate (Na 2 S 2 O 8 ) or active chlorine, in separate RR-coupled electrochemical processes. The system’s excellent performance and operational stability is demonstrated by continuous operation over 100 cycles (~36 h) to produce H 2 O 2 and Na 2 S 2 O 8 with a high voltage efficiency. The concept presented here highlights the prospects for using RRs to enable efficient, modular, and on-demand electrochemical synthesis of valuable chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗