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At least 703 records · Page 39

Femtosecond stimulated Raman spectro-microscopy for probing chemical reaction dynamics in solid-state materials

Femtosecond stimulated Raman spectroscopy (FSRS) is a chemically specific vibrational technique that has the ability to follow structural dynamics during photoinduced processes such as charge transfer on the ultrafast timescale. FSRS has a strong background in following structural dynamics and elucidating chemical mechanisms; however, its use with solid-state materials has been limited. As photovoltaic and electronic devices rely on solid-state materials, having the ability to track the evolving dynamics during their charge transfer and transport processes is crucial. Following the structural dynamics in these solid-state materials will lead to the identification of specific chemical structures responsible for various photoinduced charge transfer reactions, leading to a greater understanding of the structure–function relationships needed to improve upon current technologies. Furthermore, isolating the specific nuclear motions and molecular structures that drive a desired physical process will provide a chemical blueprint, leading to the rational design and fabrication of efficient electronic and photovoltaic devices. In this perspective, we discuss technical challenges and experimental developments that have facilitated the use of FSRS with solid-state samples, explore previous studies that have identified structure–function relationships in charge transfer reactions, and analyze the future developments that will broaden and advance the field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Collisional coupling in counterstreaming laser-produced plasmas

The collisional processes which transfer momentum between counterstreaming plasmas are reviewed and applied to the example of a laser-produced plasma expanding into a partially ionized background. Experimental measurements of the dependence of the ion flow field on collisional momentum transfer demonstrate the validity of the simplified treatment of collision processes which have been adopted. A numerical model which simulates the laser-plasma interaction with the background confirms the importance of collisions in previous experimental studies of momentum coupling, and provides some insight into the distinction between collisional and collisionless flow regimes.

Koopman, D. W.↗

Technology Transfer

The objective of this summer's work was to attempt to enhance Technology Application Group (TAG) ability to measure the outcomes of its efforts to transfer NASA technology. By reviewing existing literature, by explaining the economic principles involved in evaluating the economic impact of technology transfer, and by investigating the LaRC processes our William & Mary team has been able to lead this important discussion. In reviewing the existing literature, we identified many of the metrics that are currently being used in the area of technology transfer. Learning about the LaRC technology transfer processes and the metrics currently used to track the transfer process enabled us to compare other R&D facilities to LaRC. We discuss and diagram impacts of technology transfer in the short run and the long run. Significantly, it serves as the basis for analysis and provides guidance in thinking about what the measurement objectives ought to be. By focusing on the SBIR Program, valuable information regarding the strengths and weaknesses of this LaRC program are to be gained. A survey was developed to ask probing questions regarding SBIR contractors' experience with the program. Specifically we are interested in finding out whether the SBIR Program is accomplishing its mission, if the SBIR companies are providing the needed innovations specified by NASA and to what extent those innovations have led to commercial success. We also developed a survey to ask COTR's, who are NASA employees acting as technical advisors to the SBIR contractors, the same type of questions, evaluating the successes and problems with the SBIR Program as they see it. This survey was developed to be implemented interactively on computer. It is our hope that the statistical and econometric studies that can be done on the data collected from all of these sources will provide insight regarding the direction to take in developing systematic evaluations of programs like the SBIR Program so that they can reach their maximum effectiveness.

Smith, Nanette R.↗

Acetylene-chromene terminated resins as high temperature thermosets

A novel phase transfer catalyzed process for the preparation of propargyl ethers has been developed. The propargyl ethers serve as precursors to a new class of thermosetting resins called acetylene-chromene terminated (ACT) resins. Heat treatment of a solution of propargyl ethers with various catalysts, followed by removal of solvent leads to the ACT resins via partial conversion of the propargyl ether groups to chromenes. This process reduces the energy content of the resin systems and reduces the amount of shrinkage found during cure. Due to the presence of the solvent the process is safe and gives rise to low viscosity products suitable for resin transfer molding and filament winding type applications. Due to the high glass transition temperature, high modulus, and low moisture uptake the cured resins display better than 232 C/wet performance. The thermal stability of the ACT resins in air at 204 C is superior to that of conventional bismaleimide resins. The resins also display excellent electrical properties.

Godschalx, J. P.↗

Determination of Vibrational Motions Driving Photoinduced Electron Transfer Reactions in Molecular Crystals and Organic Thin Films

The objective of this research is to develop an understanding of how nuclear motions can be used to drive and control photo-induced charge transfer and singlet fission reactions in molecular crystals and thin films. By following the structural evolution of reacting molecules and nanostructures on the timescale of their nuclear motion, we will determine what interplay of nuclear coordinates is most efficient in driving electron transfers, a necessary first step in most photovoltaic and photocatalytic processes. We will identify which nuclear coordinates effectively promote desirable electron transfer processes, or ineffectively dissipate photon energy into unwanted thermal energy, thus guiding the design and implementation of molecular systems tailored for high efficiency processes. Specifically, we aim to identify which nuclear coordinates are responsible for driving electron transfer and singlet fission reactions at different points along the reaction coordinate, particularly in regimes which deviate from Marcus theory predictions. We will do so by investigating systems with electron transfer and singlet fission occurring from non-thermalized states due to strong donor-acceptor electronic coupling. First, we will prove that specific vibrational modes are responsible for charge transfer processes in molecular crystals. Secondly, we will investigate how vibrational coherences and specific nuclear motions can be used to drive high yield singlet fission processes. Finally, we will determine how complex film morphology affects long-range charge transport, a key limiting factor in our ability to make gains in efficiency.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Upgrading Biogas through in situ Conversion of Carbon Dioxide to Biomethane in Anaerobic Digesters

Organic waste streams generated by wastewater treatment plants, agricultural operations, and food processing industries represent an important yet underutilized opportunity for renewable energy production in the United States. Through anaerobic digestion, these waste streams can produce biogas, a mixture primarily composed of methane (CH4) and carbon dioxide (CO2), that can be upgraded to pipeline-quality natural gas. However, most existing upgrading technologies remove CO2 from biogas rather than utilizing it, leaving a significant portion of the potential energy unused. This project investigates a novel biological upgrading approach that converts CO2 into additional CH4 by supplying hydrogen (H2) to specialized microorganisms capable of performing hydrogenotrophic methanation. The main challenges associated with biological biogas upgrading are related to hydrogen supply, gas-liquid mass transfer, and process stability. First, due to the high cost of hydrogen gas, it is preferable that H2 be produced on-site using renewable energy sources such as wind or solar power. Second, hydrogen has low solubility in liquids, which limits its availability to microorganisms and requires strategies to improve gas dissolution and transfer within the reactor. Third, process inhibition may occur as a result of increased pH caused by CO2 consumption or elevated H2 partial pressure, both of which can negatively affect methanogenic activity. Although research in these areas has advanced during the course of this project, these challenges have not yet been fully resolved. To date, the biological systems that have achieved the highest methane concentrations are typically ex-situ reactors, where operational conditions can be more easily controlled. For this reason, the findings of the present project remain highly relevant. The project goal was to develop an innovative system that can accomplish biogas upgrading via biological conversion of CO2 to CH4, in a novel hybrid approach that combines the advantages of both in-situ and ex-situ systems. The proposed system employs a three-phase upflow anaerobic bioreactor with H2 delivery through a gas-permeable membrane, enabling efficient hydrogen transfer and microbial conversion. Under optimized operating conditions, the system achieved 99% H2 consumption and 90% CO2 conversion. A subsequent gas cleaning stage was implemented to further improve gas quality and meet target purity standards. The upgraded gas composition reached 97.7% CH4, 2.2% CO2, and 0.97% O2, while H2S concentrations remained below detection limits. In addition, a flue gas-driven inorganic thermoelectric generator (TEG) system was designed and experimentally validated as a potential source of electricity for H2 production. The system consisted of six TEG modules connected in series and achieved an open-circuit voltage of 4.5 V and a maximum power output of 224 mW at a temperature difference of approximately 53.5 °C, demonstrating effective conversion of waste heat into electrical power under simulated flue gas conditions. Finally, a comprehensive techno-economic analysis was completed to evaluate the capital and operating costs associated with the proposed system. The results provide important insights to guide future scale-up, optimization, and potential deployment of integrated biological biogas upgrading technologies.

09 BIOMASS FUELS↗

Systems and methods for determining ground water-surface water interactions

Systems for determining GW/SW interaction are provided. The systems can include: a sensing assembly comprising sensors for pressure, fluid conductivity, temperature, and transfer resistance; processing circuitry operatively coupled to the sensing assembly and configured to receive data from the sensing assembly and process the data to provide a GW/SW interaction, wherein the data includes pressure, fluid conductivity, temperature, transfer resistance data. Methods for determining GW/SW interaction are provided. The methods can include: receiving real time data including pressure, fluid conductivity, temperature, and transfer resistance; from at least some of the data received simulating the SW/GW interaction; and fitting the real time data with the simulated data to provide actual SW/GW interaction.

Johnson, Timothy C.↗

Systems and methods for determining ground water-surface water interactions

Systems for determining GW/SW interaction are provided. The systems can include: a sensing assembly comprising sensors for pressure, fluid conductivity, temperature, and transfer resistance; processing circuitry operatively coupled to the sensing assembly and configured to receive data from the sensing assembly and process the data to provide a GW/SW interaction, wherein the data includes pressure, fluid conductivity, temperature, transfer resistance data. Methods for determining GW/SW interaction are provided. The methods can include: receiving real time data including pressure, fluid conductivity, temperature, and transfer resistance; from at least some of the data received simulating the SW/GW interaction; and fitting the real time data with the simulated data to provide actual SW/GW interaction.

Johnson, Timothy C.↗

Space Station technology experiments and uses

The use of the proposed Space Station for technological experimentation is discussed. The general objectives and capabilities of the Station and the status of planning are reviewed; the external and internal environmental conditions at the 500-km 28.5-deg-inclination Station orbit are described; and six conceptual Technology Development Missions designed by NASA and included in the Mission Requirements Data Base are briefly characterized and illustrated with drawings. The missions considered concern spacecraft-materials performance, solar dynamic power, data transfer and processing microelectronics, long-term cryogenic-fluid storage, active-optics technology, and cryogenic-propellant transfer, storage, and reliquefaction.

Breckenridge, R. A.↗

Synthesis, Structure, and Redox Reactivity of Ni Complexes Bearing a Redox and Acid–Base Non-innocent Ligand with Ni II , Ni III , and Ni IV Formal Oxidation States

Here, a series of Ni complexes bearing a redox and acid–base noninnocent tetraamido macrocyclic ligand, H 4 -(TAML-4) {H 4 -(TAML-4) = 15,15-dimethyl-5,8,13,17-tetrahydro-5,8,13,17-tetraaza-dibenzo[a,g]cyclotridecene-6,7,14,16-tetraone}, with formal oxidation states of Ni II , Ni III , and Ni IV were synthesized and characterized structurally and spectroscopically. The X-ray crystallographic analysis of the Ni complexes revealed a square planar geometry, and the [Ni(TAML-4)] complex with the formal oxidation state of Ni IV was characterized to be [Ni III (TAML-4 •+ )] with the oxidation state of the Ni III ion and the one-electron oxidized TAML-4 ligand, TAML-4 •+ . The Ni III oxidation state and the TAML-4 radical cation ligand, TAML-4 •+ , were supported by X-ray absorption spectroscopy and density functional theory calculations. The reversible interconversions between [Ni II (TAML-4)] 2– and [Ni III (TAML-4)] − and between [Ni III (TAML-4)] − and [Ni III (TAML-4 •+ )] were demonstrated in spectroelectrochemical measurements as well as in chemical oxidation and reduction reactions. The reactivities of [Ni III (TAML-4)] − and [Ni III (TAML-4 •+ )] were then investigated in hydride transfer reactions using NADH analogs. Hydride transfer from 9,10-dihydro-10-methylacridine (AcrH 2 ) to [Ni III (TAML-4 •+ )] was found to proceed via electron transfer (ET) from AcrH 2 to [Ni III (TAML-4 •+ )] with no deuterium kinetic isotope effect (k H /k D = 1.0(2)). In contrast, hydride transfer from AcrH 2 to [NiIII(TAML-4)] − proceeded much more slowly via a concerted proton-coupled electron transfer (PCET) process with k H /k D = 7.0(5). In the latter reaction, an electron and a proton were transferred to the Ni III center and the TAML-4 ligand, respectively. The mechanisms of the ET by [Ni III (TAML-4 •+ )] and the concerted PCET by [Ni III (TAML-4)] − were ascribed to the different redox potentials of the Ni complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

XPS analysis of the effect of fillers on PTFE transfer film development in sliding contacts

The development of transfer films atop steel counterfaces in contact with unfilled and bronze-filled PTFE has been studied using X-ray photoelectron spectroscopy. The sliding apparatus was contained within the vacuum of the analytical system, so the effects of the native oxide, hydrocarbon, and adsorbed gaseous surface layers of the steel upon the PTFE transfer behavior could be studied in situ. For both the filled and the unfilled PTFE, cleaner surfaces promoted greater amounts of transfer. Metal fluorides, which formed at the transfer film/counterface interface, were found solely in cases where the native oxide had been removed to expose the metallic surface prior to sliding. These fluorides also were found at clean metal/PTFE interfaces formed in the absence of frictional contact. A fraction of these fluorides resulted from irradiation damage inherent in XPS analysis. PTFE transfer films were found to build up with repeated sliding passes, by a process in which strands of transfer filled in the remaining counterface area. Under these reported test conditions, the transfer process is not expected to continue atop previously deposited transfer films. The bronze-filled composite generated greater amounts of transfer than the unfilled PTFE. The results are discussed relative to the observed increase in wear resistance imparted to PTFE by a broad range of inorganic fillers.

Blanchet, T. A.↗

Process and system for hot and/or cold energy transfer, transport and/or storage

A thermal conveyance system and process for absorbing, transporting, storing, and recovering thermal energy (both hot and cold energy) over a wide range of temperatures from up to 2,100° F., or higher, or cool energy at subzero temperatures in inert and stable particles without the need to maintain a minimum temperature or requiring high system pressures. The process involving the transferring thermal energy to a first transfer fluid and recovering thermal energy from a second transfer fluid wherein the first and the second transfer fluids comprise a two phase thermal media including a gaseous carrier containing a quantity of micron to millimeter sized solid particles.

25 ENERGY STORAGE↗

Clouds in ECMWF's 30 KM Resolution Global Atmospheric Forecast Model (TL639)

Global models of the general circulation of the atmosphere resolve a wide range of length scales, and in particular cloud structures extend from planetary scales to the smallest scales resolvable, now down to 30 km in state-of-the-art models. Even the highest resolution models do not resolve small-scale cloud phenomena seen, for example, in Landsat and other high-resolution satellite images of clouds. Unresolved small-scale disturbances often grow into larger ones through non-linear processes that transfer energy upscale. Understanding upscale cascades is of crucial importance in predicting current weather, and in parameterizing cloud-radiative processes that control long term climate. Several movie animations provide examples of the temporal and spatial variation of cloud fields produced in 4-day runs of the forecast model at the European Centre for Medium-Range Weather Forecasts (ECMWF) in Reading, England, at particular times and locations of simultaneous measurement field campaigns. model resolution is approximately 30 km horizontally (triangular truncation TL639) with 31 vertical levels from surface to stratosphere. Timestep of the model is about 10 minutes, but animation frames are 3 hours apart, at timesteps when the radiation is computed. The animations were prepared from an archive of several 4-day runs at the highest available model resolution, and archived at ECMWF. Cloud, wind and temperature fields in an approximately 1000 km X 1000 km box were retrieved from the archive, then approximately 60 Mb Vis5d files were prepared with the help of Graeme Kelly of ECMWF, and were compressed into MPEG files each less than 3 Mb. We discuss the interaction of clouds and radiation in the model, and compare the variability of cloud liquid as a function of scale to that seen in cloud observations made in intensive field campaigns. Comparison of high-resolution global runs to cloud-resolving models, and to lower resolution climate models is leading to better understanding of the upscale cascade and suggesting new cloud-radiation parameterizations for climate models.

Cahalan, R. F.↗

The Spacecraft Mass Balance as a Diagnostic Tool for Cabin Air Quality

The spacecraft-level mass balance is a powerful tool for diagnosing and decoupling factors influencing cabin air quality, especially with respect to trace contaminant propagation. Successful implementation of this approach relies upon accurate and temporally relevant air quality measurements, which are often challenging to attain for emerging trace contaminants. In addition to the proper interpretation of air quality data trends, a thorough understanding of subsystem-level mass transfer is required to characterize process performance. For many Environmental Control and Life Support System processes, subsystem mass transfer may be predicted based on physicochemical properties and classic unit operation design approaches. Gaps in understanding of process performance should be supplemented with thorough ground testing. A high confidence in the fidelity of one of these two aspects, air quality data or process performance, may help offset uncertainties in the other. At minimum, thresholding assumptions and numerical methods can be imposed to constrain unknown parameters within the physical envelope of the situation at hand. Finally, the complexity of cabin-wide integrated mass balances may be reduced by implementing a phenomenological approach towards subsystem discretization.

Cabin Air-quality↗

Slow Auger Recombination of Trapped Excitons Enables Efficient Multiple Electron Transfer in CdS–Pt Nanorod Heterostructures

We report solar-to-fuel conversion reaction often requires multiple proton-coupled electron transfer (PCET) processes powered by the energetic electrons and/or holes generated by the absorption of multiple photons. The effective coupling of multiple electron transfer from the light absorber with the multiple PCET reactions at the catalytic center is one of the key challenges in efficient and selective conversion of solar energy to chemical fuels. In this paper, we examine the dynamics of multiple electron transfer in quantum confined CdS nanorods with a Pt tip, in which the CdS rod functions as the light absorber and the Pt tip the catalytic center. By excitation-fluence-dependent transient absorption spectroscopic measurements, we show that the multiexciton Auger recombination rate in CdS rods follows a carrier-collision model, k n A = n 2 (n – 1)/4k 2 A , with a biexciton lifetime (1/k 2 A ) of 2.0 ± 0.2 ns. In CdS–Pt nanorods, electron transfer kinetics from the CdS conduction band edge to the Pt show negligible dependence on the excitation fluence, occurring with a half-life time of 5.6 ± 0.6 ps. The efficiency of multiple exciton dissociation by multiple electron transfer to Pt decreases from 100% in biexciton states to ~41% at 22 exciton state due to the competition with Auger recombination. The half-lifetime of the n-charge separated state recombination (with n electrons in the Pt and n holes in the CdS) decreases from 10 μs in the single charge separated state to 42 ns in nine charge separated states. Our findings suggest the possibility of driving multielectron photocatalytic reactions under intense illumination and controlling product selectivity through multielectron transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High performance remote sensing data analysis using parallel computation

This paper examines the JPL/Caltech parallel processing system designed for rapid processing and transfer of large quantities of data from remote sensing instruments flown on NASA missions. Two remote sensing analysis applications that use this processing system are described: (1) an analysis system for retrieval of atmospheric parameters (such as species abundance, atmospheric temperature, and water vapor profiles) from data obtained by a Fourier transform IR spectrometer and (2) a prototype airborne SAR processing system. It is shown that a parallel processing system such as the JPL/Caltech system can offer supercomputer computational capability and high-volume data throughput and still be cost-effective.

Patterson, Jean E.↗

Orbit Transfers for Dawn's Vesta Operations : Navigation and Mission Design Experience

Dawn, a mission belonging to NASA's Discovery Program, was launched on September 27, 2007 to explore main belt asteroids in order to yield insights into important questions about the formation and evolution of the solar system. From July of 2011 to August of 2012, the Dawn spacecraft successfully returned valuable science data, collected during the four planned mapping orbits at its first target asteroid, Vesta. Each mapping orbit was designed to enable a different set of scientific observations. Such a mission would have been impossible without the low thrust ion propulsion system (IPS). Maneuvering a spacecraft using only the IPS for the transfers between the mapping orbits posed many technical challenges to Dawn's flight team at NASA's Jet Propulsion Laboratory. Each transfer needs a robust plan that accounts for uncertainties in maneuver execution, orbit determination, and physical characteristics of Vesta. This paper discusses the mission design and navigational experience during Dawn's Vesta operations. Topics include requirements and constraints from Dawn's science and spacecraft teams, orbit determination and maneuver design and building process for transfers, developing timelines for thrust sequence build cycles, and the process of scheduling very demanding coverage with ground antennae at NASA's Deep Space Network.

low thrust↗