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DOE OSTI2018

Efficient modeling of optically-complex, non-coplanar exterior shading: Validation of matrix algebraic methods

It has long been established that shading windows with overhangs, fins, and other types of non-coplanar systems (NCS) is one of the most effective ways of controlling solar heat gains in buildings because they intercept solar radiation prior to entry into the building. Designers however often specify non-opaque materials (e.g., louvers, fritted glass, expanded metal mesh) for these systems in order to admit daylight, reduce lighting energy use, and improve indoor environmental quality. Most simulation tools rely on geometric calculations and radiosity methods to model the solar heat gain impacts of NCS and cannot model optically-complex materials or geometries. For daylighting analysis, optically-complex NCS can be modeled using matrix algebraic methods, although time-efficient parametric analysis has not yet been implemented. Determining the best design and/or material for static or operable NCS that minimize cooling, heating, and lighting energy use and peak demand requires an iterative process. This study describes and validates a matrix algebraic method that enables parametric energy analysis of NCS. Such capabilities would be useful not only for design but also for development of prescriptive energy-efficiency standards, rating and labeling systems for commercial products, development of design guidelines, and development of more optimal NCS technologies. A facade or “F” matrix, which maps the transfer of flux from the NCS to the surface of the window, is introduced and its use is explained. A field study was conducted in a full-scale outdoor testbed to measure the daylight performance of an operable drop-arm awning. Simulated data were compared to measured data in order to validate the models. Results demonstrated model accuracy: simulated workplane illuminance was within 11–13%, surface luminance was within 16–18%, and the daylight glare probability was within 6–9% of measured results. Methods used to achieve accurate results are discussed. Results of the validation of daylighting performance are applicable to solar heat gain performance. Since exterior shading can also significantly reduce peak demand, these models enable stakeholders to more accurately assess HVAC and lighting impacts in support of grid management and resiliency goals.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2020

Remote Radiation Sensing Using Aerial and Ground Platforms

Remote sensing of ionizing radiation has a significant role in waste management, nuclear material management and nonproliferation, and radiation safety. Robotic platforms can surpass the number of tasks that are achieved by humans. With this technique, the operator's radiation exposure can be decreased. Remote sensing allows for the evaluation and monitoring of radiological contamination. Gamma-ray and neutron sensors were integrated onto the robotic platforms. This approach allows for the radiation sensor data to be dynamically tracked and mapped thus enabling further analysis of the radiation flux in temporal and spatial domains. The goal is to complete scheduled tasks while the robot is being irradiated. To achieve this, electronic components must be shielded and radiation hardened. CZT Detector: Cadmium Zinc Telluride (CZT) detector technology has been a promising solution for gamma-ray and x-ray measurements. Detector data is transferred to the Odroid minicomputer that controls and powers the module via the USB. Robot Operating System (ROS) was utilized for data acquisition and data fusion. The Mariscotti method was employed for the spectrum analysis. A function was programmed in ROS for the automatic identification of photopeaks. CLYC Detector: A Cs{sub 2}LiYCl{sub 6}:Ce{sup 3+} (CLYC) detector was used for simultaneous medium-resolution gamma-ray measurements and neutron counting. A 2.54 cm diameter photomultiplier tube (PMT) was equipped with a high voltage supply and a miniature digitizer. Gamma-ray excitation: fast core-to-valence luminescence (CVL) with 1 ns decay constant, and prompt Ce{sup 3+} emission with 50 ns decay constant. Neutron excitation: slow cerium self-trapped excitation (Ce{sup 3+} STE), 1000 ns decay constant. Radiation Source Localization: Maximum Likelihood Estimation (MLE) and gradient-based methods were used to locate the position of a radiation source based on measured radiation intensities. Multi-Particle Transport Code FLUKA: Estimation of radiation damage of the electronic components is important in order to optimize the robot's operational time while it is irradiated. Displacement per atom (DPA) represents the radiation damage in materials exposed to the ionizing radiation. Various shielding layers of different thickness t were analyzed (< 5% statistical error). The model of the controller of the UAS was designed in FLUKA. Conclusion: CZT and CLYC detectors were integrated onto the robotic platforms. Radiation source localization and contour mapping using robotic platforms were studied. Functions for data analysis and fusion were developed in ROS. FLUKA code was utilized to analyze DPA values. Layers of low-density and high-density materials were used to shield the UAS electronics.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2021

A large-scale comparison of Artificial Intelligence and Data Mining (AI&DM) techniques in simulating reservoir releases over the Upper Colorado Region

In recent years, the Artificial Intelligence and Data Mining (AI&DM) models have become popular tools in assisting various aspects of reservoir operation. However, the practical uses are still rarely reported. Comparison experiment of many AI&DM models over a large number of reservoir cases is particularly valuable to help reservoir operators first examine the usefulness and transferability of different AI&DM models, and then identify the most stable and reliable AI&DM model in assist of various decision-making processes. In this study, a total of 12 AI&DM models with different parameterizations and simulation scenarios are comprehensively tested out and compared in simulating the controlled reservoir outflows of 33 reservoir cases over the Upper Colorado Region, United States. Results show that the Random Forecast and the Long-Short-Term-Memory model could consistently derive the best statistical performance than other models under the baseline simulation scenario. The employed AI&DM models could obtain satisfactory statistical interquartile ranges (25–75%) between [0.6–0.9], [0.3–0.8], and [0.2–0.8], for CORR, NSE, and KGE measurements, respectively, and [1.5–6.5], [–15 to 20], and [0.5–8.5] for the normalized RMSE, PBIAS and RSR measurements, respectively. Results also show Multi-Layer Perceptron model and Extreme Gradient Boosting Tree Algorithm produced more stable and superior performance than other models under more complex input scenarios. We also found that the performance of different AI&DM models are closely relevant to the reservoir elevations, sizes, and functionalities. Discussions were made about the sensitivity of AI&DM models’ parameterizations and the key advantages of AI&DM models over the rule-based reservoir models. We further identify that the main advantage of AI&DM models is the flexibility in designing input structures, whereas the rule-based simulation model is rather limited. Future studies were suggested regarding the best way reservoir operators and researchers could use, select, and apply different AI&DM models in simulating reservoir releases under different natural and modeling environments. Finally, this comparison study also serves as a reference and a piece of groundwork for further promoting the practical uses of AI&DM models in assisting reservoir operation.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Measurement of Neutron Multiplicity in Charged Current Neutrino Interactions on Oxygen

The Accelerator Neutrino Neutron Interaction Experiment (ANNIE) is a 26-ton gadolinium-doped water Cherenkov detector located 100~meters downstream in the Booster Neutrino Beam (BNB) at the Fermi National Accelerator Laboratory (Fermilab). Its primary goals are to (1) measure the neutron yield from $\nu_\mu$ interactions as a function of momentum transfer $Q^2$ so that neutrino-nucleus interaction models can be better constrained, and (2) demonstrate the power of novel, fast-timing detectors with the first deployment of Large Area Picosecond PhotoDetectors (LAPPDs). Current knowledge of neutrino-nucleus interactions fall short in modeling the topologies of such interactions, leading to inaccurate reconstruction of event kinematics such as particle energy, direction, and vertex. As a consequence, the accuracy of cross section measurements is impacted, which is necessary for precise physics measurements. Neutrons are an indication of inelasticity and affect the determination of the energy of the parent neutrino. Quantifying the neutron yield is a step towards reducing the associated uncertainties, and thus improving our understanding of these complex interactions and benefiting the next generation of long-baseline neutrino experiments. ANNIE will make use of LAPPDs to measure neutron multiplicity of CC-0$\pi$ $\nu_\mu$ interactions on oxygen, making it the first experiment to deploy an array of these photodetectors. Because the LAPPD is a novel photodetection technology, much customization is required to integrate it into existing electronics. The first half of this thesis covers the significant progress made towards the first deployment of the LAPPD system. From its test stand at Fermilab, the LAPPD system was systematically tested and put together until deployment readiness was achieved. I present my contributions to the design, fabrication, and testing of the waterproof housing and cables, and the commissioning of the LVHV board that powers the LAPPD and its readout electronics. These efforts brought the LAPPD system significantly closer to deployment, and eventually first data. The second half of this thesis presents the vertex and energy reconstruction algorithms developed to analysis the beam data with PMT-only information. While much progress has been made towards the deployment of LAPPDs, with several in the detector tank, efforts to integrate the LAPPD datastream are in progress. Thus, I developed a ring edge detection technique using PMT data to fit the muon vertex and determine its energy. The analysis in this thesis finds average neutron yields of $\Bar{n}_{data} = 0.452 \pm 0.039 (\text{stat}) \pm 0.27 (\text{sys})$ for a selection of muon neutrino candidates in the fiducial volume of ANNIE and corrected with an averaged neutron detection efficiency. An equivalent analysis for simulated beam data results in an average neutron yield of $\Bar{n}_{MC} = 0.582 \pm 0.018 (\text{stat}) \pm 0.25 (\text{sys})$. Future work includes application of efficiency corrections at a positional level, quantification of all systematic uncertainties, and neutron multiplicity measurements with other event topologies.

43 PARTICLE ACCELERATORS↗

NASA NTRS2003

Solar Thermal Propulsion Improvements at Marshall Space Flight Center

Solar Thermal Propulsion (STP) is a concept which operates by transferring solar energy to a propellant, which thermally expands through a nozzle. The specific impulse performance is about twice that of chemical combustions engines, since there is no need for an oxidizer. In orbit, an inflatable concentrator mirror captures sunlight and focuses it inside an engine absorber cavity/heat exchanger, which then heats the propellant. The primary application of STP is with upperstages taking payloads from low earth orbit to geosynchronous earth orbit or earth escape velocities. STP engines are made of high temperature materials since heat exchanger operation requires temperatures greater than 2500K. Refractory metals such as tungsten and rhenium have been examined. The materials must also be compatible with hot hydrogen propellant. MSFC has three different engine designs, made of different refractory metal materials ready to test. Future engines will be made of high temperature carbide materials, which can withstand temperatures greater than 3000K, hot hydrogen, and provide higher performance. A specific impulse greater than 1000 seconds greatly reduces the amount of required propellant. A special 1 OkW solar ground test facility was made at MSFC to test various STP engine designs. The heliostat mirror, with dual-axis gear drive, tracks and reflects sunlight to the 18 ft. diameter concentrator mirror. The concentrator then focuses sunlight through a vacuum chamber window to a small focal point inside the STP engine. The facility closely simulates how the STP engine would function in orbit. The flux intensity at the focal point is equivalent to the intensity at a distance of 7 solar radii from the sun.

Gerrish, Harold P.↗

NASA NTRS1999

A Study of Nucleate Boiling with Forced Convection in Microgravity

The ultimate objective of basic studies of flow boiling in microgravity is to improve the understanding of the processes involved, as manifested by the ability to predict its behavior. This is not yet the case for boiling heat transfer even in earth gravity, despite the considerable research activity over the past 30 years. The elements that constitute the nucleate boiling process - nucleation, growth, motion, and collapse of the vapor bubbles (if the bulk liquid is subcooled) - are common to both pool and flow boiling. It is well known that the imposition of bulk liquid motion affects the vapor bubble behavior relative to pool boiling, but does not appear to significantly influence the heat transfer. Indeed, it has been recommended in the past that empirical correlations or experimental data of pool boiling be used for design purposes with forced convection nucleate boiling. It is anticipated that such will most certainly not be possible for boiling in microgravity, based on observations made with pool boiling in microgravity. In earth gravity buoyancy will act to remove the vapor bubbles from the vicinity of the heater surface regardless of how much the imposed bulk velocity is reduced, depending, of course, on the geometry of the system. Vapor bubbles have been observed to dramatically increase in size in pool boiling in microgravity, and the heat flux at which dryout took place was reduced considerably below what is generally termed the critical heat flux (CHF) in earth gravity, depending on the bulk liquid subcooling. However, at heat flux levels below dryout, the nucleate pool boiling process was enhanced considerably over that in earth gravity, in spite of the large vapor bubbles formed in microgravity and perhaps as a consequence. These large vapor bubbles tended to remain in the vicinity of the heater surface, and the enhanced heat transfer appeared to be associated with the presence of what variously has been referred to as a liquid microlayer between the bubble and the heater surface. The enhancement of the boiling process with low velocities in earth gravity for those orientations producing the formation of a liquid macrolayer described above, accompanied by "sliding" vapor bubbles, has been demonstrated. The enhancement was presented as a function of orientation, subcooling, and heated length, while a criterion for the heat transfer for mixed natural/forced convection nucleate boiling was given previously. A major unknown in the prediction and application of flow boiling heat transfer in microgravity is the upper limit of the heat flux for the onset of dryout (or critical heat flux - CHF), for given conditions of fluid-heater surfaces, including geometry, system pressure and bulk liquid subcooling. It is clearly understood that the behavior in microgravity will be no different than on earth with sufficiently high flow velocities, and would require no space experimentation. However, the boundary at which this takes place is still an unknown. Previous results of CHF measurements were presented for low velocity flow boiling at various orientations in earth gravity as a function of flow velocity and bulk liquid subcooling, along with preliminary measurements of bubble residence times on a flat heater surface. This showed promise as a parameter to be used in modeling the CHF, both in earth gravity and in microgravity. The objective of the work here is to draw attention to and show results of current modeling efforts for the CHF, with low velocities in earth gravity at different orientations and subcoolings. Many geometrical possibilities for a heater surface exist in flowing boiling, with boiling on the inner and outer surfaces of tubes perhaps being the most common. If the vapor bubble residence time on and departure size from the heater surface bear a relationship to the CHF, as results to be given indicate, it is important that visualization of and access to vapor bubble growth be conveniently available for research purposes. In addition, it is desirable to reduce the number of variables as much as possible in a fundamental study. These considerations dictated the use of a flat heater surface, which is rectangular in shape, 1.91 cm by 3.81 cm (0.75 x 1.5 inches), consisting either of a 400 Angstrom thick semi-transparent gold film sputtered on a quartz substrate which serves simultaneously as a heater and a resistance thermometer, or a copper substrate of the same size. The heater substrate is a disc which can be rotated so that the heated length in the flow direction can be changed from 1.91 to 3.81 cm (0.75 to 1.5 inches). The fluid is R-113, and the velocities can be varied between 0.5 cm/s and 60 cm/s. For a sufficiently low velocity the CHF can be modeled reasonably well at various orientations by the correlation for pool boiling corrected for the influence of bulk liquid subcooling, multiplied by the square root of q, the angle relative to horizontal. This arises from equating buoyancy and drag forces in the inverted positions where the vapor bubbles are held against the heater surface as they slide. A distortion of the measurements relative to pool boiling occurs as the flow velocity increases. In modeling this effect at different levels of subcooling it appeared appropriate to estimate the volumetric rate of vapor generation, using measurements of bubble frequency (or residence time), void fraction and average bubble boundary layer thickness. These were determined with the use of a platinum hot wire probe 0.025 mm in diameter by 1.3 mm long, applying a constant current to distinguish between contact with liquid or vapor. Two-dimensional spatial variations are obtained with a special mechanism to resolve displacements in increments of 0.025 mm. From such measurements it was determined that the fraction of the surface heat transfer resulting in evaporation varies inversely with the subcooling correction factor for the CHF. The measured inverse bubble residence time is normalized relative to that predicted for an infinite horizontal flat plate at the CHF, and is correlated well with the CHF normalized relative to that for pool boiling, for various orientation angles and subcooling levels. This correspondence is then combined with a normalizing factor for the energy flux leaving the heater surface at the CHF and the computed bubble radius at departure, determined from the balance between the outward velocity of the interface due to evaporation and the buoyance induced velocity of the center of mass of the bubble. The product of the CHF and the corresponding residence time was determined to be a constant for all orientations at a given bulk flow velocity and liquid subcooling, and must be determined empirically for each velocity and subcooling at present. It then becomes possible to predict the CHF for the different orientations, velocities, and subcoolings. These are compared with normalized measurements of the CHF for velocities ranging from 4 cm/s to 55 cm/s, subcoolings from 2.8 to 22.2 K, over orientations angles of 360 degrees.

Merte, Herman, Jr.↗

NASA NTRS2000

An Integrated MEMS Sensor Cluster System for Aerospace Applications

Efforts to reduce viscous drag on airfoils could results in a considerable saving for the operation of flight vehicles including those of space transportation. This reduction of viscous drag effort requires measurement and active control of boundary layer flow property on an airfoil. Measurement of viscous drag of the boundary layer flow over an airfoil with minimal flow disturbance is achievable with newly developed MEMS sensor clusters. These sensor clusters provide information that can be used to actively control actuators to obtain desired flow properties or design a vehicle to satisfy particular boundary layer flow criteria. A series of MEMS sensor clusters has been developed with a data acquisition and control module for local measurements of shear stress, pressure, and temperature on an airfoil. The sensor cluster consists of two shear stress sensors, two pressure sensors, and two temperature sensors on a surface area of 1.24 mm x 1.86 mm. Each sensor is 300 microns square and is placed on a flexible polyimide sheet. The shear stress sensor is a polysilicon hot-film resistor, which is insulated by a vacuum cavity of 200 x 200 x 2 microns. The pressure sensors are silicon piezoresistive type, and the temperature sensors are also hot film polysilicon resistors. The total size of the cluster including sensors and electrical leads is 1 Omm x 1 Omm x 0.1 mm. A typical sensitivity of shear stress sensor is 150 mV/Pascal, the pressure sensors are an absolute type with a measurement range from 9 to 36 psia with 0.8mV/V/psi sensitivity, and the temperature sensors have a measurement resolution of 0.1 degree C. The sensor clusters are interfaced to a data acquisition and control module that consists of two custom ASICs (Application Specific Integrated Circuits) and a micro-controller. The data acquisition and control module transfers data to a host PC that configures and controls a total of three sensor clusters. Functionality of the entire system has been tested in the laboratory, and preliminary test results are presented.

Kahng, Seun↗

DOE OSTI2019

Horizontal transfer of a pathway for coumarate catabolism unexpectedly inhibits purine nucleotide biosynthesis

A microbe’s ecological niche and biotechnological utility are confirmed by its specific set of co-evolved metabolic pathways. The acquisition of new pathways, through horizontal gene transfer or genetic engineering, can have unpredictable consequences. In this work, we show that two different pathways for coumarate catabolism failed to function when initially transferred into Escherichia coli . Using laboratory evolution, we elucidated the factors limiting activity of the newly acquired pathways and the modifications required to overcome these limitations. Both pathways required host mutations to enable effective growth with coumarate, but the necessary mutations differed. In one case, a pathway intermediate inhibited purine nucleotide biosynthesis, and this inhibition was relieved by single amino acid replacements in IMP dehydrogenase. A strain that natively contains this coumarate catabolism pathway, Acinetobacter baumannii , is resistant to inhibition by the relevant intermediate, indicating that natural pathway transfers have faced and overcome similar challenges. Molecular dynamics simulation of the wild type and a representative single-residue mutant provide insight into the structural and dynamic changes that relieve inhibition. These results reflect how deleterious interactions can limit pathway transfer, that these interactions can be traced to specific molecular interactions between host and pathway, and how evolution or engineering can alleviate these limitations.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2020

Understanding how chemical structure affects ignition-delay-time $\phi$-sensitivity

$\phi$-sensitivity is the change in ignition delay time (IDT) with respect to the fuel-to-air equivalence ratio ($\phi$). High $\phi$-sensitivity is a desirable fuel property for applications in advanced compression ignition and multi-mode engine designs. Understanding how $\phi$-sensitivity depends on chemical structure is essential for selecting promising biofuels from the ever-growing list of proposed candidates. Here, we investigate the effect of chemical structure on $\phi$-sensitivity with experiment, simulation, and theory. Experimental Advanced Fuel Ignition Delay Analyzer (AFIDA) measurements for 2,4-dimethylpentane and diisopropyl ether provide evidence that branching and functional groups strongly impact $\phi$-sensitivity. Further insights into this dependence are obtained with 0-D kinetic simulations with existing mechanisms for n-pentane, diethyl ether, 3-pentanone, n-heptane, 2-methylhexane, 2,4-dimethylpentane, and 2,2,3-trimethylbutane. Quantum mechanical (QM) G4 calculations of low-temperature reactions help explain the observed experimental and simulation trends. Specifically, these QM calculations provide theoretical estimates of the ketohydroperoxide (KHP) dissociation rates, the HO 2 formation rates from peroxy radical (ROO), and the “cross-over” temperatures, i.e., the temperature at which ROO dissociation is favored compared to hydroperoxyl radical (QOOH) formation. Each of these reaction rates is compared to the n-alkane reference point to determine the impact of branching and different functional groups. Although kinetic mechanisms typically assume that KHP dissociation rates are invariant of chemical environment, our QM results suggest that this rate can span a range of roughly two orders of magnitude. We also discuss the importance of including the peroxy-hydroperoxy (OO-OOH) hydrogen transfer reaction for branched ethers. Finally, the insights gained assist in proposing a highly $\phi$-sensitive compound, namely, isopropyl propyl ether.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Calculations of theoretical efficiencies for electrochemically-mediated tandem solar water splitting as a function of bandgap energies and redox shuttle potential

Tandem Z-scheme solar water splitting devices composed of two light-absorbers that are connected electrochemically by a soluble redox shuttle constitute a promising technology for cost-effective solar hydrogen production. In this work, efficiency limits of these devices are modeled by combining the detailed-balance model of the light-absorbers with Butler–Volmer electron-transfer kinetics. The impacts of the redox shuttle thermodynamic potential, light-absorber bandgaps, and electrocatalytic parameters on the solar-to-hydrogen conversion (STH) efficiency are modeled. We report that the thermodynamic potential of the redox shuttle with respect to the hydrogen and oxygen evolution potentials has a direct effect on both the STH efficiency and the optimal tandem light-absorber bandgaps needed to achieve the maximum possible STH efficiency. At 1 sun illumination and assuming ideal and optimally selective electrocatalytic parameters, the STH efficiency varies from a minimum of 21%, for a redox shuttle potential of 0 V vs. the reversible hydrogen electrode (RHE), to a maximum of 34%, for a redox shuttle potential of either 0.36 V or 1.06 V vs. RHE. To attain the maximum possible STH efficiency of 34%, the light-absorber bandgaps must be 1.53 eV and 0.75 eV, yet the optimal redox shuttle potential depends on whether the hydrogen-evolving or oxygen-evolving light-absorber has the larger bandgap. Results also underscore the importance of optimizing the absorptance of the top light-absorber, which enables large STH efficiencies to be achieved with a wider range of bandgap combinations. Moreover, given the large overpotentials for the oxygen evolution reaction and reasonably low overpotentials for most redox shuttle reactions, the tandem design is more efficient than a single light-absorber design even when the potential of the redox shuttle exceeds 1.23 V vs. RHE. When the exchange current density of the redox shuttle reactions is as low as 10 -5 mA cm -2 , STH efficiencies as large as 22% are still achievable as long as selective catalysis and optimal redox shuttle potential are assumed, suggesting that even slow redox shuttle reactions may not limit the practicality of these devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1991

A guide to NASA's Pilot Land Data System (PLDS)

NASA's Pilot Land Data System (PLDS) is a distributed information management system designed to support NASA's land science community. The PLDS provides a wide range of services including management of information about scientific data, access to a library of scientific data, a data ordering capability, communications, connection to data analysis facilities, and electronic mail. The PLDS provides these services by offering the scientist the capability to search for and order data, and to communicate electronically with other scientists and computers. Three functions enable scientists to find what data are available and where they reside. The first two, Find data summaries and Read detailed descriptions give summary and detailed descriptions about data sets or groups of related data sets, science, projects, and institutions which archive land data. The third, gives information about specific pieces of data. This last function has two components, Search systemwide inventory and Search local inventory. The first component enables the user to find data elements (images, geological samples, transects, maps, etc.) that exist anywhere in the PLDS while the second has only information about data at the local site. The first enables the user to find pieces of data from several different data sets with the same temporal and spatial coverage and other elements common to most data sets, while the second allows the user to select a data set based on these descriptors and on those that are unique to a data set. The PLDS provides capabilities that enable electronic file transfers, intercomputer connection, and electronic mail. Both TCP/IP and DECnet protocols are supported via the NASA Science Internet (NIS). Access is also available through Telenet.

Source record↗

NASA NTRS2002

Low Melt Viscosity Resins for Resin Transfer Molding

In recent years, resin transfer molding (RTM) has become one of the methods of choice for high performance composites. Its cost effectiveness and ease of fabrication are major advantages of RTM. RTM process usually requires resins with very low melt viscosity (less than 10 Poise). The optimum RTM resins also need to display high thennal-oxidative stability, high glass transition temperature (T(sub g)), and good toughness. The traditional PMR-type polyimides (e.g. PMR-15) do not fit this requirement, because the viscosities are too high and the nadic endcap cures too fast. High T(sub g), low-melt viscosity resins are highly desirable for aerospace applications and NASA s Reusable Launch Vehicle (RLV) program. The objective of this work is to prepare low-melt viscosity polyimide resins for RTM or resin film infusion (RFI) processes. The approach involves the synthesis of phenylethynyl-terminated imide oligomers. These materials have been designed to minimize their melt viscosity so that they can be readily processed. During the cure, the oligomers undergo both chain extension and crosslinking via the thermal polymerization of the phenylethynyl groups. The Phenylethynyl endcap is preferred over the nadic group due to its high curing temperature, which provides broader processing windows. This work involved the synthesis and polymerization of oligomers containing zig-zag backbones and twisted biphenyl structures. Some A-B type precursors which possessed both nitro and anhydride functionality, or both nitro and amine functionality, were also synthesized in order to obtain the well defined oligomers. The resulting zig-zag structured oligomers were then end-capped with 4-phenylethynylphthalic anhydride (PEPA) for further cure. The properties of these novel imide oligomers are evaluated.

Harris, Frank W.↗

DOE OSTI2024

From Coherence to Function: Exploring the Connection in Chemical Systems

The role of quantum mechanical coherences or coherent superposition states in excited state processes has received considerable attention in the last two decades largely due to advancements in ultrafast laser spectroscopy. These coherence effects hold promise for enhancing the efficiency and robustness of functionally relevant processes, even when confronted with energy disorder and environmental fluctuations. Understanding coherence deeply drives us to unravel mechanisms and dynamics controlled by order and synchronization at a quantum mechanical level, envisioning optical control of coherence to enhance functions or create new ones in molecular and material systems. In this frontier, the interplay between electronic and vibrational dynamics, specifically the influence of vibrations in directing electronic dynamics, has emerged as the leading principle. Here, two energetically disparate quantum degrees of freedom work in-sync to dictate the trajectory of an excited state reaction. Moreover, with the vibrational degree being directly related to the structural composition of molecular or material systems, new molecular designs could be inspired by tailoring certain structural elements. In the realm of chemical kinetics, our understanding of the dynamics of chemical transformations is underpinned by fundamental theories, such as transition state theory, activated rate theory, and Marcus theory. These theories elucidate reaction rates by considering the energy barriers that must be overcome for reactants to transform into products. Those barriers are surmounted by the stochastic nature of energy gap fluctuations within reacting systems, emphasizing that the reaction coordinate, the pathway from reactants to products, is not rigidly defined by a specific vibrational motion but encompasses a diverse array of molecular motions. While less is known about the involvement of specific intramolecular vibrational modes, their significance in certain cases cannot be overlooked. In this Account, we summarize key experimental findings that offer deeper insights into the complex electronic–vibrational trajectories encompassing excited states afforded from state-of-the-art ultrafast laser spectroscopy in three exemplary processes: photoinduced electron transfer, singlet–triplet intersystem crossing, and intramolecular vibrational energy flow in molecular systems. We delve into the rapid decoherence, or loss of phase and amplitude correlations, of vibrational coherences along promoter vibrations during subpicosecond intersystem crossing dynamics in a series of binuclear platinum complexes. This rapid decoherence illustrates the vibration-driven reactive pathways from the Franck–Condon state to the curve crossing region. We also explore the generation of new vibrational coherences induced by impulsive reaction dynamics rather than by the laser pulse in these systems, which sheds light on specific energy dissipation pathways and thereby on the progression of the reaction trajectory in the vicinity of the curve crossing on the product side. Another property of vibrational coherences, amplitude, reveals how energy can flow from one vibration to another in the electronic excited state of a terpyridine–molybdenum complex hosting a nonreactive dinitrogen substrate. In conclusion, a slight change in vibrational energy triggers a quasi-resonant interaction, leading to constructive wavepacket interference and ultimately intramolecular vibrational redistribution from a Franck–Condon active terpyridine vibration to a dinitrogen stretching vibration, energizing the dinitrogen bond.

Electrical energy↗

NASA NTRS2012

Thermal Vacuum Integrated System Test at B-2

The National Aeronautics and Space Administration (NASA) Glenn Research Center (GRC) Plum Brook Station (PBS) Space Propulsion Research Facility, commonly referred to as B-2, is NASA s third largest thermal vacuum facility. It is the largest designed to store and transfer large quantities of liquid hydrogen and liquid oxygen, and is perfectly suited to support developmental testing of chemical propulsion systems as well as fully integrated stages. The facility is also capable of providing thermal-vacuum simulation services to support testing of large lightweight structures, Cryogenic Fluid Management (CFM) systems, electric propulsion test programs, and other In-Space propulsion programs. A recently completed integrated system test demonstrated the refurbished thermal vacuum capabilities of the facility. The test used the modernized data acquisition and control system to monitor the facility during pump down of the vacuum chamber, operation of the liquid nitrogen heat sink (or cold wall) and the infrared lamp array. A vacuum level of 1.3x10(exp -4)Pa (1x10(exp -6)torr) was achieved. The heat sink provided a uniform temperature environment of approximately 77 K (140deg R) along the entire inner surface of the vacuum chamber. The recently rebuilt and modernized infrared lamp array produced a nominal heat flux of 1.4 kW/sq m at a chamber diameter of 6.7 m (22 ft) and along 11 m (36 ft) of the chamber s cylindrical vertical interior. With the lamp array and heat sink operating simultaneously, the thermal systems produced a heat flux pattern simulating radiation to space on one surface and solar exposure on the other surface. The data acquired matched pretest predictions and demonstrated system functionality.

Kudlac, Maureen T.↗

NASA NTRS2019

Investigation of Transient Gas Phase Column Density Due to Droplet Evaporation

A NASA robotic refueling mission experiment on board the International Space Station (ISS) was designed to repeatedly transfer simulated cryogenic propellant between two dewars. After each metered transfer, the cryogen was to be vented overboard via sublimation or evaporation. ISS payload providers must conduct analyses to demonstrate that any planned gaseous venting generate no more than a certain level of material that may interfere with optical measurements from other payloads that may be located nearby. This requirement is expressed in terms of a maximum column number density (CND). For the experiment under consideration, fluid droplets likely would accompany any such vapor. Earlier related studies led to development of analytical expressions for column density along general paths for a number of practical cases under steady conditions, including droplet evaporation. These expressions are not appropriate for rapid evaporation of small droplets however, since the droplets cannot sustain mass flow rates consistent with steady conditions. In this work, analytical expressions are developed for estimating column density near a rapidly evaporating droplet along general paths. The influence for instantaneous evaporation is created first as a limiting case, where it is found the peak value occurs at the time it takes a wave of vapor to reach the closest point along the optical path traveling at its most probable thermal speed. Next, the case for finite-period evaporation is evaluated for constant conditions. Compared to the instantaneous case, peak column density occurs shortly after droplet extinction, but at a lower intensity. A new mathematical function is discovered that solves the integrals associated with this case. Finally, ways to account for droplet motion and changes in evaporation rate with size and temperature are discussed in this framework.

Woronowicz, M. S.↗

NASA NTRS2001

Pulse Detonation Engine Modeled

Pulse Detonation Engine Technology is currently being investigated at Glenn for both airbreathing and rocket propulsion applications. The potential for both mechanical simplicity and high efficiency due to the inherent near-constant-volume combustion process, may make Pulse Detonation Engines (PDE's) well suited for a number of mission profiles. Assessment of PDE cycles requires a simulation capability that is both fast and accurate. It should capture the essential physics of the system, yet run at speeds that allow parametric analysis. A quasi-one-dimensional, computational-fluid-dynamics-based simulation has been developed that may meet these requirements. The Euler equations of mass, momentum, and energy have been used along with a single reactive species transport equation, and submodels to account for dominant loss mechanisms (e.g., viscous losses, heat transfer, and valving) to successfully simulate PDE cycles. A high-resolution numerical integration scheme was chosen to capture the discontinuities associated with detonation, and robust boundary condition procedures were incorporated to accommodate flow reversals that may arise during a given cycle. The accompanying graphs compare experimentally measured and computed performance over a range of operating conditions for a particular PDE. Experimental data were supplied by Fred Schauer and Jeff Stutrud from the Air Force Research Laboratory at Wright-Patterson AFB and by Royce Bradley from Innovative Scientific Solutions, Inc. The left graph shows thrust and specific impulse, Isp, as functions of equivalence ratio for a PDE cycle in which the tube is completely filled with a detonable hydrogen/air mixture. The right graph shows thrust and specific impulse as functions of the fraction of the tube that is filled with a stoichiometric mixture of hydrogen and air. For both figures, the operating frequency was 16 Hz. The agreement between measured and computed values is quite good, both in terms of trend and magnitude. The error is under 10 percent everywhere except for the thrust value at an equivalence ratio of 0.8 in the left figure, where it is 14 percent. The simulation results shown were made using 200 numerical cells. Each cycle of the engine, approximately 0.06 sec, required 2.0 min of CPU time on a Sun Ultra2. The simulation is currently being used to analyze existing experiments, design new experiments, and predict performance in propulsion concepts where the PDE is a component (e.g., hybrid engines and combined cycles).

Paxson, Daniel E.↗

DOE OSTI2018

Organic Linker Effect on the Growth and Diffusion of Cu Clusters in a Metal–Organic Framework

One reason that metal nanoparticles encapsulated in metal-organic frameworks are of interest is that confinement effects on the particle size and shape may lead to superior catalytic activity. The interior of a metal–organic framework has the possibility to influence nucleation and aggregation of metal nanoparticles and to strongly affect their in situ shape and electronic properties. We apply density functional theory and ab initio molecular dynamics (AIMD) to model the nucleation and diffusion of Cun (n = 1–19) clusters on the tetratopic 1,3,6,8-(p-benzoate)pyrene (TBAPy 4– ) linkers of NU-1000 frameworks. We find that Cu atoms and Cu clusters are stabilized by the TBAPy linker, especially by the edge site of aromatic rings. The stabilization increases when the Cu cluster interacts with two linkers. We confirmed the most favorable site for Cu cluster adsorption as the window site that connects the c pore and the triangular pore. A Pt atom is found to bind much more strongly than a Cu atom on the TBAPy linker, and AIMD simulations show that this promotes Pt atom diffusion from the center of a Cu 15 cluster to the interface between the linker and the cluster. The strong interaction between a Pt atom and a linker is attributed to the greater metal-to-linker charge transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2017

MS Non-Pharmacological Countermeasure to Decrease Landing Sickness and Improve Functional Performance While Disorientad

Upon return from spaceflight, a majority of crewmembers experience motion sickness (MS) symptoms. The interactions between crewmembers' adaptation to a gravitational transition, the performance decrements resulting from MS and/or use of promethazine (PMZ), and the constraints imposed by mission task demands could significantly challenge and limit an astronaut's ability to perform functional tasks during gravitational transitions. No operational countermeasure currently exists to mitigate the risks associated with these sensorimotor disturbances. Stochastic resonance (SR) can be thought of simply as "noise benefit" or an increase in information transfer by a system when in the presence of a non-zero level of noise. We have shown that low levels of stochastic vestibular stimulation (SVS) improve balance and locomotor performance due to SR (Goel et al. 2015, Mulavara et al. 2011, 2015). Additionally, a study in a 6-hydroxydopamine (6-OHDA) hemi-lesioned rat model of Parkinson's disease demonstrated improvements in locomotor activity after low-level SVS delivery possibly due to an increase in nigral gamma-aminobutyric acid (GABA) release in a dopamine independent way (Samoudi et al. 2012). SVS specifically increased GABA release on the lesioned, but not the intact side. These results suggest that SVS can cause targeted alterations of GABA release to affect performance of functional tasks. Activation of the GABA pathway is important in modulating MS and promoting adaptability (Cohen 2008). Magnusson et al. (2000) supported this finding by showing that the administration of a GABAB agonist caused a reversal of the symptoms that is normally seen after unilateral labyrinthectomy. Thus, GABA could play a significant role in reducing MS and promoting adaptability. We have taken advantage of the SR mechanism as a modulator of neurotransmitters to develop a unique SVS countermeasure system to mitigate MS symptoms and improve functional performance after landing. Healthy subjects (n=20) participated in two test sessions, one in which they received +/-400 microA of SVS and one where they received no stimulation (0 microA); the study design was counterbalanced. Subjects began by performing a series of four functional tasks 3-5 times as baseline measurements of task performance. Then, to induce MS, subjects walked an obstacle course with up-down reversing prisms. If they completed the course before achieving our pre-determined level of MS, they were asked to read a poster while making large up-down head movements to a metronome while still wearing the reversing prism goggles. Subjects were stopped every two minutes and asked to report their MS symptoms. Using the Pensacola Scale for motion sickness, test operators evaluated the level of MS of each subject. Once a subject reached an 8 on this scale, which is equivalent to mild malaise, or 30 minutes had passed since the start of the MS induction, this protocol was stopped. Finally, immediately after MS induction, subjects were asked to complete the four functional tasks again. Although, 100% of our subjects experienced at least one MS symptom, only 55% of our subjects experienced stomach awareness to any degree. Without SVS, only 40% of subjects lasted the full 30-minute MS induction protocol, while 65% of subjects lasted the full 30 minutes with SVS, which is nearly a significant increase (p=0.056). In addition, subjects showed significant improvement from baseline when performing a tandem walk and a prone-to-stand test immediately after the MS induction protocol was stopped but the stimulation level was continued. The results are promising and future work includes comparing MS progression between PMZ and SVS directly in subjects that are provoked to a minimum of nausea. Low levels of SVS stimulation may serve as a non-pharmacological countermeasure to replace or reduce the PMZ dosage requirements and concurrently improve functional performance during transitions to new gravitational environments after spaceflight.

Rosenberg, M. J. F.↗