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DOE OSTI2024

Influence of Ordered Mesoporous Oxides in Plasma-Assisted Ammonia Synthesis

Widespread implementation of dielectric barrier discharge (DBD)-assisted NH 3 synthesis, a nascent technology operating under sustainable, ambient conditions, is hindered by low energy yields due to, in part, poor fundamental understanding. Porous oxides used to support metal nanoparticle catalysts have shown significant energy yield contributions for DBD-assisted NH 3 synthesis even without metal. Using an AC-powered, coaxial, single-stage reactor at 16 kV with equimolar (N 2 /H 2 ) feed, we measured NH 3 synthesis rates in the presence of different nonordered oxides, ordered SiO 2 structures (SBA-15 and MCM-41), and ordered Al-incorporated analogues (γ-Al 2 O 3 -coated with varying Al-loadings and Al-substitution, respectively: Al 2 O 3 -SBA-15 and Al-MCM-41). We systematically quantified NH 3 energy yield dependence on pore structures and material identities (i.e., ordered pores and Al incorporation) known to facilitate higher DBD-assisted NH 3 synthesis rates. SBA-15 displayed a higher steady-state energy yield than MCM-41, indicating that framework type is a crucial factor, with both ordered porous systems outperforming fumed SiO 2 . 10 wt % Al maximized in situ NH 3 uptake among the various Al loadings, exhibiting a higher steady-state energy yield and similar power to SBA-15. However, Al-MCM-41 had a similar steady-state energy yield and lower power than MCM-41, likely due to the extended γ-Al 2 O 3 surface that has a dielectric constant higher than that of SiO 2 . Both Al-incorporated analogues benefit from surface acid sites that can adsorb NH 3 in situ, resulting in higher overall NH 3 energy yields than that of their parent ordered SiO 2 . Al 2 O 3 -SBA-15 shielded more NH 3 than Al-MCM-41, likely due to a higher acid site density than the acid site identity. Furthermore, Al incorporation via γ-Al 2 O 3 coating more successfully improves the NH 3 energy yield; together with the high-performing ordered framework, these analogues are potential metal catalyst supports with promising energy yields for DBD-assisted synthesis of NH 3 and other chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1976

Application of thick-film technology to solar cell fabrication

Several uses of thick-film technology in solar cell fabrication are discussed. Wrap-around contacts are obtained by first printing and firing a dielectric over the edge and subsequently applying a low-firing temperature conductor. Interconnection of cells into arrays can be achieved by printing and co-firing thick-film pastes, soldering, or with heat-curing conductive epoxies on low-cost substrates. Despite ongoing research, printed (thick) film vitreous protective coatings do not yet offer sufficient optical uniformity and transparency for use on silicon. Ohmic contacts on n- and p-type silicon are considered.

Field, M. B.↗

NASA NTRS2012

Plasma Actuators for Turbomachinery Flow Control

This report is Part I of the final report of NASA Cooperative Agreement contract no. NNX07AC02A. The period of performance was January 1, 2007 to December 31, 2010. This report includes the project summary, a list of publications and reprints of the publications that appeared in archival journals. Part II of the final report includes a Ph.D. dissertation and is published separately as NASA/CR-2012-2172655. The research performed under this project was focused on the operation of surface dielectric barrier discharge (DBD) devices driven by high voltage, nanosecond scale pulses plus constant or time varying bias voltages. The main interest was in momentum production and the range of voltages applied eliminated significant heating effects. The approach was experimental supplemented by computational modeling. All the experiments were conducted at Princeton University. The project provided comprehensive understanding of the associated physical phenomena. Limitations on the performance of the devices for the generation of high velocity surface jets were established and various means for overcoming those limitations were proposed and tested. The major limitations included the maximum velocity limit of the jet due to electrical breakdown in air and across the dielectric, the occurrence of backward breakdown during the short pulse causing reverse thrust, the buildup of surface charge in the dielectric offsetting the forward driving potential of the bias voltage, and the interaction of the surface jet with the surface through viscous losses. It was also noted that the best performance occurred when the nanosecond pulse and the bias voltage were of opposite sign. Solutions include the development of partially conducting surface coatings, the development of a semiconductor diode inlaid surface material to suppress the backward breakdown. Extension to long discharge channels was studied and a new ozone imaging method developed for more quantitative determination of surface jet properties.

Miles, Richard, B↗

NASA NTRS1991

In-situ ellipsometric studies of optical and surface properties of GaAs(100) at elevated temperatures

A rotating-polarizer ellipsometer was attached to an ultrahigh vacuum (UHV) chamber. A GaAs(100) sample was introduced into the UHV chamber and heated at anumber of fixed elevated temperatures, without arsenic overpressure. In-situ spectroscopic ellipsometric (SE) measurements were taken, through a pair of low-strain quartz windows, to monitor the surface changes and measure the pseudodielectric functions at elevated temperatures. Real-time data from GaAs surface covered with native oxide showed clearly the evolution of oxide desorption at approximately 580 C. In addition, surface degradation was found before and after the oxide desorption. An oxide free and smooth GaAs surface was obtained by depositing an arsenic protective coating onto a molecular beam epitaxy grown GaAs surface. The arsenic coating was evaporated immediately prior to SE measurements. A comparison showed that our room temperature data from this GaAs surface, measured in the UHV, are in good agreement with those in the literature obtained by wet-chemical etching. The surface also remained clean and smooth at higher temperatures, so that reliable temperature-dependent dielectric functions were obtained.

Yao, Huade↗

DOE OSTI2023

Rheo-electric measurements of carbon black suspensions containing polyvinylidene difluoride in N -methyl-2-pyrrolidone

Lithium-ion battery cathode slurries have a microstructure that depends sensitively on how they are processed due to carbon black's (CB) evolving structure when subjected coating flows. While polyvinylidene difluoride (PVDF), one of the main components of the cathode slurry, plays an important role in modifying the structure and rheology of CB, a quantitative understanding is lacking. In this work, we explore the role of PVDF in determining the structural evolution of Super C65 CB in N-methyl-2-pyrrolidinone (NMP) with rheo-electric measurements. We find that PVDF enhances the viscosity of NMP resulting in a more extensive structural erosion of CB agglomerates with increasing polymer concentration and molecular weight. We also show that the relative viscosity of all suspensions can be collapsed by the fluid Mason number (Mnf), which compares the hydrodynamic forces imposed by the medium to cohesive forces holding CB agglomerates together. Using simultaneous rheo-electric measurements, we find at high Mnf, the dielectric strength (Δε) scales with Mnf, and the power-law scaling can be quantitatively predicted by considering the self-similar break up of CB agglomerates. The collapse of the relative viscosity and scaling of Δε both suggest that PVDF increases the hydrodynamic force of the suspending medium without directly changing the CB agglomerate structure. These findings are valuable for optimizing the rheology of lithium ion battery cathode slurries. We also anticipate that these findings can be extended to understand the microstructure of similar systems under flow.

Mechanics↗

NASA NTRS1975

Combined environmental effects on polymers

A series of space simulation tests on FEP Teflon and other polymeric thermal control coatings was conducted using UV, electrons, protons and Lyman-alpha wavelength vacuum UV radiation. Interest was centered on simulating synchronous altitude radiation environment conditions. Physical changes in materials included loss of specularity and introduction of a high density of photographable tracking defects on a microscopic scale. An example shows the discharge of trapped electrons when dielectric strength is exceeded. This leaves a portion of the Teflon volume no longer clear, but diffusely transmitting and reflecting. Thermophysical changes included degradation of solar absorptance coefficients as much as five-fold. The situation that prevails for earth orbit contrasted with polymer performance in the solar wind. It is suggested that conductive overcoatings be developed for polymers and other flexible materials, comparable or superior to those available for fused silica SSMs.

Fogdall, L. B.↗

NASA NTRS1995

High efficient radiation stable AlGaAs/GaAs solar cells with internal Bragg reflector

An investigation of solar cells based on AlGaAs/GaAs heterostructures with an internal Bragg reflector as the back-surface reflector is presented. The Bragg reflector is grown by low pressure metalorganic chemical vapor deposition on n-GaAs substrates in a horizontal resistively heated reactor. The Bragg reflector with its maximum reflectance centered at a wavelength of 860 nm consists of 12 pairs of AlAs/GaAs layers. The resulting Bragg reflector has a thickness of 0.072 micrometers for AlAs and 0.059 micrometers for GaAs. The multi-layered quasi-dielectric stack selectively reflects weakly absorbed photons with energies near to the GaAs band gap for a second pass through the photoactive region, thus increasing the photocurrent. The use of the Bragg reflector allows the external quantum efficiency to be increased in the long wavelength of the spectrum. The use of the Bragg reflector and an antireflective coating and prismatic cover allowed an efficiency of 23.4 percent to be obtained.

Andreev, V. M.↗

NASA NTRS2000

Increasing Importance of Material Electrical Interaction with the Space Environment

The electrical properties of materials have always been important for spacecraft in charging environments. However, in recent years consideration of interactions of materials and systems with the plasma environment has become more and more important in spacecraft design. This has primarily been driven by independent factors including increase in power and high voltage power systems, operation of tethered satellites, and science requirements for electrostatic clean spacecraft. Increased need for power has led to increased operating voltages for spacecraft. The Upper Atmospheric Research Satellite (UARS) was one of the first to operate at near 100 V solar array potential and demonstrate that the spacecraft floated nearly the entire voltage negative of the ionospheric plasma. The high voltage, 160 V, of the solar arrays on the International Space Station (ISS) led to the requirement to have a plasma contactor to control structure potential relative to the local plasma. Issues such as sputtering, dielectric breakdown, capacitive energy storage in the structure, space debris impact induced arcs and other arcing mechanisms had to be addressed. Recently commercial satellites, driven to higher voltages for efficiency, have experienced arcing problems which led to severe, permanent power degradation. The first tethered satellite, Tethered Satellite System (TSS), was deployed from the Space Shuttle. A conductive coating was developed which provided a low resistivity and also the required solar absorptivity and emittance. Other tether systems are being designed which will have similar requirements but also long life and "bare tether" designs are also being built for flight experiments. The wire requires an electrically conductive coating with proper thermal control properties, which a bare wire doesn't possess. Increasing sophistication of scientific instruments and measurements which scientists want to make have led to increasing requirements for conducting thermal control coatings to provide electrostatic cleanliness. These issues, which are increasing the importance of electrical interaction of materials to the space environment, will be discussed in this paper as well as research into material development to meet thermal and electrical requirements and research to understand phenomena regarding such interactions.

Carruth, M. R., Jr.↗

NASA NTRS2015

Solid State Ultracapacitor

NASA analyzes, tests, packages, and fabricates electrical, electronic, and electromechanical (EEE) parts used in space vehicles. One area that NASA wishes to advance is energy storage and delivery. Currently, space vehicles use rechargeable batteries that utilize silver zinc or lithium ion electrochemical processes. These current state-of-the-art rechargeable batteries cannot be rapidly charged, contain harmful chemicals, and suffer from early wear-out mechanisms. A solid state ultracapacitor is an EEE part that offers significant advantages over current electrochemical and electrolytic devices. The objective of this research is to develop an internal barrier layer ultracapacitor (IBLC) using novel dielectric materials as a battery replacement with a focus on these advantages: longer life, lower mass-toweight ratio, rapid charging, on-demand pulse power, improved on-pad standby time without maintenance, and environmental friendliness. The approach is unique in two areas. A deposition technique is used that has been shown to produce a more uniformly coated nanoparticle than sol-gel, which has resulted in colossal permittivities. These particles are then distributed in an ink formulation developed at NASA Marshall Space Flight Center (MSFC) and deposited utilizing a 3D aerosol jet technique. This additive manufacturing technique controls layer thickness, resulting in extremely large capacitance and energy density.

Rolin, Terry D.↗

NASA NTRS1981

Development of urethane coating and potting material with improved hydrolytic and oxidative stability

A series of saturated hydrocarbon based urethanes was prepared and characterized for hydrolytic and oxidative stability. A series of ether based urethanes was used as a basis for comparison. The alkane base urethanes were found to be hydrolytically and oxidatively stable and had excellent electrical properties. The alkane based materials absorbed little or no water and were reversion resistant. There was little loss in hardness or weight when exposed to high temperature and humidity. Dielectric properties were excellent and suffered little adverse effects from the high temperature/humidity conditions. The alkane based urethanes were not degraded by ozone exposure.

Morris, D. E.↗

DOE OSTI2022

Temporal and spatial laser intensification within nodular defects overcoated with multilayer dielectric mirrors over a wide range of defect geometries

The nodular defect shape and the laser incidence angle have a dramatic impact on the spatial distribution of light intensification within the nodule as well as how the laser light is drained from the defect. Nodular defect geometries unique to ion beam sputtering, ion-assisted deposition, and electron-beam (e-beam) deposition, respectively, are modeled in this parametric study over a wide range of nodular inclusion diameters and layer count for optical interference mirror coatings constructed with quarter-wave thicknesses and capped with a half wave of the low index material. It was found for hafnia ($n$=1.9) and silica ($n$=1.45) multilayer mirrors that the light intensification in nodular defects with a $C$ factor of 8, typical of e-beam deposited coatings deposited with a wide range of deposition angles, was maximized for a 24-layer design. For intermediate size inclusion diameters, increasing the layer count for normal incidence multilayer mirrors reduced the light intensification within the nodular defect. A second parametric study explored the impact of the nodule shape on the light intensification for a fixed number of layers. In this case, there is a strong temporal trend for the different nodule shapes. Narrow nodules tend to drain more laser energy through the bottom of the nodule into the substrate while wide nodules tend to drain more laser energy through the top of the nodule when irradiated at normal incidence. Further, at a 45° incidence angle, waveguiding is an additional method to drain laser energy from the nodular defect. Finally, laser light resonates within nodular defects longer than within the adjacent nondefective multilayer structure.

47 OTHER INSTRUMENTATION↗

DOE OSTI2022

Surface Impedance of Nb$_3$Sn and YBa$_2$Cu$_3$O$_{7-\sigma}$ in High Magnetic Fields

New potential rf applications of superconductors emerged with the need to operate in high dc magnetic fields (up to 16 T) where vortex motion dictates the response: the beam screen coating of the Future Circular Collider (FCC) [1] and haloscopes, i.e. rf cavities for the axions detection [2]. However, very few data are available in the required regimes. We present in this work measurements of the surface impedance Z up to 12 T on bulk Nb₃Sn and YBCO thin films grown by different techniques. The measurements are performed with a dielectric loaded resonator operating at 15 GHz. We obtained the vortex motion resistivity and extracted the high frequency vortex motion parameters [3]: the depinning frequency, the flux-flow resistivity and the pinning constant, as well as their temperature and field dependences. Substantial differences are highlighted in the high frequency pinning properties of the studied materials, providing useful information on possible improvements in view of applications. A comparison with the results obtained in the microwave frequency range at lower fields (up to 1 T) is given.

43 PARTICLE ACCELERATORS↗

NASA NTRS2009

NASA Tech Briefs, February 2009

Tech Briefs are short announcements of innovations originating from research and development activities of the National Aeronautics and Space Administration. They emphasize information considered likely to be transferable across industrial, regional, or disciplinary lines and are issued to encourage commercial application. Topics covered include: Measuring Low Concentrations of Liquid Water in Soil; The Mars Science Laboratory Touchdown Test Facility; Non-Contact Measurement of Density and Thickness Variation in Dielectric Materials; Compact Microwave Fourier Spectrum Analyzer; InP Heterojunction Bipolar Transistor Amplifiers to 255 GHz; Combinatorial Generation of Test Suites; In-Phase Power-Combined Frequency Tripler at 300 GHz; Electronic System for Preventing Airport Runway Incursions; Smaller but Fully Functional Backshell for Cable Connector; Glove-Box or Desktop Virtual-Reality System; Composite Layer Manufacturing with Fewer Interruptions; Improved Photoresist Coating for Making CNT Field Emitters; A Simplified Diagnostic Method for Elastomer Bond Durability; Complex Multifunctional Polymer/Carbon-Nanotube Composites; Very High Output Thermoelectric Devices Based on ITO Nanocomposites; Reducing Unsteady Loads on a Piggyback Miniature Submarine; Ultrasonic/Sonic Anchor; Grooved Fuel Rings for Nuclear Thermal Rocket Engines; Pulsed Operation of an Ion Accelerator; Autonomous Instrument Placement for Mars Exploration Rovers; Mission and Assets Database; TCP/IP Interface for the Satellite Orbit Analysis Program (SOAP); Trajectory Calculator for Finite-Radius Cutter on a Lathe; Integrated System Health Management Development Toolkit.

Source record↗

NASA NTRS1971

Development of integral covers on solar cells

The electron-beam technique for evaporating a dielectric material onto solar cells is investigated. A process has been developed which will provide a highly transparent, low stress, 2 mil thick cover capable of withstanding conventional space type qualification tests including humidity, thermal shock, and thermal cycling. The covers have demonstrated the ability to withstand 10 to the 15th power 1 MeV electrons and UV irradiation with minor darkening. Investigation of the cell AR coating has produced a space qualifiable titanium oxide coating which will give an additional 6% current output over similar silicon oxide coated cells when covered by glass.

Stella, P.↗

DOE OSTI2025

Selective Isolation of Surface Grain Boundaries by Oxide Dielectrics Improves Cd(Se,Te) Device Performance

Cd(Se,Te) photovoltaics (PV) are the most widely deployed thin-film solar technology globally, yet continued efficiency improvements are stymied by challenges at the device hole contacts. The inclusion of solution-processed oxide layers such as AlGaO x in the contact stack has yielded improved device open-circuit voltages (V OC ) and fill factors (FF). However, contradictory mechanisms by which these layers improve the device properties have been proposed by the research community. We demonstrate in this work that an underappreciated property of such spin-coated layers is the preferential deposition at grain boundaries, a process that isolates the grain boundaries during contact metallization. The effects of grain-boundary isolation are probed by varying the coverage of solution-processed AlGaO x “barrier” layers on the Cd(Se,Te) surface, quantified by scanning Auger microscopy. Examining coverage-dependent V OC and FF, it was observed that isolating the grain boundaries during metallization is sufficient to prevent damage to the absorber that occurs in devices lacking a barrier layer, while additional coverage contributes to the increased series resistance. Such an effect is agnostic to the material used as a barrier layer, as long as the material does not itself damage the absorber. Spin-coated SiO x was used in place of AlGaO x for an equally beneficial effect. This grain-boundary isolation phenomenon is also observed during Mo deposition and in absorbers that have been contacted with a nitrogen-doped ZnTe layer. The mechanisms by which metallization may degrade the absorber are discussed, as are contact design strategies leveraging barrier layers, which may lead to improved device efficiencies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2005

Polymer Crosslinked 3-D Assemblies of Nanoparticles: Mechanically Strong Lightweight Porous Materials

In analogy to supramolecular assemblies, which are pursued because of properties above and beyond those of the individual molecules, self-standing monolithic three-dimensional assemblies of nanoparticles also have unique properties attributed to their structure. For example, ultra low-density 3-D assemblies of silica nanoparticles, known as silica aerogels, are characterized by large internal void space, high surface area and very low thermal conductivity. Aerogels, however, are also extremely fragile materials, limiting their application to a few specialized environments, e.g., in nuclear reactors as Cerenkov radiation detectors, in space (refer to NASA's Stardust Program) and aboard certain planetary vehicles (thermal insulators on Mars Rovers in 1997 and 2004). The fragility problem is traced to well-defined weak points in the aerogel skeletal framework, the interparticle necks. Using the surface functionality of the nanoparticle building blocks as a focal point, we have directed attachment of a conformal polymer coating over the entire framework, rendering all necks wider. Thus, although the bulk density may increase only by 3x, the mesoporosity (pores in the range 2-50 nm) remains unchanged, while the strength of the material increases by up to 300... Having addressed the fragility problem, aerogels are now robust materials, and a variety of applications, ranging from thermal/acoustic insulators to catalyst supports, to platform for sensors, and dielectrics are all within reach. Our approach employs molecular science to manipulate nanoscopic matter for achieving useful macroscopic properties, and in our view it resides at the core of what defines nanotechnology. In that spirit, this technology is expandable in three directions. Thus, we have already crosslinked successfully amine-modified silica, and we anticipate that more rich chemistry will be realized by been creative with the nanoparticle surface modifiers. On the other hand, although we do not expect orders-of-magnitude increase in strength, nevertheless, by varying the polymer we expect to impart other properties such as hydrophobicity, thermal stability and perhaps electrical conductivity. Besides polymers, crosslinkers will include metals and ceramics (e.g., through POSS precursors). Finally, network morphology directs load dissipation, and of approximately 30 different crosslinked oxide aerogels, vanadia, whose structure is fibrous rather than particulate, yields a much stronger (by 4..) material than silica of the same density. It seems imperative to implement control of network morphology, even through templating.

Leventis, Nicholas↗

DOE OSTI2024

The Key Role of Grain Boundary Dynamics in Revolutionizing the Potential of Solid Electrolytes

Solid electrolytes (SEs) have the potential to enhance the safety and performance of Li-metal batteries. However, the existence of grain boundaries in polycrystalline SEs presents a significant challenge for both ionic and electronic migration, promoting the propagation of detrimental lithium dendrites. This study compares the roles of grain boundaries in electrical properties of three distinct SEs including garnet-type Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZO), argyrodite-type Li 6 PS 5 Cl (LPSC), and NASICON-type Li 1+x+y Al x (Ti,Ge) 2-x Si y P 3-y O 12 (LATP). Results demonstrate that the electronic and ionic conductivities of solid-state electrolytes are affected differently by grain boundaries, depending on the specific type of electrolyte. For instance, LLZO and LATP experience dielectric breakdown at 3.7 and 5.3 V, respectively, while LPSC does not exhibit such behavior. Here, a new chemical modification is proposed that simultaneously alters the composition of both the surface and grain boundaries of SEs, ultimately reducing electronic conductivity for the LLZO SEs. Consequently, the proposed LLZO exhibits unprecedented dendrite-free cycling stability, achieving a remarkable 12 000-h lifetime at room temperature, surpassing conventional strategies such as surface coatings in dendrite mitigation. This study highlights the significance of modifying grain boundaries to design safe and durable Li-metal batteries. It provides new insights for developing SEs that are highly resistant to dendrite formation.

36 MATERIALS SCIENCE↗

NASA NTRS1982

Environmentally induced discharges on satellites

A discharge process whose trigger conditions are a negative exposed metallic surface surrounded by a less negative dielectric, and a large voltage gradient at a dielectric/metal interface is proposed. Analysis of SCATHA data for a discharge substantiates the postulation. Surface discharges cause a small transient charge transfer to space which results in voltage transients. A method of computing these transients, based on the charge lost through the capacitance to space and a fraction of charge stored in the dielectric at the discharge source was developed. It gives an estimate of the discharge transients at the discharge site, which is used as input for coupling code analysis of structure/system response. The transient computations were applied to a three-axis stabilized, geosynchronous satellite for both sunlight and eclipse charging. The energy of the transient pulses are about 1 mJ for sunlight discharge and 8 mJ for eclipse. Changing of selected coatings on the satellite would relieve the stress.

Stevens, N. J.↗