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NASA NTRS1999

Soil Analysis Micro-Mission Concepts Derived from the MSP 2001 Mars Environmental Compatibility Assessment (MECA)

The Mars Environmental Compatibility Assessment (MECA) will evaluate the Martian environment for soil and dust-related hazards to human exploration as part of the Mars Surveyor Program 2001 Lander. The integrated MECA payload contains a wet-chemistry laboratory, a microscopy station, an electrometer to characterize the electrostatic environment, and arrays of material patches to study abrasion and adhesion. Heritage will be all-important for low cost micro-missions, and adaptations of instruments developed for the Pathfinder, '98 and '01 Landers should be strong contenders for '03 flights. This talk has three objectives: (1) Familiarize the audience with MECA instrument capabilities; (2) present concepts for stand-alone and/or mobile versions of MECA instruments; and (3) broaden the context of the MECA instruments from human exploration to a comprehensive scientific survey of Mars. Due to time limitations, emphasis will be on the chemistry and microscopy experiments. Ion-selective electrodes and related sensors in MECA's wet-chemistry laboratory will evaluate total dissolved solids, redox potential, pH, and the concentration of many soluble ions and gases in wet Martian soil. These electrodes can detect potentially dangerous heavy-metal ions, emitted pathogenic gases, and the soil's corrosive potential, and experiments will include cyclic voltammetry and anodic stripping. For experiments beyond 2001, enhancements could allow multiple use of the cells (for mobile experiments) and reagent addition (for quantitative mineralogical and exobiological analysis). MECA's microscopy station combines optical and atomic-force microscopy (AFM) in an actively focused, controlled illumination environment to image particles from millimeters to nanometers in size. Careful selection of substrates allows controlled experiments in adhesion, abrasion, hardness, aggregation, magnetic and other properties. Special tools allow primitive manipulation (brushing and scraping) of samples. Soil particle properties including size, shape, color, hardness, adhesive potential (electrostatic and magnetic), will be determined using an array of sample receptacles and collection substrates. The simple, rugged atomic-force microscope will image in the submicron size range and has the capability of performing a particle-by-particle analysis of the dust and soil. Future implementations might enhance the optical microscopy with spectroscopy, or incorporate advanced AFM techniques for thermogravimetric and chemical analysis.

Hecht, M. H.↗

DOE OSTI2014

Efficient C–C bond splitting on Pt monolayer and sub-monolayer catalysts during ethanol electro-oxidation: Pt layer strain and morphology effects

Efficient catalytic C–C bond splitting coupled with complete 12-electron oxidation of the ethanol molecule to CO 2 is reported on nanoscale electrocatalysts comprised of a Pt monolayer (ML) and sub-monolayer (sML) deposited on Au nanoparticles (Au@Pt ML/sML). The Au@Pt electrocatalysts were synthesized using surface limited redox replacement (SLRR) of an underpotentially deposited (UPD) Cu monolayer in an electrochemical cell reactor. Au@Pt ML showed improved catalytic activity for ethanol oxidation reaction (EOR) and, unlike their Pt bulk and Pt sML counterparts, was able to generate CO 2 at very low electrode potentials owing to efficient C–C bond splitting. To explain this, we explore the hypothesis that competing strain effects due to the Pt layer coverage/morphology (compressive) and the Pt–Au lattice mismatch (tensile) control surface chemisorption and overall activity. Control experiments on well-defined model Pt monolayer systems are carried out involving a wide array of methods such as high-energy X-ray diffraction, pair-distribution function (PDF) analysis, in situ electrochemical FTIR spectroscopy, and in situ scanning tunneling microscopy. The vibrational fingerprints of adsorbed CO provide compelling evidence on the relation between surface bond strength, layer strain and morphology, and catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1979

Efficiency optimization of a thermionic converter array

Intensive study of the outer planets of the solar system requires the use of nuclear power for electric propulsion of spacecraft. Among the power conversion devices being considered for this application are thermionic converters. This paper presents the results of computer modeling of thermionic converters to identify the major design variables and select an optimum size for each of the thermionic converters for the power conversion system under consideration. Among the variables investigated were electrical and thermal losses in electrodes, leads and heat chokes. Those elements which minimized the electrical losses tended to increase thermal losses and system weight. Overall mechanical design and relative positioning of components also had impacts on converter efficiency and the power subsystem weight. Numerical calculations were made using the computer heat transfer code SINDA coupled with electrical loss parameters. The results of the computations are presented in this paper.

Kuo, Y. S.↗

NASA NTRS1972

Dielectric breakdown in a dilute plasma: A 20 kilovolt limited study

A dielectric breakdown study was made of several materials proposed for high-voltage (16-kV) use on solar-cell arrays at space conditions. The tests were made in an argon plasma whose electron density and temperature approximately simulated conditions at an altitude of 300 km. The maximum voltage used was 20 kV. The results indicate that the breakdown voltages of the materials tested are larger than those quoted in the literature for dielectric between two metal electrodes.

Mckinzie, D. J., Jr.↗

DOE OSTI2013

Microbial Electricity Generation Enhances Decabromodiphenyl Ether (BDE-209) Degradation

Due to environmental persistence and biotoxicity of polybrominated diphenyl ethers (PBDEs), it is urgent to develop potential technologies to remediate PBDEs. Introducing electrodes for microbial electricity generation to stimulate the anaerobic degradation of organic pollutants is highly promising for bioremediation. However, it is still not clear whether the degradation of PBDEs could be promoted by this strategy. In this study, we hypothesized that the degradation of PBDEs (e.g., BDE-209) would be enhanced under microbial electricity generation condition. The functional compositions and structures of microbial communities in closed-circuit microbial fuel cell (c-MFC) and open-circuit microbial fuel cell (o-MFC) systems for BDE-209 degradation were detected by a comprehensive functional gene array, GeoChip 4.0, and linked with PBDE degradations. The results indicated that distinctly different microbial community structures were formed between cMFCs and o-MFCs, and that lower concentrations of BDE-209 and the resulting lower brominated PBDE products were detected in c-MFCs after 70-day performance. The diversity and abundance of a variety of functional genes in c-MFCs were significantly higher than those in o-MFCs. Most genes involved in chlorinated solvent reductive dechlorination, hydroxylation, methoxylation and aromatic hydrocarbon degradation were highly enriched in c-MFCs and significantly positively correlated with the removal of PBDEs. Various other microbial functional genes for carbon, nitrogen, phosphorus and sulfur cycling, as well as energy transformation process, were also significantly increased in c-MFCs. Together, these results suggest that PBDE degradation could be enhanced by introducing the electrodes for microbial electricity generation and by specifically stimulating microbial functional genes.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

Flexible Soft X-Ray Image Sensors based on Metal Halide Perovskites With High Quantum Efficiency

Soft X-ray imaging is a powerful tool to explore the structure of cells, probe material with nanometer resolution, and investigate the energetic phenomena in the universe. Conventional soft X-ray image sensors are by and large Si-based charge coupled devices that suffer from low frame rates, complex fabrication processes, mechanical inflexibility, and required cooling below -60 °C. Here, a soft X-ray photodiode is reported based on low-cost metal halide perovskite with comparable performance to commercial Si-based device. Nanothrough network electrode minimized the optical loss due to the shadowing of insensitive layers, while a multidimensional perovskite heterojunction is generated to reduce the photo-generated carrier loss. Further, this strategy promoted a record quantum efficiency of 8 × 10 3 % without cooling, several orders of magnitude greater than the previously achieved. Flexible and curved soft X-ray imaging arrays are fabricated based on this high-performance device structure, demonstrating stable soft X-ray response and sharp imaging capabilities. This work highlights the low-cost and efficient perovskite photodiode as a strong candidate for the next-generation soft X-ray image sensors.

36 MATERIALS SCIENCE↗

NASA NTRS1993

On Machine Capacitance Dimensional and Surface Profile Measurement System

A program was awarded under the Air Force Machine Tool Sensor Improvements Program Research and Development Announcement to develop and demonstrate the use of a Capacitance Sensor System including Capacitive Non-Contact Analog Probe and a Capacitive Array Dimensional Measurement System to check the dimensions of complex shapes and contours on a machine tool or in an automated inspection cell. The manufacturing of complex shapes and contours and the subsequent verification of those manufactured shapes is fundamental and widespread throughout industry. The critical profile of a gear tooth; the overall shape of a graphite EDM electrode; the contour of a turbine blade in a jet engine; and countless other components in varied applications possess complex shapes that require detailed and complex inspection procedures. Current inspection methods for complex shapes and contours are expensive, time-consuming, and labor intensive.

Resnick, Ralph↗

DOE OSTI2018

Surface Passivation and Carrier Collection in {110}, {100} and Circular Si Microwire Solar Cells

Surface recombination is a major bottleneck for realizing highly efficient micro/nanostructure solar cells. Parametric studies of the influence of Si microwire (SiMW) surface-facet orientation (rectangular with flat-facets, {110}, {100} and circular), with a fixed height of 10 µm, diameter (D = 1.5–9.5 µm), and sidewall spacing (S = 2.5–8.5 µm), and mesh-grid density (1–16 mm -2 ) on recombination and carrier collection in SiMW solar cells with radial p-n junctions are reported. An effective surface passivation layer composed of thin thermally grown silicon dioxide (SiO 2 ) and silicon nitride (SiN x ) layers is employed. For a fixed D of 1.5 µm, tight SiMW spacing results in improved short-circuit current density (J sc = 30.1 mA cm -2 ) and sparse arrays result in open-circuit voltages (V oc = 0.552 V) that are similar to those of control Si planar cells. For a fixed S, smaller D results in better light trapping at shorter wavelengths and higher J sc while larger D exhibits better light trapping at larger wavelengths and a higher V oc . With a mesh-grid electrode the power conversion efficiency increases to 15.3%. Finally, these results provide insights on the recombination mechanisms in SiMW solar cells and provide general design principles for optimizing their performance.

14 SOLAR ENERGY↗

DOE OSTI2022

Multi-channel front-end ASIC for a 3D position-sensitive detector

Arrays of 3D position-sensitive detectors (3DPSD), operating at room temperature and using cadmium zinc telluride (CZT) and thallium bromide (TIBr) sensors, are suitable for gamma-ray spectrometry in many applications. One detector configuration, the 3D position-sensitive Virtual Frisch-Grid detector (VFG), is particularly advantageous for integrating into large area arrays. The signals generated inside each detector of the array are captured with the anode, cathode and four pads that enable the reconstruction of the position and energy of the ionizing interaction by measurements of amplitude and timing of the signals. For these applications, a low-noise front-end ASIC has been developed, capable of processing bipolar signals (needed because of AC-coupling of certain electrodes). The ASIC can be coupled to an ADC in order to form a compound “waveform digitizer” capable of post-processing the analog signals and determining amplitude and timing information. This paper describes a 32-channel front-end ASIC that is suitable for reading out a 3 × 3 or 4 × 4 element matrix in the VFG configuration. Each channel is composed of a low-noise charge amplifier with an adaptive continuous reset feedback circuit suitable for both positive and negative charge, a first order shaper and a single-to-differential converter output stage. Voltage and current references are all internally generated by 10-bit DACs and the chip is fully controllable with the I 2 C communication protocol. The readout channel response has been verified using the implemented injection circuit. Linear behavior up to ~75 ke ± with the gain of ~80 mV/fC, and up to ~200 ke ± with the gain of ~30 mV/fC was demonstrated. In conclusion, the first test result waveforms using a 137 Cs radioactive source on a 5 × 5 × 12 mm 3 TIBr crystal are reported.

47 OTHER INSTRUMENTATION↗

DOE OSTI2015

Microfluidic device for acoustic cell lysis

A microfluidic acoustic-based cell lysing device that can be integrated with on-chip nucleic acid extraction. Using a bulk acoustic wave (BAW) transducer array, acoustic waves can be coupled into microfluidic cartridges resulting in the lysis of cells contained therein by localized acoustic pressure. Cellular materials can then be extracted from the lysed cells. For example, nucleic acids can be extracted from the lysate using silica-based sol-gel filled microchannels, nucleic acid binding magnetic beads, or Nafion-coated electrodes. Integration of cell lysis and nucleic acid extraction on-chip enables a small, portable system that allows for rapid analysis in the field.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1999

The MSP 2001 Mars Environmental Compatibility Assessment (MECA)

A chemical analysis of soil-water mixtures and the first microscopic images of martian soil will be among the results to be returned by the Mars Environmental Compatibility Assessment (MECA) payload on the Mars Surveyor Program 2001 Lander. Sponsored by the Human Exploration and Development of Space (HEDS) enterprise, MECA's primary goal is to evaluate potential geochemical and environmental hazards that may confront future martian explorers, and to guide HEDS scientists in the development of high fidelity Mars soil simulants. As a survey of soil properties, the MECA data set will also be rich in information relevant to basic geology, paleoclimate, and exobiology. The integrated MECA payload contains a wet-chemistry laboratory, a microscopy station, an electrometer to characterize the electrostatics of the soil and its environment, and arrays of material patches to study the abrasive and adhesive properties of soil grains. MECA is allocated a mass of 10 kg and a peak power usage of 15 W within an enclosure of 35 x 25 x 15 cm. The Wet Chemistry Laboratory (WCL) consists of four identical cells that will accept samples from surface and subsurface regions accessible to the Lander's robotic arm, mix them with water, and perform extensive analysis of the solution. Ion-selective electrodes and related sensors will evaluate total dissolved solids, redox potential, pH, and the concentration of many soluble ions and gases. Cyclic voltammetry will address oxidants, and anodic stripping voltammetry will probe potentially hazardous trace metals. MECA's microscopy station combines optical and atomic-force microscopy (AFM) in a controlled illumination environment to image dust and soil particles from millimeters to nanometers in size. Careful selection of substrates and an abrasion tool allows experimental study of size distribution, adhesion, abrasion, hardness, color, shape, aggregation, magnetic and other properties. Mounted on the end of the robot arm, MECA's electrometer consists of four types of sensors: an electric field meter, several triboelectricity monitors, an ion gauge, and a thermometer. Tempered only by ultra-violet- light-induced ions and a low-voltage break-down threshold, the dry, cold, dusty martian environment presents an imposing electrostatic hazard to both robots and humans. In addition, the electrostatic environment is key to transport of dust and, consequently, martian meteorology. MECA will also observe natural dust accumulation on engineering materials. Viewed with the robot arm camera, the abrasion and adhesion plates are strategically placed to allow direct observation of the inter-action between materials and soils on a macroscopic scale. Materials of graded hardness are placed directly under the robot arm scoop to sense wear and soil hardness. A second array, placed on the lander deck, is deployed after the dust plume of landing has settled. It can be manipulated in a primitive fashion by the arm, first having dirt deposited on it from the scoop and subsequently shaken clean. Dust accumulation as a function of conductivity, magnetic field strength, and other parameters will be explored. The MECA instruments described above will assess potential hazards that the Martian soil might present to human explorers and their equipment. In addition, MECA will provide information on the composition of ancient surface water environments, observing microscopic evidence of geological (and biological?) processes, inferring soil and dust transport, comminution and weathering mechanisms, and characterizing soil horizons that might be encountered during excavation. Additional information is contained in the original extended abstract.

Hecht, M. H.↗

DOE OSTI2014

Highly featured amorphous silicon nanorod arrays for high-performance lithium-ion batteries

High aspect-ratio vertical structures of amorphous silicon have been realized using hydrogen-assisted low-density plasma reactive ion etching. Amorphous silicon layers with the thicknesses ranging from 0.5 to 10 μm were deposited using radio frequency plasma enhanced chemical vapor deposition technique. Standard photolithography and nanosphere colloidal lithography were employed to realize ultra-small features of the amorphous silicon. The performance of the patterned amorphous silicon structures as a lithium-ion battery electrode was investigated using galvanostatic charge-discharge tests. The patterned structures showed a superior Li-ion battery performance compared to planar amorphous silicon. Such structures are suitable for high current Li-ion battery applications such as electric vehicles.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2016

Advanced Sensor Arrays and Packaging

Novel sensor packaging elements were designed, fabricated, and tested in order to facilitate the transition of electrochemical mixed-potential sensors toward commercialization. Of the two designs completed, the first is currently undergoing field trials, taking direct measurements within vehicle exhaust streams, while the second is undergoing preliminary laboratory testing. The sensors’ optimal operating conditions, sensitivity to hydrogen, and long-term baseline stability were also investigated. The sensing capabilities of lanthanum chromite (La 0.8 Sr 0.2 CrO 3 ) and indium-doped tin oxide (ITO) working electrodes were compared, and the ITO devices were selected for pre-commercial field trials testing at a hydrogen fuel cell vehicle fueling station in California. Previous data from that fueling station were also analyzed, and the causes of anomalous baseline drift were identified.

47 OTHER INSTRUMENTATION↗

DOE OSTI2021

Mathematical modeling of novel porous transport layer architectures for proton exchange membrane electrolysis cells

Thin foil based porous transport layers (PTLs) that contain highly structured pore arrays have shown promise as anode PTLs in proton exchange membrane electrolysis cells. These novel PTLs, fabricated with advanced manufacturing techniques, produce thin, tunable, multifunctional layers with reduced flow and interfacial resistances and high thermal and electric conductivities. To further optimize their design, it is important to understand their fundamental impact on the transport of protons, electrons, and liquid/vapor mixtures in the electrode. In this work, we develop a two-dimensional multiphysics model to simulate the coupled electrochemistry and multiphase transport in an electrolysis cell operated with the novel PTL architecture. The results show that larger pores improve access of water to the anode catalyst layer, which is beneficial for both the oxygen evolution reaction and membrane hydration. Larger pore sizes also improve oxygen gas transport from the catalyst layer, because generated oxygen gas is forced to travel in-plane through the anode catalyst layer until it reaches a pore opening that is connected to a channel. The discussed results confirm that the proposed thin foil based PTLs are fundamentally different from conventional PTLs, such as felts or layered meshes. The model developed in this work also provides generalizable insight into fundamental PEMEC phenomena, such as the competition between liquid and gas phase transport, membrane hydration and water management, and nonuniform electrochemical reactions, which are processes relevant to all PEMEC designs.

25 ENERGY STORAGE↗

NASA NTRS2004

Electrochemical Reconstitution of Biomolecules for Applications as Electrocatalysts for the Bionanofuel Cell

Platinum-cored ferritins were synthesized as electrocatalysts by electrochemical biomineralization of immobilized apoferritin with platinum. The platinum cored ferritin was fabricated by exposing the immobilized apoferritin to platinum ions at a reduction potential. On the platinum-cored ferritin, oxygen is reduced to water with four protons and four electrons generated from the anode. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This results in a smaller catalyst loading of the electrodes for fuel cells or other electrochemical devices. In addition, the catalytic activity of the ferritin-stabilized platinum nanoparticles is enhanced by the large surface area and particle size phenomena. The work presented herein details the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritin with different inorganic cores, and the fabrication of self-assembled 2-D arrays with thiolated ferritin.

Kim, Jae-Woo↗

NASA NTRS2011

Carbon Nanotube-Based Structural Health Monitoring Sensors

Carbon nanotube (CNT)-based sensors for structural health monitoring (SHM) can be embedded in structures of all geometries to monitor conditions both inside and at the surface of the structure to continuously sense changes. These CNTs can be manipulated into specific orientations to create small, powerful, and flexible sensors. One of the sensors is a highly flexible sensor for crack growth detection and strain field mapping that features a very dense and highly ordered array of single-walled CNTs. CNT structural health sensors can be mass-produced, are inexpensive, can be packaged in small sizes (0.5 micron(sup 2)), require less power than electronic or piezoelectric transducers, and produce less waste heat per square centimeter than electronic or piezoelectric transducers. Chemically functionalized lithographic patterns are used to deposit and align the CNTs onto metallic electrodes. This method consistently produces aligned CNTs in the defined locations. Using photo- and electron-beam lithography, simple Cr/Au thin-film circuits are patterned onto oxidized silicon substrates. The samples are then re-patterned with a CNT-attracting, self-assembled monolayer of 3-aminopropyltriethoxysilane (APTES) to delineate the desired CNT locations between electrodes. During the deposition of the solution-suspended single- wall CNTs, the application of an electric field to the metallic contacts causes alignment of the CNTs along the field direction. This innovation is a prime candidate for smart skin technologies with applications ranging from military, to aerospace, to private industry.

Wincheski, Russell↗

DOE OSTI2019

Dendrite-Free Flexible Fiber-Shaped Zn Battery with Long Cycle Life in Water and Air

Fiber-shaped aqueous rechargeable Zn batteries (FARZBs) show flexibility, good reliability, cost-effectiveness, high energy/power densities, and high safety that have attracted increasing attention as promising energy storage devices for future wearable applications. However, the development of FARZB is limited by its poor cycling life and inferior charge-discharge performance, mainly suffering from zinc dendrite growth and increasing electrode irreversibility. In this work, dendrite-free fiber-shaped Zn//Co 3 O 4 rechargeable batteries with a long cycle life tested in water and air, are obtained via tuning the surface binding energy of Zn on the anode using the zincophilic N,O-functional carbon fiber, as well as engineering the Co 3 O 4 cathode with a nanowire array structure. The fiber-shaped Zn//Co 3 O 4 full battery demonstrates remarkable long cycle life in water and air with high energy density, impressive flexibility, and excellent waterproof ability (fully immersed and charged/discharged under water for more than 33 h for 3000 cycles with capacity retention of ≈80%). The reversible electrochemical mechanisms of the FARZBs, without obvious zinc dendrite deposits and structural change of Co 3 O 4 nanowires, are confirmed by a series of characterizations. Furthermore, these results demonstrate that the FARZBs are promising power sources for emerging wearable electronics.

25 ENERGY STORAGE↗

DOE OSTI2016

Extended-Charge-Transfer Excitons in Crystalline Supramolecular Photocatalytic Scaffolds

Coupling among chromophores in molecular assemblies is responsible for phenomena such as resonant energy transfer and intermolecular charge transfer. These processes are central to the fields of organic photovoltaics and photocatalysis, where it is necessary to funnel energy or charge to specific regions within the system. As such, a fundamental understanding of these transport processes is essential for developing new materials for photovoltaic and photocatalytic applications. Recently, photocatalytic systems based on photosensitizing perylene monomimide (PMI) chromophore amphiphiles were found to show variation in hydrogen gas (H 2 ) production as a function of nanostructure crystallinity. The 2D crystalline systems form in aqueous electrolyte solution, which provides a high dielectric environment where the Coulomb potential between charges is mitigated. This results in relatively weakly bound excitons that are ideal for reducing protons. Furthermore, in order to understand how variations in crystalline structure affect H 2 generation, two representative PMI systems are investigated theoretically using a modified Holstein Hamiltonian. The Hamiltonian includes both molecular Frenkel excitations (FE) and charge-transfer excitations (CTE) coupled nonadiabatically to local intramolecular vibrations. Signatures of FE/CTE mixing and the extent of electron/hole separation are identified in the optical absorption spectrum and are found to correlate strongly to the observed H 2 production rates. The absorption spectral signatures are found to sensitively depend on the relative phase between the electron and hole transfer integrals, as well as the diabatic energy difference between the Frenkel and CT exciton bands. Our analysis provides design rules for artificial photosynthetic systems based on organic chromophore arrays.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗