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At least 19 records

Method and system for near-field spectroscopy using targeted deposition of nanoparticles

There is provided in one embodiment of the invention a method for analyzing a sample material using surface enhanced spectroscopy. The method comprises the steps of imaging the sample material with an atomic force microscope (AFM) to select an area of interest for analysis, depositing nanoparticles onto the area of interest with an AFM tip, illuminating the deposited nanoparticles with a spectrometer excitation beam, and disengaging the AFM tip and acquiring a localized surface enhanced spectrum. The method may further comprise the step of using the AFM tip to modulate the spectrometer excitation beam above the deposited nanoparticles to obtain improved sensitivity data and higher spatial resolution data from the sample material. The invention further comprises in one embodiment a system for analyzing a sample material using surface enhanced spectroscopy.

Anderson, Mark S.↗

Cascaded Photoenhancement: Implications for Photonic Chemical and Biological Sensors

Our analysis shows that coupling of gold nanoparticles to microspheres will evoke a cascading effect from the respective photoenhancement mechanisms. We refer to this amplification process as cascaded photoenhancement, and the resulting cavity amplification of surface-enhanced Raman scattering (SERS) and fluorescence as CASERS and CAF, respectively. Calculations, based on modal analysis of scattering and absorption by compound spheres, presented herein indicate that the absorption cross sections of metal nanoparticles immobilized onto dielectric microspheres can be greatly enhanced by cavity resonances in the microspheres without significant degradation of the resonators. Gain factors associated with CSP of 10(exp 3) - 10(exp 4) are predicted for realistic experimental conditions using homogenous microspheres. Cascaded surface photoenhancement thus has the potential of dramatically increasing the sensitivities of fluorescence and vibrational spectroscopies.

Fuller, Kirk A.↗

Determining Concentration of Nanoparticles from Ellipsometry

A method of using ellipsometry or polarization analysis of light in total internal reflection of a surface to determine the number density of gold nanoparticles on a smooth substrate has been developed. The method can be modified to enable determination of densities of sparse distributions of nanoparticles in general, and is expected to be especially useful for measuring gold-nanoparticle-labeled biomolecules on microarrays. The method is based on theoretical calculations of the ellipsometric responses of gold nanoparticles. Elements of the calculations include the following: For simplicity, the gold nanoparticles are assumed to be spherical and to have the same radius. The distribution of gold nanoparticles is assumed to be a sub-monolayer (that is, sparser than a monolayer). The optical response of the sub-monolayer is modeled by use of a thin-island-film theory, according to which the polarizabilities parallel and perpendicular to the substrate are functions of the wavelength of light, the dielectric functions (permittivities expressed as complex functions of frequency or wavelength) of the gold and the suspending medium (in this case, the suspending medium is air), the fraction of the substrate area covered by the nanoparticles, and the radius of the nanoparticles. For the purpose of the thin-island-film theory, the dielectric function of the gold nanoparticles is modeled as the known dielectric function of bulk gold plus a correction term that is necessitated by the fact that the mean free path length for electrons in gold decreases with decreasing radius, in such a manner as to cause the imaginary part of the dielectric function to increase with decreasing radius (see figure). The correction term is a function of the nanoparticle radius, the wavelength of light, the mean free path and the Fermi speed of electrons in bulk gold, the plasma frequency of gold, and the speed of light in a vacuum. These models are used to calculate ellipsometric responses for various concentrations of gold nanoparticles having an assumed radius. The modeled data indicates distinct spectral features for both the real and the imaginary part of the dielectric function. An ellipsometric measurement would determine this distinct feature and thus can be used to measure nanoparticle concentration. By "ellipsometric responses" is meant the intensities of light measured in various polarization states as functions of the angle of incidence and the polarization states of the incident light. These calculated ellipsometric responses are used as calibration curves: Data from subsequent ellipsometric measurements on real specimens are compared with the calibration curves. The concentration of the nanoparticles on a specimen is assumed to be that of the calibration curve that most closely matches the data pertaining to that specimen.

Venkatasubbarao, Srivatsa↗

Nanocrystalline Chalcopyrite Materials (CuInS2 and CuInSe2) via Low-Temperature Pyrolysis of Molecular Single-Source Precursors

Nanometer sized particles of the chalcopyrite compounds CuInS2 and CuInSe2 were synthesized by thermal decomposition of molecular single-source precursors (PPh3)2CuIn(SEt)4 and (PPh3)2CuIn(SePh)4, respectively, in the non-coordinating solvent dioctyl phthalate at temperatures between 200 and 300 C. The nanoparticles range in size from 3 - 30 nm and are aggregated to form roughly spherical clusters of about 500 nm in diameter. X-ray diffraction of the nanoparticle powders shows greatly broadened lines indicative of very small particle sizes, which is confirmed by TEM. Peaks present in the XRD can be indexed to reference patterns for the respective chalcopyrite compounds. Optical spectroscopy and elemental analysis by energy dispersive spectroscopy support the identification of the nanoparticles as chalcopyrites.

Castro, Stephanie L.↗

NASA Tech Briefs, August 2005

Topics include: Hidden Identification on Parts: Magnetic Machine-Readable Matrix Symbols; System for Processing Coded OFDM Under Doppler and Fading; Multipurpose Hyperspectral Imaging System; Magnetic-Flux-Compensated Voltage Divider; High-Performance Satellite/Terrestrial-Network Gateway; Internet-Based System for Voice Communication With the ISS; Stripline/Microstrip Transition in Multilayer Circuit Board; Dual-Band Feed for a Microwave Reflector Antenna; Quadratic Programming for Allocating Control Effort; Range Process Simulation Tool; Simulator of Space Communication Networks; Computing Q-D Relationships for Storage of Rocket Fuels; Contour Error Map Algorithm; Portfolio Analysis Tool; Glass Frit Filters for Collecting Metal Oxide Nanoparticles; Anhydrous Proton-Conducting Membranes for Fuel Cells; Portable Electron-Beam Free-Form Fabrication System; Miniature Laboratory for Detecting Sparse Biomolecules; Multicompartment Liquid-Cooling/Warming Protective Garments; Laser Metrology for an Optical-Path-Length Modulator; PCM Passive Cooling System Containing Active Subsystems; Automated Electrostatics Environmental Chamber; Estimating Aeroheating of a 3D Body Using a 2D Flow Solver; Artificial Immune System for Recognizing Patterns; Computing the Thermodynamic State of a Cryogenic Fluid; Safety and Mission Assurance Performance Metric; Magnetic Control of Concentration Gradient in Microgravity; Avionics for a Small Robotic Inspection Spacecraft; and Simulation of Dynamics of a Flexible Miniature Airplane.

Source record↗

Ultra-Lightweight Hybrid Thin-Film Solar Cells: A Survey of Enabling Technologies for Space Power Applications

The development of hybrid inorganic/organic thin-film solar cells on flexible, lightweight, space-qualified, durable substrates provides an attractive solution for fabricating solar arrays with high mass specific power (W/kg). Next generation thin-film technologies may well involve a revolutionary change in materials to organic-based devices. The high-volume, low-cost fabrication potential of organic cells will allow for square miles of solar cell production at one-tenth the cost of conventional inorganic materials. Plastic solar cells take a minimum of storage space and can be inflated or unrolled for deployment. We will explore a cross-section of in-house and sponsored research efforts that aim to provide new hybrid technologies that include both inorganic and polymer materials as active and substrate materials. Research at University of Texas at Arlington focuses on the fabrication and use of poly(isothianaphthene-3,6-diyl) in solar cells. We describe efforts at Norfolk State University to design, synthesize and characterize block copolymers. A collaborative team between EIC Laboratories, Inc. and the University of Florida is investigating multijunction polymer solar cells to more effectively utilize solar radiation. The National Aeronautics and Space Administration (NASA)/Ohio Aerospace Institute (OAI) group has undertaken a thermal analysis of potential metallized substrates as well as production of nanoparticles of CuInS2 and CuInSe2 in good yield at moderate temperatures via decomposition of single-source precursors. Finally, preliminary work at the Rochester Institute of Technology (R.I.T.) to assess the impact on performance of solar cells of temperature and carbon nanotubes is reported. Technologies that must be developed to enable ultra-lightweight solar arrays include: monolithic interconnects, lightweight array structures, and new ultra-light support and deployment mechanisms. For NASA applications, any solar cell or array technology must not only meet weight and AMO efficiency goals, but also must be durable enough to survive launch conditions and space environments.

Hepp, Aloysius F.↗

Space Weathering Products Found on the Surfaces of the Itokawa Dust Particles: A Summary of the Initial Analysis

Surfaces of airless bodies exposed to interplanetary space gradually have their structures, optical properties, chemical compositions, and mineralogy changed by solar wind implantation and sputtering, irradiation by galactic and solar cosmic rays, and micrometeorite bombardment. These alteration processes and the resultant optical changes are known as space weathering [1, 2, 3]. Our knowledge of space weathering has depended almost entirely on studies of the surface materials returned from the Moon and regolith breccia meteorites [1, 4, 5, 6] until the surface material of the asteroid Itokawa was returned to the Earth by the Hayabusa spacecraft [7]. Lunar soil studies show that space weathering darkens the albedo of lunar soil and regolith, reddens the slopes of their reflectance spectra, and attenuates the characteristic absorption bands of their reflectance spectra [1, 2, 3]. These changes are caused by vapor deposition of small (<40 nm) metallic Fe nanoparticles within the grain rims of lunar soils and agglutinates [5, 6, 8]. The initial analysis of the Itokawa dust particles revealed that 5 out of 10 particles have nanoparticle-bearing rims, whose structure varies depending on mineral species. Sulfur-bearing Fe-rich nanoparticles (npFe) exist in a thin (5-15 nm) surface layer (zone I) on olivine, low-Ca pyroxene, and plagioclase, suggestive of vapor deposition. Sulfur-free npFe exist deeper inside (<60 nm) ferromagnesian silicates (zone II). Their texture suggests formation by amorphization and in-situ reduction of Fe2+ in ferromagnesian silicates [7]. On the other hand, nanophase metallic iron (npFe0) in the lunar samples is embedded in amorphous silicate [5, 6, 8]. These textural differences indicate that the major formation mechanisms of the npFe0 are different between the Itokawa and the lunar samples. Here we report a summary of the initial analysis of space weathering of the Itokawa dust particles.

Noguchi, T.↗

Thermal Conductivity of Copoly(ethylene vinyl acetate)/Nano-Filler Blends

The development of flexible, thermally conductive fabrics and plastic tubes for the Liquid Cooling and Ventilation Garment (LCVG) are needed to reduce weight and improve the mobility, comfort, and performance of future spacesuits. Such improvements would allow astronauts to operate more efficiently and safely for extended extravehicular activities. As a continuation of our work on the improvement of thermal conductivity (TC) of polymeric materials, nanocomposites were prepared from copoly(ethylene vinyl acetate), trade name Elvax 260TradeMark), metallized carbon nanofibers (CNFs), nickel (Ni) nanostrands, boron nitride both alone and as mixtures with aluminum powder. The nanocomposites were prepared by melt mixing at various loading levels and subsequently fabricated into several material forms (i.e., ribbons, tubes, and compression molded plaques) for analysis. Ribbons and tubes were extruded to form samples in which the nanoparticles were aligned in the direction of flow. The degree of dispersion and alignment of the nanoparticles were investigated using high-resolution scanning electron microscopy. Tensile properties of the aligned samples were determined at room temperature. TC measurements were performed using a laser flash (Nanoflash(TradeMark) technique. The TC of the samples was measured in both the direction of alignment as well as transverse. Tubing of comparable dimensions to that used in the LCVG was extruded from select compositions and the thermal conductivities of the tubes measured.

Ghose, S.↗

Thermal Conductivity of Polymer Copoly(Ethylene Vinyl Acetate)/Nano-Filler Blends

The development of flexible, thermally conductive fabrics and plastic tubes for the Liquid Cooling and Ventilation Garment (LCVG) are needed to reduce weight and improve the mobility, comfort, and performance of future spacesuits. Such improvements would allow astronauts to operate more efficiently and safely for extended extravehicular activities. As a continuation of our work on the improvement of thermal conductivity (TC) of polymeric materials, nanocomposites were prepared from copoly(ethylene vinyl acetate), trade name Elvax 260 , metallized carbon nanofibers (CNFs), nickel (Ni) nanostrands, boron nitride both alone and as mixtures with aluminum powder. The nanocomposites were prepared by melt mixing at various loading levels and subsequently fabricated into several material forms (i.e., ribbons, tubes, and compression molded plaques) for analysis. Ribbons and tubes were extruded to form samples in which the nanoparticles were aligned in the direction of flow. The degree of dispersion and alignment of the nanoparticles were investigated using high-resolution scanning electron microscopy. Tensile properties of the aligned samples were determined at room temperature. TC measurements were performed using a laser flash (Nanoflash ) technique. The TC of the samples was measured in both the direction of alignment as well as transverse. Tubing of comparable dimensions to that used in the LCVG was extruded from select compositions and the thermal conductivities of the tubes measured.

Ghose, S.↗

Laboratory Spectroscopy of Large Carbon Molecules and Ions in Support of Space Missions

One of the major objectives of Laboratory Astrophysics is the optimization of data return from space missions by measuring spectra of atomic and molecular species in laboratory environments that mimic interstellar conditions (WhitePaper (2002, 2006)). Among interstellar species, PAHs are an important and ubiquitous component of carbon-bearing materials that represents a particularly difficult challenge for gas-phase laboratory studies. We present the absorption spectra of jet-cooled neutral and ionized PAHs and discuss the implications for astrophysics. The harsh physical conditions of the interstellar medium have been simulated in the laboratory. We are now, for the first time, in the position to directly compare laboratory spectra of PAHs and carbon nanoparticles with astronomical observations. This new phase offers tremendous opportunities for the data analysis of current and upcoming space missions geared toward the detection of large aromatic systems (HST/COS, FUSE, JWST, Spitzer).

Salana, Farid↗

Nanoscale Analysis of Space-Weathering Features in Soils from Itokawa

Space weathering alters the spectral properties of airless body surface materials by redden-ing and darkening their spectra and attenuating characteristic absorption bands, making it challenging to characterize them remotely [1,2]. It also causes a discrepency between laboratory analysis of meteorites and remotely sensed spectra from asteroids, making it difficult to associate meteorites with their parent bodies. The mechanisms driving space weathering include mi-crometeorite impacts and the interaction of surface materials with solar energetic ions, particularly the solar wind. These processes continuously alter the microchemical and structural characteristics of exposed grains on airless bodies. The change of these properties is caused predominantly by the vapor deposition of reduced Fe and FeS nanoparticles (npFe(sup 0) and npFeS respectively) onto the rims of surface grains [3]. Sample-based analysis of space weathering has tra-ditionally been limited to lunar soils and select asteroidal and lunar regolith breccias [3-5]. With the return of samples from the Hayabusa mission to asteroid Itoka-wa [6], for the first time we are able to compare space-weathering features on returned surface soils from a known asteroidal body. Analysis of these samples will contribute to a more comprehensive model for how space weathering varies across the inner solar system. Here we report detailed microchemical and microstructal analysis of surface grains from Itokawa.

Thompson, M. S.↗

Understanding the Space Weathering of Mercury Through Laboratory Experiments

Introduction: Airless surfaces across the solar system are continually modified by energetic particles from solar wind and micrometeoroid bombardment [1,2]. This process is known as space weathering, and it alters the chemical, microstructural, and optical properties of surface regoliths on airless bodies, including Mercury. On the Moon and S-type asteroids, the reflectance spectral signatures of space weathering include reddening (increasing reflectance with increasing wavelength), darkening (lowering of reflectance), and the attenuation of characteristic absorption bands [2]. Such spectral changes are driven by the production of Fe-bearing nanoparticles(npFe) through both solar wind irradiation and micrometeoroid bombardment. While our understanding of space weathering for the Moon and near-Earth S-types asteroids is advanced, insight into how these processes operate on other planetary bodies is limited. In particular, Mercury experiences a uniquely intense space weathering environment than planetary counterparts at 1 AU, including a moreintense solar wind flux and higher velocity micrometeoroid impacts [4]. Additionally, Mercury has a surface composition unique in the inner solar system, including regions of the surface with very low albedo known as the low reflectance material (LRM), which is enriched in carbon, likely graphite, up to 4wt.% [5].In addition, the concentration of Fe across Mercury’s surface islow (<2 wt.%) compared to the Moonor S-type asteroids asteroids[6]. Our understanding of the effects of space weathering on C-rich and Fe-poor phases is limited. Since Fe plays a critical role inthe development of space weathering characteristicson other airless surfaces(e.g., npFe), its limited availability may significantly affect the development of space weathering features in Mercury surface materials. We can simulate space weathering processes in the laboratory to explore their effects on the microstructural, chemical, and spectral characteristics of Mercury surface materials[7]. Here we used pulsed laser irradiation to simulate the short duration, high-temperature events associated with micrometeoroid impacts. We performed coordinated analyses including reflectance spectroscopy and electron microscopy to investigate the spectral, chemical, and microstructural changes in these mercurian analog samples. Methods: For these experiments, we usedforsteritic olivine with varying FeOcontents, a mineral phase proposed to be abundant on the surface of Mercury. We mixed each sample with graphite to simulate LRM regions of the surface. Wesynthesized the olivinesamplesat 1-bar at NASA’s Johnson Space Centerand prepared pressed powder pellets for laser irradiation [8].We prepared three samples, each with a base layer of olivineto maintain structural integrity and topped witha surface layer containing the graphite-olivine mixture: 1) Sample SC-001 San Carlos olivine(Fo90.91),2)Sample F-S-002 with0.05 wt.% FeO olivine, and 3) F-T-004 with 0.53 wt.% FeO olivine. Each sample was mixed with 5 wt.% powdered graphite and had grain sizes ranging from 45to 125μm. We irradiated each sample usinga pulsed Nd-YAG laser, (l=1064 nm, ~6 ns pulse duration, energy of 48 mJ/pulse) while undervacuumat Northern Arizona University. The laser was rastered1x and then 5x over the surfaceof each sample to simulate progressive space weathering. We collected in situreflectance spectra from the samples after each laser pulse witha Nicolet IS50 Fourier-Transform Infrared spectrometer (lfrom 0.65-2.5 μm). We used an FEI Nova NanoSEM200scanning electron microscope (SEM) and a Hitachi TM4000 Plus benchtop SEM at Purdue University to image the surface morphology and topography of the samples. We extracted thin sections for analysis in the transmission electron microscope(TEM)using the FEI Helios NanoLab 660 focused ion beam (FIB) SEM at the University of Arizona.We performed analysis of the microstructural and chemical characteristics of the samples using the 200 keV JEOL 2500 scanning TEM at Johnson Space Center. Reflectance Spectroscopy Results:Reflectance spectra for each sample are shown in Fig. 1.SC-001:The spectrum of the unirradiated sample exhibits a weak 1.0 μm absorption feature, associated with Fe2+in the olivine,and low overall reflectance (Fig. 1a). Thereflectance and the depth of the absorption band increases after 1x laser raster but are at their lowest after 5x laser rasters.F-T-004:The unirradiated sample has a blue-sloped spectrum with low reflectance without identifiable absorption features (Fig. 1b). With progressive laser irradiation, the sample reflectance increases and becomes strongly red-sloped.F-S-002:The unirradiated sample exhibits a dark, blue-slopedspectrum. The brightness of the sample increases significantly from <0.2average reflectance over >0.8 reflectance in the most irradiated sampleand thespectral slope also becomesslightly reddened (Fig. 1c). Microstructural and Chemical Analysis: Two primary alteration textures were observed in the samples exposed to simulated space weathering: 1) fluffy C-rich,and 2) vesiculated melt. The fluffy C-rich texture is composed oflow-densitydeposits distributed across the surface of the sample(Fig. 2A). Analysis of a FIB section extracted from a low-density C-rich region in sample SC-001 reveals multiple globule-type deposits, discrete from stacked graphite, likely produced via melting from the laser irradiation [9].The vesiculated melt textureis smooth and uniformly distributed across isolated regions of the sample surface. The vesicles measure up to 100s of nmin diameter. Analysis of a FIB section from this texture was extracted from sample F-T-004 reveals a layer of amorphous melt material, close to 100 nm thick and uniform across the FIB section (Fig. 2B). Isolated regions of this melt layer contain small nanoparticles, <5 nm in diameter. Chemical analysis through energy dispersive X-ray spectroscopy reveals the composition of this layer is enriched in Si and depleted in Mg and O compared to the underlying sample. Implications for Space Weathering on Mercury: Previous experiments simulating space weathering of Mercury have showndarkening and reddening of spectra[7,10].However, our use of low-Fe materials and graphite to create a sample set more analogous to the mercurian surface. Our results indicate that sample composition plays a significant and important role in the space weathering of Mercury. In particular, our spectral data demonstrates a strong correlation between spectral slope, Fe content, and simulated space weathering. While the variation in FeO content between samples F-S-002 and F-T-004 is <0.6 wt.%, the spectra deviate from flat to strongly red-sloped(F-T-004). This reddeningmay be linked to the presence of very small nanoparticles observed in the melt textures extracted from sample F-T-004. For the SC-001 sample, the fluffy C-rich textures may be developed by the amalgamation of small graphite particles into these unique morphologies. Such observations indicate that space weathering on Mercury may result in both familiar and new microstructural and chemical characteristics. References: [1]Hapke B. (2001) J. Geophys. Res.-Planet.,106,10039–10073. [2]Pieters C.M. and Noble S.K. (2016) J. Geophys. Res-Planet., 121, 1865–1884. [3] Lucey P.G., and Riner, M.A. (2011) Icarus,212, 451-462.[4]CintalaM.J.(1992)J. Geophys. Res.-Planet.,97,947–973.[5]Klima R.L.et al.(2018)Geophys.Res.Letters, 45, 2945–2953. [6]Nittler L.R., et al. (2011) Science 333, 1847-1850.[7]Sasaki S. and Kurahashi E. (2004) Space weathering on Mercury, Adv.Space Res., 33, 2152-2155.[8] Vander KaadenK.E., et al. (2018) LPSCXLIX, Abstract 1230. [9] McGlaun M.L. et al. (2019) LPSCL, Abstract 2019. [10] TrangD.et al. (2018)LPSCXLIX,Abstract2083

M S Thompson↗

ChIPPS: Charged Information-storage Polymer Preparation System

Technological advances are required to support principal science objectives of missions to the solar system’s icy worlds to seek biosignatures of past/extant life. Sensitivity and reliability are key concerns due to small sample sizes (µL – mL) and the extraordinary import of the results. The preparation and processing of small samples can constrain limits of detection (LoDs); therefore, the Charged Information-storage Polymer Preparation System (ChIPPS) project is advancing the technologies of autonomous sample preparation and processing to add a new class of reliably detectable biosignatures: charged polymers and particles, which can be the information storage-and-transmission means for life. Specifically, we are developing an integrated microfluidic sample-processing unit to prepare icy-world samples to support complementary solid-state nanopore-based analyses: 1) charged-polymer analysis, to characterize variations in polymer chain size, shape, and charge vs. position along the chain; 2) polymer and nanoparticle sizing-and-counting, to characterize the relative abundance of polymer chains, as well as small (virus-sized) particles, by their dimensions and charge. Although no such autonomous system presently exists, such measurements can reveal the nature and abundance of charged polymers that could be used by biological systems to store and transfer information—as DNA and RNA are used terrestrially—without limitation to terrestrial nucleic acids, given that life elsewhere may utilize different information store-and-transfer moieties. Key system components include (a) a lysis unit for mechanical sample disruption; b) an ion-exchange column for charged macromolecule/nanoparticle purification; c) dialyzer to remove excess salt; d) concentrator to enhance signal; e) supporting pumps, valves, bubble traps, connectors, filters, etc.; f) interface to nanopore detection instruments.

Space Biology↗

Nanoelectric Materials Laboratory Development

The Ultracapacitor Research and Development project is a collaborative effort between the NASA Marshall Space Flight Center's (MSFC's) ES43 Parts, Packaging, and Fabrication Branch and the EM41 Nonmetallic Materials Branch. NASA's Ultracapacitor Research is an effort to develop solid-state energy storage devices through processing of ceramic materials into printable dielectric inks, which can be formed and treated to produce solid state ultracapacitor cells capable of exceeding lithium-ion battery energy density at a fraction of the weight. Research and development efforts into solid state ultracapacitors have highlighted a series of technical challenges such as understanding as-received nature of ceramic powders, treatment and optimization of ceramic powders, dielectric and conductor ink formulation, and firing of printed (green) ultracapacitor cells. Two facilities have been continually developed since project inception: the Additive Electronics Lab in Bldg. 4487 and the Nanoelectric Materials Lab in Bldg. 4602. The Nanoelectric Materials Lab has become a unique facility at MSFC, capable of custom processing a wide range of media for additive electronics. As research has progressed, it was discovered that additional in-house processing was necessary to achieve smaller, more uniform particle diameters. A vibratory mill was obtained that can agitate powder and media in three directions, which has shown to be much more effective than ball milling. However, in order to understand the effects of milling, a particle size analysis system has been installed to characterize as-received and milled materials Continued research into the ultracapacitor technology included advanced milling and optimization of ceramic nanoparticles, fluidized bed treatment of atomic-layer deposition- (ALD-) coated ceramic particles, custom development of dielectric and conductor inks, as well as custom ink precursors such as polyvinylidene diflouride- (PVDF-) loaded vehicles. Experiments with graphene-based inks were also conducted.

Allen, Lee↗

Synthesis, Decomposition and Characterization of Fe and Ni Sulfides and Fe and CO Nanoparticles for Aerospace Applications

We describe several related studies where simple iron, nickel, and cobalt complexes were prepared, decomposed, and characterized for aeronautics (Fischer-Tropsch catalysts) and space (high-fidelity lunar regolith simulant additives) applications. We describe the synthesis and decomposition of several new nickel dithiocarbamate complexes. Decomposition resulted in a somewhat complicated product mix with NiS predominating. The thermogravimetric analysis of fifteen tris(diorganodithiocarbamato)iron(III) has been investigated. Each undergoes substantial mass loss upon pyrolysis in a nitrogen atmosphere between 195 and 370 C, with major mass losses occurring between 279 and 324 C. Steric repulsion between organic substituents generally decreased the decomposition temperature. The product of the pyrolysis was not well defined, but usually consistent with being either FeS or Fe2S3 or a combination of these. Iron nanoparticles were grown in a silica matrix with a long-term goal of introducing native iron into a commercial lunar dust simulant in order to more closely simulate actual lunar regolith. This was also one goal of the iron and nickel sulfide studies. Finally, cobalt nanoparticle synthesis is being studied in order to develop alternatives to crude processing of cobalt salts with ceramic supports for Fischer-Tropsch synthesis.

Cowen, Jonathan E.↗

Determination of a Two-Phase Structure of Nanocrystals: GaN and SiC

The properties of nano-crystalline materials are critically dependent on the structure of the constituent grains. Experimental conditions necessary to perform structural analysis of nanocrystalline materials as a two-phase core-surface shell system are discussed. It is shown, that a standard X-ray diffraction measurements and analysis are insufficient and may lead to incorrect conclusions as to the real structure of the materials. A new method of evaluation of powder diffraction data based on the analysis of the shift of the Bragg reflections from their perfect-lattice positions was developed. "Apparent lattice parameters" quantity, alp, was introduced and calculated from the actual positions of each individual Bragg reflection. The alp values plotted versus diffraction vector (Q) show characteristic features that are used for evaluation of the experimental results. The study was based on modeling of nano-grains and simulations of theoretical intensity profiles using the Debye functions. The method was applied to the analysis of synchrotron X-ray diffraction data of GaN and SiC nanocrystals. A presence of strained surface shell and a considerable internal pressure (GaN) in the nanoparticles was concluded.

Palosz, W.↗

Analysis of Crystallization Kinetics

A realistic computer model for polymorphic crystallization (i.e., initial and final phases with identical compositions), which includes time-dependent nucleation and cluster-size-dependent growth rates, is developed and tested by fits to experimental data. Model calculations are used to assess the validity of two of the more common approaches for the analysis of crystallization data. The effects of particle size on transformation kinetics, important for the crystallization of many systems of limited dimension including thin films, fine powders, and nanoparticles, are examined.

Kelton, Kenneth F.↗

Experimental Demonstration and System Analysis for Plasmonic Force Propulsion

This project developed a higher-fidelity model of a recently envisioned small spacecraft propulsion system for precision pointing and proximity control. Plasmonic force propulsion harnesses solar light focused onto plasmon reactive subwavelength nanostructures to accelerate and expel nanoparticle propellant via strong optical forces. The goal of the project was to show that plasmonic space propulsion can provide the level of proximity and attitude control envisioned for future NASA nano/picosatellite missions, a level that is better than state-of-the-art approaches. We achieved this goal by showing that plasmonic force thrusters are feasible for a range of advanced mission concepts requiring swarm formations in a deep space environment. We performed three case studies that evaluated the performance of the plasmonic force propulsion thruster in a deep space, microsatellite swarm formation. These case studies assumed the propulsion system could generate thrust at the level predicted from our Phase 1 study (1.6 μN). Through these cases we were able to analyze the concept within a mission specific context through detailed orbital dynamics calculations. Results indicate that, with the Phase 1 estimated thrust level, the approach is promising for providing attitude control to swarm formation spacecraft. Further, we achieved goals related to technology development. Specifically, we experimentally demonstrated nanoparticle acceleration due to plasmonic forces with asymmetric nanostructures excited by focused laser light. Additionally, we investigated the thrust sensitivity and nanoparticle propellant injection dependencies upon thermal effects. As a result of our study, plasmonic force propulsion is at an early TRL 3. Active research and design has been conducted analytically and in the laboratory. Furthermore, practical applications such as the three case studies have been identified for the scientific basic principles that were observed. Future efforts related to fundamental understanding of these techniques should focus on 1) developing a standalone array of asymmetric nanostructures that can effectively interact with a stream or reservoir of particles or 2) experimentally evaluate a dielectrophoretic injector for nanoparticle propellant. The main limitation discovered about plasmonic propulsion regards performance estimates significantly below the Phase 1 estimations. Specifically, original assumptions in the Phase 1 project (notably, a linear array of asymmetric nanostructures) is not a viable approach to achieving significant acceleration, high exhaust velocity, of nanoparticles. More specifically, we assumed in Phase 1 that nanoparticles would be accelerated in series by a long linear array of asymmetric nanostructures. That is, the acceleration of the nanoparticle would build and increase with the kick received by each subsequent nanostructure. This is fundamentally flawed. The potential profile of a single nanostructure is such that it prohibits this phenomenon. The potential energy associated with the plasmon-generated dielectrophoretic force is a potential well, which is good for trapping nanoparticles, but cannot provide significant acceleration of particles to expel them out and away from the nanostructure. Further, a nanoparticle expelled from the first nanostructure would need to overcome the potential barrier for entry into the next nanostructure accelerating stage. Fundamentally, this effect means that a linear array of nanostructures is not a viable accelerating structure. Correspondingly then, acceleration can, or should, only be provided by one nanostructure, and the net acceleration and thrust force of a single nanostructure is small (~cm/s exhaust velocities, sub-nN level thrust vs. the 100’s m/s, μN originally envisioned). While our experiments demonstrated acceleration and manipulation of a nanoparticle using laser light in aqueous environment, the achievable energy and momentum addition to the nanoparticle from a single nanostructure stage is too low for useful propulsion. In terms of thrust prediction, the estimated thrust of 1.6 μN in Phase 1 is reduced to a few nN of thrust with this new insight and understanding of the concept. This thrust level is too small to achieve attitude control of swarms as originally envisioned.

Plasmonic Force↗