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The Application of Metal Oxide Nanomaterials for Chemical Sensor Development

NASA Glenn Research Center (GRC) has been developing miniature chemical sensors for a variety of applications including fire detection, emissions monitoring, fuel leak detection, and environmental monitoring. Smart Lick and Stick sensor technology which integrates a sensor array, electronics, telemetry, and power into one microsystem are being developed. These microsystems require low power consumption for long-term aerospace applications. One approach to decreasing power consumption is the use of nanotechnology. Nanocrystalline tin oxide (SnO2) carbon monoxide (CO) sensors developed previously by this group have been successfully used for fire detection and emissions monitoring. This presentation will briefly review the overall NASA GRC chemical sensor program and discuss our further effort in nanotechnology applications. New carbon dioxide (CO2) sensing material using doped nanocrystalline SnO2 will be discussed. Nanocrystalline SnO2 coated solid electrolyte CO2 sensors and SnO2 nanorod and nanofiber hydrogen (H2) sensors operated at reduced or room temperatures will also be discussed.

Xu, Jennifer C.↗

Miniature Gas-Turbine Power Generator

A proposed microelectromechanical system (MEMS) containing a closed- Brayton-cycle turbine would serve as a prototype of electric-power generators for special applications in which high energy densities are required and in which, heretofore, batteries have been used. The system would have a volume of about 6 cm3 and would operate with a thermal efficiency >30 percent, generating up to 50 W of electrical power. The energy density of the proposed system would be about 10 times that of the best battery-based systems now available, and, as such, would be comparable to that of a fuel cell. The working gas for the turbine would be Xe containing small quantities of CO2, O2, and H2O as gaseous lubricants. The gas would be contained in an enclosed circulation system, within which the pressure would typically range between 5 and 50 atm (between 0.5 and 5 MPa). The heat for the Brayton cycle could be supplied by any of a number of sources, including a solar concentrator or a combustor burning a hydrocarbon or other fuel. The system would include novel heat-transfer and heat-management components. The turbine would be connected to an electric power generator/starter motor. The system would include a main rotor shaft with gas bearings; the bearing surfaces would be made of a ceramic material coated with nanocrystalline diamond. The shaft could withstand speed of 400,000 rpm or perhaps more, with bearing-wear rates less than 10(exp -)4 those of silicon bearings and 0.05 to 0.1 those of SiC bearings, and with a coefficient of friction about 0.1 that of Si or SiC bearings. The components of the system would be fabricated by a combination of (1) three-dimensional xray lithography and (2) highly precise injection molding of diamond-compatible metals and ceramic materials. The materials and fabrication techniques would be suitable for mass production. The disadvantages of the proposed system are that unlike a battery-based system, it could generate a perceptible amount of sound, and, if it were to burn fuel, then it would also generate exhaust, similarly to other combustion-based power sources.

Wiberg, Dean↗

Wide Temperature Magnetization Characteristics of Transverse Magnetically Annealed Amorphous Tapes for High Frequency Aerospace Magnetics

100 kHz magnetization properties of sample transverse magnetically annealed, cobalt-based amorphous and iron-based nanocrystalline tape wound magnetic cores are presented over the temperature range of -150 C to 150 C, at selected values of B(sub peak). Frequency resolved characteristics are given over the range of 50 kHz to 1 MHz, but at B(sub peak) = 0.1 T and 50 C only. Basic exciting winding current and induced voltage data were taken on bare toroidal cores, in a standard type measurement setup. A linear permeability model, which represents the core by a parallel L-R circuit, is used to interpret and present the magnetization characteristics and several figures of merit applicable to inductor materials are reviewed. The 100 kHz permeability thus derived decreases with increasing temperature for the Fe-based, nanocrystalline material, but increases roughly linearly with temperature for the two Co-based materials, as long as B(sub peak) is sufficiently low to avoid saturation effects. Due to the high permeabilities, rather low values of the 'quality factor' Q, from about 20 to below unity, were obtained over the frequency range of 50 kHz to 1 MHz (50 C, B(sub peak) = 0.1 T). Therefore these cores must be gapped in order to make up high Q or high current inductors. However, being rugged, low core loss materials with flat B-H loop characteristics, they may provide new solutions to specialty inductor applications.

Niedra, Janis M.↗

Diffraction Studies of the Atomic Vibrations of Bulk and Surface Atoms in the Reciprocal and Real Spaces of Nanocrystalline SiC

To describe and evaluate the vibrational properties of nanoparticles it is necessary to distinguish between the surface and the core of the particles. Theoretical calculations show that vibrational density of states of the inner atoms of nanograins is similar to bulk material but shifted to higher energies which can be explained by the fact that the gain core is stressed (hardened) due to the presence of internal pressure. Theoretical calculations also show that there is a difference between vibrational properties of a crystal lattice of the grain interior in isolated particles and in a dense (sintered) nanocrystalline material. This is probably due to a coupling of the modes inside the grains via the grain boundaries in dense nanocrystalline bodies. We examined strains present in the surface shell based on examination of diamond and Sic nanocrystals in reciprocal (Bragg-type scattering) and real (PDF analysis) space analysis of neutron diffraction data. Recently we examined the atomic thermal motions in nanocrystalline Sic based on the assumption of a simple Einstein model for uncorrelated atomic notions. According to this model, the Bragg intensity is attenuated as a function of scattering angle by the Debye-Waller factor. Based on this assumption overall temperature factors were determined from the Wilson plots.

Stelmakh, S.↗

Microchemical and Structural Evidence for Space Weathering in Soils from Asteroid Itokawa

The chemistry, microstructure and optical properties of grains on the surfaces of airless bodies are continu-ously modified due to their interactions predominantly with solar energetic ions and micrometeorite impacts. Collectively known as space weathering, this phenomenon results in a discrepancy between remotely sensed spectra from asteroids and those ac-quired directly from meteorites. The return of pristine samples from the asteroid Itokawa provides insight into surface processes on airless bodies and will help in correlating remote sensing data with laboratory analysis of meteorites. Samples and Methods: We examined Itokawa samples RA-QD02-0042-01 and RA-QD-02-0042-02, ultramicrotomed sec-tions of a singular grain prepared by the Hayabusa sample cura-tion team. We analyzed these slices using a 200 keV JEOL 2010F transmission electron microscope (TEM) at Arizona State Uni-versity and a 200 keV JEOL 2500SE TEM at NASA JSC. Both field emission TEMs are equipped with energy-dispersive X-ray spectrometers (EDS) and scanning TEM (STEM) detectors. Results and Discussion: TEM observations reveal that the sectioned grain predominantly consists of a single crystal of low-Ca orthopyroxene, with subsidiary smaller regions of olivine, Fe-Ni sulfide, and Fe-Ni metal. EDS-spectrum imaging and high-resolution TEM (HRTEM) show local, nanocrystalline regions of the outermost 2 to 5 nm of the pyroxene are composed of an Fe-Mg-S-rich and Si- and O-depleted layer that is underlain by a 2- to 5-nm thick amorphous zone enriched in Si. These layers occur in multiple microtome slices and have uniform thicknesses. We also observe localized 'islands' of material on the surface of the pyroxene which HRTEM imaging indicates are amorphous and EDS measurements show are compositionally heterogeneous. A 10- to 60-nm thick partially amorphous zone occurs below the compositionally distinct rim. While this this zone is associated with the compositionally heterogeneous outer layer, it also occurs as a local stand-alone feature on the exterior rim of the grain. Ar-eas of the pyroxene grain rim also exhibit a vesicular texture. The TEM data indicate a complex history of space weather-ing for samples RA-QD02-0042-01 and -02. The outermost layer of nanocrystalline material with varied composition is consistent with previously suggested [3-4] chemical and structural pro-cessing by solar wind ions, with a possible additional role for im-pact vapor deposition [3-4]. The amorphous and compositionally distinct islands on the surface of this grain, similar to lunar glasses, suggest formation through vapor deposition via micrometeor-ite impact events. In comparison, the amorphization and vesicula-tion textures are likely a product of radiation damage from the solar wind. The depth and degree of amorphization, in conjunction with model calculations, will help provide an upper limit on exposure time for these particles.

Thompson, M. S.↗

Multiscale Modeling of Intergranular Fracture in Aluminum: Constitutive Relation For Interface Debonding

Intergranular fracture is a dominant mode of failure in ultrafine grained materials. In the present study, the atomistic mechanisms of grain-boundary debonding during intergranular fracture in aluminum are modeled using a coupled molecular dynamics finite element simulation. Using a statistical mechanics approach, a cohesive-zone law in the form of a traction-displacement constitutive relationship, characterizing the load transfer across the plane of a growing edge crack, is extracted from atomistic simulations and then recast in a form suitable for inclusion within a continuum finite element model. The cohesive-zone law derived by the presented technique is free of finite size effects and is statistically representative for describing the interfacial debonding of a grain boundary (GB) interface examined at atomic length scales. By incorporating the cohesive-zone law in cohesive-zone finite elements, the debonding of a GB interface can be simulated in a coupled continuum-atomistic model, in which a crack starts in the continuum environment, smoothly penetrates the continuum-atomistic interface, and continues its propagation in the atomistic environment. This study is a step towards relating atomistically derived decohesion laws to macroscopic predictions of fracture and constructing multiscale models for nanocrystalline and ultrafine grained materials.

Yamakov, V.↗

Atomistic Cohesive Zone Models for Interface Decohesion in Metals

Using a statistical mechanics approach, a cohesive-zone law in the form of a traction-displacement constitutive relationship characterizing the load transfer across the plane of a growing edge crack is extracted from atomistic simulations for use within a continuum finite element model. The methodology for the atomistic derivation of a cohesive-zone law is presented. This procedure can be implemented to build cohesive-zone finite element models for simulating fracture in nanocrystalline or ultrafine grained materials.

Yamakov, Vesselin I.↗

Transmission Electron Microscopy of Itokawa Regolith Grains

Introduction: In a remarkable engineering achievement, the JAXA space agency successfully recovered the Hayabusa space-craft in June 2010, following a non-optimal encounter and sur-face sampling mission to asteroid 25143 Itokawa. These are the first direct samples ever obtained and returned from the surface of an asteroid. The Hayabusa samples thus present a special op-portunity to directly investigate the evolution of asteroidal sur-faces, from the development of the regolith to the study of the effects of space weathering. Here we report on our preliminary TEM measurements on two Itokawa samples. Methods: We were allocated particles RA-QD02-0125 and RA-QD02-0211. Both particles were embedded in low viscosity epoxy and thin sections were prepared using ultramicrotomy. High resolution images and electron diffraction data were ob-tained using a JEOL 2500SE 200 kV field-emission scanning-transmission electron microscope. Quantitative maps and anal-yses were obtained using a Thermo thin-window energy-dispersive x-ray (EDX) spectrometer. Results: Both particles are olivine-rich (Fo70) with μm-sized inclusions of FeS and have microstructurally complex rims. Par-ticle RA-QD02-0125 is rounded and has numerous sub-μm grains attached to its surface including FeS, albite, olivine, and rare melt droplets. Solar flare tracks have not been observed, but the particle is surrounded by a continuous ~50 nm thick, stuctur-ally disordered rim that is compositionally similar to the core of the grain. One of the surface adhering grains is pyrrhotite show-ing a S-depleted rim (~8-10 nm thick) with nanophase Fe metal grains (<5 nm) decorating the outermost surface. The pyrrhotite displays a complex superstructure in its core that is absent in the S-depleted rim. Particle RA-QD02-0211 contains solar flare particle tracks (~2x109 cm-2) and shows a structurally disordered rim ~100 nm thick. The track density corresponds to a surface exposure of ~103-104 years based on the track production rate of [1]. The dis-ordered rim is nanocrystalline with minor amorphous material between crystalline domains. Quantitative element maps show the outermost ~10 nm of the disordered rim is Si-rich. Discussion and Conclusions: Both particles record the ef-fects of space weathering processes on Itokawa. Noguchi et al. [2] proposed that the disordered rims they observed on Itokawa particles largely result from solar wind radiation damage and we arrive at a similar conclusion for the two particles we analyzed. The microstructure of the S-depleted layer on the pyrrhotite grain in RA-QD02-0125 is similar to that observed in troilite irradiated with ~1018 4 kV He+ [3, 4]. Prolonged irradiation has also been shown to disorder pyrrhotite such that the superstructure reflec-tions are lost [5].

Keller, Lindsay P.↗

Magnetic and Electrical Characteristics of Permalloy Thin Tape Bobbin Cores

The core loss, that is, the power loss, of a soft ferromagnetic material is a function of the flux density, frequency, temperature, excitation type (voltage or current), excitation waveform (sine, square, etc.) and lamination or tape thickness. In previously published papers we have reported on the specific core loss and dynamic B-H loop results for several polycrystalline, nanocrystalline, and amorphous soft magnetic materials. In this previous research we investigated the effect of flux density, frequency, temperature, and excitation waveform for voltage excitation on the specific core loss and dynamic B-H loop. In this paper, we will report on an experimental study to investigate the effect of tape thicknesses of 1, 1/2, 1/4, and 1/8-mil Permalloy type magnetic materials on the specific core loss. The test cores were fabricated by winding the thin tapes on ceramic bobbin cores. The specific core loss tests were conducted at room temperature and over the frequency range of 10 kHz to 750 kHz using sine wave voltage excitation. The results of this experimental investigation will be presented primarily in graphical form to show the effect of tape thickness, frequency, and magnetic flux density on the specific core loss. Also, the experimental results when applied to power transformer design will be briefly discussed.

Schwarze, Gene E.↗

Investigation of the Surface Stress in SiC and Diamond Nanocrystals by In-situ High Pressure Powder Diffraction Technique

The real atomic structure of nanocrystals determines key properties of the materials. For such materials the serious experimental problem lies in obtaining sufficiently accurate measurements of the structural parameters of the crystals, since very small crystals constitute rather a two-phase than a uniform crystallographic phase system. As a result, elastic properties of nanograins may be expected to reflect a dual nature of their structure, with a corresponding set of different elastic property parameters. We studied those properties by in-situ high-pressure powder diffraction technique. For nanocrystalline, even one-phase materials such measurements are particularly difficult to make since determination of the lattice parameters of very small crystals presents a challenge due to inherent limitations of standard elaboration of powder diffractograms. In this investigation we used our methodology of the structural analysis, the 'apparent lattice parameter' (alp) concept. The methodology allowed us to avoid the traps (if applied to nanocrystals) of standard powder diffraction evaluation techniques. The experiments were performed for nanocrystalline Sic and GaN powders using synchrotron sources. We applied both hydrostatic and isostatic pressures in the range of up to 40 GPa. Elastic properties of the samples were examined based on the measurements of a change of the lattice parameters with pressure. The results show a dual nature of the mechanical properties (compressibilities) of the materials, indicating a complex, core-shell structure of the grains.

Palosz, B.↗

Organic Matter in Itokawa Particles

The first Hayabusa mission returned samples from the near-Earth S-type asteroid 25143 Itokawa to Earth in 2010[1]. Although Itokawa has a lithology related to ordinary chondrites(OCs) that typically have low organic contents, several Itokawa particles were found to contain organic matter (OM)[2-5]. However, there was not an explicit conclusion to the origin of the observed OMin these early studies. We have extended our search for OM into other Itokawa grains. Here, we report extraterrestrial OM (macromolecular carbon and amino acids) observed in six Itokawa particles(including a category1 particle: RA-QD02-0162[#62; also nicknamed “Amazon”],and five category3 carbon-rich particles:RA-QD02-0012[#12], RA-QD02-0078[#78], RB-CV-0029[#29], RB-CV-0080 [#80] and RB-QD04-0052[#52]).All allocated Itokawa samples were initially analysed by spot and point-by-point mapping Raman spectroscopic analysis at the Open University, UK. Amazon was then transferred and mounted into indium on an aluminium stub, which was studied with a NanoSIMS 50L ion microprobe for its H,C,N isotopic compositions. The rest of the samples were mounted in sterile gold foils, and the amino acid contents of their acid hydrolysed hot water extracts were obtained with a liquid chromatography with tandem fluorescence and accurate mass detection at NASA Goddard Space Flight Center, USA. Based on the observation of the Raman parameters(e.g. the peak locations and widths of the defect (D) and graphite (G) bands)[6], a significant variety of carbonaceous materials has been observed in Amazon. The carbonaceous materials include primitive and unaltered OM that shares similarity with the IOM in primitive (CI,CM,CR) carbonaceous chondrites, as well as OM that has been heavily graphitised. The organic structure of the heated material is best represented by nanocrystalline graphite, comparable to that observed for metamorphosed meteorites (e.g., L3–6 Inman, Tieschitz and New Concord,CV3 Allende, and EH4 Indarch),suggesting peak metamorphic temperatures (PMT) of >~600°C. The thermal history recorded in the graphitic OM agrees with PMT estimates for returned Itokawa regolith grains (600–800°C)[7].We have obtained the H,C,N isotopic compositions for the primitive OM in Amazon, which exhibits unambiguously extraterrestrial isotopic signatures (δD = +4868±2288‰; δ13C = −24±5‰; δ15N = +344±20‰), contrasting to the typically negative isotopic values obtained for terrestrial organic matter[8]. The δD and δ13C values of the organic material in Amazon are comparable to OCs, however, the δ15N value is higher than that typically observed for OCs (δ15N = −47 to +36‰), and is similar to that of CRs (δ15N = +153 to +309‰)[9].Our data suggest a genetic link between the primitive organic material observed in Itokawa to CRs and IDPs for they share similar D, 13C and 15N enrichments[10].The high carbon contents of the five category 3 Itokawa particles suggest potentially higher OM abundances, hence we extracted and analysed amino acids in these samples. Although terrestrial contamination was observed primarily as L-protein amino acids, several terrestrially uncommon non-protein amino acids were also observed at low abundances, such as β-aminoisobutyric acid (β-AIB),β-amino-n-butyric acid (β-ABA), and β-alanine. Itokawa amino acid content observed here was dissimilar to thermally altered OCs, but preliminarily analogous to more aqueously altered CR2s.Continued evolution of Itokawa is evident by the in fall of primitive organic material derived from CRs/IDPs, accounting for a complex interplay between the remnant Itokawa silicates with exogenous organics. The results reported here are the first evidence of extraterrestrial OM in asteroid material from a sample-return mission, showcasing a working protocol for analysing samples returned by the Hayabusa2 and OSIRIS-REx missions

Q. H. S. Chan↗

Dye-Sensitized Solar Cells for Space Power

During the course of this grant, dye-sensitized solar cells were prepared and characterized. The solar cells were prepared using materials (dyes, electrolytes, transparent conductive oxide coated glass, nanocrystalline TiO2) entirely prepared in-house, as well as prepared using materials available commercially. Complete cells were characterized under simulated AM0 illumination. The best cell prepared at NASA had an AM0 efficiency of 1.22% for a 1.1 sq cm cell. Short circuit current (Isc), open circuit voltage (Voc) and fill factor (FF) for the cell were 6.95 mA, 618 mV and 42.8%, respectively. For comparison purposes, two commercially prepared dye-sensitized solar cells were obtained from Solaronix SA, Aubonne, Switzerland. The Solaronix cells were also characterized under simulated AM0 illumination. The best cell from Solaronix had an active area of 3.71 sq cm and measured an AM0 efficiency of 3.16%. with Isc, Voc and FF of 45.80 mA, 669.6 mV and 52.3%, respectively. Both cells from Solaronix were rapid thermal cycled between -80 C and 80 C. Thermal cycling led to a 4.6% loss of efficiency in one of the cells and led to nearly a complete failure in the second cell.

Harris, Jerry D.↗

Possible Gems and Ultra-Fine Grained Polyphase Units in Comet Wild 2.

GEMS and ultrafine grained polyphase units (UFG-PU) in anhydrous IDPs are probably some of the most primitive materials in the solar system. UFG-PUs contain nanocrystalline silicates, oxides, metals and sulfides. GEMS are rounded approximately 100 nm across amorphous silicates containing embedded iron-nickel metal grains and sulfides. GEMS are one of the most abundant constituents in some anhydrous CPIDPs, often accounting for half the material or more. When NASA's Stardust mission returned with samples from comet Wild 2 in 2006, it was thought that UFG-PUs and GEMS would be among the most abundant materials found. However, possibly because of heating during the capture process in aerogel, neither GEMS nor UFG-PUs have been clearly found.

Gainsforth, Z.↗

Short Range-Ordered Minerals: Insight into Aqueous Alteration Processes on Mars

Short range-ordered (SRO) aluminosilicates (e.g., allophane) and nanophase ferric oxides (npOx) are common SRO minerals derived during aqueous alteration of basaltic materials. NpOx refers to poorly crystalline or amorphous alteration products that can be any combination of superparamagnetic hematite and/or goethite, akaganeite, schwertmannite, ferrihydrite, iddingsite, and nanometer-sized ferric oxide particles that pigment palagonitic tephra. Nearly 30 years ago, SRO phases were suggested as alteration phases on Mars based on similar spectral properties for altered basaltic tephra on the slopes of Mauna Kea in Hawaii and Martian bright regions measured by Earth-based telescopes. Detailed characterization of altered basaltic tephra on Mauna Kea have identified a variety of alteration phases including allophane, npOx, hisingerite, jarosite, alunite, hematite, goethite, ferrihydrite, halloysite, kaolinite, smectite, and zeolites. The presence of npOx and other Fe-bearing minerals (jarosite, hematite, goethite) was confirmed by the M ssbauer Spectrometer onboard the Mars Exploration Rovers. Although the presence of allophane has not been definitely identified on Mars robotic missions, chemical analysis by the Spirit and Opportunity rovers and thermal infrared spectral orbital measurements suggest the presence of allophane or allophane-like phases on Mars. SRO phases form under a variety of environmental conditions on Earth ranging from cold and arid to warm and humid, including hydrothermal conditions. The formation of SRO aluminosilicates such as allophane (and crystalline halloysite) from basaltic material is controlled by several key factors including activity of water, extent of leaching, Si activity in solution, and available Al. Generally, a low leaching index (e.g., wet-dry cycles) and slightly acidic to alkaline conditions are necessary. NpOx generally form under aqueous oxidative weathering conditions, although thermal oxidative alteration may occasional be involved. The style of aqueous alteration (hydrolytic vs. acid sulfate) impacts which phases will form (e.g., oxides, oxysulfates, and oxyhydroxides). Knowledge on the formation processes of SRO phases in basaltic materials on Earth has allowed significant enhancement in our understanding of the aqueous processes at work on Mars. The 2011 Mars Science Laboratory (MSL) will provide an instrument suite that should improve our understanding of the mineralogical and chemical compositions of SRO phases. CheMin is an X-ray diffraction instrument that may provide broad X-ray diffraction peaks for SRO phases; e.g., broad peaks around 0.33 and 0.23 nm for allophane. Sample Analysis at Mars (SAM) heats samples and detects evolved gases of volatile-bearing phases including SRO phases (i.e., carbonates, sulfates, hydrated minerals). The Alpha Particle X-ray Spectrometer (APXS) and ChemCam element analyzers will provide chemical characterization of samples. The identification of SRO phases in surface materials on MSL will be challenging due to their nanocrystalline properties; their detection and identification will require utilizing the MSL instrument suite in concert. Ultimately, sample return missions will be required to definitively identify and fully characterize SRO minerals with state-of-the-art laboratory instrumentation back on Earth.

Ming, Douglas W.↗

Superhard Nanocrystalline Homometallic Stainless Steel on Steel for Seamless Coatings

The objective of this work is to deposit nanocrystalline stainless steel onto steel substrates (homometallic) for enhanced wear and corrosion resistance. Homometallic coatings provide superior adhesion, and it has been shown that ultrafine-grained materials exhibit the increased hardness and decreased permeability desired for protective coatings. Nanocrystals will be produced by controlling nucleation and growth and use of an ion beam during deposition by e-beam evaporation or sputtering. Phase I is depositing 31 6L nanocrystalline stainless steel onto 31 6L stainless steel substrates. These coatings exhibit hardnesses comparable to those normally obtained for ceramic coatings such ZrO2, and possess the superior adhesion of seamless, homometallic coatings. Hardening the surface with a similar material also enhances adhesion, by avoiding problems associated with thermal and lattice mismatch. So far we have deposited nanocrystalline homometallic 316L stainless steel coatings by varying the ions and the current density of the ion beams. For all deposition conditions we have produced smooth, uniform, superhard coatings. All coatings exhibit hardness of at least 200% harder than that of bulk materials. Our measurements indicate that there is a direct relationship between nanohardness and the current density of the ion beam. Stress measurements indicate that stress in the films is increasingly proportional to current density of the ion beam. TEM, XPS, and XRD results indicate that the coated layers consist of FCC structure nanocrystallites with a dimension of about 10 to 20 nm. The Ni and Mo concentration of these coating are lower than those of bulk 316L but the concentration of Cr is higher.

Tobin, Eric J.↗

Reflectance spectroscopy of palagonite and iron-rich montmorillonite clay mixtures: Implications for the surface composition of Mars

Because of the power of remote sensing reflectance spectroscopy in determining mineralogy, it was used as the major method of identifying possible mineral analogs of the Martian surface. A summary of proposed Martian surface compositions from reflectance spectroscopy before 1979 was presented. Since that time, iron-rich montmorillonite clay, nanocrystalline or nanophase hematite, and palagonite were suggested as Mars soil analog materials.

Orenberg, J. B.↗

Examination of Short- and Long-Range Atomic Order Nanocrystalline SiC and Diamond by Powder Diffraction Methods

The real atomic structure of nanocrystals determines unique, key properties of the materials. Determination of the structure presents a challenge due to inherent limitations of standard powder diffraction techniques when applied to nanocrystals. Alternate methodology of the structural analysis of nanocrystals (several nanometers in size) based on Bragg-like scattering and called the "apparent lattice parameter" (alp) is proposed. Application of the alp methodology to examination of the core-shell model of nanocrystals will be presented. The results of application of the alp method to structural analysis of several nanopowders were complemented by those obtained by determination of the Atomic Pair Distribution Function, PDF. Based on synchrotron and neutron diffraction data measured in a large diffraction vector of up to Q = 25 Angstroms(exp -1), the surface stresses in nanocrystalline diamond and SiC were evaluated.

Palosz, B.↗

Reflectance spectroscopy and GEX simulation of palagonite and iron-rich montmorillonite clay mixtures: Implications for the surface composition of Mars

Because of the power of remote sensing reflectance spectroscopy in determining mineralogy, it has been used as the major method of identifying a possible mineral analogue of the martian surface. A summary of proposed martian surface compositions from reflectance spectroscopy before 1979 was presented by Singer et al. Since that time, iron-rich montmorillonite clay, nanocrystalline or nanophase hematite, and palagonite have been suggested as Mars soil analogue materials. Palagonite in petrological terms is best described as an amorphous, hydrated, ferric iron, silica gel. Montmorillonite is a member of the smectite clay group, and its structure is characterized by an octahedral sheet in coordination with two tetrahedral sheets in which oxygen atoms are shared. The crystal unity of montmorillonite is well defined in contrast to palagonite where it is considered amorphous or poorly crystalline at best. Because of the absence of the diagnostic strong 2.2-micron reflectance band characteristic of clays in the near-infrared (NIR) spectrum of Mars and palagonite and based upon a consideration of wide wavelength coverage (0.3-50 microns), Roush et al. concluded that palagonite is a more likely Mars surface analogue. In spite of the spectral agreement of palagonite and the Mars reflectance spectrum in the 2.2-micron region, palagonite shows poor correspondence with the results of the Viking LR experiment. In contrast, iron-rich montmorillonite clays show relatively good agreement with the results of the Viking LR experiment. This spectral study was undertaken to evaluate the spectral properties of mixtures of palagonite and Mars analogue iron-rich montmorillonite clay (16-18 wt. percent Fe as Fe2O3) as a Mars surface mineralogical model. Mixtures of minerals as Mars surface analogue materials have been studied before, but the mixtures were restricted to crystalline clays and iron oxides.

Orenberg, J. B.↗