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Raman Study of Uncoated and P-bn/sic-coated Hi-nicalon Reinforced Celsian Matrix Composites: Residual Stress in the Fibers - Part 2

Band shifts on Raman spectra were used to assess, at a microscopic scale, the residual strain existing in Hi-Nicalon fibers reinforcing celsian matrix composites. Uncoated as well as p-BN/SiC- and p-B(Si)N/SiC-coated Hi-Nicalon fibers were used as the reinforcements. We unambiguously conclude that the fibers are in a state of compressive residual stress. Quantitative determination of the residual stress was made possible by taking into account the heating induced by laser probing and by using a reference line, of fixed wavenumber. We found fiber compressive residual stress values between 110 and 960 MPa depending on the fiber/matrix coating in the composite. A stress relaxation-like phenomenon was observed at the surface of p-BN/SiC-coated Hi-Nicalon fibers whereas the uncoated or p-B(Si)N/SiC-coated Hi-Nicalon fibers did not show any stress relaxation in the Celsian matrix composites.

Gouadec, Gwenael↗

Automated Rock Identification for Future Mars Exploration Missions

A key task for human or robotic explorers on the surface of Mars is choosing which particular rock or mineral samples should be selected for more intensive study. The usual challenges of such a task are compounded by the lack of sensory input available to a suited astronaut or the limited downlink bandwidth available to a rover. Additional challenges facing a human mission include limited surface time and the similarities in appearance of important minerals (e.g. carbonates, silicates, salts). Yet the choice of which sample to collect is critical. To address this challenge we are developing science analysis algorithms to interface with a Geologist's Field Assistant (GFA) device that will allow robotic or human remote explorers to better sense and explore their surroundings during limited surface excursions. We aim for our algorithms to interpret spectral and imaging data obtained by various sensors. The algorithms, for example, will identify key minerals, rocks, and sediments from mid-IR, Raman, and visible/near-IR spectra as well as from high resolution and microscopic images to help interpret data and to provide high-level advice to the remote explorer. A top-level system will consider multiple inputs from raw sensor data output by imagers and spectrometers (visible/near-IR, mid-IR, and Raman) as well as human opinion to identify rock and mineral samples.

Gulick, V. C.↗

Electron Beam Irradiated Intercalated CNT Yarns For Aerospace Applications

Multi-walled CNT yarns have been experimentally and commercially created to yield lightweight, high conductivity fibers with good tensile properties for application as electrical wiring and multifunctional tendons. Multifunctional tendons are needed as the cable structures in tensegrity robots for use in planetary exploration. These lightweight robust tendons can provide mechanical strength for movement of the robot in addition to power distribution and data transmission. In aerospace vehicles, such as Orion, electrical wiring and harnessing mass can approach half of the avionics mass. Use of CNT yarns as electrical power and data cables could reduce mass of the wiring by thirty to seventy percent. These fibers have been intercalated with mixed halogens to increase their specific electrical conductivity to that near copper. This conductivity, combined with the superior strength and fatigue resistance makes it an attractive alternative to copper for wiring and multifunctional tendon applications. Electron beam irradiation has been shown to increase mechanical strength in pristine CNT fibers through increased cross-linking. Both pristine and intercalated CNT yarns have been irradiated using a 5-megavolt electron beam for various durations and the conductivities and tensile properties will be discussed. Structural information obtained using a field emission scanning electron microscope, energy dispersive X-ray spectroscopy (EDS), and Raman spectroscopy will correlate microstructural details with bulk properties.

electrical wiring↗

Calibration and Validation of the SHERLOC Instrument Operating in Jezero Crater, Mars

The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemistry (SHERLOC) is an instrument onboard the Mars 2020 Perseverance rover. It consists of a spectrometer that measures deep ultraviolet (DUV) resonance Raman and native fluorescence photons generated through surface interactions with a 248.6 nm pulsed laser. Two microscopic imagers, the Autofocus Context Imager (ACI) and the Wide-Angle Topographic Sensor for Operations and eNgineering (WATSON), provide high-resolution context images of SHERLOC targets. The ACI is co-boresighted with the spectrometer. To ensure proper calibration, the SHERLOC calibration target (SCT) is mounted on the front of the rover and consists of ten different materials. The SCT was designed, fabricated, assembled, and tested by Jacobs Technology, Inc., and NASA Johnson Space Center. The dimensions of the calibration target housing are 150 x 89 x 33 mm and it weighs ~437 g. The ten targets are arranged in two rows; the first six are hard targets (AlGaN for Raman and fluorescence, diffuse transmission target, a slice of the SaU008 Mars meteorite, an intensity maze, and polycarbonate over geocache coin) and the remaining four are soft-goods targets (Vectran, Ortho-Fabric, Teflon, and nGimat-coated Teflon). The hard targets calibrate the spectrometer’s Raman and fluorescence spectral accuracy, ambient light reflection, and Raman response curve, while the soft-goods targets are spacesuit materials that function as human exploration targets, some of which are also used for spectral calibration. SHERLOC also has an internal calibration target consisting of AlGaN on sapphire (275 nm) located inside the ACI opaque dust cover to ensure proper instrument functioning between calibration target analyses. Initial SHERLOC, ACI, and WATSON calibration and validation on Mars was performed using the internal calibration target on sols 59, 83, 98, and 141; WATSON imaging of the SCT on sols 26 and 62, and SHERLOC spectroscopy and ACI imaging of the SCT on sol 59. These early data provide initial insights into instrument performance and the stability and degradation of the calibration target materials relative to the Martian surface and dust environment. Early observations also have implications for future astronaut spacesuit materials.

Trevor G Graff↗

Femtosecond resolution of soft mode dynamics in structural phase transitions

The microscopic pathway along which ions or molecules in a crystal move during structural phase transition can often be described in terms of a collective vibrational mode of the lattice. In many cases, this mode, called a 'soft' phonon mode because of its characteristically low frequency near the phase transition temperature, is difficult to characterize through conventional frequency-domain spectroscopies such as light or neutron scattering. A femtosecond time-domain analog of light-scattering spectroscopy called impulsive stimulated Raman scattering (ISRS) has been used to examine the soft modes of two perovskite ferroelectric crystals. The low-frequency lattice dynamics of KNbO3 and BaTiO3 are clarified in a manner that permits critical evaluation of microscopic models for their ferroelectric transitions. The results illustrate the advantages of ISRS over conventional Raman spectroscopy of low-frequency, heavily damped soft modes.

Dougherty, Thomas P.↗

Ramdb: The NASA Raman Spectral Database (version 1.00).

Given that, in most instances, minimal sample preparation is required and due to its contactless instrument design, Raman spectroscopy is one of the most versatile vibrational spectroscopic techniques for the chemical analysis of environmental and biological specimens. The diversity of applications of Raman spectroscopy ranges anywhere from art [1] to planetary science missions [2]. The advancement in the use of Raman spectroscopy in Solar System missions, notably in post-mission sample return analysis, requires a spectral library holding the broad range of specimens that could be found in Solar System sources. For this purpose, we have initiated the development of a Raman spectral database (Ramdb) at NASA Ames Research Center. Currently, the database includes experimental and theoretical Raman spectra of PAHs [3, 4], as well as laboratory Raman spectra of amino acids, carbon allotropes, minerals, and analogs relevance to Earth Sciences [5], Exobiology [6], Planetary [7], and Astrochemistry [8] to name just a few examples. Ramdb can be found on the web at www.astrochemistry.org/ramdb, where raw and processed Raman spectra can be downloaded in CSV format. The laboratory Raman spectra are measured using a laser Raman spectrometer (JASCO NRS-5500-532QRI). The Raman instrument is equipped with three excitation lasers, with wavelengths of 405, 532, and 785 nm. A clean silicon substrate is used as the internal standard for wavenumber calibration. Powdered samples were prepared (microscopic >10 um, grounded microscopic < 10 um) on glass slides. Some raw data exhibited a background signal arising as a combination of laser-induced fluorescence from the sample. To correct this background, we developed a Python pipeline that uses open-source Python libraries. Ramdb provides both raw and processed (using Python pipeline) data, which includes tabulated Raman shift transitions and other measurement details. The theoretical Raman band positions of PAHs (pyrene monomers and tetramer clusters) were computed using density functional theory (DFT) with the help of the Gaussian 16 suite of programs [9]. In the near future, Ramdb will serve as a repository of Raman spectral data from Laboratory Astrophysics and Planetary Science experiments involving the irradiation of organic compounds under simulated space and planetary conditions. In addition, online and offline tools will be developed for utilising the database for comparison to the user’s sample.

N Punnakayathil↗

NASA Tech Briefs, June 2003

Topics covered include: Nulling Infrared Radiometer for Measuring Temperature; The Ames Power Monitoring System; Hot Films on Ceramic Substrates for Measuring Skin Friction; Probe Without Moving Parts Measures Flow Angle; Detecting Conductive Liquid Leaking from Nonconductive Pipe; Adaptive Suppression of Noise in Voice Communications; High-Performance Solid-State W-Band Power Amplifiers; Microbatteries for Combinatorial Studies of Conventional Lithium-Ion Batteries; Correcting for Beam Aberrations in a Beam-Waveguide Antenna; Advanced Rainbow Solar Photovoltaic Arrays; Metal Side Reflectors for Trapping Light in QWIPs; Software for Collaborative Engineering of Launch Rockets; Software Assists in Extensive Environmental Auditing; Software Supports Distributed Operations via the Internet; Software Estimates Costs of Testing Rocket Engines; yourSky: Custom Sky-Image Mosaics via the Internet; Software for Managing Inventory of Flight Hardware; Lower-Conductivity Thermal-Barrier Coatings; Process for Smoothing an Si Substrate after Etching of SiO2; Flexible Composite-Material Pressure Vessel; Treatment to Destroy Chlorohydrocarbon Liquids in the Ground; Noncircular Cross Sections Could Enhance Mixing in Sprays; Small, Untethered, Mobile Roots for Inspecting Gas Pipes; Paint-Overspray Catcher; Preparation of Regular Specimens for Atom Probes; Inverse Tomo-Lithography for Making Microscopic 3D Parts; Predicting and Preventing Incipient Flameout in Combustors; MEMS-Based Piezoelectric/Electrostatic Inchworm Actuator; Metallized Capillaries as Probes for Raman Spectroscopy; Adaptation of Mesoscale Weather Models to Local Forecasting; Aerodynamic Design using Neural Networks; Combining Multiple Gyroscope Outputs for Increased Accuracy; and Improved Collision-Detection Method for Robotic Manipulator.

Source record↗

Measuring the Chemical Potential of the Martian Regolith to Generate and Sustain Life

A critical component for identifying chemical biosignatures is the ability to assess in-situ the potential of an aqueous geochemical environment to generate and sustain life. On Mars or other solar bodies, in-situ chemical characterization could provide evidence as to whether the chemical composition of the regolith or evaporites in suspected ancient water bodies have been biologically influenced or possess the chemical parameters within which life may have existed, or may still exist. A variety of analytical techniques have been proposed for use in detecting and identify signatures of past or present life. These techniques fall into two groups; visual observation with instruments such as cameras or optical/atomic-force microscopes; or elemental chemical analysis with such instruments as X-ray fluorescence (XRF) and diffraction (XRD), a-proton backscatter (APX), y-ray, Mossbauer, Raman, IR, UV/VIS spectroscopies, gas chromatography (GC), or mass spectrometry (MS). Direct observation of an identifiable lifeform by the first set of instruments in a single sample is highly unlikely, especially for extinct organisms or on the surface. The later instruments can provide vital data as to the elemental mineralogy and geological history of the planet, but are highly inadequate for understanding the chemistry of the planet in terms of indigenous life or interactions with human explorers. Techniques such as XRD, XRF, and APX, provide elemental composition at high limits of detection. Some of this data can be extrapolated or interpolated to provide chemical parameters such as oxidation state or composition. Gas chromatography (GC) without standards and non-specific detectors, has little chance of identifying a mixture of unknown components. Combined with GC or by itself, mass spectrometry (MS) can provide identification of compounds, but in both cases the sample must be appropriately prepared for accurate and reliable analysis. Life as we know it, and probably identify it as such, requires an aqueous environment. Deciphering die chemical speciation of this aqueous environment is the key to recognizing therein the biosignatures of any extinct or present life forms. Identifying the soluble (ionic and nonionic) components by reacting a currently dormant environment can provide a "picture" of the thermodynamics and chemical components of a possibly bioactive environment. The only devices which can provide such information are electrochemical sensors based on the potentiometric ion selective electrodes (ISEs) and on dynamic techniques such as cyclic voltammetry (CV) and stripping voltammetry (SV). Such an array of devices can provide not only the chemical composition of a water-soluble Martian soil sample, but also several other vital chemical parameters such as pH, conductivity, redox potential, and dissolved gases. To address these issues we have been investigating the possible use of an electrochemically-based ion sensor array as a new integrated approach to quantitative analytical and chemometric electrochemical measurements. The sensor array will consist of specific and semispecific ion selective and amperometric transducers, which can simultaneously and continuously identify and semiquantitatively determine over 50 organic and inorganic analytes in water-based environments. Several individual sensors, based on the same principle, have been flight-tested and have been installed as part of the MECA instrumentation on the Mars 2001 Lander for in-situ analyses. However, the microfabrication, integration and multiplexing of such a large number of these sensors on a single substrate have not been previously attempted.

Kounaves, S. P.↗

Scanning tunneling microscopy studies of diamond films and optoelectronic materials

In this report, we report on progress achieved from 12/1/92 to 10/1/93 under the grant entitled 'Scanning Tunneling Microscopy Studies of Diamond Films and Optoelectronic Materials'. We have set-up a chemical vapor deposition (CVD) diamond film growth system and a Raman spectroscopy system to study the nucleation and growth of diamond films with atomic resolution using scanning tunneling microscopy (STM). A unique feature of the diamond film growth system is that diamond films can be transferred directly to the ultrahigh vacuum (UHV) chamber of a scanning tunneling microscope without contaminating the films by exposure to air. The University of North Texas (UNT) provided $20,000 this year as matching funds for the NASA grant to purchase the diamond growth system. In addition, UNT provided a Coherent Innova 90S Argon ion laser, a Spex 1404 double spectrometer, and a Newport optical table costing $90,000 to set-up the Raman spectroscopy system. The CVD diamond growth system and Raman spectroscopy system will be used to grow and characterize diamond films with atomic resolution using STM as described in our proposal. One full-time graduate student and one full-time undergraduate student are supported under this grant. In addition, several graduate and undergraduate students were supported during the summer to assist in setting-up the diamond growth and Raman spectroscopy systems. We have obtained research results concerning STM of the structural and electronic properties of CVD grown diamond films, and STM and scanning tunneling spectroscopy of carbon nanotubes. In collaboration with the transmission electron microscopy (TEM) group at UNT, we have also obtained results concerning the optoelectronic material siloxene. These results were published in refereed scientific journals, submitted for publication, and presented as invited and contributed talks at scientific conferences.

Perez, Jose M.↗

STXM-C-XANES, IR Microspectroscopy, and Raman Microspectroscopy Analysis of Organic Matter in the Chwichiya 002 C3.00-Ungrouped Chondrite

Chwichiya 002 is a C3.00-ungrouped carbonaceous chondrite discovered in Western Sahara in 2018. The presence of hydrated phases in Chwichiya 002 was not confirmed by XRD analysis, and only a faint water and Si-O band attributed to phyllosilicate were observed by infrared transmission spectroscopy, indicating a very low degree of aqueous alteration (Meteoritical Bulletin, 2020). The structural order of polycyclic aromatic hydrocarbons evaluated by Raman spectroscopy indicates that the effect of thermal metamorphism is less severe than in the Semarkona meteorite, an LL3.00 ordinary chondrite (Meteoritical Bulletin, 2020). Chiwichiya 002 is a very primitive carbonaceous chondrite and an important information source for the early stage of the evolution of organic matter in the solar system. In this study, we investigated the molecular structure and distribution of organic matter in Chiwichiya 002 by Carbon X-ray Absorption Near Edge Structure (C-XANES) analysis using a Scanning Transmission X-ray Microscope (STXM). The STXM-C-XANES analysis has a spatial resolution of 20~100 nm and can observe the spatial distribution of organic materials in microstructures. In addition, to investigate the degree of thermal metamorphism of the organic matter, micro-IR, and micro-Raman spectroscopic analyses were performed. In addition, the Murchison CM2 chondrite was also analyzed for comparison. To evaluate contamination during analytical procedures, antigorite, which was heated in air at 500°C for 5 hours to eliminate organic matter was also analyzed in the same manner. The samples were milled into 100 nm-thick, thin sections using a Focused Ion Beam (FIB), and C-XANES spectra were obtained using the STXM at the High Energy Accelerator Research Organization, Photon Factory (PF), BL-19B. The obtained C-XANES spectra were smoothed and then fitted with Gaussian functions using the method of Le Guillou et al. (2018). The C-XANES showed that the ratio of oxygenated functional group (ketone, phenolic) carbons in Chwichiya 002 was lower than in Murchison, whereas the ratio of aliphatic carbons was almost the same. This may reflect the low degree of aqueous alteration of Chwichiya 002. In addition, contamination peaks were detected at 287.3-287.7 eV and 288.3-288.7 eV in the C-XANES spectra of some of the antigorite samples. The source of these peaks is under investigation. Raman spectroscopic analysis showed that the intensity ratio of the D band to the G band of Chwichiya 002 was slightly higher than that of Murchison. IR absorption spectra showed aromatic absorption at 1630 cm -1 , but there was little absorption due to aliphatic C-H around 2900 cm -1 . These results suggest that the organic matter in Chwichiya 002 may be more heated than in Murchison.

Chwichiya 002↗

Design and Calibration of a Raman Spectrometer for use in a Laser Spectroscopy Instrument Intended to Analyze Martian Surface and Atmospheric Characteristics for NASA

This project's goal is the design of a Raman spectroscopy instrument to be utilized by NASA in an integrated spectroscopy strategy that will include Laser-Induced Breakdown Spectroscopy (LIBS) and Laser-Induced Florescence Spectroscopy (LIFS) for molecule and element identification on Mars Europa, and various asteroids. The instrument is to be down scaled from a dedicated rover mounted instrument into a compact unit with the same capabilities and accuracy as the larger instrument. The focus for this design is a spectrometer that utilizes Raman spectroscopy. The spectrometer has a calculated range of 218 nm wavelength spectrum with a resolution of 1.23 nm. To filter out the laser source wavelength of 532 nm the spectrometer design utilizes a 532 nm wavelength dichroic mirror and a 532 nm wavelength notch filter. The remaining scatter signal is concentrated by a 20 x microscopic objective through a 25-micron vertical slit into a 5mm diameter, 1cm focal length double concave focusing lens. The light is then diffracted by a 1600 Lines per Millimeter (L/mm) dual holographic transmission grating. This spectrum signal is captured by a 1-inch diameter double convex 3 cm focal length capture lens. An Intensified Charge Couple Device (ICCD) is placed within the initial focal cone of the capture lens and the Raman signal captured is to be analyzed through spectroscopy imaging software. This combination allows for accurate Raman spectroscopy to be achieved. The components for the spectrometer have been bench tested in a series of prototype developments based on theoretical calculations, alignment, and scaling strategies. The mounting platform is 2.5 cm wide by 8.8 cm long by 7 cm height. This platform has been tested and calibrated with various sources such as a neon light source and ruby crystal. This platform is intended to be enclosed in a ruggedized enclosure for mounting on a rover platform. The size and functionality of the Raman spectrometer allows for the rover to carry other mission critical devices. This project will be continued at NASA until the requirements are met for the expected initial 2020 launch date.

Lucas, John F.↗

Some optical and electron microscope comparative studies of excimer laser-assisted and nonassisted molecular-beam epitaxically grown thin GaAs films on Si

The quality of GaAs thin films grown via MBE under pulsed excimer laser irradiation on Si substrates is examined in both laser-irradiated and nonirradiated areas using Raman scattering, Rayleigh scattering, and by photoluminescence (PL), as a function of temperature, and by TEM. The temperature dependence of the PL and Raman peak positions indicates the presence of compressive stress in the thin GaAs films in both laser-irradiated and nonirradiated areas. This indicates incomplete homogeneous strain relaxation by dislocations at the growth temperature. The residual compressive strain at the growth temperature is large enough such that even with the introduction of tensile strain arising from the difference in thermal expansion coefficients of GaAs and Si, a compressive strain is still present at room temperature for these thin GaAs/Si films.

Lao, Pudong↗

The Athena Mars Rover Science Payload

The Mars Surveyor missions that will be launched in April of 2001 will include a highly capable rover that is a successor to the Mars Pathfinder mission's Sojourner rover. The design goals for this rover are a total traverse distance of at least 10 km and a total lifetime of at least one Earth year. The rover's job will be to explore a site in Mars' ancient terrain, searching for materials likely to preserve a record of ancient martian water, climate, and possibly biology. The rover will collect rock and soil samples, and will store them for return to Earth by a subsequent Mars Surveyor mission in 2005. The Athena Mars rover science payload is the suite of scientific instruments and sample collection tools that will be used to perform this job. The specific science objectives that NASA has identified for the '01 rover payload are to: (1) Provide color stereo imaging of martian surface environments, and remotely-sensed point discrimination of mineralogical composition. (2) Determine the elemental and mineralogical composition of martian surface materials. (3) Determine the fine-scale textural properties of these materials. (4) Collect and store samples. The Athena payload has been designed to meet these objectives. The focus of the design is on field operations: making sure the rover can locate, characterize, and collect scientifically important samples in a dusty, dirty, real-world environment. The topography, morphology, and mineralogy of the scene around the rover will be revealed by Pancam/Mini-TES, an integrated imager and IR spectrometer. Pancam views the surface around the rover in stereo and color. It uses two high-resolution cameras that are identical in most respects to the rover's navigation cameras. The detectors are low-power, low-mass active pixel sensors with on-chip 12-bit analog-to-digital conversion. Filters provide 8-12 color spectral bandpasses over the spectral region from 0.4 to 1.1 micron Narrow-angle optics provide an angular resolution of 0.28 mrad/pixel, nearly a factor of four higher than that of the Mars Pathfinder and Mars Surveyor '98 cameras. Image compression will be performed using a wavelet compression algorithm. The Mini-Thermal Emission Spectrometer (Mini-TES) is a point spectrometer operating in -the thermal IR. It produces high spectral resolution (5 /cm) image cubes with a wavelength range of 5-40 gm, a nominal signal/noise ratio of 500:1, and a maximum angular resolution of 7 mrad (7 cm at a distance of 10 in). The wavelength region over which it operates samples the diagnostic fundamental absorption features of rockforming minerals, and also provides some capability to see through dust coatings that could tend to obscure spectral features. The mineralogical information that Mini-TES provides will be used to select from a distance the rocks and soils that will be investigated in more detail and ultimately sampled. Mini-TES is derived from the MO/MGS TES instrument, but is significantly smaller and simpler. The instrument uses an 8-cm Cassegrain telescope, a Michelson interferometer, and uncooled pyroelectric detectors. Along with its mineralogical capabilities, Mini-TES can provide information on the thermophysical properties of rocks and soils. Viewing upward, it can also provide temperature profiles through the martian atmospheric boundary layer. Elemental and Mineralogical Composition: Once promising samples have been identified from a distance using Pancam/Mini-TES, they will be studied in detail using up to three compositional sensors that can be placed directly against them by an Instrument Arm. The two compositional sensors, presently on the payload are an Alpha-Proton-X-Ray Spectrometer (APXS), and a Mossbauer Spectrometer. The APXS is derived closely from the instrument that flew on Mars Pathfinder. Radioactive alpha sources and three detection modes (alpha, proton, and x-ray) provide elemental abundances of rocks and soils to complement and constrain mineralogical data. The Athena APXS will have a revised mechanical design that will cut down significantly on backscattering of alpha particles from martian atmospheric carbon. It will also include a target of known elemental composition that will be used for calibration purposes. The Athena Mossbauer Spectrometer is a diagnostic instrument for the mineralogy and oxidation state of Fe-bearing phases, which are particularly important on Mars. The instrument measures the resonant absorption of gamma rays produced by a Co-57 source to determine splitting of nuclear energy levels in Fe atoms that is related to the electronic environment surrounding them. It has been under development for space flight for many years at the Technical University of Darmstadt. The Mossbauer Spectrometer (and the other arm instruments) will be able to view a small permanent magnet array that will attract magnetic particles in the martian soil. The payload may also include a Raman Spectrometer. If included, the Raman Spectrometer will provide precise identification of major and minor mineral phases. It requires no sample preparation, and is also sensitive to organics. Fine-Scale Texture: The Instrument Arm a also carries a Microscopic Imager that will obtain high-resolution monochromatic images of the same materials for which compositional data will be obtained. Its spatial resolution is 20 micron/pixel over a 1 cm depth of field, and 40 micron/pixel over a 1-cm depth of field. Like Pancam, it uses the same active pixel sensor detectors and electronics as the rover's navigation cameras. The Instrument Arm is a three degree-of-freedom arm that uses designs and components from the Mars Pathfinder and Mars Surveyor '98 projects. Its primary function is instrument positioning. Along with the instruments noted above, it also carries a brush that can be used to remove dust and other loose coatings from rocks. Sample Collection and Storage: Martian rock and soil samples will be collected using a low-power rotary coring drill called the Mini-Corer. An important characteristic of this device is that it can obtain intact samples of rock from up to 5 cm within strong boulders and bedrock, Nominal core dimensions are 8xl7 mm. The Mini-Corer drills a core to the commanded depth in a rock, shears it off, retains it, and extracts it. It can also acquire samples of loose soil, using soil sample cups that are pressed downward into loose material. The Mini-Corer can drill at angles from vertical to 45' off vertical. It has six interchangeable bits for long life. Mechanical damage to the sample during drilling is minimal, and heating is negligible. After acquisition, the sample may be viewed by the arm instruments, and/or placed in one of 104 compartments in the Sample Container. A subset of the acquired samples may be replaced with other samples obtained later if desired. The Sample Container has no moving parts, and is mounted external to the rover for easy removal by the Mars Surveyor 2005 flight system. Operation of the rover will make extensive use of automated onboard navigation and hazard avoidance capabilities. Otherwise, use of onboard autonomy is minimal. Data downlink capability is about 40 Mbit/sol, and the use of the Mars Surveyor '01 orbiter for data relay imposes a limit of at most two command cycles per sol. Because of the significant amount of time available between command cycles, all payload elements will be operated sequentially, rather than in parallel.; this approach also significantly simplifies operations and minimizes peak power usage. The landing site for the '01 rover has not been selected yet. Site selection will make as full use as possible of Mars Global Surveyor data, and will involve substantial input from the broad Mars science community. Summary: The following table describes the mass, power, providers, and key scientific objectives of all the major elements of the Athena payload. Additional Athena payload information may be found at: http://astrosun.tn.cornell.edu/athena/index.html. Additional information contained in the original.

Squyes, S. W.↗

Near-Field Spectroscopy with Nanoparticles Deposited by AFM

An alternative approach to apertureless near-field optical spectroscopy involving an atomic-force microscope (AFM) entails less complexity of equipment than does a prior approach. The alternative approach has been demonstrated to be applicable to apertureless near-field optical spectroscopy of the type using an AFM and surface enhanced Raman scattering (SERS), and is expected to be equally applicable in cases in which infrared or fluorescence spectroscopy is used. Apertureless near-field optical spectroscopy is a means of performing spatially resolved analyses of chemical compositions of surface regions of nanostructured materials. In apertureless near-field spectroscopy, it is common practice to utilize nanostructured probe tips or nanoparticles (usually of gold) having shapes and dimensions chosen to exploit plasmon resonances so as to increase spectroscopic-signal strengths. To implement the particular prior approach to which the present approach is an alternative, it is necessary to integrate a Raman spectrometer with an AFM and to utilize a special SERS-active probe tip. The resulting instrumentation system is complex, and the tasks of designing and constructing the system and using the system to acquire spectro-chemical information from nanometer-scale regions on a surface are correspondingly demanding.

Anderson, Mark S.↗

Infrared Spectroscopy as a Chemical Fingerprinting Tool

Infrared (IR) spectroscopy is a powerful analytical tool in the chemical fingerprinting of materials. Any sample material that will interact with infrared light produces a spectrum and, although normally associated with organic materials, inorganic compounds may also be infrared active. The technique is rapid, reproducible and usually non-invasive to the sample. That it is non-invasive allows for additional characterization of the original material using other analytical techniques including thermal analysis and RAMAN spectroscopic techniques. With the appropriate accessories, the technique can be used to examine samples in liquid, solid or gas phase. Both aqueous and non-aqueous free-flowing solutions can be analyzed, as can viscous liquids such as heavy oils and greases. Solid samples of varying sizes and shapes may also be examined and with the addition of microscopic IR (microspectroscopy) capabilities, minute materials such as single fibers and threads may be analyzed. With the addition of appropriate software, microspectroscopy can be used for automated discrete point or compositional surface area mapping, with the latter providing a means to record changes in the chemical composition of a material surface over a defined area. Due to the ability to characterize gaseous samples, IR spectroscopy can also be coupled with thermal processes such as thermogravimetric (TG) analyses to provide both thermal and chemical data in a single run. In this configuration, solids (or liquids) heated in a TG analyzer undergo decomposition, with the evolving gases directed into the IR spectrometer. Thus, information is provided on the thermal properties of a material and the order in which its chemical constituents are broken down during incremental heating. Specific examples of these varied applications will be cited, with data interpretation and method limitations further discussed.

Huff, Timothy L.↗

Atomic Force Microscope for Imaging and Spectroscopy

We have developed, built, and tested an atomic force microscope (AFM) for extraterrestrial applications incorporating a micromachined tip array to allow for probe replacement. It is part of a microscopy station originally intended for NASA's 2001 Mars lander to identify the size, distribution, and shape of Martian dust and soil particles. As well as imaging topographically down to nanometer resolution, this instrument can be used to reveal chemical information and perform infrared and Raman spectroscopy at unprecedented resolution.

Pike, W. T.↗

New Potential Sources for Black Onaping Carbon

One intriguing and important issue of the Sudbury Structure concerns the source of the relatively large amount of C in the Onaping Formation Black member. This dilemma was recently addressed, and the conclusion was reached that an impactor could not have delivered all of the requisite C. Becker et al. have suggested that much of the C came from the impactor and reported the presence of interstellar He "caged" inside some fullerenes that may have survived the impact. So, conceivably, the C inventory in the Sudbury Structure comes from both target and impactor materials, although the known target rocks have little C. We discuss here the possibility of two terrestrial sources for at least some of the C: (1) impact evaporation/dissociation of C from carbonate target rocks and (2) the presence of heretofore-unrecognized C-rich (up to 26 wt%) siliceous "shale," fragments, which are found in the upper, reworked Black member. Experimental: Hypervelocity impact of a 0.635-diameter Al projectile into dolomite at 5.03 km/s (performed at the Ames Research Center vertical gun range) produced a thin, black layer (= 0.05 mm thick) that partially lined the crater and coated impactor remnants. Scanning electronic microscope (SEM) imagery shows this layer to be spongelike on a submicron scale and Auger spectroscopic analyses yield: 33% C, 22% Mg, 19% 0, and 9% Al (from the projectile). Elemental mapping shows that all of the available 0 is combined with Ca and Mg, Al is not oxidized, and C is in elemental form. Dissociation efficiency of C from CO2 is estimated to be <10% of crater volume. Raman spectroscopy indicates that the C is highly disorganized graphite. Another impact experiment [4] also produced highly disordered graphite from a limestone target (reducing collector), in addition to small amounts of diamond/lonsdaleite/chaoite (oxidizing collector). These experiments confirm the reduction of C from carbonates in impact vapor plumes. Observational: SEM observations and microprobe analyses of small, black shalelike inclusions in the upper Black Onaping indicate high C contents (7-26 wt% avg. = 16%). They contain mostly quartz and carbonaceous matter with small amounts of altered K-feldspar, clays, Fe oxide, and a sulfide. No evidence of shock is seen in quartz, and overall characteristics indicate a natural, lightly metamorphosed carbonaceous shale or mudstone that probably existed as a preimpact rock in the target region and distal fragments washed in during early crater filling. Fragments range in size from tens of microns to cm and increase in abundance in the upper Black toward the Onwatin contact, although their distribution is highly irregular. This increase corresponds to an increase in "organic" C with increasingly negative delta-13 C values and S, together with a decrease in fullerene abundance. In addition, we have found soot in acid-demineralized residues of the Onwatin but not in the Onaping samples. These data could be consistent with impact plume and atmospheric chemical processes, with possible diageneric ovedays. We are analyzing carbonaceous fractions of the Onaping and Onwatin to determine diagnostic C isotopic signatures Analyses by Whitehead et al. on bulk samples revealed no definitive source or processes, although delta-13 C values for "organic" C overlapped those for some meteorites. Discussion: If impact evaporation of Sudbury target carbonates did occur, then where are the carbonates? Distal carbonate (limestone/dolostone) exposures of the Espanola Formation (Huronian Supergroup) are generally thin-bedded, although remnants that partially encompass the Sudbury Crater are variable in thickness and may locally reach 250 m . If a carbonate thickness of 100-200 in existed at the target site, then copious amounts of C could have been reduced by impact processing of carbonates and also C-shale, depending on the efficiency of the processing and the amount of postimpact oxidation. Conclusion: The Sudbury crater offers a unique opportunity to study preserved characteristics of immediate carbonaceous fallback matter and particles of short-term residency in the impact plume as well as dust/aerosols from postimpact atmospheric processing.

Bunch, T. E.↗

Lunar and Planetary Science XXXV: Missions and Instruments: Hopes and Hope Fulfilled

The titles in this section include: 1) Mars Global Surveyor Mars Orbiter Camera in the Extended Mission: The MOC Toolkit; 2) Mars Odyssey THEMIS-VIS Calibration; 3) Early Science Operations and Results from the ESA Mars Express Mission: Focus on Imaging and Spectral Mapping; 4) The Mars Express/NASA Project at JPL; 5) Beagle 2: Mission to Mars - Current Status; 6) The Beagle 2 Microscope; 7) Mars Environmental Chamber for Dynamic Dust Deposition and Statics Analysis; 8) Locating Targets for CRISM Based on Surface Morphology and Interpretation of THEMIS Data; 9) The Phoenix Mission to Mars; 10) First Studies of Possible Landing Sites for the Phoenix Mars Scout Mission Using the BMST; 11) The 2009 Mars Telecommunications Orbiter; 12) The Aurora Exploration Program - The ExoMars Mission; 13) Electron-induced Luminescence and X-Ray Spectrometer (ELXS) System Development; 14) Remote-Raman and Micro-Raman Studies of Solid CO2, CH4, Gas Hydrates and Ice; 15) The Compact Microimaging Spectrometer (CMIS): A New Tool for In-Situ Planetary Science; 16) Preliminary Results of a New Type of Surface Property Measurement Ideal for a Future Mars Rover Mission; 17) Electrodynamic Dust Shield for Solar Panels on Mars; 18) Sensor Web for Spatio-Temporal Monitoring of a Hydrological Environment; 19) Field Testing of an In-Situ Neutron Spectrometer for Planetary Exploration: First Results; 20) A Miniature Solid-State Spectrometer for Space Applications - Field Tests; 21) Application of Laser Induced Breakdown Spectroscopy (LIBS) to Mars Polar Exploration: LIBS Analysis of Water Ice and Water Ice/Soil Mixtures; 22) LIBS Analysis of Geological Samples at Low Pressures: Application to Mars, the Moon, and Asteroids; 23) In-Situ 1-D and 2-D Mapping of Soil Core and Rock Samples Using the LIBS Long Spark; 24) Rocks Analysis at Stand Off Distance by LIBS in Martian Conditions; 25) Evaluation of a Compact Spectrograph/Detection System for a LIBS Instrument for In-Situ and Stand-Off Detection; 26) Analysis of Organic Compounds in Mars Analog Samples; 27) Report of the Organic Contamination Science Steering Group; 28) The Water-Wheel IR (WIR) - A Contact Survey Experiment for Water and Carbonates on Mars; 29) Mid-IR Fiber Optic Probe for In Situ Water Detection and Characterization; 30) Effects of Subsurface Sampling & Processing on Martian Simulant Containing Varying Quantities of Water; 31) The Subsurface Ice Probe (SIPR): A Low-Power Thermal Probe for the Martian Polar Layered Deposits; 32) Deploying Ground Penetrating Radar in Planetary Analog Sites to Evaluate Potential Instrument Capabilities on Future Mars Missions; 33) Evaluation of Rock Powdering Methods to Obtain Fine-grained Samples for CHEMIN, a Combined XRD/XRF Instrument; 34) Novel Sample-handling Approach for XRD Analysis with Minimal Sample Preparation; 35) A New Celestial Navigation Method for Mars Landers; 36) Mars Mineral Spectroscopy Web Site: A Resource for Remote Planetary Spectroscopy.

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