MEMS fabrication of a microelectrode for local electrode atom probe microanalysis
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Engineering topics
Publications and source records attributed to Kuhlman, K. R..
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To demonstrate the potential scientific and technical merits of in situ microscopy on Mars, we analyzed a possible Martian regolith analog - an acolian red dune sand from the central Australian desert (near Mt. Olga). This sand was chosen for its ubiquitous red coating and the desert environment in which is it found. Grains of this sand were analyzed using a variety of microanalytical techniques. A database of detailed studies of such terrestrial analogs would assist the study of geological and astrobiological specimens in future missions to Mars. Potential instrument concepts for in situ deployment on Mars include local electrode atom probe nanoanalysis (LEAP), vertical scanning white light interferometry (VSWLI), scanning electron microscopies, energy dispersive x-ray microanalysis (EDX), atomic force microscopy (AFM) and X-ray diffraction (XRD). While in situ deployment of these techniques is many years away, ground-based studies using these analytical techniques extend our understanding of the data obtained from instruments to be flown in the near future.
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Both, the search for evidence of life on Mars and the assessment of the Martian environment in respect to its compatibility with human explorers, will require the ability to measure and understand the aqueous chemistry of the Martian regolith. Direct in-situ chemical analysis is the only method by which chemical biosignatures can be reliably recognized and the toxicity of the regolith accurately assessed. Qualitative and quantitative determination of the aqueous ionic constituents and their concentrations is critical in developing kinetic and thermodynamic models that can be used to accurately predict the potential of the past or present Martian geochemical environment to have either generated or still sustain life. In-situ chemical characterization could provide evidence as to whether the chemical composition of the regolith or evaporates in suspected ancient water bodies have been biologically influenced.
The Mars Environmental Compatibility Assessment (MECA) experiment, an instrument suite to be flown on Mars Surveyor 2001, will include a tool for doing simple mineralogical scratch and streak tests on particles from the Martian regolith. The Abrasion Tool will be applied to particles that adhere to highly polished substrates of various hardnesses. Granular soil components will be subjected to a compressive force of about 3 N using a leaf spring. The spring will be applied with a paraffin actuator capable of a 0.76 mm throw to achieve a maximum displacement of about 7.5 mm at the tip of the tool. The pressure per grain will be dependent on the grain size, the number of grains that adhere to the substrate and the number of grains in compression. The pressure per particle is expected to be on the order of 100 MPa - 1 GPa. The MECA sample wheel containing the substrates will be rotated after the particles are placed in compression to produce scratches or pits. A primary goal of the Abrasion Tool is to identify quartz (Mohs' hardness = 7) using substrates of varying hardnesses. Quartz is considered hazardous to future human explorers of Mars because it can cause silicosis of the lungs if it is of respirable size. It is also hazardous to machinery, structures, and space suits because of its ability to abrade and scratch surfaces. Since large quantities of minerals harder than quartz are not expected, any scratches produced on polished quartz substrates might be reasonably attributed to quartz particles, although there may be minerals such as impact metamorphic diamond in the soils. Careful calibration of the tool will be necessary to ensure that grains are not overloaded; for example, a steel ball pressed into glass will produce a Hertzian fracture, even though it is softer than glass. Other minerals, such as magnetite (Mohs'hardness = 6.5) have been shown to scratch glass ceramics such as Zerodur (Mohs' hardness = 6.5). Thus, minerals can be differentiated: note that regardless of the mineral species, if any particle is harder than 6.5 it will certainly be an interesting discovery for both planetary geology and human exploration concerns. The scratches will be identified using the 6X optical microscope and profiled with the atomic force microscope included in the MECA instrument suite. Analysis of the scratch morphology will yield evidence concerning the shape of the particle responsible for producing each scratch. For example, angular grains should leave vertical cracks with microconchoidal lateral chipping, while rounded grains might leave chattermarks, or nested partial Hertzian cracks. Particle shape can thus be inferred from these indentation modes, as well as material hardness. In addition, particle size information may also be available if pits caused by rolling particles can be identified. Converse to scratching, the minerals may be crushed at their contact points, and be smeared onto the target substrates to leave what geologists refer to as "streaks". These are coldwelded trails of mineral material that have structure and color indicative of mineral composition. The AFM will determine the morphology of these streaks, while the microscope will ascertain the color. On the harder substrates, we might expect streaking to dominate; on the softer substrates, scratching may dominate. Progressions of material interactions across the substrate selection will be a valuable source of data for mineral discrimination. It should also be noted that many minerals have coatings (such as iron oxides), and these will have to be differentiated from the host mineral grains; laboratory tests will establish the effects of such coatings on the scratch results. Finally, we note that the microscope will provide corroborative data regarding likely mineral species by grain shapes, fracture patterns, surface textures, colr, and UV fluorescence reactions.
The Mars Environmental Compatibility Assessment (MECA) experiment, an instrument suite to be flown on Mars Surveyor 2001, will include a tool for doing simple mineralogical scratch and streak tests on particles from the Martian regolith. The Abrasion Tool will be applied to particles that adhere themselves to highly polished substrates of various hardnesses. Granular soil components will be subjected to a compressive force of about 3 N using a leaf spring. The spring will be applied with a paraffin actuator capable of a 0.76 mm throw to achieve a maximum displacement of about 7.5 mm at the tip of the tool. The pressure per grain will be dependent on the grain size, the number of grains that adhere to the substrate and the number of grains in compression. The pressure per particle is expected to be on the order of 100 MPa - 1 GPa. The MECA sample wheel containing the substrates will be rotated after the particles are placed in compression to produce scratches or pits. A primary goal of the Abrasion Tool is to identify quartz (Mohs' hardness = 7) using substrates of varying hardnesses. Quartz is considered hazardous to future human explorers of Mars because it can cause silicosis of the lungs if it is of respirable size. It is also hazardous to machinery, structures, and space suits because of its ability to abrade and scratch surfaces. Since large quantities of minerals harder than quartz are not expected, any scratches produced on polished quartz substrates might be reasonably attributed to quartz particles, although there may be minerals such as impact metamorphic diamond in the soils. Careful calibration of the tool will be necessary to ensure that grains are not overloaded; for example, a steel ball pressed into glass will produce a Hertzian fracture, even though it is softer than glass. Other minerals, such as magnetite (Mohs' hardness = 6.5) have been shown to scratch glass ceramics such as Zerodur (Mohs' hardness = 6.5). Thus, minerals can be differentiated: note that regardless of the mineral species, if any particle is harder than 6.5 it will certainly be an interesting discovery for both planetary geology and human exploration concerns. The scratches will be identified using the 6X optical microscope and profiled with the atomic force microscope included in the MECA instrument suite. Analysis of the scratch morphology will yield evidence concerning the shape of the particle responsible for producing each scratch. For example, angular grains should leave vertical cracks with microconchoidal lateral chipping, while rounded grains might leave chatter marks, or nested partial Hertzian cracks. Particle shape can thus be inferred from these indentation modes, as well as material hardness. In addition, particle size information may also be available if pits caused by rolling particles can be identified. Converse to scratching, the minerals may be crushed at their contact points, and be smeared onto the target substrates to leave what geologists refer to as "streaks". These are cold-welded trails of mineral material that have structure and color indicative of mineral composition. The AFM will determine the morphology of these streaks, while the microscope will ascertain the color. On the harder substrates, we might expect streaking to dominate; on the softer substrates, scratching may dominate. Progressions of material interactions across the substrate selection will be a valuable source of data for mineral discrimination. It should also be noted that many minerals have coatings (such as iron oxides), and these will have to be differentiated from the host mineral grains; laboratory tests will establish the effects of such coatings on the scratch results. Finally, we note that the microscope will provide corroborative data regarding likely mineral species by grain shapes, fracture patterns, surface textures, color, and UV fluorescence reactions. Additional information is contained in the original extended abstract.
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.