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NASA NTRS2016

Comet Dust: The Diversity of "Primitive" Particles and Implications

Comet dust is primitive and shows significant diversity. Our knowledge of the properties of primitive particles has expanded significantly through microscale investigations of cosmic dust samples ( IDP's(Interplanetary Dust Particles) and AMM's (Antarctic Micrometeorites)) and of comet dust samples (Stardust and Rosetta's COSIMA), as well as through remote sensing (spectroscopy and imaging) via Spitzer and via spacecraft encounters with 103P/Hartley 2 and 67P/Churyumov-Gerasimenko. Microscale investigations show that comet dust and cosmic dust are particles of unequilibrated materials, including aggregates of materials unequilibrated at submicron scales. We call unequilibrated materials "primitive" and we deduce they were incorporated into ice-rich (H2O-, CO2-, and CO-ice) parent bodies that remained cold, i.e., into comets, because of the lack of aqueous or thermal alteration since particle aggregation; yet some Stardust olivines suggest mild thermal metamorphism. Primitive particles exhibit a diverse range of: structure and typology; size and size distribution of constituents; concentration and form of carbonaceous and organic matter; D-, N-, and O- isotopic enhancements over solar; Mg-, Fe-contents of the silicate minerals; the compositions and concentrations of sulfides, and of less abundant mineral species such as chondrules, CAIs and carbonates. The uniformity within a group of samples points to: aerodynamic sorting of particles and/or particle constituents; the inclusion of a limited range of oxygen fugacities; the inclusion or exclusion of chondrules; a selection of organics. The properties of primitive particles imply there were disk processes that resulted in different comets having particular selections of primitive materials. The diversity of primitive particles has implications for the diversity of materials in the protoplanetary disk present at the time and in the region where the comets formed.

Wooden, Diane H.↗
NASA NTRS1996

Design of intelligent mesoscale periodic array structures utilizing smart hydrogel

Mesoscale Periodic Array Structures (MPAS, also known as crystalline colloidal arrays), composed of aqueous or nonaqueous dispersions of self-assembled submicron colloidal spheres are emerging toward the development of advanced optical devices for technological applications. This is because of their unique optical diffraction properties and the ease with which these intriguing properties can be modulated experimentally. Moreover our recent advancements in this area which include 'locking' the liquid MPAS into solid or semisolid polymer matrices for greater stability with longer life span, and incorporation of CdS quantum dots and laser dyes into colloidal spheres to obtain nonlinear optical (NLO) responses further corroborate the use of MPAS in optical technology. Our long term goal is fabrication of all-optical and electro-optical devices such as spatial light modulators for optical signal processing and flat panel display devices by utilizing intelligent nonlinear periodic array structural materials. Here we show further progress in the design of novel linear MPAS which have the ability to sense and respond to an external source such as temperature. This is achieved by combining the self-assembly properties of polymer colloidal spheres and thermoshrinking properties of smart polymer gels. At selected temperatures the periodic array efficiently Bragg diffracts light and transmits most of the light at other temperatures. Hence these intelligent systems are of potential use as fixed notch filters optical switches or limiters to protect delicate optical sensors from high intensity laser radiation.

Sunkara, H. B.↗
NASA NTRS2001

Exploring the Martian Highlands using a Rover-Deployed Ground Penetrating Radar

The Martian highlands record a long and often complex history of geologic activity that has shaped the planet over time. Results of geologic mapping and new data from the Mars Global Surveyor spacecraft reveal layered surfaces created by multiple processes that are often mantled by eolian deposits. Knowledge of the near-surface stratigraphy as it relates to evolution of surface morphology will provide critical context for interpreting rover/lander remote sensing data and for defining the geologic setting of a highland lander. Rover-deployed ground penetrating radar (GPR) can directly measure the range and character of in situ radar properties, thereby helping to constrain near-surface geology and structure. As is the case for most remote sensing instruments, a GPR may not detect water unambiguously on Mars. Nevertheless, any local, near-surface occurrence of liquid water will lead to large, easily detected dielectric contrasts. Moreover, definition of stratigraphy and setting will help in evaluating the history of aqueous activity and where any water might occur and be accessible. GPR data can also be used to infer the degree of any post-depositional pedogenic alteration or weathering, thereby enabling assessment of pristine versus secondary morphology. Most importantly perhaps, GPR can provide critical context for other rover and orbital instruments/data sets. Hence, rover-deployment of a GPR deployment should enable 3-D mapping of local stratigraphy and could guide subsurface sampling.

Grant, J. A.↗
NASA NTRS2004

Kinetics of organic transformations under mild aqueous conditions: implications for the origin of life and its metabolism

The rates of thermal transformation of organic molecules containing carbon, hydrogen, and oxygen were systematically examined in order to identify the kinetic constraints that governed origin-of-life organic chemistry under mild aqueous conditions. Arrhenius plots of the kinetic data were used to estimate the reaction of half-lifes at 50 degrees C. This survey showed that hydrocarbons and organic substances containing a single oxygenated group were kinetically the most stable; whereas organic substances containing two oxygenated groups in which one group was an alpha- or beta-positioned carbonyl group were the most reactive. Compounds with an alpha- or beta-positioned carbonyl group (aldehyde or ketone) had rates of reaction that were up to 10(24)-times faster than rates of similar molecules lacking the carbonyl group. This survey of organic reactivity, together with estimates of the molecular containment properties of lipid vesicles and liquid spherules, indicates that an origins process in a small domain that used C,H,O-intermediates had to be catalytic and use the most reactive organic molecules to prevent escape of its reaction intermediates.

Biogenesis↗
NASA NTRS2004

Extraction of Organic Molecules from Terrestrial Material: Quantitative Yields from Heat and Water Extractions

In the robotic search for life on Mars, different proposed missions will analyze the chemical and biological signatures of life using different platforms. The analysis of samples via analytical instrumentation on the surface of Mars has thus far only been attempted by the two Viking missions. Robotic arms scooped relogith material into a pyrolysis oven attached to a GC/MS. No trace of organic material was found on any of the two different samples at either of the two different landing sites. This null result puts an upper limit on the amount of organics that might be present in Martian soil/rocks, although the level of detection for each individual molecular species is still debated. Determining the absolute limit of detection for each analytical instrument is essential so that null results can be understood. This includes investigating the trade off of using pyrolysis versus liquid solvent extraction to release organic materials (in terms of extraction efficiencies and the complexity of the sample extraction process.) Extraction of organics from field samples can be accomplished by a variety of methods such utilizing various solvents including HCl, pure water, supercritical fluid and Soxhelt extraction. Utilizing 6N HCl is one of the most commonly used method and frequently utilized for extraction of organics from meteorites but it is probably infeasible for robotic exploration due to difficulty of storage and transport. Extraction utilizing H2O is promising, but it could be less efficient than 6N HCl. Both supercritical fluid and Soxhelt extraction methods require bulky hardware and require complex steps, inappropriate for inclusion on rover spacecraft. This investigation reports the efficiencies of pyrolysis and solvent extraction methods for amino acids for different terrestrial samples. The samples studied here, initially created in aqueous environments, are sedimentary in nature. These particular samples were chosen because they possibly represent one of the best terrestrial analogs of Mars and they represent one of the absolute best case scenarios for finding organic molecules on the Martian surface.

Beegle, L. W.↗
NASA NTRS2017

A Volume Flux Approach to Cryolava Dome Emplacement on Europa

We previously modeled a subset of domes on Europa with morphologies consistent with emplacement by viscous extrusions of cryolava. These models assumed instantaneous emplacement of a fixed volume of fluid onto the surface, followed by relaxation to form domes. However, this approach only allowed for the investigation of late-stage eruptive processes far from the vent and provided little insight into how cryolavas arrived at the surface. Consideration of dome emplacement as cryolavas erupt at the surface is therefore pertinent. A volume flux approach, in which lava erupts from the vent at a constant rate, was successfully applied to the formation of steep-sided volcanic domes on Venus. These domes are believed to have formed in the same manner as candi-date cryolava domes on Europa. In order to gain a more complete understanding of the potential for the emplacement of Europa domes via extrusive volcanism, we have applied this new volume flux approach to the formation of putative cryovolcanic domes on Europa. Assuming as in that europan cryolavas are briny, aqueous solutions which may or may not contain some ice crystal fraction, we present the results of this modeling and explore theories for the formation of low-albedo moats that surround some domes.

Cryolava Dome Emplacement↗
NASA NTRS2022

Limitations in Representation of Physical Processes Prevents Successful Simulation of PM2.5 During KORUS-AQ

High levels of fine particulate matter (PM2.5) pollution in East Asia often exceed local air quality standards. Observations from the Korea United States-Air Quality (KORUS-AQ) field campaign in May and June 2016 showed that development of extreme pollution (haze) occurred through a combination of long-range transport and favorable meteorological conditions that enhanced local production of PM2.5. Atmospheric models often have difficulty simulating PM2.5 chemical composition during haze, which is of concern for the development of successful control measures. We use observations from KORUS-AQ to examine the ability of the GEOS-Chem chemical transport model to simulate PM2.5 composition throughout the campaign and identify the mechanisms driving the pollution event. At the surface, the model underestimates sulfate by -64% but overestimates nitrate by +36%. The largest underestimate in sulfate occurs during the pollution event, where models typically struggle to generate elevated sulfate concentrations due to missing heterogeneous chemistry in aerosol liquid water in the polluted boundary layer. Hourly surface observations show that the model nitrate bias is driven by an overestimation of the nighttime peak. In the model, nitrate formation is limited by the supply of nitric acid, which is biased by +100% against aircraft observations. We hypothesize that this is due to a large missing sink, which we implement here as a factor of five increase in dry deposition. We show that the resulting increased deposition velocity is consistent with observations of total nitrate as a function of photochemical age. The model does not account for factors such as the urban heat island effect or the heterogeneity of the built-up urban landscape resulting in insufficient model turbulence and surface area over the study area that likely results in insufficient dry deposition. Other species such as NH3 could be similarly affected but were not measured during the campaign. Nighttime production of nitrate is driven by NO2 hydrolysis in the model, while observations show that unexpectedly elevated nighttime ozone (not present in the model) should result in N2O5 hydrolysis as the primary pathway. The model is unable to represent nighttime ozone due to an overly rapid collapse of the afternoon mixed layer and excessive titration by NO. We attribute this to missing nighttime heating driving deeper nocturnal mixing that would be expected to occur in a city like Seoul. This urban heating is not considered in air quality models run at large enough scales to treat both local chemistry and long-range transport. Key model failures in simulating nitrate, mainly overestimated daytime nitric acid, incorrect representation of nighttime chemistry, and an overly shallow and insufficiently turbulent nighttime mixed layer, exacerbate the model’s inability to simulate the buildup of PM2.5 during haze pollution. To address the underestimate in sulfate most evident during the haze event, heterogeneous aerosol uptake of SO2 is added to the model which previously only considered aqueous production of sulfate from SO2 in cloud water. Implementing a simple parameterization of this chemistry improves the model abundance of sulfate but degrades the SO2 simulation implying that emissions are underestimated. We find that improving model simulations of sulfate has direct relevance to determining local vs. transboundary contributions to PM2.5. During the haze pollution event, the inclusion of heterogeneous aerosol uptake of SO2 decreases the fraction of PM2.5 attributable to long-range transport from 66% to 54%. Locally-produced sulfate increased from 1% to 25% of locally-produced PM2.5, implying that local emissions controls would have a larger effect than previously thought. However, this additional uptake of SO2 is coupled to the model nitrate prediction which affects the aerosol liquid water abundance and chemistry driving sulfate-nitrate-ammonium partitioning. An additional simulation of the haze pollution with heterogeneous uptake of SO2 to aerosol and simple improvements to the model nitrate simulation results in 30% less sulfate due to 40% less nitrate and aerosol water, and results in an underestimate of sulfate during the haze event. Future studies need to better consider the impact of model physical processes such as dry deposition and nighttime boundary layer mixing on the simulation of nitrate and the effect of improved nitrate simulations on the overall simulation of secondary inorganic aerosol (sulfate+nitrate+ammonium) in East Asia. Foreign emissions are rapidly changing, increasing the need to understand the impact of local emissions on PM2.5 in South Korea to ensure continued air quality improvements.

Katherine R. Travis↗
NASA NTRS1993

Crustal structure and igneous processes in a chondritic Io

Liquid sulfur can form when metal-free C1 or C2 chondrites are heated. It may be obtained either by direct melting of native sulfur in disequilibrated C1 or C2 chondrites or by incongruent melting of pyrite and other sulfides in thermodynamically equilibrated rocks of the same composition. Hence, Lewis considered C2 chondrites to be the best meteoritic analog for Io's bulk composition. Metal-bearing C3 and ordinary chondrites are too chemically reduced to yield liquid sulfur and are not thought to represent plausible analogs of Io's bulk composition. An important aspect of Lewis' work is that CaSO4 and MgSO4 are predicted to be important in Io. Real C1 and C2 chondrites contain averages of, respectively, 11 percent and 3 percent by mass of salts (plus water of hydration). The most abundant chondritic salts are magnesium and calcium sulfates, but other important components include sulfates of sodium, potassium, and nickel and carbonates of magnesium, calcium, and iron. It is widely accepted that chondritic salts are formed by low-temperature aqueous alteration. Even if Io originally did not contain salts, it is likely that aqueous alteration would have yielded several percent sulfates and carbonates. In any event, Io probably contains sulfates and carbonates. This report presents the results of a model of differentiation of a simplified C2 chondrite-like composition that includes 1.92 percent MgSO4, 0.56 percent CaSO4, 0.53 percent CaCO3, and 0.094 percent elemental sulfur. The temperature of the model is gradually increased; ensuing fractional melting results in these components extruding or intruding at gravitationally stable levels in Io's crust. Relevant phase equilibria were reviewed. A deficiency of high-pressure phase equilibria renders the present model qualitative.

Kargel, J. S.↗
NASA NTRS2008

Enigmatic Isovaline: Investigating the Stability, Racemization, and Formation of a Non-biological Meteoritic Amino Acid

Among the Murchison meteoritic amino acids, isovaline stands out as being both nonbiological (non-protein) and having a relatively high abundance. While approximately equal amounts of D- and L-isovaline have been reported in Murchison and other CM meteorites, the molecule's structure appears to prohibit its racemization in aqueous solutions. We recently have investigated the low-temperature solid-phase chemistry of both isovaline and valine with an eye toward each molecule's formation, stability, and possible interconversions of D and L enantiomers. Ion-irradiated isovaline- and valinecontaining ices were examined by IR spectroscopy and highly-sensitive liquid chromatography/time-of-flight mass spectral methods to assess both amino acid destruction and racemization. Samples were studied in the presence and in the absence of water-ice, and the destruction of both isovaline and valine was measured as a function of radiation dose. In addition, we have undertaken experiments to synthesize isovaline, valine, and their amino acid isomers by solid-phase radiation-chemical pathways other than the oft-invoked Strecker process. This presentation will review and summarize some of our recent findings. -- Our work has been supported by a grant to the Goddard Center for Astrobiology through the NASA Astrobiology Institute. Experiments were performed in the Cosmic Ice Laboratory (RLH, MHM, AL) and the Astrobiology Analytical Laboratory (JPD, DPG) at the NASA Goddard Space Flight Center.

Hudson, Reggie↗
NASA NTRSDate not supplied

TEM and XRD Investigation of Impact Glass Alteration Products: Amorphous Materials, Phyllosilicates and Everything in Between

Impact cratering is one of the most ubiquitous geologic processes shaping the surface of all solid bodies in our solar system. Impacts are also a major source of clay minerals and poorly crystalline, clay-like materials on Earth and Mars[1,2].These phyllosilicates and related clay-like phases comprise an incredibly complex group of materials, and their characterization, even in controlled laboratory settings, remains a challenging endeavor. The nature and origin of clay minerals and amorphous materials on Mars, which form a major component (~20-70 wt %) of rock and soil samples in Gale Crater as determined by the CheMin instrument on Curiosity, have remained ambiguous[3]. These amorphous phases likely fall on a spectrum between pristine volcanic and/or impact-produced primary materials and clay minerals and related phases formed from aqueous alteration. Amorphous materials are common weathering products in terrestrial sediments, soils, and paleosols [e.g., 4,5].Primary impact materials (glass, melt rocks)are comparable in some ways to those generated volcanically [6], and so it may be possible that an amorphous component is preserved within altered impactites. There are hundreds of thousands of impact craters on Mars, and Curiosity and Perseverance are currently exploring ancient impact craters. We hypothesize that the sediments and lithologies in Gale and Jezero Craters and elsewhere contain altered impact products; it is therefore important to better understand the composition and structure of these materials. Here we present the first results from a study characterizing materials produced from impact glass alteration–clay minerals, poorly crystalline/amorphous materials–in terrestrial craters using Transmission Electron Microscopy (TEM), powder X-ray diffraction (pXRD)and chemical (EDS) analysis.

Impact crater↗
NASA NTRS2001

Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid surfaces. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants; (i.e., amphiphiles with a hydrophobic moiety consisting of an extended chain of (aliphatic) methylene -CH2- groups attached to a large polar group to give aqueous solubility) are capable of reducing the contact angles on surfaces which are not very hydrophobic, but do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm, polyethylene or self assembled monolayers. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3) and an extended ethoxylate (-(OCH2CH2)a-) polar group in the form of a chain with four or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (termed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread. We propose that the trisiloxane surfactants superspread because their structure allows them to strongly lower the high hydrophobic solid/aqueous tension when they adsorb to the solid surface. When the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross-sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space-filling mat on the surface which removes a significant amount of the surface water. In this presentation, we report the results of measurements of the molecular packing and rates of kinetic exchange of the trisiloxane surfactants at the air/water interface in order to confirm our picture of trisiloxane packing, and provide additional insight into the superspreading process. We used the pendant bubble technique as a Langmuir trough to measure the trisiloxane equation of state which relates the tension to the surface concentration. From these measurements we obtain accurate values for the maximum packing density. We find that trisiloxanes with 4 and 8 ethoxylate groups have the same maximum packing concentration, indicating that the maximum packing is controlled by the cross section of the head group. For trisiloxanes with larger than eight ethoxylates, the maximum packing increases with ethoxylate number, indicating that the disposition of the ethoxylate chain (i.e., its effective size) is controlling. This supports our picture of superspreading: The superspreading ability of trisiloxanes decreases considerably for trisiloxanes with larger than eight ethoxylates; the packing measurements indicate that for the higher ethoxylate number trisiloxanes, the compact nonpolar head groups are pushed apart by the ethoxylate chain. They leave spaces of surface water on adsorption and do not lower the solid tension as much as their lower chain analogues. Finally the report measurements of the dynamic tension reduction accompanying the adsorption of trisiloxanes onto an initially clean interface using the pendant bubble technique, and we obtain from these relaxations, the equation of state and a mass transfer model, the rate constants for kinetic exchange. We find that the rate constants for desorption of trisiloxanes are generally much slower than for analogous aliphatic polyethoxylate surfactants with identical ethoxylate chain lengths. When an aqueous drop of a superspreader solution is placed on a hydrophobic surface and begins to spread, the lower desorption rates allows the tension at the drop center to remain reduced relative to the tension of the expanding periphery, thus strengthening Marangoni forces which can assist the spreading. Marangoni forces can be especially significant in the case of superspreaders because their maximum equilibrium reduction in tension is several dynes/cm lower than for aliphatic surfactants.

Kumar, Nitin↗
NASA NTRS1991

Environmental fatigue of an Al-Li-Cu alloy. Part 1: Intrinsic crack propagation kinetics in hydrogenous environments

Deleterious environmental effects on steady-state, intrinsic fatigue crack propagation (FCP) rates (da/dN) in peak aged Al-Li-Cu alloy 2090 are established by electrical potential monitoring of short cracks with programmed constant delta K and K(sub max) loading. The da/dN are equally unaffected by vacuum, purified helium, and oxygen but are accelerated in order of decreasing effectiveness by aqueous 1 percent NaCl with anodic polarization, pure water vapor, moist air, and NaCl with cathodic polarization. While da/dN depends on delta K(sup 4.0) for the inert gases, water vapor and chloride induced multiple power-laws, and a transition growth rate 'plateau'. Environmental effects are strongest at low delta K. Crack tip damage is ascribed to hydrogen embrittlement because of the following: (1) accelerated da/dN due to part-per-million levels of H2O without condensation; (2) impeded molecular flow model predictions of the measured water vapor pressure dependence of da/dN as affected by mean crack opening; (3) the lack of an effect of film-forming O2; (4) the likelihood for crack tip hydrogen production in NaCl, and (5) the environmental and delta K-process zone volume dependencies of the microscopic cracking modes. For NaCl, growth rates decrease with decreasing loading frequency, with the addition of passivating Li2CO3, and upon cathodic polarization. These variables increase crack surface film stability to reduce hydrogen entry efficiency. The hydrogen environmental FCP resistance of 2090 is similar to other 2000 series alloys and is better than 7075.

Piascik, Robert S.↗
NASA NTRS1991

Environmental fatigue of an Al-Li-Cu alloy. I - Intrinsic crack propagation kinetics in hydrogenous environments

Deleterious environmental effects on steady-state, intrinsic fatigue crack propagation (FCP) rates (da/dN) in peak aged Al-Li-Cu alloy 2090 are established by electrical potential monitoring of short cracks with programmed constant delta K and K(sub max) loading. The da/dN are equally unaffected by vacuum, purified helium, and oxygen but are accelerated in order of decreasing effectiveness of aqueous 1 percent NaCl with anodic polarization, pure water vapor, moist air, and NaCl with cathodic polarization. While da/dN depends on delta K(sup 4.0) for the inert gases, water vapor and chloride induced multiple power-laws, and a transition growth rate 'plateau'. Environmental effects are strongest at low delta K. Crack tip damage is ascribed to hydrogen embrittlement because of the following: (1) accelerated da/dN due to part-per-million levels of H2O without condensation; (2) impeded molecular flow model predictions of the measured water vapor pressure dependence of da/dN as affected by mean crack opening; (3) the lack of an effect of film-forming O2; (4) the likelihood for crack tip hydrogen production in NaCl; and (5) the environmental and delta K-process zone volume dependencies of the microscopic cracking modes. For NaCl, growth rates decrease with decreasing loading frequency, with the addition of passivating Li2CO3, and upon cathodic polarization. These variables increase crack surface film stability to reduce hydrogen entry efficiency. The hydrogen environmental FCP resistance of 2090 is similar to other 2000 series alloys and is better than 7075.

Piascik, Robert S.↗
NASA NTRS1979

Cell partition in two phase polymer systems

Aqueous phase-separated polymer solutions can be used as support media for the partition of biological macromolecules, organelles and cells. Cell separations using the technique have proven to be extremely sensitive to cell surface properties but application of the systems are limited to cells or aggregates which do not significantly while the phases are settling. Partition in zero g in principle removes this limitation but an external driving force must be applied to induce the phases to separate since their density difference disappears. We have recently shown that an applied electric field can supply the necessary driving force. We are proposing to utilize the NASA FES to study field-driven phase separation and cell partition on the ground and in zero g to help define the separation/partition process, with the ultimate goal being to develop partition as a zero g cell separation technique.

Brooks, D. E.↗
NASA NTRS2001

Fabrication of poly(ethylene glycol) hydrogel microstructures using photolithography

The fabrication of hydrogel microstructures based upon poly(ethylene glycol) diacrylates, dimethacrylates, and tetraacrylates patterned photolithographically on silicon or glass substrates is described. A silicon/silicon dioxide surface was treated with 3-(trichlorosilyl)propyl methacrylate to form a self-assembled monolayer (SAM) with pendant acrylate groups. The SAM presence on the surface was verified using ellipsometry and time-of-flight secondary ion mass spectrometry. A solution containing an acrylated or methacrylated poly(ethylene glycol) derivative and a photoinitiator (2,2-dimethoxy-2-phenylacetophenone) was spin-coated onto the treated substrate, exposed to 365 nm ultraviolet light through a photomask, and developed with either toluene, water, or supercritical CO2. As a result of this process, three-dimensional, cross-linked PEG hydrogel microstructures were immobilized on the surface. Diameters of cylindrical array members were varied from 600 to 7 micrometers by the use of different photomasks, while height varied from 3 to 12 micrometers, depending on the molecular weight of the PEG macromer. In the case of 7 micrometers diameter elements, as many as 400 elements were reproducibly generated in a 1 mm2 square pattern. The resultant hydrogel patterns were hydrated for as long as 3 weeks without delamination from the substrate. In addition, micropatterning of different molecular weights of PEG was demonstrated. Arrays of hydrogel disks containing an immobilized protein conjugated to a pH sensitive fluorophore were also prepared. The pH sensitivity of the gel-immobilized dye was similar to that in an aqueous buffer, and no leaching of the dye-labeled protein from the hydrogel microstructure was observed over a 1 week period. Changes in fluorescence were also observed for immobilized fluorophore labeled acetylcholine esterase upon the addition of acetyl acholine.

NASA Discipline Life Sciences Technologies↗
NASA NTRS2016

NiTi Alloys for Tribological Applications: The Role of In-Situ Nanotechnology

Beginning in 2004, NASA initiated the investigation and development of, Nitinol 60, a nickel-rich and dimensionally stable version of shape memory alloy Nitinol 55, as an alternative to bearing steel. Early investigations showed it to be hard and impervious to aqueous corrosion but the fundamental reasons for these properties were unknown. Shape memory alloys made from equiatomic Ni-Ti are widely known for their unique dimensional instability behavior that can be triggered by thermal and mechanical stress. The nickel-rich alloys exhibit no such dimension change property and have high hardness but have largely been overlooked by industry and the engineering community. Though steel is the dominant material of choice for mechanical components (bearings and gears) it has intrinsic limitations related to corrosion and plastic deformation. In contrast, Ni-Ti alloys are intrinsically rustproof and can withstand high contact loads without damage (denting). Over the last decade, focused RD to exploit these alloys for new applications has revealed that in-situ nano-scale phases that form during processing are largely responsible for NiTis remarkable properties. In this presentation, the state-of-art of nickel-rich NiTi alloys will be introduced and the nanotechnology behind their intriguing behavior will be addressed. The presentation will include discussion of how NASA is adopting this new technology inside the space station water recycling system as a pathfinder for more down-to-earth tribological challenges.

metals↗
NASA NTRS2016

Similarities Across Mars: Acidic Fluids at Both Meridiani Planum and Gale Crater in the Formation of Magnesium-Nickel Sulfates

In-situ identification of sulfates at the martian surface by the Mars Exploration Rovers and the Mars Science Laboratory have included calcium sulfates with various states of hydration (gypsum, bassanite, anhydrite), iron sulfates of likely fumarolic origin, massive deposits of iron hydroxysulfates indicative of an acidic history, and minor occurrences of magnesium sulfates. Recent measurements by the Opportunity and Curiosity Alpha Particle X-ray Spectrometers (APXS) have indicated the presence of Ni-substituted Mg-sulfates at the Meridiani Planum and Gale Crater landing sites. The Opportunity rover has traversed nearly 43 km and is currently exploring the impact breccias of the rim of Endeavour crater, near a location where signatures of aqueous alteration have been established from orbit. APXS analyses of subsurface materials excavated by a rover wheel show clear evidence for a Mg(Ni)-sulfate with Mg:Ni (is) approximately 100:1 (molar). On the other side of the planet, Curiosity is continuing its climb up Mount Sharp after driving (is) approximately 13 km since landing. Over the last 4 km of the traverse, there have been multiple chemical analyses of erosionally-resistant nodules and dendritic features in a finely laminated mudstone unit which also indicate Mg(Ni)-sulfate (Mg:Ni (is) approximately 30:1, molar). The geologic settings for the Endeavour rim and the Mount Sharp mudstones are clearly different, but similar formation conditions for these sulfates may be possible. Ni(2+) readily substitutes for Mg(2+) in a variety of geochemical processes due to their comparable ionic radii. The availability of soluble Ni at the time of Mg-sulfate precipitation suggests acidic solutions. The fluids responsible for alteration in the Endeavour rim and for the formation of nodules in Gale mudstones may have had similar chemical characteristics at the time the Mg-sulfates were formed.

Yen, Albert S.↗
NASA NTRS2009

Origins of Magnetite Nanocrystals in Martian Meteorite ALH84001

The Martian meteorite ALH84001 preserves evidence of interaction with aqueous fluids while on Mars in the form of microscopic carbonate disks. These carbonate disks are believed to have precipitated 3.9 Ga ago at beginning of the Noachian epoch on Mars during which both the oldest extant Martian surfaces were formed, and perhaps the earliest global oceans. Intimately associated within and throughout these carbonate disks are nanocrystal magnetites (Fe3O4) with unusual chemical and physical properties, whose origins have become the source of considerable debate. One group of hypotheses argues that these magnetites are the product of partial thermal decomposition of the host carbonate. Alternatively, the origins of mag- netite and carbonate may be unrelated; that is, from the perspective of the carbonate the magnetite is allochthonous. For example, the magnetites might have already been present in the aqueous fluids from which the carbonates were believed to have been deposited. We have sought to resolve between these hypotheses through the detailed characterized of the compo- sitional and structural relationships of the carbonate disks and associated magnetites with the orthopyroxene matrix in which they are embedded. Extensive use of focused ion beam milling techniques has been utilized for sample preparation. We then compared our observations with those from experimental thermal decomposition studies of sideritic carbonates under a range of plausible geological heating scenarios. We conclude that the vast majority of the nanocrystal magnetites present in the car- bonate disks could not have formed by any of the currently proposed thermal decomposition scenarios. Instead, we find there is considerable evidence in support of an alternative allochthonous origin for the magnetite unrelated to any shock or thermal processing of the carbonates.

Thomas-Keprta, Kathie L.↗