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NASA NTRS2003

Optimized bioregenerative space diet selection with crew choice

Previous studies on optimization of crew diets have not accounted for choice. A diet selection model with crew choice was developed. Scenario analyses were conducted to assess the feasibility and cost of certain crew preferences, such as preferences for numerous-desserts, high-salt, and high-acceptability foods. For comparison purposes, a no-choice and a random-choice scenario were considered. The model was found to be feasible in terms of food variety and overall costs. The numerous-desserts, high-acceptability, and random-choice scenarios all resulted in feasible solutions costing between 13.2 and 17.3 kg ESM/person-day. Only the high-sodium scenario yielded an infeasible solution. This occurred when the foods highest in salt content were selected for the crew-choice portion of the diet. This infeasibility can be avoided by limiting the total sodium content in the crew-choice portion of the diet. Cost savings were found by reducing food variety in scenarios where the preference bias strongly affected nutritional content.

Non-NASA Center↗

NASA NTRS2018

Molecular Dynamics Simulations of Liquid and Polymer Electrolytes for Energy Storage Devices

Advancing beyond current lithium-ion technology is necessary in order to enable energy storage devices for electric airplanes. Electrolyte stability is a key limiting factor, yet the design of improved electrolytes remains a formidable challenge. Molecular dynamics (MD) simulations are a powerful tool for studying electrolytes, since they can be used to evaluate structural, thermodynamic, and transport properties, and can provide molecular-level detail often inaccessible to experimental techniques. Our computational materials groups at the NASA Ames Research Center has developed models and methods to accurately simulate both liquid and polymer electrolytes.We report the results from atomistic MD simulations of several electrolyte materials, with lithium salts dissolved in ionic liquids, dimethoxyethane (DME), and polyethylene oxide (PEO). For improved accuracy, we employ polarizable models, where each atom is given an environment-dependent atomic dipole. The simulations accurately predict bulk transport properties, including viscosity, diffusion, and ionic conductivity, in quantitative agreement with available experimental data. Moreover, the simulations provide important insights into the solvation structure of the lithium ions.We also report the results from coarse-grained MD simulations of polyanion electrolytes. In order to more efficiently capture the longer length- and time-scales of these systems, we employ a generic bead-spring model. These simulations provide important insight into how the polymer chain architecture and ionic interaction strengths affect the ionic aggregation behavior and cation dynamics. Despite the simplicity of the model, the simulations yield qualitative agreement with experimental data for similar systems.

Abbott, Lauren J.↗

NASA NTRS1993

Characterization of auxin-binding proteins from zucchini plasma membrane

We have previously identified two auxin-binding polypeptides in plasma membrane (PM) preparations from zucchini (Cucurbita pepo L.) (Hicks et al. 1989, Proc. Natl. Acad. Sci. USA 86, 4948-4952). These polypeptides have molecular weights of 40 kDa and 42 kDa and label specifically with the photoaffinity auxin analog 5-N3-7-3H-IAA (azido-IAA). Azido-IAA permits both the covalent and radioactive tagging of auxin-binding proteins and has allowed us to characterize further the 40-kDa and 42-kDa polypeptides, including the nature of their attachment to the PM, their relationship to each other, and their potential function. The azido-IAA-labeled polypeptides remain in the pelleted membrane fraction following high-salt and detergent washes, which indicates a tight and possibly integral association with the PM. Two-dimensional electrophoresis of partially purified azido-IAA-labeled protein demonstrates that, in addition to the major isoforms of the 40-kDa and 42-kDa polypeptides, which possess isoelectric points (pIs) of 8.2 and 7.2, respectively, several less abundant isoforms that display unique pIs are apparent at both molecular masses. Tryptic and chymotryptic digestion of the auxin-binding proteins indicates that the 40-kDa and 42-kDa polypeptides are closely related or are modifications of the same polypeptide. Phase extraction with the nonionic detergent Triton X-114 results in partitioning of the azido-IAA-labeled polypeptides into the aqueous (hydrophilic) phase. This apparently paradoxical behavior is also exhibited by certain integral membrane proteins that aggregate to form channels. The results of gel filtration indicate that the auxin-binding proteins do indeed aggregate strongly and that the polypeptides associate to form a dimer or multimeric complex in vivo. These characteristics are consistent with the hypothesis that the 40-kDa and 42-kDa polypeptides are subunits of a multimeric integral membrane protein which has an auxin-binding site, and which may possess transporter or channel function.

NASA Program Space Biology↗

NASA NTRSDate not supplied

Overview of ACTIVATE’s First Year of Flights Targeting Aerosol-Cloud-Meteorology Interactions

The Aerosol Cloud meTeorology Interactions oVer the western ATlantic Experiment (ACTIVATE) included 40 research flights in the winter and summer months of 2020 using a two-aircraft approach to simultaneously obtain in situ and remote sensing data of regions below, inside, and above boundary layer clouds. This presentation will summarize early findings from the first year of ACTIVATE flights with focus on aerosol and cloud droplet number concentration behavior, formation and evolution of clouds, and analysis of remote sensing retrievals of aerosol and cloud properties. There is a clear annual cycle in cloud droplet number concentration suggesting a marked annual cycle in aerosol-cloud interactions. Although aerosol particles are more abundant in spring and summer, the conditions needed to activate those particles into cloud droplets are weaker than in other colder months. Several flights targeted post-frontal clouds associated with cold air outbreaks pointing to enhanced levels of nucleated particles immediately above such clouds, and that ice formation hastens the transition from closed to open cloud structures in the sampled CAO events. Also observed in the marine boundary layer during CAOs is the frequent occurrence of non-spherical sea salt particles, which has significant implications for remote sensing retrievals.

Taylor Shingler↗

NASA NTRS2000

Generation of Bubbly Suspensions in Low Gravity

Generation of a uniform monodisperse bubbly suspension in low gravity is a rather difficult task because bubbles do not detach as easily as on Earth. Under microgravity, the buoyancy force is not present to detach the bubbles as they are formed from the nozzles. One way to detach the bubbles is to establish a detaching force that helps their detachment from the orifice. The drag force, established by flowing a liquid in a cross or co-flow configuration with respect to the nozzle direction, provides this additional force and helps detach the bubbles as they are being formed. This paper is concerned with studying the generation of a bubbly suspension in low gravity in support of a flight definition experiment titled "Behavior of Rapidly Sheared Bubbly Suspension." Generation of a bubbly suspension, composed of 2 and 3 mm diameter bubbles with a standard deviation <10% of the bubble diameter, was identified as one of the most important engineering/science issues associated with the flight definition experiment. This paper summarizes the low gravity experiments that were conducted to explore various ways of making the suspension. Two approaches were investigated. The first was to generate the suspension via a chemical reaction between the continuous and dispersed phases using effervescent material, whereas the second considered the direct injection of air into the continuous phase. The results showed that the reaction method did not produce the desired bubble size distribution compared to the direct injection of bubbles. However, direct injection of air into the continuous phase (aqueous salt solution) resulted in uniform bubble-diameter distribution with acceptable bubble-diameter standard deviation.

Nahra, Henry K.↗

NASA NTRSDate not supplied

Novel Aprotic Heterocyclic Anion-based Ionic Liquids for Carbon Dioxide Capture

Ionic liquids (ILs), or organic salts with melting points at or below room temperature are an incredibly versatile class of materials with many possible applications for NASA’s exploration needs. In particular, appropriately designed ILs can have a high affinity for absorbing carbon dioxide, making them excellent candidates for use as liquid sorbents in cabin air revitalization systems. Unfortunately, many of these ILs have high viscosity, which is only exacerbated by carbon dioxide uptake. High viscosity limits the rate of carbon dioxide uptake. A new class of IL sorbent containing aprotic heterocyclic anions (AHA) has been shown to offer excellent carbon dioxide uptake without a corresponding increase in viscosity. However, there is a paucity of sorption data for these AHA ILs at low partial pressures of carbon dioxide. This paper reports on the characterization of sorption behavior for AHA ILs previously reported in the literature at low concentrations of carbon dioxide and the synthesis and characterization of new, water miscible AHA ILs. Characterization of the new ILs includes measurement of density, viscosity, thermal stability, carbon dioxide capacity, carbon dioxide absorption kinetics, and water-IL vapor liquid equilibrium. Overall, these news ILs are promising alternatives to many of the commonly used IL sorbents.

Eric Townsend Fox↗

NASA NTRS2016

Computational and Experimental Study of Li-doped Ionic Liquids at Electrified Interfaces

We evaluate the influence of Li-salt doping on the dynamics, capacitance, and structure of three ionic liquid electrolytes, [pyr14][TFSI], [pyr13][FSI], and [EMIM][BF4], using molecular dynamics and polarizable force fields. In this respect, our focus is on the properties of the electric double layer (EDL) formed by the electrolytes at the electrode surface as a function of surface potential (Psi). The rates of EDL formation are found to be on the order of hundreds of picoseconds and only slightly influenced by the addition of Li-salt. The EDLs of three electrolytes are shown to have different energy storage capacities, which we relate to the EDL formation free energy. The differential capacitance obtained from our computations exhibits asymmetry about the potential of zero charge and is consistent with the camel-like profiles noted from mean field theories and experiments on metallic electrodes. The introduction of Li-salt reduces the noted asymmetry in the differential capacitance profile. Complementary experimental capacitance measurements have been made on our three electrolytes in their neat forms and with Li-salt. The measurements, performed on glassy carbon electrodes, produce U-like profiles, and Li-salt doping is shown to strongly affect capacitance at high magnitudes of Psi. Differences in the theoretical and experimental shapes and magnitudes of capacitance are rationalized in terms of the electrode surface and pseudocapacitive effects. In both neat and Li-doped liquids, the details of the computational capacitance profile are well described by Psi-induced changes in the density and molecular orientation of ions in the molecular layer closest to the electrode. Our results suggest that the addition of Li+ induces disorder in the EDL, which originates from the strong binding of anions to Li+. An in-depth analysis of the distribution of Li+ in the EDL reveals that it does not readily enter the molecular layer at the electrode surface, preferring instead to be localized farther away from the surface in the second molecular layer. This behavior is validated through an analysis of the free energy of Li+ solvation as a function of distance from the electrode. Free energy wells are found to coincide with localized concentrations of Li+, the depths of which increase with Psi and suggest a source of impedance for Li+ to reach the electrode.

Haskins, Justin B.↗

NASA NTRS1998

Lateral Parabrachial Nucleus Serotonergic Mechanisms and Salt Appetite Induced by Sodium Depletion

This study investigated the effects of bilateral injections of a serotonin (5-HT) receptor agonist into the lateral parabrachial nucleus on the intake of NaCl and water induced by 24-h water deprivation or by sodium depletion followed by 24 h of sodium deprivation (injection of the diuretic furosemide plus 24 h of d sodium-deficient diet). Rats had stainless steel cannulas implanted bilaterally into the LPBN. Bilateral LPBN injections of the serotonergic 5-HT(1/2) receptor antagonist methysergide (4 micro-g/200 nl at each site) increased hypertonic NaCl intake when tested 24 h after sodium depletion and after 24 h of water deprivation. Water intake also increased after bilateral injections of methysergide into the LPBN. In contrast, the intake of a palatable solution (0.06 M sucrose) under body fluid-replete conditions was not changed after bilateral LPBN methysergide injections. The results show that serotonergic mechanisms in the LPBN modulate water and sodium intake induced by volume depletion and sodium loss. The finding that sucrose intake was not affected by LPBN serotonergic blockade suggests that the effects of the methysergide treatment on the intakes of water and NaCl are not due to a mechanism producing a nonspecific enhancement of all ingestive behaviors.

Menani, Jose Vanderlei↗

NASA NTRS1991

Experiments with phase change thermal energy storage canisters for Space Station Freedom

The solar dynamic power module proposed for the Space Station Freedom (SSF) uses the heat of fusion of a phase change material (PCM) to efficiently store thermal energy for use during eclipse periods. The PCM, a LiF-20CaF2 salt, is contained in annular, metal canisters located in a heat receiver at the focus of a solar concentrator. PCM canister ground-based experiments and analytical heat transfer studies are discussed. The hardware, test procedures, and test results from these experiments are discussed. After more than 900 simulated SSF orbital cycles, no canister cracks or leaks were observed and all data were successfully collected. The effect of 1-g test orientation on canister wall temperatures was generally small while void position was strongly dependent on test orientation and canister cooling. In one test orientation, alternating wall temperature data were measured that supports an earlier theory of oscillating vortex flow in the PCM melt. Analytical canister wall temperatures compared very favorably with experimental temperature data. This illustrates that ground-based canister thermal performance can be predicted well by analyses that employ straight-forward, engineering models of void behavior and liquid PCM free convection.

Kerslake, Thomas W.↗

NASA NTRS2004

Anhydrite EOS and Phase Diagram in Relation to Shock Decomposition

In the context of the Chicxulub impact, it became recently obvious that experimental and theoretical research on the shock behavior of sulfates is essential for an assessment of the role of shock-released gases in the K/T mass extinction. The Chicxulub crater is the most important large impact structure where the bolide penetrated a sedimentary layer with large amounts of interbedded anhydrite (Haughton has also significant anhydrite in the target). The sulfuric gas production by shock compression/decompression of anhydrite is an important issue, even if the size of Chicxulub crater is only half of the so far assumed size. The comparison of experimental data for anhydrite, shocked with different techniques at various laboratories, reveals large differences in the threshold pressures for melting and decomposition. To gain insight into this issue, we have made a theoretical investigation of the thermodynamic properties of anhydrite. The project includes the review of data published in the last 40 years - reasons to study anhydrite cover a wide field of interests: from industrial problems of cement and ceramic production to the analysis of nuclear underground explosions in salt domes, conducted in the USA and USSR in the 1970th.

Ivanov, B. A.↗

NASA NTRS2003

Small Scale Polygons and the History of Ground Ice on Mars

Recent progress on polygon modeling has focused on the diameter and surface relief that we expect of thermal-contraction polygons in martian permafrost. With this in mind, we developed a finite-element model of thermal-contraction-crack behavior in permafrost in a martian climate. This model was generated from a finite element code by Jay Melosh (called TECTON) originally developed for terrestrial and planetary crustal-deformation studies. We adapted this model to martian permafrost by including time (and temperature) dependent rheologies, boundary conditions, and isotropic thermal-contraction, as well as several small adaptations to a martian environment. We tested our model extensively, including comparison to an analytic solution of pre-fracture stress. We recently published an analysis of two potential sources of water for forming the recent gullies. In this work we first evaluated the potential for near-surface ground ice (in the top meter or so of soil) to melt under conditions of solar heating on sloped surfaces at high obliquity, utilizing both thermal and diffusion-based ground-ice-stability models; our results suggested that the ground ice will sublimate, and the ice table will recede to greater depths before the melting temperature can be reached. An exception can occur only for extremely salt-rich ice, depressing the freezing point.

Mellon, Michael T.↗

NASA NTRS1992

Dielectric surface properties of Venus

It has been known for over a decade that certain high-altitude regions on Venus exhibit bizarre radar-scattering and radiothermal-emission behavior. For example, observed values for normal-incidence power reflection coefficients in these areas can exceed 0.5; enhanced back scatter in some mountainous areas in the Magellan SAR images creates a bright surface with the appearance of snow; and reduced thermal emission in the anomalous areas makes the surface there appear hundreds of degrees cooler than the corresponding physical surface temperatures. The inferred radio emissivity in several of these regions falls to 0.3 for horizontal linear polarization at viewing angles in the range 20 deg - 40 deg. Several explanations have been offered for these linked phenomena. One involves single-surface reflection from a sharp discontinuity separating two media that have extremely disparate values of electromagnetic propagation. The mismatch may occur in either or both the real (associated with propagation velocity) or imaginary (associated with absorption) components of the relevant indices of refraction, and the discontinuity must take place over a distance appreciably shorter than a wavelength. An example of such an interaction of Earth would occur at the surface of a body of water. At radio wavelengths, water has an index of refraction of 9 (dielectric permittivity of about 80), and an associated loss factor that varies strongly with the amount of dissolved salts, but is generally significant. Its single-surface radar reflectivity at normal incidence is about 0.65, and the corresponding emissivity (viewed at the same angle) is therefore 0.35. Both these values are similar to the extremes found on Venus, but in the absence of liquid water, the process on Venus requires a different explanation. Two of the present authors (Pettengill and Ford) have suggested that scattering from a single surface possessing a very high effective dielectric permittivity could explain many of the unusual characteristics displayed by the Venus surface. A second explantion relates to the volume scattering that results from successive interactions with one or more interfaces interior to the planetary surface. If the near-surface material has a moderately low index of refraction (to ensure that a substantial fraction of the radiation incident from outside is not reflected, but rather penetrates into the surface), and a very low internal propagation loss, successive internal reflections can eventually redirect much of the energy back through the surface toward the viewer. The necessary conditions for this process to be effective are a low internal propagation loss coupled with efficient internal reflection. At sufficiently low temperatures, fractured water ice displays both the necessary low loss and near-total internal reflection. The possibility that this mechanism might be acting on Venus has recently been put forward.

Pettengill, G. H.↗

NASA NTRS2003

Interactions of Hydrazine and Blowby Gases

The interactions between hydrazine and blowby gases from pyrovalves was explored in this research project. Investigating the decomposition chemistry of hydrazine through detailed chemical kinetic modeling is a project started last summer while participating in the Summer Faculty Fellowship program. During the 1999-2000 academic year, the chemical kinetic mechanism for hydrazine decomposition developed while a SFF at NASA's White Sands Test Facility was further revised and validated against the limited experimental data in the literature. This mechanism was then used in assessing the effects of blowby gas species on hydrazine decomposition. The combustion products introduced into the fuel line by pyrovalve actuation consist primarily of hydrogen gas. Hydrogen is also a product of the decomposition of hydrazine. Additional gaseous chemical species are introduced into the fuel, as well as metals and metal salts that deposit onto the walls of the fuel line. The deposition process is undoubtedly very rapid, and exothermic. Therefore, the major focus of this summer's work was examining the effects of hydrogen presence on hydrazine decomposition, with some representative calculations including the remaining gaseous species found to exist in blowby gases. Since hydrogen is a product of hydrazine decomposition, all reactions necessary to evaluate its effect on hydrazine decomposition chemistry were in the original mechanism developed. However, the mechanism needed to be considerably expanded to include the reactions of the other gaseous blowby species with hydrazine, all the intermediate species formed in its decomposition, and each other. The expanded mechanism consists of 70 species interacting via a network of 452 reactions. Calculations with molecular hydrogen introduced into hydrazine gas in an inert bath gas indicate that H2 presence as an initial reactant in substantial amounts can dramatically impact the decomposition process for hydrazine. The other gaseous blowby species (CO, CO2, H2O, CH4, O2, and N2) were found to have little effect compared to the inclusion of hydrogen itself as an initial reagent. This result is undoubtedly due, in part, to the fact that the blowby gas used in these calculations consisted of 94.6% H2. A more rigorous examination of the behavior of the full detailed mechanism under a variety of conditions was not performed.

Meagher, Nancy E.↗

NASA NTRS1997

Chaos: Understanding and Controlling Laser Instability

In order to characterize the behavior of tunable diode lasers (TDL), the first step in the project involved the redesign of the TDL system here at the University of Tennessee Molecular Systems Laboratory (UTMSL). Having made these changes it was next necessary to optimize the new optical system. This involved the fine adjustments to the optical components, particularly in the monochromator, to minimize the aberrations of coma and astigmatism and to assure that the energy from the beam is focused properly on the detector element. The next step involved the taking of preliminary data. We were then ready for the analysis of the preliminary data. This required the development of computer programs that use mathematical techniques to look for signatures of chaos. Commercial programs were also employed. We discovered some indication of high dimensional chaos, but were hampered by the low sample rate of 200 KSPS (kilosamples/sec) and even more by our sample size of 1024 (1K) data points. These limitations were expected and we added a high speed data acquisition board. We incorporated into the system a computer with a 40 MSPS (million samples/sec) data acquisition board. This board can also capture 64K of data points so that were then able to perform the more accurate tests for chaos. The results were dramatic and compelling, we had demonstrated that the lead salt diode laser had a chaotic frequency output. Having identified the chaotic character in our TDL data, we proceeded to stage two as outlined in our original proposal. This required the use of an Occasional Proportional Feedback (OPF) controller to facilitate the control and stabilization of the TDL system output. The controller was designed and fabricated at GSFC and debugged in our laboratories. After some trial and error efforts, we achieved chaos control of the frequency emissions of the laser. The two publications appended to this introduction detail the entire project and its results.

Blass, William E.↗

NASA NTRS2012

High-Temperature Shape Memory Polymers

physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing radiation ( radiation, neutrons), or by chemical crosslinking to form a covalent permanent network. With respect to other shape memory polymers, this invention is novel in that it describes the use of a thermoplastic composition that can be thermally molded or solution-cast into complex "permanent" shapes, and then reheated or redissolved and recast from solution to prepare another shape. It is also unique in that the shape memory behavior is provided by a non-polymer additive.

Yoonessi, Mitra↗

NASA NTRS2000

Does Warming a Lysozyme Solution Cook Ones Data?

Chicken egg white lysozyme has a well characterized thermally driven phase transition. Between pH 4.0 and 5.2, the transition temperature, as defined by the point where the tetragonal and orthorhombic solubility are equal, is a function of the pH, salt (precipitant) type and concentration, and most likely of the buffer concentration as well. This phase transition can be carried out with protein solution alone, prior to the initiation of the crystallization process. We have now measured the kinetics of this process and investigated its reversibility. An aliquot of a stock protein solution is held at a given temperature, and at periodic intervals used to set up batch crystallization experiments. The batch solutions were incubated at 20 C until macroscopic crystals were obtained, at which point the number of crystals in each well were counted. The transition effects increased with temperature, slowly falling off at 30 C with a half time (time to approx. 1/2 the t = 0 number of crystals) of approx. 5 hours, and an estimated half time of approx. 0.5 hours at 43 C. Further, the process was not reversible by simple cooling. After holding a lysozyme solution at 37 C (prior to addition of precipitant) for 16 hours, then cooling and holding it at 4 C, no return to the pre-warmed nucleation kinetics are observed after at least 4 weeks. Thus every thermal excursion above the phase transition point results in a further decrease in the nucleation rate of that solution, the extent being a function of the time and temperature. Orthorhombic lysozyme crystals apparently do not undergo the flow-induced growth cessation of tetragonal lysozyme crystals. We have previously shown that putting the protein in the orthorhombic form does not affect the averaged face growth kinetics, only nucleation, for tetragonal crystals. We may be able to use this differential behavior to elucidate how flow affects tile lysozyme crystal growth process.

Pusey, Marc↗

NASA NTRS1993

Synthesis of phthalocyanine doped sol-gel materials

The synthesis of sol-gel silica materials doped with three different types of metallophthalocyanines has been studied. Homogeneous materials of good optical quality were prepared and the first optical limiting measurements of dyes in sol-gel hosts were carried out. The properties of these solid state limiters are similar to limiters based on phthalocyanine (Pc) in solution. Sol-gel silica materials containing copper, tin and germanium phthalocyanines were investigated. The initial step in all cases was to prepare silica sols by the sonogel method using tetramethoxy silane (TMOS), HCl and distilled water. Thereafter, the synthesis depended upon the specific Pc and its solubility characteristics. Copper phthalocyanine tetrasulfonic acid tetra sodium salt (CuPc4S) is soluble in water and various doping levels (1 x 10 (exp -4) M to 1 x 10 (exp -5) M) were added to the sol. The group IV Pc's, SnPc(OSi(n-hexyl)3)2 and GePc(OSi(n-hexyl)3)2, are insoluble in water and the process was changed accordingly. In these cases, the compounds were dissolved in THF and then added to the sol. The Pc concentration in the sol was 2 x 10(exp -5)M. The samples were then aged and dried in the standard method of making xerogel monoliths. Comparative nanosecond optical limiting experiments were performed on silica xerogels that were doped with the different metallophthalocyanines. The ratio of the net excited state absorption cross section (sigma(sub e)) to the ground state cross section (sigma(sub g)) is an important figure of merit that is used to characterize these materials. By this standard the SnPc sample exhibits the best limiting for the Pc doped sol-gel materials. Its cross section ratio of 19 compares favorably with the value of 22 that was measured in toluene. The GePc materials appear to not be as useful as those containing SnPc. The GePc doped solids exhibit a higher onset energy (2.5 mj and lower cross section ratio, 7. The CuPc4S sol-gel material has a still lower cross section ratio, 4, however, the tetrasulfonate groups make the dye soluble in water which greatly facilitates its incorporation into the sol-gel matrix. The nonlinear transmission of CuPc4S in a pH 2 buffer solution and in a silica xerogel were compared. It is evident that the CuPc4S preserves its optical limiting behavior in the sol-gel matrix, indicating that the fundamental excited state absorption process is essentially the same for a molecule in solution or in the solid state. Although the spectroscopic details of energy level lifetimes are unknown, the significance is that passive optical limiting has been achieved in the solid state via incorporation of a dye into an inorganic host. The only compromise occurs at the extremely high energy regime where photobleaching is observed. This is a result of the limited mobility of the dye molecules in the solid silica host relative to a liquid host. The effects of photodegradation in the xerogel are additive, whereas the solution provides a supply of fresh molecules that are free to enter the active volume between pulses.

Dunn, Bruce↗

NASA NTRS2013

Non-Magnetic, Tough, Corrosion- and Wear-Resistant Knives From Bulk Metallic Glasses and Composites

Quality knives are typically fabricated from high-strength steel alloys. Depending on the application, there are different requirements for mechanical and physical properties that cause problems for steel alloys. For example, diver's knives are generally used in salt water, which causes rust in steel knives. Titanium diver's knives are a popular alternative due to their salt water corrosion resistance, but are too soft to maintain a sharp cutting edge. Steel knives are also magnetic, which is undesirable for military applications where the knives are used as a tactical tool for diffusing magnetic mines. Steel is also significantly denser than titanium (8 g/cu cm vs. 4.5 g/cu cm), which results in heavier knives for the same size. Steel is hard and wear-resistant, compared with titanium, and can keep a sharp edge during service. A major drawback of both steel and titanium knives is that they must be ground or machined into the final knife shape from a billet. Since most knives have a mirrored surface and a complex shape, manufacturing them is complex. It would be more desirable if the knife could be cast into a net or near-net shape in a single step. The solution to the deficiencies of titanium, steel, and ceramic knives is to fabricate them using bulk metallic glasses (or composites). These alloys can be cast into net or near-net shaped knives with a combination of properties that exceed both titanium and steel. A commercially viable BMG (bulk metallic glass) or composite knife is one that exhibits one or all of the following properties: It is based on titanium, has a self-sharpening edge, can retain an edge during service, is hard, is non-magnetic, is corrosion-resistant against a variety of corrosive environments, is tough (to allow for prying), can be cast into a net-shape with a mirror finish and a complex shape, has excellent wear resistance, and is low-density. These properties can be achieved in BMG and composites through alloy chemistry and processing. For each desired property for knife fabrication and performance, there is an alloy development strategy that optimizes behavior. Although BMG knives have been demonstrated as far back as 1995, they never found commercial success because they had to be ground (which presented problems because the alloys contained beryllium), they weren't low cost (because they weren't cast to a net-shape), they were brittle (because they were made with a low-quality commercial material), and they had extremely poor corrosion resistance (because corrosion was not well-understood in these materials). Ultimately, these shortcomings prevented the widespread commercialization. In the current work, the inventors have applied more than a decade of research on BMGs from Caltech and JPL to develop a better understanding of how to make BMG knives that exhibit an optimal combination of properties, processing and cost. Alloys have been developed based in titanium (and other metals), that exhibit high toughness, high hardness, excellent corrosion resistance, no ferromagnetism, edge-retaining selfsharpening, and the ability to be cast like a plastic using commercially available casting techniques (currently used by commercial companies such as Liquidmetal Technologies and Visser Precision Casting). The inventors argue that depending on the application (diving, military, tactical, utility, etc.) there is an optimal combination of design and alloy composition. Moreover, with new casting technologies not available at the inception of these materials, net-shaped knives can be cast into complex shapes that require no aftermarket forming, except for sharpening using water-cooled polishing wheel. These combinations of discoveries seek to make low-cost BMG knives commercially viable products that have no equal among metal or ceramic knives. Current work at JPL focuses on net-shape casting of these alloys and testing their mechanical properties versus commercially available knives to demonstrate their benefits.

Hoffman, Douglas C.↗