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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 163 records · Page 9

The Effects of Acid Passivation, Tricresyl Phosphate Presoak, and UV/Ozone Treatment on the Tribology of Perfluoropolyether-Lubricated 440C Stainless Steel Couples

The boundary-lubrication performance of two perfluoropolyether (PFPE) thin films in the presence of passivated 440C stainless steel is presented. The study used a standard ball on disk (BoD) tribometer in dry nitrogen and a vacuum spiral orbit tribometer (SOT). Stainless steel surfaces were passivated with one of four techniques: high and low temperature chromic acid bath, a tricresyl phosphate (TCP) soak, or UV/Ozone treated for 15 min. After passivation, each BoD disk had a 400A film of Krytox 16256 (PFPE) applied to it. The lifetimes of these films were quantified by measuring the number of sliding cycles before an increase in friction occurred. The lubricated lifetime of the 440C couple was not altered as a result of the various passivation techniques. The resulting surface chemistry of each passivation technique was examined using X-ray photoelectron spectroscopy (XPS). The SOT was used to examine the effects of the TCP treatment on the lubricated lifetime of another PFPE, Brayco 815Z, under rolling conditions. None of the passivation techniques were found to dramatically increase the oxide film thickness or lubricated lifetimes.

Shogrin, Bradley A.↗

Ionization Cross Sections and Dissociation Channels of the DNA Sugar-Phosphate Backbone by Electron Collisions

It has been suggested that the genotoxic effects of ionizing radiation in living cells are not caused by the highly energetic incident radiation, but rather are induced by less energetic secondary species generated, the most abundant of which are free electrons.' The secondary electrons will further react to cause DNA damage via indirect and direct mechanisms. Detailed knowledge of these mechanisms is ultimately important for the development of global models of cellular radiation damage. We are studying one possible mechanism for the formation cf DNA strand breaks involving dissociative ionization of the DNA sugar-phosphate backbone induced by secondary electron co!lisions. We will present ionization cross sections at electron collision energies between threshold and 10 KeV using the improved binary encounter dipole (iBED) formulation' Preliminary results of the possible dissociative ionization pathways will be presented. It is speculated that radical fragments produced from the dissociative ionization can further react, providing a possible mechanism for double strand breaks and base damage.

Dateo, Christopher↗

Solubility and cation exchange in phosphate rock and saturated clinoptilolite mixtures

Mixtures of zeolite and phosphate rock (PR) have the potential to provide slow-release fertilization of plants in synthetic soils by dissolution and ion-exchange reactions. This study was conducted to examine solubility and cation-exchange relationships in mixtures of PR and NH4- and K-saturated clinoptilolite (Cp). Batch-equilibration experiments were designed to investigate the effect of PR source, the proportion of exchangeable K and NH4, and the Cp to PR ratio on solution N, P, K, and Ca concentrations. The dissolution and cation-exchange reactions that occurred after mixing NH4- and K-saturated Cp with PR increased the solubility of the PR and simultaneously released NH4 and K into solution. The more reactive North Carolina (NC) PR rendered higher solution concentrations of NH4 and K when mixed with Cp than did Tennessee (TN) PR. Solution P concentrations for the Cp-NC PR mixture and the Cp-TN PR mixture were similar. Solution concentrations of N, P, K, and Ca and the ratios of these nutrients in solution varied predictably with the type of PR, the Cp/PR ratio, and the proportions of exchangeable K and NH4 on the Cp. Our research indicated that slow-release fertilization using Cp/PR media may provide adequate levels of N, P, and K to support plant growth. Solution Ca concentrations were lower than optimum for plant growth.

NASA Discipline Number 61-10↗

Site-directed mutagenesis of serine 158 demonstrates its role in spinach leaf sucrose-phosphate synthase modulation

Site-directed mutagenesis of spinach sucrose-phosphate synthase (SPS) was performed to investigate the role of Ser158 in the modulation of spinach leaf SPS. Tobacco plants expressing the spinach wild-type (WT), S158A, S158T and S157F/S158E SPS transgenes were produced. Expression of transgenes appeared not to reduce expression of the tobacco host SPS. SPS activity in the WT and the S158T SPS transgenics showed light/dark modulation, whereas the S158A and S157F/S158E mutants were not similarly light/dark modulated: the S158A mutant enzyme was not inactivated in the dark, and the S157F/S158E was not activated in the light. The inability to modulate the activity of the S158A mutant enzyme by protein phosphorylation was demonstrated in vitro. The WT spinach enzyme immunopurified from dark transgenic tobacco leaves had a low initial activation state, and could be activated by PP2A and subsequently inactivated by SPS-kinase plus ATP. Rapid purification of the S158A mutant enzyme from dark leaves of transgenic plants using spinach-specific monoclonal antibodies yielded enzyme that had a high initial activation state, and pre-incubation with leaf PP2A or ATP plus SPS-kinase (the PKIII enzyme) caused little modulation of activity. The results demonstrate the regulatory significance of Ser158 as the major site responsible for dark inactivation of spinach SPS in vivo, and indicate that the significance of phosphorylation is the introduction of a negative charge at the Ser158 position.

Non-NASA Center↗

Site-specific regulatory interaction between spinach leaf sucrose-phosphate synthase and 14-3-3 proteins

We report an Mg2+-dependent interaction between spinach leaf sucrose-phosphate synthase (SPS) and endogenous 14-3-3 proteins, as evidenced by co-elution during gel filtration and co-immunoprecipitation. The content of 14-3-3s associated with an SPS immunoprecipitate was inversely related to activity, and was specifically reduced when tissue was pretreated with 5-aminoimidazole-4-carboxamide riboside, suggesting metabolite control in vivo. A synthetic phosphopeptide based on Ser-229 was shown by surface plasmon resonance to bind a recombinant plant 14-3-3, and addition of the phosphorylated SPS-229 peptide was found to stimulate the SPS activity of an SPS:14-3-3 complex. Taken together, the results suggest a regulatory interaction of 14-3-3 proteins with Ser-229 of SPS.

Non-NASA Center↗

Olivine and Ca-Phosphate in the Diogenites Manegaon and Roda

The textural relationships between the different primary minerals in igneous rocks provide one of the most fundamental pieces of evidence available for inferring the crystallization history of their parent magmas. Unfortunately, the high degree of brecciation that characterizes most diogenites, along with the low modal abundance and small grain sizes of minerals other than orthopyroxene, combine to make identifying and interpreting such textural relationships extremely difficult in this class of meteorites. A few descriptions of primary igneous contacts between orthopyroxene and chromite, troilite, and to a lesser extent, olivine in diogenites have been provided in the literature. In addition to these, in previous work, our research group has characterized several types of igneous contacts between Ca-pyroxene, plagioclase and orthopyroxene in the Bilanga diogenite. We have also described primary igneous inclusions of troilite + kamacite + chromite + Ca-pyroxene +/- Ca-phosphate in orthopyroxene (i.e. Metal/Troilite- Ball inclusions) in the diogenites Bilanga, Manegaon, Johnstown, Roda, Shalka, and Tatahouine. However, for the most part, detailed data on igneous textural relations between minerals other than orthopyroxene in diogenites are still sparse. Of the diogenite samples that we have examined,

Domanik, K. J.↗

Phosphate Reactions as Mechanisms of High-Temperature Lubrication

One of the major problems preventing the operation of advanced gas turbine engines at higher temperatures is the inability of currently used liquid lubricants to survive at these higher temperatures under friction and wear conditions. Current state-of-the-art organic liquid lubricants rapidly degrade at temperatures above 300 C; hence some other form of lubrication is necessary. Vapor-phase lubrication is a promising new technology for high-temperature lubrication. This lubrication method employs a liquid phosphate ester that is vaporized and delivered to bearings or gears; the vapor reacts with the metal surfaces, generating a solid lubricious film that has proven very stable at high temperatures. In this study, solid lubricious films were grown on cast-iron foils in order to obtain reaction and diffusion rate data to help characterize the growth mechanism. A phenomenological mathematical model of the film deposition process was derived incorporating transport and kinetic parameters that were coupled to the experimental data. This phenomenological model can now be reliably used as a predictive and scale-up tool for future vapor-phase lubrication studies.

Nagarajan, Anitha↗

Lithium Iron Phosphate Cell Performance Evaluations for Lunar Extravehicular Activities

Lithium-ion battery cells are being evaluated for their ability to provide primary power and energy storage for NASA s future Exploration missions. These missions include the Orion Crew Exploration Vehicle, the Ares Crew Launch Vehicle Upper Stage, Extravehicular Activities (EVA, the advanced space suit), the Lunar Surface Ascent Module (LSAM), and the Lunar Precursor and Robotic Program (LPRP), among others. Each of these missions will have different battery requirements. Some missions may require high specific energy and high energy density, while others may require high specific power, wide operating temperature ranges, or a combination of several of these attributes. EVA is one type of mission that presents particular challenges for today s existing power sources. The Portable Life Support System (PLSS) for the advanced Lunar surface suit will be carried on an astronaut s back during eight hour long sorties, requiring a lightweight power source. Lunar sorties are also expected to occur during varying environmental conditions, requiring a power source that can operate over a wide range of temperatures. Concepts for Lunar EVAs include a primary power source for the PLSS that can recharge rapidly. A power source that can charge quickly could enable a lighter weight system that can be recharged while an astronaut is taking a short break. Preliminary results of Al23 Ml 26650 lithium iron phosphate cell performance evaluations for an advanced Lunar surface space suit application are discussed in this paper. These cells exhibit excellent recharge rate capability, however, their specific energy and energy density is lower than typical lithium-ion cell chemistries. The cells were evaluated for their ability to provide primary power in a lightweight battery system while operating at multiple temperatures.

Reid, Concha↗

Optimized Li-Ion Electrolytes Containing Triphenyl Phosphate as a Flame-Retardant Additive

A number of future NASA missions involving the exploration of the Moon and Mars will be human-rated and thus require high-specific-energy rechargeable batteries that possess enhanced safety characteristics. Given that Li-ion technology is the most viable rechargeable energy storage device for near-term applications, effort has been devoted to improving the safety characteristics of this system. There is also a strong desire to develop Li-ion batteries with improved safety characteristics for terrestrial applications, most notably for hybrid electric vehicle (HEV) and plug-in hybrid electric vehicle (PHEV) automotive applications. Therefore, extensive effort has been devoted recently to developing non-flammable electrolytes to reduce the flammability of the cells/battery. A number of electrolyte formulations have been developed, including systems that (1) incorporate greater concentrations of the flame-retardant additive (FRA); (2) use di-2,2,2-trifluoroethyl carbonate (DTFEC) as a co-solvent; (3) use 2,2,2- trifluoroethyl methyl carbonate (TFEMC); (4) use mono-fluoroethylene carbonate (FEC) as a co-solvent and/or a replacement for ethylene carbonate in the electrolyte mixture; and (5) utilize vinylene carbonate as a "SEI promoting" electrolyte additive, to build on the favorable results previously obtained. To extend the family of electrolytes developed under previous work, a number of additional electrolyte formulations containing FRAs, most notably triphenyl phosphate (TPP), were investigated and demonstrated in experimental MCMB (mesocarbon micro beads) carbon- LiNi(0.8)Co(0.2)O2 cells. The use of higher concentrations of the FRA is known to reduce the flammability of the electrolyte solution, thus, a concentration range was investigated (i.e., 5 to 20 percent by volume). The desired concentration of the FRA is the highest amount tolerable without adversely affecting the performance in terms of reversibility, ability to operate over a wide temperature range, and the discharge rate capability. The use of fluorinated carbonates, much in the same manner as the incorporation of fluorinated ester-based solvents, was employed to reduce the inherent flammability of mixtures. Thus, electrolyte formulations that embody both approaches are anticipated to have much lower flammability, resulting in enhanced safety.

Smart, Marshall C.↗

The Evaluation of Triphenyl Phosphate as a Flame Retardant Additive to Improve the Safety of Lithium-Ion Battery Electrolytes

With the intent of improving the safety characteristics of lithium ion cells, electrolytes containing flame retardant additives have been investigated. A number of triphenyl phosphate-containing electrolytes were evaluated in both coin cells and experimental three electrode lithium-ion cells (containing reference electrodes). A number of chemistries were investigated, including MCMB carbon/LiNi(0.8)Co(0.2)O2 (NCO), graphite/LiNi(0.8)Co(0.15)Al(0.05)O2 (NCA), Li/Li(Li(0.17)Ni(0.25)Mn(0.58))O2, Li/LiNiMnCoO2 (NMC) and graphite/LiNiMnCoO2 (NMC), to study the effect that different electrolyte compositions have upon performance. A wide range of TPP-containing electrolytes were demonstrated to have good compatibility with the C/NCO, C/NCA, and Li/NMC systems, however, poor performance was initially observed with the high voltage C/NMC system. This necessitated the development of improved electrolytes with stabilizing additives, leading to formulations containing lithium bis(oxalato)borate (LiBOB) that displayed substantially improved performance.

rechargable batteries↗

Free-Space Quantum Key Distribution with a High Generation Rate Potassium Titanyl Phosphate Waveguide Photon-Pair Source

A high generation rate photon-pair source using a dual element periodically-poled potassium titanyl phosphate (PP KTP) waveguide is described. The fully integrated photon-pair source consists of a 1064-nanometer pump diode laser, fiber-coupled to a dual element waveguide within which a pair of 1064-nanometer photons are up-converted to a single 532-nanometer photon in the first stage. In the second stage, the 532-nanometer photon is down-converted to an entangled photon-pair at 800 nanometer and 1600 nanometer which are fiber-coupled at the waveguide output. The photon-pair source features a high pair generation rate, a compact power-efficient package, and continuous wave (CW) or pulsed operation. This is a significant step towards the long term goal of developing sources for high-rate Quantum Key Distribution (QKD) to enable Earth-space secure communications. Characterization and test results are presented. Details and preliminary results of a laboratory free-space QKD experiment with the B92 protocol are also presented.

photons↗

Coordinated Microanalysis of Phosphates in High-Titanium Lunar Basalts

Laboratory studies of lunar apatite [Ca5(PO4)3(F,Cl,OH)] have been important for determining the volatile inventory of the interior and the roles volatiles played during the magmatic evolution of the Moon. It has been suggested that high-Ti mare basalts sample volatiles from a distinct reservoir in the lunar mantle. However, there is still debate surrounding the crystallization and post-crystallization history of apatite in those basalts. This information is required before we can use apatite to characterize the abundance or isotopic composition of volatiles in melts or magmatic source regions. Our goal is to investigate the mineral chemistry, crystal structure, and volatile inventory of phosphates in high-Ti basalts from Apollo 11, which will allow us to determine the crystallization history of apatite in these rocks and identify any potential secondary processes that have changed the volatile composition that apatite acquired from the melt.

Barnes, J. J.↗

Coordinated Analysis of Phosphates in Samples From Asteroid (101955) Bennu

Asteroid (101955) Bennu is a B-type asteroid and a prime candidate for investigating the remnants of planet formation and enhancing our understanding of potential sources of crucial bio-essential elements for the early Earth. Remote observations of the surface of Bennu unveiled a terrain of boulders primarily composed of hydrated phyllosilicates, organic molecules, and carbonates. The hydrated nature of Bennu, the abundance of carbonates, and the presence of cm-scale carbonate veins provide clues to the nature of the building blocks of Bennu’s parent body and to its complex geological history. Here we present the first mineralogical, chemical, and isotopic results of analysis of phosphates in samples returned from Bennu by NASA’s OSIRIS-REx mission. We seek to test the hypothesis that heating of Bennu’s parent asteroid resulted in hydrothermal alteration in which melted ice reacted with the initial constituents.

J. J. Barnes↗

Evolutionary Flexibility and Rigidity in the Bacterial Methylerythritol Phosphate (Mep) Pathway

Terpenoids are a diverse class of compounds with wide-ranging uses including as industrial solvents, pharmaceuticals, and fragrances. Efforts to produce terpenoids sustainably by engineering microbes for fermentation are ongoing, but industrial production still largely relies on nonrenewable sources. The methylerythritol phosphate (MEP) pathway generates terpenoid precursor molecules and includes the enzyme Dxs and two iron–sulfur cluster enzymes: IspG and IspH. IspG and IspH are rate limiting-enzymes of the MEP pathway but are challenging for metabolic engineering because they require iron–sulfur cluster biogenesis and an ongoing supply of reducing equivalents to function. Therefore, identifying novel alternatives to IspG and IspH has been an on-going effort to aid in metabolic engineering of terpenoid biosynthesis. We report here an analysis of the evolutionary diversity of terpenoid biosynthesis strategies as a resource for exploration of alternative terpenoid biosynthesis pathways. Using comparative genomics, we surveyed a database of 4,400 diverse bacterial species and found that some may have evolved alternatives to the first enzyme in the pathway, Dxs making it evolutionarily flexible. In contrast, we found that IspG and IspH are evolutionarily rigid because we could not identify any species that appear to have enzymatic routes that circumvent these enzymes. The ever-growing repository of sequenced bacterial genomes has great potential to provide metabolic engineers with alternative metabolic pathway solutions. With the current state of knowledge, we found that enzymes IspG and IspH are evolutionarily indispensable which informs both metabolic engineering efforts and our understanding of the evolution of terpenoid biosynthesis pathways.

Bailey Marshall↗

Synthesis and Crystal Structures of Alkali (Na, Rb, Cs) Iron Phosphate Crystals

Three alkali-containing diphosphate crystals of A FeP 2 O 7 (A = Na, Rb, Cs) were synthesized through melt-crystallization. The crystal structures were determined using single-crystal X-ray diffraction (XRD) data. The synthesized diphosphates crystallized within the P 2 1 /c space group, and the structural parameters were compared to literature data of other A FeP 2 O 7 crystals within the P 2 1 /c space group.

36 MATERIALS SCIENCE↗

The Freundlich isotherm equation best represents phosphate sorption across soil orders and land use types in tropical soils of Puerto Rico

Biomass production in the lowland wet tropical forest is greater than in any other biome, and it is typically limited by soil phosphorus (P) availability. However, the mechanisms involved in the P cycle remain poorly represented in Earth System Models (ESMs). Soil P sorption processes are key in the P cycle and for understanding the extent of P limitation for plant productivity. Currently, a few ESMs include isotherm equations to model these processes. Although the Langmuir equation is widely cited, other isotherm equations may better describe sorption in tropical soils. Here, we use a diverse range of soil samples from Puerto Rico to test the validity of the Langmuir, Freundlich, and Temkin equation. We found that across four soil orders (Inceptisols, Mollisols, Oxisols, Ultisols), and forested and cultivated land use types, the Freundlich equation best represented soil P sorption. Furthermore, the Langmuir and the Temkin equations poorly represent soil P adsorption, especially at low P concentrations. Specifically, the Langmuir equation underestimated soil P adsorption by 40% and the Temkin equation overestimated adsorption by 76%. We also found, as expected, that soil clay content and pH were the most important parameters explaining the variability of the Freundlich (K f ) constant. Greater clay content and lower pH, common in highly weathered Ultisols and Oxisols which are abundant in the tropics, led to greater K f values. Overall, our results suggest that a diversity of soils can prompt underestimation of P sorption when using the Langmuir isotherm, which leads to an overestimation of available P that can have repercussions on ESM predictions of the P cycle and tropical forest productivity.

Earth system models↗