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At least 19 records

The role of P2O5 in silicate melts

Phase equilibria data in the systems SiO2-P2O5, P2O5-M(x)O(y), and P2O5-M(x)O(y)-SiO2 are employed in conjunction with chromatographic and spectral data to investigate the role of P2O5 in silicate melts. P2O5 depolymerizes pure SiO2 melts by entering the network as a four-fold coordinated cation, but polymerizes melts in which an additional metal cation other than silicon is present. In this complex system P2O5 acts to increase phase separation by further enrichment of the high charge density cations Ti, Fe, Mg, Mn, Ca, in the ferrobasaltic liquid. The dual behavior of P2O5 is explained in a model which requires complexing of phosphate anions and metal cations in the melt. This interaction destroys Si-O-M-O-Si bonds polymerizing the melt. The higher concentration of Si-O-M-O-Si bond complexes in immiscible ferrobasaltic liquids relative to their conjugate immiscible granite liquids explains the partitioning of P2O5 into the ferrobasaltic liquid.

Ryerson, F. J.↗

Materials Data on P2O5 by Materials Project

P2O5 crystallizes in the orthorhombic Pnma space group. The structure is two-dimensional and consists of two P2O5 sheets oriented in the (0, 0, 1) direction. there are two inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form corner-sharing PO4 tetrahedra. There are a spread of P–O bond distances ranging from 1.45–1.60 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form corner-sharing PO4 tetrahedra. There is one shorter (1.46 Å) and three longer (1.59 Å) P–O bond length. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 150 degrees geometry to two P5+ atoms. In the second O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the fourth O2- site, O2- is bonded in a bent 150 degrees geometry to two P5+ atoms.

36 MATERIALS SCIENCE↗

Cl, P2O5, U and Br associated with mineral separates from a low and a high Ti mare basalt

Low Ti basalt 12040 and high Ti basalt 75055 have approximately the same Cl/P2O5 ratio; the Cl is that remaining after a hot water leach. Pyroxene, plagioclase and ilmenite minerals separated from the basalts also tend to have this same Cl/P2O5 ratio. This is evidence that these major minerals do not control the ratio since Cl and P would not be expected to partition to the same extent into each mineral. Olivine appears to be a special case. It is proposed that the grains measured contained inclusions with leachable and P2O5-related Cl. Dilute acid leaches of whole rock and separated minerals have the same or nearly the same Cl/P2O5 ratios as the residual samples. Apatite and whitlockite were probably the phases leached. They must be constituents of the mesostasis and are present as microminerals or coatings on major mineral grains. The acid leach results imply little or no partition of Cl and P2O5 into major minerals.

Jovanovic, S.↗

Materials Data on P2O5 by Materials Project

P2O5 crystallizes in the orthorhombic Fdd2 space group. The structure is three-dimensional. P5+ is bonded to four O2- atoms to form corner-sharing PO4 tetrahedra. There are a spread of P–O bond distances ranging from 1.46–1.61 Å. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the second O2- site, O2- is bonded in a bent 120 degrees geometry to two equivalent P5+ atoms. In the third O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two equivalent P5+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on P2O5 by Materials Project

P2O5 is Tungsten structured and crystallizes in the trigonal R3c space group. The structure is zero-dimensional and consists of six phosphoric anhydride molecules. there are two inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form corner-sharing PO4 tetrahedra. There is one shorter (1.45 Å) and three longer (1.62 Å) P–O bond length. In the second P5+ site, P5+ is bonded to four O2- atoms to form corner-sharing PO4 tetrahedra. There is one shorter (1.45 Å) and three longer (1.62 Å) P–O bond length. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 120 degrees geometry to two equivalent P5+ atoms. In the second O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the fourth O2- site, O2- is bonded in a bent 120 degrees geometry to two P5+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on P2O5 by Materials Project

P2O5 crystallizes in the orthorhombic Pmmm space group. The structure is three-dimensional. there are two inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to six O2- atoms to form corner-sharing PO6 octahedra. The corner-sharing octahedra tilt angles range from 0–54°. There are a spread of P–O bond distances ranging from 1.55–1.84 Å. In the second P5+ site, P5+ is bonded to six O2- atoms to form a mixture of corner and edge-sharing PO6 octahedra. The corner-sharing octahedra tilt angles range from 0–54°. There is two shorter (1.63 Å) and four longer (1.91 Å) P–O bond length. There are five inequivalent O2- sites. In the first O2- site, O2- is bonded in a trigonal planar geometry to three P5+ atoms. In the second O2- site, O2- is bonded in a linear geometry to two equivalent P5+ atoms. In the third O2- site, O2- is bonded in a trigonal planar geometry to three P5+ atoms. In the fourth O2- site, O2- is bonded in a linear geometry to two equivalent P5+ atoms. In the fifth O2- site, O2- is bonded in a linear geometry to two equivalent P5+ atoms.

36 MATERIALS SCIENCE↗

Electrical resistivity surface for FeO-Fe2O3-P2O5 glasses

The dc electrical properties and microstructure of x(FeO-Fe2O3)-(100-x)P2O5 glasses were investigated up to a maximum of x = 75 mol %. Results indicate that, in general, the minimum resistivity of the glass does not occur at equal Fe(2+) and Fe(3+) concentrations, although for the special case where x = 55 mol % the minimum does occur at Fe(2+)/Fe total = 0.5, as reported by other investigators. Evidence presented shows that the position of the minimum resistivity is a function of total iron content. The minimum shifts to glasses richer in Fe(2+) at higher total iron concentrations.

Vaughan, J. G.↗

Partitioning of Nb, Mo, Ba, Ce, Pb, Th and U between immiscible carbonate and silicate liquids: Evaluating the effects of P2O5,F, and carbonate composition

Previously we have reported carbonate liq./silicate liq. partition coefficients (D) for a standard suite of trace elements (Nb, Mo, Ba, Ce, Pb, Th, and U) and Ra and Pa as well. In brief, we have found that immiscible liquid partitioning is a strong function of temperature. As the critical temperature of the carbonate-silicate solvus is approached, all partition coefficients approach unity. Additionally, for the overwhelming majority of the partitioning elements, InD is a linear function of 'ionic field strength,' z/r, where z is the charge of the partitioned cation and r is its ionic radius.

Jones, J. H.↗

Phosphorus Equilibria Among Mafic Silicate Phases

Phosphorus incorporation in major rock-forming silicate minerals has the following implications: (1) Reactions between phosphorus-hosting major silicates and accessory phosphates, which are also major trace element carriers, may control the stability of the latter and thus may affect the amount of phosphorus and other trace elements released to the coexisting melt or fluid phase. (2) Less of a phosphate mineral is needed to account for the bulk phosphorus of planetaty mantles. (3) During partial melting of mantle mineral assemblages or equilibrium fractional crystallization of basaltic magmas, and in the absence or prior to saturation with a phosphate mineral, silicate melts may become enriched in phosphorus, especially in the geochemically important low melt fraction regime, Although the small differences in the ionic radii of IVp5+, IVSi4+, and IV Al3+ makes phosphoms incorporation into crystalline silicates perhaps unsurprising, isostructural silicate and phosphate crystalline solids do not readily form solutions, e.g., (Fe, Mg)2SiO4 vs. LiMgPO4, SiO)2 VS. AlPO4. Nonetheless, there are reports of, poorly characterized silico-phosphate phases in angrites , 2-4 wt% P2O5 in olivine and pyroxene grains in pallasites and reduced terestrial basalts which are little understood but potentially useful, and up to 17 wt% P2O5 in olivine from ancient slags. However, such enrichments are rare and only underscore the likelihood of phosphoms incorporation in silicate minerals. The mechanisms that allow phosphorus to enter major rock-forming silicate minerals (e.g., Oliv, Px, Gt) remain little understood and the relevant data base is limited. Nonetheless, old and new high-pressure (5-10 GPa) experimental data suggest that P2O5 wt% decreases from silica-poor to silica-rich compositions or from orthosilicate to chain silicate structures (garnet > olivine > orthopyroxene) which implies that phosphorus incorporation in silicates is perhaps more structure-than site-specific. The data also indicate that DXVliQP2O5 decrease in the same order, but DOVLiQP2O5 and DOpx/LiQP205 are likely constant, respectively equal to 0.08(3) and 0.007(4), in contrast, DG1ILiQP205 increases from 0.15(3) to 0.36(10) as garnet becomes majoritic, thus silica-enriched, and may also depend on liquid composition (SiO2, P2O5 and Na2O wt%).

Berlin, Jana↗

Importance of Sulfur for Phosphorus Mobility on the Martian Surface

Sulfur and phosphorus were mobile on the martian surface, and we present evidence that sulfate was likely a control on phosphate mobility. Mobility of the two elements on the martian surface is crucial for the habitability of Mars because their availability for biochemical reactions and biological structures is a major constraint on life. In the sedimentary rocks of Gale crater, the rover Curiosity has discovered evidence of mobile S and P with the alpha particle X-ray spectrometer (APXS). Sulfur-rich fluids are evident in ubiquitous Ca-sulfate veins that crosscut the bedrock. Compelling evidence of P mobility is in nodules, veins, crusts, and haloes with P2O5 enrichments (1.5-7.5 wt%) relative to the median bedrock (0.9-1.2 wt%) and average basaltic crust (~0.9 wt%). We have investigated phosphorus mobility in Hawaiian analogues, where the primary P2O5 (0.2-2.1 wt%) is contained in Ca-apatite. Four relevant processes have emerged: (1) In open-system, circumneutral regolith weathering profiles, we found up to 40% of the P was leached over 10s-100s ka. (2) Natural acid-sulfate alteration at the Maunakea summit resulted in the dissolution of apatite and mobilization of phosphate 10s-1000s µm to rock surfaces where it formed Al-phosphates and substituted into crystalline sulfates (alunite and jarosite). (3) Experimental results indicate that basaltic sediment chemisorbs phosphate (pH < 7). (4) In experimental systems containing water, basaltic sediment, and a starting pH = 2-7, phosphate has higher solubility in chloride-rich fluids, but significantly lower solubility in sulfate-rich fluids. For example, in water doped with phosphate (~100-500 mg/L), ~60-80% of the PO43- was removed from the sulfate-rich fluid, whereas ~20% of the PO43- was removed from the Cl-rich and pure water fluids (likely via adsorption). Gypsum precipitated from the sulfate-rich fluids; the fate of phosphate in the solid residue is unconfirmed. The potential for phosphate incorporation in martian sulfates is reflected in the enrichment of P2O5 in Gale Ca-sulfate veins, based on preliminary analyses of APXS data. Models for the mobility of phosphorus in Gale crater should consider these conflicting P characteristics: (1) P solubility may have been inhibited by sulfate and (2) P¬ is enriched in diagenetic features and was therefore mobile.

Jeff A. Berger↗

Convection cells in the early lunar magma ocean - Trace-element evidence

A method was proposed for recognizing suites of samples which are related to the differentiation of distinct and regionally separated magmas in the early lunar surface ocean. The sample suites were identified by three Cl-P2O5 compositional groups. New experimental data continue to add samples to these groups. Each magma was associated with a convection cell the boundaries of which are proposed. Independent geochemical evidence supporting a limited number of early magmas is cited. Two new possible Cl-P2O5 groups are identified. Samples not indigenous to a given site and their possible source regions are identified. It is proposed that many Apollo 17 basalts are not locally derived.

Jovanovic, S.↗

The significance of Cl/P2O5 ratios from lunar samples

The Cl(r)/P2O5 ratios of lunar samples are reported to occur in three groups (Jovanovic and Reed, 1975; etc.). These data have been modeled as representative of three discrete volumes of differentiating magma and correlated with large convection cells and moon-wide heterogeneities. The assumptions inherent to their model are not valid. That the Cl(r)/P2O5 ratio of apatite or a rock is indicative of a magma system is unrealistic. A range of ratios can be generated during the fractionation of a magma. Apatite is not the major Cl- and P-bearing phase in most of the samples analyzed; rust, FeO(OH, Cl) and schreibersite, (FeNi)3P, occur in over 2/3 rds of the Apollo 16 rocks where they constitute 0.1-0.6 modal %, enough to account for most of the Cl(r) and P2O5 analyzed. Due to the complexities and presence of these minerals in soils and breccias, Cl(r)/P2O5 ratios have no real significance in non-igneous samples. However, basaltic rocks alone do not define any statistically significant Cl(r)P2O5 groupings.

Taylor, L. A.↗

Achondrite ALHA77005 - Alteration of chromite and olivine

The olivine crystals of the 77005 achondrite are brown except for colorless shock lamellae, mottled patches, and grains adjacent to pools of impact melt. Sporadic dark alteration patches in brown olivine and Cr-rich spinel gave the following average electron-microprobe analyses: (olivine) P2O5 0.9, SiO2 57.9, TiO2 0, Al2O3 0.7, Cr2O3 0.4, V2O3 0, Fe2O3 (assumed oxidation state) 17.0, MgO 1.6, CaO 0.2, Na2O 0, K2O 1.8, SO3 (assumed oxidation state) 9.2, Cl 0.1, sum 89.8 wt pct; (spinel) P2O5 3.5, SiO2 2.1, TiO2 2.2, Al2O3 2.1, Cr2O3 13.4, V2O3 0.8, Fe2O3 40.7, MgO 0.9, CaO 0.1, Na2O 0, K2O 2.0, SO3 11.1, Cl 0.1, sum 79.0 wt pct. Ion-microprobe analyses revealed H in both. Rare orange patches in brown olivine from another area gave SiO2 33-35, FeO 30-28, MgO 28-32, sum 93 wt pct. Thermal metamorphism under dry oxidizing conditions is discussed as a possible alternative to shock-induced oxidation for generation of the brown olivine (McSween and Stoeffler, 1980). Because alteration patches transgress shock lamellae, and because sulfatic alteration occurs in fusion crusts of Antarctic meteorites (Gibson et al., 1983), alteration of the 77005 achondrite at the Antarctic surface is preferred to a complex series of processes needed for preterrestrial alteration.

Smith, J. V.↗

Dependence of the critical cooling rate for lithium-silicate glass on nucleating agents

The critical cooling rate, Rc, for glass formation of a glass containing 40 mol pct Li2O and 60 mol pct SiO2, doped with small amounts of Pt, Au, P2O5, and TiO2 nucleating agents, has been measured. Rc increases with increasing Pt and Au additions, but Pt has a larger effect than Au. Additions of P2O5 tend to decrease Rc, whereas TiO2 has practically no effect on Rc. The devitrified glass nucleated with Pt contains only crystalline Li2O-SiO2, but all the other devitrified glasses, including the undoped glass, contain both Li2O-SiO2 and Li2O-2SiO2. Analysis shows that Rc increases as the concentration of the Li2O-SiO2 phase in the devitrified glass increases.

Huang, W.↗

Developments in Processing Criteria for Iron Phosphate Waste Form Design for Treating Electrorefiner Salt Wastes

This report describes work done under a Nuclear Energy University Partnership (NEUP) project that included a collaborative effort between Pacific Northwest National laboratory, University of Nevada Reno, University to Utah, and Missouri University of Science and Technology. In this project, the main goals were the following: (1) to assess H3PO4 dechlorination parameters for halide removal from salt simulants, (2) to evaluate crucible compatibility with iron phosphate glass melts, and (3) to evaluate waste form properties within a ternary system of P2O5 (added as H3PO4), Fe2O3 and fission product simulants.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A dunite-norite lunar microbreccia.

An olivine-rich microbreccia with noritic affinities, collected on the Apollo 14 mission to Fra Mauro, is described and analyzed. A photomicrograph (by plain transmitted light) of the microbreccia is discussed. One of three distinct areas on the microbreccia is shown to be a dunite containing over 90% olivine. The other two are more gabbroic in composition, though most of the mineral clasts are olivine. The fine grained matrix material contains significant amounts of K2O and P2O5, suggesting a relation to norites.

Taylor, G. J.↗

Effects of vaporization and condensation on Apollo 11 glass spherules - Implications for cooling rates.

Fourteen of 40 glass spherules present in a section of the Apollo 11 microbreccia 10019,22 were found to exhibit steep concentration gradients at their rims; the oxides of the relatively volatile elements Na, K, and P increase by, respectively, factors of up to 67, 16, and greater than 54 at the spherule rims in comparison to the homogeneous centers. These gradients usually extend over 25-30 microns. Furthermore, the natural surfaces of 11 unpolished glass spherules separated from the fines 10084,97, in 60-80% of all cases, show higher concentrations in Na2O, K2O, and P2O5 than the averages for the central portions of 45 independently analyzed glass spherules. It is suggested that the concentration gradients observed are diffusion gradients and are the result of the impact event which produced the glasses; in the impact melting process, splash drops of melt formed that lost volatiles by vaporization. A procedure is described to determine the cooling rate of a spherule from measured concentration gradients, provided the diffusion coefficients are known for the particular glass compositions in question.

Kurat, G.↗

Ecology and thermal inactivation of microbes in and on interplanetary space vehicle components

The thermal inactivation curve for Bacillus subtilis var. niger spores on the Viking lander is examined. Tests were conducted at 113 C and 25% RH, and over a wide range of temperatures using .001% RH and additions of P2O5 to dry the environment. Results show the 25% RH environment did not significantly reduce the survival curve, while the survival curves for spores treated under the drier .001% RH environment was reduced by a factor of 3.

Campbell, J. E.↗