Removal of nitrate and phosphate using chitosan/Al2O3/Fe3O4 composite nanofibrous adsorbent: Comparison with chitosan/Al2O3/Fe3O4 beads.

PubMed

Bozorgpour, Farahnaz; Ramandi, Hossein Fasih; Jafari, Pooya; Samadi, Saman; Yazd, Shabnam Sharif; Aliabadi, Majid

2016-12-01

In the present study the chitosan/Al 2 O 3 /Fe 3 O 4 composite nanofibrous adsorbent was prepared by electrospinning process and its application for the removal of nitrate and phosphate were compared with chitosan/Al 2 O 3 /Fe 3 O 4 composite bead adsorbent. The influence of Al 2 O 3 /Fe 3 O 4 composite content, pH, contact time, nitrate and phosphate initial concentrations and temperature on the nitrate and phosphate sorption using synthesized bead and nanofibrous adsorbents was investigated in a single system. The reusability of chitosan/Al 2 O 3 /Fe 3 O 4 composite beads and nanofibers after five sorption-desorption cycles were carried out. The Box-Behnken design was used to investigate the interaction effects of adsorbent dosage, nitrate and phosphate initial concentrations on the nitrate and phosphate removal efficiency. The pseudo-second-order kinetic model and known Freundlich and Langmuir isotherm models were used to describe the kinetic and equilibrium data of nitrate and phosphate sorption using chitosan/Al 2 O 3 /Fe 3 O 4 composite beads and nanofibers. The influence of other anions including chloride, fluoride and sulphate on the sorption efficiency of nitrate and phosphate was examined. The obtained results revealed the higher potential of chitosan/Al 2 O 3 /Fe 3 O 4 composite nanofibers for nitrate and phosphate compared with chitosan/Al 2 O 3 /Fe 3 O 4 composite beads. Copyright © 2016 Elsevier B.V. All rights reserved.

Cathodoluminescence of rare earth implanted Ga2O3 and GeO2 nanostructures.

PubMed

Nogales, E; Hidalgo, P; Lorenz, K; Méndez, B; Piqueras, J; Alves, E

2011-07-15

Rare earth (RE) doped gallium oxide and germanium oxide micro- and nanostructures, mostly nanowires, have been obtained and their morphological and optical properties have been characterized. Undoped oxide micro- and nanostructures were grown by a thermal evaporation method and were subsequently doped with gadolinium or europium ions by ion implantation. No significant changes in the morphologies of the nanostructures were observed after ion implantation and thermal annealing. The luminescence emission properties have been studied with cathodoluminescence (CL) in a scanning electron microscope (SEM). Both β-Ga(2)O(3) and GeO(2) structures implanted with Eu show the characteristic red luminescence peak centered at around 610 nm, due to the (5)D(0)-(7)F(2) Eu(3+) intraionic transition. Sharpening of the luminescence peaks after thermal annealing is observed in Eu implanted β-Ga(2)O(3), which is assigned to the lattice recovery. Gd(3+) as-implanted samples do not show rare earth related luminescence. After annealing, optical activation of Gd(3+) is obtained in both matrices and a sharp ultraviolet peak centered at around 315 nm, associated with the Gd(3+) (6)P(7/2)-(8)S(7/2) intraionic transition, is observed. The influence of the Gd ion implantation and the annealing temperature on the gallium oxide broad intrinsic defect band has been analyzed.

Metal sulfide and rare-earth phosphate nanostructures and methods of making same

DOEpatents

Wong, Stanislaus; Zhang, Fen

2016-06-28

The present invention provides a method of producing a crystalline rare earth phosphate nanostructure. The method comprising: providing a rare earth metal precursor solution and providing a phosphate precursor solution; placing a porous membrane between the metal precursor solution and the phosphate precursor solution, wherein metal cations of the metal precursor solution and phosphate ions of the phosphate precursor solution react, thereby producing a crystalline rare earth metal phosphate nanostructure.

A vibrational spectroscopic study of the silicate mineral lomonosovite Na5Ti2(Si2O7)(PO4)O2

NASA Astrophysics Data System (ADS)

Frost, Ray L.; López, Andrés; Theiss, Frederick L.; Graça, Leonardo M.; Scholz, Ricardo

2015-01-01

The mineral lomonosovite has been studied using a combination of scanning electron microscopy with energy dispersive X-ray analysis and vibrational spectroscopy. Qualitative chemical analysis gave Si, P, Na and Ti as the as major elements with small amounts of Mn, Ca, Fe and Al. The mineral lomonosovite has a formula Na5Ti2(Si2O7)(PO4)O2. Raman bands observed at 909, 925 and 939 cm-1 are associated with phosphate units. Raman bands found at 975, 999, 1070, 1080 and 1084 cm-1 are attributed to siloxane stretching vibrations. The observation of multiple bands in both the phosphate stretching and bending regions supports the concept that the symmetry of the phosphate anion in the structure of lomonosovite is significantly reduced. Infrared spectroscopy identifies bands in the water stretching and bending regions, thus suggesting that water is involved with the structure of lomonosovite either through adsorption on the surface or by bonding to the phosphate units.

Structural and Crystal Chemical Properties of Alkali Rare-earth Double Phosphates

DOE PAGES

Farmer, James Matthew; Boatner, Lynn A.; Chakoumakos, Bryan C.; ...

2016-01-01

When appropriately activated, alkali rare-earth double phosphates of the form: M 3RE(PO 4) 2 (where M denotes an alkali metal and RE represents either a rare-earth element or Y or Sc) are of interest for use as inorganic scintillators for radiation detection at relatively long optical emission wavelengths. These compounds exhibit layered crystal structures whose symmetry properties depend on the relative sizes of the rare-earth and alkali-metal cations. Single-crystal X-ray and powder neutron diffraction methods were used here to refine the structures of the series of rare-earth double phosphate compounds: K 3RE(PO 4) 2 with RE = Lu, Er, Ho,more » Dy, Gd, Nd, Ce, plus Y and Sc - as well as the compounds: A 3Lu(PO 4) 2, with A = Rb, and Cs. The double phosphate K 3Lu(PO 4) 2 was reported and structurally refined previously. This material had a hexagonal unit cell at room temperature with the Lu ion six-fold coordinated with oxygen atoms of the surrounding phosphate groups. Additionally two lower-temperature phases were observed for K 3Lu(PO 4) 2. The first phase transition to a monoclinic P21/m phase occurred at ~230 K, and the Lu ion retained its six-fold coordination. The second K 3Lu(PO 4) 2 phase transition occurred at ~130 K. The P21/m space group symmetry was retained, however, one of the phosphate groups rotated to increase the oxygen coordination number of Lu from six to seven. This structure then became isostructural with the room-temperature form of the compound K 3Yb(PO 4) 2 reported here that also exhibits an additional high-temperature phase which occurs at T = 120 °C with a transformation to hexagonal P-3 space group symmetry and a Yb-ion coordination number reduction from seven to six. This latter result was confirmed using EXAFS. The single-crystal growth methods structural systematics, and thermal expansion properties of the present series of alkali rare-earth double phosphates, as determined by X-ray and neutron diffraction methods, are treated

Structural and Crystal Chemical Properties of Alkali Rare-earth Double Phosphates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farmer, James Matthew; Boatner, Lynn A.; Chakoumakos, Bryan C.

When appropriately activated, alkali rare-earth double phosphates of the form: M 3RE(PO 4) 2 (where M denotes an alkali metal and RE represents either a rare-earth element or Y or Sc) are of interest for use as inorganic scintillators for radiation detection at relatively long optical emission wavelengths. These compounds exhibit layered crystal structures whose symmetry properties depend on the relative sizes of the rare-earth and alkali-metal cations. Single-crystal X-ray and powder neutron diffraction methods were used here to refine the structures of the series of rare-earth double phosphate compounds: K 3RE(PO 4) 2 with RE = Lu, Er, Ho,more » Dy, Gd, Nd, Ce, plus Y and Sc - as well as the compounds: A 3Lu(PO 4) 2, with A = Rb, and Cs. The double phosphate K 3Lu(PO 4) 2 was reported and structurally refined previously. This material had a hexagonal unit cell at room temperature with the Lu ion six-fold coordinated with oxygen atoms of the surrounding phosphate groups. Additionally two lower-temperature phases were observed for K 3Lu(PO 4) 2. The first phase transition to a monoclinic P21/m phase occurred at ~230 K, and the Lu ion retained its six-fold coordination. The second K 3Lu(PO 4) 2 phase transition occurred at ~130 K. The P21/m space group symmetry was retained, however, one of the phosphate groups rotated to increase the oxygen coordination number of Lu from six to seven. This structure then became isostructural with the room-temperature form of the compound K 3Yb(PO 4) 2 reported here that also exhibits an additional high-temperature phase which occurs at T = 120 °C with a transformation to hexagonal P-3 space group symmetry and a Yb-ion coordination number reduction from seven to six. This latter result was confirmed using EXAFS. The single-crystal growth methods structural systematics, and thermal expansion properties of the present series of alkali rare-earth double phosphates, as determined by X-ray and neutron diffraction methods, are treated

Methods for preparation of nanocrystalline rare earth phosphates for lighting applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Comanzo, Holly Ann; Manoharan, Mohan; Martins Loureiro, Sergio Paulo

Disclosed here are methods for the preparation of optionally activated nanocrystalline rare earth phosphates. The optionally activated nanocrystalline rare earth phosphates may be used as one or more of quantum-splitting phosphor, visible-light emitting phosphor, vacuum-UV absorbing phosphor, and UV-emitting phosphor. Also disclosed herein are discharge lamps comprising the optionally activated nanocrystalline rare earth phosphates provided by these methods.

Synergistic effect of PANI-ZrO2 composite as antibacterial, anti-corrosion, and phosphate adsorbent material: synthesis, characterization and applications.

PubMed

Masim, Frances Camille P; Tsai, Cheng-Hsien; Lin, Yi-Feng; Fu, Ming-Lai; Liu, Minghua; Kang, Fei; Wang, Ya-Fen

2017-11-03

The increasing number of bacteria-related problems and presence of trace amounts of phosphate in treated wastewater effluents have become a growing concern in environmental research. The use of antibacterial agents and phosphate adsorbents for the treatment of wastewater effluents is of great importance. In this study, the potential applications of a synthesized polyaniline (PANI)-zirconium dioxide (ZrO 2 ) composite as an antibacterial, phosphate adsorbent and anti-corrosion material were systematically investigated. The results of an antibacterial test reveal an effective area of inhibition of 14 and 18 mm for the Escherichia coli and Staphylococcus aureus bacterial strains, respectively. The antibacterial efficiency of the PANI-ZrO 2 composite is twice that of commercial ZrO 2 . In particular, the introduction of PANI increased the specific surface area and roughness of the composite material, which was beneficial to increase the contact area with bacterial and phosphate. The experimental results demonstrated that phosphate adsorption studies using 200 mg P/L phosphate solution showed a significant phosphate removal efficiency of 64.4%, and the maximum adsorption capacity of phosphate on the solid surface of PANI-ZrO 2 is 32.4 mg P/g. Furthermore, PANI-ZrO 2 coated on iron substrate was tested for anti-corrosion studies by a natural salt spray test (7.5% NaCl), which resulted in the formation of no rust. To the best of our knowledge, no works have been reported on the synergistic effects of the PANI-ZrO 2 composite as an antibacterial, anti-corrosion, and phosphate adsorbent material. PANI-ZrO 2 composite is expected to be a promising comprehensive treatment method for water filters in the aquaculture industry and for use in water purification applications.

Theoretical Studies of the Spin Hamiltonian Parameters and Local Distortions for Cu2+ in Alkaline Earth Lead Zinc Phosphate Glasses

NASA Astrophysics Data System (ADS)

Wang, Bo-Kun; Wu, Shao-Yi; Yuan, Zi-Yi; Liu, Zi-Xuan; Jiang, Shi-Xin; Liu, Zheng; Yao, Zi-Jian; Teng, Bao-Hua; Wu, Ming-He

2016-08-01

The spin Hamiltonian parameters and local structures are theoretically studied for Cu2+-doped alkaline earth lead zinc phosphate (RPPZ, R=Mg, Ca, Sr, and Ba) glasses based on the high-order perturbation calculations for a tetragonally elongated octahedral 3d9 cluster. The relative elongation ratios are found to be ρ≈3.2%, 4.4%, 4.6%, and 3.3% for R=Mg, Ca, Sr, and Ba, respectively, because of the Jahn-Teller effect. The whole decreasing crystal-field strength Dq and orbital reduction factor k from Mg to Sr are ascribed to the weakening electrostatic coulombic interactions and the increasing probability of productivity of nonbridge oxygen (and hence increasing Cu2+-O2- electron cloud admixtures) under PbO addition, respectively, with increasing alkali earth ionic radius. The anomalies (the largest Dq and the next highest k among the systems) for R=Ba are attributed to the cross linkage of this large cation in the network. The overall increasing order (Mg≤Ba2+-O2- bonds. The present studies would be helpful to understand local structures and the influences on the optical properties of RPPZ glasses containing copper dopants.

Effect of rare-earth ion size on local electron structure in RBa 2Cu 3O 7- δ (R = Tm, Dy, Gd, Eu, Nd and Y) superconductors: A positron study

NASA Astrophysics Data System (ADS)

Chen, Zhenping; Zhang, Jincang; Su, Yuling; Xue, Yuncai; Cao, Shixun

2006-02-01

The effects of rare-earth ionic size on the local electron structure, lattice parameters and superconductivity have been investigated by positron annihilation technique (PAT) and related experiments for RBa 2Cu 3O 7- δ (R = Tm, Dy, Gd, Eu, Nd and Y) superconductors. The local electron density ne is evaluated as a function of the rare-earth radius. The results show that both the bulk-lifetime τB and the defect lifetime τ2 increase with increasing rare-earth ionic radius, while the local electron density ne decrease with increasing rare-earth ionic radius. These results prove that the changes of ne, the degree of orthorhombic distortion and the coupling between the Cu-O chains and the CuO 2 planes all have an effect on the superconductivity of RBa 2Cu 3O 7- δ systems.

Crystal structure and ion conductivity of a new mixed-anion phosphate LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Sung-Chul; Lee, Mi-Sun; Kang, Jinyeong

2015-05-15

A new lithium-containing phosphate, LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7}, was prepared by a solid-state reaction, and it was characterized by an ab initio structure determination method on the basis of synchrotron powder X-ray diffraction data. LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7} was found to be orthorhombic (space group Pnma) with lattice parameters a=9.0387(1) Å, b=10.6072(1) Å, c=8.3065(1) Å, and V=796.39(1) Å{sup 3}. The structure features infinite [Mg{sub 3}O{sub 10}]{sub ∞} layers that are parallel to the bc plane and that are interconnected along the a axis by PO{sub 4} and P{sub 2}O{sub 7} groups. The [Mg{sub 3}O{sub 10}]{sub ∞} layer containsmore » Mg{sub 3}O{sub 14} trimers that are formed by three edge-shared MgO{sub 6} octahedra. The PO{sub 4} and P{sub 2}O{sub 7} groups are located alternatively between [Mg{sub 3}O{sub 10}]{sub ∞} layers. This gives rise to a three-dimensional framework that contains large tunnels along the directions [1 0 0] and [0 1 0]; the Li{sup +} ions are stabilized in these tunnels. AC impedance spectroscopy shows that LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7} has an ionic conductivity of 3.40×10{sup −5} S cm{sup −1} at 769 K, with an activation energy of 1.17 eV. - Graphical abstract: Polyhedral view of LiMg3(PO4)P2O7. Li+ ions are represented by orange spheres, MgO6 groups by octahedra, and PO4 groups by tetrahedra. - Highlights: • New compound LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7} is reported. • The crystal structure is investigated by synchrotron XRD analysis. • The structure features [Mg{sub 3}O{sub 10}]{sub ∞} layers with interconnecting PO{sub 4} and P{sub 2}O{sub 7} groups. • Correlation between the crystal structure and ionic conductivity is discussed.« less

Effect of alkaline earth modifier on the optical and structural properties of Cu2+ doped phosphate glasses as a bandpass filter

NASA Astrophysics Data System (ADS)

Farouk, M.; Samir, A.; El Okr, M.

2018-02-01

Glasses of composition [16RO-3Al2O3sbnd 6CuOsbnd 20Na2Osbnd 55P2O5], where R is the alkaline earth (R = Mg, Ca, Sr and Ba mol. %), were prepared by conventional melt quenching technique. The glass samples were characterized by X-ray diffraction, infrared spectroscopy, and spectrophotometer. XRD patterns show no sharp peaks indicating the non-crystalline nature of the prepared glasses. The density and molar volume of the glass systems were determined in order to study their structures. These results revealed that addition of alkaline earth elements leads to the formation of non-bridging oxygens (NBOs) and expands (opens up) the structure. The infrared spectra were analyzed to quantify the present phosphate groups. The optical absorption spectra of Cu2+ ions show the characteristic broadband single of Cu2+ ions in octahedral symmetry. The band gap was estimated following two methodologies. The first method considers the band edge of the transmission, while the second approach relays on the estimated values of the optical constants. A decent agreement for the band gap values using the two methods was obtained.

In vitro bioactivity behavior of modified multicomponent borate glasses containing dopants of Ag2O, CuO, CeO2 or V2O5

NASA Astrophysics Data System (ADS)

Marzouk, M. A.; ElBatal, F. H.; Ghoneim, N. A.

2018-02-01

Some multi-component borate glasses containing dopants of Ag2O, CuO, CeO2 or V2O5 were prepared. Multi-characterization techniques were carried out to investigate their bioactivity, corrosion weight loss after immersion in phosphate solution. Controlled thermal heat-treatment by two-step technique was done to convert the prepared glasses to their corresponding glass-ceramic derivatives. X-ray diffraction analysis was performed to identify the crystalline phases formed by thermal treatment. Infrared absorption of glasses and glass-ceramics reveal vibrational bands due to combined main triangular and tetrahedral borate groups in their specific wavenumbers besides some sharing of phosphate group. After immersion in the phosphate solution, two extra characteristic peaks are generated indicating the bioactivity of the studied glasses and glass-ceramics through the formation of calcium phosphate (hydroxyapatite). X-ray diffraction data indicate the formation of crystalline phases which are variable with the introduced dopants. The main crystalline phase identified is calcium borate together with some other phases some of which contain phosphate ions. These data indicate that the presence of CaO and P2O5 initiates phase separation and subsequent crystallization of the parent and doped glasses. Weight loss data indicate that glass-ceramics are obviously durable than the parent glasses. SEM micrographs of glass-ceramics before immersion show multiconstituent crystalline phases due to the basic chemical composition consisting of multicomponent mixed alkali and alkaline earth oxides beside P2O5 and with the main B2O3 constituent. After immersion, the crystalline phases are identified to be more distinct in different shapes because of the multi-composition involved.

Earth's early O2 cycle suppressed by primitive continents

NASA Astrophysics Data System (ADS)

Smit, Matthijs A.; Mezger, Klaus

2017-10-01

Free oxygen began to accumulate in Earth's surface environments between 3.0 and 2.4 billion years ago. Links between oxygenation and changes in the composition of continental crust during this time are suspected, but have been difficult to demonstrate. Here we constrain the average composition of the exposed continental crust since 3.7 billion years ago by compiling records of the Cr/U ratio of terrigenous sediments. The resulting record is consistent with a predominantly mafic crust prior to 3.0 billion years ago, followed by a 500- to 700-million-year transition to a crust of modern andesitic composition. Olivine and other Mg-rich minerals in the mafic Archaean crust formed serpentine minerals upon hydration, continuously releasing O2-scavenging agents such as dihydrogen, hydrogen sulfide and methane to the environment. Temporally, the decline in mafic crust capable of such process coincides with the first accumulation of O2 in the oceans, and subsequently the atmosphere. We therefore suggest that Earth's early O2 cycle was ultimately limited by the composition of the exposed upper crust, and remained underdeveloped until modern andesitic continents emerged.

Theoretical study of the alkaline-earth metal superoxides BeO2 through SrO2

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Sodupe, Mariona; Langhoff, Stephen R.

1992-01-01

Three competing bonding mechanisms have been identified for the alkaline-earth metal superoxides: these result in a change in the optimal structure and ground state as the alkaline-earth metal becomes heavier. For example, BeO2 has a linear 3Sigma(-)g ground-state structure, whereas both CaO2 and SrO2 have C(2v)1A1 structures. For MgO2, the theoretical calculations are less definitive, as the 3A2 C(2v) structure is computed to lie only about 3 kcal/mol above the 3Sigma(-)g linear structure. The bond dissociation energies for the alkaline-earth metal superoxides have been computed using extensive Gaussian basis sets and treating electron correlation at the modified coupled-pair functional or coupled-cluster singles and doubles level with a perturbational estimate of the triple excitations.

Nanoscale mechanochemical wear of phosphate laser glass against a CeO2 particle in humid air

NASA Astrophysics Data System (ADS)

Yu, Jiaxin; He, Hongtu; Zhang, Yafeng; Hu, Hailong

2017-01-01

Using an atomic force microscope, the friction and wear of phosphate laser glass against a CeO2 particle were quantitatively studied both in humid air and in vacuum, to reveal the water molecules induced mechanochemical wear mechanism of phosphate laser glass. The friction coefficient of the glass/CeO2 pair in air was found to be 5-7 times higher than that in vacuum due to the formation of a capillary water bridge at the friction interface, with a contribution of the capillary-related friction to the total friction coefficient as high as 65-79%. The capillary water bridge further induced a serious material removal of glass and CeO2 particle surfaces, while supplying both a local liquid water environment to corrode the glass surface and a high shearing force to assist the stretching of the Cesbnd Osbnd P bond, accelerating the reaction between water and the glass/CeO2 pair. In vacuum, however, no discernable wear phenomena were observed, but the phase images captured by AFM tapping mode suggested the occurrence of potential strain hardening in the friction area of the glass surface.

Polymorphism in the Sc 2Si 2O 7-Y 2Si 2O 7 system

NASA Astrophysics Data System (ADS)

Escudero, Alberto; Alba, María D.; Becerro, Ana. I.

2007-04-01

This paper examines the structural changes with temperature and composition in the Sc 2Si 2O 7-Y 2Si 2O 7 system; members of this system are expected to form in the intergranular region of Si 3N 4 and SiC structural ceramics when sintered with the aid of Y 2O 3 and Sc 2O 3 mixtures. A set of different compositions have been synthesized using the sol-gel method to obtain a xerogel, which has been calcined at temperatures between 1300 and 1750 °C during different times. The temperature-composition diagram of the system, obtained from powder XRD data, is dominated by the β- RE2Si 2O 7 polymorph, with γ- RE2Si 2O 7 and δ- RE2Si 2O 7 showing very reduced stability fields. Isotherms at 1300 and 1600 °C have been analysed in detail to evaluate the solid solubility of the components. Although, the XRD data show a complete solid solubility of β-Sc 2Si 2O 7 in β-Y 2Si 2O 7 at 1300 °C, the 29Si MAS-NMR spectra indicate a local structural change at x ca. 1.15 (Sc 2-xY xSi 2O 7) related to the configuration of the Si tetrahedron, which does not affect the long-range order of the β- RE2Si 2O 7 structure. Finally, it is interesting to note that, although Sc 2Si 2O 7 shows a unique stable polymorph ( β), Sc 3+ is able to replace Y 3+ in γ-Y 2Si 2O 7 in the compositional range 1.86⩽ x⩽2 (where x is Sc 2-xY xSi 2O 7) as well as in δ-Y 2Si 2O 7 for compositions much closer to the pure Y 2Si 2O 7.

Increased transcription of the phosphate-specific transport system of Escherichia coli O157:H7 after exposure to sodium benzoate.

PubMed

Critzer, Faith J; D'Souza, Doris H; Saxton, Arnold M; Golden, David A

2010-05-01

Sodium benzoate is a widely used food antimicrobial in drinks and fruit juices. A microarray study was conducted to determine the transcriptional response of Escherichia coli O157:H7 to 0.5% (wt/vol) sodium benzoate. E. coli O157:H7 grown in 150 ml of Luria-Bertani broth was exposed to 0% (control) and 0.5% sodium benzoate. Each treatment was duplicated and sampled at 0 (immediately after exposure), 5, 15, 30, and 60 min. Total RNA was extracted and analyzed with E. coli 2.0 Gene Chips. Significant ontology categories affected by sodium benzoate exposure were determined with JProGO software. The phosphate-specific transport (Pst) system transports inorganic phosphate into bacterial cells, under phosphate-limited conditions. The Pst system was found to be highly upregulated. Increased expression of the Pst system was observed after the short 5 min of exposure to sodium benzoate; pstS, pstA, pstB, and pstC genes were upregulated more than twofold (linear scale) at 5, 15, 30, and 60 min. Increased expression of several other efflux systems, such as AcrAB-TolC, was also observed. The Pst system may act as an efflux pump under these stress-adapted conditions, as well as increase transport of phosphorus to aid in DNA, RNA, ATP, and phospholipid production. Understanding adaptations of Escherichia coli O157:H7 under antimicrobial exposure is essential to better understand and implement methods to inhibit or control its survival in foods.

Amorphous cobalt potassium phosphate microclusters as efficient photoelectrochemical water oxidation catalyst

NASA Astrophysics Data System (ADS)

Zhang, Ye; Zhao, Chunsong; Dai, Xuezeng; Lin, Hong; Cui, Bai; Li, Jianbao

2013-12-01

A novel amorphous cobalt potassium phosphate hydrate compound (KCoPO4·H2O) is identified to be active photocatalyst for oxygen evolution reaction (OER) to facilitate hydrogen generation from water photolysis. It has been synthesized through a facile and cost-effective solution-based precipitation method using earth-abundant materials. Its highly porous structure and large surface areas are found to be responsible for the excellent electrochemical performance featuring a low OER onset at ∼550 mVSCE and high current density in alkaline condition. Unlike traditional cobalt-based spinel oxides (Co3O4, NiCo2O4) and phosphate (Co-Pi, Co(PO3)2) electrocatalysts, with proper energy band alignment for light-assisted water oxidation, cobalt potassium phosphate hydrate also exhibits robust visible-light response, generating a photocurrent density of ∼200 μA cm-2 at 0.7 VSCE. This catalyst could thus be considered as a promising candidate to perform photoelectrochemical water splitting.

Isomorphous rare-earth tris[bis(2,6-diisopropylphenyl) phosphate] complexes and their catalytic properties in 1,3-diene polymerization and in the inhibited oxidation of polydimethylsiloxane.

PubMed

Minyaev, Mikhail E; Tavtorkin, Alexander N; Korchagina, Sof'ya A; Bondarenko, Galina N; Churakov, Andrei V; Nifant'ev, Ilya E

2018-05-01

Crystals of mononuclear tris[bis(2,6-diisopropylphenyl) phosphato-κO]pentakis(methanol-κO)lanthanide methanol monosolvates of lanthanum, [La(C 24 H 34 O 4 P) 3 (CH 3 OH) 5 ]·CH 3 OH, (1), cerium, [Ce(C 24 H 34 O 4 P) 3 (CH 3 OH) 5 ]·CH 3 OH, (2), and neodymium, [Nd(C 24 H 34 O 4 P) 3 (CH 3 OH) 5 ]·CH 3 OH, (3), have been obtained by reactions between LnCl 3 (H 2 O) n (n = 6 or 7) and lithium bis(2,6-diisopropylphenyl) phosphate in a 1:3 molar ratio in methanol media. Compounds (1)-(3) crystallize in the monoclinic P2 1 /c space group and have isomorphous crystal structures. All three bis(2,6-diisopropylphenyl) phosphate ligands display a κO-monodentate coordination mode. The coordination number of the metal atom is 8. Each [Ln{O 2 P(O-2,6- i Pr 2 C 6 H 3 ) 2 } 3 (CH 3 OH) 5 ] molecular unit exhibits four intramolecular O-H...O hydrogen bonds, forming six-membered rings. The unit forms two intermolecular O-H...O hydrogen bonds with one noncoordinating methanol molecule. All six hydroxy H atoms are involved in hydrogen bonding within the [Ln{O 2 P(O-2,6- i Pr 2 C 6 H 3 ) 2 } 3 (CH 3 OH) 5 ]·CH 3 OH unit. This, along with the high steric hindrance induced by the three bulky diaryl phosphate ligands, prevents the formation of a hydrogen-bond network. Complexes (1)-(3) exhibit disorder of two of the isopropyl groups of the phosphate ligands. The cerium compound (2) demonstrates an essential catalytic inhibition in the thermal decomposition of polydimethylsiloxane in air at 573 K. Catalytic systems based on the neodymium complex tris[bis(2,6-diisopropylphenyl) phosphato-κO]neodymium, (3'), which was obtained as a dry powder of (3) upon removal of methanol, display a high catalytic activity in isoprene and butadiene polymerization.

Hydrothermal Syntheses and Structures of Three-Dimensional Oxo-fluorovanadium Phosphates: [H 2N(C 2H 4) 2NH 2] 0.5[(VO) 4V(HPO 4) 2(PO 4) 2F 2(H 2O) 4] · 2H 2O and K 2[(VO) 3(PO 4) 2F 2(H 2O)] · H 2O

NASA Astrophysics Data System (ADS)

Bonavia, Grant; Haushalter, R. C.; Zubieta, Jon

1996-11-01

The hydrothermal reactions of FPO3H2with vanadium oxides result in the incorporation of fluoride into V-P-O frameworks as a consequence of metal-mediated hydrolysis of the fluorophosphoric acid to produce F-and PO3-4. By exploiting this convenient source of F-, two 3-dimensional oxo-fluorovanadium phosphate phases were isolated, [H2N(C2H4)2NH2]0.5[(VO)4V(HOP4)2(PO4)2F2(H2O)4) · 2H2O (1 · 2H2O) and K2[(VO)3(PO4)2F2(H2O)] · H2O (2 · H2O). Both anionic frameworks contain (VIVO)-F--phosphate layers, with confacial bioctahedral {(VIVO)2FO6} units as the fundamental motif. In the case of 1, the layers are linked through {VIIIO6} octahedra, while for 2 the interlayer connectivity is provided by edge-sharing {(VIVO)2F2O6} units. Crystal data are 1 · 2H2O, CH10FN0.5O13P2V2.5, monoclinicC2/m,a= 18.425(4) Å,c= 8.954(2) Å, β = 93.69(2)0,V= 1221.1(4) Å3,Z= 4,Dcalc= 2.423 g cm-3; 2 · H2O, H4F2K2O13P2V3, triclinicPoverline1,a= 7.298(1) Å,b= 8.929(2) Å,c = 10.090(2) Å, α = 104.50(2)0, β = 100.39(2)0, δ = 92.13(2)0,V= 623.8(3) Å3,Z= 2,Dcalc= 2.891 g cm-3.

Ultrafast phosphate hydration dynamics in bulk H{sub 2}O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Costard, Rene, E-mail: costard@mbi-berlin.de; Tyborski, Tobias; Fingerhut, Benjamin P., E-mail: fingerhut@mbi-berlin.de

2015-06-07

Phosphate vibrations serve as local probes of hydrogen bonding and structural fluctuations of hydration shells around ions. Interactions of H{sub 2}PO{sub 4}{sup −} ions and their aqueous environment are studied combining femtosecond 2D infrared spectroscopy, ab-initio calculations, and hybrid quantum-classical molecular dynamics (MD) simulations. Two-dimensional infrared spectra of the symmetric (ν{sub S}(PO{sub 2}{sup −})) and asymmetric (ν{sub AS}(PO{sub 2}{sup −})) PO{sub 2}{sup −} stretching vibrations display nearly homogeneous lineshapes and pronounced anharmonic couplings between the two modes and with the δ(P-(OH){sub 2}) bending modes. The frequency-time correlation function derived from the 2D spectra consists of a predominant 50 fs decaymore » and a weak constant component accounting for a residual inhomogeneous broadening. MD simulations show that the fluctuating electric field of the aqueous environment induces strong fluctuations of the ν{sub S}(PO{sub 2}{sup −}) and ν{sub AS}(PO{sub 2}{sup −}) transition frequencies with larger frequency excursions for ν{sub AS}(PO{sub 2}{sup −}). The calculated frequency-time correlation function is in good agreement with the experiment. The ν(PO{sub 2}{sup −}) frequencies are mainly determined by polarization contributions induced by electrostatic phosphate-water interactions. H{sub 2}PO{sub 4}{sup −}/H{sub 2}O cluster calculations reveal substantial frequency shifts and mode mixing with increasing hydration. Predicted phosphate-water hydrogen bond (HB) lifetimes have values on the order of 10 ps, substantially longer than water-water HB lifetimes. The ultrafast phosphate-water interactions observed here are in marked contrast to hydration dynamics of phospholipids where a quasi-static inhomogeneous broadening of phosphate vibrations suggests minor structural fluctuations of interfacial water.« less

Availability of O(2) and H(2)O(2) on pre-photosynthetic Earth.

PubMed

Haqq-Misra, Jacob; Kasting, James F; Lee, Sukyoung

2011-05-01

Old arguments that free O(2) must have been available at Earth's surface prior to the origin of photosynthesis have been revived by a new study that shows that aerobic respiration can occur at dissolved oxygen concentrations much lower than had previously been thought, perhaps as low as 0.05 nM, which corresponds to a partial pressure for O(2) of about 4 × 10(-8) bar. We used numerical models to study whether such O(2) concentrations might have been provided by atmospheric photochemistry. Results show that disproportionation of H(2)O(2) near the surface might have yielded enough O(2) to satisfy this constraint. Alternatively, poleward transport of O(2) from the equatorial stratosphere into the polar night region, followed by downward transport in the polar vortex, may have brought O(2) directly to the surface. Thus, our calculations indicate that this "early respiration" hypothesis might be physically reasonable.

Luminescence properties of Eu2+ in M2MgSi2O7 (M=Ca, Sr, and Ba) phosphors

NASA Astrophysics Data System (ADS)

Kim, T.; Kim, Y.; Kang, S.

2012-03-01

The photoluminescence properties of alkali-earth magnesium silicates (M2MgSi2O7, M=Ca, Sr, and Ba) doped with Eu2+ were investigated. Solid solutions of Ba x Sr2- x Si2O7, Ca2MgSi2O7, and Sr2MgSi2O7 were prepared. Ba x Sr2- x Si2O7 retained a tetragonal crystal structure similar to the structure of the other compounds up to a stoichiometry of x=1.6, which enabled a systematic study of the common structure. Monoclinic Ba2MgSi2O7 was prepared, and the luminescence properties were compared with those of other samples. The emission and excitation spectra of tetragonal M2MgSi2O7 (M=Ca, Sr, and Ba) changed as a function of the covalency, site symmetry, and crystal field strength. The luminescence properties showed excellent agreement with theoretical predictions based on these factors. The Stokes shift differentiated the emission behaviors of the tetragonal and monoclinic structures.

Extended X-ray Absorption Fine Structure (EXAFS) Analysis of Vitreous Rare Earth Sodium Phosphates

NASA Astrophysics Data System (ADS)

Yoo, Changhyeon; Marasinghe, Kanishka; Segre, Carlo; Shibata, Tomohiro

2015-03-01

The local structure around rare-earth ions (RE3+) in rare-earth ultraphosphate (REUP) glasses has been studied using RE LIII edge (RE = Nd, Er, Dy, and Eu) and K edge (RE = Nd, Pr, Dy, and Eu) extended X-ray absorption fine structure (EXAFS) spectroscopy. (RE2O3)x (Na2O)y(P2O5) 1 - x - y glasses in the compositional range 0 <= x <= 0.14 and x + y = 0.3 and 0.4 were studied. RE-oxygen (RE-O) coordination number decreases from ~ 10 to ~ 7.5 with increasing RE-content for Nd, Pr, Eu, and Dy. For Er, RE-O coordination number increases from ~ 8.7 to ~ 10 with increasing RE-content. For the first oxygen shell, the RE-O distance ranges between 2.41-2.43 Å, 2.44-2.46 Å, 2.24-2.26 Å, 2.28-2.32 Å, and 2.32-2.36 Å for Nd, Pr, Er, Dy, and EU glasses, respectively. Second shell around RE ions consists of phosphorus atoms, with RE-P distance about 3.0-3.5 Å and coordination number ranging from 1 to 3. The third shell primarily contains oxygen and is at a distance about 4.0-4.1 Å from RE ions.

Core-exsolved SiO2 Dispersal in the Earth's Mantle

NASA Astrophysics Data System (ADS)

Helffrich, G. R.; Ballmer, M.; Hirose, K.

2017-12-01

SiO2 may have been expelled from the core following its formation in the early stages of Earth's accretion and onwards through the present day. On account of SiO2's low density with respect to both the core and the lowermost mantle, we examine the process of SiO2 accumulation at the core-mantle boundary (CMB) and its incorporation into the mantle by buoyant rise. Today, the if SiO2 is 100-10000 times more viscous than lower mantle material, the dimensions of SiO2 diapirs formed by the viscous Rayleigh-Taylor instability at the CMB would cause them to be swept into the mantle as inclusions of 100 m - 10 km diameter. Under early Earth conditions of rapid heat loss after core formation, SiO2 diapirs of 5-80 km diameter could have risen independently of mantle flow to their level of neutral buoyancy in the mantle, trapping them there due to a combination of high viscosity and neutral buoyancy. We examine the SiO2 yield by assuming Si+O saturation at the conditions found at the base of a magma ocean and find that for a range of conditions, dispersed bodies could reach as high as 2 volume percent in shallow parts of the lower mantle, with their abundance decreasing with depth. At such low concentrations, their effect on aggregate seismic wavespeeds would be within the uncertainty of the radial Earth model PREM. However, their presence would be revealed by small-scale scattering in the lower mantle due to the bodies' large velocity contrast. We conclude that the shallow lower mantle (700-1500 km depth) could harbor SiO2 released in early Earth times.

New metal-organic frameworks of [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La, Ce) and [Ce2(C2O4)(C6H6O7)2] . 4H2O

NASA Astrophysics Data System (ADS)

Weng, Sheng-Feng; Wang, Yun-Hsin; Lee, Chi-Shen

2012-04-01

Two novel materials, [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La(1a), Ce(1b)) and [Ce2(C2O4)(C6H6O7)2] . 4H2O (2), with a metal-organic framework (MOF) were prepared with hydrothermal reactions and characterized with photoluminescence, magnetic susceptibility, thermogravimetric analysis and X-ray powder diffraction in situ. The crystal structures were determined by single-crystal X-ray diffraction. Compound 1 crystallized in triclinic space group P1¯ (No. 2); compound 2 crystallized in monoclinic space group P21/c (No. 14). The structure of 1 is built from a 1D MOF, composed of deprotonated citric ligands of three kinds. Compound 2 contains a 2D MOF structure consisting of citrate and oxalate ligands; the oxalate ligand arose from the decomposition in situ of citric acid in the presence of CuII ions. Photoluminescence spectra of compounds 1b and 2 revealed transitions between the 5d1 excited state and two levels of the 4f1 ground state (2F5/2 and 2F7/2). Compounds 1b and 2 containing CeIII ion exhibit a paramagnetic property with weak antiferromagnetic interactions between the two adjacent magnetic centers.

Atomic-Level Structure Studies of Rare-Earth Doped Sodium Phosphate Glasses Using High Energy X-Ray Diffraction and Complementary Techniques

NASA Astrophysics Data System (ADS)

Amir, Faisal

The atomic-scale structure of a series of (RE2 O3)x ( Na2O)y ( P2O5)1- x-y glasses (RE = Pr, Nd, Er) where has been characterized by high-energy X-ray diffraction technique (HEXRD). In addition, differential thermal analysis (DTA), Fourier transform infrared (FTIR) spectroscopy, and absorption and emission spectroscopy in visible and near IR ranges have been used as supplementary tools to validate structural features obtained from HEXRD techniques.Structural features such as inter-atomic distances and coordination numbers and their dependence on the concentration of RE 2 O3 have been obtained by analyzing pair distribution functions (PDF) extracted from diffraction data. Coordination numbers for P-O, Na-O, O-O, and P-P were found to be independent of the RE 2 O3 concentration. In contrast, the RE-O coordination number varies between ≈ 8 and 7.2 as the RE2 O3 concentration increases from 0.005 to 0.05. The variation of the bond distance between large rare-earth ions (Pr, Nd) and small rare-earth ion (Er) is approximately 0.2 A, which is attributed to lanthanide contraction. The Na-O coordination number in these glasses was observed to ≈ 5.0 as the RE2 O 3 content increases. The overlapping correlation of RE-O, Na-O, and O-O in the same vicinity makes it difficult to calculate these coordination numbers. DTA measurements were used for the investigation of thermal characteristics of glasses. From these measurements, it is evident that the glass transition temperature increases with increasing the RE2 O3 (RE=Pr, Er) content. FTIR was used to inspect the structural changes of the glasses. The doping of RE 2 O3 (RE=Pr, Er) induces depolymerization of the glasses at the Q3 tetrahedral sites. The forming of the ionic linkages between phosphate chains is attributed to the increase in non-bridging oxygen (NBO). The cross-linkages density (CLD) increases with the RE2 O3 (RE=Pr, Er) concentrations. Absorption spectra for x = 0.01 of Er 3+ and 0.005-0.05 for Nd3+ doped

The influence of SrO and CaO in silicate and phosphate bioactive glasses on human gingival fibroblasts.

PubMed

Massera, J; Kokkari, A; Närhi, T; Hupa, L

2015-06-01

In this paper, we investigate the effect of substituting SrO for CaO in silicate and phosphate bioactive glasses on the human gingival fibroblast activity. In both materials the presence of SrO led to the formation of a CaP layer with partial Sr substitution for Ca. The layer at the surface of the silicate glass consisted of HAP whereas at the phosphate glasses it was close to the DCPD composition. In silicate glasses, SrO gave a faster initial dissolution and a thinner reaction layer probably allowing for a continuous ion release into the solution. In phosphate glasses, SrO decreased the dissolution process and gave a more strongly bonded reaction layer. Overall, the SrO-containing silicate glass led to a slight enhancement in the activity of the gingival fibroblasts cells when compared to the SrO-free reference glass, S53P4. The cell activity decreased up to 3 days of culturing for all phosphate glasses containing SrO. Whereas culturing together with the SrO-free phosphate glass led to complete cell death at 7 days. The glasses containing SrO showed rapid cell proliferation and growth between 7 and 14 days, reaching similar activity than glass S53P4. The addition of SrO in both silicate and phosphate glasses was assumed beneficial for proliferation and growth of human gingival fibroblasts due to Sr incorporation in the reaction layer at the glass surface and released in the cell culture medium.

Three new d10 transition metal selenites containing PO4 tetrahedron: Cd7(HPO4)2(PO4)2(SeO3)2, Cd6(PO4)1.34(SeO3)4.66 and Zn3(HPO4)(SeO3)2(H2O)

NASA Astrophysics Data System (ADS)

Ma, Yun-Xiang; Gong, Ya-Ping; Hu, Chun-li; Mao, Jiang-Gao; Kong, Fang

2018-06-01

Three new d10 transition metal selenites containing PO4 tetrahedron, namely, Cd7(HPO4)2(PO4)2(SeO3)2 (1), Cd6(PO4)1.34(SeO3)4.66 (2) and Zn3(HPO4)(SeO3)2(H2O) (3), have been synthesized by hydrothermal reaction. They feature three different structural types. Compound 1 exhibits a novel 3D network composed of 3D cadmium selenite open framework with phosphate groups filled in the 1D helical tunnels. The structure of compound 2 displays a new 3D framework consisted of 2D cadmium oxide layers bridged by SeO3 and PO4 groups. Compound 3 is isostructural with the reported solids of Co3(SeO3)3-x(PO3OH)x(H2O) when x is equal to 1.0. Its structure could be viewed as a 3D zinc oxide open skeleton with SeO3 and HPO4 polyhedra attached on the wall of the tunnels. They represent the only examples in metal selenite phosphates in addition to the above cobalt compounds. Optical diffuse reflectance spectra revealed that these solids are insulators, which are consistent with the results of band structure computations based on DFT algorithm.

The effect of crystal structure of TiO2 nanotubes on the formation of calcium phosphate coatings during biomimetic deposition

NASA Astrophysics Data System (ADS)

Liu, Yi; Kim, Sun; McLeod, John A.; Li, Jun; Guo, Xiaoxuan; Sham, Tsun-Kong; Liu, Lijia

2017-02-01

The crystallization process of bioactive calcium phosphate (CaP) species via biomimetic deposition onto anodic TiO2 nanotubes is investigated. The porous surface of nanostructured TiO2 provides an ideal substrate for CaP crystallization. The compositions of CaP coatings are studied using X-ray absorption near-edge structures (XANES) at the Ca K-edge. Using detection modes with different probing depths, both the surface of the CaP coating and the CaP-TiO2 interface are simultaneously analyzed. Calcium phosphate (CaP) species, such as hydroxyapatite (HAp), octacalcium phosphate (Ca8(HPO4)2(PO4)4·5H2O, OCP), brushite (CaHPO4·2H2O, DCPD), and amorphous calcium phosphate (ACP), are found in the CaP coatings. TiO2 nanotubes of amorphous and anatase phases are comparatively studied to determine their effect on the efficiency of CaP formation and the phase transformation among CaP species in prolonged deposition time. It is found the composition of CaP coating has a strong dependency on the crystal structure of TiO2 substrate and the kinetics (deposition time).

Synthesis and optical properties of polycrystalline Li2Al2B2O7 (LABO)

NASA Astrophysics Data System (ADS)

Dagdale, S. R.; Muley, G. G.

2016-05-01

A polycrystalline lithium aluminum borate (Li2Al2B2O7, LABO) has been synthesized by using simple solid-state technique. The obtained LABO polycrystalline was characterized by powder X-ray diffraction; Fourier transform infrared (FT-IR) spectroscopy and second harmonic generation (SHG) efficiency measurement. The functional groups were identified using the FT-IR spectroscopic data. The SHG efficiency of the polycrystalline material was obtained by the classic Kurtz powder technique using a fundamental wavelength 1064 nm of Nd:YAG laser and it is found to be 1.4 times that of potassium dihydrogen phosphate (KDP).

Solid solubility of Yb 2Si 2O 7 in β-, γ- and δ-Y 2Si 2O 7

NASA Astrophysics Data System (ADS)

Fernández-Carrión, A. J.; Alba, M. D.; Escudero, A.; Becerro, A. I.

2011-07-01

This paper examines the structural changes with temperature and composition in the Yb 2Si 2O 7-Y 2Si 2O 7 system; members of this system are expected to form in the intergranular region of Si 3N 4 and SiC structural ceramics when sintered with the aid of Yb 2O 3 and Y 2O 3 mixtures. A set of different compositions have been synthesised using the sol-gel method to obtain a xerogel, which has been calcined at temperatures between 1300 and 1650 °C during different times. Isotherms at 1300 and 1600 °C have been analysed in detail to evaluate the solid solubility of Yb 2Si 2O 7 in β-Y 2Si 2O 7 and γ-Y 2Si 2O 7. Although Yb 2Si 2O 7 shows a unique stable polymorph (β), Yb 3+ is able to replace Y 3+ in γ-Y 2Si 2O 7 and δ-Y 2Si 2O 7 at high temperatures and low Yb contents. IR results confirm the total solid solubility in the system and suggest a constant SiOSi angle of 180° in the Si 2O 7 unit across the system. The temperature-composition diagram of the system, obtained from powder XRD data, is dominated by the β- RE2Si 2O 7 polymorph, with γ- RE2Si 2O 7 and δ- RE2Si 2O 7 showing reduced stability fields. The diagram is in accordance with Felsche's diagram if average ionic radii are assumed for the members of the solid solution at any temperature, as long as the β-γ phase boundary is slightly shifted towards higher radii.

Compositional dependence of bioactivity of glasses in the system Na2O-K2O-MgO-CaO-B2O3-P2O5-SiO2.

PubMed

Brink, M; Turunen, T; Happonen, R P; Yli-Urpo, A

1997-10-01

The bioactivity, i.e., bone-bonding ability, of 26 glasses in the system Na2O-K2O-MgO-CaO-B2O3-P2O5-SiO2 was studied in vivo. This investigation of bioactivity was performed to establish the compositional dependence of bioactivity, and enabled a model to be developed that describes the relation between reactions in vivo and glass composition. Reactions in vivo were investigated by inserting glass implants into rabbit tibia for 8 weeks. The glasses and the surrounding tissue were examined using scanning electron microscopy (SEM), light microscopy, and energy-dispersive X-ray analysis (EDXA). For most of the glasses containing < 59 mol % SiO2, SEM and EDXA showed two distinct layers at the glass surface after implantation, one silica-rich and another containing calcium phosphate. The build-up of these layers in vivo was taken as a sign of bioactivity. The in vivo experiments showed that glasses in the investigated system are bioactive when they contain 14-30 mol % alkali oxides, 14-30 mol % alkaline earth oxides, and < 59 mol % SiO2. Glasses containing potassium and magnesium bonded to bone in a similar way as bioactive glasses developed so far.

Computer modeling of lithium phosphate and thiophosphate electrolyte materials

NASA Astrophysics Data System (ADS)

Holzwarth, N. A. W.; Lepley, N. D.; Du, Yaojun A.

In this work, several lithium phosphate and thiophosphate materials are modeled to determine their optimized lattice structures, their total energies, and their electronic structures. Included in this study are materials characterized by isolated phosphate and thiophosphate groups - Li 3PS 4 and Li 3PO 4 and materials characterized by phosphate and thiophosphate dimers - Li 4P 2S 6 and Li 4P 2O 6 and Li 4P 2S 7 and Li 4P 2O 7. In addition, the superionic conducting material Li 7P 3S 11 is also modeled as are recently discovered crystalline argyrodite materials Li 7PS 6 and Li 6PS 5Cl. A comparison of Li ion vacancy migration in Li 4P 2S 7 and Li 4P 2O 7 shows the migration energy barriers in the thiophosphate to be smaller (less than one-half) than in the phosphate.

Synthesis and characterization of oxyanion (phosphate, sulphate) doped Ba{sub 2}Sc{sub 2-y}Ga{sub y}O{sub 5}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, A.D.; Shin, J.F.; Slater, P.R., E-mail: p.r.slater@bham.ac.uk

2013-02-15

In this paper we examine the effect of partial substitution of Ga for Sc in the oxyanion (phosphate, sulphate) containing perovskites, Ba{sub 2}Sc{sub 2-x}P{sub x}O{sub 5+x} and Ba{sub 2}Sc{sub 2-x}S{sub x}O{sub 5+3x/2} with the samples analysed through a combination of X-ray diffraction, TGA, Raman spectroscopy and conductivity measurements. The results demonstrate that in both cases, Ga can be incorporated in place of Sc up to 40%. In order to accommodate the increasing Ga content, a reduction in the oxyanion content is required. Thus for the highest Ga content sample achieved, only 10% oxyanion incorporation was achieved giving endmember compositions ofmore » Ba{sub 2}ScGa{sub 0.8}P{sub 0.2}O{sub 5.2} and Ba{sub 2}ScGa{sub 0.8}S{sub 0.2}O{sub 5.3} for phosphate and sulphate doping respectively. While the Ga doping was shown to significantly improve the stability of the systems towards CO{sub 2} containing atmospheres, conductivity measurements showed a reduction in the conductivity with increasing Ga content. - Graphical abstract: Phosphate and sulphate doped Ba{sub 2}Sc{sub 2-x}Ga{sub x}O{sub 5} perovskites have been successfully prepared, with the highest conductivities observed for samples with the lowest Ga content. Highlights: Black-Right-Pointing-Pointer The successful synthesis of phosphate and sulphate doped Ba{sub 2}Sc{sub 2-x}Ga{sub x}O{sub 5} perovskites. Black-Right-Pointing-Pointer The demonstration of significant oxide ion and proton conduction in these perovskites. Black-Right-Pointing-Pointer The demonstration of improved CO{sub 2} stability with increasing Ga content.« less

Synthesis and characterization of insulin/zirconium phosphate@TiO2 hybrid composites for enhanced oral insulin delivery applications.

PubMed

Safari, Mostafa; Kamari, Younes; Ghiaci, Mehran; Sadeghi-Aliabadi, Hojjat; Mirian, Mina

2017-05-01

In this work, a series of composites of insulin (Ins)/zirconium phosphate (ZrP) were synthesized by intercalation method, then, these composites were coated with TiO 2 by sol-gel method to prepare Ins/ZrP@TiO 2 hybrid composites and the drug release of the composites was investigated by using UV-Vis spectroscopy. Ins/ZrP (10, 30, 60 wt%) composites were prepared by intercalation of insulin into the ZrP layers in water. Then Ins/ZrP composites were coated with different amounts of TiO 2 (30, 50, 100 wt %) by using titanium tetra n-butoxide, as precursor. Formation of intercalated Ins/ZrP and Ins/ZrP@TiO 2 hybrid composites was characterized by FT-IR, FE-SEM, BET and XRD analysis. Zeta potential of the optimized Ins/ZrP@TiO 2 hybrid composite was determined -27.2 mV. Cytotoxic effects of the optimized Ins/ZrP@TiO 2 hybrid composite against HeLa and Hek293T cell lines were evaluated using MTT assay and the results showed that designed drug delivery system was not toxic in biological environment. Compared to the Ins/ZrP composites, incorporation of TiO 2 coating enhanced the drug entrapment considerably, and reduced the drug release. The Ins/ZrP composites without TiO 2 coating released the whole drug after 30 min in pH 7.4 (phosphate buffer solution) while the TiO 2 -coated composites released the entrapped drug after 20 h. In addition to increasing the shelf life of hormone, this nanoencapsulation and nanocoating method can convert the insulin utilization from injection to oral and present a painless and more comfortable treatment for diabetics.

Core-Exsolved SiO2 Dispersal in the Earth's Mantle

NASA Astrophysics Data System (ADS)

Helffrich, George; Ballmer, Maxim D.; Hirose, Kei

2018-01-01

SiO2 may have been expelled from the core directly following core formation in the early stages of Earth's accretion and onward through the present day. On account of SiO2's low density with respect to both the core and the lowermost mantle, we examine the process of SiO2 accumulation at the core-mantle boundary (CMB) and its incorporation into the mantle by buoyant rise. Today, if SiO2 is 100-10,000 times more viscous than lower mantle material, the dimensions of SiO2 diapirs formed by the viscous Rayleigh-Taylor instability at the CMB would cause them to be swept into the mantle as inclusions of 100 m-10 km diameter. Under early Earth conditions of rapid heat loss after core formation, SiO2 diapirs of ˜1 km diameter could have risen independently of mantle flow to their level of neutral buoyancy in the mantle, trapping them there due to a combination of intrinsically high viscosity and neutral buoyancy. We examine the SiO2 yield by assuming Si + O saturation at the conditions found at the base of a magma ocean and find that for a range of conditions, dispersed bodies could reach as high as 8.5 vol % in parts of the lower mantle. At such low concentration, their effect on aggregate seismic wave speeds is within observational seismology uncertainty. However, their presence can account for small-scale scattering in the lower mantle due to the bodies' large-velocity contrast. We conclude that the shallow lower mantle (700-1,500 km depth) could harbor SiO2 released in early Earth times.

Fast preconcentration of trace rare earth elements from environmental samples by di(2-ethylhexyl)phosphoric acid grafted magnetic nanoparticles followed by inductively coupled plasma mass spectrometry detection

NASA Astrophysics Data System (ADS)

Yan, Ping; He, Man; Chen, Beibei; Hu, Bin

2017-10-01

In this work, di(2-ethylhexyl)phosphoric acid (P204) grafted magnetic nanoparticles were synthesized by fabricating P204 onto Fe3O4@TiO2 nanoparticles based on Lewis acid-base interaction between Ti and phosphate group under weakly acidic condition. The prepared Fe3O4@TiO2@P204 nanoparticles exhibited excellent selectivity for rare earth elements, and good anti-interference ability. Based on it, a method of magnetic solid phase extraction (MSPE) combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for fast preconcentration and determination of trace rare earth elements in environmental samples. Under the optimal conditions, the detection limits of rare earth elements were in the range of 0.01 (Tm)-0.12 (Nd) ng L- 1 with an enrichment factor of 100-fold, and the relative standard deviations ranged from 4.9 (Pr) to 10.7% (Er). The proposed method was successfully applied to the determination of rare earth elements in environmental samples, including river water, lake water, seawater and sediment.

Lethality of a Heat- and Phosphate-Catalyzed Glucose By-Product to Escherichia coli O157:H7 and Partial Protection Conferred by the rpoS Regulon

PubMed Central

Byrd, Jeffrey J.; Cheville, Ann M.; Bose, Jeffrey L.; Kaspar, Charles W.

1999-01-01

A by-product of glucose produced during sterilization (121°C, 15 lb/in2, 15 min) at neutral pH and in the presence of phosphate (i.e., phosphate-buffered saline) was bactericidal to Escherichia coli O157:H7 (ATCC 43895). Other six-carbon (fructose and galactose) and five-carbon (arabinose, ribose, and xylose) reducing sugars also produced a toxic by-product under the same conditions. Fructose and the five-carbon sugars yielded the most bactericidal activity. Glucose concentrations of 1% (wt/vol) resulted in a 99.9% decline in the CFU of stationary-phase cells per milliliter in 2 days at 25°C. An rpoS mutant (pRR10::rpoS) of strain 43895 (FRIK 816-3) was significantly (P < 0.001) more sensitive to the glucose-phosphate by-product than the parent strain, as glucose concentrations from 0.05 to 0.25% resulted in a 2- to 3-log10 reduction in CFU per milliliter in 2 days at 25°C. Likewise, log-phase cells of the wild-type strain, 43895, were significantly more sensitive (P < 0.001) to the glucose-phosphate by-product than were stationary-phase cells, which is consistent with the stability of rpoS and the regulation of rpoS-regulated genes. The bactericidal effect of the glucose-phosphate by-product was reduced when strains ATCC 43895 and FRIK 816-3 were incubated at a low temperature (4°C). Also, growth in glucose-free medium (i.e., nutrient broth) did not alleviate the sensitivity to the glucose-phosphate by-product and excludes the possibility of substrate-accelerated death as the cause of the bactericidal effect observed. The glucose-phosphate by-product was also bactericidal to Salmonella typhimurium, Shigella dysenteriae, and a Klebsiella sp. Attempts to identify the glucose-phosphate by-product were unsuccessful. These studies demonstrate the production of a glucose-phosphate by-product bactericidal to E. coli O157:H7 and the protective effects afforded by rpoS-regulated gene products. Additionally, the detection of sublethally injured bacteria may be

Pyrochlore structure and spectroscopic studies of titanate ceramics. A comparative investigation on SmDyTi2O7 and YDyTi2O7 solid solutions

NASA Astrophysics Data System (ADS)

Garbout, A.; Férid, M.

2018-06-01

Considering the features in changing the structure and properties of rare earth titanates pyrochlores, the substituted Dy2Ti2O7 may be very attractive for various applications. Effect of Sm and Y substitution on the structural properties of Dy2Ti2O7 ceramic was established. These ceramics were prepared by solid-state reaction and characterized by X-ray diffraction and Raman spectroscopy. Both analysis show that YDyTi2O7 with the pyrochlore structure is obtained after heating at 1400 °C, but SmDyTi2O7 has already formed after sintering at 1200 °C. SEM images revealed that the average grain size was increased with the increase of heating temperature, and an un-homogeneous grain growth was detected. The average size was about 37 nm and 135 nm for the SmDyTi2O7 and YDyTi2O7 particles, respectively. Structural Rietveld refinements indicate that all prepared ceramics crystallize in cubic structure with space group of Fd3m. The refined cell parameters demonstrate an almost linear correlation with the ionic radius of Ln3+. The vibrational spectra revealed that the positions of bands are sensitive to the Ln3+-ionic radius, and the Tisbnd O bond strength decreased linearly with the increase of cubic lattice parameter. Raman spectra indicate that the wavenumber of Osbnd Tisbnd O bending mode is considerably shifted to lower region with increasing in mass of the Ln atom. This paper provides solid foundations for additional research of these solid solutions, which are very attractive for different fields as promising catalytic compounds for combustion applications or as frustrated magnetic pyrochlore ceramics.

Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2.

PubMed

Yang, Jingying; Xie, Zuowei

2015-04-14

Rare-earth metallacarborane alkyls can be stabilized by the incorporation of a functional sidearm into both π and σ ligands. Reaction of [Me3NH][7,8-O(CH2)2-7,8-C2B9H10] with one equiv. of Ln(CH2C6H4-o-NMe2)3 gave metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2 (Ln = Y (), Gd (), Er ()) via alkane elimination. They represent the first examples of rare-earth metallacarborane alkyls. Treatment of with RN[double bond, length as m-dash]C[double bond, length as m-dash]NR (R = Cy, (i)Pr) or 2-benzoylpyridine afforded the corresponding mono-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[η(2)-(RN)2C(CH2C6H4-o-NMe2)](DME) (R = Cy (), (i)Pr ()) or [η(1):η(5)-O(CH2)2C2B9H9]Y[C5H4NC(Ph)(CH2C6H4-o-NMe2)O](THF)2 (), respectively. Complex also reacted with ArNCO or ArNC (Ar = 2,6-diisopropylphenyl, 2,6-dimethylphenyl) to give di-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[OC([double bond, length as m-dash]NC6H3Me2)N(C6H3Me2)C(CH2C6H4-o-NMe2)O](THF)2 () or [η(1):η(5)-O(CH2)2C2B9H9]Y[C([double bond, length as m-dash]NC6H3(i)Pr2)C([double bond, length as m-dash]NC6H3(i)Pr2)(CH2C6H4-o-NMe2)](DME) (). These results showed that the reactivity pattern of the Ln-C σ bond in rare-earth metallacarborane alkyls was dependent on the nature of the unsaturated organic molecules. New complexes were characterized by various spectroscopic techniques and elemental analysis. Some were further confirmed by single-crystal X-ray analysis.

In situ DRIFTS investigation of NH3-SCR reaction over CeO2/zirconium phosphate catalyst

NASA Astrophysics Data System (ADS)

Zhang, Qiulin; Fan, Jie; Ning, Ping; Song, Zhongxian; Liu, Xin; Wang, Lanying; Wang, Jing; Wang, Huimin; Long, Kaixian

2018-03-01

A series of ceria modified zirconium phosphate catalysts were synthesized for selective catalytic reduction of NO with ammonia (NH3-SCR). Over 98% NOx conversion and 98% N2 selectivity were obtained by the CeO2/ZrP catalyst with 20 wt.% CeO2 loading at 250-425 °C. The interaction between CeO2 and zirconium phosphate enhanced the redox abilities and surface acidities of the catalysts, resulting in the improvement of NH3-SCR activity. The in situ DRIFTS results indicated that the NH3-SCR reaction over the catalysts followed both Eley-Rideal and Langmuir-Hinshelwood mechanisms. The amide (sbnd NH2) groups and the NH4+ bonded to Brønsted acid sites were the important intermediates of Eley-Rideal mechanism.

Mutual effects of copper and phosphate on their interaction with γ-Al2O3: combined batch macroscopic experiments with DFT calculations.

PubMed

Ren, Xuemei; Yang, Shitong; Tan, Xiaoli; Chen, Changlun; Sheng, Guodong; Wang, Xiangke

2012-10-30

The mutual effects of Cu(II) and phosphate on their interaction with γ-Al(2)O(3) are investigated by using batch experiments combined with density functional theory (DFT) calculations. The results of batch experiments show that coexisting phosphate promotes the retention of Cu(II) on γ-Al(2)O(3), whereas phosphate retention is not affected by coexisting Cu(II) at low initial phosphate concentrations (≤ 3.6 mg P/L). Cu-phosphate aqueous complexes control Cu(II) retention through the formation of type B ternary surface complexes (where phosphate bridges γ-Al(2)O(3) and Cu(II)) at pH 5.5. This deduction is further supported by the results of DFT calculations. More specifically, the DFT calculation results indicate that the type B ternary surface complexes prefer to form outer-sphere or monodentate inner-sphere binding mode under our experimental conditions. The enhancement of phosphate retention on γ-Al(2)O(3) in the presence of Cu(II) at high initial phosphate concentrations (>3.6 mg P/L) may be attributed to the formation of 1:2 Cu(II)-phosphate species and/or surface precipitates. Understanding the mutual effects of phosphate and Cu(II) on their mobility and transport in mineral/water environments is more realistic to design effective remediation strategies for reducing their negative impacts on aquatic/terrestrial environments. Copyright © 2012 Elsevier B.V. All rights reserved.

CaO-MgO-Al 2O 3-SiO 2 (CMAS) corrosion of Gd 2Zr 2O 7 and Sm 2Zr 2O 7

DOE PAGES

Wang, Honglong; Bakal, Ahmet; Zhang, Xingxing; ...

2016-08-08

Ceramic thermal barrier coatings are applied to superalloys used in gas turbine engineering to increase the operating temperature and the energy conversion efficiency. However, dust consisting of CaO-MgO-Al 2O 3-SiO 2 (CMAS) from the air can be injected into the engines and corrode the thermal barrier coatings. Lanthanide zirconates are promising materials in thermal barrier coatings due to their low thermal conductivities, good phase stability and good corrosion resistance. However, the corrosion resistance mechanism of CMAS on lanthanide zirconates is still not clearly understood. In this work, the corrosion mechanism of Gd 2Zr 2O 7 and Sm 2Zr 2O 7more » in CMAS is studied. Here, the results show that the CMAS can easily react with lanthanide zirconate thermal barrier coatings to form a dense layer, which can resist further corrosion« less

Interactions of phosphate solubilising microorganisms with natural rare-earth phosphate minerals: a study utilizing Western Australian monazite.

PubMed

Corbett, Melissa K; Eksteen, Jacques J; Niu, Xi-Zhi; Croue, Jean-Philippe; Watkin, Elizabeth L J

2017-06-01

Many microbial species are capable of solubilising insoluble forms of phosphate and are used in agriculture to improve plant growth. In this study, we apply the use of known phosphate solubilising microbes (PSM) to the release of rare-earth elements (REE) from the rare-earth phosphate mineral, monazite. Two sources of monazite were used, a weathered monazite and mineral sand monazite, both from Western Australia. When incubated with PSM, the REE were preferentially released into the leachate. Penicillum sp. released a total concentration of 12.32 mg L -1 rare-earth elements (Ce, La, Nd, and Pr) from the weathered monazite after 192 h with little release of thorium and iron into solution. However, cultivation on the mineral sands monazite resulted in the preferential release of Fe and Th. Analysis of the leachate detected the production of numerous low-molecular weight organic acids. Gluconic acid was produced by all microorganisms; however, other organic acids produced differed between microbes and the monazite source provided. Abiotic leaching with equivalent combinations of organic acids resulted in the lower release of REE implying that other microbial processes are playing a role in solubilisation of the monazite ore. This study demonstrates that microbial solubilisation of monazite is promising; however, the extent of the reaction is highly dependent on the monazite matrix structure and elemental composition.

Phosphate Changes Effect of Humic Acids on TiO2 Photocatalysis: From Inhibition to Mitigation of Electron-Hole Recombination.

PubMed

Long, Mingce; Brame, Jonathon; Qin, Fan; Bao, Jiming; Li, Qilin; Alvarez, Pedro J J

2017-01-03

A major challenge for photocatalytic water purification with TiO 2 is the strong inhibitory effect of natural organic matter (NOM), which can scavenge photogenerated holes and radicals and occlude ROS generation sites upon adsorption. This study shows that phosphate counteracts the inhibitory effect of humic acids (HA) by decreasing HA adsorption and mitigating electron-hole recombination. As a measure of the inhibitory effect of HA, the ratios of first-order reaction rate constants between photocatalytic phenol degradation in the absence versus presence of HA were calculated. This ratio was very high, up to 5.72 at 30 mg/L HA and pH 4.8 without phosphate, but was decreased to 0.76 (5 mg/L HA, pH 8.4) with 2 mM phosphate. The latter ratio indicates a surprising favorable effect of HA on TiO 2 photocatalysis. FTIR analyses suggest that this favorable effect is likely due to a change in the conformation of adsorbed HA, from a multiligand exchange arrangement to a complexation predominantly between COOH groups in HA and the TiO 2 surface in the presence of phosphate. This configuration can reduce hole consumption and facilitate electron transfer to O 2 by the adsorbed HA (indicated by linear sweep voltammetry), which mitigates electron-hole recombination and enhances contaminant degradation. A decrease in HA surface adsorption and hole scavenging (the predominant inhibitory mechanisms of HA) by phosphate (2 mM) was indicated by a 50% decrease in the photocatalytic degradation rate of HA and 80% decrease in the decay rate coefficient of interfacial-related photooxidation in photocurrent transients. These results, which were validated with other compounds (FFA and cimetidine), indicate that anchoring phosphate - or anions that exert similar effects on the TiO 2 surface - might be a feasible strategy to counteract the inhibitory effect of NOM during photocatalytic water treatment.

The ultimate mineral processing challenge: Recovery of rare earths, phosphorus and uranium from Florida phosphatic clay

DOE PAGES

Zhang, Patrick; Liang, Haijun; Jin, Zhen; ...

2017-11-01

We report phosphate beneficiation in Florida generates more than one tonne of phosphatic clay, or slime, per tonne of phosphate rock produced. Since the start of the practice of large-scale washing and desliming for phosphate beneficiation, more than 2 Gt of slime has accumulated, containing approximately 600 Mt of phosphate rock, 600 kt of rare earth elements (REEs) and 80 million kilograms of uranium. The recovery of these valuable elements from the phosphatic clay is one of the most challenging endeavors in mineral processing, because the clay is extremely dilute, with an average solids concentration of 3 percent, and finemore » in size, with more than 50 percent having particle size smaller than 2 μm, and it contains nearly 50 percent clay minerals as well as large amounts of magnesium, iron and aluminum. With industry support and under funding from the Critical Materials Institute, the Florida Industrial and Phosphate Research Institute in conjunction with the Oak Ridge National Laboratory undertook the task to recover phosphorus, rare earths and uranium from Florida phosphatic clay. This paper presents the results from the preliminary testing of two approaches. The first approach involves three-stage cycloning using cyclones with diameters of 12.4 cm (5 in.), 5.08 cm (2 in.) and 2.54 cm (1 in.), respectively, to remove clay minerals followed by flotation and leaching. The second approach is a two-step leaching process. In the first step, selective leaching was conducted to remove magnesium, thus allowing the production of phosphoric acid suitable for the manufacture of diammonium phosphate (DAP) in the second leaching step. The results showed that multistage cycloning with small cyclones is necessary to remove clay minerals. Finally, selective leaching at about pH 3.2 using sulfuric acid was found to be effective for removing more than 80 percent of magnesium from the feed with minimal loss of phosphorus.« less

The ultimate mineral processing challenge: Recovery of rare earths, phosphorus and uranium from Florida phosphatic clay

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Patrick; Liang, Haijun; Jin, Zhen

We report phosphate beneficiation in Florida generates more than one tonne of phosphatic clay, or slime, per tonne of phosphate rock produced. Since the start of the practice of large-scale washing and desliming for phosphate beneficiation, more than 2 Gt of slime has accumulated, containing approximately 600 Mt of phosphate rock, 600 kt of rare earth elements (REEs) and 80 million kilograms of uranium. The recovery of these valuable elements from the phosphatic clay is one of the most challenging endeavors in mineral processing, because the clay is extremely dilute, with an average solids concentration of 3 percent, and finemore » in size, with more than 50 percent having particle size smaller than 2 μm, and it contains nearly 50 percent clay minerals as well as large amounts of magnesium, iron and aluminum. With industry support and under funding from the Critical Materials Institute, the Florida Industrial and Phosphate Research Institute in conjunction with the Oak Ridge National Laboratory undertook the task to recover phosphorus, rare earths and uranium from Florida phosphatic clay. This paper presents the results from the preliminary testing of two approaches. The first approach involves three-stage cycloning using cyclones with diameters of 12.4 cm (5 in.), 5.08 cm (2 in.) and 2.54 cm (1 in.), respectively, to remove clay minerals followed by flotation and leaching. The second approach is a two-step leaching process. In the first step, selective leaching was conducted to remove magnesium, thus allowing the production of phosphoric acid suitable for the manufacture of diammonium phosphate (DAP) in the second leaching step. The results showed that multistage cycloning with small cyclones is necessary to remove clay minerals. Finally, selective leaching at about pH 3.2 using sulfuric acid was found to be effective for removing more than 80 percent of magnesium from the feed with minimal loss of phosphorus.« less

Rare earth elements in the phosphatic-enriched sediment of the Peru shelf

USGS Publications Warehouse

Piper, D.Z.; Baedecker, P.A.; Crock, J.G.; Burnett, W.C.; Loebner, B.J.

1988-01-01

Apatite-enriched materials from the Peru shelf have been analyzed for their major oxide and rare earth element (REE) concentrations. The samples consist of (1) the fine fraction of sediment, mostly clay material, (2) phosphatic pellets and fish debris, which are dispersed throughout the fine-grained sediment, (3) tabular-shaped phosphatic crusts, which occur within the uppermost few centimeters of sediment, and (4) phosphatic nodules, which occur on the seafloor. The bulk REE concentrations of the concretions suggest that these elements are partitioned between the enclosed detrital material and the apatite fraction. Analysis of the fine-grained sediment with which the samples are associated suggested that this detrital fraction in the concretions should have shale REE values; the analysis of the fish debris suggested that the apatite fraction might have seawater values. The seawater contribution of REE's is negligible in the nodules and crust, in which the apatite occurs as a fine-grained interstitial cement. That is, the concentration of REE's and the REE patterns are predominantly a function of the amount of enclosed fine-grained sediment. By contrast, the REE pattern of the pelletal apatite suggests a seawater source and the absolute REE concentrations are relatively high. The REE P2O5 ratios of the apatite fraction of these samples thus vary from approximately zero (in the case of the crust and nodules) to as much as approximately 1.2 ?? 10-3 (in the case of the pellets). The range of this ratio suggests that rather subtle variations in the depositional environment might cause a significant variation in the REE content of this authigenic fraction of the sediment. Pelletal glauconite was also recovered from one sediment core. Its REE concentrations closely resemble those of the fish debris. ?? 1988.

Spectroscopic and neutron detection properties of rare earth and titanium doped LiAlO 2 single crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dickens, Peter T.; Marcial, José; McCloy, John

In this study, LiAlO2 crystals doped with rare-earth elements and Ti were produced by the CZ method and spectroscopic and neutron detection properties were investigated. Photoluminescence revealed no clear luminescent activation of LiAlO2 by the rare-earth dopants though some interesting luminescence was observed from secondary phases within the crystal. Gamma-ray pulse height spectra collected using a 137Cs source exhibited only a Compton edge for the crystals. Neutron modeling using Monte Carlo N-Particle Transport Code revealed most neutrons used in the detection setup are thermalized, and while using natural lithium in the crystal growth, which contains 7.6 % 6Li, a 10more » mm Ø by 10 mm sample of LiAlO2 has a 70.7 % intrinsic thermal neutron capture efficiency. Furthermore, the pulse height spectra collected using a 241Am-Be neutron source demonstrated a distinct neutron peak.« less

Spectroscopic and neutron detection properties of rare earth and titanium doped LiAlO 2 single crystals

DOE PAGES

Dickens, Peter T.; Marcial, Jose; McCloy, John; ...

2017-05-17

In this study, LiAlO 2 crystals doped with rare-earth elements and Ti were produced by the CZ method and spectroscopic and neutron detection properties were investigated. Photoluminescence revealed no clear luminescent activation of LiAlO 2 by the rare-earth dopants though some interesting luminescence was observed from secondary phases within the crystal. Gamma-ray pulse height spectra collected using a 137Cs source exhibited only a Compton edge for the crystals. Neutron modeling using Monte Carlo N-Particle Transport Code revealed most neutrons used in the detection setup are thermalized, and while using natural lithium in the crystal growth, which contains 7.6% 6Li, amore » 10 mm Ø by 10 mm sample of LiAlO 2 has a 70.7% intrinsic thermal neutron capture efficiency. Furthermore, the pulse height spectra collected using a 241Am-Be neutron source demonstrated a distinct neutron peak.« less

Earth Sky GT-7

NASA Image and Video Library

1965-12-07

S65-63784 (7 Dec. 1965) --- Algeria, south of Celemb Bechar, as seen from the orbiting Gemini-7 spacecraft during its 42nd revolution of Earth. Note rain runoff on the desert floor. Astronaut Frank Borman and James A. Lovell Jr. were aboard the National Aeronautics and Space Administration?s Gemini-7 spacecraft. The photograph was taken with a modified 70mm Hasselblad camera, using Eastman Kodak, Ektachrome MS (S.O. 217) color film. Photo credit: NASA

New stable ternary alkaline-earth metal Pb(II) oxides: Ca / Sr / BaPb 2 O 3 and BaPbO 2

DOE PAGES

Li, Yuwei; Zhang, Lijun; Singh, David J.

2017-10-16

The different but related chemical behaviors of Pb(II) oxides compared to Sn(II) oxides, and the existence of known alkali/alkali-earth metal Sn(II) ternary phases, suggest that there should be additional ternary Pb(II) oxide phases. Here, we report structure searches on the ternary alkaline-earth metal Pb(II) oxides leading to four new phases. These are two ternary Pb(II) oxides, SrPb 2O 3 and BaPb 2O 3, which have larger chemical potential stability ranges compared with the corresponding Sn(II) oxides, and additionally two other ternary Pb(II) oxides, CaPb 2O 3 and BaPbO 2, for which there are no corresponding Sn(II) oxides. Those Pb(II) oxidesmore » are stabilized by Pb-rich conditions. These structures follow the Zintl behavior and consist of basic structural motifs of (PbO 3) 4- anionic units separated and stabilized by the alkaline-earth metal ions. They show wide band gaps ranging from 2.86 to 3.12 eV, and two compounds (CaPb 2O 3 and SrPb 2O 3) show rather light hole effective masses (around 2m 0). The valence band maxima of these compounds have a Pb-6s/O-2p antibonding character, which may lead to p-type defect (or doping) tolerant behavior. This then suggests alkaline-earth metal Pb(II) oxides may be potential p-type transparent conducting oxides.« less

New stable ternary alkaline-earth metal Pb(II) oxides: Ca / Sr / BaPb 2 O 3 and BaPbO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yuwei; Zhang, Lijun; Singh, David J.

The different but related chemical behaviors of Pb(II) oxides compared to Sn(II) oxides, and the existence of known alkali/alkali-earth metal Sn(II) ternary phases, suggest that there should be additional ternary Pb(II) oxide phases. Here, we report structure searches on the ternary alkaline-earth metal Pb(II) oxides leading to four new phases. These are two ternary Pb(II) oxides, SrPb 2O 3 and BaPb 2O 3, which have larger chemical potential stability ranges compared with the corresponding Sn(II) oxides, and additionally two other ternary Pb(II) oxides, CaPb 2O 3 and BaPbO 2, for which there are no corresponding Sn(II) oxides. Those Pb(II) oxidesmore » are stabilized by Pb-rich conditions. These structures follow the Zintl behavior and consist of basic structural motifs of (PbO 3) 4- anionic units separated and stabilized by the alkaline-earth metal ions. They show wide band gaps ranging from 2.86 to 3.12 eV, and two compounds (CaPb 2O 3 and SrPb 2O 3) show rather light hole effective masses (around 2m 0). The valence band maxima of these compounds have a Pb-6s/O-2p antibonding character, which may lead to p-type defect (or doping) tolerant behavior. This then suggests alkaline-earth metal Pb(II) oxides may be potential p-type transparent conducting oxides.« less

Improved epitaxial texture of thick YBa2Cu3O7-δ/GdBa2Cu3O7-δ films with periodic stress releasing

NASA Astrophysics Data System (ADS)

Lin, Jianxin; Yang, Wentao; Gu, Zhaohui; Shu, Gangqiang; Li, Minjuan; Sang, Lina; Guo, Yanqun; Liu, Zhiyong; Cai, Chuanbing

2015-04-01

Thick high-Tc superconducting films consisting of a YBa2Cu3O7-δ/GdBa2Cu3O7-δ periodic architecture are developed on oxid-buffered Hastelloy tapes using a pulsed laser deposition process. It is revealed that multilayer intermittent structures for superconducting layers are effective to avoid the presence of a-axis grains and microcracks that occur with increasing thickness, which are frequently observed in monolayer films of REBa2Cu3O7-δ (RE = Y, Gd, or other rare earths), such grains and cracks being the significant challenge for obtaining high critical current in coated conductors. Presently, the thicknesses of multilayer films vary from 0.5 μm to 3 μm and, based on the SEM images and x-ray φ-scans, hardly show the influences on the microstructures and grain orientation of the c-axis. Also, the characteristic Raman spectrum patterns and their shifting with increasing the thickness of YBCO/GdBCO imply that the superior texture is obtained due to the evolution of stress dominated by the compressive stress rather than tensile stress.

Glucose-6-phosphate dehydrogenase deficiency does not increase the susceptibility of sperm to oxidative stress induced by H2O2.

PubMed

Roshankhah, Shiva; Rostami-Far, Zahra; Shaveisi-Zadeh, Farhad; Movafagh, Abolfazl; Bakhtiari, Mitra; Shaveisi-Zadeh, Jila

2016-12-01

Glucose-6-phosphate dehydrogenase (G6PD) deficiency is the most common human enzyme defect. G6PD plays a key role in the pentose phosphate pathway, which is a major source of nicotinamide adenine dinucleotide phosphate (NADPH). NADPH provides the reducing equivalents for oxidation-reduction reductions involved in protecting against the toxicity of reactive oxygen species such as H 2 O 2 . We hypothesized that G6PD deficiency may reduce the amount of NADPH in sperms, thereby inhibiting the detoxification of H 2 O 2 , which could potentially affect their motility and viability, resulting in an increased susceptibility to infertility. Semen samples were obtained from four males with G6PD deficiency and eight healthy males as a control. In both groups, motile sperms were isolated from the seminal fluid and incubated with 0, 10, 20, 40, 60, 80, and 120 µM concentrations of H 2 O 2 . After 1 hour incubation at 37℃, sperms were evaluated for motility and viability. Incubation of sperms with 10 and 20 µM H 2 O 2 led to very little decrease in motility and viability, but motility decreased notably in both groups in 40, 60, and 80 µM H 2 O 2 , and viability decreased in both groups in 40, 60, 80, and 120 µM H 2 O 2 . However, no statistically significant differences were found between the G6PD-deficient group and controls. G6PD deficiency does not increase the susceptibility of sperm to oxidative stress induced by H 2 O 2 , and the reducing equivalents necessary for protection against H 2 O 2 are most likely produced by other pathways. Therefore, G6PD deficiency cannot be considered as major risk factor for male infertility.

Synthesis, characterization, electrochemical investigation and antioxidant activities of a new hybrid cyclohexaphosphate: Cu1.5Li(C2H10N2)P6O18·7H2O

NASA Astrophysics Data System (ADS)

Sleymi, Samira; Lahbib, Karima; Rahmouni, Nihed; Rzaigui, Mohamed; Besbes-Hentati, Salma; Abid, Sonia

2017-09-01

A new organic-inorganic hybrid transition metal phosphate, Cu1.5Li(C2H10N2)P6O18·7H2O, has been prepared and characterized by X-ray diffraction, spectroscopy (infrared, Raman, diffuse reflectance and UV-Vis) and thermal analysis (TG). In addition, its electrochemical behaviors, as well as its antioxidant and antibacterial activities, have been investigated. Its structure is built up by the alternate linkages between copper and phosphate polyhedra, forming puckered layers with intersecting 12-membered rings, in which the ethylenediammonium cations reside. This compound is the first framework structure constructed from cyclohexaphosphates and three distinct copper cations. Cyclic voltammetry study in an acetonitrile solution reveals the facile anodic oxidation of its organic part on a platinum disk and a progressive growing of a thin film, though the repetitive cycling of potential. The title compound was tested for its in vitro antioxidant activities by 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2‧-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), Ferrous chelating ability (FIC) and Ferric Reducing Power (FRP) methods. The antioxidant activity of Cu1.5Li(C2H10N2)P6O18·7H2O was analyzed simultaneously with its antibacterial capacity against Escherichia coli, Salmonella typhimurium, Staphylococus aureus, Enterococcus feacium, Streptococcus agalactiae and Candida albicans. The tested compound showed significant antioxidant activities with low antibacterial properties.

Phase and Physicochemical Properties Diagrams of Quaternary System Li2B4O7 + Na2B4O7 + Mg2B6O11 + H2O

NASA Astrophysics Data System (ADS)

Wang, Shi-qiang; Du, Xue-min; Jing, Yan; Guo, Ya-fei; Deng, Tian-long

2017-12-01

The phase and physicochemical properties diagrams of the quaternary system (Li2B4O7 + Na2B4O7 + Mg2B6O11) at 288.15 K and 0.1 MPa were constructed using the solubilities, densities, and refractive indices measured. In the phase diagrams of the system there are one invariant point, three univariant isothermic dissolution curves, and three crystallization regions corresponding to Li2B4O7 · 3H2O, Na2B4O7 · 10H2O, and Mg2B6O11 · 15H2O, respectively. The solution density, refractive index of the quaternary system changes regularly with the increasing of Li2B4O7 concentration. The calculated values of density and refractive index using empirical equations of the quaternary system are in good agreement with the experimental values.

High-pressure synthesis and characterizations of the R2Pt2O7 pyrochlores.

NASA Astrophysics Data System (ADS)

Cai, Yunqi; Cui, Qi; Cheng, Jinguang; Dun, Zhiling; Zhou, Haidong; Ma, Jie; Cruz, C. Dela; Yan, Jiaqiang; Li, Xiang; Zhou, Jianshi

Pyrochlore R2B2O7 where R3 + stands for rear-earth ion and B4 + for a nonmagnetic cation such as Sn4 +or Ti4 +consist of an important family of geometrically frustrated magnets, which have been the focus of extensive investigations over last decades. To further enlarge the R2B2O7, we have chosen to stabilize the Pt-based cubic pyrochlores under HPHT conditions for two reasons: (1) Pt4 + is in a low-spin state which ionic radius is located in between Ti4 + (0.605\\x85) and Sn4 + (0.69\\x85), and (2) Pt4 + has a spatially much more extended 5d orbitals and thus enhanced Pt 5d-O 2p hybridizations that might modify the local anisotropic exchange interactions. Such an effect has never been taken into account in the previous studies. In this work, we will present the detailed characterizations on the pyrochlores R2Pt2O7 obtained under HPHT conditions. This work is supported by the National Science Foundation of China (Grant Nos.11304371, 11574377), part of the work was supported by the CEM, and NSF MRSEC, under Grant DMR-1420451, and Grant No. NSF-DMR-1350002.

Structural and redox properties of mitochondrial cytochrome c co-sorbed with phosphate on hematite (alpha-Fe2O3) surfaces.

PubMed

Khare, Nidhi; Eggleston, Carrick M; Lovelace, David M; Boese, Steven W

2006-11-15

The interaction of metalloproteins with oxides has implications not only for bioanalytical systems and biosensors but also in the areas of biomimetic photovoltaic devices, bioremediation, and bacterial metal reduction. Here, we investigate mitochondrial ferricytochrome c (Cyt c) co-sorption with 0.01 and 0.1 M phosphate on hematite (alpha-Fe2O3) surfaces as a function of pH (2-11). Although Cyt c sorption to hematite in the presence of phosphate is consistent with electrostatic attraction, other forces act upon Cyt c as well. The occurrence of multilayer adsorption, and our AFM observations, suggest that Cyt c aggregates as the pH approaches the Cyt c isoelectric point. In solution, methionine coordination of heme Fe occurs only between pH 3 and 7, but in the presence of phosphate this coordination is retained up to pH 10. Electrochemical evidence for the presence of native Cyt c occurs down to pH 3 and up to pH 10 in the absence of phosphate, and this range is extended to pH 2 and 11 in the presence of phosphate. Cyt c that initially adsorbs to a hematite surface may undergo conformation change and coat the surface with unfolded protein such that subsequently adsorbing protein is more likely to retain the native conformational state. AFM provides evidence for rapid sorption kinetics for Cyt c co-sorbed with 0.01 or 0.1 M phosphate. Cyt c co-sorbed with 0.01 M phosphate appears to unfold on the surface of hematite while Cyt c co-sorbed with 0.1 M phosphate possibly retains native conformation due to aggregation.

Earth Sky- GT-7

NASA Image and Video Library

1965-12-12

S65-63766 (12 Dec. 1965) --- Ras Azir on the coast of the Republic of Somali, looking east, as seen from the National Aeronautics and Space Administration's Gemini-7 spacecraft during its 117th revolution of Earth. Taken with a modified 70mm Hasselblad camera, using Eastman Kodak, Ektachrome MS (S.O. 217) color film. Photo credit: NASA

Neutron spectroscopic study of crystal field excitations in Tb 2Ti 2O 7 and Tb 2Sn 2O 7

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, J.; Fritsch, Katharina; Hao, Z.

2014-04-01

We present time-of-flight inelastic neutron scattering measurements at low temperature on powder samples of the magnetic pyrochlore oxides Tb 2Ti 2O 7 and Tb 2Sn 2O 7. These two materials possess related, but different ground states, with Tb 2Sn 2O 7 displaying "soft" spin ice order below T N approx 0.87 K, while Tb 2Ti 2O 7 enters a hybrid, glassy-spin ice state below T g approx 0.2 K. Our neutron measurements, performed at T = 1.5 K and 30 K, probe the crystal field states associated with the J = 6 states of Tb 3+ within the appropriate Fd3-barmmore » pyrochlore environment. These crystal field states determine the size and anisotropy of the Tb 3+ magnetic moment in each material's ground state, information that is an essential starting point for any description of the low temperature phase behavior and spin dynamics in Tb 2Ti 2O 7 and Tb 2Sn 2O 7. While these two materials have much in common, the cubic stanate lattice is expanded compared to the cubic titanate lattice. As our measurements show, this translates into a factor of approx 2 increase in the crystal field bandwidth of the 2J +1 = 13 states in Tb 2Ti 2O 7 compared with Tb 2Sn 2O 7. Our results are consistent with previous measurements on crystal field states in Tb 2Sn 2O 7, wherein the ground state doublet corresponds primarily to mJ = {vert_bar}+-5> and the first excited state doublet to mJ = {vert_bar}+-4>. In contrast, our results on Tb 2Ti 2O 7 differ markedly from earlier studies, showing that the ground state doublet corresponds to a significant mixture of mJ = {vert_bar}+-5>, mJ = {vert_bar}+-4> and mJ = {vert_bar}+-2>, while the first excited state doublet corresponds to a mixture of mJ = {vert_bar}+-4>, mJ = {vert_bar}+-5> and mJ = {vert_bar}+-1>. We discuss these results in the context of proposed mechanisms for the failure of Tb 2Ti 2O 7 to develop conventional long range order down to 50 mK.« less

Synthesis of novel magnesium ferrite (MgFe2O4)/biochar magnetic composites and its adsorption behavior for phosphate in aqueous solutions.

PubMed

Jung, Kyung-Won; Lee, Soonjae; Lee, Young Jae

2017-12-01

In this work, magnesium ferrite (MgFe 2 O 4 )/biochar magnetic composites (MFB-MCs) were prepared and utilized to remove phosphate from aqueous solutions. MFB-MCs were synthesized via co-precipitation of Fe and Mg ions onto a precursor, followed by pyrolysis. Characterization results confirmed that MgFe 2 O 4 nanoparticles with a cubic spinel structure were successfully embedded in the biochar matrix, and this offered magnetic separability with superparamagnetic behavior and enabled higher phosphate adsorption performance than that of pristine biochar and sole MgFe 2 O 4 nanoparticles. Batch experiments indicated that phosphate adsorption on the MFB-MCs is highly dependent on the pH, initial phosphate concentration, and temperature, while it was less affected by ionic strength. Analysis of activation and thermodynamic parameters as well as the isosteric heat of adsorption demonstrated that the phosphate adsorption is an endothermic and physisorption process. Lastly, highly efficient recyclability of the MFB-MCs suggested that they are a promising adsorbent for phosphate removal from wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

An aqueous, organic dye derivatized SnO 2 /TiO 2 core/shell photoanode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wee, Kyung-Ryang; Sherman, Benjamin D.; Brennaman, M. Kyle

2016-01-01

Visible light driven water splitting in a dye-sensitized photoelectrochemical cell (DSPEC) based on a phosphonic acid-derivatized donor–π–acceptor (D–π–A) organic dye (P–A–π–D) is described with the dye anchored to an FTO|SnO 2/TiO 2core/shell photoanode in a pH 7 phosphate buffer solution.

Luminescence characteristics of C5+ ions and 60Co irradiated Li2BaP2O7:Dy3+ phosphor

NASA Astrophysics Data System (ADS)

Wani, J. A.; Dhoble, N. S.; Lochab, S. P.; Dhoble, S. J.

2015-04-01

In this work a study on some thermoluminescence characteristics of Li2BaP2O7:Dy phosphor is presented. The phosphor was synthesized by solid state diffusion method and characterized for its phase purity by X-ray diffraction (XRD). FT-IR spectrum was also carried out to confirm the presence of phosphate family and vibrations corresponding to P-O-P group. Spectroscopic investigation was approached through photoluminescence (PL) and thermoluminescence (TL). PL emission spectrum of Dy3+ ions corresponding to 4F9/2 → 6H13/2 (483 nm) and 4F9/2 → 6H15/2 (574 nm) transitions is revealed under 351 nm excitation wavelength. This characteristic emission confirms the presence of Dy3+ ions in the Li2BaP2O7 host matrix. To induce TL properties in Li2BaP2O7:Dy phosphor was irradiated with C5+ ion beams and gamma rays (60Co). A nearly simple glow curve was observed for Li2BaP2O7:Dy under two different excitation sources. TL response is almost linear over a wide range. Average absorbed dose (D bar) and mean linear energy transfer (LET ‾) of C5+ ion beams in Li2BaP2O7:Dy have also been calculated. Values of parameters like E and S known as trap depth and frequency factor respectively were obtained by using TLanal computer program. Also SRIM based calculations were performed to study the effect of C5+ ion beams on the samples of Li2BaP2O7:Dy. SRIM calculations show that Ba2+ vacancies are highest in number. Till date no such luminescence information on Li2BaP2O7:Dy phosphor is available.

Geology and phosphate resources of the Hawley Creek area, Lemhi County, Idaho

USGS Publications Warehouse

Oberlindacher, Peter; Hovland, Robert David

1979-01-01

Phosphate resources occur within the Retort Phosphatic Shale Member of the Permian Phosphoria Formation in the Hawley Creek area, near Leadore, in east-central Idaho. About 12 square miles (31 km2 ) of the Retort Member and enclosing rocks were mapped at a scale of 1:12,000 to evaluate the leasable Federal mineral resources. The Retort has an average thickness of 73 feet (22.3 m) and 12.9 linear miles (20.8 linear km) of outcrop within the area mapped. Rock samples taken from a bulldozer trench were analyzed for phosphate content and for minor trace elements. Analyses show a cumulative thickness of 8.7 feet ( 2.7 m) of medium-grade phosphate rock ( 24 to 31 percent P2O5) and 33.4 feet (10.2 m) of low-grade phosphate rock (16 to 24 percent P2O5). Minor elements in the Retort include uranium, vanadium, fluorine, cadmium, chromium, nickel, molybdenum, silver, and rare earths. These minor elements are potential byproducts of any future phosphate production in the Hawley Creek area. In addition, analyses of six phosphate rock samples taken from a prospect trench show a cumulative thickness of 14.9 ft (4.5 m) at 17.6 percent P2O5. Indicated phosphate resources are calculated for phosphate beds under less than 600 feet (183.0 m) of overburden. Approximately 36.5 feet (11.1 m), representing 50 percent of the total Retort Member, were measured in trench CP-71. There are 80.42 million short tons (72.96 million metric tons) of medium-grade phosphate rock, and 308.76 million short tons ( 280.10 million metric tons) of low-grade phosphate rock in the Retort Member within the map area. Because the thickness and grade of the phosphate beds for each block are based on the recovered section from CP-71, the calculated phosphate resource estimates represent a minimum. Other mineral resources in the area are thorium (35 ppm) in a Precambrian (?) granite body located immediately west of the Hawley Creek area; oil and gas accumulations may occur beneath the Medicine Lodge thrust system

Peroxy defects in Rocks and H2O2 formation on the early Earth

NASA Astrophysics Data System (ADS)

Gray, A.; Balk, M.; Mason, P.; Freund, F.; Rothschild, L.

2013-12-01

An oxygen-rich atmosphere appears to have been a prerequisite for complex life to evolve on Earth and possibly elsewhere in the Universe. The question is still shrouded in uncertainty how free oxygen became available on the early Earth. Here we study processes of peroxy defects in silicate minerals which, upon weathering, generate mobilized electronic charge carriers resulting in oxygen formation in an initially anoxic subsurface environment. Reactive Oxygen Species (ROS) are precursors to molecular oxygen during this process. Due to their toxicity they may have strongly influenced the evolution of life. ROS are generated during hydrolysis of peroxy defects, which consist of pairs of oxygen anions. A second pathway for formation occurs during (bio) transformations of iron sulphide minerals. ROS are produced and consumed by intracellular and extracellular reactions of Fe, Mn, C, N, and S species. We propose that despite an overall reducing or neutral oxidation state of the macroenvironment and the absence of free O2 in the atmosphere, microorganisms on the early Earth had to cope with ROS in their microenvironments. They were thus under evolutionary pressure to develop enzymatic and other defenses against the potentially dangerous, even lethal effects of ROS and oxygen. We have investigated how oxygen might be released through weathering and test microorganisms in contact with rock surfaces. Our results show how early Life might have adapted to oxygen. Early microorganisms must have "trained" to detoxify ROS prior to the evolution of aerobic metabolism and oxygenic photosynthesis. A possible way out of this dilemma comes from a study of igneous and high-grade metamorphic rocks, whose minerals contain a small but significant fraction of oxygen anions in the valence state 1- , forming peroxy links of the type O3Si-OO-SiO3 [1, 2]. As water hydrolyzes the peroxy links hydrogen peroxide, H2O2, forms. Continued experimental discovery of H2O2 formation at rock

Novel ZnO/MgO/Fe2O3 composite optomagnetic nanoparticles.

PubMed

Kamińska, I; Sikora, B; Fronc, K; Dziawa, P; Sobczak, K; Minikayev, R; Paszkowicz, W; Elbaum, D

2013-05-15

A facile sol-gel synthesis of novel ZnO/MgO/Fe2O3 nanoparticles (NPs) is reported and their performance is compared to that of ZnO/MgO. Powder x-ray diffraction (XRD) patterns reveal the crystal structure of the prepared samples. The average particle size of the sample was found to be 4.8 nm. The optical properties were determined by UV-vis absorption and fluorescence measurements. The NPs are stable in biologically relevant solutions (phosphate buffered saline (PBS), 20 mM, pH = 7.0) contrary to ZnO/MgO NPs which degrade in the presence of inorganic phosphate. Superparamagnetic properties were determined with a superconducting quantum interference device (SQUID). Biocompatible and stable in PBS ZnO/MgO/Fe2O3 core/shell composite nanocrystals show luminescent and magnetic properties confined to a single NP at room temperature (19-24 ° C), which may render the material to be potentially useful for biomedical applications.

A sodium gadolinium phosphate with two different types of tunnel structure: Synthesis, crystal structure, and optical properties of Na 3GdP 2O 8

NASA Astrophysics Data System (ADS)

Fang, M.; Cheng, W.-D.; Zhang, H.; Zhao, D.; Zhang, W.-L.; Yang, S.-L.

2008-09-01

A sodium gadolinium phosphate crystal, Na 3GdP 2O 8, has been synthesized by a high-temperature solution reaction, and it exhibits a new structural family of the alkali-metal-rare-earth phosphate system. Although many compounds with formula M 3LnP 2O 8 have been reported, but they were shown to be orthorhombic [R. Salmon, C. Parent, M. Vlasse, G. LeFlem, Mater. Res. Bull. 13 (1978) 439] rather than monoclinic as shown in this paper. Single-crystal X-ray diffraction analysis shows the structure to be monoclinic with space group C2/ c and the cell parameters: a=27.55 (25), b=5.312 (4), c=13.935(11) Å, β=91.30(1)°, and V=2038.80 Å 3, Z=4. Its structure features a three-dimensional GdP 2O 83- anionic framework with two different types of interesting tunnels at where Na atoms are located by different manners. The framework is constructed by Gd polyhedra and isolated PO 4 tetrahedra. It is different from the structure of K 3NdP 2O 8 [R. Salmon, C. Parent, M. Vlasse, G. LeFlem, Mater. Res. Bull. 13 (1978) 439] with space group P2 1/ m that shows only one type of tunnel. The emission spectrum and the absorption spectrum of the compound have been investigated. Additionally, the calculations of band structure, density of states, dielectric constants, and refractive indexes have been also performed with the density functional theory method. The obtained results tend to support the experimental data.

Experimental ammonia-free phosphate-bonded investments using Mg(H2PO4)2.

PubMed

Zhang, Z; Tamaki, Y; Miyazaki, T

2001-12-01

In previous study, we found that Mg(H2PO4)2 instead of NH4H2PO4 was available as a binder material for phosphate-bonded investments and possibly could be used to develop the phosphate-bonded investment without ammonia gas release. The purpose of the present study was to develop the experimental ammonia-free phosphate-bonded investments by investigating suitable refractories. Mg(H2PO4)2.nH2O and MgO were prepared as a binder. Cristobalite and quartz were selected as refractories. The power ratio of MgO/Mg(H2PO4)2.nH2O was set constant at 1.2 according to our previous findings. Fundamental properties of dental investment such as strength, manipulation and expansion were evaluated. Using cristobalite as the refractory material, further investigations were performed. The refractory/binder ratio was definitely effective. The increase of this ratio led to low mold strength and large mold expansion. The present findings suggested that C5 was desirable for dental investment.

Phosphate uptake behavior of layered rare earth hydroxides l-RE(OH)3 (RE = Sm, Gd, Er, and Y) from water

NASA Astrophysics Data System (ADS)

Jeon, Hong-Gu; Kim, Hyunsub; Jung, Hyunjin; Byeon, Song-Ho

2018-07-01

The use of rare earths (REs) provides various advantages for removal and recovery of phosphate from water because they have high affinity to form stable complexes with phosphates even at low concentrations. Very low solubility of rare earth phosphate REPO4 in water was expected to induce a high phosphate adsorption rate and capacity. In this study, layered rare earth hydroxides, l-RE(OH)3 (RE = Sm, Gd, Er, and Y), have been employed to remove or recover phosphate from aqueous solution. This layered polymorph of l-RE(OH)3, which is composed of hydroxocation layers, exhibited a high point of zero charge (pHpzc > 10) and significantly enhanced adsorptive ability for phosphates over a wide pH range. The isotherm and kinetics of phosphate adsorption on l-RE(OH)3 were explained dominantly by the Langmuir isotherm model and pseudo-second-order kinetic model, respectively. A strong dependence of isotherm and kinetic parameters on RE demonstrated that the adsorption of phosphate on l-RE(OH)3 is a chemisorption dominated process involving the replacement of -OH by phosphate ion to be included into the coordination polyhedra of RE. The desorption of phosphate from l-RE(OH)3 was slow but the desorption efficiency for all RE members was higher than 97% in a 1.0 M NaOH solution after 4 days at room temperature. Considering high capacity and stability as well as no significant interference in recovery of phosphate from waters containing common competing anions, this rare earth adsorbent series is proposed as a promising alternative for efficient and sensitive phosphate recovery from natural and wastewaters.

Enhancement of CO Evolution by Modification of Ga2O3 with Rare-Earth Elements for the Photocatalytic Conversion of CO2 by H2O.

PubMed

Tatsumi, Hiroyuki; Teramura, Kentaro; Huang, Zeai; Wang, Zheng; Asakura, Hiroyuki; Hosokawa, Saburo; Tanaka, Tsunehiro

2017-12-12

Modification of the surface of Ga 2 O 3 with rare-earth elements enhanced the evolution of CO as a reduction product in the photocatalytic conversion of CO 2 using H 2 O as an electron donor under UV irradiation in aqueous NaHCO 3 as a pH buffer, with the rare-earth species functioning as a CO 2 capture and storage material. Isotope experiments using 13 CO 2 as a substrate clearly revealed that CO was generated from the introduced gaseous CO 2 . In the presence of the NaHCO 3 additive, the rare-earth (RE) species on the Ga 2 O 3 surface are transformed into carbonate hydrates (RE 2 (CO 3 ) 3 ·nH 2 O) and/or hydroxycarbonates (RE 2 (OH) 2(3-x) (CO 3 ) x ) which are decomposed upon photoirradiation. Consequently, Ag-loaded Yb-modified Ga 2 O 3 exhibits much higher activity (209 μmol h -1 of CO) than the pristine Ag-loaded Ga 2 O 3 . The further modification of the surface of the Yb-modified Ga 2 O 3 with Zn afforded a selectivity toward CO evolution of 80%. Thus, we successfully achieved an efficient Ag-loaded Yb- and Zn-modified Ga 2 O 3 photocatalyst with high activity and controllable selectivity, suitable for use in artificial photosynthesis.

Response of Gd 2 Ti 2 O 7 and La 2 Ti 2 O 7 to swift-heavy ion irradiation and annealing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Sulgiye; Lang, Maik; Tracy, Cameron L.

2015-07-01

Swift heavy ion (2 GeV 181Ta) irradiation-induced amorphization and temperature-induced recrystallization of cubic pyrochlore Gd2Ti2O7 (Fd3¯m) are compared with the response of a compositionally-similar material with a monoclinic-layered perovskite-type structure, La2Ti2O7 (P21). The averaged electronic energy loss, dE/dx, was 37 keV/nm and 35 keV/nm in Gd2Ti2O7 and La2Ti2O7, respectively. Systematic analysis of the structural modifications was completed using transmission electron microscopy, synchrotron X-ray diffraction, Raman spectroscopy, and small-angle X-ray scattering. Increasing ion-induced amorphization with increasing ion fluence was evident in the X-ray diffraction patterns of both compositions by a reduction in the intensity of the diffraction maxima concurrent with themore » growth in intensity of a broad diffuse scattering halo. Transmission electron microscopy analysis showed complete amorphization within ion tracks (diameter: ~10 nm) for the perovskite-type material; whereas a concentric, core–shell morphology was evident in the ion tracks of the pyrochlore, with an outer shell of disordered yet still crystalline material with the fluorite structure surrounding an amorphous track core (diameter: ~9 nm). The radiation response of both titanate oxides with the same stoichiometry can be understood in terms of differences in their structures and compositions. While the radiation damage susceptibility of pyrochlore A2B2O7 materials decreases as a function of the cation radius ratio rA/rB, the current study correlates this behavior with the stability field of monoclinic structures, where rLa/rTi > rGd/rTi. Isochronal annealing experiments of the irradiated materials showed complete recrystallization of La2Ti2O7 at 775 °C and of Gd2Ti2O7 at 850 °C. The annealing behavior is discussed in terms of enhanced damage recovery in La2Ti2O7, compared to the pyrochlore compounds Gd2Ti2O7. The difference in the recrystallization behavior may be related to

Luminescence Spectroscopy and Crystal Field Simulations of Europium Propylenediphosphonate EuH[O 3P(CH 2) 3PO 3] and Europium Glutarate [Eu(H 2O)] 2[O 2C(CH 2) 3CO 2] 3·4H 2O

NASA Astrophysics Data System (ADS)

Serpaggi, F.; Férey, G.; Antic-Fidancev, E.

1999-12-01

The results of investigations on the photoluminescence of two europium hybrid compounds, EuH[O3P(CH2)3PO3] (Eu[diph]) and [Eu(H2O)]2[O2C(CH2)3CO2]3·4H2O (Eu[glut]), are presented. In both compounds one local environment is found for the rare earth (Re) ion and the symmetry of the Re polyhedron is low (Cs) as evidenced by the Eu3+ luminescence studies. The electrostatic crystal field (cf) parameters of the 7F multiplet are obtained by the application of the phenomenological cf theory. The simulations using C2v symmetry for the rare earth ion give good agreement between the calculated and the experimental 7F0-4 energy level schemes. The observed optical data are discussed in relation to the crystal structure of the compounds.

Physicochemical degradation studies of calcium phosphate glass ceramic in the CaO-P2O5-MgO-TiO2 system.

PubMed

Dias, A G; Gibson, I R; Santos, J D; Lopes, M A

2007-03-01

The aim of this work was to evaluate the in vitro degradation behaviour of a 45CaO-37P(2)O(5)-5MgO-13TiO(2) (mol.%) glass ceramic, under two different simulated physiological conditions: normal physiological pH 7.4, and pH 3.0, which was designed to simulate the acidic conditions produced by osteoclast cells. The in vitro testing was carried out at 37 degrees C for up to 42 days for the pH 7.4 solution and for up to 1 day for the pH 3.0 solution. The incorporation of TiO(2) into the glass structure leads to the precipitation of specific crystalline phases in the glass matrix, namely alpha- and beta-Ca(2)P(2)O(7), TiP(2)O(7) and CaTi(4)(PO(4))(6). The degradation testing at pH 3.0 showed a higher weight loss compared with degradation testing at pH 7.4; the weight loss under the acidic condition after 1 day (24 h) was about 10 times higher than the weight loss after 42 days of immersion at pH 7.4. The ionic release profile of Ca(2+), PO(4)(3-), Mg(2+) and Ti(4+) showed a continuous increase in concentration over all immersion times for both testing solutions. After 1 day of immersion at pH 3.0, the concentration levels of Mg(2+), Ca(2+), PO(4)(3-) were about six times higher than the levels achieved after 42 days of immersion at pH 7.4. The glass ceramic showed similar degradation to hydroxyapatite, and therefore has potential to be used in certain clinical applications where relatively slow resorption of the implant and replacement by bone is required, e.g. cranioplasty.

Titanium-bearing phases in the Earth's mantle (evidence from experiments in the MgO-SiO2-TiO2 ±Al2O3 system at 10-24 GPa)

NASA Astrophysics Data System (ADS)

Sirotkina, Ekaterina; Bobrov, Andrey; Bindi, Luca; Irifune, Tetsuo

2017-04-01

Introduction Despite significant interest of experimentalists to the study of geophysically important phase equilibria in the Earth's mantle and a huge experimental database on a number of the model and multicomponent systems, incorporation of minor elements in mantle phases was mostly studied on a qualitative level. The influence of such elements on structural peculiarities of high-pressure phases is poorly investigated, although incorporation of even small portions of them may have a certain impact on the PT-parameters of phase transformations. Titanium is one of such elements with the low bulk concentrations in the Earth's mantle (0.2 wt % TiO2) [1]; however, Ti-rich lithologies may occur in the mantle as a result of oceanic crust subduction. Thus, the titanium content is 0.6 wt% in Global Oceanic Subducted Sediments (GLOSS) [2], and 1.5 wt% TiO2, in MORB [3]. In this regard, accumulation of titanium in the Earth's mantle is related to crust-mantle interaction during the subduction of crustal material at different depths of the mantle. Experimental methods At 10-24 GPa and 1600°C, we studied the full range of the starting materials in the MgSiO3 (En) - MgTiO3 (Gkl) system in increments of 10-20 mol% Gkl and 1-3 GPa, which allowed us to plot the phase PX diagram for the system MgSiO3-MgTiO3 and synthesize titanium-bearing phases with a wide compositional range. The experiments were performed using a 2000-t Kawai-type multi-anvil high-pressure apparatus at the Geodynamics Research Center, Ehime University (Japan). The quenched samples were examined by single-crystal X-ray diffractometer, and the composition of phases was analyzed using SEM-EDS. Results The main phases obtained in experiments were rutile, wadsleyite, MgSiO3-enstatite, MgTiO3-ilmenite, MgTiSi2O7 with the weberite structure type (Web), Mg(Si,Ti)O3 and MgSiO3 with perovskite-type structure. At a pressure of 13 GPa for Ti-poor bulk compositions, an association of En+Wad+Rt is replaced by the

Experience melting through the Earth's lower mantle via LH-DAC experiments on MgO-SiO2 and CaO-MgO-SiO2 systems

NASA Astrophysics Data System (ADS)

Baron, Marzena A.; Lord, Oliver T.; Walter, Michael J.; Trønnes, Reidar G.

2015-04-01

system CaO-MgO-SiO2 (CMS). The eutectic melting temperatures (Te) were determined by multi-chamber DAC-experiments on near-eutectic compositions [3,9]. Ultra-fine W-powder mixed into the samples absorbed the laser energy. The samples were heated at a rate of 500-1500 K/min by increasing the laser power. More than 75-90% eutectic melt is produced at the the solidus, resulting in rapid aggregation of the W-powder and inefficient laser energy absorption. The resulting plateau in the temperature versus power curve is interpreted as Te. Our preliminary results show an expected positive p-Te correlation, with lower Te for the CMS-system. The dTe/dp slope for the bm-silica eutectic is lower than for the bm-pc eutectic in the MS-system. The experimental results agree with the DFT-studies and thermodynamic models. We have also developed a novel technique for micro-fabrication of metal-encapsulated samples (Re, W, Mo), to investigate more precisely the melting phase relations in the lower mantle pressure range. The metal-covered, 20 μm thick sample disc, placed between thermal insulation layers in the DAC, will be laser-heated at the two flat surfaces, providing low thermal gradients and preventing reaction between the sample and the pressure medium. [1] Lay and Garnero (2007, AGU Monograph); [2] Labrosse et al (2007, Nature); [3] Liebske and Frost (2012, EPSL); [4] Elkins-Tanton (2012, Ann Rev Earth Planet Sci); [5] Hirose et al (1999, Nature); [6] Fiquet et al (2010, Science); [7] Andrault et al (2011, EPSL); [8] Andrault et al (2014, Science); [9] de Koker et al (2013, EPSL); [10] de Koker and Strixrude (2009, Geophys J Int).

Preparation and cathodoluminescence characteristics of rare earth activated BaAl2O4 phosphors.

PubMed

Benourdja, S; Kaynar, Ümit H; Ayvacikli, M; Karabulut, Y; Guinea, J Garcia; Canimoglu, A; Chahed, L; Can, N

2018-04-18

Undoped and Pr, Sm and Tb activated BaAl 2 O 4 phosphors have been synthesized by solid state reaction method and combustion method. The structure and morphological observation of the phosphor samples were monitored by X-ray powder diffraction (XRD) and environmental scanning electron microscope (ESEM) coupled to an energy dispersive X-ray spectrometer (EDS). The all diffraction peaks are well assigned to standard data card (PDF♯17-306). Emission properties of the samples were explored using light emission induced by an electron beam (i.e cathodoluminescence, CL) at room temperature (RT). Undoped BaAl 2 O 4 sample exhibits a broad defect emission from 300 to 500 nm from the aluminate defect centres. CL spectra recorded at room temperature display that the as-prepared BaAl 2 O 4 :Ln (Ln=Pr, Sm and Tb) phosphors exhibit different luminescence colors coming from different rare earth activator ions. The transition 4 G 5/2 → 6 H 7/2 located at 606 and 610 nm for Sm 3+ can occur as hypersensitive transition having the selection rule ΔJ = ± 1. For the Tb 3+ doped samples, they exhibit D45 green line emissions. The proposed luminescent mechanisms of all doped rare earth ions are also discussed. Copyright © 2018 Elsevier Ltd. All rights reserved.

Modifications of structural and physical properties induced by swift heavy ions in Gd2Ti2O7 and Y2Ti2O7 pyrochlores

NASA Astrophysics Data System (ADS)

Sellami, N.; Sattonnay, G.; Grygiel, C.; Monnet, I.; Debelle, A.; Legros, C.; Menut, D.; Miro, S.; Simon, P.; Bechade, J. L.; Thomé, L.

2015-12-01

The structural transformations induced by ionization processes in Gd2Ti2O7 and Y2Ti2O7 pyrochlores irradiated with swift heavy ions have been studied using XRD and Raman experiments. Results show that irradiation induces amorphization and that the phase transformation build-up can be accounted for in the framework of a model involving a single-impact mechanism. The radiation induced amorphization build-up is faster in Gd2Ti2O7 than in Y2Ti2O7. Moreover, a decrease of the thermal conductivity (measured by the laser flash method) is induced by irradiation both in Gd2Ti2O7 and Y2Ti2O7.

Earth Sky GT-7

NASA Image and Video Library

1965-12-07

S65-63829 (5 Dec. 1965) --- Algeria, south of the Fort Flatters area, as seen from the National Aeronautics and Space Administration?s Gemini-7 spacecraft during its 13th revolution of Earth. The orange color area is the Tifermine Sand Dunes that reach a height of 1,000 feet. The photograph was taken with a modified 70mm Hasselblad camera, with Eastman Kodak, Ektachrome MS (S.O. 217) color film. Photo credit: NASA

Method for determination of small amounts of rare earths and thorium in phosphate rocks

USGS Publications Warehouse

Waring, C.L.; Mela, H.

1953-01-01

In laboratory investigations, interest developed in the possible rare-earth content of phosphate samples from Florida and the northwestern United States. Because of the difficulty of making chemical determinations of traces of individual rare earths, a combined chemical-spectrographic method was investigated. After removal of iron by the extraction of the chloride with ether, the rare earths and thorium are concentrated by double oxalate precipitation, using calcium as a carrier. The rare earths are freed from calcium by an ammonium hydroxide precipitation with a fixed amount of aluminum as a carrier. The aluminum also serves as an internal standard in the final spectrographic analysis. The method will determine from 0.02 to 2 mg. of each rare earth with an error no greater than 10%. The investigation has resulted in a fairly rapid and precise procedure, involving no special spectrographic setup. The method could be applied to other types of geologic materials with the same expected accuracy.

Interplay of rare-earth and transition-metal subsystems in C u3Yb (SeO3) 2O2Cl

NASA Astrophysics Data System (ADS)

Markina, M. M.; Zakharov, K. V.; Ovchenkov, E. A.; Berdonosov, P. S.; Dolgikh, V. A.; Kuznetsova, E. S.; Olenev, A. V.; Klimin, S. A.; Kashchenko, M. A.; Budkin, I. V.; Yatsyk, I. V.; Demidov, A. A.; Zvereva, E. A.; Vasiliev, A. N.

2017-10-01

We present the synthesis and the experimental and theoretical study of the new member of the francisite family, C u3Yb (SeO3) 2O2Cl . The compound reaches an antiferromagnetic order at TN=36.7 K and experiences first-order spin-reorientation transition to weakly ferromagnetic phase at TR=8.7 K evidenced in specific heat Cp and magnetic susceptibility χ measurements. Distinctly different magnetization loops in T earth and transition-metal subsystems. At low temperatures, the saturation magnetization Ms˜5.2 μB is reached in pulsed magnetic-field measurements. The electron spin resonance data reveal the complicated character of the absorption line attributed to response from both copper and ytterbium ions. Critical broadening of the linewidth at the phase transitions points to quasi-two-dimensional character of the magnetic correlations. The spectroscopy of Y b3 + ions evidences splitting of the lowest-energy Kramers doublet of 2F5 /2 excited multiplet at TR

High-precision determination of 18O/16O ratios of silver phosphate by EA-pyrolysis-IRMS continuous flow technique.

PubMed

Lécuyer, Christophe; Fourel, François; Martineau, François; Amiot, Romain; Bernard, Aurélien; Daux, Valérie; Escarguel, Gilles; Morrison, John

2007-01-01

A high-precision, and rapid on-line method for oxygen isotope analysis of silver phosphate is presented. The technique uses high-temperature elemental analyzer (EA)-pyrolysis interfaced in continuous flow (CF) mode to an isotopic ratio mass spectrometer (IRMS). Calibration curves were generated by synthesizing silver phosphate with a 13 per thousand spread in delta(18)O values. Calibration materials were obtained by reacting dissolved potassium dihydrogen phosphate (KH(2)PO(4)) with water samples of various oxygen isotope compositions at 373 K. Validity of the method was tested by comparing the on-line results with those obtained by classical off-line sample preparation and dual inlet isotope measurement. In addition, silver phosphate precipitates were prepared from a collection of biogenic apatites with known delta(18)O values ranging from 12.8 to 29.9 per thousand (V-SMOW). Reproducibility of +/- 0.2 per thousand was obtained by the EA-Py-CF-IRMS method for sample sizes in the range 400-500 microg. Both natural and synthetic samples are remarkably well correlated with conventional (18)O/(16)O determinations. Silver phosphate is a very stable material and easy to degas and, thus, could be considered as a good candidate to become a reference material for the determination of (18)O/(16)O ratios of phosphate by high-temperature pyrolysis. Copyright 2006 John Wiley & Sons, Ltd.

Reductions in mitochondrial O(2) consumption and preservation of high-energy phosphate levels after simulated ischemia in chronic hibernating myocardium.

PubMed

Hu, Qingsong; Suzuki, Gen; Young, Rebeccah F; Page, Brian J; Fallavollita, James A; Canty, John M

2009-07-01

We performed the present study to determine whether hibernating myocardium is chronically protected from ischemia. Myocardial tissue was rapidly excised from hibernating left anterior descending coronary regions (systolic wall thickening = 2.8 +/- 0.2 vs. 5.4 +/- 0.3 mm in remote myocardium), and high-energy phosphates were quantified by HPLC during simulated ischemia in vitro (37 degrees C). At baseline, ATP (20.1 +/- 1.0 vs. 26.7 +/- 2.1 micromol/g dry wt, P < 0.05), ADP (8.1 +/- 0.4 vs. 10.3 +/- 0.8 micromol/g, P < 0.05), and total adenine nucleotides (31.2 +/- 1.3 vs. 40.1 +/- 2.9 micromol/g, P < 0.05) were depressed compared with normal myocardium, whereas total creatine, creatine phosphate, and ATP-to-ADP ratios were unchanged. During simulated ischemia, there was a marked attenuation of ATP depletion (5.6 +/- 0.9 vs. 13.7 +/- 1.7 micromol/g at 20 min in control, P < 0.05) and mitochondrial respiration [145 +/- 13 vs. 187 +/- 11 ng atoms O(2).mg protein(-1).min(-1) in control (state 3), P < 0.05], whereas lactate accumulation was unaffected. These in vitro changes were accompanied by protection of the hibernating heart from acute stunning during demand-induced ischemia. Thus, despite contractile dysfunction at rest, hibernating myocardium is ischemia tolerant, with reduced mitochondrial respiration and slowing of ATP depletion during simulated ischemia, which may maintain myocyte viability.

Oxygen miscibility gap and spin glass formation in the pyrochlore Lu{sub 2}Mo{sub 2}O{sub 7}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, L.; Ritter, C.; Harrison, A.

2013-07-15

Rare earth (R) molybdate pyrochlores, R{sub 2}Mo{sub 2}O{sub 7}, are of interest as frustrated magnets. Polycrystalline samples of Lu{sub 2}Mo{sub 2}O{sub 7−x} prepared at 1600 °C display a coexistence of cubic pyrochlore phases. Rietveld fits to powder neutron diffraction data and chemical analyses show that the miscibility gap is between a stoichiometric x=0 and an oxygen-deficient x≈0.4 phase. Lu{sub 2}Mo{sub 2}O{sub 7} behaves as a spin glass material, with a divergence of field cooled and zero field cooled DC magnetic susceptibilities at a spin freezing temperature T{sub f}=16 K, that varies with frequency in AC measurements following a Vogel–Fulcher law.more » Lu{sub 2}Mo{sub 2}O{sub 6.6} is more highly frustrated spin glass and has T{sub f}=20 K. - Graphical abstract: The cubic Lu{sub 2}Mo{sub 2}O{sub 7−x} system exhibits a miscibility gap between coexisting pyrochlore phases at 1600 °C. Neutron powder diffraction refinement and chemical analysis shows that the gap separates stoichiometric x=0 and oxygen-deficient x≈0.4 phases. Lu{sub 2}Mo{sub 2}O{sub 7−x} has a frustrated spin glass ground state that is sensitive to the oxygen content. - Highlights: • The cubic Lu{sub 2}Mo{sub 2}O{sub 7−x} system has a miscibility gap between coexisting pyrochlore phases at 1600 °C. • Neutron powder diffraction shows that the gap separates x=0 and oxygen-deficient x≈0.4 phases. • Lu{sub 2}Mo{sub 2}O{sub 7−x} has a frustrated spin glass ground state that is sensitive to the oxygen content.« less

XRD and 29Si MAS-NMR spectroscopy across the β-Lu 2Si 2O 7- β-Y 2Si 2O 7 solid solution

NASA Astrophysics Data System (ADS)

Becerro, Ana I.; Escudero, Alberto

2005-01-01

Samples in the system Lu 2-xY xSi 2O 7 (0⩽ x⩽2) have been synthesized following the sol-gel method and calcined to 1300 °C, a temperature at which the β-polymorph is known to be the stable phase for the end-members Lu 2Si 2O 7 and Y 2Si 2O 7. The XRD patterns of all the compositions studied are compatible with the structure of the β-polymorph. Unit cell parameters are calculated as a function of composition from XRD patterns. They show a linear change with increasing Y content, which indicates a solid solubility of β-Y 2Si 2O 7 in β-Lu 2Si 2O 7 at 1300 °C. 29Si MAS NMR spectra of the different members of the system agree with the XRD results, showing a linear decrease of the 29Si chemical shift with increasing Y content. Finally, a correlation reported in the literature to predict 29Si chemical shifts in silicates is applied here to obtain the theoretical variation in 29Si chemical shift values in the system Lu 2Si 2O 7-Y 2Si 2O 7 and the results compare favorably with the values obtained experimentally.

Crystal Growth and Optical Properties of Co2+ Doped SrLaGa3O7

DTIC Science & Technology

2001-01-01

Electron Spin Resonance, absorption spectra, gallate crystals, thermal annealing. 1. INTRODUCTION SrLaGa307 (SLGO) belongs to the family of binary... gallates of alkaline and rare earth metals. Crystal of these compounds have the tetragonal gehlenite (Ca 2AS12SiO 7) structure (space group: P-421ml, D 3 2d

A precise method for the analysis of d18O of dissolved inorganic phosphate in seawater

USGS Publications Warehouse

McLaughlin, K.; Silva, S.; Kendall, C.; Stuart-Williams, Hilary; Paytan, A.

2004-01-01

A method for preparation and analysis of the oxygen isotope composition (d18O) of dissolved inorganic phosphate (DIP) has been developed and preliminary results for water samples from various locations are reported. Phosphate is extracted from seawater samples by coprecipitation with magnesium hydroxide. Phosphate is further purified through a series of precipitations and resin separation and is ultimately converted to silver phosphate. Silver phosphate samples are pyrolitically decomposed to carbon monoxide and analyzed for d18O. Silver phosphate samples weighing 0.7 mg (3.5 mol oxygen) can be analyzed routinely with an average standard deviation of about 0.3. There is no isotope fractionation during extraction and blanks are negligible within analytical error. Reproducibility was determined for both laboratory standards and natural samples by multiple analyses. A comparison between filtered and unfiltered natural seawater samples was also conducted and no appreciable difference was observed for the samples tested. The d18O values of DIP in seawater determined using this method range from 18.6 to 22.3, suggesting small but detectable natural variability in seawater. For the San Francisco Bay estuary DIP d18O is more variable, ranging from 11.4 near the San Joaquin River to 20.1 near the Golden Gate Bridge, and was well correlated with salinity, phosphate concentration, and d18O of water.

Stability and anisotropy of (FexNi1-x)2O under high pressure and implications in Earth's and super-Earths' core.

PubMed

Huang, Shengxuan; Wu, Xiang; Qin, Shan

2018-01-10

Oxygen is thought to be an important light element in Earth's core but the amount of oxygen in Earth's core remains elusive. In addition, iron-rich iron oxides are of great interest and significance in the field of geoscience and condensed matter physics. Here, static calculations based on density functional theory demonstrate that I4/mmm-Fe 2 O is dynamically and mechanically stable and becomes energetically favorable with respect to the assemblage of hcp-Fe and [Formula: see text]-FeO above 270 GPa, which indicates that I4/mmm-Fe 2 O can be a strong candidate phase for stable iron-rich iron oxides at high pressure, perhaps even at high temperature. The elasticity and anisotropy of I4/mmm-(Fe x Ni 1-x ) 2 O at high pressures are also determined. Based on these results, we have derived the upper limit of oxygen to be 4.3 wt% in Earth's lower outer core. On the other hand, I4/mmm-(Fe x Ni 1-x ) 2 O with high AV S is likely to exist in a super-Earth's or an ocean planet's solid core causing the locally seismic heterogeneity. Our results not only give some clues to explore and synthesize novel iron-rich iron oxides but also shed light on the fundamental information of oxygen in the planetary core.

Spectroscopic identification of rare earth elements in phosphate glass

NASA Astrophysics Data System (ADS)

Devangad, Praveen; Tamboli, Maktum; Muhammed Shameem, K. M.; Nayak, Rajesh; Patil, Ajeetkumar; Unnikrishnan, V. K.; Santhosh, C.; Kumar, G. A.

2018-01-01

In this work, rare earth-doped phosphate glasses were synthesized and characterized using three different spectroscopic techniques. The absorption spectra of the prepared praseodymium (Pr) and samarium (Sm) doped glasses, recorded by a UV-VIS-NIR spectrophotometer, show the characteristic absorption bands of these elements. To confirm this inference, laser-induced fluorescence spectra of Pr and Sm were obtained at a laser excitation of 442 nm. Their emission bands are reported here. The elemental analysis of these samples was carried out using a laser-induced breakdown spectroscopy (LIBS) system. Characteristic emission lines of Pr and Sm have been identified and reported by the recorded LIBS spectra of glass samples. Results prove that using these three complimentary spectroscopic techniques (absorption, fluorescence and LIBS), we can meaningfully characterize rare earth-doped glass samples.

Rare earth elements in sedimentary phosphate deposits: Solution to the global REE crisis?

USGS Publications Warehouse

Emsbo, Poul; McLaughlin, Patrick I.; Breit, George N.; du Bray, Edward A.; Koenig, Alan E.

2015-01-01

The critical role of rare earth elements (REEs), particularly heavy REEs (HREEs), in high-tech industries has created a surge in demand that is quickly outstripping known global supply and has triggered a worldwide scramble to discover new sources. The chemical analysis of 23 sedimentary phosphate deposits (phosphorites) in the United States demonstrates that they are significantly enriched in REEs. Leaching experiments using dilute H2SO4 and HCl, extracted nearly 100% of their total REE content and show that the extraction of REEs from phosphorites is not subject to the many technological and environmental challenges that vex the exploitation of many identified REE deposits. Our data suggest that phosphate rock currently mined in the United States has the potential to produce a significant proportion of the world's REE demand as a byproduct. Importantly, the size and concentration of HREEs in some unmined phosphorites dwarf the world's richest REE deposits. Secular variation in phosphate REE contents identifies geologic time periods favorable for the formation of currently unrecognized high-REE phosphates. The extraordinary endowment, combined with the ease of REE extraction, indicates that such phosphorites might be considered as a primary source of REEs with the potential to resolve the global REE (particularly for HREE) supply shortage.

Rare earth patterns in shergottite phosphates and residues

NASA Technical Reports Server (NTRS)

Laul, J. C.

1987-01-01

Leaching experiments with 1M HCl on ALHA 77005 powder show that rare earth elements (REE) are concentrated in accessory phosphate phases (whitlockite, apatite) that govern the REE patterns of bulk shergottites. The REE patterns of whitlockite are typically light REE-depleted with a negative Eu anomaly and show a hump at the heavy REE side, while the REE pattern of apatite (in Shergotty) is light REE-enriched. Parent magmas are calculated from the modal compositions of residues of ALHA 77005, Shergotty, and EETA 79001. The parent magmas lack a Eu anomaly, indicating that plagioclase was a late-stage crystallizing phase and that it probably crystallized before the phosphates. The parent magmas of ALHA 77005 and Shergotty have similar REE patterns, with a subchondritic Nd/Sm ratio. However, the Sm/Nd isotopoics require a light REE-depleted source for ALHA 77005 (if the crystallization age is less than 600 Myr) and a light REE-enriched source for Shergotty. Distant Nd and Sr isotopic signatures may suggest different source regions for shergottites.

Air Plasma-Sprayed La2Zr2O7-SrZrO3 Composite Thermal Barrier Coating Subjected to CaO-MgO-Al2O3-SiO2 (CMAS)

NASA Astrophysics Data System (ADS)

Cai, Lili; Ma, Wen; Ma, Bole; Guo, Feng; Chen, Weidong; Dong, Hongying; Shuang, Yingchai

2017-08-01

La2Zr2O7-SrZrO3 composite thermal barrier coatings (TBCs) were prepared by air plasma spray (APS). The La2Zr2O7-SrZrO3 composite TBCs covered with calcium-magnesium-aluminum-silicate (CMAS) powder, as well as the powder mixture of CMAS and spray-dried La2Zr2O7-SrZrO3 composite powder, were heat-treated at 1250 °C in air for 1, 4, 8, and 12 h. The phase constituents and microstructures of the reaction products were characterized by x-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. Experimental results showed that the La2Zr2O7-SrZrO3 composite TBCs had higher CMAS resistance than 8YSZ coating. A dense new layer developed between CMAS and La2Zr2O7-SrZrO3 composite TBCs during interaction, and this new layer consisted mostly of apatite (Ca2La8(SiO4)6O2) and c-ZrO2. The newly developed layer effectively protected the La2Zr2O7-SrZrO3 composite TBCs from further CMAS attack.

Bonding Transition in SiO2 Glass at High Pressures: Applications to SiO2 Liquid in Earth's Interior

NASA Astrophysics Data System (ADS)

Yoo, C.; Lin, J.; Fukui, H.; Prendergast, D.; Okuchi, T.; Cai, Y.; Hiraoka, N.; Trave, A.; Eng, P.; Hu, M. Y.; Chow, P.

2006-12-01

SiO2 and MgSiO3 liquids are two major components in the magma deep inside the Earth. Knowledge of their electronic bonding characters at high pressures is essential to understanding the complex properties of the materials in the melts. The nature of pressure-induced bonding change in amorphous SiO2 has been an intriguing and long-standing problem that remains to be further understood. For example, previous infrared and X-ray diffraction studies suggested that a continuous transformation from the four- to six-fold coordinated silicon occurred in amorphous SiO2 at high pressures, whereas separate optical Raman studies attributed to a pressure-induced shift in the local ring statistics and a breakdown in the intermediate-range order. Here we have studied the oxygen near K-edge spectra of SiO2 glass to 51 GPa obtained using X-ray Raman scattering in a diamond-anvil cell, which directly probes the electronic bonding character of the sample. Our results provide conclusive evidence for a pressure-induced electronic bonding transition in SiO2 glass at high pressures. Although a progressive decrease in the mean Si-O-Si angle in the SiO4 tetrahedra is believed to be responsible for the irreversible densification in SiO2 glass at high pressures, our observed transition is reversible upon decompression. A similar transformation is also expected to occur in silicate glasses and melts, which will most definitely alter their physical, mechanical and transport properties in the magma chamber deep in the Earth's interior. This work was performed under the auspices of the U.S. DOE by UC/LLNL under Contract W-7405-Eng-48.

Hydration energies and structures of alkaline earth metal ions, M2+(H2O)n, n = 5-7, M = Mg, Ca, Sr, and Ba.

PubMed

Rodriguez-Cruz, S E; Jockusch, R A; Williams, E R

1999-09-29

The evaporation of water from hydrated alkaline earth metal ions, produced by electrospray ionization, was studied in a Fourier transform mass spectrometer. Zero-pressure-limit dissociation rate constants for loss of a single water molecule from the hydrated divalent metal ions, M(2+)(H(2)O)(n) (M = Mg, Ca, and Sr for n = 5-7, and M = Ba for n = 4-7), are measured as a function of temperature using blackbody infrared radiative dissociation. From these values, zero-pressure-limit Arrhenius parameters are obtained. By modeling the dissociation kinetics using a master equation formalism, threshold dissociation energies (E(o)) are determined. These reactions should have a negligible reverse activation barrier; therefore, E(o) values should be approximately equal to the binding energy or hydration enthalpy at 0 K. For the hepta- and hexahydrated ions at low temperature, binding energies follow the trend expected on the basis of ionic radii: Mg > Ca > Sr > Ba. For the hexahydrated ions at high temperature, binding energies follow the order Ca > Mg > Sr > Ba. The same order is observed for the pentahydrated ions. Collisional dissociation experiments on the tetrahydrated species result in relative dissociation rates that directly correlate with the size of the metals. These results indicate the presence of two isomers for hexahydrated magnesium ions: a low-temperature isomer in which the six water molecules are located in the first solvation shell, and a high-temperature isomer with the most likely structure corresponding to four water molecules in the inner shell and two water molecules in the second shell. These results also indicate that the pentahydrated magnesium ions have a structure with four water molecules in the first solvation shell and one in the outer shell. The dissociation kinetics for the hexa- and pentahydrated clusters of Ca(2+), Sr(2+), and Ba(2+) are consistent with structures in which all the water molecules are located in the first solvation shell.

Physical and optical properties of calcium sulfate ultra-phosphate glass-doped Er2O3

NASA Astrophysics Data System (ADS)

Aliyu, Aliyu Mohammed; Hussin, R.; Deraman, Karim; Ahmad, N. E.; Danmadami, Amina M.; Yamusa, Y. A.

2018-03-01

The influence of erbium on physical and optical properties of calcium sulfate ultra-phosphate glass was investigated using conventional melt quench process. Selected samples of composition 20CaSO4 (80 - x) P2O5- xEr2O3 with 0.1 ≤x ≤ 0.9 mol.% were prepared and assessed. X-ray diffraction (XRD) techniques were used to confirm the amorphous nature of the said samples. The structural units of phosphate-based glass were assessed from Raman spectra as ultra-(Q3), meta-(Q2), pyro-(Q1) and orthophosphate (Q0) units. Depolymerization process of the glasses was testified for higher calcium oxide content and UV-visible for optical measurement. Thermal analysis have been investigated by means of thermogravimetric analysis. The results show the decomposition of materials in the temperature range of 25∘C-1000∘C. Er3+ absorption spectra were measured in the range of 400-1800nm. PL measurement was carried out in order to obtain the excitation and emission spectra of the samples. The emission spectra excited at 779nm comprises of 518nm, 550nm and 649nm of transition 4F9/2, 4S3/2 and 2H11/2 excited states to 4I15/2 ground state. In physical properties, the density calculated using Archimedes method is inversely proportional to molar volume with increase in Er3+ ions. Optical bandgap (Eg) were determined using Tauc’s plots for direct transitions where Eg (direct) decreases with increase in erbium content. The refractive index increases with decreasing molar volume; this may have a tendency for larger optical bandgap. The result obtained from the glass matrix indicates that erbium oxide-doped calcium sulfate ultra-phosphate may give important information for wider development of functional glasses.

Influence of CuO and ZnO addition on the multicomponent phosphate glasses: Spectroscopic studies

NASA Astrophysics Data System (ADS)

Szumera, Magdalena; Wacławska, Irena; Sułowska, Justyna

2016-06-01

The spectra of phosphate-silicate glasses from the P2O5-SiO2-K2O-MgO-CaO system modified with the addition of CuO or ZnO have been studied by means of FTIR, Raman and 31P MAS NMR spectroscopy. All glasses were synthesized by the conventional melt-quenching technique and their homogeneous chemical composition was controlled and confirmed. By using the aforementioned research techniques, the presence of structural units with various degrees of polymerization was shown in the structure of analyzed phosphate-silicate glasses: Q3, Q2, Q1 and Q0. It was found that an increase in the content of CuO or ZnO in the composition of analyzed glasses, which are introduced at the expense of decreasing amounts of CaO and MgO, has a different influence on the phospho-oxygen network. It was shown that copper ions cause its gradual polymerization, while zinc ions cause its depolymerization. At the same time, polymerization of the silico-oxygen subnetwork was found. Additionally, in the case of glasses containing increasing amounts of ZnO, a change of the role of zinc ions in the vitreous matrix was confirmed (from the modifier to a structure-forming component).

The effect of temperature cycling typical of low earth orbit satellites on thin films of YBa2Cu3O(7-x)

NASA Technical Reports Server (NTRS)

Mogro-Campero, A.; Turner, L. G.; Bogorad, A.; Herschitz, R.

1991-01-01

Thin films of YBa2Cu3O(7-x) (YBCO) were temperature cycled to simulate conditions of a low earth orbit satellite. In one series of tests, epitaxial and polycrystalline YBCO films were cycled between temperatures of +/- 80 C in vacuum and in nitrogen for hundreds of cycles. The room temperature resistance of an epitaxial YBCO film increased by about 10 percent, but the superconducting transition temperature was unchanged. The largest changes were for a polycrystalline YBCO film on oxidized silicon with a zirconia buffer layer, for which the transition temperature decreased by 3 K. An extended test was carried out for epitaxial films. After 3200 cycles (corresponding to about 230 days in space), transition temperatures and critical current densities remained unchanged.

1D nanostructured Na7V4(P2O7)4(PO4) as high-potential and superior-performance cathode material for sodium-ion batteries.

PubMed

Deng, Chao; Zhang, Sen

2014-06-25

Tailoring materials into nanostructure offers unprecedented opportunities in the utilization of their functional properties. High-purity Na7V4(P2O7)4(PO4) with 1D nanostructure is prepared as a cathode material for rechargeable Na-ion batteries. An efficient synthetic approach is developed by carefully controlling the crystal growth in the molten sodium phosphate. Based on the XRD, XPS, TG, and morphological characterization, a molten-salt assisted mechanism for nanoarchitecture formation is revealed. The prepared Na7V4(P2O7)4(PO4) nanorod has rectangle sides and preferential [001] growth orientation. GITT evaluation indicates that the sodium de/intercalation of Na7V4(P2O7)4(PO4) nanorod involves V(3+)/V(4+) redox reaction and Na5V(3.5+)4(P2O7)4(PO4) as intermediate phase, which results in two pairs of potential plateaus at the equilibrium potentials of 3.8713 V (V(3+)/V(3.5+)) and 3.8879 V (V(3.5+)/V(4+)), respectively. The unique nanoarchitecture of the phase-pure Na7V4(P2O7)4(PO4) facilitates its reversible sodium de/intercalation, which is beneficial to the high-rate capability and the cycling stability. The Na7V4(P2O7)4(PO4) cathode delivers 80% of the capacity (obtained at C/20) at the 10 C rate and 95% of the initial capacity after 200 cycles. Therefore, it is feasible to design and fabricate an advanced rechargeable sodium-ion battery by employment of 1D nanostructured Na7V4(P2O7)4(PO4) as the cathode material.

Exposure to tri-o-cresyl phosphate detected in jet airplane passengers.

PubMed

Liyasova, Mariya; Li, Bin; Schopfer, Lawrence M; Nachon, Florian; Masson, Patrick; Furlong, Clement E; Lockridge, Oksana

2011-11-01

The aircraft cabin and flight deck ventilation are supplied from partially compressed unfiltered bleed air directly from the engine. Worn or defective engine seals can result in the release of engine oil into the cabin air supply. Aircrew and passengers have complained of illness following such "fume events". Adverse health effects are hypothesized to result from exposure to tricresyl phosphate mixed esters, a chemical added to jet engine oil and hydraulic fluid for its anti-wear properties. Our goal was to develop a laboratory test for exposure to tricresyl phosphate. The assay was based on the fact that the active-site serine of butyrylcholinesterase reacts with the active metabolite of tri-o-cresyl phosphate, cresyl saligenin phosphate, to make a stable phosphorylated adduct with an added mass of 80 Da. No other organophosphorus agent makes this adduct in vivo on butyrylcholinesterase. Blood samples from jet airplane passengers were obtained 24-48 h after completing a flight. Butyrylcholinesterase was partially purified from 25 ml serum or plasma, digested with pepsin, enriched for phosphorylated peptides by binding to titanium oxide, and analyzed by mass spectrometry. Of 12 jet airplane passengers tested, 6 were positive for exposure to tri-o-cresyl phosphate that is, they had detectable amounts of the phosphorylated peptide FGEpSAGAAS. The level of exposure was very low. No more than 0.05 to 3% of plasma butyrylcholinesterase was modified. None of the subjects had toxic symptoms. Four of the positive subjects were retested 3 to 7 months following their last airplane trip and were found to be negative for phosphorylated butyrylcholinesterase. In conclusion, this is the first report of an assay that detects exposure to tri-o-cresyl phosphate in jet airplane travelers. Copyright © 2011 Elsevier Inc. All rights reserved.

Exposure to tri-o-cresyl phosphate detected in jet airplane passengers

PubMed Central

Liyasova, Mariya; Li, Bin; Schopfer, Lawrence M.; Nachon, Florian; Masson, Patrick; Furlong, Clement E.; Lockridge, Oksana

2011-01-01

The aircraft cabin and flight deck ventilation are supplied from partially compressed unfiltered bleed air directly from the engine. Worn or defective engine seals can result in the release of engine oil into the cabin air supply. Aircrew and passengers have complained of illness following such “fume events”. Adverse health effects are hypothesized to result from exposure to tricresyl phosphate mixed esters, a chemical added to jet engine oil and hydraulic fluid for its anti-wear properties. Our goal was to develop a laboratory test for exposure to tricresyl phosphate. The assay was based on the fact that the active-site serine of butyrylcholinesterase reacts with the active metabolite of tri-o-cresyl phosphate, cresyl saligenin phosphate, to make a stable phosphorylated adduct with an added mass of 80 Da. No other organophosphorus agent makes this adduct in vivo on butyrylcholinesterase. Blood samples from jet airplane passengers were obtained 24–48 hours after completing a flight. Butyrylcholinesterase was partially purified from 25 ml serum or plasma, digested with pepsin, enriched for phosphorylated peptides by binding to titanium oxide, and analyzed by mass spectrometry. Of 12 jet airplane passengers tested, 6 were positive for exposure to tri-o-cresyl phosphate that is, they had detectable amounts of the phosphorylated peptide FGEpSAGAAS. The level of exposure was very low. No more than 0.05 to 3% of plasma butyrylcholinesterase was modified. None of the subjects had toxic symptoms. Four of the positive subjects were retested 3 to 7 months following their last airplane trip and were found to be negative for phosphorylated butyrylcholinesterase. In conclusion, this is the first report of an assay that detects exposure to tri-o-cresyl phosphate in jet airplane travelers. PMID:21723309

The impact of transport processes on rare earth element patterns in marine authigenic and biogenic phosphates

NASA Astrophysics Data System (ADS)

Auer, Gerald; Reuter, Markus; Hauzenberger, Christoph A.; Piller, Werner E.

2017-04-01

Rare earth elements (REEs) are commonly used proxies to reconstruct water chemistry and oxygen saturation during the formation of authigenic and biogenic phosphates in marine environments. In the modern ocean REEs exhibit a distinct pattern with enrichment of heavy REEs and strong depletion in cerium (Ce). The wide range of REE enrichment patterns found in ancient marine phosphates lead to the proposition that water chemistry has been very different in the Earth's past. However, both early and late diagenesis are known to affect REE signatures in phosphates altering primary marine signals. Herein we present a dataset of REE signatures in 38 grain specific LA-ICP-MS measurements of isolated phosphate and carbonate grains in three discrete rock samples. The phosphates mainly consist of authigenic phosphates and phosphatized microfossils that formed in a microbially mediated micro-milieu. In addition, isolated biogenic and reworked phosphatic grains are also present. The phosphates are emplaced in bioclastic grain- to packstones deposited on a carbonate ramp setting in the central Mediterranean Sea during the middle Miocene Monterey event. The results reveal markedly different REE patterns (normalized to the Post Archean Australian Shale standard) in terms of total enrichment and pattern shape. Analyses of REE diagenesis proxies show that diagenetic alteration affected the samples only to a minor degree. Grain shape and REE patterns together indicate that authigenic, biogenic and reworked phosphates have distinct REE patterns irrespective of the sample. Our study shows that while REE patterns in phosphates do reflect water chemistry during authigenesis, they are often already heavily altered during reworking, a process, which can occur in geologically negligible timespans. REE patterns are therefore more likely to reflect complex enrichment processes after their formation. Similarities in the REE patterns of reworked and biogenic phosphate further suggest that the

Improved photocatalytic degradation of chlorophenol over Pt/Bi2WO6 on addition of phosphate

NASA Astrophysics Data System (ADS)

Meng, Jie; Xiong, Xianqiang; Zhang, Xiao; Xu, Yiming

2018-05-01

Bismuth tungstate (BiW) is a promising visible light photocatalyst. Herein we report a synergism between Pt and phosphate that increases the UV and visible light activities of BiW by factors of 32 and 15, respectively, for phenol degradation in neutral aqueous solution. BiW was home-made, followed by a photochemical deposition of Pt (Pt/BiW). On the addition of phosphate, the reaction rates on BiW and Pt/BiW in aqueous solution were decreased and increased, respectively. Such a phosphate effect was also observed from the reduction of O2 to H2O2, and from 2,4-dichlorophenol degradation. Moreover, the rate of phenol degradation was proportional to the amount of phosphate adsorption on Pt/BiW, and the phosphate activity increased in the order H3PO4 < H2PO4- < HPO42-. A (photo)electrochemical measurement revealed that Pt and phosphate catalyzed the electron reduction of O2 and the hole oxidation of phenol, respectively. A possible mechanism is proposed, involving the hole oxidation of phosphate into a phosphate radical, followed by phenol oxidation in aqueous phase. As phosphate loading exceeded 0.50 mM, however, the rates of phenol degradation on Pt/BiW under UV and visible light decreased with the phosphate loading. This is ascribed to recombination of the phosphate radicals into a less reactive peroxobiphosphate.

Photophysical Property and Photocatalytic Activity of New Gd2InSbO7 and Gd2FeSbO7 Compounds under Visible Light Irradiation

PubMed Central

Luan, Jingfei; Xu, Yong

2013-01-01

Gd2InSbO7 and Gd2FeSbO7 were synthesized first, and their structural and photocatalytic properties were studied. The lattice parameters and the band gaps for Gd2InSbO7 and Gd2FeSbO7 were 10.449546 Å, 10.276026 Å, 2.897 eV and 2.151 eV. The photocatalytic degradation of rhodamine B was performed with Gd2InSbO7 and Gd2FeSbO7 under visible light irradiation. Gd2InSbO7 and Gd2FeSbO7 had higher catalytic activity compared with Bi2InTaO7. Gd2FeSbO7 exhibited higher catalytic activity than Gd2InSbO7. The photocatalytic degradation of rhodamine B followed with the first-order reaction kinetics, and the first-order rate constant k was 0.01606, 0.02220 or 0.00329 min−1 with Gd2InSbO7, Gd2FeSbO7 or Bi2InTaO7 as photocatalyst. Complete removal of rhodamine B was observed after visible light irradiation for 225 min or 260 min with Gd2FeSbO7 or Gd2InSbO7 as photocatalyst. The evolution of CO2 was realized, and it indicated continuous mineralization of rhodamine B during the photocatalytic process. The possible photocatalytic degradation pathway of rhodamine B was proposed. PMID:23296275

Phonon-mediated spin-flipping mechanism in the spin ices Dy 2 Ti 2 O 7 and Ho 2 Ti 2 O 7

DOE PAGES

Ruminy, M.; Chi, S.; Calder, S.; ...

2017-02-21

To understand emergent magnetic monopole dynamics in the spin ices Ho 2Ti 2O 7 and Dy 2Ti 2O 7, it is necessary to investigate the mechanisms by which spins flip in these materials. Presently there are thought to be two processes: quantum tunneling at low and intermediate temperatures and thermally activated at high temperatures. We identify possible couplings between crystal field and optical phonon excitations and construct a strictly constrained model of phonon-mediated spin flipping that quantitatively describes the high-temperature processes in both compounds, as measured by quasielastic neutron scattering. We support the model with direct experimental evidence of themore » coupling between crystal field states and optical phonons in Ho 2Ti 2O 7.« less

Preparation and characterization of TiO2 and Si-doped octacalcium phosphate composite coatings on zirconia ceramics (Y-TZP) for dental implant applications

NASA Astrophysics Data System (ADS)

Bao, Lei; Liu, Jingxiao; Shi, Fei; Jiang, Yanyan; Liu, Guishan

2014-01-01

In order to prevent the low temperature degradation and improve the bioactivity of zirconia ceramic implants, TiO2 and Si-doped octacalcium phosphate composite coating was prepared on zirconia substrate. The preventive effect on low temperature degradation and surface morphology of the TiO2 layer were studied. Meanwhile, the structure and property changes of the bioactive coating after doping Si were discussed. The results indicate that the dense TiO2 layer, in spite of some microcracks, inhibited the direct contact of the water vapor with the sample's surface and thus prevented the low temperature degradation of zirconia substrates. The acceleration aging test shows that the ratio of the monoclinic phase transition decreased from 10% for the original zirconia substrate to 4% for the TiO2-coated substrate. As to the Si-doped octacalcium phosphate coating prepared by biomimetic method, the main phase composition of the coating was octacalcium phosphate. The morphology of the coating was lamellar-like, and the surface was uniform and continuous with no cracks being observed. It is suggested that Si was added into the coating both through substituting for PO43- and doping as NaSiO3.

Silver indium diphosphate, AgInP(2)O(7).

PubMed

Zouihri, Hafid; Saadi, Mohamed; Jaber, Boujemaa; El Ammari, Lehcen

2010-12-18

Polycrystalline material of the title compound, AgInP(2)O(7), was synthesized by traditional high-temperature solid-state methods and single crystals were grown from the melt of a mixture of AgInP(2)O(7) and B(2)O(3) as flux in a platinium crucible. The structure consists of InO(6) octa-hedra, which are corner-shared to PO(4) tetra-hedra into a three-dimensional network with hexa-gonal channels running parallel to the c axis. The silver cation, located in the channel, is bonded to seven O atoms of the [InP(2)O(7)] framework with Ag-O distances ranging from 2.370 (2) to 3.015 (2) Å. The P(2)O(7) diphosphate anion is characterized by a P-O-P angle of 137.27 (9) and a nearly eclipsed conformation. AgInP(2)O(7) is isotypic with the M(I)FeP(2)O(7) (M(I) = Na, K, Rb, Cs and Ag) diphosphate family.

Dithallium(III)-Containing 30-Tungsto-4-phosphate, [Tl2Na2(H2O)2(P2W15O56)2]16-: Synthesis, Structural Characterization, and Biological Studies.

PubMed

Ayass, Wassim W; Fodor, Tamás; Farkas, Edit; Lin, Zhengguo; Qasim, Hafiz M; Bhattacharya, Saurav; Mougharbel, Ali S; Abdallah, Khaled; Ullrich, Matthias S; Zaib, Sumera; Iqbal, Jamshed; Harangi, Sándor; Szalontai, Gábor; Bányai, István; Zékány, László; Tóth, Imre; Kortz, Ulrich

2018-06-18

Here we report on the synthesis and structural characterization of the dithallium(III)-containing 30-tungsto -4-phosphate [Tl 2 Na 2 (H 2 O) 2 {P 2 W 15 O 56 } 2 ] 16- (1) by a multitude of solid-state and solution techniques. Polyanion 1 comprises two octahedrally coordinated Tl 3+ ions sandwiched between two trilacunary {P 2 W 15 } Wells-Dawson fragments and represents only the second structurally characterized, discrete thallium-containing polyoxometalate to date. The two outer positions of the central rhombus are occupied by sodium ions. The title polyanion is solution-stable as shown by 31 P and 203/205 Tl NMR. This was also supported by Tl NMR spectra simulations including several spin systems of isotopologues with half-spin nuclei ( 203 Tl, 205 Tl, 31 P, 183 W). 23 Na NMR showed a time-averaged signal of the Na + counter cations and the structurally bonded Na + ions. 203/205 Tl NMR spectra also showed a minor signal tentatively attributed to the trithallium-containing derivative [Tl 3 Na(H 2 O) 2 (P 2 W 15 O 56 ) 2 ] 14- , which could also be identified in the solid state by single-crystal X-ray diffraction. The bioactivity of polyanion 1 was also tested against bacteria and Leishmania.

The primary solar-type atmosphere surrounding the accreting Earth: H2O-induced high surface temperature.

NASA Astrophysics Data System (ADS)

Sasaki, S.

In the solar nebula, a growing planet attracts ambient gas to form a solar-type atmosphere. The structure of this H2-He atmosphere is calculated assuming the Earth was formed in the nebula. The blanketing effect of the atmosphere renders the planetary surface molten when the planetary mass exceeds 0.2 ME (ME being the present Earth's mass). Reduction of the surface melt by atmospheric H2 should add a large amount of H2O to the atmosphere: under the quartz-iron-fayalite oxygen buffer, partial pressure ratio P(H2O)/P(H2) becomes higher than 0.1. Enhancing opacity and gas mean molecular weight, the excess H2O raises the temperature and renders the atmosphere in convective equilibrium, while the dissociation of H2 suppresses the adiabatic temperature gradient. The surface temperature of the proto-Earth can be as high as 4700K when its mass is 1 ME. Such a high temperature may accelerate the evaporation of surface materials. A deep totally-molten magma ocean should exist in the accretion Earth.

Catalase activity is stimulated by H2O2 in rich culture medium and is required for H2O2 resistance and adaptation in yeast☆

PubMed Central

Martins, Dorival; English, Ann M.

2014-01-01

Catalases are efficient scavengers of H2O2 and protect cells against H2O2 stress. Examination of the H2O2 stimulon in Saccharomyces cerevisiae revealed that the cytosolic catalase T (Ctt1) protein level increases 15-fold on H2O2 challenge in synthetic complete media although previous work revealed that deletion of the CCT1 or CTA1 genes (encoding peroxisomal/mitochondrial catalase A) does not increase the H2O2 sensitivity of yeast challenged in phosphate buffer (pH 7.4). This we attributed to our observation that catalase activity is depressed when yeast are challenged with H2O2 in nutrient-poor media. Hence, we performed a systematic comparison of catalase activity and cell viability of wild-type yeast and of the single catalase knockouts, ctt1∆ and cta1∆, following H2O2 challenge in nutrient-rich medium (YPD) and in phosphate buffer (pH 7.4). Ctt1 but not Cta1 activity is strongly induced by H2O2 when cells are challenged in YPD but suppressed when cells are challenged in buffer. Consistent with the activity results, exponentially growing ctt1∆ cells in YPD are more sensitive to H2O2 than wild-type or cta1∆ cells, whereas in buffer all three strains exhibit comparable H2O2 hypersensitivity. Furthermore, catalase activity is increased during adaptation to sublethal H2O2 concentrations in YPD but not in buffer. We conclude that induction of cytosolic Ctt1 activity is vital in protecting yeast against exogenous H2O2 but this activity is inhibited by H2O2 when cells are challenged in nutrient-free media. PMID:24563848

Optical evaluation on Nd3+-doped phosphate glasses for O-band amplification.

PubMed

Lei, Weihong; Chen, Baojie; Zhang, Xiangling; Pun, Edwin Yun Bun; Lin, Hai

2011-02-20

We have fabricated and characterized optically Nd3+-doped phosphate [Li2O-CaO-BaO-Al2O3-La2O3-P2O5 (LCBALP)] glasses for drawing single-mode glass fiber. The 4F3/2→4I13/2 transition emission from the Nd3+ is at the 1.327 μm wavelength with a full width at half-maximum of 43 nm, and the spontaneous transition probability and quantum efficiency are calculated to be 1836 s-1 and 52%, respectively. The maximum stimulated emission cross sections for 4F3/2→4I11/2 and 4F3/2→4I13/2 transitions are derived to be 1.82×10(-20) cm2 and 6.97×10(-21) cm2, respectively, and the theoretical gain coefficient at the 1.327 μm wavelength is evaluated to be 0.182 dB/cm when the fractional factor of the excited neodymium ions equals 0.6, which indicates that Nd3+-doped LCBALP phosphate glasses are potential candidates in developing O-band optical fiber amplifiers.

Feasibility studies for the detection of O{sub 2} in an Earth-like exoplanet

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodler, Florian; López-Morales, Mercedes

2014-01-20

We present the results of simulations on the detectability of O{sub 2} in the atmosphere of Earth twins around nearby low mass stars using high resolution transmission spectroscopy. We explore such detectability with each of the three upcoming Extremely Large Telescopes (ELTs), i.e., GMT, TMT, and E-ELT, and high resolution spectrographs, assuming such instruments will be available in all ELTs. With these simulations we extend previous studies by taking into account atmospheric refraction in the transmission spectrum of the exo-Earth and observational white and red noise contributions. Our studies reveal that the number of transits necessary to detect O{sub 2}more » in the atmosphere of an Earth twin around an M dwarf is by far higher than the number of transits estimated by Snellen et al. In addition, our simulations show that, when accounting for typical noise levels associated with observations in the optical and near-infrared, the O{sub 2} A band at 760 nm is more favorable for detecting the exoplanetary signal than the O{sub 2} band at 1268 nm for all the spectral types, except M9V. We conclude that, unless unpredicted instrumental limitations arise, the implementation of pre-slit optics such as image slicers appears to be key to significantly improving the yield of this particular science case. However, even in the most optimistic cases, we conclude that the detection of O{sub 2} in the atmosphere of an Earth twin will only be feasible with the ELTs if the planet is orbiting a bright close by (d ≤ 8 pc) M dwarf with a spectral type later than M3.« less

Suitability of the rare-earth compounds Dy2Ti2O7 and Gd3Al5O12 for low temperature (4K-20K) magnetic refrigeration cycle

NASA Technical Reports Server (NTRS)

Flood, D. J.

1973-01-01

Measurements were made of the magnetic entropy and magnetization of powered samples of the compounds Dy2Ti2O7 and Gd3Al5O12. The magnetization was measured for temperatures at and below 4.2 K, in applied fields ranging to 7.0 tesla. Isothermal changes in magnetic entropy were measured for temperatures from 1.2 to 20 K, in applied fields up to 10 tesla. The results of the measurements are consistent with a doublet ground state for Dy2Ti2O7, and an eight-fold degenerate ground state for Gd3Al5O12. Absolute values of magnetic entropy have been obtained at the lower temperatures, permitting the isotherms to be properly located in the S-H plane with the use of adiabatic magnetization data. The iso-field lines in the S-T plane were determined. The results indicate that Dy2Ti2O7 can absorb a maximum of 71 + or - 4 joules/kg of heat at 4.2 K, while Gd3Al5O12 can absorb 233 + or - joules/kg at the same temperature. The large difference between the two is most likely a result of crystal field interactions in the dysoprosium compound. Both materials can be cycled adiabatically between 4.2 and 20 K.

The role of Bi2O3 on the thermal, structural, and optical properties of tungsten-phosphate glasses.

PubMed

Manzani, Danilo; de Araújo, Cid B; Boudebs, Georges; Messaddeq, Younès; Ribeiro, Sidney J L

2013-01-10

Glasses in the ternary system (70 - x)NaPO(3)-30WO(3)-xBi(2)O(3), with x = 0-30 mol %, were prepared by the conventional melt-quenching technique. X-ray diffraction (XRD) measurements were performed to confirm the noncrystalline nature of the samples. The influence of the Bi(2)O(3) on the thermal, structural, and optical properties was investigated. Differential scanning calorimetry analysis showed that the glass transition temperature, T(g), increases from 405 to 440 °C for 0 ≤ x ≤ 15 mol % and decreases to 417 °C for x = 30 mol %. The thermal stability against devitrification decreases from 156 to 67 °C with the increase of the Bi(2)O(3) content. The structural modifications were studied by Raman scattering, showing a bismuth insertion into the phosphate chains by Bi-O-P linkage. Furthermore, up to 15 mol % of Bi(2)O(3) formation of BiO(6) clusters is observed, associated with Bi-O-Bi linkage, resulting in a progressive break of the linear phosphate chains that leads to orthophosphate Q(0) units. The linear refractive index, n(0), was measured using the prism-coupler technique at 532, 633, and 1550 nm, whereas the nonlinear (NL) refractive index, n(2) was measured at 1064 nm using the Z-scan technique. Values of 1.58 ≤ n(0) ≤ 1.88, n(2) ≥ 10(-15) cm(2)/W and NL absorption coefficient, α(2) ≤ 0.01 cm/GW, were determined. The linear and NL refractive indices increase with the increase of the Bi(2)O(3) concentration. The large values of n(0) and n(2), as well as the very small α(2), indicate that these materials have large potential for all-optical switching applications in the near-infrared.

Extraction of trivalent rare-earth metal nitrates by solutions of tributyl phosphate and diisooctylmethylphosphonate in kerosene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pyartman, A.K.; Puzikov, E.A.; Kopyrin, A.A.

1995-01-01

Isotherms of extraction of trivalent rare-earth metal nitrates in the series lanthanum-lutetium, yttrium by 0.5-2.5 M solutions of tri-n-buty1 phosphate and diisooctyl methylphosphonate in kerosene at 298.15 K, pH 2 are presented. The influence of the ionic strength of aqueous phase and extractant concentration on the concentration extraction constants in the case of formation of metal(III) trisolvates in organic phase is given by equation.

A mini-review on rare earth metal-doped TiO2 for photocatalytic remediation of wastewater.

PubMed

Saqib, Najm Us; Adnan, Rohana; Shah, Irfan

2016-08-01

Titanium dioxide (TiO2) has been considered a useful material for the treatment of wastewater due to its non-toxic character, chemical stability and excellent electrical and optical properties which contribute in its wide range of applications, particularly in environmental remediation technology. However, the wide band gap of TiO2 photocatalyst (anatase phase, 3.20 eV) limits its photocatalytic activity to the ultraviolet region of light. Besides that, the electron-hole pair recombination has been found to reduce the efficiency of the photocatalyst. To overcome these problems, tailoring of TiO2 surface with rare earth metals to improve its surface, optical and photocatalytic properties has been investigated by many researchers. The surface modifications with rare earth metals proved to enhance the efficiency of TiO2 photocatalyts by way of reducing the band gap by shifting the working wavelength to the visible region and inhibiting the anatase-to-rutile phase transformations. This review paper summarises the attempts on modification of TiO2 using rare earth metals describing their effect on the photocatalytic activities of the modified TiO2 photocatalyst.

FeO and H-2O and the homogeneous accretion of the earth

NASA Technical Reports Server (NTRS)

Lange, M. A.; Ahrens, T. J.

1983-01-01

Shock devolatilization recovery data for brunite (Mg(OH)2) shocked to 13 and 23 GPa are presented. These data combined with previous data for serpentine (Mg3Si2O5(OH)4) are used to constrain the minimum size terrestrial planet for which planetesimal infall will result in an impact generated water atmosphere. Assuming, in hydrous phyllosilicates, model calculations simulating the interaction of metallic iron with impact released free water on the surface of the accreting Earth were carried out. It is assumed that the reaction of water with iron in the presence of enstatite is the prime source of the terrestrial FeO component of silicates and oxides. Lower and upper bounds on the terrestrial FeO budget are based on mantle FeO content and possible incorporation of FeO in the outer core. We demonstrate that the iron water reaction would result in the absence of atmospheric/hydrospheric water, if homogeneous accretion is assumed.

FeO and H2O and the homogeneous accretion of the earth

NASA Technical Reports Server (NTRS)

Lange, M. A.; Ahrens, T. J.

1984-01-01

Shock devolatilization recovery data for brunite (Mg(OH)2) shocked to 13 and 23 GPa are presented. These data combined with previous data for serpentine (Mg3Si2O5(OH)4) are used to constrain the minimum size terrestrial planet for which planetesimal infall will result in an impact generated water atmosphere. Assuming, in hydrous phyllosilicates, model calculations simulating the interaction of metallic iron with impact released free water on the surface of the accreting earth were carried out. It is assumed that the reaction of water with iron in the presence of enstatite is the prime source of the terrestrial FeO component of silicates and oxides. Lower and upper bounds on the terrestrial FeO budget are based on mantle FeO content and possible incorporation of FeO in the outer core. We demonstrate that the iron water reaction would resuit in the absence of atmospheric/hydrospheric water, if homogeneous accretion is assumed.

Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln3OsO7 (Ln=Pr, Tb)

NASA Astrophysics Data System (ADS)

Hinatsu, Yukio; Doi, Yoshihiro

2013-02-01

Ternary rare-earth osmates Ln3OsO7 (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr3OsO7 exhibits magnetic transitions at 8 and 73 K, and Tb3OsO7 magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln3+ sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice.

Mn0.95I0.02[PO3(OH)] · 2H2O phosphate-iodate, an inorganic analogue of phosphonates

NASA Astrophysics Data System (ADS)

Belokoneva, E. L.; Dimitrova, O. V.; Volkov, A. S.

2015-09-01

The new Mn0.95I0.02[PO3(OH)] · 2H2O phosphate-iodate (space group Pnam = Pnma, D {2/h 16}) is obtained under hydrothermal conditions. The crystal structure is determined without preliminary knowledge of the chemical formula. The structure consists of layers of MnО6 octahedra connected with PO4 tetrahedra. Water molecules are located between the layers. [IO3]- groups having a typical umbrella-like coordination are statistically implanted in layers of MnО6 octahedra at a distance of 1.2 Å from Mn atoms. Their content in the crystal is minor. The structures of the phosphate-iodate coincides with the structures of phosphonates with consideration for the replacement of one (OH) vertex of the РО4 tetrahedron by the organic methyl radical СН3. In the structures of phosphonates and earlier studied phosphates, identical layers are distinguished and the cause of the existence of two MDO varieties is established based on the analysis within the OD theory. Possible hybrid structures derived from the prototypes under consideration are predicted.

Short range structure of 0.35Sb2O3-0.65(Li2O-P2O5) glass: A neutron diffraction study

NASA Astrophysics Data System (ADS)

Shinde, A. B.; Krishna, P. S. R.

2018-04-01

Neutron diffraction studies on Li2O-P2O5 and 0.35Sb2O3-0.65(Li2O-P2O5) glass are performed up to a Qmax of 15 Å-1 on the High-Q diffractometer, Dhruva. MCGR method is used to find pair correlation functions (g(r)) functions from experimentally obtained S(Q). We found that the Li-O and first Sb-O correlations to be around 2.04 Å & 2.15 Å. The O-O correlation from Phosphate & Antimony networks are found to be around 2.7 Å. The short range order of Sb is similar to its crystalline polymorph of valentinite instead of senarmonite. The short range order and network connectivity in this glass implies a structure composed of chains of corner sharing SbO3 pyramidal units connected to PO4 tetrahedra while Li acts as a modifier.

Dual spectra band emissive Eu2+/Mn2+ co-activated alkaline earth phosphates for indoor plant growth novel phosphor converted-LEDs.

PubMed

Yun, Young Jun; Kim, Jin Kyu; Ju, Ji Young; Choi, Seul Ki; Park, Woon Ik; Suh, Jae Yong; Jung, Ha-Kyun; Kim, Yongseon; Choi, Sungho

2017-05-10

This paper reports designing a novel single composition blue/red color illuminating phosphor followed by fabricating "smart" agricultural/horticultural LED lighting. Color-tunable Eu 2+ /Mn 2+ co-activated alkaline earth phosphates, Na(Sr,Ba)PO 4 and Ca 3 Mg 3 (PO 4 ) 4 , are considered, and the stable doping sites for the corresponding activators are identified by using first-principle DFT calculations. We can realize the designated color purity with stable thermal quenching preserved luminescence behavior is induced by the Eu 2+ center positioned at different coordination states with intermixed Sr 2+ /Ba 2+ sites in Na(Sr,Ba)PO 4 hosts. Moreover, we demonstrate that the resultant LED lighting adopting the proposed novel phosphor composition stimulates the enhanced photosynthesis reaction for indoor hydroponics plants, such as oats and onions, which is superior to the narrow line emission band induced by the mixture of conventional red/green/blue LEDs. Thus, using the color-tunable single composition luminescent material may produce an innovative energy-efficient artificial lighting for indoor plant growth.

Two isotypic diphosphates LiM{sub 2}H{sub 3}(P{sub 2}O{sub 7}){sub 2} (M=Ni, Co) containing ferromagnetic zigzag MO{sub 6} chains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang Tao; Yang Sihai; Liao Fuhui

2008-06-15

Two new isotypic phosphates LiNi{sub 2}H{sub 3}(P{sub 2}O{sub 7}){sub 2} (1) and LiCo{sub 2}H{sub 3}(P{sub 2}O{sub 7}){sub 2} (2) have been hydrothermally synthesized and structurally characterized by the single-crystal X-ray diffraction technique. They crystallize in the monoclinic space group C2/c with the lattice: a=10.925(2) A, b=12.774(3) A, c=8.8833(18) A, {beta}=123.20(3){sup o} for 1 and a=10.999(2) A, b=12.863(3) A, c=8.9419(18) A, {beta}=123.00(3){sup o} for 2. The transition metal atoms are octahedrally coordinated, whereas the lithium and phosphorus atoms are all tetrahedrally coordinated. As the lithium-induced derivatives of MH{sub 2}P{sub 2}O{sub 7} (M=Ni, Co), 1 and 2 possess the same structure withmore » MH{sub 2}P{sub 2}O{sub 7} in terms of topology, comprising the MO{sub 6} zigzag chains and P{sub 2}O{sub 7} as the interchain groups. The magnetisms of 1 and 2 could be interpreted by adopting a quasi-one-dimensional (1D) zigzag chain model as that in their parent compounds: both 1 and 2 have ferromagnetic (FM) NiO{sub 6}/CoO{sub 6} chains; 1 shows a FM cluster glass behavior at low temperatures, which is originated from the possible antiferromagnetic (AFM) next-nearest-neighbour intrachain interactions; 2 shows a AFM ordering at T{sub N}=2.6 K and a metamagnetic transition at H{sub C}=4.2 kOe at 1.8 K. - Graphical abstract: LiNi{sub 2}H{sub 3}(P{sub 2}O{sub 7}){sub 2} (1) and LiCo{sub 2}H{sub 3}(P{sub 2}O{sub 7}){sub 2} (2) have been hydrothermally synthesized and structurally characterized. The MO{sub 6} octahedra share edges forming zigzag chains with P{sub 2}O{sub 7} as the interchain groups. Both of them are quasi-one-dimensional magnets and have ferromagnetic MO{sub 6} chains; 1 is a ferromagnet, whereas 2 is a metamagnet.« less

Synthesis of rare earth doped TiO2 nanorods as photocatalysts for lignin degradation.

PubMed

Song, Liang; Zhao, Xueyuan; Cao, Lixin; Moon, Ji-Won; Gu, Baohua; Wang, Wei

2015-10-28

A two-step process is developed to synthesize rare earth doped titania nanorods (RE-TiO2 NRs) as photocatalysts for efficient degradation of lignin under simulated sunlight irradiation. In this approach, protonated titanate nanotubes with layered structures were first prepared by a hydrothermal approach, and rare earth metal ions were subsequently bound to the negatively charged surface of the synthesized titanate via electrostatic incorporation. The as-synthesized RE-TiO2 NRs after calcination generally showed much higher photocatalytic efficiencies than those of undoped TiO2 NRs or the commercial P25 TiO2 photocatalyst. Using methyl orange (MO) as a probing molecule, we demonstrate that Eu-TiO2 NRs are among the best for degrading MO, with an observed rate constant of 4.2 × 10(-3) s(-1). The La(3+), Sm(3+), Eu(3+) and Er(3+) doped TiO2 NRs also showed higher photocatalytic efficiencies in degrading MO than the commercial P25 TiO2. We further demonstrate that lignin can be photodegraded effectively and rapidly at room temperature under simulated sunlight through two reaction routes, which could be important in controlling ways of lignin depolymerization or the formation of reaction products.

Synthesis of rare earth doped TiO 2 nanorods as photocatalysts for lignin degradation

DOE PAGES

Song, Liang; Zhao, Xueyuan; Cao, Lixin; ...

2015-09-10

In this paper, a two-step process is developed to synthesize rare earth doped titania nanorods (RE–TiO 2 NRs) as photocatalysts for efficient degradation of lignin under simulated sunlight irradiation. In this approach, protonated titanate nanotubes with layered structures were first prepared by a hydrothermal approach, and rare earth metal ions were subsequently bound to the negatively charged surface of the synthesized titanate via electrostatic incorporation. The as-synthesized RE–TiO 2 NRs after calcination generally showed much higher photocatalytic efficiencies than those of undoped TiO 2 NRs or the commercial P25 TiO 2 photocatalyst. Using methyl orange (MO) as a probing molecule,more » we demonstrate that Eu–TiO 2 NRs are among the best for degrading MO, with an observed rate constant of 4.2 × 10 -3 s -1. The La 3+, Sm 3+, Eu 3+ and Er 3+ doped TiO 2 NRs also showed higher photocatalytic efficiencies in degrading MO than the commercial P25 TiO 2. Finally, we further demonstrate that lignin can be photodegraded effectively and rapidly at room temperature under simulated sunlight through two reaction routes, which could be important in controlling ways of lignin depolymerization or the formation of reaction products.« less

Topological analysis of void space in phosphate frameworks: Assessing storage properties for the environmentally important guest molecules and ions: CO 2, H 2O, UO 2, PuO 2, U, Pu, Sr 2+, Cs +, CH 4, and H 2

DOE PAGES

Cramer, Alisha J.; Cole, Jacqueline M.

2016-06-27

The entrapment of environmentally important materials to enable containment of polluting wastes from industry or energy production, storage of alternative fuels, or water sanitation, is of vital and immediate importance. Many of these materials are small molecules or ions that can be encapsulated via their adsorption into framework structures to create a host-guest complex. This is an ever-growing field of study and, as such, the search for more suitable porous materials for environmental applications is fundamental to progress. However, many industrial areas that require the use of adsorbents are fraught with practical challenges such as high temperatures, rapid gas expansion,more » radioactivity, or repetitive gas cycling, that the host material must withstand. Inorganic phosphates have a proven history of rigid structures, thermal stability, and are suspected to possess good resistance to radiation over geologic time scales. Furthermore, various experimental studies have established their ability to adsorb small molecules, such as water. In light of this, all known crystal structures of phosphate frameworks with meta- (P 3O 9) or ultra- (P 5O 14) stoichiometries are combined in a data-mining survey together with all theoretically possible structures of Ln aP bO c (where a, b, c are any integer, and Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, or Tm) that are statistically likely to form. Topological patterns within these framework structures are used to assess their suitability for hosting a variety of small guest molecules or ions that are important for environmental applications: CO 2, H 2O, UO 2, PuO 2, U, Pu, Sr 2+, Cs +, CH 4 and H 2. A range of viable phosphate-based host-guest complexes are identified from this data-mining and pattern-based structural analysis. Moreover, distinct topological preferences for hosting such guests are found, and metaphosphate stoichiometries are generally preferred over ultraphosphate configurations.« less

Fe(III) reduction-mediated phosphate removal as vivianite (Fe3(PO4)2⋅8H2O) in septic system wastewater.

PubMed

Azam, Hossain M; Finneran, Kevin T

2014-02-01

Phosphate is a water contaminant from fertilizers, soaps, and detergents that enters municipal and onsite wastewater from households, businesses, and other commercial operations. Phosphate is a limiting nutrient for algae, and is one of the molecules that promotes eutrophication of water bodies. Phosphate is especially problematic in onsite wastewater because there are few removal mechanisms under normal operating conditions; a system must be amended specifically with compounds to bond to or adsorb phosphate in the septic tank or within the leach field. Vivianite (Fe3(PO4)2⋅8H2O) is a stable mineral formed from ferrous iron and phosphate, often as the result of Fe(III) reducing microbial activity. What was unknown was the concentration of phosphate that could be removed by this process, and whether it was relevant to mixed microbial systems like septic tank wastewater. Data presented here demonstrate that significant concentrations of phosphate (12-14mM) were removed as vivianite in growing cultures of Geobacter metallireducens strain GS-15. Vivianite precipitates were identified on the cell surfaces and within multi cell clusters using TEM-EDX; the mineral phases were directly characterized using XRD. Phosphate was also removed in dilute and raw (undiluted) septic wastewater amended with different forms of Fe(III) including solid phase and soluble Fe(III). Vivianite precipitates were recovered and identified using XRD, along with siderite (ferrous carbonate), which was expected given that the systems were likely bicarbonate buffered. These data demonstrate that ferric iron amendments in septic wastewater increase phosphate removal as the mineral vivianite, and this may be a good strategy for phosphate attenuation in the septic tank portion of onsite wastewater systems. Copyright © 2013 Elsevier Ltd. All rights reserved.

Synthesis of the missing oxide of xenon, XeO2, and its implications for Earth's missing xenon.

PubMed

Brock, David S; Schrobilgen, Gary J

2011-04-27

The missing Xe(IV) oxide, XeO(2), has been synthesized at 0 °C by hydrolysis of XeF(4) in water and 2.00 M H(2)SO(4(aq)). Raman spectroscopy and (16/18)O isotopic enrichment studies indicate that XeO(2) possesses an extended structure in which Xe(IV) is oxygen bridged to four neighboring oxygen atoms to give a local square-planar XeO(4) geometry based on an AX(4)E(2) valence shell electron pair repulsion (VSEPR) arrangement. The vibrational spectra of Xe(16)O(2) and Xe(18)O(2) amend prior vibrational assignments of xenon doped SiO(2) and are in accordance with prior speculation that xenon depletion from the Earth's atmosphere may occur by xenon insertion at high temperatures and high pressures into SiO(2) in the Earth's crust.

Disappearance of the metal-insulator transition in iridate pyrochlores on approaching the ideal R2Ir2O7 stoichiometry

NASA Astrophysics Data System (ADS)

Sleight, Arthur W.; Ramirez, Arthur P.

2018-07-01

Recently, rare earth iridates, R2Ir2O7, with the pyrochlore structure have been intensively investigated due to their promise as either topological Mott insulators or Weyl semimetals. Single crystals of such pyrochlores with R = Nd, Sm, Eu, and Dy were prepared hydrothermally in sealed gold tubes at 975 K and show significantly higher electrical resistivities than previously reported for either crystals or polycrystalline samples. Furthermore, none of the present crystals exhibit the metal-insulator transition found for some samples of these phases. Lower resistivities are ascribed to lack of control of x and y in R2-xIr2O7-y in other more commonly used synthesis methods, yielding uncertainty in the Ir oxidation state. We also report resistivity of R2Ru2O7 crystals for R = Yb, Gd, Eu, and Nd, prepared in the same manner. These results suggest that the observed charge transport in hydrothermally grown iridate crystals is that of essentially stoichiometric phases and is consistent a with the existence of Weyl nodes.

Identification and structural characterization of O-beta-ribosyl-(1"----2')-adenosine-5"-phosphate in yeast methionine initiator tRNA.

PubMed Central

Keith, G; Glasser, A L; Desgrès, J; Kuo, K C; Gehrke, C W

1990-01-01

We report in this paper on the complete structure determination of the modified nucleotide A*, now called Ar(p), that was previously identified in yeast methionine initiator tRNA as an isomeric form of O-ribosyl-adenosine bearing an additional phosphoryl-monoester group on its ribose2 moiety. By using the chemical procedure of periodate oxidation and subsequent beta-elimination with cyclohexylamine on mono- and dinucleotides containing Ar(p), we characterized the location of the phosphate group on the C-5" of the ribose2 moiety, and the linkage between the two riboses as a (1"----2')-glycosidic bond. Since the structural difference between phosphatase treated Ar(p) and authentic O-alpha-ribosyl-(1"----2')-adenosine from poly(ADP-Ribose) was previously assigned to an isomeric difference in the ribose2-ribose1 linkage, the (1"----2')-glycosidic bond of Ar(p) was deduced to have a beta-spatial configuration. Thus, final chemical structure for Ar(p) at the position 64 in yeast initiator tRNA(Met) has been established as O-beta-ribosyl-(1"----2')-adenosine-5"-phosphate. This nucleotide is linked by a 3',5'-phosphodiester bond to G at the position 65. PMID:2235481

Identification and structural characterization of O-beta-ribosyl-(1"----2')-adenosine-5"-phosphate in yeast methionine initiator tRNA.

PubMed

Keith, G; Glasser, A L; Desgrès, J; Kuo, K C; Gehrke, C W

1990-10-25

We report in this paper on the complete structure determination of the modified nucleotide A*, now called Ar(p), that was previously identified in yeast methionine initiator tRNA as an isomeric form of O-ribosyl-adenosine bearing an additional phosphoryl-monoester group on its ribose2 moiety. By using the chemical procedure of periodate oxidation and subsequent beta-elimination with cyclohexylamine on mono- and dinucleotides containing Ar(p), we characterized the location of the phosphate group on the C-5" of the ribose2 moiety, and the linkage between the two riboses as a (1"----2')-glycosidic bond. Since the structural difference between phosphatase treated Ar(p) and authentic O-alpha-ribosyl-(1"----2')-adenosine from poly(ADP-Ribose) was previously assigned to an isomeric difference in the ribose2-ribose1 linkage, the (1"----2')-glycosidic bond of Ar(p) was deduced to have a beta-spatial configuration. Thus, final chemical structure for Ar(p) at the position 64 in yeast initiator tRNA(Met) has been established as O-beta-ribosyl-(1"----2')-adenosine-5"-phosphate. This nucleotide is linked by a 3',5'-phosphodiester bond to G at the position 65.

Intrinsically modified thermoelectric performance of alkaline-earth isovalently substituted [Bi2AE2O4][CoO2]y single crystals

NASA Astrophysics Data System (ADS)

Sun, N.; Dong, S. T.; Zhang, B. B.; Chen, Y. B.; Zhou, J.; Zhang, S. T.; Gu, Z. B.; Yao, S. H.; Chen, Y. F.

2013-07-01

Alkaline-earth elements isovalently substituted into a [Bi2AE2O4][CoO2]y (AE2 = Ca2, Sr2, and CaSr) single crystal with a layered structure were grown by the optical floating zone method. Structural characterization by X-ray diffraction and electron microscopy showed that the layers were oriented perpendicular to the c-axis, as well as the growth of direction was parallel to the ab-plane. The thermoelectric properties, including the Seebeck effect, electrical conductivity and thermal conductivity were investigated. The results of the thermoelectric measurements showed that the full substitution of Ca for Sr in [Bi2Sr2-xCaxO4][CoO2]y has the best overall thermoelectric performance. Compared with the other two cases studied, the full Ca substituted crystal [Bi2Ca2O4][CoO2]y exhibits both reduced resistivity and thermal conductivity, but not a reduced Seebeck coefficient. The enhanced thermoelectric property in [Bi2Ca2O4][CoO2]y is mainly due to lower structural symmetry, which is confirmed by electron microscopy characterization. This work demonstrates that even isovalently substitution can play a crucial role in the thermoelectric effect of layered cobalt oxides.

Processing of Phosphorus Slag with Recovery of Rare Earth Metals and Obtaining Silicon Containing Cake

NASA Astrophysics Data System (ADS)

Karshigina, Zaure; Abisheva, Zinesh; Bochevskaya, Yelena; Akcil, Ata; Sharipova, Aynash; Sargelova, Elmira

2016-10-01

The present research is devoted to the processing of slag generating during the yellow phosphorus production. In this paper are presented studies on leaching of phosphorus production slag by nitric acid with recovery of rare earth metals (REMs) into solution. REMs recovery into the solution achieved 98 % during the leaching process with using 7.5 mol/L of HNO3, liquid-to-solid ratio is 2.6:1, temperature is 60°C, process duration is 1 hour and stirrer speed is 500 rpm. Behaviour during the leaching of associated components such as calcium, aluminium, and iron was studied. After the leaching cake contains ∼⃒75-85 % of SiO2 and it might be useful for obtaining of precipitated silicon dioxide. With the purpose of separation from the impurities, recovery and concentrating of REMs, the obtained solution after leaching was subjected to extraction processing methods. The influence of ratio of organic and aqueous phases (O: A) on the extraction of rare earth metals by tributyl phosphate (TBP) with concentrations from 20 up to 100 % was studied. The REMs extraction with increasing TBP concentration under changes O:A ratio from 1:20 down to 1:1 into the organic phase from the solutions after nitric acid leaching increased from 22.2 up to 99.3%. The duration effect of REMs extraction process was studied by tributyl phosphate. It is revealed that with increasing of duration of the extraction process from 10 to 30 minutes REMs recovery into the organic phase almost did not changed. The behaviour of iron in the extraction process by TBP was studied. It was found that such accompanying components as calcium and aluminium by tributyl phosphate didn't extracted. To construct isotherm of REMs extraction of by tributyl phosphate was used variable volume method. It was calculated three-step extraction is needed for REMs recovery from the solutions after nitric acid leaching of phosphorus production slag. The process of the three-steps counter current extraction of rare earth

Preparation of photocatalytic ZnO nanoparticles and application in photochemical degradation of betamethasone sodium phosphate using taguchi approach

NASA Astrophysics Data System (ADS)

Giahi, M.; Farajpour, G.; Taghavi, H.; Shokri, S.

2014-07-01

In this study, ZnO nanoparticles were prepared by a sol-gel method for the first time. Taguchi method was used to identify the several factors that may affect degradation percentage of betamethasone sodium phosphate in wastewater in UV/K2S2O8/nano-ZnO system. Our experimental design consisted of testing five factors, i.e., dosage of K2S2O8, concentration of betamethasone sodium phosphate, amount of ZnO, irradiation time and initial pH. With four levels of each factor tested. It was found that, optimum parameters are irradiation time, 180 min; pH 9.0; betamethasone sodium phosphate, 30 mg/L; amount of ZnO, 13 mg; K2S2O8, 1 mM. The percentage contribution of each factor was determined by the analysis of variance (ANOVA). The results showed that irradiation time; pH; amount of ZnO; drug concentration and dosage of K2S2O8 contributed by 46.73, 28.56, 11.56, 6.70, and 6.44%, respectively. Finally, the kinetics process was studied and the photodegradation rate of betamethasone sodium phosphate was found to obey pseudo-first-order kinetics equation represented by the Langmuir-Hinshelwood model.

Lanthanide Contraction Effect In Magnetic Thermoelectric Materials Of Rare Earth-doped Bi1.5Pb0.5Ca2Co2O8

NASA Astrophysics Data System (ADS)

Sutjahja, Inge Magdalena; Akbar, Taufik; Nugroho, Agung

2010-12-01

We report in this paper the result of synthesis and crystal structure characterization of magnetic thermoelectric materials of rare-earth-doped Bi1.5Pb0.5Ca2Co2O8, namely Bi1.5Pb0.5Ca1.9RE0.1Co2O8 (RE = La, Pr, Sm, Eu, Gd, Ho). Single phase samples have been prepared by solid state reaction process using precursors of Bi2O3, PbO, CaCO3, RE2O3, and Co3O4. The precursors were pulverized, calcinated, and sintered in air at various temperatures for several hours. Analysis of XRD data shows that Bi1.5Pb0.5Ca1.9RE0.1Co2O8 compound is a layered system consisting of an alternate stack of CoO2 layer and Bi2Sr2O4 block along the c-axis. The misfit structure along b-direction is revealed from the difference of the b-axis length belonging to two sublattices, namely hexagonal CdI2-type CoO2 layer and rock-salt (RS) NaCl-type Bi2Sr2O4 block, while they possess the common a- and c-axis lattice parameters and β angles. The overall crystal structure parameters (a, b, and c) increases with type of doping from La to Ho, namely by decreasing the ionic radii of rare-earth ion. We discuss this phenomenon in terms of the lanthanide contraction, an effect commonly found in the rare-earth compound, results from poor shielding of nuclear charge by 4f electrons. In addition, the values of b-lattice parameters in these rare-earth doped samples are almost the same with those belongs to undoped parent compound (Bi1.5Pb0.5Sr2Co2O8) and its related Y-doped (Bi1.5Pb0.5Ca1.9Y0.1Co2O8) samples, while the c-values reduced significantly in rare-earth doped samples, with opposite trend with those of variation of a-axis length. Morevover, the misfit degree in rare-earth doped compound is higher in compared to parent compound and Y-doped samples. We argue that these structural changes induced by rare-earth doping may provide information for the variation of electronic structure of Co-ions (Co3+ and Co4+), in particular their different spin states of low-spin, intermediate-spin, and high-spin. This, in

Nimbus-7 Earth radiation budget calibration history. Part 2: The Earth flux channels

NASA Technical Reports Server (NTRS)

Kyle, H. Lee; Hucek, Douglas Richard R.; Ardanuy, Philip E.; Hickey, John R.; Maschhoff, Robert H.; Penn, Lanning M.; Groveman, Brian S.; Vallette, Brenda J.

1994-01-01

Nine years (November 1978 to October 1987) of Nimbus-7 Earth radiation budget (ERB) products have shown that the global annual mean emitted longwave, absorbed shortwave, and net radiation were constant to within about + 0.5 W/sq m. Further, most of the small annual variations in the emitted longwave have been shown to be real. To obtain this measurement accuracy, the wide-field-of-view (WFOV) Earth-viewing channels 12 (0.2 to over 50 micrometers), 13 (0.2 to 3.8 micrometers), and 14 (0.7 to 2.8 micrometers) have been characterized in their satellite environment to account for signal variations not considered in the prelaunch calibration equations. Calibration adjustments have been derived for (1) extraterrestrial radiation incident on the detectors, (2) long-term degradation of the sensors, and (3) thermal perturbations within the ERB instrument. The first item is important in all the channels; the second, mainly in channels 13 and 14, and the third, only in channels 13 and 14. The Sun is used as a stable calibration source to monitor the long-term degradation of the various channels. Channel 12, which is reasonably stable to both thermal perturbations and sensor degradation, is used as a reference and calibration transfer agent for the drifting sensitivities of the filtered channels 13 and 14. Redundant calibration procedures were utilized. Laboratory studies complemented analyses of the satellite data. Two nearly independent models were derived to account for the thermal perturbations in channels 13 and 14. The global annual mean terrestrial shortwave and longwave signals proved stable enough to act as secondary calibration sources. Instantaneous measurements may still, at times, be in error by as much as a few Wm(exp -2), but the long-term averages are stable to within a fraction of a Wm(exp -2).

Long-range magnetic order in the Heisenberg pyrochlore antiferromagnets G d2G e2O7 and G d2P t2O7 synthesized under high pressure

NASA Astrophysics Data System (ADS)

Li, X.; Cai, Y. Q.; Cui, Q.; Lin, C. J.; Dun, Z. L.; Matsubayashi, K.; Uwatoko, Y.; Sato, Y.; Kawae, T.; Lv, S. J.; Jin, C. Q.; Zhou, J.-S.; Goodenough, J. B.; Zhou, H. D.; Cheng, J.-G.

2016-12-01

G d2S n2O7 and G d2T i2O7 have been regarded as good experimental realizations of the classical Heisenberg pyrochlore antiferromagnet with dipolar interaction. The former was found to adopt the Palmer-Chalker state via a single, first-order transition at TN≈1 K , while the latter enters a distinct, partially ordered state through two successive transitions at TN 1≈1 K and TN 2= 0.75 K . To shed more light on their distinct magnetic ground states, we have synthesized two more gadolinium-based pyrochlore oxides, G d2G e2O7 and G d2P t2O7 , under high-pressure conditions and performed detailed characterizations via x-ray powder diffraction, dc and ac magnetic susceptibility, and specific heat measurements down to 100 mK. We found that both compounds enter a long-range antiferromagnetically ordered state through a single, first-order transition at TN= 1.4 K for G d2G e2O7 and TN= 1.56 K for G d2P t2O7 , with the specific heat anomaly similar to that of G d2S n2O7 rather than G d2T i2O7 . Interestingly, the low-temperature magnetic specific heat values of both G d2G e2O7 and G d2P t2O7 were found to follow nicely the T3 dependence as expected for a three-dimensional antiferromagnet with gapless spin-wave excitations. We have rationalized the enhancement of TN in terms of the reduced Gd-Gd distances for the chemically pressurized G d2G e2O7 and the addition of extra superexchange pathways through the empty Pt -eg orbitals for G d2P t2O7 . Our current study has expanded the family of gadolinium-based pyrochlores and permits us to achieve a better understanding of their distinct magnetic properties in a more comprehensive perspective.

Proton Environments in Biomimetic Calcium Phosphates Formed from Mesoporous Bioactive CaO-SiO2-P2O5 Glasses in Vitro: Insights from Solid-State NMR.

PubMed

Mathew, Renny; Turdean-Ionescu, Claudia; Yu, Yang; Stevensson, Baltzar; Izquierdo-Barba, Isabel; García, Ana; Arcos, Daniel; Vallet-Regí, María; Edén, Mattias

2017-06-22

When exposed to body fluids, mesoporous bioactive glasses (MBGs) of the CaO-SiO 2 -P 2 O 5 system develop a bone-bonding surface layer that initially consists of amorphous calcium phosphate (ACP), which transforms into hydroxy-carbonate apatite (HCA) with a very similar composition as bone/dentin mineral. Information from various 1 H-based solid-state nuclear magnetic resonance (NMR) experiments was combined to elucidate the evolution of the proton speciations both at the MBG surface and within each ACP/HCA constituent of the biomimetic phosphate layer formed when each of three MBGs with distinct Ca, Si, and P contents was immersed in a simulated body fluid (SBF) for variable periods between 15 min and 30 days. Directly excited magic-angle-spinning (MAS) 1 H NMR spectra mainly reflect the MBG component, whose surface is rich in water and silanol (SiOH) moieties. Double-quantum-single-quantum correlation 1 H NMR experimentation at fast MAS revealed their interatomic proximities. The comparatively minor H species of each ACP and HCA component were probed selectively by heteronuclear 1 H- 31 P NMR experimentation. The initially prevailing ACP phase comprises H 2 O and "nonapatitic" HPO 4 2- /PO 4 3- groups, whereas for prolonged MBG soaking over days, a well-progressed ACP → HCA transformation was evidenced by a dominating O 1 H resonance from HCA. We show that 1 H-detected 1 H → 31 P cross-polarization NMR is markedly more sensitive than utilizing powder X-ray diffraction or 31 P NMR for detecting the onset of HCA formation, notably so for P-bearing (M)BGs. In relation to the long-standing controversy as to whether bone mineral comprises ACP and/or forms via an ACP precursor, we discuss a recently accepted structural core-shell picture of both synthetic and biological HCA, highlighting the close relationship between the disordered surface layer and ACP.

Critical current density in (YBa2Cu3O7-δ)1-x-(PrBa2Cu3O7-δ)x melt-textured composites

NASA Astrophysics Data System (ADS)

Opata, Yuri Aparecido; Monteiro, João Frederico Haas Leandro; Jurelo, Alcione Roberto; Siqueira, Ezequiel Costa

2018-06-01

Melt textured (YBa2Cu3O7-δ)1-x-(PrBa2Cu3O7-δ)x composites (x = 0.00 and x = 0.05) were grown using the top seeding method. The effect of the PrBa2Cu3O7-δ phase on the growth process and the modification of the microstructure as well as on the physical properties was analyzed. X-ray analyses indicated that both pure and Pr-doped samples present an orthorhombic superconducting phase. From resistivity measurements for YBa2Cu3O7-δ and (YBa2Cu3O7-δ)0.95-(PrBa2Cu3O7-δ)0.05 samples, the Tcab did not change and was around 90.5 K. However, from magnetic measurements, the superconductivity was observed in critical temperatures TC = 92.9 K and 92.4 K for YBa2Cu3O7-δ and (YBa2Cu3O7-δ)0.95-(PrBa2Cu3O7-δ)0.05 samples, respectively. The YBa2Cu3O7-δ sample showed higher critical current densities than those shown by the (YBa2Cu3O7-δ)0.95-(PrBa2Cu3O7-δ)0.05 sample, with values of JC = 5.85 × 105 A/cm2 and 4.72 × 105 A/cm2, respectively. This paper also discusses the importance of Pr substitution on nano- and micro-meter scales to enhance JC(H).

Luminescence in Ba2 Sr2 Al2 O7 :RE (RE = Tb(3) (+) ,Eu(3) (+) and Dy(3) (+) ) novel aluminate phosphors.

PubMed

Pardhi, S A; Panse, V R; Dhoble, S J

2016-09-01

The luminescence of novel rare earth (Tb(3) (+) , Eu(3) (+) and Dy(3) (+) )-activated Ba2 Sr2 Al2 O7 phosphors for solid-state lighting is presented. The aluminate phosphors were synthesized using a one-step combustion method. X-Ray diffraction, scanning electron microscopy and photoluminescence characterizations were performed to understand the mechanism of excitation and the corresponding emission in the as-prepared phosphor, as characterized the phase purity and microstructure. Improvements in the luminescence properties of the phosphors with rare earth concentration were observed. The phosphor hue could be tuned from blue, green and red by proper selection of rare earth ions in typical concentrations. Effective absorption in the near-ultraviolet region was observed, which makes the phosphor a potential candidate for ultraviolet light-emitting diodes. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Synthesis, Characterization and Comparative Luminescence Studies of Rare-Earth-Doped Gd2O3 Nanoparticles

NASA Astrophysics Data System (ADS)

Pyngrope, D.; Singh, L. R.; Prasad, A. I.; Bora, A.

2018-04-01

A facile direct precipitation method was used for the synthesis of luminescence nanomaterial. Gd2O3 doped with rare earth element Eu3+ is synthesized by polyol route. The synthesized nanoparticles show their characteristic red emission. The nanoparticles are characterized by x-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and photoluminescence (PL) study. The synthesized nanoparticles are spherical particles with 30 nm size. The photoluminescence studies show the characteristic Eu3+ red emission. The PL study shows the intensity of the magnetic dipole transition ( 5 D0 \\to 7 F1 ) at 592 nm compared to that of the electronic dipole transition ( 5 D0 \\to 7 F2 ) at 615 nm. The nanomaterials can show significant application in various display devices and biomedical applications for tracking.

Improved synthesis of ceramic superconductors with alkaline earth peroxides - Synthesis and processing of Ba2YCu3O(7-x)

NASA Technical Reports Server (NTRS)

Hepp, A. F.; Gaier, J. R.; Philipp, W. H.; Warner, J. D.; Aron, P. R.; Pouch, J. J.

1988-01-01

Synthesis processes for the preparation of ceramic conductors Ba2YCu3O(7-x) from BaO2 or BaCO3 in flowing O2 or N2 are described, and the characteristics of the materials produced in these processes are compared. Results of EDAX, XRD, SEM, and dc resistivity analyses demonstrated that superconducting materials made from BaO2 were more homogeneous, denser, and more metallic than materials produced from BaCO3, because of the higher reactivity of BaO2. Potential applications of this processes are discussed.

Ultraviolet stellar occultation measurement of the H2 and O2 densities near 100 km in the earth's atmosphere

NASA Technical Reports Server (NTRS)

Atreya, S. K.; Wasser, B.; Donahue, T. M.; Sharp, W. E.; Drake, J. F.; Riegler, G. R.

1976-01-01

Results are presented for an experimental study designed to measure the density of H2 near 100 km in the earth's atmosphere from occultation of a star, Gamma Vel, by the earth's atmosphere at several wavelengths near the H2 absorption line at 1108.128 A by a spectrometer on an orbiting astronomical observatory. Measurement of the O2 density between 95 and 123 km is also reported. Attention is focused on testing the predictions of a model of the distribution of hydrogen constituents, H, H2, H2O, CH4, OH, and H2O in the upper atmosphere related to a theory of hydrogen escape developed by Hunten and Strobel (1974) and by Liu and Donahue (1974). The measured H2 densities are found to be in good agreement with recent theoretical predictions, whereas the measured O2 density profile generally agrees with the models except for a wavelike structure in the range 104-114 km.

Manganese Vanadate Chemistry in Hydrothermal BaF 2 Brines: Ba 3 Mn 2 (V 2 O 7 ) 2 F 2 and Ba 7 Mn 8 O 2 (VO 4 ) 2 F 23

DOE PAGES

Sanjeewa, Liurukara D.; McMillen, Colin D.; McGuire, Michael A.; ...

2016-12-05

We synthesized manganese vanadate fluorides using high-temperature hydrothermal techniques with BaF 2 as a mineralizer. Ba 3Mn 2(V 2O 7) 2F 2 crystallizes in space group C2/c and consists of dimers built from edge-sharing MnO 4F 2 trigonal prisms with linking V 2O 7 groups. Ba 7Mn 8O 2(VO 4) 2F 23 crystallizes in space group Cmmm, with a manganese oxyfluoride network built from edge- and corner-sharing Mn 2+/3+(O,F) 6 octahedra. The resulting octahedra form alternating Mn 2+ and Mn 2+/3+ layers separated by VO 4 tetrahedra. This latter compound exhibits a canted antiferromagnetic order below TN = 25 K.

Comparison of the Supercooled Spin Liquid States in the Pyrochlore Magnets Dy2Ti2O7 and Ho2Ti2O7

NASA Astrophysics Data System (ADS)

Eyal, Anna; Eyvazov, Azar B.; Dusad, Ritika; Munsie, Timothy J. S.; Luke, Graeme M.; Davis, J. C. Séamus

Despite a well-ordered crystal structure and strong magnetic interactions between the Dy or Ho ions, no long-range magnetic order has been detected in the pyrochlore titanates Ho2Ti2O7 and Dy2Ti2O7. The low temperature state in these materials is governed by spin-ice rules. These constrain the Ising like spins in the materials, yet does not result in a global broken symmetry state. To explore the actual magnetic phases, we simultaneously measure the time- and frequency-dependent magnetization dynamics of Dy2Ti2O7 and Ho2Ti2O7 using toroidal, boundary-free magnetization transport techniques. We demonstrate a distinctive behavior of the magnetic susceptibility of both compounds, that is indistinguishable in form from the permittivity of supercooled dipolar liquids. Moreover, we show that the microscopic magnetic relaxation times for both materials increase along a super-Arrhenius trajectory also characteristic of supercooled glass-forming liquids. Both materials therefore exhibit characteristics of a supercooled spin liquid. Strongly-correlated dynamics of loops of spins is suggested as a possible mechanism which could account for these findings. Potential connections to many-body spin localization will also be discussed.

A DFT+U study of Pu immobilization in Gd2Zr2O7

NASA Astrophysics Data System (ADS)

Zhao, F. A.; Xiao, H. Y.; Jiang, M.; Liu, Z. J.; Zu, X. T.

2015-12-01

The solubility of Pu in Gd2Zr2O7 has been investigated by the density functional theory plus Hubbard U correction. It is found that the formation of PuGdZr2O7, Gd2PuZrO7 and Gd2Pu1.5Zr0.5O7 are exothermic, whereas Pu0.5Gd1.5Zr2O7, Pu1.5Gd0.5Zr2O7 and Gd2Pu0.5Zr1.5O7 are energetically less stable than their respective separated states. The calculations show that both the Gd and Zr lattice sites can be substituted by the Pu, which is consistent with the immobilization behavior of uranium in Gd2Zr2O7 observed experimentally. The site preference of Pu in Gd2Zr2O7 is found to be dependent on the chemical environment, i.e., Pu prefers to substitute for Gd-site under Gd-rich and O2-rich conditions and for Zr-site under Zr-rich and O2-rich conditions.

Redetermination of clinobaryl-ite, BaBe(2)Si(2)O(7).

PubMed

Domizio, Adrien J Di; Downs, Robert T; Yang, Hexiong

2012-10-01

Clinobaryl-ite, ideally BaBe(2)Si(2)O(7) (chemical name barium diberyllium disilicate), is a sorosilicate mineral and dimorphic with baryl-ite. It belongs to a group of compounds characterized by the general formula BaM(2+) (2)Si(2)O(7), with M(2+) = Be, Mg, Fe, Mn, Zn, Co, or Cu, among which the Be-, Fe-, and Cu-members have been found in nature. The crystal structure of clinobaryl-ite has been re-examined in this study based on single-crystal X-ray diffraction data collected from a natural sample from the type locality (Khibiny Massif, Kola Peninsula, Russia). The structure of clinobaryl-ite can be considered as a framework of BeO(4) and SiO(4) tetra-hedra, with one of the O atoms coordinated to two Be and one Si, one coordinated to two Si, and two O atoms coordinated to one Si and one Be atom. The BeO(4) tetra-hedra share corners, forming chains parallel to the c axis, which are inter-linked by the Si(2)O(7) units oriented parallel to the a axis. The Ba(2+) cations (site symmetry m..) are in the framework channels and are coordinated by eleven O atoms in form of an irregular polyhedron. The Si-O(br) (bridging O atom, at site symmetry m..) bond length, the Si-O(nbr) (non-bridging O atoms) bond lengths, and the Si-O-Si angle within the Si(2)O(7) unit are in marked contrast to the corresponding values determined in the previous study [Krivovichev et al. (2004 ▶). N. Jb. Miner. Mh. pp. 373-384].

Neuroprotective Effect of CeO2@PAA-LXW7 Against H2O2-Induced Cytotoxicity in NGF-Differentiated PC12 Cells.

PubMed

Jia, Jingjing; Zhang, Ting; Chi, Jieshan; Liu, Xiaoma; Sun, Jingjing; Xie, Qizhi; Peng, Sijia; Li, Changyan; Yi, Li

2018-06-07

CeO 2 nanoparticles (nanoceria) have been used in many studies as a powerful free radical scavenger, and LXW7, a small-molecule peptide, can specifically target the integrin αvβ3, whose neuroprotective effects have also been demonstrated. The objective of this study is to observe the neuroprotective effect and potential mechanism of CeO 2 @PAA-LXW7, a new compound that couples CeO 2 @PAA (nanoceria modified with the functional group of polyacrylic acid) with LXW7 via a series of chemical reactions, in H 2 O 2 -induced NGF-differentiated PC12 cells. We examined the effects of LXW7, CeO 2 @PAA, and CeO 2 @PAA-LXW7 on the viability of primary hippocampal neurons and found that there was no significant difference under control conditions, but increased cellular viability was observed in the case of H 2 O 2 -induced injury. We used H 2 O 2 -induced NGF-differentiated PC12 cells as the classical injury model to investigate the neuroprotective effect of CeO 2 @PAA-LXW7. In this study, LXW7, CeO 2 @PAA, and CeO 2 @PAA-LXW7 inhibit H 2 O 2 -induced oxidative stress by reducing the production of reactive oxygen species (ROS) and regulating Bax/Bcl-2, cleaved caspase-3 and mitochondrial cytochrome C (cyto C) in the apoptotic signaling pathways. We found that the levels of phosphorylation of focal adhesion kinase (FAK) and of signal transducer and activator of transcription 3 (STAT3) increased significantly in H 2 O 2 -induced NGF-differentiated PC12 cells, whereas LXW7, CeO 2 @PAA, and CeO 2 @PAA-LXW7 suppressed the increase to different degrees. Among the abovementioned changes, the inhibitory effect of CeO 2 @PAA-LXW7 on H 2 O 2 -induced changes, including the increases in the levels of p-FAK and p-STAT3, is more obvious than that of LXW7 or CeO 2 @PAA alone. In summary, these results suggest that integrin signaling participates in the regulation of apoptosis via the regulation of ROS and of the apoptosis pathway in H 2 O 2 -induced NGF-differentiated PC12 cells. LXW7, CeO

Mechanical Properties of Layered La2Zr2O7 Thermal Barrier Coatings

NASA Astrophysics Data System (ADS)

Guo, Xingye; Li, Li; Park, Hyeon-Myeong; Knapp, James; Jung, Yeon-Gil; Zhang, Jing

2018-04-01

Lanthanum zirconate (La2Zr2O7) has been proposed as a promising thermal barrier coating (TBC) material due to its low thermal conductivity and high stability at high temperatures. In this work, both single and double-ceramic-layer (DCL) TBC systems of La2Zr2O7 and 8 wt.% yttria-stabilized zirconia (8YSZ) were prepared using air plasma spray (APS) technique. The thermomechanical properties and microstructure were investigated. Thermal gradient mechanical fatigue (TGMF) tests were applied to investigate the thermal cycling performance. The results showed that DCL La2Zr2O7 + 8YSZ TBC samples lasted fewer cycles compared with single-layered 8YSZ TBC samples in TGMF tests. This is because DCL La2Zr2O7 TBC samples had higher residual stress during the thermal cycling process, and their fracture toughness was lower than that of 8YSZ. Bond strength test results showed that 8YSZ TBC samples had higher bond strength compared with La2Zr2O7. The erosion rate of La2Zr2O7 TBC samples was higher than that of 8YSZ samples, due to the lower critical erodent velocity and fracture toughness of La2Zr2O7. DCL porous 8YSZ + La2Zr2O7 had a lower erosion rate than other SCL and DCL La2Zr2O7 coatings, suggesting that porous 8YSZ serves as a stress-relief buffer layer.

Ising versus XY anisotropy in frustrated R(2)Ti(2)O(7) compounds as "Seen" by Polarized Neutrons.

PubMed

Cao, H; Gukasov, A; Mirebeau, I; Bonville, P; Decorse, C; Dhalenne, G

2009-07-31

We studied the field induced magnetic order in R(2)Ti(2)O(7) pyrochlore compounds with either uniaxial (R=Ho, Tb) or planar (R=Er, Yb) anisotropy, by polarized neutron diffraction. The determination of the local susceptibility tensor {chi(parallel to),chi(perpendicular)} provides a universal description of the field induced structures in the paramagnetic phase (2-270 K), whatever the field value (1-7 T) and direction. Comparison of the thermal variations of chi(parallel to) and chi(perpendicular) with calculations using the rare earth crystal field shows that exchange and dipolar interactions must be taken into account. We determine the molecular field tensor in each case and show that it can be strongly anisotropic.

Proton transport by phosphate diffusion--a mechanism of facilitated CO2 transfer

PubMed Central

1976-01-01

We have measured CO2 fluxes across phosphate solutions at different carbonic anhydrase concentrations, bicarbonate concentration gradients, phosphate concentrations, and mobilities. Temperature was 22-25 degrees C, the pH of the phosphate solutions was 7.0-7.3. We found that under physiological conditions of pH and pCO2 a facilitated diffusion of CO2 occurs in addition to free diffusion when (a) sufficient carbonic anhydrase is present, and (b) a concentration gradient of HCO3- is established along with a pCO2 gradient, and (c) the phosphate buffer has a mobility comparable to that of bicarbonate. When the phosphate was immobilized by attaching 0.25-mm-long cellulose particles, no facilitation of CO2 diffusion was detectable. A mechanism of facilitated CO2 diffusion in phosphate solutions analogous to that in albumin solutions was proposed on the basis of these findings: bicarbonate diffusion together with a facilitated proton transport by phosphate diffusion. A mathematical model of this mechanism was formulated. The CO2 fluxed predicted by the model agree quantitatively with the experimentally determined fluxes. It is concluded that a highly effective proton transport mechanism acts in solutions of mobile phosphate buffers. By this mechanism; CO2 transfer may be increased up to fivefold and proton transfer may be increased to 10,000-fold. PMID:6619

Solvent Extraction of Rare Earth Elements from a Nitric Acid Leach Solution of Apatite by Mixtures of Tributyl Phosphate and Di-(2-ethylhexyl) Phosphoric Acid

NASA Astrophysics Data System (ADS)

Ferdowsi, Ali; Yoozbashizadeh, Hossein

2017-12-01

Solvent extraction of rare earths from nitrate leach liquor of apatite using mixtures of tributyl phosphate (TBP) and di-(2-ethylhexyl) phosphoric acid (D2EHPA) was studied. The effects of nitrate and hydrogen ion concentration of the aqueous phase as well as the composition and concentration of extractants in the organic phase on the extraction behavior of lanthanum, cerium, neodymium, and yttrium were investigated. The distribution ratio of REEs increases by increasing the nitrate concentration in aqueous phase and concentration of extractants in organic phase, but the hydrogen ion concentration in aqueous phase has a decreasing effect. Yttrium as a heavy rare earth is more sensitive to these parameters than light rare earth elements. Although the composition of organic phase has a minor effect on the extraction of light rare earths, the percent of extraction of yttrium decreases dramatically by increasing the TBP content of organic phase. Mixtures of TBP and D2EHPA can show either synergism or antagonism extraction depending on the concentration and composition of extractants in organic phase. The best condition for separating rare earth elements in groups of heavy and light REEs can be achieved at high nitrate concentration, low H+ concentration, and high concentration of D2EHPA in organic phase. Separation of Ce and La by TBP and D2EHPA is practically impossible in the studied conditions; however, low nitrate concentration and high hydrogen ion concentration in aqueous phase and low concentration of extractants in organic phase favor the separation of Nd from other light rare earth elements.

Rare earth activated NaY (MoO4)2 phosphors for NIR emission

NASA Astrophysics Data System (ADS)

Tawalare, P. K.; Bhatkar, V. B.; Talewar, R. A.; Joshi, C. P.; Moharil, S. V.

2018-05-01

Efficient NIR emission is reported for NaY(MoO4)2 activated with Nd3+ or Yb3+. Characteristic emission of rare earth ions is sensitized by MoO4-2 group. The excitation is in the near UV region of 350-400 nm. These phosphors could be useful for modifying the solar spectrum so as to match with the spectral response of c-Si solar cells.

Fiber-optic thermometer application of thermal radiation from rare-earth end-doped SiO{sub 2} fiber

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katsumata, Toru, E-mail: katsumat@toyo.jp; Morita, Kentaro; Komuro, Shuji

2014-08-15

Visible light thermal radiation from SiO{sub 2} glass doped with Y, La, Ce, Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu were studied for the fiber-optic thermometer application based on the temperature dependence of thermal radiation. Thermal radiations according to Planck's law of radiation are observed from the SiO{sub 2} fibers doped with Y, La, Ce, Pr, Eu, Tb, and Lu at the temperature above 1100 K. Thermal radiations due to f-f transitions of rare-earth ions are observed from the SiO{sub 2} fibers doped with Nd, Dy, Ho, Er, Tm, and Yb at the temperature above 900more » K. Peak intensities of thermal radiations from rare-earth doped SiO{sub 2} fibers increase sensitively with temperature. Thermal activation energies of thermal radiations by f-f transitions seen in Nd, Dy, Ho, Er, Tm, and Yb doped SiO{sub 2} fibers are smaller than those from SiO{sub 2} fibers doped with Y, La, Ce, Pr, Eu, Tb, and Lu. Thermal radiation due to highly efficient f-f transitions in Nd, Dy, Ho, Er, Tm, and Yb ions emits more easily than usual thermal radiation process. Thermal radiations from rare-earth doped SiO{sub 2} are potentially applicable for the fiber-optic thermometry above 900 K.« less

The crystal structure of the monohydrate R{sub 2}Mo{sub 6}O{sub 21}.H{sub 2}O (R=Pr, Nd, Sm, and Eu): a layer structure containing disordered [Mo{sub 2}O{sub 7}]{sup 2-} groups

DOE Office of Scientific and Technical Information (OSTI.GOV)

Naruke, Haruo; Yamase, Toshihiro

2005-03-15

Although R{sub 2}O{sub 3}:MoO{sub 3}=1:6 (R=rare earth) compounds are known in the R{sub 2}O{sub 3}-MoO{sub 3} phase diagrams since a long time, no structural characterization has been achieved because a conventional solid-state reaction yields powder samples. We obtained single crystals of R{sub 2}Mo{sub 6}O{sub 21}.H{sub 2}O (R=Pr, Nd, Sm, and Eu) by thermal decomposition of [R{sub 2}(H{sub 2}O){sub 12}Mo{sub 8}O{sub 27}].nH{sub 2}O at around 685-715{sup o}C for 2h, and determined their crystal structures. The simulated XRD patterns of R{sub 2}Mo{sub 6}O{sub 21}.H{sub 2}O were consistent with those of previously reported R{sub 2}O{sub 3}:MoO{sub 3}=1:6 compounds. All R{sub 2}Mo{sub 6}O{sub 21}.H{submore » 2}O compounds crystallize isostructurally in tetragonal, P4/ncc (No. 130), a=8.9962(5), 8.9689(6), 8.9207(4), and 8.875(2)A; c=26.521(2), 26.519(2), 26.304(2), and 26.15(1)A; Z=4; R{sub 1}=0.026, 0.024, 0.024, and 0.021, for R=Pr, Nd, Sm, and Eu, respectively. The crystal structure of R{sub 2}Mo{sub 6}O{sub 21}.H{sub 2}O consists of two [Mo{sub 2}O{sub 7}]{sup 2-}-containing layers (A and B layers) and two interstitial R(1){sup 3+} and R(2){sup 3+} cations. Each [Mo{sub 2}O{sub 7}]{sup 2-} group is composed of two corner-sharing [MoO{sub 4}] tetrahedra. The [Mo{sub 2}O{sub 7}]{sup 2-} in the B layer exhibits a disorder to form a pseudo-[Mo{sub 4}O{sub 9}] group, in which four Mo and four O sites are half occupied. R(1){sup 3+} achieves 8-fold coordination by O{sup 2-} to form a [R(1)O{sub 8}] square antiprism, while R(2){sup 3+} achieves 9-fold coordination by O{sup 2-} and H{sub 2}O to form a [R(2)(H{sub 2}O)O{sub 8}] monocapped square antiprism. The disorder of the [Mo{sub 2}O{sub 7}]{sup 2-} group in the B layer induces a large displacement of the O atoms in another [Mo{sub 2}O{sub 7}]{sup 2-} group (in the A layer) and in the [R(1)O{sub 8}] and [R(2)(H{sub 2}O)O{sub 8}] polyhedra. A remarkable broadening of the photoluminescence spectrum of Eu{sub 2}Mo

Hot corrosion behavior of YSZ, Gd2Zr2O7 and YSZ/Gd2Zr2O7 thermal barrier coatings exposed to molten sulfate and vanadate salt

NASA Astrophysics Data System (ADS)

Ozgurluk, Yasin; Doleker, Kadir Mert; Karaoglanli, Abdullah Cahit

2018-04-01

Thermal barrier coatings (TBCs) are mostly used in critical components of aircraft gas turbine engines. Hot corrosion is among the main deteriorating factors in TBCs which results from the effect of molten salt on the coating-gas interface. This type of corrosion is observed as a result of contamination accumulated during combustion processes. Fuels used in aviation industry generally contain impurities such as vanadium oxide (V2O5) and sodium sulfate (Na2SO4). These impurities damage turbines' inlet at elevated temperatures because of chemical reaction. Yttria stabilized zirconia (YSZ) is a conventional top coating material for TBCs while Gd2Zr2O7 is a new promising top coating material for TBCs. In this study, CoNiCrAlY metallic bond coat was deposited on Inconel 718 nickel based superalloy substrate material with a thickness about 100 μm using cold gas dynamic spray (CGDS) method. Production of TBCs were done with deposition of YSZ, Gd2Zr2O7, YSZ/Gd2Zr2O7 ceramic top coating materials using EB-PVD method, having a total thickness of 300 μm. Hot corrosion behavior of YSZ, Gd2Zr2O7, YSZ/Gd2Zr2O7 TBC systems were exposed to 45 wt.% Na2SO4 and 55 wt.% V2O5 molten salt mixtures at 1000 °C temperature. TBC samples were investigated and compared using scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) analysis and X-ray diffractometer (XRD). The hot corrosion failure mechanisms of YSZ, Gd2Zr2O7 and YSZ/Gd2Zr2O7 TBCs in the molten salts were evaluated.

Magnetic interactions in rhenium-containing rare earth double perovskites Sr{sub 2}LnReO{sub 6} (Ln=rare earths)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nishiyama, Atsuhide; Doi, Yoshihiro; Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.jp

The perovskite-type compounds containing both rare earth and rhenium Sr{sub 2}LnReO{sub 6} (Ln=Y, Tb-Lu) have been prepared. Powder X-ray diffraction measurements and Rietveld analysis show that Ln{sup 3+} and Re{sup 5+} ions are structurally ordered at the B site of the perovskite SrBO{sub 3}. Magnetic anomalies are found in their magnetic susceptibility and specific heat measurements at 2.6–20 K for Ln=Y, Tb, Dy, Yb, Lu compounds. They are due to magnetic interactions between Re{sup 5+} ions. The results of the magnetic hysteresis and remnant magnetization measurements for Sr{sub 2}YReO{sub 6} and Sr{sub 2}LuReO{sub 6} indicate that the antiferromagnetic interactions betweenmore » Re{sup 5+} ions below transition temperatures have a weak ferromagnetic component. The analysis of the magnetic specific heat data for Sr{sub 2}YbReO{sub 6} shows that both the Yb{sup 3+} and Re{sup 5+} ions magnetically order at 20 K. For the case of Sr{sub 2}DyReO{sub 6}, magnetic ordering of the Re{sup 5+} moments occurs at 93 K, and with decreasing temperature, the moments of Dy{sup 3+} ferromagnetically order at 5 K from the measurements of magnetic susceptibility and specific heat. - Graphical abstract: Crystal structure of double perovskite Sr{sub 2}LnReO{sub 6}. Red and black lines show cubic and monoclinic unit cells, respectively. - Highlights: • Double perovskites Sr{sub 2}LnReO{sub 6} (Ln=rare earths) were prepared. • They show an antiferromagnetic transition at 2.6–20 K. • In Sr{sub 2}DyReO{sub 6}, Dy and Re moments magnetically order at 5 and 93 K, respectively.« less

Thermodynamic Assessment of the Y2o3-yb2o3-zro2 System

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Liu, Zi-Kui; Kaufman, Larry; Zhang, Fan

2002-01-01

Yttria-zirconia (Y2O3-ZrO2) is the most widely used of the rare earth oxide-zirconia systems. There are numerous experimental studies of the phase boundaries in this system. In this paper, we assess these data and derive parameters for the solution models in this system. There is current interest in other rare earth oxide-zirconia systems as well as systems with several rare earth oxides and zirconia, which may offer improved properties over the Y2O3-ZrO2 system. For this reason, we also assess the ytterbia-zirconia (Yb2O3-ZrO2) and Y2O3-Yb2O3-ZrO2 system.

Photocatalytic properties of amine functionalized Bi2Sn2O7/rGO nanocomposites

NASA Astrophysics Data System (ADS)

Gnanamoorthy, G.; Muthamizh, S.; Sureshbabu, K.; Munusamy, S.; Padmanaban, A.; Kaaviya, A.; Nagarajan, R.; Stephen, A.; Narayanan, V.

2018-07-01

The binary metal oxide nanomaterials are having applications in various fields like sensors, optics, electrocatalyst and photocatalyst so on. Bi2Sn2O7 with pyrochlore structure is having low band gap energy; hence it is utilized in battery storage and gas sensor applications. In the present work, we have made an attempt to synthesis amine-functionalized Bi2Sn2O7/rGO nanocomposites by a thermal decomposition method and in-situ method; the synthesized nanocomposites were confirmed by XRD, FT-IR and Raman analysis. The AF-Bi2Sn2O7/rGO nanocomposites morphology was confirmed by FE-SEM along with EDX spectroscopy, we obtained different flowers and nest-like morphology. The pure and composite material band gap energy is decreases from 2.6 eV to 1.6 eV. All three nanomaterials Bi2Sn2O7, AF-Bi2Sn2O7, AF-Bi2Sn2O7/rGO nanocomposites (AF-amine functionalized) were utilized for the photocatalytic degradation of methylene blue dye under visible light irradiation. AF-Bi2Sn2O7/rGO nanocomposite showed an excellent photocatalytic activity than pure Bi2Sn2O7 and AF- Bi2Sn2O7.

Selective separation of phosphate and fluoride from semiconductor wastewater.

PubMed

Warmadewanthi, B; Liu, J C

2009-01-01

Hydrofluoric acid (HF) and phosphoric acid (H(3)PO(4)) are widely used in semiconductor industry for etching and rinsing purposes. Consequently, significant amount of wastewater containing phosphate and fluoride is generated. Selective separation of phosphate and fluoride from the semiconductor wastewater, containing 936 mg/L of fluoride, 118 mg/L of phosphate, 640 mg/L of sulfate, and 26.7 mg/L of ammonia, was studied. Chemical precipitation and flotation reactions were utilized in the two-stage treatment processes. The first-stage reaction involved the addition of magnesium chloride (MgCl(2)) to induce selective precipitation of magnesium phosphate. The optimal condition was pH 10 and molar ratio, [Mg(2 + )]/[(PO(4) (3-))], of 3:1, and 66.2% of phosphate was removed and recovered as bobierrite (Mg(3)(PO(4))(2).8H(2)O). No reaction was found between MgCl(2) and fluoride. Calcium chloride (CaCl(2)) was used in the second-stage reaction to induce precipitation of calcium fluoride and calcium phosphate. The optimum molar ratio, [Ca(2 + )]/[F(-)], was 0.7 at pH 10, and residual fluoride concentration of 10.7 mg/L and phosphate concentration of lower than 0.5 mg/L was obtained. Thermodynamic equilibrium was modeled with PHREEQC and compared with experimental results. Sodium dodecylsulfate (SDS) was an effective collector for subsequent solid-liquid removal via dispersed air flotation (DiAF). The study demonstrated that phosphate can be selectively recovered from the wastewater. Potential benefits include recovery of phosphate for reuse, lower required dosage of calcium for fluoride removal, and less amount of CaF(2) sludge.

Crystal chemistry and the role of ionic radius in rare earth tetrasilicates: Ba2RE2Si4O12F2 (RE = Er3+-Lu3+) and Ba2RE2Si4O13 (RE = La3+-Ho3+).

PubMed

Fulle, Kyle; Sanjeewa, Liurukara D; McMillen, Colin D; Kolis, Joseph W

2017-10-01

Structural variations across a series of barium rare earth (RE) tetrasilicates are studied. Two different formulas are observed, namely those of a new cyclo-silicate fluoride, BaRE 2 Si 4 O 12 F 2 (RE = Er 3+ -Lu 3+ ) and new compounds in the Ba 2 RE 2 Si 4 O 13 (RE = La 3+ -Ho 3+ ) family, covering the whole range of ionic radii for the rare earth ions. The Ba 2 RE 2 Si 4 O 13 series is further subdivided into two polymorphs, also showing a dependence on rare earth ionic radius (space group P{\\overline 1} for La 3+ -Nd 3+ , and space group C2/c for Sm 3+ -Ho 3+ ). Two of the structure types identified are based on dinuclear rare earth units that differ in their crystal chemistries, particularly with respect to the role of fluorine as a structural director. The broad study of rare earth ions provides greater insight into understanding structural variations within silicate frameworks and the nature of f-block incorporation in oxyanion frameworks. The single crystals are grown from high-temperature (ca 953 K) hydrothermal fluids, demonstrating the versatility of the technique to access new phases containing recalcitrant rare earth oxides, enabling the study of structural trends.

Decaying shock studies of phase transitions in MgO-SiO2 systems: implications for the Super-Earths' interiors

NASA Astrophysics Data System (ADS)

Bolis, R.; Morard, G.; Vinci, T.; Ravasio, A.; Bambrink, E.; Guarguaglini, M.; Koenig, M.; Musella, R.; Françoise, R.; Bouchet, J.; Ozaki, N.; Miyanishi, K.; Sekine, T.; Sakawa, Y.; Sano, T.; Kodama, R.; Guyot, F. J.; Benuzzi, A.

2016-12-01

Mantles of telluric exoplanets, so-called Earth-like and Super-Earths, are expected to be mainly composed of different type of oxides, such as periclase (MgO), enstatite (MgSiO3) and forsterite (Mg2SiO4). Determining the phase diagrams, melting curves and liquid properties of these compounds under extreme pressure (0.2-1 TPa) is crucial to model the internal dynamic of these exoplanets, as the melting of mantle components controls planetary temperature profiles [6]. Experimentally, these planetary thermodynamic states can be achieved with laser-shock compression. Here we present laser-driven decaying shock experiments on MgO, MgSiO3 and Mg2SiO4 samples performed at LULI and GEKKO laser facilities, where we focused 1.2-2.5 ns laser pulses with an intensity between 3-8 1013 W/cm2 exploring pressures between 0.2 and 1 TPa and temperature between 5000 and 30000 K. We determined the thermodynamic states using rear side optical diagnostics. We observed a single transition for MgO associated to melting (at 0.47 TPa ± 0.04 and 9863 ± 812 K) and no evidence of a liquid-liquid transition, dissociation or melting for all the other compounds in the range 150-500 Gpa and 200-800 Gpa respectively for MgSiO3 and Mg2SiO4. Some implications are presented comparing our data experimental and theoretical data found in literature [1, 2, 3, 4, 5]. In particular these results represent a key input to solve the controversy on a possible MgSiO3 liquid-liquid phase transition. Moreover we propose a revision of the phase diagram of MgO, with a lower melting line which results in a lower temperature profile for super-Earths. Finally our data evidence the presence of a poor electrically conducting liquid in the phase diagram of all the studied material, with implications for the modelling of magnetic field generation via dynamo mechanism.[1] McWilliams et al., Science 338 (2012): 1330-1333. [2] Spaulding et al., Physical Review Letters108 (2012): 065701. [3] Root et al., Physical Review

Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO2 and H2O

USGS Publications Warehouse

Chen, S.G.; Yang, R.T.

1997-01-01

From molecular orbital calculations, a unified mechanism is proposed for the gasification reactions of graphite by CO2 and H2O, both uncatalyzed and catalyzed by alkali and alkaline earth catalysts. In this mechanism, there are two types of oxygen intermediates that are bonded to the active edge carbon atoms: an in-plane semiquinone type, Cf(O), and an off-plane oxygen bonded to two saturated carbon atoms that are adjacent to the semiquinone species, C(O)Cf(O). The rate-limiting step is the decomposition of these intermediates by breaking the C-C bonds that are connected to Cf(O). A new rate equation is derived for the uncatalyzed reactions, and that for the catalyzed reactions is readily available from the proposed mechanism. The proposed mechanism can account for several unresolved experimental observations: TPD and TK (transient kinetics) desorption results of the catalyzed systems, the similar activation energies for the uncatalyzed and catalyzed reactions, and the relative activities of the alkali and alkaline earth elements. The net charge of the edge carbon active site is substantially changed by gaining electron density from the alkali or alkaline earth element (by forming C-O-M, where M stands for metal). The relative catalytic activities of these elements can be correlated with their abilities of donating electrons and changing the net charge of the edge carbon atom. As shown previously (Chen, S. G.; Yang, R. T. J. Catal. 1993, 141, 102), only clusters of the alkali compounds are active. This derives from the ability of the clusters to dissociate CO2 and H2O to form O atoms and the mobility of the dissociated O atoms facilitated by the clusters.

Characterization of the activity of L-ascorbic acid 2-[3,4-dihydro-2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-2H-1-be nzopyran-6-yl-hydrogen phosphate] potassium salt in hydroxyl radical elimination.

PubMed

Tomita, T; Kashima, M; Tsujimoto, Y

2000-03-01

The effect of L-ascorbic acid 2-[3,4-dihydro-2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-2H -1-benzopyran-6-yl-hydrogen phosphate] potassium salt (EPC-K1) on hydroxyl radical (*OH) elimination was studied using electron spin resonance (ESR) and spectrophotometric experiments. The addition of EPC-K, and *OH scavengers eliminated the *OH generated from Cu2+/H2O2, Fe2+/H2O2 and H2O2/UV-irradiation reaction systems. However, in competitive reactions using different concentrations of a spin-trap agent, the addition of the *OH scavenger altered the IC50 values, whereas the addition of EPC-K1 and a metal chelater did not change the value in the Cu2+/H2O2 and Fe2+/H2O2 reaction systems. The addition of EPC-K1 and metal chelater changed the ESR signal for free Cu2+. The spectrophotometric experiments confirmed that the addition of EPC-K1 and metal chelater altered the absorption spectra due to CuCl2 and FeSO4, whereas the *OH scavenger did not alter the spectra. Therefore, it was demonstrated that EPC-K, has the ability both to scavenge *OH directly and to inhibit the generation of *OH by the chelation of Cu2+ and Fe2+.

Mahlmoodite, FeZr(PO4).4H2O, a new iron zirconium phosphate mineral from Wilson Springs, Arkansas

USGS Publications Warehouse

Milton, C.; McGee, J.J.; Evans, H.T.

1993-01-01

Small (<0.5 mm) cream white spheres observed in V ore have been identified as ferrous zirconium phosphate tetrahedrate, FeZr(PO4)2.4H2O. This new mineral, named mahlmoodite, occurs as spherules of radiating fibers usually perched on crystals of pyroxene in vugs. The optical and crystallographic properties of mahlmoodite are described. -after Authors

Effect of PbO on the spectral and thermo-optical properties of Nd3+-doped phosphate laser glass

NASA Astrophysics Data System (ADS)

Yin, Qianwen; Kang, Shuai; Wang, Xue; Li, Shunguang; He, Dongbing; Hu, Lili

2017-04-01

Nd3+-doped P2O5-K2O-Al2O3-BaO-PbO phosphate glasses with various PbO/BaO ratios were synthesized using the melt quenching technique. Raman, absorption, and emission spectra were measured to investigate the effects of PbO/BaO ratios on the structures and spectroscopic properties of the glasses. The emission cross-sections of the Nd3+-doped phosphate glasses were calculated using the Judd-Ofelt theory, and were found to increase from 4.37 × 10-20 to 4.50 × 10-20 cm2 as the PbO/BaO ratio increased. In addition, thermo-optical properties were measured using an interferometric technique. The thermo-optical coefficients, which were -1.49 × 10-6, -1.65 × 10-6, and -1.64 × 10-6 K-1, respectively, were all largely negative values. The thermal expansion coefficients of the three glass samples varied within a small range. The results showed that increasing the PbO/BaO ratio of phosphate glasses can improve the laser properties while maintaining their good thermo-optical properties.

Local atomic arrangement and scintillation properties of Eu- and Ce-doped NaYP{sub 2}O{sub 7}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Novais, S.M.V., E-mail: suellen.mvn@gmail.com; Macedo, Z.S.

2016-01-15

Direct determination of rare earth location and local environment in NaYP{sub 2}O{sub 7} are presented. Undoped and Ln-doped NaYP{sub 2}O{sub 7} (Ln=Eu, Ce) were produced via PVA-assisted sol–gel method. Lattice parameters were determined from Rietveld refinement, showing monoclinic structure. XAS results suggested Eu{sup 3+} and Ce{sup 3+} are incorporated into NaYP{sub 2}O{sub 7} host in substitution to Y{sup 3+} site, with first coordination shell formed by six oxygen ions. Measurements at Eu edge showed a single peak in R space for Eu–O distribution. In this case, uniform interatomic distances implied to absence of significant disorder. Analysis at Ce edge presentedmore » different behavior, with Ce–O distribution characterized by a split peak in R space. Nearest neighborhood was found to be distributed with Ce occupying an off-center position in Y site. Under X-ray excitation, {sup 5}D{sub 0}→{sup 7}F{sub J} emission lines of Eu{sup 3+} were identified for NaYP{sub 2}O{sub 7}:Eu. NaYP{sub 2}O{sub 7}:Ce presented a broad emission formed by 5d→{sup 2}F{sub J} transitions of Ce{sup 3+}, with the superposition attributed to the effect of distorted oxygen octahedra around the dopant ions. - Graphical abstract: EuO{sub 6} and CeO{sub 6} octahedral arrangement relative to Y site in NaYP{sub 2}O{sub 7} host, and XEOL emission of corresponding doped samples. - Highlights: • Lattice parameters of NaYP{sub 2}O{sub 7} undoped sample confirmed monoclinic structure. • Dopants Eu and Ce are incorporated in the trivalent state. • Local order of Eu{sup 3+} and Ce{sup 3+} dopants substituting Y{sup 3+} consist of octahedral symmetry. • Off-center displacement in the case of Ce{sup 3+} position was discussed. • Luminescent properties under X-ray excitation may allow practical applications.« less

Electronic structure of layered titanate Nd 2Ti 2O 7

NASA Astrophysics Data System (ADS)

Atuchin, V. V.; Gavrilova, T. A.; Grivel, J.-C.; Kesler, V. G.

2008-10-01

The electronic structure of the binary titanate Nd 2Ti 2O 7 has been studied by X-ray photoelectron spectroscopy (XPS). Spectral features of the valence band and all constituent element core levels have been considered. The Auger parameters of titanium and oxygen in Nd 2Ti 2O 7 are determined as αTi = 873.5 and αO = 1042.2 eV. Chemical bonding effects have been discussed with the binding energies differences ΔTi = (BE O 1s - BE Ti 2p 3/2) = 71.5 eV and ΔNd = (BE Nd 3d 5/2 - BE O 1s) = 452.5 eV as key parameters in comparison with those in other titanium- and neodymium-bearing oxides.

Epitaxial growth of iridate pyrochlore Nd 2Ir 2O 7 films

DOE PAGES

Gallagher, J. C.; Esser, B. D.; Morrow, R.; ...

2016-02-29

Epitaxial films of the pyrochlore Nd 2Ir 2O 7 have been grown on (111)-oriented yttria-stabilized zirconia (YSZ) substrates by off-axis sputtering followed by post-growth annealing. X-ray diffraction (XRD) results demonstrate phase-pure epitaxial growth of the pyrochlore films on YSZ. Scanning transmission electron microscopy (STEM) investigation of an Nd 2Ir 2O 7 film with a short post-annealing provides insight into the mechanism for crystallization of Nd 2Ir 2O 7 during the post-annealing process. STEM images reveal clear pyrochlore ordering of Nd and Ir in the films. As a result, the epitaxial relationship between the YSZ and Nd 2Ir 2O 7 ismore » observed clearly while some interfacial regions show a thin region with polycrystalline Ir nanocrystals.« less

31P T2s of phosphomonoesters, phosphodiesters, and inorganic phosphate in the human brain at 7T

PubMed Central

Klomp, Dennis W.J.; Wijnen, Jannie P.

2017-01-01

Purpose To determine the phosphorus‐31 T2s of phosphomonoesters, phosphodiesters, and inorganic phosphate in the healthy human brain at 7T. Methods A 3D chemical shift imaging multi‐echo sequence with composite block pulses for refocusing was used to measure one free induction decay (FID) and seven full echoes with an echo spacing of 45 ms on the brain of nine healthy volunteers (age range 22–45 years; average age 27 ± 8 years). Spectral fitting was used to determine the change in metabolic signal amplitude with echo time. Results The average apparent T2s with their standard deviation were 202 ± 6 ms, 129 ± 6 ms, 86 ± 2 ms, 214 ± 10 ms, and 213 ± 11 ms for phosphoethanolamine, phosphocholine, inorganic phosphate, glycerophosphoethanolamine, and glycerophosphocholine, respectively. Conclusion The determined apparent T2 for phosphoethanolamine, glycerophosphocholine, and glycerophosphoethanolamine is approximately 200 ms. The lower apparent T2 value for phosphocholine is attributed to the overlap of this resonance with the 3‐phosphorous resonance of 2,3‐diphosphoglycerate from blood, with an apparent shorter T2. Omitting the FID signal and the first echo of phosphocholine leads to a T2 of 182 ± 7 ms, whereas a biexponential analysis leads to 203 ± 4 ms. These values are more in line with phosphoethanolamine and the phosphodiesters. The short T2 of inorganic phosphate is subscribed to the fast reversible exchange with γ‐adenosine triphosphate, which is mediated by glyceraldehyde‐3‐phosphate dehydrogenase and phosphoglycerate kinase within the glycolytic pathway. Magn Reson Med 80:29–35, 2018. © 2017 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution NonCommercial License, which permits use, distribution and reproduction in any

The luminescence of nanoscale Y2Si2O7:Eu3+ materials.

PubMed

Lu, Shaozhe; Zhang, Jishen; Zhang, Jiahua

2010-03-01

The Y2Si2O7:Eu3+ sample was prepared with the sol-gel method. The Y2O3:EU3 was dispersed in SiO2, and the complex Y2Si2O7:Eu3+ particles were synthesized at high annealing temperature. The sample consisted of nearly spherical particles with an average size about 60 nm. The ultraviolet excitation spectra and emission spectra were measured. The sample excited by short ultraviolet light showed strongly red luminescence and fine monochromaticity. The luminescence was strongest from the 5D0 --> 7F2 electric dipole transition located at 611 nm. The excitation spectra of Y2Si2O7:Eu3+ excited with ultraviolet lights showed that the peak of the Eu(3+)-O2- charge transition band located at about 240 nm. During monitoring of different emission peaks of 5D0 --> 7F2, the charge transition band in the excitation spectra shifted, and the relative intensity of emission spectra changed obviously under the excitation of different ultraviolet wavelengths. These results confirmed that the Eu3+ could be excited with ultraviolet radiation of different wavelengths. At low temperature, using Eu3+ ions as fluorescence probes, we monitored the emission peaks of 5D0 --> 7F1 and 5D0 --> 7F2 transitions and measured the excitation spectra of 7F0 --> 5D0, 5D0 --> 7F1, and 5D0 --> 7F2 site-selective excitation spectra. These results indicated that Eu3+ ions are located in different local environments in the Y2Si2O7 host.

Na7Cr4(P2O7)4PO4

PubMed Central

Bourguiba Fakhar, Noura; Zid, Mohamed Faouzi; Driss, Ahmed

2013-01-01

The title compound, hepta­sodium tetra­chromium(III) tetra­kis­(diphosphate) orthophosphate, was synthesized by solid-state reaction. Its structure is isotypic with that of Na7 M 4(P2O7)4PO4 (M = In, Al) compounds and is made up from a three-dimensional [(CrP2O7)4PO4]7− framework with channels running along [001]. The three Na+ cations are located in the voids of the framework. One of the cations is situated on a general position, one is equally disordered around a twofold rotation axis and one is on a fourfold rotoinversion axis. The isolated PO4 tetra­hedron of the anionic framework is also situated on the -4 axis. Structural relationships between the title compound and different diphosphates containing MP2O11 units (M = Mo, V) are discussed. PMID:23723751

The Structural, Photocatalytic Property Characterization and Enhanced Photocatalytic Activities of Novel Photocatalysts Bi2GaSbO7 and Bi2InSbO7 during Visible Light Irradiation

PubMed Central

Luan, Jingfei; Shen, Yue; Li, Yanyan; Paz, Yaron

2016-01-01

In order to develop original and efficient visible light response photocatalysts for degrading organic pollutants in wastewater, new photocatalysts Bi2GaSbO7 and Bi2InSbO7 were firstly synthesized by a solid-state reaction method and their chemical, physical and structural properties were characterized. Bi2GaSbO7 and Bi2InSbO7 were crystallized with a pyrochlore-type structure and the lattice parameter of Bi2GaSbO7 or Bi2InSbO7 was 10.356497 Å or 10.666031 Å. The band gap of Bi2GaSbO7 or Bi2InSbO7 was estimated to be 2.59 eV or 2.54 eV. Compared with nitrogen doped TiO2, Bi2GaSbO7 and Bi2InSbO7, both showed excellent photocatalytic activities for degrading methylene blue during visible light irradiation due to their narrower band gaps and higher crystallization perfection. Bi2GaSbO7 showed higher catalytic activity compared with Bi2InSbO7. The photocatalytic degradation of methylene blue followed by the first-order reaction kinetics and the first-order rate constant was 0.01470 min−1, 0.00967 min−1 or 0.00259 min−1 with Bi2GaSbO7, Bi2InSbO7 or nitrogen doped TiO2 as a catalyst. The evolution of CO2 and the removal of total organic carbon were successfully measured and these results indicated continuous mineralization of methylene blue during the photocatalytic process. The possible degradation scheme and pathway of methylene blue was also analyzed. Bi2GaSbO7 and Bi2InSbO7 photocatalysts both had great potential to purify textile industry wastewater. PMID:28773922

Phosphate Tether-Mediated Ring-Closing Metathesis for the Generation of P-Stereogenic, Z-Configured Bicyclo[7.3.1]- and Bicyclo[8.3.1]phosphates.

PubMed

Markley, Jana L; Maitra, Soma; Hanson, Paul R

2016-02-05

A phosphate tether-mediated ring-closing metathesis (RCM) study to the synthesis of Z-configured, P-stereogenic bicyclo[7.3.1]- and bicyclo[8.3.1]phosphates is reported. Investigations suggest that C3-substitution, olefin substitution, and proximity of the forming olefin to the bridgehead carbon of the bicyclic affect the efficiency and stereochemical outcome of the RCM event. This study demonstrates the utility of phosphate tether-mediated desymmetrization of C2-symmetric, 1,3-anti-diol-containing dienes in the generation of macrocyclic phosphates with potential synthetic and biological utility.

Development of magnesium calcium phosphate biocement for bone regeneration.

PubMed

Jia, Junfeng; Zhou, Huanjun; Wei, Jie; Jiang, Xin; Hua, Hong; Chen, Fangping; Wei, Shicheng; Shin, Jung-Woog; Liu, Changsheng

2010-08-06

Magnesium calcium phosphate biocement (MCPB) with rapid-setting characteristics was fabricated by using the mixed powders of magnesium oxide (MgO) and calcium dihydrogen phosphate (Ca(H(2)PO(4))(2).H(2)O). The results revealed that the MCPB hardened after mixing the powders with water for about 7 min, and the compressive strength reached 43 MPa after setting for 1 h, indicating that the MCPB had a short setting time and high initial mechanical strength. After the acid-base reaction of MCPB containing MgO and Ca(H(2)PO(4))(2).H(2)O in a molar ratio of 2 : 1, the final hydrated products were Mg(3)(PO(4))(2) and Ca(3)(PO(4))(2). The MCPB was degradable in Tris-HCl solution and the degradation ratio was obviously higher than calcium phosphate biocement (CPB) because of its fast dissolution. The attachment and proliferation of the MG(63) cells on the MCPB were significantly enhanced in comparison with CPB, and the alkaline phosphatase activity of MG(63) cells on the MCPB was significantly higher than on the CPB at 7 and 14 days. The MG(63) cells with normal phenotype spread well on the MCPB surfaces, and were attached in close proximity to the substrate, as seen by scanning electron microscopy (SEM). The results demonstrated that the MCPB had a good ability to support cell attachment, proliferation and differentiation, and exhibited good cytocompatibility.

An investigation of ESSA 7 radiation data for use in long-term earth energy experiments, phases 1 and 2

NASA Technical Reports Server (NTRS)

House, F. B.

1974-01-01

The results are presented of an investigation of ESSA 7 satellite radiation data for use in long-term earth energy experiments. Satellite systems for performing long-term earth radiation balance measurements over geographical areas, hemispheres, and the entire earth for periods of 10 to 30 years are examined. The ESSA 7 satellite employed plate and cone radiometers to measure earth albedo and emitted radiation. Each instrument had a black and white radiometer which discriminated the components of albedo and emitted radiation. Earth measurements were made continuously from ESSA 7 for ten months. The ESSA 7 raw data is processed to a point where it can be further analyzed for: (1) development of long-term earth energy experiments; and (2) document climate trends.

Intense 2.7 µm emission and structural origin in Er3+-doped bismuthate (Bi2O3-GeO2-Ga2O3-Na2O) glass.

PubMed

Guo, Yanyan; Li, Ming; Hu, Lili; Zhang, Junjie

2012-01-15

The 2.7 μm emission properties in Er3+-doped bismuthate (Bi2O3-GeO2-Ga2O3-Na2O) glass were investigated in the present Letter. An intense 2.7 μm emission in Er3+-doped bismuthate glass was observed. It is found that Er3+-doped bismuthate glass possesses high spontaneous transition probability A (65.26 s(-1)) and large 2.7 μm emission cross section σ(em) (9.53×10(-21) cm2) corresponding to the stimulated emission of Er3+:4I11/2→4I13/2 transition. The emission characteristic and energy transfer process upon excitation of a conventional 980 nm laser diode in bismuthate glass were analyzed. Additionally, the structure of bismuthate glass was analyzed by the Raman spectrum. The advantageous spectroscopic characteristics of Er3+ single-doped bismuthate glass together with the prominent thermal property indicate that bismuthate glass might become an attractive host for developing solid-state lasers around 2.7 μm.

Oxygen isotope effect in YBa2Cu3O7 prepared by burning YBa2Cu3 in 16O and 18O

NASA Astrophysics Data System (ADS)

Yvon, Pascal J.; Schwarz, R. B.; Pierce, C. B.; Bernardez, L.; Conners, A.; Meisenheimer, R.

1989-04-01

We prepared YBa2Cu3 powder by ball milling a 2:1 molar mixture of the intermetallics BaCu and CuY. We synthesized YBa2Cu3(16O)7-x and YBa2Cu3(18O)7-x by oxidizing the YBa2Cu3 powder in 16O and 18O. The 16O/18O ratios were determined by laser-ionization and sputtering-ionization mass spectroscopy. The YBa2Cu3(160)7-x sample had 99.8 at. %16O, and the YBa2Cu3(18O)7-x sample had 96.5 at. %18O. Susceptibility measurements of the superconducting transition temperature (Tc=91.7 K for 16O; half-point transition at 84 K show an isotope effect of 0.4+/-0.1 K.

Influence of phosphate and solution pH on the mobility of ZnO nanoparticles in saturated sand.

PubMed

Li, Lingxiangyu; Schuster, Michael

2014-02-15

The mobility of nanoparticles (NPs) strongly depends on the chemical characterization of the environmental medium. However, the influence of phosphate on NPs mobility was ignored by scientists despite the serious phosphate contamination in natural environments. Hence, the influence of phosphate and solution pH on the mobility of zinc oxide nanoparticles (ZnO-NPs) was investigated in water-saturated sand representative of groundwater aquifers, which encompassed a range of P/Zn molar ratios (P/Zn: 0-4) and pH (4.8-10.0). The transport of ZnO-NPs was dramatically enhanced in the presence of phosphate, even at a low P/Zn molar ratio namely 0.25, and the retention of ZnO-NPs in the saturated sand decreased with increasing P/Zn molar ratio. Moreover, attachment efficiencies (α) and deposition rates (kd) of ZnO-NPs rapidly decreased with increasing P/Zn molar ratio. In contrast, the solution pH had negligible effects on ZnO-NP transport behavior under phosphate-abundant condition (P/Zn: 4). The distinct effects may be explained by the energy interaction between ZnO-NPs and sand surface under different conditions. Interestingly, under phosphate-abundant condition (P/Zn: 4), solution pH could strongly affect the transport of Zn(2+) in the water-saturated sand. Overall, this study outlines the importance of taking account of phosphate into risk assessment of NPs in the environment. Copyright © 2013 Elsevier B.V. All rights reserved.

Study of a hydraulic dicalcium phosphate dihydrate/calcium oxide-based cement for dental applications.

PubMed

el-Briak, Hasna; Durand, Denis; Nurit, Josiane; Munier, Sylvie; Pauvert, Bernard; Boudeville, Phillipe

2002-01-01

By mixing CaHPO(4) x 2H(2)O (DCPD) and CaO with water or sodium phosphate buffers as liquid phase, a calcium phosphate cement was obtained. Its physical and mechanical properties, such as compressive strength, initial and final setting times, cohesion time, dough time, swelling time, dimensional and thermal behavior, and injectability were investigated by varying different parameters such as liquid to powder (L/P) ratio (0.35-0.7 ml g(-1)), molar calcium to phosphate (Ca/P) ratio (1.67-2.5) and the pH (4, 7, and 9) and the concentration (0-1 M) of the sodium phosphate buffer. The best results were obtained with the pH 7 sodium phosphate buffer at the concentration of 0.75 M. With this liquid phase, physical and mechanical properties depended on the Ca/P and L/P ratios, varying from 3 to 11 MPa (compressive strength), 6 to 10 min (initial setting time), 11 to 15 min (final setting time), 15 to 30 min (swelling time), 7 to 20 min (time of 100% injectability). The dough or working time was over 16 min. This cement expanded during its setting (1.2-5 % according to Ca/P and L/P ratios); this would allow a tight filling. Given the mechanical and rheological properties of this new DCPD/CaO-based cement, its use as root canal sealing material can be considered as classical calcium hydroxide or ZnO/eugenol-based pastes, without or with a gutta-percha point. Copyright 2002 Wiley Periodicals, Inc. J Biomed Mater Res (Appl Biomater) 63: 447-453, 2002

Gallium incorporation into phosphate based glasses: Bulk and thin film properties.

PubMed

Stuart, Bryan W; Grant, Colin A; Stan, George E; Popa, Adrian C; Titman, Jeremy J; Grant, David M

2018-06-01

The osteogenic ions Ca 2+ , P 5+ , Mg 2+ , and antimicrobial ion Ga 3+ were homogenously dispersed into a 1.45 µm thick phosphate glass coating by plasma assisted sputtering onto commercially pure grade titanium. The objective was to deliver therapeutic ions in orthopaedic/dental implants such as cementeless endoprostheses or dental screws. The hardness 4.7 GPa and elastic modulus 69.7 GPa, of the coating were comparable to plasma sprayed hydroxyapatite/dental enamel, whilst superseding femoral cortical bone. To investigate the manufacturing challenge of translation from a target to vapour condensed coating, structural/compositional properties of the target (P51MQ) were compared to the coating (P40PVD) and a melt-quenched equivalent (P40MQ). Following condensation from P51MQ to P40PVD, P 2 O 5 content reduced from 48.9 to 40.5 mol%. This depolymerisation and reduction in the P-O-P bridging oxygen content as determined by 31 P NMR, FTIR and Raman spectroscopy techniques was attributed to a decrease in the P 2 O 5 network former and increases in alkali/alkali-earth cations. P40PVD appeared denser (3.47 vs. 2.70 g cm -3 ) and more polymerised than it's compositionally equivalent P40MQ, showing that structure/ mechanical properties were affected by manufacturing route. Copyright © 2018. Published by Elsevier Ltd.

The Pressure-Induced Structural Response of A2Hf2O7 (A=Y, Sm, Eu, Gd, Dy, Yb) Compounds from 0.1-50 GPa

NASA Astrophysics Data System (ADS)

Turner, K. M.; Rittman, D.; Heymach, R.; Turner, M.; Tracy, C.; Mao, W. L.; Ewing, R. C.

2016-12-01

and anionic sites as pressure is increased. The pressure of their phase transitions correlates directly with their radius ratio. Our results are comparable to many high-pressure studies of rare earth zirconates and titanates, but contrast from previous experiments performed on rare earth hafnates, specifically La2Hf2O7.

Mechanism for converting Al2O3-containing borate glass to hydroxyapatite in aqueous phosphate solution.

PubMed

Zhao, Di; Huang, Wenhai; Rahaman, Mohamed N; Day, Delbert E; Wang, Deping

2009-05-01

The effect of replacing varying amounts (0-2.5 mol.%) of B2O3 with Al2O3 in a borate glass on (1) the conversion of the glass to HA in an aqueous phosphate solution and (2) the compressive strength of the as-formed HA product was investigated. Samples of each glass (10 x 10 x 8 mm) were placed in 0.25 M K2HPO4 solution at 60 degrees C, and the conversion kinetics to HA were determined from the weight loss of the glass and the pH of the solution. The structure and composition of the solid reaction products were characterized using X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. While the conversion rate of the glass to HA decreased considerably with increasing Al2O3 content, the microstructure of the HA product became denser and the compressive strength of the HA product increased. The addition of SiO2 to the Al2O3-containing borate glass reversed the deterioration of the conversion rate, and produced a further improvement in the strength of the HA product. The compressive strength of the HA formed from the borate glass with 2.5 mol.% Al2O3 and 5 mol.% SiO2 was 11.1 +/- 0.2 MPa, which is equal to the highest strengths reported for trabecular bone. The results indicated that simultaneous additions of Al2O3 and SiO2 could be used to control the bioactivity of the borate glass and to enhance the mechanical strength of the HA product. Furthermore, the HA product formed from the glass containing both SiO2 and Al2O3 could be applied to bone repair.

Possibility of Flat-Band Ferromagnetism in Hole-Doped Pyrochlore Oxides Sn2 Nb2 O7 and Sn2 Ta2 O7

NASA Astrophysics Data System (ADS)

Hase, I.; Yanagisawa, T.; Aiura, Y.; Kawashima, K.

2018-05-01

Quantum mechanics tells us that the hopping integral between local orbitals makes the energy band dispersive. In a lattice with geometric frustration, however, dispersionless flat bands may appear due to quantum interference. Several models possessing flat bands have been proposed theoretically, and many attracting magnetic and electronic properties are predicted. However, despite many attempts to realize these models experimentally, compounds that are appropriately described by this model have not been found so far. Here we show that pyrochlore oxides Sn2 Nb2 O7 and Sn2Ta2O7 are such examples, by performing first-principles band calculation and several tight-binding analyses. Moreover, spin-polarized band calculation shows that the hole-doped systems Sn2 Nb2 O6 N and Sn2 Ta2 O6 N have complete spin polarization, and their magnetic moments are mostly carried by Sn-s and N-p orbitals, which are usually nonmagnetic. These compounds are not only candidates for ferromagnets without a magnetic element, but also will provide an experimental platform for a flat-band model which shows a wide range of physical properties.

Effect of boron oxide addition on fibre drawing, mechanical properties and dissolution behaviour of phosphate-based glass fibres with fixed 40, 45 and 50 mol% P2O5

PubMed Central

Sharmin, Nusrat; Parsons, Andrew J; Rudd, Chris D

2014-01-01

Previous studies investigating manufacture of phosphate-based glass fibres from glasses fixed with P2O5 content less than 50 mol% showed that continuous manufacture without breakage was very difficult. In this study, nine phosphate-based glass formulations from the system P2O5-CaO-Na2O-MgO-B2O3 were prepared with P2O5 contents fixed at 40, 45 and 50 mol%, where Na2O was replaced by 5 and 10 mol% B2O3 and MgO and CaO were fixed to 24 and 16 mol%, respectively. The effect of B2O3 addition on the fibre drawing, fibre mechanical properties and dissolution behaviour was investigated. It was found that addition of 5 and 10 mol% B2O3 enabled successful drawing of continuous fibres from glasses with phosphate (P2O5) contents fixed at 40, 45 and 50 mol%. The mechanical properties of the fibres were found to significantly increase with increasing B2O3 content. The highest tensile strength (1200 ± 130 MPa) was recorded for 45P2O5-16CaO-5Na2O-24MgO-10B2O3 glass fibres. The fibres were annealed, and a comparison of the mechanical properties and mode of degradation of annealed and non-annealed fibres were investigated. A decrease in tensile strength and an increase in tensile modulus were observed for the annealed fibres. An assessment of the change in mechanical properties of both the annealed and non-annealed fibres was performed in phosphate-buffered saline (PBS) at 37℃ for 28 and 60 days, respectively. Initial loss of mechanical properties due to annealing was found to be recovered with degradation. The B2O3-containing glass fibres were found to degrade at a much slower rate as compared to the non-B2O3-containing fibres. Both annealed and non-annealed fibres exhibited a peeling effect of the fibre's outer layer during degradation. PMID:24939962

Effect of boron oxide addition on fibre drawing, mechanical properties and dissolution behaviour of phosphate-based glass fibres with fixed 40, 45 and 50 mol% P2O5.

PubMed

Sharmin, Nusrat; Parsons, Andrew J; Rudd, Chris D; Ahmed, Ifty

2014-11-01

Previous studies investigating manufacture of phosphate-based glass fibres from glasses fixed with P2O5 content less than 50 mol% showed that continuous manufacture without breakage was very difficult. In this study, nine phosphate-based glass formulations from the system P2O5-CaO-Na2O-MgO-B2O3 were prepared with P2O5 contents fixed at 40, 45 and 50 mol%, where Na2O was replaced by 5 and 10 mol% B2O3 and MgO and CaO were fixed to 24 and 16 mol%, respectively. The effect of B2O3 addition on the fibre drawing, fibre mechanical properties and dissolution behaviour was investigated. It was found that addition of 5 and 10 mol% B2O3 enabled successful drawing of continuous fibres from glasses with phosphate (P2O5) contents fixed at 40, 45 and 50 mol%. The mechanical properties of the fibres were found to significantly increase with increasing B2O3 content. The highest tensile strength (1200 ± 130 MPa) was recorded for 45P2O5-16CaO-5Na2O-24MgO-10B2O3 glass fibres. The fibres were annealed, and a comparison of the mechanical properties and mode of degradation of annealed and non-annealed fibres were investigated. A decrease in tensile strength and an increase in tensile modulus were observed for the annealed fibres. An assessment of the change in mechanical properties of both the annealed and non-annealed fibres was performed in phosphate-buffered saline (PBS) at 37℃ for 28 and 60 days, respectively. Initial loss of mechanical properties due to annealing was found to be recovered with degradation. The B2O3-containing glass fibres were found to degrade at a much slower rate as compared to the non-B2O3-containing fibres. Both annealed and non-annealed fibres exhibited a peeling effect of the fibre's outer layer during degradation. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

LiFePO4 Nanostructures Fabricated from Iron(III) Phosphate (FePO4 x 2H2O) by Hydrothermal Method.

PubMed

Saji, Viswanathan S; Song, Hyun-Kon

2015-01-01

Electrode materials having nanometer scale dimensions are expected to have property enhancements due to enhanced surface area and mass/charge transport kinetics. This is particularly relevant to intrinsically low electronically conductive materials such as lithium iron phosphate (LiFePO4), which is of recent research interest as a high performance intercalation electrode material for Li-ion batteries. Many of the reported works on LiFePO4 synthesis are unattractive either due to the high cost of raw materials or due to the complex synthesis technique. In this direction, synthesis of LiFePO4 directly from inexpensive FePO4 shows promise.The present study reports LiFePO4 nanostructures prepared from iron (III) phosphate (FePO4 x 2H2O) by precipitation-hydrothermal method. The sintered powder was characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), Inductive coupled plasma-optical emission spectroscopy (ICP-OES), and Electron microscopy (SEM and TEM). Two synthesis methods, viz. bulk synthesis and anodized aluminum oxide (AAO) template-assisted synthesis are reported. By bulk synthesis, micro-sized particles having peculiar surface nanostructuring were formed at precipitation pH of 6.0 to 7.5 whereas typical nanosized LiFePO4 resulted at pH ≥ 8.0. An in-situ precipitation strategy inside the pores of AAO utilizing the spin coating was utilized for the AAO-template-assisted synthesis. The template with pores filled with the precipitate was subsequently subjected to hydrothermal process and high temperature sintering to fabricate compact rod-like structures.

Modifying the Surface of γ-Al2 O3 with Y2 Sn2 O7 Pyrochlore: Monolayer Dispersion Behaviour of Composite Oxides.

PubMed

Xu, Xianglan; Liu, Fang; Tian, Jinshu; Peng, Honggen; Liu, Wenming; Fang, Xiuzhong; Zhang, Ning; Wang, Xiang

2017-06-20

To investigate the dispersion behaviour of composite oxides on supports, and to obtain better supports for Pd for CO oxidation, a series of Y 2 Sn 2 O 7 /Al 2 O 3 composite oxides with different Y 2 Sn 2 O 7 loadings were prepared by a deposition-precipitation method. XRD and X-ray photoelectron spectroscopic extrapolation methods revealed that, similar to single-component metal oxides, composite oxides can also disperse spontaneously on support surfaces to form a monolayer with a certain capacity. The monolayer dispersion capacity/threshold for Y 2 Sn 2 O 7 on the surface of γ-Al 2 O 3 is 0.109 mmol per 100 m 2 γ-Al 2 O 3 , corresponding to 7.2 wt % Y 2 Sn 2 O 7 loading. This is the first work to demonstrate monolayer dispersion of a composite oxide on a support. After combining Y 2 Sn 2 O 7 with γ-Al 2 O 3 , active oxygen species can be introduced onto the catalyst surfaces. Thus, the interaction between Pd and the support is strengthened, the dispersion of Pd is improved in comparison with the single-component Y 2 Sn 2 O 7 support, and a synergistic effect is induced between Pd and the composite support, which is beneficial to catalyst activity. By tuning the γ-Al 2 O 3 surface with different amounts of pyrochlore Y 2 Sn 2 O 7 , CO oxidation activity on 1 % Pd/Y 2 Sn 2 O 7 /Al 2 O 3 was improved. These findings may provide new insights into the design and preparation of effective supported noble metal catalysts with lower contents of noble metals. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of Phosphate Species on Hydrated Anatase TiO2 Surfaces.

PubMed

Tielens, Frederik; Gervais, Christel; Deroy, Geraldine; Jaber, Maguy; Stievano, Lorenzo; Coelho Diogo, Cristina; Lambert, Jean-François

2016-02-02

The adsorption/interaction of KH2PO4 with solvated (100) and (101) TiO2 anatase surfaces is investigated using periodic DFT calculations in combination with GIPAW NMR calculations and experimental IR and solid state (17)O, and (31)P NMR spectroscopies. A complete and realistic model has been used to simulate the solvent by individual water molecules. The most stable adsorption configurations are characterized theoretically at the atomic scale, and experimentally supported by NMR and IR spectroscopies. It is shown that H2PO4(-) chemisorbs on the (100) and (101) anatase surfaces, preferentially via a bidentate geometry. Dimer (H3P2O7(-)) and trimer (H4P3O10(-)) adsorption models are confronted with monomer adsorption models, in order to rationalize their occurrence.

Hydrothermal synthesis of copper zirconium phosphate hydrate [Cu(OH)2Zr(HPO4)2·2H2O] and an investigation of its lubrication properties in grease.

PubMed

Zhang, Xiaosheng; Xu, Hong; Zuo, Zhijun; Lin, Zhi; Ferdov, Stanislav; Dong, Jinxiang

2013-08-28

Copper zirconium phosphate hydrate (Cu(OH)2Zr(HPO4)2·2H2O, hereafter referred to as Cu-α-ZrP) with high crystallinity was directly synthesized in a NaF-CuO-ZrO-P2O5-H2O system under hydrothermal conditions. The copper ion was confirmed to be an exchangeable cation in the Cu-α-ZrP through elemental analysis and a proton ion exchange process. The crystal structure of the Cu-α-ZrP was determined ab initio by using X-ray powder diffraction data. In the structure, the CuO6 octahedron would be located in an exchangeable atom position. Moreover, Cu-α-ZrP was evaluated as an additive in grease in a four ball test. The maximum nonseizure load (PB, representing the load-carrying capacity) of the base grease containing Cu-α-ZrP was increased from 353 to 1235 N. The excellent load-carrying capacity may be explained by the easier adherence of the material to the worn surface forming a tight protective film.

Stability of the high pressure phase Fe3S2 up to Earth's core pressures in the Fe-S-O and the Fe-S-Si systems

NASA Astrophysics Data System (ADS)

Zurkowski, C. C.; Chidester, B.; Davis, A.; Brauser, N.; Greenberg, E.; Prakapenka, V. B.; Campbell, A.

2017-12-01

Earth's core is comprised of an iron-nickel alloy that contains 5-15% of a light element component. The abundance and alloying capability of sulfur, silicon and oxygen in the bulk Earth make them important core alloy candidates; therefore, the high-pressure phase equilibria of the Fe-S-O and Fe-S-Si systems are relevant for understanding the possible chemistry of Earth's core. Previously, a Fe3S2 phase was recognized as a low-pressure intermediate phase in the Fe-FeS system that is stable from 14-21 GPa, but the structure of this phase has not been resolved. We report in-situ XRD and chemical analysis of recovered samples to further examine the stability and structure of Fe3S2 as it coexists with other phases in the Fe-S-O and Fe-S-Si systems. In situ high P-T synchrotron XRD experiments were conducted in the laser-heated diamond anvil cell to determine the equilibrium phases in Fe75S7O18 and Fe80S5Si15 compositions between 30 and 174 GPa and up to 3000 K. In the S,O-rich samples, an orthorhombic Fe3S2 phase coexists with hcp-Fe, Fe3S and FeO and undergoes two monoclinic distortions between 60 and 174 GPa. In the S,Si-rich samples, the orthorhombic Fe3S2 phase was observed up to 115 GPa. With increasing pressure, the Fe3S2 phase becomes stable to higher temperatures in both compositions, suggesting possible Fe3(S,O)2 or Fe3(S,Si)2 solid solutions. SEM analysis of a laser heated Fe75S7O18 sample recovered from 40 GPa and 1450 K confirms a Fe3(S,O)2 phase with O dissolved into the structure. Based on the current melting data in the Fe-S-O and Fe-S-Si systems, the Fe3(S,O)2 stability field intersects the solidus in the outer core and could be a possible liquidus phase in Fe,S,O-rich planetary cores, whereas Fe3S is the stable sulfide at outer core pressures in Fe,S,Si-rich systems.

Controls on O2 Production in Cyanobacterial Mats and Implications for Earth's Oxygenation

NASA Astrophysics Data System (ADS)

Dick, Gregory J.; Grim, Sharon L.; Klatt, Judith M.

2018-05-01

Cyanobacterial mats are widely assumed to have been globally significant hot spots of biogeochemistry and evolution during the Archean and Proterozoic, but little is known about their quantitative contributions to global primary productivity or Earth's oxygenation. Modern systems show that mat biogeochemistry is the outcome of concerted activities and intimate interactions between various microbial metabolisms. Emerging knowledge of the regulation of oxygenic and sulfide-driven anoxygenic photosynthesis by versatile cyanobacteria, and their interactions with sulfur-oxidizing bacteria and sulfate-reducing bacteria, highlights how ecological and geochemical processes can control O2 production in cyanobacterial mats in unexpected ways. This review explores such biological controls on O2 production. We argue that the intertwined effects of light availability, redox geochemistry, regulation and competition of microbial metabolisms, and biogeochemical feedbacks result in emergent properties of cyanobacterial mat communities that are all critical yet largely overlooked mechanisms to potentially explain the protracted nature of Earth's oxygenation.

Redetermination of clinobaryl­ite, BaBe2Si2O7

PubMed Central

Domizio, Adrien J. Di; Downs, Robert T.; Yang, Hexiong

2012-01-01

Clinobaryl­ite, ideally BaBe2Si2O7 (chemical name barium diberyllium disilicate), is a sorosilicate mineral and dimorphic with baryl­ite. It belongs to a group of compounds characterized by the general formula BaM 2+ 2Si2O7, with M 2+ = Be, Mg, Fe, Mn, Zn, Co, or Cu, among which the Be-, Fe-, and Cu-members have been found in nature. The crystal structure of clinobaryl­ite has been re-examined in this study based on single-crystal X-ray diffraction data collected from a natural sample from the type locality (Khibiny Massif, Kola Peninsula, Russia). The structure of clinobaryl­ite can be considered as a framework of BeO4 and SiO4 tetra­hedra, with one of the O atoms coordinated to two Be and one Si, one coordinated to two Si, and two O atoms coordinated to one Si and one Be atom. The BeO4 tetra­hedra share corners, forming chains parallel to the c axis, which are inter­linked by the Si2O7 units oriented parallel to the a axis. The Ba2+ cations (site symmetry m..) are in the framework channels and are coordinated by eleven O atoms in form of an irregular polyhedron. The Si—Obr (bridging O atom, at site symmetry m..) bond length, the Si—Onbr (non-bridging O atoms) bond lengths, and the Si—O—Si angle within the Si2O7 unit are in marked contrast to the corresponding values determined in the previous study [Krivovichev et al. (2004 ▶). N. Jb. Miner. Mh. pp. 373–384]. PMID:23125568

Optical properties of Eu3+ & Tb3+ ions doped alkali oxide (Li2O/ Na2O/ K2O) modified boro phosphate glasses for red, green lasers and display device applications

NASA Astrophysics Data System (ADS)

Moulika, G.; Sailaja, S.; Reddy, B. Naveen Kumar; Reddy, V. Sahadeva; Dhoble, S. J.; Reddy, B. Sudhakar

2018-04-01

In this article we report on alkali oxide modified borophosphate glasses doped with Eu3+and Tb3+ ions, with the chemical composition of 69.5 B2O3+10P2O5 + 10CaF2 + 5 Li2O+ 5ZnO+ R+ 0.5 Eu2O3 [where R = 5 (LiO2/Na2O/K2O)] have been prepared by conventional melt quenching technique, and the spectroscopic properties of the prepared glasses have been studied by XRD, Optical absorption, excitation and emission spectral analysis. XRD spectrum of the glasses have shown the amorphous nature of the glasses. The red emission corresponding to 5D0 → 7F2 (613 nm) transition was observed under the excitation of 394 nm wavelength, corresponding to Eu3+ ions, for all the prepared glasses. For Eu3+ ion doped glasses, emission bands were observed, such as; 5D1→ 7F1 (538 nm), 5D0→ 7F0 (580 nm), 5D0→ 7F1 (592 nm), 5D0→ 7F2 (613 nm), 5D0→ 7F3 (613 nm) and 5D0→ 7F4 (702 nm) are identified. In the case of Tb3+ ion doped glasses, four emission lines were observed, such as 5D4→ (7F6, 7F5, 7F4), which are located at 489 nm, 545 nm and 585 nm, respectively, after the samples were excited with 376 nm ultraviolet source. The green emission corresponding to 5D4 → 7F5 (543 nm) transition was observed under excitation wavelength 376 nm of the Tb3+ ions for all the prepared glasses. For all these emission bands, the decay curves were recorded to evaluate the emission life times. The mechanism underlying the observed emission from the glasses was explained in terms of energy levels.

Exploring the Atmosphere of Neoproterozoic Earth: The Effect of O2 on Haze Formation and Composition

NASA Astrophysics Data System (ADS)

Hörst, Sarah M.; He, Chao; Ugelow, Melissa S.; Jellinek, A. Mark; Pierrehumbert, Raymond T.; Tolbert, Margaret A.

2018-05-01

Previous studies of haze formation in the atmosphere of the early Earth have focused on N2/CO2/CH4 atmospheres. Here, we experimentally investigate the effect of O2 on the formation and composition of aerosols to improve our understanding of haze formation on the Neoproterozoic Earth. We obtained in situ size, particle density, and composition measurements of aerosol particles produced from N2/CO2/CH4/O2 gas mixtures subjected to FUV radiation (115–400 nm) for a range of initial CO2/CH4/O2 mixing ratios (O2 ranging from 2 ppm to 0.2%). At the lowest O2 concentration (2 ppm), the addition increased particle production for all but one gas mixture. At higher oxygen concentrations (20 ppm and greater), particles are still produced, but the addition of O2 decreases the production rate. Both the particle size and number density decrease with increasing O2, indicating that O2 affects particle nucleation and growth. The particle density increases with increasing O2. The addition of CO2 and O2 not only increases the amount of oxygen in the aerosol, but it also increases the degree of nitrogen incorporation. In particular, the addition of O2 results in the formation of nitrate-bearing molecules. The fact that the presence of oxygen-bearing molecules increases the efficiency of nitrogen fixation has implications for the role of haze as a source of molecules required for the origin and evolution of life. The composition changes also likely affect the absorption and scattering behavior of these particles but optical property measurements are required to fully understand the implications for the effect on the planetary radiative energy balance and climate.

A comparison of empirical and experimental O7+, O8+, and O/H values, with applications to terrestrial solar wind charge exchange

NASA Astrophysics Data System (ADS)

Whittaker, Ian C.; Sembay, Steve

2016-07-01

Solar wind charge exchange occurs at Earth between the neutral planetary exosphere and highly charged ions of the solar wind. The main challenge in predicting the resultant photon flux in the X-ray energy bands is due to the interaction efficiency, known as the α value. This study produces experimental α values at the Earth, for oxygen emission in the range of 0.5-0.7 keV. Thirteen years of data from the Advanced Composition Explorer are examined, comparing O7+ and O8+ abundances, as well as O/H to other solar wind parameters allowing all parameters in the αO7,8+ calculation to be estimated based on solar wind velocity. Finally, a table is produced for a range of solar wind speeds giving average O7+ and O8+ abundances, O/H, and αO7,8+ values.

Dynamic model constraints on oxygen-17 depletion in atmospheric O2 after a snowball Earth.

PubMed

Cao, Xiaobin; Bao, Huiming

2013-09-03

A large perturbation in atmospheric CO2 and O2 or bioproductivity will result in a drastic pulse of (17)O change in atmospheric O2, as seen in the Marinoan Oxygen-17 Depletion (MOSD) event in the immediate aftermath of a global deglaciation 635 Mya. The exact nature of the perturbation, however, is debated. Here we constructed a coupled, four-box, and quick-response biosphere-atmosphere model to examine both the steady state and dynamics of the MOSD event. Our model shows that the ultra-high CO2 concentrations proposed by the "snowball' Earth hypothesis produce a typical MOSD duration of less than 10(6) y and a magnitude of (17)O depletion reaching approximately -35‰. Both numbers are in remarkable agreement with geological constraints from South China and Svalbard. Moderate CO2 and low O2 concentration (e.g., 3,200 parts per million by volume and 0.01 bar, respectively) could produce distinct sulfate (17)O depletion only if postglacial marine bioproductivity was impossibly low. Our dynamic model also suggests that a snowball in which the ocean is isolated from the atmosphere by a continuous ice cover may be distinguished from one in which cracks in the ice permit ocean-atmosphere exchange only if partial pressure of atmospheric O2 is larger than 0.02 bar during the snowball period and records of weathering-derived sulfate are available for the very first few tens of thousands of years after the onset of the meltdown. In any case, a snowball Earth is a precondition for the observed MOSD event.

Electron traps in Gd3Ga3Al2O12:Ce garnets doped with rare-earth ions

NASA Astrophysics Data System (ADS)

Khanin, V. M.; Rodnyi, P. A.; Wieczorek, H.; Ronda, C. R.

2017-05-01

The curves of thermally stimulated luminescence of Gd3Ga3Al2O12:Ce3+ ceramics (a nominally pure sample and samples doped with rare-earth ions) are measured in the temperature range of 80-550 K. The depth and the frequency factor of electron traps established by Eu and Yb impurities are determined. An energy-level diagram of rare-earth ions in the bandgap of Gd3Ga3Al2O12 is presented.

The effect of phosphate loading on erythrocyte 2,3-bisphosphoglycerate levels.

PubMed

Bremner, Kyla; Bubb, William A; Kemp, Graham J; Trenell, Michael I; Thompson, Campbell H

2002-09-01

Phosphate supplementation has been used in an effort to enhance athletic performance by increasing erythrocyte 2,3-bisphosphoglycerate levels ([2,3-BPG]) and hence improve oxygen offloading from haemoglobin. Claimed effects of phosphate loading upon both exercise performance and erythrocyte [2,3-BPG] are inconsistent, and the basis of any change in [2,3-BPG] is unknown. We analysed plasma inorganic phosphate concentration ([P(i)]) and erythrocyte [P(i)] and [2,3-BPG] in venous blood samples from 12 healthy subjects. We re-examined a subset of five of these subjects after 7 days of phosphate loading. There were significant positive correlations between plasma [P(i)] and erythrocyte [P(i)] (r(2)=0.51, p=0.009) and between erythrocyte [P(i)] and [2,3-BPG] (r(2)=0.68, p<0.001). Following phosphate loading, there was a 30% increase in plasma [P(i)] (1.02+/-0.22 to 1.29+/-0.15 mmol/l (mean+/-S.D.), p=0.03) and a 25% increase in erythrocyte [2,3-BPG] (6.77+/-1.12 to 9.11+/-1.87 mmol/l cells, p=0.03). There is no relation between [2,3-BPG] and plasma [P(i)]. Phosphate loading increases both plasma and erythrocyte phosphate pools and the rise in [2,3-BPG] is probably a consequence of the rise in cell [P(i)].

Crystallisation of Ba1-xSrxZn2Si2O7 from BaO/SrO/ZnO/SiO2 glass with different ZrO2 and TiO2 concentrations

NASA Astrophysics Data System (ADS)

Vladislavova, Liliya; Kracker, Michael; Zscheckel, Tilman; Thieme, Christian; Rüssel, Christian

2018-04-01

The effect of different nucleation agents such as ZrO2 and TiO2 was investigated for a first time with respect to their crystallisation behaviour in the glass system BaO-SrO-ZnO-SiO2. In all studied glasses, a Ba1-xSrxZn2Si2O7 (0.1 ≤ x ≤ 0.9) solid solution crystallized. This phase was first described in 2015 to possess a similar structure as the high temperature phase of BaZn2Si2O7 and a thermal expansion close to zero or even negative. It may find applications e.g. as cook panels, telescope mirrors, and furnace windows. Kinetic parameters of the crystallisation process were determined by supplying different heating rates in a differential scanning calorimeter (DSC). The results were evaluated using the equations of Ozawa and Kissinger with respect to the activation energies. Furthermore, the Ozawa method was used for the determination of Avrami parameters, which provides further information on the nucleation and crystallisation processes. Scanning electron microscopy including electron backscatter diffraction (EBSD) was used to characterise the microstructure, to determine the crystallite size and the crystal orientation. For the characterisation of the occurring crystalline phases, X-ray diffraction was used.

Phytic acid derived bioactive CaO-P2O5-SiO2 gel-glasses.

PubMed

Li, Ailing; Qiu, Dong

2011-12-01

The possibility of using phytic acid as a precursor to synthesize CaO-P(2)O(5)-SiO(2) glasses by sol-gel method has been explored and the pseudo ternary phase diagram has been established. It was shown that gel-glasses over a broader range of compositions could be prepared compared to other phosphorus precursors or melt-quenching method. Furthermore, phytic acid was found to assist calcium being incorporated into glass networks. In vitro tests in simulated body fluid (SBF) were performed on the above gel-glasses and it was found that they were bioactive over a much broader compositional range especially at high phosphate content, thus enabling one to design bioactive materials with various degradation rates by adjusting the phosphate content.

Coulomb spin liquid in anion-disordered pyrochlore Tb 2Hf 2O 7

DOE PAGES

Sibille, Romain; Lhotel, Elsa; Hatnean, Monica Ciomaga; ...

2017-10-12

Here, the charge ordered structure of ions and vacancies characterizing rare-earth pyrochlore oxides serves as a model for the study of geometrically frustrated magnetism. The organization of magnetic ions into networks of corner-sharing tetrahedra gives rise to highly correlated magnetic phases with strong fluctuations, including spin liquids and spin ices. It is an open question how these ground states governed by local rules are affected by disorder. Here we demonstrate in the pyrochlore Tb 2Hf 2O 7, that the vicinity of the disordering transition towards a defective fluorite structure translates into a tunable density of anion Frenkel disorder while cationsmore » remain ordered. Quenched random crystal fields and disordered exchange interactions can therefore be introduced into otherwise perfect pyrochlore lattices of magnetic ions. We show that disorder can play a crucial role in preventing long-range magnetic order at low temperatures, and instead induces a strongly fluctuating Coulomb spin liquid with defect-induced frozen magnetic degrees of freedom.« less

17O solid-state NMR spectroscopy of A2B2O7 oxides: quantitative isotopic enrichment and spectral acquisition?

PubMed

Fernandes, Arantxa; Moran, Robert F; Sneddon, Scott; Dawson, Daniel M; McKay, David; Bignami, Giulia P M; Blanc, Frédéric; Whittle, Karl R; Ashbrook, Sharon E

2018-02-13

The potential of 17 O NMR spectroscopy for the investigation of A 2 B 2 O 7 ceramic oxides important in the encapsulation of radioactive waste is demonstrated, with post-synthetic enrichment by exchange with 17 O 2 gas. For Y 2 Sn 2 O 7 , Y 2 Ti 2 O 7 and La 2 Sn 2 O 7 pyrochlores, enrichment of the two distinct O species is clearly non quantitative at lower temperatures (∼700 °C and below) and at shorter times, despite these being used in prior work, with preferential enrichment of OA 2 B 2 favoured over that of OA 4 . At higher temperatures, the 17 O NMR spectra suggest that quantitative enrichment has been achieved, but the integrated signal intensities do not reflect the crystallographic 1 : 6 (O1 : O2) ratio until corrected for differences in T 1 relaxation rates and, more importantly, the contribution of the satellite transitions. 17 O NMR spectra of Y 2 Zr 2 O 7 and Y 2 Hf 2 O 7 defect fluorites showed little difference with any variation in enrichment temperature or time, although an increase in the absolute level of enrichment (up to ∼7.5%) was observed at higher temperature. DFT calculations show that the six distinct resonances observed cannot be assigned unambiguously, as each has contributions from more than one of the five possible next nearest neighbour environments. For La 2 Ti 2 O 7 , which adopts a layered perovskite-like structure, little difference in the spectral intensities is observed with enrichment time or temperature, although the highest absolute levels of enrichment (∼13%) were obtained at higher temperature. This work demonstrates that 17 O NMR has the potential to be a powerful probe of local structure and disorder in oxides, but that considerable care must be taken both in choosing the conditions for 17 O enrichment and the experimental acquisition parameters if the necessary quantitative measurements are to be obtained for more complex systems.

Structural study and physical properties of a new phosphate KCuFe(PO 4) 2

NASA Astrophysics Data System (ADS)

Badri, Abdessalem; Hidouri, Mourad; López, María Luisa; Pico, Carlos; Wattiaux, Alain; Amara, Mongi Ben

2011-04-01

Single crystals of a new phosphate KCuFe(PO 4) 2 have been prepared by the flux method and its structural and physical properties have been investigated. This compound crystallizes in the monoclinic system with the space group P2 1/ n and its parameters are: a=7.958(3) Å, b=9.931(2) Å, c=9.039(2) Å, β=115.59(3)° and Z=4. Its structure consists of FeO 6 octahedra sharing corners with Cu 2O 8 units of edge-sharing CuO 5 polyhedra to form undulating chains extending infinitely along the b-axis. These chains are connected by the phosphate tetrahedra giving rise to a 3D framework with six-sided tunnels parallel to the [101] direction, where the K + ions are located. The Mössbauer spectroscopy results confirm the exclusive presence of octahedral Fe 3+ ions. The magnetic measurements show the compound to be antiferromagnetic with Cm=5.71 emu K/mol and θ=-156.5 K. The derived experimental effective moment μex=6.76 μB is somewhat higher than the theoretical one of μth=6.16 μB, calculated taking only into account the spin contribution for Fe 3+ and Cu 2+ cations. Electrical measurements allow us to obtain the activation energy (1.22 eV) and the conductivity measurements suggest that the charge carriers through the structure are the potassium cations.

Effect of pyrophosphate ions on the conversion of calcium-lithium-borate glass to hydroxyapatite in aqueous phosphate solution.

PubMed

Fu, Hailuo; Rahaman, Mohamed N; Day, Delbert E; Huang, Wenhai

2010-10-01

The conversion of glass to a hydroxyapatite (HA) material in an aqueous phosphate solution is used as an indication of the bioactive potential of the glass, as well as a low temperature route for preparing biologically useful materials. In this work, the effect of varying concentrations of pyrophosphate ions in the phosphate solution on the conversion of a calcium-lithium-borate glass to HA was investigated. Particles of the glass (150-355 μm) were immersed for up to 28 days in 0.25 M K(2)HPO(4) solution containing 0-0.1 M K(4)P(2)O(7). The kinetics of degradation of the glass particles and their conversion to HA were monitored by measuring the weight loss of the particles and the ionic concentration of the solution. The structure and composition of the conversion products were analyzed using X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy. For K(4)P(2)O(7) concentrations of up to 0.01 M, the glass particles converted to HA, but the time for complete conversion increased from 2 days (no K(4)P(2)O(7)) to 10 days (0.01 M K(4)P(2)O(7)). When the K(4)P(2)O(7) concentration was increased to 0.1 M, the product consisted of an amorphous calcium phosphate material, which eventually crystallized to a pyrophosphate product (predominantly K(2)CaP(2)O(7) and Ca(2)P(2)O(7)). The consequences of the results for the formation of HA materials and devices by the glass conversion route are discussed.

Effect of pyrophosphate ions on the conversion of calcium–lithium–borate glass to hydroxyapatite in aqueous phosphate solution

PubMed Central

Fu, Hailuo; Day, Delbert E.; Huang, Wenhai

2010-01-01

The conversion of glass to a hydroxyapatite (HA) material in an aqueous phosphate solution is used as an indication of the bioactive potential of the glass, as well as a low temperature route for preparing biologically useful materials. In this work, the effect of varying concentrations of pyrophosphate ions in the phosphate solution on the conversion of a calcium–lithium–borate glass to HA was investigated. Particles of the glass (150–355 µm) were immersed for up to 28 days in 0.25 M K2HPO4 solution containing 0–0.1 M K4P2O7. The kinetics of degradation of the glass particles and their conversion to HA were monitored by measuring the weight loss of the particles and the ionic concentration of the solution. The structure and composition of the conversion products were analyzed using X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy. For K4P2O7 concentrations of up to 0.01 M, the glass particles converted to HA, but the time for complete conversion increased from 2 days (no K4P2O7) to 10 days (0.01 M K4P2O7). When the K4P2O7 concentration was increased to 0.1 M, the product consisted of an amorphous calcium phosphate material, which eventually crystallized to a pyrophosphate product (predominantly K2CaP2O7 and Ca2P2O7). The consequences of the results for the formation of HA materials and devices by the glass conversion route are discussed. PMID:20680413

Local induction of calcium phosphate formation on TiO2 coatings on titanium via surface treatment with a CO2 laser.

PubMed

Moritz, N; Jokinen, M; Peltola, T; Areva, S; Yli-Urpo, A

2003-04-01

Sol-gel-derived TiO(2) coatings are known to promote bonelike hydroxyapatite formation on their surfaces in vitro and in vivo. Hydroxyapatite integrates into bone tissue. In some clinical applications, the surface of an implant is simultaneously interfaced with soft and hard tissues, so it should match the properties of both. A new method is introduced for treating the coatings locally in a controlled manner. The local densification of sol-gel-derived titania coatings on titanium substrates with a CO(2) laser was studied in terms of the in vitro calcium phosphate-inducting properties. CO(2)-laser-treated multilayer coatings were compared with furnace-fired coatings prepared with the same recipe and previously shown to be bioactive. Additionally, local areas of furnace-fired multilayer coatings (previously shown to be bioactive in vitro) were further laser-treated to achieve various properties in the same implant. Topological surface properties were examined with atomic force microscopy. The formation of hydroxyapatite was studied with Fourier transform infrared and scanning electron microscopy energy-dispersive X-ray analysis. The results show that calcium phosphate formation can be adjusted locally by laser treatment. Calcium phosphate is a bonelike hydroxyapatite. The local treatment of sol-gel-derived coatings with a CO(2) laser is a promising technique for creating implants with various properties to interface different tissues and a possible way of coating implants that do not tolerate furnace firing. Copyright 2003 Wiley Periodicals, Inc.

Synthesis, Crystal Structure, and Magnetic Properties of the YbFeTi2O7 Compound

NASA Astrophysics Data System (ADS)

Drokina, T. V.; Petrakovskii, G. A.; Molokeev, M. S.; Velikanov, D. A.

2018-03-01

We report on the synthesis conductions and results of experimental investigations of the crystal structure and magnetic properties of a new magnetic compound YbFeTi2O7. According to the X-ray diffractometry data, the crystal structure of the investigated compound is described by the rhombic space group Pcnb with unit cell parameters of a = 9.8115(1) Å, b = 13.5106(2) Å, and c = 7.31302(9) Å and atomic disordering in the distribution of iron ions Fe3+ over five structural sites. The magnetic measurements in the lowtemperature region revealed a kink in the temperature dependence of the magnetic moment and its dependence on the sample magnetic prehistory. The experimental results obtained suggest that with a decrease in temperature the sample passes from the paramagnetic state to the spin-glass-like magnetic state characterized by a freezing temperature of T f = 4.5 K at the preferred antiferromagnetic exchange coupling in the sample spin system. The chemical pressure variation upon replacement of rare-earth ion R by Yb in the RFeTi2O7 system does not change the crystal lattice symmetry and magnetic state.

The aluminum phosphate zone in the Peace River area, land-pebble phosphate field, Florida

USGS Publications Warehouse

Cathcart, James B.

1953-01-01

The Peace River area, comprising T. 30 and 31 S., R. 24 and 25 E., contains a thicker and more persistent aluminum phosphate zone, and one that is higher in P2O5 and uranium content than is known elsewhere in the land-pebble phosphate district. This report has been prepared to bring together all of the information on the aluminum phosphate zone in the area where the first plant to treat this material will probably be located. The area may be divided into three physiographic units, (1) the ridge, (2) the flatwoods, and (3) the valley. Maps showing distribution and grade of the aluminum phosphate zone indicate that the zone is thin or absent in the ridge unit, thickest and most persistent, and of the best grade in P2O5 and uranium in the flatwoods unit, and absent or very low in grade in the valley unit. Maps of thickness and of chemical composition show that even in favorable areas there are places where the aluminum phosphate zone is missing or of questionable economic importance. The distribution maps also show that areas of high P2O5 and high uranium content coincide closely. Areas containing thick aluminum phosphate material usually have high uranium and P2O5 contents. It is estimated that an average of 13,000 tons per day of aluminum phosphate material might be mined from this area. This figure is based on the probable amount of time, per year, that mining would be in favorable ground. When all mines in the area are in favorable ground, the tonnage per day might be about 23,000 tons. Tonnages of aluminum phosphate material have been computed for about 36 percent of the area of T. 30 S., R. 25 E., and for 18 percent of the area of T. 31 S., R. 25 E. The total inferred tonnage is about 150,000,000 short tons, with an average grade of 0.012 percent U3O8.

SiO2 and ZnO dopants in three-dimensionally printed tricalcium phosphate bone tissue engineering scaffolds enhance osteogenesis and angiogenesis in vivo.

PubMed

Fielding, Gary; Bose, Susmita

2013-11-01

Calcium phosphate (CaP) scaffolds with three-dimensionally-interconnected pores play an important role in mechanical interlocking and biological fixation in bone implant applications. CaPs alone, however, are only osteoconductive (able to guide bone growth). Much attention has been given to the incorporation of biologics and pharmacologics to add osteoinductive (able to cause new bone growth) properties to CaP materials. Because biologics and pharmacologics are generally delicate compounds and also subject to increased regulatory scrutiny, there is a need to investigate alternative methods to introduce osteoinductivity to CaP materials. In this study silica (SiO2) and zinc oxide (ZnO) have been incorporated into three-dimensional printed β-tricalcium phosphate (β-TCP) scaffolds to investigate their potential to trigger osteoinduction in vivo. Silicon and zinc are trace elements that are common in bone and have also been shown to have many beneficial properties, from increased bone regeneration to angiogenesis. Implants were placed in bicortical femur defects introduced to a murine model for up to 16 weeks. The addition of dopants into TCP increased the capacity for new early bone formation by modulating collagen I production and osteocalcin production. Neovascularization was found to be up to three times more than the pure TCP control group. The findings from this study indicate that the combination of SiO2 and ZnO dopants in TCP may be a viable alternative to introducing osteoinductive properties to CaPs. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Effect of dilution in the cobalt subsystem on phase transitions in rare-earth cobaltites RBaCo4- x M x O7 (R = Dy-Er, Yb, Y; M = Al, Zn)

NASA Astrophysics Data System (ADS)

Kazei, Z. A.; Snegirev, V. V.; Kozeeva, L. P.; Kameneva, M. Yu.

2016-01-01

We have experimentally studied the structural and elastic characteristics of rare-earth cobaltites RBaCo4- x M x O7 (R = Dy-Er, Yb, Y), in which cobalt ions are partly substituted by diamagnetic Al or Zn ions. It was found that small substitution of Co3+ ions by Al3+ ions in the YbRBaCo4- x M x O7 system ( x = 0.1, 0.2, 0.5) leads to a rapid decrease and smearing of Δ E( T) /E 0 anomalies of the Young's modulus in the region of the structural phase transition, which is accompanied by increasing hysteresis. Pure rare-earth cobaltites RBaCo4O7 (R = Dy-Er, Y) exhibit a correlation between the room-temperature structure distortion and hysteresis on the Δ E( T)/ E 0 curve in a temperature interval of 80-280 K. In Zn-substituted cobaltites RBaCoZn3O7, both the hysteresis and Δ E( T)/ E 0 anomalies disappear, as do low-temperature sound absorption maxima. This behavior is evidence of the suppression of structural and magnetic phase transitions and the retention of only short-range correlations of the order parameter in Zn-substituted samples.

Vibrational spectroscopy of the phosphate mineral kovdorskite - Mg2PO4(OH)ṡ3H2O

NASA Astrophysics Data System (ADS)

Frost, Ray L.; López, Andrés; Xi, Yunfei; Granja, Amanda; Scholz, Ricardo; Lima, Rosa Malena Fernandes

2013-10-01

The mineral kovdorskite Mg2PO4(OH)ṡ3H2O was studied by electron microscopy, thermal analysis and vibrational spectroscopy. A comparison of the vibrational spectroscopy of kovdorskite is made with other magnesium bearing phosphate minerals and compounds. Electron probe analysis proves the mineral is very pure. The Raman spectrum is characterized by a band at 965 cm-1 attributed to the PO43- ν1 symmetric stretching mode. Raman bands at 1057 and 1089 cm-1 are attributed to the PO43- ν3 antisymmetric stretching modes. Raman bands at 412, 454 and 485 cm-1 are assigned to the PO43- ν2 bending modes. Raman bands at 536, 546 and 574 cm-1 are assigned to the PO43- ν4 bending modes. The Raman spectrum in the OH stretching region is dominated by a very sharp intense band at 3681 cm-1 assigned to the stretching vibration of OH units. Infrared bands observed at 2762, 2977, 3204, 3275 and 3394 cm-1 are attributed to water stretching bands. Vibrational spectroscopy shows that no carbonate bands are observed in the spectra; thus confirming the formula of the mineral as Mg2PO4(OH)ṡ3H2O.

Acousto-optic interaction in alpha-BaB(2)O(4)and Li(2)B(4)O(7) crystals.

PubMed

Martynyuk-Lototska, Irina; Mys, Oksana; Dudok, Taras; Adamiv, Volodymyr; Smirnov, Yevgen; Vlokh, Rostyslav

2008-07-01

Experimental studies and analysis of acousto-optic diffraction in alpha-BaB(2)O(4) and Li(2)B(4)O(7) crystals are given. Ultrasonic wave velocity, elastic compliance and stiffness coefficients, and piezo-optic and photoelastic coefficients of alpha-BaB(2)O(4) and Li(2)B(4)O(7) crystals are determined. The acousto-optic figure of merit has been estimated for different possible geometries of acousto-optic interaction. It is shown that the acousto-optic figures of merit for alpha-BaB(2)O(4) crystals reach the value M(2)=(270 +/- 70) x 10(-15) s(3)/kg for the case of interaction with the slowest ultrasonic wave. The directions of propagation and polarization of those acoustic waves are obtained on the basis of construction of acoustic slowness surfaces. The acousto-optic diffraction is experimentally studied for alpha-BaB(2)O(4) and Li(2)B(4)O(7) crystals.