Phase transition and multicolor luminescence of Eu2+/Mn2+-activated Ca3(PO4)2 phosphors

International Nuclear Information System (INIS)

Li, Kai; Chen, Daqin; Xu, Ju; Zhang, Rui; Yu, Yunlong; Wang, Yuansheng

2014-01-01

Graphical abstract: We have synthesized Eu 2+ doped and Eu 2+ /Mn 2+ co-doped Ca 3 (PO 4 ) 2 phosphors. The emitting color varies from blue to green with increasing of Eu 2+ content for the Eu 2+ -doped phosphor, and the quantum yield of the 0.05Eu 2+ : Ca 2.95 (PO 4 ) 2 sample reaches 56.7%. Interestingly, Mn 2+ co-doping into Eu 2+ : Ca 3 (PO 4 ) 2 leads to its phase transition from orthorhombic to rhombohedral, and subsequently generates tunable multi-color luminescence from green to red via Eu 2+ → Mn 2+ energy transfer. - Highlights: • A series of novel Eu 2+ : Ca 3 (PO 4 ) 2 phosphors were successfully synthesized. • Phase transition of Ca 3 (PO 4 ) 2 from orthorhombic to rhombohedral occurred when Mn 2+ ions were doped. • The phosphors exhibited tunable multi-color luminescence. • The quantum yield of 0.05Eu 2+ : Ca 2.95 (PO 4 ) 2 phosphor can reach 56.7%. • The analyses of phosphors were carried out by many measurements. - Abstract: Intense blue-green-emitting Eu 2+ : Ca 3 (PO 4 ) 2 and tunable multicolor-emitting Eu 2+ /Mn 2+ : Ca 3 (PO 4 ) 2 phosphors are prepared via a solid-state reaction route. Eu 2+ -doped orthorhombic Ca 3 (PO 4 ) 2 phosphor exhibits a broad emission band in the wavelength range of 400–700 nm with a maximum quantum yield of 56.7%, and the emission peak red-shifts gradually from 479 to 520 nm with increase of Eu 2+ doping content. Broad excitation spectrum (250–420 nm) of Eu 2+ : Ca 3 (PO 4 ) 2 matches well with the near-ultraviolet LED chip, indicating its potential applications as tri-color phosphors in white LEDs. Interestingly, Mn 2+ co-doping into Eu 2+ : Ca 3 (PO 4 ) 2 leads to its phase transition from orthorhombic to rhombohedral, and subsequently generates tunable multi-color luminescence from green to red via Eu 2+ → Mn 2+ energy transfer, under 365 nm UV lamp excitation

Properties and Crystallization Phenomena in Li2Si2O5–Ca5(PO4)3F and Li2Si2O5–Sr5(PO4)3F Glass–Ceramics Via Twofold Internal Crystallization

Science.gov (United States)

Rampf, Markus; Dittmer, Marc; Ritzberger, Christian; Schweiger, Marcel; Höland, Wolfram

2015-01-01

The combination of specific mechanical, esthetic, and chemical properties is decisive for the application of materials in prosthodontics. Controlled twofold crystallization provides a powerful tool to produce special property combinations for glass–ceramic materials. The present study outlines the potential of precipitating Ca5(PO4)3F as well as Sr5(PO4)3F as minor crystal phases in Li2Si2O5 glass–ceramics. Base glasses with different contents of CaO/SrO, P2O5, and F− were prepared within the glasses of the SiO2–Li2O–K2O–CaO/SrO–Al2O3–P2O5–F system. Preliminary studies of nucleation by means of XRD and scanning electron microscopy (SEM) of the nucleated base glasses revealed X-ray amorphous phase separation phenomena. Qualitative and quantitative crystal phase analyses after crystallization were conducted using XRD in combination with Rietveld refinement. As a main result, a direct proportional relationship between the content of apatite-forming components in the base glasses and the content of apatite in the glass–ceramics was established. The microstructures of the glass–ceramics were investigated using SEM. Microstructural and mechanical properties were found to be dominated by Li2Si2O5 crystals and quite independent of the content of the apatite present in the glass–ceramics. Biaxial strengths of up to 540 MPa were detected. Ca5(PO4)3F and Sr5(PO4)3F influence the translucency of the glass–ceramics and, hence, help to precisely tailor the properties of Li2Si2O5 glass–ceramics. The authors conclude that the twofold crystallization of Li2Si2O5–Ca5(PO4)3F or Li2Si2O5–Sr5(PO4)3F glass–ceramics involves independent solid-state reactions, which can be controlled via the chemical composition of the base glasses. The influence of the minor apatite phase on the optical properties helps to achieve new combinations of features of the glass–ceramics and, hence, displays new potential for dental applications. PMID:26389112

Synthesis of xLiMnPO4·yLi3V2(PO43/C Nanocomposites for Lithium Ion Batteries Using Tributyl Phosphate as Phosphor Source

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Yanming Wang

2017-01-01

Full Text Available The xLiMnPO4·yLi3V2(PO43/C (x/y = 1 : 0, 12 : 1, 8 : 1, 6 : 1, 4 : 1, 0 : 1 composite cathode materials are synthesized using tributyl phosphate as a novel organic phosphor source via a solid-state reaction process. All obtained xLiMnPO4·yLi3V2(PO43/C composites present similar particles morphology with an average size of ca. 100 nm and low extent agglomeration. The electrochemical performance of pristine LiMnPO4/C can be effectively improved by adding small amounts of Li3V2(PO43 additives. The 4LiMnPO4·Li3V2(PO43/C has a high discharge capacity of 143 mAh g−1 at 0.1 C and keeps its 94% at the end of 100 cycles.

Structural features of AgCaCdMg2(PO4)3 and AgCd2Mg2(PO4)3, two new compounds with the alluaudite-type structure, and their catalytic activity in butan-2-ol conversion

International Nuclear Information System (INIS)

Kacimi, Mohammed; Ziyad, Mahfoud; Hatert, Frederic

2005-01-01

AgCaCdMg 2 (PO 4 ) 3 and AgCd 2 Mg 2 (PO 4 ) 3 , two new compounds with the alluaudite-type structure, were synthesized by a solid state reaction in air at 750 deg. C. The X-ray powder diffraction pattern of AgCaCdMg 2 (PO 4 ) 3 indicates the presence of small amounts of (Ca, Mg) 3 (PO 4 ) 2 with the whitlockite structure, as impurity, whereas AgCd 2 Mg 2 (PO 4 ) 3 is constituted by pure alluaudite. The Rietveld refinements of the X-ray powder diffraction patterns indicate an ordered cationic distribution for AgCd 2 Mg 2 (PO 4 ) 3 , with Ag on A(2)', Cd on A(1) and M(1), and Mg on M(2), whereas a disordered distribution of Cd and Ca between the A(1) and M(1) sites is observed for AgCaCdMg 2 (PO 4 ) 3 . The catalytic properties of these compounds has been measured in reaction of butan-2-ol dehydrogenation. In the absence of oxygen, both samples exhibit poor dehydrogenation activity. All samples displayed no dehydration activity. Introduction of oxygen into the feed changed totally the catalytic behavior of the catalysts. The production of methyl ethyl ketone increases with time on stream and the reaction temperature. AgCaCdMg 2 (PO 4 ) 3 is more efficient than AgCd 2 Mg 2 (PO 4 ) 3

Synthesis, structural and morphological characterization of Ca0.45Eu0.05Zr2(PO4)3 nano phosphors

International Nuclear Information System (INIS)

Alcaraz, L.; Isasi, J.; Peiteado, M.; Cabalero, A.

2015-01-01

Ca 0 .45Eu 0 .05Zr 2 (PO 4 ) 3 samples were synthesized by a preparation process in two step: a sol-gel method using two pH values, acid (pH ∼ 2) and basic pH (∼ 10), and a subsequent treatment of the precursor powders in a N 2 :H 2 (90:10) flow in order to stabilized 2+ oxidation state of europium. X-ray diffraction patterns exhibit diffraction maxima typical of NASICON type structure of rhombohedral symmetry and space group R-3. Most intense diffraction maxima are seen for the samples prepared in a basic reaction medium. Magnetic measurements confirm 2+ oxidation state of europium cations in the synthesized samples. Microscopy images show particles of spherical shape and nano metric size according to X-ray diffraction results, indicating that these samples may be useful in certain luminescent devices. (Author)

Hexagonal perovskites with cationic vacancies. 28. Structure of rhombohedral 9 L stacking polytypes Ba/sub 3/Wsub(2-x)sup(VI)Nbsub(x)sup(V)vacantOsub(9-x/2)vacantsub(x/2)

Energy Technology Data Exchange (ETDEWEB)

Kemmler-Sack, S; Treiber, U [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1981-07-01

According to the intensity calculations for Ba/sub 3/Wsub(4/3)Nbsub(2/3)vacantOsub(26/3)vacantsub(1/3) and Ba/sub 3/Nb/sub 2/vacantO/sub 8/vacant(II) these rhombohedral 9 L compounds crystallize in the space group R-3m, sequence (hhc)/sub 3/. The refined, intensity related R' values are 6.9% (Ba/sub 3/Wsub(4/3)Nbsub(2/3)vacantOsub(26/3)vacantsub(1/3)) and 7.2% (Ba/sub 3/Nb/sub 2/vacantO/sub 8/vacant(II)). The relations between the rhombohedral 9 L structure (A/sub 3/M/sub 2/vacantO/sub 9/) and the palmierite type (A/sub 3/M/sub 2/vacantO/sub 8/vacant) are discussed.

The preparation and graphene surface coating NaTi_2(PO_4)_3 as cathode material for lithium ion batteries

International Nuclear Information System (INIS)

Li, Na; Wang, Yanping; Rao, Richuan; Dong, Xiongzi; Zhang, Xianwen; Zhu, Sane

2017-01-01

Graphical abstract: The NaTi_2(PO_4)_3/graphene composite is used directly as cathode electrode material for lithium-ion battery by using metal lithium as an anode electrode. Meanwhile, the electrochemical properties of the composite in this system is firstly studied in detail. The NaTi_2(PO_4)_3/graphene composite exhibits the better rate and cyclic performance than NaTi_2(PO_4)_3, which is ascribed to its stable 3-D framework and the enhanced electronic conduction resulting from the graphene sheets surface modification. - Highlights: • The graphene coated NaTi_2(PO_4)_3 was prepared by a simple sol-gel method followed by calcination. • The electrochemical properties of the NaTi_2(PO_4)_3/graphene composite was firstly studied in detail when used as cathode electrode material for lithium-ion batteries. • The electrochemical reaction mechanism of NaTi_2(PO_4)_3/graphene composite was investigated by ex situ XRD. - Abstract: The graphene coated NaTi_2(PO_4)_3 has been fabricated via a simple sol-gel process followed by calcination. The NaTi_2(PO_4)_3/graphene (NTP/G) composite is used directly as cathode electrode material for lithium-ion battery and the electrochemical properties of the composite in this system is firstly studied in detail. In the charge-discharge process, two Li"+ can occupy octahedral M (2) site and be reversibly intercalated into the 3D framework of NTP through the ion conduction channel where almost all of Na"+ are immobilized to sustain the framework. At 5C rate, the capacity retention of the NTP/G composite after 800 cycles is still up to 82.7%. The superior electrochemical properties of NTP/G is ascribed to its stable 3-D framework and the enhanced electronic conduction resulting from the graphene sheets surface modification.

Cubic KTi2(PO4)3 as electrode materials for sodium-ion batteries.

Science.gov (United States)

Han, Jin; Xu, Maowen; Niu, Yubin; Jia, Min; Liu, Ting; Li, Chang Ming

2016-12-01

A novel cubic KTi2(PO4)3 is successfully synthesized via a facile hydrothermal method combined with a subsequent annealing treatment and further used as electrode material for sodium-ion batteries for the first time. For comparison, carbon-coated KTi2(PO4)3 obtained by a normal cane sugar-assisted method reveals superior electrochemical performances in sodium-ion battery. Besides of the high coulombic efficiency of nearly 100% after 100 cycles, a stable capacity of 112mAhg(-1) can be achieved at 0.5C after 100 cycles, and still maintains to 105mAhg(-1) after 500 cycles with capacity retention of approximately 90%. Copyright © 2016 Elsevier Inc. All rights reserved.

Mixing transition-metal phosphates Li_3V_2_−_xFe_x(PO_4)_3 (0≤x≤2): the synthesis, structure and electrochemical properties

International Nuclear Information System (INIS)

Liu, Xudong; Zhao, Yanming; Kuang, Quan; Li, Xiaoming; Dong, Youzhong; Jing, Zhenzhen; Hou, Shiyu

2016-01-01

Highlights: • Monoclinic structure Li_3V_2_−_xFe_x(PO_4)_3 (0≤ x≤2) solid solutions have been successfully fabricated via a two-step synthesis method. • Trace amounts of acetylene black would play a role of deoxidizer during the sintering process in an inert atmosphere. • V1-site is the preferred position when Fe"3"+ ions doped into Li_3V_2(PO_4)_3 from our structural analysis. - Abstract: Mixing transition-metal phosphates Li_3V_2_−_xFe_x(PO_4)_3 (0≤x≤2) were first designed to be a type of intercalated and deintercalated cathodes to obtain high specific capacity for safe Li-ion batteries. Since the residual oxygen in the quartz tube furnace and pellet would oxidize the V"3"+ to V"4"+ in the Ar ambience during the sintering process, trace amounts of acetylene black inside and outside the pellet could play a role of deoxidizer to protect V"3"+ meanwhile ensure Fe"3"+ not reducing to Fe"2"+. With the concerted effort of inside and outside acetylene black, monoclinic structure Li_3V_2_−_xFe_x(PO_4)_3 (0≤x≤2) solid solutions had been successfully fabricated via a two-step synthesis method. X-ray diffractions with Rietveld refinement revealed that V1-sites were the preferred position when Fe"3"+ ions doped into Li_3V_2(PO_4)_3, which means, every V1-site was occupied with the same probability by V"3"+ and Fe"3"+ when 0< x<1, and then for V2-site when 1< x<2. X-ray photoelectron spectroscopy result showed the presence of trace amounts of acetylene black had realized the coexist of V"3"+ and Fe"3"+ in the Li_3M_2(PO_4)_3 framework. When evaluated as cathodes for Li-ion batteries, the pure Li_3V_2(PO_4)_3 electrode displayed the highest charge (137.2 mAh g"−"1) and discharge (121.5 mAh g"−"1) capacities in the first cycle, with the increase of Fe"3"+ content, all the charge and discharge capacities reduced drastically. Furthermore, the EIS results showed that the incorporation of the sluggish Fe"3"+ ions reduced the electronic conductivity and

Rietveld refinement of the langbeinite-type mixed-metal phosphate K2Ni0.5Zr1.5(PO43

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Igor V. Zatovsky

2014-07-01

Full Text Available Dipotassium [nickel(II zirconium(IV] tris(orthophosphate was prepared from a self-flux in the system K2O–P2O5–NiO–K2ZrF6. The title compound belongs to the langbeinite family and is built up from two [MO6] octahedra [M = Ni:Zr with mixed occupancy in ratios of 0.21 (4:0.79 (4 and 0.29 (4:0.71 (4, respectively] and [PO4] tetrahedra interlinked via vertices into a 3∞[M2(PO43] framework. Two independent K+ cations are located in large cavities of the framework, with coordination numbers to O2− anions of nine and twelve. The K, Ni, and Zr sites are located on threefold rotation axes.

Supervalent doping of LiFePO4 for enhanced electrochemical performance

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N. V. Kosova

2015-12-01

Full Text Available The orthophosphates LiFe0.9M0.1PO4 with the structure of olivine doped with vanadium and titanium were obtained by mechanochemically stimulated solidphase synthesis using high-energy planetary mill AGO-2 and subsequent annealing at 750 °C. It is shown that V- and Ti- ions do not completely substitute for Fe2+ ions in the LiFePO4 structure. The remaining part of these ions involve in the formation of second phase with nashiko-like structure: monoclinic Li3V2(PO43 (space group P21/n and rhombohedral LiTi2(PO43 (space group R-3c. According to TEM, the average size of the particle of nanocomposites is about 100-300 nm. EMF of microanalysis showed that the small particles of secondary phases are segregated at the surface of larger particles of LiFePO4. On the charge-discharge curves of LiFe0.9M0.1PO4 there are plateau corresponding to LiFePO4 and the second phase. The doping with vanadium increases the resistance of the cycling of LiFePO4 and improves its cyclability at high speeds to a greater extent than in the case of doping with titanium.

Wet chemical synthesis and luminescence in Ca5(PO4)3M:Eu2+ (M = Br, I) phosphors for solid state lighting

Science.gov (United States)

Mungmode, C. D.; Gahane, D. H.; Moharil, S. V.

2018-05-01

A simple wet chemical synthesis of Eu2+ activated Ca5(PO4)3Br and Ca5(PO4)3I phosphors and their photoluminescence is reported. Formation of Ca5(PO4)3Br is confirmed by X-ray diffraction (XRD). Synthesized phosphors are analyzed for photoluminescence (PL) spectrum. A bright blue emission is observed when phosphors are excited by near Ultra Violet (nUV) radiations. Photoluminescence emission spectrum for (Ca0.985Eu0.015)5(PO4)3Br is centered at 457 nm and for (Ca0.985Eu0.015)5(PO4)3 I it peaks at 455 nm when excited by 365 nm near UV radiation. Eu2+ luminescence in Ca5(PO4)3Br is reported for the first time. The phosphors can be efficiently excited by nUV radiations. This shows that phosphors may be used as blue phosphor in pcLED for Solid State Lighting.

Carbon coated nano-LiTi2(PO4)3 electrodes for non-aqueous hybrid supercapacitors.

Science.gov (United States)

Aravindan, V; Chuiling, W; Reddy, M V; Rao, G V Subba; Chowdari, B V R; Madhavi, S

2012-04-28

The Pechini type polymerizable complex decomposition method is employed to prepare LiTi(2)(PO(4))(3) at 1000 °C in air. High energy ball milling followed by carbon coating by the glucose-method yielded C-coated nano-LiTi(2)(PO(4))(3) (LTP) with a crystallite size of 80(±5) nm. The phase is characterized by X-ray diffraction, Rietveld refinement, thermogravimetry, SEM, HR-TEM and Raman spectra. Lithium cycling properties of LTP show that 1.75 moles of Li (~121 mA h g(-1) at 15 mA g(-1) current) per formula unit can be reversibly cycled between 2 and 3.4 V vs. Li with 83% capacity retention after 70 cycles. Cyclic voltammograms (CV) reveal the two-phase reaction mechanism during Li insertion/extraction. A hybrid electrochemical supercapacitor (HEC) with LTP as negative electrode and activated carbon (AC) as positive electrode in non-aqueous electrolyte is studied by CV at various scan rates and by galvanostatic cycling at various current rates up to 1000 cycles in the range 0-3 V. Results show that the HEC delivers a maximum energy density of 14 W h kg(-1) and a power density of 180 W kg(-1). This journal is © the Owner Societies 2012

Crystal structure and Temperature-Dependent Luminescence Characteristics of KMg4(PO4)3:Eu2+ phosphor for White Light-emitting diodes

Science.gov (United States)

Chen, Jian; Liu, Yangai; Mei, Lefu; Liu, Haikun; Fang, Minghao; Huang, Zhaohui

2015-01-01

The KMg4(PO4)3:Eu2+ phosphor was prepared by the conventional high temperature solid-state reaction. The crystal structure, luminescence and reflectance spectra, thermal stability, quantum efficiency and the application for N-UV LED were studied respectively. The phase formation and crystal structure of KMg4(PO4)3:Eu2+ were confirmed from the powder X-ray diffraction and the Rietveld refinement. The concentration quenching of Eu2+ in the KMg4(PO4)3 host was determined to be 1mol% and the quenching mechanism was certified to be the dipole–dipole interaction. The energy transfer critical distance of as-prepared phosphor was calculated to be about 35.84Å. Furthermore, the phosphor exhibited good thermal stability and the corresponding activation energy ΔE was reckoned to be 0.24eV. Upon excitation at 365nm, the internal quantum efficiency of the optimized KMg4(PO4)3:Eu2+ was estimated to be 50.44%. The white N-UV LEDs was fabricated via KMg4(PO4)3:Eu2+, green-emitting (Ba,Sr)2SiO4:Eu2+, and red-emitting CaAlSiN3:Eu2+ phosphors with a near-UV chip. The excellent color rendering index (Ra = 96) at a correlated color temperature (5227.08K) with CIE coordinates of x = 0.34, y = 0.35 of the WLED device indicates that KMg4(PO4)3:Eu2+ is a promising blue-emitting phosphor for white N-UV light emitting diodes (LEDs). PMID:25855866

Reaping the redox switching capability of vanadium in Li3V2(PO4)3/HHC composite to demonstrate the rocking chair electrode performance

Science.gov (United States)

Saravanan, Karuppiah; Kalaiselvi, Nallathamby

2017-10-01

The study exploits the functional advantages of vanadium with variable oxidation states to extract maximum energy from Li3V2(PO4)3/HHC composite containing human hair derived carbon. Vanadium, present in the form of V3+ in Li3V2(PO4)3 stabilizes itself electrochemically as V4+ by forming LiV2(PO4)3 through oxidation in the potential range 3.0-4.5 V and as V1+ by forming Li7V2(PO4)3 due to the reduction of V3+ into V1+ in the 0.01-3.0 V region, thus qualifying LVP as a rocking chair electrode. In other words, Li3V2(PO4)3/HHC composite demonstrates itself as anode and as cathode for lithium-ion batteries. Li3V2(PO4)3/HHC cathode exhibits ultra high capacity, excellent rate capability at 50C and retains about 99% capacity up to 1000 cycles. As anode, Li3V2(PO4)3/HHC delivers a capacity of 428 mAh g-1 at 50 mA g-1 and tolerates 5 A g-1 condition up to 1000 cycles with a negligible capacity fade. The dual electrode behavior of Li3V2(PO4)3/HHC may be attributed to the unique architecture of HHC that provides high electronic conductivity, facilitates rapid diffusion of lithium ions and admits volume changes during intercalation/deintercalation. More importantly, HHC is a cheap and eco-friendly carbon additive derived from filthy human hair, which in turn offers ample scope for the commercial exploitation of title electrode.

Study on luminescence and thermal stability of blue-emitting Sr_5(PO_4)_3F: Eu"2"+phosphor for application in InGaN-based LEDs

International Nuclear Information System (INIS)

Liu, Jie; Zhang, Zhi-Ming; Wu, Zhan-Chao; Wang, Fang-Fang; Li, Zhen-Jiang

2017-01-01

Highlights: • A blue phosphor Sr_5(PO_4)_3F: Eu"2"+ was prepared at low temperature of 800 °C. • The broad excitation band of the phosphor matches well with NUV LED chips. • The phosphor shows high color purity and good color stability. • A bright blue-emitting LED was fabricated with this phosphor on an InGaN chip. - Abstract: A series of blue-emitting phosphors Sr_5(PO_4)_3F: Eu"2"+ were synthesized by traditional high temperature solid-state reaction method. The micro-morphology and photoluminescence properties of the phosphors were investigated. The Sr_5(PO_4)_3F: Eu"2"+ phosphors exhibit broad excitation spectra ranging from 250 to 420 nm, and an intense asymmetric blue emission band peaking at 435 nm. Two different Eu"2"+ emission centers in Sr_5(PO_4)_3F: Eu"2"+ phosphors were confirmed via their fluorescence properties. The concentration quenching mechanism, fluorescence lifetime and thermal stability of Sr_5(PO_4)_3F: Eu"2"+ phosphors were studied in detail. The thermal stability can be improved obviously by anion substitution. The CIE chromaticity coordinates of Sr_5(PO_4)_3F: Eu"2"+ phosphors with different Eu"2"+-doped concentrations were calculated. A blue light-emitting diode was fabricated by combination of a 370 nm InGaN chip and the prepared phosphor Sr_5(PO_4)_3F: Eu"2"+. The present work suggests that Sr_5(PO_4)_3F: Eu"2"+ is a potential phosphor applied in InGaN-based LEDs.

Systems of Ba(PO3)2-Sr(Pu3)2, Cd(PO3)2-Ca(PO3)2

International Nuclear Information System (INIS)

Tokman, I.A.; Bukhalova, G.A.

1977-01-01

Phase diagrams of the Ba(PO 3 ) 2 -Sr(PO 3 ) 2 and Cd(PO 3 ) 2 -Ca(PO 3 ) 2 systems have been studied and plotted by the methods of differential-thermal analysis (DTA), visual-polythermal, X-ray phase and infrared spectroscopy. The Ba(PO 3 ) 2 -Sr(PO 3 ) 2 system is of the eutectic type. In the binary system Cd(PO 3 ) 2 -Ca(PO 3 ) 2 the existence of a continuous series of solid solutions with a minimum at 858 deg C and 27.5 mol.% Ca(PO 3 ) 2 has been established

Ion conductivity and phase transitions in the Na3Sc2(PO4)3 - NaGe2(PO4)3 system

International Nuclear Information System (INIS)

Nogaj, A.S.

2002-01-01

Influence of heteropolyvalent substitution on dipole ordering of sodium-scandium phosphate, as well as on ion conductivity and phase transitions in the system Na 3 Sc 2 (PO 4 ) 3 - NaGe 2 (PO 4 ) 3 , was studied using the methods of solid phase synthesis, X-ray diffraction, laser spectroscopy and measurement of electric conductivity. Boundaries of the dipole-ordered and superionic phases existence ranges in the given system were identified. It is shown that expansion of the dipole-ordered phase existence range with increase in substituent cation concentration is characteristic of the phase on the basis of α-Na 3 Sc 2 (PO 4 ) 3 [ru

Effect of VO43− substitution for PO43− on electrochemical properties of the Li3Fe2(PO4)3 cathode materials

International Nuclear Information System (INIS)

Yang, Yonggang; Zhang, Yongguang; Hua, Zhengshen; Wang, Xin; Peng, Huifen; Bakenov, Zhumabay

2016-01-01

Graphical abstract: VO 4 3− –substituted Li 3 Fe 2 (PO 4 ) 3 samples were prepared by sol-gel method. The VO 4 3− substitution remarkably improves the rate capability and cycling performance of the Li 3 Fe 2 (PO 4 ) 3 due to improved conductivity and enhanced lithium ion diffusion. - Highlights: • Mixed anion effect was used to improve electrochemical properties of Li 3 Fe 2 (PO 4 ) 3 . • The VO 4 3− substitution improved rate capability and cyclability of Li 3 Fe 2 (PO 4 ) 3 . • The Li 3 Fe 2 (PO 4 ) 2.55 (VO 4 ) 0.45 material shows the excellent electrochemical performance. - Abstract: In this research, VO 4 3− substitution was used to improve electrochemical properties of the Nasicon Li 3 Fe 2 (PO 4 ) 3 cathode material. The VO 4 3− substitution resulted in formation of a homogeneous compound Li 3 Fe 2 (PO 4 ) 3-x (VO 4 ) x in a composition range of x ≤ 0.45; further introduction of VO 4 3− led to precipitation of some other phases. It was shown that the VO 4 3− substituted samples presented discharging capacity higher than that of bare non-substituted Nasicon and the reported Ti 4+ and Mn 2+ doped ones. The Li 3 Fe 2 (PO 4 ) 2.55 (VO 4 ) 0.45 material exhibited excellent cycling stability and rate capability, and retained a capacity of 91.8 mAh g −1 after 60 cycles at 2C charge-discharge rate. This value is one of the highest reported to date for the Li 3 Fe 2 (PO 4 ) 3 compound, and was about 48% higher than that of the latter. The electrochemical performance enhancements for the VO 4 3− substituted samples were attributed to the reduction of charge transfer resistance, increase of electrical conductivity, and fast lithium ion diffusion behavior. Hence, the obtained results proved that the VO 4 3− anion substitution for PO 4 3− is a powerful technique to improve the electrochemical performance of the studied Nasicon compound.

Systematic investigation of the strontium zirconium phosphate ceramic form for nuclear waste immobilization

Science.gov (United States)

Pet'kov, Vladimir; Asabina, Elena; Loshkarev, Vladimir; Sukhanov, Maksim

2016-04-01

We have summarized our data and literature ones on the thermophysical properties and hydrolytic stability of Sr0.5Zr2(PO4)3 compound as a host NaZr2(PO4)3-type (NZP) structure for immobilization of 90Sr-containing radioactive waste. Absence of any polymorphic transformations on the temperature dependence of its heat capacity between 7 and 665 K is caused by the stability of crystalline Sr0.5Zr2(PO4)3. Calculated values of thermal conductivity coefficients at zero porosity in the range 298-673 K were 1.86-2.40 W·m-1 K-1. The compound may be classified as low thermal expanding material due to its average linear thermal expansion coefficient. Study of the hydrolytic stability in acid and alkaline media has shown that the relative mass fraction of Sr2+ ions, released into aggressive leaching media, didn't exceed 1% of the mass of sample. Soxhlet leaching studies have shown substantial resistance towards the release of Sr2+ ions into distilled water. Feeble sinterability constrains practical applications of NZP substances, that is why known in literature methods of Sr0.5Zr2(PO4)3 dense ceramics obtaining have been reviewed.

Some properties of tetravalent actinide phosphates of M1M42(PO4)3 type and peculiarities of their structure

International Nuclear Information System (INIS)

Burnaeva, A.A.; Volkov, Yu.F.; Kryukova, A.I.; Skiba, O.V.; Spiryakov, V.I.; Korshunov, I.A.; Samojlova, T.K.

1987-01-01

Generalizing analysis of data on crystallographic and IR spectral properties of double phosphates of actinide and alkali elements of M (1) M 2 (4) (PO 4 ) 3 type is conducted. It is shown, that Li - , Na - , K - , Rb - , CsTh 2 (PO 4 ) 3 , Li - , Na - , KU 2 (PO 4 ) 3 , NaNp 2 (PO 4 ) 3 compounds crystallize in a monoclinic type structure and form an isostructural phosphate series. It is ascertained, that in rubidium-uranium, uranium-cesium systems double salt formation is not observed. Plutonium-sodium phosphate has a rhombic-type structure, which points out to the existence of a morphotropic transition in NaM 2 4 (PO 4 ) 3 phosphate series at the Np-Pu boundary. Some regularities of structure and effect of M 1 and M 4 nature on the double phosphate structure are revealed

In Situ Studies of Fe4+ Stability in β-Li3Fe2(PO4)3 Cathodes for Li Ion Batteries

DEFF Research Database (Denmark)

Christiansen, Ane Sælland; Johnsen, Rune E.; Norby, Poul

2015-01-01

In commercial Fe-based batteries the Fe2+/Fe3+ oxidation states are used, however by also utilizing the Fe4+ oxidation state, intercalation of up to two Li ions per Fe ion could be possible. In this study, we investigate whether Fe4+ can be formed and stabilized in β-Li3Fe2(PO4)3. The work includes...... of Fe4+ formation. Oxidation of the organic electrolyte is inevitable at 4.5 V but this alone cannot explain the volume change. Instead, a reversible oxygen redox process (O2− → O−) could possibly explain and charge compensate for the reversible extraction of lithium ions from β-Li3Fe2(PO4)3....... in situ synchrotron X-ray powder diffraction studies (XRPD) during charging of β-Li3Fe2(PO4)3 up to 5.0 V vs. Li/Li+. A novel capillary-based micro battery cell for in situ XRPD has been designed for this. During charge, a plateau at 4.5 V was found and a small contraction in volume was observed...

Microwave-assisted preparation of Li3V2(PO4)3/C composite with high-rate capacity

International Nuclear Information System (INIS)

Yan, Ji; Mao, Wen-feng; Xie, Hui; Tang, Zhi-yuan; Yuan, Wei; Chen, Xue-cheng; Xu, Qiang; Ma, Li

2012-01-01

Highlights: ► High-rate Li 3 V 2 (PO 4 ) 3 /C is firstly reported via a microwave-assisted method. ► The reduced particle size is responsible for the improved high-rate performance. ► A discharge capacity of 100 mAh g −1 is obtained at 20 C charge–discharge rate. -- Abstract: A fast sol–gel assisted microwave heating approach has been developed for the synthesis of high-rate Li 3 V 2 (PO 4 ) 3 /C cathode material. This approach can synthesize Li 3 V 2 (PO 4 ) 3 /C particles with high purity and good crystallinity in 12 min at a low microwave power of 320 W. In the voltage range of 3.0–4.3 V, the obtained Li 3 V 2 (PO 4 ) 3 /C delivers a reversible discharge capacity of 100 mAh g −1 after 100 cycles at 20 °C, exhibiting excellent rate capability and cycling performance. The rate-recovery performance also suggests that the Li 3 V 2 (PO 4 ) 3 /C material possesses excellent structure stability after high-rate cycles, presenting excellent application value in high-power lithium ion batteries.

Enhancement of white-light-emission from single-phase Sr5(PO4)3F:Eu(2+),Mn(2+) phosphors for near-UV white LEDs.

Science.gov (United States)

Feng, Yaomiao; Huang, Jinping; Liu, Lili; Liu, Jie; Yu, Xibin

2015-09-07

A series of single-phase broadband white-light-emitting Sr5(PO4)3F:Eu(2+),Mn(2+) phosphors were prepared by a solid state reaction. The luminescence property, and the crystal and electronic structures of the fluorophosphates were studied by photoluminescence analysis, XRD Rietveld refinement and density functional theory calculation (DFT), respectively. Under near ultraviolet excitation in the 250 to 430 nm wavelength range, the phosphors exhibit two emission bands centered at 440 and 556 nm, caused by the Eu(2+) and Mn(2+) ions. By altering the relative ratios of Eu(2+) and Mn(2+) in the compounds, the emission color could be modulated from blue to white. The efficient energy transfer from the Eu(2+) to Mn(2+) ions could be ascribed to the well crystallized host lattice and the facile substitution of Eu(2+) and Mn(2+) for Sr(2+) sites due to similar ionic radii. A series of fluxes were investigated to improve the photoluminescence intensity. When KCl was used as flux in the synthesis, the photoluminescence intensity of Sr5(PO4)3F:Eu(2+),Mn(2+) was enhanced by 85% compared with no fluxes added. These results demonstrate that the single-phase Sr5(PO4)3F:Eu(2+),Mn(2+) with enhanced luminescence efficiency could be promising as a near UV-convertible direct white-light-emitting phosphor for WLED applications.

Energy transfer between Pr3+ and Mn2+ in K2YZr(PO4)3: Pr, Mn phosphor

International Nuclear Information System (INIS)

Liang Wei; Wang Yuhua

2011-01-01

Research highlights: → Pr 3+ , Mn 2+ co-doped K 2 YZr(PO 4 ) 3 phosphor is a novel type of practical visible quantum cutting phosphor in promising application. → The optimal quantum efficiency (QE) of this co-doped system K 2 YZr(PO 4 ) 3 : Pr 3+ , Mn 2+ reached to 126.3%. → The Mn 2+6 A 1g → 4 E g - 4 A 1g transition was found to coincide well with the 1 S 0 → 1 I 6 transition of Pr 3+ . → The energy transfer from Pr 3+ to Mn 2+ was also observed, converting the first photon from the PCE of Pr 3+ into the red emission of Mn 2+ , and the QC process occurred in this Pr 3+ , Mn 2+ co-doped K 2 YZr(PO 4 ) 3 phosphor. - Abstract: Pr 3+ , Mn 2+ co-doped K 2 YZr(PO 4 ) 3 samples were prepared by solid-state reaction method and their photoluminescence (PL) properties were investigated in ultra-violet (UV) and vacuum ultra-violet (VUV) region. The results indicated that in Pr 3+ singly doped K 2 YZr(PO 4 ) 3 sample, the first-step transition ( 1 S 0 → 1 I 6 , 3 P J around 405 nm) of Pr 3+ is near the ultraviolet (UV) range, not useful for practical application. When Mn 2+ was doped as a co-activator ion, the energy of 1 S 0 → 1 I 6 , 3 P J transition can be transferred synchronously from Pr 3+ to Mn 2+ and then emit a visible photon. The optimal quantum efficiency (QE) of this co-doped system K 2 YZr(PO 4 ) 3 : Pr 3+ , Mn 2+ reached to 126.3%, suggesting a novel type of practical visible quantum cutting phosphor in promising application.

Sodium intercalation in the phosphosulfate cathode NaFe2(PO4)(SO4)2

Science.gov (United States)

Ben Yahia, Hamdi; Essehli, Rachid; Amin, Ruhul; Boulahya, Khalid; Okumura, Toyoki; Belharouak, Ilias

2018-04-01

The compound NaFe2(PO4)(SO4)2 is successfully synthesized via a solid state reaction route and its crystal structure is determined using powder X-ray diffraction data. NaFe2(PO4)(SO4)2 phase is also characterized by cyclic voltammetry, galvanostatic cycling and electrochemical impedance spectroscopy. NaFe2(PO4)(SO4)2 crystallizes with the well-known NASICON-type structure. SAED and HRTEM experiments confirm the structural model, and no ordering between the PO4-3 and SO4-2 polyanions is detected. The electrochemical tests indicate that NaFe2(PO4)(SO4)2 is a 3 V sodium intercalating cathode. The electrical conductivity is relatively low (2.2 × 10-6 Scm-1 at 200 °C) and the obtained activation energy is ∼0.60eV. The GITT experiments indicate that the diffusivity values are in the range of 10-11-10-12 cm2/s within the measured sodium concentrations.

Cation mobility in NASICON compounds Li1-xZr2-xNbx(PO4)3 and Li1+xZr2-xScx(PO4)3

International Nuclear Information System (INIS)

Stenina, I.A.; Yaroslavtsev, A.B.; Aliev, A.D.; Antipov, E.V.; Velikodnyj, Yu.A.; Rebrov, A.I.

2002-01-01

Compounds featuring NASICON structure of the composition Li 1-x Zr 2-x Nb x (PO 4 ) 3 and Li 1+x Zr 2-x Sc x (PO 4 ) 3 were studied by the method of X-ray phase analysis and 7 Li and 31 P NMR. Structure of Li 0.8 Zr 1.8 Nb 0.2 (PO 4 ) 3 was refined on the basis of X-ray powder pattern. It is shown that cationic disordering in LiZr 2 (PO 4 ) 3 is stimulated both by cationic vacancies and interstitial atoms formation. The cationic vacancies are characterized by a higher mobility. The level of intrinsic disordering was estimated and the Frenkel constant for the compound was calculated [ru

Bio-assisted synthesis of mesoporous Li3V2(PO4)3 for high performance lithium-ion batteries

DEFF Research Database (Denmark)

He, W.; Zhang, X.D.; Du, X.Y.

2013-01-01

The mesoporous biocarbon coated Li3V2(PO4)3(MBC-LVP) cathode material is synthesized by abiotemplate-assisted sol–gel reaction process using low-cost beer waste brewing yeasts (BWBYs) as bothstructural template and biocarbon source. The structure and electrochemical performances of MBC-LVPwere in...

Synthesis of nanostructured LiTi2(PO4)3 powder by a Pechini-type polymerizable complex method

International Nuclear Information System (INIS)

Mariappan, C.R.; Galven, C.; Crosnier-Lopez, M.-P.; Le Berre, F.; Bohnke, O.

2006-01-01

The nanostructured NASICON-type LiTi 2 (PO 4 ) 3 (LTP) material has been synthesized by Pechini-type polymerizable complex method. The use of water-soluble ammonium citratoperoxotitanate (IV) metal complex instead of alkoxides as precursor allows to prepare monophase material. Thermal analyses have been carried out on the powder precursor to check the weight loss and synthesis temperature. X-ray powder diffraction analysis (XRD) has been performed on the LTP powder obtained after heating the powder precursor over a temperature range from 550 to 1050 deg. C for 2 h. By varying the molar ratio of citric acid to metal ion (CA/Ti) and citric acid to ethylene glycol (CA/EG), the grain size of the LTP powder could be modified. The formation of small and well-crystalline grains, in the order of 50-125 nm in size, has been determined from the XRD patterns and confirmed by transmission electron microscopy

Co3(PO42·4H2O

Directory of Open Access Journals (Sweden)

Yang Kim

2008-10-01

Full Text Available Single crystals of Co3(PO42·4H2O, tricobalt(II bis[orthophosphate(V] tetrahydrate, were obtained under hydrothermal conditions. The title compound is isotypic with its zinc analogue Zn3(PO42·4H2O (mineral name hopeite and contains two independent Co2+ cations. One Co2+ cation exhibits a slightly distorted tetrahedral coordination, while the second, located on a mirror plane, has a distorted octahedral coordination environment. The tetrahedrally coordinated Co2+ is bonded to four O atoms of four PO43− anions, whereas the six-coordinate Co2+ is cis-bonded to two phosphate groups and to four O atoms of four water molecules (two of which are located on mirror planes, forming a framework structure. In addition, hydrogen bonds of the type O—H...O are present throughout the crystal structure.

Synthesis, crystal structure, and ionic conductivity of a new layered metal phosphate, Li2Sr2Al(PO4)3

International Nuclear Information System (INIS)

Kim, Sung-Chul; Kwak, Hyun-Jung; Yoo, Chung-Yul; Yun, Hoseop; Kim, Seung-Joo

2016-01-01

A new layered metal phosphate, Li 2 Sr 2 Al(PO 4 ) 3 , was synthesized in the form of either a single-crystal or polycrystalline powder using the molten hydroxide flux method or a solid-state reaction, respectively. Li 2 Sr 2 Al(PO 4 ) 3 crystallizes to the P2 1 /n (Z=4) monoclinic space group with lattice parameters a≈4.95 Å, b≈22.06 Å, c≈8.63 Å, and β≈91.5°. The structure is composed of stacked [LiSrAl(PO 4 ) 2 ] layers alternating regularly with [LiSrPO 4 ] layers. In the [LiSrAl(PO 4 ) 2 ] sublattice, the AlO 6 octahedra and PO 4 tetrahedra are tilted cooperatively to form an anionic, corrugated, two-dimensional [Al(PO 4 ) 2 ] 3− framework that can be regarded as a “distorted-glaserite” structure. The [LiSrPO 4 ] sublattice is that of a layered block containing a six-membered ring formed from alternating linkages of LiO 4 and PO 4 tetrahedra. The six-membered rings show a boat-type arrangement with the up(U) or down(D) pointing sequence, UUDUUD. The interspace between the two sublattices generates a two-dimensional pathway for Li + ion conduction. The impedance measurement indicated that Li 2 Sr 2 Al(PO 4 ) 3 had a moderate ion conductivity (σ≈1.30×10 −4 S cm −1 at 667 K), with an activation energy E a ≈1.02 eV. - Graphical abstract: Polyhedral view of Li 2 Sr 2 Al(PO 4 ) 3 . Li + ions are represented by green spheres, Sr atoms by white spheres, AlO 6 groups by octahedra, and PO 4 groups by tetrahedra. - Highlights: • New compound Li 2 Sr 2 Al(PO 4 ) 3 is reported. • The crystal structure is investigated by single-crystal XRD analysis. • The structure is formed by the alternate stacking of two different sublattices. • Correlation between the crystal structure and ionic conductivity is discussed.

Freeze-drying synthesis of Li3V2(PO4)3/C cathode material for lithium-ion batteries

International Nuclear Information System (INIS)

Qiao, Y.Q.; Wang, X.L.; Mai, Y.J.; Xia, X.H.; Zhang, J.; Gu, C.D.; Tu, J.P.

2012-01-01

Highlights: ► Li 3 V 2 (PO 4 ) 3 /C was synthesized by freeze-drying method. ► A specific capacity of 105.6 mAh g −1 can be obtained at 14.8 C. ► 93.3 mAh g −1 can be delivered at a higher current density of 29.6 C. ► The Li 3 V 2 (PO 4 ) 3 /C electrode shows a good cycling performance. - Abstract: Li 3 V 2 (PO 4 ) 3 /C cathode material was synthesized by using a freeze-drying method followed by carbon-thermal reduction. This as-prepared material has a uniform particle size distribution and a well carbon coating on the surface of Li 3 V 2 (PO 4 ) 3 particles. The Li 3 V 2 (PO 4 ) 3 /C exhibits good electrochemical performance and cycling stability. Between 3.0 and 4.3 V, the composite delivered a reversible capacity of 125.2 mAh g −1 at a charge–discharge rate of 1.48 C (1 C = 133 mA g −1 ) and without obviously capacity fading after 100 cycles. Even at 14.8 C and 29.6 C rates, it can still deliver discharge capacities of 105.6 mAh g −1 and 93.3 mAh g −1 , and the discharge capacities of 84.5 and 60.5 mAh g −1 are sustained after 500 cycles, respectively.

A frogspawn-inspired hierarchical porous NaTi2(PO4)3-C array for high-rate and long-life aqueous rechargeable sodium batteries

Science.gov (United States)

Zhao, Baidan; Lin, Bo; Zhang, Sen; Deng, Chao

2015-11-01

Hollow micro/nano-arrays have attracted tremendous attention in the field of energy conversion and storage, but such structures usually compromise the volumetric energy density of the electrode materials. Frogspawn consists of a spawn core and a transparent jelly shell organized in a hierarchical porous array, which exhibits superior mechanical strength and high-efficiency oxygen permeability. It can be used as a model for designing a new high-performance electrode material, which has advantages such as a high surface area, fast mass transport and superior durability. Herein, we report a frogspawn-like NaTi2(PO4)3/C array prepared by a facile preform impregnation strategy. The framework is formed by a hollow carbon sphere connected by the NaTi2(PO4)3/C skeleton, and its hollow is filled with the NaTi2(PO4)3 nanospheres. The whole hierarchical porous three-dimensional array copies the structure of a frogspawn. This unique structure not only enables easy electrolyte percolation and fast electron/ion transport, but also enhances the reversible capacity and cycling durability. When it is applied as an anode of the aqueous sodium ion battery, it exhibits favorable high rate capability and superior cycling stability, and retains 89% of the initial capacity after two thousand cycles at 20 C. Moreover, the full cell using the frogspawn-inspired NaTi2(PO4)3-C as the anode and Na0.44MnO2 as the cathode is capable of ultralong cycling up to one thousand cycles at alternate 10 and 60 C, which is among the best of state-of-the-art aqueous sodium ion systems. Therefore, the frogspawn-inspired architecture provides a new strategy to the tailored design of polyanion materials for high-power applications.Hollow micro/nano-arrays have attracted tremendous attention in the field of energy conversion and storage, but such structures usually compromise the volumetric energy density of the electrode materials. Frogspawn consists of a spawn core and a transparent jelly shell organized in

3.0 V High Energy Density Symmetric Sodium-Ion Battery: Na4V2(PO4)3∥Na3V2(PO4)3.

Science.gov (United States)

Yao, Xuhui; Zhu, Zixuan; Li, Qi; Wang, Xuanpeng; Xu, Xiaoming; Meng, Jiashen; Ren, Wenhao; Zhang, Xinhe; Huang, Yunhui; Mai, Liqiang

2018-03-28

Symmetric sodium-ion batteries (SIBs) are considered as promising candidates for large-scale energy storage owing to the simplified manufacture and wide abundance of sodium resources. However, most symmetric SIBs suffer from suppressed energy density. Here, a superior congeneric Na 4 V 2 (PO 4 ) 3 anode is synthesized via electrochemical preintercalation, and a high energy density symmetric SIB (Na 3 V 2 (PO 4 ) 3 as a cathode and Na 4 V 2 (PO 4 ) 3 as an anode) based on the deepened redox couple of V 4+ /V 2+ is built for the first time. When measured in half cell, both electrodes show stabilized electrochemical performance (over 3000 cycles). The symmetric SIBs exhibit an output voltage of 3.0 V and a cell-level energy density of 138 W h kg -1 . Furthermore, the sodium storage mechanism under the expanded measurement range of 0.01-3.9 V is disclosed through an in situ X-ray diffraction technique.

Co-modification of nitrogen-doped graphene and carbon on Li3V2(PO4)3 particles with excellent long-term and high-rate performance for lithium storage

Science.gov (United States)

Ren, Manman; Yang, Mingzhi; Liu, Weiliang; Li, Mei; Su, Liwei; Wu, Xianbin; Wang, Yuanhao

2016-09-01

In this work, N-doped graphene and carbon co-modified Li3V2(PO4)3 composites (LVP/NGC) are successfully fabricated through a xerogel method for the first time. The obtained architecture combines two types of electronic contact with Li3V2(PO4)3 particles: the point-to-face contact of N-doped graphene and the face-to-face contact of N-doped carbon coating layers. Profiting from the favorable complex structure, graphene and carbon coating layers offer an extraordinary network for electron transfer and hence an excellent long-term and high-rate performance. Even tested at the rate of 40 C, the reversible capacity still maintains 86.9 mAh g-1 after 800 cycles without any fading. This work provides a promising route to improve the long-term and high-rate performance of cathodes for LIBs and enlightens us on exploring preferable strategies to develop advanced electrode materials for other energy storage devices.

Evolution of electrochemical performance in Li3V2(PO4)3/C composites caused by cation incorporation

International Nuclear Information System (INIS)

Zhang, Lu-Lu; Liang, Gan; Peng, Gang; Jiang, Yan; Fang, Hui; Huang, Yun-Hui; Croft, Mark C.; Ignatov, Alexander

2013-01-01

Graphical abstract: Four electrochemically active cations (M = Fe, Co, Ni, Mn) are doped into Li 3 V 2 (PO 4 ) 3 . M-incorporation does not change the monoclinic structure of Li 3 V 2 (PO 4 ) 3 , but forms some solid solutions. Minor LiMPO 4 impurity phases can be formed in the LVMP/C samples. Moreover, FePO 4 also exists as impurity in the LVFeP/C sample. Compared with pristine LVP/C, LVNiP/C electrode exhibits the lowest capacity, resulting from the decreased electronic conductivity and the lowest Li-ion diffusion coefficient, whereas LVFeP/C shows the best electrochemical performance. -- Highlights: • Cation-incorporated Li 3 V 2 (PO 4 ) 3 /C have been systematically investigated. • Cation incorporation in Li 3 V 2 (PO 4 ) 3 does not change the monoclinic structure but form solid solution. • Fe-incorporation shows the best electrochemical performance whereas Ni-incorporation shows the poorest performance. • A clear profile of cation incorporation with Fe, Co, Ni, Mn ions in Li 3 V 2 (PO 4 ) 3 /C is obtained. -- Abstract: Li 3 V 2 (PO 4 ) 3 /C (LVP/C) composites incorporated by a series of electrochemically active cations (Fe, Co, Ni, Mn) have been successfully prepared by a conventional solid-state reaction. M-incorporation (M = Fe, Co, Ni, Mn) in Li 3 V 2 (PO 4 ) 3 does not change the monoclinic structure. Analyzed with X-ray photoelectron spectroscopy, X-ray absorption spectroscopy and high-resolution transmission electron microscopy, we find that the valence is between +2.67 and +3 for Fe, and is +2 for Co, Ni and Mn. M-doped LVP and LiMPO 4 phases coexist in the incorporated LVP/C composites. Compared with pristine LVP/C, Fe-incorporated LVP/C shows the best electrochemical performance with the highest initial discharge capacity of 131.4 mAh g −1 at 0.1 C between 2.5 and 4.3 V. The Fe-incorporated LVP/C sample also exhibits excellent rate capability with an average capacity of 122.4 mAh g −1 at 1 C and 93.5 mAh g −1 at 5 C, resulting from the

Site preferences of actinide cations in [NZP] compounds

Science.gov (United States)

Hawkins, H. T.; Spearing, D. R.; Smith, D. M.; Hampel, F. G.; Veirs, D. K.; Scheetz, B. E.

2000-07-01

Compounds adopting the sodium dizirconium tris(phosphate) (NaZr2(PO4)3) structure type belong to the [NZP] structural family of compounds. [NZP] compounds possess desirable properties that would permit their application as hosts for the actinides. These properties include compositional flexibility (i.e., three structural sites that can accommodate a variety of different cations), high thermal stability, negligible thermal expansion, and resistance to radiation damage. Experimental data indicate that [NZP] compounds resist dissolution and release of constituents over a wide range of experimental conditions. Moreover, [NZP] compounds may be synthesized by both conventional and novel methods and may be heat treated or sintered at modest temperatures (800 °C-1350 °C) in open or restricted systems.

The system Ba(H2PO4)2-Sr(H2PO4)2-H3PO4(30%)-H2O at 25, 40 and 60 deg C

International Nuclear Information System (INIS)

Taranenko, N.P.; Serebrennikova, G.M.; Stepin, B.D.; Oboznenko, Yu.V.

1982-01-01

The system Ba(H 2 PO 4 ) 2 -Sr(H 2 PO 4 ) 2 -H 3 PO 4 (30%)-H 2 O (25 deg C) belongs to eutonic type systems. Solubility isotherms of salt components at 40 and 60 deg C are calculated. Polytherms (25-60 deg C) of solubility of monosubstituted barium and strontium phosphates in 30-60% H 3 PO 4 are obtained. The value of cocrystallization coefficient of Sr 2 + and Ba(H 2 PO 4 ) 2 Dsub(Sr)=0.042+-0.005 remains stable in the temperature range of 25-60 deg C and concentrations 30-60% phosphoric acid at initial content [Sr 2 + ]=1x10 - 2 mass%

Crystal structures and magnetic properties of iron (III)-based phosphates: Na{sub 4}NiFe(PO{sub 4}){sub 3} and Na{sub 2}Ni{sub 2}Fe(PO{sub 4}){sub 3}

Energy Technology Data Exchange (ETDEWEB)

Essehli, Rachid, E-mail: rachid_essehli@yahoo.fr [Laboratory of Mineral Solid and Analytical Chemistry ' LCSMA' , Department of Chemistry, Faculty of Sciences, University Mohamed I, Po. Box 717, 60000 Oujda (Morocco); Bali, Brahim El [Laboratory of Mineral Solid and Analytical Chemistry ' LCSMA' , Department of Chemistry, Faculty of Sciences, University Mohamed I, Po. Box 717, 60000 Oujda (Morocco); Benmokhtar, Said [LCMS, Laboratoire de Chimie des Materiaux Solides, Departement de chimie, Faculte des Sciences Ben M' SIK, Casablanca (Morocco); Bouziane, Khalid [Physics Department, College of Science, Sultan Qaboos University, PO Box 36, Postal Code 123 Al Khod, Sultanate of Oman (Oman); Manoun, Bouchaib [Laboratoire de Physico-Chimie des Materiaux, Departement de Chimie, FST Errachidia, University Moulay Ismail, B.P. 509 Boutalamine, Errachidia (Morocco); Abdalslam, Mouner Ahmed [Materials Science, Technical University Darmstadt, Darmstadt (Germany); Ehrenberg, Helmut [IFW Dresden, Helmholtzstr. 20, D-01069 Dresden (Germany)

2011-01-28

Graphical abstract: A perspective view of the Na{sub 2}Ni{sub 2}Fe(PO{sub 4}){sub 3} structure along the [0 0 1] direction. Both compounds seem to exibit antiferromagnetic interactions between magnetic entities at low temperature. Display Omitted Research highlights: > Nasicon and Alluaudite compounds, Iron(III)-based phosphates, Crystal structures of Na{sub 4}NiFe(PO{sub 4}){sub 3} and Na{sub 2}Ni{sub 2}Fe(PO{sub 4}){sub 3}. > Magnetism behaviours of Na{sub 4}NiFe(PO{sub 4}){sub 3} and Na{sub 2}Ni{sub 2}Fe(PO{sub 4}){sub 3}. > Antiferromagnetism interactions. > Mossbauer spectroscopy. - Abstract: Crystal structures from two new phosphates Na{sub 4}NiFe(PO{sub 4}){sub 3} (I) and Na{sub 2}Ni{sub 2}Fe(PO{sub 4}){sub 3} (II) have been determined by single crystal X-ray diffraction analysis. Compound (I) crystallizes in a rhombohedral system (S. G: R-3c, Z = 6, a = 8.7350(9) A, c = 21.643(4) A, R{sub 1} = 0.041, wR{sub 2}=0.120). Compound (II) crystallizes in a monoclinic system (S. G: C2/c, Z = 4, a = 11.729(7) A, b = 12.433(5) A, c = 6.431(2) A, {beta} = 113.66(4){sup o}, R{sub 1} = 0.043, wR{sub 2}=0.111). The three-dimensional structure of (I) is closely related to the Nasicon structural type, consisting of corner sharing [(Ni/Fe)O{sub 6}] octahedra and [PO{sub 4}] tetrahedra forming [NiFe(PO{sub 4}){sub 3}]{sup 4+} units which align in chains along the c-axis. The Na{sup +} cations fill up trigonal antiprismatic sites within these chains. The crystal structure of (II) belongs to the alluaudite type. Its open framework results from [Ni{sub 2}O{sub 10}] units of edge-sharing [NiO{sub 6}] octahedra, which alternate with [FeO{sub 6}] octahedra that form infinite chains. Coordination of these chains yields two distinct tunnels in which site Na{sup +}. The magnetization data of compound (I) reveal antiferromagnetic (AFM) interactions by the onset of deviations from a Curie-Weiss behaviour at low temperature as confirmed by Moessbauer measurements performed at 4.2 K. The

Upconversion luminescence of Er3+/Yb3+ doped Sr5(PO4)3OH phosphor powders

Science.gov (United States)

Mokoena, P. P.; Swart, H. C.; Ntwaeaborwa, O. M.

2018-04-01

Sr5(PO4)3OH co-doped with Er3+and Yb3+ powder phosphors were synthesized by urea combustion method. The crystal structure was analyzed using X-ray diffraction (XRD). Particle morphology was analyzed using a Jeol JSM 7800F thermal field emission scanning electron microscope (FE-SEM) and the chemical composition analysis was carried out using an Oxford Instruments AzTEC energy dispersive spectrometer (EDS) attached to the FE-SEM. Upconversion emission was measured by using a FLS980 Spectrometer equipped with a 980 nm NIR laser as the excitation source, and a photomultiplier (PMT) detector. The XRD data of the Sr5(PO4)3OH powder exhibited characteristic diffraction patterns of the hexagonal structure referenced in the standard JCPDS card number 00-033-1348. The sharp peaks revealed the formation of crystalline Sr5(PO4)3OH. The powders were made up of hexagonal nanospheres. The enhanced red emission due to the 4F9/2 → 4I15/2 transitions of Er3+ was observed and was attributed to up conversion (UC) energy transfer from Yb3+. The upconversion energy transfer mechanism from Yb3+ to Er3+ is discussed.

Phase transformations, ionic conductivity and dipole ordering of NASICON-like double phosphates Na3M2(PO4)3 (M-Sc,Fe,Cr)

International Nuclear Information System (INIS)

Kalinin, V.B.

1990-01-01

Experimental data obtained using ceramic samples of Na 3 M 2 (PO 4 ) 3 and solid solutions on their basis have been analyzed and generalized. It is shown that isostoichiometry of Na 3 M 2 (PO 4 ) 3 compounds and different types of dipole ordering in their α-phases stimulate investigations of subsolidus regions in the systems Na 3 Sc 2 (PO 4 ) 3 -Na 3 Fe 2 (PO 4 ) 3 , Na 3 Sc 2 (PO 4 ) 3 -Na 3 Cr 2 (PO 4 ) 3 , Na 3 Fe 2 (PO 4 ) 3 -Na 3 Cr 2 (PO 4 ) 3 .It proved possible to detect changes of the properties in case of ferroelectric-antiferroelectric, antiferroelectric-antiferroelectric transitions

Rigid'' skeleton dynamics of Li sub 3 In sub 2 (PO sub 4 ) sub 3 superionic conductor

Energy Technology Data Exchange (ETDEWEB)

Naganovsky, Y K; Sigaryov, S E [Inst. of Crystallography, Academy of Sciences, Moscow (USSR)

1992-01-01

The effect studied is made by the thermal prehistory of the Li{sub 3}In{sub 2}(PO{sub 4}){sub 3} ceramics on their structural and electrophysical characteristics. Annealing at T>1290 K is shown to result in a monoclinic (HT) and at T<1230 K, rhombohedral (LT) modifications of the crystal structure of Li{sub 3}In{sub 2}(PO{sub 4}){sub 3}. At the same temperature the ionic conductivity ({sigma}) of the HT-modification is found to be higher than that of LT-modification. Annealing of LT-ceramics at {proportional to}985 K leads to a decrease of {sigma} by as much as two order of magnitude seems due to Li{sup +}-ions redistribution in the (In{sub 2}P{sub 3}O{sub 12}){sub 3{infinity}}{sup 3-} skeleton cavities. In the 290-650 K temperature range phase transitions both in LT- and HT-Li{sub 3}In{sub 2}(PO{sub 4}){sub 3} are observed. (orig.).

Charge Localization in the Lithium Iron Phosphate Li3Fe2(PO4)3at High Voltages in Lithium-Ion Batteries

DEFF Research Database (Denmark)

Younesi, Reza; Christiansen, Ane Sælland; Loftager, Simon

2015-01-01

Possible changes in the oxidation state of the oxygen ion in the lithium iron phosphate Li3Fe2(PO4)3 at high voltages in lithium-ion (Li-ion) batteries are studied using experimental and computational analysis. Results obtained from synchrotron-based hard X-ray photoelectron spectroscopy...

Síntesis mediante química sol gel de compuestos Li1+xMiiixTi2-x(PO43 con estructura tipo Nasicon. Estudio de la relación microestructura-propiedades eléctricas

Directory of Open Access Journals (Sweden)

Santamaría, J.

2010-02-01

Full Text Available Compounds of formula Li1+xMIIIxTi2-x(PO43 with MIII = Cr, Fe and x = 0 and 0.05 have been prepared at soft temperatures using the Pechini synthesis method, based on sol-gel chemistry. The structural and microstructural characterization by X-ray diffraction and Scanning Electron Microscopy (SEM, shows that all of them crystallize in a NASICON-type structure with similar lattice parameters. Doping with Fe and Cr, causes an increase of the density of the samples after sinterization what clearly improves the ionic conductivity of the original material, LiTi2(PO43 until values of 9x10-4 S cm-1 at room temperature in the chromium-doped material.Haciendo uso de la química sol-gel, se han preparado ortofosfatos de composición LiTi2(PO43 y Li1.05(Cr/Fe0.05Ti1.95(PO43 a temperaturas moderadas mediante el método Pechini. Estas fases han sido caracterizadas estructural y microestructuralmente por difracción de rayos X de polvo y microscopía electrónica de barrido (SEM, encontrándose que todas cristalizan en una estructura tipo NASICON, con parámetros de red muy similares. El dopaje con Fe y Cr permite aumentar la densidad de las muestras en la sinterización, mejorando de forma apreciable su conductividad iónica. Se ha observado un incremento de hasta cuatro órdenes de magnitud en la conductividad a temperatura ambiente obteniéndose una energía de activación de 0.29 eV para el material dopado con Cr.

First-principles determination of the Raman fingerprint of rhombohedral graphite

Science.gov (United States)

Torche, Abderrezak; Mauri, Francesco; Charlier, Jean-Christophe; Calandra, Matteo

2017-09-01

Multilayer graphene with rhombohedral stacking is a promising carbon phase possibly displaying correlated states like magnetism or superconductivity due to the occurrence of a flat surface band at the Fermi level. Recently, flakes of thickness up to 17 layers were tentatively attributed to ABC sequences although the Raman fingerprint of rhombohedral multilayer graphene is currently unknown and the 2D resonant Raman spectrum of Bernal graphite is not understood. We provide a first principles description of the 2D Raman peak in three and four layers graphene (all stackings) as well as in Bernal, rhombohedral, and an alternation of Bernal and rhombohedral graphite. We give practical prescriptions to identify long range sequences of ABC multilayer graphene. Our work is a prerequisite to experimental nondestructive identification and synthesis of rhombohedral graphite.

Thermal expansion of NZP-family alkali-metal (Na, K) zirconium phosphates

International Nuclear Information System (INIS)

Orlova, A.I.; Kemenov, D.V.; Pet'kov, V.I.; Samojlov, S.G.; Kazantsev, G.N.

2000-01-01

By means of high-temperature X-ray diffraction one investigated into thermal expansion of alkali-zirconium phosphates crystallizing in NaZr 2 (PO 4 ) 3 structure type within 20-700 deg C temperature range. One synthesized phosphates of A x Zr 2.25-0.25x (PO 4 ) 3 type two series where A-Na (x = 0.5; 1.0; 2.0; 3.0; 4.0; 5.0) and K (x = 1.0; 3.0; 5.0). One calculated for them a and c parameters of the elementary cells and α a and α c linear expansion temperature coefficients. Anisotropy of thermal expansion the maximum one for AZr 2 (PO 4 ) 3 and Na 5 Zr(PO 4 ) 3 phosphates was determined. K 5 Zr(PO 4 ) 3 compound was characterized by the minimum thermal expansion at the near-zero anisotropy of Na 5 Zr(PO 4 ) 3 [ru

Crystal structure of Na3Sc2(PO4)3 at 60 deg C

International Nuclear Information System (INIS)

Lazoryak, B.I.; Kalinin, V.B.; Stefanovich, S.Yu.; Efremov, V.A.

1980-01-01

The structure of the ferroelectric phase of Na 3 Sc 2 (PO 4 ) 3 compound was studied. Na 3 Sc 2 (PO 4 ) 3 monocrystal heated by a jet of warm N 2 was investigated at 60 deg C. The rhombohedron modification was determined: a=8.927(3), c=22.34(4) A, Z=6, space group R anti 3c. Interatomic distances and inner angles of polyhedrons in Na 3 Sc 2 (PO 4 ) 3 structure were determined

Biochar produced from oak sawdust by Lanthanum (La)-involved pyrolysis for adsorption of ammonium (NH4(+)), nitrate (NO3(-)), and phosphate (PO4(3-)).

Science.gov (United States)

Wang, Zhanghong; Guo, Haiyan; Shen, Fei; Yang, Gang; Zhang, Yanzong; Zeng, Yongmei; Wang, Lilin; Xiao, Hong; Deng, Shihuai

2015-01-01

A series of biochars were prepared by pyrolyzing oak sawdust with/without LaCl3 involvement at temperature of 300-600 °C, and approximate and ultimate analyses were carried out to check their basic characteristics. Meanwhile, the releases of readily soluble NH4(+), NO3(-) and PO4(3-) from biochars and the adsorption of NH4(+), NO3(-) and PO4(3-) by biochars were investigated. Results indicated that the involvement of LaCl3 in pyrolysis could advance the temperature of maximum mass loss by 10 °C compared with oak sawdust (CK), and potentially promoted biochar yield. Overall, the releases of readily soluble NH4(+), NO3(-) and PO4(3-) from biochars were negatively related to pyrolysis temperature, and the releases were greatly weakened by La-biochars. Additionally, the adsorption to NH4(+) can be promoted by the biochars produced at low temperature. On the contrary, the NO3(-) adsorption can be improved by increasing pyrolysis temperature. The highest PO4(3-) adsorption was achieved by the biochars produced at 500 °C. According to the results of adsorption isotherms, the maximum adsorption capacity of NH4(+), NO3(-) and PO4(3-) can be significantly promoted by 1.9, 11.2, and 4.5 folds using La-biochars. Based on the observations of FT-IR, SEM-EDS, and surface functional groups, the improvement of NH4(+) adsorption was potentially associated with the existing acidic function groups (phenolic-OH and carboxyl C=O). The increased basic functional groups on La-biochars were beneficial to improve NO3(-) and PO4(3-) adsorption. Besides, PO4(3-) adsorption was also potentially related to the formed La2O3. Copyright © 2014 Elsevier Ltd. All rights reserved.

NaTi2(PO4)3 as an Aqueous Anode: Degradation Mechanisms and Mitigation Techniques

Science.gov (United States)

Mohamed, Alexander I.

With the proliferation of renewable energy sources, there has been a growing interest in battery chemistries for grid scale energy storage. Aqueous sodium ion batteries are particularly interesting for large scale energy storage because of their low cost and high safety, however, they tend to show poor long term stability. NaTi2(PO4)3 (NTP) shows promise as an anode for these systems with excellent long term stability when cycled quickly. When cycled slowly, NaTi2(PO4) 3 shows rapid capacity fade. The reasons for this rate depend capacity fade is poorly understood and is the topic of this document. It has been found that the products of the hydrogen evolution reaction, H2(g) and OH-, are the two largest contributors to capacity fade. High electrolyte pH caused by generation of OH- promotes dissolution of NTP during extend cycling, this is exacerbated when the pH increase above 11. The single greatest cause of apparent capacity fade for this material is loss of electrochemical surface area due to hydrogen gas entrapment within the porous structure of the electrode. Capacity lost in this manner can be recovered through reinfiltration of the electrode. The detrimental effects of gas entrapment within the electrode can be partially mitigated through compositing of the electrode with activated carbon and enhancing the wettability of the pores through addition of a surfactant to the electrolyte.

Luminescence properties and energy transfer investigations of Sr_3Lu(PO_4)_3:Ce"3"+, Tb"3"+ phosphors

International Nuclear Information System (INIS)

Yang, Zaifa; Xu, Denghui; Sun, Jiayue; Du, Jiangnan; Gao, Xuedong

2016-01-01

Highlights: • A phosphor Sr_3Lu(PO_4)_3:Ce"3"+, Tb"3"+ for UV-based white LEDs was firstly synthesized successfully. • The phase structure and photoluminescence properties of samples were studied in detail. • The energy transfer process from Ce"3"+ to Tb"3"+ ions was illustrated in detail. • Sr_3Lu(PO_4)_3:Ce"3"+, Tb"3"+ phosphor has potential applications as an UV-convertible phosphor for white light emitting diodes. - Abstract: A series of Ce"3"+ or Tb"3"+ doped and Ce"3"+/Tb"3"+ co-doped Sr_3Lu(PO_4)_3 phosphors were prepared via the conventional high temperature solid-state reaction. The phase structure, photoluminescence and energy transfer properties of samples were studied in detail. The optimal proportion of Ce"3"+ single doping is 4 mol% with maximal fluorescence intensity. The Sr_3Lu(PO_4)_3:Ce"3"+, Tb"3"+ phosphor shows both a blue emission (428 nm) from Ce"3"+ and a yellowish-green emission (545 nm) from Tb"3"+ with considerable intensity under ultraviolet (UV) excitation (268 nm). The energy transfer from Ce"3"+ to Tb"3"+ ions takes place in the Sr_3Lu(PO_4)_3:Ce"3"+, Tb"3"+ phosphor on the basis of the analysis of the luminescence spectra. The energy transfer mechanism from Ce"3"+ to Tb"3"+ ions was proved to be dipole–dipole interaction. The energy transfer behaviors in Sr_3Lu(PO_4)_3:Ce"3"+, Tb"3"+ phosphor is also investigated by the lifetime measurement. The results show that this phosphor has potential applications for UV white-light LEDs.

Synthesis, characterization and application of Li3Fe2(PO4)3 nanoparticles as cathode of lithium-ion rechargeable batteries

Science.gov (United States)

Karami, Hassan; Taala, Foroozandeh

2011-08-01

This work introduces a new method to synthesize Li3Fe2(PO4)3 nanoparticles in the nanopowder form and study its electrochemical performance by cyclic voltammetry and battery tests. Li3Fe2(PO4)3 is synthesized by the gel combustion method based on polyvinyl alcohol (PVA) as gel making agent. The optimum conditions of the synthesis include 8 wt% PVA, 0.34 wt% lithium slat, 1 wt% iron salt, 0.57 wt% ammonium dihydrogen phosphate, ethanol-water 50:50 as solvent, 675 °C combustion temperature and 4 h combustion time. Characterization of the samples is performed by the scanning electron microscopy (SEM), transmission electron microscopy (TEM), EDX analysis, XRD patterns, BET specific surface area and DSL size distribution. In the optimum conditions, a nanopowder is obtained that consisting of uniform nanoparticles with an average diameter of 70 nm. The optimized sample shows 12.5 m2 g-1 specific surface areas. Cyclic voltammetry (CV) studies show that the synthesized compound has good reversibility and high cyclic stability. The CV results are confirmed by the battery tests. The obtained results show that the synthesized cathodic material has high practical discharge capacity (average 125.5 mAh g-1 approximately same with its theoretical capacity 128.2 mA h-1) and long cycle life.

Ferroelasticity in palmierite-type(1  -  x)Pb3(PO4)2 - xPb3(AsO4)2

Science.gov (United States)

Bismayer, Ulli; Mihailova, Boriana; Angel, Ross

2017-06-01

Lead phosphate-arsenate Pb3(P1-x As x O4)2 undergoes an improper ferroelastic phase transition from a rhombohedral paraphase R\\bar{3}m to a monoclinic ferrophase C2/c leading to distinct twin boundary patterns. On cooling compounds with x larger than 0.8 undergo further transitions to monoclinic low-temperature phases, whereas the composition with x  =  0.8 shows order-parameter coupling phenomena. The transformation R\\bar{3}m -C2/c was described on the basis of a three-state Potts model and the existence of precursors of monoclinic clusters in the rhombohedral paraphase. The system is one of the best studied improper ferroelastics. Due to its two-mode phonon behaviour the solid solution exhibits multistep temperature- as well as pressure-driven structural transformations with different length and time scales. Relevant investigations and findings of this palmierite-type material have been made by Prof E K H Salje. Some of the most prominent results from x-ray diffraction, optical microscopy and Raman scattering are reviewed, and the potential implications for domain-wall structures and engineering are discussed.

Touching the theoretical capacity: synthesizing cubic LiTi2(PO4)3/C nanocomposites for high-performance lithium-ion battery.

Science.gov (United States)

Deng, Wenjun; Wang, Xusheng; Liu, Chunyi; Li, Chang; Xue, Mianqi; Li, Rui; Pan, Feng

2018-04-05

A cubic LiTi2(PO4)3/C composite is successfully prepared via a simple solvothermal method and further glucose-pyrolysis treatment. The as-fabricated LTP/C material delivers an ultra-high reversible capacity of 144 mA h g-1 at 0.2C rate, which is the highest ever reported, and shows considerable performance improvement compared with before. Combining this with the stable cycling performance and high rate capability, such material has a promising future in practical application.

Hexagonal perovskites with cationic vacancies. 15. Ba/sub 9/Nb/sub 6/Wvacant/sub 2/O/sub 27/ - the first perovskite stacking polytype of rhombohedral 27 L-type

Energy Technology Data Exchange (ETDEWEB)

Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1980-02-01

The perovskite stacking polytype Ba/sub 9/Nb/sub 6/sup(V)Wsup(VI)vacant/sub 2/O/sub 27/ (white) is the first representative of a rhombohedral 27 L-type. The lattice parameters (trigonal setting) are: a = 5.79/sub 3/ A; c = 63.4/sub 1/ A; Z = 3 (rhosub(exp) = 6.4/sub 6/ g/cm/sup 3/; rhosub(calc) = 6.51/sub 2/ g/cm/sup 3/). The corresponding Tasup(V)-compound is isotypic; it tends to develop stacking faults.

Hexagonal perovskites with cationic vacancies. 14. The rhombohedral 12 L-stacking polytypes Ba/sub 2/La/sub 2/Bsup(II)(W/sub 2/sup(VI)vacantO/sub 12/)

Energy Technology Data Exchange (ETDEWEB)

Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1980-02-01

Rhombohedral 12 L-stacking polytypes with cationic vacancies of type Ba/sub 2/La/sub 2/Bsup(II)(W/sub 2/sup(VI)vacantO/sub 12/) are reported for Bsup(II) = Mg, Zn (white), Ni (light brown) and Co (brown). For Bsup(II) = Cu, as a consequence of the Jahn Teller effect, a triclinic distorted lattice is observed.

Enhanced Coagulation-Flocculation Performance of Iron-Based Coagulants: Effects of PO4(3-) and SiO3(2-) Modifiers.

Science.gov (United States)

Chen, Wei; Zheng, Huaili; Teng, Houkai; Wang, Yili; Zhang, Yuxin; Zhao, Chuanliang; Liao, Yong

2015-01-01

PO4(3-) and SiO3(2-) are often used as modifier to improve stability and aggregating ability of the iron-base coagulants, however, there are few reports about their detailed comparison between the coagulation performance and mechanisms. In this study, three coagulants--polyferric phosphoric sulfate (PFPS), polysilicon ferric sulfate (PFSS), and polyferric sulfate (PFS) were synthesized; their structure and morphology were characterized by Fourier transformed infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) and Scanning electron microscope (SEM). Alkali titration and Ferron species analysis were employed to investigate the hydrolysis performance and species distribution. Jar test was conducted to measure their coagulation behaviors at different dosage, pH, and temperatures in which the flocs properties were measured. The results showed that a number of new compounds were formed due to the presence of PO4(3-) and SiO3(2-). Moreover, PFPS and PFSS had similar level in Fea as well as Feb. Among them, PFPS produced more multi-core iron atoms polymer and content of Feb, and the formed flocs were larger and denser. It exhibited superior coagulation performance in terms of turbidity reduction, UV254 removal and residual ferric concentration. Jar test and floc breakage/regrowth experiments indicated other than charge neutrality, the dominated mechanism involved in PFSS was the adsorption between polysilicic acid and solution particle, while PFPS was sweeping, entrapment/adsorption resulting from larger polymer colloid of Fe-P chemistry bond.

Enhanced Coagulation-Flocculation Performance of Iron-Based Coagulants: Effects of PO4(3- and SiO3(2- Modifiers.

Directory of Open Access Journals (Sweden)

Wei Chen

Full Text Available PO4(3- and SiO3(2- are often used as modifier to improve stability and aggregating ability of the iron-base coagulants, however, there are few reports about their detailed comparison between the coagulation performance and mechanisms. In this study, three coagulants--polyferric phosphoric sulfate (PFPS, polysilicon ferric sulfate (PFSS, and polyferric sulfate (PFS were synthesized; their structure and morphology were characterized by Fourier transformed infrared (FT-IR spectroscopy, X-ray diffraction (XRD and Scanning electron microscope (SEM. Alkali titration and Ferron species analysis were employed to investigate the hydrolysis performance and species distribution. Jar test was conducted to measure their coagulation behaviors at different dosage, pH, and temperatures in which the flocs properties were measured. The results showed that a number of new compounds were formed due to the presence of PO4(3- and SiO3(2-. Moreover, PFPS and PFSS had similar level in Fea as well as Feb. Among them, PFPS produced more multi-core iron atoms polymer and content of Feb, and the formed flocs were larger and denser. It exhibited superior coagulation performance in terms of turbidity reduction, UV254 removal and residual ferric concentration. Jar test and floc breakage/regrowth experiments indicated other than charge neutrality, the dominated mechanism involved in PFSS was the adsorption between polysilicic acid and solution particle, while PFPS was sweeping, entrapment/adsorption resulting from larger polymer colloid of Fe-P chemistry bond.

The Ca(PO3)2-Sr(PO3)2 system

International Nuclear Information System (INIS)

Bukhalova, G.A.; Tokman, I.A.

1977-01-01

Phase diagram of the system Ca(PO 3 ) 2 -Sr(PO 3 ) 2 has been studied and plotted with the aid of differential thermal, visual polythermal, X-ray analysis, and infrared spectroscopy. Continuous solid solutions are formed in the system with a minimum at 968 deg C and 25 mol.% of Sr(PO 3 ) 2 . Solid solutions decompose with the formation of about 30 mol.% of Sr(PO 3 ) 2

Advanced LiTi2(PO4)3@N-doped carbon anode for aqueous lithium ion batteries

International Nuclear Information System (INIS)

He, Zhangxing; Jiang, Yingqiao; Meng, Wei; Zhu, Jing; Liu, Yang; Dai, Lei; Wang, Ling

2016-01-01

Highlights: • LiTi 2 (PO 4 ) 3 @N-doped carbon anode was prepared by in-situ coating approach for aqueous lithium ion batteries. • The well-proportioned N-doped carbon layer and loose nanoporous structure was obtained using urea as nitrogen source and pore former. • LiTi 2 (PO 4 ) 3 @N-doped carbon demonstrates excellent rate performance and good cycling stability. - Abstract: In this paper, LiTi 2 (PO 4 ) 3 @N-doped carbon anode has been synthesized by in situ carbon coating approach. The well-proportioned N-doped carbon layer and loose nanoporous structure was obtained by using urea as nitrogen source and pore former. LiTi 2 (PO 4 ) 3 @N-doped carbon as anode demonstrates much better rate capability than LiTi 2 (PO 4 ) 3 @carbon in ALIBs. The optimized anode delivers the discharge capacity of 93.7 mAh g −1 and 74.2 mAh g −1 at rates of 10C and 20C, 22.5 mAh g −1 and 50.0 mAh g −1 larger than that of LiTi 2 (PO 4 ) 3 @carbon. Moreover, LiTi 2 (PO 4 ) 3 @N-doped carbon exhibits excellent cycling performance with capacity retention of 84.3% at 5C after 1000 cycles. As verified, the well-proportioned N-doped carbon layer could reduce charge transfer resistance and improve electrical conductivity. The loose nanoporous structure could shorten pathway and facilitate diffusion for Li ion. Therefore, LiTi 2 (PO 4 ) 3 @N-doped carbon gets the superior electrochemical properties benefiting from those two characteristics.

First-principles study on the structural, cohesive and electronic properties of rhombohedral Mo2B5 as compared with hexagonal MoB2

International Nuclear Information System (INIS)

Shein, I.R.; Shein, K.I.; Ivanovskii, A.L.

2007-01-01

The full-potential linearized augmented plane wave method using the generalized gradient approximation (FLAPW-GGA) has been applied to provide comparison and contrast for Mo borides with various structural types: rhombohedral Mo 2 B 5 versus hexagonal MoB 2 . The equilibrium lattice parameters, energies of formations, total and partial densities of states, electronic density distributions and the theoretical shapes of boron K-edge X-ray emission spectra are obtained and compared to available data

Efficient UV-emitting X-ray phosphors: octahedral Zr(PO4)6 luminescence centers in potassium hafnium-zirconium phosphates K2Hf1-xZrx(PO4)2 and KHf2(1-x)Zr2x(PO4)3

International Nuclear Information System (INIS)

Torardi, C.C.; Miao, C.R.; Li, J.

2003-01-01

Potassium hafnium-zirconium phosphates, K 2 Hf 1-x Zr x (PO 4 ) 2 and KHf 2(1-x) Zr 2x (PO 4 ) 3 , are broad-band UV-emitting phosphors. At room temperature, they have emission peak maxima at approximately 322 and 305 nm, respectively, under 30 kV peak molybdenum X-ray excitation. Both phosphors demonstrate luminescence efficiencies that make them up to ∼60% as bright as commercially available CaWO 4 Hi-Plus. The solid-state and flux synthesis conditions, and X-ray excited UV luminescence of these two phosphors are discussed. Even though the two compounds have different atomic structures, they contain zirconium in the same active luminescence environment as that found in highly efficient UV-emitting BaHf 1-x Zr x (PO 4 ) 2 . All the three materials have hafnium and zirconium in octahedral coordination via oxygen-atom corner sharing with six separate PO 4 tetrahedra. This octahedral Zr(PO 4 ) 6 moiety appears to be an important structural element for efficient X-ray excited luminescence, as are the edge-sharing octahedral TaO 6 chains for tantalate emission

Crystal structure of alluaudite-type Na4Co(MoO4)3.

Science.gov (United States)

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

2014-09-01

The title compound, tetra-sodium cobalt(II) tris-[molyb-date(IV)], was prepared by solid-state reactions. The structure is isotypic with Na3In2(AsO4)3 and Na3In2(PO4)3. The main structural feature is the presence of infinite chains of edge-sharing X 2O10 (X = Co/Na) dimers, which are linked by MoO4 tetra-hedra, forming a three-dimensional framework enclosing two types of hexa-gonal tunnels in which Na(+) cations reside. In this alluaudite structure, Co and Na atoms are located at the same general site with occupancies of 0.503 (5) and 0.497 (6), respectively. The other three Na and one of the two Mo atoms lie on special positions (site symmetries 2, -1, 2 and 2, respectively). The structure is compared with similar structures and other members of alluaudite family.

Li3V2(PO4)3/LiFePO4 composite hollow microspheres for wide voltage lithium ion batteries

International Nuclear Information System (INIS)

He, Wen; Wei, Chuanliang; Zhang, Xudong; Wang, Yaoyao; Liu, Qinze; Shen, Jianxing; Wang, Lianzhou; Yue, Yuanzheng

2016-01-01

Highlights: • Using yeast cells to control the in-situ growth of crystal particle. • Heterogeneous isomorphism nanocomposite hollow microspheres are synthesized. • The cathode exhibits a higher discharge capacity and energy density. - Abstract: Li 3 V 2 (PO 4 ) 3 (LVP)/LiFePO 4 (LVP) composite hollow microspheres (LVP/LFP-CHMs) for lithium-ion batteries have been synthesized by a combination method, using yeast cells as both structure templates and biocarbon source. The stable heterogeneous isomorphism solid solution with superlattice structure is formed in the joint of LVP and LFP particles. A detailed analysis of the formation mechanism of solid solution with superlattice structure and the influences of different Fe:V mole ratios on the structure and electrochemical properties of composites are presented. When the LVP/LFP-CHMs with a Fe:V mole ratio of 1:3 were used as cathode material in coin cells with metallic Li as anode, the cell exhibits a discharge capacity of 221.5 mAh g −1 for 5 cycles and discharge specific energy of 682 Wh kg −1 at 0.1C in a wide voltage range (1.5–4.3 V). Its capacity is far higher than the capacity of unsubstituted LFP and LVP in the same wide voltage range. The energy density of this cell is about 4 times higher than that of modern commercial lithium-ion batteries (157 Wh kg −1 ). The wide voltage range not only increases the discharge capacity and energy density of cathode materials, but also could expand the range of its applications in electronic equipment.

Sol–gel synthesis and electrochemical properties of 9LiFePO4·Li3V2(PO4)3/C composite cathode material for lithium ion batteries

International Nuclear Information System (INIS)

Zhong Shengkui; Wu Ling; Liu Jiequn

2012-01-01

Highlights: ► Nano-sized 9LiFePO 4 ·Li 3 V 2 (PO 4 ) 3 /C powders are prepared by a sol–gel method. ► Mutual doping in 9LiFePO 4 ·Li 3 V 2 (PO 4 ) 3 /C can improve its electronic conductivity. ► The addition of Li 3 V 2 (PO 4 ) 3 can improve the ionic diffusivity of LiFePO 4 . ► LiFePO 4 , Li 3 V 2 (PO 4 ) 3 and LiFePO 4 –Li 3 V 2 (PO 4 ) 3 unit cells coexist in the composite. - Abstract: 9LiFePO 4 ·Li 3 V 2 (PO 4 ) 3 /C composite cathode material is prepared by a sol–gel method, using ferric citrate, V 2 O 5 , Li 2 CO 3 , NH 4 H 2 PO 4 and citric acid as raw materials. The composite material is composed of the olivine LiFePO 4 and monoclinic Li 3 V 2 (PO 4 ) 3 phases. XRD results indicate that most of the iron and vanadium in the raw materials tend to form the LiFePO 4 and Li 3 V 2 (PO 4 ) 3 phases, and only small amounts of Fe and V as the dopants enter into the lattice of Li 3 V 2 (PO 4 ) 3 and LiFePO 4 , respectively. The electronic conductivity and Li + diffusion coefficient of 9LiFePO 4 ·Li 3 V 2 (PO 4 ) 3 /C are 6.615 × 10 −3 S cm −1 and ∼10 −10 cm 2 s −1 , which are three orders of magnitude and one order of magnitude larger than those of the LiFePO 4 /C, respectively. The composite material shows a first discharge specific capacity of 131.3 mAh g −1 and capacity retention of 95.1% after 200 cycles at 10 C rate. Compared with the LiFePO 4 /C, its rate capability and cycle performance are both remarkably improved.

Combustion synthesized nanocrystalline Li3V2(PO4)3/C cathode for lithium-ion batteries

International Nuclear Information System (INIS)

Nathiya, K.; Bhuvaneswari, D.; Gangulibabu; Kalaiselvi, N.

2012-01-01

Graphical abstract: Nanocrystalline Li 3 V 2 (PO 4 ) 3 /C compound has been synthesized using a novel corn assisted combustion (CAC) method, wherein the composite prepared at 850 °C is found to exhibit superior physical and electrochemical properties than the one synthesized at 800 °C (Fig. 1). Despite the charge disproportionation of V 4+ and a possible solid solution behavior of Li 3 V 2 (PO 4 ) 3 cathode upon insertion and de-insertion of Li + ions, the structural stability of the same is appreciable, even with the extraction of third lithium at 4.6 V (Fig. 2). An appreciable specific capacity of 174 mAh g −1 with an excellent columbic efficiency (99%) and better capacity retention upon high rate applications have been exhibited by Li 3 V 2 (PO 4 ) 3 /C cathode, thus demonstrating the feasibility of CAC method in preparing the title compound to best suit with the needs of lithium battery applications. Display Omitted Highlights: ► Novel corn assisted combustion method has been used to synthesize Li 3 V 2 (PO 4 ) 3 /C. ► Corn is a cheap and eco benign combustible fuel to facilitate CAC synthesis. ► Li 3 V 2 (PO 4 ) 3 /C exhibits an appreciable specific capacity of 174 mAh g −1 (C/10 rate). ► Currently observed columbic efficiency of 99% is better than the reported behavior. ► Suitability of Li 3 V 2 (PO 4 ) 3 /C cathode up to 10C rate is demonstrated. -- Abstract: Nanocrystalline Li 3 V 2 (PO 4 ) 3 /C composite synthesized using a novel corn assisted combustion method at 850 °C exhibits superior physical and electrochemical properties than the one synthesized at 800 °C. Despite the charge disproportionation of V 4+ and a possible solid solution behavior of Li 3 V 2 (PO 4 ) 3 cathode upon insertion and extraction of Li + ions, the structural stability of the same is appreciable, even with the extraction of third lithium at 4.6 V. An appreciable specific capacity of 174 mAh g −1 and better capacity retention upon high rate applications have been

[Removal of PO4(3-) from solution, wastewater and seawater by modification and granulation magnesium and aluminium layered double hydroxide].

Science.gov (United States)

Xing, Kun; Wang, Hai-Zeng

2013-04-01

Powder layered double hydroxide of Mg-Al LDH were prepared by hydrothermal technology with 500 kg x batch(-1), modified and granulated (MG Mg-Al CLDH) by deposition method. After the modification and granulation, the fixed bed can not be accumulated and clogged by the adsorbents. The PO4(3-) is removed from aqueous solution, wastewater and seawater by MG Mg-Al CLDH with column experiments. It shows that MG Mg-Al CLDH is an effective adsorbent. After removal, the water quality can satisfy with the first degree of integrated wastewater discharge or seawater standards. The mechanism of removal PO4(3-) is ion exchange and 'memory effect'. The breakthrough adsorption capacity of PO4(3-) from solution is 13.49 mg x g(-1), more than 6 times higher than that by Mg-Al LDH without modification. The exhausted MG Mg-Al CLDH can be desorbed with 0.1 mol x L(-1) NaOH and 3 mol x L(-1) NaCl and regenerated with 25% MgCl2. The regeneration rate is 126.24%. The breakthrough curves are influenced by bed depth, flow rate, initial concentration and initial pH. The adsorption processes are controlled by film diffusion. When the initial concentration is as low as 0.38 micromol x L(-1), PO4(3-) can be removed from seawater to satisfy with the first degree of seawater quality. So this work is very useful for the practical application of Mg-Al LDH and the removal of phosphorus.

Neodymium-doped Sr5(PO4)3F and Sr5(VO4)3F

International Nuclear Information System (INIS)

Corker, D.L.; Nicholls, J.; Loutts, G.B.

1995-01-01

Neodymium-doped Sr 5 (PO 4 ) 3 F [neodymium strontium fluoride phosphate, (Nd,Sr) 5 (PO 4 ) 3 F] and neodymium-doped Sr 5 (VO 4 ) 3 F [neodymium strontium fluoride vanadate, (Nd,Sr) 5 (VO 4 ) 3 F] crystallize in space group P6 3 /m and are isostructural with calcium fluorophosphate, Ca 5 (PO 4 ) 3 F. There are two different Sr sites in Sr 5 (XO 4 ) 3 F, denoted Sr(1) and Sr(2). Using single-crystal X-ray diffraction the two structures were refined to R factors of 2.3 and 2.2%, respectively, showing that Nd is present at both Sr sites in (Sr,Nd) 5 (VO 4 ) 3 F but only at the Sr(2) site in (Sr,Nd) 5 (PO 4 ) 3 F. (orig.)

Collective modes in superconducting rhombohedral graphite

Energy Technology Data Exchange (ETDEWEB)

Kauppila, Ville [O.V. Lounasmaa Laboratory, Aalto University (Finland); Hyart, Timo; Heikkilae, Tero [University of Jyvaeskylae (Finland)

2015-07-01

Recently it was realized that coupling particles with a Dirac dispersion (such as electrons in graphene) can lead to a topologically protected state with flat band dispersion. Such a state could support superconductivity with unusually high critical temperatures. Perhaps the most promising way to realize such coupling in real materials is in the surface of rhombohedrally stacked graphite. We consider collective excitations (i.e. the Higgs modes) in surface superconducting rhombohedral graphite. We find two amplitude and two phase modes corresponding to the two surfaces of the graphite where the superconductivity lives. We calculate the dispersion of these modes. We also derive the Ginzburg-Landau theory for this material. We show that in superconducting rhombohedral graphite, the collective modes, unlike in conventional BCS superconductors, give a large contribution to thermodynamic properties of the material.

Crystal structures of Th(OH)PO4, U(OH)PO4 and Th2O(PO4)2. Condensation mechanism of M(IV)(OH)PO4 (M= Th, U) into M2O(PO4)2

International Nuclear Information System (INIS)

Dacheux, N.; Clavier, N.; Wallez, G.; Quarton, M.

2007-01-01

Three new crystal structures, isotypic with β-Zr 2 O(PO 4 ) 2 , have been resolved by the Rietveld method. All crystallize with an orthorhombic cell (S.G.: Cmca) with a = 7.1393(2) Angstroms, b = 9.2641(2) Angstroms, c 12.5262(4) Angstroms, V = 828.46(4) (Angstroms) 3 and Z = 8 for Th(OH)PO 4 ; a = 7.0100(2) Angstroms, b = 9.1200(2) Angstroms, c = 12.3665(3) Angstroms, V 790.60(4) (Angstroms) 3 and Z = 8 for U(OH)PO 4 ; a 7.1691(3) Angstroms, b 9.2388(4) Angstroms, c = 12.8204(7) Angstroms, V 849.15(7) (Angstroms) 3 and Z = 4 for Th 2 O(PO 4 ) 2 . By heating, the M(OH)PO 4 (M Th, U) compounds condense topotactically into M 2 O(PO 4 ) 2 , with a change of the environment of the tetravalent cation that lowers from 8 to 7 oxygen atoms. The lower stability of Th 2 O(PO 4 ) 2 compared to that of U 2 O(PO 4 ) 2 seems to result from this unusual environment for tetravalent thorium. (authors)

Neutron diffraction studies of the Na-ion battery electrode materials NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3}

Energy Technology Data Exchange (ETDEWEB)

Yahia, H. Ben [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, Qatar Foundation, P.O. Box 5825 Doha (Qatar); Essehli, R., E-mail: ressehli@qf.org.qa [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, Qatar Foundation, P.O. Box 5825 Doha (Qatar); Avdeev, M. [Australian Nuclear Science and Technology Organisation, New Illawarra Road, Lucas Heights NSW 2234 (Australia); Park, J-B.; Sun, Y-K. [Department of Energy Engineering Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul 133-791 (Korea, Republic of); Al-Maadeed, M.A. [Center for Advanced Materials (CAM), Qatar University, 2713 Doha (Qatar); Belharouak, I., E-mail: ibelharouak@qf.org.qa [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, Qatar Foundation, P.O. Box 5825 Doha (Qatar)

2016-06-15

The new compounds NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} were synthesized by sol-gel method and their crystal structures were determined by using neutron powder diffraction data. These compounds were characterized by galvanometric cycling and cyclic voltammetry. NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} crystallize with a stuffed α-CrPO{sub 4}-type structure. The structure consists of a 3D-framework made of octahedra and tetrahedra that are sharing corners and/or edges generating channels along [100] and [010], in which the sodium atoms are located. Of significance, in the structures of NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} a statistical disorder Ni{sup 2+}/Cr{sup 3+} was observed on both the 8g and 4a atomic positions, whereas in NaCoCr{sub 2}(PO{sub 4}){sub 3} the statistical disorder Co{sup 2+}/Cr{sup 3+} was only observed on the 8g atomic position. When tested as negative electrode materials, NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} delivered specific capacities of 352, 385, and 368 mA h g{sup −1}, respectively, which attests to the electrochemical activity of sodium in these compounds. - Highlights: • NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} were synthesized by sol-gel method. • The crystal structures were determined by using neutron powder diffraction data. • The three compounds crystallize with a stuffed α-CrPO{sub 4}-type structure. • The three compounds were tested as anodes in sodium-ion batteries. • Relatively high specific capacities were obtained for these compounds.

(PO_4)"3"− polyanions doped LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2: An ultrafast-rate, long-life and high-voltage cathode material for Li-ion rechargeable batteries

International Nuclear Information System (INIS)

Cong, Lina; Zhao, Qin; Wang, Zhao; Zhang, Yuhang; Wu, Xinglong; Zhang, Jingping; Wang, Rongshun; Xie, Haiming; Sun, Liqun

2016-01-01

Highlights: • LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2 layered structure is doped with (PO_4)"3"− polyanions. • Results confirm that (PO_4)"3"− influences MO_6 octahedral environment in LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2 lattice. • Charge–discharge properties are investigated under high voltage battery operation. • Cycling and rate performance of the doped materials is markedly enhanced. • Pre-cycling treatment inhibits microcracks at the grain boundaries at 4.7–2.8 V. - Abstract: Layered compounds LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2 have recently received much attention as they have been regarded as a promising cathode materials for industrial application. However, its fast energy density decay and poor rate performance which originate from structure disruption especially at high rate and high cut-off voltage limit its large-scale application. Here, a novel designed concept and facile method were firstly used to fabricate (PO_4)"3"− polyanions doped layered LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2 (LNMC-(PO_4) _0_._0_1_5-O_1_._9_4) structure, which could offer more stable high-voltage cycling performance and high rate capability. We attribute this improved performance to the robust P_t_e_t-O covalence, which will stabilize the oxygen close-packed structure during repeated cycling. Moreover, our stepwise pre-cycling treatments could effectively restrain the formation of micro-cracks and non-crystallization defects, and significantly improve cyclic durability with high charge voltage of 4.7V. The LNMC-(PO_4) _0_._0_1_5-O_1_._9_4 electrode can still delivers capacity retention of 81% after 200 cycles at a current density of 300mA g"−"1. The preliminary results reported here manifest that this novel-designed LNMC-(PO_4) _0_._0_1_5-O_1_._9_4 material represents an attractive alternative to ultrafast-rate, long-life and high-voltage electrode material for lithium ion batteries.

Characterization, Dissolution, and Solubility of Lead Hydroxypyromorphite [Pb5(PO43OH] at 25–45°C

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Yinian Zhu

2015-01-01

Full Text Available Dissolution of the hydroxypyromorphite [lead hydroxyapatite, Pb5(PO43OH] in HNO3 solution (pH = 2.00, ultrapure water (pH = 5.60, and NaOH solution (pH = 9.00 was experimentally studied at 25°C, 35°C, and 45°C. The XRD, FT-IR, and FE-SEM analyses indicated that the hydroxypyromorphite solids were observed to have indistinguishable change during dissolution. For the hydroxypyromorphite dissolution in aqueous acidic media at initial pH 2.00 and 25°C, the aqueous phosphate concentrations rose quickly and reached the peak values after 1 h dissolution, while the aqueous lead concentrations rose slowly and reached the peak values after 1440 h. The solution Pb/P molar ratio increased constantly from 1.10 to 1.65 near the stoichiometric ratio of 1.67 to 209.85~597.72 and then decreased to 74.76~237.26 for the dissolution at initial pH 2.00 and 25°C~45°C. The average Ksp values for Pb5(PO43OH were determined to be 10−80.77 (10−80.57−10−80.96 at 25°C, 10−80.65 (10−80.38−10−80.99 at 35°C, and 10−79.96 (10−79.38−10−80.71 at 45°C. From the obtained solubility data for the dissolution at initial pH 2.00 and 25°C, the Gibbs free energy of formation [ΔGfo] for Pb5(PO43OH was calculated to be −3796.71 kJ/mol (−3795.55~−3797.78 kJ/mol.

Vibrational spectroscopy of the phosphate mineral lazulite--(Mg, Fe)Al2(PO4)2·(OH)2 found in the Minas Gerais, Brazil.

Science.gov (United States)

Frost, Ray L; Xi, Yunfei; Beganovic, Martina; Belotti, Fernanda Maria; Scholz, Ricardo

2013-04-15

This research was done on lazulite samples from the Gentil mine, a lithium bearing pegmatite located in the municipality of Mendes Pimentel, Minas Gerais, Brazil. Chemical analysis was carried out by electron microprobe analysis and indicated a magnesium rich phase with partial substitution of iron. Traces of Ca and Mn, (which partially replaced Mg) were found. The calculated chemical formula of the studied sample is: (Mg0.88, Fe0.11)Al1.87(PO4)2.08(OH)2.02. The Raman spectrum of lazulite is dominated by an intense sharp band at 1060 cm(-1) assigned to PO stretching vibrations of of tetrahedral [PO4] clusters presents into the HPO4(2-) units. Two Raman bands at 1102 and 1137 cm(-1) are attributed to both the HOP and PO antisymmetric stretching vibrations. The two infrared bands at 997 and 1007 cm(-1) are attributed to the ν1PO4(3-) symmetric stretching modes. The intense bands at 1035, 1054, 1081, 1118 and 1154 cm(-1) are assigned to the ν3PO4(3-) antisymmetric stretching modes from both the HOP and tetrahedral [PO4] clusters. A set of Raman bands at 605, 613, 633 and 648 cm(-1) are assigned to the ν4 out of plane bending modes of the PO4, HPO4 and H2PO4 units. Raman bands observed at 414, 425, 460, and 479 cm(-1) are attributed to the ν2 tetrahedral PO4 clusters, HPO4 and H2PO4 bending modes. The intense Raman band at 3402 and the infrared band at 3403 cm(-1) are assigned to the stretching vibration of the OH units. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral lazulite to be understood. Copyright © 2013 Elsevier B.V. All rights reserved.

Crystal structure of a silver-, cobalt- and iron-based phosphate with an alluaudite-like structure: Ag1.655Co1.64Fe1.36(PO43

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Adam Bouraima

2017-06-01

Full Text Available The new silver-, cobalt- and iron-based phosphate, silver cobalt iron tris(orthophosphate, Ag1.655Co1.64Fe1.36(PO43, was synthesized by solid-state reactions. Its structure is isotypic to that of Na2Co2Fe(PO43, and belongs to the alluaudite family, with a partial cationic disorder, the AgI atoms being located on an inversion centre and twofold rotation axis sites (Wyckoff positions 4a and 4e, with partial occupancies of 0.885 (2 and 0.7688 (19, respectively. One of the two P atoms in the asymmetric unit completely fills one 4e site while the Co and Fe atoms fill another 4e site, with partial occupancies of 0.86 (5 and 0.14 (5, respectively. The remaining Co2+ and Fe3+ cations are distributed on a general position, 8f, in a 0.39 (4:0.61 (4 ratio. All O atoms and the other P atoms are in general positions. The structure is built up from zigzag chains of edge-sharing [MO6] (M = Fe/Co octahedra stacked parallel to [101]. These chains are linked together through PO4 tetrahedra, forming polyhedral sheets perpendicular to [010]. The resulting framework displays two types of channels running along [001], in which the AgI atoms (coordination number eight are located.

The system La(PO3)3-Ca(PO3)2-P2O5

International Nuclear Information System (INIS)

Jungowska, W.; Znamierowska, T.

1993-01-01

Ternary system La(PO 3 ) 3 -Ca(PO 3 ) 2 -P 2 O 5 has been studied by means of thermal and roentgenography analysis. The existence of single intermediate compound CaLa(PO 3 ) 5 has been observed. The phase diagrams for the ternary system as well as for two binary systems La(PO 3 ) 3 -Ca(PO 3 ) 2 and CaLa(PO 3 ) 5 -LaP 5 O 11 have been shown. 7 refs, 3 figs

Investigation of Hard Boron Rich Solids: Osmium Diboride and β-Rhombohedral Boron

Science.gov (United States)

Hebbache, M.; Živković, D.

Recently, we succeeded in synthesizing three osmium borides, i.e., OsB1.1, Os2B3 and OsB2. Up to date, almost nothing is known about the physical properties of these materials. Microhardness measurements show that OsB2 is extremely hard. Ab initio calculations show that it is due to formation of covalent bonds between boron atoms. OsB2 is also a low compressibility material. It can be used for hard coatings. The β-rhombohedral polymorph of boron is the second hardest elemental crystal (H ≈ 33 GPa). It is also very light and a p-type semiconductor. In early 1970s, it has been shown that the doping of boron with 3d transition elements enhances its hardness by about 25%. We predict that, in general, heavily doped samples MBx, with x ≤ 31 or equivalently a dopant concentration larger than 3.2 at.%, should be ultrahard, i.e., H > 43 GPa. The relevant dopants M are Al, Cu, Sc, Mn, Mg and Li. In addition to these properties, boron-rich materials have a very low volatility, a high chemical inertness and high melting point. They are suitable for applications under extreme conditions and thermoelectric equipment.

(Solid + liquid) phase equilibria of (Ca(H2PO2)2 + CaCl2 + H2O) and (Ca(H2PO2)2 + NaH2PO2 + H2O) ternary systems at T = 323.15 K

International Nuclear Information System (INIS)

Cao, Hong-yu; Zhou, Huan; Bai, Xiao-qin; Ma, Ruo-xin; Tan, Li-na; Wang, Jun-min

2016-01-01

Graphical abstract: Solubility diagram of the (Ca(H 2 PO 2 ) 2 + NaH 2 PO 2 + H 2 O) system at T = (323.15 and 298.15) K. - Highlights: • Phase diagrams of Ca 2+ -H 2 PO 2 − -Cl − -H 2 O, Ca 2+ -Na + -H 2 PO 2 − -H 2 O at 323.15 K were obtained. • Incompatible double salt of NaCa(H 2 PO 2 ) 3 in Ca 2+ -Na + -H 2 PO 2 − -H 2 O system was determined. • Density diagram of the corresponding liquid were simultaneously measured. - Abstract: Calcium hypophosphite has been widely used as an anti-corrosive agent, flame retardant, fertilizer, assistant for Ni electroless plating, and animal nutritional supplement. High purity calcium hypophosphite can be synthesized via the replacement reaction of sodium hypophosphite and calcium chloride. In this work, the (solid + liquid) phase equilibria of (Ca(H 2 PO 2 ) 2 + CaCl 2 + H 2 O) and (Ca(H 2 PO 2 ) 2 + NaH 2 PO 2 + H 2 O) ternary systems at T = 323.15 K were studied experimentally via the classical isothermal solubility equilibrium method, and the phase diagrams for these two systems were obtained. It was found that two solid salts of CaCl 2 ·2H 2 O and Ca(H 2 PO 2 ) 2 exist in the (Ca(H 2 PO 2 ) 2 + CaCl 2 + H 2 O) system, and three salts of Ca(H 2 PO 2 ) 2 , NaH 2 PO 2 ·H 2 O and one incompatible double salt, NaCa(H 2 PO 2 ) 3 occur in the (Ca(H 2 PO 2 ) 2 + NaH 2 PO 2 + H 2 O) system.

Crystal structures of lazulite-type oxidephosphates TiIIITiIV3O3(PO4)3 and MIII4TiIV27O24(PO4)24 (MIII=Ti, Cr, Fe)

International Nuclear Information System (INIS)

Schoeneborn, M.; Glaum, R.; Reinauer, F.

2008-01-01

Single crystals of the oxidephosphates Ti III Ti IV 3 O 3 (PO 4 ) 3 (black), Cr III 4 Ti IV 27 O 24 (PO 4 ) 24 (red-brown, transparent), and Fe III 4 Ti IV 27 O 24 (PO 4 ) 24 (brown) with edge-lengths up to 0.3 mm were grown by chemical vapour transport. The crystal structures of these orthorhombic members (space group F2dd ) of the lazulite/lipscombite structure family were refined from single-crystal data [Ti III Ti IV 3 O 3 (PO 4 ) 3 : Z=24, a=7.3261(9) A, b=22.166(5) A, c=39.239(8) A, R 1 =0.029, wR 2 =0.084, 6055 independent reflections, 301 variables; Cr III 4 Ti IV 27 O 24 (PO 4 ) 24 : Z=1, a=7.419(3) A, b=21.640(5) A, c=13.057(4) A, R 1 =0.037, wR 2 =0.097, 1524 independent reflections, 111 variables; Fe III 4 Ti IV 27 O 24 (PO 4 ) 24 : Z=1, a=7.4001(9) A, b=21.7503(2) A, c=12.775(3) A, R 1 =0.049, wR 2 =0.140, 1240 independent reflections, 112 variables). For Ti III Ti IV O 3 (PO 4 ) 3 a well-ordered structure built from dimers [Ti III,IV 2 O 9 ] and [Ti IV,IV 2 O 9 ] and phosphate tetrahedra is found. The metal sites in the crystal structures of Cr 4 Ti 27 O 24 (PO 4 ) 24 and Fe 4 Ti 27 O 24 (PO 4 ) 24 , consisting of dimers [M III Ti IV O 9 ] and [Ti IV,IV 2 O 9 ], monomeric [Ti IV O 6 ] octahedra, and phosphate tetrahedra, are heavily disordered. Site disorder, leading to partial occupancy of all octahedral voids of the parent lipscombite/lazulite structure, as well as splitting of the metal positions is observed. According to Guinier photographs Ti III 4 Ti IV 27 O 24 (PO 4 ) 24 (a=7.418(2) A, b=21.933(6) A, c=12.948(7) A) is isotypic to the oxidephosphates M III 4 Ti IV 27 O 24 (PO 4 ) 24 (M III : Cr, Fe). The UV/vis spectrum of Cr 4 Ti 27 O 24 (PO 4 ) 24 reveals a rather small ligand-field splitting Δ o =14,370 cm -1 and a very low nephelauxetic ratio β=0.72 for the chromophores [Cr III O 6 ] within the dimers [Cr III Ti IV O 9 ]. - Graphical abstract: Single crystals of the oxidephosphates Ti III Ti IV 3 O 3 (PO 4 ) 3 (black), Cr III 4 Ti IV 27 O

Blue photoluminescence and long lasting phosphorescence properties of a novel chloride phosphate phosphor: Sr5(PO4)3Cl:Eu2+

International Nuclear Information System (INIS)

Wu, Chuanqiang; Zhang, Jiachi; Feng, Pengfei; Duan, Yiming; Zhang, Zhiya; Wang, Yuhua

2014-01-01

A novel blue emitting long lasting phosphorescence phosphor Sr 5 (PO 4 ) 3 Cl:Eu 2+ is synthesized by solid state method at 1223 K in reducing atmosphere. The afterglow emission spectrum shows one broad band centered at 441 nm due to the 5d–4f transition of Eu 2+ at six coordinated Sr(II) sites and the color coordinates are calculated to be (0.149, 0.095) which is close to the light blue region. The excitation band is in 240–430 nm and partly overlaps the solar irradiation on Earth's surface. The long lasting phosphorescence of the optimal sample doping by 0.1 mol%Eu 2+ can be recorded for about 1040 s (0.32 mcd/m 2 ). Thermoluminescence shows that there are at least three types of traps corresponding to peaks at 340 K, 382 K, 500 K, respectively. The filling and fading experiments reveal that the traps in Sr 5 (PO 4 ) 3 Cl:Eu 2+ are independent. The shallow traps (340 K) essentially contribute to the visible long lasting phosphorescence, while the deep traps (382 K and 500 K) are proved to be very stable. Thus, the Sr 5 (PO 4 ) 3 Cl:Eu 2+ material shows potential applications as not only a long lasting phosphorescence phosphor, but also an optical storage material. -- Highlights: • The blue long lasting phosphorescence of Sr 5 (PO 4 ) 3 Cl:Eu 2+ is first reported. • Filling and fading experiments are carried out for revealing natures of traps. • The afterglow mechanism for independent traps of Sr 5 (PO 4 ) 3 Cl:Eu 2+ is proposed

Effect of Phosphate Salts (Na3PO4, Na2HPO4, and NaH2PO4) on Ag3PO4 Morphology for Photocatalytic Dye Degradation under Visible Light and Toxicity of the Degraded Dye Products

NARCIS (Netherlands)

Amornpitoksuk, P; Intarasuwan, K; Suwanboon, S; Baltrusaitis, Jonas

2013-01-01

Ag3PO4 was synthesized by the precipitation method using three different types of phosphate salts (Na3PO4, Na2HPO4, and NaH2PO4) as a precipitating agent. Hydrolysis of each phosphate salt gave a specific pH that affected the purity and morphology of the prepared Ag3PO4. The Ag3PO4 prepared from

On thermal expansion of RbD2PO4, CsH2PO4 and CsDrPO4 crystals

International Nuclear Information System (INIS)

Vlokh, O.G.; Shchur, Ya.I.; Klymiv, I.M.

1994-01-01

Thermal expansion of RbD 2 PO 4 , CsH 2 PO 4 , CsD 2 PO 4 crystals in a wide range of temperatures embracing points of phase transitions was studied. An explanation of anomalous behaviour of thermal expansion factor along directions b and c in the course of RbD 2 PO 4 transfer into intermediate phase was suggested. 10 refs., 4 figs

On the thermal stability of the copper-titanium-zirconium phosphate solid solution series: CuTi_2-xZr_x(PO₄)₃ (0 < x < 2) under air

DEFF Research Database (Denmark)

Warner, Terence Edwin; Skou, Eivind Morten

2011-01-01

The solid copper(I) electrolytes: CuTi2(PO4)3; CuTiZr(PO4)3; and CuZr2(PO4)3; were prepared as powders by high temperature synthesis and analysed by powder XRD. These materials were then annealed in air at 400 °C for 72 h. The results of powder XRD showed that the degree of oxidation under...

Transition from Endothermic to Exothermic Dissolution of Hydroxyapatite Ca5(PO43OH–Johnbaumite Ca5(AsO43OH Solid Solution Series at Temperatures Ranging from 5 to 65 °C

Directory of Open Access Journals (Sweden)

Bartosz Puzio

2018-06-01

Full Text Available Five crystalline members of the hydroxyapatite (HAP; Ca5(PO43OH–johnbaumite (JBM; Ca5(AsO43OH series were crystallized at alkaline pH from aqueous solutions and used in dissolution experiments at 5, 25, 45, and 65 °C. Equilibrium was established within three months. Dissolution was slightly incongruent, particularly at the high-P end of the series. For the first time, the Gibbs free energy of formation ΔGf0, enthalpy of formation ΔHf0, entropy of formation Sf0, and specific heat of formation Copf were determined for HAP–JBM solid solution series. Based on the dissolution reaction, Ca5(AsO4m(PO43−mOH = 5Ca2+(aq + mAsO43−(aq + (3 − mPO43−(aq + OH−(aq, their solubility product Ksp,298.15 was determined. Substitution of arsenic (As for phosphorus (P in the structure of apatite resulted in a linear increase in the value of Ksp: from HAP logKsp,298.15 = −57.90 ± 1.57 to JBM logKsp,298.15 = −39.22 ± 0.56. The temperature dependence of dissolution in this solid solution series is very specific; in the temperature range of 5 °C to 65 °C, the enthalpy of dissolution ΔHr varied around 0. For HAP, the dissolution reaction at 5 °C and 25 °C was endothermic, which transitioned at around 40 °C and became exothermic at 45 °C and 65 °C.

Li3-xNaxV2(PO4)3 (0≤x≤3): Possible anode materials for rechargeable lithium-ion batteries

International Nuclear Information System (INIS)

Wang, Pengfei; Shao, Lianyi; Qian, Shangshu; Yi, Ting-Feng; Yu, Haoxiang; Yan, Lei; Li, Peng; Lin, Xiaoting; Shui, Miao; Shu, Jie

2016-01-01

Highlights: • Li 3-x Na x V 2 (PO 4 ) 3 (0 ≤ x ≤ 3) series are firstly evaluated as anode materials. • Li 3-x Na x V 2 (PO 4 ) 3 anodes show lithium storage activity in 1.0–3.0 V. • The lithium storage capability of different Li 3-x Na x V 2 (PO 4 ) 3 is compared. • Structural reversibility of Li 3-x Na x V 2 (PO 4 ) 3 is studied by in-situ XRD. - Abstract: In this paper, a series of Li 3-x Na x V 2 (PO 4 ) 3 (0 ≤ x ≤ 3) are prepared by a solid state reaction and systematically evaluated as anode materials for lithium-ion batteries. Structural analysis shows that the phase structure of Li 3-x Na x V 2 (PO 4 ) 3 changes along with the evolution of Na content. Charge-discharge tests exhibit that Li 3 V 2 (PO 4 ) 3 shows the highest initial charge specific capacity as high as 88.3 mAh g −1 among all the seven samples, and the reversible capacity is kept at 68.3 mAh g −1 after 45 cycles, corresponding to 77.3% of the initial charge capacity. With increasing of Na content in Li 3-x Na x V 2 (PO 4 ) 3 , the as-obtained sample show poorer lithium storage capability than Li 3 V 2 (PO 4 ) 3 . As a result, Na 3 V 2 (PO 4 ) 3 shows the inferior cycling performance than other Li 3-x Na x V 2 (PO 4 ) 3 . It can only deliver a reversible capacity of 20.9 mAh g −1 after 45 cycles, corresponding to 45.9% of the initial charge capacity. In-situ X-ray diffraction observations demonstrate that the poor electrochemical property of Na 3 V 2 (PO 4 ) 3 anode is due to the irreversible structural evolution during charge-discharge process. Therefore, reducing the Na 3 V 2 (PO 4 ) 3 phase in as-obtained sample is a feasible route to improve the lithium storage capability of Li 3-x Na x V 2 (PO 4 ) 3 .

Synthesis and electrochemical properties of xLiMn0.9Fe0.1PO4·yLi3V2(PO4)3/C composite cathode materials for lithium–ion batteries

International Nuclear Information System (INIS)

Wu, Ling; Lu, JiaJia; Wei, Gui; Wang, Pengfei; Ding, Hao; Zheng, Junwei; Li, Xiaowei; Zhong, Shengkui

2014-01-01

Highlights: • xLiMn 0.9 Fe 0.1 PO4·yLi 3 V 2 (PO 4 ) 3 /C composites are prepared by a solid-state method. • The addition of Li 3 V 2 (PO 4 ) 3 can improve the properties of LiMn 0.9 Fe 0.1 PO 4 . • Mutual doping occurrs between the LiMn 0.9 Fe 0.1 PO 4 and Li 3 V 2 (PO 4 ) 3 phases. • 5LiMn 0.9 Fe 0.1 PO 4 ·Li 3 V 2 (PO 4 ) 3 /C shows the best electrochemical properties. - Abstract: The xLiMn 0.9 Fe 0.1 PO 4 ·yLi 3 V 2 (PO 4 ) 3 /C (x:y=1:0, 9:1 5:1, 3:1, 1:1 and 0:1) cathode materials are synthesized by a ball–milling and post–calcination method. XRD results reveal that the xLiMn 0.9 Fe 0.1 PO 4 ·yLi 3 V 2 (PO 4 ) 3 /C (x,y≠0) composites are composed of LiMn 0.9 Fe 0.1 PO 4 and Li 3 V 2 (PO 4 ) 3 phases, and no impurities are detected. In LiMn 0.9 Fe 0.1 PO 4 –Li 3 V 2 (PO 4 ) 3 system, most of the manganese, iron and vanadium elements in the raw materials tend to form the two major phases, and only small amounts of V, Mn and Fe as dopants enter into the lattice of LiMn 0.9 Fe 0.1 PO 4 and Li 3 V 2 (PO 4 ) 3 . Electrochemical tests show that the xLiMn 0.9 Fe 0.1 PO 4 ·yLi 3 V 2 (PO 4 ) 3 /C (x,y≠0) composites exhibit much better performance than the single LiMn 0.9 Fe 0.1 PO 4 /C. Among the samples, 5LiMn 0.9 Fe 0.1 PO 4 ·Li 3 V 2 (PO 4 ) 3 /C shows the best electrochemical performance. The sample delivers the specific capacities of 158.1, 140.7 and 100.2 mAh g −1 at 0.05, 1 and 4 C rates in the potential range of 2.5–4.5 V, and exhibits very long and flat discharge plateau around 4.0 V up to 1 C rate. The sample also shows good cycling performance at various C–rates

Thermodynamics, dielectric permittivity and phase diagrams of the Rb1-x(NH4xH2PO4 type proton glasses

Directory of Open Access Journals (Sweden)

S.I. Sorokov

2010-01-01

Full Text Available The cluster pseudospin model of proton glasses, which takes into account the energy levels of protons around the PO4 group, the long-range interactions between the hydrogen bonds, and an internal random deformational field is used to investigate thermodynamical characteristics, longitudinal and transverse dielectric permittivities of Rb1-x(ND4xD2PO4 and Rb1-x(NH4xH2AsO4 compounds. A review of experimental and theoretical works on the Rb1-x(NH4xH2PO4 type crystals is presented.

Energy transfer and color tunable emission in Tb3 +,Eu3 + co-doped Sr3LaNa(PO4)3F phosphors

Science.gov (United States)

Li, Shuo; Guo, Ning; Liang, Qimeng; Ding, Yu; Zhou, Huitao; Ouyang, Ruizhuo; Lü, Wei

2018-02-01

A group of color tunable Sr3LaNa(PO4)3F:Tb3 +,Eu3 + phosphors were prepared by conventional high temperature solid state method. The phase structures, luminescence properties, fluorescence lifetimes and energy transfer were investigated in detail. Under 369 nm excitation, owing to efficient energy transfer of Tb3 + → Eu3 +, the emission spectra both have green emission of Tb3 + and red emission of Eu3 +. An efficient energy transfer occur in Tb3 +, Eu3 + co-doped Sr3LaNa(PO4)3F phosphors. The most possible mechanism of energy transfer is dipole-dipole interaction by Dexter's theoretical model. The energy transfer of Tb3 + and Eu3 + was confirmed by the variations of emission and excitation spectra and Tb3 +/Eu3 + decay lifetimes in Sr3LaNa(PO4)3F:Tb3 +,Eu3 +. The color tone can tuned from yellowish-green through yellow and eventually to reddish-orange with fixed Tb3 + content by changing Eu3 + concentrations. The results show that the prepared Tb3 +, Eu3 + co-doped color tunable Sr3LaNa(PO4)3F phosphor can be used for white LED.

Mechanical and thermal-expansion characteristics of Ca10(PO46(OH2-Ca3(PO42 composites

Directory of Open Access Journals (Sweden)

Ruseska G.

2006-01-01

Full Text Available Three types of composites consisting of Ca10(PO46(OH2 and Ca3(PO42 with composition: 75% (wt Ca10(PO46(OH2: 25%(wt Ca3(PO42; 50%(wt Ca10(PO46(OH2: 50%(wtCa3(PO42 and 25 %(wt Ca10(PO46(OH2: 75%(wt Ca3(PO42 were the subject of our investigation. Sintered compacts were in thermal equilibrium, which was proved by the absence of hysteresis effect of the dependence ΔL/L=f(T during heating /cooling in the temperature interval 20-1000-200C. Sintered compacts with the previously mentioned composition possess 26-50% higher values of the E-modulus, G-modulus and K-modulus indicating the presence of a synergism effect. Several proposed model equations for predicting the thermal expansion coefficient in dependence of the thermal and elastic properties of the constitutive phases and their volume fractions, given by: Turner, Kerner, Tummala and Friedberg, Thomas and Taya, were used for making correlations between mechanical and thermal-expansion characteristics of the Ca10(PO46(OH2 - Ca3(PO42 composites. Application of the previously mentioned model equations to all kinds of composites leads to the conclusion that the experimentally obtained results for the thermal expansion coefficient are in an excellent agreement with the theoretical calculated values on account of the volume fraction of each constitutive phase and with all applied model equations, with a coefficient of correlation from 98.16-99.86 %.

Synthesis and electrochemical properties of Ti4+ doped Li3-xFe2-xTix(PO4)3/C cathode materials

International Nuclear Information System (INIS)

Liu Zhanqiang; Huang Fuqiang; Sun Junkang

2011-01-01

Highlights: → Li 3-x Fe 2-x Ti x (PO 4 ) 3 /C composite cathodes were prepared by ball-milling method. Ti-doping can improve the electrochemical property of Li 3 Fe 2 (PO 4 ) 3 . → The optimized doping level was found to be x = 0.2. → The second phase of LiTi 2 (PO 4 ) 3 will emerge if the doping level higher than 0.2. - Abstract: Li 3-x Fe 2-x Ti x (PO 4 ) 3 /C (x = 0-0.4) cathodes designed with Fe doped by Ti was studied. Both Li 3 Fe 2 (PO 4 ) 3 /C (x = 0) and Li 2.8 Fe 1.8 Ti 0.2 (PO 4 ) 3 /C (x = 0.2) possess two plateau potentials of Fe 3+ /Fe 2+ couple (around 2.8 V and 2.7 V vs. Li + /Li) upon discharge observed from galvanostatic charge/discharge and cyclic voltammetry. Li 2.8 Fe 1.8 Ti 0.2 (PO 4 ) 3 /C has higher reversibility and better capacity retention than that of the undoped Li 3 Fe 2 (PO 4 ) 3 /C. A much higher specific capacity of 122.3 mAh/g was obtained at C/20 in the first cycle, approaching the theoretical capacity of 128 mAh/g, and a capacity of 100.1 mAh/g was held at C/2 after the 20th cycle.

Co3(PO4)2·4H2O

Science.gov (United States)

Lee, Young Hoon; Clegg, Jack K.; Lindoy, Leonard F.; Lu, G. Q. Max; Park, Yu-Chul; Kim, Yang

2008-01-01

Single crystals of Co3(PO4)2·4H2O, tricobalt(II) bis­[ortho­phosphate(V)] tetra­hydrate, were obtained under hydro­thermal conditions. The title compound is isotypic with its zinc analogue Zn3(PO4)2·4H2O (mineral name hopeite) and contains two independent Co2+ cations. One Co2+ cation exhibits a slightly distorted tetra­hedral coordination, while the second, located on a mirror plane, has a distorted octa­hedral coordination environment. The tetra­hedrally coordinated Co2+ is bonded to four O atoms of four PO4 3− anions, whereas the six-coordinate Co2+ is cis-bonded to two phosphate groups and to four O atoms of four water mol­ecules (two of which are located on mirror planes), forming a framework structure. In addition, hydrogen bonds of the type O—H⋯O are present throughout the crystal structure. PMID:21200978

Investigation of the Na2(H2PO2)2 - Ba(H2PO2)2 - H2O Water-Salt Ternary System at Room Temperature

OpenAIRE

Erge, Hasan; Turan, Hakan; Kul, Ali Riza

2016-01-01

Objective: In this study, the solubility, density, conductivity and phase equilibria of the Na2(H2PO2)2-Ba(H2PO2)2-H2O ternary system located in the structure of the Na+, Ba2+, (H2PO2)-//H2O quaternary reciprocal water-salt system were investigated using physicochemical analysis methods. Material and Methods: Riedel-de Haen and Merck salts were used to investigate the solubility and phase equilibria of the Na2(H2PO2)2 -Ba(H2PO2)2-H2O ternary water–salt system at room temperature Res...

Synthesis and electrochemical properties of Co-doped Li3V2(PO4)3 cathode materials for lithium-ion batteries

International Nuclear Information System (INIS)

Kuang Quan; Zhao Yanming; An Xiaoning; Liu Jianmin; Dong Youzhong; Chen Ling

2010-01-01

Co-doped Li 3 V 2-x Co x (PO 4 ) 3 /C (x = 0.00, 0.03, 0.05, 0.10, 0.13 or 0.15) compounds were prepared via a solid-state reaction. The Rietveld refinement results indicated that single-phase Li 3 V 2-x Co x (PO 4 ) 3 /C (0 ≤ x ≤ 0.15) with a monoclinic structure was obtained. The X-ray photoelectron spectroscopy (XPS) analysis revealed that the cobalt is present in the +2 oxidation state in Li 3 V 2-x Co x (PO 4 ) 3 . XPS studies also revealed that V 4+ and V 3+ ions were present in the Co 2+ -doped system. The initial specific capacity decreased as the Co-doping content increased, increasing monotonically with Co content for x > 0.10. Differential capacity curves of Li 3 V 2-x Co x (PO 4 ) 3 /C compounds showed that the voltage peaks associated with the extraction of three Li + ions shifted to higher voltages with an increase in Co content, and when the Co 2+ -doping content reached 0.15, the peak positions returned to those of the unsubstituted Li 3 V 2 (PO 4 ) 3 phase. For the Li 3 V 1.85 Co 0.15 (PO 4 ) 3 /C compound, the initial capacity was 163.3 mAh/g (109.4% of the initial capacity of the undoped Li 3 V 2 (PO 4 ) 3 ) and 73.4% capacity retention was observed after 50 cycles at a 0.1 C charge/discharge rate. The doping of Co 2+ into V sites should be favorable for the structural stability of Li 3 V 2-x Co x (PO 4 ) 3 /C compounds and so moderate the volume changes (expansion/contraction) seen during the reversible Li + extraction/insertion, thus resulting in the improvement of cell cycling ability.

Accessing alkali-free NASICON-type compounds through mixed oxoanion sol–gel chemistry: Hydrogen titanium phosphate sulfate, H{sub 1−x}Ti{sub 2}(PO{sub 4}){sub 3−x}(SO{sub 4}){sub x} (x=0.5–1)

Energy Technology Data Exchange (ETDEWEB)

Mieritz, Daniel; Davidowski, Stephen K.; Seo, Dong-Kyun, E-mail: dseo@asu.edu

2016-10-15

We report a direct sol–gel synthesis and characterization of new proton-containing, rhombohedral NASICION-type titanium compounds with mixed phosphate and sulfate oxoanions. The synthetic conditions were established by utilizing peroxide ion as a decomposable and stabilizing ligand for titanyl ions in the presence of phosphates in a strong acidic medium. Thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), induction-coupled plasma optical emission spectroscopic (ICP-OES) elemental analysis, and Raman and {sup 1}H magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopic studies have determined the presence of sulfate and proton ions in the structure, for which the compositional range has been found to be H{sub 1−x}Ti{sub 2}(PO{sub 4}){sub 3−x}(SO{sub 4}){sub x} (x=0.5–1). The particulate products exhibit a nanocrystalline nature observed through characterization with scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The N{sub 2} sorption isotherm measurements and subsequent Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH) analyses confirmed the presence of the textural meso- and macropores in the materials. Future studies would determine the potential of the new compounds in various applications as battery materials, proton conductors and solid acid catalysts. - Graphical abstract: A series of proton-containing NASICON-type compounds, H{sub 1−x}Ti{sub 2}(PO{sub 4}){sub 3−x}(SO{sub 4}){sub x} (x=0.5–1), were discovered through a new sol–gel synthetic method that utilizes peroxide ion as a decomposable and stabilizing ligand for titanyl ions in the presence of phosphates in a strong acidic medium.

In vitro cell culture pO2 is significantly different from incubator pO2.

Science.gov (United States)

Bambrick, L L; Kostov, Y; Rao, G

2011-07-01

Continuous noninvasive monitoring of peri-cellular liquid phase pO2 in adherent cultures is described. For neurons and astrocytes, this approach demonstrates that there is a significant difference between predicted and observed liquid phase pO2. Particularly at low gas phase pO2s, cell metabolism shifts liquid phase pO2 significantly lower than would be predicted from the O2 gas/air equilibrium coefficient, indicating that the cellular oxygen uptake rate exceeds the oxygen diffusion rate. The results demonstrate the need for direct pO2 measurements at the peri-cellular level, and question the widely adopted current practice of relying on setting the incubator gas phase level as means of controlling pericellular oxygen tension, particularly in static culture systems that are oxygen mass transfer limited. Copyright © 2011 American Institute of Chemical Engineers (AIChE).

Synthesis and crystal structure of hydrogen phosphites RbH2PO3, CsH2PO3, and TlH2PO3

International Nuclear Information System (INIS)

Kosterina, E.V.; Troyanov, S.I.; Kemnits, Eh.; Aslanov, L.A.

2001-01-01

The crystal acid phosphites RbH 2 PO 3 , CsH 2 PO 3 and TlH 2 PO 3 were separated during reaction of Rb, Cs and Tl carbonates with phosphorous acid solution. The crystal structure of the compounds was analyzed by X-ray diffraction method at 150 K. CsH 2 PO 3 has a monoclinic system, a = 7.930(2), b = 8.929(2), c = 13.163(3) A, β = 104.84(3) Deg, V = 900.9(4) A 3 , Z 8, sp. gr. P2 1 /c, R 1 = 0.239. In the structure hydrogen bonds integrate the PHO 3 tetrahedrons in the unlimited zigzag chains [HPHO 3 ] n n- laying at the layers, which are alternate to the layers of metal cations. The layers of anion chains have a wavy form [ru

A multifunctional fluorescence sensor for Cd2+, PO43- and Cr3+ in different system and the practical application.

Science.gov (United States)

Wang, Qingming; Tan, Yingzi; Wang, Nianhua; Lu, Zhixiang; Wang, Wenling

2018-05-07

A fluorescence probe based on thiosemicarbazide has been synthesized and well characterized by 1 H NMR, 13 C NMR, Elemental analysis, Electrospray ionization mass spectra. The probe 1 functions as a multitarget ion sensor, detect biologically and ecologically important Cd 2+ , PO 4 3- and Cr 3+ . Meanwhile, probe 1 displays selectivity for Cd 2+ over other metal ions and anions in DMF by emission spectrum. Interestingly, probe 1 has been explored to recognize PO 4 3- in CH 3 OH-H 2 O (v:v = 1:9). The binding stoichiometry of probe 1 with Cd 2+ and PO 4 3- are 2:1 and 1:1, respectively, which are confirmed by Electrospray ionization mass spectra. Probe 1 is selective, sensitive and reversibility/reusability to Cd 2+ and PO 4 3- with the detection limit as low as 0.035 μM and 0.011 μM respectively. Besides, the designed probe 1 has shown potential applications in the area of photo-printing. Copyright © 2018. Published by Elsevier B.V.

Conductivity And Thermal Stability of Solid Acid Composites CsH2PO4 /NaH2PO4/ SiO2

International Nuclear Information System (INIS)

Norsyahida Mohammad; Abu Bakar Mohamad; Abu Bakar Mohamad; Abdul Amir Hassan Kadhum

2016-01-01

Solid acid composites CsH 2 PO 4 / NaH 2 PO 4 / SiO 2 with different mole ratios of CsH 2 PO 4 and NaH 2 PO 4 to SiO 2 were synthesized and characterized. Preliminary infrared measurements of CsH 2 PO 4 and its composites indicated that hydrogen bonds breaking and formation were detected between 1710 to 2710 cm -1 , while the rotation of phosphate tetrahedral anions occurred between 900 and 1200 cm -1 . The superprotonic transition of CsH 2 PO 4 / NaH 2 PO 4 / SiO 2 composite was identified at superprotonic temperatures between 230 and 260 degree Celcius, under atmospheric pressure. This study reveals higher conductivity values for composites with higher CsH 2 PO 4 (CDP) content. Solid acid composite CDP 613 appeared as the composite with the highest conductivity that is 7.2x10 -3 S cm -1 at 230 degree Celcius. Thermal stability of the solid acid composites such as temperature of dehydration, melting and decomposition were investigated. The addition of NaH 2 PO 4 lowers the dehydration temperature of the solid acid composites. (author)

Neutralization of Na2PO4: Reaction between Na3PO4 and CaCL2

International Nuclear Information System (INIS)

Xia Shenglan; Wang Luning

1990-01-01

The results of reaction Na 3 PO 4 with CaCl 2 in water at ambient and higher temperature are described. The reaction rate of Na 3 PO 4 with CaCl 2 is slow at ambient temperature and the reaction is complete at 260 deg C after 2 h. The products are Ca(OH) 2 and Ca 5 (PO 4 ) 3 (OH). The quantity of them is dependent upon the quanity of Na 3 PO 4 and CaCl 2 contained in water, all of them control pH of water

Sheet-like Li3V2(PO4)3 nanocomposite coated by SiO2 + C with better electrochemical properties for lithium-ion batteries

International Nuclear Information System (INIS)

Lai, Chunyan; Wu, Tingting; Wang, Zhen

2016-01-01

Sheet-like Li 3 V 2 (PO 4 ) 3 nanocomposite coated by SiO 2  + C layer was synthesized with one-step solid-state method. Dihydroxydiphenylsilane (DPSD) was used as the source of SiO 2 and C. The sheet-like Li 3 V 2 (PO 4 ) 3 nanocomposite has a thickness in the range of 20–30 nm. Because of the SiO 2  + C-coated layer and the sheet-like morphology, the Li 3 V 2 (PO 4 ) 3 /(SiO 2  + C) composites show better stability and higher capacity than pure Li 3 V 2 (PO 4 ) 3 material and granular Li 3 V 2 (PO 4 ) 3 /(SiO 2  + C) composites. The best sample, Li 3 V 2 (PO 4 ) 3 /(SiO 2  + C)(2:8), shows a discharge capacity of 193.7 mAh g −1 at 1C within the voltage range of 3.0–4.8 V and retains almost 90 % of the capacity after 50 cycles.

pO2 measurements in arteriolar networks.

Science.gov (United States)

Torres Filho, I P; Kerger, H; Intaglietta, M

1996-03-01

Previous studies from our laboratory have shown that the average arteriolar pO2 in the hamster skinfold preparation is lower than arterial systemic pO2. In the present work we tested the hypothesis that there is a longitudinal gradient of pO2 along precapillary vessels. Experiments were performed in Syrian golden hamsters bearing a dorsal skin chamber. The oxygen-dependent quenching of phosphorescence of palladium-porphyrin complexes was used to measure intravascular pO2 in the microcirculation. Arterioles were classified in four orders according to their position in the network, first-order vessels being the entrance points. Simultaneous determinations of diameter (D), red blood cell velocity, and systemic blood gases were also made. There was a significant fall of pO2 between vessels of different orders. First-order arterioles (mean D = 64 microns) had pO2 of 51.8 +/- 9.8 mm Hg (mean +/- SD) which was equivalent to approximately equal to 73% of the arterial systemic pO2. Within the arteriolar network, further decreases of intravascular pO2 were measured, leading to a pO2 of 34.0 +/- 7.9 mm Hg in terminal arterioles (mean D = 7.7 microns). In some vessels pO2 was measured in different positions of the same arteriole. The average longitudinal arteriolar oxygen saturation gradient was 3.4 +/- 0.4 delta %/mm (range 0.8-7.2). A significant and positive correlation was found between pO2 and microhemodynamic parameters when arterioles were grouped according to their order. This relation was not significant for venules which showed a mean pO2 of 30.8 +/- 10.8 mm Hg. Tissue pO2 averaged 24.6 +/- 5.8 mm Hg. We conclude that: (1) There is an oxygen loss in arterial vessels larger than 100 micrograms in diameter, (2) arteriolar pO2 in this preparation depends on the position of the vessel within the network, (3) a substantial portion of oxygen delivery to the hamster skin is provided by the arteriolar network, and (4) only a small pO2 gradient exists between terminal

Photoluminescence properties of whitlockite-type Ca{sub 9}MgK(PO{sub 4}){sub 7}:Eu{sup 2+},Mn{sup 2+} phosphor

Energy Technology Data Exchange (ETDEWEB)

Guo, Ning, E-mail: guoning@usst.edu.cn [Department of Chemistry, University of Shanghai for Science and Technology, Shanghai 200093 (China); Li, Shuo; Chen, Jishen; Li, Jing; Zhao, Yuefeng; Wang, Lu; Jia, Chengzheng; Ouyang, Ruizhuo [Department of Chemistry, University of Shanghai for Science and Technology, Shanghai 200093 (China); Lü, Wei [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China)

2016-11-15

Novel single-phased Eu{sup 2+}/Mn{sup 2+}-coactivated whitlockite-type Ca{sub 9}MgK(PO{sub 4}){sub 7} phosphors which can emit white light upon UV light excitation, are prepared by the solid-state method, and their luminescence properties are systematically investigated via a combination of X-ray powder diffraction and spectroscopy measurements. For Eu{sup 2+}–Mn{sup 2+} codoped samples, an efficient energy transfer process can takes place and its mechanism is a resonant type via a dipole-quadrupole interaction which can be elucidated by DexterГ—Віs theoretical model. Following the principle of energy transfer, myriad luminescence colors with a large gamut from blue to purplish red and across white zone in a line in the chromaticity diagram of the CIE can be obtained by simply adjusting the concentration ratio of Eu{sup 2+} to Mn{sup 2+}. Photoluminescence spectra reveal that the white color emission is originated from the combination of two emission bands of Eu{sup 2+} and Mn{sup 2+} ions. Additionally, their CIE chromaticity coordinates and correlated color temperatures (CCT) have been calculated and discussed in detail. The luminescence suggest that whitlockite-type phosphor, Ca{sub 9}MgK(PO{sub 4}){sub 7}, co-activated with europium and manganese, is a promising single-phased white-emitting candidate for use in ultraviolet-chip-based white LEDs.

Single-phased white-light-emitting Sr3NaLa(PO4)3F: Eu2+,Mn2+ phosphor via energy transfer

International Nuclear Information System (INIS)

Shanshan, Hu; Wanjun, Tang

2014-01-01

Single-phased white-light-emitting Sr 3 NaLa(PO 4 ) 3 F:Eu 2+ ,Mn 2+ phosphor is synthesized via the combustion-assisted synthesis technique. Upon excitation of 344 nm ultraviolet (UV) light, two intense broad bands have clearly been obtained due to the allowed 5d–4f transition of Eu 2+ and the forbidden 4 T 1 − 6 A 1 transition of Mn 2+ , respectively. As a result of fine-tuning of the emission composition of the Eu 2+ and Mn 2+ ions, white-light emission can be realized by combining the emission of Eu 2+ and Mn 2+ in a single host lattice under UV light excitation. The obtained phosphor exhibits a strong excitation band between 250 and 420 nm, matching well with the dominant emission band of a UV light-emitting-diode (LED) chip, which could be a promising candidate for UV-converting white-light-emitting diodes (LEDs). -- Highlights: • Single-phased Sr 3 NaLa(PO 4 ) 3 F:Eu 2+ ,Mn 2+ phosphors are synthesized. • Sr 3 NaLa(PO 4 ) 3 F:Eu 2+ ,Mn 2+ shows a blue emission band and a yellow emission band. • White-emitting can be obtained by tuning the compositions of the Eu 2+ and Mn 2+

Optical and crystal chemistry studies of Na3Ln(PO4)2-K3Ln(PO4)2 (Ln=Eu, Gd)

International Nuclear Information System (INIS)

Mesnaoui, M.; Maazaz, M.

1987-01-01

In these systems, large single phase domains are separated by two phase regions. The structural evolution as a function of composition is analysed both by X-ray diffraction and by using Eu 3+ and Gd 3+ as luminescent local structural probes. Due to layer type structure of the K 3 Ln(PO 4 ) 2 phases an exchange reaction resulting in total substitution of sodium for potassium can be carried out with formation of metastable Na 3 Ln(PO 4 ) 2 phases, the structure of which is close to those of the potassium compounds. 10 refs.; 18 figs [fr

Complex phosphates in the Li(Na)3PO4-InPO4 systems

International Nuclear Information System (INIS)

Potapova, A.M.; Zimina, G.V.; Smirnova, I.N.; Novoselov, A.V.; Spiridonov, F.M.; Stefanovich, S.Yu.

2008-01-01

Subsolidus sections in the systems Li 3 PO 4 -InPO 4 (950 deg C) and Na 3 PO 4 -InPO 4 (800, 900, and 1000 deg C) have been studied by X-ray powder diffraction. The compound Li 3 In(PO 4 ) 2 has been synthesized, and the NASICON-type solid solution Li 3(1-x) In 2+x (PO 4 ) 3 (0.67 ≤ x ≤ 0.80) has been found to exist. In the system Na 3 PO 4 -InPO 4 , the solid solution Na 3(1-x) In x/3 PO 4 (0 ≤ x ≤ 0.2) and two complex phosphates exist: Na 3 In(PO 4 ) 2 and Na 3 In 2 (PO 4 ) 3 . These complex phosphates are dimorphic, with the irreversible-transition temperature equal to 675 and 820 deg C, respectively. Na 3 In(PO 4 ) 2 degrades at 920 deg C. Ionic conductivity has been measured in some phases in the system [ru

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)

Science.gov (United States)

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.

Superacid univalent metal phosphites (MH2PO3)2·H3PO3 (M Rb, Tl+) and MH2PO3·H3PO3 (M = K, Cs): synthesis and structure

International Nuclear Information System (INIS)

Kosterina, E.V.; Troyanov, S.I.; Aslanov, L.A.; Kemnits, Eh.

2001-01-01

Crystal superacid phosphites α-CsH 2 PO 3 ·H 3 PO 3 (1) and β-CsH 2 PO 3 ·H 3 PO 3 (2) were prepared by means of interaction between cesium carbonate and phosphoric acid excess. The structure of the compounds, i.e.: 1-rhombic crystal system, sp.gr. P2 1 2 1 2 1 , a = 6.033 (1), b = 6.444 (1), c = 18.345 (4) A: 2-monoclinic crystal system, sp.gr. C2/c, a = 9.990 (3), b = 12.197 (4), c = 6.866 (2) A, β = 118.14 (3) deg, was determined by the method of X-ray diffraction analysis of monocrystals at 150 K. Comparative analysis of the crystal structure and hydrogen bond systems in acid phosphites of different composition was conducted [ru

Enhanced apatite formation on Ti metal heated in PO2-controlled nitrogen atmosphere.

Science.gov (United States)

Hashimoto, Masami; Hayashi, Kazumi; Kitaoka, Satoshi

2013-10-01

The oxynitridation of biomedical titanium metal under a precisely regulated oxygen partial pressure (PO2) of 10(-14)Pa in nitrogen atmosphere at 973 K for 1 h strongly enhanced apatite formation compared with that on Ti heated in air. The factors governing the high apatite-forming ability are discussed from the viewpoint of the surface properties of Ti heated under a PO2 of 10(-14)Pa in nitrogen atmosphere determined from X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and zeta potential measurements. Nitrogen (N)-doped TiO2 (interstitial N) was formed on pure Ti heated under a PO2 of 10(-14)Pa in nitrogen atmosphere at 973 K. The XPS O1s main peak shifted toward a lower binding energy upon heating under a PO2 of 10(-14)Pa. This shift may be due to the formation of oxygen vacancies. This Ti surface had a positive zeta potential of approximately 20 mV. According to time-of-flight secondary ion mass spectroscopy results, PO4(3-) ions were predominantly adsorbed on Ti soaked in simulated body fluid (SBF) after heat treatment, followed by calcium ions. It was concluded that the apatite formation kinetics can be described using the Avrami-Erofeev equation with an Avrami index of n=2, which implies the instantaneous nucleation of apatite on the surface of Ti soaked in SBF after heat treatment at 973 K under a PO2 of 10(-14)Pa. Copyright © 2013 Elsevier B.V. All rights reserved.

Symmetry and topology code of the cluster self-assembly of framework MT structures of alumophosphates AlPO4(H2O)2 (metavariscite and variscite) and Al2(PO4)2(H2O)3 (APC)

Science.gov (United States)

Ilyushin, G. D.; Blatov, V. A.

2017-03-01

The supramolecular chemistry of alumophosphates, which form framework 3D MT structures from polyhedral AlO4(H2O)2 clusters with octahedral O coordination (of M polyhedra) and PO4 and AlO4 with tetrahedral O coordination (of T polyhedra), is considered. A combinatorial-topological modeling of the formation of possible types of linear (six types) and ring (two types) tetrapolyhedral cluster precursors M2T2 from MT monomers is carried out. Different versions of chain formation from linked (MT)2 rings (six types) are considered. The model, which has a universal character, has been used to simulate the cluster selfassembly of the crystal structure of AlPO4(H2O)2 minerals (metavariscite, m-VAR, and variscite, VAR) and zeolite [Al2(PO4)2(H2O)2] · H2O (APC). A tetrapolyhedral linear precursor is established for m-VAR and a ring precursor (MT)2 is established for VAR and APC. The symmetry and topology code of the processes of crystal structure self-assembly from cluster precursors is completely reconstructed. The functional role of the O-H···O hydrogen bonds is considered for the first time. The cluster self-assembly model explains the specific features of the morphogenesis of single crystals: m-VAR prisms, flattened VAR octahedra, and needleshaped APC square-base prisms.

CINETIQUE DES IONS PHOSPHORIQUES H2PO4- ET HPO4-2 EN MILIEU GYPSEUX

Directory of Open Access Journals (Sweden)

Hacène BOUZIANE

2011-06-01

Full Text Available L’étude de la fixation des ions H2PO4- et HPO4-2 par les divers types de gypse (tassé ; feuilleté ; fibreux. Donne une réaction positive quelle que soit la solution phosphaté et le type de gypse utilisé. Il convient de noter que l’adsorption est beaucoup plus forte pour les ions H2PO4- que celle des ions HPO4-2 et qu’elle varie d’un type de gypse à l’autre.                 L’étude de l’influence du temps, de la granulométrie et de la concentration des solutions montrent en effet que : plus le diamètre du grain est petit, plus l’adsorption est forte. La fixation se produit même pour une solution phosphatée à très faible concentration ; il se produit toujours une réaction avec précipitation et non un équilibre d’adsorption. La réaction des ions phosphatés augment rapidement dans les premières minutes quel que soit le type de gypse et la concentration utilisée. Nous avons abouti à la formation d’un gel phosphaté, visqueux et non soluble. L’analyse chimique de ce gel donne les résultats suivants : PO4=54,20% ,Ca=11,30% , K=32,94%; si l’on compare ces résultats avec les résultats calculés pour K3CaH,(PO42=PO4=54,59%, Ca=11,19%, K=33,62%, nos valeurs sont très voisines de celles-ci. Il s’agit donc du même sel sur lequel aucun travail sur la formation de K3CaH(PO42 à partir de CaSO42H2O ne semble avoir été publié.

Po2 temperature blood factor for blood gas apparatus.

Science.gov (United States)

Teisseire, B P; Hérigault, R A; Teisseire, L J; Laurent, D N

1984-01-01

PO2 temperature formulae supplied by manufacturers on automatic blood gas apparatus, PO2 corr. = PO2 37 degrees C X 10F X delta T were studied and compared to the experimental determination of the delta log PO2/delta T ratio (Hérigault et al. [10]). Acid-base status at 37 degrees C appeared to have a measurable influence on the PO2 temperature factor; alkalosis increased the delta log PO2/delta T ratio, and the contrary was found for acidosis in comparison with normal acid-base status at 37 degrees C. For the same PO2, measured at 37 degrees C, all the proposed formulae of commercial blood gas automatic apparatus did not give the same temperature corrected PO2. The observed difference between the corrected PO2 may be important and greater than the precision of the initial measurement. To correct the measured PO2 for temperature, a relationship between delta log PO2/delta T and PO2 is proposed, between PO2 zero and PO2 180 mmHg, which takes into account measured pH and PO2 values at 37 degrees C:delta log PO2/delta T = [(-0.35 pH + 0.658) X 10(-4) X PO2] + 0.035.

Synthesizing Porous NaTi2(PO4)3 Nanoparticles Embedded in 3D Graphene Networks for High-Rate and Long Cycle-Life Sodium Electrodes.

Science.gov (United States)

Wu, Chao; Kopold, Peter; Ding, Yuan-Li; van Aken, Peter A; Maier, Joachim; Yu, Yan

2015-06-23

Sodium ion batteries attract increasing attention for large-scale energy storage as a promising alternative to the lithium counterparts in view of low cost and abundant sodium source. However, the large ion radius of Na brings about a series of challenging thermodynamic and kinetic difficulties to the electrodes for sodium-storage, including low reversible capacity and low ion transport, as well as large volume change. To mitigate or even overcome the kinetic problems, we develop a self-assembly route to a novel architecture consisting of nanosized porous NASICON-type NaTi2(PO4)3 particles embedded in microsized 3D graphene network. Such architecture synergistically combines the advantages of a 3D graphene network and of 0D porous nanoparticles. It greatly increases the electron/ion transport kinetics and assures the electrode structure integrity, leading to attractive electrochemical performance as reflected by a high rate-capability (112 mAh g(-1) at 1C, 105 mAh g(-1) at 5C, 96 mAh g(-1) at 10C, 67 mAh g(-1) at 50C), a long cycle-life (capacity retention of 80% after 1000 cycles at 10C), and a high initial Coulombic efficiency (>79%). This nanostructure design provides a promising pathway for developing high performance NASICON-type materials for sodium storage.

Modifications in the rhombohedral degree of distortion and magnetic properties of Ba-doped BiFeO3 as a function of synthesis methodology

International Nuclear Information System (INIS)

Rojas-George, G.; Silva, J.; Castañeda, R.; Lardizábal, D.; Graeve, O.A.; Fuentes, L.; Reyes-Rojas, A.

2014-01-01

We present an analysis of crystallographic symmetry and the origin of the pseudo-cubic character of doped BiFeO 3 . Specifically, barium-doped bismuth ferrite, Bi 1−x Ba x FeO 3 (x = 0.05, 0.075, 0.1, 0.125), perovskite-type nanoparticles have been synthesized by implementing five modifications to the sol–gel technique (citric acid-assisted sol–gel method, ethylene glycol method, tartaric acid-assisted sol–gel method, polyvinyl alcohol–ethylene glycol method, and EDTA complexing sol–gel method) and their final pseudo-cubic character is discussed. The effect of the carboxylic groups and hydroxyl groups during synthesis is critical to obtain single phase BBFO. Fourier transform infrared spectroscopy and thermogravimetric analysis is used to study the decomposition and thermal behavior of the precursors and their relation to the final nanoparticle characteristics. X-ray diffraction analysis shows a single phase with symmetry changes for four of the five synthesis methodologies employed. Only the EDTA complexing sol–gel method, where EDTA is used as dissolver and chelating agent, is not satisfactory in all concentration ranges. Rietveld results suggest that the degree of distortion of the rhombohedral symmetry in the crystallized BiFeO 3 powders decreases 12% as a result of progressive substitution of Bi 3+ by Ba 2+ and that there is no shift from rhombohedral to tetragonal symmetry. Magnetization properties of samples with a low-distortion rhombohedral structure show higher magnetic saturation and remanent magnetization than samples with high-distortion rhombohedral structure. - Highlights: • Ba–BiFeO 3 : rhombohedral distortion degree is highly affected by the chemical method. • Rietveld results show no shift in BBFO from rhombohedral to tetragonal symmetry. • The low-distortion rhombohedral structure show higher magnetic saturation. • To stabilize a metal complex is necessary a balance between COOH − and OH − groups

Tumor blood flow, pO2, and radioresponse are improved by mild temperature hyperthermia

International Nuclear Information System (INIS)

Shakil, Abdus; Griffin, Robert J.; Song, Chang W.

1997-01-01

Purpose/Objective: The purpose of this study was to elucidate the changes in tumor blood flow, tumor pO 2 and the radiation response of the tumors caused by mild temperature hyperthermia (MTH). Materials And Methods: Experiments were carried out using the R3230 Adenocarcinoma (R3230 AC tumor), grown subcutaneously in the right hind limbs of male Fischer rats. Tumors were heated once at 40.5 deg.to 43.5 deg.C for 30 or 60 min, or twice at a 24 hr interval. Tumor blood flow and tumor pO 2 were measured immediately after the hyperthermic treatments or after 24 hr using a radioactive microsphere method and by an Eppendorf pO 2 Histograph, respectively. The influence of MTH on the effect of X-irradiation (250 kVp) on this tumor was investigated with tumor growth delay and the in vivo/in vitro excision assay for surviving tumor cell fraction. Results: Tumor blood flow and pO 2 increased upon heating for 30 min at 40.5 deg.C to 43.5 deg.C, but following 60 min heating, the pO 2 was similar to that in control tumors. The tumor blood flow increased about 1.4-fold and the tumor pO 2 increased more than 3 times after 30 min heating at 42.5 deg.C. Therefore, the in vivo/in vitro assay and the growth delay were carried out following treatment with 42.5 deg.C for 30 min. As shown in Table 1, the reduction in surviving fraction by MTH before radiation was markedly greater than that by MTH after radiation. Table 1 also shows that MTH alone caused no growth delay compared to control and while heat after radiation increased the growth delay by 2 days, MTH before radiation increased the growth delay by 5 days compared to radiation alone. Conclusion: The results indicate that MTH is effective in increasing tumor blood flow and oxygenation and that MTH for 30 min at 42.5 deg.C, applied before radiation, significantly improves the radiation response of R3230 AC tumors

Comparison of GPS-TEC measurements with NeQuick2 and IRI model predictions in the low latitude East African region during varying solar activity period (1998 and 2008-2015)

Science.gov (United States)

Mengistu, E.; Damtie, B.; Moldwin, M. B.; Nigussie, M.

2018-03-01

This paper examines the performances of NeQuick2, the latest available IRI-2016, IRI-2012 and IRI-2007 models in describing the monthly and seasonal mean total electron content (TEC) over the East African region. This is to gain insight into the success of the various model types and versions at characterizing the ionosphere within the equatorial ionization anomaly. TEC derived from five Global Positioning System (GPS) receivers installed at Addis Ababa (ADD, 5.33°N, 111.99°E Geog.), Asab (ASAB, 8.67°N, 116.44°E Geog.), Ambo (ABOO, 5.43°N, 111.05°E Geog.), Nairobi (RCMN, -4.48°N, 108.46°E Geog.) and Nazret (NAZR, 4.78°N, 112.43°E Geog.), are compared with the corresponding values computed using those models during varying solar activity period (1998 and 2008-2015). We found that different models describe the equatorial and anomaly region ionosphere best depending on solar cycle, season and geomagnetic activity levels. Our results show that IRI-2016 is the best model (compared to others in terms of discrepancy range) in estimating the monthly mean GPS-TEC at NAZR, ADD and RCMN stations except at ADD during 2008 and 2012. It is also found that IRI-2012 is the best model in estimating the monthly mean TEC at ABOO station in 2014. IRI show better agreement with observations during June solstice for all the years studied at ADD except in 2012 where NeQuick2 better performs. At NAZR, NeQuick2 better performs in estimating seasonal mean GPS-TEC during 2011, while IRI models are best during 2008-2009. Both NeQuick2 and IRI models underestimate measured TEC for all the seasons at ADD in 2010 but overestimate at NAZR in 2009 and RCMN in 2008. The periodic variations of experimental and modeled TEC have been compared with solar and geomagnetic indices at ABOO and ASAB in 2014 and results indicate that the F10.7 and sunspot number as indices of solar activity seriously affects the TEC variations with periods of 16-32 days followed by the geomagnetic activity on

Canted antiferromagnetism in KNi3[PO3(F,OH)]2[PO2(OH)2]F2 with a stair-case Kagomé lattice

Science.gov (United States)

Liu, Li-Chen; Ren, Wei-Jian; Huang, Ya-Xi; Pan, Yuanming; Mi, Jin-Xiao

2017-10-01

A new nickel phosphate KNi3[PO3(F,OH)]2[PO2(OH)2]F2 has been synthesized using a modified hydrothermal method. Structural characterizations show that it adopts a 3D framework structure with 2D layers of Ni octahedra in a stair-case Kagomé lattice. The Ni2 octahedron at the inversion center shares two trans-faces with Ni1 octahedra to form a linear trimer (Ni3O8F6) as the basic structural unit. The Ni-trimers are linked between themselves by sharing F-corners and to [PO3(F,OH)] tetrahedral groups by sharing O-corners to form 2D stair-case Kagomé layers, which are parallel to the (100) plane and are stacked along the a-axis. Successive Kagomé layers are combined together by [PO2(OH)2] tetrahedral groups and interstice cations K+. Magnetic measurements reveal that KNi3[PO3(F,OH)]2[PO2(OH)2]F2 exhibits a canted antiferromagnetic ordering with a ferromagnetic component at low temperatures.

Aberrant PO2 values in proficiency testing.

Science.gov (United States)

Fonzi, C E; Clausen, J L; Mahoney, J

1993-03-01

We prospectively determined the frequency of aberrant vials of fluorocarbon/buffer used for proficiency testing of measurements of pH, PCO2, and PO2, using 20 duplicate vials from 12 lots of fluorocarbon/buffer and two arterial blood gas analyzers in eight reference laboratories. We defined aberrant vials as vials for which both duplicate measurements differed from the mean value of repeated measurements for the specific instrument (for each lot of testing materials) by > 0.04 for pH, > 10% of the mean or 3.0 mm Hg, whichever was greater, for PCO2; or > 10% of the mean or 6 mm Hg, whichever was greater, for PO2. Four of 1620 vials (0.25%) were aberrant, all based on PO2 measurements (range of mean values: pH, 7.181-7.631; PCO2, 12.7-65.9; PO2, 32.5-150.1) were 0.0055 for pH, 0.67 mm Hg for PCO2, and 1.65 mm Hg for PO2. Deliberate contamination of the fluorocarbon emulsion with room air, as might occur during sampling from the vial, indicated that only minor increases in PO2 (e.g., 1.0 mm Hg at PO2 of 56 mm Hg) occur when samples are aspirated. Larger increases in PO2 (mean 7.1 mm Hg at a PO2 of 66 mm Hg) occurred when the syringe samples were contaminated with room air. We conclude that isolated aberrant measurements of PO2 in blood gas proficiency testing attributable to vial contents can occur, but the frequency is very low.

Local rhombohedral symmetry in Tb0.3Dy0.7Fe2 near the morphotropic phase boundary

International Nuclear Information System (INIS)

Ma, Tianyu; Liu, Xiaolian; Pan, Xingwen; Li, Xiang; Jiang, Yinzhu; Yan, Mi; Li, Huiying; Fang, Minxia; Ren, Xiaobing

2014-01-01

The recently reported morphotropic phase boundary (MPB) in a number of giant magnetostrictive materials (GMMs) has drawn considerable interest to the local symmetry/structure near MPB region of these materials. In this letter, by in-situ X-ray diffraction and AC magnetic susceptibility measurements, we show that Tb 0.3 Dy 0.7 Fe 2 , the typical composition of Terfenol-D GMMs, has coexistence of rhombohedral and tetragonal phases over a wide temperature range in the vicinity of MPB. High resolution transmission electron microscopy provides direct evidence for local rhombohedral symmetry of the ferromagnetic phase and reveals regular-shaped nanoscale domains below 10 nm. The nano-sized structural/magnetic domains are hierarchically inside a single micron-sized stripe-like domain with the same average magnetization direction. Such domain structures are consistent with the low magnetocrystalline anisotropy and easy magnetic/structural domain switching under magnetic field, thus generating large magnetostriction at low field

Hexagonal perovskites with cationic vacancies. 19. The rhombohedral 12 L stacking polytypes Ba/sub 3/LaBsup(III) (W/sub 2/sup(VI)vacantO/sub 12/)

Energy Technology Data Exchange (ETDEWEB)

Rother, H J; Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1980-06-01

Hexagonal perovskites are described for the new type Ba/sub 3/LaBsup(III)(W/sub 2/sup(VI)vacantO/sub 12/) with Bsup(III) = Sc, In, Lu, Yb. According to the intensity calculations for Ba/sub 3/LaIn(W/sub 2/vacantO/sub 12/) they crystallize in a rhombohedral 12 L structure with the sequence (3)(1) respectively (hhcc)/sub 3/; space group R3m. The refined, intensity related R' value is 6.7%.

Diode-pumped Yb:Sr5(PO4)3F laser performance

International Nuclear Information System (INIS)

Marshall, C.D.; Payne, S.A.; Smith, L.K.

1995-01-01

The performance of the first diode-pumped Yb 3+ -doped Sr 5 (PO 4 ) 3 F (Yb:S-FAP) laser is discussed. We found the pumping dynamics and extraction cross-sections of Yb:S-FAP crystals to be similar to those previously inferred by purely spectroscopic techniques. The saturation fluence for pumping was measured to be 2.2 J/cm 2 using three different methods based on either the spatial, temporal, or energy transmission properties of a Yb:S-FAP rod. The small signal gain implies an emission cross section of 6.0 x 10 -20 cm 2 that falls within error bars of the previously reported value of 7.3 x 10 -20 cm 2 , obtained from spectroscopic techniques. Up to 1.7 J/cm 3 of stored energy density was achieved in a 6 x 6 x 44 mm Yb:S-FAP amplifier rod. An InGaAs diode array has been fabricated that has suitable specifications for pumping a 3 x 3 x 30 mm Yb:S-FAP rod. In a free running configuration diode-pumped slope efficiencies up to 43% were observed with output energies up to ∼0.5 J per 1 ms pulse. When the rod was mounted in a copper block for cooling, 13 W of average power was produced with power supply limited operation at 70 Hz and 500 μs pulses

Heat capacity of Sr10(PO4)6Cl2 and Ca10(PO4)6Cl2 by DSC

International Nuclear Information System (INIS)

Venkata Krishnan, R.; Jena, Hrudananda; Govindan Kutty, K.V.; Nagarajan, K.

2008-01-01

Strontium and calcium chloroapatites were synthesized by wet chemical method, characterized by X-ray diffraction and are found to be phase pure materials. The measured room temperature lattice parameter of Ca 10 (PO 4 ) 6 Cl 2 is a = 9.523 A, c = 6.855 A and for Sr 10 (PO 4 ) 6 Cl 2 is a = 9.876 A, c = 7.188 A. Heat capacity measurements were carried out on Ca 10 (PO 4 ) 6 Cl 2 and Sr 10 (PO 4 ) 6 Cl 2 by DSC in the temperature range 298-800 K. The heat capacity values of Sr 10 (PO 4 ) 6 Cl 2 is higher at all temperatures than Ca 10 (PO 4 ) 6 Cl 2 . Enthalpy and entropy increments were computed. Heat capacity values of Ca 10 (PO 4 ) 6 Cl 2 and Sr 10 (PO 4 ) 6 Cl 2 at 298 K are 758 and 868 J K -1 mol -1 , respectively

Orientation-dependent effects of EPR-measurements on β-rhombohedral boron

International Nuclear Information System (INIS)

Siems, C.D.; Geist, D.

1976-01-01

EPR studies on β-rhombohedral boron have been reported by several authors. Two EPR-lines with the same g-value have been found by measurements with and without illumination. The microwave frequency used was 9 GHz, as far as is known. In this paper EPR-measurements at 35 GHz on β-rhombohedral boron single crystals are reported. The investigations concerning the 'dark EPR-line' were made at 300 K. (Auth.)

Specific absorption spectra of hemoglobin at different PO2 levels: potential noninvasive method to detect PO2 in tissues.

Science.gov (United States)

Liu, Peipei; Zhu, Zhirong; Zeng, Changchun; Nie, Guang

2012-12-01

Hemoglobin (Hb), as one of main components of blood, has a unique quaternary structure. Its release of oxygen is controlled by oxygen partial pressure (PO2). We investigate the specific spectroscopic changes in Hb under different PO2 levels to optimize clinical methods of measuring tissue PO2. The transmissivity of Hb under different PO2 levels is measured with a UV/Vis fiber optic spectrometer. Its plotted absorption spectral curve shows two high absorption peaks at 540 and 576 nm and an absorption valley at 560 nm when PO2 is higher than 100 mm Hg. The two high absorption peaks decrease gradually with a decrease in PO2, whereas the absorption valley at 560 nm increases. When PO2 decreases to approximately 0 mm Hg, the two high absorption peaks disappear completely, while the absorption valley has a hypochromic shift (8 to 10 nm) and forms a specific high absorption peak at approximately 550 nm. The same phenomena can be observed in visible reflectance spectra of finger-tip microcirculation. Specific changes in extinction coefficient and absorption spectra of Hb occur along with variations in PO2, which could be used to explain pathological changes caused by tissue hypoxia and for early detection of oxygen deficiency diseases in clinical monitoring.

Study of the solubility, viscosity and density in Na+, Zn2+/Cl− − H2O, Na+ − Zn2+ − (H2PO2)− − H2O, Na+, Cl−/(H2PO2)− − H2O, and Zn2+, Cl−/(H2PO2)− − H2O ternary systems, and in Na+, Zn2+/Cl−, (H2PO2)−//H2O reciprocal quaternary system at 273.15 K

International Nuclear Information System (INIS)

Adiguzel, Vedat; Erge, Hasan; Alisoglu, Vahit; Necefoglu, Hacali

2014-01-01

Highlights: • The physicochemical properties of ternary and one quaternary have been studied. • Reciprocal quaternary systems’ solubility and phase equilibrium have been studied. • In all systems the solid phases have been found. • It was found that Zn(H 2 PO 2 ) 2 salt contains 70% of the general crystallization field. - Abstract: The solubility and the physicochemical properties (density, viscosity) in the Na-Zn- Cl-H 2 O), (Na + Zn + H 2 PO 2 + H 2 O), (Na + Cl + H 2 PO 2 + H 2 O), and (Zn + Cl + H 2 PO 2 + H 2 O) ternaries, and in Na + , Zn 2+ /Cl − , (H 2 PO 2 ) − //H 2 O reciprocal quaternary systems at T = 273.15 K were investigated by using the isothermal method. The diagrams of ternary salts systems, (NaCl + ZnCl 2 + H 2 O), (NaCl + NaH 2 PO 2 + H 2 O), (NaH 2 PO 2 + Zn(H 2 PO 2 ) 2 + H 2 O), (ZnCl 2 + Zn(H 2 PO 2 ) 2 + H 2 O), are plotted in figures 1–4. However, whole ions of reciprocal quaternary salt systems are plotted in figure 5. Additionally, the density and viscosity values of ternary systems vs. their corresponding composition values in weight per cent are plotted in figures 6–10. At the (i) (ZnCl 2 + Zn(H 2 PO 2 ) 2 + H 2 O), (ii) (NaCl + ZnCl 2 + H 2 O), (iii) (NaCl + NaH 2 PO 2 + H 2 O), (iv) (NaH 2 PO 2 + Zn(H 2 PO 2 ) 2 + H 2 O) ternary systems the solid phase compositions have been determined as: (i) Zn(H 2 PO 2 ) 2 ⋅ H 2 O, Zn(H 2 PO 2 ) 2 , ZnCl 2 ⋅ 2H 2 O, (ii) NaCl, 2NaCl ⋅ ZnCl 2 ⋅ 2H 2 O, and ZnCl 2 ⋅ 2H 2 O, (iii) NaCl and NaH 2 PO 2 ⋅ H 2 O, (iv) Zn(H 2 PO 2 ) 2 ⋅ H 2 O and NaH 2 PO 2 ⋅ H 2 O, respectively. On the other hand reciprocal quaternary system was observed as: ZnCl 2 ⋅ 2H 2 O, 2NaCl ⋅ ZnCl 2 ⋅ 2H 2 O, Zn(H 2 PO 2 ) 2 ⋅ H 2 O, NaH 2 PO 2 ⋅ H 2 O, NaCl. According to results, the least soluble salt was Zn(H 2 PO 2 ) 2 . The crystallization field of this salt, being the largest in comparison with those of other salts, occupied 70% of the general crystallization field

Hexagonal perovskites with cationic vacancies. 24. Rhombohedral 9 L stacking polytypes in the systems Ba/sub 3/Wsub(2-x)sup(VI)Msub(x)sup(V)vacantOsub(9-x/2)vacantsub(x/2) with Msup(V) = Nb, Ta

Energy Technology Data Exchange (ETDEWEB)

Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1980-12-01

In the system Ba/sub 3/Wsub(2-x)sup(VI)Nbsub(x)sup(V)vacantOsub(9-x/2)vacantsub(x/2) stacking polytypes of rhombohedral 9 L type (sequence (hhc)/sub 3/; space group R-3m) can be prepared with approximately 1/3 <= x <= 2. For x = 2(Ba/sub 3/Nb/sub 2/vacantO/sub 8/vacant) two modifications are formed. In the corresponding Ta system the phase width is reduced to a smaller region with x approximately 1/3.

Different magnetic properties of rhombohedral and cubic Ni2+ doped indium oxide nanomaterials

Directory of Open Access Journals (Sweden)

Qingbo Sun

2011-12-01

Full Text Available Transition metal ions doped indium oxide nanomaterials were potentially used as a kind of diluted magnetic semiconductors in transparent spintronic devices. In this paper, the influences of Ni2+ doped contents and rhombohedral or cubic crystalline structures of indium oxide on magnetic properties were investigated. We found that the magnetic properties of Ni2+ doped indium oxide could be transferred from room temperature ferromagnetisms to paramagnetic properties with increments of doped contents. Moreover, the different crystalline structures of indium oxide also greatly affected the room temperature ferromagnetisms due to different lattice constants and almost had no effects on their paramagnetic properties. In addition, both the ferromagnetic and paramagnetic properties were demonstrated to be intrinsic and not caused by impurities.

Lifetime measurement in {sup 195}Po

Energy Technology Data Exchange (ETDEWEB)

Grahn, T.; Page, R.D. [University of Liverpool, Department of Physics, Oliver Lodge Laboratory, Liverpool (United Kingdom); Dewald, A.; Jolie, J.; Melon, B.; Pissulla, T. [Universitaet zu Koeln, Institut fuer Kernphysik, Koeln (Germany); Greenlees, P.T.; Jakobsson, U.; Jones, P.; Julin, R.; Juutinen, S.; Ketelhut, S.; Leino, M.; Nyman, M.; Peura, P.; Rahkila, P.; Saren, J.; Scholey, C.; Sorri, J.; Uusitalo, J. [University of Jyvaeskylae, Department of Physics, P.O. Box 35, Jyvaeskylae (Finland); Kroell, T.; Kruecken, R.; Maierbeck, P. [TU Muenchen, Physik-Department E12, Garching (Germany)

2009-03-15

The lifetime of the 17/2{sup +} yrast state in {sup 195}Po has been measured using the recoil distance Doppler-shift technique to be {tau}=43(11) ps. The lifetime was extracted from the singles {gamma}-ray spectra obtained by using the recoil-decay tagging method. The present work provides more information of the coupling schemes, shapes and configuration mixing in neutron-deficient odd-mass Po nuclei. (orig.)

Thermodynamic properties of crystalline Sr0.5Zr2(PO4)3 phosphate from T → 0 to 665 K

International Nuclear Information System (INIS)

Pet'kov, V.I.; Markin, A.V.; Bykova, T.A.; Sukhanov, M.V.; Smirnova, N.N.; Loshkarev, V.N.

2007-01-01

The temperature dependence of the heat capacity of crystalline Sr 0.5 Zr 2 (PO 4 ) 3 phosphate was studied by precision adiabatic vacuum and dynamic scanning calorimetry over the temperature range 7-665 K. The low-temperature dependence of the heat capacity was analyzed using the Debye theory of the heat capacity of solids and its multifractal generalization, which allowed conclusions to be drawn about the heterodynamic characteristics of the structure. The experimental data obtained were used to calculate the standard thermodynamic functions of Sr 0.5 Zr 2 (PO 4 ) 3 from T → 0 to 665 K. The standard absolute entropy of Sr 0.5 Zr 2 (PO 4 ) 3 was in turn used to calculate the standard entropy of its formation from simple substances at 298.15 K [ru

Synthesis and characterization of carbon-coated Li3V2(PO4)3 cathode materials with different carbon sources

International Nuclear Information System (INIS)

Rui, X.H.; Li, C.; Chen, C.H.

2009-01-01

The carbon-coated monoclinic Li 3 V 2 (PO 4 ) 3 (LVP) cathode materials were synthesized by a solid-state reaction process under the same conditions using citric acid, glucose, PVDF and starch, respectively, as both reduction agents and carbon coating sources. The carbon coating can enhance the conductivity of the composite materials and hinder the growth of Li 3 V 2 (PO 4 ) 3 particles. Their structures and physicochemical properties were investigated using X-ray diffraction (XRD), thermogravimetric (TG), scanning electron microscopy (SEM) and electrochemical methods. In the voltage region of 3.0-4.3 V, the electrochemical cycling of these LVP/C electrodes all presents good rate capability and excellent cycle stability. It is found that the citric acid-derived LVP owns the largest reversible capacity of 118 mAh g -1 with no capacity fading during 100 cycles at the rate of 0.2C, and the PVDF-derived LVP possesses a capacity of 95 mAh g -1 even at the rate of 5C. While in the voltage region of 3.0-4.8 V, all samples exhibit a slightly poorer cycle performance with the capacity retention of about 86% after 50 cycles at the rate of 0.2C. The reasons for electrochemical performance of the carbon coated Li 3 V 2 (PO 4 ) 3 composites are also discussed. The solid-state reaction is feasible for the preparation of the carbon coated Li 3 V 2 (PO 4 ) 3 composites which can offer favorable properties for commercial applications

Ternary phosphates in Ca3(PO4)2-Na3Ln(PO4)2 (Ln-Nd, Eu, Er) systems

International Nuclear Information System (INIS)

Lazoryak, B.I.; Ivanov, L.N.; Strunenkova, T.V.; Golubev, V.N.; Viting, B.N.

1990-01-01

Ternary phosphates, formed in Ca 3 (PO 4 ) 2 -Na 3 Ln(PO 4 ) 2 (Ln-Nd, Eu, Er) systems were investigated by the methods of X-ray phase, luminescent analyses and IR spectroscopy. 5 regions of homogeneity were found. Two of them (I and II) were distinguished for all systems. Samples in the region of up to 14.285 mol.% Na 3 Ln(PO 4 ) 2 crystallize on the basis of β-Ca 3 (PO 4 ) 2 structure, and in other homogeneity regions - on the basis of β-K 2 SO 4 structure

Evidence for a pressure-induced spin transition in olivine-type LiFePO4 triphylite

Science.gov (United States)

Núñez Valdez, Maribel; Efthimiopoulos, Ilias; Taran, Michail; Müller, Jan; Bykova, Elena; McCammon, Catherine; Koch-Müller, Monika; Wilke, Max

2018-05-01

We present a combination of first-principles and experimental results regarding the structural and magnetic properties of olivine-type LiFePO4 under pressure. Our investigations indicate that the starting P b n m phase of LiFePO4 persists up to 70 GPa. Further compression leads to an isostructural transition in the pressure range of 70-75 GPa, inconsistent with a former theoretical study. Considering our first-principles prediction for a high-spin to low-spin transition of Fe2 + close to 72 GPa, we attribute the experimentally observed isostructural transition to a change in the spin state of Fe2 + in LiFePO4. Compared to relevant Fe-bearing minerals, LiFePO4 exhibits the largest onset pressure for a pressure-induced spin state transition.

PO2 measurements in the microcirculation using phosphorescence quenching microscopy at high magnification.

Science.gov (United States)

Golub, Aleksander S; Pittman, Roland N

2008-06-01

In phosphorescence quenching microscopy (PQM), the multiple excitation of a reference volume produces the integration of oxygen consumption artifacts caused by individual flashes. We analyzed the performance of two types of PQM instruments to explain reported data on Po2 in the microcirculation. The combination of a large excitation area (LEA) and high flash rate produces a large oxygen photoconsumption artifact manifested differently in stationary and flowing fluids. A LEA instrument strongly depresses Po2 in a motionless tissue, but less in flowing blood, creating an apparent transmural Po2 drop in arterioles. The proposed model explains the mechanisms responsible for producing apparent transmural and longitudinal Po2 gradients in arterioles, a Po2 rise in venules, a hypothetical high respiration rate in the arteriolar wall and mesenteric tissue, a low Po2 in lymphatic microvessels, and both low and uniform tissue Po2. This alternative explanation for reported paradoxical results of Po2 distribution in the microcirculation obviates the need to revise the dominant role of capillaries in oxygen transport to tissue. Finding a way to eliminate the photoconsumption artifact is crucial for accurate microscopic oxygen measurements in microvascular networks and tissue. The PQM technique that employs a small excitation area (SEA) together with a low flash rate was specially designed to avoid accumulated oxygen photoconsumption in flowing blood and lymph. The related scanning SEA instrument provides artifact-free Po2 measurements in stationary tissue and motionless fluids. Thus the SEA technique significantly improves the accuracy of microscopic Po2 measurements in the microcirculation using the PQM.

One-pot syntheses of Li3V2(PO4)3/C cathode material for lithium ion batteries via ascorbic acid reduction approach

International Nuclear Information System (INIS)

Huang, J.S.; Yang, L.; Liu, K.Y.

2011-01-01

Highlights: → Ascorbic acid (C 6 H 8 O 6 ) was used as reducing agent and organic carbon source. → The strategy shortened the period of material preparation and lowered energy cost. → Li 3 V 2 (PO 4 ) 3 /C was obtained with enhanced electrochemical performance. → Effects of reagents on electrochemical performance of Li 3 V 2 (PO 4 ) 3 were evaluated. - Abstract: Monoclinic Li 3 V 2 (PO 4 ) 3 /C composite synthesized by ascorbic acid reduction method is examined as a cathode material for Li-ion batteries. Transmission electron microscopy (TEM) images show that the nano-size particles are obtained. The reversible capacity of Li 3 V 2 (PO 4 ) 3 /C prepared with LiOH and H 3 PO 4 is 141.2 mAh g -1 after 100 cycles at 1C discharge rate between 3 V and 4.8 V, and the retention rates of discharge capacity is 93.4%. Ascorbic acid plays not only as reduction reagent, but also as carbon sources. This strategy shortens the time of solid state reaction and facilitates the procedure of synthesis. Effects of different precursors materials on the performance of the Li 3 V 2 (PO 4 ) 3 /C are investigated.

Research Report: Intermittent hypobaric hypoxia and hyperbaric oxygen on GAP-43 in the rat carotid body.

Science.gov (United States)

Peng, Zhengwu; Fan, Juan; Liu, Ling; Kuang, Fang; Xue, Fen; Wang, Bairen

2015-01-01

Adaptive changes in the carotid body (CB) including the expression of the growth-associated protein-43 (GAP-43) have been studied in response to low, but not high, oxygen exposure. Expression of GAP-43 in the CB of rats under different atmospheric pressures and oxygen partial pressure (PO2) conditions was investigated. Mature male Sprague-Dawley rats were exposed to intermittent hypobaric hypoxia (IHH, 0, 1, 2 and 3 weeks), intermittent hyperbaric oxygen (IHBO2, 0, 1, 5 and 10 days, sacrificed six hours or 24 hours after the last HBO2 exposure), and intermittent hyperbaric normoxia (IHN, same treatment pattern as IHBO2). GAP-43 was highly expressed (mainly in type I cells) in the CB of normal rats. IHH u-regulated GAP-43 expression in the CB with significant differences (immunohistochemical staining [IHC]: F(3,15)=40.64, P GAP-43 expression in the CB was inhibited by IHBO2 (controls vs. IHBO2 groups, IHC: F(6,30) = 15.85, P GAP-43 expression were found for IHN. These findings indicated that different PO2 conditions, but not air pressures, played an important role in the plasticity of the CB, and that GAP-43 might be a viable factor for the plasticity of the CB.

Thermally stable green Ba(3)Y(PO(4))3:Ce(3+),Tb(3+) and red Ca(3)Y(AlO)(3)(BO(3))4:Eu(3+) phosphors for white-light fluorescent lamps.

Science.gov (United States)

Huang, Chien-Hao; Kuo, Te-Wen; Chen, Teng-Ming

2011-01-03

A class of thermal stable of green-emitting phosphors Ba(3)Y(PO(4))(3):Ce(3+),Tb(3+) (BYP:Ce(3+),Tb(3+)) and red-emitting phosphors Ca(3)Y(AlO)(3)(BO(3))(4):Eu(3+) (CYAB:Eu(3+)) for white-light fluorescent lamps were synthesized by high temperature solid-state reaction. We observed a decay of only 3% at 150 °C for BYP:0.25Ce3+,0.25Tb3+ (3% for LaPO4:Ce(3+),Tb(3+)), and a decay of 4% for CYAB:0.5Eu(3+) (7% for Y(2)O(3):Eu(3+), 24% for Y(2)O(2)S:Eu(3+)). The emission intensity of composition-optimized Ba(3)(Y(0.5)Ce(0.25)Tb(0.25))(PO(4))(3) is 70% of that of commercial LaPO(4):Ce(3+),Tb(3+) phosphors, and the CIE chromaticity coordinates are found to be (0.323, 0.534). The emission intensity of Ca(3)(Y(0.5)Eu(0.5))(AlO)(3)(BO(3))(4) is 70% and 83% of those of Y(2)O(3):Eu(3+) and Y(2)O(2)S:Eu(3+) phosphors, respectively, and the CIE chromaticity coordinates are redder (0.652, 0.342) than those of Y(2)O(3):Eu(3+) (0.645, 0.347) and Y(2)O(2)S:Eu(3+) (0.647, 0.343). A white-light fluorescent lamp is fabricated using composition-optimized Ba(3)(Y(0.5)Ce(0.25)Tb(0.25))(PO(4))(3) and Ca(3)(Y(0.5)Eu(0.5))(AlO)(3)(BO(3))(4) phosphors and matching blue-emitting phosphors. The results indicate that the quality of the brightness and color reproduction is suitable for application in shortwave UV fluorescent lamps. The white-light fluorescent lamp displays CIE chromaticity coordinates of x = 0.33, y = 0.35, a warm white light with a correlated color temperature of 5646 K, and a color-rendering index of Ra = 70.

Bio-assisted synthesis of mesoporous Li3V2(PO4)3 for high performance lithium-ion batteries

International Nuclear Information System (INIS)

He, Wen; Zhang, Xudong; Du, Xiaoyong; Zhang, Yang; Yue, Yuanzheng; Shen, Jianxing; Li, Mei

2013-01-01

Graphical abstract: - Highlights: • We present a biomimetic way for obtaining mesoporous biocarbon coated Li 3 V 2 (PO 4 ) 3 (MBC-LVP). • This method is to apply yeasts as a structural template and a biocarbon source. • The MBC-LVP has uniform particles and fine biocarbon coating network structure. • The MBC-LVP exhibits outstanding electrochemical performances. - Abstract: The mesoporous biocarbon coated Li 3 V 2 (PO 4 ) 3 (MBC-LVP) cathode material is synthesized by a biotemplate-assisted sol–gel reaction process using low-cost beer waste brewing yeasts (BWBYs) as both structural template and biocarbon source. The structure and electrochemical performances of MBC-LVP were investigated using Raman spectra, thermogravimetric measurements (TGA), adsorption–desorption isotherms and pore-size-distribution curves, X-ray diffraction (XRD), transmission electron microscope (TEM and HRTEM), and electrochemical methods. The results show that the MBC-LVP synthesized at 750 °C has a hierarchical nanostructure, which consist of Li 3 V 2 (PO 4 ) 3 crystal nanoparticles and amorphous biocarbons network (11.5%) with hierarchical mesoporous structures (slit shape mesopores, open wormlike mesopores and plugged mesopores). This hierarchical nanostructure facilitates electron and lithium ion diffusion. The MBC-LVP electrode has high discharge capacity (about 205 mAh g −1 ) at a current density of 0.2 C in the voltage region of 3.0–4.8 V and the diffusion coefficient of Li + -ions determined by CV and EIS is higher than those of olivine LiFePO 4 . We have revealed the formation mechanism of MBC-LVP, the possible lithium pathways in the MBC-LVP and established a relation between the structure and the ionic and electronic transport properties

Self-assembled Li3V2(PO4)3/reduced graphene oxide multilayer composite prepared by sequential adsorption

Science.gov (United States)

Kim, Myeong-Seong; Bak, Seong-Min; Lee, Suk-Woo; Cho, Byung-Won; Roh, Kwang Chul; Kim, Kwang-Bum

2017-11-01

Herein, we report on Li3V2(PO4)3 (LVP)/reduced graphene oxide (rGO) multilayer composites prepared via a sequential adsorption method and subsequent heat treatment, and their use as cathodes for high-rate lithium-ion batteries. The sequential adsorption process includes adsorbing oppositely charged components of anionic inorganic species and cationic head of a surfactant adsorbed to graphite oxide sheets, which is a key step in the fabrication of the LVP/rGO multilayer composites. The multilayer structure has open channels between the highly conductive rGO layers while achieving a relatively high tap density, which could effectively improve the rate capability. Consequently, the LVP/rGO multilayer composites exhibit a high tap density (0.6 g cm-3) and good electrochemical properties. Specifically, in the voltage range of 3.0-4.3 V, the composite exhibits a specific capacity of 131 mAh g-1 at 0.1C, a good rate capabilities (88% capacity retention at 60C), and long cycling performance (97% capacity retention after 500 cycles at 10C). Moreover, in the extended voltage range of 3.0-4.8 V, it exhibits a high specific capacity of 185 mAh g-1 at 0.2C, a good rate capability (66% capacity retention at 30C), and stable cycling performance (96% capacity retention after 500 cycles at 10C).

High performance Li3V2(PO4)3/C composite cathode material for lithium ion batteries studied in pilot scale test

International Nuclear Information System (INIS)

Chen Zhenyu; Dai Changsong; Wu Gang; Nelson, Mark; Hu Xinguo; Zhang Ruoxin; Liu Jiansheng; Xia Jicai

2010-01-01

Li 3 V 2 (PO 4 ) 3 /C composite cathode material was synthesized via carbothermal reduction process in a pilot scale production test using battery grade raw materials with the aim of studying the feasibility for their practical applications. XRD, FT-IR, XPS, CV, EIS and battery charge-discharge tests were used to characterize the as-prepared material. The XRD and FT-IR data suggested that the as-prepared Li 3 V 2 (PO 4 ) 3 /C material exhibits an orderly monoclinic structure based on the connectivity of PO 4 tetrahedra and VO 6 octahedra. Half cell tests indicated that an excellent high-rate cyclic performance was achieved on the Li 3 V 2 (PO 4 ) 3 /C cathodes in the voltage range of 3.0-4.3 V, retaining a capacity of 95% (96 mAh/g) after 100 cycles at 20C discharge rate. The low-temperature performance of the cathode was further evaluated, showing 0.5C discharge capacity of 122 and 119 mAh/g at -25 and -40 o C, respectively. The discharge capacity of graphite//Li 3 V 2 (PO 4 ) 3 batteries with a designed battery capacity of 14 Ah is as high as 109 mAh/g with a capacity retention of 92% after 224 cycles at 2C discharge rates. The promising high-rate and low-temperature performance observed in this work suggests that Li 3 V 2 (PO 4 ) 3 /C is a very strong candidate to be a cathode in a next-generation Li-ion battery for electric vehicle applications.

Structural and spectroscopic properties of MITh2(PO4)32 (M = Cu+, Ag+, Na+, K+)

International Nuclear Information System (INIS)

Arsalane, S.; Ziyad, M.

1996-01-01

Phosphates of general formulae M I Th 2 (PO 4 ) 3 where M = Cu + and Ag + were synthesized using sol-gel type methods and Cu + /Ag + ion exchange. Their structures were investigated by X-ray diffraction, FTIR, and 31 P MAS NMR spectroscopies. AgTh 2 (PO 4 ) 3 and NaTh 2 (PO 4 ) 3 were found to be isostructural. Their 31 P NMR spectra exhibit three resonances agreeing with the noncentrosymmetric space group Cc to which they belong. On the other hand, CuTh 2 (PO 4 ) 3 does not show a real crystallographic resemblance with the other M I Th 2 (PO 4 ) 3 phosphates of this family. Its 31 P NMR spectrum is similar to that of KTh 2 (PO 4 ) 3 and exhibits two sharp resonances in good agreement with the C2/c space group. Nevertheless, the [PO 4 ] groups in this phosphate are highly distorted because of the linear coordination of the Cu + copper ions

Structural and electrochemical characterization of 0.7LiFePO4·0.3Li3V2(PO4)3/C cathode materials using PEG and glucose as carbon sources

International Nuclear Information System (INIS)

Ma, Pingping; Hu, Pu; Liu, Zhijian; Xia, Jianhua; Xia, Dingguo; Chen, Yu; Liu, Zhengang; Lu, Zhichao

2013-01-01

0.7LiFePO 4 ·0.3Li 3 V 2 (PO 4 ) 3 /C composites (LFVP/C) were synthesized via spray-drying technique followed by solid-state reaction approach using polyethylene glycol (PEG) and glucose as carbon sources. The samples were characterized by X-ray diffraction (XRD), X-ray absorption fine-structure spectroscopy (XAFS) and Raman spectroscopy. The results show that the bi-phase composite structure of LFVP/C contains olivine LiFePO 4 (LFP) and monoclinic Li 3 V 2 (PO 4 ) 3 (LVP). The lower intensity ratio of the I D /I G and A sp 3 /A sp 2 for PEG-200 indicates the formation of higher degree of graphitized carbon during the process, which would enhance the electronic conductivity. The composite obtained using PEG-200 as carbon source show excellent rate performance, delivering the discharge capacity of 120 mAh/g at the current density of 1.5 A/g

High-pressure synthesis of rhombohedral α-AgGaO{sub 2} via direct solid state reaction

Energy Technology Data Exchange (ETDEWEB)

Akhtar, Meysam [Department of Physics and Astronomy, University of Louisville, 102 Natural Science Building, Louisville, KY 40292 (United States); Menon, Madhu [Center for Computational Sciences, University of Kentucky, 325 McVey Hall, Lexington, KY 40506 (United States); Sunkara, Mahendra [Conn Center for Renewable Energy Research, University of Louisville, Ernst Hall Room 102A, Louisville, KY 40292 (United States); Sumanasekera, Gamini [Department of Physics and Astronomy, University of Louisville, 102 Natural Science Building, Louisville, KY 40292 (United States); Conn Center for Renewable Energy Research, University of Louisville, Ernst Hall Room 102A, Louisville, KY 40292 (United States); Durygin, Andriy [Center for the Study of Matter at Extreme Conditions, Florida International University, VH 140, University Park, Miami, FL 33199 (United States); Jasinski, Jacek B., E-mail: jacek.jasinski@louisville.edu [Conn Center for Renewable Energy Research, University of Louisville, Ernst Hall Room 102A, Louisville, KY 40292 (United States)

2015-08-25

Highlights: • Direct synthesis of α-AgGaO{sub 2} via a solid state reaction of Ag{sub 2}O and Ga{sub 2}O{sub 3} powders. • Utilizing high pressure diamond anvil cell to facilitate solid state reaction. • Experimental and theoretical study of vibrational modes for α-AgGaO{sub 2}. • Extensive characterization of synthesized α-AgGaO{sub 2} samples. • GGA + U formalism-based DFT calculations of electronic structure and band gap in α-AgGaO{sub 2}. - Abstract: In this work, we demonstrate the application of high pressure conditions to enable the direct synthesis of α-AgGaO{sub 2} via a solid state reaction of Ag{sub 2}O and Ga{sub 2}O{sub 3}. Synthesis experiments were carried out at pressures and temperatures up to ∼10 GPa and ∼600 °C, respectively, using a resistively-heated diamond anvil cell. Thus synthesized α-AgGaO{sub 2} samples were characterized and their chemical composition and crystal structure were confirmed. In particular, electron diffraction confirmed the rhombohedral delafossite crystal structure of the synthesized AgGaO{sub 2} and its corresponding lattice parameters of a = 2.99 Å and c = 18.43 Å. The vibrational modes analysis was also conducted using a combination of ab initio density functional theory (DFT) and Raman spectroscopy. This analysis yielded good agreement between the calculated Raman-active modes and experimental Raman data. Finally, the application of the GGA + U formalism-based on DFT to calculate the electronic band structure of α-AgGaO{sub 2} provided a more realistic theoretical band gap value than those reported previously.

Radiation Response of Rhombohedral Oxides

International Nuclear Information System (INIS)

Devanathan, R.; Weber, W.J.; Mitchell, J.N.; Sickafus, K.E.; Nastasi, M.

1997-05-01

The radiation response of three rhombohedral oxides, namely, sapphire (α-Al 2 O 3 ), ilmenite (FeTiO 3 ), and geikielite (MgTiO 3 ), has been examined by irradiating electron transparent samples with 1 MeV Kr(+) and 1.5 MeV Xe(+)ions. The microstructural changes during irradiation were observed in situ in a high-voltage electron microscope using electron diffraction and microscopy. The irradiation conditions were designed to minimize beam heating and chemical effects due to the implanted ion. Of the three oxides studied, ilmenite is the most susceptible to radiation-induced amorphization while sapphire is the least susceptible. In all three materials, the critical temperature for amorphization was below 300 K indicating good room temperature resistance to amorphization by energetic beams

Natural levels of {sup 2}10Po in human urine; Niveles naturales de {sup 2}10Po en orina humana

Energy Technology Data Exchange (ETDEWEB)

Diaz-Frances, I.; Garcia-Tenorio, R.; Mantero, J.; Diaz, J.; Manjon, G.

2013-07-01

The daily activity of {sup 2}10Po concentrations in the urine of a volunteer for a month analyzed studies show a high variability with a difference of up to an order of magnitude between the maximum and minimum values obtained, and a clear dependence on the type of diet followed in the various phases of the experiment. (Author)

Modifications in the rhombohedral degree of distortion and magnetic properties of Ba-doped BiFeO{sub 3} as a function of synthesis methodology

Energy Technology Data Exchange (ETDEWEB)

Rojas-George, G. [Centro de Investigación en Materiales Avanzados S.C., Miguel de Cervantes 120, Complejo Industrial Chihuahua, Chihuahua, Chih. 31109 (Mexico); Silva, J. [Universidad Autónoma de Ciudad Juárez, Ave. del Charro 450 Norte, Cd. Juárez, Chih. 32310 (Mexico); Castañeda, R.; Lardizábal, D. [Centro de Investigación en Materiales Avanzados S.C., Miguel de Cervantes 120, Complejo Industrial Chihuahua, Chihuahua, Chih. 31109 (Mexico); Graeve, O.A. [Department of Mechanical and Aerospace Engineering, University of California, San Diego, 9500 Gilman Dr. – MC 0411, La Jolla, CA 92093-0411 (United States); Fuentes, L. [Centro de Investigación en Materiales Avanzados S.C., Miguel de Cervantes 120, Complejo Industrial Chihuahua, Chihuahua, Chih. 31109 (Mexico); Reyes-Rojas, A., E-mail: armando.reyes@cimav.edu.mx [Centro de Investigación en Materiales Avanzados S.C., Miguel de Cervantes 120, Complejo Industrial Chihuahua, Chihuahua, Chih. 31109 (Mexico)

2014-07-01

We present an analysis of crystallographic symmetry and the origin of the pseudo-cubic character of doped BiFeO{sub 3}. Specifically, barium-doped bismuth ferrite, Bi{sub 1−x}Ba{sub x}FeO{sub 3} (x = 0.05, 0.075, 0.1, 0.125), perovskite-type nanoparticles have been synthesized by implementing five modifications to the sol–gel technique (citric acid-assisted sol–gel method, ethylene glycol method, tartaric acid-assisted sol–gel method, polyvinyl alcohol–ethylene glycol method, and EDTA complexing sol–gel method) and their final pseudo-cubic character is discussed. The effect of the carboxylic groups and hydroxyl groups during synthesis is critical to obtain single phase BBFO. Fourier transform infrared spectroscopy and thermogravimetric analysis is used to study the decomposition and thermal behavior of the precursors and their relation to the final nanoparticle characteristics. X-ray diffraction analysis shows a single phase with symmetry changes for four of the five synthesis methodologies employed. Only the EDTA complexing sol–gel method, where EDTA is used as dissolver and chelating agent, is not satisfactory in all concentration ranges. Rietveld results suggest that the degree of distortion of the rhombohedral symmetry in the crystallized BiFeO{sub 3} powders decreases 12% as a result of progressive substitution of Bi{sup 3+} by Ba{sup 2+} and that there is no shift from rhombohedral to tetragonal symmetry. Magnetization properties of samples with a low-distortion rhombohedral structure show higher magnetic saturation and remanent magnetization than samples with high-distortion rhombohedral structure. - Highlights: • Ba–BiFeO{sub 3}: rhombohedral distortion degree is highly affected by the chemical method. • Rietveld results show no shift in BBFO from rhombohedral to tetragonal symmetry. • The low-distortion rhombohedral structure show higher magnetic saturation. • To stabilize a metal complex is necessary a balance between COOH{sup �

Reduced Graphene Oxide Decorated Na3V2(PO43 Microspheres as Cathode Material With Advanced Sodium Storage Performance

Directory of Open Access Journals (Sweden)

Hezhang Chen

2018-05-01

Full Text Available Reduced graphene oxide (rGO sheet decorated Na3V2(PO43 (NVP microspheres were successfully synthesized by spray-drying method. The NVP microspheres were embedded by rGO sheets, and the surface of the particles were coated by rGO sheets and amorphous carbon. Thus, the carbon conductive network consisted of rGO sheets and amorphous carbon generated in the cathode material. NVP microspheres decorated with different content of rGO (about 0, 4, 8, and 12 wt% were investigated in this study. The electrochemical performance of NVP exhibited a significant enhancement after rGO introduction. The electrode containing about 8 wt% rGO (NVP/G8 showed the best rate and cycle performance. NVP/G8 electrode exhibited the discharge capacity of 64.0 mAh g−1 at 70°C, and achieved high capacity retention of 95.5% after cycling at 10°C for 100 cycles. The polarization of the electrode was inhibited by the introduction of rGO sheets. Meanwhile, compared with the pristine NVP electrode, NVP/G8 electrode exhibited small resistance and high diffusion coefficient of sodium ions.

Twinning induced by the rhombohedral to orthorhombic phase transition in lanthanum gallate (LaGaO3)

Science.gov (United States)

Wang, W. L.; Lu, H. Y.

2006-10-01

Phase-transformation-induced twins in pressureless-sintered lanthanum gallate (LaGaO3) ceramics have been analysed using the transmission electron microscopy (TEM). Twins are induced by solid state phase transformation upon cooling from the rhombohedral (r, Rbar{3}c) to orthorhombic ( o, Pnma) symmetry at ˜145°C. Three types of transformation twins {101} o , {121} o , and {123} o were found in grains containing multiple domains that represent orientation variants. Three orthorhombic orientation variants were distinguished from the transformation domains converged into a triple junction. These twins are the reflection type as confirmed by tilting experiment in the microscope. Although not related by group-subgroup relation, the transformation twins generated by phase transition from rhombohedral to orthorhombic are consistent with those derived from taking cubic Pm {bar {3}}m aristotype of the lowest common supergroup symmetry as an intermediate metastable structure. The r→ o phase transition of first order in nature may have occurred by a diffusionless, martensitic-type or discontinuous nucleation and growth mechanism.

PO2 cycling reduces diaphragm fatigue by attenuating ROS formation.

Science.gov (United States)

Zuo, Li; Diaz, Philip T; Chien, Michael T; Roberts, William J; Kishek, Juliana; Best, Thomas M; Wagner, Peter D

2014-01-01

Prolonged muscle exposure to low PO2 conditions may cause oxidative stress resulting in severe muscular injuries. We hypothesize that PO2 cycling preconditioning, which involves brief cycles of diaphragmatic muscle exposure to a low oxygen level (40 Torr) followed by a high oxygen level (550 Torr), can reduce intracellular reactive oxygen species (ROS) as well as attenuate muscle fatigue in mouse diaphragm under low PO2. Accordingly, dihydrofluorescein (a fluorescent probe) was used to monitor muscular ROS production in real time with confocal microscopy during a lower PO2 condition. In the control group with no PO2 cycling, intracellular ROS formation did not appear during the first 15 min of the low PO2 period. However, after 20 min of low PO2, ROS levels increased significantly by ∼30% compared to baseline, and this increase continued until the end of the 30 min low PO2 condition. Conversely, muscles treated with PO2 cycling showed a complete absence of enhanced fluorescence emission throughout the entire low PO2 period. Furthermore, PO2 cycling-treated diaphragm exhibited increased fatigue resistance during prolonged low PO2 period compared to control. Thus, our data suggest that PO2 cycling mitigates diaphragm fatigue during prolonged low PO2. Although the exact mechanism for this protection remains to be elucidated, it is likely that through limiting excessive ROS levels, PO2 cycling initiates ROS-related antioxidant defenses.

PO2 cycling reduces diaphragm fatigue by attenuating ROS formation.

Directory of Open Access Journals (Sweden)

Li Zuo

Full Text Available Prolonged muscle exposure to low PO2 conditions may cause oxidative stress resulting in severe muscular injuries. We hypothesize that PO2 cycling preconditioning, which involves brief cycles of diaphragmatic muscle exposure to a low oxygen level (40 Torr followed by a high oxygen level (550 Torr, can reduce intracellular reactive oxygen species (ROS as well as attenuate muscle fatigue in mouse diaphragm under low PO2. Accordingly, dihydrofluorescein (a fluorescent probe was used to monitor muscular ROS production in real time with confocal microscopy during a lower PO2 condition. In the control group with no PO2 cycling, intracellular ROS formation did not appear during the first 15 min of the low PO2 period. However, after 20 min of low PO2, ROS levels increased significantly by ∼30% compared to baseline, and this increase continued until the end of the 30 min low PO2 condition. Conversely, muscles treated with PO2 cycling showed a complete absence of enhanced fluorescence emission throughout the entire low PO2 period. Furthermore, PO2 cycling-treated diaphragm exhibited increased fatigue resistance during prolonged low PO2 period compared to control. Thus, our data suggest that PO2 cycling mitigates diaphragm fatigue during prolonged low PO2. Although the exact mechanism for this protection remains to be elucidated, it is likely that through limiting excessive ROS levels, PO2 cycling initiates ROS-related antioxidant defenses.

Characterization of quasi-one-dimensional S=1/2 Heisenberg antiferromagnets Sr2Cu(PO4)2 and Ba2Cu(PO4)2 with magnetic susceptibility, specific heat, and thermal analysis

International Nuclear Information System (INIS)

Belik, A.A.; Azuma, M.; Takano, M.

2004-01-01

Properties of Sr 2 Cu(PO 4 ) 2 and Ba 2 Cu(PO 4 ) 2 having [Cu(PO 4 ) 2 ] ∞ linear chains in their structures with Cu-O-P-O-Cu linkages were studied by magnetic susceptibility (T=2-400 K, H=100 Oe) and specific heat measurements (T=0.45-21 K). Magnetic susceptibility versus temperature curves, χ(T), showed broad maxima at T M =92 K for Sr 2 Cu(PO 4 ) 2 and T M =82 K for Ba 2 Cu(PO 4 ) 2 characteristic of quasi-one-dimensional systems. The χ(T) data were excellently fitted by the spin susceptibility curve for the uniform S=1/2 chain (plus temperature-independent and Curie-Weiss terms) with g=2.153(4) and J/k B =143.6(2) K for Sr 2 Cu(PO 4 ) 2 and g=2.073(4) and J/k B =132.16(9) K for Ba 2 Cu(PO 4 ) 2 (Hamiltonian H=JΣS i S i+1 ). The similar J/k B values were obtained from the specific heat data. No anomaly was observed on the specific heat from 0.45 to 21 K for both compounds indicating that the temperatures of long-range magnetic ordering, T N , were below 0.45 K. Sr 2 Cu(PO 4 ) 2 and Ba 2 Cu(PO 4 ) 2 are an excellent physical realization of the S=1/2 linear chain Heisenberg antiferromagnet with k B T N /J 2 CuO 3 (k B T N /J∼0.25%) and γ-LiV 2 O 5 (k B T N /J 2 Cu(PO 4 ) 2 and Ba 2 Cu(PO 4 ) 2 were stable in air up to 1280 and 1150 K, respectively

Polyanion‐Type Electrode Materials for Sodium‐Ion Batteries

Science.gov (United States)

Ni, Qiao; Wu, Feng

2017-01-01

Sodium‐ion batteries, representative members of the post‐lithium‐battery club, are very attractive and promising for large‐scale energy storage applications. The increasing technological improvements in sodium‐ion batteries (Na‐ion batteries) are being driven by the demand for Na‐based electrode materials that are resource‐abundant, cost‐effective, and long lasting. Polyanion‐type compounds are among the most promising electrode materials for Na‐ion batteries due to their stability, safety, and suitable operating voltages. The most representative polyanion‐type electrode materials are Na3V2(PO4)3 and NaTi2(PO4)3 for Na‐based cathode and anode materials, respectively. Both show superior electrochemical properties and attractive prospects in terms of their development and application in Na‐ion batteries. Carbonophosphate Na3MnCO3PO4 and amorphous FePO4 have also recently emerged and are contributing to further developing the research scope of polyanion‐type Na‐ion batteries. However, the typical low conductivity and relatively low capacity performance of such materials still restrict their development. This paper presents a brief review of the research progress of polyanion‐type electrode materials for Na‐ion batteries, summarizing recent accomplishments, highlighting emerging strategies, and discussing the remaining challenges of such systems. PMID:28331782

Bi∼3.785Cd∼3.575Cu∼1.5(PO4)3.5O5.5, a new arrangement of double (n=2) and triple (n=3) [M4Bi2n-2O2n]x+ polycationic ribbons in the bismuth-transition metal oxy-phosphate series

International Nuclear Information System (INIS)

Colmont, Marie; Huve, Marielle; Abraham, Francis; Mentre, Olivier

2004-01-01

This work is dedicated to investigation of new disordered bismuth-containing oxy-phosphates compounds with an original structure type. As previously observed in this series, they are formed of [M 4 Bi 2n-2 O 2n ] x+ polycationic ribbons of width n O(Bi,M) 4 tetrahedra, surrounded by PO 4 groups. In the new crystal structure type, double (=D), triple (=T) and tunnels (=t) alternate along a common axis obeying the TtDtTtDt/TTtTTt sequence in respect to a nomenclature previously described and recalled in this work. The existence this new polymorph has first been detected by electron diffraction in a multi-phased sample. Then, the crystal structure type, i.e., the TtDtTtDt/TTtTTt sequence, has been deduced from HREM images help to a contrast-interpreting code available for these series of polycations-formed compounds. The subsequent compounds formulation leads to a number of new materials that verify the general formula: [Bi 2 (Bi,M) 4 O 4 ] 2 [Bi 4 (Bi,M) 4 O 6 ] 6 (PO 4 ) 28 M x , with x= 2+ , Cd 2+ cations. Single crystals of the nominal [O6Bi 4.57 Cd 3.43 ] 4 +8.57 [O 6 Bi 4 Cd 4 ] 2 +8 [O 4 Bi 2 Cd 3.56 Cu 0.44 ] 2 +6 (PO 4 ) 28 Cu 10.86 have been prepared in a further stage and confirms the predicted crystal structure, Bi ∼3.785 Cd ∼3.575 Cu ∼1.5 (PO 4 ) 3.5 O 5.5 , a=11.506(8)A, b=5.416(4)A, c=53.94 (4)A, β=90.10(1) o , RF=0.0835, RwF=0.0993, SG=A2/m, Z=8. As already observed for other elements of this family such as Bi ∼1.2 M ∼1.2 O 1.5 (PO 4 ), Bi ∼6.2 Cu ∼6.2 O 8 (PO 4 ) 5 or Bi ∼3 Cd ∼3.72 M ∼1.28 O 5 (PO 4 ) 3 (M=Cu, Co, Zn), this compound shows an additional example of PO 4 disorder due to the presence of mixed Bi 3+ /M 2+ sites at the edges of ribbons. The origin and consequence of this so-called disorder mostly occurring on PO 4 configurations is intensively discussed and has been characterized by infrared spectroscopy and by neutron diffraction on similar compounds. It is noticeable that the great number of antagonist PO 4

Vibrational modes of deuterium in KD2PO4

International Nuclear Information System (INIS)

Mizoguchi, Kohji; Agui, Akane; Tominaga, Yasunori; Nakai, Yusuke; Ikeda, Susumu.

1993-01-01

In order to study the deuteration effect in hydrogen-bonded compounds such as KH 2 PO 4 , hydrogen and deuterium modes in KH 2 PO 4 and K(D x H 1-x ) 2 PO 4 (x = 95 %) were investigated by means of inelastic neutron-scattering measurements over a wide energy range. By comparing Raman spectra of KH 2 PO 4 and KD 2 PO 4 with neutron-scattering spectra, the vibrational modes of deuterium and those of PO 4 tetrahedrons in the energy range of 30 < ε < 150 meV have been investigated. At least two deuterium modes have been found at 87 meV and 106 meV. (author)

Hexagonal perovskites with cationic vacancies. 13. Rhombohedral 12 L-stacking polytypes Ba/sub 4/M/sub 2/sup(V)WvacantO/sub 12/ with Msup(V) = Nb, Ta

Energy Technology Data Exchange (ETDEWEB)

Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.)

1979-10-01

The white quaternary oxides Ba/sub 4/Nb/sub 2/WvacantO/sub 12/ and Ba/sub 4/Ta/sub 2/WvacantO/sub 12/ belong to the group of hexagonal perovskites with cationic vacancies. They crystallize in the rhombohedral 12 L-type: Sequence (3)(1) = (hhcc)/sub 3/; space group R/sup -/3m (Ba/sub 4/Nb/sub 2/WvacantO/sub 12/: a = 5.77/sub 6/ A; c = 28.0/sub 55/ A; Ba/sub 4/Ta/sub 2/WvacantO/sub 12/: a = 5.77/sub 3/ A; c = 28.0/sub 75/ A; Z = 3).

Synthesis and electrochemical performance of Sn-doped Li3V2(PO4)3/C cathode material for lithium ion battery by microwave solid-state technique

International Nuclear Information System (INIS)

Liu, Haiping; Bi, Sifu; Wen, Guangwu; Teng, Xiangguo; Gao, Peng; Ni, Zujun; Zhu, Yongming; Zhang, Fang

2012-01-01

Highlights: ► Li 3 V 2−x Sn x (PO 4 ) 3 /C (0 ⩽ x ⩽ 0.10) cathode is first reported. ► Sn doping improves the initial discharge capacity and the cycle stability of Li 3 V 2 (PO 4 ) 3 /C. ► Sn doping improves the conductivity and reversibility of the Li 3 V 2 (PO 4 ) 3 /C. - Abstract: Li 3 V 2−x Sn x (PO 4 ) 3 /C cathode materials with uniform and fine particle sizes were successfully and fast synthesized by a microwave solid-state synthesis method. X-ray diffraction patterns demonstrated that the appropriate addition of Sn did not destroy the lattice structure of Li 3 V 2 (PO 4 ) 3 /C, but decreased the unit cell volume. X-ray photoelectron spectroscopy analysis demonstrated that the main chemical state of V in the Li 3 V 1.95 Sn 0.05 (PO 4 ) 3 /C composite is +3 valence, while the chemical state of Sn in the Li 3 V 1.95 Sn 0.05 (PO 4 ) 3 /C is +4 valence. Scanning electron microscope analysis illustrated that the addition of Sn slightly affected the morphology of samples. As the cathode materials for Li-ion batteries, Li 3 V 2−x Sn x (PO 4 ) 3 /C (x ⩽ 0.10) exhibited higher discharge capacity and better cycle stability than the pure one. At a discharge rate of 0.5 C in the potential range of 2.5–4.5 V at room temperature, the initial discharge capacity of Li 3 V 1.95 Sn 0.05 (PO 4 ) 3 /C was 136 mA h/g. The low charge-transfer resistances and large lithium ion diffusion coefficients confirmed that Sn-doped Li 3 V 2 (PO 4 ) 3 /C samples possessed better electronic conductivity and lithium ion mobility. These improved electrochemical performances can be attributed to the appropriate amount of Sn doping in Li 3 V 2 (PO 4 ) 3 /C system by enhancing structural stability and electrical conductivity. The present study also demonstrates that the microwave processing is a fast, simple and useful method for the fabrication of Li 3 V 2 (PO 4 ) 3 /C crystals.

Topotactic insertion of lithium in the layered structure Li4VO(PO4)2: The tunnel structure Li5VO(PO4)2

International Nuclear Information System (INIS)

Satya Kishore, M.; Pralong, V.; Caignaert, V.; Malo, S.; Hebert, S.; Varadaraju, U.V.; Raveau, B.

2008-01-01

A new V(III) lithium phosphate Li 5 VO(PO 4 ) 2 has been synthesized by electrochemical insertion of lithium into Li 4 VO(PO 4 ) 2 . This phase, which crystallizes in the space group I4/mcm, exhibits a tunnel structure closely related to the layered structure of Li 4 VO(PO 4 ) 2 and to the tunnel structure of VO(H 2 PO 4 ) 2 . The topotactic reactions that take place during lithium exchange and intercalation, starting from VO(H 2 PO 4 ) 2 and going to the final phase Li 5 VO(PO 4 ) 2 are explained on the basis of the flexible coordinations of V 4+ and V 3+ species. The electrochemical and magnetic properties of this new phase are also presented and explained on the basis of the structure dimensionality. - Graphical abstract: Electrochemical synthesis of a new 3D V(III) lithium phosphate, Li 5 VO(PO 4 ) 2 . Starting from the 2D Li 4 VO(PO 4 ) 2 , the topotactic reaction that take place during lithium intercalation is explained on the basis of the flexible coordinations of V 4+ and V 3+ species

The use of cross-linked chitosan beads for nutrients (nitrate and orthophosphate) removal from a mixture of P-PO4, N-NO2 and N-NO3.

Science.gov (United States)

Jóźwiak, Tomasz; Filipkowska, Urszula; Szymczyk, Paula; Kuczajowska-Zadrożna, Małgorzata; Mielcarek, Artur

2017-11-01

A hydrogel chitosan sorbent ionically cross-linked with sodium citrate and covalently cross-linked with epichlorohydrin was used to remove nutrients from an equimolar mixture of P-PO 4 , N-NO 2 and N-NO 3 . The scope of the study included, among other things, determination of the influence of pH on nutrient sorption effectiveness, nutrient sorption kinetics as well as determination of the maximum sorption capacity of cross-linked chitosan sorbents regarding P-PO 4 (H 2 PO 4 - , HPO 4 2- ), N-NO 2 (HNO 2 , NO 2 - ), and N-NO 3 (NO 3 - ). The effect of the type of the cross-linking agent on the affinity of the modified chitosan to each nutrient was studied as well. The kinetics of nutrient sorption on the tested chitosan sorbents was best described with the pseudo-second order model. The model of intramolecular diffusion showed that P-PO 4 , N-NO 2 and N-NO3 sorption on cross-linked hydrogel chitosan beads proceeded in two phases. The best sorbent of nutrients turned out to be chitosan cross-linked covalently with epichlorohydrin; with P-PO 4 , N-NO 2 and N-NO 3 sorption capacity reaching: 1.23, 0.94 and 0.76mmol/g, respectively (total of 2.92mmol/g). For comparison, the sorption capacity of chitosan cross-linked ionically with sodium citrate was: 0.43, 0.39 and 0.39mmol/g for P-PO 4 , N-NO 2 and N-NO 3 , respectively (total of 1.21mmol/g). Copyright © 2017 Elsevier B.V. All rights reserved.

Tilts and Ionic Shifts in Rhombohedral Perovskites

NARCIS (Netherlands)

Noheda, Beatriz; Duan, Ning; Cereceda, Noé; Gonzalo, Julio A.

1998-01-01

We make a comparative analysis of rhombohedral perovskites (ABO3) with/without oxygen rotations and ionic shifts, within the framework of a generalised effective field approach. We analyse available data on LaAlO3 and LiTaO3 and new data on Zr-rich PZT, examples of three different ways of structural

Local rhombohedral symmetry in Tb{sub 0.3}Dy{sub 0.7}Fe{sub 2} near the morphotropic phase boundary

Energy Technology Data Exchange (ETDEWEB)

Ma, Tianyu, E-mail: maty@zju.edu.cn [State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering, Key Laboratory of Novel Materials for Information Technology of Zhejiang Province, Cyrus Tang Center for Sensor Materials and Applications, Zhejiang University, Hangzhou 310027 (China); Ferroic Physics Group, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba 305-0047, Ibaraki (Japan); Liu, Xiaolian; Pan, Xingwen; Li, Xiang; Jiang, Yinzhu; Yan, Mi, E-mail: mse-yanmi@zju.edu.cn [State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering, Key Laboratory of Novel Materials for Information Technology of Zhejiang Province, Cyrus Tang Center for Sensor Materials and Applications, Zhejiang University, Hangzhou 310027 (China); Li, Huiying; Fang, Minxia [Multi-disciplinary Materials Research Center, Frontier Institute of Science and Technology, Xi' an Jiaotong University, Xi' an 710049 (China); Ren, Xiaobing, E-mail: ren.xiaobing@nims.go.jp [Ferroic Physics Group, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba 305-0047, Ibaraki (Japan); Multi-disciplinary Materials Research Center, Frontier Institute of Science and Technology, Xi' an Jiaotong University, Xi' an 710049 (China)

2014-11-10

The recently reported morphotropic phase boundary (MPB) in a number of giant magnetostrictive materials (GMMs) has drawn considerable interest to the local symmetry/structure near MPB region of these materials. In this letter, by in-situ X-ray diffraction and AC magnetic susceptibility measurements, we show that Tb{sub 0.3}Dy{sub 0.7}Fe{sub 2}, the typical composition of Terfenol-D GMMs, has coexistence of rhombohedral and tetragonal phases over a wide temperature range in the vicinity of MPB. High resolution transmission electron microscopy provides direct evidence for local rhombohedral symmetry of the ferromagnetic phase and reveals regular-shaped nanoscale domains below 10 nm. The nano-sized structural/magnetic domains are hierarchically inside a single micron-sized stripe-like domain with the same average magnetization direction. Such domain structures are consistent with the low magnetocrystalline anisotropy and easy magnetic/structural domain switching under magnetic field, thus generating large magnetostriction at low field.

Crystal structure of polyphosphates NaCd(PO3)3 and NaMn(PO3)3

International Nuclear Information System (INIS)

Murashova, E.V.; Chudinova, N.N.

1997-01-01

Crystal structure of NaCd(PO 3 ) 3 (1) and NaMn(PO 3 ) 3 (2) isostructural polyphosphates was determined for twin samples. Rhombic lattice parameters of (1): a = 14.678, b = 14.669, c = 14.705 A, sp. gr. P2 1 2 1 2 1 , Z = 16. The structure of compounds is of frame type. Polyphosphate chain with repetition period of 24 PO 4 tetrahedrons contacts with NaO 6 and M 2 O 6 octahedrons by means of common oxygen vertices. Similarities and differences in structure of mentioned polyphosphates and earlier analyzed NaMg(PO 3 ) 3 polyphosphate are noted [ru

Photoluminescence properties and thermal stability of blue-emitting Ba5-xCl(PO4)3:xEu2+ (0.004≤x≤0.016) phosphors.

Science.gov (United States)

Liu, Jie; Zhang, Zhi-Ming; Wu, Zhan-Chao; Wang, Fang-Fang; Li, Zhen-Jiang; Kuang, Shao-Ping; Wu, Ming-Mei

2017-01-15

A series of blue-emitting Ba 5-x Cl(PO 4 ) 3 :xEu 2+ (0.004≤x≤0.016) phosphors were synthesized by conventional high-temperature solid state reaction. The structure and photoluminescence (PL) properties of the phosphors were investigated. The as-prepared phosphors exhibit broad excitation band ranging from 250 to 420nm, and strong asymmetric blue emission band peaking at 436nm. The optimum concentration of Eu 2+ in the Ba 5 Cl(PO 4 ) 3 :Eu 2+ phosphor is x=0.01, and the concentration quenching mechanism is verified to be the combined actions of dipole-dipole interaction and radiation re-absorption mechanism. The thermal stability of Ba 5 Cl(PO 4 ) 3 :Eu 2+ was evaluated by temperature-dependent PL spectra. Compared with that of commercial BaMgAl 10 O 17 :Eu 2+ (BAM) phosphor, the Ba 5-x Cl(PO 4 ) 3 :xEu 2+ phosphors exhibit similarly excellent thermal quenching property. In addition, the CIE chromaticity coordinates of Ba 5-x Cl(PO 4 ) 3 :xEu 2+ (0.004≤x≤0.016) were calculated to evaluate the color quality. All the results indicate that Ba 5 Cl(PO 4 ) 3 :Eu 2+ is a promising candidate phosphor for near-ultraviolet (n-UV) pumped LED. Copyright © 2016 Elsevier B.V. All rights reserved.

Confinement and surface effects on the physical properties of rhombohedral-shape hematite (α-Fe_2O_3) nanocrystals

International Nuclear Information System (INIS)

Luna, Carlos; Cuan-Guerra, Aída D.; Barriga-Castro, Enrique D.; Núñez, Nuria O.; Mendoza-Reséndez, Raquel

2016-01-01

Highlights: • Uniform rhombohedral hematite nanocrystals (RHNCs) have been obtained. • A detailed formation mechanism of these HNCS has been proposed. • Phonon confinement effects were revealed in the RHNCS vibrational bands. • Quantum confinement effects on the optical and electronic properties were found. - Abstract: Morphological, microstructural and vibrational properties of hematite (α-Fe_2O_3) nanocrystals with a rhombohedral shape and rounded edges, obtained by forced hydrolysis of iron(III) solutions under a fast nucleation, have been investigated in detail as a function of aging time. These studies allowed us to propose a detailed formation mechanism and revealed that these nanocrystals are composed of four {104} side facets, two {110} faces at the edges of the long diagonal of the nanocrystals and two {−441} facets as the top and bottom faces. Also, the presence of nanoscopic pores and fissures was evidenced. The vibrational bands of such nanocrystals were shifted to lower frequencies in comparison with bulk hematite ones as the nanocrystal size was reduced due to phonon confinement effects. Also, the indirect and direct transition band gaps displayed interesting dependences on the aging time arising from quantum confinement and surface effects

Synthesis and tunable luminescence properties of Eu2+ and Tb3+-activated Na2Ca4(PO4)3F phosphors based on energy transfer

International Nuclear Information System (INIS)

Zhou, Jun; Xia, Zhiguo; You, Hongpeng; Shen, Kai; Yang, Mengxia; Liao, Libing

2013-01-01

A series of color-tunable blue–green emitting Na 2 Ca 4 (PO 4 ) 3 F:Eu 2+ ,Tb 3+ phosphors were prepared by a high temperature solid-state reaction. Their luminescence properties reveal that there is an efficient energy transfer from Eu 2+ to Tb 3+ ions via a dipole–quadrupole mechanism where Eu 2+ ions exhibit a strong excitation band in near ultraviolet (UV) region, matching well with the dominant emission band of near UV (350–420 nm) LED chips, and Eu 2+ and Tb 3+ ions can give characteristic blue and green emission light. The varied color of the phosphors from blue to green can be achieved by properly tuning the relative ratio of Eu 2+ to Tb 3+ dopant through the energy transfer from Eu 2+ to Tb 3+ ions. Thermal quenching luminescence results reveal that Na 2 Ca 4 (PO 4 ) 3 F:Eu 2+ ,Tb 3+ exhibits good thermal stability. These results demonstrate that Tb 3+ ion with low 4f–4f absorption efficiency in near UV region can play the role of an activator in narrow green-emitting phosphor through efficient energy feeding by allowing 4f–5d absorption of Eu 2+ with high oscillator strength. The present Eu 2+ –Tb 3+ codoped Na 2 Ca 4 (PO 4 ) 3 F phosphor will have potential application for the near UV white LEDs. - Highlights: ► Color-tunable blue–green Na 2 Ca 4 (PO 4 ) 3 F:Eu 2+ ,Tb 3+ phosphors were prepared. ► Eu 2+ –Tb 3+ energy transfer process and mechanism discussed. ► Thermal quenching properties of blue and green phosphors were studied.

Facile synthesis technology of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C adding H{sub 2}O{sub 2} in ball mill process

Energy Technology Data Exchange (ETDEWEB)

Min, Xiujuan [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, Harbin Institute of Technology, School of Chemistry and Chemical Engineering, Harbin 150001 (China); Mu, Deying [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, Harbin Institute of Technology, School of Chemistry and Chemical Engineering, Harbin 150001 (China); Department of Environmental Engineering, Harbin University of Commerce, Harbin 150076 (China); Li, Ruhong [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, Harbin Institute of Technology, School of Chemistry and Chemical Engineering, Harbin 150001 (China); Dai, Changsong, E-mail: changsd@hit.edu.cn [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, Harbin Institute of Technology, School of Chemistry and Chemical Engineering, Harbin 150001 (China)

2016-11-15

Highlights: • Sintering time of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} reduced to 6 hours by adding hydrogen peroxide. • Electrochemical performance of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} was improved by reducing sintering time. • The Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} production process was simplified during material synthesis stage. - Abstract: Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C has stable structure, high theory specific capacity and good safety performance, therefore it has become the research focus of lithium-ion batteries in recent years. The facile synthesis technology of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C was characterized by adding different amounts of H{sub 2}O{sub 2}. Structure and morphology characteristics were examined by XRD, TG, Raman Spectroscopy, XPS and SEM. Electrochemical performance was investigated by constant current charging and discharging test. The results revealed that the Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C electrochemical performance of adding 15 mL H{sub 2}O{sub 2} was better after sintering during 6 h. At the charge cut-off voltage of 4.3 V, the first discharge capacity at 0.2 C rate reached 127 mAh g{sup −1}. Because of adding H{sub 2}O{sub 2} in the ball-mill dispersant, the vanadium pentoxide formed the wet sol. The molecular-leveled mixture increased the homogeneity of raw materials. Therefore, the addition of H{sub 2}O{sub 2} shortened the sintering time and significantly improved the electrochemical performance of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C.

Magnetic susceptibility, specific heat and magnetic structure of CuNi2(PO4)2

International Nuclear Information System (INIS)

Escobal, Jaione; Pizarro, Jose L.; Mesa, Jose L.; Larranaga, Aitor; Fernandez, Jesus Rodriguez; Arriortua, Maria I.; Rojo, Teofilo

2006-01-01

The CuNi 2 (PO 4 ) 2 phosphate has been synthesized by the ceramic method at 800 deg. C in air. The crystal structure consists of a three-dimensional skeleton constructed from MO 4 (M II =Cu and Ni) planar squares and M 2 O 8 dimers with square pyramidal geometry, which are interconnected by (PO 4 ) 3- oxoanions with tetrahedral geometry. The magnetic behavior has been studied on powdered sample by using susceptibility, specific heat and neutron diffraction data. The bimetallic copper(II)-nickel(II) orthophosphate exhibits a three-dimensional magnetic ordering at, approximately, 29.8 K. However, its complex crystal structure hampers any parametrization of the J-exchange parameter. The specific heat measurements exhibit a three-dimensional magnetic ordering (λ-type) peak at 29.5 K. The magnetic structure of this phosphate shows ferromagnetic interactions inside the Ni 2 O 8 dimers, whereas the sublattice of Cu(II) ions presents antiferromagnetic couplings along the y-axis. The change of the sign in the magnetic unit-cell, due to the [1/2, 0, 1/2] propagation vector determines a purely antiferromagnetic structure. - Graphical abstract: Magnetic structure of CuNi2(PO4)2

The endogenous langur type D retrovirus PO-1-Lu and its exogenous counterparts in macaque and langur monkeys

International Nuclear Information System (INIS)

Sommerfelt, Maja A.; Harkestad, Nina; Hunter, Eric

2003-01-01

PO-1-Lu, the endogenous type D retrovirus of langurs (Trachypithecus obscurus) has previously been considered a progenitor to the prototype type D retrovirus, Mason Pfizer monkey virus (M-PMV/SRV-3), that became established in macaque monkeys (Macaca spp.) following a zoonosis. This study reevaluates this hypothesis to include other exogenous SRVs. New sequence information from the gp70(SU)-encoding region of PO-1-Lu shows striking similarity to the newly identified exogenous langur retrovirus, SRV-6, recently isolated from the Hanuman Langur (Semnopithecus entellus). An unrooted, bootstrapped neighbor-joining tree derived from env gene nucleotide sequences shows PO-1-Lu and SRV-6 appear more closely related genetically to SRV-2 than SRV-1 or SRV-3 (M-PMV). This is also reflected in our observations that the M-PMV envelope glycoprotein precursor gPr86 Env and gp70(SU) were antigenically distinct from PO-1-Lu, although the gp22(TM) glycoproteins were antigenically cross-reactive. The potential that SRV-6 represents an exogenous form of PO-1-Lu that has arisen following a recent zoonosis is discussed

Experimental evidence for rhombohedral phase of C70 after irradiation

International Nuclear Information System (INIS)

Misof, K.; Fratzl, P.; Vogl, G.

1993-01-01

Purely f.c.c. C 70 was irradiated with high-energy heavy ions at low temperature. This led to the appearance of additional Bragg peaks attributed to an irradiation-induced f.c.c.-to-rhombohedral phase transition. On heating to about 570 K the retrasition to the pure f.c.c. phase occurred. Since no irradiation-induced phase transition was obsered in C 60 , the rhombohedral phase appears to be connected with the ''rugby-ball shape'' of C 70 which favours the alignment of the molecules. We propose that irradiation provides the agitation enabling the C 70 molecules to overcome the small energy barriers which otherwise prevent the alignment of the rugby balls over larger regions. (orig.)

A Comparative Study of Structural Stability and Mechanical and Optical Properties of Fluorapatite (Ca5(PO4)3F) and Lithium Disilicate (Li2Si2O5) Components Forming Dental Glass-Ceramics: First Principles Study

Science.gov (United States)

Biskri, Z. E.; Rached, H.; Bouchear, M.; Rached, D.; Aida, M. S.

2016-10-01

The aim of this paper is a comparative study of structural stability and mechanical and optical properties of fluorapatite (FA) (Ca5(PO4)3F) and lithium disilicate (LD) (Li2Si2O5), using the first principles pseudopotential method based on density functional theory (DFT) within the generalized gradient approximation (GGA). The stability of fluorapatite and lithium disilicate compounds has been evaluated on the basis of their formation enthalpies. The results show that fluorapatite is more energetically stable than lithium disilicate. The independent elastic constants and related mechanical properties, including bulk modulus ( B), shear modulus ( G), Young's modulus ( E) and Poisson's ratio ( ν) as well as the Vickers hardness ( H v), have been calculated for fluorapatite compound and compared with other theoretical and experimental results. The obtained values of the shear modulus, Young's modulus and Vickers hardness are smaller in comparison with those of lithium disilicate compound, implying that lithium disilicate is more rigid than fluorapatite. The brittle and ductile properties were also discussed using B/ G ratio and Poisson's ratio. Optical properties such as refractive index n( ω), extinction coefficient k( ω), absorption coefficient α( ω) and optical reflectivity R( ω) have been determined from the calculations of the complex dielectric function ɛ( ω), and interpreted on the basis of the electronic structures of both compounds. The calculated values of static dielectric constant ɛ 1(0) and static refractive index n(0) show that the Li2Si2O5 compound has larger values compared to those of the Ca5(PO4)3F compound. The results of the extinction coefficient show that Li2Si2O5 compound exhibits a much stronger ultraviolet absorption. According to the absorption and reflectivity spectra, we inferred that both compounds are theoretically the best visible and infrared transparent materials.

Adaptive ferroelectric state at morphotropic phase boundary: Coexisting tetragonal and rhombohedral phases

International Nuclear Information System (INIS)

Zhang, Yang; Xue, Dezhen; Wu, Haijun; Ding, Xiangdong; Lookman, Turab; Ren, Xiaobing

2014-01-01

With a focus on local symmetry, the microstructural basis for high piezoelectric performance in PbMg 1/3 Nb 2/3 O 3 –xPbTiO 3 (PMN–PT) ceramics at the morphotropic phase boundary (MPB) composition was investigated by means of convergent-beam electron diffraction analysis and twin diffraction pattern analysis. The local structure was found to consist of coexisting (1 0 1)-type tetragonal nanotwins and (0 0 1)-type rhombohedral nanotwins. A phenomenological theory based on crystallography is proposed to show that such nanoscale coexistence can give rise to an average monoclinic structure through strain accommodation. The average monoclinic structures (Ma and Mc) vary with temperature and composition due to the dependence on temperature and composition of the lattice parameters. Based on in situ X-ray diffraction data, we demonstrate how the polarization rotates across the MPB region in PMN–PT ceramics with varying temperatures and compositions

Hexagonal perovskites with cationic vacancies. 22. Polymorphism of the rhombohedral 12 L stacking polytypes in the system Sr/sub 4-x/Ba/sub x/NiRe/sub 2/vacantO/sub 12/

Energy Technology Data Exchange (ETDEWEB)

Herrmann, M; Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1980-10-01

In the system Sr/sub 4-x/Ba/sub x/NiRe/sub 2/vacantO/sub 12/ two different stacking polytypes of the rhombohedral 12 L type are present. Both crystallize in the space group R-3m with the same sequence of the close packed AO/sub 3/ sheets: (3)(1) = (hhcc)/sub 3/. Accordingly the octahedral net consists of groups of three face connected octahedra which are linked by another through single corner sharing octahedra. In the strontium compound, Sr/sub 4/NiRe/sub 2/vacantO/sub 12/, the occupation of the octahedral holes is the same as in other rhombohedral 12 L perovskites of type A/sub 4/(B, M)/sub 3/vacantO/sub 12/ (The two outer octahedra are occupied by rhenium, the center is vacant and the nickel is located in the single octahedron). In the barium stacking polytype, Ba/sub 4/NiRe/sub 2/vacantO/sub 12/, the distribution is completely altered: The rhenium atoms occupy the central position in the block of three face connected octahedra and the single octahedron, the nickel atom and the vacancy are distributed statistically over the two outer positions in the block of three octahedra. Intensity calculations on powder data gave the intensity related R' value of 7.2% for Sr/sub 4/NiRe/sub 2/vacantO/sub 12/ and 6.2% for Ba/sub 4/NiRe/sub 2/vacantO/sub 12/.

Crystal structure of 4-RbHo(PO3)4, 4-RbTm(PO3)4 and 4-CsEr(PO3)4

International Nuclear Information System (INIS)

Maksimova, S.I.; Palkina, K.K.; Chibiskova, N.T.

1982-01-01

X-ray structural study of 4-RbLn(PO 3 ) 4 (Ln=Mo, Tm) and 4-CsEr(PO 3 ) 4 is carried out. The compounds are crystallized in monoclinic crystal system, sp. gr P2 1 /n. Parameters of their unit cell, atom coordinates, anisotropic heat parameters, interatomic distances and valent angles are given. 4-RbHo(PO 3 ) 4 , 4-RbTm(PO 3 ) 4 , 4-CsEr(PO 3 ) 4 are isostructural to previously studied TlNd(PO 3 ) and 4-RbNd(PO 3 ) 4 . Using as an example the structural type 4-M 1 Ln(PO 3 ) 4 it is shown that the change of the shortest distances Ln-Ln, M 1 -M 1 and M 1 -Ln, as well as of degree of polymorphous chain corrugation to a higher extent depends on rare earth atom dimensions, than on monovalent metal ion dimensions [ru

Pyro-synthesis of a high rate nano-Li3V2(PO4)3/C cathode with mixed morphology for advanced Li-ion batteries.

Science.gov (United States)

Kang, Jungwon; Mathew, Vinod; Gim, Jihyeon; Kim, Sungjin; Song, Jinju; Im, Won Bin; Han, Junhee; Lee, Jeong Yong; Kim, Jaekook

2014-02-10

A monoclinic Li3V2(PO4)3/C (LVP/C) cathode for lithium battery applications was synthesized by a polyol-assisted pyro-synthesis. The polyol in the present synthesis acts not only as a solvent, reducing agent and a carbon source but also as a low-cost fuel that facilitates a combustion process combined with the release of ultrahigh exothermic energy useful for nucleation process. Subsequent annealing of the amorphous particles at 800°C for 5 h is sufficient to produce highly crystalline LVP/C nanoparticles. A combined analysis of X-ray diffraction (XRD) and neutron powder diffraction (NPD) patterns was used to determine the unit cell parameters of the prepared LVP/C. Electron microscopic studies revealed rod-type particles of length ranging from nanometer to micrometers dispersed among spherical particles with average particle-sizes in the range of 20-30 nm. When tested for Li-insertion properties in the potential windows of 3-4.3 and 3-4.8 V, the LVP/C cathode demonstrated initial discharge capacities of 131 and 196 mAh/g (~100% theoretical capacities) at 0.15 and 0.1 C current densities respectively with impressive capacity retentions for 50 cycles. Interestingly, the LVP/C cathode delivered average specific capacities of 125 and 90 mAh/g at current densities of 9.6 C and 15 C respectively within the lower potential window.

Na1.25Ni1.25Fe1.75(PO4)3 nanoparticles as a janus electrode material for Li-ion batteries

Science.gov (United States)

Karegeya, Claude; Mahmoud, Abdelfattah; Hatert, Frédéric; Vertruyen, Bénédicte; Cloots, Rudi; Lippens, Pierre-Emmanuel; Boschini, Frédéric

2018-06-01

A solvothermal method was used to prepare Na1.25Ni1.25Fe1.75(PO4)3 nanoparticles, a new promising electrode material for lithium-ion batteries. The composition and the crystal structure were determined by 57Fe Mössbauer spectroscopy and powder X-ray diffraction Rietveld refinements and confirmed by magnetic measurements. The structural formula □0.75Na1.25Ni1.25Fe1.75(PO4)3 was obtained showing a significant amount of Na vacancies, which enhances Li diffusion. Na1.25Ni1.25Fe1.75(PO4)3 was used as negative and positive electrode material and shows excellent electrochemical performances. As negative electrode in the voltage range 0.03-3.5 V vs. Li+/Li, the first discharge at current density of 40 mA g-1 delivers a specific capacity of 1186 mAh g-1, which is almost three times its theoretical capacity (428 mAh g-1). Then, reversible capacity of 550 mAh g-1 was obtained at 50 mA g-1 with high rate capability (150 mAh g-1 at 500 mA g-1) and capacity retention of 350 cycles. As positive electrode material, specific capacities of about 145 and 99 mAh g-1 were delivered at current densities of 5 and 50 mA g-1, respectively, in the voltage range of 1.5-4.5 V vs. Li+/Li. In addition, we show that the use of solvothermal synthesis contributes to the synthesis of small sized particles leading to good electrochemical performances.

Vanishing of T sub c and appearance of quantum paraelectricity in KD sub 2 PO sub 4 and KH sub 2 PO sub 4 under high pressure

CERN Document Server

Endo, S; Tokunaga, M

2002-01-01

The temperature dependences of the dielectric constants of the hydrogen-bond ferroelectrics KH sub 2 PO sub 4 (KDP) and KD sub 2 PO sub 4 (DKDP) were measured under high hydrostatic pressure. Their ferroelectric transition temperatures T sub c monotonically decreased with increasing pressure and the ferroelectric state vanished at p sub c : 1.7 GPa for KDP and 6.1 GPa for DKDP. On the other hand, the Curie constant remained finite at p sub c , which indicates that the ferroelectric phase transition at high pressure is of displacive type. At pressures around p sub c , quantum paraelectricity was observed in KDP and DKDP.

Formación de hidroxiapatita, Ca5(PO43∙OH, en presencia de silicatos

Directory of Open Access Journals (Sweden)

Puertas, F.

1994-12-01

Full Text Available Hydroxyapatite Ca5(PO43OH (HAp is a crystalline phase which has several applications within the domain of special cements. This phase takes an important role in the cement reactions for the reconstruction of skeletal functions (medical domain. It is used also to improve properties of dental material. On the other hand, it is investigated to develop chemically bonded ceramics. In this paper we study the formation of HAp with β-C2S and C5PS, using some compositions in the rich lime portion of the system CaO-SiO2-P2O5-H2O (at atmospheric pressure and open system. These compositions lie in the range of: CaO: 67-71 %; SiO2: 3-18%; P2O5: 9-29% (Wt%. The preparations are made using solid state reactions, with thermal treatment at open system. The identification of phases was carried out using X-ray diffraction, Infra-Red absorption and Differential Thermal Analysis. We delimit a spectroscopy little domain lies in the range of CaO-69,5-70%; P2O5-16,2-19,5%; SiO2-11,1-13,6%. Within this domain, the crystalline phases solid state compatibility at temperature near 1000ºC are HAp, β-C2S, C5PS.La hidroxiapatita, Ca5(PO43OH (HAp, es una fase cristalina que tiene diversas aplicaciones en el ámbito de determinados cementos especiales. Esa fase juega un importante papel en las reacciones de cementos utilizados en medicina para la reconstrucción defunciones del esqueleto. Se utiliza también para mejorar propiedades de materiales de aplicación odontológica. Por otra parte, se está estudiando para desarrollar conglomerantes cerámicos. En el presente trabajo se estudia la compatibilidad en estado sólido de la HAp con β-C2S y C5PS utilizando, a presión atmosférica y recinto abierto, composiciones en la zona rica en cal del sistema CaO-SiO2-P2O5-H2O dentro de los límites siguientes. CaO: 67-71 %; SiO2: 3-18%; P2O5: 9-29% (en peso. El tratamiento térmico se realizó en estado sólido y en atmósfera abierta. La identificación de las fases se realizó a

Co-precipitation synthesis and photoluminescence properties of K2GdZr (PO4)3:Eu3+—a deep red luminomagnetic nanophosphor

International Nuclear Information System (INIS)

Chawla, Santa; Ravishanker,; Rajkumar,; Khan, A.F.; Kotnala, R.K.

2013-01-01

Nanoparticles of Eu 3+ activated K 2 GdZr(PO 4 ) 3 has been successfully synthesized by controlled inclusive co-precipitation method in high alkaline environment to enable complex crystalline phase formation. Much enhanced deep red luminescence, broadened emission bands with unusually prominent 5 D 0 – 7 F 4 transition at 699 nm are defining characteristics of the nanoparticles compared to bulk counterpart synthesized by solid state reaction route. Among various excitation pathways such as charge transfer from O 2− –Eu 3+ , Gd 3+ –Eu 3+ , the direct excitation of Eu 3+ at 394 nm is the most effective as revealed by photoluminescence and time resolved studies. Occurrence and variation of superparamagnetism in undoped and Eu 3+ doped nanoparticles indicate the role of unpaired 4f electron spin of Gd 3+ in making the nanoparticles superparamagnetic. A room temperature cost effective synthesis process of Eu 3+ doped multimetallic complex phosphate supermagnetic nanophosphor can pave way for applications requiring such functionality. -- Highlights: ► Eu 3+ doped K 2 GdZr(PO 4 ) 3 nanocrystals have been synthesized successfully by coprecipitation. ► K 2 GdZr(PO 4 ) 3 :Eu 3+ emit intense deep red fluorescence. ► Red emitting K 2 GdZr(PO 4 ) 3 :Eu 3+ nanocrystals show superparamagnetism due to Gd 3+ . ► Luminomagnetic KGP:Eu 3+ have application potential in biology, lighting and display

Synthesis, crystal structure and spectroscopy properties of Na 3AZr(PO 4) 3 ( A=Mg, Ni) and Li 2.6Na 0.4NiZr(PO 4) 3 phosphates

Science.gov (United States)

Chakir, M.; El Jazouli, A.; de Waal, D.

2006-06-01

Na 3AZr(PO 4) 3 ( A=Mg, Ni) phosphates were prepared at 750 °C by coprecipitation route. Their crystal structures have been refined at room temperature from X-ray powder diffraction data using Rietveld method. Li 2.6Na 0.4NiZr(PO 4) 3 was synthesized through ion exchange from the sodium analog. These materials belong to the Nasicon-type structure. Raman spectra of Na 3AZr(PO 4) 3 ( A=Mg, Ni) phosphates present broad peaks in favor of the statistical distribution in the sites around PO 4 tetrahedra. Diffuse reflectance spectra indicate the presence of octahedrally coordinated Ni 2+ ions.

Ni2Sr(PO42·2H2O

Directory of Open Access Journals (Sweden)

Lahcen El Ammari

2010-12-01

Full Text Available The title compound, dinickel(II strontium bis[orthophosphate(V] dihydrate, was obtained under hydrothermal conditions. The crystal structure consists of linear chains ∞1[NiO2/2(OH22/2O2/1] of edge-sharing NiO6 octahedra (overline{1} symmetry running parallel to [010]. Adjacent chains are linked to each other through PO4 tetrahedra (m symmetry and arranged in such a way to build layers parallel to (001. The three-dimensional framework is accomplished by stacking of adjacent layers that are held together by SrO8 polyhedra (2/m symmetry. Two types of O—H...O hydrogen bonds involving the water molecule are present, viz. one very strong hydrogen bond perpendicular to the layers and weak trifurcated hydrogen bonds parallel to the layers.

Removal of FePO4 and Fe3(PO4)2 crystals on the surface of passive fillers in Fe0/GAC reactor using the acclimated bacteria

International Nuclear Information System (INIS)

Lai, Bo; Zhou, Yuexi; Yang, Ping; Wang, Juling; Yang, Jinghui; Li, Huiqiang

2012-01-01

Highlights: ► Fe 3 (PO 4 ) 2 and FePO 4 crystals would weaken treatment efficiency of Fe 0 /GAC reactor. ► Fe 3 (PO 4 ) 2 and FePO 4 crystals could be removed by the acclimated bacteria. ► FeS and sulfur in the passive film would be removed by the sulfur-oxidizing bacteria. ► Develop a cost-effective bio-regeneration technology for the passive fillers. - Abstract: As past studies presented, there is obvious defect that the fillers in the Fe 0 /GAC reactor begin to be passive after about 60 d continuous running, although the complicated, toxic and refractory ABS resin wastewater can be pretreated efficiently by the Fe 0 /GAC reactor. During the process, the Fe 3 (PO 4 ) 2 and FePO 4 crystals with high density in the passive film are formed by the reaction between PO 4 3− and Fe 2+ /Fe 3+ . Meanwhile, they obstruct the formation of macroscopic galvanic cells between Fe 0 and GAC, which will lower the wastewater treatment efficiency of Fe 0 /GAC reactor. In this study, in order to remove the Fe 3 (PO 4 ) 2 and FePO 4 crystals on the surface of the passive fillers, the bacteria were acclimated in the passive Fe 0 /GAC reactor. According to the results, it can be concluded that the Fe 3 (PO 4 ) 2 and FePO 4 crystals with high density in the passive film could be decomposed or removed by the joint action between the typical propionic acid type fermentation bacteria and sulfate reducing bacteria (SRB), whereas the PO 4 3− ions from the decomposition of the Fe 3 (PO 4 ) 2 and FePO 4 crystals were released into aqueous solution which would be discharged from the passive Fe 0 /GAC reactor. Furthermore, the remained FeS and sulfur (S) in the passive film also can be decomposed or removed easily by the oxidation of the sulfur-oxidizing bacteria. This study provides some theoretical references for the further study of a cost-effective bio-regeneration technology to solve the passive problems of the fillers in the zero-valent iron (ZVI) or Fe 0 /GAC reactor.

Expression of growth-associated protein 43 in the skin nerve fibers of patients with type 2 diabetes mellitus.

Science.gov (United States)

Bursova, Sarka; Dubovy, Petr; Vlckova-Moravcova, Eva; Nemec, Martin; Klusakova, Ilona; Belobradkova, Jana; Bednarik, Josef

2012-04-15

The growth-associated protein 43 (GAP-43) is known as a marker of regenerating nerve fibers and their continuous remodeling in the adult human skin. The purpose of this pilot study was to investigate a possible role for GAP-43 in the detection of the early stages of small-fiber neuropathy in patients with type 2 diabetes mellitus (DM2) as compared with a well- established and validated parameter - intra-epidermal nerve fiber density (IENFD) of protein gene product 9.5 (PGP 9.5) immunoreactive intra-epidermal C fibers. In a group of 21 patients with DM2 within three years of diagnosis (13 men, 8 women; mean age 53.9±12.8; range 30-74) and a group of 17 healthy volunteers (8 men, 9 women; mean age 55.8±8.5; range 45-70 years), skin punch biopsies were taken from a distal calf and double immunostained with both PGP 9.5 and GAP-43. In healthy controls, 96.8% of 629 PGP 9.5 immunoreactive fibers were immunostained with GAP-43; the proportion of PGP 9.5 intra-epidermal nerve fibers immunoreactive for GAP-43 in control subjects ranged from 86.5 to 100%. In DM2 patients, IENFD was significantly lower compared to controls (median, 1.5 vs. 11.2/mm; pDM2 patients compared to healthy controls (73.6% of 337 PGP 9.5 positive fibers; p<0.001); ranged from 0 to 98.1%. In conclusion, these results show that impaired regeneration of intra-epidermal C fibers in the early stages of type 2 diabetes mellitus, as indicated by GAP-43, might be a marker of incipient diabetic neuropathy. Copyright © 2011 Elsevier B.V. All rights reserved.

Ternary rhombohedral Laves phases RE_2Rh_3Ga (RE = Y, La-Nd, Sm, Gd-Er)

International Nuclear Information System (INIS)

Seidel, Stefan; Benndorf, Christopher; Heletta, Lukas; Poettgen, Rainer; Eckert, Hellmut; Sao Paulo Univ., Sao Carlos

2017-01-01

The ordered Laves phases RE_2Rh_3Ga (RE=Y, La-Nd, Sm, Gd-Er) were synthesized by arc-melting of the elements and subsequent annealing. The samples were characterized by powder X-ray diffraction (XRD). They crystallize with the rhombohedral Mg_2Ni_3Si type structure, space group R3m. Three structures were refined from single crystal X-ray diffractometer data: a=557.1(1), c=1183.1(2), wR2=0.0591, 159 F"2 values, 10 variables for Y_2Rh_3Ga, a=562.5(2), c=1194.4(2) pm, wR2=0.0519, 206 F"2 values, 11 variables for Ce_2Rh_3Ga and a=556.7(2), c=1184.1(3) pm, wR2=0.0396, 176 F"2 values, 11 variables for Tb_2Rh_3Ga. The Rh_3Ga tetrahedra are condensed via common corners and the large cavities left by the network are filled by the rare earth atoms. The RE_2Rh_3Ga Laves phases crystallize with a translationengleiche subgroup of the cubic RERh_2 Laves phases with MgCu_2 type. Magnetic susceptibility measurements reveal Pauli paramagnetism for Y_2Rh_3Ga and La_2Rh_3Ga. Ce_2Rh_3Ga shows intermediate cerium valence while all other RE_2Rh_3Ga phases are Curie-Weiss paramagnets which order magnetically at low temperatures. The "8"9Y and "7"1Ga solid state nuclear magnetic resonance (NMR) spectra of the diamagnetic representative Y_2Rh_3Ga show well-defined single resonances in agreement with an ordered bulk phase. In comparison to the binary Laves phase YRh_2 a strongly increased "8"9Y resonance frequency is observed owing to a higher s-electron spin density at the "8"9Y nuclei as proven by density of states (DOS) calculations.

Structural and Electrochemical Characterization of Pure LiFePO4 and Nanocomposite C-LiFePO4 Cathodes for Lithium Ion Rechargeable Batteries

Directory of Open Access Journals (Sweden)

Arun Kumar

2009-01-01

Full Text Available Pure lithium iron phosphate (LiFePO4 and carbon-coated LiFePO4 (C-LiFePO4 cathode materials were synthesized for Li-ion batteries. Structural and electrochemical properties of these materials were compared. X-ray diffraction revealed orthorhombic olivine structure. Micro-Raman scattering analysis indicates amorphous carbon, and TEM micrographs show carbon coating on LiFePO4 particles. Ex situ Raman spectrum of C-LiFePO4 at various stages of charging and discharging showed reversibility upon electrochemical cycling. The cyclic voltammograms of LiFePO4 and C-LiFePO4 showed only a pair of peaks corresponding to the anodic and cathodic reactions. The first discharge capacities were 63, 43, and 13 mAh/g for C/5, C/3, and C/2, respectively for LiFePO4 where as in case of C-LiFePO4 that were 163, 144, 118, and 70 mAh/g for C/5, C/3, C/2, and 1C, respectively. The capacity retention of pure LiFePO4 was 69% after 25 cycles where as that of C-LiFePO4 was around 97% after 50 cycles. These results indicate that the capacity and the rate capability improved significantly upon carbon coating.

Syntheses, crystal structures, NMR spectroscopy, and vibrational spectroscopy of Sr(PO{sub 3}F).H{sub 2}O and Sr(PO{sub 3}F)

Energy Technology Data Exchange (ETDEWEB)

Jantz, Stephan G.; Hoeppe, Henning A. [Lehrstuhl fuer Festkoerperchemie, Institut fuer Physik, Universitaet Augsburg (Germany); Wuellen, Leo van; Fischer, Andreas [Lehrstuhl fuer Chemische Physik und Materialwissenschaften, Institut fuer Physik, Universitaet Augsburg (Germany); Libowitzky, Eugen [Institute for Mineralogy and Crystallography, Faculty of Geosciences, Geography and Astronomy, University of Vienna (Austria); Baran, Enrique J. [Centro de Quimica Inorganica (CEQUINOR/CONICET, UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata (Argentina); Weil, Matthias [Institute for Chemical Technologies and Analytics, Division Structural Chemistry, Vienna University of Technology (Austria)

2016-03-15

Single crystals of Sr(PO{sub 3}F).H{sub 2}O {P2_1/c, Z = 4, a = 7.4844(2) Aa, b = 7.0793(2) Aa, c = 8.4265(2) Aa, β = 108.696(1) , V = 422.91(2) Aa"3, 2391 F_o"2, 70 parameters, R_1[F"2 > 2σ(F"2)] = 0.036; wR_2(F"2 all) = 0.049, S = 1.054} were grown from an aqueous solution by a metathesis reaction. The structure comprises [SrO{sub 8}] polyhedra and PO{sub 3}F tetrahedra that form a layered arrangement parallel to (100). The topotactic dehydration of this phase proceeds between 80 and 140 C to afford Sr(PO{sub 3}F). The monazite-type crystal structure of Sr(PO{sub 3}F) was elucidated from the X-ray powder data by simulated annealing [P2{sub 1}/c, Z = 4, a = 6.71689(9) Aa, b = 7.11774(11) Aa, c = 8.66997(13) Aa, β = 128.0063(7) , V = 326.605(8) Aa{sup 3}, R{sub p} = 0.010, R{sub wp} = 0.015, R{sub F} = 0.030]. During dehydration, the structure of Sr(PO{sub 3}F) .H{sub 2}O collapses along [100] from a layered arrangement into a framework structure, accompanied by a change of the coordination number of the Sr{sup 2+} ions from eight to nine. The magic-angle spinning (MAS) NMR and vibrational spectroscopy data of both phases are discussed. (Copyright copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Direct and Repeated Clinical Measurements of pO2 for Enhancing Cancer Therapy and Other Applications.

Science.gov (United States)

Swartz, Harold M; Williams, Benjamin B; Hou, Huagang; Khan, Nadeem; Jarvis, Lesley A; Chen, Eunice Y; Schaner, Philip E; Ali, Arif; Gallez, Bernard; Kuppusamy, Periannan; Flood, Ann B

2016-01-01

The first systematic multi-center study of the clinical use of EPR oximetry has begun, with funding as a PPG from the NCI. Using particulate oxygen sensitive EPR, materials in three complementary forms (India Ink, "OxyChips", and implantable resonators) the clinical value of the technique will be evaluated. The aims include using repeated measurement of tumor pO2 to monitor the effects of treatments on tumor pO2, to use the measurements to select suitable subjects for the type of treatment including the use of hyperoxic techniques, and to provide data that will enable existing clinical techniques which provide data relevant to tumor pO2 but which cannot directly measure it to be enhanced by determining circumstances where they can give dependable information about tumor pO2.

Electric conductivity of solid solutions of the Na3-2xMxPO4 (M=Cd, Pb) systems

International Nuclear Information System (INIS)

Shekhtman, G.Sh.; Burmakin, E.I.; Smirnov, N.B.; Esina, N.O.

2002-01-01

Electric conductivity, phase composition and conductivity character in the system Na 3-2x Cd x PO 4 in the temperature range of 300-750 deg C were studied by the methods of conductometry, X-ray phase and thermal analyses. It was ascertained that maximum values of electric conductivity (6.25x10 -3 S/cm at 300 deg C) are observed near upper concentration boundaries (x ≅ 0.4) of monophase regions in γ-solid solutions. Conductivity of the solid electrolytes studied is of cocationic character. The values of activation energies of Na + and Cd 2+ cation jumping over in solid electrolytes Na 2.7 Cd 0.15 PO 4 are 38.7 and 43.6 kJ/mol respectively according to the NMR data [ru

Improved in vivo performance of amperometric oxygen (PO2) sensing catheters via electrochemical nitric oxide generation/release.

Science.gov (United States)

Ren, Hang; Coughlin, Megan A; Major, Terry C; Aiello, Salvatore; Rojas Pena, Alvaro; Bartlett, Robert H; Meyerhoff, Mark E

2015-08-18

A novel electrochemically controlled release method for nitric oxide (NO) (based on electrochemical reduction of nitrite ions) is combined with an amperometric oxygen sensor within a dual lumen catheter configuration for the continuous in vivo sensing of the partial pressure of oxygen (PO2) in blood. The on-demand electrochemical NO generation/release method is shown to be fully compatible with amperometric PO2 sensing. The performance of the sensors is evaluated in rabbit veins and pig arteries for 7 and 21 h, respectively. Overall, the NO releasing sensors measure both venous and arterial PO2 values more accurately with an average deviation of -2 ± 11% and good correlation (R(2) = 0.97) with in vitro blood measurements, whereas the corresponding control sensors without NO release show an average deviation of -31 ± 28% and poor correlation (R(2) = 0.43) at time points >4 h after implantation in veins and >6 h in arteries. The NO releasing sensors induce less thrombus formation on the catheter surface in both veins and arteries (p < 0.05). This electrochemical NO generation/release method could offer a new and attractive means to improve the biocompatibility and performance of implantable chemical sensors.

Ion-conduction mechanisms in NaSICON-type membranes for energy storage and utilization

Energy Technology Data Exchange (ETDEWEB)

McDaniel, Anthony H. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Sandia National Laboratories, Albuquerque, NM (United States); Ihlefeld, Jon F. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Sandia National Laboratories, Albuquerque, NM (United States); Bartelt, Norman Charles [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Sandia National Laboratories, Albuquerque, NM (United States)

2015-10-01

Next generation metal-ion conducting membranes are key to developing energy storage and utilization technologies like batteries and fuel ce lls. Sodium super-ionic conductors (aka NaSICON) are a class of compounds with AM 1 M 2 (PO 4 ) 3 stoichiometry where the choice of "A" and "M" cation varies widely. This report, which de scribes substitutional derivatives of NZP (NaZr 2 P 3 O 12 ), summarizes the accomplishments of a Laboratory D irected Research and Development (LDRD) project to analyze transport mec hanisms using a combination of in situ studies of structure, composition, and bonding, com bined with first principles theory and modeling. We developed an experimental platform and applied methods, such as synchrotron- based X-ray spectroscopies, to probe the electronic structure of compositionally well-controlled NaSICON films while in operation ( i.e ., conducting Na ions exposed to oxygen or water va por atmospheres). First principles theory and modeling were used to interpret the experimental observations and develop an enhanced understanding of atomistic processes that give rise to, and affect, ion conduction.

A high-temperature Raman scattering study of the phase transitions in GaPO{sub 4} and in the AlPO{sub 4}-GaPO{sub 4} system

Energy Technology Data Exchange (ETDEWEB)

Angot, E [Laboratoire des Colloides, des Verres et des Nanomateriaux, UMR CNRS 5587, Universite Montpellier II, cc026, Place E Bataillon, F-34095 Montpellier Cedex 5 (France); Parc, R Le [Laboratoire des Colloides, des Verres et des Nanomateriaux, UMR CNRS 5587, Universite Montpellier II, cc026, Place E Bataillon, F-34095 Montpellier Cedex 5 (France); Levelut, C [Laboratoire des Colloides, des Verres et des Nanomateriaux, UMR CNRS 5587, Universite Montpellier II, cc026, Place E Bataillon, F-34095 Montpellier Cedex 5 (France); Beaurain, M [Laboratoire de Physicochimie de la Matiere Condensee, UMR CNRS 5617, Universite Montpellier II, cc003, Place E Bataillon, F-34095 Montpellier Cedex 5 (France); Armand, P [Laboratoire de Physicochimie de la Matiere Condensee, UMR CNRS 5617, Universite Montpellier II, cc003, Place E Bataillon, F-34095 Montpellier Cedex 5 (France); Cambon, O [Laboratoire de Physicochimie de la Matiere Condensee, UMR CNRS 5617, Universite Montpellier II, cc003, Place E Bataillon, F-34095 Montpellier Cedex 5 (France); Haines, J [Laboratoire de Physicochimie de la Matiere Condensee, UMR CNRS 5617, Universite Montpellier II, cc003, Place E Bataillon, F-34095 Montpellier Cedex 5 (France)

2006-05-03

Al{sub 1-x}Ga{sub x}PO{sub 4} solid solutions (x = 0.2, 0.3, 0.38, 0.7) and the pure AlPO{sub 4} (x = 0) and GaPO{sub 4} (x = 1) end members with the {alpha}-quartz-type structure were studied by Raman scattering. An investigation as a function of composition enabled the various modes to be assigned, in particular coupled and decoupled vibrations. The tetrahedral tilting modes, which have been linked to high-temperature phase transitions to {beta}-quartz-type forms, were found to be decoupled. In addition, it is shown that Raman spectroscopy is a powerful technique for determining the gallium content of these solid solutions. Single crystals with x = 0.2, 0.38, and 1.0 (GaPO{sub 4}) were investigated at high temperature. The composition Al{sub 0.8}Ga{sub 0.2}PO{sub 4} was found to exhibit sequential transitions upon heating to the {beta}-quartz and {beta}-cristobalite forms at close to 993 K and 1073 K, respectively. Direct {alpha}-quartz-{beta}-cristobalite transitions were observed for the two other compositions at close to 1083 K and 1253 K, respectively, upon heating. The spectra of the {beta}-quartz and {beta}-cristobalite forms indicate the presence of significant disorder. Back transformation to the {alpha}-quartz-type form occurred readily with a hysteresis of less than 100 K for the composition x = 0.38 and for pure GaPO{sub 4}. Rapid cooling was necessary to obtain the metastable {alpha}-cristobalite form. In contrast, for Al{sub 0.80}Ga{sub 0.20}PO{sub 4}, the {alpha}-cristobalite form was obtained even upon slow cooling.

pO2 Fluctuation Pattern and Cycling Hypoxia in Human Cervical Carcinoma and Melanoma Xenografts

International Nuclear Information System (INIS)

Ellingsen, Christine; Øvrebø, Kirsti Marie; Galappathi, Kanthi; Mathiesen, Berit; Rofstad, Einar K.

2012-01-01

Purpose: Blood perfusion in tumors is spatially and temporally heterogeneous, resulting in local fluctuations in tissue oxygen tension (pO 2 ) and tissue regions showing cycling hypoxia. In this study, we investigated whether the pO 2 fluctuation pattern and the extent of cycling hypoxia differ between tumor types showing high (e.g., cervical carcinoma xenograft) and low (e.g., melanoma xenograft) fractions of connective tissue-associated blood vessels. Methods and Materials: Two cervical carcinoma lines (CK-160 and TS-415) and two melanoma lines (A-07 and R-18) transplanted into BALB/c nu/nu mice were included in the study. Tissue pO 2 was measured simultaneously in two positions in each tumor by using a two-channel OxyLite fiber-optic oxygen-sensing device. The extent of acute and chronic hypoxia was assessed by combining a radiobiological and a pimonidazole-based immunohistochemical assay of tumor hypoxia. Results: The proportion of tumor regions showing pO 2 fluctuations, the pO 2 fluctuation frequency in these regions, and the relative amplitude of the pO 2 fluctuations were significantly higher in the melanoma xenografts than in the cervical carcinoma xenografts. Cervical carcinoma and melanoma xenografts did not differ significantly in the fraction of acutely hypoxic cells or the fraction of chronically hypoxic cells. However, the ratio between fraction of acutely hypoxic cells and fraction of chronically hypoxic cells was significantly higher in melanoma than in cervical carcinoma xenografts. Conclusions: Temporal heterogeneity in blood flow and tissue pO 2 in tumors may depend on tumor histology. Connective tissue surrounding microvessels may stabilize blood flow and pO 2 and, thus, protect tumor tissue from cycling hypoxia.

Hydrothermal synthesis and rate capacity studies of Li3V2(PO4)3 nanorods as cathode material for lithium-ion batteries

International Nuclear Information System (INIS)

Liu Haowen; Cheng Cuixia; Huang Xintang; Li Jinlin

2010-01-01

It is an effective method by synthesizing one-dimensional nanostructure to improve the rate performances of cathode materials for Li-ion batteries. In this paper, Li 3 V 2 (PO 4 ) 3 nanorods were successfully prepared by hydrothermal reaction method. The structure, composition and shape of the prepared were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scan electron microscope (SEM) and transmission electron microscope (TEM), respectively. The data indicate the as-synthesis powders are defect-rich nanorods and the sizes are the length of several hundreds of nanometers to 1 μm and the diameter of about 60 nm. The preferential growth direction of the prepared material was the [1 2 0]. The electrodes consisting of the Li 3 V 2 (PO 4 ) 3 nanorods show the better discharge capacities at high rates over a potential range of 3.0-4.6 V. These results can be attributed to the shorter distance of electron transport and the fact that ion diffusion in the electrode material is limited by the nanorod radius. All these results indicate that the resulting Li 3 V 2 (PO 4 ) 3 nanorods are promising cathode materials in lithium-ion batteries.

Rhombohedral iron trifluoride with a hierarchized macroporous/mesoporous texture from gaseous fluorination of iron disilicide

Energy Technology Data Exchange (ETDEWEB)

Guérin, Katia, E-mail: katia.araujo_da_silva@univ-bpclermont.fr [Université Clermont Auvergne, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 Clermont-Ferrand (France); CNRS, UMR 6296, ICCF, F-63171 Aubière (France); Delbègue, Diane; Louvain, Nicolas; Doubtsof, Léa; Hamwi, André [Université Clermont Auvergne, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 Clermont-Ferrand (France); CNRS, UMR 6296, ICCF, F-63171 Aubière (France); Laik, Barbara; Pereira-Ramos, Jean-Pierre [Université Paris Est Créteil, Institut de Chimie et des Matériaux Paris-Est, UMR CNRS 7182, Thiais (France); Tahar-sougrati, Moulay; Jumas, Jean-Claude [Université Montpellier II, Institut Charles Gerhardt de Montpellier, UMR CNRS 5253, Montpellier (France); Willmann, Patrick; Cénac-Morthe, Céline [Centre National d' Etudes Spatiales, Toulouse (France)

2016-04-15

Stable low temperature rhombohedral iron trifluoride has been obtained by the fluorination under the pure fluorine gas of iron disilicide. The combination of both unusual fluorination process and precursor avoids to get unhydrated crystalline FeF{sub 3} particles and allows the formation of hierarchized channels of mesoporous/macroporous texture favorable for lithium diffusion. The fluorination mechanism proceeds by temperature steps from the formation, for a fluorination temperature below 200 °C, of an amorphous phase and an intermediate iron difluoride identified mainly by {sup 57}Fe Mössbauer spectroscopy before getting, as soon as a fluorination temperature of 260 °C is reached, the rhombohedral FeF{sub 3}. Both amorphous and crystallized samples display good ability for electrochemical process when used as cathode in lithium-ion battery. The low diameter of rhombohedral structure channels is balanced by an appropriate mesoporous texture and a capacity of 225 mAh.g{sup −1} after 5 cycles for a discharge cut-off of 2.5 V vs. Li{sup +}/Li at a current density of C/20 has been obtained and stabilized at 95 mAh.g{sup −1} after 116 cycles. - Highlights: • We investigated the synthesis of rhombohedral FeF{sub 3} by solid–gas reaction from iron disilicide. • We demonstrated that depending on the fluorination temperature various phases are stabilized. • We got a hierarchized macroporous/mesoporous texture. • We studied the electrochemical performances of amorphous and crystallized FeF{sub 3}. • Crystallized FeF{sub 3} presents a high faradic yield at first cycle focusing on insertion process.

High-Rate, Durable Sodium-Ion Battery Cathode Enabled by Carbon-Coated Micro-Sized Na ₃ V ₂ (PO ₄ ) ₃ Particles with Interconnected Vertical Nanowalls

Energy Technology Data Exchange (ETDEWEB)

Li, Hui [Beijing Key Laboratory of Environment Science and Engineering, School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081 China; Bi, Xuanxuan [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South, Cass Avenue Lemont IL 60439 USA; Bai, Ying [Beijing Key Laboratory of Environment Science and Engineering, School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081 China; Yuan, Yifei [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South, Cass Avenue Lemont IL 60439 USA; Department of Materials Science and Engineering, Michigan Technological University, 1400 Townsend Drive Houghton MI 49931 USA; Shahbazian-Yassar, Reza [Department of Materials Science and Engineering, Michigan Technological University, 1400 Townsend Drive Houghton MI 49931 USA; Wu, Chuan [Beijing Key Laboratory of Environment Science and Engineering, School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081 China; Collaborative Innovation Center of Electric Vehicles in Beijing, Beijing 100081 China; Wu, Feng [Beijing Key Laboratory of Environment Science and Engineering, School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081 China; Collaborative Innovation Center of Electric Vehicles in Beijing, Beijing 100081 China; Lu, Jun [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South, Cass Avenue Lemont IL 60439 USA; Amine, Khalil [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South, Cass Avenue Lemont IL 60439 USA

2016-02-08

Na-ion batteries have been regarded as promising alternatives for Li-ion batteries due to the extensive sodium reserves in the world. Na3V2(PO4)3 has been proved to be a good candidate of the cathode materials in Na-ion batteries but the intrinsic low electrical conductivity and sluggish kinetics handicapped its application. Here, 3D hierarchical Na3V2(PO4)3 particles are synthesized by a facile hydrothermal method, constructed by carbon-coated 2D Na3V2(PO4)3 nanowalls. Superior cell performance of high rate capability and cycle stability are observed in the well-defined structure. As the cathode in Na-ion batteries, it delivers a high capacity almost reaching the theoretical one and exhibits high capacity retention. The enhanced rate capability and cycle performance can be attributed to the improved electrical conductivity from the interconnected carbon layer and the shortened ion diffusion length and high specific surface area from the nanowalls.

High-pressure structural, elastic, and thermodynamic properties of zircon-type HoPO4 and TmPO4

International Nuclear Information System (INIS)

Gomis, O; Lavina, B; Rodríguez-Hernández, P; Muñoz, A; Errandonea, R; Errandonea, D; Bettinelli, M

2017-01-01

Zircon-type holmium phosphate (HoPO 4 ) and thulium phosphate (TmPO 4 ) have been studied by single-crystal x-ray diffraction and ab initio calculations. We report on the influence of pressure on the crystal structure, and on the elastic and thermodynamic properties. The equation of state for both compounds is accurately determined. We have also obtained information on the polyhedral compressibility which is used to explain the anisotropic axial compressibility and the bulk compressibility. Both compounds are ductile and more resistive to volume compression than to shear deformation at all pressures. Furthermore, the elastic anisotropy is enhanced upon compression. Finally, the calculations indicate that the possible causes that make the zircon structure unstable are mechanical instabilities and the softening of a silent B 1u mode. (paper)

Confinement and surface effects on the physical properties of rhombohedral-shape hematite (α-Fe{sub 2}O{sub 3}) nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Luna, Carlos, E-mail: carlos.lunacd@uanl.edu.mx [Universidad Autónoma de Nuevo León (UANL), Av. Universidad S/N, San Nicolás de los Garza, Nuevo León 66455 (Mexico); Cuan-Guerra, Aída D. [Universidad Autónoma de Nuevo León (UANL), Av. Universidad S/N, San Nicolás de los Garza, Nuevo León 66455 (Mexico); Barriga-Castro, Enrique D. [Centro de Investigación en Química Aplicada (CIQA), Blvd. Enrique Reyna Hermosillo No. 140, Saltillo, 25294 Coahuila (Mexico); Núñez, Nuria O. [Instituto de Ciencia de Materiales de Sevilla (ICMS), CSIC-US, Avda. Americo Vespucio n° 49, Isla de la Cartuja, 41092 Sevilla (Spain); Mendoza-Reséndez, Raquel [Universidad Autónoma de Nuevo León (UANL), Av. Universidad S/N, San Nicolás de los Garza, Nuevo León 66455 (Mexico)

2016-08-15

Highlights: • Uniform rhombohedral hematite nanocrystals (RHNCs) have been obtained. • A detailed formation mechanism of these HNCS has been proposed. • Phonon confinement effects were revealed in the RHNCS vibrational bands. • Quantum confinement effects on the optical and electronic properties were found. - Abstract: Morphological, microstructural and vibrational properties of hematite (α-Fe{sub 2}O{sub 3}) nanocrystals with a rhombohedral shape and rounded edges, obtained by forced hydrolysis of iron(III) solutions under a fast nucleation, have been investigated in detail as a function of aging time. These studies allowed us to propose a detailed formation mechanism and revealed that these nanocrystals are composed of four {104} side facets, two {110} faces at the edges of the long diagonal of the nanocrystals and two {−441} facets as the top and bottom faces. Also, the presence of nanoscopic pores and fissures was evidenced. The vibrational bands of such nanocrystals were shifted to lower frequencies in comparison with bulk hematite ones as the nanocrystal size was reduced due to phonon confinement effects. Also, the indirect and direct transition band gaps displayed interesting dependences on the aging time arising from quantum confinement and surface effects.

Synthesis, structures and properties of the new lithium cobalt(II) phosphate Li4Co(PO4)2

International Nuclear Information System (INIS)

Glaum, R.; Gerber, K.; Schulz-Dobrick, M.; Herklotz, M.; Scheiba, F.; Ehrenberg, H.

2012-01-01

α-Li 4 Co(PO 4 ) 2 has been synthesized and crystallized by solid-state reactions. The new phosphate crystallizes in the monoclinic system (P2 1 /a, Z=4, a=8.117(3) Å, b=10.303(8) Å, c=8.118(8) Å, β=104.36(8) Å) and is isotypic to α-Li 4 Zn(PO 4 ) 2 . The structure of α-Li 4 Co(PO 4 ) 2 has been determined from single-crystal X-ray diffraction data {R 1 =0.040, wR 2 =0.135, 2278 unique reflections with F o >4σ(F o )}. The crystal structure, which might be regarded as a superstructure of the wurtzite structure type, is build of layers of regular CoO 4 , PO 4 and Li1O 4 tetrahedra. Lithium atoms Li2, Li3 and Li4 are located between these layers. Thermal investigations by in-situ XRPD, DTA/TG and quenching experiments suggest decomposition followed by formation and phase transformation of Li 4 Co(PO 4 ) 2 : α-Li 4 Co(PO 4 ) 2 ⟹ 442°C β-Li 3 PO 4 +LiCoPO 4 ⇌ 773°C β-Li 4 Co(PO 4 ) 2 ⟹ quenchingto25°C α-Li 4 Co(PO 4 ) 2 According to HT-XRPD at θ=850°Cβ-Li 4 Co(PO 4 ) 2 (Pnma, Z=2, 10.3341(8) Å, b=6.5829(5) Å, c=5.0428(3) Å) is isostructural to γ-Li 3 PO 4 . The powder reflectance spectrum of α-Li 4 Co(PO 4 ) 2 shows the typical absorption bands for the tetrahedral chromophore [Co II O 4 ]. - Graphical abstract: The complex formation and decomposition behavior of Li 4 Co(PO 4 ) 2 with temperature has been elucidated. The crystal structure of its α-phase was determined from single crystal data, HT-XRPD allowed derivation of a structure model for the β-phase. Both modifications belong to the Li 3 PO 4 structure family. Highlights: ► Li 4 Co(PO 4 ) 2 exhibits complex thermal behavior. ► The new phosphate belongs to the Li 3 PO 4 structure family. ► A single-crystal structure analysis is provided for the metastable α-Li 4 Co(PO 4 ) 2 . ► From HT-XRPD data a cation distribution model is developed for β-Li 4 Co(PO 4 ) 2 . ► No electrochemical delithiation is observed up to 5 V.

A second polymorph with composition Co3(PO4)2·H2O

Science.gov (United States)

Lee, Young Hoon; Clegg, Jack K.; Lindoy, Leonard F.; Lu, G. Q. Max; Park, Yu-Chul; Kim, Yang

2008-01-01

Single crystals of Co3(PO4)2·H2O, tricobalt(II) bis­[ortho­phosphate(V)] monohydrate, were obtained under hydro­thermal conditions. The compound is the second polymorph of this composition and is isotypic with its zinc analogue, Zn3(PO4)2·H2O. Three independent Co2+ cations are bridged by two independent orthophosphate anions. Two of the metal cations exhibit a distorted tetra­hedral coordination while the third exhibits a considerably distorted [5 + 1] octa­hedral coordination environment with one very long Co—O distance of 2.416 (3) Å. The former cations are bonded to four different phosphate anions, and the latter cation is bonded to four anions (one of which is bidentate) and one water mol­ecule, leading to a framework structure. Additional hydrogen bonds of the type O—H⋯O stabilize this arrangement. PMID:21200979

Scaled-up solvothermal synthesis of nanosized metastable indium oxyhydroxide (InOOH) and corundum-type rhombohedral indium oxide (rh-In{sub 2}O{sub 3})

Energy Technology Data Exchange (ETDEWEB)

Schlicker, Lukas; Bekheet, Maged F.; Gurlo, Aleksander [Technische Univ. Berlin (Germany). Fachgebiet Keramische Werkstoffe

2017-03-01

Phase pure metastable indium oxyhydroxide (InOOH) with crystallite size in the range ca. 2-7 nm is synthesized by a nonaqueous solvothermal synthesis route in ethanol. The influence of synthesis parameters such as temperature, basicity (pH), synthesis time, and water content is carefully addressed. T-pH maps summarize the impact of synthesis temperature and pH and reveal that phase pure InOOH is obtained in water-free solutions at mild temperatures (150-180 C) in highly basic conditions (pH>12). Subsequent calcination of InOOH at 375-700 C in ambient air atmosphere results in metastable nanoscaled rhombohedral indium oxide (rh-In{sub 2}O{sub 3}). The synthesis protocol for phase pure nanocrystalline InOOH material was successfully upscaled allowing for obtaining ca. 3 g of phase-pure InOOH with a yield of ca. 78%. The upscaled InOOH and rh-In{sub 2}O{sub 3} batches are now available for a detailed in-situ characterization of the mechanism of decomposition of InOOH to rh-In{sub 2}O{sub 3} to c-In{sub 2}O{sub 3} as well as for the characterization of the functional properties of InOOH and rh-In{sub 2}O{sub 3} materials.

BaO-Nd2O3-CuOx subsolidus equilibria under carbonate-free conditions at pO2=100 Pa and at pO2=21 kPa

International Nuclear Information System (INIS)

Wong-Ng, W.; Cook, L.P.; Suh, J.; Coutts, R.; Stalick, J.K.; Levin, I.; Huang, Q.

2003-01-01

Subsolidus phase equilibria of the BaO-Nd 2 O 3 -CuO x system at pO 2 =100 Pa (0.1% O 2 volume fraction, 810 deg. C) and at pO 2 =21 kPa (21% O 2 volume fraction, 930 deg. C) have been investigated by applying controlled-atmosphere methods to minimize the presence of carbonate and CO 2 and H 2 O contamination. Under carbonate-free conditions, the BaO-Nd 2 O 3 -CuO x phase diagrams at pO 2 =100 Pa and at pO 2 =21 kPa are similar to one another except for differences in the extent of the solid solutions. Apart from the limiting binary phases, the ternary system consists of three solid solutions and one stoichiometric ternary compound. The first solid solution is the high T c series, Ba 2-x Nd 1+x Cu 3 O 6+z (0.3≥x≥0 at pO 2 =100 Pa; 0.95≥x≥ 0 at pO 2 =21 kPa). At pO 2 =21 kPa, a compositionally dependent phase change was detected, from tetragonal (0.7>x≥0) to orthorhombic (0.95≥x≥0.7). The second solid solution series, the 'brown-phase' Ba 1+x Nd 2-x CuO z , has a narrow homogeneity region (0.10>x≥0 at pO 2 =100 Pa; 0.15>x≥0 at pO 2 =21 kPa). In the high BaO part of the phase diagram, a third solid solution (Ba 2-x Nd x )CuO 3+z (x=0 to ∼ 0.3 at pO 2 =100 Pa; x=0-0.45 at pO 2 =21 kPa) was confirmed, as well as a nominally stoichiometric phase, Ba 4 Nd 2 Cu 2 O z . The latter phase is an insulator, with a structure comprised of unusual CuO 5 linear chains. A significant difference in tie line distribution involving the Ba 2-x Nd 1+x Cu 3 O 6+z superconductor was found under carbonate-free conditions relative to literature studies completed in air. Instead of the BaCuO 2+x -Ba 2+x Nd 4-x Cu 2 O z tie line normally encountered in air, a Ba 2-x Nd 1+x Cu 3 O 6+z -(Ba,Nd) 2 CuO 3+x tie line was established. This tie line substantially expands the field of stability of the Ba 2-x Nd 1+x Cu 3 O 6+z superconductor phase into the BaO-rich region of the phase diagram. Implications for the processing of materials based on the Ba 2-x Nd 1+x Cu 3 O 6+z

Re-entrant spin glass and stepped magnetization in mixed-valence SrFe3(PO4)3

International Nuclear Information System (INIS)

Shang Mingyu; Chen Yan; Tian Ge; Yuan Hongming; Feng Shouhua

2013-01-01

The 2 D channel mixed-valent iron (II/III) monophosphate SrFe 3 (PO 4 ) 3 was synthesized via one step mild hydrothermal method at 210 °C and characterized by X-ray diffraction techniques and magnetization measurements. Coexistence of antiferromagnetic superexchange and ferromagnetic superexchange interactions was supposed to be in the lattice according to the Goodenough-Kanamori-Anderson rules. Temperature dependent DC magnetization measurement shows that SrFe 3 (PO 4 ) 3 is ferrimagnet with three magnetic transitions between 2 and 350 K. Through AC magnetization measurement, re-entrant spin glass was observed due to the competition between ferromagnetic and antiferromagnetic interactions. Furthermore, an interesting field induced stepped magnetization was observed in SrFe 3 (PO 4 ) 3 at 2 K with the saturation magnetization Ms=2.4 μ B /f.u. at 5 T.

High-performance Li3V2(PO4)3/C cathode materials prepared via a sol–gel route with double carbon sources

International Nuclear Information System (INIS)

Zhang Lulu; Li Ying; Peng Gang; Wang Zhaohui; Ma Jun; Zhang Wuxing; Hu Xianluo; Huang Yunhui

2012-01-01

Graphical abstract: Double carbon sources were employed to prepare core–shell Li 3 V 2 (PO 4 ) 3 /C composites, giving rise to uniform carbon coating and high conducting network. The as-obtained composites showed remarkably enhanced capacity and rate capability. Highlights: ► Double carbon sources were used to prepare core–shell Li 3 V 2 (PO 4 ) 3 /C composites. ► An improved oxalic acid-based sol–gel method was developed. ► Uniform carbon coating and high conducting network were attained for Li 3 V 2 (PO 4 ) 3 . ► Remarkably enhanced capacity and rate capability were obtained. - Abstract: Li 3 V 2 (PO 4 ) 3 /C (LVP/C) composites have been successfully synthesized via an oxalic acid-based sol–gel process assisted by glucose, in which oxalic acid and glucose serve as double carbon sources. X-ray diffraction patterns show that all samples are well crystallized. Transmission electron microscopy images reveal that the LVP/C sample prepared with 15 wt% glucose is uniformly coated by carbon layer with an appropriate thickness of 8–10 nm, resulting in a high electrical conductivity and a fast kinetics. The Li + -ion diffusion coefficient in the LVP/C sample prepared with glucose is ∼10 −10 cm 2 s −1 , which is larger than that of the LVP/C sample prepared without glucose. The LVP/C sample prepared with 15 wt% glucose exhibits the best electrochemical performance with discharge capacity as high as 171 mAh g −1 at 0.1 C and 119 mAh g −1 at 10 C. The present work provides a valuable route for preparing lithium metal phosphates with double carbon sources to improve the conductivity and hence the electrochemical performance.

The phase transition of the incommensurate phases β-Ln(PO3)3(Ln=Y,Tb...Yb), crystal structures of α-Ln(PO3)3(Ln=Y,Tb...Yb) and Sc(PO3)3

International Nuclear Information System (INIS)

Hoeppe, Hennig A.

2009-01-01

The incommensurately modulated room-temperature phases β-Ln(PO 3 ) 3 (Ln=Y,Tb...Yb) undergo a topotactic phase transition monitored by vibrational spectroscopy below 180 K leading to α-Ln(PO 3 ) 3 (Ln=Y,Dy...Yb), above 200 K the incommensurate phases are reobtained. The low-temperature phases exhibit a new structure type (α-Dy(PO 3 ) 3 ,P2 1 /c,Z=12,a=14.1422(6),b=20.0793(9),c=10.1018(4)A, β=127.532(3) 0 ). α-Tb(PO 3 ) 3 is isotypic with Gd(PO 3 ) 3 (α-Tb(PO 3 ) 3 ,I2/a,Z=16,a=25.875(6),b=13.460(3),c=10.044(2)A, β=119.13(3) 0 ). The symmetry relations between the involved phases of the phase transition are discussed. The crystal structure of Sc(PO 3 ) 3 is isotypic with that of Lu(PO 3 ) 3 and C-type phosphates. The polyphosphates consist of infinite zig-zag chains of corner-sharing PO 4 tetrahedra, the cations are coordinated sixfold in an almost octahedral arrangement. To confirm the quality of the determined crystal structures the deviation of the phosphate tetrahedra from ideal symmetry was determined and discussed. - Abstract: Basic structure from which all crystal structures of the late lanthanoids' polyphosphates at room temperature and below can be derived.

Biological reduction-deposition and luminescent properties of nanostructured CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) and CePO{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Yu, Xiaoniu [School of Materials Science and Engineering, Southeast University, Nanjing 211189 (China); Research Institute of Green Construction Materials, Southeast University, Nanjing 211189 (China); Qian, Chunxiang, E-mail: cxqian@seu.edu.cn [School of Materials Science and Engineering, Southeast University, Nanjing 211189 (China); Research Institute of Green Construction Materials, Southeast University, Nanjing 211189 (China)

2016-03-01

Nano-sized CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) and CePO{sub 4} with hexagonal phase have been prepared by simply varying the reactant P/Ce molar ratio in bacterial liquid. The phase composition of two samples was checked via Fourier transform infrared spectroscopy (FTIR), energy dispersive analysis of X-rays (EDS) and X-ray diffraction (XRD) analyses, displaying the presence of CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) and CePO{sub 4} with average crystallite size are 32.34 and 15.61 nm, respectively. The scanning electron microscopy (SEM) images show that nano-clusters and sphere-like in shape with a narrow diameter distribution were observed in two samples. The transmission electron microscopy (TEM) photographs further indicate obtained CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) and CePO{sub 4} nanoparticles correspond to nanosheets and nanorods, respectively. The emission spectra of CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) and CePO{sub 4} display a broad band of 300–380 nm range with the strongest emission at 342 nm in the violet region. - Highlights: • A new method was found to synthesize CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) and CePO{sub 4} nanoparticles. • CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) nanoparticles have good luminescent properties. • Size and luminescent properties of two samples have been studied and compared.

Crystal structure, energy transfer and tunable luminescence properties of Ca8ZnCe(PO4)7:Eu2+,Mn2+ phosphor

Science.gov (United States)

Ding, Chong; Tang, Wanjun

2018-02-01

Single-phased Ca8ZnCe(PO4)7:Eu2+,Mn2+ phosphors with whitlockite-type structure have been prepared via the combustion-assisted synthesis technique. The XRD pattern show that the as-obtained phosphors crystallize in a trigonal phase with space group of R-3c (161). Ca8ZnCe(PO4)7 host is full of sensitizers (Ce3+) and the Ce3+ emission at different lattice sites has been discussed. The efficient energy transfers from Ce3+ ions to Eu2+/Mn2+ ions and from Eu2+ to Mn2+ have been validated. Under UV excitation, the emitting color of Ca8ZnCe(PO4)7:Eu2+/Mn2+ samples can be modulated from violet blue to green and from violet blue to red-orange by the energy transfers of Ce3+→Eu2+ and Ce3+→Mn2+, respectively. Additionally, white emission has been obtained through adjusting the relative concentrations of Eu2+ and Mn2+ ions in the Ca8ZnCe(PO4)7 host under UV excitation. These results indicate that as-prepared Ca8ZnCe(PO4)7:Eu2+,Mn2+ may be a potential candidate as color-tunable white light-emitting phosphors.

The phase transition of the incommensurate phases β-Ln(PO3)3(Ln=Y,Tb…Yb), crystal structures of α-Ln(PO3)3(Ln=Y,Tb…Yb) and Sc(PO3)3

Science.gov (United States)

Höppe, Hennig A.

2009-07-01

The incommensurately modulated room-temperature phases β-Ln(PO3)3(Ln=Y,Tb…Yb) undergo a topotactic phase transition monitored by vibrational spectroscopy below 180 K leading to α-Ln(PO3)3(Ln=Y,Dy…Yb), above 200 K the incommensurate phases are reobtained. The low-temperature phases exhibit a new structure type (α-Dy(PO3)3, P21/c, Z=12,a=14.1422(6), b=20.0793(9),c=10.1018(4) A˚, β=127.532(3)∘). α-Tb(PO3)3 is isotypic with Gd(PO3)3(α-Tb(PO3)3, I2/a,Z=16,a=25.875(6), b=13.460(3), c=10.044(2) A˚, β=119.13(3)∘). The symmetry relations between the involved phases of the phase transition are discussed. The crystal structure of Sc(PO3)3 is isotypic with that of Lu(PO3)3 and C-type phosphates. The polyphosphates consist of infinite zig-zag chains of corner-sharing PO4 tetrahedra, the cations are coordinated sixfold in an almost octahedral arrangement. To confirm the quality of the determined crystal structures the deviation of the phosphate tetrahedra from ideal symmetry was determined and discussed.

A combined transcutaneous PO2-PCO2 electrode with electrochemical HCO3- stabilization.

Science.gov (United States)

Severinghaus, J W

1981-10-01

Combined transcutaneous PO2-PCO2 electrodes are described in which the interaction between the two electrodes due to OH- production at the O2 cathode has been eliminated. An anode of either anodized aluminum or platinum has been driven at a current equal to cathode current to force stoichiometric consumption of OH- at its rate of production. The AgCl reference electrode operates at zero current. O2 sensitivity was not significantly altered by electrolyte pH variation from 6.7 to 9.0 with variations by PCO2. These electrodes have been found stable both with and without spacers, and with electrolytes dissolved in 50-100% ethylene glycol. In 22 anesthetized patients, with electrode temperature of 43 degrees C (s refers to skin surface, a to arterial blood); PsO2 = 0.52PaO2 + 15 (range 54-300) (r = 0.66; Sy . x = 29.6; n = 46); and PsCO2 = 1.39PaCO2 + 2.1 (range 24-98) (r = 0.99; Sy . x = 2.28; n = 48).

Síntesis, caracterización estructural y morfológica de nanofósforos Ca0,45Eu0,05Zr2(PO43

Directory of Open Access Journals (Sweden)

Lorena Alcaraz

2015-11-01

Full Text Available Muestras de composición Ca0,45Eu0,05Zr2(PO43 se sintetizaron utilizando un método de preparación que transcurre en 2 etapas: uso de un proceso sol-gel empleando medios de reacción ácido (pH ≈ 2 y básico (pH ≈ 10 y un calentamiento posterior de los polvos precursores en corriente de N2:H2 (90:10 con el objeto de estabilizar el estado de oxidación 2+ en el europio. Los perfiles de difracción de rayos X obtenidos muestran reflexiones características de una estructura tipo NASICON de simetría romboédrica y grupo espacial R-3. Se aprecian máximos de reflexión más intensos para las muestras que se preparan usando un medio de reacción básico. Las medidas magnéticas confirman el estado de oxidación 2+ del europio en las muestras sintetizadas. Las imágenes de microscopia hacen visibles partículas de morfología esférica y tamaño nanométrico, en buen acuerdo con los resultados de difracción de rayos X, lo que indica que estas muestras pueden resultar de utilidad en ciertos dispositivos luminiscentes.

Density functional theory study of lithium diffusion at the interface between olivine-type LiFePO4 and LiMnPO4

Science.gov (United States)

Shi, Jianjian; Wang, Zhiguo; Qing Fu, Yong

2016-12-01

Coating LiMnPO4 with a thin layer of LiFePO4 shows a better electrochemical performance than the pure LiFePO4 and LiMnPO4, thus it is critical to understand Li diffusion at their interfaces to improve the performance of electrode materials. Li diffusion at the (1 0 0)\\text{LiFeP{{\\text{O}}4}} //(1 0 0)\\text{LiMnP{{\\text{O}}4}} , (0 1 0)\\text{LiFeP{{\\text{O}}4}} //(0 1 0)\\text{LiMnP{{\\text{O}}4}} , and (0 0 1)\\text{LiFeP{{\\text{O}}4}} //(0 0 1)\\text{LiMnP{{\\text{O}}4}} interfaces between LiFePO4 and LiMnPO4 was investigated using density functional theory. The calculated diffusion energy barriers are 0.55 eV for Li to diffuse along the (0 0 1) interface, 0.44 and 0.49 eV for the Li diffusion inside the LiMnPO4 and along the (1 0 0) interface, respectively. When Li diffuses from the LiFePO4 to LiMnPO4 by passing through the (0 1 0) interfaces, the diffusion barriers are 0.45 and 0.60 eV for the Li diffusions in both sides. The diffusion barriers for Li to diffuse in LiMnPO4 near the interfaces decrease compared with those in the pure LiMnPO4. The calculated diffusion coefficient of Li along the (1 0 0) interface is in the range of 3.65  ×  10-11-5.28  ×  10-12 cm2 s-1, which is larger than that in the pure LiMnPO4 with a value of 7.5  ×  10-14 cm2 s-1. Therefore, the charging/discharging rate performance of the LiMnPO4 can be improved by surface coating with the LiFePO4.

Hexagonal perovskites with cationic vacancies. 5. Structure determination on H-Ba/sub 2/Lusub(2/3)vacantsub(1/3)WO/sub 6/ - a novel rhombohedral stacking polytype with 18 layers

Energy Technology Data Exchange (ETDEWEB)

Wischert, W; Schittenhelm, H J; Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Inst. fuer Chemie

1979-01-01

Compounds of type Ba/sub 2/Bsub(2/3)sup(III)vacantsub(1/3)Wsup(VI)O/sub 6/ with Bsup(III) = Gd-Lu, Y are polymorphic. They crystallize in a cubic 1:1 ordered perovskite structure and in a new rhombohedral perovskite stacking polytype of 18 L respectively. By intensity calculations out of the three possible stacking sequences (4)(2), (5)(1) and (3)1(1)1 (all space group R3m) the sequence (5)(1) can be selected. For H-Ba/sub 2/Lusub(2/3)vacant sub(1/3)WO/sub 6/ the refined R' factor is 14.1%. The structure contains groups of three octahedra connected with another by common faces which are linked with each other by three corner sharing octahedra. In the block of three face sharing octahedra the central octahedral lattice site is vacant, the two outer positions are occupied by tungsten atoms. According to this distribution a direct contact of occupied face sharing octahedra is absent.

Photoluminescence and Energy Transfer Properties with Y+SiO4 Substituting Ba+PO4 in Ba3Y(PO4)3:Ce(3+)/Tb(3+), Tb(3+)/Eu(3+) Phosphors for w-LEDs.

Science.gov (United States)

Li, Kai; Liang, Sisi; Shang, Mengmeng; Lian, Hongzhou; Lin, Jun

2016-08-01

A series of Ce(3+), Tb(3+), Eu(3+) doped Ba2Y2(PO4)2(SiO4) (BYSPO) phosphors were synthesized via the high-temperature solid-state reaction route. X-ray diffraction, high-resolution transmission electron microscopy, Fourier transform infrared, solid-state NMR, photoluminescence (PL) including temperature-dependent PL, and fluorescent decay measurements were conducted to characterize and analyze as-prepared samples. BYSPO was obtained by the substitution of Y+SiO4 for Ba+PO4 in Ba3Y(PO4)3 (BYPO). The red shift of PL emission from 375 to 401 nm occurs by comparing BYSPO:0.14Ce(3+) with BYPO:0.14Ce(3+) under 323 nm UV excitation. More importantly, the excitation edge can be extended from 350 to 400 nm, which makes it be excited by UV/n-UV chips (330-410 nm). Tunable emission color from blue to green can be observed under 365 nm UV excitation based on the energy transfer from Ce(3+) to Tb(3+) ions after codoping Tb(3+) into BYSPO:0.14Ce(3+). Moreover, energy transfer from Tb(3+) to Eu(3+) ions also can be found in BYSPO:Tb(3+),Eu(3+) phosphors, resulting in the tunable color from green to orange red upon 377 nm UV excitation. Energy transfer properties were demonstrated by overlap of excitation spectra, variations of emission spectra, and decay times. In addition, energy transfer mechanisms from Ce(3+) to Tb(3+) and Tb(3+) to Eu(3+) in BYSPO were also discussed in detail. Quantum yields and CIE chromatic coordinates were also presented. Generally, the results suggest their potential applications in UV/n-UV pumped LEDs.

Gradient stress induced coexistence of tetragonal and rhombohedral phases in Pb(Zr,Ti)O3 films

International Nuclear Information System (INIS)

Li Liben; Chen Qingdong; Li Xinzhong; Hu Zhixiang; Zhen Zhiqiang

2009-01-01

Thermodynamic theory has been used to explain quantitatively the coexistence of tetragonal and rhombohedral phases in Zr-rich Pb(Zr, Ti)O 3 (PZT) films grown on a compressive substrate. The key is to consider a set of gradient thermal stresses imposed on the films. The 'stress-temperature' phase diagrams were developed for PZT films of several different compositions (Ti/Zr=20/80, 30/70, 40/60, 50/50). The characteristic feature of the phase diagrams for Zr-rich PZT films is the coexistence of tetragonal and rhombohedral phases in the compressive stress region. The volume fractions of the rhombohedral phase were calculated for the Zr-rich PZT films grown on MgO substrate. The result agrees with the experiment.

Synthesis and Characterization of New Nickel Phosphates, ANi4(PO4)3 (A=K, Rb)

International Nuclear Information System (INIS)

Im, Yoonmi; Kim, Pilsoo; Yun, Hoseop

2014-01-01

Quaternary nickel orthophosphates, ANi 4 (PO 4 ) 3 (A=Alkali metals) have been extensively investigated because they show interesting properties such as ionic conductivities, optical, and magnetic behaviors. They are built up from NiO 6 octahedra and PO 4 tetrahedra. These basic building blocks are connected via common oxygen atoms to form the three-dimensional frameworks and the alkali metal ions reside in the empty space. For NaNi 4 (PO 4 ) 3 , two different structures have been reported and this can be caused by the different reaction conditions. While NaNi 4 (PO 4 ) 3 prepared as single crystals with the use of NaCl flux at 1373 K crystallizes in the space group Amam and show a partial disorder of one of the PO 4 tetrahedra, NaNi 4 (PO 4 ) 3 and KNi 4 (PO 4 ) 3 synthesized with alkali metal nitrate at 1073 K as powders adopt an ordered structure with the space group Pnnm. As far as we know, no structural studies of KNi 4 (PO 4 ) 3 from single crystal diffraction data have been reported yet and RbNi 4 (PO 4 ) 3 is a new compound. In this paper we report on the synthesis and structural investigations using single crystals of two nickel orthophosphates, KNi 4 (PO 4 ) 3 and RbNi 4 (PO 4 ) 3

Low-temperature structural phase transition in synthetic libethenite Cu2PO4OH

International Nuclear Information System (INIS)

Belik, Alexei A.; Naumov, Pance; Kim, Jungeun; Tsuda, Shunsuke

2011-01-01

Low-temperature structural properties of the synthetic mineral libethenite Cu 2 PO 4 OH were investigated by single-crystal X-ray diffraction, synchrotron X-ray powder diffraction, specific heat measurements, and Raman spectroscopy. A second-order structural phase transition from the Pnnm symmetry (a=8.0553(8) A, b=8.3750(9) A, c=5.8818(6) A at 180 K) to the P2 1 /n symmetry (a=8.0545(8) A, b=8.3622(9) A, c=5.8755(6) A, β=90.0012(15) at 120 K) was found at 160 K during cooling. At 120 K, the monoclinic angle is 90.0012(15) from single crystal X-ray data vs 90.083(1) from powder X-ray diffraction data. The P2 1 /n-to-Pnnm transition may be a general feature of the adamite-type compounds, M 2 XO 4 OH. - Graphical Abstract: Fragments of experimental synchrotron X-ray powder diffraction patterns of Cu 2 PO 4 OH between 100 and 280 K. Arrows show additional reflections that appear below 160 K in the monoclinic P2 1 /n phase. Highlights: → A low-temperature phase transition was found in the mineral libethenite Cu 2 PO 4 OH. → No magnetic anomalies and weak specific heat anomalies are detected. → Phase transition is of the second order. → Libethenite may exemplify a general feature of the adamite-type compounds.

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

Science.gov (United States)

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.

Concentration of Po-210 and Pb-210 in human tissues

International Nuclear Information System (INIS)

Zhao Lancai; Takizawa, Y.; Yamamoto, M.

1990-01-01

The levels of Pb-210 and Po-210 in human tissues of people in Japan were determined. Various tissue samples were obtained at autopsy from the cadavers of 22 oncologic cases, mainly in Niigata Prefecture in northern Japan during the period of 1986 to 1988. Wet ashing, followed by electrochemical deposition and alpha-ray spectrometry were used to separate and determine the Pb-210 and Po-210 presented. Among the tissues analyzed the highest concentrations of Pb-210 and Po-210 were observed in bone, liver and kidneys: 1.29, 1.69 and 1.22 Bq.kg -1 respectively for Po-210, and 1.27, 0.56 and 0.43 Bq/kg for Pb-210 respectively. The Po-210/Pb-210 ratios in liver and kidney are 3.0 and 2.9 respectively. Po-210/Pb-210 ratios in other tissues are close to one. The total body burden of Pb-210 and Po-210 was found to be approximately 15.8 Bq and 19.1 Bq respectively

Synthesis of LiFePO4/Li2SiO3/reduced Graphene Oxide (rGO) Composite via Hydrothermal Method

Science.gov (United States)

Arifin, M.; Iskandar, F.; Aimon, A. H.; Munir, M. M.; Nuryadin, B. W.

2016-08-01

LiFePO4 is a type of cathode active material used for lithium ion batteries. It has a high electrochemical performance. However, it suffers from certain disadvantages such as a very low intrinsic electronic conductivity and low ionic diffusion. This study was conducted to increase the conductivity of LiFePO4. We have investigated the addition of Li2SiO3 and reduced graphene oxide (rGO) to LiFePO4. The objective of this research was to synthesize LiFePO4/Li2SiO3/rGO via hydrothermal method. Fourier transform infrared spectroscopy (FTIR) measurement showed that the peaks corresponded to the vibration of LiFePO4/Li2SiO3. Further, X-ray diffraction (XRD) measurement confirmed a single phase of LiFePO4. Finally, scanning electron microscopy (SEM) images showed that rGO was distributed on the LiFePO4/Li2SiO3 structure.

Synthesis of LiFePO4/Li2SiO3/reduced Graphene Oxide (rGO) Composite via Hydrothermal Method

International Nuclear Information System (INIS)

Arifin, M; Iskandar, F; Aimon, A H; Munir, M M; Nuryadin, B W

2016-01-01

LiFePO 4 is a type of cathode active material used for lithium ion batteries. It has a high electrochemical performance. However, it suffers from certain disadvantages such as a very low intrinsic electronic conductivity and low ionic diffusion. This study was conducted to increase the conductivity of LiFePO4. We have investigated the addition of Li2SiO3 and reduced graphene oxide (rGO) to LiFePO4. The objective of this research was to synthesize LiFePO 4 /Li 2 SiO 3 /rGO via hydrothermal method. Fourier transform infrared spectroscopy (FTIR) measurement showed that the peaks corresponded to the vibration of LiFePO 4 /Li 2 SiO 3 . Further, X-ray diffraction (XRD) measurement confirmed a single phase of LiFePO4. Finally, scanning electron microscopy (SEM) images showed that rGO was distributed on the LiFePO 4 /Li 2 SiO 3 structure. (paper)

Low collectivity of the first 2+ states of 212,210Po

Science.gov (United States)

Kocheva, D.; Rainovski, G.; Jolie, J.; Pietralla, N.; Blazhev, A.; Astier, A.; Altenkirch, R.; Bast, M.; Beckers, M.; Ansari, S.; Braunroth, Th.; Cappellazzo, M.; Cortés, M. L.; Dewald, A.; Diel, F.; Djongolov, M.; Fransen, C.; Gladnishki, K.; Goldkuhle, A.; Hennig, A.; Karayonchev, V.; Keatings, J. M.; Kluge, E.; Kröll, Th.; Litzinger, J.; Moschner, K.; Müller-Gatermann, C.; Petkov, P.; Rudigier, M.; Scheck, M.; Spagnoletti, P.; Scholz, Ph.; Schmidt, T.; Spieker, M.; Stahl, C.; Stegmann, R.; Stolz, A.; Vogt, A.; Stoyanova, M.; Thöle, P.; Warr, N.; Werner, V.; Witt, W.; Wölk, D.; Zamora, J. C.; Zell, K. O.; Van Isacker, P.; Ponomarev, V. Yu.

2018-05-01

The lifetimes of the first 2+ excited states of 212,210Po were measured in two transfer reactions 208Pb(12C,8Be)212Po and 208Pb(12C,10Be)210Po by the Recoil Distance Doppler Shift (RDDS) method and by the Doppler Shift Attenuation method (DSAM), respectively. The derived absolute B(E2) values of 2.6(3) W.u. for 212Po and 1.83(28) W.u. for 210Po indicate low collectivity. It is shown that the properties of the yrast {2}1+, {4}1+, {6}1+ and {8}1+ states in both nuclei cannot be described consistently in the framework of nuclear shell models. It is also demonstrated in the case of 210Po that Quasi-particle Phonon Model (QPM) calculations cannot overcome this problem thus indicating the existence of a peculiarity which is neglected in both theoretical approaches.

Conductivity of Composite Material Based on System NdPO4·nH2OCsH2PO4

DEFF Research Database (Denmark)

Anfimova, Tatiana; Bjerrum, Niels J.; Li, Qingfeng

2013-01-01

The goal of the present study was to obtain a comprehensive knowledge about synthesis conditions, structure, thermal behavior and conductivity properties of neodymiumorthophosphates in order to analyze of use this material in intermediate temperature fuel cells due to their thermal and chemical...... stability properties.The impedance spectroscopy technique (IS) was used to measure the conductivity. The conductivity of composites observed to be lower than conductivity of pure CsH2PO4 but had improved sufficiently conductivity of pure NdPO4·nH2O...

New equations to calculate temperature correction factors for PO2 in human blood.

Science.gov (United States)

Inaba, H; Ohwada, T; Sato, J; Mizuguchi, T; Hirasawa, H

1986-01-01

Effects of hemoglobin concentration (Hb), pH, and body temperature (T) on the relationships between delta log PO2/delta T and PO2 were studied by means of a mathematical model using a Newton-Raphson iteration method. The functions between delta log PO2/delta T and PO2 were affected by the above three factors. New equations considering the effects of Hb, pH, and T were proposed by modifying the equation reported by Severinghaus: delta log PO2/delta T = (L +(U-L)/(A(vPO237)B + 1))(10(-2) where U = 3.15-0.45(7.4-pH37) L = 0.68-0.09(7.4-pH37) A = 5.86(exp10(0.074(T)-0.294(7.4-pH37)-11))((Hb)0.913) B = 6.33(exp10(-0.0051(T)))((Hb)-0.113) + 0.24(7.4-pH37) and vPO237 is virtual PO237 which may exist when PO237 is corrected to standard conditions (pH = 7.4, BE = 0) by the following equations: vPO237 = PO237(exp10(fB(7.4-pH37)-0.0013(BE))) fB = (PO237/26.6)0.08-1.52 where fB is the Bohr factor. The above equations provided values of delta log PO2/delta T which fit closely to those obtained by the complex iteration method with maximum differences of less than 1.3 X 10(-3) at T = 27, indicating that maximum % errors for PO2 at T (PO2T) are less than 3.0% at T = 27 and that our equations can be applied over a wide range of Hb, pH37 and T.

Hexagonal perovskites with cationic vacancies. 17. Structure determination on Ba/sub 9/Nb/sub 6/Wvacant/sub 2/O/sub 27/ - the first stacking polytype of a rhombohedral 27 L-type

Energy Technology Data Exchange (ETDEWEB)

Kemmler-Sack, S; Treiber, U [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1980-03-01

The hexagonal stacking polytype of rhombohedral 27 L-type, Ba/sub 9/Nb/sub 6/Wvacant/sub 2/O/sub 27/, crystallizes in the space group R3m with the sequence (4)1(3)1 = (hhccchhcc)/sub 3/ and three formula units for the trigonal setting. The refined, intensity, related, R'-value is 9.7%. The octahedral net consists of blocks of three face connected octahedra which are linked to each other alternately through one or two octahedra connected exclusively by common vertices. The cationic vacancies are located in the centers of the groups of three octahedra. With this distribution direct contact between occupied face-sharing octahedra is avoided. The niobium and tungsten atoms are distributed statistically between the remaining octahedral holes. In the blocks of three octahedra they are displaced by approximately 0.29 A from their ideal positions in the direction of the central void. The Ba atoms neighbouring a vacancy (all in hexagonal packed BaO/sub 3/ sheets) are dislocated in the direction of the void, while the cubic packed BaO/sub 3/ sheets maintain nearly regular form.

Structural relationships in rhombohedral perovskites with R-3C symmetry

Energy Technology Data Exchange (ETDEWEB)

Bogush, A K; Pavlov, V I [AN Belorusskoj SSR, Minsk. Inst. Fiziki Tverdogo Tela i Poluprovodnikov

1982-05-01

In rhombohedral perovskites the structure parameters, e.g. the interaxial angle alpha/sub rh/ or the hexagonal lattice parameters a/sub H/ and c/sub H/ are completely determined by the tilt angle omega. The geometrical relations between these structural parameters and the tilt angle omega are reported.

PO2 Cycling Reduces Diaphragm Fatigue by Attenuating ROS Formation

OpenAIRE

Zuo, Li; Diaz, Philip T.; Chien, Michael T.; Roberts, William J.; Kishek, Juliana; Best, Thomas M.; Wagner, Peter D.

2014-01-01

Prolonged muscle exposure to low PO2 conditions may cause oxidative stress resulting in severe muscular injuries. We hypothesize that PO2 cycling preconditioning, which involves brief cycles of diaphragmatic muscle exposure to a low oxygen level (40 Torr) followed by a high oxygen level (550 Torr), can reduce intracellular reactive oxygen species (ROS) as well as attenuate muscle fatigue in mouse diaphragm under low PO2. Accordingly, dihydrofluorescein (a fluorescent probe) was used to monito...

Skeletal muscle microvascular and interstitial PO2 from rest to contractions.

Science.gov (United States)

Hirai, Daniel M; Craig, Jesse C; Colburn, Trenton D; Eshima, Hiroaki; Kano, Yutaka; Sexton, William L; Musch, Timothy I; Poole, David C

2018-03-01

Oxygen pressure gradients across the microvascular walls are essential for oxygen diffusion from blood to tissue cells. At any given flux, the magnitude of these transmural gradients is proportional to the local resistance. The greatest resistance to oxygen transport into skeletal muscle is considered to reside in the short distance between red blood cells and myocytes. Although crucial to oxygen transport, little is known about transmural pressure gradients within skeletal muscle during contractions. We evaluated oxygen pressures within both the skeletal muscle microvascular and interstitial spaces to determine transmural gradients during the rest-contraction transient in anaesthetized rats. The significant transmural gradient observed at rest was sustained during submaximal muscle contractions. Our findings support that the blood-myocyte interface provides substantial resistance to oxygen diffusion at rest and during contractions and suggest that modulations in microvascular haemodynamics and red blood cell distribution constitute primary mechanisms driving increased transmural oxygen flux with contractions. Oxygen pressure (PO2) gradients across the blood-myocyte interface are required for diffusive O 2 transport, thereby supporting oxidative metabolism. The greatest resistance to O 2 flux into skeletal muscle is considered to reside between the erythrocyte surface and adjacent sarcolemma, although this has not been measured during contractions. We tested the hypothesis that O 2 gradients between skeletal muscle microvascular (PO2 mv ) and interstitial (PO2 is ) spaces would be present at rest and maintained or increased during contractions. PO2 mv and PO2 is   were determined via phosphorescence quenching (Oxyphor probes G2 and G4, respectively) in the exposed rat spinotrapezius during the rest-contraction transient (1 Hz, 6 V; n = 8). PO2 mv was higher than PO2 is in all instances from rest (34.9 ± 6.0 versus 15.7 ± 6.4) to contractions (28.4 ± 5

Temperature effect on uranium retention onto Zr2O(PO4)2 surface

International Nuclear Information System (INIS)

Almazan Torres, M.G.

2007-03-01

Uranium sorption onto Zr 2 O(PO 4 ) 2 has been studied between 298 K and 363 K, in 0.1 M NaClO 4 medium. Potentiometric titrations were realized to determine temperature dependency of the acid-base properties (pH(pcn), acidity constants). Classical batch experiments were performed at different temperatures. The sorption experiments revealed that the uranium sorption onto Zr 2 O(PO 4 ) 2 is favoured with the temperature. Structural characterization of the surface complexes was performed by both Time-Resolved Laser-Induced Fluorescence (TRLIF) and EXAFS spectroscopy. The TRLIF measurements vs. temperature revealed two uranyl surface complexes. No influence of the temperature onto the nature surface complex was observed. The EXAFS analysis showed a splitting of the equatorial oxygen atoms in two shells, corresponding to uranyl bidentate, inner-sphere complexes. The obtained structural uranyl surface complex information was used to simulate (using a constant capacitance model) the sorption edges. The proposed complexes equilibrium model consists of the following surface complexes: (ZrOH) 2 UO 2 2+ and (PO) 2 UO 2 . Besides the stability constants for the surface complexes, the thermodynamic parameters ΔH 0 and ΔS 0 were determined using the van't Hoff equation. The enthalpy values associated to the U(VI) retention onto Zr 2 O(PO 4 ) 2 , determined by the temperature dependence of the stability constants, testify that the formation of the complex (PO) 2 UO 2 (55 kJ/mol) is endothermic, while no influence of the temperature was observed for the formation of the complex (ZrOH) 2 UO 2 2+ . The adsorption reaction of the last complex is then driven by entropy. In addition, calorimetric measurements of uranium sorption onto Zr 2 O(PO 4 ) 2 were carried out to directly quantify the enthalpy associated to the retention processes. (author)

Measuring interstitial pH and pO2 in mouse tumors.

Science.gov (United States)

Jain, Rakesh K; Munn, Lance L; Fukumura, Dai

2013-07-01

This protocol outlines methods to measure two extravascular parameters, interstitial pH and partial pressure of oxygen (pO2), in mouse tumors. The method for measuring interstitial pH uses fluorescence ratio imaging microscopy (FRIM) of the pH-sensitive fluorescent dye 2',7'-bis-(2-carboxyethyl)-5,6-carboxyfluorescein (BCECF). The method for measuring interstitial pO2 is based on the oxygen-dependent quenching of the phosphorescence of albumin-bound palladium meso-tetra(4-carboxyphenyl)porphyrin, and can be used to measure microvascular as well as interstitial pO2. In addition, the two methods can be used sequentially to measure both pH and pO2 in the same tissues.

Enhanced lithium-ion storage performance by structural phase transition from two-dimensional rhombohedral Fe_2O_3 to cubic Fe_3O_4

International Nuclear Information System (INIS)

Ren, Yurong; Wang, Jiawei; Huang, Xiaobing; Ding, Jianning

2016-01-01

Highlights: • The rhombohedral Fe_2O_3 transforms to the cubic Fe_3O_4 via a calcination treatment. • Phase structure of anodes has great influences on their electrochemical performances. • Fe_3O_4/reduced graphene oxide shows a high capacity of 825.3 mAh g"−"1 at 50 mA g"−"1. - Abstract: The electrochemical performance of a material varies with its structural phase transition. It is found that the rhombohedral Fe_2O_3 can transform to the cubic Fe_3O_4 via a calcination treatment in a nitrogen atmosphere, and lithium-ion storage performances of Fe_3O_4 get an obvious improvement due to its structural advantages. On the basis of data calculated by X-ray diffraction, the larger unit cell volume as well as the higher void fraction of cubic Fe_3O_4 provides lithium-ions with more transport channels for Li ions diffusion and storage without serious volume change, and thus the cubic Fe_3O_4 delivers an excellent reversible capacity of 921.1 mAh g"−"1 after 15 cycles at the current density of 50 mA g"−"1, which is much higher than 328.3 mAh g"−"1 for the rhombohedral Fe_2O_3. To further enhance the structural stability of electrodes, reduced graphene oxide is introduced. The Fe_3O_4/reduced graphene oxide show an excellent specific capacity of 825.3 mAh g"−"1 after 40 cycles and impressive rate performance of 600 mAh g"−"1 at the current density of 400 mA g"−"1, which are much higher than that of Fe_3O_4 (417 and 300 mAh g"−"1), Fe_2O_3 (137.4 and 95 mAh g"−"1) and Fe_2O_3/reduced graphene oxide (390.1 and 480 mAh g"−"1). These results demonstrate that the structural phase transition and reduced graphene oxide of Fe_3O_4/reduced graphene oxide composites offer unique characteristics suitable for high-performance energy storage application.

[Experimental branch vein occlusion: the effect of carbogen breathing on preretinal PO2].

Science.gov (United States)

Pournaras, J-A C; Poitry, S; Munoz, J-L; Pournaras, C J

2003-10-01

To evaluate the variations in preretinal PO2 in normal and in ischemic postexperimental branch vein occlusion (BRVO) retinal areas during normoxia, hyperoxia (100% O2) and carbogen (95% O2, 5% CO2) breathing. Preretinal PO2 measurements were obtained in intervascular retinal areas far from the retinal vessels of 13 anesthetized miniature pigs with oxygen-sensitive microelectrodes (10 microm tip diameter) introduced through the vitreous cavity by a micromanipulator. The microelectrode tip was placed at 50 microm from the vitreoretinal interface in the preretinal vitreous. PO2 was measured continuously for 10 minutes in systemic normoxia, hyperoxia (100% O2 breathing) and carbogen (95% O2, 5% CO2) breathing. A BRVO was induced with an argon green laser, and oxygen measurements were repeated in normoxia, hyperoxia and carbogen breathing. In hyperoxia, preretinal PO2 remained almost constant in both normal retinas (DeltaPO2=1.33 mmHg +/- 3.39; n=13) and ischemic retinas (DeltaPO2=3.73 mmHg +/- 2.84; n=8), although systemic PaO2 significantly increased. Carbogen breathing induced a significant increase in systemic PaO2 and PaCO2. Furthermore, it significantly increased preretinal PO2: DeltaPO2=23.05 mmHg +/- 17.06 (n=12) in normal retinas, and DeltaPO2=22.54 mmHg +/- 5.96 (n=6) in ischemic retinal areas. Systemic hyperoxia does not increase preretinal PO2 significantly in normal and ischemic post-BRVO retinal areas of miniature pigs, as hyperoxia induces a decrease in the retinal blood flow. Carbogen breathing significantly increases preretinal PO2 in normal and in ischemic post-BRVO retinal areas. This effect is probably due to the vasodilatation of the retinal arterioles induced by the intravascular PaCO2 increase.

Interplay of tumor vascular oxygenation and tumor pO2 observed using near-infrared spectroscopy, an oxygen needle electrode, and 19F MR pO2 mapping.

Science.gov (United States)

Kim, Jae G; Zhao, Dawen; Song, Yulin; Constantinescu, Anca; Mason, Ralph P; Liu, Hanli

2003-01-01

This study investigates the correlation of tumor blood oxygenation and tumor pO(2) with respect to carbogen inhalation. After having refined and validated the algorithms for calculating hemoglobin concentrations, we used near-infrared spectroscopy (NIRS) to measure changes of oxygenated hemoglobin concentration (delta[HbO(2)]) and used an oxygen needle electrode and (19)F MRI for pO(2) measurements in tumors. The measurements were taken from Dunning prostate R3327 tumors implanted in rats, while the anesthetized rats breathed air or carbogen. The NIRS results from tumor measurements showed significant changes in tumor vascular oxygenation in response to carbogen inhalation, while the pO(2) electrode results showed an apparent heterogeneity for tumor pO(2) response to carbogen inhalation, which was also confirmed by (19)F MR pO(2) mapping. Furthermore, we developed algorithms to estimate hemoglobin oxygen saturation, sO(2), during gas intervention based on the measured values of delta[HbO(2)] and pO(2). The algorithms have been validated through a tissue-simulating phantom and used to estimate the values of sO(2) in the animal tumor measurement based on the NIRS and global mean pO(2) values. This study demonstrates that the NIRS technology can provide an efficient, real-time, noninvasive approach to monitoring tumor physiology and is complementary to other techniques, while it also demonstrates the need for an NIR imaging technique to study spatial heterogeneity of tumor vasculature under therapeutic interventions. Copyright 2003 Society of Photo-Optical Instrumentation Engineers

Rat muscle microvascular PO2 kinetics during the exercise off-transient.

Science.gov (United States)

McDonough, P; Behnke, B J; Kindig, C A; Poole, D C

2001-05-01

Dependent upon the relative speed of pulmonary oxygen consumption (VO2) and blood flow (Q) kinetics, the exercise off-transient may represent a condition of sub- or supra-optimal perfusion. To date, there are no direct measurements of the dynamics of the VO2/Q relationship within the muscle at the onset of the work/recovery transition. To address this issue, microvascular PO2 (PO2,m) dynamics were studied in the spinotrapezius muscles of 11 female Sprague-Dawley rats (weight approximately 220 g) during and following electrical stimulation (1 Hz) to assess the adequacy of Q. relative to VO2 post exercise. The exercise blood flow response (radioactive microspheres: muscle Q increased approximately 240 %), and post-exercise arterial blood pH (7.40 +/- 0.02) and blood lactate (1.3 +/- 0.4 mM x l(-1)) values were consistent with moderate-intensity exercise. Recovery PO2,m (i.e. off-transient) rose progressively until baseline values were achieved ((Delta)end-recovery exercise PO2,m, 14.0 +/- 1.9 Torr) and at no time fell below exercising PO2,m. The off-transient PO2,m was well fitted by a dual exponential model with both fast (tau = 25.4 +/- 5.1 s) and slow (tau = 71.2 +/- 34.2 s) components. Furthermore, there was a pronounced delay (54.9 +/- 10.7 s) before the onset of the slow component. These data, obtained at the muscle microvascular level, support the notion that muscle VO2 falls with faster kinetics than muscle Q during the off-transient, such that PO2,m increases systematically, though biphasically, during recovery.

Determination of the PO2 temperature blood factor from oxygen dissociation curves.

Science.gov (United States)

Hérigault, R A; Soulard, C D; Teisseire, B P; Laurent, D N

1983-01-01

The variation with saturation of the temperature coefficient of PO2 in human blood (delta log PO2/delta T) was determined by continuous recording of the oxygen dissociation curve (ODC), at 37 degrees C and 25 degrees C, on the same blood samples. PCO2 and pH were held constant through an ODC run, and PCO2 was reduced at 25 degrees C to the value measured by anaerobic cooling of the same sample. delta log PO2/delta T was calculated from isosaturation points on the 37 and 25 degrees C curves. The temperature coefficient was also computed as an independent check on this method by determination of the effects of temperature (25, 30, 37 and 40 degrees C) on hemoglobin ligand interaction: fixed acid Bohr effect (delta log PO2/delta pH), carbamino-formation (delta log PO2/delta log PCO2) and hemoglobin oxygen affinity. The values of delta log PO2/delta T ratio obtained from the two different approaches were found to be in good agreement. The coefficient decreased when [H+] concentration was increased. A linear relationship between the Bohr factor and the temperature was found: delta log PO2/delta pH = 0.00267 T-0.520 (r = 0.85; n = 40) At 25 degrees C, the carbamino-formation was one order of magnitude lower than at 37 degrees C. Acid-base state and saturation value appeared to be major determinant factors for the temperature correction coefficient to be applied to blood PO2 values measured at standard (37 degrees C) temperature.

Neutron diffraction, specific heat and magnetic susceptibility of Ni3(PO4)2

International Nuclear Information System (INIS)

Escobal, J.; Pizarro, J.L.; Mesa, J.L.; Rojo, J.M.; Bazan, B.; Arriortua, M.I.; Rojo, T.

2005-01-01

The Ni 3 (PO 4 ) 2 phosphate was synthesized by the ceramic method in air atmosphere. The crystal structure consists of a three-dimensional skeleton constructed from Ni 3 O 14 edge-sharing octahedra, which are interconnected by (PO 4 ) 3- oxoanions with tetrahedral geometry. The magnetic behavior was studied on powdered sample by using susceptibility, specific heat and neutron diffraction data. The nickel(II) orthophosphate exhibits a three-dimensional magnetic ordering at approximately 17.1 K. However, its complex crystal structure hampers any parametrization of the J-exchange parameter. The specific heat measurements of Ni 3 (PO 4 ) 2 exhibit a three-dimensional magnetic ordering (λ-type) peak at 17.1 K. Measurements above T N suggest the presence of a small short-range order in this phase. The total magnetic entropy was found to be 28.1 KJ/mol at 50 K. The magnetic structure of the nickel(II) phosphate exhibits ferromagnetic interactions inside the Ni 3 O 14 trimers which are antiferromagnetically coupled between them, giving rise to a purely antiferromagnetic structure

Magnetism in olivine-type LiCo(1-x)Fe(x)PO4 cathode materials: bridging theory and experiment.

Science.gov (United States)

Singh, Vijay; Gershinsky, Yelena; Kosa, Monica; Dixit, Mudit; Zitoun, David; Major, Dan Thomas

2015-12-14

In the current paper, we present a non-aqueous sol-gel synthesis of olivine type LiCo1-xFexPO4 compounds (x = 0.00, 0.25, 0.50, 0.75, 1.00). The magnetic properties of the olivines are measured experimentally and calculated using first-principles theory. Specifically, the electronic and magnetic properties are studied in detail with standard density functional theory (DFT), as well as by including spin-orbit coupling (SOC), which couples the spin to the crystal structure. We find that the Co(2+) ions exhibit strong orbital moment in the pure LiCoPO4 system, which is partially quenched upon substitution of Co(2+) by Fe(2+). Interestingly, we also observe a non-negligible orbital moment on the Fe(2+) ion. We underscore that the inclusion of SOC in the calculations is essential to obtain qualitative agreement with the observed effective magnetic moments. Additionally, Wannier functions were used to understand the experimentally observed rising trend in the Néel temperature, which is directly related to the magnetic exchange interaction paths in the materials. We suggest that out of layer M-O-P-O-M magnetic interactions (J⊥) are present in the studied materials. The current findings shed light on important differences observed in the electrochemistry of the cathode material LiCoPO4 compared to the already mature olivine material LiFePO4.

Electronic Properties of LiFePO4 and Li doped LiFePO4

International Nuclear Information System (INIS)

Zhuang, G.V.; Allen, J.L.; Ross, P.N.; Guo, J.-H.; Jow, T.R.

2005-01-01

The potential use of different iron phosphates as cathode materials in lithium-ion batteries has recently been investigated.1 One of the promising candidates is LiFePO4. This compound has several advantages in comparison to the state-of-the-art cathode material in commercial rechargeable lithium batteries. Firstly, it has a high theoretical capacity (170 mAh/g). Secondly, it occurs as mineral triphylite in nature and is inexpensive, thermally stable, non-toxic and non-hygroscopic. However, its low electronic conductivity (∼10-9 S/cm) results in low power capability. There has been intense worldwide research activity to find methods to increase the electronic conductivity of LiFePO4, including supervalent ion doping,2 introducing non-carbonaceous network conduction3 and carbon coating, and the optimization of the carbon coating on LiFePO4 particle surfaces.4 Recently, the Li doped LiFePO4 (Li1+xFe1-xPO4) synthesized at ARL has yield electronic conductivity increase up to 106.5 We studied electronic structure of LiFePO4 and Li doped LiFePO4 by synchrotron based soft X-ray emission (XES) and X-ray absorption (XAS) spectroscopies. XAS probes the unoccupied partial density of states, while XES the occupied partial density of states. By combining XAS and XES measurements, we obtained information on band gap and orbital character of both LiFePO4 and Li doped LiFePO4. The occupied and unoccupied oxygen partial density of states (DOS) of LiFePO4 and 5 percent Li doped LiFePO4 are presented in Fig. 1. Our experimental results clearly indicate that LiFePO4 has wideband gap (∼ 4 eV). This value is much larger than what is predicted by DFT calculation. For 5 percent Li doped LiFePO4, a new doping state was created closer to the Fermi level, imparting p-type conductivity, consistent with thermopower measurement. Such observation substantiates the suggestion that high electronic conductivity in Li1.05Fe0.95 PO4 is due to available number of charge carriers in the material

Synthesis, crystal growth and structure of Mg containing β-rhombohedral boron: MgB17.4

International Nuclear Information System (INIS)

Adasch, Volker; Hess, Kai-Uwe; Ludwig, Thilo; Vojteer, Natascha; Hillebrecht, Harald

2006-01-01

For the first time, single crystals of Mg containing β-rhombohedral boron MgB 17.4 were synthesised from the elements in a Mg/Cu melt at 1600deg. C. The crystal structure determined by the refinement of single crystal data (space group R-3m, a=10.991(2)A, c=24.161(4)A, 890 reflections, 123 variables, R 1 (F)=0.049, wR 2 (I)=0.122) improves and modifies the former structure model derived from earlier investigations on powder samples. Mg is located on four different positions with partial occupation. While the occupation of the sites D (53.3%), E (91%) and F (7.2%) is already known from other boron-rich borides related to β-rhombohedral boron, the occupation of the fourth position (18h, 6.7%) is observed for the first time. Two boron positions show partial occupation. The summation reveals the composition MgB 17.4 and Mg 5.85 B 101.9 , respectively, confirmed by WDX measurements. The single crystals of MgB 17.4 show the highest Mg content ever found. Preliminary measurements indicate no superconductivity

Hexagonal perovskites with cationic vacancies. 26. Ba/sub 12/Ba/sub 2//sub 2/3/M/sub 7//sup V//sub 1/3/vacant/sub 2/O/sub 33/vacant/sub 3/ (Msup(V) =Nb, Ta) - the first stacking polytypes of a rhombohedral 36 L-type

Energy Technology Data Exchange (ETDEWEB)

Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1981-05-01

In the systems BaO-M/sub 2//sup V/O/sub 5/ (M/sup V/ = Nb, Ta) for a Ba:M/sup V/ ratio of 2:1 polymorphism is observed. Here the low temperature modifications are described. They crystallize in a rhombohedral 36 L structure with three formula units Ba/sub 12/Ba/sub 2//sub 2/3/M/sub 7//sup V//sub 1/3/vacant/sub 2/O/sub 33/vacant/sub 3/ for the trigonal setting (M/sup V/ = Nb: a = 5.92/sub 2/ A; c = 93./sub 25/ A; Ta: a = 5.92/sub 2/ A; c = 93.4 A).

Electronic structure and lattice dynamics of rhombohedral BiAlO_3 from first-principles

International Nuclear Information System (INIS)

Kaczkowski, J.

2016-01-01

The structural, elastic, electronic, dynamical (zone-center phonon modes and Born effective charge tensors), and ferroelectric properties of the rhombohedral BiAlO_3 were calculated within various exchange-correlation functionals. The standard local-density (LDA) and generalized gradient (GGA) approximations, and nonlocal hybrid Heyd-Scuseria-Ernzerhof (HSE) were used. We have also performed the electronic structure calculations with meta-GGA Tran-Blaha functional. BiAlO_3 is indirect band gap semiconductor with the value of band gap: 2.87 eV (GGA), 4.14 eV (HSE), and 3.78 eV (TB-mBJ). The calculated spontaneous polarization is 81 μC/cm"2 (87 μC/cm"2) for GGA (HSE). The vibrational spectrum including LO-TO splitting was calculated within GGA. The zone-center phonon modes with LO-TO splitting for BiAlO_3 were compared with those in isostructural BiFeO_3. - Highlights: • Electronic structure of the rhombohedral phase of BiAlO_3 were calculated. • Structural, elastic, dynamical, and ferroelectric properties were investigated. • Calculations were done within GGA, hybrid HSE, and TB-mBJ functionals. • The lattice dynamics with LO-TO splitting were investigated within GGA functional.

Copper(II) manganese(II) orthophosphate, Cu_0.5Mn_2.5(PO₄)₂

DEFF Research Database (Denmark)

Warner, Terence Edwin; Bond, Andrew; Foghmoes, Søren Preben Vagn

2011-01-01

The title compound, Cu0.5Mn2.5(PO4)2, is a copper-manganese phosphate solid solution with the graftonite-type structure, (Mn,Fe,Ca,Mg)3(PO4)2. The structure has three distinct metal cation sites, two of which are occupied exclusively by MnII, and one of which accommodates CuII. Incorporation of C......II into the structure distorts the coordination geometry of the metal cation site from 5-coordinate square-pyramidal towards 4-coordinate flattened tetrahedral, and serves to contract the structure principally along the c axis....

Highly-efficient photocatalytic degradation of methylene blue by PoPD-modified TiO 2 nanocomposites due to photosensitization-synergetic effect of TiO2 with PoPD.

Science.gov (United States)

Yang, Chuanxi; Dong, Wenping; Cui, Guanwei; Zhao, Yingqiang; Shi, Xifeng; Xia, Xinyuan; Tang, Bo; Wang, Weiliang

2017-06-21

Poly-o-phenylenediamine modified TiO 2 nanocomposites were successfully synthesized via an 'in situ' oxidative polymerization method. The modified nanocomposites were characterized by BET, XRD, TEM, FT-IR, TGA, XPS, EA and UV-Vis DRS. The photocatalytic degradation of methylene blue was chosen as a model reaction to evaluate the photocatalytic activities of TiO 2 and PoPD/TiO 2 . The results indicated that PoPD/TiO 2 nanocomposites exhibited good photocatalytic activity and stability. The photocatalytic activity of PoPD/TiO 2 increased as the initial pH increased because of electrostatic adsorption between the photocatalyst and MB as well as the generation of ·OH, whereas it exhibited an earlier increasing and later decreasing trend as the concentration of the photocatalyst increased owing to the absorption of visible light. The photocatalytic stability of the PoPD/TiO 2 nanocomposite was dependent on the stability of its structure. Based on radical trapping experiments and ESR measurements, the origin of oxidizing ability of PoPD/TiO 2 nanocomposites on photocatalytic degradation of MB was proposed, which taking into account of ·OH and ·O 2 - were the first and second important ROS, respectively. The possible photocatalytic mechanism and photocatalytic activity enhanced mechanism has been proposed, taking into account the photosensitization effect and synergetic effect of TiO 2 with PoPD.

Hexagonal perovskites with cationic vacancies. 1. Compounds of the type Ba/sub 2/Bsub(1/3)sup(III) vacantsub(2/3) Resup(VII)O/sub 6/

Energy Technology Data Exchange (ETDEWEB)

Kemmler-Sack, S; Jooss, I [Tuebingen Univ. (Germany, F.R.). Inst. fuer Chemie

1978-04-01

Compounds of type Ba/sub 2/Bsub(1/3)sup(III)vacantsub(2/3)Resup(VII)O/sub 6/ are formed with Bsup(III) = Sm-Gd, Ho-Lu, Y, Sc, In (yellow); Tb (black-brown); Dy (yellow-orange). They crystallize with Bsup(III) = Sm-Lu, Y and Sc in a rhombohedral layer structure of 12 L-type (space group R3m; sequence: cchhcchhcchh) with 6 formula units in the unit cell.

Synthesis, crystal structure, and ionic conductivity of a new layered metal phosphate, Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3}

Energy Technology Data Exchange (ETDEWEB)

Kim, Sung-Chul; Kwak, Hyun-Jung [Department of Energy Systems Research, Ajou University, Suwon 16499 (Korea, Republic of); Yoo, Chung-Yul [Advanced Materials & Devices Laboratory, Korea Institute of Energy Research, Daejeon 34129 (Korea, Republic of); Yun, Hoseop [Department of Energy Systems Research, Ajou University, Suwon 16499 (Korea, Republic of); Kim, Seung-Joo, E-mail: sjookim@ajou.ac.kr [Department of Energy Systems Research, Ajou University, Suwon 16499 (Korea, Republic of)

2016-11-15

A new layered metal phosphate, Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3}, was synthesized in the form of either a single-crystal or polycrystalline powder using the molten hydroxide flux method or a solid-state reaction, respectively. Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3} crystallizes to the P2{sub 1}/n (Z=4) monoclinic space group with lattice parameters a≈4.95 Å, b≈22.06 Å, c≈8.63 Å, and β≈91.5°. The structure is composed of stacked [LiSrAl(PO{sub 4}){sub 2}] layers alternating regularly with [LiSrPO{sub 4}] layers. In the [LiSrAl(PO{sub 4}){sub 2}] sublattice, the AlO{sub 6} octahedra and PO{sub 4} tetrahedra are tilted cooperatively to form an anionic, corrugated, two-dimensional [Al(PO{sub 4}){sub 2}]{sup 3−} framework that can be regarded as a “distorted-glaserite” structure. The [LiSrPO{sub 4}] sublattice is that of a layered block containing a six-membered ring formed from alternating linkages of LiO{sub 4} and PO{sub 4} tetrahedra. The six-membered rings show a boat-type arrangement with the up(U) or down(D) pointing sequence, UUDUUD. The interspace between the two sublattices generates a two-dimensional pathway for Li{sup +} ion conduction. The impedance measurement indicated that Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3} had a moderate ion conductivity (σ≈1.30×10{sup −4} S cm{sup −1} at 667 K), with an activation energy E{sub a}≈1.02 eV. - Graphical abstract: Polyhedral view of Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3}. Li{sup +} ions are represented by green spheres, Sr atoms by white spheres, AlO{sub 6} groups by octahedra, and PO{sub 4} groups by tetrahedra. - Highlights: • New compound Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3} is reported. • The crystal structure is investigated by single-crystal XRD analysis. • The structure is formed by the alternate stacking of two different sublattices. • Correlation between the crystal structure and ionic conductivity is discussed.

Synthesis and Structural Characterization of a CHA-type AlPO4 Molecular Sieve with Penta-Coordinated Framework Aluminum Atoms.

Science.gov (United States)

Park, Gi Tae; Jo, Donghui; Ahn, Nak Ho; Cho, Jung; Hong, Suk Bong

2017-07-17

The structure-directing effects of a series of polymethylimidazolium cations with different numbers of methyl groups as organic structure-directing agents (OSDAs) in the synthesis of aluminophosphate (AlPO 4 )-based molecular sieves in both fluoride and hydroxide media are investigated. On the one hand, among the OSDAs studied here, the smallest 1,3-dimethylimidazolium and the largest 1,2,3,4,5-pentamethylimidazolium cations were found to direct the synthesis of a new variant of the triclinic chabazite (CHA)-type AlPO 4 material, designated AlPO 4 -34(t) V , and the one-dimensional small-pore silicoaluminophosphate (SAPO) molecular sieve STA-6 in hydroxide media, respectively. On the other hand, the intermediate-sized 1,2,3,4-tetramethylimidazolium cation gave SSZ-51, a two-dimensional large-pore SAPO material, in fluoride media. Synchrotron powder X-ray diffraction and Rietveld analyses reveal that as-made AlPO 4 -34(t) V contains penta-coordinated framework Al species connected by hydroxyl groups, as well as tetrahedral framework Al, which contrasts with the distortions arising from the two F - or OH - bridges between octahedral Al atoms in all already known AlPO 4 -34 materials. The presence of Al-OH-Al linkages in this triclinic AlPO 4 -34 molecular sieve has been further corroborated by thermal analysis, variable-temperature IR,27Al magic-angle spinning NMR, and dispersion-corrected density functional theory calculations.

21 CFR 862.1120 - Blood gases (PCO2, PO2) and blood pH test system.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Blood gases (PCO2, PO2) and blood pH test system... Test Systems § 862.1120 Blood gases (PCO2, PO2) and blood pH test system. (a) Identification. A blood gases (PCO2, PO2) and blood pH test system is a device intended to measure certain gases in blood, serum...

Nasicon-Type Surface Functional Modification in Core-Shell LiNi0.5Mn0.3Co0.2O2@NaTi2(PO4)3 Cathode Enhances Its High-Voltage Cycling Stability and Rate Capacity toward Li-Ion Batteries.

Science.gov (United States)

Liang, Longwei; Sun, Xuan; Wu, Chen; Hou, Linrui; Sun, Jinfeng; Zhang, Xiaogang; Yuan, Changzhou

2018-02-14

Surface modifications are established well as efficient methodologies to enhance comprehensive Li-storage behaviors of the cathodes and play a significant role in cutting edge innovations toward lithium-ion batteries (LIBs). Herein, we first logically devised a pilot-scale coating strategy to integrate solid-state electrolyte NaTi 2 (PO 4 ) 3 (NTP) and layered LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC) for smart construction of core-shell NMC@NTP cathodes. The Nasicon-type NTP nanoshell with exceptional ion conductivity effectively suppressed gradual encroachment and/or loss of electroactive NMC, guaranteed stable phase interfaces, and meanwhile rendered small sur-/interfacial electron/ion-diffusion resistance. By benefiting from immanently promoting contributions of the nano-NTP coating, the as-fabricated core-shell NMC@NTP architectures were competitively endowed with superior high-voltage cyclic stabilities and rate capacities within larger electrochemical window from 3.0 to 4.6 V when utilized as advanced cathodes for advanced LIBs. More meaningfully, the appealing electrode design concept proposed here will exert significant impact upon further constructing other high-voltage Ni-based cathodes for high-energy/power LIBs.

[H3N(CH2)4NH3]2[Al4(C2O4)(H2PO4)2(PO4)4].4[H2O]: A new layered aluminum phosphate-oxalate

International Nuclear Information System (INIS)

Peng Li; Li Jiyang; Yu Jihong; Li Guanghua; Fang Qianrong; Xu Ruren

2005-01-01

A new layered inorganic-organic hybrid aluminum phosphate-oxalate [H 3 N(CH 2 ) 4 NH 3 ] 2 [Al 4 (C 2 O 4 )(H 2 PO 4 ) 2 (PO 4 ) 4 ].4[H 2 O](AlPO-CJ25) has been synthesized hydrothermally, by using 1,4-diaminobutane (DAB) as structure-directing agent. The structure has been solved by single-crystal X-ray diffraction analysis and further characterized by IR, 31 P MAS NMR, TG-DTA as well as compositional analyses. Crystal data: the triclinic space group P-1, a=8.0484(7) A, b=8.8608(8) A, c=13.2224(11) A, α=80.830(6) deg. , β=74.965(5) deg. , γ=78.782(6) deg. , Z=2, R 1[ I >2 σ ( I )] =0.0511 and wR 2(alldata) =0.1423. The alternation of AlO 4 tetrahedra and PO 4 tetrahedra gives rise to the four-membered corner-sharing chains, which are interconnected through AlO 6 octahedra to form the layered structure with 4,6-net sheet. Interestingly, oxalate ions are bis-bidentately bonded by participating in the coordination of AlO 6 , and bridging the adjacent AlO 6 octahedra. The layers are held with each other through strong H-bondings between the terminal oxygens. The organic ammonium cations and water molecules are located in the large cavities between the interlayer regions. -- Graphical abstract: The alternation of AlO 4 tetrahedra and PO 4 tetrahedra gives rise to the four-membered corner-sharing chains, which are interconnected through AlO 6 octahedra to form the layered structure with 4,6-net sheet. Oxalate ions are bis-bidentately boned by participating in the coordination of AlO 6 , and bridging the adjacent AlO 6 octahedra

A simple diethylene glycol-assisted synthesis and high rate performance of Li3V2(PO4)3/C composites as cathode material for Li-ion batteries

International Nuclear Information System (INIS)

Liu, Qianjin; Yang, Fei; Wang, Shuping; Feng, Lijun; Zhang, Wenjing; Wei, Huiying

2013-01-01

Spherical Li 3 V 2 (PO 4 ) 3 /C(LVP/C) composites were synthesized by sol–gel method using diethylene glycol as the spheroidizing medium and glucose as the carbon source. The crystal structure, morphology, the lithium diffusion behavior and high rates capacities were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and electrochemical methods. Results indicated that the sphere-like LVP/C sample prepared with 10 wt% glucose has a uniform carbon layer about 10 nm on the surfaces, and presented a high discharge capacity of 131.8, 126.5, 102.4, 82.8 mAh g −1 at 0.1, 2, 10, 20 C between 3.0 and 4.3 V with no obvious capacity fading during 200 cycles at the rate of 2 C. While in the voltage region of 3.0–4.8 V, it owned the largest reversible capacity of 169.4, 139.8, 121.7 mAh g −1 at 0.5, 1, 5 C, respectively. Its capacity retained 79.9% after 200 cycles at 2 C, and the apparent Li-ion diffusion coefficient was calculated to be 3.37 × 10 −9 cm 2 s −1

Low Po2 conditions induce reactive oxygen species formation during contractions in single skeletal muscle fibers

Science.gov (United States)

Shiah, Amy; Roberts, William J.; Chien, Michael T.; Wagner, Peter D.; Hogan, Michael C.

2013-01-01

Contractions in whole skeletal muscle during hypoxia are known to generate reactive oxygen species (ROS); however, identification of real-time ROS formation within isolated single skeletal muscle fibers has been challenging. Consequently, there is no convincing evidence showing increased ROS production in intact contracting fibers under low Po2 conditions. Therefore, we hypothesized that intracellular ROS generation in single contracting skeletal myofibers increases during low Po2 compared with a value approximating normal resting Po2. Dihydrofluorescein was loaded into single frog (Xenopus) fibers, and fluorescence was used to monitor ROS using confocal microscopy. Myofibers were exposed to two maximal tetanic contractile periods (1 contraction/3 s for 2 min, separated by a 60-min rest period), each consisting of one of the following treatments: high Po2 (30 Torr), low Po2 (3–5 Torr), high Po2 with ebselen (antioxidant), or low Po2 with ebselen. Ebselen (10 μM) was administered before the designated contractile period. ROS formation during low Po2 treatment was greater than during high Po2 treatment, and ebselen decreased ROS generation in both low- and high-Po2 conditions (P Po2. Force was reduced >30% for each condition except low Po2 with ebselen, which only decreased ∼15%. We concluded that single myofibers under low Po2 conditions develop accelerated and more oxidative stress than at Po2 = 30 Torr (normal human resting Po2). Ebselen decreases ROS formation in both low and high Po2, but only mitigates skeletal muscle fatigue during reduced Po2 conditions. PMID:23576612

Core/shell-type nanorods of Tb{sup 3+}-doped LaPO{sub 4}, modified with amine groups, revealing reduced cytotoxicity

Energy Technology Data Exchange (ETDEWEB)

Runowski, Marcin [Adam Mickiewicz University, Department of Rare Earths, Faculty of Chemistry (Poland); Dąbrowska, Krystyna [Polish Academy of Sciences, Bacteriophage Laboratory, Institute of Immunology and Experimental Therapy (Poland); Grzyb, Tomasz [Adam Mickiewicz University, Department of Rare Earths, Faculty of Chemistry (Poland); Miernikiewicz, Paulina [Polish Academy of Sciences, Bacteriophage Laboratory, Institute of Immunology and Experimental Therapy (Poland); Lis, Stefan, E-mail: blis@amu.edu.pl [Adam Mickiewicz University, Department of Rare Earths, Faculty of Chemistry (Poland)

2013-11-15

A simple co-precipitation reaction between Ln{sup 3+} cations (Ln = lanthanide) and phosphate ions in the presence of polyethylene glycol (PEG), including post-treatment under hydrothermal conditions, leads to the formation of Tb{sup 3+}-doped LaPO{sub 4} crystalline nanorods. The nanoparticles obtained can be successfully coated with amorphous and porous silica, forming core/shell-type nanorods. Both products reveal intensive green luminescence under UV lamp irradiation. The surface of the core/shell-type product can also be modified with –NH{sub 2} groups via silylation procedure, using 3-aminopropyltriethoxysilane as a modifier. Powder X-ray diffraction, transmission electron microscopy, and scanning electron microscopy confirm the desired structure and needle-like shape of the products synthesized. Fourier transform infrared spectroscopy and specific surface area measurements by Brunauer–Emmett–Teller method reveal a successful surface modification with amine groups of the core/shell-type nanoparticles prepared. The nanomaterials synthesized exhibit green luminescence characteristic of Tb{sup 3+} ions, as solid powders and aqueous colloids, examined by spectrofluorometry. The in vitro cytotoxicity studies reveal different degree toxicity of the products. LaPO{sub 4}:Tb{sup 3+}@SiO{sub 2}@NH{sub 2} exhibits the smallest toxicity against B16F0 mouse melanoma cancer cells and human skin microvascular endothelial cell lines, in contrast to the most toxic LaPO{sub 4}:Tb{sup 3+}@SiO{sub 2}.Graphical Abstract.

Sintering behavior, ac conductivity and dielectric relaxation of Li1.3Ti1.7Al0.3(PO43 NASICON compound

Directory of Open Access Journals (Sweden)

Tasiu Zangina

Full Text Available The phenomenon of relaxation in dielectric materials is described as one of the powerful tools to determine the behavior and properties of ion transport. The kinetics of ionic species and dipole in solid-state electrolyte are dependent on frequency, temperature, and dielectric relaxation. Li1+xTi2−xAlx(PO43 conducting solid state electrolyte with x = 0.3 was synthesized via conventional solid state technique using the raw materials Li2CO3, TiO2, Al2O3, and NH4H2PO4 as starting materials. TGA/DTG and X-ray diffraction measurements were carried out to study the thermal behavior and phases of the composition. It was observed from the TGA/DTA curves that there is no mass loss above 500 °C. The XRD peaks were observed to start appearing at 500 °C which corresponds to small peaks in TGA. It was also pointed out that at increasing sintering temperatures from 700 °C to 1000 °C the number of phases drastically decreased which is attributed to the complete chemical reaction. Temperature and frequency dependence of dielectric relaxation and electric modulus of the compounds were investigated at temperatures 30–230 °C and at frequencies of 40 kHz–1 MHz. The findings showed that the dielectric relaxation peaks shift to higher temperature as frequency increases and the change in ac conductivity with frequency is in agreement with Jonscher’s power law. Keywords: Sintering behavior, Dielectric permittivity, Universal power law, Electric modulus

Calcioferrite with composition (Ca3.94Sr0.06Mg1.01(Fe2.93Al1.07(PO46(OH4·12H2O

Directory of Open Access Journals (Sweden)

Barbara Lafuente

2014-03-01

Full Text Available Calcioferrite, ideally Ca4MgFe3+4(PO46(OH4·12H2O (tetracalcium magnesium tetrairon(III hexakis-phosphate tetrahydroxide dodecahydrate, is a member of the calcioferrite group of hydrated calcium phosphate minerals with the general formula Ca4AB4(PO46(OH4·12H2O, where A = Mg, Fe2+, Mn2+ and B = Al, Fe3+. Calcioferrite and the other three known members of the group, montgomeryite (A = Mg, B = Al, kingsmountite (A = Fe2+, B = Al, and zodacite (A = Mn2+, B = Fe3+, usually occur as very small crystals, making their structure refinements by conventional single-crystal X-ray diffraction challenging. This study presents the first structure determination of calcioferrite with composition (Ca3.94Sr0.06Mg1.01(Fe2.93Al1.07(PO46(OH4·12H2O based on single-crystal X-ray diffraction data collected from a natural sample from the Moculta quarry in Angaston, Australia. Calcioferrite is isostructural with montgomeryite, the only member of the group with a reported structure. The calcioferrite structure is characterized by (Fe/AlO6 octahedra (site symmetries 2 and -1 sharing corners (OH to form chains running parallel to [101]. These chains are linked together by PO4 tetrahedra (site symmetries 2 and 1, forming [(Fe/Al3(PO43(OH2] layers stacking along [010], which are connected by (Ca/Sr2+ cations (site symmetry 2 and Mg2+ cations (site symmetry 2; half-occupation. Hydrogen-bonding interactions involving the water molecules (one of which is equally disordered over two positions and OH function are also present between these layers. The relatively weaker bonds between the layers account for the cleavage of the mineral parallel to (010.

Photoluminescence characterization of Dy3+ and Eu2+ ion in M5(PO4)3F (M = Ba, Sr, Ca) phosphors

International Nuclear Information System (INIS)

Nagpure, I.M.; Shinde, K.N.; Dhoble, S.J.; Kumar, Animesh

2009-01-01

Photoluminescence investigation of Eu and Dy activated phosphate based phosphors prepared by combustion synthesis, characterized by XRD (X-ray diffraction) and photoluminescence techniques, has been reported. PL excitation spectrum of M 5 (PO 4 ) 3 F:Dy phosphors shows the excitation peaks ranging from 300 to 400 nm due to 4f → 4f transitions of Dy 3+ ions. PL emission spectrum of Dy 3+ ion under 348 nm excitation gives PL emission at 482 nm (blue) due to 4 F 9/2 → 6 H 15/2 transitions, 574 nm (yellow) emission due to 4 F 9/2 → 6 H 13/2 transitions and 670 nm (red) due to 4 F 9/2 → 6 H 11/2 transitions, gives BYR (blue-yellow-red) emissions. The Eu 2+ broad band PL emission spectrum was observed in M 5 (PO 4 ) 3 F:Eu phosphor at 440 nm in the blue region of the spectrum due to 5d → 4f transition at 352 nm excitation. The 300-400 nm is Hg-free excitation (Hg excitation is 85% 254 nm wavelength of light and 15% other wavelengths), which is characteristic of solid-state lighting phosphors. Hence PL emission in divalent europium and trivalent dysprosium may be efficient photoluminescent materials for solid-state lighting phosphors.

Ternary rhombohedral Laves phases RE{sub 2}Rh{sub 3}Ga (RE = Y, La-Nd, Sm, Gd-Er)

Energy Technology Data Exchange (ETDEWEB)

Seidel, Stefan; Benndorf, Christopher; Heletta, Lukas; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Janka, Oliver [Oldenburg Univ. (Germany). Inst. fuer Chemie; Mausolf, Bernhard [RWTH Aachen (Germany). Inst. fuer Anorganische Chemie; Haarmann, Frank [RWTH Aachen (Germany). Inst. fuer Anorganische Chemie; Max-Planck-Institut fuer Chemische Physik fester Stoffe, Dresden (Germany); Eckert, Hellmut [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Sao Paulo Univ., Sao Carlos (Brazil). Inst. of Physics

2017-06-01

The ordered Laves phases RE{sub 2}Rh{sub 3}Ga (RE=Y, La-Nd, Sm, Gd-Er) were synthesized by arc-melting of the elements and subsequent annealing. The samples were characterized by powder X-ray diffraction (XRD). They crystallize with the rhombohedral Mg{sub 2}Ni{sub 3}Si type structure, space group R3m. Three structures were refined from single crystal X-ray diffractometer data: a=557.1(1), c=1183.1(2), wR2=0.0591, 159 F{sup 2} values, 10 variables for Y{sub 2}Rh{sub 3}Ga, a=562.5(2), c=1194.4(2) pm, wR2=0.0519, 206 F{sup 2} values, 11 variables for Ce{sub 2}Rh{sub 3}Ga and a=556.7(2), c=1184.1(3) pm, wR2=0.0396, 176 F{sup 2} values, 11 variables for Tb{sub 2}Rh{sub 3}Ga. The Rh{sub 3}Ga tetrahedra are condensed via common corners and the large cavities left by the network are filled by the rare earth atoms. The RE{sub 2}Rh{sub 3}Ga Laves phases crystallize with a translationengleiche subgroup of the cubic RERh{sub 2} Laves phases with MgCu{sub 2} type. Magnetic susceptibility measurements reveal Pauli paramagnetism for Y{sub 2}Rh{sub 3}Ga and La{sub 2}Rh{sub 3}Ga. Ce{sub 2}Rh{sub 3}Ga shows intermediate cerium valence while all other RE{sub 2}Rh{sub 3}Ga phases are Curie-Weiss paramagnets which order magnetically at low temperatures. The {sup 89}Y and {sup 71}Ga solid state nuclear magnetic resonance (NMR) spectra of the diamagnetic representative Y{sub 2}Rh{sub 3}Ga show well-defined single resonances in agreement with an ordered bulk phase. In comparison to the binary Laves phase YRh{sub 2} a strongly increased {sup 89}Y resonance frequency is observed owing to a higher s-electron spin density at the {sup 89}Y nuclei as proven by density of states (DOS) calculations.

A second polymorph with composition Co3(PO42·H2O

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Yang Kim

2008-10-01

Full Text Available Single crystals of Co3(PO42·H2O, tricobalt(II bis[orthophosphate(V] monohydrate, were obtained under hydrothermal conditions. The compound is the second polymorph of this composition and is isotypic with its zinc analogue, Zn3(PO42·H2O. Three independent Co2+ cations are bridged by two independent orthophosphate anions. Two of the metal cations exhibit a distorted tetrahedral coordination while the third exhibits a considerably distorted [5 + 1] octahedral coordination environment with one very long Co—O distance of 2.416 (3 Å. The former cations are bonded to four different phosphate anions, and the latter cation is bonded to four anions (one of which is bidentate and one water molecule, leading to a framework structure. Additional hydrogen bonds of the type O—H...O stabilize this arrangement.

Crystal structure of CsTb(PO3)4 compound

International Nuclear Information System (INIS)

Palkina, K.K.; Maksimova, S.I.; Kuznetsov, V.G.; Chibiskova, N.T.

1978-01-01

The X-ray structural study of compounds of the CsLn(PO 3 ) 4 series has been made. Found is the presence of two structural types for CsPr(PO 3 ) 4 (cubic and monoclinic modifications), one type for CsNd(PO 3 ) 4 (cubic modification) and for CsTb(PO 3 ) 4 (monoclinic modification). For the CsTb(PO 3 ) 4 monocrystal the lattice parameters are determined: a=7.032 +- 0.001; b=8.705 +- 0.001; c=9.051 +- 0.001 A; α=90 deg, β=90 deg, γ=100 deg, Z=2, V=545.68 A 3 , dsub(exp)=3.70 g/cm 3 . The structure character is presented as infinite chains of (PO 4 ) tetrahedrons, stretched along the ''C'' period. Tb and Cs atoms are rounded by 8 atoms of oxygen. Tb polyhedron are irregular octaapexes or strongly deformed tetragonal antiprisms. Tb-Tb shortest distance is 6.59 A

A new three-dimensional cobalt phosphate: Co5(OH2)4(HPO4)2(PO4)2

International Nuclear Information System (INIS)

Han Zhangang; Tian Aixiang; Peng Jun; Zhai Xueliang

2006-01-01

A three-dimensional (3D) cobalt phosphate: Co 5 (OH 2 ) 4 (HPO 4 ) 2 (PO 4 ) 2 (1), has been synthesized by hydrothermal reaction and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic techniques. The title compound is a template free cobalt phosphate. Compound 1 exhibits a complex net architecture based on edge- and corner-sharing of CoO 6 and PO 4 polyhedra. The magnetic susceptibility measurements indicated that the title compound obeys Curie-Weiss behavior down to a temperature of 17 K at which an antiferromagnetic phase transition occurs. - Graphical abstract: A 3D cobalt phosphate with a neutral framework: Co 5 (OH 2 ) 4 (HPO 4 ) 2 (PO 4 ) 2 (1), has been synthesized and characterized. Compound 1 exhibits a complex net architecture based on edge- and corner-sharing of CoO 6 and PO 4 polyhedra. Its magnetic property was researched

Low Band Gap Donor–Acceptor Type Polymers Containing 2,3-Bis(4-(decyloxyphenylpyrido[4,3-b]pyrazine as Acceptor and Different Thiophene Derivatives as Donors

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Yan Zhang

2016-10-01

Full Text Available Four donor–acceptor type conducting polymers, namely poly(2,3-bis(4-decyloxyphenyl-5,8-bis(4-thiophen-2-ylpyrido[4,3-b]pyrazine (P1, poly(2,3-bis(4-decyloxyphenyl-5,8-bis(4-butylthiophen-2-ylpyrido[4,3-b]pyrazine (P2, poly(2,3-bis(4-(decyloxyphenyl-5,8-bis(4-hexyloxythiophen-2-ylpyrido[4,3-b]pyrazine (P3 and poly(2,3-bis(4-(decyloxyphenyl-5,8-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-ylpyrido[4,3-b]pyrazine (P4, containing thiophene or its derivative as the donor and pyrido[4,3-b]pyrazine as the acceptor were prepared and characterized by cyclic voltammetry, scanning electron microscopy, and UV-Vis spectroscopy to detect the influence of the donor units’ strength on the electrochromic performances. The results demonstrated that all of the polymers could be reversibly reduced and oxidized by p-type doping and n-type doping, and showed near-infrared activities and different color changes in p-type doping process. Especially, P3 and P4 showed lower optical band gap than P1 and P2 due to the strong electron-donating hexyloxythiophen group of P3 and ethylenedioxythiophene group of P4. Besides, P3 and P4 displayed the saturated green color at the neutral state and the desirable transparency at the oxidized state. All the polymers displayed desirable optical contrasts, satisfactory coloration efficiency, excellent stability and short switching time, which made the polymers fascinating candidates in the electrochromic device applications.

Correlation of regional disease and in vivo PO2 in rat mammary adenocarcinoma.

Science.gov (United States)

Cole, M A; Crawford, D W; Warner, N E; Puffer, H W

1983-07-01

A knowledge of the distribution of oxygen tension (PO2) and vascularization in neoplasia has been fundamental to understanding relationships between tumor growth, hypoxia, and therapy. We have combined recessed oxygen microcathode and freeze-substitution techniques to correlate in situ PO2 profiles and morphologic features in 7,12-dimethylbenz(a)anthracene (DMBA) tumors in rats. Overlying connective tissue of transplanted tumor was exposed by a 1-2 mm incision and a cross-stitch pattern demarcated electrode puncture sites for histologic reference. Three buffered salt solutions (BSS) with different PO2 were each allowed to flow through a well over the tumor where electrodes were placed for calibration. Zero electrode oxygen current was recorded from a buffered yeast-agar mixture of zero torr. PO2 was recorded at 5-mu intervals to approximately 1-2 mm. Atmospheric contamination was eliminated by continuous well flow of BSS, 30 torr. Finally, the tumor and surrounding tissues were quick-frozen in vivo with Freon 22 and liquid nitrogen. The tissue block was freeze-substituted and sectioned. PO2 profiles were superimposed onto correspondingly scaled photomicrographs. A viable periphery with a PO2 range of 50-82 torr and a transition to necrotic areas of PO2, 2-13 torr were observed. This transition was characterized by PO2 gradients within distances of 50-300 mu at variable puncture depths. This technique should be useful in further studies of growth, necrosis, and therapy.

Increased intraretinal PO2 in short-term diabetic rats.

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Lau, Jennifer C M; Linsenmeier, Robert A

2014-12-01

In diabetic retinopathy, neovascularization is hypothesized to develop due to hypoxia in the retina. However, evidence for retinal hypoxia is limited, and the progressive changes in oxygenation are unknown. The objective of this study was to determine if retinal hypoxia occurs early in the development of diabetes. Intraretinal oxygen (PO2) profiles were recorded with oxygen-sensitive microelectrodes in control and diabetic Long-Evans rats at 4 and 12 weeks after induction of diabetes. Diabetes did not affect oxygen consumption in the photoreceptors in either dark or light adaptation. Oxygenation of the inner retina was not affected after 4 weeks of diabetes, although vascular endothelial growth factor levels increased. At 12 weeks, average inner retinal PO2, normalized to choriocapillaris PO2, was higher in diabetic rats than in age-matched controls, which was opposite to what was expected. Thus retinal hypoxia is not a condition of early diabetes in rat retina. Increased inner retinal PO2 may occur because oxygen consumption decreases in the inner retina. © 2014 by the American Diabetes Association. Readers may use this article as long as the work is properly cited, the use is educational and not for profit, and the work is not altered.

Preparation, Characterization, and Structure of Two Layered Molybdenum(VI) Phosphates: KMo(H 2O)O 2PO 4 and NH 4Mo(H 2O)O 2PO 4

Science.gov (United States)

Millini, Roberto; Carati, Angela

1995-08-01

New layered Mo(VI) compounds, KMo(H 2O)O 2PO 4 (I) and NH 4Mo(H 2O)O 2PO 4 (II), were synthesized hydrothermally and their structures were determined from single-crystal X-ray analysis. Compounds (I) and (II) are isostructural and crystallize in the monoclinic P2 1/ n space group with a = 12.353(3), b = 8.623(2), c = 5.841(1) Å, β = 102.78(1)°, V = 606.8(2) Å 3, Z = 4, and R = 0.027 ( Rw = 0.030) for compound (I) and a = 12.435(3), b = 8.761(2), c = 6.015(1), β = 103.45(1)°, V = 637.3(2) Å 3, Z = 4, and R = 0.040 ( Rw = 0.041) for compound (II). The structure consists of layers built up of eight- and four-membered rings resulting from the alternation of corner-sharing [MoO 6] octahedra and [PO 4] tetrahedra. The layers stack along the (1¯01) direction by intercalating K and NH 4 ions.

Role of PO4 tetrahedron in LiFePO4 and FePO4 system.

Science.gov (United States)

Zeng, Yuewu

2015-06-01

Using high resolution transmission electron microscopy with image simulation and Fourier analysis, the Li1- x FePO4 (x < 0.01), Li1- x FePO4 (x ∼ 0.5), and FePO4 particles, prepared by charging or discharging the 053048 electrochemical cells (thickness: 5 mm, width: 30 mm, height: 48 mm) and dismantled inside an Ar-filled dry box, were investigated. The high resolution images reveal: (1) the solid solution of Li1- x FePO4 (x < 0.01) contains some missing Li ions leading PO4 group distorted around M1 tunnel of the unit cell; (2) the texture of the particles of Li1- x FePO4 (x ∼0.5) has homogeneously distributed compositional domains of LiFePO4 and FePO4 resulting from spinodal decomposition which promote Li ion easily getting into the particle due to uphill diffusion, (3) the particles of FePO4 formed in charging have heavily distorted lattice and contain some isolated LiFePO4 , (4) interface between LiFePO4 and FePO4 and between amorphous and crystal region provides the lattice distortion of small polarons. © 2015 Wiley Periodicals, Inc.

Synthesis and photoluminescence of Eu3+ and Mn2+ doped double phosphates KMLa(PO4)2 (M = Zn, Mg)

International Nuclear Information System (INIS)

Pan Yuexiao; Zhang Qinyuan; Jiang Zhonghong

2006-01-01

Two compounds, KMgLa(PO 4 ) 2 and KZnLa(PO 4 ) 2 doped with Eu 3+ and Mn 2+ ions, have been synthesized by a conventional solid-state method at 850 deg. C. Structures of KMgLa(PO 4 ) 2 and KZnLa(PO 4 ) 2 have been investigated and confirmed by X-ray diffraction and photoluminescence spectra. The results indicate that the compounds have remained the monoclinic structure of LaPO 4 with space group of C s when (K + , Mg 2+ ) or (K + , Zn 2+ ) could substitute half of the La 3+ ions. Under an ultraviolet source, KMgLa(PO 4 ) 2 :Mn 2+ has shown a bright red phosphorescent color, while KZnLa(PO 4 ) 2 :Mn 2+ has shown an orange-red emission which is assigned to the electronic transition of 4 T 1 ( 4 G)- 6 A 1 ( 6 S) of Mn 2+ in strong crystal field

Structural transitions, ion mobility, and conductivity in CsSbF3(H2PO4)

Science.gov (United States)

Kavun, V. Ya.; Uvarov, N. F.; Slobodyuk, A. B.; Ulihin, A. S.; Kovaleva, E. V.; Zemnukhova, L. A.

2018-02-01

Structural transitions, ion mobility, and conductivity in CsSbF3(H2PO4) (I) have been investigated by the methods of 1H, 19F, 31P NMR (including 1H, 19F, 31P MAS NMR), DSC, X-ray diffraction, and impedance spectroscopy. It was found that the fundamental changes in 1H, 19F, 31P NMR spectra (above 390 K) were associated with the formation of a crystalline disorder phase I with high ionic mobility in the proton and fluoride sublattices, as a result of a phase transition in the 400-420 K range. In the same temperature range, the transition of PO2(OH)2- anions from the "rigid lattice" to fast reorientations takes place. Above 430 K, there occurs a transition from the crystalline disordered phase to the amorphous one. The types of ion mobility in CsSbF3(H2PO4) and its amorphous phase have been established and temperature ranges of their realization have been determined (150-450 K). According to the NMR data, the diffusion in the proton sublattice of the disordered crystalline and amorphous phases is preserved even at room temperature. The ionic conductivity in CsSbF3(H2PO4) reaches the values of 2.6 × 10-4 S/cm in the temperature range 410-425 K and decreases down to 2.0 × 10-5 S/cm upon transition to the amorphous phase (435-445 K).

Growth of rhombohedral insulin crystals and in vitro modeling of their dissolution in the blood stream

Energy Technology Data Exchange (ETDEWEB)

Nanev, C.N.; Dimitrov, I.L.; Hodzhaoglu, F.V. [Rostislaw Kaischew Institute of Physical Chemistry, Bulgarian Academy of Sciences, Sofia (Bulgaria)

2011-02-15

Insulin is the only protein that is secreted in a crystalline form in a human healthy body. To mimic the secretion process we used NaCl salting-out to growing tiny rhombohedral Zn-insulin crystals. The dissolution of the insulin crystals is of special interest for the therapeutical praxis, because the human body is supplied with the physiologically active monomers of the insulin through dissolution of the crystalline granules secreted in the pancreatic {beta}-cells. Sets of tiny rhombohedral Zn-insulin crystals, which resembled the granules secreted in the {beta}-cells, were subjected to dissolution in blood plasma and model solutions. The impacts of the solution composition, flow rate, pH and ionic strength on the insulin crystal dissolution were investigated. The effect of the blood plasma was determinant because it dissolved the rhombohedral Zn-insulin crystals almost instantly, while the effects of solution's physicochemical characteristics were of minor importance. In addition, we found that the presence of abundant zinc ions suppressed the dissolution of the insulin crystals. (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Magnetoelastic coupling in TbFe2 (110) thin films

International Nuclear Information System (INIS)

Ciria, M.; Arnaudas, J.I.; Dufour, C.; Oderno, V.; Dumesnil, K.; del Moral, A.

1997-01-01

We have determined the rhombohedral magnetoelastic stress of a Laves phase TbFe 2 (110) single-crystal film, grown by molecular-beam epitaxy. The film thickness was 1300 Angstrom. The magnetoelastic stress was directly measured by using a low-temperature cantilever capacitive method, between 300 and 10 K. The isotherms clearly display the coercive field but, unlike bulk alloy behavior, do not saturate even at the maximum field of 12 T. The determined rhombohedral magnetoelastic parameter of the film is B ε,2 =-0.43 GPa, at 0 K and 12 T, which is 0.67 times the value for bulk TbFe 2 . B ε,2 follows a power m 3 of the reduced magnetization m, indicating a single-ion volume origin for the rhombohedral magnetoelastic stress of this film. Measurements performed in a 300 Angstrom TbFe 2 (110) film deposited onto a YFe 2 buffer show that the coercive field is drastically lowered and that the magnetoelastic distortion is negligible. copyright 1997 American Institute of Physics

Experimental Evaluation of the Transport Mechanisms of PoIFN-α in Caco-2 Cells

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Xin Liu

2017-11-01

Full Text Available For the development of an efficient intestinal delivery system for Porcine interferon-α (PoIFN-α, the understanding of transport mechanisms of which in the intestinal cell is essential. In this study, we investigated the absorption mechanisms of PoIFN-α in intestine cells. Caco-2 cells and fluorescein isothiocyanate-labeled (FITC-PoIFN-α were used to explore the whole transport process, including endocytosis, intracellular trafficking, exocytosis, and transcytosis. Via various techniques, the transport pathways of PoIFN-α in Caco-2 cells and the mechanisms were clarified. Firstly, the endocytosis of PoIFN-α by Caco-2 cells was time, concentration and temperature dependence. And the lipid raft/caveolae endocytosis was the most likely endocytic pathway for PoIFN-α. Secondly, both Golgi apparatus and lysosome were involved in the intracellular trafficking of PoIFN-α. Thirdly, the treatment of indomethacin resulted in a significant decrease of exocytosis of PoIFN-α, indicating the participation of cyclooxygenase. Finally, to evaluate the efficiency of PoIFN-α transport, the transepithelial electrical resistance (TEER value was measured to investigate the tight junctional integrity of the cell monolayers. The fluorescence microscope results revealed that the transport of PoIFN-α across the Caco-2 cell monolayers was restricted. In conclusion, this study depicts a probable picture of PoIFN-α transport in Caco-2 cells characterized by non-specificity, partial energy-dependency and low transcytosis.

pO2 and regional blood flow in a rabbit model of limb ischemia.

Science.gov (United States)

Grinberg, Oleg Y; Hou, Huagang; Grinberg, Stalina A; Moodie, Karen L; Demidenko, Eugene; Friedman, Bruce J; Post, Mark J; Swartz, Harold M

2004-06-01

Oxygen tension (pO2) in muscles and regional blood flow were measured in a rabbit model of limb ischemia. pO2 was measured repetitively by EPR oximetry with EMS char in four different muscle groups in the same animals. Blood flow in the same muscles at several time points was measured using microspheres. A linear mixed effects model was developed to analyze the data on pO2 and blood flow. The results suggest that while under normal conditions pO2 in muscles does not depend significantly on blood flow, immediately after arterial occlusion pO2 correlates linearly with blood flow. Within two weeks of occlusion the pO2 is recovered to 45% of baseline. This study demonstrates, for the first time, the applicability of EPR oximetry in animals larger than rodents.

[Synthesis and characterization of CO-3(2-) doping nano-hydroxyapatite].

Science.gov (United States)

Liao, Jian-Guo; Li, Yan-Qun; Duan, Xing-Ze; Liu, Qiong

2014-11-01

CO3(2-) doping is an effective method to increase the biological activity of nano-hydroxyapatite (n-HA). In the present study, calcium nitrate and trisodium phosphate were chosen as raw materials, with a certain amount of Na2CO3 as a source of CO-3(2-) ions, to synthesize nano-carbonate hydroxyapatite (n-CHA) slurry by solution precipitation method. The structure and micro-morphology of n-CHA were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FTIR) and Raman spectroscopy (RS). The results revealed that the synthetic n-HA crystals are acicular in nanometer scale and have a crystal size of 20-30 nm in diameter and 60-80 nm in length, which are similar to natural bone apatite. And the crystallinity of n-CHA crystals decreases to the increment of CO3(2-). Samples with more CO3(2) have composition and structure more similar to the bone apatite. The value of lattice parameters a decreases, value of c increases, and c/a value increases with the increase in the amount of CO3(2-), in accordance with crystal cell parameters change rule of type B replacement. In the AB mixed type (substitution OH- and PO4(3-)) CHA, IR characteristic peak of CO3(2-) out-of-plane bending vibration appears at 872 cm(-1), meanwhile, the asymmetry flexible vibration band is split into band at 1 454 cm(-1) and band at 1 420 cm(-1), while weak CO3(2)-peak appears at 1 540 cm(-1). CO3(2-) Raman peak of symmetric stretching vibration appears at 1 122 cm(-1). CO3(2-) B-type (substitution PO4(3-)) peak appeared at 1 071 cm(-1). Through the calculation of integral area ratio of PO4(3-)/ CO3(2-), OH-/CO3(2-), and PO4(3-)/OH-, low quantity CO3(2-) is B-type and high quantity CO3(2-) is A-type (substitution OH-). The results show that the synthesized apatite crystals are AB hybrid substitued nano-carbonate hydroxyapatite, however B-type replacement is the main substitute mode. Due to similarity inthe shape, size, crystal structure