Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 ­(H 2 O)]·7H 2 O and (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 (H 2 O)]·4H 2 O, and a Uranyl Selenate-Selenite [C 5 H 6 N][(UO 2 )(SeO 4 )(HSeO 3 )

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

Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

2012-08-08

Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less

Oxothiomolybdenum derivatives of the superlacunary crown heteropolyanion {P8W48}: structure of [K4{Mo4O4S4(H2O)3(OH)2}2(WO2)(P8W48O184)]30– and studies in solution.

PubMed

Korenev, Vladimir S; Floquet, Sébastien; Marrot, Jérôme; Haouas, Mohamed; Mbomekallé, Israël-Martyr; Taulelle, Francis; Sokolov, Maxim N; Fedin, Vladimir P; Cadot, Emmanuel

2012-02-20

Reaction of the cyclic lacunary [H(7)P(8)W(48)O(184)](33-) anion (noted P(8)W(48)) with the [Mo(2)S(2)O(2)(H(2)O)(6)](2+) oxothiocation led to two compounds, namely, [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) (denoted 1) and [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) (denoted 2), which were characterized in the solid state and solution. In the solid state, the structure of [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) reveals the presence of two disordered {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) "handles" connected on both sides of the P(8)W(48) ring. Such a disorder is consistent with the presence of two geometrical isomers where the relative disposition of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles are arranged in a perpendicular or parallel mode. Such an interpretation is fully supported by (31)P and (183)W NMR solution studies. The relative stability of both geometrical isomers appears to be dependent upon the nature of the internal alkali cations, i.e., Na(+) vs K(+), and increased lability of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles, compared to the oxo analogous, was clearly identified by significant broadening of the (31)P and (183)W NMR lines. Solution studies carried out by UV-vis spectroscopy showed that formation of the adduct [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) occurs in the 1.5-4.7 pH range and corresponds to a fast and quantitative condensation process. Furthermore, (31)P NMR titrations in solution reveal formation of the "monohandle" derivative [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(P(8)W(48)O(184))](38-) as an intermediate prior to formation of the "bishandle" derivatives. Furthermore, the electrochemical behavior of [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) was studied in aqueous medium and compared with the parent anion P(8)W(48).

High-throughput and in situ EDXRD investigation on the formation of two new metal aminoethylphosphonates - Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) and Ca(OH)(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3}){center_dot}2H{sub 2}O

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

Schmidt, Corinna; Feyand, Mark; Rothkirch, Andre

2012-04-15

The system Ca{sup 2+}/2-aminoethylphosphonic acid/H{sub 2}O/NaOH was systematically investigated using high-throughput methods. The experiments led to one new compound Ca(O{sub 3}PC{sub 2} H{sub 4}NH{sub 2}) (1) and the crystal structure was determined using in house X-ray powder diffraction data (monoclinic, P2{sub 1}/c, a=9.7753(3), b=6.4931(2), c=8.4473(2) A, {beta}=106.46(2) Degree-Sign , V=514.20(2) A{sup 3}, Z=4). The formation of 1 was investigated by in situ energy dispersive X-ray diffraction measurements (EDXRD) at beamline F3 at HASYLAB (light source DORIS III), DESY, Hamburg. An intermediate, Ca(OH)(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3}){center_dot}2H{sub 2}O (2), was observed and could be isolated from the reaction mixture at ambientmore » temperatures by quenching the reaction. The crystal structure of 2 was determined from XRPD data using synchrotron radiation (monoclinic, P2{sub 1}/m, a=11.2193(7), b=7.1488(3), c=5.0635(2) A, {beta}=100.13(4) Degree-Sign , V=399.78(3) A{sup 3}, Z=2). - Graphical abstarct: The detailed in situ energy dispersive X-ray diffraction (EDXRD) investigation on the formation of the new inorganic-organic hybrid compound Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) leads to the discovery of a new crystalline intermediate phase. Both crystal structures were elucidated using X-ray powder diffraction data. Highlights: Black-Right-Pointing-Pointer High-throughput investigation led to new metal aminoethylphosphonate Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}). Black-Right-Pointing-Pointer The formation of Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) was followed by in situ EDXRD measurements. Black-Right-Pointing-Pointer The crystalline intermediate Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3})(OH){center_dot}2H{sub 2}O was discovered. Black-Right-Pointing-Pointer Isolation of Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3})(OH){center_dot}2H{sub 2}O was accomplished by quenching experiments. Black-Right-Pointing-Pointer The structures were determined using X

Structural investigations of vanadyl doped Nb2O5·K2O·B2O3 glasses

NASA Astrophysics Data System (ADS)

Anshu; Sanghi, S.; Agarwal, A.; Lather, M.; Bhatnagar, V.; Khasa, S.

2009-07-01

Pottasium nioborate glasses of composition xNb2O5·(30-x)K2O·69B2O3 containing 1 mol % of V2O5 were prepared by melt quench technique (1473K, 1h). The electron paramagnetic resonance spectra of VO2+ in these glasses have been recorded in X- band (v approx 9.14 GHz) at room temperature (RT). The spin Hamiltonian parameters, dipolar hyperfine coupling parameters, P and Fermi contact interaction parameter, K have been calculated. It is found that V4+ ions in these glasses exist as VO2+ in octahedral coordination with a tetragonal distortion. The tetragonality of V4+O6 complex decreases with increasing Nb2O5: K2O ratio and also there is an expansion of 3dXY orbit of unpaired electron in the vanadium ion. The study of IR transmission spectra over a range 400- 4000 cm-1 depicts the presence of both BO3 and BO4 structural units and Nb5+ ions are incorporated into the glass network as NbO6 octahedra, substituting BO4 groups.

Dachiardite-K, (K2Ca)(Al4Si20O48) · 13H2O, a new zeolite from Eastern Rhodopes, Bulgaria

NASA Astrophysics Data System (ADS)

Chukanov, N. V.; Encheva, S.; Petrov, P.; Pekov, I. V.; Belakovskiy, D. I.; Britvin, S. N.; Aksenov, S. M.

2016-12-01

Dachiardite-K (IMA No. 2015-041), a new zeolite, is a K-dominant member of the dachiardite series with the idealized formula (K2Ca)(Al4Si20O48) · 13H2O. It occurs in the walls of opal-chalcedony veinlets cutting hydrothermally altered effusive rocks of the Zvezdel paleovolcanic complex near the village of Austa, Momchilgrad Municipality, Eastern Rhodopes, Bulgaria. Chalcedony, opal, dachiardite-Ca, dachiardite-Na, ferrierite-Mg, ferrierite-K, clinoptilolite-Ca, clinoptilolite-K, mordenite, smectite, celadonite, calcite, and barite are associated minerals. The mineral forms radiated aggregates up to 8 mm in diameter consisting of split acicular individuals. Dachiardite-K is white to colorless. Perfect cleavage is observed on (100). D meas = 2.18(2), D calc = 2.169 g/cm3. The IR spectrum is given. Dachiardite-K is biaxial (+), α = 1.477 (calc), β = 1.478(2), γ = 1.481(2), 2 V meas = 65(10)°. The chemical composition (electron microprobe, mean of six point analyses, H2O determined by gravimetric method) is as follows, wt %: 4.51 K2O, 3.27 CaO, 0.41 BaO, 10.36 A12O3, 67.90 SiO2, 13.2 H2O, total is 99.65. The empirical formula is H26.23K1.71Ca1.04Ba0.05Al3.64Si20.24O61. The strongest reflections in the powder X-ray diffraction pattern [ d, Å (I, %) (hkl)] are: 9.76 (24) (001), 8.85 (58) (200), 4.870 (59) (002), 3.807 (16) (202), 3.768 (20) (112, 020), 3.457 (100) (220), 2.966 (17) (602). Dachiardite-K is monoclinic, space gr. C2/m, Cm or C2; the unit cell parameters refined from the powder X-ray diffraction data are: a = 18.670(8), b = 7.511(3), c = 10.231(4) Å, β = 107.79(3)°, V= 1366(1) Å3, Z = 1. The type specimen has been deposited in the Earth and Man National Museum, Sofia, Bulgaria, with the registration number 23927.

X-ray fluorescence analysis of Cr(6+) component in mixtures of Cr(2)O(3) and K(2)CrO(4).

PubMed

Tochio, Tatsunori; Sakakura, Shusuke; Oohashi, Hirofumi; Mizota, Hirohisa; Zou, Yanhui; Ito, Yoshiaki; Fukushima, Sei; Tanuma, Shigeo; Shoji, Takashi; Fujimura, Hajime; Yamashita, Michiru

2010-01-01

X-ray fluorescence analysis using Cr K(alpha) spectra was applied to the determination of the mixing ratio of Cr(6+) to (Cr(6+) + Cr(3+)) in several mixtures of K(2)CrO(4) and Cr(2)O(3). Because the powder of K(2)CrO(4) contained large particles that were more than 50 microm in diameter, it was ground between a pestle and a mortar for about 8 h. The coarse particles still remaining were removed by using a sieve with 325-mesh (44 microm) in order to reduce the difference in absorption effects between emissions from Cr(6+) and those from Cr(3+). The mixing ratio, K(2)CrO(4)/(K(2)CrO(4) + Cr(2)O(3)), of the five mixtures investigated is 0.50, 0.40, 0.20, 0.10, and 0.05 in weight, respectively. Each spectrum obtained was analyzed by decomposing it into two reference spectra, those of the two pure materials, K(2)CrO(4) and Cr(2)O(3), with a constant background. The results for the mixtures containing K(2)CrO(4) of more than 20 wt% are that the relative deviation from the true value is less than approximately 5%. On the other hand, when the content of K(2)CrO(4) decreases to less than 10 wt%, the relative deviation gets so large as 20 - 25%. The error coming from a peak separation of spectrum involved in our results were estimated by applying our method to five sets of data for each mixture computationally generated, taking into account the uncertainty in total counts of real measurements.

A neodymium(III)-ammonium complex involving oxalate and carbonate ligands: (NH4)2[Nd2(C2O4)3(CO3)(H2O)].H2O.

PubMed

Trombe, Jean-Christian; Galy, Jean; Enjalbert, Renée

2002-10-01

The title compound, diammonium aqua-mu-carbonato-tri-mu-oxalato-dineodymium(III) hydrate, (NH(4))(2)[Nd(2)(CO(3))(C(2)O(4))(3)(H(2)O)].H(2)O, involving the two ligands oxalate and carbonate, has been prepared hydrothermally as single crystals. The Nd atoms form a tetranuclear unit across the inversion centre at (1/2, 1/2, 1/2). Starting from this tetranuclear unit, the oxalate ligands serve to develop a three-dimensional network. The carbonate group acts as a bis-chelating ligand to two Nd atoms, and is monodentate to a third Nd atom. The oxalate groups are all bis-chelating. The two independent Nd atoms are ninefold coordinated and the coordination polyhedron of these atoms is a distorted monocapped antiprism.

Ab Initio Reaction Kinetics of CH 3 O$$\\dot{C}$$(=O) and $$\\dot{C}$$H 2 OC(=O)H Radicals

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

Tan, Ting; Yang, Xueliang; Ju, Yiguang

The dissociation and isomerization kinetics of the methyl ester combustion intermediates methoxycarbonyl radical (CH3Omore » $$\\dot{C}$$(=O)) and (formyloxy)methyl radical ($$\\dot{C}$$H2OC(=O)H) are investigated theoretically using high-level ab initio methods and Rice–Ramsperger–Kassel–Marcus (RRKM)/master equation (ME) theory. Geometries obtained at the hybrid density functional theory (DFT) and coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) levels of theory are found to be similar. We employ high-level ab initio wave function methods to refine the potential energy surface: CCSD(T), multireference singles and doubles configuration interaction (MRSDCI) with the Davidson–Silver (DS) correction, and multireference averaged coupled-pair functional (MRACPF2) theory. MRSDCI+DS and MRACPF2 capture the multiconfigurational character of transition states (TSs) and predict lower barrier heights than CCSD(T). The temperature- and pressure-dependent rate coefficients are computed using RRKM/ME theory in the temperature range 300–2500 K and a pressure range of 0.01 atm to the high-pressure limit, which are then fitted to modified Arrhenius expressions. Dissociation of CH3O$$\\dot{C}$$(=O) to $$\\dot{C}$$H3 and CO2 is predicted to be much faster than dissociating to CH3$$\\dot{O}$$ and CO, consistent with its greater exothermicity. Isomerization between CH3O$$\\dot{C}$$(=O) and $$\\dot{C}$$H2OC(=O)H is predicted to be the slowest among the studied reactions and rarely happens even at high temperature and high pressure, suggesting the decomposition pathways of the two radicals are not strongly coupled. The predicted rate coefficients and branching fractions at finite pressures differ significantly from the corresponding high-pressure-limit results, especially at relatively high temperatures. Finally, because it is one of the most important CH3$$\\dot{O}$$ removal mechanisms under atmospheric conditions, the reaction kinetics of

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

First investigations on the quaternary system Na2O-K2O-CaO-SiO2: synthesis and crystal structure of the mixed alkali calcium silicate K1.08Na0.92Ca6Si4O15

NASA Astrophysics Data System (ADS)

Kahlenberg, Volker; Mayerl, Michael Jean-Philippe; Schmidmair, Daniela; Krüger, Hannes; Tribus, Martina

2018-04-01

In the course of an exploratory study on the quaternary system Na2O-K2O-CaO-SiO2 single crystals of the first anhydrous sodium potassium calcium silicate have been obtained from slow cooling of a melt in the range between 1250 and 1050 °C. Electron probe micro analysis suggested the following idealized molar ratios of the oxides for the novel compound: K2O:Na2O:CaO:SiO2 = 1:1:12:8 (or KNaCa6Si4O15). Single-crystal diffraction measurements on a crystal with chemical composition K1.08Na0.92Ca6Si4O15 resulted in the following basic crystallographic data: monoclinic symmetry, space group P 21/ c, a = 8.9618(9) Å, b = 7.3594(6) Å, c = 11.2453(11) Å, β= 107.54(1)°, V = 707.2(1) Å3, Z = 2. Structure solution was performed using direct methods. The final least-squares refinement converged at a residual of R(|F|) = 0.0346 for 1288 independent reflections and 125 parameters. From a structural point of view, K1.08Na0.92Ca6Si4O15 belongs to the group of mixed-anion silicates containing [Si2O7]- and [SiO4]-units in the ratio 1:2. The mono- and divalent cations occupy a total of four crystallographically independent positions located in voids between the tetrahedra. Three of these sites are exclusively occupied by calcium. The fourth site is occupied by 54(1)% K and 46%(1) Na, respectively. Alternatively, the structure can be described as a heteropolyhedral framework based on corner-sharing silicate tetrahedra and [CaO6]-octahedra. The network can build up from kröhnkite-like [Ca(SiO4)2O2]-chains running along [001]. A detailed comparison with other A2B6Si4O15-compounds including topological and group-theoretical aspects is presented.

Quenching of I(2P1/2) by NO2, N2O4, and N2O.

PubMed

Kabir, Md Humayun; Azyazov, Valeriy N; Heaven, Michael C

2007-10-11

Quenching of excited iodine atoms (I(5p5, 2P1/2)) by nitrogen oxides are processes of relevance to discharge-driven oxygen iodine lasers. Rate constants at ambient and elevated temperatures (293-380 K) for quenching of I(2P1/2) atoms by NO2, N2O4, and N2O have been measured using time-resolved I(2P1/2) --> I(2P3/2) 1315 nm emission. The excited atoms were generated by pulsed laser photodissociation of CF3I at 248 nm. The rate constants for I(2P1/2) quenching by NO2 and N2O were found to be independent of temperature over the range examined with average values of (2.9 +/- 0.3) x 10(-15) and (1.4 +/- 0.1) x 10(-15) cm3 s(-1), respectively. The rate constant for quenching of I(2P1/2) by N2O4 was found to be (3.5 +/- 0.5) x 10(-13) cm3 s(-1) at ambient temperature.

Processes of Molecular Relaxation in Binary Crystalline Systems KNO3-KClO4, KNO3-KNO2, and K2CO3-K2SO4

NASA Astrophysics Data System (ADS)

Aliev, A. R.; Akhmedov, I. R.; Kakagasanov, M. G.; Aliev, Z. A.; Gafurov, M. M.; Rabadanov, K. Sh.; Amirov, A. M.

2018-03-01

The processes of molecular relaxation in binary crystalline systems KNO3-KClO4, KNO3-KNO2, and K2CO3-K2SO4 are studied via differential thermal analysis and Raman spectroscopy. It is found that the relaxation time of the vibrations ν1( A) of anions NO- 3 and CO2- 3 in systems KNO3-KClO4, KNO3-KNO2, and K2CO3-K2SO4 is less than that in KNO3 and K2CO3, respectively. It is shown that the increased rate of relaxation is explained by an additional relaxation mechanism presented in the system. This mechanism is associated with the excitation of vibrations of anions ClO- 4, NO- 2, and SO2- 4 and the lattice phonons that emerge. It is found that this relaxation mechanism requires correspondence of the frequency difference of these vibrations to the region of sufficiently high density of states of the phonon spectrum.

Crystallization of MgFe2O4 from a glass in the system K2O/B2O3/MgO/P2O5/Fe2O3

NASA Astrophysics Data System (ADS)

El Shabrawy, Samha; Bocker, Christian; Rüssel, Christian

2016-10-01

Spherical magnetic Mg-Fe-O nanoparticles were successfully prepared by the crystallization of glass in the system K2O/B2O3/MgO/P2O5/Fe2O3. The magnetic glass ceramics were prepared by melting the raw materials using the conventional melt quenching technique followed by a thermal treatment at temperatures in the range 560-700 °C for a time ranging from 2 to 8 h. The studies of the X-ray diffraction, electron microscopy and FTIR spectra confirmed the precipitation of finely dispersed spherical (Mg, Fe) based spinel nanoparticles with a minor quantity of hematite (α-Fe2O3) in the glass matrix. The average size of the magnetic nano crystals increases slightly with temperature and time from 9 to 15 nm as determined by the line broadening from the XRD patterns. XRD studies show that annealing the glass samples for long periods of time at temperature ≥604 °C results in an increase of the precipitated hematite concentration, dissolution of the spinel phase and the formation of magnesium di-borate phase (Mg2B2O5). For electron microscopy, the particles were extracted by two methods; (i) replica extraction technique and (ii) dissolution of the glass matrix by diluted acetic acid. An agglomeration of the nano crystals to larger particles (25-35 nm) was observed.

Oxygen potentials in Ni + NiO and Ni + Cr2O3 + NiCr2O4 systems

NASA Astrophysics Data System (ADS)

Kale, G. M.; Fray, D. J.

1994-06-01

The chemical potential of O for the coexistence of Ni + NiO and Ni + Cr2O3 + NiCr2O4 equilibria has been measured employing solid-state galvanic cells, (+) Pt, Cu + Cu2O // (Y2O3)ZrO2 // Ni + NiO, Pt (-) and (+) Pt, Ni + NiO // (Y2O3)ZrO2 // Ni + Cr2O3 + NiCr2O4, Pt (-) in the temperature range of 800 to 1300 K and 1100 to 1460 K, respectively. The electromotive force (emf) of both the cells was reversible, reproducible on thermal cycling, and varied linearly with temperature. For the coexistence of the two-phase mixture of Ni + NiO, δΜO 2(Ni + NiO) = -470,768 + 171.77T (±20) J mol-1 (800 ≤ T ≤ 1300 K) and for the coexistence of Ni + Cr2O3 + NiCr2O4, δΜO 2(Ni + Cr2O3 + NiCr2O4) = -523,190 + 191.07T (±100) J mol-1 (1100≤ T≤ 1460 K) The “third-law” analysis of the present results for Ni + NiO gives the value of ‡H{298/o} = -239.8 (±0.05) kJ mol-1, which is independent of temperature, for the formation of one mole of NiO from its elements. This is in excellent agreement with the calorimetric enthalpy of formation of NiO reported in the literature.

Atmospheric chemistry of the reaction ClO + O2 reversible reaction ClO (center dot) O2: Where it stands, what needs to be done, and why?

NASA Technical Reports Server (NTRS)

Prasad, Sheo S.; Lee, Timothy J.

1994-01-01

Possible existence and chemistry of ClO (center dot) O2 was originally proposed to explain the Norrish-Neville effect that O2 suppresses chlorine photosensitized loss of ozone. It was also thought that ClO (center dot) O2 might have some atmospheric chemistry significance. Recently, doubts have been cast on this proposal, because certain laboratory data seem to imply that the equilibrium constant of the title reaction is so small that ClO (center dot) O2 may be too unstable to matter. However, those data create only a superficial illusion to that effect, because on a closer analysis they do not disprove a moderately stable and chemically significant ClO (center dot) O2. Furthermore, our state-of-the-science accurate computational chemistry calculations also suggest that ClO (center dot) O2 may be a weakly bound ClOOO radical with a reactive (2)A ground electronic state. There is therefore a need to design and perform definitive experimental tests of the existence and chemistry of the ClO (center dot) O2 species, which we discuss and which have the potential to mediate the chlorine-catalyzed stratospheric ozone depletion.

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

NASA Astrophysics Data System (ADS)

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.

Crystal structures of Sr(ClO4)2·3H2O, Sr(ClO4)2·4H2O and Sr(ClO4)2·9H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The title compounds, strontium perchlorate trihydrate {di-μ-aqua-aquadi-μ-perchlorato-strontium, [Sr(ClO4)2(H2O)3]n}, strontium perchlorate tetra­hydrate {di-μ-aqua-bis­(tri­aqua­diperchloratostrontium), [Sr2(ClO4)4(H2O)8]} and strontium perchlorate nona­hydrate {hepta­aqua­diperchloratostrontium dihydrate, [Sr(ClO4)2(H2O)7]·2H2O}, were crystallized at low temperatures according to the solid–liquid phase diagram. The structures of the tri- and tetra­hydrate consist of Sr2+ cations coordinated by five water mol­ecules and four O atoms of four perchlorate tetra­hedra in a distorted tricapped trigonal–prismatic coordination mode. The asymmetric unit of the trihydrate contains two formula units. Two [SrO9] polyhedra in the trihydrate are connected by sharing water mol­ecules and thus forming chains parallel to [100]. In the tetra­hydrate, dimers of two [SrO9] polyhedra connected by two sharing water mol­ecules are formed. The structure of the nona­hydrate contains one Sr2+ cation coordinated by seven water mol­ecules and by two O atoms of two perchlorate tetra­hedra (point group symmetry ..m), forming a tricapped trigonal prism (point group symmetry m2m). The structure contains additional non-coordinating water mol­ecules, which are located on twofold rotation axes. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in each of the three structures. PMID:25552979

Crystal structures of ZnCl2·2.5H2O, ZnCl2·3H2O and ZnCl2·4.5H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The formation of different complexes in aqueous solutions is an important step in understanding the behavior of zinc chloride in water. The structure of concentrated ZnCl2 solutions is governed by coordination competition of Cl− and H2O around Zn2+. According to the solid–liquid phase diagram, the title compounds were crystallized below room temperature. The structure of ZnCl2·2.5H2O contains Zn2+ both in a tetra­hedral coordination with Cl− and in an octa­hedral environment defined by five water mol­ecules and one Cl− shared with the [ZnCl4]2− unit. Thus, these two different types of Zn2+ cations form isolated units with composition [Zn2Cl4(H2O)5] (penta­aqua-μ-chlorido-tri­chlorido­di­zinc). The trihydrate {hexa­aqua­zinc tetra­chlorido­zinc, [Zn(H2O)6][ZnCl4]}, consists of three different Zn2+ cations, one of which is tetra­hedrally coordinated by four Cl− anions. The two other Zn2+ cations are each located on an inversion centre and are octa­hedrally surrounded by water mol­ecules. The [ZnCl4] tetra­hedra and [Zn(H2O)6] octa­hedra are arranged in alternating rows parallel to [001]. The structure of the 4.5-hydrate {hexa­aqua­zinc tetra­chlorido­zinc trihydrate, [Zn(H2O)6][ZnCl4]·3H2O}, consists of isolated octa­hedral [Zn(H2O)6] and tetra­hedral [ZnCl4] units, as well as additional lattice water mol­ecules. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ZnCl4 tetra­hedra and water mol­ecules as acceptor groups leads to the formation of a three-dimensional network in each of the three structures. PMID:25552980

Phase transitions in (NH4)2MoO2F4 crystal

NASA Astrophysics Data System (ADS)

Krylov, Alexander; Laptash, Natalia; Vtyurin, Alexander; Krylova, Svetlana

2016-11-01

The mechanisms of temperature and high pressure phase transitions have been studied by Raman spectroscopy. Room temperature (295 K) experiments under high hydrostatic pressure up to 3.6 GPa for (NH4)2 MoO2 F4 have been carried out. Experimental data indicates a phase transition into a new high-pressure phase for (NH4)2 MoO2 F4 at 1.2 GPa. This phase transition is related to the ordering anion octahedron groups [MoO2 F4]2- and is not associated with ammonium group. Raman spectra of small non-oriented crystals ranging from 10 to 350 K have been observed. The experiment shows anion groups [MoO2 F4]2- and ammonium in high temperature phase are disordered. The phase transition at T1 = 269.8 K is of the first-order, close to the tricritical point. The first temperature phase transition is related to the ordering anion octahedron groups [MoO2 F4]2-. Second phase transitions T2 = 180 K are associated with the ordering of ammonium. The data presented within this study demonstrate that 2D correlation analysis combined with traditional Raman spectroscopy are powerful tool to study phase transitions in the crystals.

K0.78Na0.22MoO2AsO4

PubMed Central

Jouini, Raja; Bouzidi, Chahira; Zid, Mohamed Faouzi; Driss, Ahmed

2013-01-01

The title compound, potassium sodium dioxidomolybden­um(VI) arsenate, K0.78Na0.22MoO2AsO4, was synthesized by a solid-state reaction route. The structure is built up from corner-sharing MoO6 octa­hedra and AsO4 tetra­hedra, creating infinite [MoAsO8]∞ chains running along the b-axis direction. As, Mo and all but one O atom are on special positions (4c) with m symmetry and K (occupancy 0.78) is on a position (4a) of -1 in the tunnels. The possible motion of the alkali cations has been investigated by means of the bond-valance sum (BVS) model. The simulation shows that the Na+ motion appears to be easier mainly along the b-axis direction. Structural relationships between the different compounds of the AMoO2AsO4 (A = Ag, Li, Na, K, Rb) series and MXO8 (M = V; X = P, As) chains are discussed. PMID:24109253

Electron excitation cross sections for the 2s(2)2p(3)4S(O) -- 2s(2)2p(3)2D(O) (forbidden) and 4S(O) -- 2s2p(4) 4P (resonance) transitions in O II

NASA Technical Reports Server (NTRS)

Zuo, M.; Smith, Steven J.; Chutjian, A.; Williams, I. D.; Tayal, S. S.; Mclaughlin, Brendan M.

1995-01-01

Experimental and theoretical excitation cross sections are reported for the first forbidden transition 4S(O) -- 2S(2)2p(3) 2D(O) (lambda-lambda 3726, 3729) and the first allowed (resonance) transition 4S(O) -- 2s2p(4) 4P(lambda-833) in O II. Use is made of electron energy loss and merged-beams methods. The electron energy range covered is 3.33 (threshold) to 15 eV for the S -- D transition, and 14.9 (threshold) to 40 eV for the S -- P transition. Care was taken to assess and minimize the metastable fraction of the O II beam. An electron mirror was designed and tested to reflect inelastically backscattered electrons into the forward direction to account for the full range of polar scattering angles. Comparisons are made between present experiments and 11-state R-matrix calculations. Calculations are also presented for the 4S(O) -- 2s(2)2p(3)2P(O) (lambda-2470) transition.

New silicate-germanate Cs2Pb2[(Si0.6Ge0.4)2O7] from the series A2Pb2[B2O7], A = K, Cs, B = Si, Ge with the umbrella-like [PbO3]4- group

NASA Astrophysics Data System (ADS)

Belokoneva, Elena L.; Morozov, Ivan A.; Volkov, Anatoly S.; Dimitrova, Olga V.; Stefanovich, Sergey Yu.

2018-04-01

New silicate-germanate Cs2Pb2[(Si0.6Ge0.4)2O7] was synthesized in multi-components hydrothermal solution with 20 w.% concentration of Cs2CO3 mineralizer, pH = 10. Novel mixed compound belongs to the structure type A2Pb2[B2O7] previously indicated for powders with A = K, B=Si or Ge. Singe crystal structure determination of Cs2Pb2[(Si0.6Ge0.4)2O7] revealed the need for the correction of the space group of the earlier suggested structural model from P-3 to P-3m1, as well as for the splitting of the Pb-atom position. Umbrella-like groups [PbO3]4- are located between [(Si,Ge)O4]4- tetrahedra in mica-like honeycomb layers and play the role of tetrahedra with the Pb-lone-pair as the forth apex. Crystal chemical comparison revealed similarities and differences with the classical structure type of α-celsian Ba[Al2Si2O8] with the tetrahedral double layer. Recently investigated nonlinear optical acentric borates Pb2(BO3)(NO3) and Pb2(BO3)Cl are both related to this structural type, possessing umbrella-like groups [PbO3]4- and honeycomb layers [Pb2(BO3)]+ with the BO3-triangles on the tetrahedral positions.

Crystal structure of bis-[tetra-kis-(tetra-hydro-furan-κO)lithium] bis[μ-2,2',2''-methanetriyltris(4,6-di-tert-butylphenolato)-κ4O,O':O',O'']-dimagnesiate.

PubMed

Zhou, Hongyan; Wang, Lei

2017-07-01

The title ion-association metal complex, [Li(C 4 H 8 O) 4 ] 2 [Mg 2 (C 43 H 61 O 3 ) 2 ], has been synthesized from the tridentate phenolic ligand tris-(3,5-di- tert -butyl-2-hy-droxy-phen-yl)methane in tetra-hydro-furan (THF). The aryl-oxo magnesiate complex anion is binuclear with each Mg 2 O 4 complex unit inversion-related and bridged through the two tridentate chelating phenolate O-donors of the ligand. The complex centres have a distorted tetra-hedral stereochemistry [Mg-O range 1.8796 (17)-2.0005 (16) Å] and an Mg⋯Mg separation of 2.9430 (14) Å]. The LiO 4 coodination sphere of the cation comprises four THF O-donor atoms and has a slightly distorted tetra-hedral conformation [Li-O range 1.899 (5)- 1.953 (5) Å]. In the crystal, a number of stabilizing intra-anion C-H⋯O hydrogen-bonding inter-actions are present but no inter-species associations are found.

Environmental risk assessment of engineered nano-SiO2 , nano iron oxides, nano-CeO2 , nano-Al2 O3 , and quantum dots.

PubMed

Wang, Yan; Nowack, Bernd

2018-05-01

Many research studies have endeavored to investigate the ecotoxicological hazards of engineered nanomaterials (ENMs). However, little is known regarding the actual environmental risks of ENMs, combining both hazard and exposure data. The aim of the present study was to quantify the environmental risks for nano-Al 2 O 3 , nano-SiO 2 , nano iron oxides, nano-CeO 2 , and quantum dots by comparing the predicted environmental concentrations (PECs) with the predicted-no-effect concentrations (PNECs). The PEC values of these 5 ENMs in freshwaters in 2020 for northern Europe and southeastern Europe were taken from a published dynamic probabilistic material flow analysis model. The PNEC values were calculated using probabilistic species sensitivity distribution (SSD). The order of the PNEC values was quantum dots < nano-CeO 2  < nano iron oxides < nano-Al 2 O 3  < nano-SiO 2 . The risks posed by these 5 ENMs were demonstrated to be in the reverse order: nano-Al 2 O 3  > nano-SiO 2  > nano iron oxides > nano-CeO 2  > quantum dots. However, all risk characterization values are 4 to 8 orders of magnitude lower than 1, and no risk was therefore predicted for any of the investigated ENMs at the estimated release level in 2020. Compared to static models, the dynamic material flow model allowed us to use PEC values based on a more complex parameterization, considering a dynamic input over time and time-dependent release of ENMs. The probabilistic SSD approach makes it possible to include all available data to estimate hazards of ENMs by considering the whole range of variability between studies and material types. The risk-assessment approach is therefore able to handle the uncertainty and variability associated with the collected data. The results of the present study provide a scientific foundation for risk-based regulatory decisions of the investigated ENMs. Environ Toxicol Chem 2018;37:1387-1395. © 2018 SETAC. © 2018 SETAC.

Decomposition of Potassium Ferrate(VI) (K2FeO4) and Potassium Ferrate(III) (KFeO2): In-situ Mössbauer Spectroscopy Approach

NASA Astrophysics Data System (ADS)

Machala, Libor; Zboril, Radek; Sharma, Virender K.; Homonnay, Zoltan

2008-10-01

Mössbauer spectroscopy was shown to be very useful technique studying the mechanism of thermal decomposition or aging processes of the most known ferrate(VI), K2FeO4. In-situ Mössbauer spectroscopy approach was used to monitor the phase composition during the studied processes. The experimental set-up was designed to perform in-situ measurements at high temperatures and at different air humid conditions at room temperature. The potassium ferrate(III), KFeO2 was demonstrated to be the primary product of thermal decomposition of K2FeO4. The KFeO2 was unstable in a humid air at room temperature and reacted with components of air, H2O and CO2 to give Fe2O3 nanoparticles and KHCO3. The aging kinetics of K2FeO4 and KFeO2 under humid air were significantly dependent on the relative air humidity.

Polyoxometal cations within polyoxometalate anions. Seven-coordinate uranium and zirconium heteroatom groups in [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- and [Zr4(μ3-O)2(μ2-OH)2(H2O)4 (P2W16O59)2]14-

NASA Astrophysics Data System (ADS)

Gaunt, Andrew J.; May, Iain; Collison, David; Travis Holman, K.; Pope, Michael T.

2003-08-01

Two new composite polyoxotungstate anions with unprecedented structural features, [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- (1) and [Zr4(μ3-O)2(μ2-OH)2(H2O)4 (P2W16O59)2]14- (2) contain polyoxo-uranium and -zirconium clusters as bridging units. The anions are synthesized by reaction of Na12[P2W15O56] with solutions of UO2(NO3)2 and ZrCl4. The structure of 1 in the sodium salt contains four [P2W15O56]12- anions assembled into an overall tetrahedral cluster by means of trigonal bridging groups formed by three equatorial-edge-shared UO7 pentagonal bipyramids. The structure of anion 2 consists of a centrosymmetric assembly of two [P2W16O59]12- anions linked by a {Zr4O2(OH)2(H2O)4}10+ cluster. Both complexes in solution yield the expected two-line 31P-NMR spectra with chemical shifts of -2.95, -13.58 and -6.45, -13.69 ppm, respectively.

Non-Potassic Melts In CMAS-CO2-H2O-K2O Model Peridotite

NASA Astrophysics Data System (ADS)

Buisman, I.; Walter, M. J.; Keshav, S.

2009-12-01

Volatile mediated model systems have been fundamental in shaping our knowledge about the way we view melting phase relations of peridotite at various depths in the Earth. Volatiles not only affect the melting temperatures, but the resulting liquids are, in some case, dramatically different than those witnessed in melting of dry peridotite. For example, the influence of CO2 and H2O on the melting phase relations of model peridotite shows a remarkable decrease in the solidus temperatures when compared to the dry peridotite (Gudfinnsson and Presnall, 2005). These model systems illustrate a gradational change above the solidus from carbonatites to kimberlites over several hundreds of degrees. Group-II kimberlites are ultrapotassic rocks with high water content where the mineral phlogopite is abundant. To get a better understanding of the melting phase relations related to carbonatitic and kimberlitic magmas, K2O was added to the system CMAS-CO2-H2O. In these systems, fluid and melt can co-exist in P-T space. However, from past studies, it is also known that in hydrous systems, both the fluid and melt will become indistinguishable from one another creating a singularity (second critical endpoint). Starting from the solidus located in six components (Keshav and Gudfinnsson, AGU abstract, 2009), with seven phases, melting phase relations in CMAS-CO2-H2O-K2O involving, fo-opx-cpx-garnet-carbonate-melt-fluid, are divariant. Fluid was recognized with the observation of large cavities seen in exposed capsules. Moreover, the presence of bright, needle-like grains found in large cavities in backscattered images implies the presence of solute in the fluid phase. Significantly, liquids on this divariant region have about 1000 ppm K2O, and so is the case with accompanying cpx. Hence, with this non-interesting amount of K2O in the mentioned phases, fluid must have all the potassium. At 30 kbar/1100C, with fo-opx-cpx-garnet-carbonate-phlogopite-melt-fluid, the melting phase

Interfaces in La2NiO4- La2CuO4 superlattices

NASA Astrophysics Data System (ADS)

Smadici, S.; Lee, J. C. T.; Wang, S.; Abbamonte, P.; Logvenov, G.; Gozar, A.; Bozovic, I.

2009-03-01

Ni substitution on Cu sites in underdoped La2-xSrxCuO4 quickly restores Neel order. This was attributed to strong interaction between the Ni and doped holes. An open question was whether the additional Ni empty orbital or the different spin on Ni sites was at the origin of this strong interaction. We have addressed this problem with resonant soft x-ray scattering on a La2NiO4- La2CuO4 heterostructure. La2NiO4 and La2CuO4 have close lattice structures and electronic configurations. However, the x-ray scattering contrast between superlattice layers is greatly enhanced at soft x-ray resonant energies. Based on our measurements at the O K, La M, Cu L and Ni L edges a model of the charge, orbital and spin structures in these superlattices will be presented with a special emphasis on the interface region. This work was supported by Grants. DE-FG02- 06ER46285, DE-AC02-98CH10886, MA-509-MACA, DE-FG02-07ER46453 and DE-FG02-07ER46471.

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

NASA Astrophysics Data System (ADS)

Johannes, Wilhelm

1980-09-01

Beginning of melting and subsolidus relationships in the system K2O-CaO-Al2O3-SiO2-H2O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt. The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K2O-CaO-Al2O3-SiO2-H2O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al2O3-SiO2-H2O. The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al2O3-SiO2-H2O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this

Infrared spectroscopy of solid normal hydrogen doped with CH3F and O2 at 4.2 K: CH3F:O2 complex and CH3F migration

NASA Astrophysics Data System (ADS)

Abouaf-Marguin, L.; Vasserot, A.-M.

2011-04-01

Double doping of solid normal hydrogen with CH3F and O2 at about 4.2 K gives evidence of (ortho-H2)n:CH3F clusters and of O2:CH3F complex formation. FTIR analysis of the time evolution of the spectra in the region of the v3 C-F stretching mode indicates that these clusters behave very differently from (ortho-H2)n:H2O clusters. The main point is the observed migration of CH3F molecules in solid para-H2 at 4.2 K which differs from that of H2O under identical experimental conditions. This is confirmed by an increase over time of the integrated intensity of the CH3F:O2 complex with a rate constant K = 2.7(2) . 10-4 s-1.

Quantum Dot Sensitized Solar Cells Based on TiO2/AgInS2

NASA Astrophysics Data System (ADS)

Pawar, Sachin A.; Jeong, Jae Pil; Patil, Dipali S.; More, Vivek M.; Lee, Rochelle S.; Shin, Jae Cheol; Choi, Won Jun

2018-05-01

Quantum dot heterojunctions with type-II band alignment can efficiently separate photogenerated electron-hole pairs and, hence, are useful for solar cell studies. In this study, a quantum dot sensitized solar cell (QDSSC) made of TiO2/AgInS2 is achieved to boost the photoconversion efficiency for the TiO2-based system by varying the AgInS2 layer's thickness. The TiO2 nanorods array film is prepared by using a simple hydrothermal technique. The formation of a AgInS2 QD-sensitized TiO2-nanorod photoelectrode is carried out by successive ionic layer adsorption and reaction (SILAR) technique. The effect of the QD layer on the performance of the solar cell is studied by varying the SILAR cycles of the QD coating. The synthesized electrode materials are characterized by using X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, high resolution transmission electron microscopy and solar cell performances. The results indicate that the nanocrystals have effectively covered the outer surfaces of the TiO2 nanorods. The interfacial structure of quantum dots (QDs)/TiO2 is also investigated, and the growth interface is verified. A careful comparison between TiO2/AgInS2 sensitized cells reveals that the trasfer of electrons and hole proceeds efficiently, the recombination is suppressed for the optimum thickness of the QD layer and light from the entire visible spectrum is utilised. Under AM 1.5G illumination, a high photocurrent of 1.36 mAcm-2 with an improved power conversion efficiency of 0.48% is obtained. The solar cell properties of our photoanodes suggest that the TiO2 nanorod array films co-sensitized by AgInS2 nanoclusters have potential applications in solar cells.

Crystal structures of Ca(ClO4)2·4H2O and Ca(ClO4)2·6H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The title compounds, calcium perchlorate tetra­hydrate and calcium perchlorate hexa­hydrate, were crystallized at low temperatures according to the solid–liquid phase diagram. The structure of the tetra­hydrate consists of one Ca2+ cation eightfold coordinated in a square-anti­prismatic fashion by four water mol­ecules and four O atoms of four perchlorate tetra­hedra, forming chains parallel to [01-1] by sharing corners of the ClO4 tetra­hedra. The structure of the hexa­hydrate contains two different Ca2+ cations, each coordinated by six water mol­ecules and two O atoms of two perchlorate tetra­hedra, forming [Ca(H2O)6(ClO4)]2 dimers by sharing two ClO4 tetra­hedra. The dimers are arranged in sheets parallel (001) and alternate with layers of non-coordinating ClO4 tetra­hedra. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in the two structures. Ca(ClO4)2·6H2O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1 in each of the two structures. PMID:25552974

A V(IV) Hydroxyhydrogenomonophosphate with an Intersecting Tunnel Structure: HK 4[V 10O 10(H 2O) 2(OH) 4(PO 4) 7]·9H 2O

NASA Astrophysics Data System (ADS)

Berrah, F.; Guesdon, A.; Leclaire, A.; Borel, M. M.; Provost, J.; Raveau, B.

1999-12-01

A V(IV) hydroxyhydrogenomonophosphate HK4[V10O10(H2O)2(OH)4(PO4)7]·9H2O has been obtained, using hydrothermal conditions. Its structure, closely related to that of (CH3)2NH2K4[V10O10(H2O)2(OH)4(PO4)7]·4H2O, differs from the latter by its I41/a space group (instead of P43). This difference corresponds to a "disordering" of the vanadium atoms, with respect to the dimethyl ammonium phase. It is shown that this disorder, which appears in the form of "V5O22" units distributed at random, does not affect the oxygen framework. The analysis of this complex structure shows that it can be described from the stacking along c of [V8P7O38(OH)4(H2O)2]∞ layers interconnected through layers of isolated VO6 octahedra. In this structure, built up of VO6, VO5OH, and VO4(OH)(H2O) octahedra, of VO4OH pyramids, and of PO4 tetrahedra, large "toffee" tunnels and smaller ones with a tulip-shape section are running along a (or b). The first ones are stuffed with H2O molecules forming aquo tubes, where protons are likely "delocalized," whereas the second ones are occupied by K+ cations.

Water activities of NaClO4, Ca(ClO4)2, and Mg(ClO4)2 brines from experimental heat capacities: Water activity >0.6 below 200 K

NASA Astrophysics Data System (ADS)

Toner, J. D.; Catling, D. C.

2016-05-01

Perchlorate salts found on Mars are extremely hygroscopic and form low eutectic temperature aqueous solutions, which could allow liquid water to exist on Mars despite cold and dry conditions. The formation, dynamics, and potential habitability of perchlorate salt solutions can be broadly understood in terms of water activity. Water activity controls condensation and evaporation of water vapor in brines, deliquescence and efflorescence of crystalline salts, and ice formation during freezing. Furthermore, water activity is a basic parameter defining the habitability of aqueous solutions. Despite the importance of water activity, its value in perchlorate solutions has only been measured at 298.15 K and at the freezing point of water. To address this lack of data, we have determined water activities in NaClO4, Ca(ClO4)2, and Mg(ClO4)2 solutions using experimental heat capacities measured by Differential Scanning Calorimetry. Our results include concentrations up to near-saturation and temperatures ranging from 298.15 to 178 K. We find that water activities in NaClO4 solutions increase with decreasing temperature, by as much as 0.25 aw from 298.15 to 178 K. Consequently, aw reaches ∼0.6-0.7 even for concentrations up to 15 molal NaClO4 below 200 K. In contrast, water activities in Ca(ClO4)2 and Mg(ClO4)2 solutions generally decrease with decreasing temperature. The temperature dependence of water activity indicates that low-temperature NaClO4 solutions will evaporate and deliquesce at higher relative humidity, crystallize ice at higher temperature, and potentially be more habitable for life (at least in terms of water activity) compared to solutions at 298.15 K. The opposite effects occur in Ca(ClO4)2 and Mg(ClO4)2 solutions.

Mechanism of thermal decomposition of K2FeO4 and BaFeO4: A review

NASA Astrophysics Data System (ADS)

Sharma, Virender K.; Machala, Libor

2016-12-01

This paper presents thermal decomposition of potassium ferrate(VI) (K2FeO4) and barium ferrate(VI) (BaFeO4) in air and nitrogen atmosphere. Mössbauer spectroscopy and nuclear forward scattering (NFS) synchrotron radiation approaches are reviewed to advance understanding of electron-transfer processes involved in reduction of ferrate(VI) to Fe(III) phases. Direct evidences of Fe V and Fe IV as intermediate iron species using the applied techniques are given. Thermal decomposition of K2FeO4 involved Fe V, Fe IV, and K3FeO3 as intermediate species while BaFeO3 (i.e. Fe IV) was the only intermediate species during the decomposition of BaFeO4. Nature of ferrite species, formed as final Fe(III) species, of thermal decomposition of K2FeO4 and BaFeO4 under different conditions are evaluated. Steps of the mechanisms of thermal decomposition of ferrate(VI), which reasonably explained experimental observations of applied approaches in conjunction with thermal and surface techniques, are summarized.

The photosensitivity of carbon quantum dots/CuAlO2 films composites.

PubMed

Pan, Jiaqi; Sheng, Yingzhuo; Zhang, Jingxiang; Wei, Jumeng; Huang, Peng; Zhang, Xin; Feng, Boxue

2015-07-31

Carbon quantum dots/CuAlO2 films were prepared by a simple route through which CuAlO2 films prepared by sol-gel on crystal quartz substrates were composited with carbon quantum dots on their surface. The characterization results indicated that CuAlO2 films were well combined with carbon quantum dots. The photoconductivity of carbon quantum dots/CuAlO2 films was investigated under illumination and darkness switching, and was demonstrated to be significantly enhanced compared with CuAlO2 films. Through analysis, this enhancement of photoconductivity was attributed to the carbon quantum dots with unique up-converted photoluminescence behavior.

The photosensitivity of carbon quantum dots/CuAlO2 films composites

NASA Astrophysics Data System (ADS)

Pan, Jiaqi; Sheng, Yingzhuo; Zhang, Jingxiang; Wei, Jumeng; Huang, Peng; Zhang, Xin; Feng, Boxue

2015-07-01

Carbon quantum dots/CuAlO2 films were prepared by a simple route through which CuAlO2 films prepared by sol-gel on crystal quartz substrates were composited with carbon quantum dots on their surface. The characterization results indicated that CuAlO2 films were well combined with carbon quantum dots. The photoconductivity of carbon quantum dots/CuAlO2 films was investigated under illumination and darkness switching, and was demonstrated to be significantly enhanced compared with CuAlO2 films. Through analysis, this enhancement of photoconductivity was attributed to the carbon quantum dots with unique up-converted photoluminescence behavior.

Large hydrogen-bonded pre-nucleation (HSO4-)(H2SO4)m(H2O)k and (HSO4-)(NH3)(H2SO4)m(H2O)k clusters in the earth's atmosphere.

PubMed

Herb, Jason; Xu, Yisheng; Yu, Fangqun; Nadykto, A B

2013-01-10

The importance of pre-nucleation cluster stability as the key parameter controlling nucleation of atmospheric airborne ions is well-established. In this Article, large ternary ionic (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(H(2)O)(n) clusters have been studied using Density Functional Theory (DFT) and composite ab initio methods. Twenty classes of clusters have been investigated, and thermochemical properties of common atmospheric (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(0)(H(2)O)(k) and (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(1)(H(2)O)(n) clusters (with m, k, and n up to 3) have been obtained. A large amount of new themochemical and structural data ready-to-use for constraining kinetic nucleation models has been reported. We have performed a comprehensive thermochemical analysis of the obtained data and have investigated the impacts of ammonia and negatively charged bisulfate ion on stability of binary clusters in some detail. The comparison of theoretical predictions and experiments shows that the PW91PW91/6-311++G(3df,3pd) results are in very good agreement with both experimental data and high level ab initio CCSD(T)/CBS values and suggest that the PW91PW91/6-311++G(3df,3pd) method is a viable alternative to higher level ab initio methods in studying large pre-nucleation clusters, for which the higher level computations are prohibitively expensive. The uncertainties in both theory and experiments have been investigated, and possible ways of their reduction have been proposed.

Disappearance of superconductivity in the solid solution between (Ca4Al2O6)(Fe2As2) and (Ca4Al2O6)(Fe2P2) superconductors.

PubMed

Shirage, Parasharam M; Kihou, Kunihiro; Lee, Chul-Ho; Takeshita, Nao; Eisaki, Hiroshi; Iyo, Akira

2012-09-19

The effect of alloying the two perovskite-type iron-based superconductors (Ca(4)Al(2)O(6))(Fe(2)As(2)) and (Ca(4)Al(2)O(6))(Fe(2)P(2)) was examined. While the two stoichiometric compounds possess relatively high T(c)'s of 28 and 17 K, respectively, their solid solutions of the form (Ca(4)Al(2)O(6))(Fe(2)(As(1-x)P(x))(2)) do not show superconductivity over a wide range from x = 0.50 to 0.95. The resultant phase diagram is thus completely different from those of other typical iron-based superconductors such as BaFe(2)(As,P)(2) and LaFe(As,P)O, in which superconductivity shows up when P is substituted for As in the non-superconducting "parent" compounds. Notably, the solid solutions in the non-superconducting range exhibit resistivity anomalies at temperatures of 50-100 K. The behavior is reminiscent of the resistivity kink commonly observed in various non-superconducting parent compounds that signals the onset of antiferromagnetic/orthorhombic long-range order. The similarity suggests that the suppression of the superconductivity in the present case also has a magnetic and/or structural origin.

From {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} to {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} infinite chains in A{sub 6}U{sub 2}Mo{sub 4}O{sub 21} (A=Na, K, Rb, Cs) compounds: Synthesis and crystal structure of Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})

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

Yagoubi, S.; Groupe de Radiochimie, Institut de Physique Nucleaire d'Orsay, Universite Paris-Sud XI, 91406 Orsay Cedex; Obbade, S., E-mail: said.obbade@phelma.grenoble-inp.f

2011-05-15

A new caesium uranyl molybdate belonging to the M{sub 6}U{sub 2}Mo{sub 4}O{sub 21} family has been synthesized by solid-state reaction and its structure determined from single-crystal X-ray diffraction data. Contrary to the other alkali uranyl molybdates of this family (A=Na, K, Rb) where molybdenum atoms adopt only tetrahedral coordination and which can be formulated A{sub 6}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}], the caesium compound Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 21} should be written Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] with molybdenum atoms in tetrahedral and square pyramidal environments. Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] crystallizes in the triclinic symmetry withmore » space group P1-bar and a=10.4275(14) A, b=15.075(2) A, c=17.806(2) A, {alpha}=70.72(1){sup o}, {beta}=80.38(1){sup o} and {gamma}=86.39(1){sup o}, V=2604.7(6) A{sup 3}, Z=4, {rho}{sub mes}=5.02(2) g/cm{sup 3} and {rho}{sub cal}=5.08(3) g/cm{sup 3}. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R{sub 1}=0.0464 and wR{sub 2}=0.0950 for 596 parameters with 6964 independent reflections with I{>=}2{sigma}(I) collected on a BRUKER AXS diffractometer with Mo(K{alpha}) radiation and a CCD detector. The crystal structure of Cs compound is characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} parallels chains built from U{sub 2}O{sub 13} dimeric units, MoO{sub 4} tetrahedra and MoO{sub 5} square pyramids, whereas, Na, K and Rb compounds are characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} parallel chains formulated simply of U{sub 2}O{sub 13} units and MoO{sub 4} tetrahedra. Infrared spectroscopy measurements using powdered samples synthesized by solid-state reaction, confirm the structural results. The thermal stability and the electrical conductivity are also studied. The four compounds decompose at low temperature (between 540 and 610

Role of SiO2 coating in multiferroic CoCr2O4 nanoparticles

NASA Astrophysics Data System (ADS)

Kamran, M.; Ullah, Asmat; Mehmood, Y.; Nadeem, K.; Krenn, H.

2017-02-01

Effect of silica (SiO2) coating concentration on structural and magnetic properties of multiferroic cobalt chromite (CoCr2O4) nanoparticles have been studied. The nanoparticles with average crystallite size in the range 19 to 28 nm were synthesised by sol-gel method. X-ray diffraction (XRD) analysis has verified the composition of single-phase cubic normal spinel structure of CoCr2O4 nanoparticles. The average crystallite size and cell parameter decreased with increasing SiO2 concentration. TEM image revealed that the shape of nanoparticles was non-spherical. Zero field cooled/field cooled (ZFC/FC) curves revealed that nanoparticles underwent a transition from paramagnetic (PM) state to collinear short-range ferrimagnetic (FiM) state, and this PM-FiM transition temperature decreased from 101 to 95 K with increasing SiO2 concentration or decreasing crystallite size. A conical spin state at Ts = 27 K was also observed for all the samples which decreased with decreasing average crystallite size. Low temperature lock-in transition was also observed in these nanoparticles at 12 K for uncoated nanoparticles which slightly shifted towards low temperature with decreasing average crystallite size. Saturation magnetization (Ms) showed decreasing trend with increasing SiO2 concentration, which was due to decrease in average crystallite size of nanoparticles and enhanced surface disorder in smaller nanoparticles. The temperature dependent AC-susceptibility also showed the decrease in the transition temperature (Tc), broadening of the Tc peak and decrease in magnetization with increasing SiO2 concentration or decreasing average crystallite size. In summary, the concentration of SiO2 has significantly affected the structural and magnetic properties of CoCr2O4 nanoparticles.

Silicate liquid immiscibility in magmas and in the system K2O-FeO-AI2O3-SiO2: an example of serendipity

USGS Publications Warehouse

Roedder, E.

1978-01-01

The concept of silicate liquid immiscibility was invoked early in the history of petrology to explain certain pairs of compositionally divergent rocks, but. as a result of papers by Greig (Am. J. Sci. 13, 1-44, 133-154) and Bowen (The Evolution of the Igneous Rocks), it fell into disfavor for many years. The discovery of immiscibility in geologically reasonable temperature ranges and compositions in experimental work on the system K2O-FeO-Al2O3-SiO2, and of evidence for immiscibility in a variety of lunar and terrestrial rocks, has reinstated the process. Phase equilibria in the high-silica corner of the tetrahedron representing the system K2O- FeO-Al2O3-SiO2 are presented, in the form of constant FeO sections through the tetrahedron, at 10% increments. Those sections, showing the tentative relationships of the primary phase volumes, are based on 5631 quenching runs on 519 compositions, made in metallic iron containers in pure nitrogen. Thirteen crystalline compounds are involved, of which at least six show two or more crystal modifica-tions. Two separate phase volumes, in each of which two immiscible liquids, one iron-rich and the other iron-poor, are present at the liquidus. One of these volumes is entirely within the quaternary system, astride the 1:1 K2O:Al2O3 plane. No quaternary compounds as such have been found, but evidence does point toward at least partial quaternary solid solution, with rapidly lowering liquidus temperatures, from K2O??Al2O3?? 2SiO2 ('potash nepheline', kalsilite. kaliophilite) to the isostructural compound K2O??FeO??3SiO2, and from K2O??Al2O3??4SiO2 (leucite) to the isostructural compound K2O??FeO??5SiO2, Both of these series apparently involve substitution, in tetrahedral coordination. of a ferrous iron and a silicon ion for two aluminum ions. Some of the 'impurities' found in analyses of the natural phases may reflect these substitutions. As a result of the geometry of the immiscibility volume located entirely within the quaternary

The Vaporization of B2O3(l) to B2O3(g) and B2O2(g)

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Myers, Dwight L.

2011-01-01

The vaporization of B2O3 in a reducing environment leads to formation of both B2O3(g) and B2O2(g). While formation of B2O3(g) is well understood, many questions about the formation of B2O2(g) remain. Previous studies using B(s) + B2O3(l) have led to inconsistent thermodynamic data. In this study, it was found that after heating, B(s) and B2O3(l) appear to separate and variations in contact area likely led to the inconsistent vapor pressures of B2O2(g). To circumvent this problem, an activity of boron is fixed with a two-phase mixture of FeB and Fe2B. Both second and third law enthalpies of formation were measured for B2O2(g) and B2O3(g). From these the enthalpies of formation at 298.15 K are calculated to be -479.9 +/- 41.5 kJ/mol for B2O2(g) and -833.4 +/- 13.1 kJ/mol for B2O3(g). Ab initio calculations to determine the enthalpies of formation of B2O2(g) and B2O3(g) were conducted using the W1BD composite method and show good agreement with the experimental values.

ZnO Quantum Dot Decorated Zn2SnO4 Nanowire Heterojunction Photodetectors with Drastic Performance Enhancement and Flexible Ultraviolet Image Sensors.

PubMed

Li, Ludong; Gu, Leilei; Lou, Zheng; Fan, Zhiyong; Shen, Guozhen

2017-04-25

Here we report the fabrication of high-performance ultraviolet photodetectors based on a heterojunction device structure in which ZnO quantum dots were used to decorate Zn 2 SnO 4 nanowires. Systematic investigations have shown their ultrahigh light-to-dark current ratio (up to 6.8 × 10 4 ), specific detectivity (up to 9.0 × 10 17 Jones), photoconductive gain (up to 1.1 × 10 7 ), fast response, and excellent stability. Compared with a pristine Zn 2 SnO 4 nanowire, a quantum dot decorated nanowire demonstrated about 10 times higher photocurrent and responsivity. Device physics modeling showed that their high performance originates from the rational energy band engineering, which allows efficient separation of electron-hole pairs at the interfaces between ZnO quantum dots and a Zn 2 SnO 4 nanowire. As a result of band engineering, holes migrate to ZnO quantum dots, which increases electron concentration and lifetime in the nanowire conduction channel, leading to significantly improved photoresponse. The enhancement mechanism found in this work can also be used to guide the design of high-performance photodetectors based on other nanomaterials. Furthermore, flexible ultraviolet photodetectors were fabricated and integrated into a 10 × 10 device array, which constitutes a high-performance flexible ultraviolet image sensor. These intriguing results suggest that the band alignment engineering on nanowires can be rationally achieved using compound semiconductor quantum dots. This can lead to largely improved device performance. Particularly for ZnO quantum dot decorated Zn 2 SnO 4 nanowires, these decorated nanowires may find broad applications in future flexible and wearable electronics.

Synthesis and X-ray crystal structure of (OsO(3)F(2))(2)2XeOF(4) and the Raman spectra of (OsO(3)F(2))(infinity), (OsO(3)F(2))(2), and (OsO(3)F(2))(2)2XeOF(4).

PubMed

Hughes, Michael J; Mercier, Hélène P A; Schrobilgen, Gary J

2009-05-18

The adduct, (OsO(3)F(2))(2)2XeOF(4), was synthesized by dissolution of the infinite chain polymer, (OsO(3)F(2))(infinity), in XeOF(4) solvent at room temperature followed by removal of excess XeOF(4) under dynamic vacuum at 0 degrees C. Continued pumping at 0 degrees C resulted in removal of associated XeOF(4), yielding (OsO(3)F(2))(2), a new low-temperature phase of OsO(3)F(2). Upon standing at 25 degrees C for 1(1)/(2) h, (OsO(3)F(2))(2) underwent a phase transition to the known monoclinic phase, (OsO(3)F(2))(infinity). The title compounds, (OsO(3)F(2))(infinity), (OsO(3)F(2))(2), and (OsO(3)F(2))(2)2XeOF(4) have been characterized by low-temperature (-150 degrees C) Raman spectroscopy. Crystallization of (OsO(3)F(2))(2)2XeOF(4) from XeOF(4) solution at 0 degrees C yielded crystals suitable for X-ray structure determination. The structural unit contains the (OsO(3)F(2))(2) dimer in which the OsO(3)F(3) units are joined by two Os---F---Os bridges having fluorine bridge atoms that are equidistant from the osmium centers (2.117(5) and 2.107(4) A). The dimer coordinates to two XeOF(4) molecules through Os-F...Xe bridges in which the Xe...F distances (2.757(5) A) are significantly less than the sum of the Xe and F van der Waals radii (3.63 A). The (OsO(3)F(2))(2) dimer has C(i) symmetry in which each pseudo-octahedral OsO(3)F(3) unit has a facial arrangement of oxygen ligands with XeOF(4) molecules that are only slightly distorted from their gas-phase C(4v) symmetry. Quantum-chemical calculations using SVWN and B3LYP methods were employed to calculate the gas-phase geometries, natural bond orbital analyses, and vibrational frequencies of (OsO(3)F(2))(2), (OsO(3)F(2))(2)2XeOF(4), XeOF(4), OsO(2)F(4), and (mu-FOsO(3)F(2))(2)OsO(3)F(-) to aid in the assignment of the experimental vibrational frequencies of (OsO(3)F(2))(2), (OsO(3)F(2))(2)2XeOF(4), and (OsO(3)F(2))(infinity). The vibrational modes of the low-temperature polymeric phase, (OsO(3)F(2))(infinity), have been

Empirical electronic polarizabilities: deviations from the additivity rule. I. M2+SO4·nH2O, blödite Na2M2+(SO4)2·4H2O, and kieserite-related minerals with sterically strained structures

NASA Astrophysics Data System (ADS)

Gagné, Olivier; Hawthorne, Frank; Shannon, Robert D.; Fischer, Reinhard X.

2017-09-01

Empirical electronic polarizabilities allow the prediction of total mineral polarizabilities and mean refractive indices of the vast majority of minerals and synthetic oxides. However, deviations from the valence-sum rule at cations in some minerals are associated with large deviations of observed from calculated total polarizabilities. We have identified several groups of minerals and compounds where deviations from the valence-sum rule at cations lead to polarizability deviations of 2-5%: M(SO4)·nH2O, n = 1-6, blödite-group minerals [Na2M2+(SO4)2·4H2O], and the kieserite-related minerals: isokite, panasqueiraite and tilasite. In these minerals, the environment of the M ions contains both O and H2O: Mg[O4(H2O)2] in kieserite, szmikite, and szomolnokite; Mg[O2(H2O)4] in starkeyite, ilesite, and rozenite, and Mg[(H2O)6] in hexahydrite. In compounds where the ligands are only H2O, deviations from the valence-sum rule at the M(H2O)6 groups are not accompanied by significant polarizability deviations. This is the case for epsomite, MgSO4·7H2O; bieberite, CoSO4·7H2O; goslarite, ZnSO4·7H2O, six silicofluorides, MSiF6·6H2O; eighteen Tutton's salts, M2M'(SO4)2·6H2O, where M = K, Rb, Cs and M' = Mg, Mn, Fe, Co, Ni, Cu, and Zn; and eleven MM'(SO4)2·12H2O alums, where M = Na, K, Rb and Cs, and M' = Al, Cr, Ga and In. This is also the case for the sulfates alunogen, Al2(SO4)3·17H2O and halotrichite, FeAl2(SO4)4·22H2O; three hydrated nitrates; one phosphate; three antimonates and two hydrated perchlorates. A possible explanation for this different behavior is that the bond-valence model treats O and H separately, whereas polarizability calculations treat the polarizability of the entire H2O molecule.

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

PubMed

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

1997-10-01

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

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

DOE PAGES

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

2016-12-05

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

Submillimeter H2O and H2O+emission in lensed ultra- and hyper-luminous infrared galaxies at z 2-4

NASA Astrophysics Data System (ADS)

Yang, C.; Omont, A.; Beelen, A.; González-Alfonso, E.; Neri, R.; Gao, Y.; van der Werf, P.; Weiß, A.; Gavazzi, R.; Falstad, N.; Baker, A. J.; Bussmann, R. S.; Cooray, A.; Cox, P.; Dannerbauer, H.; Dye, S.; Guélin, M.; Ivison, R.; Krips, M.; Lehnert, M.; Michałowski, M. J.; Riechers, D. A.; Spaans, M.; Valiante, E.

2016-11-01

We report rest-frame submillimeter H2O emission line observations of 11 ultra- or hyper-luminous infrared galaxies (ULIRGs or HyLIRGs) at z 2-4 selected among the brightest lensed galaxies discovered in the Herschel-Astrophysical Terahertz Large Area Survey (H-ATLAS). Using the IRAM NOrthern Extended Millimeter Array (NOEMA), we have detected 14 new H2O emission lines. These include five 321-312ortho-H2O lines (Eup/k = 305 K) and nine J = 2 para-H2O lines, either 202-111(Eup/k = 101 K) or 211-202(Eup/k = 137 K). The apparent luminosities of the H2O emission lines are μLH2O 6-21 × 108 L⊙ (3 <μ< 15, where μ is the lens magnification factor), with velocity-integrated line fluxes ranging from 4-15 Jy km s-1. We have also observed CO emission lines using EMIR on the IRAM 30 m telescope in seven sources (most of those have not yet had their CO emission lines observed). The velocity widths for CO and H2O lines are found to be similar, generally within 1σ errors in the same source. With almost comparable integrated flux densities to those of the high-J CO line (ratios range from 0.4 to 1.1), H2O is found to be among the strongest molecular emitters in high-redshift Hy/ULIRGs. We also confirm our previously found correlation between luminosity of H2O (LH2O) and infrared (LIR) that LH2O LIR1.1-1.2, with ournew detections. This correlation could be explained by a dominant role of far-infrared pumping in the H2O excitation. Modelling reveals that the far-infrared radiation fields have warm dust temperature Twarm 45-75 K, H2O column density per unit velocity interval NH2O /ΔV ≳ 0.3 × 1015 cm-2 km-1 s and 100 μm continuum opacity τ100> 1 (optically thick), indicating that H2O is likely to trace highly obscured warm dense gas. However, further observations of J ≥ 4 H2O lines are needed to better constrain the continuum optical depth and other physical conditions of the molecular gas and dust. We have also detected H2O+ emission in three sources. A tight correlation

Photolysis of H2O-H2O2 Mixtures: The Destruction of H2O2

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Fama, M.; Baragiola, R. A.; Carlson, R. W.

2013-01-01

We present laboratory results on the loss of H2O2 in solid H2O + H2O2 mixtures at temperatures between 21 and 145 K initiated by UV photolysis (193 nm). Using infrared spectroscopy and microbalance gravimetry, we measured the decrease of the 3.5 micrometer infrared absorption band during UV irradiation and obtained a photodestruction cross section that varies with temperature, being lowest at 70 K. We use our results, along with our previously measured H2O2 production rates via ionizing radiation and ion energy fluxes from the spacecraft to compare H2O2 creation and destruction at icy satellites by ions from their planetary magnetosphere and from solar UV photons. We conclude that, in many cases, H2O2 is not observed on icy satellite surfaces because the H2O2 photodestruction rate is much higher than the production rate via energetic particles, effectively keeping the H2O2 infrared signature at or below the noise level.

Thermal and fragility studies on microwave synthesized K2O-B2O3-V2O5 glasses

NASA Astrophysics Data System (ADS)

Harikamalasree, Reddy, M. Sudhakara; Viswanatha, R.; Reddy, C. Narayana

2016-05-01

Glasses with composition xK2O-60B2O3-(40-x) V2O5 (15 ≤ x ≤ 39 mol %) was prepared by an energy efficient microwave method. The heat capacity change (ΔCp) at glass transition (Tg), width of glass transition (ΔTg), heat capacities in the glassy (Cpg) and liquid (Cpl) state for the investigated glasses were extracted from Modulated Differential Scanning Calorimetry (MDSC) thermograms. The width of glass transition is less than 30°C, indicating that these glasses belongs to fragile category. Fragility functions [NBO]/(Vm3Tg) and (ΔCp/Cpl)increases with increasing modifier oxide concentration. Increase in fragility is attributed to the increasing coordination of boron. Further, addition of K2O creates NBOs and the flow mechanism involves bond switching between BOs and NBOs. Physical properties exhibit compositional dependence and these properties increase with increasing K2O concentration. The observed variations are qualitatively analyzed.

Optical and dielectric properties of isothermally crystallized nano-KNbO3 in Er3+-doped K2O-Nb2O5-SiO2 glasses.

PubMed

Chaliha, Reenamoni Saikia; Annapurna, K; Tarafder, Anal; Tiwari, V S; Gupta, P K; Karmakar, Basudeb

2010-01-01

Precursor glass of composition 25K(2)O-25Nb(2)O(5)-50SiO(2) (mol%) doped with Er(2)O(3) (0.5 wt% in excess) was isothermally crystallized at 800 degrees C for 0-100 h to obtain transparent KNbO(3) nanostructured glass-ceramics. XRD, FESEM, TEM, FTIRRS, dielectric constant, refractive index, absorption and fluorescence measurements were carried out to analyze the morphology, dielectric, structure and optical properties of the glass-ceramics. The crystallite size of KNbO(3) estimated from XRD and TEM is found to vary in the range 7-23 nm. A steep rise in the dielectric constant of glass-ceramics with heat-treatment time reveals the formation of ferroelectric nanocrystalline KNbO(3) phase. The measured visible photoluminescence spectra have exhibited green emission transitions of (2)H(11/2), (4)S(3/2)-->(4)I(15/2) upon excitation at 377 nm ((4)I(15/2)-->(4)G(11/2)) absorption band of Er(3+) ions. The near infrared (NIR) emission transition (4)I(13/2)-->(4)I(15/2) is detected around 1550 nm on excitation at 980 nm ((4)I(15/2)-->(4)I(11/2)) of absorption bands of Er(3+) ions. It is observed that photoluminescent intensity at 526 nm ((2)H(11/2)-->(4)I(15/2)), 550 nm ((4)S(3/2)-->(4)I(15/2)) and 1550 nm ((4)I(13/2)-->(4)I(15/2)) initially decrease and then gradually increase with increase in heat-treatment time. The measured lifetime (tau(f)) of the (4)I(13/2)-->(4)I(15/2) transition also possesses a similar trend. The measured absorption and fluorescence spectra reveal that the Er(3+) ions gradually enter into the KNbO(3) nanocrystals. Copyright 2009 Elsevier B.V. All rights reserved.

Decomposition of Potassium Ferrate(VI)(K{sub 2}FeO{sub 4}) and Potassium Ferrate(III)(KFeO{sub 2}): In-situ Moessbauer Spectroscopy Approach

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

Machala, Libor; Zboril, Radek; Sharma, Virender K.

2008-10-28

Moessbauer spectroscopy was shown to be very useful technique studying the mechanism of thermal decomposition or aging processes of the most known ferrate(VI), K{sub 2}FeO{sub 4}. In-situ Moessbauer spectroscopy approach was used to monitor the phase composition during the studied processes. The experimental set-up was designed to perform in-situ measurements at high temperatures and at different air humid conditions at room temperature. The potassium ferrate(III), KFeO{sub 2} was demonstrated to be the primary product of thermal decomposition of K{sub 2}FeO{sub 4}. The KFeO{sub 2} was unstable in a humid air at room temperature and reacted with components of air, H{submore » 2}O and CO{sub 2} to give Fe{sub 2}O{sub 3} nanoparticles and KHCO{sub 3}. The aging kinetics of K{sub 2}FeO{sub 4} and KFeO{sub 2} under humid air were significantly dependent on the relative air humidity.« less

Design and syntheses of hybrid metal-organic materials based on K3[M(C2O4)3]·3H2O [M(III)=Fe, Al, Cr] metallotectons

NASA Astrophysics Data System (ADS)

Sun, Yayong; Zong, Yingxia; Ma, Haoran; Zhang, Ao; Liu, Kang; Wang, Debao; Wang, Wenqiang; Wang, Lei

2016-05-01

By using K3[M(C2O4)3]·3H2O [M(III)=Fe, Al, Cr] (C2O42-=oxalate) metallotectons as the starting material, we have synthesized eight novel complexes with formulas [{Fe(C2O4)2(H2O)2}2]·(H-L1)2·H2O 1, [Fe(C2O4)Cl2]·(H2-L2)0.5·(L2)0.5·H2O 2, [{Fe(C2O4)1.5Cl2}2]·(H-L3)43, [Fe2(C2O4)Cl8]·(H2-L4)2·2H2O 4, K[Al(C2O4)3]·(H2-L5)·2H2O 5, K[Al(C2O4)3]·(H-L6)2·2H2O 6, K[Cr(C2O4)3]·2H2O 7, Na[Fe(C2O4)3]·(H-L6)2·2H2O 8 (with L1=4-dimethylaminopyridine, L2=2,3,5,6-tetramethylpyrazine, L3=2-aminobenzimidazole, L4=1,4-bis-(1H-imidazol-1-yl)benzene, L5=1,4-bis((2-methylimidazol-1-yl)methyl)benzene, L6=2-methylbenzimidazole). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra and thermogravimetric analyses. Compound 3 is a 2D H-bonded supramolecular architecture. Others are 3D supramolecular structures. Compound 1 shows a [Fe(C2O4)2(H2O)2]- unit and 3D antionic H-bonded framework. Compound 2 features a [Fe(C2O4)Cl2]- anion and 1D iron-oxalate-iron chain. Compound 3 features a [Fe2(C2O4)3Cl4]4- unit. Compound 4 features distinct [Fe2(C2O4)Cl8]4- units, which are mutual linked by water molecules to generated a 2D H-bonded network. Compound 5 features infinite ladder-like chains constructed by [Al(C2O4)3]3- units and K+ cations. The 1D chains are further extended into 3D antionic H-bonded framework through O-H···O H-bonds. Compounds 6-8 show 2D [KAl(C2O4)3]2- layer, [KCr(C2O4)3]2- layer and [NaFe(C2O4)3]2- layer, respectively.

Kinetics of OH- and Cl-initiated oxidation of CH2dbnd CHC(O)O(CH2)2CH3 and CH2dbnd CHCH2C(O)O(CH2)2CH3 and fate of the alkoxy radicals formed

NASA Astrophysics Data System (ADS)

Rivela, Cynthia; Blanco, María B.; Teruel, Mariano A.

2016-05-01

Rate coefficients of the reactions of OH and Cl radicals with vinyl and allyl butyrate were determined for the first time at 298 K and 1 atm using the relative method to be (in cm3 molecule-1 s-1): k1(OH + CH2dbnd CHC(O)O(CH2)2CH3) = (2.61 ± 0.31) × 10-11, k2(Cl + CH2dbnd CHC(O)O(CH2)2CH3) = (2.48 ± 0.89) × 10-10, k3(OH + CH2dbnd CHCH2C(O)O(CH2)2CH3) = (2.89 ± 0.31) × 10-11, and k4(Cl + CH2dbnd CHCH2C(O)O(CH2)2CH3) = (2.25 ± 0.96) × 10-10. Reactivity trends and atmospheric lifetimes of esters are presented. Additionally, a product study shown butyric acid and polifunctional products for the reactions of vinyl and allyl butyrate, respectively and general mechanism is proposed.

Mesoporous Cu2O-CeO2 composite nanospheres with enhanced catalytic activity for 4-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Pang, Juanjuan; Li, Wenting; Cao, Zhenhao; Xu, Jingjing; Li, Xue; Zhang, Xiaokai

2018-05-01

In this paper, mesoporous Cu2O-CeO2 nanospheres were fabricated via a facile, low-temperature solution route in the presence of poly(2-vinylpyridine)-b-poly(ethylene Oxide) (P2VP-b-PEO) block copolymers. The prepared mesoporous Cu2O-CeO2 nanospheres were characterized systematically by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and nitrogen adsorption/desorption. The formation mechanism of mesoporous Cu2O-CeO2 nanospheres was discussed. The results show that the molar ratios of Ce3+/Cu2+ and the reaction time have an important influence on the nanostructure of Cu2O-CeO2 composite spheres. The resultant Cu2O-CeO2 nanospheres exhibit superior catalytic activities in the reduction of 4-nitrophenol to 4-aminophenol by NaBH4. The activity factor (K = k/m) for the Cu2O-CeO2 nanospheres prepared with the molar ratio of Ce3+/Cu2+ of 5/1 is 3006.6 s-1 g-1, which is much higher than reported values. This paper demonstrates a highly controllable approach to the production of mesoporous Cu2O-CeO2 nanospheres, which have potential applications in the areas of catalysis, adsorption, sensors and so on.

Synthesis of Fe3O4@SiO2@OSi(CH2)3NHRN(CH2PPh2)2PdCl2 type nanocomposite complexes: Highly efficient and magnetically-recoverable catalysts in vitamin K3 synthesis.

PubMed

Uruş, Serhan

2016-12-15

The synthesis of aminomethylphosphine-metal complexes have opened a new perspective to the catalytic applications of organic compounds. Magnetic Fe3O4 nano-core was synthesized using the closed quartz tube with Teflon cover and microwaved 200°C for 1h with power controlled instrument set to max. 600W. Novel nano-composite supported; Fe3O4@SiO2(CH2)3NHArN(CH2PPh2)2 and Fe3O4@SiO2(CH2)3N(CH2PPh2)2 type bis(diphenylphosphinomethyl)amino ligands and their Pd(II) complexes have been synthesized and characterized with FT-IR, SEM, EDX, TEM, UV-Visible, XRD and TG/DTA techniques. All the complexes were used as heterogeneous catalysts in the oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1, 4-naphthoquinone (vitamin K3, menadione, 2MNQ) in the presence of hydrogen peroxide and acetic acid. Selectivity reached about 55-60% with a conversion of 90-96% using the nano-magnetite supported aminomethylphosphine-Pd(II) complexes. The complexes were very active in three times in the catalytic recycling experiments in five catalytic cycles. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Novel Dimeric Ni-Substituted beta-Keggin Silicotungstate: Structure and Magnetic Properties of K(12)[{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)].20H(2)O.

PubMed

Kortz, Ulrich; Jeannin, Yves P.; Tézé, André; Hervé, Gilbert; Isber, Samih

1999-08-09

The novel dimeric polyoxometalate [{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)](12)(-) (1) has been synthesized and characterized by IR spectroscopy, polarography, elemental analysis, thermogravimetric analysis, and magnetic measurements. An X-ray single-crystal analysis was carried out on K(12)[{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)].20H(2)O, which crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.701(4) Å, b = 24.448(11) Å, c = 13.995(5) Å, beta = 99.62(3) degrees, and Z = 4. The anion consists of two [beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)] Keggin moieties linked via two OH bridging groups, leading to a planar Ni(2)(OH)(2) unit. The two half-units are related by an inversion center and each contain one Ni atom in the rotated triad. The formation of the new anion involves insertion, isomerization, and dimerization. Magnetic measurements show that the central Ni(4) unit exhibits ferromagnetic (J' = 4.14 cm(-)(1)) as well as weak antiferromagnetic (J = -0.65 cm(-)(1)) Ni-Ni exchange interactions.

K-shell photoabsorption coefficients of O2, CO2, CO, and N2O

NASA Technical Reports Server (NTRS)

Barrus, D. M.; Blake, R. L.; Burek, A. J.; Chambers, K. C.; Pregenzer, A. L.

1979-01-01

The total photoabsorption coefficient has been measured from 500 to 600 eV around the K edge of oxygen in gases O2, CO2, CO, and N2O by means of a gold continuum source and crystal spectrometer with better than 1-eV resolution. The cross sections are dominated by discrete molecular-orbital transitions below the K-edge energy. A few Rydberg transitions were barely detectable. Broad shape resonances appear at or above the K edge. Additional broad, weak features above the K edge possibly arise from shake up. Quantitative results are given that have about 10% accuracy except on the very strong peaks. All the measured features are discussed in relation to other related measurements and theory.

Measurements of the O+ plus N2 and O+ plus O2 reaction rates from 300 to 900 K

NASA Technical Reports Server (NTRS)

Chen, A.; Johnsen, R.; Biondi, M. A.

1977-01-01

Rate coefficients for the O(+) + N2 atom transfer and O(+) + O2 charge transfer reactions are determined at thermal energies between 300 K and 900 K difference in a heated drift tube mass spectrometer apparatus. At 300 K the values K(O(+) + N2) = (1.2 plus or minus 0.1) x 10 to the negative 12 power cubic cm/sec and k(O(+) + O2) = (2.1 plus or minus 0.2) x 10 to the negative 11 power cubic cm/sec were obtained, with a 50% difference decrease in the reaction rates upon heating to 700 K. These results are in good agreement with heated flowing afterglow results, but the O(+) + O2 thermal rate coefficients are systematically lower than equivalent Maxwellian rates inferred by conversion of nonthermal drift tube and flow drift data.

Seasonal variations in VO2max, O2-cost, O2-deficit, and performance in elite cross-country skiers.

PubMed

Losnegard, Thomas; Myklebust, Håvard; Spencer, Matt; Hallén, Jostein

2013-07-01

Long-term effects of training are important information for athletes, coaches, and scientists when associating changes in physiological indices with changes in performance. Therefore, this study monitored changes in aerobic and anaerobic capacities and performance in a group of elite cross-country skiers during a full sport season. Thirteen men (age, 23 ± 2 years; height, 182 ± 6 cm; body mass, 76 ± 8 kg; V2 roller ski skating VO2max, 79.3 ± 4.4 ml·kg·min or 6.0 ± 0.5 L·min) were tested during the early, middle, and late preparation phase: June (T1), August (T2), and October (T3); during the competition phase: January/February (T4); and after early precompetition phase: June (T5). O2-cost during submaximal efforts, V[Combining Dot Above]O2peak, accumulated oxygen deficit (ΣO2-deficit), and performance during a 1,000-m test were determined in the V2 ski skating technique on a roller ski treadmill. Subjects performed their training on an individual basis, and detailed training logs were categorized into different intensity zones and exercise modes. Total training volume was highest during the summer months (early preseason) and decreased toward and through the winter season, whereas the volume of high-intensity training increased (all p < 0.05). There was a significant main effect among testing sessions for 1,000 m time, O2-cost, and ΣO2-deficit (Cohen's d effect size; ES = 0.63-1.37, moderate to large, all p < 0.05). In general, the changes occurred between T1 and T3 with minor changes in the competitive season (T3 to T4). No significant changes were found in V[Combining Dot Above]O2peak across the year (ES = 0.17, trivial). In conclusion, the training performed by elite cross-country skiers induced no significant changes in V[Combining Dot Above]O2peak but improved performance, O2-cost, and ΣO2-deficit.

The two-dimensional tunnel structures of K3Sb5O14 and K2Sb4O11

NASA Technical Reports Server (NTRS)

Hong, H. Y.-P.

1974-01-01

The structures of K3Sb5O14 and K2Sb4O11 have been solved by the single-crystal X-ray direct method and the heavy-atom method, respectively. The structure of K3Sb5O14 is orthorhombic, with space group Pbam and cell parameters a = 24.247 (4), b = 7.157 (2), c = 7.334 (2) A, Z = 4. The structure of K2Sb4O11 is monoclinic, with space group C2/m and cell parameters a = 19.473 (4), b = 7.542 (1), c = 7.198 (1) A, beta = 94.82 (2) deg, Z = 4. A full-matrix least-squares refinement gave R = 0.072 and R = 0.067, respectively. In both structures, oxygen atoms form an octahedron around each Sb atom and an irregular polyhedron around each K atom. By sharing corners and edges, the octahedra form a skeleton network having intersecting b-axis and c-axis tunnels. The K(+) ions, which have more than ten oxygen near neighbors, are located in these tunnels. Evidence for K(+)-ion transport within and between tunnels comes from ion exchange of the alkali ions in molten salts and anisotropic temperature factors that are anomalously large in the direction of the tunnels.

Bulk Kosterlitz-Thouless Type Molecular Superconductor β″-(BEDT-TTF)2[(H2O)(NH4)2Cr(C2O4)3]·18-crown-6.

PubMed

Martin, Lee; Lopez, Jordan R; Akutsu, Hiroki; Nakazawa, Yasuhiro; Imajo, Shusaku

2017-11-20

A new molecular superconductor, β″-(BEDT-TTF) 2 [(H 2 O)(NH 4 ) 2 Cr(C 2 O 4 ) 3 ]·18-crown-6, has been synthesized from the organic donor molecule BEDT-TTF with the anion Cr(C 2 O 4 ) 3 3- . The crystal structure consists of conducting organic layers of BEDT-TTF molecules which adopt the β″ packing motif (layer A), layers of NH 4 + and Λ-Cr(C 2 O 4 ) 3 3- (layer B), layers of (H 2 O)(NH 4 )18-crown-6 (layer C), and layers of NH 4 + and Δ-Cr(C 2 O 4 ) 3 3- (layer D) which produce a superstructure with a repeating pattern of ABCDABCDA. As a result of this packing arrangement, this is the 2D superconductor with the widest gap between conducting layers where only a single donor packing motif is present (β″). Superconducting critical temperatures at ambient pressure observed by electrical transport and magnetic measurements are 4.0-4.9 and 2.5 K, respectively. The strong 2D nature of this system, the broad transition to T zero at 1.8K, and the transition of α of V ∝ I α from 1 to 3 on I-V curves strongly suggest that the superconducting transition is very close to a Kosterlitz-Thouless transition. The magnetic field dependence of the superconducting critical temperature parallel to the conducting plane gives an upper critical field μ 0 H c2∥ > 8 T, which is over the calculated Pauli-Clogston limit for this material.

A Structural Molar Volume Model for Oxide Melts Part I: Li2O-Na2O-K2O-MgO-CaO-MnO-PbO-Al2O3-SiO2 Melts—Binary Systems

NASA Astrophysics Data System (ADS)

Thibodeau, Eric; Gheribi, Aimen E.; Jung, In-Ho

2016-04-01

A structural molar volume model was developed to accurately reproduce the molar volume of molten oxides. As the non-linearity of molar volume is related to the change in structure of molten oxides, the silicate tetrahedral Q-species, calculated from the modified quasichemical model with an optimized thermodynamic database, were used as basic structural units in the present model. Experimental molar volume data for unary and binary melts in the Li2O-Na2O-K2O-MgO-CaO-MnO-PbO-Al2O3-SiO2 system were critically evaluated. The molar volumes of unary oxide components and binary Q-species, which are model parameters of the present structural model, were determined to accurately reproduce the experimental data across the entire binary composition in a wide range of temperatures. The non-linear behavior of molar volume and thermal expansivity of binary melt depending on SiO2 content are well reproduced by the present model.

Effects of addition of Bi2Ca2Co2O y on the thermoelectric properties of Ca3Co4O9 polycrystalline ceramics

NASA Astrophysics Data System (ADS)

Feng, Ningbo; Liao, Y. W.; Lu, Y.; He, Y.; Jin, Y. R.; Liu, X. R.

2018-06-01

Thermoelectric properties of Ca3Co4O9 polycrystalline ceramics with sheet grains were optimized by adding Bi2Ca2Co2O y phase. Therefore, the (1 - x) Ca3Co4O9/ x Bi2Ca2Co2O y (0 ≤ x ≤ 1) composites were prepared. The phase constitution and micro-structure of the samples were analyzed by XRD and SEM, respectively. With the addition of Bi2Ca2Co2O y , the apparent density D a and the relative density D r of the samples continuously increases. When x ≤ 0.4, the electrical resistivity of the samples declines, however, when x ≥ 0.4, the electrical resistivity of the samples increases. The Seebeck coefficient of the samples grows with the increase of the x monotonously. The power factor of the 0.6 Ca3Co4O9/0.4 Bi2Ca2Co2O y samples reaches 0.24 mW m-1K-2 at 973 K. Thermal conductivity κ of the 0.6 Ca3Co4O9/0.4 Bi2Ca2Co2O y monotonously decreases with the temperature rising, achieving the minimum about 1.34 W m-1K-1 at 973 K. The ZT of 0.6 Ca3Co4O9/0.4 Bi2Ca2Co2O y composites gets to 0.18, which is comparable to that of most doped Ca3Co4O9 polycrystalline ceramics, implying higher ZT can be realized by combining the strategy of doping and introducing the Bi2Ca2Co2O y .

Synthesis of biocompatible SiO2 coated ZnO quantum dots for cell imaging

NASA Astrophysics Data System (ADS)

Zhang, Min; Wang, Qian; Chen, Haiyan; Gu, Yueqing

2014-09-01

Quantum dots (QDs) is a promising candidate for biomedical imaging. However, the bio-toxicity of traditional quantum dots obstructed their further application seriously. In this work, a simple solution growth method was utilized to synthesize ZnO QDs. However, their self-assemble feature makes them unstable in aqueous solution. Furthermore, (3-Aminopropyl) triethoxysilane was selected as a capping agent to stabilize ZnO QDs and then ZnO@SiO2 nanoparticles were obtained. They dispersed excellently in water and exhibited favorable fluorescence properties owing to the protection of silane. The biocompatability of ZnO@SiO2 nanoparticles was verified by MTT assy. The cell affinity studies demonstrated that ZnO@SiO2 nanoparticles could be uptaken by cells efficiently. Therefore, the as-prepared ZnO@SiO2 nanoparticles is a promising candidate for applications in cell imaging.

High-pressure Phase Relation In The MgAl2O4-Mg2SiO4 System

NASA Astrophysics Data System (ADS)

Kojitani, H.; Hisatomi, R.; Akaogi, M.

2005-12-01

at Gakushuin University (RINT 2500V, Cr Kα, 45 kV, 250 mA). Composition analysis of the recovered samples was made using SEM-DES. The RIETAN-2000 program was used to perform the Rietveld refinement. The results of the high-pressure phase relation experiments show that stability field of single phase of MgAl2O4-Mg2SiO4 solid solutions spreads at lower pressure than that of pure MgAl2O4 calcium ferrite. The lowest pressure at which the calcium ferrite solid solution can be synthesized is about 23 GPa. The maximum solubility of Mg2SiO4 component is about 35%. Lattice parameters of pure MgAl2O4 calcium ferrite were determined as a = 9.9495(6) Å, b = 8.6466(5) Å, c = 2.7901(2) Å ( Pbnm space group) by the Rietveld refinement. Obtained atomic positions for calcium ferrite-type MgAl2O4 are very similar to those of CaFe2O4 calcium ferrite. Lattice parameters of MgAl2O4-Mg2SiO4 calcium ferrite solid solutions with various compositions indicate that c-axis does not change with the composition and that a- and b-axes have a linear increase and decrease trend with increasing Mg2SiO4 component, respectively.

Low-temperature molar heat capacities and entropies of MnO2 (pyrolusite), Mn3O4 (hausmanite), and Mn2O3 (bixbyite)

USGS Publications Warehouse

Robie, R.A.; Hemingway, B.S.

1985-01-01

Pyrolusite (MnO2), hausmanite (Mn3O4), and bixbyite (Mn2O3), are important ore minerals of manganese and accurate values for their thermodynamic properties are desirable to understand better the {p(O2), T} conditions of their formation. To provide accurate values for the entropies of these important manganese minerals, we have measured their heat capacities between approximately 5 and 380 K using a fully automatic adiabatically-shielded calorimeter. All three minerals are paramagnetic above 100 K and become antiferromagnetic or ferrimagnetic at lower temperatures. This transition is expressed by a sharp ??-type anomaly in Cpmo for each compound with Ne??el temperatures TN of (92.2??0.2), (43.1??0.2), and (79.45??0.05) K for MnO2, Mn3O4, and Mn2O3, respectively. In addition, at T ??? 308 K, Mn2O3 undergoes a crystallographic transition, from orthorhombic (at low temperatures) to cubic. A significant thermal effect is associated with this change. Hausmanite is ferrimagnetic below TN and in addition to the normal ??-shape of the heat-capacity maxima in MnO2 and Mn2O3, it has a second rounded maximum at 40.5 K. The origin of this subsidiary bump in the heat capacity is unknown but may be related to a similar "anomalous bump" in the curve of magnetization against temperature at about 39 K observed by Dwight and Menyuk.(1) At 298.15 K the standard molar entropies of MnO2, Mn3O4, and Mn2O3, are (52.75??0.07), (164.1??0.2), and (113.7??0.2) J??K-1??mol-1, respectively. Our value for Mn3O4 is greater than that adopted in the National Bureau of Standards tables(2) by 14 per cent. ?? 1985.

Preparation and photocatalytic properties of nanometer-sized magnetic TiO2/SiO2/CoFe2O4 composites.

PubMed

Li, Hansheng; Zhang, Yaping; Wu, Qin; Wang, Xitao; Liu, Changhao

2011-11-01

Magnetic TiO2/SiO2/CoFe2O4 nanoparticles (TiO2/SCFs) were prepared by a sol-gel process in a reverse microemulsion combined with solvent-thermal technique. TiO2/SCFs were characterized by Fourier transform infrared spectrometry, thermogravimetric analysis-differential scanning calorimetry, X-ray diffraction, Raman spectrometry, TEM, BET specific surface area measurement, and magnetic analysis. Structure analyses indicated that TiO2/SCFs presented a core-shell structure with TiO2 uniformly coating on SiO2/CoFe2O4 nanomagnets (SCFs) and typical ferromagnetic hysteresis. TiO2/SCFs showed larger specific surface area and better photocatalytic activities than TiO2 and TiO2/CoFe2O4 photocatalysts prepared by the same method. The doping interaction between TiO2 and CoFe2O4 reduced thanks to the inert SiO2 mesosphere.

Heat capacity and entropy of Ni2SiO4-olivine from 5 to 1000 K and heat capacity of Co2SiO4 from 360 to 1000 K.

USGS Publications Warehouse

Robie, R.A.; Hemingway, B.S.; Ito, J.; Krupka, K.M.

1984-01-01

The heat capacity of Ni2SiO4-olivine has been measured between 5 and 387 K by cryogenic adiabatic-shield calorimetry and between 360 and 1000 K by differential scanning calorimetry. The heat capacity of Co2SiO4-olivine was measured between 360 and 1000 K by differential scanning calorimetry.-J.A.Z.

Thermal equation of state of CaFe 2O 4-type MgAl 2O 4

NASA Astrophysics Data System (ADS)

Sueda, Yuichiro; Irifune, Tetsuo; Sanehira, Takeshi; Yagi, Takehiko; Nishiyama, Norimasa; Kikegawa, Takumi; Funakoshi, Ken-ichi

2009-05-01

In situ X-ray diffraction measurements of CaFe 2O 4-type MgAl 2O 4 have been conducted at pressures up to 42 GPa and temperatures to 2400 K using Kawai-type multianvil apparatus with sintered diamond anvils. Additional measurements have also been conducted at pressures to 12 GPa using diamond anvil cell with helium as a pressure medium at room temperature, and at temperatures to 836 K at the ambient pressure using a high-temperature X-ray diffractometer. The analysis of room-temperature data yielded V0 = 240.1(2) Å 3, K0 = 205(6) GPa, and K0=4.1(3). A fit of the present data to high-temperature Birch-Murnaghan equation of state (EOS) yielded (∂ K0/∂ T) P = -0.030(2) GPa/K and α0 = a0 + b0T with values of a0 = 1.96(13) × 10 -5 K -1 and b0 = 1.64(24) × 10 -8 K -2. The present data set was also fitted to Mie-Grüneisen-Debye (MGD) EOS and we obtained γ0 = 1.73(7), q = 2.03(37), and θ0 = 1546(104) K. Density changes of MORB have been estimated using the newly obtained thermoelastic parameters, assuming that the Al-rich phase in this composition possesses the CaFe 2O 4-type structure under the lower mantle P, T conditions. The calculated densities along geotherms for the normal mantle and subducting cold slabs are both significantly higher than those of typical seismological models, confirming the conclusion of some recent results on MORB by laser-heated diamond anvil cell experiments.

Attikaite, Ca3Cu2Al2(AsO4)4(OH)4 · 2H2O, a new mineral species

NASA Astrophysics Data System (ADS)

Chukanov, N. V.; Pekov, I. V.; Zadov, A. E.

2007-12-01

Attikaite, a new mineral species, has been found together with arsenocrandalite, arsenogoyazite, conichalcite, olivenite, philipsbornite, azurite, malachite, carminite, beudantite, goethite, quartz, and allophane at the Christina Mine No. 132, Kamareza, Lavrion District, Attiki Prefecture (Attika), Greece. The mineral is named after the type locality. It forms spheroidal segregations (up to 0.3 mm in diameter) consisting of thin flexible crystals up to 3 × 20 × 80 μm in size. Its color is light blue to greenish blue, with a pale blue streak. The Mohs’ hardness is 2 to 2.5. The cleavage is eminent mica-like parallel to {001}. The density is 3.2(2) g/cm3 (measured in heavy liquids) and 3.356 g/cm3 (calculated). The wave numbers of the absorption bands in the infrared spectrum of attikaite are (cm-1; sh is shoulder; w is a weak band): 3525 sh, 3425, 3180, 1642, 1120 w, 1070 w, 1035 w, 900 sh, 874, 833, 820, 690 w, 645 w, 600 sh, 555, 486, 458, and 397. Attikaite is optically biaxial, negative, α = 1.642(2), β = γ = 1.644(2) ( X = c) 2 V means = 10(8)°, and 2 V calc = 0°. The new mineral is microscopically colorless and nonpleochroic. The chemical composition (electron microprobe, average over 4 point analyses, wt %) is: 0.17 MgO, 17.48 CaO, 0.12 FeO, 16.28 CuO, 10.61 Al2O3, 0.89 P2O5, 45.45 As2O5, 1.39 SO3, and H2O (by difference) 7.61, where the total is 100.00. The empirical formula calculated on the basis of (O,OH,H2O)22 is: Ca2.94Cu{1.93/2+} Al1.97Mg0.04Fe{0.02/2+} [(As3.74S0.16P0.12)Σ4.02O16.08](OH)3.87 · 2.05H2 O. The simplified formula is Ca3Cu2Al2(AsO4)4(OH)4 · 2H2O. Attikaite is orthorhombic, space group Pban, Pbam or Pba2; the unit-cell dimensions are a = 10.01(1), b = 8.199(5), c = 22.78(1) Å, V = 1870(3) Å3, and Z = 4. In the result of the ignition of attikaite for 30 to 35 min at 128 140°, the H2O bands in the IR spectrum disappear, while the OH-group band is not modified; the weight loss is 4.3%, which approximately corresponds to two H2O

Superconductivity at 33-37 K in A L n2Fe4As4O2 (A =Kand Cs;L n =lanthanides)

NASA Astrophysics Data System (ADS)

Wu, Si-Qi; Wang, Zhi-Cheng; He, Chao-Yang; Tang, Zhang-Tu; Liu, Yi; Cao, Guang-Han

2017-09-01

We have synthesized ten iron oxyarsenides, K L n2Fe4As4O2 (L n =Gd,Tb,Dy, and Ho) and Cs L n2Fe4As4O2 (L n =Nd,Sm,Gd,Tb,Dy, and Ho) , with the aid of the lattice-match approach. The resultant compounds possess hole-doped conducting double FeAs layers [AFe4As4] 2 - that are separated by the insulating [Ln2O2] 2 + slabs. Measurements of electrical resistivity and dc magnetic susceptibility demonstrate bulk superconductivity at Tc=33 -37 K. We find that Tc correlates with the axial ratio c /a for all 12442-type superconductors discovered. Also, Tc tends to increase with the lattice mismatch, implying that lattice instability plays a role in the enhancement of superconductivity.

Trap level spectroscopic investigations of U: ZnAl2O4: Role of defect centres in the TSL process

NASA Astrophysics Data System (ADS)

Mohapatra, M.; Kumar, Mithlesh; Kadam, R. M.

2018-03-01

In order to evaluate the trap level spectroscopic properties of Uranium in ZnAl2O4 spinel host, undoped and Uranium doped ZnAl2O4 samples were synthesized. From photoluminescence (PL) data it was confirmed that uranium gets stabilized in the system as UO66- (octahedral uranate). Electron spin resonance (ESR) studies for the gamma irradiated sample suggested the formation of O2-, F+ and V centres. From the TSL (thermally stimulated luminescence) data, the trap parameters such as frequency factor and activation energy etc. were evaluated. From ESR-TSL correlation it was confirmed that the destruction of O2- ion coincides with TSL glow peak appeared at 332 K.

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

NASA Technical Reports Server (NTRS)

Flood, D. J.

1973-01-01

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

Structure disordering and thermal decomposition of manganese oxalate dihydrate, MnC2O4·2H2O

NASA Astrophysics Data System (ADS)

Puzan, Anna N.; Baumer, Vyacheslav N.; Lisovytskiy, Dmytro V.; Mateychenko, Pavel V.

2018-04-01

It is found that the known regular structures of MnC2O4·2H2O (I) do not allow to refine the powder X-ray pattern of (I) properly using the Rietveld method. Implementation of order-disorder scheme [28] via the including of appropriate displacement vector improves the refinement results. Also it is found that in the case of (I) the similar improvement may be achieved using the data on two phases of (I) obtained as result of decomposition MnC2O4·3H2O single crystal in the mother solution after growth. Thermal decomposition of (I) produce the anhydrous γ-MnC2O4 (II) the structure of which is differ from the known α- and β-modifications of VIIIb transition metal oxalates. The solved ab initio from the powder pattern structure (II) (space group Pmna, a = 7.1333 (1), b = 5.8787 (1), c = 9.0186 (2) Å, V = 378.19 (1) Å3, Z = 4 and Dx = 2.511 Mg m-3) contains seven-coordinated Mn atoms with Mn-O distances of 2.110-2.358 Å, and is not close-packed. Thermal decomposition of (II) in air flows via forming of amorphous MnO, the heating of which up to 723 K is accompanied by oxidation of MnO to Mn2O3 and further recrystallization of the latter.

Hydrothermal syntheses, structures, and properties of the new uranyl selenites Ag(2)(UO(2))(SeO(3))(2), M[(UO(2))(HSeO(3))(SeO(3))] (M = K, Rb, Cs, Tl), and Pb(UO(2))(SeO(3))(2).

PubMed

Almond, Philip M; Albrecht-Schmitt, Thomas E

2002-03-11

The transition metal, alkali metal, and main group uranyl selenites, Ag(2)(UO(2))(SeO(3))(2) (1), K[(UO(2))(HSeO(3))(SeO(3))] (2), Rb[(UO(2))(HSeO(3))(SeO(3))] (3), Cs[(UO(2))(HSeO(3))(SeO(3))] (4), Tl[(UO(2))(HSeO(3))(SeO(3))] (5), and Pb(UO(2))(SeO(3))(2) (6), have been prepared from the hydrothermal reactions of AgNO(3), KCl, RbCl, CsCl, TlCl, or Pb(NO(3))(2) with UO(3) and SeO(2) at 180 degrees C for 3 d. The structures of 1-5 contain similar [(UO(2))(SeO(3))(2)](2-) sheets constructed from pentagonal bipyramidal UO(7) units that are joined by bridging SeO(3)(2-) anions. In 1, the selenite oxo ligands that are not utilized within the layers coordinate the Ag(+) cations to create a three-dimensional network structure. In 2-5, half of the selenite ligands are monoprotonated to yield a layer composition of [(UO(2))(HSeO(3))(SeO(3))](1-), and coordination of the K(+), Rb(+), Cs(+), and Tl(+) cations occurs through long ionic contacts. The structure of 6 contains a uranyl selenite layered substructure that differs substantially from those in 1-5 because the selenite anions adopt both bridging and chelating binding modes to the uranyl centers. Furthermore, the Pb(2+) cations form strong covalent bonds with these anions creating a three-dimensional framework. These cations occur as distorted square pyramidal PbO(5) units with stereochemically active lone pairs of electrons. These polyhedra align along the c-axis to create a polar structure. Second-harmonic generation (SHG) measurements revealed a response of 5x alpha-quartz for 6. The diffuse reflectance spectrum of 6 shows optical transitions at 330 and 440 nm. The trailing off of the 440 nm transition to longer wavelengths is responsible for the orange coloration of 6.

Phase Equilibria Study in the TeO2-Na2O-SiO2 System in Air Between 723 K (500 °C) and 1473 K (1200 °C)

NASA Astrophysics Data System (ADS)

Santoso, Imam; Taskinen, Pekka

2016-08-01

Knowledge of phase equilibria in the TeO2-Na2O-SiO2 system at elevated temperatures is important for ceramic and glass industries and for improving the operation of the smelting process of tellurium-containing materials. A review of previous investigations has indicated, however, that there are omissions in the available datasets on the liquidus temperatures of the molten TeO2-Na2O-SiO2 mixtures. The employed experimental method included equilibration of mixtures made from high purity oxides, rapid quenching of the equilibrated samples in water and followed by compositional analysis of the phases using an electron probe X-ray microanalyzer. The liquidus and phase equilibria in the TeO2-SiO2, TeO2-Na2O, and SiO2-TeO2-Na2O systems have been studied for a wide range of compositions between 723 K (500 °C) and 1473 K (1200 °C) at TeO2, SiO2, and Na2SiO3 saturations. New data have been generated in the SiO2-TeO2-Na2O system at SiO2 saturation. The liquidus compositions in the TeO2-Na2O system at TeO2 saturation have been compared with the previous data and an assessed phase diagram.

Crystal Structures and Thermal Properties of Two Transition-Metal Compounds {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O and Pb(DNI)2(H2O)4 (DNI = 2,4-Dinitroimidazolate)

PubMed Central

Zhang, Guo-Fang; Cai, Mei-Yu; Jing, Ping; He, Chong; Li, Ping; Zhao, Feng-Qi; Li, Ji-Zhen; Fan, Xue-Zhong; Ng, Seik Weng

2010-01-01

Two transition-metal compounds derived from 2,4-dinitroimidazole, {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O, 1, and Pb(DNI)2(H2O)4, 2, were characterized by elemental analysis, FT-IR, TG-DSC and X-ray single-crystal diffraction analysis. Crystal data for 1: monoclinic, space group C2/c, a = 26.826(3), b = 7.7199(10), c = 18.579(2) Å, β = 111.241(2)° and Z = 4; 2: monoclinic, space group C2/c, a = 6.5347(6), b = 17.1727(17), c = 14.1011(14) Å, β = 97.7248(10) and Z = 4. Compound 1 contains two isolated nickel centers in its structure, one being six-coordinate and another five-coordinate. The structure of 2 contains a lead (II) center surrounded by two chelating DNI ligands and four water molecules in distorted square-antiprism geometry. The abundant hydrogen bonds in two compounds link the molecules into three-dimensional network and stabilize the molecules. The TG-DSC analysis reveals that the first step is the loss of water molecules and the final residue is the corresponding metal oxides and carbon. PMID:20526419

The influence of excess K2O on the electrical properties of (K,Na)1/2Bi1/2TiO3 ceramics

NASA Astrophysics Data System (ADS)

Li, Linhao; Li, Ming; Sinclair, Derek C.

2018-04-01

The solid solution (KxNa0.50-x)Bi0.50TiO3 (KNBT) between Na1/2Bi1/2TiO3 and K1/2Bi1/2TiO3 (KBT) has been extensively researched as a candidate lead-free piezoelectric material because of its relatively high Curie temperature and good piezoelectric properties, especially near the morphotropic phase boundary (MPB) at x ˜ 0.10 (20 mol. % KBT). Here, we show that low levels of excess K2O in the starting compositions, i.e., (Ky+0.03Na0.50-y)Bi0.50TiO3.015 (y-series), can significantly change the conduction mechanism and electrical properties compared to a nominally stoichiometric KNBT series (KxNa0.50-x)Bi0.50TiO3 (x-series). Impedance spectroscopy measurements reveal significantly higher bulk conductivity (σb) values for y ≥ 0.10 samples [activation energy (Ea) ≤ 0.95 eV] compared to the corresponding x-series samples which possess bandgap type electronic conduction (Ea ˜ 1.26-1.85 eV). The largest difference in electrical properties occurs close to the MPB composition (20 mol. % KBT) where y = 0.10 ceramics possess σb (at 300 °C) that is 4 orders of magnitude higher than that of x = 0.10 and the oxide-ion transport number in the former is ˜0.70-0.75 compared to <0.05 in the latter (between 600 and 800 °C). The effect of excess K2O can be rationalised on the basis of the (K + Na):Bi ratio in the starting composition prior to ceramic processing. This demonstrates the electrical properties of KNBT to be sensitive to low levels of A-site nonstoichiometry and indicates that excess K2O in KNBT starting compositions to compensate for volatilisation can lead to undesirable high dielectric loss and leakage currents at elevated temperatures.

White LED based on CaAl2Si2O8:Eu2+ Mn2+ phosphor and CdS/ZnS quantum dots

NASA Astrophysics Data System (ADS)

Shen, Changyu; Zhong, Chuan; Hou, Qianglong; Li, Ke

2011-02-01

Core/shell CdS/ZnS quantum dots (QDs) with the emission wavelength of 610nm, was synthesized by thermal deposition using cadmium oxide and selenium as precursors in a hot lauric acid and hexadecylamine trioctylphosphine oxide hybrid. CaAl2Si2O8:Eu2+ Mn2+ phosphor was synthesized by high-temperature solid state reaction at 1290 °C for 2 hours under the H2 reducing atmosphere, and X-ray powder diffraction analysis confirmed the formation of it. It has two emission bands peaking at 420 nm and 580nm originated from the transition 5d to 4f of Eu2+ and 4T1-6A1 of Mn2+, respectively. Blends of CaAl2Si2O8:Eu2+,Mn2+ phosphor and CdS/ZnS QDs exhibited the prominent spectral evolution with an increasing content of QDs. A hybrid white LED, which combines a blue LED with the blend of CaAl2Si2O8:Eu2+ Mn2+ phosphor and QDs with a weight ratio of 2:1, with the CIE coordinate of (0.3183, 0.3036) and CRI of 85 was obtained.

Photodegradation of 4-tert-butylphenol in aqueous solution by UV-C, UV/H2O2 and UV/S2O8(2-) system.

PubMed

Wu, Yanlin; Zhu, Xiufen; Chen, Hongche; Dong, Wenbo; Zhao, Jianfu

2016-01-01

The photolytic degradation of 4-tert-butylphenol (4-t-BP) in aqueous solution was investigated using three kinds of systems: UV-C directly photodegradation system, UV/H2O2 and UV/S2O8(2-) system. Under experimental conditions, the degradation rate of 4-t-BP was in the order: UV/S2O8(2-) > UV/H2O2 > UV-C. The reaction kinetics of UV/S2O8(2-) system were thoroughly investigated. The increase of S2O8(2-) concentration enhanced the 4-t-BP degradation rate, which was inhibited when the concentration of S2O8(2-) exceeded 4.0 mM. The highest efficacy in 4-t-BP degradation was obtained at pH 6.5. The oxidation rate of 4-t-BP could be accelerated by increasing the reaction temperature and irradiation intensity. The highest rate constant (kobs = 8.4 × 10(-2) min(-1)) was acquired when the reaction temperature was 45 °C. The irradiation intensity was measured by irradiation distance, and the optimum irradiation distance was 10 cm. Moreover, the preliminary mechanism of 4-t-BP degradation was studied. The bond scission of the 4-t-BP molecule occurred by the oxidation of SO4(•-), which dimerized and formed two main primary products. Under the conditions of room temperature (25 °C ± 1 °C) and low concentration of K2S2O8 (0.5 mM), 35.4% of total organic carbon (TOC) was removed after 8.5-h irradiation. The results showed that UV/S2O8(2-) system was effective for the degradation of 4-t-BP.

Two new three-dimensional zinc phosphites templated by piperazine: [H2pip][Zn3(HPO3)4(H2O)2] and K[H2pip]0.5[Zn3(HPO3)4

NASA Astrophysics Data System (ADS)

Zhang, Xiao; Wang, Guo-Ming; Wang, Zong-Hua; Wang, Ying-Xia; Lin, Jian-Hua

2014-01-01

Two three-dimensional open-framework zinc phosphites with the same organically templated, [H2pip][Zn3(HPO3)4(H2O)2] (1) and K[H2pip]0.5[Zn3(HPO3)4] (2) (pip = piperazine), have been solvothermally synthesized and structurally characterized by IR, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffractions. Compound 1 consists of ZnO4 tetrahedra, [HPO3] pseudopyramids and [ZnO4(H2O)2] octahedra, which are linked through their vertexes to generate three-dimensional architecture with intersecting 8-membered channels along the [1 0 0], [0 0 1] and [1 0 1] directions. Compound 2 is constructed from strictly alternating ZnO4 tetrahedra and [HPO3] pseudopyramids, and exhibits (3,4)-connected inorganic framework with 8-, and 12-membered channels, in which the K+ and diprotonated H2pip2+ extra-framework cations reside, respectively. The coexistence of inorganic K+ and organic piperazine mixed templates in the structure is unique and, to the best of our knowledge, firstly observed in metal-phosphite materials. In addition, the participation of left-handed and right-handed helical chains in construction of the puckered 4.82 sheet structure in 2 is also noteworthy.

Compositions of supersaturated solutions for enhanced growth of {alpha}-NiSO{sub 4} . 6H{sub 2}O, Me{sub 2}Ni(SO{sub 4}){sub 2} . 6H{sub 2}O, MeH{sub 2}PO{sub 4} [Me = Li, Na, K, Rb, Cs, NH{sub 4}], and K(H{sub x}D{sub 1-x}){sub 2}PO{sub 4} single crystals

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

Soboleva, L. V., E-mail: afkonst@ns.crys.ras.ru

2008-05-15

The possibility of determining the optimal compositions and temperatures of supersaturated solutions for enhanced growth of single crystals of congruently and incongruently dissolving solid phases from the solubility diagrams of ternary systems is shown, and this approach is justified. The NiSO{sub 4}-H{sub 2}SO{sub 4}-H{sub 2}O, Me{sub 2}SO{sub 4}-NiSO{sub 4}-H{sub 2}O, and Me{sub 2}O-P{sub 2}O{sub 5}-H{sub 2}O(D{sub 2}O) systems have been used to determine the optimal compositions and temperatures of supersaturated solutions for growth of {alpha}-NiSO{sub 4} . 6H{sub 2}O, Me{sub 2}Ni(SO{sub 4}){sub 2} . 6H{sub 2}O, MeH{sub 2}PO{sub 4} [Me = Li, Na, K, Rb, Cs, NH{sub 4}], and Kmore » (H{sub x} D{sub 1-x}){sub 2}PO{sub 4} (D is deuterium) single crystals.« less

High-pressure X-ray diffraction and Raman spectroscopy of CaFe2O4-type β-CaCr2O4

NASA Astrophysics Data System (ADS)

Zhai, Shuangmeng; Yin, Yuan; Shieh, Sean R.; Shan, Shuangming; Xue, Weihong; Wang, Ching-Pao; Yang, Ke; Higo, Yuji

2016-04-01

In situ high-pressure synchrotron X-ray diffraction and Raman spectroscopic studies of orthorhombic CaFe2O4-type β-CaCr2O4 chromite were carried out up to 16.2 and 32.0 GPa at room temperature using multi-anvil apparatus and diamond anvil cell, respectively. No phase transition was observed in this study. Fitting a third-order Birch-Murnaghan equation of state to the P-V data yields a zero-pressure volume of V 0 = 286.8(1) Å3, an isothermal bulk modulus of K 0 = 183(5) GPa and the first pressure derivative of isothermal bulk modulus K 0' = 4.1(8). Analyses of axial compressibilities show anisotropic elasticity for β-CaCr2O4 since the a-axis is more compressible than the b- and c-axis. Based on the obtained and previous results, the compressibility of several CaFe2O4-type phases was compared. The high-pressure Raman spectra of β-CaCr2O4 were analyzed to determine the pressure dependences and mode Grüneisen parameters of Raman-active bands. The thermal Grüneisen parameter of β-CaCr2O4 is determined to be 0.93(2), which is smaller than those of CaFe2O4-type CaAl2O4 and MgAl2O4.

Structure and temperature-dependent phase transitions of lead-free Bi 1/2Na 1/2TiO 3-Bi 1/2K 1/2TiO 3-K 0.5Na 0.5NbO 3 piezoceramics

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

Anton, Eva-Maria; Schmitt, Ljubomira Ana; Hinterstein, Manuel

2014-05-28

Structure and phase transitions of (1-y)((1-x)Bi 1/2Na 1/2TiO 3-xBi 1/2K 1/2TiO 3)-yK 0.5Na 0.5NbO 3 (x; y) piezoceramics (0.1 ≤ x ≤ 0.4; 0 ≤ y ≤ 0.05) were investigated by transmission electron microscopy, neutron diffraction, temperature-dependent x-ray diffraction, and Raman spectroscopy. The local crystallographic structure at room temperature (RT) does not change by adding K 0.5Na 0.5NbO 3 to Bi 1/2Na 1/2TiO 3-xBi 1/2K 1/2TiO 3 for x = 0.2 and 0.4. The average crystal structure and microstructure on the other hand develop from mainly long-range polar order with ferroelectric domains to short-range order with polar nanoregions displaying amore » more pronounced relaxor character. The (0.1; 0) and (0.1; 0.02) compositions exhibit monoclinic Cc space group symmetry, which transform into Cc + P4bm at 185 and 130 °C, respectively. This high temperature phase is stable at RT for the morphotropic phase boundary compositions of (0.1; 0.05) and all compositions with x = 0.2. For the compositions of (0.1; 0) and (0.1; 0.02), local structural changes on heating are evidenced by Raman; for all other compositions, changes in the long-range average crystal structure were observed.« less

Synthesis of Zr2WP2O12/ZrO2 Composites with Adjustable Thermal Expansion.

PubMed

Zhang, Zhiping; Sun, Weikang; Liu, Hongfei; Xie, Guanhua; Chen, Xiaobing; Zeng, Xianghua

2017-01-01

Zr 2 WP 2 O 12 /ZrO 2 composites were fabricated by solid state reaction with the goal of tailoring the thermal expansion coefficient. XRD, SEM and TMA were used to investigate the composition, microstructure, and thermal expansion behavior of Zr 2 WP 2 O 12 /ZrO 2 composites with different mass ratio. Relative densities of all the resulting Zr 2 WP 2 O 12 /ZrO 2 samples were also tested by Archimedes' methods. The obtained Zr 2 WP 2 O 12 /ZrO 2 composites were comprised of orthorhombic Zr 2 WP 2 O 12 and monoclinic ZrO 2 . As the increase of the Zr 2 WP 2 O 12 , the relative densities of Zr 2 WP 2 O 12 /ZrO 2 ceramic composites increased gradually. The coefficient of thermal expansion of the Zr 2 WP 2 O 12 /ZrO 2 composites can be tailored from 4.1 × 10 -6 K -1 to -3.3 × 10 -6 K -1 by changing the content of Zr 2 WP 2 O 12 . The 2:1 Zr 2 WP 2 O 12 /ZrO 2 specimen shows close to zero thermal expansion from 25 to 700°C with an average linear thermal expansion coefficient of -0.09 × 10 -6 K -1 . These adjustable and near zero expansion ceramic composites will have great potential application in many fields.

Popcorn balls-like ZnFe2O4-ZrO2 microsphere for photocatalytic degradation of 2,4-dinitrophenol

NASA Astrophysics Data System (ADS)

Chen, Xi; Liu, Yutang; Xia, Xinnian; Wang, Longlu

2017-06-01

In this paper, novel popcorn balls-like ZnFe2O4-ZrO2 composite microspheres were successfully fabricated by a simple hydrothermal method. The morphology, structure and optical property of the microspheres were characterized. The microspheres were used as the photocatalysts to degrade 2,4-dinitrophenol, and exhibited superior photocatalytic performance. Under simulated solar visible light irradiation, the degradation rate of ZnFe2O4-ZrO2 photocatalyst (mass ratio of ZnFe2O4/ZrO2 = 2:1) was almost 7.4 and 2.4 times higher than those of pure ZnFe2O4 and ZrO2. The enhancement could attribute to stronger light absorption, lower carrier recombination and multi-porous structure of the microspheres. Moreover, the popcorn balls-like photocatalysts can be easily separated, because of the magnetism of the samples. After five times runs, the photocatalyst still showed 90% of its photocatalytic degradation efficiency. This work demonstrated a good prospect for removing organic pollutants in water.

Dipole defects in MgAl2O4 spinel crystals

NASA Astrophysics Data System (ADS)

Ayres, F.; de Souza, S. S.; Blak, A. R.

In order to study defects of dipole origin in normal and inverse spinel structures, Thermally Stimulated Depolarisation Current (TSDC) measurements have been carried out in MgAl2O4 spinel crystals doped with Fe, Cr, Mn and Co. The TSDC spectrum of the as-received sample labelled R shows two bands at 160K and 290K. Temperatures above 700K destroy the 290K band and γ-irradiation up to 1,500kGy restores the peak. In another sample labelled UC, the 290K band, of dipole origin, is only detected after γ-irradiation. The dipole origin of the 160K band has already been verified. This band is affected neither by γ-irradiation nor by thermal treatment. The reduction of the 290K band is observed when heating the samples between 350K and 480K for three minutes at each temperature. The correlation between the thermal reduction of the 290K band and the study of V-centres in MgAl2O4 spinels indicates the possible attribution of the band to V-type centres.

Neutron diffraction study of the inverse spinels Co2TiO4 and Co2SnO4

NASA Astrophysics Data System (ADS)

Thota, S.; Reehuis, M.; Maljuk, A.; Hoser, A.; Hoffmann, J.-U.; Weise, B.; Waske, A.; Krautz, M.; Joshi, D. C.; Nayak, S.; Ghosh, S.; Suresh, P.; Dasari, K.; Wurmehl, S.; Prokhnenko, O.; Büchner, B.

2017-10-01

We report a detailed single-crystal and powder neutron diffraction study of Co2TiO4 and Co2SnO4 between the temperature 1.6 and 80 K to probe the spin structure in the ground state. For both compounds the strongest magnetic intensity was observed for the (111)M reflection due to ferrimagnetic ordering, which sets in below TN=48.6 and 41 K for Co2TiO4 and Co2SnO4 , respectively. An additional low intensity magnetic reflection (200)M was noticed in Co2TiO4 due to the presence of an additional weak antiferromagnetic component. Interestingly, from both the powder and single-crystal neutron data of Co2TiO4 , we noticed a significant broadening of the magnetic (111)M reflection, which possibly results from the disordered character of the Ti and Co atoms on the B site. Practically, the same peak broadening was found for the neutron powder data of Co2SnO4 . On the other hand, from our single-crystal neutron diffraction data of Co2TiO4 , we found a spontaneous increase of particular nuclear Bragg reflections below the magnetic ordering temperature. Our data analysis showed that this unusual effect can be ascribed to the presence of anisotropic extinction, which is associated to a change of the mosaicity of the crystal. In this case, it can be expected that competing Jahn-Teller effects acting along different crystallographic axes can induce anisotropic local strain. In fact, for both ions Ti3 + and Co3 +, the 2 tg levels split into a lower dx y level yielding a higher twofold degenerate dx z/dy z level. As a consequence, one can expect a tetragonal distortion in Co2TiO4 with c /a <1 , which we could not significantly detect in the present work.

Chemistry of CCl 4 on Fe 3O 4(1 1 1)-(2 × 2) surfaces in the presence of adsorbed D 2O studied by temperature programmed desorption

NASA Astrophysics Data System (ADS)

Adib, K.; Totir, G. G.; Fitts, J. P.; Rim, K. T.; Mueller, T.; Flynn, G. W.; Joyce, S. A.; Osgood, R. M.

2003-07-01

Temperature programmed desorption (TPD) was used to study surface reactions of Fe 3O 4(1 1 1)-(2 × 2) sequentially exposed, at ˜100 K, to vapor-phase D 2O and CCl 4. Previous TPD and XPS results have indicated that in the absence of D 2O, CCl 4 dissociatively adsorbs on Fe 3O 4(1 1 1) producing chemisorbed Cl and CCl 2. Subsequent heating of the surface results in abstraction of lattice iron and oxygen atoms and causes them to desorb as FeCl 2 and OCCl 2, respectively. This study shows that when this Fe 3O 4 surface is exposed only to D 2O, TPD measures a rich surface chemistry with multiple desorption events extending as high as ˜800 K, indicating dissociative adsorption of D 2O on the Fe 3O 4(1 1 1) surface. After sequential exposure to D 2O and then CCl 4, the production of FeCl 2 and OCCl 2 from adsorbed CCl 4 is suppressed, indicating that D 2O fragments block the surface reactive sites.

Radiation-induced amorphization of Ce-doped Mg2Y8(SiO4)6O2 silicate apatite

NASA Astrophysics Data System (ADS)

Zhou, Jianren; Yao, Tiankai; Lian, Jie; Shen, Yiqiang; Dong, Zhili; Lu, Fengyuan

2016-07-01

Ce-doped Mg2Y8(SiO4)6O2 silicate apatite (Ce = 0.05 and 0.5) were irradiated with 1 MeV Kr2+ ion beam irradiation at different temperatures and their radiation response and the cation composition dependence of the radiation-induced amorphization were studied by in situ TEM. The two Ce-doped Mg2Y8(SiO4)6O2 silicate apatites are sensitive to ion beam induced amorphization with a low critical dose (0.096 dpa) at room temperature, and exhibits significantly different radiation tolerance at elevated temperatures. Ce concentration at the apatite AI site plays a critical role in determining the radiation response of this silicate apatite, in which the Ce3+ rich Mg2Y7.5Ce0.5(SiO4)6O2 displays lower amorphization susceptibility than Mg2Y7.95Ce0.05(SiO4)6O2 with a lower Ce3+ occupancy at the AI sites. The critical temperature (Tc) and activation energy (Ea) change from 667.5 ± 33 K and 0.162 eV of Mg2Y7.5Ce0.5(SiO4)6O2 to 963.6 ± 64 K and 0.206 eV of Mg2Y7.95Ce0.05(SiO4)6O2. We demonstrate that the radiation tolerance can be controlled by varying the chemical composition, and enhanced radiation tolerance is achieved by increasing the Ce concentration at the AI site.

Enhanced interfacial contact between PbS and TiO2 layers in quantum dot solar cells using 2D-arrayed TiO2 hemisphere nanostructures

NASA Astrophysics Data System (ADS)

Lee, Wonseok; Ryu, Ilhwan; Lee, Haein; Yim, Sanggyu

2018-02-01

Two-dimensionally (2D) arrayed hemispherical nanostructures of TiO2 thin films were successfully fabricated using a simple procedure of spin-coating or dip-coating TiO2 nanoparticles onto 2D close-packed polystyrene (PS) nanospheres, followed by PS extraction. The nanostructured TiO2 film was then used as an n-type layer in a lead sulfide (PbS) colloidal quantum dot solar cell. The TiO2 nanostructure could provide significantly increased contacts with subsequently deposited PbS quantum dot layer. In addition, the periodically arrayed nanostructure could enhance optical absorption of the cell by redirecting the path of the incident light and increasing the path length passing though the active layer. As a result, the power conversion efficiency (PCE) reached 5.13%, which is approximately a 1.7-fold increase over that of the control cell without nanostructuring, 3.02%. This PCE enhancement can mainly be attributed to the increase of the short-circuit current density from 19.6 mA/cm2 to 30.6 mA/cm2, whereas the open-circuit voltage and fill factor values did not vary significantly.

Electrical and mechanical properties of ZrO{sub 2} (2 mol% Y{sub 2}O{sub 3})/MoSi{sub 2} composites and their laminated materials

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

Muraoka, Yoshiyuki; Yoshikawa, Fumihito; Hirota, Ken

1996-04-01

Well-densified composites with the compositions ZrO{sub 2} (2Y)/MoSi{sub 2} = 60/40 and 80/20 mol% have been fabricated by hot isostatic pressing for 2 h at 1,400 C and 196 MPa. Electric resistivities ({rho}) of the two composites are very different; the former and latter composites correspond to metallic and insulating materials, respectively. The properties are strongly dependent on the textures. Laminated materials with the compositions ZrO{sub 2} (2Y)/MoSi{sub 2} = (60/40)/(80/20)/(60/40) mol% have been prepared by the same technique. Overall electric resistivities in directions perpendicular and parallel to the interfaces have been determined to be {rho}{sub {perpendicular}} {approx} 1 {times}more » 10{sup 11} {Omega} {center_dot} cm and {rho}{sub {parallel}} {approx} 1 {times} 10{sup {minus}4} {Omega} {center_dot} cm, respectively. Residual stress as much as {approx} 150 MPa is induced in the interfaces. The fracture toughness (K{sub Ic}) is greatly affected by the residual stress.« less

CdS/CdSe co-sensitized SnO2 photoelectrodes for quantum dots sensitized solar cells

NASA Astrophysics Data System (ADS)

Lin, Yibing; Lin, Yu; Meng, Yongming; Tu, Yongguang; Zhang, Xiaolong

2015-07-01

SnO2 nanoparticles were synthesized by hydrothermal method and applied to photo-electrodes of quantum dots-sensitized solar cells (QDSSCs). After sensitizing SnO2 films via CdS quantum dots, CdSe quantum dots was decorated on the surface of CdS/SnO2 photo-electrodes to further improve the power conversion efficiency. CdS and CdSe quantum dots were deposited by successive ionic layer absorption and reaction method (SILAR) and chemical bath deposition method (CBD) respectively. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to identify the surface profile and crystal structure of SnO2 photo-electrodes before and after deposited quantum dots. After CdSe co-sensitized process, an overall power conversion efficiency of 1.78% was obtained in CdSe/CdS/SnO2 QDSSC, which showed 66.4% improvement than that of CdS/SnO2 QDSSC.

Photodeposition of Ag2S on TiO2 nanorod arrays for quantum dot-sensitized solar cells

PubMed Central

2013-01-01

Ag2S quantum dots were deposited on the surface of TiO2 nanorod arrays by a two-step photodeposition. The prepared TiO2 nanorod arrays as well as the Ag2S deposited electrodes were characterized by X-ray diffraction, scanning electron microscope, and transmission electron microscope, suggesting a large coverage of Ag2S quantum dots on the ordered TiO2 nanorod arrays. UV–vis absorption spectra of Ag2S deposited electrodes show a broad absorption range of the visible light. The quantum dot-sensitized solar cells (QDSSCs) based on these electrodes were fabricated, and the photoelectrochemical properties were examined. A high photocurrent density of 10.25 mA/cm2 with a conversion efficiency of 0.98% at AM 1.5 solar light of 100 mW/cm2 was obtained with an optimal photodeposition time. The performance of the QDSSC at different incident light intensities was also investigated. The results display a better performance at a lower incident light level with a conversion efficiency of 1.25% at 47 mW/cm2. PMID:23286551

Lateral variation of H2O/K2O ratios in Quaternary Magma of the Northeastern Japan arc

NASA Astrophysics Data System (ADS)

Miyagi, I.

2012-12-01

Water plays a fundamental role in the magma genesis beneath subduction zones. In order to estimate a spatial distribution of the density of water flux in the wedge mantle of the Northeastern Japan arc, this study examines a lateral variation of pre-eruptive bulk rock H2O/K2O contents among volcanoes located both in the frontal and in back arc settings. The analytical targets are the frontal volcanoes Nigorikawa (N42.12 E140.45), Zenikame (N41.74 E140.85), Adachi (N38.22 E140.65), and Nanashigure (N40.07 E141.11), and the back arc ones Hijiori (N38.61 E140.17) and Kanpu (N39.93 E139.88). The bulk magmatic H2O content (TH2O) is calculated from a mass balance of hydrogen isotopic ratios among three phases in a batch of magma; dissolved water in melt, excess H2O vapor, and hydrous phenocrysts such as amphiboles (Miyagi and Matsubaya, 2003). Since the amount of H2O in hydrous phenocryst is negligible, the bulk magmatic H2O content can be written as TH2O = (30 XD CD) / (15 - dT + dMW), where dMW is the measured hydrogen isotopic ratio of hydrous phenocrysts, XD is a melt fraction of magma, CD is a water concentration of the melt, and dT is hydrogen isotopic ratios of a bulk magma (assumed to be -50 per-mil). Both XD and CD are estimated from bulk rock chemistry of the sample using the MELTS program (Ghiorso and Sack, 1995). Hydrogen isotopic fractionation factors are assumed to be -15 and -30 per-mil for vapor and hydrous mineral, and vapor and silicate melt, respectively. There observed a clear difference among the H2O/K2O ratios of bulk magmas from the frontal and back arc volcanoes. For instance higher H2O/K2O wt ratios was observed in the frontal volcanoes (Nigorikawa 5.3, Zenikame 11-12, Adachi 8-10, and Nanashigure 4-18), while lower H2O/K2O wt ratios was observed in the back arc ones (Kanpu 0-2.5 and Hijiori 1.4). The lateral variation of H2O/K2O ratios infer the higher water flux through the frontal side of wedge mantle, which can be a potential cause of the

Bis(2,4-dibromo-6-formyl­phenolato-κ2 O,O′)copper(II)

PubMed Central

Li, Guang Zhao; Zhang, Shu Hua; Liu, Zheng

2008-01-01

In the title compound, [Cu(C7H3Br2O2)2], the CuII atom, which lies on an inversion centre, is coordinated by four O atoms from two chelating bidentate 2,4-dibromo-6-formyl­phenolate ligands in a slightly distorted square-planar coordination geometry. In the crystal structure, short inter­molecular Br⋯Br [3.516 (4) and 3.653 (4) Å] and Cu⋯Br [3.255 (1) Å] contacts together with C—H⋯O hydrogen bonds generate a three-dimensional network. PMID:21200624

Critical Evaluations and Thermodynamic Optimizations of the MnO-Mn2O3-SiO2 and FeO-Fe2O3-MnO-Mn2O3-SiO2 Systems

NASA Astrophysics Data System (ADS)

Kang, Youn-Bae; Jung, In-Ho

2017-06-01

A critical evaluation and thermodynamic modeling for thermodynamic properties of all oxide phases and phase diagrams in the Fe-Mn-Si-O system (MnO-Mn2O3-SiO2 and FeO-Fe2O3-MnO-Mn2O3-SiO2 systems) are presented. Optimized Gibbs energy parameters for the thermodynamic models of the oxide phases were obtained which reproduce all available and reliable experimental data within error limits from 298 K (25°C) to above the liquidus temperatures at all compositions covering from known oxide phases, and oxygen partial pressure from metal saturation to 0.21 bar. The optimized thermodynamic properties and phase diagrams are believed to be the best estimates presently available. Slag (molten oxide) was modeled using the modified quasichemical model in the pair approximation. Olivine (Fe2SiO4-Mn2SiO4) was modeled using two-sublattice model in the framework of the compound energy formalism (CEF), while rhodonite (MnSiO3-FeSiO3) and braunite (Mn7SiO_{12} with excess Mn2O3) were modeled as simple Henrian solutions. It is shown that the already developed models and databases of two spinel phases (cubic- and tetragonal-(Fe, Mn)3O4) using CEF [Kang and Jung, J. Phys. Chem. Solids (2016), vol. 98, pp. 237-246] can successfully be integrated into a larger thermodynamic database to be used in practically important higher order system such as silicate. The database of the model parameters can be used along with a software for Gibbs energy minimization in order to calculate any type of phase diagram section and thermodynamic properties.

High-Pressure Phase Relations and Crystal Structures of Postspinel Phases in MgV2O4, FeV2O4, and MnCr2O4: Crystal Chemistry of AB2O4 Postspinel Compounds.

PubMed

Ishii, Takayuki; Sakai, Tsubasa; Kojitani, Hiroshi; Mori, Daisuke; Inaguma, Yoshiyuki; Matsushita, Yoshitaka; Yamaura, Kazunari; Akaogi, Masaki

2018-06-04

We have investigated high-pressure, high-temperature phase transitions of spinel (Sp)-type MgV 2 O 4 , FeV 2 O 4 , and MnCr 2 O 4 . At 1200-1800 °C, MgV 2 O 4 Sp decomposes at 4-7 GPa into a phase assemblage of MgO periclase + corundum (Cor)-type V 2 O 3 , and they react at 10-15 GPa to form a phase with a calcium titanite (CT)-type structure. FeV 2 O 4 Sp transforms to CT-type FeV 2 O 4 at 12 GPa via decomposition phases of FeO wüstite + Cor-type V 2 O 3 . MnCr 2 O 4 Sp directly transforms to the calcium ferrite (CF)-structured phase at 10 GPa and 1000-1400 °C. Rietveld refinements of CT-type MgV 2 O 4 and FeV 2 O 4 and CF-type MnCr 2 O 4 confirm that both the CT- and CF-type structures have frameworks formed by double chains of edge-shared B 3+ O 6 octahedra (B 3+ = V 3+ and Cr 3+ ) running parallel to one of orthorhombic cell axes. A relatively large A 2+ cation (A 2+ = Mg 2+ , Fe 2+ , and Mn 2+ ) occupies a tunnel-shaped space formed by corner-sharing of four double chains. Effective coordination numbers calculated from eight neighboring oxygen-A 2+ cation distances of CT-type MgV 2 O 4 and FeV 2 O 4 and CF-type MnCr 2 O 4 are 5.50, 5.16, and 7.52, respectively. This implies that the CT- and CF-type structures practically have trigonal prism (six-coordinated) and bicapped trigonal prism (eight-coordinated) sites for the A 2+ cations, respectively. A relationship between cation sizes of VIII A 2+ and VI B 3+ and crystal structures (CF- and CT-types) of A 2+ B 2 3+ O 4 is discussed using the above new data and available previous data of the postspinel phases. We found that CF-type A 2+ B 2 3+ O 4 crystallize in wide ionic radius ranges of 0.9-1.4 Å for VIII A 2+ and 0.55-1.1 Å for VI B 3+ , whereas CT-type phases crystallize in very narrow ionic radius ranges of ∼0.9 Å for VIII A 2+ and 0.6-0.65 Å for VI B 3+ . This would be attributed to the fact that the tunnel space of CT-type structure is geometrically less flexible due to the smaller coordination

K2Ho(PO4)(WO4)

PubMed Central

Terebilenko, Katherina V.; Zatovsky, Igor V.; Baumer, Vyacheslav N.; Slobodyanik, Nikolay S.; Shishkin, Oleg V.

2008-01-01

A new compound, dipotassium holmium(III) phosphate(V) tungstate(VI), K2Ho(PO4)(WO4), has been obtained during investigation of the K2O–P2O5–WO3–HoF3 phase system using the flux technique. The compound is isotypic with K2Bi(PO4)(WO4). Its framework structure consists of flat ∞ 2[HoPO4] layers parallel to (100) that are made up of ∞ 1[HoO8] zigzag chains inter­linked via slightly distorted PO4 tetra­hedra. WO4 tetra­hedra are attached above and below these layers, leaving space for the K+ counter-cations. The HoO8, PO4 and WO4 units exhibit 2 symmetry. PMID:21580811

Polymer dots grafted TiO2 nanohybrids as high performance visible light photocatalysts.

PubMed

Li, Gen; Wang, Feng; Liu, Peng; Chen, Zheming; Lei, Ping; Xu, Zhongshan; Li, Zengxi; Ding, Yanfen; Zhang, Shimin; Yang, Mingshu

2018-04-01

As a new member of carbon dots (CDs), Polymer dots (PDs) prepared by hydrothermal treatment of polymers, usually consist of the carbon core and the connected partially degraded polymer chains. This type of CDs might possess aqueous solubility, non-toxicity, excellent stability against photo-bleaching and high visible light activity. In this research, PDs were prepared by a moderate hydrothermal treatment of polyvinyl alcohol, and PDs grafted TiO 2 (PDs-TiO 2 ) nanohybrids with TiOC bonds were prepared by a facile in-situ hydrothermal treatment of PDs and Ti (SO 4 ) 2 . Under visible light irradiation, the PDs-TiO 2 demonstrate excellent photocatalytic activity for methyl orange degradation, and the photocatalytic rate constant of PDs-TiO 2 is 3.6 and 9.5 times higher than that of pure TiO 2 and commercial P25, respectively. In addition, the PDs-TiO 2 exhibit good recycle stability under UV-Vis light irradiation. The interfacial TiOC bonds and the π-conjugated structures in PDs-TiO 2 can act as the pathways to quickly transfer the excited electrons between PDs and TiO 2 , therefore contribute to the excellent photocatalytic activity. Copyright © 2018 Elsevier Ltd. All rights reserved.

Preparation and crystal structure of K/sub 2/Nb/sub 2/As/sub 2/O/sub 11/

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

Faouzi Zid, M.; Jouini, T.; Juoini, N.

1988-06-01

K/sup 2/Nb/sub 2/As/sub 2/O/sub 11/ crystallizes in the monoclinic system, space group P21/a, with a = 10.342(6), b = 10.446(5), c = 9.971(4) A, ..beta.. = 96.72(4)/sup 0/, M = 589.86, V = 1069.8(5) A/sup 3/, Z = 4, rho = 3.67 g cm/sup -1/. The crystal structure was refined (105 variables) from 1782 independent reflections collected on a Philips PW 1100 automatic diffractometer with AgK anti ..cap alpha.. radiation. The final R index and weighted R/sub w/ index are 0.058 and 0.056, respectively. The structure consists of NbO/sub 6/ octahedra and AsO/sub 4/ tetrahedra sharing vertices, forming infinite chainsmore » (NbO/sub 6/-AsO/sub 4/)infinity parallel to the a axis. Two chains are linked together by Nb-O-Nb and Nb-O-As bonds. These double chains are connected by vertices, forming a three-dimensional network. The potassium atoms are located in tunnels parallel to the a axis.« less

RNA adducts with Na 2SeO 4 and Na 2SeO 3 - Stability and structural features

NASA Astrophysics Data System (ADS)

Nafisi, Shohreh; Manouchehri, Firouzeh; Montazeri, Maryam

2011-12-01

Selenium compounds are widely available in dietary supplements and have been extensively studied for their antioxidant and anticancer properties. Low blood Se levels were found to be associated with an increased incidence and mortality from various types of cancers. Although many in vivo and clinical trials have been conducted using these compounds, their biochemical and chemical mechanisms of efficacy are the focus of much current research. This study was designed to examine the interaction of Na 2SeO 4 and Na 2SeO 3 with RNA in aqueous solution at physiological conditions, using a constant RNA concentration (6.25 mM) and various sodium selenate and sodium selenite/polynucleotide (phosphate) ratios of 1/80, 1/40, 1/20, 1/10, 1/5, 1/2 and 1/1. Fourier transform infrared, UV-Visible spectroscopic methods were used to determine the drug binding modes, the binding constants, and the stability of Na 2SeO 4 and Na 2SeO 3-RNA complexes in aqueous solution. Spectroscopic evidence showed that Na 2SeO 4 and Na 2SeO 3 bind to the major and minor grooves of RNA ( via G, A and U bases) with some degree of the Se-phosphate (PO 2) interaction for both compounds with overall binding constants of K(Na 2SeO 4-RNA) = 8.34 × 10 3 and K(Na 2SeO 3-RNA) = 4.57 × 10 3 M -1. The order of selenium salts-biopolymer stability was Na 2SeO 4-RNA > Na 2SeO 3-RNA. RNA aggregations occurred at higher selenium concentrations. No biopolymer conformational changes were observed upon Na 2SeO 4 and Na 2SeO 3 interactions, while RNA remains in the A-family structure.

Synthesis, crystal structure, and vibrational study of K2Cu(HPO4)2·6H2O: A new metal hydrogenphosphate compound

NASA Astrophysics Data System (ADS)

Ettoumi, Houda; Bulou, Alain; Suñol, Joan Josep; Mhiri, Tahar

2015-11-01

The study reports on the synthesis, single-crystal X-ray structure, and infrared and polarized Raman spectra of a new metal phosphate. The chemical formula of the compound K2Cu(HPO4)2·6H2O resembled that of Tutton salts. The compound crystallized in the monoclinic system, space group P21/c, with a = 6.166(9), b = 12.118(19), c = 9.077(14) Å, β = 104.33(2), and Z = 2. The compound consisted of transition metal cations octahedrally coordinated by six water molecules, [Cu(H2O)6]2+, HPO4 pseudo-tetrahedra, and KO8 polyhedra. The KO8 polyhedra shared two edges with two HPO4 groups, two corners with the two other HPO4 groups, and two corners with Cu(H2O)6. The connection between [Cu(H2O)6]2+ octahedral and (HPO4)2- pseudo-tetrahedra was reinforced by hydrogen bonds formed between the water molecules and other oxygen atoms linked to the P atom. These structural results were corroborated by infrared and polarized Raman spectroscopy.

Antitumor activity of JS-K [O2-(2,4-dinitrophenyl) 1-[(4-ethoxycarbonyl)piperazin-1-yl]diazen-1-ium-1,2-diolate] and related O2-aryl diazeniumdiolates in vitro and in vivo.

PubMed

Shami, Paul J; Saavedra, Joseph E; Bonifant, Challice L; Chu, Jingxi; Udupi, Vidya; Malaviya, Swati; Carr, Brian I; Kar, Siddhartha; Wang, Meifeng; Jia, Lee; Ji, Xinhua; Keefer, Larry K

2006-07-13

The literature provides evidence that metabolic nitric oxide (NO) release mediates the cytotoxic activities (against human leukemia and prostate cancer xenografts in mice) of JS-K, a compound of structure R(2)N-N(O)=NO-Ar for which R(2)N is 4-(ethoxycarbonyl)piperazin-1-yl and Ar is 2,4-dinitrophenyl. Here we present comparative data on the potencies of JS-K and 41 other O(2)-arylated diazeniumdiolates as inhibitors of HL-60 human leukemia cell proliferation, as well as in the NCI 51-cell-line screen for six of them. The data show JS-K to be the most potent of the 42 in both screens and suggest that other features of its structure and metabolism besides NO release may contribute importantly to its activity. Results with control compounds implicate JS-K's arylating ability, and the surprisingly low IC(50) value of the N-(ethoxycarbonyl)piperazine byproduct of NO release suggests a role for the R(2)N moiety. In addition to the above-mentioned in vivo activities, JS-K is shown here to be carcinostatic in a rat liver cancer model.

Co3(PO4)2·4H2O

PubMed Central

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

H2O2/TiO2 photocatalytic oxidation of metol. Identification of intermediates and reaction pathways.

PubMed

Aceituno, Mónica; Stalikas, Constantine D; Lunar, Loreto; Rubio, Soledad; Pérez-Bendito, Dolores

2002-08-01

The applicability of H2O2 to increase the efficiency of TiO2 photocatalytic degradations was investigated. The photographic developer metol [N-methyl-p-aminophenol] that does not adsorb on the surface of TiO2 particulates was used as a model for this purpose. It was proved that metol was mineralised under oxidation with H2O2/TiO2/UV through different thermal and photochemical reactions. Identification of intermediates by both HPLC-electron impact-MS and HPLC-electrospray ionisation-MS helped to elucidate the role of H2O2 and TiO2 in the degradation process and to establish degradation pathways. Intermediates yielded were partially oxygenated aromatic species and dimers, which were amenable to oxidation. The optimal degradation conditions found for mineralisation were 0.4 M H2O2, 5 mg/ml TiO2, pH 9 and irradiation centred at 360 nm (4.9 mW/cm2). The use of oxidants opens an interesting medium to the treatment of effluents containing a diversity of organics since they increase substantially the efficiency of TiO2 photocatalytic degradations.

Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on Forsterite, Mg2SiO4(011)

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

Smith, R. Scott; Li, Zhenjun; Dohnalek, Zdenek

We have examined the adsorbate-substrate interaction kinetics of CO2 and H2O on a natural forsterite crystal surface, Mg2SiO4(011), with 10-15% of substitutional Fe2+. We use temperature programmed desorption (TPD) and molecular beam techniques to determine the adsorption, desorption, and displacement kinetics for H2O and CO2. Neither CO2 nor H2O has distinct sub-monolayer desorption peaks but instead both have a broad continuous desorption feature that evolve smoothly into multilayer desorption. Inversion of the monolayer coverage spectra for both molecules reveals that the corresponding binding energies for H2O are greater than that for CO2 on all sites. The relative strength of thesemore » interactions is the dominant factor in the competitive adsorption/displacement kinetics. In experiments where the two adsorbates are co-dosed, H2O always binds to the highest energy binding sites available and displaces CO2. The onset of CO2 displacement by H2O occurs between 65 and 75 K.« less

MnTiO3-driven low-temperature oxidative coupling of methane over TiO2-doped Mn2O3-Na2WO4/SiO2 catalyst

PubMed Central

Wang, Pengwei; Zhao, Guofeng; Wang, Yu; Lu, Yong

2017-01-01

Oxidative coupling of methane (OCM) is a promising method for the direct conversion of methane to ethene and ethane (C2 products). Among the catalysts reported previously, Mn2O3-Na2WO4/SiO2 showed the highest conversion and selectivity, but only at 800° to 900°C, which represents a substantial challenge for commercialization. We report a TiO2-doped Mn2O3-Na2WO4/SiO2 catalyst by using Ti-MWW zeolite as TiO2 dopant as well as SiO2 support, enabling OCM with 26% conversion and 76% C2-C3 selectivity at 720°C because of MnTiO3 formation. MnTiO3 triggers the low-temperature Mn2+↔Mn3+ cycle for O2 activation while working synergistically with Na2WO4 to selectively convert methane to C2-C3. We also prepared a practical Mn2O3-TiO2-Na2WO4/SiO2 catalyst in a ball mill. This catalyst can be transformed in situ into MnTiO3-Na2WO4/SiO2, yielding 22% conversion and 62% selectivity at 650°C. Our results will stimulate attempts to understand more fully the chemistry of MnTiO3-governed low-temperature activity, which might lead to commercial exploitation of a low-temperature OCM process. PMID:28630917

Study on the Growth Mechanism of K2Ti4O9 Crystal

NASA Astrophysics Data System (ADS)

Zhou, Xuesong; Fan, Jing; Wei, Xiaoli; Shen, Yi; Meng, Yanzhi

2018-04-01

Potassium hexatitanate (K2Ti4O9) whiskers were prepared by the kneading-drying-calcination method. After the preparation of products under different calcination temperatures and holding times, their morphology and structure were characterized by thermogravimetric and differential thermal, X-ray diffraction (XRD), scanning electron microscopy and transmission electron microscopy. The XRD analysis showed that the reaction mixture was completely converted to K2Ti4O9 crystals at 800 °C when the T/K ratio was 3. Based on the analysis of LS (liquid-solid) growth mechanism, the corresponding transformation reaction mechanism during the roasting was elucidated. K2Ti4O9 whiskers grow mainly through the parallel action at a low temperature. With the increase in temperature, the series effect is obvious.

Preparation and characterization of Fe3O4-Ag2O quantum dots decorated cellulose nanofibers as a carrier of anticancer drugs for skin cancer.

PubMed

Fakhri, Ali; Tahami, Shiva; Nejad, Pedram Afshar

2017-10-01

The Best performance drug delivery systems designed with Fe 3 O 4 -Ag 2 O quantum dots decorated cellulose nanofibers which that grafted with Etoposide and Methotrexate. Morphology properties were characterized by Scanning and Transmittance electron microscopy. The crystalline structure of prepared sample was evaluated using by X-ray diffraction. The vibrating sample magnetometer analysis was used for magnetic behavior of samples. The size distributions of Fe 3 O 4 -Ag 2 O QDs/Cellulose fibers nanocomposites indicate that the average diameter was 62.5nm. The Saturation magnetization (Ms) indicates the Fe 3 O 4 -Ag 2 O QDs/Cellulose fibers nanocomposites have ferromagnetic properties in nature. For make carrier, the Iron and Silver should be binds to cellulose nanofibers and to drug molecules and observe in UV-vis spectroscopy. The drug release kinetics was studied in vitro as spectrophotometrically. The release of Etoposide and Methotrexate were carried out with a constant speed, and the equilibrium reached at 24 and 30h with a total amount 78.94% and 63.84%, respectively. The results demonstrated that the obtained Fe 3 O 4 -Ag 2 O quantum dots/cellulose fibers nanocomposites could be applied for drug delivery systems. Cytotoxicity and antioxidant study confirmed the activity of the drug incorporated in nanocomposites. In addition, the cytotoxicity of drug was increased when loaded on nanocomposites, compared to pure Fe 3 O 4 -Ag 2 O quantum dots/cellulose fibers nanocomposites. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular dynamic simulations of selective self-diffusion of CH4/CO2/H2O/N2 in coal

NASA Astrophysics Data System (ADS)

Song, Y.; Jiang, B.; Li, F. L.

2017-06-01

The self-diffusion coefficients (D) of CH4/CO2/H2O/N2 at a relatively broad range of temperatures(298.15∼ 458.15K)and pressures (1∼6MPa) under the NPT, NPH, NVE, and NVT ensembles were obtained after the calculations of molecular mechanics(MM), annealing kinetics(AK), giant canonical Monte Carlo(GCMC), and molecular dynamics (MD) based on Wiser bituminous coal model (WM). The Ds of the adsorbates at the saturated adsorption configurations are D CH422O2(NPT, 298.15K, 0.1MPa). The diffusion activation energy (E) is E H2O (1.07kJ/mol)2(1.82kJ/mol)2 (2.94kJ/mol)4(10.88kJ/mol), indicating that CH4 diffusion requires to overcome the highest adsorption energy barrier and N2 and H2O to the lowest. The order of different ensembles is D N2 (NVE)< D N2 (NVT)≈D N2 (NPH)≈D N2 (NPT) (T<418K) and D N2 (NVE) is remarkable higher than other ensembles when T>418K. The average swelling ratios manifest as H2O (14.7∼35.18%)>CO2 (13.38∼32.25%)>CH4 (15.35∼23.71%)> N2 (11.47∼22.14%) (NPH, 1∼6MPa). There exits differences in D, swelling ratios and E among various ensembles, indicating that the selection of ensembles has an important influence on the MD calculations for self-diffusion coefficients.

Raman spectroscopy, thermal and optical properties of TeO2-ZnO-Nb2O5-Nd2O3 glasses

NASA Astrophysics Data System (ADS)

Kamalaker, V.; Upender, G.; Ramesh, Ch.; Chandra Mouli, V.

2012-04-01

The glasses with composition 75TeO2-10ZnO-(15-x)Nb2O5-xNd2O3 (0 ≤ x ≤ 9 mol%) were prepared using melt quenching method and their physical properties such as density (ρ), molar volume (VM), average crosslink density (n¯), oxygen packing density (OPD) and number of bonds per unit volume (nb) were determined. Raman spectroscopic studies showed that the glass network consists of TeO4, TeO3+1, TeO3 and NbO6 units as basic structural units. The glass transition temperature (Tg), crystallization onset (To) and thermal stability (ΔT) were determined from DSC thermograms. The Raman and DSC results were found to be correlated with the physical properties. In the optical absorption spectra six absorption bands were observed with different relative intensities at around 464, 522, 576, 742, 801 and 871 nm which are assigned to the transition of electrons from (ground state) 4I9/2 → G11/2; 4I9/2 → 2K3/2, 2G7/2; 4I9/2 → 4G5/2, 4G7/2; 4I9/2 → 4S3/2; 4F7/2 → 2H9/2, 4F5/2 and 4I9/2 → 2F3/2 respectively. From optical absorption data the energy band gap (Eopt) and Urbach energy (ΔE) were calculated.

Optical properties of nanocrystalline potassium lithium niobate in the glass system (100-x) TeO2-x(1.5K2O-Li2O-2.5Nb2O5).

PubMed

Ahamad, M Niyaz; Varma, K B R

2009-08-01

Optically clear glasses of various compositions in the system (100-x) TeO2-x(1.5K2O-Li2O-2.5Nb2O5) (2 < or = x < or = 12, in molar ratio) were prepared by the melt-quenching technique. The glassy nature of the as-quenched samples was established via differential scanning calorimetry (DSC). The amorphous and the crystalline nature of the as-quenched and heat-treated samples were confirmed by the X-ray powder diffraction and transmission electron microscopic (TEM) studies. Transparent glasses comprising potassium lithium niobate (K3Li2Nb5O15) microcrystallites on the surface and nanocrystallites within the glass were obtained by controlled heat-treatment of the as-quenched glasses just above the glass transition temperature (T(g)). The optical transmission spectra of these glasses and glass-crystal composites of various compositions were recorded in the 200-2500 nm wavelength range. Various optical parameters such as optical band gap, Urbach energy, refractive index were determined. Second order optical non-linearity was established in the heat-treated samples by employing the Maker-Fringe method.

Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO2, PrO2, and TbO2.

PubMed

Minasian, Stefan G; Batista, Enrique R; Booth, Corwin H; Clark, David L; Keith, Jason M; Kozimor, Stosh A; Lukens, Wayne W; Martin, Richard L; Shuh, David K; Stieber, S Chantal E; Tylisczcak, Tolek; Wen, Xiao-Dong

2017-12-13

Understanding the nature of covalent (band-like) vs ionic (atomic-like) electrons in metal oxides continues to be at the forefront of research in the physical sciences. In particular, the development of a coherent and quantitative model of bonding and electronic structure for the lanthanide dioxides, LnO 2 (Ln = Ce, Pr, and Tb), has remained a considerable challenge for both experiment and theory. Herein, relative changes in mixing between the O 2p orbitals and the Ln 4f and 5d orbitals in LnO 2 are evaluated quantitatively using O K-edge X-ray absorption spectroscopy (XAS) obtained with a scanning transmission X-ray microscope and density functional theory (DFT) calculations. For each LnO 2 , the results reveal significant amounts of Ln 5d and O 2p mixing in the orbitals of t 2g (σ-bonding) and e g (π-bonding) symmetry. The remarkable agreement between experiment and theory also shows that significant mixing with the O 2p orbitals occurs in a band derived from the 4f orbitals of a 2u symmetry (σ-bonding) for each compound. However, a large increase in orbital mixing is observed for PrO 2 that is ascribed to a unique interaction derived from the 4f orbitals of t 1u symmetry (σ- and π-bonding). O K-edge XAS and DFT results are compared with complementary L 3 -edge and M 5,4 -edge XAS measurements and configuration interaction calculations, which shows that each spectroscopic approach provides evidence for ground state O 2p and Ln 4f orbital mixing despite inducing very different core-hole potentials in the final state.

Na2O-Al2O3 system: Activity of Na2O in (α + β)- and (β + β)-alumina

NASA Astrophysics Data System (ADS)

Kale, G. M.

1992-12-01

The activity of Na2O in a biphasic mixture of (α + β)-alumina has been measured in the temperature range of 700 to 1100 K using the solid-state galvanic cell: 11663_2007_Article_BF02656462_TeX2GIFE1.gif _{(1:1)}^{Pt,CO_2 + O_2 /Na_2 CO_3 /(α + β ) - alumin a//(Y_2 O_3 )ZrO_2 //In + In_2 O_3 ,Ta,Pt} Similarly, the activity of Na2O in a (β + β’’)-alumina two-phase mixture has been measured between 700 and 1100 K employing the galvanic cell: 11663_2007_Article_BF02656462_TeX2GIFE2.gif _{(1:1)}^{Pt,CO_2 + O_2 /Na_2 CO_3 /(β + β ) - alumin a//(Y_2 O_3 )ZrO_2 //In + In_2 O_3 ,Ta,Pt} The reversible electromotive force (emf ) of both the cells was found to vary linearly with temperature over the entire temperature range of measurement. From the measured reversible emf and auxiliary thermodynamic data for In2O2, Na2O, CO2 and Na2CO3 reported in the literature, the temperature dependence of the logarithm of activity of Na2O in (α + β)-alumina is obtained: 11663_2007_Article_BF02656462_TeX2GIFE3.gif log α _{Na_2 O} (α + β ) = 1.85 - 14,750/T(K)( ± 0.015)(700 ≤slant T ≤slant 1100) For (β + β'’)-alumina, 11663_2007_Article_BF02656462_TeX2GIFE4.gif log α _{Na_2 O} (β + β ) = 3.9 - 13,000/T(K)( ± 0.015)(700 ≤slant T ≤slant 1100)

Characteristics of Pt-K/MgAl2O4 lean NOx trap catalysts

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

Kim, Do Heui; Mudiyanselage, Kumudu K.; Szanyi, Janos

2012-04-30

We report the various characteristics of Pt-K/MgAl{sub 2}O{sub 4} lean NOx trap (LNT) catalysts including the effect of K loading on nitrate formation/decomposition, NOx storage activity and durability. Upon the adsorption of NO{sub 2} on K/MgAl{sub 2}O{sub 4} samples, potassium nitrates formed on Mg-related sites in MgAl{sub 2}O{sub 4} support are observed, in addition to the typical two potassium nitrates (ionic and bidentate) formed also on Al{sub 2}O{sub 3} supported sample. Based on NO{sub 2} TPD and FTIR results, the Mg-bound KNO{sub 3} thermally decompose at higher temperature than Al-bound KNO{sub 3}, implying its superior thermal stability. At a potassiummore » loading of 5wt%, the temperature of maximum NOx uptake (T{sub max}) is 300 C. Increasing the potassium loading from 5wt% to 10 wt%, the T{sub max} gradually shifted from 300 C to 450 C, indicating the dependence of T{sub max} on the potassium loading. However, increase in potassium loading above 10 wt% only gives rise to the reduction in the overall NOx storage capacity. This work also underlines the obstacles these materials have prior to their practical application (e.g., durability and sulfur poisoning/ removal). This work provides fundamental understanding of Pt-K/MgAl{sub 2}O{sub 4}-based lean NOx trap catalysts, which could be good candidates for high temperature LNT applications.« less

NO2 Gas Sensing Properties of Multiple Networked ZnGa2O4 Nanorods Coated with TiO2.

PubMed

An, Soyeon; Park, Sunghoon; Ko, Hyunsung; Jin, Changhyun; Lee, Chongmu

2015-01-01

The NO2 gas sensing properties of ZnGa2O4-TiO2 heterostructure nanorods was examined. ZnGa2O4-core/TiO2-shell nanorods were fabricated by the thermal evaporation of a mixture of Zn and GaN powders and the sputter deposition of TiO2. Multiple networked ZnGa2O4-core/TiO2-shell nanorod sensors showed the response of 876% at 10 ppm NO2 at 300 degrees C. This response value at 10 ppm NO2 is approximately 4 times larger than that of bare ZnGa2O4 nanorod sensors. The response values obtained by the ZnGa2O4-core/TiO2-shell nanorods in this study are more than 13 times higher than those obtained previously by the SnO2-core/ZnO-shell nanofibers at 5% NO2. The significant enhancement in the response of ZnGa2O4 nanorods to NO2 gas by coating them with TiO2 can be explained based on the space-charge model.

Structures of M2(SO2)6B12F12 (M = Ag or K) and Ag2(H2O)4B12F12: Comparison of the Coordination of SO2 versus H2O and of B12F122- versus Other Weakly Coordinating Anions to Metal Ions in the Solid State.

PubMed

Malischewski, Moritz; Peryshkov, Dmitry V; Bukovsky, Eric V; Seppelt, Konrad; Strauss, Steven H

2016-12-05

The structures of three solvated monovalent cation salts of the superweak anion B 12 F 12 2- (Y 2- ), K 2 (SO 2 ) 6 Y, Ag 2 (SO 2 ) 6 Y, and Ag 2 (H 2 O) 4 Y, are reported and discussed with respect to previously reported structures of Ag + and K + with other weakly coordinating anions. The structures of K 2 (SO 2 ) 6 Y and Ag 2 (SO 2 ) 6 Y are isomorphous and are based on expanded cubic close-packed arrays of Y 2- anions with M(OSO) 6 + complexes centered in the trigonal holes of one expanded close-packed layer of B 12 centroids (⊙). The K + and Ag + ions have virtually identical bicapped trigonal prism MO 6 F 2 coordination spheres, with M-O distances of 2.735(1)-3.032(2) Å for the potassium salt and 2.526(5)-2.790(5) Å for the silver salt. Each M(OSO) 6 + complex is connected to three other cationic complexes through their six μ-SO 2 -κ 1 O,κ 2 O' ligands. The structure of Ag 2 (H 2 O) 4 Y is unique [different from that of K 2 (H 2 O) 4 Y]. Planes of close-packed arrays of anions are offset from neighboring planes along only one of the linear ⊙···⊙···⊙ directions of the close-packed arrays, with [Ag(μ-H 2 O) 2 Ag(μ-H 2 O) 2 )] ∞ infinite chains between the planes of anions. There are two nearly identical AgO 4 F 2 coordination spheres, with Ag-O distances of 2.371(5)-2.524(5) Å and Ag-F distances of 2.734(4)-2.751(4) Å. This is only the second structurally characterized compound with four H 2 O molecules coordinated to a Ag + ion in the solid state. Comparisons with crystalline H 2 O and SO 2 solvates of other Ag + and K + salts of weakly coordinating anions show that (i) N[(SO 2 ) 2 (1,2-C 6 H 4 )] - , BF 4 - , SbF 6 - , and Al(OC(CF 3 ) 3 ) 4 - coordinate much more strongly to Ag + than does Y 2- , (ii) SnF 6 2- coordinates somewhat more strongly to K + than does Y 2- , and (iii) B 12 Cl 12 2- coordinates to K + about the same as, if not slightly weaker than, Y 2- .

O(2)-dependent K(+) fluxes in trout red blood cells: the nature of O(2) sensing revealed by the O(2) affinity, cooperativity and pH dependence of transport.

PubMed

Berenbrink, M; Völkel, S; Heisler, N; Nikinmaa, M

2000-07-01

The effects of pH and O(2) tension on the isotonic ouabain-resistant K(+) (Rb+) flux pathway and on haemoglobin O2 binding were studied in trout red blood cells (RBCs) in order to test for a direct effect of haemoglobin O(2) saturation on K(+) transport across the RBC membrane. At pH values corresponding to in vivo control arterial plasma pH and higher, elevation of the O(2) partial pressure (PO(2)) from 7.8 to 157 mmHg increased unidirectional K(+) influx across the RBC membrane several-fold. At lower extracellular pH values, stimulation of K(+) influx by O(2) was depressed, exhibiting an apparent pK(a) (pK'(a)) for the process of 8.0. Under similar conditions the pK'(a) for acid-induced deoxygenation of haemoglobin (Hb) was 7.3. When trout RBCs were exposed to PO(2) values between 0 and 747 mmHg, O(2) equilibrium curves typical of Hb O(2) saturation were also obtained for K(+) influx and efflux. However, at pH 7.9, the PO(2) for half-maximal K(+) efflux and K(+) influx (P50) was about 8- to 12-fold higher than the P(50) for Hb-O(2) binding. While K(+) influx and efflux stimulation by O(2) was essentially non-cooperative, Hb-O(2) equilibrium curves were distinctly sigmoidal (Hill parameters close to 1 and 3, respectively). O(2)-stimulated K(+) influx and efflux were strongly pH dependent. When the definition of the Bohr factor for respiratory pigments (Phi = delta logP50 x delta pH(-1)) was extended to the effect of pH on O(2)-dependent K(+) influx and efflux, extracellular Bohr factors (Phi(o) of -2.00 and -2.06 were obtained, values much higher than that for Hb (Phi(o) = -0.49). The results of this study are consistent with an O(2) sensing mechanism differing markedly in affinity and cooperativity of O(2) binding, as well as in pH sensitivity, from bulk Hb.

Comparison between Slow Components of HR and V[Combining Dot Above]O2 Kinetics: Functional Significance.

PubMed

Zuccarelli, Lucrezia; Porcelli, Simone; Rasica, Letizia; Marzorati, Mauro; Grassi, Bruno

2018-03-22

Aerobic exercise prescription is often based on a linear relationship between pulmonary oxygen consumption (V[Combining Dot Above]O2) and heart rate (HR). The aim of the present study was to test the hypothesis that during constant work rate (CWR) exercises at different intensities the slow component of HR kinetics occurs at lower work rate and is more pronounced that the slow component of V[Combining Dot Above]O2 kinetics. Seventeen male (age, 27±4yr) subjects performed on a cycle ergometer an incremental exercise to voluntary exhaustion and several CWR exercises: 1) moderate CWR exercises (MODERATE), below gas exchange threshold (GET); 2) heavy CWR exercise (HEAVY), at 45% of the difference between GET and V[Combining Dot Above]O2 peak (□); 3) severe CWR exercise (SEVERE), at 95% of Δ; 4) "HRCLAMPED" exercise in which work rate was continuously adjusted to maintain a constant HR, slightly higher than that determined at GET. Breath-by-breath V[Combining Dot Above]O2, HR and other variables were determined. In MODERATE, no slow component of V[Combining Dot Above]O2 kinetics was observed, whereas a slow component with a relative amplitude (with respect to the total response) of 24.8±11.0% was observed for HR kinetics. During HEAVY, the relative amplitude of the HR slow component was more pronounced than that for V[Combining Dot Above]O2 (31.6±11.2 and 23.3±9.0%, respectively). During HRCLAMPED the decrease in work rate (~14%) needed in order to maintain a constant HR was associated with a decreased V[Combining Dot Above]O2 (~10%). The HR slow component occurred at a lower work rate and was more pronounced than the V[Combining Dot Above]O2 slow component. Exercise prescriptions at specific HR values, when carried out for periods longer than a few minutes, could lead to premature fatigue.

SO2 Adsorption on CeO2(100) and CeO2(111)

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

Mullins, David R.

2016-09-13

The adsorption and reaction of sulfur dioxide, SO2, was studied on oxidized and reduced CeOX(100) and compared to previous results on CeOX(111). SO2 adsorbs on oxidized CeO2(100) as sulfite, SO32-, at 200 K and sulfite is the only adsorbate observed on the surface at any temperature. The sulfite desorbs monotonically from 200 to 700 K. The adsorption and desorption of SO2 does not result in any change in the Ce4+ oxidation state. SO2 also adsorbs as sulfite on reduced CeO1.7(100) at 200 K. There is also a small amount of elemental sulfur, S0, formed. As the sample is heated themore » sulfite decomposes into sulfide, S2-. Roughly 25 % of the adsorbed S either desorbs or diffuses into the bulk of the reduced ceria. The decomposition, and resulting formation of S2- and O2-, re-oxidize some of the Ce3+ to Ce4+. Unlike what has been observed following the adsorption and reaction of many other molecules, the adsorption and reaction of SO2 is virtually identical on CeOX(100) and CeOX(111).« less

A kinetic study of Ca-containing ions reacting with O, O2, CO2 and H2O: implications for calcium ion chemistry in the upper atmosphere.

PubMed

Broadley, Sarah; Vondrak, Tomas; Wright, Timothy G; Plane, John M C

2008-09-14

A series of gas-phase reactions involving molecular Ca-containing ions was studied by the pulsed laser ablation of a calcite target to produce Ca+ in a fast flow of He, followed by the addition of reagents downstream and detection of ions by quadrupole mass spectrometry. Most of the reactions that were studied are important for describing the chemistry of meteor-ablated calcium in the earth's upper atmosphere. The following rate coefficients were measured: k(CaO+ + O --> Ca+ + O2) = (4.2 +/- 2.8) x 10(-11) at 197 K and (6.3 +/- 3.0) x 10(-11) at 294 K; k(CaO+ + CO --> Ca+ + CO2, 294 K) = (2.8 +/- 1.5) x 10(-10); k(Ca+.CO2 + O2 --> CaO2+ + CO2, 294 K) = (1.2 +/- 0.5) x10(-10); k(Ca+.CO2 + H2O --> Ca+.H2O + CO2) = (13.0 +/- 4.0) x 10(-10); and k(Ca+.H2O + O2 --> CaO2+ + H2O, 294 K) = (4.0 +/- 2.5) x 10(-10) cm3 molecule(-1) s(-1). The quoted uncertainties are a combination of the 1 sigma standard errors in the kinetic data and the systematic errors in the models used to extract the rate coefficients. Rate coefficients were also obtained for the following recombination (also termed association) reactions in He bath gas: k(Ca+.CO2 + CO2 --> Ca+.(CO2)2, 294 K) = (2.6 +/- 1.0) x 10(-29); k(Ca+.H2O + H2O --> Ca+.(H2O)2) = (1.6 +/- 1.1) x 10(-27); and k(CaO2+ + O2 --> CaO2+.O2) < 1 x 10(-31) cm6 molecule(-2) s(-1). These recombination rate coefficients, as well as those for the ligand-switching reactions listed above, were then interpreted using a combination of high level quantum chemistry calculations and RRKM theory using an inverse Laplace transform solution of the master equation. The surprisingly slow reaction between CaO+ and O was explained using quantum chemistry calculations on the lowest 2A', 2A'' and 4A'' potential energy surfaces. These calculations indicate that reaction mostly occurs on the 2A' surface, leading to production of Ca+ (2S) + O2(1 Delta g). The importance of this reaction for controlling the lifetime of Ca+ in the upper mesosphere and lower

Raman spectroscopy, thermal and optical properties of TeO2-ZnO-Nb2O5-Nd2O3 glasses.

PubMed

Kamalaker, V; Upender, G; Ramesh, Ch; Mouli, V Chandra

2012-04-01

The glasses with composition 75TeO2-10ZnO-(15-x)Nb2O5-xNd2O3 (0≤x≤9 mol%) were prepared using melt quenching method and their physical properties such as density (ρ), molar volume (VM), average crosslink density (nc¯), oxygen packing density (OPD) and number of bonds per unit volume (nb) were determined. Raman spectroscopic studies showed that the glass network consists of TeO4, TeO3+1, TeO3 and NbO6 units as basic structural units. The glass transition temperature (Tg), crystallization onset (To) and thermal stability (ΔT) were determined from DSC thermograms. The Raman and DSC results were found to be correlated with the physical properties. In the optical absorption spectra six absorption bands were observed with different relative intensities at around 464, 522, 576, 742, 801 and 871 nm which are assigned to the transition of electrons from (ground state) 4I9/2→G11/2; 4I9/2→2K3/2, 2G7/2; 4I9/2→4G5/2, 4G7/2; 4I9/2→4S3/2; 4F7/2→2H9/2, 4F5/2 and 4I9/2→2F3/2 respectively. From optical absorption data the energy band gap (Eopt) and Urbach energy (ΔE) were calculated. Copyright © 2012 Elsevier B.V. All rights reserved.

Arsenite oxidation by H 2O 2 in aqueous solutions

NASA Astrophysics Data System (ADS)

Pettine, Maurizio; Campanella, Luigi; Millero, Frank J.

1999-09-01

The rates of the oxidation of As( III) with H 2O 2 were measured in NaCl solutions as a function of pH (7.5-10.3), temperature (10-50C) and ionic strength ( I = 0.01-4). The rate of the oxidation of As( III) with H 2O 2 can be described by the general expression: d[As( III)]/ dt = k[As( III)] [H 2O 2] where k (mol/L -1 min -1) can be determined from (σ = ±0.12) log k=5.29+1.41 pH-0.57 I+1.40 I0.5-4898/ T. The effect of pH on the rates indicates that the reaction is due to AsO( OH) 2-+ H2O2k 1→productsAsO2( OH) 2-+ H2O2k 2→products, AsO33-+ H2O2k 3→products where k = k1 α AsO(OH) 2- + k2 α AsO 2(OH) 2- + k3 α AsO 3 3- and α i are the molar fraction of species i. The values of k1 = 42 ± 20, k2 = (8 ± 1) × 10 4, and k3 = (72 ± 18) × 10 6 mol/L -1 min -1 were found at 25C and I = 0.01 mol/L. The undissociated As(OH) 3 does not react with H 2O 2. The effect of ionic strength on the rate constants has been attributed to the effect of ionic strength on the speciation of As( III). The rate expression has been shown to be valid for NaClO 4 solutions, northern Adriatic sea waters, and Tiber River waters. The cations Fe 2+ and Cu 2+ were found to exert a catalytic effect on the rates. Cu 2+ plays a role at concentration levels (>0.1 μmol/L) which are typical of polluted aquatic systems, while Fe 2+ is important at levels which may be found in lacustrine environments (>5-10 μmol/L). The reaction of As( III) with H 2O 2 may play a role in marine and lacustrine surface waters limiting the accumulation of As( III) resulting from biologically mediated reduction processes of As( V).

Low-T magnetometry study of S = 1 Q2D [Ni(pyz) 2(H 2O) 2](BF 4) 2 (pyz = pyrazine)

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

Manson, J. L.; Villa, D. Y.; Blackmore, W. J. A.

2017-02-13

[Ni(pyz) 2(H 2O) 2](BF 4) 2 (pyz = N 2C 4H 4) was synthesized by a solvent-free technique and its structure solved by synchrotron X-ray powder diffraction.1 The compound contains S = 1 Ni(II) ions and has tetragonal symmetry. Two-D [Ni(pyz) 2(H 2O) 2] 2+ square lattices propagate in the ab-plane and stack along the c-axis (Fig. 1). Water ligands occupy axial sites and form H-bonds with interlayer BF 4 - ions. SQUID magnetometry shows a possible transition to long-range magnetic order near 3 K. We measured the magnetization of [Ni(pyz) 2(H 2O) 2](BF 4) 2 as a function ofmore » temperature to search for field-induced phase transitions and briefly report those findings here.« less

Synthesis and Characterization of Photocatalytic TiO 2 -ZnFe 2 O 4 Nanoparticles

DOE PAGES

Srinivasan, Sesha S.; Wade, Jeremy; Stefanakos, Elias K.

2006-01-01

A new coprecipimore » tation/hydrolysis synthesis route is used to create a TiO 2 -ZnFe 2 O 4 nanocomposite that is directed towards extending the photoresponse of TiO 2 from UV to visible wavelengths ( > 400   nm ). The effect of TiO 2 's accelerated anatase-rutile phase transformation due to the presence of the coupled ZnFe 2 O 4 narrow-bandgap semiconductor is evaluated. The transformation's dependence on pH, calcinations temperature, particle size, and ZnFe 2 O 4 concentration has been analyzed using XRD, SEM, and UV-visible spectrometry. The requirements for retaining the highly photoactive anatase phase present in a ZnFe 2 O 4 nanocomposite are outlined. The visible-light-activated photocatalytic activity of the TiO 2 -ZnFe 2 O 4 nanocomposites has been compared to an Aldrich TiO 2 reference catalyst, using a solar-simulated photoreactor for the degradation of phenol.« less

KCd2[N(CN)2]5(H2O)4: an enmeshed honeycomb grid.

PubMed

Schlueter, John A; Geiser, Urs; Funk, Kylee A

2008-02-01

The title compound, poly[potassium [diaquapenta-micro(2)-dicyanamido-dicadmium(II)] dihydrate], {K[Cd(2)(C(2)N(3))(5)(H(2)O)(2)].2H(2)O}(n), contains two-dimensional anionic sheets of {[Cd(2){N(CN)(2)}(H(2)O)(2)](-)}(n) with a modified (6,3)-net (layer group cm2m, No. 35). Two sets of equivalent sheets interpenetrate orthogonally to form a tetragonal enmeshed grid.

(Zr,Ti)O2 interface structure in ZrO2-TiO2 nanolaminates with ultrathin periodicity

NASA Astrophysics Data System (ADS)

Aita, C. R.; DeLoach, J. D.; Yakovlev, V. V.

2002-07-01

A mixed cation interfacial structure in ZrO2-TiO2 nanolaminate films with ultrathin bilayer periodicity grown by sputter deposition at 297 K was identified by x-ray diffraction and nonresonant Raman spectroscopy. This structure consists of an amorphous phase at a ZrO2-on-TiO2 bilayer interface, followed by an extensive crystalline monoclinic (Zr,Ti)O2 solid solution predicted by Vegard's law. Monoclinic (Zr,Ti)O2 has previously been reported only once, in bulk powder of a single composition (ZrTiO4) at high pressure. Its stabilization in the nanolaminates is explained by the Gibbs-Thomson effect. This complex interfacial structure is shown to be a means of accommodating chemical mixing in the absence of a driving force for heteroepitaxy.

Q(n) species distribution in K2O.2SiO2 glass by 29Si magic angle flipping NMR.

PubMed

Davis, Michael C; Kaseman, Derrick C; Parvani, Sahar M; Sanders, Kevin J; Grandinetti, Philip J; Massiot, Dominique; Florian, Pierre

2010-05-06

Two-dimensional magic angle flipping (MAF) was employed to measure the Q((n)) distribution in a (29)Si-enriched potassium disilicate glass (K(2)O.2SiO(2)). Relative concentrations of [Q((4))] = 7.2 +/- 0.3%, [Q((3))] = 82.9 +/- 0.1%, and [Q((2))] = 9.8 +/- 0.6% were obtained. Using the thermodynamic model for Q((n)) species disproportionation, these relative concentrations yield an equilibrium constant k(3) = 0.0103 +/- 0.0008, indicating, as expected, that the Q((n)) species distribution is close to binary in the potassium disilicate glass. A Gaussian distribution of isotropic chemical shifts was observed for each Q((n)) species with mean values of -82.74 +/- 0.03, -91.32 +/- 0.01, and -101.67 +/- 0.02 ppm and standard deviations of 3.27 +/- 0.03, 4.19 +/- 0.01, and 5.09 +/- 0.03 ppm for Q((2)), Q((3)), and Q((4)), respectively. Additionally, nuclear shielding anisotropy values of zeta =-85.0 +/- 1.3 ppm, eta = 0.48 +/- 0.02 for Q((2)) and zeta = -74.9 +/- 0.2 ppm, eta = 0.03 +/- 0.01 for Q((3)) were observed in the potassium disilicate glass.

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

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

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

2014-04-01

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

Kinetic removal of haloacetonitrile precursors by photo-based advanced oxidation processes (UV/H2O2, UV/O3, and UV/H2O2/O3).

PubMed

Srithep, Sirinthip; Phattarapattamawong, Songkeart

2017-06-01

The objective of the study is to evaluate the performance of conventional treatment process (i.e., coagulation, flocculation, sedimentation and sand filtration) on the removals of haloacetonitrile (HAN) precursors. In addition, the removals of HAN precursors by photo-based advanced oxidation processes (Photo-AOPs) (i.e., UV/H 2 O 2 , UV/O 3 , and UV/H 2 O 2 /O 3 ) are investigated. The conventional treatment process was ineffective to remove HAN precursors. Among Photo-AOPs, the UV/H 2 O 2 /O 3 was the most effective process for removing HAN precursors, followed by UV/H 2 O 2 , and UV/O 3 , respectively. For 20min contact time, the UV/H 2 O 2 /O 3 , UV/H 2 O 2 , and UV/O 3 suppressed the HAN formations by 54, 42, and 27% reduction. Increasing ozone doses from 1 to 5 mgL -1 in UV/O 3 systems slightly improved the removals of HAN precursors. Changes in pH (6-8) were unaffected most of processes (i.e., UV, UV/H 2 O 2 , and UV/H 2 O 2 /O 3 ), except for the UV/O 3 system that its efficiency was low in the weak acid condition. The pseudo first-order kinetic constant for removals of dichloroacetonitrile precursors (k' DCANFP ) by the UV/H 2 O 2 /O 3 , UV/H 2 O 2 and standalone UV systems were 1.4-2.8 orders magnitude higher than the UV/O 3 process. The kinetic degradation of dissolved organic nitrogen (DON) tended to be higher than the k' DCANFP value. This study firstly differentiates the kinetic degradation between DON and HAN precursors. Copyright © 2017 Elsevier Ltd. All rights reserved.

Formation mechanisms of Si3N4 and Si2N2O in silicon powder nitridation

NASA Astrophysics Data System (ADS)

Yao, Guisheng; Li, Yong; Jiang, Peng; Jin, Xiuming; Long, Menglong; Qin, Haixia; Kumar, R. Vasant

2017-04-01

Commercial silicon powders are nitrided at constant temperatures (1453 K; 1513 K; 1633 K; 1693 K). The X-ray diffraction results show that small amounts of Si3N4 and Si2N2O are formed as the nitridation products in the samples. Fibroid and short columnar Si3N4 are detected in the samples. The formation mechanisms of Si3N4 and Si2N2O are analyzed. During the initial stage of silicon powder nitridation, Si on the outside of sample captures slight amount of O2 in N2 atmosphere, forming a thin film of SiO2 on the surface which seals the residual silicon inside. And the oxygen partial pressure between the SiO2 film and free silicon is decreasing gradually, so passive oxidation transforms to active oxidation and metastable SiO(g) is produced. When the SiO(g) partial pressure is high enough, the SiO2 film will crack, and N2 is infiltrated into the central section of the sample through cracks, generating Si2N2O and short columnar Si3N4 in situ. At the same time, metastable SiO(g) reacts with N2 and form fibroid Si3N4. In the regions where the oxygen partial pressure is high, Si3N4 is oxidized into Si2N2O.

Electrical characterization of ALD HfO2 high-k dielectrics on ( 2 ¯ 01) β-Ga2O3

NASA Astrophysics Data System (ADS)

Shahin, David I.; Tadjer, Marko J.; Wheeler, Virginia D.; Koehler, Andrew D.; Anderson, Travis J.; Eddy, Charles R.; Christou, Aris

2018-01-01

The electrical quality of HfO2 dielectrics grown by thermal atomic layer deposition at 175 °C on n-type ( 2 ¯ 01) β-Ga2O3 has been studied through capacitance- and current-voltage measurements on metal-oxide-semiconductor capacitors. These capacitors exhibited excellent electrical characteristics, including dual-sweep capacitance-voltage curves with low hysteresis and stretch-out and a frequency-stable dielectric constant of k˜14 when measured between 10 kHz and 1 MHz. The C-V curves exhibited a uniform and repeatable +1.05 V shift relative to the ideal case when swept from 3.5 to -5 V, yielding positively measured flatband (+2.15 V) and threshold (+1.05 V) voltages that may be useful for normally off n-channel Ga2O3 devices. Using the Terman method, an average interface trap density of 1.3 × 1011 cm-2.eV-1 was obtained between 0.2 and 0.6 eV below the conduction band edge. The forward bias current-voltage characteristic was successfully fitted to the Fowler-Nordheim tunneling model at a field strength of 5 MV/cm, allowing an extraction of a 1.3 eV conduction band offset between HfO2 and Ga2O3, which matches the value previously determined from x-ray photoelectron spectroscopy. However, a temperature dependence in the leakage current was observed. These results suggest that HfO2 is an appealing dielectric for Ga2O3 device applications.

[{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20]36-: a molecular quantum spin icosidodecahedron.

PubMed

Botar, Bogdan; Kögerler, Paul; Hill, Craig L

2005-07-07

Self-assembly of aqueous solutions of molybdate and vanadate under reducing, mildly acidic conditions results in a polyoxomolybdate-based {Mo72V30} cluster compound Na8K16(VO)(H2O)5[K10 subset{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20].150H2O, 1, a quantum spin-based Keplerate structure.

Effect of K2FeO4/US treatment on textile dyeing sludge disintegration and dewaterability.

PubMed

Ning, Xun-an; Feng, Yinfang; Wu, Junji; Chen, Changmin; Wang, Yujie; Sun, Jian; Chang, Kenlin; Zhang, Yaping; Yang, Zuoyi; Liu, Jingyong

2015-10-01

The effect of potassium ferrate/ultrasonic (K2FeO4/US) treatment on the physicochemical features of textile dyeing sludge was studied. The soluble chemical oxygen demand (SCOD), deoxyribonucleic acid (DNA), sludge volume index (SVI), sludge viscosity, capillary suction time (CST) and particle size were measured to understand the observed changes in the sludge physicochemical features. The results showed that the combined K2FeO4/US treatment presented great advantages for disrupting the sludge floc structure over K2FeO4 or ultrasonic treatments alone. The optimal parameters of sludge disintegration were found to be a K2FeO4 treatment time of 60 min, a K2FeO4 dosage of 0.5936 g/g SS, an ultrasonic time of 15 min and an ultrasonic intensity of 0.72 W/mL. The initial median diameter of the sludge particles was 15.24 μm, and this value decreased by 35.89%. The CST was initially 59.6 s and increased by 231%, whereas the SVI was 97.78 mL/g and decreased by 25.89%. Scanning electron microscope (SEM) images indicated that the sludge surface was irregular and loose with a large amount of channels or voids during K2FeO4/US treatment. K2FeO4/US treatment synergistically enhanced the sludge solubilization and reached 668.67 mg/L SCOD, which is 31.81% greater than the additive value obtained with K2FeO4 treatment alone (215.95 mg/L) or with ultrasonic treatment alone (240 mg/L). Copyright © 2015 Elsevier Ltd. All rights reserved.

A Sequential Method to Prepare Polymorphs and Solvatomorphs of [Fe(1,3-bpp)2 ](ClO4 )2 ⋅nH2 O (n=0, 1, 2) with Varying Spin-Crossover Behaviour.

PubMed

Bartual-Murgui, Carlos; Codina, Carlota; Roubeau, Olivier; Aromí, Guillem

2016-08-26

Two polymorphs of the spin crossover (SCO) compound [Fe(1,3-bpp)2 ](ClO4 )2 (1 and 2; 1,3-bpp=2-(pyrazol-1-yl)-6-(pyrazol-3-yl)pyridine) were prepared using a novel, stepwise procedure. Crystals of 1 deposit from dry solvents, while 2 is obtained from a solid-state procedure, by sequentially removing lattice H2 O molecules from the solvatomorph [Fe(1,3-bpp)2 ](ClO4 )2 ⋅2 H2 O (2⋅2 H2 O), using single-crystal-to-single-crystal (SCSC) transformations. Hydrate 2⋅2 H2 O is obtained through the same reaction as 1, now with 2.5 % of water added. Compounds 2 and 2⋅2 H2 O are unstable in the atmosphere and absorb or lose one equivalent of water, respectively, to both yield the stable solvatomorph [Fe(1,3-bpp)2 ](ClO4 )2 ⋅H2 O (2⋅H2 O), also following SCSC processes. The four derivatives have been characterised by single-crystal X-ray diffraction (SCXRD). Furthermore, the homogeneity of the various compounds as well as their SCSC interconversions have been confirmed by powder X-ray diffraction (PXRD). Polymorphs 1 and 2 exhibit abrupt SCO behaviour near room temperature with T1/2↑ =279/316 K and T1/2↓ =276/314 K (near 40 K of shift) and different cooperativity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Local structure of Rb{sub 2}Li{sub 4}(SeO{sub 4}){sub 3}{center_dot}2H{sub 2}O by the modeling of X-ray diffuse scattering - from average-structure to microdomain model

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

Komornicka, Dorota; Wolcyrz, Marek, E-mail: m.wolcyrz@int.pan.wroc.pl; Pietraszko, Adam

2012-08-15

Local structure of dirubidium tetralithium tris(selenate(VI)) dihydrate - Rb{sub 2}Li{sub 4}(SeO{sub 4}){sub 3}{center_dot} 2H{sub 2}O has been determined basing on the modeling of X-ray diffuse scattering. The origin of observed structured diffuse streaks is SeO{sub 4} tetrahedra switching between two alternative positions in two quasi-planar layers existing in each unit cell and formation of domains with specific SeO{sub 4} tetrahedra configuration locally fulfilling condition for C-centering in the 2a Multiplication-Sign 2b Multiplication-Sign c superstructure cell. The local structure solution is characterized by a uniform distribution of rather large domains (ca. thousand of unit cells) in two layers, but also monodomainsmore » can be taken into account. Inside a single domain SeO{sub 4} tetrahedra are ordered along ab-diagonal forming two-string ribbons. Inside the ribbons SeO{sub 4} and LiO{sub 4} tetrahedra share the oxygen corners, whereas ribbons are bound to each other by a net of hydrogen bonds and fastened by corner sharing SeO{sub 4} tetrahedra of the neighboring layers. - Graphical abstract: Experimental sections of the reciprocal space showing diffraction effects observed for RLSO. Bragg spots are visible on sections with integer indices (1 kl section - on the left), streaks - on sections with fractional ones (1.5 kl section - on the right). At the center: resulting local structure of the A package modeled as a microdomain: two-string ribbons of ordered oxygen-corners-sharing SeO{sub 4} and LiO{sub 4} terahedra extended along ab-diagonal are seen; ribbons are bound by hydrogen bonds (shown in pink); the multiplied 2a Multiplication-Sign 2b unit cell is shown. Highlights: Black-Right-Pointing-Pointer X-ray diffuse scattering in RLSO was registered and modeled. Black-Right-Pointing-Pointer The origin of diffuse streaks is SeO{sub 4} tetrahedra switching in two structure layers. Black-Right-Pointing-Pointer The local structure is characterized by a

The vibration-rotation-tunneling levels of N2-H2O and N2-D2O.

PubMed

Wang, Xiao-Gang; Carrington, Tucker

2015-07-14

In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

The vibration-rotation-tunneling levels of N2-H2O and N2-D2O

NASA Astrophysics Data System (ADS)

Wang, Xiao-Gang; Carrington, Tucker

2015-07-01

In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.