Science.gov

Sample records for oxides lnmo8o14 ln

  1. Magnetic properties of ternary sodium oxides Na LnO 2 ( Ln=rare earths)

    NASA Astrophysics Data System (ADS)

    Hashimoto, Yuta; Wakeshima, Makoto; Hinatsu, Yukio

    2003-11-01

    Magnetic properties of ternary sodium oxides Na LnO 2 ( Ln=rare earths) are investigated. Their crystal structures are grouped into three types of structures, which are α-LiFeO 2, β-LiFeO 2, and α-NaFeO 2, depending on the size of rare earths. Their magnetic susceptibilities and specific heats have been measured from 1.8 to 300 K. Among them, NaGdO 2, NaDyO 2, and NaHoO 2 show antiferromagnetic transitions at 2.4, 2.2, and 2.4 K, respectively, and NaNdO 2 transforms to the ferromagnetic state below 2.4 K. NaSmO 2, NaErO 2, and NaYbO 2 exhibit a magnetic anomaly below 1.8 K.

  2. Systems Ln-Fe-O ( Ln=Eu, Gd): thermodynamic properties of ternary oxides using solid-state electrochemical cells

    NASA Astrophysics Data System (ADS)

    Parida, S. C.; Rakshit, S. K.; Dash, S.; Singh, Ziley; Prasad, R.; Venugopal, V.

    2003-05-01

    The standard molar Gibbs energies of formation of LnFeO 3(s) and Ln3Fe 5O 12(s) where Ln=Eu and Gd have been determined using solid-state electrochemical technique employing different solid electrolytes. The reversible e.m.f.s of the following solid-state electrochemical cells have been measured in the temperature range from 1050 to 1255 K. Cell (I): (-)Pt / { LnFeO 3(s)+ Ln2O 3(s)+Fe(s)} // YDT/CSZ // {Fe(s)+Fe 0.95O(s)} / Pt(+); Cell (II): (-)Pt/{Fe(s)+Fe 0.95O(s)}//CSZ//{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}/Pt(+); Cell (III): (-)Pt/{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}//YSZ//{Ni(s)+NiO(s)}/Pt(+); and Cell(IV):(-)Pt/{Fe(s)+Fe 0.95O(s)}//YDT/CSZ//{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}/Pt(+). The oxygen chemical potentials corresponding to the three-phase equilibria involving the ternary oxides have been computed from the e.m.f. data. The standard Gibbs energies of formation of solid EuFeO 3, Eu 3Fe 5O 12, GdFeO 3 and Gd 3Fe 5O 12 calculated by the least-squares regression analysis of the data obtained in the present study are given by Δ fG°m(EuFeO 3, s) /kJ mol -1 (± 3.2)=-1265.5+0.2687( T/K) (1050 ⩽ T/K ⩽ 1570), Δ fG°m(Eu 3Fe 5O 12, s)/kJ mol -1 (± 3.5)=-4626.2+1.0474( T/K) (1050 ⩽ T/K ⩽ 1255), Δ fG°m(GdFeO 3, s) /kJ mol -1 (± 3.2)=-1342.5+0.2539( T/K) (1050 ⩽ T/K ⩽ 1570), and Δ fG°m(Gd 3Fe 5O 12, s)/kJ·mol -1 (± 3.5)=-4856.0+1.0021( T/K) (1050 ⩽ T/K ⩽ 1255). The uncertainty estimates for Δ fG°m include the standard deviation in the e.m.f. and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagrams for the systems Eu-Fe-O and Gd-Fe-O and chemical potential diagrams for the system Gd-Fe-O were computed at 1250 K.

  3. Exploring the effect of the Ln(III)/Ln(II) redox potential on C-F activation and on oxidation of some lanthanoid organoamides.

    PubMed

    Deacon, Glen B; Junk, Peter C; Kelly, Rory P; Wang, Jun

    2016-01-28

    The divalent europium complexes, and (L(Me/Et) = p-HC6F4N(CH2)2NMe2/Et2), have been prepared from redox-transmetallation/protolysis (RTP) reactions between Eu metal, Hg(C6F5)2 and L(Me/Et)H in thf. The complexes exhibit close (C)F-Ln interactions and the amide ligands feature tridentate N,N',F chelation. The complexes are thermally robust but on exposure to light they undergo C-F activation. From exposure of to light, the Eu(III) mixed fluoride/oxide cluster, was isolated, but other well-defined C-F activation products have proven elusive due to the stability of Eu(II). Oxidation of [Ln(L(R))2(thf)2] (Ln = Eu, R = Me; Ln = Yb, R = Et) with I2 afforded the heteroleptic iodo complexes, [Ln(L(R))2I(thf)n] (Ln = Eu, n = 1; Ln = Yb, n = 0), and the homoleptic complexes, [Ln(L(R))3]. The formation of the iodo complexes and the heteroleptic complexes appear to occur by different routes. shows interesting structural differences from reported [Ln(L(Et))3] (Ln = La, Ce, Nd) complexes, and highlights an incomplete shift towards N,N' chelation to the much smaller Yb ion. was prepared from a protolysis reaction between [Sm(CH2C6H4-NMe2-o)3] and L(Me)H. Heating a solution of in toluene at 110 °C for three days did not afford any samarium fluoride complex. An RTP reaction with Sm afforded the heteroleptic samarium complex, , in very low yield. From an attempted protolysis reaction between [Sm(DippForm)2(thf)2] and L(Me)H, the mixed ligand samarium fluoride complex, , was isolated. Overall, the instability of Sm(II) precludes control over the C-F activation reactions.

  4. Exploring the effect of the Ln(III)/Ln(II) redox potential on C-F activation and on oxidation of some lanthanoid organoamides.

    PubMed

    Deacon, Glen B; Junk, Peter C; Kelly, Rory P; Wang, Jun

    2016-01-28

    The divalent europium complexes, and (L(Me/Et) = p-HC6F4N(CH2)2NMe2/Et2), have been prepared from redox-transmetallation/protolysis (RTP) reactions between Eu metal, Hg(C6F5)2 and L(Me/Et)H in thf. The complexes exhibit close (C)F-Ln interactions and the amide ligands feature tridentate N,N',F chelation. The complexes are thermally robust but on exposure to light they undergo C-F activation. From exposure of to light, the Eu(III) mixed fluoride/oxide cluster, was isolated, but other well-defined C-F activation products have proven elusive due to the stability of Eu(II). Oxidation of [Ln(L(R))2(thf)2] (Ln = Eu, R = Me; Ln = Yb, R = Et) with I2 afforded the heteroleptic iodo complexes, [Ln(L(R))2I(thf)n] (Ln = Eu, n = 1; Ln = Yb, n = 0), and the homoleptic complexes, [Ln(L(R))3]. The formation of the iodo complexes and the heteroleptic complexes appear to occur by different routes. shows interesting structural differences from reported [Ln(L(Et))3] (Ln = La, Ce, Nd) complexes, and highlights an incomplete shift towards N,N' chelation to the much smaller Yb ion. was prepared from a protolysis reaction between [Sm(CH2C6H4-NMe2-o)3] and L(Me)H. Heating a solution of in toluene at 110 °C for three days did not afford any samarium fluoride complex. An RTP reaction with Sm afforded the heteroleptic samarium complex, , in very low yield. From an attempted protolysis reaction between [Sm(DippForm)2(thf)2] and L(Me)H, the mixed ligand samarium fluoride complex, , was isolated. Overall, the instability of Sm(II) precludes control over the C-F activation reactions. PMID:26673146

  5. Structures and magnetic properties of new fluorite-related quaternary rare earth oxides LnY2TaO7 and LaLn2RuO7 (Ln=rare earths)

    NASA Astrophysics Data System (ADS)

    Hinatsu, Yukio; Doi, Yoshihiro

    2016-01-01

    New fluorite-related quaternary rare earth oxides LnY2TaO7 (Ln=La-Dy) and LaLn2RuO7 (Ln=Eu-Tb) have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space groups C2221 and Cmcm, respectively. The results of the Rietveld analysis for LnY2TaO7 (Ln=La-Dy) indicate that there exists no structural ordering of the Ln and Y ions at the eight-coordinate 4b site and the seven-coordinate 8c site, but the larger Ln ions occupy the eight-coordinate 4b site rather than the seven-coordinate 8c site, with increasing the Ln ionic radius. On the other hand, the results of the Rietveld analysis for the X-ray diffraction profiles of LaTb2RuO7 showed that La and Tb atoms are almost situated at the eight-coordinated site (4a site) and seven-coordinated site (8g site), respectively, i.e., cation ordering occurs on the 4a and 8g sites. All compounds LnY2TaO7 (Ln=La-Dy) are paramagnetic down to 1.8 K. On the other hand, LaTb2RuO7 shows an antiferromagnetic transition at 17 K. In addition, another magnetic anomaly has been found at 10 K. Analysis of the magnetic specific heat for LaTb2RuO7 indicates that the magnetic transitions at 10 and 17 K are due to the magnetic ordering of Tb3+ and Ru5+ ions, respectively.

  6. Magnetic interactions in new fluorite-related rare earth oxides LnLn'2RuO7 (Ln, Ln'=rare earths)

    NASA Astrophysics Data System (ADS)

    Hinatsu, Yukio; Doi, Yoshihiro

    2016-07-01

    New fluorite-related quaternary rare earth oxides Pr2YRuO7 and La2TbRuO7 have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Through magnetic susceptibility and specific heat measurements, Pr2YRuO7 shows an antiferromagnetic transition at 27 K, which is considerably lowered compared with that for Pr3RuO7. Analysis of the magnetic specific heat indicates that the magnetic behavior observed at 27 K for Pr2YRuO7 is predominantly due to the magnetic interactions between Ru ions, and that the interactions between the Pr3+ and Ru5+ ions are also important. La2TbRuO7 shows magnetic ordering at 9.0 K, which is ascribed to the magnetic ordering between Ru5+ ions from the analysis of the magnetic specific heat data.

  7. Synthesis of the new layered oxides NaRbLnMO{sub 5} (Ln = La, Nd, Sm, Eu, Gd; M = Nb, Ta)

    SciTech Connect

    Cavazos, Ronaldo J.; Schak, Raymond E

    2004-07-02

    The new layered transition metal oxides NaRbLnMO{sub 5} (Ln = Nd, Sm, Eu, Gd; M = Nb, Ta) were synthesized by direct solid-state reaction. NaRbLaNbO{sub 5} crystallizes with a tetragonal unit cell [a=5.839(6) A, c=8.313(1) A] analogous to that of the related compound NaKLaNbO{sub 5}, while NaRbLaTaO{sub 5} indexes to a larger monoclinic unit cell [a=9.577(2) A, b=5.834(1) A, c=8.323(2) A, {beta}=93.00(2)]. NaRbLnNbO{sub 5} can be prepared for Ln = Nd, Sm, Eu, Gd, and NaRbLnTaO{sub 5} can be prepared for Ln = Nd, Sm. Both series of compounds show the expected decrease in unit cell volume as the size of the lanthanide decreases. NaRbLaNbO{sub 5} is also amenable to ion exchange, forming Li{sub 2-x}Rb{sub x}LaNbO{sub 5} upon reaction with molten lithium nitrate.

  8. Characterization and evaluation of double perovskites LnBaCoFeO5+δ (Ln = Pr and Nd) as intermediate-temperature solid oxide fuel cell cathodes

    NASA Astrophysics Data System (ADS)

    Jin, Fangjun; Xu, Huawei; Long, Wen; Shen, Yu; He, Tianmin

    2013-12-01

    Double perovskites LnBaCoFeO5+δ (Ln = Pr and Nd, PBCF and NBCF) are comparatively investigated as potential cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). LnBaCoFeO5+δ materials are chemically compatible with La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) electrolyte at temperatures below 1000 °C. Fe and Co ions in LnBaCoFeO5+δ exist in two oxidation states, 3+ and 4+. Pr ions are found in PBCF mostly as Pr3+. Thermal expansion coefficients (TECs) of PBCF and NBCF are 21.0 × 10-6 and 19.5 × 10-6 K-1, respectively, between 30 and 1000 °C; these are lower than the TECs of undoped LnBaCo2O5+δ. The best electrical conductivity for both materials is observed near 350 °C: 321 and 172 S cm-1 for PBCF and NBCF, respectively. Polarization resistances of PBCF and NBCF cathodes on LSGM electrolyte are 0.049 and 0.062 Ω cm2 at 800 °C, respectively. Maximum power densities of the single-cell with Ni/SDC as anode on a 0.3 mm-thick LSGM electrolyte reach 749 and 669 mW cm-2 for PBCF and NBCF cathodes at 800 °C, respectively. As cathodes for application in IT-SOFCs, the performance of PBCF and NBCF double perovskites is promising.

  9. Synthesis and characterization of ultrafine Ln{sub 2}Ti{sub 2}O{sub 7} (Ln = Sm, Gd, Dy, Er) pyrochlore oxides by stearic acid method

    SciTech Connect

    Zhang Weiguang; Zhang Lili; Zhong Hui; Lu Lude; Yang Xujie; Wang Xin

    2010-02-15

    Stearic acid method (SAM) was developed to synthesize series of pyrochlore Ln{sub 2}Ti{sub 2}O{sub 7} (Ln = Sm, Gd, Dy, Er) nanocrystals. The synthesis process was monitored by X-ray diffraction, Thermal-gravimetric-differential thermal analysis and Fourier Transform InfraRed methods. Comparing with traditional solid-state reaction (SSR), Ln{sub 2}Ti{sub 2}O{sub 7} can be synthesized at relatively low temperature (700-800 deg. C) with shortened reaction time (2-4 h). The average particle size of Ln{sub 2}Ti{sub 2}O{sub 7} was greatly reduced (ca. 40 nm) and the BET surface area was increased (ca. 12 m{sup 2}/g) by using SAM. From the X-ray diffraction patterns, we found that Ln has an effect on the crystal structure of Ln{sub 2}Ti{sub 2}O{sub 7}, every lattice peak shifted to larger angle slightly with the increasing atomic number of Ln. Also, the lattice constant of Ln{sub 2}Ti{sub 2}O{sub 7} was calculated by Jade.5 and found it decreased along with the decrease of ionic radius of Ln{sup 3+}. The morphology of obtained Ln{sub 2}Ti{sub 2}O{sub 7} was determined by transmission electron microscopy technique. Results showed that the obtained Ln{sub 2}Ti{sub 2}O{sub 7} were all square-like and the interplanar distance of Ln{sub 2}Ti{sub 2}O{sub 7} (Ln = Sm, Gd, Dy, Er) according to (111) plane was 0.65, 0.64, 0.63, and 0.62 nm respectively, which was measured from High Resolution Transmission Electron Microscopy images. Possible reason for this phenomenon was presented.

  10. Magnetic and transport properties of some Ln-Ba-Cu-O (Ln=Yb, Tm, Sm) superconducting oxides

    NASA Astrophysics Data System (ADS)

    Marcus, J.; Escribe-Filippini, C.; Schlenker, C.; Buder, R.; Devenyi, J.; Reydet, P. L.

    1987-07-01

    Powders of Yb-Ba-Cu-O, Tm-Ba-Cu-O and Sm-Ba-Cu-O have been synthetized. Electrical resistivity and magnetic susceptibility measurements show that they are superconducting with onset transition temperatures in the range 91 K - 85 K. The thermopower, in these oxides as well as in Sr xLa 2-xCuO 4-δ and Ba 2YCu 3O 7-δ, is found to be positive between T c and 300 K. Hysteresis of the diamagnetic magnetization is also reported.

  11. Structural and magnetic properties of the quaternary oxides Ba{sub 6}Ln{sub 2}Fe{sub 4}O{sub 15} (Ln=Pr and Nd)

    SciTech Connect

    Abe, Kyosuke; Doi, Yoshihiro Hinatsu, Yukio; Ohoyama, Kenji

    2009-02-15

    The crystal structures and magnetic properties of the quaternary lanthanide oxides Ba{sub 6}Ln{sub 2}Fe{sub 4}O{sub 15} (Ln=Pr and Nd) are reported. They crystallize in a hexagonal structure with space group P6{sub 3}mc and have the 'Fe{sub 4}O{sub 15} cluster' consisting of one FeO{sub 6} octahedron and three FeO{sub 4} tetrahedra. Measurements of the magnetic susceptibility, specific heat, and powder neutron diffraction reveal that this cluster behaves as a spin tetramer with a ferrimagnetic ground state of S{sub T}=5 even at room temperature. The cluster moments show a long-range antiferromagnetic ordering at 23.2 K (Ln=Pr) and 17.8 K (Nd), and the magnetic moments of the Ln{sup 3+} ions also order cooperatively. By applying the magnetic field ({approx}2 T), this antiferromagnetic ordering of the clusters changes to a ferromagnetic one. This result indicates that there exists a competition in the magnetic interaction between the clusters. - Graphical abstract: Quaternary oxides Ba{sub 6}Ln{sub 2}Fe{sub 4}O{sub 15} (Ln=Pr and Nd) have the Ba{sub 6}Nd{sub 2}Al{sub 4}O{sub 15}-type structure with space group P6{sub 3}mc. In them, the magnetic moments for the ferrimagnetic Fe{sub 4}O{sub 15} cluster (smaller circles: Fe{sup 3+} ions) and Ln{sup 3+} ions (larger ones) cooperatively show an antiferromagnetic ordering at low temperatures.

  12. Multiband orange-red photoluminescence of Eu{sup 3+} ions in new '114' LnBaZn{sub 3}GaO{sub 7} and LnBaZn{sub 3}AlO{sub 7} oxides

    SciTech Connect

    Saradhi, M.P.; Raveau, B.; Caignaert, V.; Varadaraju, U.V.

    2010-02-15

    A new series of gallozincates LnBaZn{sub 3}GaO{sub 7} (Ln=La, Nd, Sm, Eu, Gd, Dy, Y) and new aluminozincates LnBaZn{sub 3}AlO{sub 7} (Ln=Y, Eu, Dy) have been synthesized. Their structure refinements show that these phases belong to the '114' series, with hexagonal P6{sub 3}mc space group previously described for SmBaZn{sub 3}AlO{sub 7}. The photoluminescence study of these oxides shows that the Eu{sup 3+} activated LnBaZn{sub 3}MO{sub 7} oxides with Ln=Y, La, Gd; and M=Al, Ga exhibit strong magnetic and electric dipole transitions (multiband emission) which is of interest for white light production. These results also confirm that the site occupied by Eu{sup 3+} is not strictly centrosymmetric. The electric dipole transition intensity is the highest in GdBaZn{sub 3}MO{sub 7} [M=Al, Ga]: 0.05Eu{sup 3+} as compared with other Eu{sup 3+} activated compositions. This is due to the layer distortion around GdO{sub 6} octahedra when compared with YO{sub 6} and LaO{sub 6} octahedra. - Graphical abstract: The projected structure consists of alternate stacked layers of Kagome and Triangular type with statistical distribution of Zn and Ga atoms between two tetrahedral sites. Ba{sup 2+} present in anticuboctahedron coordinating with 12 oxygen atoms. The Eu{sup 3+} present in octahedral coordination with 3-fold rotational symmetry.

  13. Magnetic and electrical properties of quadruple perovskites with 12 layer structures Ba{sub 4}LnM{sub 3}O{sub 12} (Ln=rare earths; M=Ru, Ir): The role of metal-metal bonding in perovskite-related oxides

    SciTech Connect

    Shimoda, Yuki; Doi, Yoshihiro; Wakeshima, Makoto; Hinatsu, Yukio

    2010-09-15

    Structures and magnetic and electrical properties of quadruple perovskites containing rare earths Ba{sub 4}LnM{sub 3}O{sub 12} (Ln=rare earths; M=Ru, Ir) were investigated. They crystallize in the 12L-perovskite-type structure. Three MO{sub 6} octahedra are connected to each other by face-sharing and form a M{sub 3}O{sub 12} trimer. The M{sub 3}O{sub 12} trimers and LnO{sub 6} octahedra are alternately linked by corner-sharing, forming the perovskite-type structure with 12 layers. For Ln=Ce, Pr, and Tb, both the Ln and M ions are in the tetravalent state (Ba{sub 4}Ln{sup 4+}M{sup 4+}{sub 3}O{sub 12}), and for other Ln ions, Ln ions are in the trivalent state and the mean oxidation state of M ions is +4.33 (Ba{sub 4}Ln{sup 3+}M{sup 4.33+}{sub 3}O{sub 12}). All the Ba{sub 4}Ln{sup 3+}Ru{sup 4.33+}{sub 3}O{sub 12} compounds show magnetic ordering at low temperatures, while any of the corresponding iridium-containing compounds Ba{sub 4}Ln{sup 3+}Ir{sup 4.33+}{sub 3}O{sub 12} is paramagnetic down to 1.8 K. Ba{sub 4}Ce{sup 4+}Ir{sup 4+}{sub 3}O{sub 12} orders antiferromagnetically at 10.5 K, while the corresponding ruthenium-containing compound Ba{sub 4}Ce{sup 4+}Ru{sup 4+}{sub 3}O{sub 12} is paramagnetic. These magnetic results were well understood by the magnetic behavior of M{sub 3}O{sub 12}. The effective magnetic moments and the entropy change for the magnetic ordering show that the trimers Ru{sup 4.33+}{sub 3}O{sub 12} and Ir{sup 4+}{sub 3}O{sub 12} have the S=1/2 ground state, and in other cases there is no magnetic contribution from the trimers Ru{sup 4+}{sub 3}O{sub 12} or Ir{sup 4.33+}{sub 3}O{sub 12}. Measurements of the electrical resistivity of Ba{sub 4}LnM{sub 3}O{sub 12} and its analysis show that these compounds demonstrate two-dimensional Mott-variable range hopping behavior. - Graphical abstract: Structures and magnetic and electrical properties of quadruple perovskites containing rare earths Ba{sub 4}LnM{sub 3}O{sub 12} (Ln=rare earths; M = Ru, Ir

  14. Structural, thermal and electrical conductivity characteristics of Ln0.5Sr0.5Ti0.5Mn0.5O3±d (Ln: La, Nd and Sm) complex perovskites as anode materials for solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Jeong, Jihoon; Azad, Abul K.; Schlegl, Harald; Kim, Byungjun; Baek, Seung-Wook; Kim, Keunsoo; Kang, Hyunil; Kim, Jung Hyun

    2015-03-01

    The Ti and Mn replaced complex perovskites, Ln0.5Sr0.5Ti0.5Mn0.5O3±d (Ln: La, Nd and Sm), were reported as potential anode materials for high temperature-operating solid oxide fuel cells (HT-SOFCs). For the present research study, synthesis, crystallographic, thermal and electrical conductivity properties of Ln0.5Sr0.5Ti0.5Mn0.5O3±d complex perovskites were investigated using X-ray diffraction (XRD), Rietveld method, thermogravimetric analysis (TGA) and electrical conductivity to apply these oxide materials for the HT-SOFC anode materials. XRD results showed that Ln0.5Sr0.5Ti0.5Mn0.5O3±d oxide systems synthesized as single phases did not react with 8 mol% yttria stabilized zirconia (8YSZ) and 10 mol% Gd-doped cerium oxide (CGO91) up to 1500 °C and did not decompose under dry 3.9% hydrogen at 850 °C. The crystal structures of La0.5Sr0.5Ti0.5Mn0.5O3±d (LSTM), Nd0.5Sr0.5Ti0.5Mn0.5O3±d (NSTM) and Sm0.5Sr0.5Ti0.5Mn0.5O3±d (SSTM) showed orthorhombic symmetry with the space group Pbnm and SSTM showed a more distorted structure. Thermogravimetric analysis (TGA) proved weight gains in these three sample occurred under oxidizing conditions and weight loss under reducing conditions. Electrical conductivity values of NSTM were higher than those of LSTM and SSTM under oxidizing and reducing conditions.

  15. A method for the estimation of the enthalpy of formation of mixed oxides in Al{sub 2}O{sub 3}-Ln{sub 2}O{sub 3} systems

    SciTech Connect

    Vonka, P.; Leitner, J.

    2009-04-15

    A new method is proposed for the estimation of the enthalpy of formation (DELTA{sub ox}H) of various Al{sub 2}O{sub 3}-Ln{sub 2}O{sub 3} mixed oxides from the constituent binary oxides. Our method is based on Pauling's concept of electronegativity and, in particular, on the relation between the enthalpy of formation of a binary oxide and the difference between the electronegativities of the oxide-forming element and oxygen. This relation is extended to mixed oxides with a simple formula given for the calculation of DELTA{sub ox}H. The parameters of this equation were fitted using published experimental values of DELTA{sub ox}H derived from high-temperature oxide melt solution calorimetry. Using our proposed method, we obtained a standard deviation (sigma) of 4.87 kJ mol{sup -1} for this data set. Taking into account regularities within the lanthanide series, we then estimated the DELTA{sub ox}H values for Al{sub 2}O{sub 3}-Ln{sub 2}O{sub 3} mixed oxides. The values estimated using our method were compared with those obtained by Aronson's and Zhuang's empirical methods, both of which give significantly poorer results. - Graphical abstract: Enthalpy of formation of Ln-Al-O oxides from the constituent binary ones.

  16. Systematic evaluation of cobalt-free Ln0.5Sr0·5Fe0·8Cu0·2O3-δ (Ln = La, Pr, and Nd) as cathode materials for intermediate-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Pang, Shengli; Wang, Wenzhi; Chen, Tao; Shen, Xiangqian; Wang, Yonggang; Xu, Kaijie; Xi, Xiaoming

    2016-09-01

    Cobalt-free perovskites, Ln0.5Sr0·5Fe0·8Cu0·2O3-δ (Ln = La, Pr, and Nd), are systematically evaluated as the cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs) using Gd0.1Ce0·9O1.95 as the electrolyte. The samples exhibit an orthorhombic perovskite structures, and their cell volumes decrease as the ionic radius of Ln decreases. Both the oxygen vacancy content and the magnitude of lattice oxygen release per formula unit increase in the temperature range from 370 °C to 850 °C as the ionic radius of Ln decreases. Ln0.5Sr0.5Fe0.8Cu0.2O3-δ is chemically and thermally compatible with the Gd0.1Ce0·9O1.95 electrolyte. In the temperature range of 600 °C-750 °C, Nd0.5Sr0·5Fe0·8Cu0·2O3-δ possesses the highest catalytic activity for the oxygen reduction reaction with area specific resistance values of 0.071 Ω cm2 and 0.141 Ω cm2 at 750 °C and 700 °C, respectively. The maximum power densities of the anode-supported single cells at 800 °C and 700 °C are 1003.7 mW cm-2 and 516.7 mW cm-2 for Pr0.5Sr0·5Fe0·8Cu0·2O3-δ and 944.5 mW cm-2 and 530.2 mW cm-2 for Nd0.5Sr0·5Fe0·8Cu0·2O3-δ, respectively. Ln0.5Sr0.5Fe0.8Cu0.2O3-δ is shown to be a promising cathode material for IT-SOFCs.

  17. Structural, thermal and electrical conductivity characteristics of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm) complex perovskites as anode materials for solid oxide fuel cell

    SciTech Connect

    Jeong, Jihoon; Azad, Abul K.; Schlegl, Harald; Kim, Byungjun; Baek, Seung-Wook; Kim, Keunsoo; Kang, Hyunil; Kim, Jung Hyun

    2015-03-15

    The Ti and Mn replaced complex perovskites, Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm), were reported as potential anode materials for high temperature-operating solid oxide fuel cells (HT-SOFCs). For the present research study, synthesis, crystallographic, thermal and electrical conductivity properties of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} complex perovskites were investigated using X-ray diffraction (XRD), Rietveld method, thermogravimetric analysis (TGA) and electrical conductivity to apply these oxide materials for the HT-SOFC anode materials. XRD results showed that Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} oxide systems synthesized as single phases did not react with 8 mol% yttria stabilized zirconia (8YSZ) and 10 mol% Gd-doped cerium oxide (CGO91) up to 1500 °C and did not decompose under dry 3.9% hydrogen at 850 °C. The crystal structures of La{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (LSTM), Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (NSTM) and Sm{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (SSTM) showed orthorhombic symmetry with the space group Pbnm and SSTM showed a more distorted structure. Thermogravimetric analysis (TGA) proved weight gains in these three sample occurred under oxidizing conditions and weight loss under reducing conditions. Electrical conductivity values of NSTM were higher than those of LSTM and SSTM under oxidizing and reducing conditions. - Graphical abstract: The B-site cations (Ti/Mn) are surrounded by regular octahedra of oxygen in Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d}(NSTM). These octahedra are linked together in a corner sharing three dimensional framework, while Nd/Sr ion occupies 12-coordinated A-site between these octahedra. The Ti/Mn–O{sub 6} octahedra are elongated along the c-axis. The crystal structure distortion was due to the smaller ionic radius of the A-site cations, which force the (Ti

  18. Solvothermal syntheses, crystal structures, and properties of lanthanide(III) thioarsenates [Ln(dien)2(μ-1κ,2κ2-AsS4)]n (Ln==Sm, Eu, Gd) and [Ln(dien)2(1κ2-AsS4)] (Ln==Tb, Dy, Ho)

    NASA Astrophysics Data System (ADS)

    Wang, Fang; Tang, Chunying; Chen, Ruihong; Zhang, Yong; Jia, Dingxian

    2013-10-01

    Solvothermal reactions of Ln2O3, As and S in diethylenetriamine (dien) at 170 °C for 6 days afforded two structural types of lanthanide thioarsenates with the general formulae [Ln(dien)2(μ-1κ,2κ2-AsS4)]n [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien)2(1κ2-AsS4)] [Ln=Tb(4), Dy(5), Ho(6)]. The Ln2O3 oxides were converted to [Ln(dien)2]3+ complex units in the solvothermal reactions. The As atom binds four S atoms, forming a tetrahedral AsS4 unit. In 1-3, the AsS4 units interconnect the [Ln(dien)2]3+ cations via Ln-S bonds as tridentate μ-1κ,2κ2-AsS4 bridging ligands, resulting in the neutral coordination polymers [Ln(dien)2(μ-1κ,2κ2-AsS4)]n (Ln1). In 4-6, the AsS4 units coordinate with the Ln3+ ion of [Ln(dien)2]3+ as 1κ2-AsS4 chelating ligands to form neutral coordination compounds [Ln(dien)2(1κ2-AsS4)] (Ln2). The Ln3+ ions are in nine- and eight-coordinated environments in Ln1 and Ln2, respectively. The formation of Ln1 and Ln2 is related with ionic size of the Ln3+ ions. Optical absorption spectra showed that 1-6 have potential use as semiconductors with the band gaps in the range 2.18-3.21 eV.

  19. Interplay between 3d-3d and 3d-4f interactions at the origin of the magnetic ordering in the Ba2LnFeO5 oxides

    NASA Astrophysics Data System (ADS)

    Kundu, Asish K.; Hardy, Vincent; Caignaert, Vincent; Raveau, Bernard

    2015-12-01

    A new family of oxides in which 3d-3d and 3d-4f interactions are of comparable strength has been synthesized and characterized both from structural and physical viewpoints. These compounds of formulation Ba2LnFeO5 (Ln  =  Sm, Eu, Gd, Dy, Ho, Er, Yb) are isotypic to the perovskite derivative Ba2YFeO5. They exhibit an original structure consisting of isolated FeO4 tetrahedra linked via LnO6 (or YO6) octahedra. Magnetic and calorimetric measurements show that all these compounds exhibit a unique, antiferromagnetic transition involving both the 3d and 4f ions. The antiferromagnetic properties of the Ln  =  Y phase (non-magnetic Y3+) and of the Ln  =  Eu (non-magnetic ground state multiplet of Eu3+) are ascribed to super-super exchange Fe-O-O-Fe interactions, leading to the lowest T N (5.5 K for Y and 4.6 K for Eu). The introduction of a magnetic lanthanide, i.e. Ln  =  Sm, Gd, Dy, Ho, Er, Yb, in the octahedral sites, leads to larger T N values (up to 9.8 K for Ln  =  Yb). It is found that several mechanisms must be taken into account to explain the complex evolution of the magnetic properties along the Ba2LnFeO5 series. In particular, the super-exchange Ln-O-Fe, as well as the on-site Ln3+ magnetocrystalline anisotropy, are suggested to play crucial roles. This Ba2LnFeO5 series offers a rare opportunity to investigate experimentally a situation where the 3d-3d and 3d-4f interactions co-operate on an equal footing to trigger a unique long-range magnetic ordering in insulating oxides.

  20. Structural and optical properties of lanthanide oxides grown by atomic layer deposition (Ln = Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb).

    PubMed

    Hansen, Per-Anders; Fjellvåg, Helmer; Finstad, Terje; Nilsen, Ola

    2013-08-14

    Ln2O3 thin films with optically active f-electrons (Ln = Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb) have been grown on Si(100) and soda lime glass substrates by atomic layer deposition (ALD) using Ln(thd)3 (Hthd = 2,2,6,6-tetramethyl-3,5-heptanedione) and ozone as precursors. The temperature range for depositions was 200-400 °C. Growth rates were measured by spectroscopic ellipsometry and a region with a constant growth rate (ALD window) was found for Ln = Ho and Tm. All the compounds are grown as amorphous films at low temperatures, whereas crystalline films (cubic C-Ln2O3) are obtained above a certain temperature ranging from 300 to 250 °C for Nd2O3 to Yb2O3, respectively. AFM studies show that the films were smooth (rms < 1 nm) except for depositions at the highest temperatures. The refractive index was measured by spectroscopic ellipsometry and was found to depend on the deposition temperature. Optical absorption measurements show that the absorption from the f-f transitions depends strongly on the crystallinity of the material. The clear correlation between the degree of crystallinity, optical absorptions and refractive indices is discussed.

  1. Magnetic properties of EuLn{sub 2}O{sub 4} (Ln=rare earths)

    SciTech Connect

    Hirose, Keiichi; Doi, Yoshihiro; Hinatsu, Yukio

    2009-07-15

    Ternary rare earth oxides EuLn{sub 2}O{sub 4} (Ln=Gd, Dy-Lu) were prepared. They crystallized in an orthorhombic CaFe{sub 2}O{sub 4}-type structure with space group Pnma. {sup 151}Eu Moessbauer spectroscopic measurements show that the Eu ions are in the divalent state. All these compounds show an antiferromagnetic transition at 4.2-6.3 K. From the positive Weiss constant and the saturation of magnetization for EuLu{sub 2}O{sub 4}, it is considered that ferromagnetic chains of Eu{sup 2+} are aligned along the b-axis of the orthorhombic unit cell, with neighboring Eu{sup 2+} chains antiparallel. When Ln=Gd-Tm, ferromagnetically aligned Eu{sup 2+} ions interact with the Ln{sup 3+} ions, which would overcome the magnetic frustration of triangularly aligned Ln{sup 3+} ions and the EuLn{sub 2}O{sub 4} compounds show a simple antiferromagnetic behavior. - Graphical abstract: Ternary rare earth oxides EuLn{sub 2}O{sub 4} (Ln=Gd, Dy-Lu) crystallized in an orthorhombic CaFe{sub 2}O{sub 4}-type structure with space group Pnma. Moessbauer spectroscopic measurements show that the Eu ions are in the divalent state. All these compounds show an antiferromagnetic transition at 4.2-6.3 K. It is considered that ferromagnetic chains of Eu{sup 2+} are aligned along the b-axis of the orthorhombic unit cell, with neighboring Eu{sup 2+} chains antiparallel.

  2. The gas-sensing of LnMO{sub 3}/ZnO(Ln=rare earth, M=transition metal) having a heterojunction

    SciTech Connect

    Mochinaga, Ryoichi; Takemoto, Ikuko; Arakawa, T.

    1996-12-31

    There are many studies of gas sensor elements using semiconductive oxides. The authors reported the I-V characteristics and sensing properties of LnMO{sub 3}/SnO{sub 2} (Ln=rare earth, M=transition metal) which was prepared by mechanically contacting two sintered pellets in an attempt to obtain a new type of gas sensor element. In this paper, the authors report the gas-sensing of LnMO{sub 3}/ZnO.

  3. Solvothermal syntheses, crystal structures, and properties of lanthanide(III) thioarsenates [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} (Ln==Sm, Eu, Gd) and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] (Ln==Tb, Dy, Ho)

    SciTech Connect

    Wang, Fang; Tang, Chunying; Chen, Ruihong; Zhang, Yong; Jia, Dingxian

    2013-10-15

    Solvothermal reactions of Ln{sub 2}O{sub 3}, As and S in diethylenetriamine (dien) at 170 °C for 6 days afforded two structural types of lanthanide thioarsenates with the general formulae [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] [Ln=Tb(4), Dy(5), Ho(6)]. The Ln{sub 2}O{sub 3} oxides were converted to [Ln(dien){sub 2}]{sup 3+} complex units in the solvothermal reactions. The As atom binds four S atoms, forming a tetrahedral AsS{sub 4} unit. In 1−3, the AsS{sub 4} units interconnect the [Ln(dien){sub 2}]{sup 3+} cations via Ln−S bonds as tridentate μ-1κ,2κ{sup 2}-AsS{sub 4} bridging ligands, resulting in the neutral coordination polymers [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} (Ln1). In 4−6, the AsS{sub 4} units coordinate with the Ln{sup 3+} ion of [Ln(dien){sub 2}]{sup 3+} as 1κ{sup 2}-AsS{sub 4} chelating ligands to form neutral coordination compounds [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] (Ln2). The Ln{sup 3+} ions are in nine- and eight-coordinated environments in Ln1 and Ln2, respectively. The formation of Ln1 and Ln2 is related with ionic size of the Ln{sup 3+} ions. Optical absorption spectra showed that 1−6 have potential use as semiconductors with the band gaps in the range 2.18−3.21 eV. - Graphical abstract: Two types of Ln-thioarsenates [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] were prepared by solvothermal methods and the soft Lewis basic AsS{sub 4}{sup 3–} ligand to Ln(III) centers with polyamine co-ligand was obtained. Display Omitted - Highlights: • Lanthanide thioarsenates were prepared by solvothermal methods. • The soft Lewis basic AsS{sub 4} ligand coordinate Ln{sup 3+} ions with coexistence polyamine ligands. • Two structural types of Ln-thioarsenates with structural turnover at Tb were obtained along Ln series. • The Ln-thioarsenates are potential semiconductors

  4. A determination of the oxygen non-stoichiometry of the oxygen storage materials LnBaMn2O5+δ (Ln=Gd, Pr)

    NASA Astrophysics Data System (ADS)

    Jeamjumnunja, Kannika; Gong, Wenquan; Makarenko, Tatyana; Jacobson, Allan J.

    2016-07-01

    The A-site ordered double-perovskite oxides, LnBaMn2O5+δ (Ln=Gd, Pr), were synthesized and investigated to understand the effect of A site cation substitution on the oxygen storage properties of these materials. The present results are compared with our previous data for YBaMn2O5+δ. The results clearly reveal that changing the Ln cation strongly influences the oxidation/reduction behavior of LnBaMn2O5+δ. Based on thermogravimetric analysis data, oxygen uptake begins at lower temperatures in both air and oxygen in compounds with Ln3+ ions larger than Y3+. These oxides exhibit almost complete and reversible oxygen uptake/release between fully-reduced LnBaMn2O5 and fully-oxidized LnBaMn2O6 during changes of the oxygen partial pressure between air and 1.99% H2/Ar. In addition, the oxygen non-stoichiometries of GdBaMn2O5+δ and PrBaMn2O5+δ were determined as a function of pO2 at 600, 650, 700 and 750 °C by Coulometric titration at near-equilibrium conditions. The results confirm that these materials have two distinct phases on oxidation/reduction with δ≈0, 0.5 and a third phase with a range of composition with an oxygen content (5+δ) approaching ~6. The stabilities of the LnBaMn2O5+δ phases extend over a wide range of oxygen partial pressures (∼10-25≤pO2 (atm)≤∼1) depending on temperature. Isothermal experiments show that the larger the Ln3+ cation the lower pO2 for phase conversion. At some temperatures and pO2 conditions, the LnBaMn2O5+δ compounds are unstable with respect to decomposition to BaMnO3-δ and LnMnO3. This instability is more apparent in Coulometric titration experiments than in thermogravimetric analysis. The Coulometric titration experiments are necessarily slow in order to achieve equilibrium oxygen compositions.

  5. Synthesis and characterization of charge-substituted garnets YCaLnGa{sub 5}O{sub 12} (Ln = Ce,Pr,Tb)

    SciTech Connect

    Gramsch, S.A. |; Morss, L.R.

    1993-09-01

    A low temperature method is described for the preparation of the new garnet compounds YCaLnGa{sub 5}O{sub l2} (Ln=Ce, Pr, Th). In this set of compounds (Ca{sup 2+} + Ln{sup 4+}) replaces 2 Y{sup 3+} in the parent gallium based garnet Y{sub 3}Ga{sub 5}O{sub l2} in order to stabilize as effectively as possible the Ln{sup 4+} species in the eight-coordinate ``A`` site of the garnet structure. Characterization of the oxides by x-ray powder diffraction and thermogravimetric analysis is discussed with regard to the structural relationship of the substituted compound to the parent material. The tetravalent ions Pr{sup 4+} and Tb{sup 4+} exhibit increased thermal stability in reducing conditions as compared to the Ln{sup 4+} states in the fluorite (LnO{sub 2}) and perovskite (BaLnO{sub 3}) type structures. This result is discussed with reference to the complex crystal chemistry of these systems.

  6. Synthesis, structural characterization, and magnetic properties of the antiferromagnetic double perovskites Ln {sub 2}LiOsO{sub 6} (Ln=La, Pr, Nd, Sm)

    SciTech Connect

    Gemmill, William R.; Smith, Mark D.; Loye, Hans-Conrad zur . E-mail: jssc@mail.chem.sc.edu

    2006-06-15

    A series of osmium double perovskite oxides, Ln {sub 2}LiOsO{sub 6} (Ln=La, Pr, Nd, Sm), has been prepared as single crystals from acidic molten hydroxide. All four oxides crystallize in the monoclinic space group P2{sub 1}/n (Glazer tilt system no. 10, a {sup -} a {sup -} b {sup +}), forming a 1:1 ordered rock salt lattice of Li{sup +} and Os{sup 5+} cations. Magnetic susceptibility measurements show that these compounds are antiferromagnetic at low temperature with ordering temperatures of 39, 35, 23, and 32 K for Ln {sub 2}LiOsO{sub 6} (Ln=La, Pr, Nd, Sm), respectively. - Graphical abstract: Approximate (110) view of the crystal structure of Pr{sub 2}LiOsO{sub 6} (representative of the series Ln {sub 2}LiOsO{sub 6} (Ln=La, Pr, Nd, Sm) consisting of OsO{sub 6} octahedra (striped) and LiO{sub 6} octahedra (gray). Praseodymium cations are shown as gray spheres and oxygen atoms as black spheres.

  7. Synthesis, structure, magnetism, and optical properties of theordered mixed-lanthanide sulfides gamma-LnLn'S3 (Ln=La, Ce; Ln'=Er, Tm,Yb)

    SciTech Connect

    Jin, G.B.; Choi, E.S.; Guertin, R.P.; Brooks, J.S.; Bray, T.H.; Booth, C.H.; Albrecht-Schmitt, T.E.

    2006-12-12

    {gamma}-LnLn{prime}S{sub 3} (Ln = La, Ce; Ln{prime} = Er, Tm, Yb) have been prepared as dark red to black single crystals by the reaction of the respective lanthanides with sulfur in a Sb{sub 2}S{sub 3} flux at 1000 C. This isotypic series of compounds adopts a layered structure that consists of the smaller lanthanides (Er, Tm, and Yb) bound by sulfide in six- and seven-coordinate environments that are connected together by the larger lanthanides (La and Ce) in eight- and nine-coordinate environments. The layers can be broken down into three distinct one-dimensional substructures containing three crystallographically unique Ln{prime} centers. The first of these is constructed from one-dimensional chains of edge-sharing [Ln{prime}S{sub 7}] monocapped trigonal prisms that are joined to equivalent chains via edge-sharing to yield ribbons. There are parallel chains of [Ln{prime}S{sub 6}] distorted octahedra that are linked to the first ribbons through corner-sharing. These latter units also share corners with a one-dimensional ribbon composed of parallel chains of [Ln{prime}S{sub 6}] polyhedra that edge-share both in the direction of chain propagation and with adjacent identical chains. Magnetic susceptibility measurements show Curie-Weiss behavior from 2 to 300 K with antiferromagnetic coupling, and no evidence for magnetic ordering. The {theta}{sub p} values range from -0.4 to -37.5 K, and spin-frustration may be indicated for the Yb-containing compounds. All compounds show magnetic moments substantially reduced from those calculated for the free ions. The optical band gaps for {gamma}-LaLn{prime}S{sub 3} (Ln{prime} = Er, Tm, Yb) are approximately 1.6 eV, whereas {gamma}-CeLn{prime}S{sub 3} (Ln{prime} = Er, Tm, Yb) are approximately 1.3 eV.

  8. Structures and magnetic properties of rare earth double perovskites containing antimony or bismuth Ba{sub 2}LnMO{sub 6} (Ln=rare earths; M=Sb, Bi)

    SciTech Connect

    Otsuka, Shumpei Hinatsu, Yukio

    2015-07-15

    A series of double perovskite-type oxides Ba{sub 2}LnMO{sub 6} (Ln=lanthanides; M=Sb, Bi) were synthesized and their structures were studied. The Ln and M are structurally ordered in the rock-salt type at the B-site of the perovskite ABO{sub 3}. For Ba{sub 2}PrBiO{sub 6} and Ba{sub 2}TbBiO{sub 6}, it has been found that the disordering between Ln ion and Bi ion occurs at the B-site of the double perovskite and both the Pr (Tb) and Bi exist in two oxidation state in the same compound from the analysis of the X-ray diffraction and magnetic susceptibility data. Magnetic susceptibility measurements show that all these compounds are paramagnetic and have no magnetic ordering down to 1.8 K. - Graphical abstract: Tolerance factor for Ba{sub 2}LnMO{sub 6} (M=Sb, Bi) plotted against the ionic radius of Ln{sup 3+}. We have found that there is a clear relation between crystal structures and tolerance factors. - Highlights: • The Ln and M ions are structurally ordered in the rock-salt type at the B-site. • The disordering between Pr (Tb) ion and Bi ion occurs at the B-site. • Ba{sub 2}LnMO{sub 6} (M=Sb, Bi) have no magnetic ordering down to 1.8 K.

  9. Phase transformations during HLnTiO{sub 4} (Ln=La, Nd) thermolysis and photocatalytic activity of obtained compounds

    SciTech Connect

    Silyukov, Oleg I. Abdulaeva, Liliia D.; Burovikhina, Alena A.; Rodionov, Ivan A.; Zvereva, Irina A.

    2015-03-15

    Layered HLnTiO{sub 4} (Ln=La, Nd) compounds belonging to Ruddlesden–Popper phases were found to form partially hydrated compounds Ln{sub 2}Ti{sub 2}O{sub 7}·xH{sub 2}O during thermal dehydration as well as defect oxides Ln{sub 2}□Ti{sub 2}O{sub 7} as final products. Further heating of metastable defect Ln{sub 2}□Ti{sub 2}O{sub 7} substances leads to the formation of pyrochlore-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation under higher temperatures to stable layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. The occurring structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}<Ln{sub 2}Ti{sub 2}O{sub 7}·yH{sub 2}O<Ln{sub 2}□Ti{sub 2}O{sub 7}<Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}<Ln{sub 2}Ti{sub 2}O{sub 7} in the reaction of hydrogen evolution from aqueous isopropanol solution. - Graphical abstract: Layered HLnTiO{sub 4} (Ln=La, Nd) compounds form partially hydrated Ln{sub 2}Ti{sub 2}O{sub 7}·xH{sub 2}O compounds during thermal dehydration, further heating results to the formation to defect oxides Ln{sub 2}□Ti{sub 2}O{sub 7}, pyrochlor-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation to layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. Structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}<Ln{sub 2}Ti{sub 2}O{sub 7}·yH{sub 2}O<Ln{sub 2}□Ti{sub 2}O{sub 7}<Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}<Ln{sub 2}Ti{sub 2}O{sub 7}. - Highlights: • We studied dehydration and further thermolysis of HLnTiO{sub 4} (Ln=La, Nd) compounds. • XRD, STA and solid state IR studies were carried out. • A new series of metastable Ln{sub 2}Ti{sub 2}O{sub 7}·yH{sub 2}O compounds was obtained. • We examined the photocatalytic activity of all obtained compounds. The hydrogen evolution rate increased in the course of the structure changes during thermolysis.

  10. Dissociation of diglycolamide complexes of Ln3+ (Ln = La-Lu) and An3+ (An = Pu, Am, Cm): redox chemistry of 4f and 5f elements in the gas phase parallels solution behavior.

    PubMed

    Gong, Yu; Tian, Guoxin; Rao, Linfeng; Gibson, John K

    2014-11-17

    Tripositive lanthanide and actinide ions, Ln(3+) (Ln = La-Lu) and An(3+) (An = Pu, Am, Cm), were transferred from solution to gas by electrospray ionization as Ln(L)3(3+) and An(L)3(3+) complexes, where L = tetramethyl-3-oxa-glutaramide (TMOGA). The fragmentation chemistry of the complexes was examined by collision-induced and electron transfer dissociation (CID and ETD). Protonated TMOGA, HL(+), and Ln(L)(L-H)(2+) are the major products upon CID of La(L)3(3+), Ce(L)3(3+), and Pr(L)3(3+), while Ln(L)2(3+) is increasingly pronounced beyond Pr. A C-Oether bond cleavage product appears upon CID of all Ln(L)3(3+); only for Eu(L)3(3+) is the divalent complex, Eu(L)2(2+), dominant. The CID patterns of Pu(L)3(3+), Am(L)3(3+), and Cm(L)3(3+) are similar to those of the Ln(L)3(3+) for the late Ln. A striking exception is the appearance of Pu(IV) products upon CID of Pu(L)3(3+), in accord with the relatively low Pu(IV)/Pu(III) reduction potential in solution. Minor divalent Ln(L)2(2+) and An(L)2(2+) were produced for all Ln and An; with the exception of Eu(L)2(2+) these complexes form adducts with O2, presumably producing superoxides in which the trivalent oxidation state is recovered. ETD of Ln(L)3(3+) and An(L)3(3+) reveals behavior which parallels that of the Ln(3+) and An(3+) ions in solution. A C-Oether bond cleavage product, in which the trivalent oxidation state is preserved, appeared for all complexes; charge reduction products, Ln(L)2(2+) and Ln(L)3(2+), appear only for Sm, Eu, and Yb, which have stable divalent oxidation states. Both CID and ETD reveal chemistry that reflects the condensed-phase redox behavior of the 4f and 5f elements.

  11. In-situ laser synthesis of rare earth aluminate coatings in the system Ln-Al-O ( Ln = Y, Gd)

    NASA Astrophysics Data System (ADS)

    de Francisco, I.; Lennikov, V. V.; Bea, J. A.; Vegas, A.; Carda, J. B.; de la Fuente, G. F.

    2011-09-01

    Laser zone melting (LZM) was employed in this work to prepare Ln-Al-O coatings on polycrystalline Al 2O 3 substrates, using the corresponding mixtures of powdered rare-earth oxides and Al 2O 3 as starting materials. In-situ synthesis of the compounds Ln = Y, Gd was performed using a CO 2 laser, emitting at 10.6 μm. Microstructure (SEM) and phase nature (XRD) demonstrated in-situ formation of Al 2O 3/Y 3Al 5O 12(YAG) and Al 2O 3/GdAlO 3(GAP) eutectic systems. The interaction with the substrate resulted in mechanically stable, well integrated 200-500 μm thick composite coatings, as observed in nanoindentation tests. The phase relations found in these materials are consistent with the crystallographic concepts advanced by Vegas (Ramos-Gallardo & Vegas, J. Solid State Chem. 128 (1997) 69), where cation sub-arrays are proposed to play an important role in governing metal oxide structures. These sub-arrays are suggested as the structural drive behind eutectic oxide formation. LZM proves to be a convenient method to investigate the behaviour of complex oxide systems at high temperature, to apply a rational concept towards the understanding of phase relations and to develop design criteria for oxide coatings.

  12. Lanthanide Germanate Cluster Organic Frameworks Based on {Ln8Ge12} Clusters: From One-Dimensional Chains to Two-Dimensional Layers and Three-Dimensional Frameworks.

    PubMed

    Li, Lei-Lei; Cao, Gao-Juan; Zhao, Jun-Wei; He, Huan; Yang, Bai-Feng; Yang, Guo-Yu

    2016-06-01

    Under hydrothermal conditions, six series of novel lanthanide (Ln) organogermanates (LnGs) [Ln8Ge12(μ3-O)24E12(H2O)16]·14H2O (Ln(3+) = Pr(3+), 1; Nd(3+), 2; Sm(3+), 3; Eu(3+), 4; Gd(3+), 5; one-dimensional (1-D) LnG cluster organic chain (LnGCOC)), {[Nd8Ge12(μ3-O)24E12(H2O)10](μ2-H2O)2[Nd8Ge12(μ3-O)24E12(H2O)16]}·18H2O (6, two-dimensional (2-D) planar LnG cluster organic layer (LnGCOL)), {[Ln2GeE(HO)2O(H2O)(CH3COO)2(CO3)]2[Ln8Ge12E12(μ3-O)24(H2O)10]}·6H2O (Ln(3+) = Pr(3+), 7; Nd(3+), 8; 2-D wave-shaped LnGCOL), [TbGeE(HO)2O(H2O)(pca)]2[Tb8Ge12E12(μ3-O)24(H2O)8]·10H2O (9, three-dimensional (3-D) LnG cluster organic framework (LnGCOF)), {([Nd(pza)2(H2O)2]2[Nd8Ge12E12(μ3-O)24(H2O)12])([Nd(pza)2]2[Nd8Ge12E12(Hpza)2(μ3-O)24(H2O)10])}·4OH·14H2O (10, 3-D LnGCOF), {[Nd8Ge12E12(μ3-O)24(H2O)10][Nd(pca)(pda)(H2O)]2}·12H2O (11, 3-D LnGCOF) and {[Nd8Ge12E12(μ3-O)24(H2O)10][Nd(pza)(pda)(H2O)]2}·12H2O (12, 3-D LnGCOF) (Hpca = 2-picolinic acid, H2pda = 2,6-pyridinedicarboxylic acid, Hpza = 2-pyrazinecarboxylic acid) were prepared by introducing the second auxiliary ligands into the organogermanate-lanthanide-oxide reaction system. The obtainment of these LnGs realized the utilization of the second auxiliary ligands inducing the assembly from 1-D LnGCOCs to 2-D LnGCOLs and 3-D LnGCOFs based on LnG cluster (LnGC) {Ln8Ge12E12(μ3-O)24(H2O)16}({Ln8Ge12}) units and Ln-organic complexes or organic ligand connectors. It should be noted that the well-organized structural constructions of 1-12 can be visualized as the gradual replacement of active water sites located at equatorial and polar positions on the hypothetical [Ln8Ge12(μ3-O)24E12(H2O)18] LnGC core with oxygen or nitrogen atoms from organic ligands. The solid-state luminescent properties of 2, 3, 4, 6, and 8-12 have been investigated at room temperature. PMID:27216949

  13. Structure and superconducting properties of ((Ln(1-x)Ln*(x) 1/2 (Ba(1-y)Sr(y) 1/3 Ce 1/6)8Cu6O(z)

    NASA Technical Reports Server (NTRS)

    Yamauchi, H.; Wada, T.; Ichinose, A.; Taegashi, Y.; Kaneko, T.; Ikegawa, S.; Tanaka, S.

    1991-01-01

    A variety of new oxide superconductors were prepared. The crystallographic structures of the oxides were all tetragonal and of the (Ln(+),Ce)4(Ln(+),Ba)4Cu6Oz (Ln(+) = Nd, Sm or Eu) type which had been previously discovered by Akimitsu et al. As the Sr content, y, increased when Ln = Ln(excited state) = Nd, the oxygen content, z, monotonically increased and the superconducting transition temperature, T sub c, varied exhibiting a maximum. When z was controlled directly by means of high oxygen pressure sintering techniques, T sub c was changed accordingly. T sub c's of samples with different combinations of Ln and Ln(excited state) and different values of x and y were found to depend on the magnitude of the bond valence sum for a Cu atom located in the bottom plane of the Cu-O5 pyramid. Transport and magnetization measurements were carried out to investigate the magnetic field dependence of superconducting properties and to determine the phenomenological parameters. The Hall coefficients were positive below room temperature and varied yielding a maximum with respect to temperature.

  14. Structure and superconducting properties of ((Ln(1-x)Ln*(x) 1/2 (Ba(1-y)Sr(y) 1/3 Ce 1/6) 8Cu6O(z)

    NASA Technical Reports Server (NTRS)

    Yamauchi, H.; Wada, T.; Ichinose, A.; Taegashi, Y.; Kaneko, T.; Ikegawa, S.; Tanaka, Shoji

    1990-01-01

    A variety of new oxide superconductors were prepared. The crystallographic structures of the oxides were all tetragonal and of the (Ln(+), Ce)4(Ln(+),Ba)4Cu6Oz (Ln(+) = Nd, Sm or Eu) type which had been previously discovered by Akimitsu et al. As the Sr content, y, increased when Ln = Ln(excited state) = Nd, the oxygen content, z, monotonically increased and the superconducting transition temperature, T(sub c), varied exhibiting a maximum. When z was controlled directly by means of high oxygen pressure sintering techniques, T(sub c) was changed accordingly. T(sub c's) of samples with different combinations of Ln and Ln(excited state) and different values of x and y were found to depend on the magnitude of the bond valence sum for a Cu atom located in the bottom plane of the Cu-O5 pyramid. Transport and magnetization measurements were carried out to investigate the magnetic field dependence of superconducting properties and to determine the phenomenological parameters. The Hall coefficients were positive below room temperature and varied yielding a maximum with respect to temperature.

  15. Sonochemical synthesis of highly luminescent Ln2O3:Eu3+ (Y, La, Gd) nanocrystals

    DOE PAGESBeta

    Alammar, Tarek; Cybinska, Joanna; Campbell, Paul S.; Mudring, Anja -Verena

    2015-05-12

    In this study, sonication of Ln(CH3COO)3·H2O, Eu(CH3COO)3·H2O and NaOH dissolved in the ionic liquid-butyl-3-methylimidazolium bis(trifluoromethane)sulfonylamide lead to Ln(OH)3:Eu (Ln: Gd, La, Y) nanoparticles. Subsequent calcination at 800 °C for 3 h allowed to obtain Ln2O3:Eu nanopowders. Gd2O3 and Y2O3 were obtained in the C-type lanthanide sequioxide structure, whereas La2O3 crystallized in the A-type. Structure, morphology, and luminescent properties of the nano-oxides were investigated by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), dispersive X-ray (EDX), and photoluminescence (PL). SEM studies revealed that the synthesized Gd2O3:Eu, La2O3:Eu, and Y2O3:Eu formed nano-spindle, -sheets, and -rods in shape, respectively. The nanoscale materials showmore » very efficient red emission due to the intraconfigurational f–f transitions of Eu3+. The quantum yields for Ln2O3:Eu (5%) were determined to be 4.2% for Ln=Gd, 13.8% for Ln=Y and 5.2% for Ln=La. The asymmetric ratio I02/I01 of Eu3+ varies from 5.3 for Gd2O3, to 5.6 for Y2O3 to 6.5 for La2O3, which increased the color chromaticity.« less

  16. Hydride-Based Electride Material, LnH2 (Ln = La, Ce, or Y).

    PubMed

    Mizoguchi, Hiroshi; Okunaka, Masaaki; Kitano, Masaaki; Matsuishi, Satoru; Yokoyama, Toshiharu; Hosono, Hideo

    2016-09-01

    In view of the strong electron-donating nature of H(-) and extensive vacancy formation in metals by hydrogen insertion, a series of LnH2+x (Ln = La, Ce, or Y) compounds with fluorite-type structures were verified to be the first hydride-based electride, where itinerant electrons populating the cage are surrounded by H(-) anions. The electron transfer into the cage probably originates from Ln-cage covalent interaction. To the best of our knowledge, anion-rich electrides are extremely rare, and a key requirement for their formation is that the cage site is not occupied by lone pair electrons of the adjacent ions. In the case of LnH2, the cage site is surrounded by eight H(-) anions with isotopic electronic character caused by the lack of mixing of H p-orbital character. Notably, Ru-loaded LnH2+x electride powders synthesized by hydrogen embrittlement (Ln = La or Ce) were found to work as efficient catalysts for ammonia synthesis at ambient pressure, without showing serious signs of hydrogen poisoning. There are several possible origins of the observed high catalytic activity in the hydride promotors: the small work function of LnH2+x derived from the covalent interaction between Ln cation and the H(-) σ donor, and the formation of Ln nitride during catalytic reaction. PMID:27512817

  17. Formation enthalpies of LaLn'O{sub 3} (Ln'=Ho, Er, Tm and Yb) interlanthanide perovskites

    SciTech Connect

    Qi, Jianqi; Guo, Xiaofeng; Mielewczyk-Gryn, Aleksandra

    2015-07-15

    High-temperature oxide melt solution calorimetry using 3Na{sub 2}O·MoO{sub 3} at 802 °C was performed for interlanthanide perovskites LaLn'O{sub 3} (Ln'=Ho, Er, Tm and Yb) and lanthanide oxides (La{sub 2}O{sub 3}, Ho{sub 2}O{sub 3}, Er{sub 2}O{sub 3}, Tm{sub 2}O{sub 3} and Yb{sub 2}O{sub 3}). The enthalpies of formation of these interlanthanide perovskites from binary lanthanide oxides at room temperature (25 °C) were determined to be −8.3±3.4 kJ/mol for LaHoO{sub 3}, −9.9±3.0 kJ/mol for LaErO{sub 3}, −10.8±2.7 kJ/mol for LaTmO{sub 3} and −12.3±2.9 kJ/mol for LaYbO{sub 3}. There is a roughly linear relationships between these enthalpy values and the tolerance factor for these and for other LaM{sup 3+}O{sub 3} (M=In, Sc, Ga, Al, Fe and Cr) perovskites, confirming that the distortion of the perovskites as results from ionic radius difference of A-site and B-site cations, is the main factor determining the stability of these compounds. - Graphical abstract: A linear relationship between the enthalpy of formation and the tolerance factor for interlanthanide LaLn'O{sub 3} (Ln'=Ho, Er, Tm, and Yb) and other LaM{sup 3+}O{sub 3} (M=In, Sc, Ga, Al, Fe and Cr) perovskites. - Highlights: • Interlanthanide perovskites were synthesized by solid state reactions. • Their enthalpies of formation were measured by oxide melt solution calorimetry. • ΔH{sub f,ox} shows a linear relationship with tolerance factor.

  18. Formation enthalpies of LaLn'O3 (Ln'=Ho, Er, Tm and Yb) interlanthanide perovskites

    NASA Astrophysics Data System (ADS)

    Qi, Jianqi; Guo, Xiaofeng; Mielewczyk-Gryn, Aleksandra; Navrotsky, Alexandra

    2015-07-01

    High-temperature oxide melt solution calorimetry using 3Na2O·MoO3 at 802 °C was performed for interlanthanide perovskites LaLn'O3 (Ln'=Ho, Er, Tm and Yb) and lanthanide oxides (La2O3, Ho2O3, Er2O3, Tm2O3 and Yb2O3). The enthalpies of formation of these interlanthanide perovskites from binary lanthanide oxides at room temperature (25 °C) were determined to be -8.3±3.4 kJ/mol for LaHoO3, -9.9±3.0 kJ/mol for LaErO3, -10.8±2.7 kJ/mol for LaTmO3 and -12.3±2.9 kJ/mol for LaYbO3. There is a roughly linear relationships between these enthalpy values and the tolerance factor for these and for other LaM3+O3 (M=In, Sc, Ga, Al, Fe and Cr) perovskites, confirming that the distortion of the perovskites as results from ionic radius difference of A-site and B-site cations, is the main factor determining the stability of these compounds.

  19. Down-regulation of vinculin upon MK886-induced apoptosis in LN18 glioblastoma cells

    PubMed Central

    Magro, A. D.; Cunningham, C.; Miller, M. R.

    2014-01-01

    Glioblastomas are a type of malignant brain tumor and are among the most difficult cancers to treat. One strategy to treat aggressive cancers is the use of drugs that target multiple signaling pathways. MK886 is a drug known to inhibit both 5-lipoxygenase-activating-protein (FLAP) and peroxisome proliferator activated receptor-α (PPAR-α). The objectives of this study were to investigate the ability of MK886 to induce apoptotic cell death in LN18 glioblastoma cells and to characterize the cell death mechanisms. MK886 induced massive apoptotic LN18 cell death that was manifested by the release of nucleosomes, annexinV binding to phosphatidylserine in the absence of nuclear staining, and changes in the fluorescent intensity of Mito Tracker Deep Red 633 indicating changes in mitochondrial oxidative function and mass. The alteration of the mitochondrial function implied that MK886 induced apoptosis in LN18 cells via a mitochondrial pathway. The broad caspases inhibitor ZVAD-FMK inhibited MK886-induced nucleosome release, but not annexinV binding or MK886-altered mitochondrial function. Real time RT-PCR demonstrated that LN18 cells expressed significant levels of FLAP and PPAR-α mRNAs. A low level of arachidonate 5-lipoxygenase (ALOX-5) mRNA was detected, but little, if any, arachidonate 12-lipoxygenase (ALOX-12) mRNA was present. In addition, MK886-induced apoptosis in LN18 cells was accompanied by a decrease in the protein and mRNA levels of vinculin, but not other focal adhesion proteins. In summary, the data presented here indicate that disruption of the actin-vinculin-cell-cytoskeleton matrix of the LN18 glioblastoma is a component of the MK886 induced apoptosis. In addition, MK886 treated LN18 cells could provide one model in which to investigate drugs that target lipoxygenase and PPAR-α pathways in the chemotherapeutic treatment of glioblastomas. PMID:17949236

  20. Crystal Structures of Ln4Ni3O8 (Ln = La, Nd) T′-type Nickelates

    SciTech Connect

    Poltavets,K.; Lokshin, A.; Croft, M.; Mandal, T.; Egami, T.; Greenblatt, M.

    2007-01-01

    Single-phase Ln4Ni3O8 (Ln = La, Nd) nickelates were synthesized and their crystal structures were determined by Rietveld refinement of powder neutron diffraction data. The crystal structures of these mixed-valent Ni1+/Ni2+ phases belong to the T'-type and are built by intergrowth of LnO2 fluorite layers with triple NiO2 infinite-layer structural blocks. The major driving force of transformation of the LnO rock-salt block of the parent Ln4Ni3O10-d Ruddlesden-Popper phases to the fluorite arrangement in the reduced Ln4Ni3O8 phases is attributed to internal structural stress. This transformation allows longer Ni-O bonds in Ln4Ni3O8 without overstretching of the Ln-O bonds, especially in the equatorial plane. The observed displacement of Ni atoms from the outer NiO2 planes toward the Ni atom of the central NiO2 plane in Ln4Ni3O8 is ascribed to large electrostatic repulsion from the fluorite part of the structure. X-ray absorption spectra near the K-edge of Ni suggest that the charge density on the nickel ion is similar for all members of the T'-type Lnn+1NinO2n+2 homologous series, which correlates with nearly constant Ni-O bond lengths observed in all the reduced nickelates. This suggests that the formal changes in the valence state of Ni affect the covalency of the Ni-O bond.

  1. Synthesis and magnetic properties of ALnO{sub 2} (A=Cu or Ag; Ln=rare earths) with the delafossite structure

    SciTech Connect

    Miyasaka, Naoyuki; Doi, Yoshihiro; Hinatsu, Yukio

    2009-08-15

    Synthesis, structures, and magnetic properties of ternary rare earth oxides ALnO{sub 2} (A=Cu or Ag; Ln=rare earths) have been investigated. CuLnO{sub 2} (Ln=La, Pr, Nd, Sm, Eu) were synthesized by the direct solid state reaction of Cu{sub 2}O and Ln{sub 2}O{sub 3}, and AgLnO{sub 2} (Ln=Tm, Yb, Lu) were obtained by the cation-exchange reaction of NaLnO{sub 2} and AgNO{sub 3} in a KNO{sub 3} flux. These compounds crystallized in the delafossite-type structure with the rhombohedral 3R type (space group: R-3m). Magnetic susceptibility measurements showed that these compounds are paramagnetic down to 1.8 K. Specific heat measurements down to 0.4 K indicated that CuNdO{sub 2} ordered antiferromagnetically at 0.8 K. - Graphical abstract: Ternary rare earth oxides ALnO{sub 2} (A=Cu or Ag; Ln=rare earths) crystallized in the delafossite-type structure with the rhombohedral 3R poly-type (space group: R-3m). Magnetic susceptibility measurements showed that these compounds are paramagnetic down to 1.8 K. Specific heat measurements down to 0.4 K indicated that CuNdO{sub 2} ordered antiferromagnetically at 0.8 K.

  2. Growth of single-crystals of rare-earth zirconate pyrochlores, Ln2Zr2O7 (with Ln=La, Nd, Sm, and Gd) by the floating zone technique

    NASA Astrophysics Data System (ADS)

    Ciomaga Hatnean, M.; Lees, M. R.; Balakrishnan, G.

    2015-05-01

    The geometrical frustration occurring in the crystal lattice of pyrochlore oxides of the type A2B2O7 (where A=Rare Earth, B=Mo, Sn, Ti, Zr) leads to exotic magnetic properties of these materials. The present study focuses on a new class of frustrated magnets, the lanthanide zirconates. Large, high quality single-crystals of the rare-earth zirconium oxides, Ln2Zr2O7 (where Ln=La, Nd, Sm, and Gd), have been grown by the floating zone technique, using a high power xenon arc lamp furnace. The crystals have been characterized and tested for their quality using X-ray diffraction techniques.

  3. Catalytic combustion of soot particulates over rare-earth substituted Ln2Sn2O7 pyrochlores (Ln=La, Nd and Sm).

    PubMed

    Wang, Zhongpeng; Zhu, Hongjian; Ai, Lijie; Liu, Xuhui; Lv, Min; Wang, Liguo; Ma, Zhenmin; Zhang, Zhaoliang

    2016-09-15

    Catalytic combustion is one of the most promising methods for diesel soot removal. Ln2Sn2O7 pyrochlores substituted with different rare-earth (RE) elements (Ln=La, Nd and Sm) were prepared through co-precipitation method for catalytic combustion of soot particulates. The structural, textural and redox properties, together with the oxygen vacancy of the catalysts were investigated systematically. Their catalytic activities were evaluated by both temperature-programmed oxidation and isothermal reaction techniques. With the increasing in RE ionic radius (r), the SnO bond strength in Ln2Sn2O7 pyrochlores evaluated from the stretching IR band was decreased, resulting in the improved reducibility and enhanced oxygen vacancies of catalysts. The increase of oxygen vacancy concentration was further confirmed by photoluminescence (PL) investigations wherein upon excitation with UV radiation, the pyrochlores nanoparticles exhibited strong and sharp transition at 408nm attributed to oxygen vacancies. Catalytic combustion and isothermal reactions revealed that the ignition activity (ignition temperature, T5) and the intrinsic activity (turnover frequency, TOF) were shown to depend correlatedly on redox properties and oxygen vacancy concentrations, both of which were influenced by the substitution of different RE elements. Among the pyrochlore oxides, the as-synthesized La2Sn2O7 sample displayed relatively the highest ignition activity and the largest intrinsic activity with TOF of 2.33×10(-3)s(-1).

  4. Catalytic combustion of soot particulates over rare-earth substituted Ln2Sn2O7 pyrochlores (Ln=La, Nd and Sm).

    PubMed

    Wang, Zhongpeng; Zhu, Hongjian; Ai, Lijie; Liu, Xuhui; Lv, Min; Wang, Liguo; Ma, Zhenmin; Zhang, Zhaoliang

    2016-09-15

    Catalytic combustion is one of the most promising methods for diesel soot removal. Ln2Sn2O7 pyrochlores substituted with different rare-earth (RE) elements (Ln=La, Nd and Sm) were prepared through co-precipitation method for catalytic combustion of soot particulates. The structural, textural and redox properties, together with the oxygen vacancy of the catalysts were investigated systematically. Their catalytic activities were evaluated by both temperature-programmed oxidation and isothermal reaction techniques. With the increasing in RE ionic radius (r), the SnO bond strength in Ln2Sn2O7 pyrochlores evaluated from the stretching IR band was decreased, resulting in the improved reducibility and enhanced oxygen vacancies of catalysts. The increase of oxygen vacancy concentration was further confirmed by photoluminescence (PL) investigations wherein upon excitation with UV radiation, the pyrochlores nanoparticles exhibited strong and sharp transition at 408nm attributed to oxygen vacancies. Catalytic combustion and isothermal reactions revealed that the ignition activity (ignition temperature, T5) and the intrinsic activity (turnover frequency, TOF) were shown to depend correlatedly on redox properties and oxygen vacancy concentrations, both of which were influenced by the substitution of different RE elements. Among the pyrochlore oxides, the as-synthesized La2Sn2O7 sample displayed relatively the highest ignition activity and the largest intrinsic activity with TOF of 2.33×10(-3)s(-1). PMID:27295323

  5. Enthalpies of melting of LnSF compounds (Ln = La, Ce, Pr, Nd, Sm)

    NASA Astrophysics Data System (ADS)

    Andreev, P. O.; Mikhalkina, O. G.; Andreev, O. V.; Elyshev, A. V.

    2015-05-01

    The melting temperatures and enthalpies of such congruently melting compounds as LaSF ( T m = 1713 ± 7 K, Δ H = 45.7 ± 4.6 kJ/mol), CeSF ( T m = 1683 ± 7 K, Δ H = 40.7 ± 4.1 kJ/mol), PrSF ( T m = 1661 ± 7 K, Δ H = 39.7 ± 4.0 kJ/mol), NdSF ( T m = 1654 ± 7 K, Δ H = 40.2 ± 4.0 kJ/mol), and SmSF ( T m = 1587 ± 7 K, Δ H = 36.1 ± 3.6 kJ/mol) are determined via synchronous thermal analysis. The tetrad effect is evident in the change of the melting temperatures and enthalpies of LnSF compounds (Ln = La, Ce, Pr, Nd, Sm) depending on r(Ln3+).

  6. Structures and Properties of the Products of the Reaction of Lanthanide Atoms with H2O: Dominance of the +II Oxidation State.

    PubMed

    Mikulas, Tanya C; Chen, Mingyang; Fang, Zongtang; Peterson, Kirk A; Andrews, Lester; Dixon, David A

    2016-02-11

    The reactions of lanthanides with H2O have been studied using density functional theory with the B3LYP functional. H2O forms an initial Lewis acid-base complex with the lanthanides exothermically with interaction energies from -2 to -20 kcal/mol. For most of the Ln, formation of HLnOH is more exothermic than formation of H2LnO, HLnO + H, and LnOH + H. The reactions to produce HLnOH are exothermic from -25 to -75 kcal/mol. The formation of LnO + H2 for La and Ce is slightly more exothermic than formation of HLnOH and is less or equally exothermic for the rest of the lanthanides. The Ln in HLnOH and LnOH are in the formal +II and +I oxidation states, respectively. The Ln in H2LnO is mostly in the +III formal oxidation state with either Ln-O(-)/Ln-H(-) or Ln-(H2)(-)/Ln=O(2-) bonding interactions. A few of the H2LnO have the Ln in the +IV or mixed +III/+IV formal oxidation states with Ln=O(2-)/Ln-H(-) bonding interactions. The Ln in HLnO are generally in the +III oxidation state with the exception of Yb in the +II state. The orbital populations calculated within the natural bond orbital (NBO) analysis are consistent with the oxidation states and reaction energies. The more exothermic reactions to produce HLnOH are always associated with more backbonding from the O(H) and H characterized by more population in the 6s and 5d in Ln and the formation of a stronger Ln-O(H) bond. Overall, the calculations are consistent with the experiments in terms of reaction energies and vibrational frequencies.

  7. Anion-induced self-assembly of luminescent and magnetic homoleptic cyclic tetranuclear Ln4(salen)4 and Ln4(salen)2 complexes (Ln = Nd, Yb, Er, or Gd).

    PubMed

    Feng, Weixu; Zhang, Yao; Zhang, Zhao; Lü, Xingqiang; Liu, Han; Shi, Guoxiang; Zou, Dan; Song, Jirong; Fan, Daidi; Wong, Wai-Kwok; Jones, Richard A

    2012-11-01

    Unique homoleptic cyclic tetranuclear Ln(4)(Salen)(4) complexes [Ln(4)(L)(2)(HL)(2)(μ(3)-OH)(2)Cl(2)]·2Cl (Ln = Nd, 1; Ln = Yb, 2; Ln = Er, 3; Ln = Gd, 4) or Ln(4)(Salen)(2) complexes [Ln(4)(L)(2)(μ(3)-OH)(2)(OAc)(6)] (Ln = Nd, 5; Ln = Yb, 6; Ln = Er, 7; Ln = Gd, 8) have been self-assembled from the reaction of the hexadentate Salen-type Schiff-base ligand H(2)L with LnCl(3)·6H(2)O or Ln(OAc)(6)·6H(2)O (Ln = Nd, Yb, Er, or Gd), respectively (H(2)L: N,N'-bis(salicylidene)cyclohexane-1,2-diamine). The result of their photophysical properties shows that the strong and characteristic NIR luminescence for complexes 1-2 and 5-6 with emissive lifetimes in microsecond ranges are observed, and the sensitization arises from the excited state (both (1)LC and (3)LC) of the hexadentate Salen-type Schiff-base ligand with the flexible linker. Temperature dependence (1.8-300 K) magnetic susceptibility studies of the eight complexes suggest the presence of an antiferromagnetic interaction between the Ln(3+) ions.

  8. Preparation, Characterization, and Ionic Transport Properties of Nanoscale Ln2Zr2O7 (Ln = Ce, Pr, Nd, Sm, Gd, Dy, Er, and Yb) Energy Materials

    NASA Astrophysics Data System (ADS)

    Solomon, Sam; George, Aneesh; Thomas, Jijimon Kumpakkattu; John, Annamma

    2015-01-01

    Nanoparticles of lanthanide (Ln)-based zirconates have been prepared through the autoignited combustion technique. The structure of the system was analyzed by powder x-ray diffraction and vibrational spectroscopic tools. The compounds with Ln = Ce, Pr, Nd, Sm, and Gd have pyrochlore cubic structure, whereas those with Ln = Dy, Er, and Yb possess anion-deficient disordered cubic fluorite structure. The optical properties of the powder were analyzed using ultraviolet-visible spectroscopy. Pellets of the compounds were sintered in the range from 1325°C to 1530°C for 2 h. The surface morphology of sintered Nd2Zr2O7 was analyzed by scanning electron microscopy. Impedance spectroscopic studies of the samples were carried out at different temperatures. The conductivity increased to the order of 10-2 S/m at 750°C, and the highest conductivity of 13.21 × 10-2 S/m was obtained for Er2Zr2O7. All samples of this system are suitable candidates for fabrication of electrolytes for use in solid oxide fuel cells, particularly at moderate temperatures.

  9. Crystal growth, structure and magnetic properties of the double perovskites Ln{sub 2}MgIrO{sub 6} (Ln=Pr, Nd, Sm-Gd)

    SciTech Connect

    Mugavero, Samuel J. III; Fox, Adam H.; Smith, Mark D.; Loye, Hans-Conrad zur

    2010-02-15

    Single crystals of double-perovskite type lanthanide magnesium iridium oxides, Ln{sub 2}MgIrO{sub 6} (Ln=Pr, Nd, Sm-Gd) have been grown in a molten potassium hydroxide flux. The compounds crystallize in a distorted 1:1 rock salt lattice, space group P2{sub 1}/n, consisting of corner shared MO{sub 6} (M=Mg{sup 2+} and Ir{sup 4+}) octahedra, where the rare earth cations occupy the eight-fold coordination sites formed by the corner shared octahedra. Pr{sub 2}MgIrO{sub 6}, Nd{sub 2}MgIrO{sub 6}, Sm{sub 2}MgIrO{sub 6}, and Eu{sub 2}MgIrO{sub 6} order antiferromagnetically around 10-15 K. - Graphical abstract: A SEM image of a typical crystal of Ln{sub 2}MgIrO{sub 6}, which forms in the monoclinic double perovskite structure, is shown.

  10. The rare earth silicon phosphides LnSi{sub 2}P{sub 6} (Ln = La, Ce, Pr, and Nd)

    SciTech Connect

    Kaiser, P.; Jeitschko, W.

    1996-07-01

    The title compounds were prepared in well-crystallized form from a tin flux and their crystal structure was determined from single-crystal diffractometer data of LaSi{sub 2}P{sub 6}: Cmc2{sub 1}, a = 1012.9(3) pm, b = 2817.5(7) pm, c = 1037.4(5) pm, Z = 16, R = 0.034 for 3303 structure factors and 181 variable parameters. The structure of the isotypic compound CeSi{sub 2}P{sub 6} was also refined from single-crystal X-ray data: a = 1011.8(4) pm, b = 2803.1(8) pm, c = 1031.1(4) pm, R = 0.035 for 2132 F values and 181 variables. The silicon and the phosphorus atoms could be distinguished by comparing their occupancy parameters obtained from both structure refinements. The assignments agree with those deduced by structure-chemical arguments. These atoms form a three-dimensionally infinite framework polyanion, which accommodates four different kinds of rare earth atoms: three with nine and one with ten phosphorus neighbors. The silicon atoms are all in tetrahedral phosphorus coordination. There are phosphorus atoms which have only two rare earth and two silicon neighbors, but most phosphorus atoms have--in addition to the rare earth and silicon atoms--phosphorus neighbors, thus forming P{sub 3}, P{sub 4}, P{sub 5}, and P{sub 6} units. Using oxidation numbers, the compounds can be rationalized with the formulas Ln{sup 3+}(Si{sub 2}P{sub 6}){sub 3-} and Ln{sup 3+}(Si{sup 4+}){sub 2}(P{sub 6}){sup 11-}, where the octet rule is obeyed for the silicon and phosphorus atoms and two electrons are counted for each Si-P and P-P interaction.

  11. Studies on supercritical hydrothermal syntheses of uranium and lanthanide oxide particles and their reaction mechanisms

    NASA Astrophysics Data System (ADS)

    Hwang, DongKi; Tsukahara, Takehiko; Tanaka, Kosuke; Osaka, Masahiko; Ikeda, Yasuhisa

    2015-11-01

    In order to develop preparation method of raw metal oxide particles for low decontaminated MOX fuels by supercritical hydrothermal (SH) treatments, we have investigated behavior of aqueous solutions dissolving U(VI), Ln(III) (Ln: lanthanide = Ce, Pr, Nd, Sm, Tb), Cs(I), and Sr(II) nitrate or chloride compounds under SH conditions (temperature = 400-500 °C, pressure = 30-40 MPa). As a result, it was found that Ln(NO3)3 (Ln = Ce, Pr, Tb) compounds produce LnO2, that Ln(NO3)3 (Ln = Nd, Sm) compounds are hardly converted to their oxides, and that LnCl3 (Ln = Ce, Pr, Nd, Sm, Tb), CsNO3, and Sr(NO3)2 do not form their oxide compounds. Furthermore, HNO2 species were detected in the liquid phase obtained after treating HNO3 aqueous solutions containing Ln(NO3)3 (Ln = Ce, Pr, Tb) under SH conditions, and also NO2 and NO compounds were found to be produced by decomposition of HNO3. From these results, it was proposed that the Ln oxide (LnO2) particles are directly formed with oxidation of Ln(III) to Ln(IV) by HNO3 and HNO2 species in the SH systems. Moreover, the uranyl ions were found to form U3O8 and UO3 depending on the concentration of HNO3. From these results, it is expected that the raw metal oxide particles for low decontaminated MOX fuels are efficiently prepared by the SH method.

  12. Structures and Properties of the Products of the Reaction of Lanthanide Atoms with H 2 O: Dominance of the +II Oxidation State

    DOE PAGESBeta

    Mikulas, Tanya C.; Chen, Mingyang; Fang, Zongtang; Peterson, Kirk A.; Andrews, Lester; Dixon, David A.

    2016-01-07

    We studied, lanthanides and H2O reactions using density functional theory with the B3LYP functional. H2O forms an initial Lewis acid-base complex with the lanthanides exothermically with interaction energies from -2 to -20 kcal/mol. For most of the Ln, formation of HLnOH is more exothermic than formation of H2LnO, HLnO + H, and LnOH + H. Moreover, the reactions to produce HLnOH are exothermic from -25 to -75 kcal/mol. The formation of LnO + H2 for La and Ce is slightly more exothermic than formation of HLnOH and is less or equally exothermic for the rest of the lanthanides. The Lnmore » in HLnOH and LnOH are in the formal +II and +I oxidation states, respectively. The Ln in H2LnO is mostly in the +III formal oxidation state with either Ln-O-/Ln-H- or Ln-(H2)-/Ln= O2- bonding interactions. A few of the H2LnO have the Ln in the +IV or mixed +III/+IV formal oxidation states with Ln=O2-/Ln-H- bonding interactions. The Ln in HLnO are generally in the +III oxidation state with the exception of Yb in the +II state. The orbital populations calculated within the natural bond orbital (NBO) analysis are consistent with the oxidation states and reaction energies. The more exothermic reactions to produce HLnOH are always associated with more backbonding from the O(H) and H characterized by more population in the 6s and 5d in Ln and the formation of a stronger Ln-O(H) bond. Overall, the calculations are consistent with the experiments in terms of reaction energies and vibrational frequencies.« less

  13. Molybdate templated assembly of Ln12Mo4-type clusters (Ln = Sm, Eu, Gd) containing a truncated tetrahedron core.

    PubMed

    Zheng, Yong; Zhang, Qian-Chong; Long, La-Sheng; Huang, Rong-Bin; Müller, Achim; Schnack, Jürgen; Zheng, Lan-Sun; Zheng, Zhiping

    2013-01-01

    Three heterometallic cluster complexes {Ln(12)Mo(4)} featuring an Ln(12) core of a distorted truncated tetrahedron were synthesized with the assistance of four MoO(4)(2-) anions as ancillary ligands. Magnetic studies of the {Gd(12)Mo(4)} cluster revealed a large magnetocaloric effect due to the presence of the large number of weakly coupled Gd(III) ions.

  14. Computational study on the complexation behavior of tetrapropyl diglycolamide with Ln3+ (Ln = Nd, Pm, Sm, and Eu) cation series

    NASA Astrophysics Data System (ADS)

    Hosseinnejad, Tayebeh; Nikoo, Sepideh

    2015-09-01

    In the present study, we have focused mainly on the survey of interactions in Ln3+ (Ln = Nd, Pm, Sm, Eu) complexes with tetrapropyl diglycolamide (TPDGA) by means of density functional theory (DFT) methods. In the first step, the interaction of TPDGA ligand with Ln3+ cation series has been assessed thermodynamically in the gas phase and in presence of three solvents: n-hexane, chloroform and toluene, via polarized continuum model (PCM) calculations. The trend of metal-ligand interaction strength has been investigated and compared with the trend of ionic hardness within the series of lanthanide cations. Our results for the gas and solution phases demonstrate a consistency between the increasing trend in the hardness of Ln3+ cation series with the increasing in thermodynamical stability of [Ln(TPDGA)]3+ complex series. Moreover, our PCM calculations show that using n-hexane as a solvent is more favorable thermodynamically than chloroform and toluene for the complexation reaction of all [Ln(TPDGA)]3+ complex series. It should be stated that this issue has been observed in many experimental calculations. Finally the assessment of calculated deformation energies and also the variation in bond order of some selected key bonds in [Ln(TPDGA)]3+ complex series shows a similar trend with increasing in the hardness of Ln3+ cation series.

  15. Thermoelectric properties of binary LnN (Ln=La and Lu): First principles study

    NASA Astrophysics Data System (ADS)

    Sreeparvathy P., C.; Gudelli, Vijay Kumar; Kanchana, V.; Vaitheeswaran, G.; Svane, A.; Christensen, N. E.

    2015-06-01

    First principles density functional calculations were carried out to study the electronic structure and thermoelectric properties of LnN (Ln = La and Lu) using the full potential linearized augmented plane wave (FP-LAPW) method. The thermoelectric properties were calculated by solving the Boltzmann transport equation within the constant relaxation time approximation. The obtained lattice parameters are in good agreement with the available experimental and other theoretical results. The calculated band gaps using the Tran-Blaha modified Becke-Johnson potential (TB-mBJ), of both compounds are in good agreement with the available experimental values. Thermoelectric properties like thermopower (S), electrical conductivity scaled by relaxation time (σ/τ) and power-factor (S2σ/τ) are calculated as functions of the carrier concentration and temperature for both compounds. The calculated thermoelectric properties are compared with the available experimental results of the similar material ScN.

  16. Thermoelectric properties of binary LnN (Ln=La and Lu): First principles study

    SciTech Connect

    Sreeparvathy, P. C.; Gudelli, Vijay Kumar; Kanchana, V.; Vaitheeswaran, G.; Svane, A.; Christensen, N. E.

    2015-06-24

    First principles density functional calculations were carried out to study the electronic structure and thermoelectric properties of LnN (Ln = La and Lu) using the full potential linearized augmented plane wave (FP-LAPW) method. The thermoelectric properties were calculated by solving the Boltzmann transport equation within the constant relaxation time approximation. The obtained lattice parameters are in good agreement with the available experimental and other theoretical results. The calculated band gaps using the Tran-Blaha modified Becke-Johnson potential (TB-mBJ), of both compounds are in good agreement with the available experimental values. Thermoelectric properties like thermopower (S), electrical conductivity scaled by relaxation time (σ/τ) and power-factor (S{sup 2}σ/τ) are calculated as functions of the carrier concentration and temperature for both compounds. The calculated thermoelectric properties are compared with the available experimental results of the similar material ScN.

  17. Kinetic schemes of chemical transformations and particle morphology upon interaction between Ln2(SO4)3 (Ln = La, Pr, Nd, Sm) and hydrogen

    NASA Astrophysics Data System (ADS)

    Andreev, P. O.; Sal'nikova, E. I.; Andreev, O. V.; Kovenskii, I. M.

    2016-01-01

    The phase compositions of samples obtained during the treatment of anhydrous sulfates Ln2(SO4)3 (Ln = La, Pr, Nd, Sm) in a stream with an excess of hydrogen in the temperature range of 400 to 1100°C at exposures of up to 420 min are determined. Kinetic schemes are compiled for the chemical transformations and changes of phase composition of the mixtures in coordinates of temperature and time that have six fields of the phase combinations: Ln2(SO4)3, Ln2(SO4)3 + Ln2O2SO4, Ln2O2SO4, Ln2O2SO4 + Ln2O2S, Ln2O2S, and Ln2O2S + Ln2O3. Single-phase samples of Ln2O2SO4 compounds are obtained at temperatures (°C) of 540-560 (La), 460-520 (Pr), 470-520 (Nd), and 480-520 (Sm). The temperatures (°C) of Ln2O2S compounds are 580-920 (La), 600-900 (Pr), 600-900 (Nd), and 600-800 (Sm). It is shown via electron microscopy that particles of La2(SO4)3 in the shape of cylinders are converted into flakes of Ln2O2SO4, predominantly flat Ln2O2S crystallites.

  18. Crystal growth of a series of lithium garnets Ln{sub 3}Li{sub 5}Ta{sub 2}O{sub 12} (Ln=La, Pr, Nd): Structural properties, Alexandrite effect and unusual ionic conductivity

    SciTech Connect

    Roof, Irina P.; Smith, Mark D.; Cussen, Edmund J.; Loye, Hans-Conrad zur

    2009-02-15

    We report the single crystal structures of a series of lanthanide containing tantalates, Ln{sub 3}Li{sub 5}Ta{sub 2}O{sub 12} (Ln=La, Pr, Nd) that were obtained out of a reactive lithium hydroxide flux. The structures of Ln{sub 3}Li{sub 5}Ta{sub 2}O{sub 12} were determined by single crystal X-ray diffraction, where the Li{sup +} positions and Li{sup +} site occupancies were fixed based on previously reported neutron diffraction data for isostructural compounds. All three oxides crystallize in the cubic space group Ia3-bard (No. 230) with lattice parameters a=12.7735(1), 12.6527(1), and 12.5967(1) A for La{sub 3}Li{sub 5}Ta{sub 2}O{sub 12}, Pr{sub 3}Li{sub 5}Ta{sub 2}O{sub 12}, and Nd{sub 3}Li{sub 5}Ta{sub 2}O{sub 12}, respectively. A UV-Vis diffuse reflectance spectrum of Nd{sub 3}Li{sub 5}Ta{sub 2}O{sub 12} was collected to explain its unusual Alexandrite-like optical behavior. To evaluate the transport properties of Nd{sub 3}Li{sub 5}Ta{sub 2}O{sub 12}, the impedance data were collected in air in the temperature range 300{<=}T(deg. C){<=}500. - Graphical abstract: Crystal structure of garnets Ln{sub 3}Li{sub 5}Ta{sub 2}O{sub 12} (Ln=La, Pr, Nd). TaO{sub 6} polyhedra are shown in yellow and Ln{sup 3+} are shown as light blue spheres. Octahedrally and tetrahedrally coordinated Li{sup +} ions are shown in green and brown, respectively. Oxygen atoms are omitted for clarity.

  19. Cationic ordering and role of the B-site lanthanide(III) and molybdenum(V) cations on the structure and magnetism of double perovskites Sr{sub 2}LnMoO{sub 6}

    SciTech Connect

    Pinacca, R.M.; Larrégola, S.A.; López, C.A.; Pedregosa, J.C.; Pomjakushin, Vladimir; Sánchez, R.D.; Alonso, J.A.

    2015-06-15

    Highlights: • Five new double perovskites of formula Sr{sub 2}LnMoO{sub 6} were synthesized. • All the samples crystallize in the monoclinic P2{sub 1}/n space group. • Strong reducing conditions were used in order to stabilized Mo(V) cations. • A complete ordering between the rare earth and molybdenum ions was observed. • Magnetism agrees with the crystal distortions observed from Rietveld analysis. - Abstract: We describe the preparation, crystal structure determination and magnetic properties of a new series of ordered double perovskite oxides Sr{sub 2}LnMoO{sub 6} (Ln = Eu, Gd, Dy, Ho, Er, Yb) with Mo{sup 5+} and Ln{sup 3+} electronic configurations. These compounds have been obtained by solid state reaction under reducing conditions in order to stabilize Mo{sup 5+} cations. Structural characterization by XRPD and NPD was performed when Ln = Ho, Er, Yb and just XRPD for absorbing Ln = Eu, Gd, Dy. At room temperature, an excellent Rietveld fit was obtained for all the samples in a monoclinic symmetry, space group P2{sub 1}/n, with long-range ordering of Ln and Mo atoms. Magnetic susceptibility measurements show that some of these materials present magnetic ordering below 25 K and the determined effective magnetic moments are consistent with those expected for the pair Ln{sup 3+}–Mo{sup 5+}. All the phases have negative values​​ of the Weiss temperature indicating dominance of antiferromagnetic interactions.

  20. Rare-earth transition-metal chalcogenides Ln{sub 3}MGaS{sub 7} (Ln=Nd, Sm, Dy, Er; M=Co, Ni) and Ln{sub 3}MGaSe{sub 7} (Ln=Nd, Sm, Gd, Dy, M=Co; Ln=Nd, Gd, Dy, M=Ni)

    SciTech Connect

    Yin, Wenlong; Shi, Youguo; Kang, Bin; Deng, Jianguo; Yao, Jiyong; Wu, Yicheng

    2014-05-01

    Fifteen new rare-earth transition-metal chalcogenides, Ln{sub 3}MGaS{sub 7} (Ln=Nd, Sm, Dy, Er; M=Co, Ni) and Ln{sub 3}MGaSe{sub 7} (Ln=Nd, Sm, Gd, Dy, M=Co; Ln=Nd, Gd, Dy, M=Ni), have been synthesized by solid state reactions. They are isostructural, adopt Ce{sub 3}Al{sub 1.67}S{sub 7}—related structure type, and crystallize in the non-centrosymmetric hexagonal space group P6{sub 3}. They adopt a three-dimensional framework composed of LnQ{sub 7} monocapped trigonal prisms with the interesting [MQ{sub 3}]{sup 4−} chains and isolated GaQ{sub 4} tetrahedra lying in two sets of channels in the framework. The magnetic susceptibility measurements on Ln{sub 3}CoGaQ{sub 7} (Ln=Dy, Er, Q=S; Ln=Dy, Q=Se) indicate that they are paramagnetic and obey the Curie–Weiss law over the entire experimental temperature, while the magnetic susceptibility of Sm{sub 3}CoGaSe{sub 7} deviates from the Curie–Weiss law as a result of the crystal field splitting. - Graphical abstract: Ln{sub 3}MGaS{sub 7} (Ln=Nd, Sm, Dy, Er; M=Co, Ni) and Ln{sub 3}MGaSe{sub 7} (Ln=Nd, Sm, Gd, Dy, M=Co; Ln=Nd, Gd, Dy, M=Ni) adopt a three-dimensional framework composed of LnQ{sub 7} monocapped trigonal prisms with interesting [MQ{sub 3}]{sup 4−} chains and isolated GaQ{sub 4} tetrahedra lying in two sets of channels in the framework. - Highlights: • New compounds, Ln{sub 3}MGaQ{sub 7} (Ln=rare-earth; M=Co, Ni; Q=S, Se), were synthesized. • They are isostructural and crystallize in the noncentrosymmetric space group P6{sub 3}. • They adopt a three-dimensional framework built by LnQ{sub 7} monocapped trigonal prisms. • Ln{sub 3}CoGaQ{sub 7} (Ln=Dy, Er; Q=S, Se) are paramagnetic and obey the Curie–Weiss law. • The magnetic susceptibility of Sm{sub 3}CoGaSe{sub 7} deviates from the Curie–Weiss law.

  1. Crystal structures of Ln4Ni3O8 (Ln = La, Nd) triple layer T'-type nickelates.

    PubMed

    Poltavets, Viktor V; Lokshin, Konstantin A; Croft, Mark; Mandal, Tapas K; Egami, Takeshi; Greenblatt, Martha

    2007-12-10

    Single-phase Ln4Ni3O8 (Ln = La, Nd) nickelates were synthesized and their crystal structures were determined by Rietveld refinement of powder neutron diffraction data. The crystal structures of these mixed-valent Ni1+/Ni2+ phases belong to the T'-type and are built by intergrowth of LnO2 fluorite layers with triple NiO2 infinite-layer structural blocks. The major driving force of transformation of the LnO rock-salt block of the parent Ln4Ni3O10-delta Ruddlesden-Popper phases to the fluorite arrangement in the reduced Ln4Ni3O8 phases is attributed to internal structural stress. This transformation allows longer Ni-O bonds in Ln4Ni3O8 without overstretching of the Ln-O bonds, especially in the equatorial plane. The observed displacement of Ni atoms from the outer NiO2 planes toward the Ni atom of the central NiO2 plane in Ln4Ni3O8 is ascribed to large electrostatic repulsion from the fluorite part of the structure. X-ray absorption spectra near the K-edge of Ni suggest that the charge density on the nickel ion is similar for all members of the T'-type Lnn+1NinO2n+2 homologous series, which correlates with nearly constant Ni-O bond lengths observed in all the reduced nickelates. This suggests that the formal changes in the valence state of Ni affect the covalency of the Ni-O bond. PMID:17985874

  2. Heat capacity, entropy of Ln2(MoO4)3 (Ln = La, Sm, and Gd), and the high-temperature enthalpy of Ln2(MoO4)3 (Ln = Eu, Dy, and Ho)

    NASA Astrophysics Data System (ADS)

    Lazarev, V. M.; Suponitskiy, Y. L.; Liashenko, S. E.

    2016-05-01

    The low-temperature heat capacity of Ln2(MoO4)3 (Ln = La, Sm, and Gd) is investigated by means of adiabatic calorimetry within the range of 60-300 K. The temperature dependences of the heat capacity are found and the values of the standard entropy are calculated, based on extrapolations to 0 K. Characteristic temperatures for molybdates are determined from the results of IR spectroscopic studies. The high-temperature enthalpy of Ln2(MoO4)3 (Ln = Eu, Dy, and Ho) is measured via high-temperature microcalorimetry, and the temperature dependence of heat capacity is calculated in the range of 298-1000 K. Since samarium and gadolinium molybdates are of the same structural type as terbium molybdate, we can estimate the anomaly of the heat capacity in the low-temperature region using the data for terbium molybdate and find the entropy of samarium and gadolinium molybdates.

  3. DETAIL INTERIOR VIEW OF THE CYANAMIDE (LN) OVEN BUILDING LOOKING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    DETAIL INTERIOR VIEW OF THE CYANAMIDE (L-N) OVEN BUILDING LOOKING NORTHEAST AT A C. 1932 CHICAGO PNEUMATIC COMPRESSOR. (NOT ORIGINAL LOCATION). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  4. PERSPECTIVE VIEW LOOKING SOUTHWEST AT THE CYANAMIDE (LN) OVEN BUILDING, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    PERSPECTIVE VIEW LOOKING SOUTHWEST AT THE CYANAMIDE (L-N) OVEN BUILDING, AMMONIA SPHERES IN FOREGROUND. - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  5. DETAIL INTERIOR VIEW OF THE CYANAMIDE (LN) OVEN BUILDING LOOKING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    DETAIL INTERIOR VIEW OF THE CYANAMIDE (L-N) OVEN BUILDING LOOKING WEST AT INGERSOLL-RAND COMPRESSORS #BE565 & 564. (NOT ORIGINAL LOCATION). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  6. DETAIL INTERIOR VIEW OF THE CYANAMIDE (LN) OVEN BUILDING LOOKING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    DETAIL INTERIOR VIEW OF THE CYANAMIDE (L-N) OVEN BUILDING LOOKING NORTHWEST AT A C. 1932 CHICAGO PNEUMATIC COMPRESSOR. (NOT ORIGINAL LOCATION). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  7. PERSPECTIVE VIEW LOOKING NORTHWEST AT CYANAMIDE (LN) COOLING SHED, MILL ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    PERSPECTIVE VIEW LOOKING NORTHWEST AT CYANAMIDE (L-N) COOLING SHED, MILL BUILDING AND CONVEYOR BRIDGE. NOTE CORNERSTONE ON THE MILL BUILDING. - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  8. DETAIL INTERIOR VIEW OF THE CYANAMIDE (LN) OVEN BUILDING LOOKING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    DETAIL INTERIOR VIEW OF THE CYANAMIDE (L-N) OVEN BUILDING LOOKING SOUTHEAST AT INGERSOLL-RAND COMPRESSORS #BE565 & 564. (NOT ORIGINAL LOCATION). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  9. A new continuous two-step molecular precursor route to rare-earth oxysulfides Ln{sub 2}O{sub 2}S

    SciTech Connect

    De Crom, N.

    2012-07-15

    A continuous two-step molecular precursor pathway is designed for the preparation of rare-earth oxysulfides Ln{sub 2}O{sub 2}S (Ln=Y, La, Pr, Nd, Sm-Lu). This new route involves a first oxidation step leading to the rare-earth oxysulfate Ln{sub 2}O{sub 2}SO{sub 4} which is subsequently reduced to the rare-earth oxysulfide Ln{sub 2}O{sub 2}S by switching to a H{sub 2}-Ar atmosphere. The whole process occurs at a temperature significantly lower than usual solid state synthesis (T{<=}650 Degree-Sign C) and avoids the use of dangerous sulfur-based gases, providing a convenient route to the synthesis of the entire series of Ln{sub 2}O{sub 2}S. The molecular precursors consist in heteroleptic dithiocarbamate complexes [Ln(Et{sub 2}dtc){sub 3}(phen)] and [Ln(Et{sub 2}dtc){sub 3}(bipy)] (Et{sub 2}dtc=N,N-diethyldithiocarbamate; phen=1,10-phenanthroline; bipy=2,2 Prime -bipyridine) and were synthesized by a new high yield and high purity synthesis route. The nature of the molecular precursor determines the minimum synthesis temperature and influences therefore the purity of the final Ln{sub 2}O{sub 2}S crystalline phase. - Graphical abstract: A continuous two-step molecular precursor pathway was designed for the preparation of rare-earth oxysulfides Ln{sub 2}O{sub 2}S (Ln=Y, La, Pr, Nd, Sm-Lu), starting from heteroleptic dithiocarbamate complexes. The influence of the nature of the molecular precursor on the minimum synthesis temperature and on the purity of the final Ln{sub 2}O{sub 2}S crystalline phase is discussed. Highlights: Black-Right-Pointing-Pointer A new high yield and high purity synthesis route of rare earth dithiocarbamates is described. Black-Right-Pointing-Pointer These compounds are used as precursors in a continuous process leading to rare-earth oxysulfides. Black-Right-Pointing-Pointer The oxysulfides are obtained under much more moderate conditions than previously described.

  10. Gas-phase organolanthanide (Ln) chemistry: Formation of Ln{sup +}-[benzene] and Ln{sup +}-[benzyne] complexes by reactions of laser-ablated Ln{sup +} with cyclic hydrocarbons

    SciTech Connect

    Gibson, J.K.

    1996-09-26

    Nascent laser-ablated lanthanide metal ions, Ln{sup +}, were reacted with cyclohexacarbons. C{sub 6}H{sub 6+2n} (n = 0, 1, 2, or 3), and the resulting organometallic complex ions, [Ln{sup +}] - [C{sub p}H{sub q}], were identified by time-of-flight mass spectrometry. Cyclohexane and cyclohexadiene were especially reactive, primarily undergoing one or more dehydrogenations to produce adduct ions. Also identified as minor products were the `sandwich` complexes. Carbon-carbon bond activation was generally an unimportant reaction channel. Significant differences were observed in product yields and distributions, between the several Ln{sup +} studied, providing the following comparative reactivities: Ce{sup +} >= Tb{sup +} >= Gd{sup +} = Pr{sup +} >= Ho{sup +} >= Dy{sup +} >= Lu{sup +} >= [Sm{sup +}/Tm{sup +}/Eu{sup +}/Yb{sup +} unreactive]. These differences are explained by the metal ion ground state electronic configurations and promotion energies (PE) for excitation of a (nonbonding) 4f electron to a valence 5d orbital. The distinctive Ln{sup +} reactivities indicate that most ablated Ln{sup +} were in the ground or a low-lying electronic state. Contrasting the reactivities of two or more Ln{sup +} co-ablated from a multicomponent target circumvented effects of experimental variables and provided especially reliable comparative reactivities. 52 refs., 4 figs., 5 tabs.

  11. High Specific Power Motors in LN2 and LH2

    NASA Technical Reports Server (NTRS)

    Brown, Gerald V.; Jansen, Ralph H.; Trudell, Jeffrey J.

    2007-01-01

    A switched reluctance motor has been operated in liquid nitrogen (LN2) with a power density as high as that reported for any motor or generator. The high performance stems from the low resistivity of Cu at LN2 temperature and from the geometry of the windings, the combination of which permits steady-state rms current density up to 7000 A/cm2, about 10 times that possible in coils cooled by natural convection at room temperature. The Joule heating in the coils is conducted to the end turns for rejection to the LN2 bath. Minimal heat rejection occurs in the motor slots, preserving that region for conductor. In the end turns, the conductor layers are spaced to form a heat-exchanger-like structure that permits nucleate boiling over a large surface area. Although tests were performed in LN2 for convenience, this motor was designed as a prototype for use with liquid hydrogen (LH2) as the coolant. End-cooled coils would perform even better in LH2 because of further increases in copper electrical and thermal conductivities. Thermal analyses comparing LN2 and LH2 cooling are presented verifying that end-cooled coils in LH2 could be either much longer or could operate at higher current density without thermal runaway than in LN2.

  12. High Specific Power Motors in LN2 and LH2

    NASA Technical Reports Server (NTRS)

    Brown, Gerald V.; Jansen, Ralph H.; Trudell, Jeffrey J.

    2007-01-01

    A switched reluctance motor has been operated in liquid nitrogen (LN2) with a power density as high as that reported for any motor or generator. The high performance stems from the low resistivity of Cu at LN2 temperature and from the geometry of the windings, the combination of which permits steady-state rms current density up to 7000 A/sq cm, about 10 times that possible in coils cooled by natural convection at room temperature. The Joule heating in the coils is conducted to the end turns for rejection to the LN2 bath. Minimal heat rejection occurs in the motor slots, preserving that region for conductor. In the end turns, the conductor layers are spaced to form a heat-exchanger-like structure that permits nucleate boiling over a large surface area. Although tests were performed in LN2 for convenience, this motor was designed as a prototype for use with liquid hydrogen (LH2) as the coolant. End-cooled coils would perform even better in LH2 because of further increases in copper electrical and thermal conductivities. Thermal analyses comparing LN2 and LH2 cooling are presented verifying that end-cooled coils in LH2 could be either much longer or could operate at higher current density without thermal runaway than in LN2.

  13. Theoretical aspects of photonic band gap in 1D nano structure of LN: MgLN periodic layer

    SciTech Connect

    Sisodia, Namita

    2015-06-24

    By using the transfer matrix method, we have analyzed the photonic band gap properties in a periodic layer of LN:MgLN medium. The Width of alternate layers of LN and MgLN is in the range of hundred nanometers. The birefringent and ferroelectric properties of the medium (i.e ordinary, extraordinary refractive indices and electric dipole moment) is given due considerations in the formulation of photonic band gap. Effect of electronic transition dipole moment of the medium on photonic band gap is also taken into account. We find that photonic band gap can be modified by the variation in the ratio of the width of two medium. We explain our findings by obtaining numerical values and the effect on the photonic band gap due to variation in the ratio of alternate medium is shown graphically.

  14. MOLTEN SALT SYNTHESIS OF YF3:Yb3+/Ln3+(Ln = Er3+, Tm3+) MICROSHEETS WITH MULTICOLOR UPCONVERSION LUMINESCENCE

    NASA Astrophysics Data System (ADS)

    Ding, Mingye; Lu, Chunhua; Cao, Linhai; Ni, Yaru; Xu, Zhongzi

    2013-12-01

    In this paper, highly crystalline YF3:Yb3+/Ln3+(Ln = Er3+, Tm3+) microsheets were successfully synthesized by a surfactant-free molten salt method for the first time. The results indicated that the as-obtained samples belonged to orthorhombic system and exhibited microsheets morphology with side lengths of 30 to 80 μm and wall thickness from 1 to 1.5 μm. By changing the dopant's species (Ln3+), multicolor (yellow and blue) upconversion emission can be observed in YF3:Yb3+/Ln3+ microsheets under 980 nm laser diode (LD) excitation. The upconversion mechanisms in co-doping YF3 samples were analyzed in detail based on the emission spectra. Importantly, this approach not only proposes a new alternative in synthesizing such materials, but also opens the possibility to meet the increasing commercial demand.

  15. Layered phases in the composites prepared using ZrC and LnB6 (Ln = La, Ce, and Gd)

    NASA Astrophysics Data System (ADS)

    Zhao, L. Y.; Wang, K. S.

    2016-07-01

    We found some layered phases in the composite prepared by reactive hot pressing at 1800°C for 30 mins, using ZrC and LnB6 (Ln = La, Ce, and Gd) as raw materials. The layered phases are related to rare-earth metal borocarbides, but they are relatively and chemically stable in moisture environment. XRD patterns of these layered phases cannot be identified far away, indicating that the layered phases are possibly some new compounds.

  16. High pressure luminescence spectra of CaMoO4:Ln3+ (Ln = Pr, Tb).

    PubMed

    Mahlik, S; Behrendt, M; Grinberg, M; Cavalli, E; Bettinelli, M

    2013-03-13

    Photoluminescence spectra and luminescence kinetics of pure CaMoO(4) and CaMoO(4) doped with Ln(3+) (Ln = Pr or Tb) are presented. The spectra were obtained at high hydrostatic pressure up to 240 kbar applied in a diamond anvil cell. At ambient pressure undoped and doped samples exhibit a broad band emission extending between 380 and 700 nm with a maximum at 520 nm attributed to the MoO(4)(2-) luminescence. CaMoO(4) doped with Pr(3+) or Tb(3+) additionally yields narrow emission lines related to f-f transitions. The undoped CaMoO(4) crystal was characterized by a strong MoO(4)(2-) emission up to 240 kbar. In the cases of CaMoO(4):Pr(3+) and CaMoO(4):Tb(3+), high hydrostatic pressure caused quenching of Pr(3+) and Tb(3+) emission, and this effect was accompanied by a strong shortening of the luminescence lifetime. In doped samples, CaMoO(4):Pr(3+) and CaMoO(4):Tb(3+), quenching of the emission band attributed to MoO(4)(2-) was also observed, and at pressure above 130 kbar this luminescence was totally quenched. The effects mentioned above were related to the influence of the praseodymium (terbium) trapped exciton PTE (ITE-impurity trapped exciton) on the efficiency of the Pr(3+) (Tb(3+)) and MoO(4)(2-) emissions.

  17. High pressure luminescence spectra of CaMoO4:Ln3+ (Ln = Pr, Tb)

    NASA Astrophysics Data System (ADS)

    Mahlik, S.; Behrendt, M.; Grinberg, M.; Cavalli, E.; Bettinelli, M.

    2013-03-01

    Photoluminescence spectra and luminescence kinetics of pure CaMoO4 and CaMoO4 doped with Ln3+ (Ln = Pr or Tb) are presented. The spectra were obtained at high hydrostatic pressure up to 240 kbar applied in a diamond anvil cell. At ambient pressure undoped and doped samples exhibit a broad band emission extending between 380 and 700 nm with a maximum at 520 nm attributed to the {{MoO}}_{4}^{2-} luminescence. CaMoO4 doped with Pr3+ or Tb3+ additionally yields narrow emission lines related to f-f transitions. The undoped CaMoO4 crystal was characterized by a strong MoO{}_{4}^{2-} emission up to 240 kbar. In the cases of CaMoO4:Pr3+ and CaMoO4:Tb3+, high hydrostatic pressure caused quenching of Pr3+ and Tb3+ emission, and this effect was accompanied by a strong shortening of the luminescence lifetime. In doped samples, CaMoO4:Pr3+ and CaMoO4:Tb3+, quenching of the emission band attributed to {{MoO}}_{4}^{2-} was also observed, and at pressure above 130 kbar this luminescence was totally quenched. The effects mentioned above were related to the influence of the praseodymium (terbium) trapped exciton PTE (ITE—impurity trapped exciton) on the efficiency of the Pr3+ (Tb3+) and {{MoO}}_{4}^{2-} emissions.

  18. Decanuclear Ln10 Wheels and Vertex-Shared Spirocyclic Ln5 Cores: Synthesis, Structure, SMM Behavior, and MCE Properties.

    PubMed

    Das, Sourav; Dey, Atanu; Kundu, Subrata; Biswas, Sourav; Narayanan, Ramakirushnan Suriya; Titos-Padilla, Silvia; Lorusso, Giulia; Evangelisti, Marco; Colacio, Enrique; Chandrasekhar, Vadapalli

    2015-11-16

    The reaction of a Schiff base ligand (LH3) with lanthanide salts, pivalic acid and triethylamine in 1:1:1:3 and 4:5:8:20 stoichiometric ratios results in the formation of decanuclear Ln10 (Ln = Dy (1), Tb (2), and Gd (3)) and pentanuclear Ln5 complexes (Ln = Gd (4), Tb (5), and Dy (6)), respectively. The formation of Ln10 and Ln5 complexes are fully governed by the stoichiometry of the reagents used. Detailed magnetic studies on these complexes (1-6) have been carried out. Complex 1 shows a SMM behavior with an effective energy barrier for the reversal of the magnetization (Ueff) = 16.12(8) K and relaxation time (τo) = 3.3×10(-5) s under 4000 Oe direct current (dc) field. Complex 6 shows the frequency dependent maxima in the out-of-phase signal under zero dc field, without achieving maxima above 2 K. Complexes 3 and 4 show a large magnetocaloric effect with the following characteristic values: -ΔSm = 26.6 J kg(-1) K(-1) at T = 2.2 K for 3 and -ΔSm = 27.1 J kg(-1) K(-1) at T = 2.4 K for 4, both for an applied field change of 7 T. PMID:26420030

  19. New Antimony Lanthanide Disulfide Dibromides LnSbS

    SciTech Connect

    Gout, D.; Jobic, S.; Evain, M.; Brec, R.

    2001-05-01

    CeSbS{sub 2}Br{sub 2} (I), Ce{sub 1/2}La{sub 1/2}SbS{sub 2}Br{sub 2} (II), and LaSbS{sub 2}Br{sub 2} (III) have been synthesized at 700 C from a mixture of LnBr{sub 3}, Ln{sub 2}S{sub 3}, Sb, and S and characterized by single-crystal X-ray diffraction. The three phases are isostructural (space group P2{sub 1}/c, Z=4) and crystallize in a novel, dense, bidimensional structure with cell parameters a=8.709(3) {angstrom}, b=9.187(2) {angstrom}, c=17.397(5) {angstrom} {beta}=104.26(3) for I, a=8.739(7) {angstrom}, b=9.219(7) {angstrom}, c=17.41(2) {angstrom}, =104.3(1) for II, and a=8.785(1) {angstrom}, b=9.236(2) {angstrom}, c=17.372(3) {angstrom}, {beta}=104.09(2) for III. In these compounds, [Ln S{sub 5}Br{sub 4}] and [Ln S{sub 3}Br{sub 6}] (Ln=Ce, La) distorted tricapped trigonal prisms define infinite {sub {infinity}}{sup 2}[LnS{sub 2}Br{sub 2}] layers counterbalanced and capped by antimony cations. In good accordance with the structural features, the charge balance in these materials is to be written Ln{sup III}Sb{sup III}S{sup -II}{sub 2}Br{sup -I}{sub 2}. These compounds exhibit a yellow hue with a measured absorption threshold of 2.42(1), 2.55(1), and 2.72(1) eV for I, II, and III, respectively. In the two cerium containing bromothioantimonates I and II, the origin of the color is assigned to a Ce-4f{yields}Ce-5d electronic transition, which shifts to higher energy from I to II due either to a matrix effect (increase of the mean Ln-S distances under the substitution of Ce for La) or to an atomic ordering between Ce and La cations on the Ln(1) and Ln(2) crystallographic sites. In contrast, the electronic transition at play in III involves a charge transfer from the bromine and sulfur ions to the antimony ions, the latter contributing substantially to the lowermost levels of the conduction band.

  20. Nine members of a family of nine-membered cyclic coordination clusters; Fe6Ln3 wheels (Ln = Gd to Lu and Y).

    PubMed

    Kühne, Irina A; Mereacre, Valeriu; Anson, Christopher E; Powell, Annie K

    2016-01-18

    We report a family of isostructural nonanuclear Fe(III)-Ln(III) cyclic coordination clusters [Fe(III)(6)Ln(III)(3)(μ-OMe)9(vanox)6(benz)6]. (Ln = Tb (1), Dy (2), Ho (3), Er (4), Tm (5), Yb (6), Lu (7), Y (8) and Gd (9)), containing an odd number of metal ions. The planar cyclic coordination cluster cores are built up from three [Fe2Ln] subunits.

  1. Method for synthesizing fine-grained phosphor powders of the type (RE.sub.1- Ln.sub.x)(P.sub.1-y V.sub.y)O.sub.4

    DOEpatents

    Phillips, Mark L. F.

    1998-01-01

    A method for generating well-crystallized photo- and cathodoluminescent oxide phosphor powders. The method of this invention uses hydrothermal synthesis and annealing to produce nearly monosized (RE.sub.1-x Ln.sub.x)(P.sub.1-y V.sub.y)O.sub.4 (Ln.dbd.Ce.fwdarw.Lu) phosphor grains with crystallite sizes from 0.04 to 5 .mu.m. Such phosphors find application in cathode-ray tube, flat-panel, and projection displays.

  2. Sulfate Exchange of the Nitrate-Type Layered Hydroxide Nanosheets of Ln2(OH)5NO3· nH2O for Better Dispersed and Multi-color Luminescent Ln2O3 Nanophosphors (Ln = Y0.98RE0.02, RE = Pr, Sm, Eu, Tb, Dy, Ho, Er, and Tm)

    NASA Astrophysics Data System (ADS)

    Wu, Xiaoli; Liu, Weigang; Li, Ji-Guang; Zhu, Qi; Li, Xiaodong; Sun, Xudong

    2016-07-01

    Through restricting thickness growth by performing coprecipitation at the freezing temperature of ~4 °C, solid-solution nanosheets (up to 5-nm thick) of the Ln2(OH)5NO3· nH2O layered hydroxide (Ln = Y0.98RE0.02; RE = Pr, Sm, Eu, Tb, Dy, Ho, Er, and Tm, respectively) were directly synthesized without performing conventional exfoliation. In situ exchange of the interlayer NO3 - with SO4 2- produced a sulfate derivative [Ln2(OH)5(SO4)0.5· nH2O] of the same layered structure and two-dimensional crystallite morphology but substantially contracted d 002 basal spacing (from ~0.886 to 0.841 nm). The sulfate derivative was systematically compared against its nitrate parent in terms of crystal structure and phase/morphology evolution upon heating. It is shown that the interlayer SO4 2-, owing to its bonding with the hydroxide main layer, significantly raises the decomposition temperature from ~600 to 1000 °C to yield remarkably better dispersed oxide nanopowders via a monoclinic Ln2O2SO4 intermediate. The resultant (Y0.98RE0.02)2O3 nanophosphors were studied for their photoluminescence to show that the emission color, depending on RE3+, spans a wide range in the Commission Internationale de l'Eclairage (CIE) chromaticity diagram, from blue to deep red via green, yellow, orange, and orange red.

  3. Structure and magnetic properties of LnMnSbO ( Ln=La and Ce)

    DOE PAGESBeta

    Zhang, Qiang; Kumar, C. M. N.; Tian, Wei; Dennis, Kevin W.; Goldman, Alan I.; Vaknin, David

    2016-03-11

    Here, a neutron powder diffraction (NPD) study of LnMnSbO (Ln = La or Ce) reveals differences between the magnetic ground state of the two compounds due to the strong Ce-Mn coupling compared to La-Mn. The two compounds adopt the P4/nmm space group down to 2 K, and whereas magnetization measurements do not show obvious anomaly at high temperatures, NPD reveals a C-type antiferromagnetic (AFM) order below TN = 255K for LaMnSbO and 240 K for CeMnSbO. While the magnetic structure of LaMnSbO is preserved to base temperature, a sharp transition at TSR = 4.5K is observed in CeMnSbO due tomore » a spin-reorientation (SR) transition of the Mn2+ magnetic moments from pointing along the c axis to the ab plane. The SR transition in CeMnSbO is accompanied by a simultaneous long-range AFM ordering of the Ce moments, which indicates that the Mn SR transition is driven by the Ce-Mn coupling. The ordered moments are found to be somewhat smaller than those expected for Mn2+ (S = 5/2) in insulators, but large enough to suggest that these compounds belong to the class of local-moment antiferromagnets. The lower TN found in these two compounds compared to the As-based counterparts (TN = 317 for LaMnAsO, TN = 347K for CeMnAsO) indicates that the Mn-Pn (Pn=As or Sb) hybridization that mediates the superexchange Mn-Pn-Mn coupling is weaker for the Sb-based compounds.« less

  4. Nd2K2IrO7 and Sm2K2IrO7: Iridium(VI) Oxides Prepared under Ambient Pressure

    SciTech Connect

    Mugavero, III, S.; Smith, M; Yoon, W; zur Loye, H

    2009-01-01

    The most-oxidized iridium oxides known to date are prepared in a hydroxide flux under normal pressure. They contain iridium centers exclusively in the +VI oxidation state and are characterized crystallographically. The picture shows the structure of the Ln2K2IrO7 (Ln=Nd, Sm) and its structural components: IrO6 octahedra (black), KO10 polyhedra (beige), LnO10 polyhedra (blue).

  5. Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb)

    SciTech Connect

    Hinatsu, Yukio; Doi, Yoshihiro

    2013-02-15

    Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr{sub 3}OsO{sub 7} exhibits magnetic transitions at 8 and 73 K, and Tb{sub 3}OsO{sub 7} magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln{sup 3+} sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice. - Graphical abstract: Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr{sub 3}OsO{sub 7} exhibits magnetic transitions at 8 and 73 K, and Tb{sub 3}OsO{sub 7} magnetically orders at 8 and 60 K. Highlights: Black-Right-Pointing-Pointer Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) with an ordered defect-fluorite structure have been prepared. Black-Right-Pointing-Pointer Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). Black-Right-Pointing-Pointer These compounds show complex magnetic behavior at low temperatures due to magnetic ordering of Ln and Os.

  6. Hydroxide-free cubane-shaped tetranuclear [Ln4] complexes.

    PubMed

    Das, Sourav; Dey, Atanu; Biswas, Sourav; Colacio, Enrique; Chandrasekhar, Vadapalli

    2014-04-01

    The reaction of the lanthanide(III) chloride salts [Gd(III), Tb(III), and Dy(III)] with a new chelating, flexible, and sterically unencumbered multisite coordinating compartmental Schiff-base ligand (E)-2-((6-(hydroxymethyl)pyridin-2-yl)methyleneamino)phenol (LH2) and pivalic acid (PivH) in the presence of triethylamine (Et3N) affords a series of tetranuclear Ln(III) coordination compounds, [Ln4(L)4(μ2-η(1)η(1)Piv)4]·xH2O·yCH3OH (1, Ln = Gd(III), x = 3, y = 6; 2, Ln = Tb(III), x = 6, y = 2; 3, Ln = Dy(III), x = 4, y = 6). X-ray diffraction studies reveal that the molecular structure contains a distorted cubane-like [Ln4(μ3-OR)4](+8) core, which is formed by the concerted coordination action of four dianionic L(2-) Schiff-base ligands. Each lanthanide ion is eight-coordinated (2N, 6O) to form a distorted-triangular dodecahedral geometry. Alternating current susceptibility measurements of complex 3 reveal frequency- and temperature-dependent two-step out-of-phase signals under zero direct current (dc) field, which is characteristic of single-molecule magnet behavior. Analysis of the dynamic magnetic data under an applied dc field of 1000 Oe to fully or partly suppress the quantum tunneling of magnetization relaxation process affords the anisotropic barriers and pre-exponential factors: Δ/kB = 73(2) K, τ0 = 4.4 × 10(-8) s; Δ/kB = 47.2(9) K, τ0 = 5.0 × 10(-7) s for the slow and fast relaxations, respectively. PMID:24673300

  7. Observation of unusual topological surface states in half-Heusler compounds LnPtBi (Ln=Lu, Y)

    PubMed Central

    Liu, Z. K.; Yang, L. X.; Wu, S.-C.; Shekhar, C.; Jiang, J.; Yang, H. F.; Zhang, Y.; Mo, S.-K.; Hussain, Z.; Yan, B.; Felser, C.; Chen, Y. L.

    2016-01-01

    Topological quantum materials represent a new class of matter with both exotic physical phenomena and novel application potentials. Many Heusler compounds, which exhibit rich emergent properties such as unusual magnetism, superconductivity and heavy fermion behaviour, have been predicted to host non-trivial topological electronic structures. The coexistence of topological order and other unusual properties makes Heusler materials ideal platform to search for new topological quantum phases (such as quantum anomalous Hall insulator and topological superconductor). By carrying out angle-resolved photoemission spectroscopy and ab initio calculations on rare-earth half-Heusler compounds LnPtBi (Ln=Lu, Y), we directly observe the unusual topological surface states on these materials, establishing them as first members with non-trivial topological electronic structure in this class of materials. Moreover, as LnPtBi compounds are non-centrosymmetric superconductors, our discovery further highlights them as promising candidates of topological superconductors. PMID:27671444

  8. Antiferromagnetic transitions of osmium-containing rare earth double perovskites Ba{sub 2}LnOsO{sub 6} (Ln=rare earths)

    SciTech Connect

    Hinatsu, Yukio Doi, Yoshihiro; Wakeshima, Makoto

    2013-10-15

    The perovskite-type compounds containing both rare earth and osmium Ba{sub 2}LnOsO{sub 6} (Ln=Pr, Nd, Sm–Lu) have been prepared. Powder X-ray diffraction measurements and Rietveld analysis show that Ln{sup 3+} and Os{sup 5+} ions are structurally ordered at the M site of the perovskite BaMO{sub 3}. Magnetic susceptibility and specific heat measurements show that an antiferromagnetic ordering of Os{sup 5+} ions has been observed for Ba{sub 2}LnOsO{sub 6} (Ln=Pr, Nd, Sm, Eu, Gd, Lu) at 65–71 K. Magnetic ordering of Ln{sup 3+} moments occurs when the temperature is furthermore decreased. - Graphical abstract: The perovskite-type compounds containing both rare earth and osmium Ba{sub 2}LnOsO{sub 6} (Ln=Pr, Nd, Sm–Lu) have been prepared. An antiferromagnetic ordering of Os{sup 5+} ions has been observed for Ba{sub 2}LnOsO{sub 6} (Ln=Pr, Nd, Sm, Eu, Gd, Lu) at 65–71 K. Measurements and analysis of the specific heat for Ba{sub 2}PrOsO{sub 6} show that magnetic ordering of the Pr{sup 3+} moments should have occurred at ∼20 K. Display Omitted.

  9. Crystal structures and magnetic properties of lanthanide containing borates LnM(BO{sub 3}){sub 2} (Ln=Y, Ho–Lu; M=Sc, Cr)

    SciTech Connect

    Doi, Yoshihiro Satou, Tatsuya; Hinatsu, Yukio

    2013-10-15

    The synthesis, crystal structures and magnetic properties of LnM(BO{sub 3}){sub 2} (Ln=Y, Ho–Lu; M=Sc, Cr) were investigated. The LnCr(BO{sub 3}){sub 2} compounds crystallize in the dolomite-type structure with space group R3{sup ¯}, in which the Ln and Cr ions occupy two octahedral sites. From the result of structural analysis, it was found that there is an anti-site disorder between these two sites and its chemical formula is more exactly Ln{sub 1−r}Cr{sub r}[Cr{sub 1−r}Ln{sub r}](BO{sub 3}){sub 2}. On the other hand, the LnSc(BO{sub 3}){sub 2} adopt the calcite-type structure with space group R3{sup ¯}c. The Ln and Sc ions randomly occupy an octahedral site and the chemical formula is represented as (Ln{sub 0.5}Sc{sub 0.5})BO{sub 3}. From the magnetic susceptibility and specific heat measurements, we found that all the LnCr(BO{sub 3}){sub 2} show an antiferromagnetic transition at 6.1–8.1 K. This transition is mainly due to the ordering of Cr{sup 3+} magnetic moments. Among the compounds with magnetic Ln{sup 3+} ions, only YbCr(BO{sub 3}){sub 2} shows an antiferromagnetic ordering of Ln{sup 3+} ion at 2.1 K. - Graphical abstract: The lanthanide containing borates LnM(BO{sub 3}){sub 2} (Ln=Y, Ho–Lu; M=Sc, Cr) have the dolomite-type (Ln=Cr) and calcite-type (Ln=Sc) structures. Both structures are similar to each other except for the difference in the partially or fully disordered arrangements of octahedral sites. At low temperatures, the LnCr(BO{sub 3}){sub 2} compounds show an antiferromagnetic transition due to a long-range ordering of Cr{sup 3+} moments. Among them only YbCr(BO{sub 3}){sub 2} shows an antiferromagnetic ordering of Ln{sup 3+} ion at 2.1 K. Display Omitted - Highlights: • Lanthanide containing borates LnM(BO{sub 3}){sub 2} (Ln=Y, Ho–Lu; M=Sc, Cr) have been synthesized. • LnCr(BO{sub 3}){sub 2} has the dolomite-type structure with an anti-site disorder between Ln and Cr sites. • LnSc(BO{sub 3}){sub 2} has the calcite

  10. Measurement of desorption energies of H 2 and CO from SS-304 LN and inconel 625 surfaces by laser induced thermal desorption

    NASA Astrophysics Data System (ADS)

    Tagle, J. A.; Pospieszczyk, A.

    Stainless steel (AISI 304 LN) and Inconel 625 surfaces have been exposed to different pressures of H 2 and CO in the temperature range of 300-473 K. A laser heating technique for studying fast surface processes was applied to determine the desorption energies of these gasses from SS 304 LN and Inconel 625 surfaces. The Clausius-Clapeyron plots give a desorption energy value of 97 kJ mol -1 for H 2/SS 304 LN and 77.4 kJ mol -1 for H 2/Inconel 625. The adsorption of CO on these surfaces is drastically affected by the fast growing of a chromium oxide layer at the surface during the laser shots. In this case the desorption energy was determined by fitting both the experimental recoverage times and the equilibrium coverage curves. The oxide passivation layer produces a decrease of the desorption energy from 92.8 to 72.8 kJ mol -1 for CO/SS 304 LN and from 91.8 to 77.9 kJ mol -1 for CO/Inconel 625 when the oxygen surface concentration increases to 14%.

  11. Crystal growth of a series of lithium garnets Ln3Li 5Ta 2O 12 ( Ln=La, Pr, Nd): Structural properties, Alexandrite effect and unusual ionic conductivity

    NASA Astrophysics Data System (ADS)

    Roof, Irina P.; Smith, Mark D.; Cussen, Edmund J.; zur Loye, Hans-Conrad

    2009-02-01

    We report the single crystal structures of a series of lanthanide containing tantalates, Ln3Li 5Ta 2O 12 ( Ln=La, Pr, Nd) that were obtained out of a reactive lithium hydroxide flux. The structures of Ln3Li 5Ta 2O 12 were determined by single crystal X-ray diffraction, where the Li + positions and Li + site occupancies were fixed based on previously reported neutron diffraction data for isostructural compounds. All three oxides crystallize in the cubic space group Ia3¯d (No. 230) with lattice parameters a=12.7735(1), 12.6527(1), and 12.5967(1) Å for La 3Li 5Ta 2O 12, Pr 3Li 5Ta 2O 12, and Nd 3Li 5Ta 2O 12, respectively. A UV-Vis diffuse reflectance spectrum of Nd 3Li 5Ta 2O 12 was collected to explain its unusual Alexandrite-like optical behavior. To evaluate the transport properties of Nd 3Li 5Ta 2O 12, the impedance data were collected in air in the temperature range 300⩽ T(°C)⩽500.

  12. Study on optical properties of rare-earth ions in nanocrystalline monoclinic SrAl2O4: Ln (Ln = Ce3+, Pr3+, Tb3+).

    PubMed

    Fu, Zuoling; Zhou, Shihong; Zhang, Siyuan

    2005-08-01

    SrAl(2)O(4): Ln (Ln = Ce(3+), Pr(3+), Tb(3+)) nanocrystals have been synthesized by the combustion method. The results of XRD indicated that the resulting SrAl(2)O(4): Ln (Ln = Ce(3+), Pr(3+), Tb(3+)) nanocrystals have a reduced and distorted monoclinic lattice compared with bulk materials. The spectral properties are measured, and it is found that the excitation peaks of 5d energy levels red shift in nanocrystals in contrast to that in bulk crystals. The mechanism of spectra and energy changes is investigated. The order of the degree of red shift for nano SrAl(2)O(4): Ln (Ln = Ce(3+), Pr(3+), Tb(3+)) crystals is Pr(3+) > Ce(3+) > Tb(3+), which is in good agreement with our predicted results.

  13. Luminescent LuVO4:Ln3+ (Ln = Eu, Sm, Dy, Er) hollow porous spheres for encapsulation of biomolecules

    NASA Astrophysics Data System (ADS)

    Li, Dan; Liu, Chunlei; Jiang, Lianzhou

    2015-10-01

    In this study, LuVO4:Ln3+ (Ln = Eu, Sm, Dy, Er) hollow porous spheres, synthesized via self-sacrificing templated route, are developed for enzyme immobilization and protein adsorption. The four LuVO4 hollow spheres with diameter of 180 nm, 280 nm, 370 nm and 480 nm were obtained. The size of LuVO4 hollow sphere is dependent on Lu(OH)CO3 template. Upon excitation by UV light, hollow LuVO4:Ln3+ (Ln = Eu, Sm, Dy, Er) spheres exhibit red (Eu3+), orange (Sm3+), yellow-green (Dy3+), and green (Er3+) emissions. The good biocompatibility of sample is validated by MTT assay. Due to structure feature and size of obtained sample, the rapid encapsulation of biomolecules within samples has been achieved. Furthermore, the hollow spheres show different biomolecules adsorption capacities at different buffer solution pH values. The release behaviors of two kinds of biomolecules (lysozyme and bovine serum albumin) are also investigated. LuVO4 hollow spheres are suitable carriers for biomolecules. The emission intensity of Eu3+ in the LuVO4:Eu3+ varies with the released amount of LYZ. This enables the monitoring of release process by the change in the luminescence intensity.

  14. The crystal structure and luminescence of Ce3+, Tb3+ and Eu3+ in KBaLn3+(BO3)2 [Ln3+ = Sc, Y, Lu, Gd

    NASA Astrophysics Data System (ADS)

    Camardello, S. J.; Her, J. H.; Toscano, P. J.; Srivastava, A. M.

    2015-11-01

    The structure of KBaLn3+(BO3)2 [Ln3+ = Sc, Lu, Gd] was solved by Rietveld refinement of the powder X-ray diffraction data. The materials crystallize with the mineral Buetschliite [K2Ca(CO3)2] structure. The lattice parameters of KBaLn3+(BO3)2 [Ln3+ = Sc, Lu, Gd] increased with increasing ionic radius of the Ln3+ cation. In this structure, the Ln3+ cations are octahedrally coordinated. The phase formation region is dependent on the ionic radii of the Ln3+ cation. The optical properties of Ce3+, Tb3+ and Eu3+ and their dependence on the host lattice composition are investigated and discussed. It is noteworthy that the optical properties of these ions are independent of the Ln3+ cation in KBaLn3+(BO3)2. It is concluded that in this family of materials, the crystalline field strength and the covalence at the rare earth site is independent of the host lattice composition.

  15. Crystal Growth, Structure, and Physical Properties of LnCu[subscript 2](Al,Si)[subscript 5] (Ln = La and Ce)

    SciTech Connect

    Phelan, W. Adam; Kangas, Michael J.; Drake, Brenton L.; Zhao, Liang L.; Wang, Jiakui K.; DiTusa, J.F.; Morosan, Emilia; Chan, Julia Y.

    2012-03-15

    LnCu{sub 2}(Al,Si){sub 5} (Ln = La and Ce) were synthesized and characterized. These compounds adopt the SrAu{sub 2}Ga{sub 5} structure type and crystallize in the tetragonal space group P4/mmm with unit cell dimensions of a {approx} 4.2 {angstrom} and c {approx} 7.9 {angstrom}. Herein, we report the structure as obtained from single crystal X-ray diffraction. Additionally, we report the magnetic susceptibility, magnetization, resistivity, and specific heat capacity data obtained for polycrystalline samples of LnCu{sub 2}(Al,Si){sub 5} (Ln = La and Ce).

  16. Ba2LnSbO6 and Sr2LnSbO6 (Ln = Dy, Ho, Gd) double perovskites: Lanthanides in the geometrically frustrating fcc lattice

    PubMed Central

    Karunadasa, H.; Huang, Q.; Ueland, B. G.; Schiffer, P.; Cava, R. J.

    2003-01-01

    Magnetic ground states in solids often arise as a result of a delicate balance between competing factors. One currently active area of research in magnetic materials involves compounds in which long-range magnetic ordering at low temperatures is frustrated by the geometry of the crystalline lattice, a situation known as geometrical magnetic frustration. The number of systems known to display the effects of such frustration is growing, but those that are sufficiently simple from theoretical, chemical, and physical perspectives to allow for detailed understanding remain very few. A search for model compounds in this family has led us to the double perovskites Ba2LnSbO6 and Sr2LnSbO6 (Ln = Dy, Ho, and Gd) reported here. Ba2DySbO6,Ba2HoSbO6,Sr2DySbO6, and Sr2HoSbO6 are structurally characterized by powder neutron diffraction at ambient temperature. The trivalent lanthanides and pentavalent antimony are found to be fully ordered in the double-perovskite arrangement of alternating octahedra sharing corner oxygens. In such a structure, the lanthanide sublattice displays a classical fcc arrangement, an edge-shared network of tetrahedra known to result in geometric magnetic frustration. No magnetic ordering is observed in any of these compounds down to temperatures of 2 K, and in the case of the Dy-based compounds in particular, frustration of the magnetic ordering is clearly present. Lanthanide-based double perovskites are proposed to be excellent model systems for the detailed study of geometric magnetic frustration. PMID:12824460

  17. Synthesis and magnetic properties of rare earth ruthenates, Ln{sub 5}Ru{sub 2}O{sub 12} (Ln=Pr, Nd, Sm-Tb)

    SciTech Connect

    Bharathy, M.; Gemmill, W.R.; Fox, A.H.; Darriet, J.; Smith, M.D.; Hadermann, J.; Remy, M.S.; Loye, H.-C. zur

    2009-05-15

    Single crystals of Ln{sub 5}Ru{sub 2}O{sub 12} (Ln=Pr, Nd, Sm-Tb) were grown out of either NaOH or KOH fluxes in sealed silver tubes. The crystals of all the phases were observed to be twinned as confirmed by TEM studies. The series crystallize in the C2/m monoclinic system with lattice parameters, a=12.4049(4)-12.7621(6) A, b=5.8414(2)-5.9488(3) A, c=7.3489(2)-7.6424(4) A, beta=107.425(3)-107.432(2){sup o} and Z=2. The crystal structure is isotypic with the defect/disorder model of Ln{sub 5}Re{sub 2}O{sub 12} (Ln = Y, Gd) and consists of one dimensional edge shared RuO{sub 6} octahedral chains separated by a two dimensional LnO{sub x} polyhedral framework. Magnetic measurements indicate paramagnetic and antiferromagnetic behavior for Ln=Nd, Sm-Gd and Ln=Tb, respectively. - Graphical abstract: Single crystals of Ln{sub 5}Ru{sub 2}O{sub 12} (Ln=Pr, Nd, Sm-Tb) were grown out of NaOH/KOH fluxes in sealed silver tubes. The crystal structure consists of one-dimensional chains of edge-sharing RuO{sub 6} octahedral pairs along the b axis, separated by a two dimensional LnO{sub x} polyhedral framework. Each RuO{sub 6} octahedral pair is separated alternately by Ln atoms and its disordered component, observed as stacking faults in the HRTEM images.

  18. LN2 Dewar 42 Delivery Overfill Inlet Solution

    SciTech Connect

    Wu, J.; Mulholland, G.T.; /Fermilab

    1991-02-26

    Pressure vessels must be protected against overpressure scenarios. A scenario of particular concern is that from a high pressure LN2 pump, now standard on LN2 delivery trailers. A safety mechanism must be in place to prevent the overfilling, and subsequent overpressure from occurring because these pumps have a higher mass flow output than reasonably sized relief valves provide. The original solution to the problem was to close a valve on the fill line when a certain liquid level in the dewar is reached. The valve remains closed until the level drops below that threshold. The trigger level was about 13,000 gallons for the 20,000 gallon capacity dewar. The solution was in place from 1989 until present, 2004.

  19. Sonochemical synthesis of highly luminescent Ln2O3:Eu3+ (Y, La, Gd) nanocrystals

    SciTech Connect

    Alammar, Tarek; Cybinska, Joanna; Campbell, Paul S.; Mudring, Anja -Verena

    2015-05-12

    In this study, sonication of Ln(CH3COO)3·H2O, Eu(CH3COO)3·H2O and NaOH dissolved in the ionic liquid-butyl-3-methylimidazolium bis(trifluoromethane)sulfonylamide lead to Ln(OH)3:Eu (Ln: Gd, La, Y) nanoparticles. Subsequent calcination at 800 °C for 3 h allowed to obtain Ln2O3:Eu nanopowders. Gd2O3 and Y2O3 were obtained in the C-type lanthanide sequioxide structure, whereas La2O3 crystallized in the A-type. Structure, morphology, and luminescent properties of the nano-oxides were investigated by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), dispersive X-ray (EDX), and photoluminescence (PL). SEM studies revealed that the synthesized Gd2O3:Eu, La2O3:Eu, and Y2O3:Eu formed nano-spindle, -sheets, and -rods in shape, respectively. The nanoscale materials show very efficient red emission due to the intraconfigurational f–f transitions of Eu3+. The quantum yields for Ln2O3:Eu (5%) were determined to be 4.2% for Ln=Gd, 13.8% for Ln=Y and 5.2% for Ln=La. The asymmetric ratio I02/I01 of Eu3+ varies from 5.3 for Gd2O3, to 5.6 for Y2O3 to 6.5 for La2O3, which increased the color chromaticity.

  20. Chemical Substitution and High Pressure Effects on Superconductivity in the LnOBiS2 (Ln = La-Nd) System

    NASA Astrophysics Data System (ADS)

    Fang, Y.; Wolowiec, C. T.; Yazici, D.; Maple, M. B.

    2015-12-01

    A large number of compounds which contain BiS2 layers exhibit enhanced superconductivity upon electron doping. Much interest and research effort has been focused on BiS2-based compounds which provide new opportunities for exploring the nature of superconductivity. Important to the study of BiS2-based superconductors is the relation between structure and superconductivity. By modifying either the superconducting BiS2 layers or the blocking layers in these layered compounds, one can effectively tune the lattice parameters, local atomic environment, electronic structure, and other physical properties of these materials. In this article, we will review some of the recent progress on research of the effects of chemical substitution in BiS2-based compounds, with special attention given to the compounds in the LnOBiS2 (Ln = La-Nd) system. Strategieswhich are reported to be essential in optimizing superconductivity of these materials will also be discussed.

  1. Chemical Substitution and High Pressure Effects on Superconductors in the LnOBiS$_2$ (Ln = La-Nd) System

    SciTech Connect

    Fang, Yuankan; Wolowiec, Christian T.; Yazici, Duygu; Maple, M. Brian

    2015-12-14

    A large number of compounds which contain BiS$_2$ layers exhibit enhanced superconductivity upon electron doping. Much interest and research effort has been focused on BiS$_2$-based compounds which provide new opportunities for exploring the nature of superconductivity. Important to the study of BiS2-based superconductors is the relation between structure and superconductivity. By modifying either the superconducting BiS$_2$ layers or the blocking layers in these layered compounds, one can effectively tune the lattice parameters, local atomic environment, electronic structure, and other physical properties of these materials. In this article, we will review some of the recent progress on research of the effects of chemical substitution in BiS$_2$-based compounds, with special attention given to the compounds in the LnOBiSS$_2$ (Ln = La-Nd) system. Strategies which are reported to be essential in optimizing superconductivity of these materials will also be discussed.

  2. Octanuclear Heterobimetallic {Ni4Ln4} Assemblies Possessing Ln4 Square Grid [2 × 2] Motifs: Synthesis, Structure, and Magnetism.

    PubMed

    Biswas, Sourav; Goura, Joydeb; Das, Sourav; Topping, Craig V; Brambleby, Jamie; Goddard, Paul A; Chandrasekhar, Vadapalli

    2016-09-01

    Octanuclear heterobimetallic complexes, [Ln4Ni4(H3L)4(μ3-OH)4(μ2-OH)4]4Cl·xH2O·yCHCl3 (Dy(3+), x = 30.6, y = 2 (1); Tb(3+), x = 28, y = 0 (2) ; Gd(3+), x = 25.3, y = 0 (3); Ho(3+), x = 30.6, y = 3 (4)) (H5L = N1,N3-bis(6-formyl-2-(hydroxymethyl)-4-methylphenol)diethylenetriamine) are reported. These are assembled by the cumulative coordination action of four doubly deprotonated compartmental ligands, [H3L](2-), along with eight exogenous -OH ligands. Within the core of these complexes, four Ln(3+)'s are distributed to the four corners of a perfect square grid while four Ni(2+)'s are projected away from the plane of the Ln4 unit. Each of the four Ni(2+)'s possesses distorted octahedral geometry while all of the Ln(3+)'s are crystallographically equivalent and are present in an elongated square antiprism geometry. The magnetic properties of compound 3 are dominated by an easy-plane single-ion anisotropy of the Ni(2+) ions [DNi = 6.7(7) K] and dipolar interactions between Gd(3+) centers. Detailed ac magnetometry reveals the presence of distinct temperature-dependent out-of-phase signals for compounds 1 and 2, indicative of slow magnetic relaxation. Magnetochemical analysis of complex 1 implies the 3d and the 4f metal ions are engaged in ferromagnetic interactions with SMM behavior, while dc magnetometry of compound 2 is suggestive of an antiferromagnetic Ni-Tb spin-exchange with slow magnetic relaxation due to a field-induced level crossing. Compound 4 exhibits an easy-plane single-ion anisotropy for the Ho(3+) ions and weak interactions between spin centers. PMID:27500314

  3. Octanuclear Heterobimetallic {Ni4Ln4} Assemblies Possessing Ln4 Square Grid [2 × 2] Motifs: Synthesis, Structure, and Magnetism.

    PubMed

    Biswas, Sourav; Goura, Joydeb; Das, Sourav; Topping, Craig V; Brambleby, Jamie; Goddard, Paul A; Chandrasekhar, Vadapalli

    2016-09-01

    Octanuclear heterobimetallic complexes, [Ln4Ni4(H3L)4(μ3-OH)4(μ2-OH)4]4Cl·xH2O·yCHCl3 (Dy(3+), x = 30.6, y = 2 (1); Tb(3+), x = 28, y = 0 (2) ; Gd(3+), x = 25.3, y = 0 (3); Ho(3+), x = 30.6, y = 3 (4)) (H5L = N1,N3-bis(6-formyl-2-(hydroxymethyl)-4-methylphenol)diethylenetriamine) are reported. These are assembled by the cumulative coordination action of four doubly deprotonated compartmental ligands, [H3L](2-), along with eight exogenous -OH ligands. Within the core of these complexes, four Ln(3+)'s are distributed to the four corners of a perfect square grid while four Ni(2+)'s are projected away from the plane of the Ln4 unit. Each of the four Ni(2+)'s possesses distorted octahedral geometry while all of the Ln(3+)'s are crystallographically equivalent and are present in an elongated square antiprism geometry. The magnetic properties of compound 3 are dominated by an easy-plane single-ion anisotropy of the Ni(2+) ions [DNi = 6.7(7) K] and dipolar interactions between Gd(3+) centers. Detailed ac magnetometry reveals the presence of distinct temperature-dependent out-of-phase signals for compounds 1 and 2, indicative of slow magnetic relaxation. Magnetochemical analysis of complex 1 implies the 3d and the 4f metal ions are engaged in ferromagnetic interactions with SMM behavior, while dc magnetometry of compound 2 is suggestive of an antiferromagnetic Ni-Tb spin-exchange with slow magnetic relaxation due to a field-induced level crossing. Compound 4 exhibits an easy-plane single-ion anisotropy for the Ho(3+) ions and weak interactions between spin centers.

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

    NASA Astrophysics Data System (ADS)

    Hinatsu, Yukio; Doi, Yoshihiro

    2013-02-01

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

  5. Lanthanide stannate pyrochlores Ln{sub 2}Sn{sub 2}O{sub 7} (Ln = Nd, Sm, Eu, Gd, Er, Yb) nanocrystals: Synthesis, characterization, and photocatalytic properties

    SciTech Connect

    Wang, Wanjun; Liang, Shijing; Bi, Jinhong; Yu, Jimmy C.; Wong, Po Keung; Wu, Ling

    2014-08-15

    Highlights: • Ln{sub 2}Sn{sub 2}O{sub 7} (Ln = Nd, Sm, Eu, Gd, Er, Yb) are synthesized by hydrothermal method. • Light absorption edge shows red shift with decreasing Ln{sup 3+} radius from Nd{sup 3+} to Yb{sup 3+}. • Ln{sub 2}Sn{sub 2}O{sub 7} shows increasing photocatalytic activity with the decease of Ln{sup 3+} radius. • Electronic configuration reaches 4f{sup 14} under light irradiation may decrease photocatalytic activity. • Hydroxyl radicals are detected to be the major reactive species. - Abstract: A series of lanthanide stannate pyrochlores Ln{sub 2}Sn{sub 2}O{sub 7} (Ln = Nd, Sm, Eu, Gd, Er, Yb) nanocrystals have been successfully synthesized via a facile hydrothermal route. With the decrease of Ln{sup 3+} radius, the light absorption edge of the as-prepared Ln{sub 2}Sn{sub 2}O{sub 7} shows a red shift from Nd{sup 3+} to Yb{sup 3+}. Their photocatalytic activities are found to be improved with the decrease of Ln{sup 3+} radius. However, the photocatalytic activity of Yb{sub 2}Sn{sub 2}O{sub 7} is a little lower than Er{sub 2}Sn{sub 2}O{sub 7}, although the Yb{sup 3+} radius is smaller than Er{sup 3+}, which may be attributed to the full-filled electronic configuration (4f{sup 14}) of surface Yb{sup 2+} intermediates (formed by Yb{sup 3+} trapping a photo-excited electron). The crystallite size and surface area play the most important role in determining the activities. Furthermore, hydroxyl radicals are detected to be the major reactive species during the photo-degradation process. Our findings provide insights in the fabrication of highly efficient stannate photocatalysts, thus enlarging the family of photocatalysts available.

  6. Structure and stability of the low-temperature modification compounds Cs[sub 3]LnCl[sub 6] (Ln = La-Gd)

    SciTech Connect

    Seifert, H.J.; Fink, H. ); Baumgartner, B. )

    1993-11-01

    The crystal structure of the low-temperature modification of Cs[sub 3]LaCl[sub 6] has been determined from X-ray powder diffraction data by the Rietveld method. The monoclinic lattice with a = 27.286(5) [angstrom]; b = 8.291(1) [angstrom]; c = 13.305(2) [angstrom]; [beta] = 99.64(1)[degrees] belongs to the Cs[sub 3]BiCl[sub 6]-type (space group C2/c). All other compounds Cs[sub 3]LnCl[sub 6] (Ln = Gd) and the analogous Rb-compounds are isotypic. Emf measurements in a galvanic cell for solid electrolytes for the reactions CsCl + Cs[sub 2]LnCl[sub 5] = Cs[sub 3]LnCl[sub 6] reveal that the compounds with Ln = La,Ce,Pr,Nd are formed with a loss of lattice enthalpy, compensated by a considerable gain in entropy; they therefore are stable only at temperatures higher than O K. The compounds with Ln = Sm,Eu,Dg are formed with a gain in lattice enthalpy and are stable at T = OK, too. This difference is attributed to the different crystal structures of the neighboring compounds Cs[sub 2]LnCl[sub 5]: they crystallize with the K[sub 2]PrCl[sub 5]-structure (CN = 7 for Ln[sup 3+]) for the compounds with Ln = La-Nd, while the other compounds belong to the Cs[sub 2]DyCl[sub 5]-type with octahedral surroundings for the Ln[sup 3+] ions.

  7. Cooperative reduction by Ln(2+) and Cp*(-) ions: synthesis and properties of Sm, Eu, and Yb complexes with 3,6-di-tert-butyl-o-benzoquinone.

    PubMed

    Pushkarevsky, Nikolay A; Ogienko, Mikhail A; Smolentsev, Anton I; Novozhilov, Igor N; Witt, Alexander; Khusniyarov, Marat M; Cherkasov, Vladimir K; Konchenko, Sergey N

    2016-01-21

    The first examples of samarium, europium, and ytterbium complexes with 3,6-di-tert-butyl-o-benzoquinone(3,6-dbbq) in the form of catecholate have been obtained by reactions of the quinone with the corresponding lanthanocenes, [LnCp2*(thf)n] (n = 1 or 2) in solution. In the course of the reactions lanthanide ions lose one or two Cp* ligands, which take part in reduction of a quinone molecule into a catecholate anion (dbcat, 2(-)). As a result of the reactions, Sm and Yb clearly yield dimeric complexes[(LnCp*)2(dbcat)2], where each Ln ion loses one Cp* ligand. Eu forms a trimeric complex [(EuCp*)-(Eu·thf)2(dbcat)3], in which one Eu ion is coordinated by one Cp* ligand, while two Eu ions have lost all Cp* ligands and are coordinated by THF molecules instead. Magnetic properties corroborate the assignment of oxidation states made on the basis of single-crystal X-ray diffraction: all the quinone ligands are present in the catecholate state; both Sm/Yb ions in the dimers are in the +3 oxidation state, whereas the Eu trimer contains two Eu(II) and one Eu(III) ions. Cyclovoltammetry studies show the presence of two reversible oxidation waves for all complexes, presumably concerned with the redox transitions of the dbcat ligands.

  8. Cooperative reduction by Ln(2+) and Cp*(-) ions: synthesis and properties of Sm, Eu, and Yb complexes with 3,6-di-tert-butyl-o-benzoquinone.

    PubMed

    Pushkarevsky, Nikolay A; Ogienko, Mikhail A; Smolentsev, Anton I; Novozhilov, Igor N; Witt, Alexander; Khusniyarov, Marat M; Cherkasov, Vladimir K; Konchenko, Sergey N

    2016-01-21

    The first examples of samarium, europium, and ytterbium complexes with 3,6-di-tert-butyl-o-benzoquinone(3,6-dbbq) in the form of catecholate have been obtained by reactions of the quinone with the corresponding lanthanocenes, [LnCp2*(thf)n] (n = 1 or 2) in solution. In the course of the reactions lanthanide ions lose one or two Cp* ligands, which take part in reduction of a quinone molecule into a catecholate anion (dbcat, 2(-)). As a result of the reactions, Sm and Yb clearly yield dimeric complexes[(LnCp*)2(dbcat)2], where each Ln ion loses one Cp* ligand. Eu forms a trimeric complex [(EuCp*)-(Eu·thf)2(dbcat)3], in which one Eu ion is coordinated by one Cp* ligand, while two Eu ions have lost all Cp* ligands and are coordinated by THF molecules instead. Magnetic properties corroborate the assignment of oxidation states made on the basis of single-crystal X-ray diffraction: all the quinone ligands are present in the catecholate state; both Sm/Yb ions in the dimers are in the +3 oxidation state, whereas the Eu trimer contains two Eu(II) and one Eu(III) ions. Cyclovoltammetry studies show the presence of two reversible oxidation waves for all complexes, presumably concerned with the redox transitions of the dbcat ligands. PMID:26674171

  9. Controlled processing of (Gd,Ln)2O3:Eu (Ln = Y, Lu) red phosphor particles and compositional effects on photoluminescence

    NASA Astrophysics Data System (ADS)

    Lu, Bin; Li, Ji-Guang; Sakka, Yoshio

    2013-12-01

    Synthesis of (Gd0.95-xLnxEu0.05)2O3 (Ln = Y and Lu, x = 0-0.95) powders via ammonium hydrogen carbonate (AHC) precipitation has been systematically studied. The best synthesis parameters are found to be an AHC/total cation molar ratio of 4.5 and an ageing time of 3 h. The effects of Y3+ and Lu3+ substitution for Gd3+, on the nucleation kinetics of the precursors and structural features and optical properties of the oxides, have been investigated. The results show that (i) different nucleation kinetics exist in the Gd-Y-Eu and Gd-Lu-Eu ternary systems, which lead to various morphologies and particle sizes of the precipitated precursors. The (Gd,Y)2O3:Eu precursors display spherical particle morphologies and the particle sizes increase along with more Y3+ addition. The (Gd,Lu)2O3:Eu precursors, on the other hand, are hollow spheres and the particle sizes increase with increasing Lu3+ incorporation, (ii) the resultant oxide powders are ultrafine, narrow in size distribution, well dispersed and rounded in particle shape, (iii) lattice parameters of the two kinds of oxide solid solutions linearly decrease at a higher Y3+ or Lu3+ content. Their theoretical densities linearly decrease with increasing Y3+ incorporation, but increase along with more Lu3+ addition and (iv) the two kinds of phosphors exhibit typical red emissions at ˜613 nm and their charge-transfer bands blue shift at a higher Y3+ or Lu3+ content. Photoluminescence/photoluminescence excitation intensities and external quantum efficiency are found to decrease with increasing value of x, and the fluorescence lifetime mainly depends on the specific surface areas of the powders.

  10. Photorhabdus luminescens LN2 requires rpoS for nematicidal activity and nematode development.

    PubMed

    Qiu, Xuehong; Wu, Chunyan; Cao, Li; Ehlers, Ralf-Udo; Han, Richou

    2016-03-01

    Photorhabdus (Enterobacteriaceae) bacteria are pathogenic to insects and mutualistic with entomopathogenic Heterorhabditis nematodes. Photorhabdus luminescens subsp. akhurstii LN2, associated with Heterorhabditis indica LN2, shows nematicidal activity against H. bacteriophora H06 infective juveniles (IJs). In the present study, an rpoS mutant of P. luminescens LN2 was generated through allelic exchange to examine the effects of rpoS deletion on the nematicidal activity and nematode development. The results showed that P. luminescens LN2 required rpoS for nematicidal activity against H06 nematodes, normal IJ recovery and development of H. indica LN2, however, not for the bacterial colonization in LN2 and H06 IJs. This provides cues for further understanding the role of rpoS in the mutualistic association between entomopathogenic nematodes and their symbionts. PMID:26884480

  11. Method for synthesizing fine-grained phosphor powders of the type (RE{sub 1{minus}x}Ln{sub x})(P{sub 1{minus}y}V{sub y})O{sub 4}

    DOEpatents

    Phillips, M.L.F.

    1998-04-28

    A method for generating well-crystallized photo- and cathodoluminescent oxide phosphor powders is disclosed. The method of this invention uses hydrothermal synthesis and annealing to produce nearly monosized (RE{sub 1{minus}x}Ln{sub x})(P{sub 1{minus}y}V{sub y}O{sub 4}) (Ln{double_bond}Ce{yields}Lu) phosphor grains with crystallite sizes from 0.04 to 5 {micro}m. Such phosphors find application in cathode-ray tube, flat-panel, and projection displays. 4 figs.

  12. Synthesis, properties and phase transitions of pyrochlore- and fluorite-like Ln{sub 2}RMO{sub 7} (Ln = Sm, Ho; R = Lu, Sc; M = Nb, Ta)

    SciTech Connect

    Shlyakhtina, A.V.; Belov, D.A.; Pigalskiy, K.S.; Shchegolikhin, A.N.; Kolbanev, I.V.; Karyagina, O.K.

    2014-01-01

    Graphical abstract: Temperature dependences of bulk conductivity for Sm{sub 2}ScTaO{sub 7} pyrochlore prepared at (1) 1400 °C, 20 h; and (2) 1200 °C, 40 h. - Highlights: • The phase formation of Ln{sub 2}RMO{sub 7} (Ln = Sm, Ho; R = Lu, Sc; M = Nb, Ta) at 1200–1600 °C. • The bulk conductivity and magnetic susceptibility were measured. • The bulk conductivity of Sm{sub 2}ScTaO{sub 7} has oxygen ion type at T ≥ 750 °C. • The first-order structural phase transition was observed in Sm{sub 2}ScTaO{sub 7} at ∼650–700 °C. • This phase transformation is not typical for defect fluorites. - Abstract: We have studied the new compounds with fluorite-like (Ho{sub 2}RNbO{sub 7} (R = Lu, Sc)) and pyrochlore-like (Sm{sub 2}ScTaO{sub 7}) structure as potential oxide ion conductors. The phase formation process (from 1200 to 1600 °C) and physical properties (electrical, thermo mechanical, and magnetic) for these compounds were investigated. Among the niobate materials the highest bulk conductivity is offered by the fluorite-like Ho{sub 2}ScNbO{sub 7} synthesized at 1600 °C: 3.8 × 10{sup −5} S/cm at 750 °C, whereas in Sm system the highest bulk conductivity, 7.3 × 10{sup −6} S/cm at 750 °C, is offered by the pyrochlore Sm{sub 2}ScTaO{sub 7} synthesized at 1400 °C. In Sm{sub 2}ScTaO{sub 7} pyrochlore we have observed the first-order phase transformation at ∼650–700 °C is related to rearrangement process in the oxygen sublattice of the pyrochlore structure containing B-site cations in different valence state and actually is absent in the defect fluorites. The two holmium niobates show Curie–Weiss paramagnetic behavior, with the prevalence of antiferromagnetic coupling. The magnetic susceptibility of Sm{sub 2}ScTaO{sub 7} is a weak function of temperature, corresponding to Van Vleck paramagnetism.

  13. Magnetic properties of quadruple perovskites Ba{sub 4}LnRu{sub 3}O{sub 12} (Ln=La, Nd, Sm-Gd, Dy-Lu)

    SciTech Connect

    Shimoda, Yuki; Doi, Yoshihiro; Wakeshima, Makoto; Hinatsu, Yukio

    2010-01-15

    Quadruple perovskites Ba{sub 4}LnRu{sub 3}O{sub 12} (Ln=La, Nd, Sm-Gd, Dy-Lu) were prepared and their magnetic properties were investigated. They adopt the 12L-perovskite-type structure consisting of Ru{sub 3}O{sub 12} trimers and LnO{sub 6} octahedra. All of these compounds show an antiferromagnetic transition at 2.5-30 K. For Ba{sub 4}NdRu{sub 3}O{sub 12}, ferrimagnetic ordering has been observed at 11.5 K. The observed magnetic transition is due to the magnetic behavior of the Ru{sup 4.33+}{sub 3}O{sub 12} trimer with S=1/2 . Magnetic properties of Ba{sub 4}LnRu{sub 3}O{sub 12} were compared with those of triple perovskites Ba{sub 3}LnRu{sub 2}O{sub 9} and double perovskites Ba{sub 2}LnRuO{sub 6}. - Graphical abstract: Quadruple perovskites Ba{sub 4}LnRu{sub 3}O{sub 12} (Ln=La, Nd, Sm-Gd, Dy-Lu) were prepared. They adopt the 12L-perovskite-type structure consisting of Ru{sub 3}O{sub 12} trimers and LnO{sub 6} octahedra. All of these compounds show an antiferromagnetic transition at 2.5-30 K. For Ba{sub 4}NdRu{sub 3}O{sub 12}, ferrimagnetic ordering has been observed at 11.5 K. The observed magnetic transition is due to the magnetic behavior of the Ru{sup 4.33+}{sub 3}O{sub 12} trimer with S=1/2 . Magnetic properties of Ba{sub 4}LnRu{sub 3}O{sub 12} were compared with those of triple perovskites Ba{sub 3}LnRu{sub 2}O{sub 9} and double perovskites Ba{sub 2}LnRuO{sub 6}.

  14. Structural and physical properties of layered oxy-arsenides LnRuAsO (Ln=La, Nd, Sm, Gd)

    SciTech Connect

    McGuire, Michael A.; May, Andrew F.; Sales, Brian C.

    2012-07-15

    Polycrystalline samples of LaRuAsO, NdRuAsO, SmRuAsO, and GdRuAsO have been synthesized and studied using powder x-ray diffraction, electrical transport, magnetization, and heat capacity measurements. Variations in structural properties across the series reveal a trend toward more ideal tetrahedral coordination around Ru as the size of the rare earth element is reduced. The lattice parameters of these Ru compounds show a more anisotropic response to variation in Ln than their Fe analogs, and significant anisotropy in thermal expansion is also observed. Transport measurements show metallic behavior, and carrier concentrations near 10{sup 21}-10{sup 22} electrons per cm{sup 3} are inferred from simple analysis of Hall effect measurements. Anomalies in resistivity, magnetization, and heat capacity indicate antiferromagnetic ordering of rare earth moments at 5 K for GdRuAsO, 4.5 K for SmRuAsO, and <2K for NdRuAsO. Magnetization measurements on LaRuAsO show no evidence of a magnetic moment on Ru. Observed behaviors are compared to those reported for similar Fe and Ru compounds. - Graphical abstract: Analysis of crystal structure, electrical transport, magnetic susceptibility, and heat capacity of LaRuAsO, NdRuAsO, SmRuAsO, and GdRuAsO. Highlights: Black-Right-Pointing-Pointer Experimental investigation of LaRuAsO, NdRuAsO, SmRuAsO, and GdRuAsO. Black-Right-Pointing-Pointer Anisotropic lattice response to changing Ln radius and temperature. Black-Right-Pointing-Pointer Ru coordination becomes more ideal as Ln radius is reduced. Black-Right-Pointing-Pointer Transport measurements reveal metallic conduction dominated by electrons. Black-Right-Pointing-Pointer Magnetic measurements indicate antiferromagnetic ordering Nd, Sm, and Gd moments.

  15. A Study of the Magnetic and Thermal Properties of Ln

    SciTech Connect

    Harada, Daijitsu; Hinatsu, Yukio

    2001-05-01

    Crystal structures, and magnetic, electric, and thermal properties of fluorite related compounds Ln{sub 3}RuO{sub 7} (Ln=Sm, Eu) have been investigated. For Eu{sub 3}RuO{sub 7}, a magnetic transition due to Ru{sup 5+} ions is found at T{sub N}=22.5 K on the susceptibility-temperature curve. Specific heat measurements also exhibit a {lambda}-type anomaly at the same temperature. The Moessbauer spectrum measured at 10 K shows broadening of the line corresponding to magnetic splitting. For Sm{sub 3}RuO{sub 7}, two magnetic anomalies have been observed at 10.5 and 22.5 K from its magnetic susceptibility measurements. Below 22.5 K Ru{sup 5+} ions are antiferromagnetically coupled, and when the temperature is decreased through 10.5 K the ordering of Sm{sup 3+} ions occurs rapidly. Specific heat measurements show first-order transition peaks at T=280 and 190 K for Eu{sub 3}RuO{sub 7} and Sm{sub 3}RuO{sub 7}, respectively. T he results of magnetic susceptibility and electric resistivity measurements indicate that these transitions are structural phase transitions.

  16. Effect of LN2 injection station location on the drive fan power and LN2 requirements of a cryogenic wind tunnel

    NASA Technical Reports Server (NTRS)

    Adcock, J. B.

    1977-01-01

    A theoretical analysis comparing the fan power and coolant (LN2) flow rates resulting from injection of the LN2 either upstream or downstream of the drive fan of a closed circuit transonic cryogenic tunnel is presented. The analysis is restricted to steady state tunnel operation and to the condition that the tunnel walls are adiabatic. The stagnation pressure and temperature range of the tunnel is from 1.0 to 8.8 atm and from 300 K to liquefaction temperature, respectively. Calculations are made using real gas properties of nitrogen. Results show that the fan power and LN2 flow rates are lower if the LN2 is injected upstream of the fan. The lower fan inlet temperature resulting from injecting upstream of the fan has a greater influence on the power than does the additional mass flow going through the fan.

  17. Variable Emission Changes in Bi3+/Ln3+ (Ln = Eu, Sm, Dy) Co-doped Lutetium Vanadates (LuVO4)

    NASA Astrophysics Data System (ADS)

    Zheng, Yuhui; Hu, Jing; Deng, Surong; Gao, Jinwei; Wang, Qianming

    2016-06-01

    High-purity LuVO4: Ln3+/Bi3+ (Ln = Eu, Sm, Dy) phosphors with tetragonal zircon structures were successfully synthesized. The reactions have been carried out by multiple irradiations with very high efficiency. Transmission electron microscope images showed that the phosphors had rod-like structures with average lengths of about 200 nm. The host absorption edge of LuVO4: Ln3+/Bi3+ (Ln = Eu, Sm) shifted to the longer wavelength side. Furthermore, the red emission of Eu3+ ion and the orange emission of Sm3+ ion are remarkably enhanced by encapsulating Bi3+ in LuVO4 system, whereas in the case of LuVO4: Dy3+/Bi3+, the host absorption and the yellow emission from dysprosium have been suppressed in the presence of Bi3+. These novel findings will facilitate their use in the display field.

  18. Ferrocene-based compartmental ligand for the assembly of neutral Zn(II)/Ln(III) heterometallic complexes.

    PubMed

    Chandrasekhar, Vadapalli; Chakraborty, Amit; Sañudo, E Carolina

    2013-10-01

    A ferrocene-based compartmental ligand, H2L, was synthesized by the reaction of diacetyl ferrocene with hydrazine hydrate followed by a condensation reaction with o-vanillin. [L](2-) possesses a dual coordination pocket, an inner pocket of 2 imino nitrogens and two phenolate oxygens and an outer pocket of two phenolate and two methoxy oxygen atoms. Utilizing this ligand, several Zn(II)/Ln(III) heterobimetallic complexes were assembled: [LZn(μ-OAc)Dy(NO3)2] (2), [LZn(μ-OAc)Tb(NO3)2] (3), [LZn(μ-OAc)Gd(NO3)2·2CHCl3] (4), [LZn(μ-OAc)Er(NO3)2] (5), [LZn(μ-OAc)Ho(NO3)2] (6), [LZn(μ-OAc)Eu(NO3)2] (7). All of these metal complexes are neutral and isostructural: the Zn(II) ion occupies the inner coordination pocket while the Ln(III) ion occupies the outer coordination pocket of the doubly deprotonated ligand [L](2-). Zn(II) has a coordination number of 5 (2N, 3O) in a square pyramidal coordination geometry while Ln(III) has a coordination number of 9 (9O) in a distorted tricapped trigonal prismatic geometry. Zn(II) and the 4f metal ion are bridged to each other by two phenolate oxygen atoms and an acetate ligand. ESI-MS reveals that 2-7 retain their structural integrity in solution. Cyclic voltammetry of 1-7 revealed a quasi-reversible oxidation (involving the ferrocene motif) and an irreversible reduction of the hydrazone unit. Magnetic studies of 2, 3 and 6 were carried out. Ac susceptibility studies did not reveal slow relaxation of magnetization.

  19. Structures, magnetic and dielectric properties of the ordered double perovskites LnPbNiSbO6 (Ln = La, Pr)

    NASA Astrophysics Data System (ADS)

    Han, Lin; Bai, Yijia; Liu, Xiaojuan; Yao, Chuangang; Meng, Junling; Liang, Qingshuang; Wu, Xiaojie; Meng, Jian

    2014-09-01

    The crystal structures, magnetic and dielectric properties for the ordered double perovskites LnPbNiSbO6 (Ln = La, Pr) have been investigated. Rietveld refinements of x-ray diffraction data have been indexed for the monoclinic symmetry in space group P21/n (No. 14) and a highly rock-salt ordered arrangement of NiO6 and SbO6 octahedra. The B-site lattices are distorted strongly due to the substitution of rare Earth ions at the A-site. The magnetization measurements show an antiferromagnetic ordering. The effective magnetic moments μ eff are larger than the spin-only values, suggesting that the orbital component for Ni2+ is significant. The maximum values of isothermal magnetization increase due to the lattice distortion of BO6 octahedra, which may weaken the antiferromagnetic interaction via Ni2+-O-Sb5+-O-Ni2+ paths. The dielectric constants for LaPbNiSbO6 present frequency dependence and the tan δ curves exhibit relaxor-like dielectric response. The ɛ‧ decreases with the reduction of the magnetic moments of B-site transition metal ions, which reveals a relationship between the dielectric and magnetic properties.

  20. Chemical Substitution and High Pressure Effects on Superconductors in the LnOBiS$_2$ (Ln = La-Nd) System

    DOE PAGESBeta

    Fang, Yuankan; Wolowiec, Christian T.; Yazici, Duygu; Maple, M. Brian

    2015-12-14

    A large number of compounds which contain BiS$_2$ layers exhibit enhanced superconductivity upon electron doping. Much interest and research effort has been focused on BiS$_2$-based compounds which provide new opportunities for exploring the nature of superconductivity. Important to the study of BiS2-based superconductors is the relation between structure and superconductivity. By modifying either the superconducting BiS$_2$ layers or the blocking layers in these layered compounds, one can effectively tune the lattice parameters, local atomic environment, electronic structure, and other physical properties of these materials. In this article, we will review some of the recent progress on research of the effectsmore » of chemical substitution in BiS$_2$-based compounds, with special attention given to the compounds in the LnOBiSS$_2$ (Ln = La-Nd) system. Strategies which are reported to be essential in optimizing superconductivity of these materials will also be discussed.« less

  1. Linking two distinct layered networks of nanosized {Ln18} and {Cu24} wheels through isonicotinate ligands.

    PubMed

    Cheng, Jian-Wen; Zhang, Jie; Zheng, Shou-Tian; Yang, Guo-Yu

    2008-01-01

    A new series of heterolanthanide(III)-copper(I) wheel-cluster complexes [Ln6(micro3-O)2](IN)18-[Cu8(micro4-I)2(micro2-I)3].H3O (IN=isonicotinate; Ln=Y 1, Nd 2, Dy 3, Gd 4, Sm 5, Eu 6, Tb 7) were prepared by hydrothermal reaction at low pH. X-ray crystallographic studies reveal that two unusual trinuclear [Ln3(micro3-O)] and tetranuclear [Cu4(micro4-I)] cores are successfully used as secondary building units to make two different nanosized wheels [Ln18(micro3-O)6(CO2)48](6-), {Ln18}, and [Cu24(micro4-I)6(micro2-I)12]6+, {Cu24}, with 12-rings and a diameter of 26.7 and 26.4 A, respectively. The wheels are further assembled into two-dimensional (2D) {Ln18} and {Cu24} networks, the linkages between two distinct layered networks of {Ln18} and {Cu24} wheels by IN pillars along the c axis giving a series of unprecedented three-dimensional (3D) sandwich frameworks. To our knowledge, compounds 1-7 are the first examples containing two different layered networks of nanosized Ln and transition metal (TM) wheels in wheel-cluster chemistry. The IR, UV/Vis, thermogravimetric analysis (TGA), luminescent, and magnetic properties of these complexes were also studied.

  2. Deliverable for FαST project: Ln Resin based PLE

    SciTech Connect

    Peterson, Dominic S.; Armenta, Claudine E.; Rim, Jung H.

    2012-05-03

    This memo describes the fabrication of a polymer ligand extractant based on Eichrom's LN-1 resin. This work has been in support of the Fast Alpha Spectrometry Tool (F{alpha}ST) project. The first part of LANL's role in this project is to evaluate new extractants for use in polymer ligand extractants (PLEs). The first new extractant evaluated is Di(2-ethyl hexyl) phosphoric acid (HDEHP), which is an effective metal extractant. It has very efficient chelating properties for a wide variety of metal ions. HDEHP is an amphiphillic molecule with two long hydrocarbon chains and a polar end with a phosphoryl oxygen (P=O) and an acidic -OH group as shown in Figure 1. HDEHP has shown effectiveness in extracting lanthanides, selective actinides, and other trivalent elements. Several authors have reported that lanthanides and elements with +3 oxidation state have similar extraction behavior in nitric acid. The distribution ratio for lanthanides rapidly decreases at lower nitric concentration then start to increase at higher concentration as shown in. The trivalent americium, curium, and yttrium exhibit similar trend as trivalent lanthanides. This extraction trend can be also observed from hydrogen chloride solution. This work describes the use of this ligand in a PLE to extract plutonium from solution. Polymer ligand films were prepared by dissolving HDEHP ligands and polystyrene beads in THF. The solution was directly deposited onto a 40 mm diameter stainless steel substrate using an automated pipette. HDEHP based PLEs with direct stippling method are shown in Figure 2. The solution was air dried at room temperature overnight to ensure complete evaporation of THF. The plutonium tracer solution was prepared in 0.01, 0.1, 1, and 8M nitric solutions to study the effect of nitric concentration in plutonium extraction. 0.1667 Bq {sup 239}Pu tracer solution was directly stippled on each PLE and was allowed to equilibrate for 3 hours before removing the solution. The plutonium

  3. Structural and electrical properties of T'-type Ln2CuO4 (Ln = Pr, Nd, Sm, Eu and Gd) ceramics

    NASA Astrophysics Data System (ADS)

    Salame, Paresh Hiralal

    2016-05-01

    T'-type Ln2CuO4 (Ln = Pr, Nd, Sm, Eu and Gd) were successfully synthesized in phase pure form using conventional solid state reaction and sintering route. For all the Ln2CuO4 samples, the solid state reaction temperature was found to be 950 °C and pure phase was realized only after 2-3 intermediate milling and solid state reaction cycles, irrespective of the lanthanide ion radius. Effect of lanthanide ion contraction on the structural properties was clearly revealed by the powder X-ray diffraction, with the XRD peaks observed to be shifting towards higher 2θ values with the decrease in Ln ionic radii. The optimum sintering temperature of these solid state reacted Ln2CuO4 powder was found to be 1100 °C except for Pr2CuO4 powder. The conductivity of these samples were tested over a wide temperature range (-100 to 150 °C), an anomaly was observed in the conductivity of all the Ln2CuO4 samples near the antiferromagnetic ordering temperature of Cu (~ 30 °C), thus suggesting the bearing of ordering of magnetic moments on the electrical properties.

  4. B-site disordering in Ba{sub 3}Ln{sub 2}MoO{sub 9} (Ln=Ho, Er) perovskites: A neutron diffraction study

    SciTech Connect

    Larregola, S.A.; Alonso, J.A.; Garcia Hernandez, M.; Fernandez-Diaz, M.T.; Pedregosa, J.C.

    2009-06-15

    We describe the preparation, structure determination and magnetic properties of two Ba perovskites containing rare-earth cations at the B-sublattice. Ba{sub 3}Ln{sub 2}MoO{sub 9} (Ln=Ho{sup 3+} and Er{sup 3+}) were synthesized by ceramic procedures. Joint X-ray (XRPD) and neutron (NPD) powder diffraction refinements were carried out to analyse the crystal structure. At room temperature, both phases are tetragonal, space group I4/mcm, Z=4. Ln and Mo atoms are found to be distributed at random over the octahedral sites of the perovskites. Magnetic measurements at 0.1 T show that both samples are paramagnetic between 3 and 300 K, following a Curie-Weiss law. M vs. H curves show a region of paramagnetic behaviour and above 2.5 T a magnetic saturated system is observed. Finally, the temperature evolution of the NPD patterns of Ba{sub 3}Ho{sub 2}MoO{sub 9} reveals the absence of long-range magnetic ordering down to 2 K. - Graphical Abstract: Preparation, structure and magnetic properties of Ba{sub 3}Ln{sub 2}MoO{sub 9} (Ln=Ho{sup 3+} and Er{sup 3+}) are descripted. Joint XRPD and NPD refinements confirm a tetragonal I4/mcm structure. Ln and Mo atoms are found to be distributed at random over the octahedral sites of the perovskites.

  5. Intracluster interactions in "butterfly" {Fe3LnO2} molecules

    NASA Astrophysics Data System (ADS)

    Badía-Romano, L.; Rubín, J.; Bartolomé, F.; Bartolomé, J.; Luzón, J.; Prodius, D.; Turta, C.; Mereacre, V.; Wilhelm, F.; Rogalev, A.

    2016-02-01

    The magnetization contributions of the Fe3 and Ln subcluster in the "butterfly" molecule [Fe3Ln(μ3-O)2(CCl3COO)8(H2O)(THF)3], in brief {Fe3LnO2}, with Ln=Lu, Gd, Tb, Dy and Ho, have been determined by a combination of vibrating sample magnetometry and x-ray circular magnetic dichroism at low temperature and magnetic field up to 14 T. These contributions have been explained in terms of an effective spin model where the Fe3 is described by a SFe3 = 5 / 2 spin, Gd by an isotropic J=7/2, Dy by a Kramers doublet, and non-Kramers ions Tb and Ho by a ligand field split doublet. The intracluster interactions JFeLn have been found to amount to a few K.

  6. Interfacial Structure in Silicon Nitride Sintered with Lanthanide Oxide

    SciTech Connect

    Dwyer, C.; Ziegler, A.; Shibata, Naoya; Winkelman, G. B.; Satet, R. L.; Hoffmann, M. J.; Cinibulk, M. K.; Becher, Paul F; Painter, Gayle S; Browning, N. D.; Cockayne, D.J.H.; Ritchie, R O; Pennycook, Stephen J

    2006-01-01

    Three independent research groups present a comparison of their structural analyses of prismatic interfaces in silicon nitride densified with the aid of lanthanide oxide Ln{sub 2}O{sub 3}. All three groups obtained scanning transmission electron microscope images which clearly reveal the presence of well-defined Ln segregation sites at the interfaces, and, moreover, reveal that these segregation sites are element-specific. While some results differ across the three research groups, the vast majority exhibits good reproducibility.

  7. Strength of nanostructured austenitic steel 316LN at cryogenic temperatures

    NASA Astrophysics Data System (ADS)

    Czarkowski, P.; Krawczynska, A. T.; Brynk, T.; Nowacki, M.; Lewandowska, M.; Kurzydłowski, K. J.

    2014-12-01

    The aim of this work was to investigate the effect of nano-refinement on the properties of austenitic steel. The material with the initial grain size of 40-50pm was subjected to hydrostatic extrusion at a room temperature to the total accumulated strain exceeding 1. The microstructure developed was investigated by Transmission Electron Microscopy (TEM) and Focus Ion Beam (FIB). The strength of the extruded samples was tested at 293K, 77K and 4.2K by means of cryostat for static tensile tests. The results show that the hydrostatically extruded steel 316LN has excellent strength in cryogenic conditions, which make this material interesting for applications in cryogenic devices.

  8. Increasing Dietary Fat Elicits Similar Changes in Fat Oxidation and Markers of Muscle Oxidative Capacity in Lean and Obese Humans

    PubMed Central

    Bergouignan, Audrey; Gozansky, Wendolyn S.; Barry, Daniel W.; Leitner, Wayne; MacLean, Paul S.; Hill, James O.; Draznin, Boris; Melanson, Edward L.

    2012-01-01

    In lean humans, increasing dietary fat intake causes an increase in whole-body fat oxidation and changes in genes that regulate fat oxidation in skeletal muscle, but whether this occurs in obese humans is not known. We compared changes in whole-body fat oxidation and markers of muscle oxidative capacity differ in lean (LN) and obese (OB) adults exposed to a 2-day high-fat (HF) diet. Ten LN (BMI = 22.5±2.5 kg/m2, age = 30±8 yrs) and nine OB (BMI = 35.9±4.93 kg/m2, 38±5 yrs, Mean±SD) were studied in a room calorimeter for 24hr while consuming isocaloric low-fat (LF, 20% of energy) and HF (50% of energy) diets. A muscle biopsy was obtained the next morning following an overnight fast. 24h respiratory quotient (RQ) did not significantly differ between groups (LN: 0.91±0.01; OB: 0.92±0.01) during LF, and similarly decreased during HF in LN (0.86±0.01) and OB (0.85±0.01). The expression of pyruvate dehydrogenase kinase 4 (PDK4) and the fatty acid transporter CD36 increased in both LN and OB during HF. No other changes in mRNA or protein were observed. However, in both LN and OB, the amounts of acetylated peroxisome proliferator-activated receptor γ coactivator-1-α (PGC1-α) significantly decreased and phosphorylated 5-AMP-activated protein kinase (AMPK) significantly increased. In response to an isoenergetic increase in dietary fat, whole-body fat oxidation similarly increases in LN and OB, in association with a shift towards oxidative metabolism in skeletal muscle, suggesting that the ability to adapt to an acute increase in dietary fat is not impaired in obesity. PMID:22253914

  9. One-dimensional GdVO{sub 4}:Ln{sup 3+} (Ln=Eu, Dy, Sm) nanofibers: Electrospinning preparation and luminescence properties

    SciTech Connect

    Li, Xue; Yu, Min; Hou, Zhiyao; Li, Guogang; Ma, Ping'an; Wang, Wenxin; Cheng, Ziyong; Lin, Jun

    2011-01-15

    One-dimensional GdVO{sub 4}:Ln{sup 3+} (Ln=Eu, Dy, Sm) nanofibers have been prepared by a combination method of sol-gel process and electrospinning technology. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), photoluminescence (PL), quantum efficiency (QE), and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The XRD, FT-IR, and TG-DTA results show that GdVO{sub 4}:Ln{sup 3+} nanofibers samples crystallize at 700 {sup o}C. SEM images indicate that the as prepared precursor fibers are smooth. After being calcined at 700 {sup o}C for 4 h, the fibers still maintain their fiberlike morphology with rough surface. TEM image further manifests that the GdVO{sub 4}:Ln{sup 3+} nanofibers consist of nanoparticles. Under ultraviolet excitation and low-voltage electron beam excitation, GdVO{sub 4}:Ln{sup 3+} phosphors showed their strong characteristic emission due to an efficient energy transfer from vanadate groups to dopants. The optimum doping concentration of Ln{sup 3+} in the GdVO{sub 4} nanofibers also has been investigated. -- Graphical abstract: Display Omitted Research Highlights: {yields}1D and Q-1D GdVO{sub 4} fiber-like nanostructures were prepared electrospinning technique. {yields}Under ultraviolet excitation and electron beam excitation, the Ln{sup 3+} ions show their characteristic emissions, respectively. {yields}The quantum efficiencies are 14 (Eu{sup 3+}), 6 (Dy{sup 3+}), and 5 % (Sm{sup 3+}) in GdVO{sub 4}, respectively.

  10. Monodisperse lanthanide oxyfluorides LnOF (Ln = Y, La, Pr-Tm): morphology controlled synthesis, up-conversion luminescence and in vitro cell imaging

    NASA Astrophysics Data System (ADS)

    Zhang, Yang; Li, Xuejiao; Hou, Zhiyao; Lin, Jun

    2014-05-01

    Lanthanide oxyfluorides LnOF (Ln = Y, La, Pr-Tm) nano/micro-materials with a variety of well-defined morphologies including nanorods, nanospindles, nanorod-bundles and nanospheres, have been successfully synthesized via a facile precipitation technique followed by a heating treatment. It is found that the pH values, fluoride sources and dosage of urea in the initial reaction systems play critical roles in the morphology determination of the LnOF products and the possible formation mechanism for these diverse architectures has been presented. XRD, FT-IR, TG-DTA, SEM, TEM, as well as up-conversion (UC) luminescence spectra are used to characterize the synthesized samples. Under 980 nm NIR laser excitation, red, green and blue UC luminescence are observed from Yb3+/Er3+, Yb3+/Ho3+ and Yb3+/Tm3+ co-doped YOF nanospheres. The MTT assay indicates that YOF nanospheres exhibit good biocompatibility. Especially, the emission spectrum of YOF: 0.20Yb3+, 0.04Er3+ nanospheres is dominated by a single red emission at 660 nm, which falls into the ``optical window'' of biological tissues. The application of YOF: 0.20Yb3+, 0.04Er3+ nanospheres in the cell imaging is also investigated, which shows a bright-red emission without background noise.Lanthanide oxyfluorides LnOF (Ln = Y, La, Pr-Tm) nano/micro-materials with a variety of well-defined morphologies including nanorods, nanospindles, nanorod-bundles and nanospheres, have been successfully synthesized via a facile precipitation technique followed by a heating treatment. It is found that the pH values, fluoride sources and dosage of urea in the initial reaction systems play critical roles in the morphology determination of the LnOF products and the possible formation mechanism for these diverse architectures has been presented. XRD, FT-IR, TG-DTA, SEM, TEM, as well as up-conversion (UC) luminescence spectra are used to characterize the synthesized samples. Under 980 nm NIR laser excitation, red, green and blue UC luminescence are

  11. Syntheses, crystal structures and optical spectroscopy of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O

    SciTech Connect

    Kazmierczak, Karolina; Hoeppe, Henning A.

    2011-05-15

    The lanthanide sulphate octahydrates Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and the respective tetrahydrate Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O were obtained by evaporation of aqueous reaction mixtures of trivalent rare earth oxides and sulphuric acid at 300 K. Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) crystallise in space group C2/c (Z=4, a{sub Ho}=13.4421(4) A, b{sub Ho}=6.6745(2) A, c{sub Ho}=18.1642(5) A, {beta}{sub Ho}=102.006(1) A{sup 3} and a{sub Tm}=13.4118(14) A, b{sub Tm}=6.6402(6) A, c{sub Tm}=18.1040(16) A, {beta}{sub Tm}=101.980(8) A{sup 3}), Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O adopts space group P2{sub 1}/n (a=13.051(3) A, b=7.2047(14) A, c=13.316(3) A, {beta}=92.55(3) A{sup 3}). The vibrational and optical spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O are also reported. -- Graphical abstract: In the lanthanide sulphate octahydrates the cations form slightly undulated layers. Between the layers are voids in which sulphate tetrahedra and water molecules are located. The holmium compound exhibits an Alexandrite effect. Display Omitted Highlights: {yields} Determination of the optimum conditions for the growth of single-crystals of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O. {yields} Single-crystal structure elucidation of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) including hydrogen bonds. {yields} Single-crystal structure determination of Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O including hydrogen bonds. {yields} UV-vis spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted: Assignation of bands and clarification of the Alexandrite effect of the Ho compound. {yields} IR and Raman spectra of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted.

  12. Ce3+ and Ln3+ (Ln = Dy, Eu, Sm, Tb) Codoped SrF2 Nanoparticles: Synthesis and Multicolor Light Emission.

    PubMed

    Su, Yiguo; Liu, Mengqing; Han, Dan; Li, Lv; Wang, Tingting; Wang, Xiaojing

    2016-04-01

    For optically active Ln3+ ions, fluoride is a very good luminescent substrate that has been used in the field of lasers, solid-phase optical transmitters, optical communications, up/down conversion. This work reports a systematic study on bridging between structure and tunable luminescence for SrF2:Ce3+/Ln3+ (Ln = Dy, Eu, Sm, Tb) nanoparticles. Regardless of the dopant level, all nano-crystals crystallized in a single cubic phase with the diameter of ~20-30 nm. It was found that SrF2:Ce3+ exhibited intense ultraviolet emission under 288 nm excitation which can be attributed to the typical 4f-5d transition of Ce3+ ions. After the incorporation of Ln3+ ions, multicolor emission can be achieved when excited by the 4f-5d transition of Ce3+. This result gave an evidence that the excitation energy of Ce3+ can be transferred to Ln3+ leading to multicolor emission. The findings reported in this work may provide useful information in designing novel luminescent materials for tailored performances.

  13. Synthesis, crystal structures, and magnetic properties of three Mo(V)-Ln(III) (Ln = Ho, Er, Tm) magnetic chains based on [Mo(CN)8]3-

    NASA Astrophysics Data System (ADS)

    Ju, Wen-Wen; Wang, Jun; Zhou, Zhou; Xu, Xiao-Juan; Tao, Jian-Qian

    2016-05-01

    Complexes 1-3 with general formula [Ln(tmphen)2(DMF)2Mo(CN)8]∞ (Ln = Ho(1), Er(2) and Tm(3)) have been prepared by reaction of Cs3[Mo(CN)8]·4H2O and Ln(NO3)3·6H2O in the presence of the tmphen blocking ligand (tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline), and characterized by IR, elemental analysis, single crystal X-ray diffraction and magnetic measurements. The structural determination reveals that complexes 1-3 consist of 1D chains, in which [LnIII(tmphen)2(DMF)2]3+ and [MoV(CN)8]3- ions are linked in an alternating fashion. Furthermore, two adjacent 1D chain are linked by π-π interaction between the benzene and pyridine rings and hydrogen bonds to form a supramolecular three-dimensional framework. Investigation of the magnetic properties of complexes 1-3 reveals antiferromagnetic coupling interaction exists between heavy LnIII (HoIII, ErIII and TmIII) and MoV ions.

  14. Phase relations in neptunium, americium and the binary alloy systems Np-Am and Np-Ln (Ln = La, Nd, Lu)

    NASA Astrophysics Data System (ADS)

    Gibson, John K.; Haire, Richard G.

    1992-10-01

    High-temperature differential thermal analysis has been used to characterize the phase relations in neptunium, americium and the binary alloy systems, Np-Am, Np-La, Np-Nd, Np-Lu, Sm-Ce and Ce-Gd. The temperatures previously reported for the two solid-solid transformations and the fusion of Np, and for the β(fcc) → γ(bcc?) and the fusion transitions of Am were confirmed. A small endothermic event ( ~ 0.4 kJ mol -1) evident at 758°C for americium was assigned to its dhcp → fcc transition; this temperature is ~ 100°C higher than previously derived from dilatometry. Although the Np-Am DTA studies were limited in the range of alloy compositions which could be investigated, the results were useful in deciphering the nature of the phase diagram. Measurements on a sample of aggregate composition Np 0.54-Am 0.46 suggested some degree of mutual solubility, although two (terminal) solid phases, one Np-rich and one Am-rich, were found to coexist. The supporting studies of Np-Ln and Ln-Ln' (Ln and Ln' = selected lanthanides) alloy systems established the efficacy of the DTA technique and augmented the results for the Np-Am system.

  15. The absence of ferroelectric polarization in layered and rock-salt ordered NaLnMnWO6 (Ln = La, Nd, Tb) perovskites.

    PubMed

    De, Chandan; Kim, Tai Hoon; Kim, Kee Hoon; Sundaresan, A

    2014-03-21

    The ordered perovskites, NaLnMnWO6 (Ln = La, Nd, Tb), are reported to exhibit simultaneous ordering of A-site cations (Na and Ln) in layered arrangement and B-site cations (Mn and W) in rock salt structure. They have been shown to crystallize in a monoclinic structure with the polar space group P21. Based on density functional calculations and group theoretical analysis, it has recently been proposed that NaLaMnWO6 should be ferroelectric with a relatively large polarization (16 μC cm(-2)). Contrary to this prediction, our electrical measurements such as conventional P-E loop, Positive-Up and Negative-Down (PUND), piezoelectric response and Second Harmonic Generation (SHG) reveal the absence of ferroelectric polarization in NaLnMnWO6 (Ln = La, Nd, Tb). A dielectric anomaly is observed just below room temperature (∼270 K) for all the three compounds, which is related to the change in conductivity as revealed by temperature dependent ac and dc resistivity. A pyrocurrent peak is also observed at the same temperature. However, its origin cannot be attributed to a ferroelectric transition. PMID:24503958

  16. Hydrothermal synthesis, structure, and property characterization of rare earth silicate compounds: NaBa3Ln3Si6O20 (Ln = Y, Nd, Sm, Eu, Gd)

    NASA Astrophysics Data System (ADS)

    Sanjeewa, Liurukara D.; Fulle, Kyle; McMillen, Colin D.; Wang, Fenglin; Liu, Yufei; He, Jian; Anker, Jeffrey N.; Kolis, Joseph W.

    2015-10-01

    A series of new lanthanide (Ln) silicates have been synthesized using high temperature hydrothermal techniques, and structurally characterized using single crystal and powder X-ray diffraction. The compounds have the general formula NaBa3Ln3Si6O20 (Ln = Y, Nd, Sm, Eu, Gd), and crystallize in the space group Ama2 (No.40). As a representative example, the unit cell parameters of NaBa3Gd3Si6O20 are a = 14.731(3) Å, b = 23.864(5) Å, c = 5.5449(11) Å and Z = 4. The title compounds adopt a three dimensional polar acentric framework made of Ln-O-Si bonding. The framework is comprised of LnO8 and LnO7 units forming edge-sharing infinite chains along the c-axis. These oxy-bridged infinite chains are also linked by [Si4O13] tetrasilicate and [Si2O7] disilicate units to form the three-dimensional framework structure, with Ba2+ and Na+ cations residing inside channels of the framework. The polarity in the structure is imparted by the unusual tetrasilicate arrangement. The luminescence and magnetic properties were investigated on selected compounds. The temperature dependent magnetic susceptibility measurements on the Nd, Sm, and Gd derivatives reveal a Curie-Weiss behavior with an antiferromagnetic coupling parameter. For the Eu-derivative, the temperature dependent magnetic susceptibility deviates significantly from Curie-Weiss behavior. Luminescence properties of NaBa3Eu3Si6O20 and NaBa3Sm3Si6O20 compounds exhibited the characteristic transitions of Eu3+ (5D0 → 7FJ, J = 0-4) and Sm3+ (4G5/2 → 6HJ, J = 5/2, 7/2), respectively, leading to strong visible red and orange emissions, respectively.

  17. Impression Creep Behavior of 316LN Stainless Steel

    NASA Astrophysics Data System (ADS)

    Mathew, M. D.; Naveena; Vijayanand, D.

    2013-02-01

    Impression creep tests have been carried out at 923 K on 316LN SS containing 0.07, 0.14, and 0.22 wt.% nitrogen, under different applied stress levels. It was observed that the impression creep depth versus time curves were similar to the creep curves obtained from conventional uniaxial creep tests. The impression creep curves were characterized by a loading strain and primary and secondary creep stages similar to uniaxial creep curves. The tertiary stage observed in uniaxial creep curves was absent. The steady-state impression velocity was found to increase with increasing applied stress. The equivalent steady-state creep rates calculated from impression velocities were found to be in good agreement with the steady-state creep rates obtained from conventional uniaxial creep tests. Equivalence between applied stress and steady-state impression velocity with uniaxial creep stress and steady-state creep rate, respectively, has been established based on the laws of mechanics for time-dependent plasticity. It was found that impression velocity was sensitive to the variation in nitrogen content in the steel; impression velocity decreased with increasing nitrogen content, and the results obtained in this study were in agreement with those obtained from uniaxial creep tests.

  18. Hydrothermal synthesis and luminescent properties of SrF2 and SrF2:Ln3+ (Ln = Eu, Ce, Tb) nano-assembly with controllable morphology.

    PubMed

    Sun, Yuanping; Jia, Peiyun

    2014-05-01

    SrF2 and SrF2:Ln3+ (Ln = Eu, Ce, Tb) nano-assemblies with controllable size and morphology have been successfully prepared via a facile hydrothermal process. X-ray diffraction, scanning electron microscopy, and photoluminescence spectrum were used to characterize the samples. The experimental results indicate that chelating reagent and acidity play important roles in the formation of micro-crystals with uniform size and peculiar morphology. As-obtained SrF2:Eu3+ and SrF2:Ce3+, SrF2:Tb3+ samples show red, ultraviolet and green emission under the irradiation of ultraviolet.

  19. Heterotrimetallic coordination polymers: {Cu(II)Ln(III)Fe(III)} chains and {Ni(II)Ln(III)Fe(III)} layers: synthesis, crystal structures, and magnetic properties.

    PubMed

    Alexandru, Maria-Gabriela; Visinescu, Diana; Andruh, Marius; Marino, Nadia; Armentano, Donatella; Cano, Joan; Lloret, Francesc; Julve, Miguel

    2015-03-27

    The use of the [Fe(III) (AA)(CN)4](-) complex anion as metalloligand towards the preformed [Cu(II) (valpn)Ln(III)](3+) or [Ni(II) (valpn)Ln(III) ](3+) heterometallic complex cations (AA=2,2'-bipyridine (bipy) and 1,10-phenathroline (phen); H2 valpn=1,3-propanediyl-bis(2-iminomethylene-6-methoxyphenol)) allowed the preparation of two families of heterotrimetallic complexes: three isostructural 1D coordination polymers of general formula {[Cu(II) (valpn)Ln(III) (H2O)3 (μ-NC)2 Fe(III) (phen)(CN)2 {(μ-NC)Fe(III) (phen)(CN)3}]NO3 ⋅7 H2O}n (Ln=Gd (1), Tb (2), and Dy (3)) and the trinuclear complex [Cu(II) (valpn)La(III) (OH2 )3 (O2 NO)(μ-NC)Fe(III) (phen)(CN)3 ]⋅NO3 ⋅H2O⋅CH3 CN (4) were obtained with the [Cu(II) (valpn)Ln(III)](3+) assembling unit, whereas three isostructural heterotrimetallic 2D networks, {[Ni(II) (valpn)Ln(III) (ONO2 )2 (H2 O)(μ-NC)3 Fe(III) (bipy)(CN)]⋅2 H2 O⋅2 CH3 CN}n (Ln=Gd (5), Tb (6), and Dy (7)) resulted with the related [Ni(II) (valpn)Ln(III) ](3+) precursor. The crystal structure of compound 4 consists of discrete heterotrimetallic complex cations, [Cu(II) (valpn)La(III) (OH2)3 (O2 NO)(μ-NC)Fe(III) (phen)(CN)3 ](+), nitrate counterions, and non-coordinate water and acetonitrile molecules. The heteroleptic {Fe(III) (bipy)(CN)4} moiety in 5-7 acts as a tris-monodentate ligand towards three {Ni(II) (valpn)Ln(III)} binuclear nodes leading to heterotrimetallic 2D networks. The ferromagnetic interaction through the diphenoxo bridge in the Cu(II)-Ln(III) (1-3) and Ni(II)-Ln(III) (5-7) units, as well as through the single cyanide bridge between the Fe(III) and either Ni(II) (5-7) or Cu(II) (4) account for the overall ferromagnetic behavior observed in 1-7. DFT-type calculations were performed to substantiate the magnetic interactions in 1, 4, and 5. Interestingly, compound 6 exhibits slow relaxation of the magnetization with maxima of the out-of-phase ac signals below 4.0 K in the lack of a dc field, the values of the pre

  20. Bifunctional heterometallic Ln3+-Gd3+ (Ln = Eu, Tb) hybrid silica microspheres: luminescence and MRI contrast agent property.

    PubMed

    Li, Yan-Yan; Yan, Bing; Li, Qiu-Ping

    2013-02-01

    A novel series of homometallic and heterometallic lanthanide (Eu(3+)(Tb(3+))-Gd(3+)) hybrid silica microspheres (EDTA-(Eu(Tb)-Gd)-TTA-SiO(2)) are synthesized with 2-thenoyltrifluoroacetone (TTA) functionalized silane and ethylenediaminetetraacetic acid (EDTA) by sol-gel process, whose physical characterization are carried out and especially the luminescence and the magnetic resonance imaging (MRI) contrast agent properties are discussed. These hybrids present uniform silica microsphere morphology with particle size of 1 μm. Comparing to the homometallic hybrid silica microsphere EDTA-Ln-TTA-SiO(2) without Gd(3+) ion, the heterometallic hybrid silica microspheres EDTA-Eu-Gd-TTA-SiO(2) exhibit stronger luminescent intensity, longer lifetime and higher luminescent quantum efficiency, which is due to the fact that inert ion Gd(3+) can enhance the luminescence of the Eu(3+) or Tb(3+) within the hybrid system. In addition, the MRI relaxivity of the heterometallic lanthanide hybrid silica microspheres in water is assessed, showing a lower T1 relaxation rate than homometallic gadolinium hybrid one (EDTA-Gd-TTA-SiO(2)). Both of them show higher T1 relaxation rate than the conventional Gd chelate of diethylenetriamine pentaacetic acid. These bifunctional hybrid materials exhibit both luminescent and MRI magnetic contrast agent properties, whose further investigation can be expected to have potential application in practical fields such as optical storage and sensors, etc. PMID:23154785

  1. Pressure-induced phase transitions in LnTe (Ln=La, Gd, Ho, Yb) and AmTe.

    PubMed

    Zvoriste-Walters, C E; Heathman, S; Klimczuk, T

    2013-07-01

    The structural behaviour under compression of different lanthanide (La, Gd, Ho, Yb) and actinide (Am) monochalcogenides is studied by means of in situ high-pressure x-ray diffraction. All the investigated compounds crystallize at ambient conditions within a cubic (B1) NaCl-type structure but show different behaviours at high pressures. LaTe and AmTe undergo B1 to B2 (CsCl-type structure) phase transitions, starting at 9 GPa and 12 GPa, respectively. The high-pressure phase of AmTe exhibits an electronic transition, identified by an anomaly in the compression curve which is accompanied by a sample colour change. The other three monochalcogenides studied here show clear evidence of decomposition and amorphization under pressure and are, to the best of our knowledge, the first in the LnTe series to show a pressure-induced amorphization. The bulk moduli of all B1-type structure compounds are calculated using the third-order Birch-Murnaghan equation of state.

  2. Local Reversion of Cold Formed AISI 301LN

    NASA Astrophysics Data System (ADS)

    Järvenpää, A.; Jaskari, M.; Hietala, M.; Mäntyjärvi, K.

    This study demonstrates applying laser heat treatment for reversion treatments of cold-formed AISI 301LN. Sheets were cold- rolled to final thicknesses of 1.5 and 3 mm (65pct reduction), having martensite fraction of 70-95%. Sheets were heated locally by a laser beam to various peak temperatures to obtain different degrees of martensite reversion to austenite. Mechanical properties and formability of grain-refined and coarse-grained structures were measured by tensile, bending and Erichsen cup tests. In addition to standard Erichsen cup test, additional interrupted tests were carried out, where cups were first stretched close to the critical strain. Drawn cups were then heated locally by a laser beam to revitalize the structure and thereby enhance the formability in the following cupping test until failure. Various structures were produced: completely reverted microstructures (T > 700 °C) with grain sizes 0.9 - 2 μm in addition to partially reverted structure (T < 700 °C) containing nano- and ultrafine-grained austenite (0.6 μm) with some martensite. Results showed that local laser heat treatment is suitable for the reversion treatment to refine the austenite grain size. Refinement of the austenitic structures increased strength properties and the formability was better than with coarse grained structures having the same strength. Especially the yield strength was significantly enhanced, being around 900 MPa in the strongest reverted structure compared to the 300-400 MPa of the coarse grained austenitic structure. It was demonstrated that the local laser treatment restored formability of the drawn cups, allowing stretching to be continued.

  3. Fluorescent naphthalene diols as bridging ligands in Ln(III) cluster chemistry: synthetic, structural, magnetic, and photophysical characterization of Ln(III)8 "Christmas stars".

    PubMed

    Alexandropoulos, Dimitris I; Fournet, Adeline; Cunha-Silva, Luís; Mowson, Andrew M; Bekiari, Vlasoula; Christou, George; Stamatatos, Theocharis C

    2014-06-01

    The initial employment of the fluorescent bridging ligand naphthalene-2,3-diol in 4f-metal coordination chemistry has provided access to a new family of Ln(III)8 clusters with a "Christmas-star" topology, single-molecule magnetism behavior, and ligand-centered emissions.

  4. Rapid microwave-assisted sol-gel preparation of Pd-substituted LnFeO3 (Ln = Y, La): phase formation and catalytic activity

    SciTech Connect

    Misch, Lauren M.; Birkel, Alexander; Figg, C. Adrian; Fors, Brett P.; Hawker, Craig J.; Stucky, Galen D.; Seshadri, Ram

    2014-02-13

    We present a rapid microwave-assisted sol–gel approach to Pd-substituted LnFeO3 (Ln = Y, La) for applications in C–C coupling reactions. These materials could be prepared in household microwave ovens in less than 15 minutes of reaction time with the final materials displaying well-defined structure and morphology. Phase evolution was studied using time-dependent microwave heatings and then compared with the results obtained from thermogravimetric analyses. Materials were confirmed to be phase pure by laboratory and synchrotron X-ray diffraction. Substituted Pd is ionic as shown by the binding energy shift from X-ray photoelectron spectroscopy. The short heating periods required for phase purity allow these materials less time for sintering as compared to conventional solid state preparation methods, making relatively high surface areas achievable. These materials have been successfully used as catalyst precursor materials for C–C coupling reactions in which the active species is Pd0. Pd-substituted LnFeO3 (Ln = Y, La) provides Pd0 in solution which can be complexed by the ligand SPhos, allowing for aryl chloride coupling.

  5. Fluorescent naphthalene diols as bridging ligands in Ln(III) cluster chemistry: synthetic, structural, magnetic, and photophysical characterization of Ln(III)8 "Christmas stars".

    PubMed

    Alexandropoulos, Dimitris I; Fournet, Adeline; Cunha-Silva, Luís; Mowson, Andrew M; Bekiari, Vlasoula; Christou, George; Stamatatos, Theocharis C

    2014-06-01

    The initial employment of the fluorescent bridging ligand naphthalene-2,3-diol in 4f-metal coordination chemistry has provided access to a new family of Ln(III)8 clusters with a "Christmas-star" topology, single-molecule magnetism behavior, and ligand-centered emissions. PMID:24828892

  6. Co-Sputtered and Rapid-Thermal-Annealed CIAS Thin Films Using CuSe2/ln/Al Triple Targets of Varying Ln/Al Compositions.

    PubMed

    Kim, Nam-Hoon; Jun, Young-Kil; Lee, Woo-Sun

    2016-02-01

    The 20.9% conversion efficiency of I-III-VI chalcopyrite-based solar cells, the highest in the world, makes them promising candidates for high-efficiency thin film solar cells. However, Ga is one of the most expensive rare materials with the critical degradation in device efficiency. Cu(ln(1-X)Al(X))Se2 (CIAS) is considered an alternative to Cu(ln(1-X)Ga(X))Se2 because of its good structural suitability and the low cost of Al. CIAS thin films were formed using triple targets of CuSe2/ln/Al in a co-sputtering system to control the composition ratio, x = [Al]/([ln]+[Al), by varying each RF power for In/Al with rapid thermal annealing. The chalcopyrite peaks shifted toward higher 2theta as x increased. The CIAS thin films had 74.24-86.81% absorption with band gap, Eg, of 2.28-2.50 eV in the 400-1600 nm range. A low resistivity of 1.1 x 10(-2) omega(-cm) was obtained in the CIAS thin films with x of 0.74. PMID:27433625

  7. Rapid microwave-assisted sol-gel preparation of Pd-substituted LnFeO3 (Ln = Y, La): phase formation and catalytic activity.

    PubMed

    Misch, Lauren M; Birkel, Alexander; Figg, C Adrian; Fors, Brett P; Hawker, Craig J; Stucky, Galen D; Seshadri, Ram

    2014-02-01

    We present a rapid microwave-assisted sol-gel approach to Pd-substituted LnFeO3 (Ln = Y, La) for applications in C-C coupling reactions. These materials could be prepared in household microwave ovens in less than 15 minutes of reaction time with the final materials displaying well-defined structure and morphology. Phase evolution was studied using time-dependent microwave heatings and then compared with the results obtained from thermogravimetric analyses. Materials were confirmed to be phase pure by laboratory and synchrotron X-ray diffraction. Substituted Pd is ionic as shown by the binding energy shift from X-ray photoelectron spectroscopy. The short heating periods required for phase purity allow these materials less time for sintering as compared to conventional solid state preparation methods, making relatively high surface areas achievable. These materials have been successfully used as catalyst precursor materials for C-C coupling reactions in which the active species is Pd(0). Pd-substituted LnFeO3 (Ln = Y, La) provides Pd(0) in solution which can be complexed by the ligand SPhos, allowing for aryl chloride coupling. PMID:24280775

  8. Syntheses, structures, and properties of a series of novel high-nuclear 3d-4f clusters with mixed amino acids as ligands: {Ln6Cu24}(Ln = Gd, Tb, Pr and Sm).

    PubMed

    Shen, Chao-Jun; Hu, Sheng-Min; Sheng, Tian-Lu; Xue, Zhen-Zhen; Wu, Xin-Tao

    2015-04-14

    The first examples of high-nuclear 3d-4f heterometallic clusters with mixed amino acid ligands are reported. Four 30-nuclear clusters {Ln6Cu24}(Ln = Gd, Tb, Pr and Sm) were obtained through the self-assembly of Ln(III), Cu(II) and mixed amino acid ligands of glycine (HGly) and β-alanine (HAla). The metal skeleton of clusters may be described as a huge {Ln6Cu12} octahedron connected with 12 additional Cu(II) ions. The temperature dependence of magnetic susceptibilities of compounds were also studied.

  9. Syntheses, structures, and properties of a series of novel high-nuclear 3d-4f clusters with mixed amino acids as ligands: {Ln6Cu24}(Ln = Gd, Tb, Pr and Sm).

    PubMed

    Shen, Chao-Jun; Hu, Sheng-Min; Sheng, Tian-Lu; Xue, Zhen-Zhen; Wu, Xin-Tao

    2015-04-14

    The first examples of high-nuclear 3d-4f heterometallic clusters with mixed amino acid ligands are reported. Four 30-nuclear clusters {Ln6Cu24}(Ln = Gd, Tb, Pr and Sm) were obtained through the self-assembly of Ln(III), Cu(II) and mixed amino acid ligands of glycine (HGly) and β-alanine (HAla). The metal skeleton of clusters may be described as a huge {Ln6Cu12} octahedron connected with 12 additional Cu(II) ions. The temperature dependence of magnetic susceptibilities of compounds were also studied. PMID:25756855

  10. Two nanosized 3d-4f clusters featuring four Ln6 octahedra encapsulating a Zn4 tetrahedron.

    PubMed

    Zheng, Xiu-Ying; Wang, Shi-Qiang; Tang, Wen; Zhuang, Gui-Lin; Kong, Xiang-Jian; Ren, Yan-Ping; Long, La-Sheng; Zheng, Lan-Sun

    2015-07-01

    Two high-nuclearity 3d-4f clusters Ln24Zn4 (Ln = Gd and Sm) featuring four Ln6 octahedra encapsulating a Zn4 tetrahedron were obtained through the self-assembly of Zn(OAc)2 and Ln(ClO4)3. Quantum Monte Carlo (QMC) simulations show the antiferromagnetic coupling between Gd(3+) ions. Studies of the magnetocaloric effect (MCE) show that the Gd24Zn4 cluster exhibits the entropy change (-ΔSm) of 31.4 J kg(-1) K(-1).

  11. Photoluminescence and Photocatalytic Activity of Bi2MoO6:Ln3+ Nanocrystals.

    PubMed

    Feng, Li; Li, Mingxia; Pan, Kai; Li, Rong; Fan, Naiying; Wang, Guofeng

    2016-04-01

    Sheet-like Bi2MoO6:Ln3+ nanocrystals were synthesized by a hydrothermal method. The crystalline size of Bi2MoO6:Ln3+ (Ln = Eu and Gd) nanocrystals changes gradually with the increasing of Ln3+ content in the reaction solutions. The photoluminescence properties of Bi2MoO6:Ln3+ nanocrystals were investigated in detail. In the emission spectra of Bi2MoO6:Eu3+ nanocrystals the 5D0-->7F2 is much stronger than the 5D0 --> 7F1 and is the strongest when the excitation is performed at 467 nm. The relative intensity of the transitions from Eu3+ increased with increasing Eu3+ concentrations, up to about 50 mol%, and then decreased abruptly. In the excitation spectra of Bi2MoOI:Eul+ (30%)/Gd3+ monitored at 618 nm, the 7F0 --> 5D2 (~467 nm) transition is dominating when the Gd3+ concentrations were 10% or 20%. When the Gd3+ concentration was 30%, the 7FO -> D1 (~538 nm) transition is dominating. In addition, the photocatalytic activity of Bi2MoO6:Eu3+ was evaluated by the degradation of rhodamine B (RhB) aqueous solution under simulated solar light. The best photocatalytic performance was observed when the Eu3+ concentration was 1%. PMID:27451709

  12. Photoluminescence and Photocatalytic Activity of Bi2MoO6:Ln3+ Nanocrystals.

    PubMed

    Feng, Li; Li, Mingxia; Pan, Kai; Li, Rong; Fan, Naiying; Wang, Guofeng

    2016-04-01

    Sheet-like Bi2MoO6:Ln3+ nanocrystals were synthesized by a hydrothermal method. The crystalline size of Bi2MoO6:Ln3+ (Ln = Eu and Gd) nanocrystals changes gradually with the increasing of Ln3+ content in the reaction solutions. The photoluminescence properties of Bi2MoO6:Ln3+ nanocrystals were investigated in detail. In the emission spectra of Bi2MoO6:Eu3+ nanocrystals the 5D0-->7F2 is much stronger than the 5D0 --> 7F1 and is the strongest when the excitation is performed at 467 nm. The relative intensity of the transitions from Eu3+ increased with increasing Eu3+ concentrations, up to about 50 mol%, and then decreased abruptly. In the excitation spectra of Bi2MoOI:Eul+ (30%)/Gd3+ monitored at 618 nm, the 7F0 --> 5D2 (~467 nm) transition is dominating when the Gd3+ concentrations were 10% or 20%. When the Gd3+ concentration was 30%, the 7FO -> D1 (~538 nm) transition is dominating. In addition, the photocatalytic activity of Bi2MoO6:Eu3+ was evaluated by the degradation of rhodamine B (RhB) aqueous solution under simulated solar light. The best photocatalytic performance was observed when the Eu3+ concentration was 1%.

  13. Unusual full-colour phosphors: Na 3LnSi 3O 9

    NASA Astrophysics Data System (ADS)

    Ananias, D.; Carlos, L. D.; Rocha, J.

    2006-05-01

    Unusual full-colour phosphors, in the system Na 3LnSi 3O 9, have been prepared and their structure and photoluminescence properties characterized. Na 3(Y 1- aLn a)Si 3O 9 (Ln = Eu, Tb, Tm) materials are primary emitters, with chromaticity colour coordinates comparable or better than properties of the standard phosphors recommended by EBU for display devices, resulting from the emission of red (Eu 3+), green (Tb 3+) and blue (Tm 3+) light. The judicious choice and simultaneous incorporation of three different Ln 3+ ions in the Na 3LnSi 3O 9 lattice results in the integration of red, green and blue emissions in Na 3Y 0.915Tm 0.02Tb 0.04Eu 0.025Si 3O 9, affording a full-colour phosphor with ( x, y) CIE colour coordinates (0.324, 0.364) comparable to the properties of the CIE Illuminant D65, a standard for the EBU primary system colours.

  14. Crystal chemistry of the orthorhombic Ln{sub 2}TiO{sub 5} compounds with Ln=La, Pr, Nd, Sm, Gd, Tb and Dy

    SciTech Connect

    Aughterson, Robert D.; Lumpkin, Gregory R.; Thorogood, Gordon J.; Zhang, Zhaoming; Gault, Baptiste; Cairney, Julie M.

    2015-07-15

    The crystal structures of seven samples of orthorhombic (Pnma) Ln{sub 2}TiO{sub 5} compounds with Ln=La, Pr, Nd, Sm, Gd, Tb and Dy were refined by Rietveld analysis of synchrotron X-ray powder diffraction (S-XRD) data. With increasing size of the lanthanide cation, the lattice parameters increase systematically: c by only ~1.5% whereas both a and b by ~6% from Dy{sub 2}TiO{sub 5} to La{sub 2}TiO{sub 5}. The mean Ti–O bond length only increases by ~1% with increasing radius of the Ln cation from Gd to La, primarily due to expansion of the pair of Ti–O{sub 3} bonds to opposite corners of the Ti–O{sub 5} square based pyramid polyhedra. For Dy{sub 2}TiO{sub 5} and Tb{sub 2}TiO{sub 5}, a significant variation in Ti–O{sub 1} and Ti–O{sub 4} bond lengths results in an increased deformation of the Ti–O{sub 5} base. The particular configuration consists of large rhombic shaped tunnels and smaller triangular tunnels along the b axis, which have implications for defect formation and migration caused by radiation damage or the ionic conductivity. - Graphical abstract: Figure: The crystallographic study of a systematic series of compounds with nominal stoichiometry Ln{sub 2}TiO{sub 5} (with Ln representing La, Pr, Nd, Sm, Gd, Tb and Dy) and orthorhombic, Pnma, symmetry shows changes in cell parameters which fit a linear trend. However, bond lengths are shown to deviate from trend with compounds containing the smaller, heavier lanthanides. - Highlights: • First fabrication and crystallographic refinement of compound Pr{sub 2}TiO{sub 5}. • First systematic study of the crystallography, using S-XRD, for Ln{sub 2}TiO{sub 5} series. • Cation to anion bonding trends and valence states are investigated. • The densities and band-gaps of the series are experimentally determined.

  15. Characterization and luminescence properties of sol–gel derived M′-type LuTaO{sub 4}:Ln{sup 3+} (Ln = Pr, Sm, Dy) phosphors

    SciTech Connect

    Wu, Mengqiu; Liu, Xiaolin Gu, Mu; Ni, Chen; Liu, Bo; Huang, Shiming

    2014-12-15

    Graphical abstract: Emission spectra of LuTaO{sub 4}:Ln (Ln = Pr, Sm and Dy) phosphors under X-ray excitation. The insets illustrate their SEM micrographs. - Highlights: • M′-type LuTaO{sub 4}:Ln{sup 3+} (Ln = Pr, Sm, Dy) phosphors were synthesized by sol–gel technique. • The phosphors exhibited an efficient energy transfer from the host to activators. • High intensity of activator emission was achieved under X-ray excitation. • The phosphors are encouraging for application in high-spatial-resolution X-ray CT imaging. - Abstract: M′-type Lu{sub 1−x}Ln{sub x}TaO{sub 4} (Ln = Pr, Sm, Dy) phosphors have been successfully synthesized by sol–gel technique, their crystallization, morphology, photoluminescence and X-ray excited luminescence properties were investigated in detail. The phosphors had good crystallization behavior. The optimum doping concentrations of Pr{sup 3+}, Sm{sup 3+} and Dy{sup 3+} in LuTaO{sub 4} were at x = 0.003, 0.025, 0.02, respectively. They exhibited a more efficient host excitation relative to the 4f–4f excitations of the rare-earth ions, and a dominant {sup 1}D{sub 2} → {sup 3}H{sub 4}, {sup 4}G{sub 5/2} → {sup 6}H{sub 7/2} or {sup 4}F{sub 9/2} → {sup 6}H{sub 13/2} emission for Pr{sup 3+}, Sm{sup 3+} or Dy{sup 3+}, respectively, which corresponds to the average decay time of 21.7, 745.7 or 10.0 μs, respectively. It is expected that Pr{sup 3+}- or Dy{sup 3+}-doped LuTaO{sub 4} phosphors with a microsecond level decay time are very encouraging for applications in X-ray computerized tomographic imaging with high spatial resolution.

  16. Influence of flowing sodium on creep deformation and rupture behaviour of 316L(N) austenitic stainless steel

    NASA Astrophysics Data System (ADS)

    Ravi, S.; Laha, K.; Mathew, M. D.; Vijayaraghavan, S.; Shanmugavel, M.; Rajan, K. K.; Jayakumar, T.

    2012-08-01

    The influence of flowing sodium on creep deformation and rupture behaviour of AISI 316L(N) austenitic stainless steel has been investigated at 873 K over a stress range of 235-305 MPa. The results were compared with those obtained from testing in air environment. The steady state creep rates of the material were not influenced appreciably by the testing environments. The time to onset of tertiary stage of creep deformation was delayed in sodium environment. The creep-rupture lives of the material increased in sodium environment, which became more pronounced at lower applied stresses. The increase in rupture life of the material in flowing sodium was accompanied by an increase in rupture ductility. The creep damage on specimen surface as well as inside the specimen was less in specimen tested in sodium. SEM fractographic investigation revealed predominantly transgranular dimple failure for the specimen tested in sodium, whereas predominantly intergranular creep failure was observed in the air tested specimens. Almost no oxidation was observed in the specimens creep tested in the sodium environment. Absence of oxidation and less creep damage cavitation extended the secondary state in liquid sodium tests and lead to increase in creep rupture life and ductility of the material as compared to in air.

  17. Suitability of LN2 impregnated Open-Cell Foam as Electric Insulant for Superconducting Power Equipment

    NASA Astrophysics Data System (ADS)

    Sumereder, C.; Mifka, M.; Muhr, M.

    2006-06-01

    The suitability of an open-cell foam is investigated for the application as electric insulant in superconducting power equipment. The tested foam is made from melamine resin, a thermoset plastic from the aminoplastics group; it is a mechanical very flexible material with excellence compatibility to high and low temperature. The aim of these investigations was to test the aptitude of the liquid nitrogen impregnated open-cell foam with respect to the dielectric properties and the electric strength under different conditions. In this paper the results of permittivity measurements and ramp voltage tests are discussed and an outlook for future applications is given. The tests showed excellence mechanical and thermal characteristics for the application in LN2 vessels. The ACBV of the LN2 impregnated foam was 50 % less than the ACBV of pure LN2.

  18. Crystal structure and properties of complexes [Ln(Gly)4Im·(ClO4)4]n (Ln:Nd, Sm) constructed from eight-coordination containing square antiprism

    NASA Astrophysics Data System (ADS)

    Pan, Lu; Gao, Xiao-han; Lv, Xue-chuan; Tan, Zhi-cheng; Cao, Hui

    2016-08-01

    Two eight-coordination containing square antiprism polyhedra, [Ln(Gly)4Im·(ClO4)4]n (Ln:Nd, Sm) were synthesized through the self-assembly of Ln3+ (Ln:Nd, Sm) ions, glycine and imidazole in aqueous solution and characterized by X-ray single crystal diffraction. Both of the complexes crystallized in the C2/c space group. In the cluster, each Ln3+ ions was eight-coordination by eight oxygen atoms of the glycine. The coordination sphere of each Ln3+ ions could be described as a distorted square antiprism. Two central Ln3+ ions were connected by four bridging carboxyl groups from four glycine molecules. The Ln-O bond distances were related to the coordination geometries of the ligands. The complexes had two special solid-solid phase transitions at 224 K and 248 K, which were interpreted as a freezing-in phenomenon of the reorientational motion of perchlorate ions ClO4- and the orientational order/disorder process of ClO4- ions. The decomposition mechanism of the complexes was deduced to be three stages from 300 to 700 K. The fluorescent excitation and emission spectra showed that the complexes had strong fluorescent property.

  19. On the energy transfer in (Y,Gd)Al3(BO3)4:Ln3+ (Ln = Tb3+, Dy3+)

    NASA Astrophysics Data System (ADS)

    Dierkes, Tobias; Pues, Patrick; Jüstel, Thomas

    2015-08-01

    Single-phase (Y,Gd)Al3(BO3)4:Ln3+ (Ln = Tb3+, Dy3+) (YAB) samples were synthesized via solid state reactions and spectroscopic investigations were conducted in order to characterise possible energy transfer mechanisms between Gd3+ and the activator ions, Tb3+/Dy3+. Photoluminescence spectra ranging from 120 to 800 nm were recorded which made it possible to assign charge transfer absorption bands of the host structure, 4f → 5d and 4f → 4f excitations of the activators and their respective emission multiplets. Spectroscopic measurements such as reflection spectra, decay curves, emission/excitation spectra and calculations of external quantum efficiencies were presented to support the suggested energy transfer scheme in Gd3+ activated YAB.

  20. Infrared detector Dewars - Increased LN2 hold time and vacuum jacket life spans

    NASA Technical Reports Server (NTRS)

    Jennings, D. E.; Boyd, W. J.; Blass, W. E.

    1976-01-01

    IR detector Dewars commonly suffer from shorter than desired LN2 hold times and insulation jacket vacuum corruption over relatively short time periods. In an attempt to solve this problem for a 9144 detector Dewar, small 1 liter/s appendage ion pumps were selected for continuous pumping of the vacuum jackets. This procedure extended LN2 hold times from 20 to 60 h and virtually eliminated vacuum jacket corruption. Thus the detector systems are usable continuously over periods of 6 months or more.

  1. Effect of lanthanide contraction on the mixed polyamine systems Ln/Sb/Se/(en+dien) and Ln/Sb/Se/(en+trien): Syntheses and characterizations of lanthanide complexes with a tetraelenidoantimonate ligand

    SciTech Connect

    Zhao Jing; Liang Jingjing; Pan Yingli; Zhang Yong; Jia Dingxian

    2011-06-15

    Mixed polyamine systems Ln/Sb/Se/(en+dien) and Ln/Sb/Se/(en+trien) (Ln=lanthanide, en=ethylenediamine, dien=diethylenetriamine, trien=triethylenetetramine) were investigated under solvothermal conditions, and novel mixed-coordinated lanthanide(III) complexes [Ln(en){sub 2}(dien)({eta}{sup 2}-SbSe{sub 4})] (Ln=Ce(1a), Nd(1b)), [Ln(en){sub 2}(dien)(SbSe{sub 4})] (Ln=Sm(2a), Gd(2b), Dy(2c)), [Ln(en)(trien)({mu}-{eta}{sup 1},{eta}{sup 2}-SbSe{sub 4})]{sub {infinity}} (Ln=Ce(3a), Nd(3b)) and [Sm(en)(trien)({eta}{sup 2}-SbSe{sub 4})] (4a) were prepared. Two structural types of lanthanide selenidoantimonates were obtained across the lanthanide series in both en+dien and en+trien systems. The tetrahedral anion [SbSe{sub 4}]{sup 3-} acts as a monodentate ligand mono-SbSe{sub 4}, a bidentate chelating ligand {eta}{sup 2}-SbSe{sub 4} or a tridentate bridging ligand {mu}-{eta}{sup 1},{eta}{sup 2}-SbSe{sub 4} to the lanthanide(III) center depending on the Ln{sup 3+} ions and the mixed ethylene polyamines, indicating the effect of lanthanide contraction on the structures of the lanthanide(III) selenidoantimonates. The lanthanide selenidoantimonates exhibit semiconducting properties with E{sub g} between 2.08 and 2.51 eV. - Graphical Abstract: Two structural types of lanthanide(III) selenidoantimonates are formed in both en-dien and en-trien mixed polyamines across lanthanide series, indicating the lanthanide contraction effect on the structures of the lanthanide(III) selenidoantimonates. Highlights: > Two structural types of lanthanide selenidoantimonates are prepared across the lanthanide series in both Ln/Sb/Se/(en+dien) and Ln/Sb/Se/(en+trien) systems. > The [SbSe{sub 4}]{sup 3-} anion acts as a mono-SbSe{sub 4}, a {eta}{sup 2}-SbSe{sub 4} or a {mu}-{eta}{sup 1},{eta}{sup 2}-SbSe{sub 4} ligand to the Ln{sup 3+} ions. > The soft base ligand [SbSe{sub 4}]{sup 3-} can be controlled to coordinate to the Ln{sup 3+} ions with en+dien and en+trien as co-ligands.

  2. Ln{sub 2}Sr{sub 2}PtO{sub 7+{delta}} (Ln=La, Pr, and Nd): Three new Pt-containing [A{sub 2}{sup '}O{sub 1+{delta}}] [A{sub n}B{sub n-1}O{sub 3n}]-type hexagonal perovskites

    SciTech Connect

    Ebbinghaus, Stefan G. Erztoument, Chasanoglou; Marozau, Ivan

    2007-12-15

    Polycrystalline samples of Ln{sub 2}Sr{sub 2}PtO{sub 7+{delta}} (Ln=La, Pr, Nd) were prepared by conventional solid state synthesis. The three compounds are new examples for n=2 members of the [A{sub 2}{sup '}O{sub 1+{delta}}][A{sub n}B{sub n-1}O{sub 3n}] family of hexagonal perovskites containing platinum as the B-type cation. XRD Rietveld refinements show the platinates to crystallize in space group R3-bar and, in the case of Pr and Nd, revealed a complete ordering of Ln/Sr on the two distinct A-type positions, while for La a partial disorder was observed. By XANES investigations at the Pt-L{sub III} threshold the oxidation state +4 for platinum was found. Thermogravimetry revealed a small oxygen excess for Ln=La and Pr ({delta}=0.13 and 0.07), pointing to the presence of peroxide ions as already observed for isostructural Ru- and Ir-based compounds. UV-Vis measurements were done for the yellow lanthanum and the green neodymium compound. They revealed two optical band gaps of 2.52 and 3.05 eV, respectively. Magnetic measurements showed La{sub 2}Sr{sub 2}PtO{sub 7+{delta}} to be diamagnetic as expected for Pt{sup 4+} with low-spin (t{sub 2g}{sup 6}) configuration. For Ln=Pr and Nd the observed strong paramagnetism can be explained solely by the magnetic moments of the rare earths. - Graphical abstract: Hexagonal perovskites of the [A{sub 2}{sup '}O{sub 1+{delta}}][A{sub n}B{sub n-1}O{sub 3n}] family have so far only been known for the transition metals Mn, Nb, Ru, and Ir. In this paper, three new n=2 examples containing platinum as B-type cation are presented. The structure and physical properties of the three title compounds were investigated by XRD Rietveld refinements, thermogravimetry, X-ray absorption spectroscopy, magnetic measurements and optical spectroscopy.

  3. Crystal chemistry of the orthorhombic Ln2TiO5 compounds with Ln=La, Pr, Nd, Sm, Gd, Tb and Dy

    NASA Astrophysics Data System (ADS)

    Aughterson, Robert D.; Lumpkin, Gregory R.; Thorogood, Gordon J.; Zhang, Zhaoming; Gault, Baptiste; Cairney, Julie M.

    2015-07-01

    The crystal structures of seven samples of orthorhombic (Pnma) Ln2TiO5 compounds with Ln=La, Pr, Nd, Sm, Gd, Tb and Dy were refined by Rietveld analysis of synchrotron X-ray powder diffraction (S-XRD) data. With increasing size of the lanthanide cation, the lattice parameters increase systematically: c by only ~1.5% whereas both a and b by ~6% from Dy2TiO5 to La2TiO5. The mean Ti-O bond length only increases by ~1% with increasing radius of the Ln cation from Gd to La, primarily due to expansion of the pair of Ti-O3 bonds to opposite corners of the Ti-O5 square based pyramid polyhedra. For Dy2TiO5 and Tb2TiO5, a significant variation in Ti-O1 and Ti-O4 bond lengths results in an increased deformation of the Ti-O5 base. The particular configuration consists of large rhombic shaped tunnels and smaller triangular tunnels along the b axis, which have implications for defect formation and migration caused by radiation damage or the ionic conductivity.

  4. Multi-Enhanced-Phonon Scattering Modes in Ln-Me-A Sites co-substituted LnMeA11O19 Ceramics

    PubMed Central

    Lu, Haoran; Wang, Chang-An; Huang, Yong; Xie, Huimin

    2014-01-01

    Authors reported an effective path to decrease the thermal conductivity while to increase the coefficient of thermal expansion, thus enhancing the thermo-physical properties of the LnMeA11O19-type magnetoplumbite LaMgAl11O19 by simultaneously substituting La3+, Mg2+ and Al3+ ions with large ionic radius Ba2+, Zn2+ and Ti4+, respectively. The mechanism behind the lowered thermal conductivity was mainly due to the multi-enhanced-phonon scattering modes in Ln-Me-A sites co-substituted LnMeA11O19 ceramics. These modes involve the following four aspects, namely, point defect mechanism, the intrinsic scattering in the complex crystal cell and materials with stepped surface to localize phonon vibrational modes, as well as nano-platelet-like structure to incorporate additional grain boundary scattering. This study provides novel thoughts for promising candidate materials of even lower thermal conductivity for the next generation thermal barrier coatings. PMID:25351166

  5. External vs. ``internal'' pressure effect on the anti-ferromagnetic superexchange energy, J, in LnBa2Cu3O6 (Ln=La,Nd,...,Lu)

    NASA Astrophysics Data System (ADS)

    Mallett, Ben; Tallon, Jeffery; Williams, Grant; Wolf, Thomas

    2012-02-01

    What causes the difference between the effect of ``internal'' pressure, as caused by ionic substitution, and external pressure on Tc^max in the cuprates [1]? Is it the density of states, the pairing boson energy scale (φB), condensation energy (which governs fluctuations), or ...? Many models of high temperature superconductivity put the energy scale of φB as the anti-ferromagnetic super-exchange energy, J, between adjacent Cu(2) ions in the CuO2 plane. We therefore investigated Raman B1g two-magnon scattering in high quality LnBa2Cu3O6 (Ln123) single crystals, Ln(=La, Nd, Sm, Eu, Gd, Dy, Yb, Lu), at ambient pressure to determine the effect of internal pressure on J. Comparing with measurements of J under external pressure reveals that internal and external pressure have quantitatively the same effect on J. However, and most surprisingly, we find an anticorrelation between J and Tc^max when ion size or internal pressure is the implicit variable. Given the opposite effects of internal and external pressure on Tc^max, this result suggests that some energy scale other than short range anti-ferromagnetic interactions has a more dominant effect on Tc^max.[4pt] [1] e.g. M. Marezio, Physica C, 341-348, 375 (2000)

  6. Aqueous Synthesis and Structural Comparison of Rare Earth Niobates and Tantalates: (La,K,[vacancy])[subscript 2]Nb[subscript 2]O[subscript 7-x](OH)[subscript 2] and Ln2Ta2O7(OH)2 ([vacancy] = vacancy; Ln = La-Sm)

    SciTech Connect

    Nyman, May; Rodriguez, Mark A.; Alam, Todd M.; Anderson, Travis M.; Ambrosini, Andrea

    2009-06-30

    Rare-earth niobates and tantalates are functional materials that are exploited as photocatalysts, host lattices for phosphors, and ion conductors. These phases are extremely challenging to synthesize by methods other than solid-state processing, which limits expansion of this useful class of materials. Hydrothermal processing in particular is hampered by the incompatibility of base-soluble tantalate or niobate with acid-soluble rare-earth oxides. Furthermore, an added challenge with tantalates is they are especially inert and insoluble. We present here a general hydrothermal process that has produced a range of rare-earth niobate/tantalate materials; including new phases, (La,K,{sub {open_square}}){sub 2}Nb{sub 2}O{sub 7-x}(OH){sub 2} (1) and Ln{sub 2}Ta{sub 2}O{sub 7}(OH){sub 2} (2) ({open_square} = vacancy, Ln = La-Sm -- excluding radioactive promethium). The structures of 1 and the La-analogue of 2 were determined from powder X-ray diffraction data collected at the APS 11-BM line and corroborated by compositional analyses, infrared spectroscopy, {sup 139}La and {sup 1}H MAS NMR, and thermogravimetric analyses. The synthesis and characterization studies reveal that the tantalate (2) is compositionally pure with no vacancies or dopants, while the niobate (1) formed under identical conditions has both vacancies and potassium dopants. We attribute these features to the greater flexibility of Nb{sup 5+} in oxide lattices to accommodate distorted and lower coordination geometries, whereas Ta{sup 5+} is found predominantly in octahedral environments. Other differences in aqueous niobate and tantalate chemistry are noted by the different phases that form as a function of the Ln{sup 3+} radius.

  7. Enhancing the magnetic blocking temperature and magnetic coercivity of {CrLn} single-molecule magnets via bridging ligand modification.

    PubMed

    Langley, Stuart K; Wielechowski, Daniel P; Moubaraki, Boujemaa; Murray, Keith S

    2016-09-21

    Replacing bridging benzoate ligands with 2-chloro-4,5-fluorobenzoate in a family of {CrLn} (Ln = Tb, Dy and Ho) single-molecule magnets result in significant improvements in magnetic relaxation time, magnetic hysteresis blocking temperature and magnetic coercivity. PMID:27532688

  8. Anion dependent self-assembly of 56-metal Cd-Ln nanoclusters with enhanced near-infrared luminescence properties

    NASA Astrophysics Data System (ADS)

    Yang, Xiaoping; Schipper, Desmond; Zhang, Lijie; Yang, Keqin; Huang, Shaoming; Jiang, Jijun; Su, Chengyong; Jones, Richard A.

    2014-08-01

    Two series of Cd-Ln clusters: nano-drum [Ln8Cd24L12(OAc)48] and nano-double-drum [Ln12Cd44L20Cl30(OAc)54] (Ln = Nd and Yb) were prepared using a flexible Schiff base ligand bearing two aryl-Br groups. Chloride (Cl-) ions, together with the interactions of Br with other electronegative atoms, play a key role in the formation of the nano-double-drums. The structures were studied by TEM and photophysical properties were determined.Two series of Cd-Ln clusters: nano-drum [Ln8Cd24L12(OAc)48] and nano-double-drum [Ln12Cd44L20Cl30(OAc)54] (Ln = Nd and Yb) were prepared using a flexible Schiff base ligand bearing two aryl-Br groups. Chloride (Cl-) ions, together with the interactions of Br with other electronegative atoms, play a key role in the formation of the nano-double-drums. The structures were studied by TEM and photophysical properties were determined. Electronic supplementary information (ESI) available: Full experimental and characterization details for 1-4. CCDC 972369-972372. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4nr03075c

  9. Enhancing the magnetic blocking temperature and magnetic coercivity of {CrLn} single-molecule magnets via bridging ligand modification.

    PubMed

    Langley, Stuart K; Wielechowski, Daniel P; Moubaraki, Boujemaa; Murray, Keith S

    2016-09-21

    Replacing bridging benzoate ligands with 2-chloro-4,5-fluorobenzoate in a family of {CrLn} (Ln = Tb, Dy and Ho) single-molecule magnets result in significant improvements in magnetic relaxation time, magnetic hysteresis blocking temperature and magnetic coercivity.

  10. Ln3I5(S2N2)(S2)(THF)10 - a new type of molecular compounds.

    PubMed

    Fagin, A A; Fukin, G K; Cherkasov, A V; Shestakov, A F; Pushkarev, A P; Balashova, T V; Maleev, A A; Bochkarev, M N

    2016-03-21

    Unprecedented complexes of the composition Ln3I5(S2N2)(S2)(THF)10 were obtained in the reactions of neodymium and dysprosium iodide-nitrides with sulfur. The inorganic core of the molecules contains the cyclic fragments Ln(μ-S2)Ln, LnSNSN and LnSN. Ten of the fourteen atoms of the core are coplanar, the remaining four S2 and I2 atoms lie in the other two orthogonal planes. The dysprosium complex upon excitation with UV light exhibits the metal-centered luminescence characteristic of the Dy(3+) ion. Geometric parameters of the molecules, computational data, electron spectroscopy and fluorescence suggest the existence of some conjugation in the mentioned heterocycles. PMID:26842841

  11. The extended chain compounds Ln {sub 12}(C{sub 2}){sub 3}I{sub 17} (Ln=Pr, Nd, Gd, Dy): Synthesis, structure and physical properties

    SciTech Connect

    Ryazanov, Mikhail; Mattausch, Hansjuergen; Simon, Arndt

    2007-04-15

    The title compounds are obtained in high yield from stoichiometric mixtures of Ln, LnI{sub 3} and graphite, heated at 900-950 deg. C in welded Ta containers. The crystal structures of new Pr and Nd phases determined by single-crystal X-ray diffraction are related to those of other Ln {sub 12}(C{sub 2}){sub 3}I{sub 17}-type compounds (C 2/c, a=19.610(1) and 19.574(4) A, b=12.406(2) and 12.393(3) A, c=19.062(5) and 19.003(5) A, {beta}=90.45(3){sup o} and 90.41(3){sup o}, for Pr{sub 12}(C{sub 2}){sub 3}I{sub 17} and Nd{sub 12}(C{sub 2}){sub 3}I{sub 17}, respectively). All compounds contain infinite zigzag chains of C{sub 2}-centered metal atom octahedra condensed by edge-sharing into the [tcc] {sub {infinity}} sequence (c=cis, t=trans) and surrounded by edge-bridging iodine atoms as well as by apical iodine atoms that bridge between chains. The polycrystalline Gd{sub 12}(C{sub 2}){sub 3}I{sub 17} sample exhibits semiconducting thermal behavior which is consistent with an ionic formulation (Ln {sup 3+}){sub 12}(C{sub 2} {sup 6-}){sub 3}(I{sup -}){sub 17}(e{sup -}) under the assumption that one extra electron is localized in metal-metal bonding. The magnetization measurements on Nd{sub 12}(C{sub 2}){sub 3}I{sub 17}, Gd{sub 12}(C{sub 2}){sub 3}I{sub 17} and Dy{sub 12}(C{sub 2}){sub 3}I{sub 17} indicate the coexistence of competing magnetic interactions leading to spin freezing at T {sub f}=5 K for the Gd phase. The Nd and Dy compounds order antiferromagnetically at T {sub N}=25 and 29 K, respectively. For Dy{sub 12}(C{sub 2}){sub 3}I{sub 17}, a metamagnetic transition is observed at a critical magnetic field H{approx}25 kOe. - Graphical abstract: Zigzag chains of edge-sharing metal atom octahedra in Ln {sub 12}(C{sub 2}){sub 3}I{sub 17}.

  12. Syntheses, Structure, Magnetism, and Optical Properties of the Interlanthanide Sulfides delta-Ln2-xLuxS3 (Ln = Ce, Pr, Nd)

    SciTech Connect

    Booth, Corwin H; Jin, Geng Bang; Choi, Eun Sang; Guertin, Robert P.; Brooks, James S.; Bray, Travis H.; Booth, Corwin H.; Albrecht-Schmitt, Thomas E.

    2008-01-11

    {delta}-Ln{sub 2-x}LuxS{sub 3} (Ln = Ce, Pr, Nd; x = 0.67-0.71) compounds have been synthesized through the reaction of elemental rare earth metals and S using Sb{sub 2}S{sub 3} flux at 1000 C. These compounds are isotypic with CeTmS{sub 3}, which has a complex three-dimensional structure. It includes four larger Ln{sup 3+} sites in eight- and nine-coordinate environments, two disordered seven-coordinate Ln{sup 3+}/Lu{sup 3+} positions, and two six-coordinate Lu{sup 3+} ions. The structure is constructed from one-dimensional chains of LnSn (n = 6-9) polyhedra that extend along the b axis. These polyhedra share faces or edges with two neighbors within the chains, while in the [ac] plane they share edges and corners with other chains. Least square refinements gave rise to the formulas of {delta}-Ce{sub 1.30}Lu{sub 0.70}S{sub 3}, {delta}-Pr{sub 1.29}Lu{sub 0.71}S{sub 3} and {delta}-Nd{sub 1.33}Lu{sub 0.67}S{sub 3}, which are consistent with the EDX analysis and magnetic susceptibility data. {delta}-Ln{sub 2-x}LuxS{sub 3} (Ln = Ce, Pr, Nd; x = 0.67-0.71) show no evidence of magnetic ordering down to 5 K. Optical properties measurements show that the band gaps for {delta}-Ce{sub 1.30}Lu{sub 0.70}S{sub 3}, {delta}-Pr{sub 1.29}Lu{sub 0.71}S{sub 3}, and {delta}-Nd{sub 1.33}Lu{sub 0.67}S{sub 3} are 1.25 eV, 1.38 eV, and 1.50 eV, respectively. Crystallographic data: {delta}-Ce{sub 1.30}Lu{sub 0.70}S{sub 3}, monoclinic, space group P2{sub 1}/m, a = 11.0186(7), b = 3.9796(3), c = 21.6562(15) {angstrom}, {beta} = 101.6860(10), V = 929.93(11), Z = 8; {delta}-Pr{sub 1.29}Lu{sub 0.71}S{sub 3}, monoclinic, space group P2{sub 1}/m, a = 10.9623(10), b = 3.9497(4), c = 21.5165(19) {angstrom}, {beta} = 101.579(2), V = 912.66(15), Z = 8; {delta}-Nd{sub 1.33}Lu{sub 0.67}S{sub 3}, monoclinic, space group P2{sub 1}/m, a = 10.9553(7), b = 3.9419(3), c = 21.4920(15) {angstrom}, {beta} = 101.5080(10), V = 909.47(11), Z = 8.

  13. Structural integrity assessment of type 201LN stainless steel cryogenic pressure vessels

    SciTech Connect

    Rana, M.D.; Zawierucha, R.

    1995-12-01

    The ASME Boiler and Pressure Vessel Code Committee approved the Code Case 2123 in 1992 which allows the use of Type 201LN stainless steel in the construction of ASME Section VIII, Division 1 and Division 2 pressure vessels for -320{degrees}F applications. Type 201LN stainless steel is a nitrogen strengthened modified version of ASTM A240, Type 201 stainless steel with a restricted chemistry. The Code allowable design stresses for Type 201LN for Division 1 vessels are approximately 27% higher than Type 304 stainless steel and equal to that of the 5 Ni and 9 Ni steels. This paper discusses the important features of the Code Case 2123 and the structural integrity assessment of Type 201LN stainless steel cryogenic vessels. Tensile, Charpy-V-notch and fracture properties have been obtained on several heats of this steel including weldments. A linear-elastic fracture mechanics analysis has been conducted to assess the expected fracture mode and the fracture-critical crack sizes. The results have been compared with Type 304 stainless steel, 5 Ni and 9 Ni steel vessels.

  14. Large Hexadecametallic {Mn(III) -Ln(III) } Wheels: Synthesis, Structural, Magnetic, and Theoretical Characterization.

    PubMed

    Vignesh, Kuduva R; Langley, Stuart K; Moubaraki, Boujemaa; Murray, Keith S; Rajaraman, Gopalan

    2015-11-01

    The synthesis, gas sorption studies, magnetic properties, and theoretical studies of new molecular wheels of core type {Mn(III) 8 Ln(III) 8 } (Ln=Dy, Ho, Er, Y and Yb), using the ligand mdeaH2 , in the presence of ortho-toluic or benzoic acid are reported. From the seven wheels studied the {Mn8 Dy8 } and {Mn8 Y8 } analogues exhibit SMM behavior as determined from ac susceptibility experiments in a zero static magnetic field. From DFT calculations a S=16 ground state was determined for the {Mn8 Y8 } complex due to weak ferromagnetic Mn(III) -Mn(III) interactions. Ab initio CASSCF+RASSI-SO calculations on the {Mn8 Dy8 } wheel estimated the Mn(III) -Dy(III) exchange interaction as -0.1 cm(-1) . This weak exchange along with unfavorable single-ion anisotropy of Dy(III) /Mn(III) ions, however, led to the observation of SMM behavior with fast magnetic relaxation. The orientation of the g-anisotropy of the Dy(III) ions is found to be perpendicular to the plane of the wheel and this suggests the possibility of toroidal magnetic moments in the cluster. The {Mn8 Ln8 } clusters reported here are the largest heterometallic Mn(III) Ln(III) wheels and the largest {3d-4f} wheels to exhibit SMM behavior reported to date.

  15. Thermodynamic modeling of REE behavior in oxidized hydrothermal fluids of high sulfate sulfur concentrations

    NASA Astrophysics Data System (ADS)

    Shironosova, G. P.; Kolonin, G. R.; Borovikov, A. A.; Borisenko, A. S.

    2016-08-01

    Thermodynamic calculations using the HCh software were made for mineral equilibriums including REEs in the fluoride-sulfide-chloride-carbonate-sulfate-system in the presence of Na, Ca, and P with fluids of various acidities-alkalinities [11]. The obtained thermodynamic characteristics of thenardite allowed us to carry out the calculations for this phase under complicated hydrothermal conditions simulating the presence of oxidized fluids at 500-100°C and 2000-125 bar. Among other solid phases, REEs-fluorite, monazite, and REE-F-apatite were formed as CaF2-(Ln,Y)F3, LnPO4, and Ca5(PO4)3F-(Ln,Y)3(PO4)3 ideal solid solutions, respectively, where Ln is La, Ce, Pr, Nd, Sm, Eu, and Gd. Xenotime, anhydrite, elemental sulfur, and calcite were found as well.

  16. L- and D-[LnZn(IN)3(C2H4O2)]n (Ln = Eu, Sm, and Gd): Chiral Enantiomerically 3D 3d-4f Coordination Polymers Constructed by Interesting Butterfly-like Building Units and -[Ln-O-Zn]n- Helices.

    PubMed

    He, Xingxiang; Liu, Ying; Lv, Yun; Dong, Yayu; Hu, Gonghao; Zhou, Shuai; Xu, Yan

    2016-03-01

    A total of six three-dimensional chiral coordination compounds L- and D-[LnZn(IN)3(C2H4O2)]n (Ln = Eu, Sm, and Gd; HIN = isonicotinic acid) have been successfully synthesized under hydrothermal conditions without any chiral auxiliary and characterized by IR, TG, elemental analyses, and solid-state circular dichroism spectra. The structures of 1-6 were determined by single-crystal X-ray structural analysis, which shows that L-[LnZn(IN)3(C2H4O2)]n (Ln = Eu (1), Sm (2), and Gd (3)) crystallize in space group P6522 and are levogyrate. The chiral frameworks of L-[LnZn(IN)3(C2H4O2)]n are constructed from L-helical Ln-O-Zn cluster chains, while adjacent L-type helical -[Ln-O-Zn]n- chains are connected through IN(-) ligands. D-[LnZn(IN)3(C2H4O2)]n (Ln = Eu (4), Sm (5), and Gd (6)) crystallize in space group P6122, and their chiral frameworks consist of D-helical Ln-O-Zn cluster chains. The observed second-harmonic generation efficiencies of [EuZn(IN)3(C2H4O2)]n, [SmZn(IN)3(C2H4O2)]n, and [GdZn(IN)3(C2H4O2)]n are 0.4, 0.3, and 0.3 times that of urea, respectively. We also studied luminescence spectra and luminescence lifetimes of 1 and 2. The luminescence lifetimes of 1 and 2 are 1.18 ms, and 29.6 μs, respectively.

  17. Nanomaterial size distribution analysis via liquid nebulization coupled with ion mobility spectrometry (LN-IMS).

    PubMed

    Jeon, Seongho; Oberreit, Derek R; Van Schooneveld, Gary; Hogan, Christopher J

    2016-02-21

    We apply liquid nebulization (LN) in series with ion mobility spectrometry (IMS, using a differential mobility analyzer coupled to a condensation particle counter) to measure the size distribution functions (the number concentration per unit log diameter) of gold nanospheres in the 5-30 nm range, 70 nm × 11.7 nm gold nanorods, and albumin proteins originally in aqueous suspensions. In prior studies, IMS measurements have only been carried out for colloidal nanoparticles in this size range using electrosprays for aerosolization, as traditional nebulizers produce supermicrometer droplets which leave residue particles from non-volatile species. Residue particles mask the size distribution of the particles of interest. Uniquely, the LN employed in this study uses both online dilution (with dilution factors of up to 10(4)) with ultra-high purity water and a ball-impactor to remove droplets larger than 500 nm in diameter. This combination enables hydrosol-to-aerosol conversion preserving the size and morphology of particles, and also enables higher non-volatile residue tolerance than electrospray based aerosolization. Through LN-IMS measurements we show that the size distribution functions of narrowly distributed but similarly sized particles can be distinguished from one another, which is not possible with Nanoparticle Tracking Analysis in the sub-30 nm size range. Through comparison to electron microscopy measurements, we find that the size distribution functions inferred via LN-IMS measurements correspond to the particle sizes coated by surfactants, i.e. as they persist in colloidal suspensions. Finally, we show that the gas phase particle concentrations inferred from IMS size distribution functions are functions of only of the liquid phase particle concentration, and are independent of particle size, shape, and chemical composition. Therefore LN-IMS enables characterization of the size, yield, and polydispersity of sub-30 nm particles.

  18. Nanomaterial size distribution analysis via liquid nebulization coupled with ion mobility spectrometry (LN-IMS).

    PubMed

    Jeon, Seongho; Oberreit, Derek R; Van Schooneveld, Gary; Hogan, Christopher J

    2016-02-21

    We apply liquid nebulization (LN) in series with ion mobility spectrometry (IMS, using a differential mobility analyzer coupled to a condensation particle counter) to measure the size distribution functions (the number concentration per unit log diameter) of gold nanospheres in the 5-30 nm range, 70 nm × 11.7 nm gold nanorods, and albumin proteins originally in aqueous suspensions. In prior studies, IMS measurements have only been carried out for colloidal nanoparticles in this size range using electrosprays for aerosolization, as traditional nebulizers produce supermicrometer droplets which leave residue particles from non-volatile species. Residue particles mask the size distribution of the particles of interest. Uniquely, the LN employed in this study uses both online dilution (with dilution factors of up to 10(4)) with ultra-high purity water and a ball-impactor to remove droplets larger than 500 nm in diameter. This combination enables hydrosol-to-aerosol conversion preserving the size and morphology of particles, and also enables higher non-volatile residue tolerance than electrospray based aerosolization. Through LN-IMS measurements we show that the size distribution functions of narrowly distributed but similarly sized particles can be distinguished from one another, which is not possible with Nanoparticle Tracking Analysis in the sub-30 nm size range. Through comparison to electron microscopy measurements, we find that the size distribution functions inferred via LN-IMS measurements correspond to the particle sizes coated by surfactants, i.e. as they persist in colloidal suspensions. Finally, we show that the gas phase particle concentrations inferred from IMS size distribution functions are functions of only of the liquid phase particle concentration, and are independent of particle size, shape, and chemical composition. Therefore LN-IMS enables characterization of the size, yield, and polydispersity of sub-30 nm particles. PMID:26750519

  19. Assessment of surface relief and short cracks under cyclic creep in a type 316LN austenitic stainless steel

    NASA Astrophysics Data System (ADS)

    Sarkar, Aritra; Nagesha, A.; Parameswaran, P.; Sandhya, R.; Laha, K.

    2015-12-01

    Formation of surface relief and short cracks under cyclic creep (stress-controlled fatigue) in type 316LN stainless steel was studied at temperatures ranging from ambient to 923 K using scanning electron microscopy technique. The surface topography and crack distribution behaviour under cyclic creep were found to be strong functions of testing temperature due to the difference in strain accumulation. At 823 K, surface relief mainly consisted of fine slip markings due to negligible accumulation of strain as a consequence of dynamic strain ageing (DSA) which led to an increase in the cyclic life. Persistent slip markings (PSM) with distinct extrusions containing minute cracks were seen to prevail in the temperature range 873-923 K, indicating a higher slip activity causing higher strain accumulation in the absence of DSA. Besides, a large number of secondary cracks (both transgranular and intergranular) which were partially accentuated by severe oxidation, were observed. Extensive cavitation-induced grain boundary cracking took place at 923 K, which coalesced with PSM-induced transgranular cracks resulting in failure dominated by creep that in turn led to a drastic reduction in cyclic life. Investigations on the influence of stress rate were also carried out which underlined the presence of DSA at 823 K. At 923 K, lowering the stress rate caused further strengthening of the contribution from creep damage marked by a shift in the damage mechanism from cyclic slip to diffusion.

  20. Intergranular Corrosion Behavior of 304LN Stainless Steel Heat Treated at 623 K (350 °C)

    NASA Astrophysics Data System (ADS)

    Singh, Raghuvir; Kumar, Mukesh; Ghosh, Mainak; Das, Gautam; Singh, P. K.; Chattoraj, I.

    2013-01-01

    Low temperature sensitization of 304LN stainless steel from the two pipes, differing slightly in chemical composition, has been investigated; specimens were aged at 623 K (350 °C) for 20,000 hours and evaluated for intergranular corrosion and degree of sensitization. The base and heat-affected zone (HAZ) of the 304LN-1 appear resistant to sensitization, while 304LN-2 revealed a "dual" type microstructure at the transverse section and HAZ. The microstructure at 5.0-mm distance from the fusion line indicates qualitatively less sensitization as compared to that at 2.0 mm. The 304LN-2 base alloy shows overall lower degree of sensitization values as compared to the 304LN-1. A similar trend of degree of sensitization was observed in the HAZ where it was higher in the 304LN-1 as compared to the 304LN-2. The weld zone of both the stainless steels suffered from cracking during ASTM A262 practice E, while the parent metals and HAZs did not show such fissures. A mottled image within the ferrite lamella showed spinodal decomposition. The practice E test and transmission electron microscopy results indicate that the interdendritic regions may suffer from failure due to carbide precipitation and due to the evolution of brittle phase from spinodal decomposition.

  1. Reactivity at the Ln2NiO4+δ/electrolyte interface (Ln = La, Nd) studied by Electrochemical Impedance Spectroscopy and Transmission Electron Microscopy

    NASA Astrophysics Data System (ADS)

    Montenegro-Hernández, Alejandra; Soldati, Analía; Mogni, Liliana; Troiani, Horacio; Schreiber, Anja; Soldera, Flavio; Caneiro, Alberto

    2014-11-01

    Chemical reactivity between Ln2NiO4+δ (Ln: La, Nd) electrodes and Y0.08Zr0.92O1.96 (YSZ) and Ce0.9Gd0.1O1.95 (CGO) electrolytes was analyzed by Electrochemical Impedance Spectroscopy (EIS) and Focused Ion Beam-Transmission Electron Microscopy (FIB-TEM) techniques. Ln2NiO4+δ electrodes were deposited onto CGO and YSZ electrolytes by aerography and treated at 900 °C during 1 h in order to promote electrode adhesion. EIS spectra were collected between 500 and 800 °C in dry air. The Polarization Resistances (PR) values for La2NiO4/CGO/La2NiO4 cell are higher than those of La2NiO4/YSZ/La2NiO4. The PR for both cells and its evolution in time suggest that chemical reactivity is developed at 900 °C during the adhesion treatment and at T higher than 650 °C during the EIS measurements. The PR for Nd2NiO4/CGO/Nd2NiO4 and Nd2NiO4/YSZ/Nd2NiO4 are much lower than those of La2NiO4/CGO/La2NiO4 and La2NiO4/YSZ/La2NiO4 cells. These values and the slight increase of PR with time for Nd2NiO4 (NNO) electrodes indicate that the strength of chemical reactivity is much lower than that of La2NiO4 (LNO). TEM results confirmed that reactivity between CGO and LNO is much higher than that of YSZ and LNO and also confirm that the strength of reactivity is appreciably lower for NNO as electrode material.

  2. Lanthanide contraction effect on crystal structures, magnetic, and dielectric properties in ordered double perovskites LnPbCoSbO{sub 6} (Ln = La, Pr, Nd)

    SciTech Connect

    Han, L.; Yao, C. G.; Meng, J. L.; Liang, Q. S.; Bai, Y. J.; Meng, F. Z.; Liu, X. J. E-mail: jmeng@ciac.ac.cn; Wu, X. J.; Meng, J. E-mail: jmeng@ciac.ac.cn

    2014-04-28

    The crystal structures, magnetic, and dielectric properties for the ordered double perovskites LnPbCoSbO{sub 6} (Ln = La, Pr, Nd) have been investigated. The crystal structure has been solved by Rietveld refinements of X-ray diffraction data in the monoclinic space group P2{sub 1}/n (No. 14). The Co{sup 2+} and Sb{sup 5+} ions are almost fully ordered over the B-site, and the octahedral framework displays significant tilting distortion according to the Glazer's tilt system a{sup –}a{sup –}c{sup +}. As the result of lanthanide contraction from La{sup 3+} to Nd{sup 3+}, the B-site sublattice distortions become stronger accompanying with the reduction of the tolerance factor and coordination number. The magnetization measurements show an antiferromagnetic ordering with large effective magnetic moments (μ{sub eff}) suggesting that the orbital component is significant. The maximum values of isothermal magnetization increase with the decrease in radii of rare earth ions, which is attributed to the weakening of antiferromagnetic interaction via Co{sup 2+}–O–Sb{sup 5+}–O–Co{sup 2+} paths. The dielectric constants present frequency dependence and monotonically decrease with the ionic radii reduction from La{sup 3+} to Nd{sup 3+} due to the suppression of electron transfer. These results indicate that the magnetic and dielectric properties can be tuned by controlling the degree of lattice distortion, which is realized by introducing different Ln{sup 3+} ions at the A-site.

  3. Thermometry and up-conversion luminescence of Yb(3+)-Er(3+) co-doped Na2Ln2Ti3O10 (Ln = Gd, La) phosphors.

    PubMed

    Zhang, Zhiyu; Guo, Chongfeng; Suo, Hao; Zhao, Xiaoqi; Zhang, Niumiao; Li, Ting

    2016-07-28

    Yb(3+)/Er(3+)-ion co-doped Na2Ln2Ti3O10 (Ln = Gd, La) up-conversion (UC) phosphors were successfully synthesized by a sol-gel method, and their crystal structures were characterized by powder X-ray diffraction. Dazzling yellow-greenish light was emitted under the excitation of 980 nm near-infrared (NIR) light, composing green and red emission bands from the (2)H11/2/(4)S3/2→(4)I15/2 and (4)F9/2→(4)I15/2 transitions of Er(3+), respectively. The optimal composition and synthesis parameters were determined according to their UC emission intensity. The photon absorption and emission processes were illustrated based on the UC mechanism, in which energy transfer (ET) from Yb(3+) to Er(3+) plays a pivotal role and has been proved by the variation of green emission lifetime in Er(3+) singly and Yb(3+)/Er(3+) co-doped Na2Ln2Ti3O10 samples. The temperature-dependent fluorescence intensity ratios (FIR) of the two thermal coupled energy level (TCL) emission from (2)H11/2→(4)I15/2 (526 nm) and (4)S3/2→(4)I15/2 (549 nm) were calculated in the range of 290-490 K, and their sensitivity values were approximately 0.0058 K(-1) for Na2Gd2Ti3O10 at 490 K and 0.0061 K(-1) for Na2La2Ti3O10 at 470 K, as potential optical temperature sensor. PMID:27346281

  4. An investigation of structural parameters and magnetic and optical properties of EuLn{sub 2}Q{sub 4} (Ln=Tb-Lu, Q=S, Se)

    SciTech Connect

    Jin Gengbang; Choi, Eun Sang; Guertin, Robert P.; Albrecht-Schmitt, Thomas E.

    2008-01-15

    EuLn{sub 2}Q{sub 4} (Ln=Tb-Lu; Q=S, Se) has been synthesized using Sb{sub 2}Q{sub 3} (Q=S, Se) fluxes at 1000 deg. C. These compounds crystallize in a CaFe{sub 2}O{sub 4}-type three-dimensional channel structure that is built from edge-shared double rutile chains of [LnQ{sub 6}] octahedra running down the b-axis. Each double chain is connected at the vertices to four other double chains to form open channels where bicapped trigonal prismatic Eu{sup 2+} ions reside. All of these compounds show antiferromagnetic ordering with Neel temperatures, T{sub N}{approx}3-4 K. The optical band gaps for EuTb{sub 2}Se{sub 4}, EuDy{sub 2}Se{sub 4}, EuHo{sub 2}Se{sub 4}, EuEr{sub 2}Se{sub 4}, EuTm{sub 2}Se{sub 4}, EuYb{sub 2}Se{sub 4} EuLu{sub 2}Se{sub 4}, and EuYb{sub 2}S{sub 4} are found to be 2.0, 1.8, 1.8, 1.7, 1.8, 1.3, 1.7, and 1.6 eV, respectively. - Graphical abstract: A view of the three-dimensional channel structure of EuYb{sub 2}S{sub 4} down the b-axis.

  5. Dual emission tunable in the near-infrared (NIR) and visible (VIS) spectral range by mix-LnMOF.

    PubMed

    de Jesus, Roberta Anjos; da Luz, Leonis Lourenço; Santos, Danilo Oliveira; Costa, José Arnaldo Santana; Navickiene, Sandro; Gatto, Claudia Cristina; Júnior, Severino Alves; de Mesquita, Maria Eliane

    2015-10-21

    In this study, we describe the synthetic approach, crystallographic structure, luminescent behavior and elucidation of the channels of the energy conversion in heteronuclear coordination polymers with emission in the visible (Eu(3+) and organic ligand) and near-infrared (Nd(3+)) range. The [(Nd0.9Eu0.1)2(dipc)3(H2O)3]n·nH2O, [(Nd0.7Eu0.3)2(dipc)3(H2O)3]n·nH2O, [(Nd0.5Eu0.5)2(dipc)3(H2O)3]n·nH2O, [(Nd0.3Eu0.7)2(dipc)3(H2O)3]n·nH2O, [(Nd0.1Eu0.9)2(dipc)3(H2O)3]n·nH2O, [Eu2(dipc)3(H2O)3]n·nH2O and [Nd2(dipc)3(H2O)3]n·nH2O materials are obtained by hydrothermal conditions from pyridine-2,6-dicarboxylic acid (H2dipc) and Ln2O3 oxide (Ln = Eu and Nd). The fine structures in the emission spectrum and spectral profile are used to investigate the ion responsible for the emission characteristics of a material (6), based on coordination polyhedron. The heteronuclear systems show emission in the dual spectral range (NIR-VIS) tuned for blue or red. The tuning of emission on the red (Eu(3+)) or blue (organic ligand) range may be performed by controlling the stoichiometric ratio of the lanthanide ions and by controlling the excitation wavelength. Nd(3+) ions display self-absorption of emission to dipc ligand, resulting in interference on the emission band profile ranging from 400 to 600 nm. The energetic process of energy transfer is operated by a cascade of energy transfer, from dipc ligand mainly to Eu(3+) ions and finishing on the Nd(3+) ion. The efficient sensitization to Nd(3+) by Eu(3+) ions is due to the presence of many resonant energy levels and the short distance between these ions.

  6. Evaluation of the Effect of Dynamic Sodium on the Low Cycle Fatigue Properties of 316L(N) Stainless Steel Base and Weld Joints

    NASA Astrophysics Data System (ADS)

    Ganesan, V.; Kannan, R.; Mariappan, K.; Sukumaran, G.; Sandhya, R.; Rao, K. Bhanu Sankara

    2012-06-01

    Low cycle fatigue (LCF) tests on 316L(N) austenitic stainless steel base and weld joints were at 823 K and 873 K at a constant strain rate of 3 × 10 -3 s -1 with strain ranges varying from {±}0.4% to {±}1.0% in a servo-hydraulic fatigue test system under flowing sodium environment. The cyclic stress response exhibited a similar trend as that in air comprising of an initial rapid hardening, followed by a slight softening stage before saturation. The fatigue lives are significantly improved in sodium environment when compared to identical testing conditions in air environment. The lack of oxidation in sodium environment is attributed to the delayed crack initiation, reduced crack propagation rate and consequent increase in fatigue life. Comparison of the data evaluated in sodium with RCC-MR design code, derived on the basis of data obtained from air shows that the design based on air tests is conservative.

  7. Ultralow loss visible surface plasmon based waveguides formed in indium-tin-oxide coated Fe-doped LiNbO3 slabs.

    PubMed

    Zhao, Hua; Xue, Tingyu; Li, Liang; Zhang, Jingwen

    2016-09-15

    Visible reconfigurable waveguides were evidenced in a composite system formed with indium-tin-oxide (ITO) films coated on iron-doped lithium noibate (LN) slabs. Surface plasmon polaritions (SPPs) excited at the ITO/LN interface were believed to be behind the observed light guiding, which is inherent with superlow loss for its sub-nanometer modified layer. The forward near-surface-normal scattering and accompanying reduction of the specular reflectivity in the front ITO/LN interface are consistent with SPP excitation.

  8. Ultralow loss visible surface plasmon based waveguides formed in indium-tin-oxide coated Fe-doped LiNbO3 slabs.

    PubMed

    Zhao, Hua; Xue, Tingyu; Li, Liang; Zhang, Jingwen

    2016-09-15

    Visible reconfigurable waveguides were evidenced in a composite system formed with indium-tin-oxide (ITO) films coated on iron-doped lithium noibate (LN) slabs. Surface plasmon polaritions (SPPs) excited at the ITO/LN interface were believed to be behind the observed light guiding, which is inherent with superlow loss for its sub-nanometer modified layer. The forward near-surface-normal scattering and accompanying reduction of the specular reflectivity in the front ITO/LN interface are consistent with SPP excitation. PMID:27628344

  9. Hydrothermal synthesis, structure, and optical properties of two nanosized Ln26 @CO3 (Ln=Dy and Tb) cluster-based lanthanide-transition-metal-organic frameworks (Ln MOFs).

    PubMed

    Zhang, Yu; Huang, Lian; Miao, Hao; Wan, Hong Xiang; Mei, Hua; Liu, Ying; Xu, Yan

    2015-02-16

    Two Ln26 @CO3 (Ln=Dy and Tb) cluster-based lanthanide-transition-metal-organic frameworks (Ln MOFs) formulated as [Dy26 Cu3 (Nic)24 (CH3 COO)8 (CO3 )11 (OH)26 (H2 O)14 ]Cl ⋅3 H2 O (1; HNic=nicotinic acid) and [Tb26 NaAg3 (Nic)27 (CH3 COO)6 (CO3 )11 (OH)26 Cl(H2 O)15 ]⋅7.5 H2 O (2) have been successfully synthesized by hydrothermal methods and characterized by IR, thermogravimetric analysis (TGA), elemental analysis, and single X-ray diffraction. Compound 1 crystallizes in the monoclinic space group Cc with a=35.775(12) Å, b=33.346(11) Å, c=24.424(8) Å, β=93.993(5)°, V=29065(16) Å(3) , whereas 2 crystallizes in the triclinic space group P$\\bar 1$ with a=20.4929(19) Å, b=24.671(2) Å, c=29.727(3) Å, α=81.9990(10)°, β=88.0830(10)°, γ=89.9940(10)°, V=14875(2) Å(3) . Structural analysis indicates the framework of 1 is a 3D perovskite-like structure constructed out of CO3 @Dy26 building units and Cu(+) centers by means of nicotinic acid ligand bridging. In 2, however, nanosized CO3 @Tb26 units and [Ag3 Cl](2+) centers are connected by Nic(-) bridges to give rise to a 2D structure. It is worth mentioning that this kind of 4d-4f cluster-based MOF is quite rare as most of the reported analogous compounds are 3d-4f ones. Additionally, the solid-state emission spectra of pure compound 2 at room temperature suggest an efficient energy transfer from the ligand Nic(-) to Tb(3+) ions, which we called the "antenna effect". Compound 2 shows a good two-photon absorption (TPA) with a TPA coefficient of 0.06947 cm GM(-1) (1 GM=10(-50)  cm(4)  s photon(-1) ), which indicates that compound 2 might be a good choice for third-order nonlinear optical materials.

  10. High-temperature X-ray diffraction measurements of fluorite-related rare earth antimonates Ln{sub 3}SbO{sub 7} (Ln=Nd, Tb) and their magnetic properties

    SciTech Connect

    Hinatsu, Yukio Doi, Yoshihiro

    2014-09-15

    Ternary rare-earth antimonates Ln{sub 3}SbO{sub 7} (Ln=rare earths) were prepared, and their structures were determined by X-ray diffraction measurements. They crystallize in an orthorhombic superstructure of cubic fluorite (space group Cmcm for Ln=La, Pr; Ccmm for Ln=Sm–Dy), in which Ln{sup 3+} ions occupy two different crystallographic sites (the 8-coordinated and 7-coordinated). For Ln=Nd, two phases with the Cmcm and Ccmm space groups coexist at room temperature. When the temperature was increased, the Nd{sub 3}SbO{sub 7} compound transformed into a single phase with the space group Cmcm. Through magnetic susceptibility measurements, an antiferromagnetic transition was observed at 3.0 K (Ln=Nd) and 7.8 K (Ln=Tb). Analysis of the magnetic specific heat for Tb{sub 3}SbO{sub 7} indicates that the 8-coordinated Tb ions magnetically orders at 7.8 K, and with furthermore decreasing temperature, the 7-coordinated Tb ions shows antiferromagnetic ordering at 3.0 K. - Graphical abstract: Temperature dependence of the specific heat divided by temperature (C{sub p}/T) and the magnetic entropy (S{sub mag}) for Tb{sub 3}SbO{sub 7}. Two-step magnetic transition has been observed. - Highlights: • The phase transition of Nd{sub 3}SbO{sub 7} is from the Ccmm space group to the Cmcm one. • Nd{sub 3}SbO{sub 7} shows an antiferromagnetic transition at 3.0 K. • For Tb{sub 3}SbO{sub 7}, two-step magnetic transition has been observed at 7.8 and 3.0 K.

  11. Structure of trihydrated rare-earth acid diphosphates LnHP 2O 7·3H 2O ( Ln=La, Er)

    NASA Astrophysics Data System (ADS)

    Ben Moussa, S.; Ventemillas, S.; Cabeza, A.; Gutierrez-Puebla, E.; Sanz, J.

    2004-06-01

    In trihydrated lanthanum acid-diphosphates LnHP 2O 7·3H 2O, prepared from acid LnCl 3 and Na 4P 2O 7 solutions (pH=1), two crystal forms were obtained. Layered structures of two representative members of this family have been determined by single-crystal X-ray diffraction (XRD) technique. In the case of orthorhombic LaHP 2O 7·3H 2O (type I), lanthanum cations are ninefold coordinated and diphosphate groups adopt a staggered (alternated) configuration. In the case of triclinic ErHP 2O 7·3H 2O (type II), erbium cations are eightfold coordinated and diphosphate groups adopt an eclipsed configuration. In agreement with Infrared (IR) spectroscopic data, a bended configuration for diphosphate groups has been deduced. In both structures, one-dimensional chains of edge-sharing rare-earth polyhedra are linked together by diphosphate groups to form the phosphate layers. In both diphosphates, PO 4 and HPO 4 environments have been identified by 31P MAS-NMR technique. In the two compounds, OH groups of HPO 4 tetrahedra point out of diphosphate planes interacting with adjacent layers. In La-diphosphate, the interaction between HPO 4 groups and water molecules of adjacent layers is favored; however, in Er-diphosphate, the interaction between phosphate acid groups of contiguous layers is produced. Based on structural information deduced, differences detected in IR and NMR spectra of two disphosphates are discussed.

  12. Magnetic properties of layered rare-earth oxy-carbonates Ln2O2CO3 (Ln=Nd, Sm, and Dy)

    NASA Astrophysics Data System (ADS)

    Arjun, U.; Brinda, K.; Padmanabhan, M.; Nath, R.

    2016-08-01

    Polycrystalline samples of rare-earth oxy-carbonates Ln2O2CO3 (Ln=Nd, Sm, and Dy) are synthesized and their structural and magnetic properties are investigated. All of them crystallize in a hexagonal structure with space group P63 / mmc. They form a double layered structure with frustrated triangular arrangement of rare-earth magnetic ions. An antiferromagnetic transition is observed at TN ~ 1.25 K , 0.61 K, and 1.21 K for Nd2O2CO3, Sm2O2CO3, and Dy2O2CO3, respectively. From the analysis of magnetic susceptibility, the value of the Curie-Weiss temperature θCW is obtained to be ~21.7 K, 18 K, and 10.6 K for Nd2O2CO3, Sm2O2CO3, and Dy2O2CO3, respectively. The magnetic frustration parameter f(= |θCW | /TN) is calculated to be ~17.4, 31, and 8.8 for Nd2O2CO3, Sm2O2CO3, and Dy2O2CO3, respectively, which indicates that Sm2O2CO3 is strongly frustrated compared to its Nd and Dy analogues.

  13. Metamagnetic transitions in electron-doped single crystals of manganites Ca(1-x)(Ln)(x)MnO3, (Ln = La, Ce; x ≤ 0.12).

    PubMed

    Loshkareva, N N; Gerasimov, E G; Mushnikov, N V; Korolyov, A V; Balbashov, A M

    2010-09-01

    The magnetization curves of Ca(1-x)(Ln)(x)MnO(3) single crystals, where Ln denotes La or Ce, x ≤ 0.12, have been measured in pulsed magnetic fields up to 350 kOe. The metamagnetic transitions for compositions with x = 0.10 and 0.12 have been observed in the temperature range 77-240 K. The hysteresis around the transition for the sweep-up and sweep-down branches of the magnetization curve is wide for x(Ce) = 0.10 and 0.12, and relatively narrow for x(La) = 0.12. The maximum magnetization value reaches ~50% from its theoretical value for x(Ce) = 0.10 and 0.12, and ~24% for x(La) = 0.12 in a magnetic field H = 350 kOe. The metamagnetic transition has been attributed to the melting of orbital/charge ordering in the dielectric antiferromagnetic C-type phase, which is accompanied by the growth of the volume of the conductive phase with antiferromagnetic G-type ordering and ferromagnetic contribution. PMID:21403303

  14. Hardness of Carburized Surfaces in 316LN Stainless Steel after Low Temperature Neutron Irradiation

    SciTech Connect

    Byun, TS

    2005-01-31

    A proprietary surface carburization treatment is being considered to minimize possible cavitation pitting of the inner surfaces of the stainless steel target vessel of the SNS. The treatment gives a large supersaturation of carbon in the surface layers and causes substantial hardening of the surface. To answer the question of whether such a hardened layer will remain hard and stable during neutron irradiation, specimens of the candidate materials were irradiated in the High Flux Isotope Reactor (HFIR) to an atomic displacement level of 1 dpa. Considerable radiation hardening occurred in annealed 316LN stainless steel and 20% cold rolled 316LN stainless steel, and lesser radiation hardening in Kolsterised layers on these materials. These observations coupled with optical microscopy examinations indicate that the carbon-supersaturated layers did not suffer radiation-induced decomposition and softening.

  15. Creep rupture strength of activated-TIG welded 316L(N) stainless steel

    NASA Astrophysics Data System (ADS)

    Sakthivel, T.; Vasudevan, M.; Laha, K.; Parameswaran, P.; Chandravathi, K. S.; Mathew, M. D.; Bhaduri, A. K.

    2011-06-01

    316L(N) stainless steel plates were joined using activated-tungsten inert gas (A-TIG) welding and conventional TIG welding process. Creep rupture behavior of 316L(N) base metal, and weld joints made by A-TIG and conventional TIG welding process were investigated at 923 K over a stress range of 160-280 MPa. Creep test results showed that the enhancement in creep rupture strength of weld joint fabricated by A-TIG welding process over conventional TIG welding process. Both the weld joints fractured in the weld metal. Microstructural observation showed lower δ-ferrite content, alignment of columnar grain with δ-ferrite along applied stress direction and less strength disparity between columnar and equiaxed grains of weld metal in A-TIG joint than in MP-TIG joint. These had been attributed to initiate less creep cavitation in weld metal of A-TIG joint leading to improvement in creep rupture strength.

  16. TES/Aura L2 Ozone (O3) Lite Nadir (TL2O3LN)

    Atmospheric Science Data Center

    2015-08-26

    TES/Aura L2 Ozone (O3) Lite Nadir (TL2O3LN) News:  TES News ... Level:  L2 Instrument:  TES/Aura L2 Ozone Spatial Coverage:  5.3 km nadir Spatial ... OPeNDAP Access:  OPeNDAP Parameters:  Ozone Order Data:  Reverb:   Order Data Guide ...

  17. TES/Aura L2 Carbon Dioxide (CO2) Lite Nadir (TL2CO2LN)

    Atmospheric Science Data Center

    2015-06-24

    TES/Aura L2 Carbon Dioxide (CO2) Lite Nadir (TL2CO2LN) News:  TES News ... L2 Instrument:  TES/Aura L2 Carbon Dioxide Spatial Coverage:  5.3 km nadir Spatial ... OPeNDAP Access:  OPeNDAP Parameters:  Carbon Dioxide Order Data:  Reverb:   Order Data ...

  18. TES/Aura L2 Ammonia (NH3) Lite Nadir (TL2NH3LN)

    Atmospheric Science Data Center

    2015-08-26

    TES/Aura L2 Ammonia (NH3) Lite Nadir (TL2NH3LN) News:  TES News ... Level:  L2 Instrument:  TES/Aura L2 Ammonia Spatial Coverage:  5.3 km nadir Spatial ... OPeNDAP Access:  OPeNDAP Parameters:  Ammonia Order Data:  Reverb:   Order Data ...

  19. TES/Aura L2 Methane (CH4) Lite Nadir (TL2CH4LN)

    Atmospheric Science Data Center

    2015-08-31

    TES/Aura L2 Methane (CH4) Lite Nadir (TL2CH4LN) News:  TES News ... Level:  L2 Instrument:  TES/Aura L2 Methane Spatial Coverage:  5.3 km nadir Spatial ... OPeNDAP Access:  OPeNDAP Parameters:  Methane Order Data:  Reverb:   Order Data ...

  20. Pitting and Intergranular Corrosion Resistance of AISI Type 301LN Stainless Steels

    NASA Astrophysics Data System (ADS)

    Ningshen, S.; Kamachi Mudali, U.

    2010-03-01

    The pitting and intergranular corrosion (IGC) resistance of AISI type 301LN stainless steels were evaluated using ASTM methods, anodic polarization, and electrochemical impedance techniques. The IGC results indicated that the microstructure of the samples after sensitization heat treatment at 675 °C for 1 h shows step or dual structure for both imported and indigenous materials indicating insignificant Cr23C6 precipitation. The results of immersion tests in boiling 6% copper sulfate + 16% sulfuric acid + copper solution for 24 h followed by the bend test (ASTM A262 Practice-E method) indicated no crack formation in any of the tested specimens. Pitting corrosion resistance carried out in 6% FeCl3 solution at different temperatures of 22 ± 2 and 50 ± 2 °C (ASTM G 48) up to the period of 72 h revealed pitting corrosion attack in all the investigated alloys. The potentiodynamic anodic polarization results in 0.5 M NaCl revealed variation in passive current density and pitting potential depending on the alloy chemistry and metallurgical condition. The passive film properties studied by electrochemical impedance spectroscopy (EIS) correlated well with the polarization results. The x-ray diffraction (XRD) results revealed the presence of austenite (γ) and martensite (α') phases depending on the material condition. The suitability of three indigenously developed AISI type 301LN stainless steels were compared with imported type 301LN stainless steel and the results are highlighted in this article.

  1. Deterioration in Fracture Toughness of 304LN Austenitic Stainless Steel Due to Sensitization

    NASA Astrophysics Data System (ADS)

    Ghosh, Swati; Kain, V.; Ray, A.; Roy, H.; Sivaprasad, S.; Tarafder, S.; Ray, K. K.

    2009-12-01

    The aim of this report is to examine the influence of sensitization on the mechanical properties of AISI grade 304LN stainless steel with special emphasis on its fracture toughness. A series of stainless steel samples has been sensitized by holding at 1023 K for different time periods ranging from 1 to 100 hours followed by water quenching. The degree of sensitization (DOS) for each type of the varyingly heat-treated samples has been measured by an electrochemical potentiodynamic reactivation (EPR) test. The microstructures of these samples have been characterized by optical metallography, scanning electron microscopy, transmission electron microscopy (TEM), and X-ray diffraction (XRD) analyses, together with measurements of their hardness and tensile properties. The fracture toughness of the samples has been measured by the ball indentation (BI) technique and the results are validated by conducting conventional J-integral tests. It is revealed for the first time that the fracture toughness and ductility of AISI 304LN stainless steel deteriorate significantly with increased DOS, while the tensile strength (TS) values remain almost unaltered. The results have been critically discussed in terms of the depletion of solid solution strengtheners, the nature of the grain boundary precipitations, and the strain-induced martensite formation with the increasing DOS of the 304LN stainless steel.

  2. Equipping an FPGA-Based Mars Rover With an LN-200 IMU

    NASA Technical Reports Server (NTRS)

    Zola, Nicholas J.

    2005-01-01

    The Mars Exploration Rovers (MER) currently navigating the surface of Mars are outfitted with an advanced stereovision correlation algorithm which allows them to "see" three-dimensionally and autonomously avoid obstac'les in their path. A bottleneck of this system is that it is computationally intense and requires 3 minutes of processing for every correlated image and path choice. Taking advantage of the optimization and reprogrammability of FPGAs, the Mobility Avionics lab has reduced this process to under a second. The lab is demonstrating the advancement with a prototype rover, complete with an LN-200 inertial measurement unit (IMU), which is a flight spare from MER. The LN-200 is a space-grade, six degrees-of-freedom IMU using three fiber-optic gyroscopes and three silicon accelerometers and no moving parts. It has particular power-sequencing needs and communicates with a specialized serial protocol (SDLC over RS-422), requiring specific hardware and software for proper functionality and interfacing with an FPGA. The process of incorporating the LN-200 into the system is described herein.

  3. Quantitative interpretation of the very fast electronic relaxation of most Ln3+ ions in dissolved complexes

    NASA Astrophysics Data System (ADS)

    Fries, Pascal H.; Belorizky, Elie

    2012-02-01

    In a reference frame rigidly bound to the complex, we consider two Hamiltonians possibly at the origin of the very fast electronic relaxation of the paramagnetic lanthanide Ln3+ ions (Ln = Ce to Nd, Tb to Yb), namely the mean (static) ligand-field Hamiltonian and the transient ligand-field Hamiltonian. In the laboratory frame, the bombardment of the complex by solvent molecules causes its Brownian rotation and its vibration-distorsion dynamics governing the fluctuations of the static and transient terms, respectively. These fluctuations are at the origin of electronic relaxation. The electronic relaxation of a Ln3+ ion is defined by the decays of the time correlation functions (TCFs) of the longitudinal and transverse components of the total angular momentum J of its ground multiplet. The Brownian rotation of the complex and its vibration-distorsion dynamics are simulated by random walks, which enable us to compute the TCFs from first principles. It is shown that the electronic relaxation is governed mainly by the magnitude of the transient ligand-field, and not by its particular expression. The range of expected values of this ligand-field together with the lower limit of relaxation time enforced by the values of the vibration-distortion correlation time in liquids give rise to effective electronic relaxation times which are in satisfactory overall agreement with the experimental data. In particular, these considerations explain why the electronic relaxation times vary little with the coordinating ligand and are practically independent of the external field magnitude.

  4. Tetranuclear [Cu-Ln]2 single molecule magnets: synthesis, structural and magnetic studies.

    PubMed

    Costes, Jean-Pierre; Shova, Sergiu; Wernsdorfer, Wolfgang

    2008-04-14

    A trianionic ligand H3L (2-hydroxy-N-(2-[[(2-hydroxyphenyl)methylene]amino]-2-methylpropyl)benzamide) with an inner N2O2 coordination site and an oxygen atom coming from an amide function not involved in this site yields monoanionic LCu- complexes that react with Ln(hfa)3 x 2H2O (hfa = hexafluoroacetylacetonato ligand) to give dinuclear Cu-Ln complexes that self-assemble into tetranuclear species, as demonstrated by the structural determination of the [LCuDy(hfa)2(dmf)2]2 complex. High-spin species are then isolated for two ferromagnetic interactions are active in the [Cu-Gd]2 entities, through the double phenoxo bridge (J = 3.2 cm(-1)) and through the single amide bridge (j = 0.54 cm(-1)). These interactions are still present in the [Cu-Tb]2 and [Cu-Dy]2 complexes which behave as single molecule magnets (SMMs), due to the introduction of anisotropic Ln ions in place of Gd ions.

  5. Validation of the CQU-DTU-LN1 series of airfoils

    NASA Astrophysics Data System (ADS)

    Shen, W. Z.; Zhu, W. J.; Fischer, A.; Garcia, N. R.; Cheng, J. T.; Chen, J.; Madsen, J.

    2014-12-01

    The CQU-DTU-LN1 series of airfoils were designed with an objective of high lift and low noise emission. In the design process, the aerodynamic performance is obtained using XFOIL while noise emission is obtained with the BPM model. In this paper we present some validations of the designed CQU-DTU-LN118 airfoil by using wind tunnel measurements in the acoustic wind tunnel located at Virginia Tech and numerical computations with the inhouse Q3uic and EllipSys 2D/3D codes. To show the superiority of the new airfoils, comparisons with a NACA64618 airfoil are made. For the aerodynamic features, the designed Cl and Cl/Cd agrees well with the experiment and are in general higher than those of the NACA airfoil. For the acoustic features, the noise emission of the LN118 airfoil is compared with the acoustic measurements and that of the NACA airfoil. Comparisons show that the BPM model can predict correctly the noise changes.

  6. Highly stable and sensitive LnMOF ratiometric thermometers constructed with mixed ligands.

    PubMed

    Wei, Yongqin; Sa, Rongjian; Li, Qiaohong; Wu, Kechen

    2015-02-21

    The mixed-lanthanide metal-organic frameworks (M'LnMOFs) applied for accurate, non-invasive and self-reference temperature measurements have been only recently recognized. It is a great challenge for chemists to fulfil the requirements of a thermostable structure, intense luminescence and high temperature sensitivity on one LnMOF ratiometric thermometer for thermometric applications. By choosing 2,4-(2,2':6',2''-terpyridin-4'-yl)-benzenedisulfonic acid (H2DSTP) as the first ligand and changing the ancillary ligand to oxalic acid (OA) or 1,4-benzene dicarboxylic acid (BDC), we have successfully developed two types of highly stable and sensitive thermometers [Tb1-xEux(OA)0.5(DSTP)]·3H2O and [Tb1-xEux(BDC)0.5(DSTP)]·2H2O (x = 0.01, 0.02) that in addition exhibit brilliant luminescence over a wide temperature range, providing a new strategy to explore luminescence-based M'LnMOF thermometers.

  7. Encapsulation of Ln(III) ions/Ag nanoparticles within Cd(ii) boron imidazolate frameworks for tuning luminescence emission.

    PubMed

    Liu, Min; Chen, Shumei; Wen, Tian; Zhang, Jian

    2016-06-30

    Two Cd(ii) boron imidazolate frameworks (/) with different topologies have been synthesized by the targeted assembly of aromatic carboxylate, tetradentate imidazolate ligands, possessing tunable luminescence emission properties. Hydroxy-functional neutral shows an obvious blue shift of luminescence after loading Ag nanoparticles (NPs) while the first reported anionic in the BIF system with blue emission can tune the white-light emission via doping mixed Ln(3+) in an appropriate ratio (Ln = Eu and Tb). PMID:27321108

  8. Rare single-molecule magnets with six-coordinate Ln(III) ions exhibiting a trigonal antiprism configuration.

    PubMed

    Yao, Min-Xia; Zhu, Zhao-Xia; Lu, Xing-Yun; Deng, Xiao-Wei; Jing, Su

    2016-06-28

    Four Ni-Ln-Ni heterometallic complexes, [Ni2LnL2]NO3·3H2O (H3L = tri(((3-methoxysalicylidene)amino)ethyl)amine, Ln = Gd for , Tb for and Dy for , respectively) and [Ni2DyL2]ClO4·MTBE·0.65H2O (, MTBE = methyl tert-butyl ether) have been synthesized by diffusion of methyl tert-butyl ether vapor into the reaction solution. The X-ray analyses demonstrated that the Gd(III) ion in exhibits rare seven-coordination, the Tb(III) and Dy(III) ions in display unusual six-coordination, and two Ni(II) ions and one Ln(III) ion are bridged by six phenolato atoms to form linear Ni-Ln-Ni heterotrinuclear complexes for . All complexes exhibit weak ferromagnetic interactions between Ni(II) and Ln(III) ions. Alternating current susceptibility measurements demonstrated that compounds and behave as single-molecule magnets with the effective energy barriers of 14.17 and 11.13 K under zero direct current field. They are rare single-molecule magnets containing six-coordinate Dy(III) ions.

  9. Pralmorelin: GHRP 2, GPA 748, growth hormone-releasing peptide 2, KP-102 D, KP-102 LN, KP-102D, KP-102LN.

    PubMed

    2004-01-01

    Pralmorelin [GPA 748, GHRP 2, growth hormone-releasing peptide 2, KP-102 D, KP 102 LN] is an orally active, synthetic growth hormone-releasing peptide from a series of compounds that were developed by Polygen in Germany and Tulane University in the US. Researchers at Tulane University led by Dr Cyril Bowers synthesised a series of small highly active peptides ranging in size from 3-5 amino acids or partial peptides that were suitable for a variety of administration formats (subcutaneous, buccal, oral, depot). These peptides mimic the actions of ghrelin, a 28 amino acid octanoyl peptide that regulates the release of growth hormone (GH), and may play an important role in bone and muscle growth, food intake and possibly improve recovery from injury. The use of pralmorelin as a diagnostic agent for GH deficiency is based on its ability to markedly increase plasma levels of GH in healthy subjects irrespectively of gender, obesity or age. However, in patients with GH deficiency, the effect of pralmorelin on GH levels is significantly lower compared with healthy controls. Analysis of the receiver-operating characteristics curve provided the cut-off threshold value for the GH peak of 15.0 micro g/L for the identification of patients with GH deficiency from those of healthy controls. Kaken acquired worldwide manufacturing and marketing rights to pralmorelin, and then sublicensed it to Wyeth (formerly American Home Products) for the US and Canada. Kaken retains rights to pralmorelin in Japan. On 11 March 2002 American Home Products changed its name and the names of its subsidiaries Wyeth-Ayerst and Wyeth Lederle to Wyeth. Kaken also granted exclusive sublicense options in Africa, Australia, Europe, Latin America and New Zealand to unspecified partners. Pralmorelin as KP-102 D [KP-102D] is currently awaiting approval in Japan as a diagnostic agent for hypothalamo-pituitary function. It is planned to be launched in Japan for this indication in 2004. Pralmorelin is also

  10. Theoretical study of mixed LiLnX4 (Ln = La, Dy; X = F, Cl, Br, I) rare earth/alkali halide complexes.

    PubMed

    Groen, C P; Oskam, A; Kovács, A

    2000-12-25

    The structure, bonding and vibrational properties of the mixed LiLnX4 (Ln = La, Dy; X = F, Cl, Br, I) rare earth/alkali halide complexes were studied using various quantum chemical methods (HF, MP2 and the Becke3-Lee-Yang-Parr exchange-correlation density functional) in conjunction with polarized triple-zeta valence basis sets and quasi-relativistic effective core potentials for the heavy atoms. Our comparative study indicated the superiority of MP2 theory while the HF and B3-LYP methods as well as less sophisticated basis sets failed for the correct energetic relations. In particular, f polarization functions on Li and X proved to be important for the Li...X interaction in the complexes. From the three characteristic structures of such complexes, possessing 1-(C3v), 2-(C2v), or 3-fold coordination (C3v) between the alkali metal and the bridging halide atoms, the bi- and tridentate forms are located considerably lower on the potential energy surface then the monodentate isomer. Therefore only the bi- and tridentate isomers have chemical relevance. The monodentate isomer is only a high-lying local minimum in the case of X = F. For X = Cl, Br, and I this structure is found to be a second-order saddle point. The bidentate structure was found to be the global minimum for the systems with X = F, Cl, and Br. However, the relative stability with respect to the tridentate structure is very small (1-5 kJ/mol) for the heavier halide derivatives and the relative order is reversed in the case of the iodides. The energy difference between the three structures and the dissociation energy decrease in the row F to I. The ionic bonding in the complexes was characterized by natural charges and a topological analysis of the electron density distribution according to Bader's theorem. Variation of the geometrical and bonding characteristics between the lanthanum and dysprosium complexes reflects the effect of "lanthanide contraction". The calculated vibrational data indicate that

  11. S-shaped decanuclear heterometallic [Ni8Ln2] complexes [Ln(III) = Gd, Tb, Dy and Ho]: theoretical modeling of the magnetic properties of the gadolinium analogue.

    PubMed

    Hossain, Sakiat; Das, Sourav; Chakraborty, Amit; Lloret, Francesc; Cano, Joan; Pardo, Emilio; Chandrasekhar, Vadapalli

    2014-07-14

    The reaction of 8-quinolinol-2-carboaldoxime (LH2) with Ni(II) and Ln(III) salts afforded the heterometallic decanuclear compounds [Ni8Dy2(μ3-OH)2(L)8(LH)2(H2O)6](ClO4)2·16H2O (1), [Ni8Gd2(μ3-OH)2(L)8(LH)2(H2O)4(MeOH)2](NO3)2·12H2O (2), [Ni8Ho2(μ3-OH)2(L)8(LH)2(H2O)4(MeOH)2](ClO4)2·2MeOH·12H2O (3) and [Ni8Tb2 (μ3-OH)2(L)8(LH)2(MeOH)4(OMe)2]·2CH2Cl2·8H2O (4). While compounds 1-3 are dicationic, compound 4 is neutral. These compounds possess an S-shaped architecture and comprise a long chain of metal ions bound to each other. In all the complexes, the eight Ni(II) and two Ln(III) ions of the multimetallic ensemble are hold together by two μ3-OH, eight dianionic (L(2-)) and two monoanionic oxime ligands (LH(-)) whereas compound 4 has two μ3-OH, eight dianionic (L(2-)), two monoanionic oxime ligands (LH(-)) and two terminal methoxy (MeO(-)) ligands. The central portion of the S-shaped molecular wire is made up of an octanuclear Ni(II) ensemble which has at its two ends the Ln(III) caps. Magnetic studies on 1-4 reveal that the magnetic interactions between neighboring metal ions are negligible at room temperature. On the other hand, at lower temperatures in all the compounds anti-ferromagnetic interactions seem to be dominated. Analysis of the magnetic data for the Gd(III) derivative indicates Ni(II)-Ni(II) anti-ferromagnetic interactions and Gd(III)-Ni(II) ferromagnetic interactions at low temperatures. A theoretical density functional study on the magnetic behavior of the Gd(III) derivative suggests that while the weak ferromagnetic interaction between Gd(III) and Ni(II) is in line with the expectation of the magnetic interactions between orthogonal d and f orbitals, antiferromagnetic Ni(II)-Ni(II) interactions are related to the wide Ni-O-Ni angles (∼102°) and quasi-planar conformation of the Ni2O2 core. PMID:24876072

  12. Enneanuclear [Ni6Ln3] Cages: [Ln(III)3] Triangles Capping [Ni(II)6] Trigonal Prisms Including a [Ni6Dy3] Single-Molecule Magnet.

    PubMed

    Canaj, Angelos B; Tzimopoulos, Demetrios I; Siczek, Milosz; Lis, Tadeusz; Inglis, Ross; Milios, Constantinos J

    2015-07-20

    The use of (2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) ligand, H3L, in Ni/Ln chemistry has led to the isolation of three new isostructural [Ni(II)6Ln(III)3] metallic cages. More specifically, the reaction of Ni(ClO4)2·6H2O, the corresponding lanthanide nitrate salt, and H3L in MeCN, under solvothermal conditions in the presence of NEt3, led to the isolation of three complexes with the formulas [Ni6Gd3(OH)6(HL)6(NO3)3]·5.75MeCN·2Et2O·1.5H2O (1·5.75MeCN·2Et2O·1.5H2O), [Ni6Dy3(OH)6(HL)6(NO3)3]·2MeCN·2.7Et2O·2.4H2O (2·2MeCN·2.7Et2O·2.4H2O), and [Ni6Er3(OH)6(HL)6(NO3)3]·5.75MeCN·2Et2O·1.5H2O (3·5.75MeCN·2Et2O·1.5H2O). The structure of all three clusters describes a [Ln(III)3] triangle capping a [Ni(II)6] trigonal prism. Direct current magnetic susceptibility studies in the 5-300 K range for complexes 1-3 reveal the different nature of the magnetic interactions within the clusters: dominant antiferromagnetic exchange interactions for the Dy(III) and Er(III) analogues and dominant ferromagnetic interactions for the Gd(III) example. Alternating current magnetic susceptibility measurements under zero external dc field displayed fully formed temperature- and frequency-dependent out-of-phase peaks for the [Ni(II)6Dy(III)3] analogue, establishing its single molecule magnetism behavior with Ueff = 24 K.

  13. First-principles studies on linear and nonlinear optical effects in Ln{sub 4}GaSbS{sub 9} (Ln=Ce-Nd, Sm, Gd-Tm, Lu)

    SciTech Connect

    Zhou, Liu-Jiang; Chen, Ling; Li, Jun-Qian; Wu, Li-Ming

    2012-11-15

    Density functional theory (DFT) calculations have been performed on electronic structures of 11 middle-infrared (mid-IR) nonlinear optical quaternary sulfides: Ln{sub 4}GaSbS{sub 9} (Ln=Ce-Nd, Sm, Gd-Tm, Lu). Our results show that Ln{sub 4}GaSbS{sub 9} are indirect gap semiconductors with a slight band gap increase from Ce to Lu. Their linear optical properties, including refractive index, absorption coefficient and energy loss function, as well as the nonlinear optical coefficients including static d{sub 31}, d{sub 32}, d{sub 33} and dynamic d{sub 32}, are calculated. More importantly, the strong SHG response of Ln{sub 4}GaSbS{sub 9} can be attributed to the electronic transitions from S 3p states in valence bands (VB) to Sb-S and Ln-S antibonding states (CB). - Graphical Abstract: Density functional theory (DFT) calculations on Ln{sub 4}GaSbS{sub 9} reveal their linear optical properties, including refractive index, adsorption coefficient and energy loss function, the nonlinear optical coefficients including static d{sub 31}, d{sub 32}, d{sub 33} and dynamic d{sub 32}, as well as the origins of the strong SHG response. Highlights: Black-Right-Pointing-Pointer First-principles studies on a newly discovered NLO active family Ln{sub 4}GaSbS{sub 9}. Black-Right-Pointing-Pointer Reports static SHG coefficients (d{sub 31}, d{sub 32}, d{sub 33}) and dynamic d{sub 32}. Black-Right-Pointing-Pointer Reveals the origin of the strong SHG response.

  14. A Green Route to Hexagonal and Monoclinic BiPO4:Ln3+ (Ln = Sm, Eu, Tb, Dy) Nanocrystallites for Tailoring Luminescent Performance.

    PubMed

    Yang, Errui; Li, Guangshe; Zheng, Yunlong; Li, Liping

    2016-04-01

    Selective synthesis of specific phased nanomaterials via a green route is a promising yet challeng- ing task. In the present work, the hexagonal and monoclinic phases of BiPO4:Ln3+ (Ln = Sm, Eu, Tb, Dy) were prepared via room temperature co-precipitation method. For adjusting the phase of the products, the prepared mediums selected were the most common solvents, i.e., water and ethanol. It was very important that the prepared mediums could be easily recycled and reused by evapo- rating the filtrate. The formation mechanisms of hexagonal in water and monoclinic in ethanol were investigated. Interestingly, the growth behaviors of these phases were quite distinct and thus gave rise to distinct morphology and particle size. The hexagonal phase possesses a rod-like morphol- ogy with diameters of 50-160 nm and lengths of 65-400 nm while the monoclinic phase consists of almost entirely irregular nanoparticles. Also, it was found that the bending and stretching vibrations of O-H and PO4 tetrahedra were quite different for the products prepared in water and ethanol. Moreover, it was found that the luminescence properties, including emission intensity, lifetime, quan- tum efficiency, and color, could be readily tailored through controlling the phase structures and microstructures. The results showed that the monoclinic phase exhibited superior luminescent per- formance to the hexagonal phase. The methodologies reported in this work were fundamentally important, which could be easily extended to large-scale synthesis of other phased nanomaterials for potential applications as electroluminescent devices, optical integrated circuits, or biomarkers. PMID:27451664

  15. Pentanuclear heterometallic {Ni2Ln3} (Ln = Gd, Dy, Tb, Ho) assemblies. Single-molecule magnet behavior and multistep relaxation in the dysprosium derivative.

    PubMed

    Chandrasekhar, Vadapalli; Bag, Prasenjit; Kroener, Wolfgang; Gieb, Klaus; Müller, Paul

    2013-11-18

    The reaction between Ln(III) chloride and NiCl2·4H2O salts in presence of a multidentate sterically unencumbered ligand, (E)-2,2'-(2-hydroxy-3-((2-hydroxyphenylimino)methyl)-5-methylbenzylazanediyl)diethanol (LH4) leads to the synthesis of four isostructural pentanuclear hetereometallic complexes [Ni2Dy3(LH)4]Cl (1), [Ni2Gd3(LH)4]Cl (2), [Ni2Tb3(LH)3(LH2)]Cl2 (3), [Ni2 Ho3 (LH)3 (LH2)]Cl2 (4) with unprecedented topology. Here the two compounds 1 are 2 are monocationic and crystallize in chiral space group, P2(1)2(1)2(1) whereas compounds 3 and 4 are dicationic and crystallize in achiral space group P2(1)/n. The total metal framework, {Ni2Ln3} unit is held by four triply deprotonated ligands [LH](3-) in 1 and 2 whereas in case of 3 and 4 three triply deprotonated [LH](3-) and one doubly deprotonated [LH2](2-) ligands are involved. In these complexes both the lanthanide ions and the nickel(II) ions are doubly bridged and the bridging is composed of oxygen atoms derived from either phenolate or ethoxide groups. The analysis of SQUID measurements reveal a high magnetic ground state and a slow relaxation of the magnetization with two relaxation regimes for 1. For the thermally activated regime we found an effective energy barrier of U(eff) = 85 K. Micro Hall probe loop measurements directly proof the single-molecule magnet (SMM) nature of 1 with a blocking temperature of T(B) = 3 K and an open hysteresis for sweep rates faster than 50 mT/s. PMID:24236759

  16. Oxygen non-stoichiometry of Ln4Ni 2.7Fe 0.3O 10-δ ( Ln=La, Pr)

    NASA Astrophysics Data System (ADS)

    Tsipis, E. V.; Patrakeev, M. V.; Waerenborgh, J. C.; Pivak, Y. V.; Markov, A. A.; Gaczyński, P.; Naumovich, E. N.; Kharton, V. V.

    2007-06-01

    The oxygen deficiency of iron-substituted nickelates Ln4Ni 2.7Fe 0.3O 10-δ ( Ln=La, Pr) with the orthorhombic Ruddlesden-Popper structure was studied by thermogravimetric analysis and coulometric titration in the oxygen partial pressure range 6×10 -5 to 0.7 atm at 973-1223 K. In air, the non-stoichiometry values vary in the relatively narrow ranges (2.4-4.2)×10 -2 for La- and (0.01-2.0)×10 -2 for Pr-containing compositions, increasing with temperature. Due to the smaller size of praseodymium cations, Pr 4Ni 2.7Fe 0.3O 10-δ exhibits a substantially lower thermodynamic stability in comparison with La 4Ni 2.7Fe 0.3O 10-δ and La 4Ni 3O 10-δ, although the oxygen content in Pr 4Ni 2.7Fe 0.3O 10-δ lattice is higher. The partial substitution of iron for nickel has no essential effect on the low- p(O 2) stability limit corresponding to the transition of Pr 4Ni 3O 10-δ into K 2NiF 4-type Pr 2NiO 4+δ. On the contrary, doping of La 4Ni 3O 10-δ with iron decreases the oxygen vacancy concentration and shifts the phase stability boundary towards lower oxygen chemical potentials, suggesting a stabilization of the transition metal-oxygen octahedra in lanthanum nickelate lattice. The Mössbauer spectroscopy showed that the predominant state of iron cations, statistically distributed between the nickel sites, is trivalent.

  17. Host-sensitized luminescence properties in CaNb2O6:Ln(3+) (Ln(3+) = Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+)) phosphors with abundant colors.

    PubMed

    Li, Kai; Liu, Xiaoming; Zhang, Yang; Li, Xuejiao; Lian, Hongzhou; Lin, Jun

    2015-01-01

    A series of Ln(3+) (Ln(3+) = Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+)) ion doped CaNb2O6 (CNO) phosphors have been prepared via the conventional high-temperature solid-state reaction route. The X-ray diffraction (XRD) and structure refinement, diffuse reflection, photoluminescence (PL), and fluorescent decay curves were used to characterize the as-prepared samples. Under UV radiation, the CNO host present a broad emission band from about 355 to 605 nm centered around 460 nm originating from the NbO6 octahedral groups, which has spectral overlaps with the excitation of f-f transitions of Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) in CNO:Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) samples. They show both host emission and respective emission lines derived from the characteristic f-f transitions of activators, which present different emission colors owing to the energy transfer from the NbO6 group in the host to Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) with increasing activator concentrations. The decreases of decay lifetimes of host emissions in CNO:Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) demonstrate the energy transfer from the hosts to Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+). The energy transfer mechanisms in CNO:Eu(3+)/Tb(3+)/Dy(3+) phosphors have been determined to be a resonant type via dipole-dipole mechanisms. For CNO:Sm(3+), the metal-metal charge transfer transition (MMCT) might contribute to the different variations of decay lifetimes and emission intensity from CNO:Eu(3+)/Tb(3+)/Dy(3+) samples. The best quantum efficiency is 71.2% for CNO:0.01/0.02Dy(3+). The PL properties of as-prepared materials indicate the promising application in UV-pumped white-emitting lighting diodes field.

  18. Transition in Failure Mechanism Under Cyclic Creep in 316LN Austenitic Stainless Steel

    NASA Astrophysics Data System (ADS)

    Sarkar, Aritra; Nagesha, A.; Parameswaran, P.; Sandhya, R.; Mathew, M. D.

    2014-06-01

    Cyclic creep behavior of a type 316LN austenitic stainless steel was investigated in the temperature range from 823 K to 923 K (550 °C to 650 °C). A transition from fatigue-dominated to creep-dominated failure mode was observed with an increase in the mean stress. The threshold value of mean stress for the transition was seen to be a strong function of the test temperature. Occurrence of dynamic strain aging proved beneficial owing to a substantial reduction in the strain accumulation during cyclic loading.

  19. Crystal growth and characterization of tetragonal tungsten bronze FerroNiobates Ba 2LnFeNb 4O 15

    NASA Astrophysics Data System (ADS)

    Castel, E.; Veber, P.; Albino, M.; Velázquez, M.; Pechev, S.; Denux, D.; Chaminade, J. P.; Maglione, M.; Josse, M.

    2012-02-01

    Tetragonal Tungsten Bronze Ferroelectrics (TTB) are currently revisited for the elaboration of new multifunctional materials. Recent studies on Ba 2LnFeNb 4O 15 ceramics (Ln=Nd, Sm and Eu) demonstrated that these materials display both ferroelectric and ferromagnetic behaviors at room temperature due to the presence of barium hexaferrite as a secondary phase. In this paper, we report for the first time the growth of Ba 2LnFeNb 4O 15 single crystals (Ln=La, Pr, Nd, Sm and Eu) from high temperature solution using LiBO 2 flux. Inclusion free millimeter-sized single crystals were successfully grown. Structural and dielectric characterizations were performed and chemical analysis confirmed that the TTB matrix is reluctant to accommodate small rare earth as it was observed for ceramics. A paramagnetic behavior was observed for all compositions, which corroborates the composite nature of the TTB ceramic multiferroics at room temperature, while dielectric measurements on Ln=La and Pr crystals confirmed their relaxor behavior.

  20. A new family of [Cu(II)Ln(III)M(V)] heterotrimetallic complexes (Ln = La, Gd, Tb; M = Mo, W): model systems to probe exchange interactions and single-molecule magnet properties.

    PubMed

    Visinescu, Diana; Alexandru, Maria-Gabriela; Madalan, Augustin M; Jeon, Ie-Rang; Mathonière, Corine; Clérac, Rodolphe; Andruh, Marius

    2016-05-01

    Four isostructural trinuclear 3d-4f-4(5)d heterotrimetallic complexes, with the general formula [L(2)CuLn(H2O)5(μ-NC)M(CN)7], were obtained from the association of binuclear 3d-4f complexes and {M(V)(CN)8}(3-) metalloligands (M = Mo, Ln = La ; M = W, Ln = La ; M = Mo, Ln = Gd ; M = Mo; Ln = Tb , where H2L(2) = 1,2-ethanediylbis(2-iminomethylene-6-methoxy-phenol)). The metalloligand coordinates through a single-cyanido group at the apical position of the copper(ii) ion belonging to the {Cu(II)Ln(III)} binuclear complex. The analysis of the magnetic data for the La(iii) derivatives (compounds and ), in the 1.85-300 K temperature range, shows a weak ferromagnetic exchange interaction between Cu(II) and Mo(V)/W(V) ions across the cyanido bridge (JCuM/kB = 3.6(6) K; g = 2.23(5) for and JCuM/kB = 3.8(6) K, g = 2.21(5) for , with H = -2JCuMSCu·SM). These results were used to simulate the magnetic properties of compound , using the isotropic spin Hamiltonian H = -2JCuMoSCu·SMo - 2JCuGdSCu·SGd. The resulting magnetic interaction between Cu(II) and Gd(III) ions via the phenoxo-bridge was found to be weakly ferromagnetic (JCuGd/kB = +4.5(2) K with JCuMo/kB = +3.6(2) K, gGd = gCu = 2.00 and gMo = 1.98). The dc magnetic properties for compound also show a predominant ferromagnetic interaction, while the ac magnetic measurements indicate the presence of the slow relaxation of the magnetization below 3.5 K.

  1. A new family of [Cu(II)Ln(III)M(V)] heterotrimetallic complexes (Ln = La, Gd, Tb; M = Mo, W): model systems to probe exchange interactions and single-molecule magnet properties.

    PubMed

    Visinescu, Diana; Alexandru, Maria-Gabriela; Madalan, Augustin M; Jeon, Ie-Rang; Mathonière, Corine; Clérac, Rodolphe; Andruh, Marius

    2016-05-01

    Four isostructural trinuclear 3d-4f-4(5)d heterotrimetallic complexes, with the general formula [L(2)CuLn(H2O)5(μ-NC)M(CN)7], were obtained from the association of binuclear 3d-4f complexes and {M(V)(CN)8}(3-) metalloligands (M = Mo, Ln = La ; M = W, Ln = La ; M = Mo, Ln = Gd ; M = Mo; Ln = Tb , where H2L(2) = 1,2-ethanediylbis(2-iminomethylene-6-methoxy-phenol)). The metalloligand coordinates through a single-cyanido group at the apical position of the copper(ii) ion belonging to the {Cu(II)Ln(III)} binuclear complex. The analysis of the magnetic data for the La(iii) derivatives (compounds and ), in the 1.85-300 K temperature range, shows a weak ferromagnetic exchange interaction between Cu(II) and Mo(V)/W(V) ions across the cyanido bridge (JCuM/kB = 3.6(6) K; g = 2.23(5) for and JCuM/kB = 3.8(6) K, g = 2.21(5) for , with H = -2JCuMSCu·SM). These results were used to simulate the magnetic properties of compound , using the isotropic spin Hamiltonian H = -2JCuMoSCu·SMo - 2JCuGdSCu·SGd. The resulting magnetic interaction between Cu(II) and Gd(III) ions via the phenoxo-bridge was found to be weakly ferromagnetic (JCuGd/kB = +4.5(2) K with JCuMo/kB = +3.6(2) K, gGd = gCu = 2.00 and gMo = 1.98). The dc magnetic properties for compound also show a predominant ferromagnetic interaction, while the ac magnetic measurements indicate the presence of the slow relaxation of the magnetization below 3.5 K. PMID:27052800

  2. High-throughput and microwave investigation of rare earth phosphonatoethanesulfonates-Ln(O{sub 3}P-C{sub 2}H{sub 4}-SO{sub 3}) (Ln=Ho, Er, Tm, Yb, Lu, Y)

    SciTech Connect

    Sonnauer, Andreas

    2008-11-15

    Following the strategy of using bifunctional phosphonic acids for the synthesis of new metal phosphonates, the flexible ligand 2-phosphonoethanesulfonic acid, H{sub 2}O{sub 3}P-C{sub 2}H{sub 4}-SO{sub 3}H (H{sub 3}L), was used in a high-throughput (HT) and microwave investigation of rare earth phosphonatoethanesulfonates. The HT-investigation led to six isotypic compounds Ln(O{sub 3}P-C{sub 2}H{sub 4}-SO{sub 3}) with Ln=Ho (1), Er (2), Tm (3), Yb (4), Lu (5) and Y (6). The syntheses were scaled-up in glass reactor tubes in order to obtain larger amounts for a detailed characterization. Based on these results all compounds could be also synthesized by microwave-assisted heating and the influence of reaction time and stirring rate during the synthesis was established. For compound 2 the crystal structure was determined by single-crystal X-ray diffraction. The compounds contain isolated slightly distorted LnO{sub 6} octahedra that are connected by the phosphonate and sulfonate groups into a three-dimensional framework. Thermogravimetric investigations demonstrate the high thermal stability of the compounds up to 460 deg. C. - Graphical abstract: A high-throughput and microwave investigation of the System LnX{sub 3}/H{sub 2}O{sub 3}P-C{sub 2}H{sub 4}-SO{sub 3}/NaOH/H{sub 2}O led to six new compounds Ln(O{sub 3}P-C{sub 2}H{sub 4}-SO{sub 3}) with Ln=Ho, Er, Tm, Yb, Lu, Y.

  3. Low-Temperature Sintering and Microwave Dielectric Properties of Bi0.9Ln0.05Li0.05V0.9Mo0.1O4 (Ln = Sm, Nd and La) Ceramics

    NASA Astrophysics Data System (ADS)

    Wang, Zixing; Yuan, Changlai; Yang, Tao; Feng, Qin; Liu, Fei; Chen, Jinman; Zhou, Changrong; Chen, Guohua

    2016-08-01

    Microwave dielectric ceramics of Bi0.9Ln0.05Li0.05V0.9Mo0.1O4 (Ln = Sm, Nd and La) with a low firing temperature were prepared via conventional solid-state reaction. The phases and microstructures of the ceramics were characterized by x-ray diffraction and scanning electron microscopy. The temperature coefficients of resonant frequency in the three compositions increased as sintering temperature increased. It is worth noting that a phase transition of the Bi0.9Ln0.05Li0.05V0.9Mo0.1O4 (Ln = Sm, Nd and La) ceramics from a monoclinic to a tetragonal scheelite structure was found with an increase in sintering temperature. The densification temperatures of all compositions were below 700°C. Excellent microwave dielectric properties were obtained for the Bi0.9Nd0.05Li0.05V0.9Mo0.1O4 ceramic sintered at 650°C, with a dielectric constant of ~72.2, a quality factor of ~6467 GHz and a temperature coefficient of resonant frequency of ~2.6 ppm/°C. The Bi0.9Ln0.05Li0.05V0.9Mo0.1O4 (Ln = Sm, Nd and La) ceramics are chemically compatible with both Ag and Cu powders at their sintering temperatures, and are thus a promising candidate for use in LTCC technology applications.

  4. Synthesis and Characterization of a Series of Quaternary Chalcogenides Ba LnMQ3 ( Ln=Rare Earth, M=Coinage Metal, Q=Se or Te)

    NASA Astrophysics Data System (ADS)

    Yang, Yuting; Ibers, James A.

    1999-10-01

    The compounds BaGdAuSe3, BaLaCuTe3, BaYCuTe3, BaYAgTe3, BaLaAgTe3, BaYbCuTe3, BaGdAgTe3, BaNdCuTe3, and BaPrCuTe3 were prepared by the reaction in a BaBr2/KBr flux at 850°C of a rare earth, a coinage-group metal, a chalcogen, and BaSe or BaTe. The unit cells of all of the compounds and the crystal structures of the first four compounds were determined by single-crystal X-ray diffraction methods. With the exception of BaLaCuTe3, which crystallizes with four formula units in the orthorhombic space group Pnma, all of these compounds crystallize with four formula units in the orthorhombic space group Cmcm. BaLaCuTe3, isostructural with β-BaLaCuSe3 and Eu2CuS3 (i.e., Eu2+Eu3+Cu+(S2-)3), and BaGdAuSe3, BaYCuTe3, and BaYAgTe3, isostructural with KZrCuS3, crystallize in a layered structure in which there are 2∞[LnMQ2-3] layers separated by Ba2+ ions. Ln atoms are coordinated by six Q atoms at the corners of a distorted octahedron, and M atoms are coordinated by four Q atoms at the corners of a tetrahedron. The layers are formed by the connection of edge-sharing octahedral chains and corner-sharing tetrahedral chains. Ba atoms are coordinated by seven Q atoms in BaLaCuTe3 and by eight Q atoms in BaGdAuSe3, BaYCuTe3, and BaYAgTe3. BaNdAgTe3 shows temperature-dependent paramagnetism. Its magnetic susceptibility follows the Curie-Weiss law. The effective magnetic moment of 3.4(3) μB is in agreement with the theoretical value of 3.6 μB for Nd3+.

  5. Probing the magnetic and magnetothermal properties of M(II)-Ln(III) complexes (where M(II) = Ni or Zn; Ln(III) = La or Pr or Gd).

    PubMed

    Ahmed, Naushad; Das, Chinmoy; Vaidya, Shefali; Srivastava, Anant Kumar; Langley, Stuart K; Murray, Keith S; Shanmugam, Maheswaran

    2014-12-14

    We establish the coordination potential of the Schiff base ligand (2-methoxy-6-[(E)-2'-hydroxymethyl-phenyliminomethyl]-phenolate (H2L)) via the isolation of various M(II)-Ln(III) complexes (where M(II) = Ni or Zn and Ln(III) = La or Pr or Gd). Single crystals of these five complexes were isolated and their solid state structures were determined by single crystal X-ray diffraction. Structural determination revealed molecular formulae of [NiGd(HL)2(NO3)3] (1), [NiPr(HL)2(NO3)3] (2) and [Ni2La(HL)4(NO3)](NO3)2 (3), [Zn2Gd(HL)4(NO3)](NO3)2 (4), and [Zn2Pr(HL)4(NO3)](NO3)2 (5). Complexes and were found to be neutral heterometallic dinuclear compounds, whereas 3-5 were found to be linear heterometallic trinuclear cationic complexes. Direct current (dc) magnetic susceptibility and magnetization measurements conclusively revealed that complexes 1 and 4 possess a spin ground state of S = 9/2 and 7/2 respectively. Empirically calculated ΔχMT derived from the variable temperature susceptibility data for all complexes undoubtedly indicates that the Ni(II) ion is coupled ferromagnetically with the Gd(III) ion, and antiferromagnetically with the Pr(III) ion in 1 and 2 respectively. The extent of the exchange interaction for was estimated by fitting the magnetic susceptibility data using the parameters (g = 2.028, S = 9/2, J = 1.31 cm(-1) and zJ = +0.007), supporting the phenomenon observed in an empirical approach. Similarly using a HDVV Hamiltonian, the magnetic data of 3 and 4 were fitted, yielding parameters g = 2.177, D = 3.133 cm(-1), J = -0.978 cm(-1), (for 3) and g = 1.985, D = 0.508 cm(-1) (for 4). The maximum change in magnetic entropy (-ΔSm) estimated from the isothermal magnetization data for was found to be 5.7 J kg(-1) K(-1) (ΔB = 7 Tesla) at 7.0 K, which is larger than the -ΔSm value extracted from 4 of 3.5 J kg(-1) K(-1) (ΔB = 7 Tesla) at 15.8 K, revealing the importance of the exchange interaction in increasing the overall ground state of a molecule for

  6. Probing the magnetic and magnetothermal properties of M(II)-Ln(III) complexes (where M(II) = Ni or Zn; Ln(III) = La or Pr or Gd).

    PubMed

    Ahmed, Naushad; Das, Chinmoy; Vaidya, Shefali; Srivastava, Anant Kumar; Langley, Stuart K; Murray, Keith S; Shanmugam, Maheswaran

    2014-12-14

    We establish the coordination potential of the Schiff base ligand (2-methoxy-6-[(E)-2'-hydroxymethyl-phenyliminomethyl]-phenolate (H2L)) via the isolation of various M(II)-Ln(III) complexes (where M(II) = Ni or Zn and Ln(III) = La or Pr or Gd). Single crystals of these five complexes were isolated and their solid state structures were determined by single crystal X-ray diffraction. Structural determination revealed molecular formulae of [NiGd(HL)2(NO3)3] (1), [NiPr(HL)2(NO3)3] (2) and [Ni2La(HL)4(NO3)](NO3)2 (3), [Zn2Gd(HL)4(NO3)](NO3)2 (4), and [Zn2Pr(HL)4(NO3)](NO3)2 (5). Complexes and were found to be neutral heterometallic dinuclear compounds, whereas 3-5 were found to be linear heterometallic trinuclear cationic complexes. Direct current (dc) magnetic susceptibility and magnetization measurements conclusively revealed that complexes 1 and 4 possess a spin ground state of S = 9/2 and 7/2 respectively. Empirically calculated ΔχMT derived from the variable temperature susceptibility data for all complexes undoubtedly indicates that the Ni(II) ion is coupled ferromagnetically with the Gd(III) ion, and antiferromagnetically with the Pr(III) ion in 1 and 2 respectively. The extent of the exchange interaction for was estimated by fitting the magnetic susceptibility data using the parameters (g = 2.028, S = 9/2, J = 1.31 cm(-1) and zJ = +0.007), supporting the phenomenon observed in an empirical approach. Similarly using a HDVV Hamiltonian, the magnetic data of 3 and 4 were fitted, yielding parameters g = 2.177, D = 3.133 cm(-1), J = -0.978 cm(-1), (for 3) and g = 1.985, D = 0.508 cm(-1) (for 4). The maximum change in magnetic entropy (-ΔSm) estimated from the isothermal magnetization data for was found to be 5.7 J kg(-1) K(-1) (ΔB = 7 Tesla) at 7.0 K, which is larger than the -ΔSm value extracted from 4 of 3.5 J kg(-1) K(-1) (ΔB = 7 Tesla) at 15.8 K, revealing the importance of the exchange interaction in increasing the overall ground state of a molecule for

  7. Eutectoid flux growth of single crystal Ln117Ni 54-ySn112-z

    NASA Astrophysics Data System (ADS)

    Reyes, Luis Emanuel

    Single crystals of Ln117Ni57- ySn112-z (Ln = Gd--Dy) have been grown via the eutectoid flux growth method and characterized using single crystal X-ray diffraction. The series of compounds crystallizes in the Dy117Co57Sn112--type structure, which adopts a face-centered cubic unit cell with the space group Fm3m. The Gd117Ni 53.3(3)Sn107.1(1) lattice parameter is 30.070(4) A, cell dimensions decreases as a function of lanthanides to 29.862(5) and 29.823(4) A for Tb117Ni51.2(2)Sn103.6(1) and Dy 117Ni52.3(2)Sn112, respectively. To the best of our knowledge these are the first nickel containing compounds to be synthesized in the Dy117Co57Sn112--type structure. Structural disorder surrounding the 4b (1/2, 1/2, 1/2) position is found to vary within the synthesized series and is linked to the presence of an additional atomic position Ni9' (48i (1/2, x, x) x = 0.4268(4)) not seen in previous analogues. Magnetic susceptibility data are examined and shown to follow the Curie-Weiss law for each analogue and suggest the presences of ferromagnetic interactions in each compound.

  8. Damage structure of austenitic stainless steel 316LN irradiated at low temperature in HFIR

    SciTech Connect

    Hashimoto, N.; Robertson, J.P.; Grossbeck, M.L.; Rowcliffe, A.F.; Wakai, E.

    1998-03-01

    TEM disk specimens of austenitic stainless steel 316LN irradiated to damage levels of about 3 dpa at irradiation temperatures of either about 90 C or 250 C have been investigated by using transmission electron microscopy. The irradiation at 90 C and 250 C induced a dislocation loop density of 3.5 {times} 10{sup 22} m{sup {minus}3} and 6.5 {times} 10{sup 22} m{sup {minus}3}, a black dot density of 2.2 {times} 10{sup 23} m{sup {minus}3} and 1.6 {times} 10{sup 23} m{sup {minus}3}, respectively, in the steels, and a high density (<1 {times} 10{sup 22} m{sup {minus}3}) of precipitates in matrix. Cavities could be observed in the specimens after the irradiation. It is suggested that the dislocation loops, the black dots, and the precipitates cause irradiation hardening, an increase in the yield strength and a decrease in the uniform elongation, in the 316LN steel irradiated at low temperature.

  9. Kramers non-magnetic superconductivity in LnNiAsO superconductors.

    PubMed

    Li, Yuke; Luo, Yongkang; Li, Lin; Chen, Bin; Xu, Xiaofeng; Dai, Jianhui; Yang, Xiaojun; Zhang, Li; Cao, Guanghan; Xu, Zhu-an

    2014-10-22

    We investigated a series of nickel-based oxyarsenides LnNiAsO (Ln=La, Ce, Pr, Nd, Sm) compounds. CeNiAsO undergoes two successive anti-ferromagnetic transitions at TN1=9.3 K and TN2=7.3 K; SmNiAsO becomes an anti-ferromagnet below TN≃3.5 K; NdNiAsO keeps paramagnetic down to 2 K but orders anti-ferromagnetically below TN≃1.3 K. Superconductivity was observed only in Kramers non-magnetic LaNiAsO and PrNiAsO with Tc=2.7 K and 0.93 K, respectively. The superconductivity of PrNiAsO is further studied by upper critical field and specific heat measurements, which reveal that PrNiAsO is a weakly coupled Kramers non-magnetic superconductor. Our work confirms that the nickel-based oxyarsenide superconductors are substantially different in mechanism to iron-based ones, and are likely to be described by the conventional superconductivity theory. PMID:25248377

  10. On the constitutive model of nitrogen-containing austenitic stainless steel 316LN at elevated temperature.

    PubMed

    Zhang, Lei; Feng, Xiao; Wang, Xin; Liu, Changyong

    2014-01-01

    The nitrogen-containing austenitic stainless steel 316LN has been chosen as the material for nuclear main-pipe, which is one of the key parts in 3rd generation nuclear power plants. In this research, a constitutive model of nitrogen-containing austenitic stainless steel is developed. The true stress-true strain curves obtained from isothermal hot compression tests over a wide range of temperatures (900-1250°C) and strain rates (10(-3)-10 s(-1)), were employed to study the dynamic deformational behavior of and recrystallization in 316LN steels. The constitutive model is developed through multiple linear regressions performed on the experimental data and based on an Arrhenius-type equation and Zener-Hollomon theory. The influence of strain was incorporated in the developed constitutive equation by considering the effect of strain on the various material constants. The reliability and accuracy of the model is verified through the comparison of predicted flow stress curves and experimental curves. Possible reasons for deviation are also discussed based on the characteristics of modeling process.

  11. On the Constitutive Model of Nitrogen-Containing Austenitic Stainless Steel 316LN at Elevated Temperature

    PubMed Central

    Zhang, Lei; Feng, Xiao; Wang, Xin; Liu, Changyong

    2014-01-01

    The nitrogen-containing austenitic stainless steel 316LN has been chosen as the material for nuclear main-pipe, which is one of the key parts in 3rd generation nuclear power plants. In this research, a constitutive model of nitrogen-containing austenitic stainless steel is developed. The true stress-true strain curves obtained from isothermal hot compression tests over a wide range of temperatures (900–1250°C) and strain rates (10−3–10 s−1), were employed to study the dynamic deformational behavior of and recrystallization in 316LN steels. The constitutive model is developed through multiple linear regressions performed on the experimental data and based on an Arrhenius-type equation and Zener-Hollomon theory. The influence of strain was incorporated in the developed constitutive equation by considering the effect of strain on the various material constants. The reliability and accuracy of the model is verified through the comparison of predicted flow stress curves and experimental curves. Possible reasons for deviation are also discussed based on the characteristics of modeling process. PMID:25375345

  12. Intracluster interactions in butterfly {Fe3LnO2} molecules with the non-Kramers ions Tb(III) and Ho(III)

    NASA Astrophysics Data System (ADS)

    Badía-Romano, L.; Rubín, J.; Bartolomé, F.; Bartolomé, J.; Luzón, J.; Prodius, D.; Turta, C.; Mereacre, V.; Wilhelm, F.; Rogalev, A.

    2015-08-01

    The intracluster exchange interactions within the "butterfly" [Fe3Ln (μ3-O )2(CCl3COO )8(H2O )(THF )3] molecules, where Ln(III) represents a lanthanide cation, have been determined by a combination of x-ray magnetic circular dichroism (XMCD) and vibrating sample magnetometry (VSM) along with an interaction model. We have studied the compounds with Ln =Tb and Ho, both non-Kramers lanthanides and with high uniaxial anisotropy, and Ln =Lu (III) and Y(III) as pseudolanthanides, which supply nonmagnetic Ln reference cases. At low temperature, the three Fe atoms can be considered as a self-unit with total spin SFe 3=5 /2 . Using the element selectivity of the XMCD magnetometry, measured at the Ln L2 ,3 edges, together with the VSM measurements, the local magnetization of the Ln ion and the Fe3 subcluster, as a function of the field and low temperature (T ≈2.5 K ), has been determined separately. These results are described quantitatively in the framework of a theoretical model based on an effective spin Hamiltonian, which considers the competing effects of intracluster interactions and the external applied magnetic field. The Ln -Fe3 exchange interaction within the {Fe3LnO2} cluster has been determined to be antiferromagnetic, in both Tb and Ho compounds, with JFeTb/kB=-0.13 (1 ) K and JFeHo/kB=-0.18 (1 ) K , respectively. In both cases, a field-induced reorientation of the Fe3 and Ln spins from antiparallel to parallel orientation takes place at a threshold field μ0H =1.1 and 2 T, for the {Fe3TbO2} and {Fe3HoO2} compounds, respectively. By comparison with other compounds of the series with uniaxial anisotropy, it is concluded that the polarizability of the Fe3 subcluster magnetic moment decreases in the trend {Fe3YO2}→{Fe3TbO2}→{Fe3HoO2}→{Fe3DyO2} , because of the increasing opposition of the exchange antiferromagnetic field caused by the Ln ion. In the Ln =Tb , Ho, and Dy, the magnetization of the whole molecule is dominated by the anisotropy of the Ln ion

  13. Three-dimensional open-frameworks based on Ln(III) ions and open-/closed-shell PTM ligands: synthesis, structure, luminescence, and magnetic properties.

    PubMed

    Datcu, Angela; Roques, Nans; Jubera, Véronique; Imaz, Inhar; Maspoch, Daniel; Sutter, Jean-Pascal; Rovira, Concepció; Veciana, Jaume

    2011-03-21

    A series of isostructural open-framework coordination polymers formulated as [Ln(dmf)(3)(ptmtc)] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5); PTMTC = polychlorotriphenylmethyl tricarboxylate) and [Ln(dmf)(2)H(2)O(αH-ptmtc)] (Ln = Sm (1'), Eu (2'), Gd (3'), Tb (4'), Dy (5')) have been obtained by treating Ln(III) ions with PTMTC ligands with a radical (PTMTC(3-)) or a closed-shell character (αH-PTMTC(3-)). X-ray diffraction analyses reveal that these coordination polymers possess 3D architectures that combine large channels and fairly rare lattice complex T connectivity. In addition, these compounds show selective framework dynamic sorption properties. For both classes of ligands, the ability to act as an antenna in Ln sensitization processes has been investigated. No luminescence was observed for compounds 1-5, and 3' because of the PTMTC(3-) ligand and/or Gd(III) ion characteristics. Conversely, photoluminescence measurements show that 1', 2', 4', and 5' emit dark orange, red, green, and dark cyan metal-centered luminescence. The magnetic properties of all of these compounds have been investigated. The nature of the {Ln-radical} exchange interaction in these compounds has been assessed by comparing the behavior of the radical-based coordination polymers 1-5 with those of the compounds with the diamagnetic ligand set. While antiferromagnetic {Sm-radical} interactions are found in 1, ferromagnetic {Ln-radical} interactions propagate in the 3D architectures of 3, 4, and 5 (Ln = Gd, Tb, and Dy, respectively). This procedure also provided access to information on the {Ln-Ln} exchange existing in these magnetic systems.

  14. Glass Ceramic Waste Forms for Combined CS+LN+TM Fission Products Waste Streams

    SciTech Connect

    Crum, Jarrod V.; Turo, Laura A.; Riley, Brian J.; Tang, Ming; Kossoy, Anna; Sickafus, Kurt E.

    2010-09-23

    In this study, glass ceramics were explored as an alternative waste form for glass, the current baseline, to be used for immobilizing alkaline/alkaline earth + lanthanide (CS+LN) or CS+LN+transition metal (TM) fission-product waste streams generated by a uranium extraction (UREX+) aqueous separations type process. Results from past work on a glass waste form for the combined CS+LN waste streams showed that as waste loading increased, large fractions of crystalline phases precipitated upon slow cooling.[1] The crystalline phases had no noticeable impact on the waste form performance by the 7-day product consistency test (PCT). These results point towards the development of a glass ceramic waste form for treating CS+LN or CS+LN+TM combined waste streams. Three main benefits for exploring glass ceramics are: (1) Glass ceramics offer increased solubility of troublesome components in crystalline phases as compared to glass, leading to increased waste loading; (2) The crystalline network formed in the glass ceramic results in higher heat tolerance than glass; and (3) These glass ceramics are designed to be processed by the same melter technology as the current baseline glass waste form. It will only require adding controlled canister cooling for crystallization into a glass ceramic waste form. Highly annealed waste form (essentially crack free) with up to 50X lower surface area than a typical High-Level Waste (HLW) glass canister. Lower surface area translates directly into increased durability. This was the first full year of exploring glass ceramics for the Option 1 and 2 combined waste stream options. This work has shown that dramatic increases in waste loading are achievable by designing a glass ceramic waste form as an alternative to glass. Table S1 shows the upper limits for heat, waste loading (based on solubility), and the decay time needed before treatment can occur for glass and glass ceramic waste forms. The improvements are significant for both combined waste

  15. Influence of structural distortions upon photoluminescence properties of Eu{sup 3+} and Tb{sup 3+} activated Na{sub 3}Ln(BO{sub 3}){sub 2} (Ln=Y, Gd) borates

    SciTech Connect

    Asiri Naidu, S.; Boudin, S.; Varadaraju, U.V.; Raveau, B.

    2012-06-15

    The comparative study of the structure and photoluminescence (PL) properties of the Eu{sup 3+} and Tb{sup 3+} activated Na{sub 3}Ln(BO{sub 3}){sub 2}, with Ln=Y, Gd, showed the important role of the host lattice structure upon PL. Higher emission intensities of Eu{sup 3+} and Tb{sup 3+} are observed for Na{sub 3}Gd(BO{sub 3}){sub 2} than for Na{sub 3}Y(BO{sub 3}){sub 2}, through direct Eu{sup 3+} excitation at 395 nm for Eu{sup 3+} doped borates, and through Gd{sup 3+} excitation around 280 nm for Tb{sup 3+} doped borates. This higher performance for Na{sub 3}Gd(BO{sub 3}){sub 2} is due to the less regular environment of Eu{sup 3+} (Tb{sup 3+}) in the Gd sites than in the Y sites and to energy transfer from Gd{sup 3+} to Eu{sup 3+}(Tb{sup 3+}). The smaller critical concentration in Na{sub 3}Ln{sub 1-x}Tb{sub x}(BO{sub 3}){sub 2} observed for Ln=Gd, x=0.5, compared to x=0.6 for Ln=Y, is explained by shorter Ln-Ln distances (4.11 A for Gd-Gd vs. 4.59 A for Y-Y). Both Na{sub 3}Y{sub 0.4}Tb{sub 0.6}(BO{sub 3}){sub 2} and Na{sub 3}Gd{sub 0.5}Tb{sub 0.5}(BO{sub 3}){sub 2} show intense green emission under UV excitation. - Graphical abstract: The PL properties of Eu{sup 3+} and Tb{sup 3+} are studied in Na{sub 3}Ln(BO{sub 3}){sub 2} (Ln=Y, Gd) borates. Eu{sup 3+} and Tb{sup 3+}exhibits higher emission intensity in Na{sub 3}Gd(BO{sub 3}){sub 2} compared to Na{sub 3}Y(BO{sub 3}){sub 2} due to the less regular environment of the Gd{sup 3+} ion. Energy transfer from Gd{sup 3+} to Tb{sup 3+} is observed. Highlights: Black-Right-Pointing-Pointer Crystal structure of Na{sub 3}Gd(BO{sub 3}){sub 2} by X-ray powder diffraction. Black-Right-Pointing-Pointer Photoluminescence properties of Eu{sup 3+} and Tb{sup 3+} doped Na{sub 3}Ln(BO{sub 3}){sub 2} (Ln=Y, Gd). Black-Right-Pointing-Pointer Higher Eu{sup 3+} and Tb{sup 3+} emission for Na{sub 3}Gd(BO{sub 3}){sub 2} due to an irregular environment of Gd{sup 3+}. Black-Right-Pointing-Pointer Higher Eu{sup 3+} and Tb{sup 3+} emission

  16. Order-disorder transition involving the A-site cations in Ln3+Mn3V4O12 perovskites.

    PubMed

    Shimakawa, Yuichi; Zhang, Shoubao; Saito, Takashi; Lufaso, Michael W; Woodward, Patrick M

    2014-01-01

    A crossover from the A-site-ordered double-perovskite structure with Im3̅ cubic symmetry to the simple-perovskite structure with Pnma orthorhombic symmetry is found in LnMn3V4O12 (Ln = La, Nd, Gd, Y, Lu) synthesized under high-pressure conditions. Relatively large Ln(3+) ions (La(3+), Nd(3+), and Gd(3+)) induce the a(+)a(+)a(+) in-phase cooperative tilting of the VO6 octahedra, resulting in the A-site-ordered double-perovskite structure with chemical composition Ln(3+)Mn(2+)3V(3.75+)4O12. Compounds with small Ln(3+) ions like Y(3+) and Lu(3+), on the other hand, crystallize with the Pnma simple-perovskite structure with chemical composition (Ln(3+)1/4Mn(2+)3/4)V(3.75+)O3, where the Ln(3+) and Mn(2+) ions are disordered at the A site. The random distribution of the small A-site cation induces the a(-)b(+)a(-) tilting distortion of the VO6 octahedra. The observed phase crossover is well explained by the structural stability calculation based on the bond-valence-sum model, and the most stable crystal structure gives the smallest unit-cell volume. This A-site-cation size-dependent phase transition between the A-site-ordered double-perovskite and A-site-disordered simple-perovskite structures in LnMn3V4O12 is thus a result of the structural stability due to the cooperative tilting of the VO6 octahedra. The Mn(2+) ions at the A'(A) site contribute local magnetic moments, whereas the V(3.75+) ions at the B site play a role in metallic conduction. The observed magnetic behaviors are consistent with the order-disorder distribution of the Mn(2+) ions at the A site, antiferromagnetism in the A-site-ordered double perovskites, and magnetic spin glass in the A-site-disordered simple perovskites. PMID:24328260

  17. Dopant and excitation wavelength dependent color-tunable white light-emitting Ln(3+):Y2WO6 materials (Ln(3+) = Sm, Eu, Tb, Dy).

    PubMed

    Van Deun, Rik; Ndagsi, Dorine; Liu, Jing; Van Driessche, Isabel; Van Hecke, Kristof; Kaczmarek, Anna M

    2015-09-01

    Microstructured Y2WO6 materials were prepared in a hydrothermal synthesis in the presence of glycerol, which was employed as both a solvent and a structure directing agent, after which they were heat treated at 1100 °C. These materials, similar to other previously reported Y2WO6 as well as other rare-earth tungstate structures, showed interesting luminescence properties. Six Ln(3+) doped or co-doped samples, which showed white light emission, are described in this paper. It was observed that the doping ion(s)/doping percentage, heat treatment of the material, as well as the chosen excitation wavelength could be used to tune the emission color of the samples to obtain white light with a warmer or colder undertone. The luminescence lifetimes, quantum yields, CIE coordinates and correlated color temperatures for these samples were determined. Additionally, for the co-doped Y2WO6 samples the energy transfer mechanisms were proposed because a significant change in the luminescence properties was observed after heat treatment. This can be linked to the conversion from distorted tungstate groups in the precursor material to regular tungstate groups in the heat treated material. PMID:26228995

  18. Which patients with para-aortic lymph node (LN16) metastasis will truly benefit from curative pancreaticoduodenectomy for pancreatic head cancer?

    PubMed Central

    Cheng, He; Guo, Meng; Liu, Zuqiang; Xu, Jin; Long, Jiang; Liu, Liang; Fu, Deliang; Ni, Quanxing; Li, Min; Yu, Xianjun

    2016-01-01

    In patients with cancer of the pancreatic head, metastasis to para-aortic lymph nodes (LN16) is considered distant metastasis and a poor prognostic marker. However, the incidence of LN16 involvement in pancreatic head cancer is high, and it is unclear whether all such patients have poor surgical outcomes. We investigated the significance of LN16 involvement in resectable pancreatic head cancer by retrospectively analyzing 579 ductal adenocarcinoma patients treated with para-aortic lymph node dissection at two high-volume Chinese centers. Depending upon tumor location, the incidence of LN16 metastasis and the correlation between LN16 involvement and involvement of Group 1 or 2 lymph nodes significantly differed. Metastasis to LN16 indicated a high serum tumor burden and a poor prognosis, though LN16-positive patients with a lymph node ratio (LNR) < 0.25 may still benefit from radical surgery. Survival analysis of LN16-positive patients with resectable pancreatic head cancer revealed that tumor size, tumor differentiation, and tumor location are independent prognostic factors. We also found that preoperative serum CA125 < 18.62 U/ml and the level of JAK2 signaling are both indicators of who may benefit from curative surgical resection for pancreatic head cancer. PMID:27081079

  19. Correlation between slow magnetic relaxation and the coordination structures of a family of linear trinuclear Zn(II)-Ln(III)-Zn(II) complexes (Ln = Tb, Dy, Ho, Er, Tm and Yb).

    PubMed

    Maeda, Moe; Hino, Shiori; Yamashita, Kei; Kataoka, Yumiko; Nakano, Motohiro; Yamamura, Tomoo; Kajiwara, Takashi

    2012-11-28

    Six linear trinuclear [Ln{Zn(L)(AcO)}(2)]BPh(4) complexes (H(2)L denotes the Schiff-base ligand formed by a condensation reaction between ethylenediamine and two equivalents of o-vanillin), including Ln = Tb (1), Dy (2), Ho (3), Er (4), Tm (5) and Yb (6) were synthesized and were confirmed to be isostructural via X-ray crystallographic analyses. The Ln(III) ion in each complex is deca-coordinated by four equatorial oxygen donors from the methoxo groups of the Schiff-base ligands, two oxygen donors from the acetate anions and four axial oxygen donors from the phenoxo groups of the Schiff-base ligands. AC susceptibility measurements, with an oscillating frequency of 10 to 10,000 Hz, revealed that 1, 2, 4 and 6 show slow magnetic relaxation under a 1000 Oe DC bias field, which occurs via a single process, as confirmed by the semi-circular Cole-Cole plots. These complexes are considered to be field-induced single-molecule magnets under these conditions. The presence or absence of the slow magnetic relaxation process is discussed by correlating the characteristic magnetic anisotropy of each Ln(III) ion with the ligand field anisotropy.

  20. Heterometallic trinuclear {CoLn(III)} (Ln = Gd, Tb, Ho and Er) complexes in a bent geometry. Field-induced single-ion magnetic behavior of the Er(III) and Tb(III) analogues.

    PubMed

    Goura, Joydeb; Brambleby, Jamie; Topping, Craig V; Goddard, Paul A; Suriya Narayanan, Ramakirushnan; Bar, Arun Kumar; Chandrasekhar, Vadapalli

    2016-05-31

    Through the use of a multi-site compartmental ligand, 2-methoxy-6-[{2-(2-hydroxyethylamino)ethylimino}methyl]phenol (LH3), the family of heterometallic, trinuclear complexes of the formula [CoLn(L)2(μ-O2CCH3)2(H2O)3]·NO3·xMeOH·yH2O has been expanded beyond Ln = Dy(III) to include Gd(III) (), Tb(III) (), Ho(III) () and Er(III) () for , and (x = 1; y = 1) and for (x = 0; y = 2). The metallic core of these complexes consists of a (Co(III)-Ln(III)-Co(III)) motif bridged in a bent geometry resulting in six-coordinated distorted Co(III) octahedra and nine-coordinated Ln(III) monocapped square-antiprisms. The magnetic characterization of these compounds reveals the erbium and terbium analogues to display a field induced single-ion magnetic behavior similar to the dysprosium analogue but at lower temperatures. The energy barrier for the reversal of the magnetization of the CoTb(III) analogue is Ueff ≥ 15.6(4) K, while for the CoEr(III) analogue Ueff ≥ 9.9(8) K. The magnetic properties are discussed in terms of distortions of the 4f electron cloud.

  1. Up/down conversion luminescence and charge compensation investigation of Ca0.5Y1-x(WO4)2:xLn3+ (Ln = Pr, Sm, Eu, Tb, Dy, Yb/Er) phosphors

    NASA Astrophysics Data System (ADS)

    Mahalingam, Venkatakrishnan; Thirumalai, Jagannathan; Krishnan, Rajagopalan; Mantha, Srinivas

    2016-01-01

    Microstructures of Ca0.5Y(1-x)(WO4)2:xLn3+ (Ln = Pr, Sm, Eu, Tb, Dy, Yb/Er) phosphors were prepared via the solid-state reaction method. X-ray diffraction, scanning electron microscopy and photoluminescence were used to characterize the prepared phosphor samples. The results reveal that the phosphor samples have single phase scheelite structures with tetragonal symmetry of I41/a. The down/up conversion photoluminescence of the Ca0.5Y(1-x)(WO4)2:xLn3+ (Ln = Pr, Sm, Eu, Tb, Dy, Yb/Er) phosphors properties reveal characteristic visible emissions. The energy transfer process, fluorescence lifetime and color coordinates are discussed in detail. Furthermore, the phosphor Ca0.5Y(1-x)(WO4)2:xPr3+ co-doped with alkali chlorides shows the enhancement of luminescence, which was found in the sodium chloride co-doped powder phosphor. The photometric characteristics indicate the suitability of the inorganic powder phosphors for solid-state lighting and display applications.

  2. Heterometallic trinuclear {CoLn(III)} (Ln = Gd, Tb, Ho and Er) complexes in a bent geometry. Field-induced single-ion magnetic behavior of the Er(III) and Tb(III) analogues.

    PubMed

    Goura, Joydeb; Brambleby, Jamie; Topping, Craig V; Goddard, Paul A; Suriya Narayanan, Ramakirushnan; Bar, Arun Kumar; Chandrasekhar, Vadapalli

    2016-05-31

    Through the use of a multi-site compartmental ligand, 2-methoxy-6-[{2-(2-hydroxyethylamino)ethylimino}methyl]phenol (LH3), the family of heterometallic, trinuclear complexes of the formula [CoLn(L)2(μ-O2CCH3)2(H2O)3]·NO3·xMeOH·yH2O has been expanded beyond Ln = Dy(III) to include Gd(III) (), Tb(III) (), Ho(III) () and Er(III) () for , and (x = 1; y = 1) and for (x = 0; y = 2). The metallic core of these complexes consists of a (Co(III)-Ln(III)-Co(III)) motif bridged in a bent geometry resulting in six-coordinated distorted Co(III) octahedra and nine-coordinated Ln(III) monocapped square-antiprisms. The magnetic characterization of these compounds reveals the erbium and terbium analogues to display a field induced single-ion magnetic behavior similar to the dysprosium analogue but at lower temperatures. The energy barrier for the reversal of the magnetization of the CoTb(III) analogue is Ueff ≥ 15.6(4) K, while for the CoEr(III) analogue Ueff ≥ 9.9(8) K. The magnetic properties are discussed in terms of distortions of the 4f electron cloud. PMID:27180723

  3. Water Exchange on [Ln(DO3A)(H2O)2] and [Ln(DTTA-Me)(H2O)2](-) Studied by Variable Temperature, Pressure, and Magnetic Field NMR.

    PubMed

    Karimi, Shima; Helm, Lothar

    2016-05-01

    Water exchange kinetics of [Ln(L)(H2O)2](x) complexes (Ln = Pr, Nd, Dy, Tm, and Yb; L = DO3A and DTTA-Me) were studied by (17)O NMR spectroscopy as a function of temperature, pressure, and frequency and by (1)H nuclear magnetic relaxation dispersion. Water exchange rate constants of both complexes show a maximum at dysprosium. Water exchange on negatively charged complexes of the acyclic DTTA-Me ligand is much faster than on the neutral complexes of the macrocyclic DO3A. Small activation volumes |ΔV(⧧)| < 1 cm(3) mol(-1) measured for water exchange on [Ln(DO3A)(H2O)2] indicate an interchange type of mechanism (I) for the lanthanide complexes studied. In the case of [Ln(DTTA-Me)(H2O)2](-), a change in mechanism is detected from a dissociative mechanism (D, ΔV(⧧) = 7 cm(3) mol(-1)) for complexes with larger ions (Pr to Gd) to an interchange mechanism (Id, I; ΔV(⧧) = +1.8 and +0.4 cm(3) mol(-1)) for complexes with smaller ions (Dy and Tm). PMID:27082861

  4. Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb).

    PubMed

    Einkauf, Jeffrey D; Kelley, Tanya T; Chan, Benny C; de Lill, Daniel T

    2016-08-15

    A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process. PMID:27472192

  5. Examination of Compatibility of Potentially Cavitation-Resistant Modifications of Type 316LN Stainless Steel with Mercury in a Thermal Convection Loop

    SciTech Connect

    Pawel, SJ

    2002-08-29

    A 316L stainless steel thermal convection loop (TCL) containing a variety of stainless steel coupons circulated mercury for 2000 h. The TCL conditions included a maximum temperature of 307 C, a maximum temperature gradient of 90 C, and a Hg velocity of about 1.4 m/min. In addition to mill-annealed/surface-ground 316LN coupons serving as the baseline material, other coupons included 316LN that was 50% cold-worked, 316LN that was given a proprietary surface hardening treatment termed ''kolsterizing,'' and Nitronic 60. The purpose of this test was to examine Hg compatibility with these modest variations of annealed 31 6LN stainless steel that are considered potential improvements over annealed 31 6LN for cavitation-erosion resistance in the Spallation Neutron Source (SNS) target containment system. The results indicated negligible weight change for each coupon type, no significant indication of attack or surface roughening, and generally no interaction with Hg.

  6. A new family of Fe2Ln complexes built from mononuclear anionic Schiff base subunits.

    PubMed

    Nemec, Ivan; Machata, Marek; Herchel, Radovan; Boča, Roman; Trávníček, Zdeněk

    2012-12-28

    A series of the trinuclear [{Fe(3MeO-L)(2)}(2){μ(6)-Ln(η(2)-NO(3))(H(2)O)}]·nH(2)O, (Ln = Gd (2a), Tb (2b), Dy (2c), Ho (2d), Er (2e), Y (2f), H(2)-3MeO-L = 2-hydroxy-3-methoxy-phenylsalicylaldimine) complexes were prepared and thoroughly characterized. The crystal structure of 2bwas determined and it revealed that the heterotrinuclear complex consists of two anionic [Fe(3MeO-L)(2)](-) subunits coordinated to the [Tb(H(2)O)(η(2)-NO(3))](2+) bridging moiety through the phenolato and methoxy oxygen atoms. The angular distortion within the coordination polyhedron of the [Fe(3MeO-L)(2)](-) subunits grows significantly upon coordination to the Ln atom of the bridging moiety, which consequently induces an increase in the parameter of the axial magnetic anisotropy. This conclusion is obvious from the comparison and analysis of the structural (XRD) and magnetic data of the yttrium trimer 2fand the precursor complex (Pr(3)NH)[Fe(3MeO-L)(2)] (1, Pr(3)NH = the tripropylammonium cation), where D(Fe)(1) = +0.80 cm(-1) and D(Fe)(2f) = +1.64 cm(-1). Furthermore, a weak antiferromagnetic interaction between the Fe(III) centres was found in 2f(J(FeFe) = -0.26 cm(-1)). The magnetic parameters of 2f were used in the fitting of the magnetic properties of 2a as constraints. The ferromagnetic nature of the Fe-Gd interaction in 2a was confirmed, with J(GdFe) = +1.40 cm(-1), D(Gd) = -0.26 cm(-1). Moreover, in the case of the Tb (2b) and Dy (2c) compounds, a slow relaxation of the magnetization at low temperature (below 1.9 K) was observed upon the dehydration of the parent compounds. PMID:23104402

  7. Crystal growth and magnetic properties of Ln-Mn-Al (Ln=Gd, Yb) compounds of the CaCr{sub 2}Al{sub 10} and ThMn{sub 12} structure types

    SciTech Connect

    Fulfer, Bradford W.; Haldolaarachchige, Neel; Young, David P.; Chan, Julia Y.

    2012-10-15

    We report the growth and characterization of LnMn{sub 2+x}Al{sub 10-x} (Ln=Gd, Yb) crystals adopting the CaCr{sub 2}Al{sub 10} and ThMn{sub 12} structure types. Single crystals of LnMn{sub 2+x}Al{sub 10-x} were synthesized via the self-flux method and characterized with single crystal X-ray diffraction. We compare LnMn{sub 2+x}Al{sub 10-x} compounds adopting the CaCr{sub 2}Al{sub 10} and ThMn{sub 12} structure types, and outline synthesis methods to obtain each polymorph. Magnetic susceptibility measurements show paramagnetic behavior down to 3 K for both CaCr{sub 2}Al{sub 10}- and ThMn{sub 12}-type compounds, with observed magnetic moments of 1.3{mu}{sub B} for compounds adopting the CaCr{sub 2}Al{sub 10} structure type to 4.2{mu}{sub B} for those adopting the ThMn{sub 12} structure type. Compounds of both structure type exhibit metallic resistivity, with upturns at low temperature attributed to Kondo scattering. - Graphical abstract: We report the growth and characterization of LnMn{sub 2+x}Al{sub 10-x} (Ln=Gd, Yb) crystals adopting the CaCr{sub 2}Al{sub 10} and ThMn{sub 12} structure types. Single crystals of LnMn{sub 2+x}Al{sub 10-x} were synthesized via the self-flux method and characterized with single crystal X-ray diffraction. We compare LnMn{sub 2+x}Al{sub 10-x} compounds adopting the CaCr{sub 2}Al{sub 10} and ThMn{sub 12} structure types, and outline synthesis methods to obtain each polymorph. Magnetic susceptibility measurements show paramagnetic behavior down to 3 K for both CaCr{sub 2}Al{sub 10}- and ThMn{sub 12}-type compounds, with observed magnetic moments of 1.3{mu}{sub B} for compounds adopting the CaCr{sub 2}Al{sub 10} structure type to 4.2{mu}{sub B} for those adopting the ThMn{sub 12} structure type. Compounds of both structure type exhibit metallic resistivity, with upturns at low temperature attributed to Kondo scattering. Highlights: Black-Right-Pointing-Pointer We have grown Ln (Mn,Al){sub 12} (Ln=Gd, Yb) single crystals of the ThMn{sub 12

  8. Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2] (Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato).

    PubMed

    Ehama, Kiyomi; Ohmichi, Yusuke; Sakamoto, Soichiro; Fujinami, Takeshi; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Tsuchimoto, Masanobu; Re, Nazzareno

    2013-11-01

    Carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2]·solvent were synthesized through atmospheric CO2 fixation reaction of [Zn(II)L(n)(H2O)2]·xH2O, Ln(III)(NO3)3·6H2O, and triethylamine, where Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato. Each Zn(II)2Ln(III)2 structure possessing an inversion center can be described as two di-μ-phenoxo-bridged {Zn(II)L(n)Ln(III)(NO3)} binuclear units bridged by two carbonato CO3(2-) ions. The Zn(II) ion has square pyramidal coordination geometry with N2O2 donor atoms of L(n) and one oxygen atom of a bridging carbonato ion at the axial site. Ln(III) ion is coordinated by nine oxygen atoms consisting of four from the deprotonated Schiff-base L(n), two from a chelating nitrate, and three from two carbonate groups. The temperature-dependent magnetic susceptibilities in the range 1.9-300 K, field-dependent magnetization from 0 to 5 T at 1.9 K, and alternating current magnetic susceptibilities under the direct current bias fields of 0 and 1000 Oe were measured. The magnetic properties of the Zn(II)2Ln(III)2 complexes are analyzed on the basis of the dicarbonato-bridged binuclear Ln(III)-Ln(III) structure, as the Zn(II) ion with d(10) electronic configuration is diamagnetic. ZnGd1 (L(1)) and ZnGd2 (L(2)) show a ferromagnetic Gd(III)-Gd(III) interaction with J(Gd-Gd) = +0.042 and +0.028 cm(-1), respectively, on the basis of the Hamiltonian H = -2J(Gd-Gd)ŜGd1·ŜGd2. The magnetic data of the Zn(II)2Ln(III)2 complexes (Ln(III) = Tb(III), Dy(III)) were analyzed by a spin Hamiltonian including the crystal field effect on the Ln(III) ions and the Ln(III)-Ln(III) magnetic interaction. The Stark splitting of the ground state was so evaluated, and the energy pattern indicates a strong easy axis (Ising type) anisotropy. Luminescence spectra of Zn(II)2Tb(III)2 complexes were observed, while those

  9. A simple and highly efficient route to the synthesis of NaLnF4-Ag hybrid nanorice with excellent SERS performances.

    PubMed

    Zhang, Maofeng; Zhao, Aiwu; Li, Da; Sun, Henghui; Wang, Dapeng; Guo, Hongyan; Gao, Qian; Gan, Zibao; Tao, Wenyu

    2012-10-01

    This paper reports the synthesis of a new class of NaLnF(4)-Ag (Ln = Nd, Sm, Eu, Tb, Ho) hybrid nanorice and its application as a surface-enhanced Raman scattering (SERS) substrate in chemical analyses. Rice-shaped NaLnF(4) nanoparticles as templates are prepared by a modified hydrothermal method. Then, the NaLnF(4) nanorice particles are decorated with Ag nanoparticles by magnetron sputtering method to form NaLnF(4)-Ag hybrid nanostructures. The high-density Ag nanogaps on NaLnF(4) can be obtained by the prolonging sputtering times or increasing the sputtering powers. These nanogaps can serve as Raman 'hot spots', leading to dramatic enhancement of the Raman signal. The NaLnF(4)-Ag hybrid nanorice is found to be robust and is an efficient SERS substrate for the vibrational spectroscopic characterization of molecular adsorbates; the Raman enhancement factor of Rhodamine 6G (R6G) absorbed on NaLnF(4)-Ag nanorice is estimated to be about 10(13). Since the produced NaLnF(4)-Ag hybrid nanorice particles are firmly fastened on a silicon wafer, they can serve as universal SERS substrates to detect target analytes. We also evaluate their SERS performances using 4-mercaptopyridine (Mpy), and 4-mercaptobenzoic acid (MBA) molecules, and the detection limit for Mpy and MBA is as low as 10(-12) M and 10(-10) M, respectively, which meets the requirements of the ultratrace detection of analytes. This simple and highly efficient approach to the large-scale synthesis of NaLnF(4)-Ag nanorice with high SERS activity and sensitivity makes it a perfect choice for practical SERS detection applications. PMID:22898563

  10. Substitution studies of Mn and Fe in Ln{sub 6}W{sub 4}Al{sub 43} (Ln=Gd, Yb) and the structure of Yb{sub 6}Ti{sub 4}Al{sub 43}

    SciTech Connect

    Treadwell, LaRico J.; Watkins-Curry, Pilanda; McAlpin, Jacob D.; Prestigiacomo, Joseph; Stadler, Shane; Chan, Julia Y.

    2014-02-15

    The synthesis and characterization of Mn- and Fe-substituted Ln{sub 6}W{sub 4}Al{sub 43} (Ln=Gd, Yb) and Yb{sub 6}Ti{sub 4}Al{sub 43} are reported. The compounds adopt the Ho{sub 6}Mo{sub 4}Al{sub 43} structure type with lattice parameters of a∼11 Å and c∼17.8 Å with structural site preferences for Mn and Fe. The magnetization of Yb{sub 6}W{sub 4}Al{sub 43} is sensitive to Mn and Fe doping, which is evident by an increase in the field dependent magnetization. Gd{sub 6}W{sub 4}Al{sub 43}, Gd{sub 6}W{sub 4}Al{sub 42.31(11)}Mn{sub 0.69(11)}, and Gd{sub 6}W{sub 4}Al{sub 41.69(12)}Fe{sub 1.30(12)} order antiferromagnetically in the ab- and c-directions at 15, 14, and 13 K, respectively, with positive Weiss constants, suggesting the presence of ferromagnetic exchange interactions. Anisotropic magnetization data of Gd{sub 6}W{sub 4}Al{sub 43−y}T{sub y} (T=Mn, Fe) analogs are discussed. - Graphical abstract: The magnetic susceptibility of Ln{sub 6}W{sub 4−x}Al{sub 43−y}T{sub x+y} (Ln = Gd, Yb; T= Mn, Fe). Display Omitted - Highlights: • Single crystals of Ln{sub 6}W{sub 4−x}Al{sub 43−y}T{sub x+y} were grown with Al-flux. • Anisotropic magnetic behavior were determined on single crystals. • Gd{sub 6}W{sub 4−x}Al{sub 43−y}T{sub x+y} (T=Mn, Fe) analogs order antiferromagnetically.

  11. High-pressure synthesis and structures of lanthanide germanides of LnGe{sub 5} (Ln=Ce, Pr, Nd, and Sm) isotypic with LaGe{sub 5}

    SciTech Connect

    Fukuoka, Hiroshi; Baba, Kazuya; Yoshikawa, Mayumi; Ohtsu, Fumiko; Yamanaka, Shoji

    2009-08-15

    A series of lanthanide penta-germanides LnGe{sub 5} (Ln=Ce, Pr, Nd and Sm) has been prepared by high-pressure (5-13 GPa) and high-temperature (500-1200 deg. C) reaction. CeGe{sub 5} crystallizes in an orthorhombic unit cell (S.G. Immm (71)) with a=4.000(5) A, b=6.192(5) A, c=9.86(1) A, and V=244.1(5) A{sup 3}. The new germanides are isotypic with LaGe{sub 5} consisting of a Ge covalent network with tunnels where guest ions Ln{sup 3+} are situated. The network is composed of sublayers with edge-sharing Ge six-membered rings with only boat conformation. The sublayers are connected by rare eight-coordinated Ge atoms. The cell volume of the compounds systematically decreases from La to Sm compounds, except for CeGe{sub 5,} owing to the lanthanide contraction. The lattice constants of CeGe{sub 5} are smaller than those of the Pr compound because it contains Ce{sup 4+} ions. CeGe{sub 5} is paramagnetic above 2 K, but does not obey the Curie-Weiss law. PrGe{sub 5} and NdGe{sub 5} are Curie-Weiss type paramagnets with Weiss temperatures of -3.3 and -18.4 K. SmGe{sub 5} shows an antiferromagnetic transition at 10.4 K. - Graphical abstract: A series of lanthanide penta-germanides LnGe{sub 5} (Ln=Ce, Pr, Nd and Sm) has been prepared by high-pressure (5-13 GPa) and high-temperature (500-1200 deg. C) reaction.

  12. Mutual separation of Am/Cm/Ln by the use of Novel-Triamide, NTAamide and water-soluble diglycolamide

    SciTech Connect

    Sasaki, Yuji; Tsubata, Yasuhiro; Kitatsuji, Yoshihiro; Sugo, Yumi; Shirasu, Noriko; Morita, Yasuji

    2013-07-01

    The new extractant, NTAamide (C8) (N,N,N',N',N'',N''-hexa-octyl-nitriro-tri-acetamide) is a triamide having nitrogen and oxygen atoms in the central frame, then NTAamide (C8) has hybrid performance of complexation to metals by soft and hard donors. It is clear that NTAamide(C8) can extract trivalent An from diluted nitric acid showing small D(Ln), then the separation of An from Ln can be carried out. The separation factor (SF) of Am/Cm by NTAamide(C8) is approximate 1.78-2.08, which is not so high to separate each other. The combination of NTAamide(C8) of extractant and TEDGA (N,N,N',N'-tetraethyl-diglycolamide) as a masking agent shows relatively high SF(Am/Cm) of maximal 6.5. It is obvious that NTAamide(C8) is a promising extractant to achieve the mutual separation among Am/Cm/Ln. The concept of flow-sheet for Am/Cm/Ln separation is designed using NTAamide(C8) and TEDGA. (authors)

  13. Preliminary evaluation of cavitation resistance of type 316LN stainless steel in mercury using a vibratory horn

    NASA Astrophysics Data System (ADS)

    Pawel, S. J.; Manneschmidt, E. T.

    2003-05-01

    Type 316LN stainless steel in a variety of conditions (annealed, cold-worked, surface-modified) was exposed to cavitation conditions in stagnant mercury using a vibratory horn. The test conditions included peak-to-peak displacement of the specimen surface of 25 μm at a frequency of 20 kHz and a mercury temperature in the range -5 to 80 °C. Following a brief incubation period in which little or no damage was observed, specimens of annealed 316LN exhibited increasing weight loss and surface roughening with increasing exposure times. Examination of test surfaces with the scanning electron microscope revealed primarily general/uniform wastage in all cases but, for long exposure times, a few randomly oriented 'pits' were also observed. Type 316LN that was 50% cold-worked was considerably more resistant to cavitation erosion damage than annealed material, but the surface modifications (CrN coating, metallic glass coating, laser treatment to form a diamond-like surface) provided little or no protection for the substrate. In addition, the cavitation erosion resistance of other materials - Inconel 718, Nitronic 60, and Stellite 3 - was also compared with that of 316LN for identical screening test conditions.

  14. Heteronuclear Ir(III)-Ln(III) Luminescent Complexes: Small-Molecule Probes for Dual Modal Imaging and Oxygen Sensing.

    PubMed

    Jana, Atanu; Crowston, Bethany J; Shewring, Jonathan R; McKenzie, Luke K; Bryant, Helen E; Botchway, Stanley W; Ward, Andrew D; Amoroso, Angelo J; Baggaley, Elizabeth; Ward, Michael D

    2016-06-01

    Luminescent, mixed metal d-f complexes have the potential to be used for dual (magnetic resonance imaging (MRI) and luminescence) in vivo imaging. Here, we present dinuclear and trinuclear d-f complexes, comprising a rigid framework linking a luminescent Ir center to one (Ir·Ln) or two (Ir·Ln2) lanthanide metal centers (where Ln = Eu(III) and Gd(III), respectively). A range of physical, spectroscopic, and imaging-based properties including relaxivity arising from the Gd(III) units and the occurrence of Ir(III) → Eu(III) photoinduced energy-transfer are presented. The rigidity imposed by the ligand facilitates high relaxivities for the Gd(III) complexes, while the luminescence from the Ir(III) and Eu(III) centers provide luminescence imaging capabilities. Dinuclear (Ir·Ln) complexes performed best in cellular studies, exhibiting good solubility in aqueous solutions, low toxicity after 4 and 18 h, respectively, and punctate lysosomal staining. We also demonstrate the first example of oxygen sensing in fixed cells using the dyad Ir·Gd, via two-photon phosphorescence lifetime imaging (PLIM). PMID:27219675

  15. Evaluation of the photocatalytic activity of Ln3+-TiO2 nanomaterial using fluorescence technique for real wastewater treatment

    NASA Astrophysics Data System (ADS)

    Saif, M.; Aboul-Fotouh, S. M. K.; El-Molla, S. A.; Ibrahim, M. M.; Ismail, L. F. M.

    2014-07-01

    Evaluation the photocatalytic activity of different Ln3+ modified TiO2 nanomaterials using fluorescence based technique has rarely been reported. In the present work, x mol Ln3+ modified TiO2 nanomaterials (Ln = Nd3+, Sm3+, Eu3+, Gd3+, Dy3+ and Er3+ ions; x = 0.005, 0.008, 0.01, 0.02 and 0.03) were synthesized by sol-gel method and characterized using different advanced techniques. The photocatalytic efficiency of the modified TiO2 expressed in the charge carrier separation and rad OH radicals formation were assigned using TiO2 fluorescence quenching and fluorescence probe methods, respectively. The obtained fluorescence measurements confirm that doping treatment significantly decreases the electron-hole recombination probability in the obtained Ln3+/TiO2. Moreover, the rate of rad OH radicals formation is increased by doping. The highly active nanoparticles (0.02Gd3+/TiO2 and 0.01Eu3+/TiO2) were applied for industrial wastewater treatment using solar radiation as a renewable energy source.

  16. Evaluation of the photocatalytic activity of Ln3+-TiO2 nanomaterial using fluorescence technique for real wastewater treatment.

    PubMed

    Saif, M; Aboul-Fotouh, S M K; El-Molla, S A; Ibrahim, M M; Ismail, L F M

    2014-07-15

    Evaluation the photocatalytic activity of different Ln(3+) modified TiO2 nanomaterials using fluorescence based technique has rarely been reported. In the present work, xmol Ln(3+) modified TiO2 nanomaterials (Ln = Nd(3+), Sm(3+), Eu(3+), Gd(3+), Dy(3+) and Er(3+) ions; x = 0.005, 0.008, 0.01, 0.02 and 0.03) were synthesized by sol-gel method and characterized using different advanced techniques. The photocatalytic efficiency of the modified TiO2 expressed in the charge carrier separation and OH radicals formation were assigned using TiO2 fluorescence quenching and fluorescence probe methods, respectively. The obtained fluorescence measurements confirm that doping treatment significantly decreases the electron-hole recombination probability in the obtained Ln(3+)/TiO2. Moreover, the rate of OH radicals formation is increased by doping. The highly active nanoparticles (0.02Gd(3+)/TiO2 and 0.01Eu(3+)/TiO2) were applied for industrial wastewater treatment using solar radiation as a renewable energy source.

  17. Effect of surface polishing and vacuum firing on electron stimulated desorption from 316LN stainless steel

    SciTech Connect

    Malyshev, Oleg B. Hogan, Benjamin T.; Pendleton, Mark

    2014-09-01

    The reduction of thermal outgassing from stainless steel by surface polishing or vacuum firing is well-known in vacuum technology, and the consequent use of both techniques allows an even further reduction of outgassing. The aim of this study was to identify the effectiveness of surface polishing and vacuum firing for reducing electron-stimulated desorption (ESD) from 316LN stainless steel, which is a frequently used material for particle accelerator vacuum chambers and components. It was found that, unlike for thermal outgassing, surface polishing does not reduce the ESD yield and may even increase it, while vacuum firing of nonpolished sample reduces only the H{sub 2} ESD yield by a factor 2.

  18. Evaluation of Cavitation-Erosion Resistance of 316LN Stainless Steel in Mercury Containing Metallic Solutes

    SciTech Connect

    Pawel, Steven J; Mansur, Louis K

    2006-08-01

    Room temperature cavitation tests of vacuum annealed type 316LN stainless steel were performed in pure Hg and in Hg with various amounts of metallic solute to evaluate potential mitigation of erosion/wastage. Tests were performed using an ultrasonic vibratory horn with specimens attached at the tip. All of the solutes examined, which included 5 wt% In, 10 wt% In, 4.4 wt% Cd, 2 wt% Ga, and a mixture that included 1 wt% each of Pb, Sn, and Zn, were found to increase cavitation-erosion as measured by increased weight loss and/or surface profile development compared to exposures for the same conditions in pure Hg. Qualitatively, each solute appeared to increase the post-test wetting tenacity of the Hg solutions and render the Hg mixture susceptible to manipulation of droplet shape.

  19. Aqueous Ln(III) Luminescence Agents Derived from a Tasty Precursor

    SciTech Connect

    Jocher, C.J.; Moore, E.G.; Pierce, J.D.; Raymond, K.N.

    2008-06-02

    The synthesis, aqueous stability and photophysical properties are reported for a novel tetradentate ligand derived from maltol, a commonly used flavor enhancer. In aqueous solution, this chelate forms stable complexes with Ln(III) cations, and sensitized emission was observed from Eu(III), Yb(III), and Nd(III). A comparison with recently reported and structurally analogous ligands reveals a slightly higher basicity but lower complex stability with Eu(III) [pEu = 14.7 (1)]. A very poor metal centered quantum yield with Eu(III) was observed ({Phi}{sub tot} = 0.04%), which can be rationalized by the similar energy of the ligand triplet state and the Eu(III) {sup 5}D{sub 0} emissive level. Instead, sensitized emission from the Yb(III) and Nd(III) cations was observed, which emit in the Near Infra-Red (NIR).

  20. Generation of Constant Life Diagram under Elevated Temperature Ratcheting of 316LN Stainless Steel

    NASA Astrophysics Data System (ADS)

    Sarkar, Aritra; Nagesha, A.; Sandhya, R.; Mathew, M. D.

    2016-04-01

    Combined influence of mean stress and stress amplitude on the cyclic life under elevated temperature (823-923 K) ratcheting of 316LN austenitic stainless steel is discussed. Constant life Haigh diagrams have been generated, using different combinations of stress amplitude and mean stress. In the plastic domain, the allowable stress was found to increase or decrease with mean stress depending on the temperature and combination of mean stress - stress amplitude employed. Strong influence of dynamic strain aging (DSA) was found at 823 K which affected the mode of deformation of the material in comparison with 923 K. Failure mode expressed through a fracture mechanism map was found to change from fatigue to necking depending on the test temperature as well as combinations of mean stress and stress amplitude. Occurrence of DSA at 823 K proved to be beneficial by way of extending the safe zone of operation to higher R-ratios in comparison with 923 K.

  1. Fracture Behaviour of Type 304LN Stainless Steel and its Welds

    SciTech Connect

    Dubey, J.S.; Chakravartty, J.K.; Singh, P.K.; Banerjee, S.

    2006-07-01

    SA312 type 304LN stainless steel material, having closer control over impurities and inclusion content, is the intended piping material in the Advanced Heavy Water Reactors. Deformation, fatigue and fracture behaviour of this material and its weldments have been characterized at ambient temperature and at 558 K. The details of the fractographic investigations and stretch zone width measurements are also discussed. The base metals shows high initiation toughness (>500 kJ/m{sup 2}) and large tearing modulus at ambient and operating temperatures. Shielded Metal Arc Welding (SMAW) weld metal shows much much reduced initiation toughness and tearing resistance in comparison to base metal and Gas Tungsten Arc Welding (GTAW) welds. This is attributed to larger density of second phase inclusions in the SMAW weld metal. SZW measurements give a good alternate estimate of the toughness of the materials. Fatigue crack growth rate in SMAW weld metal was found to be comparable to base metal at higher load ratios. (authors)

  2. Influence of Heat Treatment on Mercury Cavitation Resistance of Surface Hardened 316LN Stainless Steel

    SciTech Connect

    Pawel, Steven J; Hsu, Julia

    2010-11-01

    The cavitation-erosion resistance of carburized 316LN stainless steel was significantly degraded but not destroyed by heat treatment in the temperature range 500-800 C. The heat treatments caused rejection of some carbon from the carburized layer into an amorphous film that formed on each specimen surface. Further, the heat treatments encouraged carbide precipitation and reduced hardness within the carburized layer, but the overall change did not reduce surface hardness fully to the level of untreated material. Heat treatments as short as 10 min at 650 C substantially reduced cavitation-erosion resistance in mercury, while heat treatments at 500 and 800 C were found to be somewhat less detrimental. Overall, the results suggest that modest thermal excursions perhaps the result of a weld made at some distance to the carburized material or a brief stress relief treatment will not render the hardened layer completely ineffective but should be avoided to the greatest extent possible.

  3. Solvothermal synthesis and luminescent properties of monodisperse LaPO{sub 4}:Ln (Ln=Eu{sup 3+}, Ce{sup 3+}, Tb{sup 3+}) particles

    SciTech Connect

    Yang Piaoping; Quan Zewei; Li Chunxia; Hou Zhiyao; Wang Wenxin; Lin Jun

    2009-05-15

    Monodisperse rare-earth ion (Eu{sup 3+}, Ce{sup 3+}, Tb{sup 3+}) doped LaPO{sub 4} particles with oval morphology were successfully prepared through a facile solvothermal process without further heat treatment. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FT-IR), photoluminescence (PL) spectra and the kinetic decays were performed to characterize these samples. The XRD results reveal that all the doped samples are well crystalline at 180 deg. C and assigned to the monoclinic monazite-type structure of the LaPO{sub 4} phase. It has been shown that all the as-synthesized samples show perfectly oval morphology with narrow size distribution. The possible growth mechanism of the LaPO{sub 4}:Ln has been investigated as well. Upon excitation by ultraviolet radiation, the LaPO{sub 4}:Eu{sup 3+} phosphors show the characteristic {sup 5}D{sub 0}-{sup 7}F{sub 1-4} emission lines of Eu{sup 3+}, while the LaPO{sub 4}:Ce{sup 3+}, Tb{sup 3+} phosphors demonstrate the characteristic {sup 5}D{sub 4}-{sup 7}F{sub 3-6} emission lines of Tb{sup 3+}. - Graphical abstract: Monodisperse rare-earth ion (Eu{sup 3+}, Ce{sup 3+}, Tb{sup 3+}) doped LaPO{sub 4} phosphors with monazite-type structure and uniform oval morphology and strong emission intensity have been prepared through a facile solvothermal process.

  4. A family of acetato-diphenoxo triply bridged dimetallic Zn(II)Ln(III) complexes: SMM behavior and luminescent properties.

    PubMed

    Oyarzabal, Itziar; Artetxe, Beñat; Rodríguez-Diéguez, Antonio; García, JoséÁngel; Seco, José Manuel; Colacio, Enrique

    2016-06-21

    Eleven dimetallic Zn(II)-Ln(III) complexes of the general formula [Zn(µ-L)(µ-OAc)Ln(NO3)2]·CH3CN (Ln(III) = Pr (1), Nd (2), Sm (3), Eu (4), Gd (5), Tb (6), Dy (7), Ho (8), Er (9), Tm (10), Yb (11)) have been prepared in a one-pot reaction from the compartmental ligand N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H2L). In all these complexes, the Zn(II) ions occupy the internal N2O2 site whereas the Ln(III) ions show preference for the O4 external site. Both metallic ions are bridged by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged Zn(II)Ln(III) compounds. The Nd, Dy, Er and Yb complexes exhibit field induced single-ion magnet (SIM) behaviour, with Ueff values ranging from 14.12 to 41.55 K. The Er complex shows two relaxation processes, but only the second relaxation process with an energy barrier of 21.0 K has been characterized. The chromophoric L(2-) ligand is able to act as an "antenna" group, sensitizing the near-infrared (NIR) Nd(III) and Yb(III)-based luminescence in complexes 2 and 11 and therefore, both compounds can be considered as magneto-luminescent materials. In addition, the Sm(III), Eu(III) and Tb(III) derivatives exhibit characteristic emissions in the visible region. PMID:27230817

  5. Multi-modal imaging and cancer therapy using lanthanide oxide nanoparticles: current status and perspectives.

    PubMed

    Park, J Y; Chang, Y; Lee, G H

    2015-01-01

    Biomedical imaging is an essential tool for diagnosis and therapy of diseases such as cancers. It is likely true that medicine has developed with biomedical imaging methods. Sensitivity and resolution of biomedical imaging methods can be improved with imaging agents. Furthermore, it will be ideal if imaging agents could be also used as therapeutic agents. Therefore, one dose can be used for both diagnosis and therapy of diseases (i.e., theragnosis). This will simplify medical treatment of diseases, and will be also a benefit to patients. Mixed (Ln(1x)Ln(2y)O3, x + y = 2) or unmixed (Ln2O3) lanthanide (Ln) oxide nanoparticles (Ln = Eu, Gd, Dy, Tb, Ho, Er) are potential multi-modal imaging and cancer therapeutic agents. The lanthanides have a variety of magnetic and optical properties, useful for magnetic resonance imaging (MRI) and fluorescent imaging (FI), respectively. They also highly attenuate X-ray beam, useful for X-ray computed tomography (CT). In addition gadolinium-157 ((157)Gd) has the highest thermal neutron capture cross section among stable radionuclides, useful for gadolinium neutron capture therapy (GdNCT). Therefore, mixed or unmixed lanthanide oxide nanoparticles can be used for multi-modal imaging methods (i.e., MRI-FI, MRI-CT, CT-FI, and MRICT- FI) and cancer therapy (i.e., GdNCT). Since mixed or unmixed lanthanide oxide nanoparticles are single-phase and solid-state, they can be easily synthesized, and are compact and robust, which will be beneficial to biomedical applications. In this review physical properties of the lanthanides, synthesis, characterizations, multi-modal imagings, and cancer therapy of mixed and unmixed lanthanide oxide nanoparticles are discussed.

  6. A DFT+U study on the contribution of 4f electrons to oxygen vacancy formation and migration in Ln-doped CeO2.

    PubMed

    Alaydrus, M; Sakaue, M; Kasai, H

    2016-05-14

    A rare earth doped form of ceria (CeO2) is of interest as a potential candidate for solid oxide fuel cells (SOFCs) because of its relatively high oxygen ion conductivity at temperatures below 600 °C. At the present time, computational chemistry has reached a certain maturity which allows the prediction of materials properties that are difficult to observe experimentally. However, understanding of the roles of dopants in the oxygen ion conduction in CeO2 is still incomplete for quantitatively reliable analysis due to the strong electron correlation of 4f electrons. In this study, density functional theory calculations with Hubbard U corrections are used to discuss ionic/covalent interactions in rare-earth-doped CeO2 and their consequences to oxygen ion conduction. This study suggests that the variable occupancy of empty 4f orbitals is important typically for early Ln elements to produce the covalent interactions that essentially affect the formation and migration of oxygen vacancies. This finding is important in understanding the factors responsible for oxygen ion diffusion in doped CeO2.

  7. Electrochemical studies of water insertion and proton - Ceramic interaction in substituted perovskite SrZr0.9Ln0.1O2.95

    NASA Astrophysics Data System (ADS)

    Lacroix, O.; Rahmouni, K.; Sirat, A.; Takenouti, H.; Deslouis, C.; Keddam, M.; Sala, B.

    2014-12-01

    Because of their high ionic conduction even at relatively low temperatures, proton conducting ceramics are one of the most promising electrolytes for fuel cell. In contrast to oxide-ion conductors, proton-conducting systems, especially in an electrolyser plant, could operate below 600 °C, critical temperature for mechanical and hot corrosion resistance of common stainless steels. Proton conduction in perovskite type ceramic was analysed under the water molecules insertion to maximize proton conduction. To this end, the SrZr0.9Ln0.1O2.95 electrolyte and its microstructure, particularly grain size was investigated. The insertion and release of water in the perovskite structure was followed by impedance spectroscopy and by using the so-called Brick Layer Model (BLM) to separate the bulk and grain boundary conductivities. It was found that the conductivity in both zones increases namely with steam pressure. It was also verified that the bulk conductivity is higher than that of grain boundaries. Consequently both the operating steam pressure and the grain size appear as the main parameters that can be tuned to enhance the proton conduction.

  8. Application of mitochondrial pyruvate carrier blocker UK5099 creates metabolic reprogram and greater stem-like properties in LnCap prostate cancer cells in vitro

    PubMed Central

    Zhong, Yali; Li, Xiaoran; Yu, Dandan; Li, Xiaoli; Li, Yaqing; Long, Yuan; Yuan, Yuan; Ji, Zhenyu; Zhang, Mingzhi; Wen, Jian-Guo; Nesland, Jahn M.; Suo, Zhenhe

    2015-01-01

    Aerobic glycolysis is one of the important hallmarks of cancer cells and eukaryotic cells. In this study, we have investigated the relationship between blocking mitochondrial pyruvate carrier (MPC) with UK5099 and the metabolic alteration as well as stemness phenotype of prostatic cancer cells. It was found that blocking pyruvate transportation into mitochondrial attenuated mitochondrial oxidative phosphorylation (OXPHOS) and increased glycolysis. The UK5099 treated cells showed significantly higher proportion of side population (SP) fraction and expressed higher levels of stemness markers Oct3/4 and Nanog. Chemosensitivity examinations revealed that the UK5099 treated cells became more resistant to chemotherapy compared to the non-treated cells. These results demonstrate probably an intimate connection between metabolic reprogram and stem-like phenotype of LnCap cells in vitro. We propose that MPC blocker (UK5099) application may be an ideal model for Warburg effect studies, since it attenuates mitochondrial OXPHOS and increases aerobic glycolysis, a phenomenon typically reflected in the Warburg effect. We conclude that impaired mitochondrial OXPHOS and upregulated glycolysis are related with stem-like phenotype shift in prostatic cancer cells. PMID:26413751

  9. Synthesis, structure, and luminescence property of a series of Ag-Ln coordination polymers with the N-heterocyclic carboxylato ligand

    NASA Astrophysics Data System (ADS)

    Jin, Jing; Chen, Chong; Gao, Yan; Zhao, Ran; Wang, Xiuyan; Lü, Chunxin; Chi, Yuxian; Niu, Shuyun

    2016-03-01

    Six Ln-Ag coordination polymers {[LnAg2(IN)4(H2O)5]·NO3·2H2O}n (Ln=Ho (1) and Tb (2), HIN=isonicotinic acid), {[PrAg2(IN)4(H2O)2]·NO3·H2O}n (3), [LnAg(pdc)2]n (Ln=Eu(4) and Pr (5), H2pdc=3,4-pyridine-dicarboxylic acid) and [NdAg(bidc)2(H2O)4]n (6) (H2bidc=benzimidazole-5,6-dicarboxylic acid) have been hydrothermally synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR, UV-vis-NIR absorption spectra, fluorescence spectra and thermogravimetric analysis. Structural analyses reveal that the six polymers exhibit 0D (polymer (1)), 1D (polymer (2)), 2D (polymers (3) and (5)) and 3D (polymers (4) and (6)) infinite structures, respectively. Polymers (1)-(6) exhibit the Ln(III) characteristic emission in the near-infrared (NIR) region or in the visible region. Especially, the NIR emission bands of polymers 1, 5 and 6 evidently present shift or splitting due to formation of the Ln-Ag coordination polymers. This can be attributed to the tune of inner levels in Ln-Ag system caused by the interact and influence between the 4d orbital of the Ag(I) ion and the 4f orbital of the Ln(III) ion, which can be confirmed by the UV-vis-NIR absorption spectra of the polymers. In addition, the distortion of coordination geometry as well as difference of the coordination number around the Ag(I) ion affect the structure framework.

  10. The structures and luminescence properties of lanthanide (Ln = Sm, Eu and Tb) metal-organic coordination polymers based on 5-(2-hydroxyethoxy)isophthalate ligand

    NASA Astrophysics Data System (ADS)

    Wang, Peng; Zhang, Yu-Jie; Qin, Jie; Chen, Yong; Zhao, Ying

    2015-03-01

    Three unreported isomorphous Ln-containing metal-organic coordination polymeric complexes {LnL(HL)ṡ(H2O)2}n (Ln = Sm (1), Eu (2) and Tb (3), CCDC 971815-971817) were synthesized based on 5-(2-hydroxyethoxy) isophthalic acid (H2L) under hydrothermal conditions. The obtained coordination polymers were characterized by IR, elemental analysis, thermal analysis and X-ray diffraction In solid state, these polymers featured 3-D supramolecular structures constructed by 2-D sheets through H-bonds. Investigation of photoluminescence properties of H2L and 1-3 showed all of them exhibited intense fluorescent emissions in the solid state at room temperature.

  11. The ionothermal synthesis of metal organic frameworks, Ln(C 9O 6H 3)((CH 3NH) 2CO) 2, using deep eutectic solvents

    NASA Astrophysics Data System (ADS)

    Himeur, Farida; Stein, Irene; Wragg, David S.; Slawin, Alexandra M. Z.; Lightfoot, Philip; Morris, Russell E.

    2010-04-01

    Three new isostructural materials Ln(TMA)(DMU) 2 (Ln(C 9O 6H 3)((CH 3NH) 2CO) 2; Ln: La 1, Nd 2, Eu 3; TMA: trimesate, DMU: dimethylurea) have been synthesised ionothermally using a choline chloride/dimethylurea deep eutectic mixture as the solvent. Normally in ionothermal synthesis the urea portion of the deep eutectic solvent is unstable, breaking down to release ammonium cations that act as templates. In the case of 1- 3, however, the dimethylurea remains intact and is incorporated into the final structure.

  12. Synthesis and Lanthanide Coordination Chemistry of Phosphine Oxide Decorated Dibenzothiophene and Dibenzothiophene Sulfone Platforms

    SciTech Connect

    Rosario-Amorin, Daniel; Ouizem, Sabrina; Dickie, D. A.; Paine, Robert T.; Cramer, Roger E.; Hay, Benjamin; Podair, Julien; Delmau, Laetitia Helene

    2014-01-01

    Syntheses for new ligands based upon dibenzothiophene and dibenzothiophene sulfone platforms, decorated with phosphine oxide and methylphosphine oxide donor groups, are described. Coordination chem. of 4, 6- bis(diphenylphosphinoylmethyl) dibenzothiophene (8) , 4, 6- bis(diphenylphosphinoylmethyl) dibenzothiophene- 5, 5- dioxide (9) and 4, 6- bis(diphenylphosphinoyl) dibenzothiophene- 5, 5- dioxide (10) with lanthanide nitrates, Ln(NO3) 3 (H2O) n is outlined, and crystal structure detns. reveal a range of chelation interactions on Ln(III) ions. The HNO3 dependence of the solvent extn. performance of 9 and 10 in 1, 2- dichloroethane for Eu(III) and Am(III) is described and compared against the extn. behavior of related dibenzofuran ligands (2, 3; R = Ph) and n- octyl(phenyl) - N, N- diisobutylcarbamoylmethyl phosphine oxide (4) measured under identical conditions.

  13. Chemical Characteristics of Cold-Pressed Blackberry, Black Raspberry, and Blueberry Seed Oils and the Role of the Minor Components in Their Oxidative Stability.

    PubMed

    Li, Quanquan; Wang, Jiankang; Shahidi, Fereidoon

    2016-07-01

    The chemical characteristics of cold-pressed blackberry, black raspberry, and blueberry seed oils were evaluated for their fatty acid composition, positional distribution of fatty acids, triacylglycerol (TAG) profile, and minor component profile. The role of minor components, including tocols and pigments, on the oxidative stability was also investigated using high-temperature- and fluorescent-lighting-induced oxidation before and after tested berry seed oils were stripped of their minor components. The results indicated that all tested berry seed oils contained significant levels of palmitic (C16:0), stearic (C18:0), oleic (18:1), linoleic (C18:2ω-6), and α-linolenic (C18:3ω-3) acids, along with a favorable ratio of ω-6/ω-3 fatty acids (1.49-3.86); palmitic, stearic, oleic, and α-linolenic acids were predominantly distributed on the terminal positions. Six TAGs, namely, LnLnLn, LnLLn, LLLn, LLL, OLL, and OLLn, were the major species detected in the tested berry seed oils. Total tocol contents were 286.3-1302.9 mg/kg, which include α-, γ-, and δ-tocopherols as well as δ-tocotrienol. Oxidative stability of the three berry seed oils was compromised after the removal of tocols under high-temperature-induced oxidation, while the loss of pigments (chlorophylls) led to weak oxidative stability when exposed to fluorescent lights. PMID:27203814

  14. Ionic-radius-driven selection of the main-group-metal cage for intermetalloid clusters [Ln@Pbx Bi14-x](q-) and [Ln@Pby Bi13-y](q-) (x/q=7/4, 6/3; y/q=4/4, 3/3).

    PubMed

    Ababei, Rodica; Massa, Werner; Weinert, Bastian; Pollak, Patrik; Xie, Xiulan; Clérac, Rodolphe; Weigend, Florian; Dehnen, Stefanie

    2015-01-01

    Reactions of the binary, pseudo-homoatomic Zintl anion (Pb2 Bi2 )(2-) with Ln(C5 Me4 H)3 (Ln=La, Ce, Nd, Gd, Sm, Tb) in the presence of [2.2.2]crypt in ethane-1,2-diamine/toluene yielded ten [K([2.2.2]crypt)](+) salts of lanthanide-doped semimetal clusters with 13 or 14 surface atoms. Single-crystal X-ray diffraction and energy-dispersive X-ray spectroscopy indicated the presence of the anions [Ln@Pb6 Bi8 ](3-), [Ln@Pb3 Bi10 ](3-), [Ln@Pb7 Bi7 ](4-), or [Ln@Pb4 Bi9 ](4-) in single or double salts; the latter showed various ratios of the components in the solid state. The anions are the first ternary intermetalloid clusters comprising only elements of the sixth period of the periodic table, namely, Pb, Bi and lanthanides. This study, which was complemented by ESI mass spectrometry and (139) La NMR spectroscopy in solution, rationalizes a continuous development of the ratio of 13:14-atom cages with the ionic radius of the embedded Ln(3+) ion, which seems to select the most suitable cage type. Quantum chemical investigations helped to analyze this situation in more detail and to explain the observed subtle influence of the atomic radii. Magnetic measurements confirmed that the embedded Ln(3+) ions keep their expected paramagnetic or diamagnetic nature. PMID:25412590

  15. Ionic-radius-driven selection of the main-group-metal cage for intermetalloid clusters [Ln@Pbx Bi14-x](q-) and [Ln@Pby Bi13-y](q-) (x/q=7/4, 6/3; y/q=4/4, 3/3).

    PubMed

    Ababei, Rodica; Massa, Werner; Weinert, Bastian; Pollak, Patrik; Xie, Xiulan; Clérac, Rodolphe; Weigend, Florian; Dehnen, Stefanie

    2015-01-01

    Reactions of the binary, pseudo-homoatomic Zintl anion (Pb2 Bi2 )(2-) with Ln(C5 Me4 H)3 (Ln=La, Ce, Nd, Gd, Sm, Tb) in the presence of [2.2.2]crypt in ethane-1,2-diamine/toluene yielded ten [K([2.2.2]crypt)](+) salts of lanthanide-doped semimetal clusters with 13 or 14 surface atoms. Single-crystal X-ray diffraction and energy-dispersive X-ray spectroscopy indicated the presence of the anions [Ln@Pb6 Bi8 ](3-), [Ln@Pb3 Bi10 ](3-), [Ln@Pb7 Bi7 ](4-), or [Ln@Pb4 Bi9 ](4-) in single or double salts; the latter showed various ratios of the components in the solid state. The anions are the first ternary intermetalloid clusters comprising only elements of the sixth period of the periodic table, namely, Pb, Bi and lanthanides. This study, which was complemented by ESI mass spectrometry and (139) La NMR spectroscopy in solution, rationalizes a continuous development of the ratio of 13:14-atom cages with the ionic radius of the embedded Ln(3+) ion, which seems to select the most suitable cage type. Quantum chemical investigations helped to analyze this situation in more detail and to explain the observed subtle influence of the atomic radii. Magnetic measurements confirmed that the embedded Ln(3+) ions keep their expected paramagnetic or diamagnetic nature.

  16. Near-infrared photoluminescence in La0.98AlO3: 0.02Ln3+(Ln = Nd/Yb) for sensitization of c-Si solar cells

    NASA Astrophysics Data System (ADS)

    Sawala, N. S.; Koparkar, K. A.; Bajaj, N. S.; Omanwar, S. K.

    2016-05-01

    The host matrix LaAlO3 was synthesized by conventional solid state reaction method in which the Nd3+ ions and Yb3+ ions successfully doped at 2mol% concentrations. The phase purity was confirmed by X ray powder diffraction (XRD) method. The photoluminescence (PL) properties were studied by spectrophotometer in near infra red (NIR) and ultra violet visible (UV-VIS) region. The Nd3+ ion doped LaAlO3 converts a visible (VIS) green photon (587 nm) into near infrared (NIR) photon (1070 nm) while Yb3+ ion doped converts ultra violet (UV) photon (221 nm) into NIR photon (980 nm). The La0.98AlO3: 0.02Ln3+(Ln = Nd / Yb) can be potentiality used for betterment of photovoltaic (PV) technology. This result further indicates its potential application as a luminescence converter layer for enhancing solar cells performance.

  17. Degenerate electrical conductive and excitonic photoluminescence properties of epitaxial films of wide gap p-type layered oxychalcogenides, LnCuOCh (Ln=La, Pr and Nd; Ch=S or Se)

    NASA Astrophysics Data System (ADS)

    Hiramatsu, H.; Ueda, K.; Takafuji, K.; Ohta, H.; Hirano, M.; Kamiya, T.; Hosono, H.

    Electrical and photoluminescence properties were investigated for epitaxial films of layered oxychalcogenides, LnCuOCh (Ln=La, Pr, and Nd, Ch=S or Se). Epitaxial films of Mg 10 at.% doped LaCuOS1-xSex are the first demonstration of degenerate conduction with high hole concentration >1020 cm-3 in wide gap p-type semiconductors. Ion substitution varied the excitonic emission energy from 3.21 eV to 2.89 eV while lanthanide and chalcogenide ion substitutions displayed the opposite tendency against cell volume. These unique properties are discussed with respect to the electronic structure originating from the layered crystal structure.

  18. Effects of Out-of-Plane Disorder on the Nodal Quasiparticle and Superconducting Gap in Single-Layer Bi_2Sr_1.6Ln_0.4CuO_6 delta (Ln = La, Nd, Gd)

    SciTech Connect

    Hashimoto, M.

    2011-01-04

    How out-of-plane disorder affects the electronic structure has been investigated for the single-layer cuprates Bi{sub 2}Sr{sub 1.6}Ln{sub 0.4}CuO{sub 6+{delta}} (Ln = La, Nd, Gd) by angle-resolved photoemission spectroscopy. We have observed that, with increasing disorder, while the Fermi surface shape and band dispersions are not affected, the quasi-particle width increases, the anti-nodal gap is enhanced and the superconducting gap in the nodal region is depressed. The results indicate that the superconductivity is significantly depressed by out-of-plane disorder through the enhancement of the anti-nodal gap and the depression of the superconducting gap in the nodal region.

  19. Studies of reaction variables for lipase-catalyzed production of alpha-linolenic acid enriched structured lipid and oxidative stability with antioxidants.

    PubMed

    Mitra, Kanika; Shin, Jung-Ah; Lee, Jeung-Hee; Kim, Seong-Ai; Hong, Soon-Taek; Sung, Chang-Keun; Xue, Cheng Lian; Lee, Ki-Teak

    2012-01-01

    Alpha-linolenic acid (ALA) enriched structured lipid (SL) was produced by lipase-catalyzed interesterification from perilla oil (PO) and corn oil (CO). The effects of different reaction conditions (substrate molar ratio [PO/CO 1:1 to 1:3], reaction time [0 to 24 h], and reaction temperature [55 to 65 °C]) were studied. Lipozyme RM IM from Rhizomucor miehei was used as biocatalyst. We obtained 32.39% of ALA in SL obtained under the optimized conditions (molar ratio-1:1 [PO:CO], temperature-60 °C, reaction time-15 h). In SL, the major triacylglycerol (TAG) species (linolenoyl-linolenoyl-linolenoyl glycerol [LnLnLn], linolenoyl-linolenoyl-linoleoyl glycerol [LnLnL]) mainly from PO and linoleoyl-linoleoyl-oleoyl glycerol (LLO), linoleoyl-oleoyl-oleoyl glycerol (LOO), palmitoyl-linoleoyl-oleoyl glycerol (PLO) from CO decreased while linolenoyl-linolenoyl-oleoyl glycerol (LnLnO) (18.41%), trilinolein (LLL) (9.06%), LLO (16.66%), palmitoyl-linoleoyl-linoleoyl glycerol (PLL) (9.69%) were increased compared to that of physical blend. Total tocopherol content (28.01 mg/100 g), saponification value (SV) (192.2), and iodine value (IV) (161.9) were obtained. Furthermore, oxidative stability of the SL was also investigated by addition of 3 different antioxidants (each 200 ppm of rosemary extract [SL-ROS], BHT [SL-BHT], catechin [SL-CAT]) was added into SL and stored in 60 °C oven for 30 d. 2-Thiobabituric acid-reactive substances (TBARS) value was 0.16 mg/kg in SL-CAT and 0.18 mg/kg in SL-ROS as compared with 0.22 mg/kg in control (SL) after oxidation. The lowest peroxide value (POV, 200.9 meq/kg) and longest induction time (29.88 h) was also observed in SL-CAT. PMID:22122200

  20. Synthesis and crystal and molecular structure of three heterometallic polymeric compounds (Ln{sub 2}[LnGe{sub 6}(μ-Oedph){sub 6}(μ-O){sub 3}(μ-OH){sub 3}(H{sub 2}O){sub 4}] · xH{sub 2}O){sub n} [Ln = Nd, x ∼ 26 (I); Er, x ∼ 24 (II); Tm, x ∼ 20 (III); H{sub 4}Oedph = 1-hydroxyethylidenediphosphonic acid

    SciTech Connect

    Sergienko, V. S.; Martsinko, E. E.; Ilyukhin, A. B.; Seifullina, I. I.

    2015-03-15

    The synthesis and X-ray diffraction study of three heterometallic compounds of general formula (Ln{sub 2}[LnGe{sub 6}(μ-Oedph){sub 6}(μ-O){sub 3}(μ-OH){sub 3}(H{sub 2}O){sub 4}] · xH{sub 2}O){sub n} [Ln = Nd, x ∼ 26 (I); Er, x ∼ 24 (II); Tm, x ∼20 (III); H{sub 4}Oedph = 1-hydroxyethylidenediphosphonic acid] are performed. The basis element of structures I–III is a hexanuclear complex anion [Ge(μ-Oedph)(μ-O){sub 0.5}(μ-OH){sub 0.5}]{sub 6}{sup 9−}, in which bridging hydroxo and oxo ligands are statistically disordered with equally probability. Hexameric units are connected by Ln1(H{sub 2}O){sub 4} fragments into a framework whose channels are completely populated by disordered lanthanide atoms and water molecules.

  1. Ethyl Acetate Abatement on Copper Catalysts Supported on Ceria Doped with Rare Earth Oxides.

    PubMed

    Carabineiro, Sónia Alexandra Correia; Konsolakis, Michalis; Marnellos, George Emmanouil-Nontas; Asad, Muhammad Faizan; Soares, Olívia Salomé Gonçalves Pinto; Tavares, Pedro Bandeira; Pereira, Manuel Fernando Ribeiro; Órfão, José Joaquim de Melo; Figueiredo, José Luís

    2016-01-01

    Different lanthanide (Ln)-doped cerium oxides (Ce0.5Ln0.5O1.75, where Ln: Gd, La, Pr, Nd, Sm) were loaded with Cu (20 wt. %) and used as catalysts for the oxidation of ethyl acetate (EtOAc), a common volatile organic compound (VOC). For comparison, both Cu-free (Ce-Ln) and supported Cu (Cu/Ce-Ln) samples were characterized by N₂ adsorption at -196 °C, scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature programmed reduction in H₂. The following activity sequence, in terms of EtOAc conversion, was found for bare supports: CeO₂ ≈ Ce0.5Pr0.5O1.75 > Ce0.5Sm0.5O1.75 > Ce0.5Gd0.5O1.75 > Ce0.5Nd0.5O1.75 > Ce0.5La0.5O1.75. Cu addition improved the catalytic performance, without affecting the activity order. The best catalytic performance was obtained for Cu/CeO₂ and Cu/Ce0.5Pr0.5O1.75 samples, both achieving complete EtOAc conversion below ca. 290 °C. A strong correlation was revealed between the catalytic performance and the redox properties of the samples, in terms of reducibility and lattice oxygen availability. Νo particular correlation between the VOC oxidation performance and textural characteristics was found. The obtained results can be explained in terms of a Mars-van Krevelen type redox mechanism involving the participation of weakly bound (easily reduced) lattice oxygen and its consequent replenishment by gas phase oxygen.

  2. Ethyl Acetate Abatement on Copper Catalysts Supported on Ceria Doped with Rare Earth Oxides.

    PubMed

    Carabineiro, Sónia Alexandra Correia; Konsolakis, Michalis; Marnellos, George Emmanouil-Nontas; Asad, Muhammad Faizan; Soares, Olívia Salomé Gonçalves Pinto; Tavares, Pedro Bandeira; Pereira, Manuel Fernando Ribeiro; Órfão, José Joaquim de Melo; Figueiredo, José Luís

    2016-01-01

    Different lanthanide (Ln)-doped cerium oxides (Ce0.5Ln0.5O1.75, where Ln: Gd, La, Pr, Nd, Sm) were loaded with Cu (20 wt. %) and used as catalysts for the oxidation of ethyl acetate (EtOAc), a common volatile organic compound (VOC). For comparison, both Cu-free (Ce-Ln) and supported Cu (Cu/Ce-Ln) samples were characterized by N₂ adsorption at -196 °C, scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature programmed reduction in H₂. The following activity sequence, in terms of EtOAc conversion, was found for bare supports: CeO₂ ≈ Ce0.5Pr0.5O1.75 > Ce0.5Sm0.5O1.75 > Ce0.5Gd0.5O1.75 > Ce0.5Nd0.5O1.75 > Ce0.5La0.5O1.75. Cu addition improved the catalytic performance, without affecting the activity order. The best catalytic performance was obtained for Cu/CeO₂ and Cu/Ce0.5Pr0.5O1.75 samples, both achieving complete EtOAc conversion below ca. 290 °C. A strong correlation was revealed between the catalytic performance and the redox properties of the samples, in terms of reducibility and lattice oxygen availability. Νo particular correlation between the VOC oxidation performance and textural characteristics was found. The obtained results can be explained in terms of a Mars-van Krevelen type redox mechanism involving the participation of weakly bound (easily reduced) lattice oxygen and its consequent replenishment by gas phase oxygen. PMID:27196886

  3. Simple correction for the sample shape and radial offset effects on SQUID magnetometers: Magnetic measurements on Ln{sub 2}O{sub 3} (Ln=Gd, Dy, Er) standards

    SciTech Connect

    Morrison, Gregory; Loye, Hans-Conrad zur

    2015-01-15

    An increased focus on magnetic measurements of oriented single crystals, thin films, and magnetically dilute systems has led to a demand for the measurement of weak magnetic moments. This level of sensitivity and precision can be achieved on SQUID magnetometers by decreasing the size of the detection coils. However, the smaller detection coils can amplify two errors in the magnitude of the measured moment, the sample shape and radial offset effects, which were small and typically unaccounted for on previous magnetometers. We report a simple method to determine the radial offset of a sample by taking advantage of the two basic scan modes, DC and lock-in, typically used on magnetometers. This technique allows for the correction of the sample shape and radial offset effects in order to obtain the true moment of a sample. To show the efficacy of this technique, we report the magnetic properties of Ln{sub 2}O{sub 3} (Ln=Gd, Dy, Er). - Graphical abstract: Correction for the sample shape and radial offset effects on SQUID magnetometers using a combination of DC and VSM scan data. - Highlights: • Sample shape and radial offset effects alter the moment measured by magnetometers. • We present a simple method to correct for these sample effects on magnetometers. • We measure magnetic susceptibilities of Ln{sub 2}O{sub 3} to show the efficacy of this method.

  4. A family of 3d-4f octa-nuclear [Mn(III)(4)Ln(III)(4)] wheels (Ln = Sm, Gd, Tb, Dy, Ho, Er, and Y): synthesis, structure, and magnetism.

    PubMed

    Li, Mengyuan; Lan, Yanhua; Ako, Ayuk M; Wernsdorfer, Wolfgang; Anson, Christopher E; Buth, Gernot; Powell, Annie K; Wang, Zheming; Gao, Song

    2010-12-20

    We present the syntheses, crystal structures, and magnetochemical characterizations for a family of isostructural [Mn(4)Ln(4)] compounds (Ln = Sm, Gd, Tb, Dy, Ho, Er, and Y). They were prepared from the reactions of formic acid, propionic acid, N-n-butyl-diethanolamine, manganese perchlorate, and lanthanide nitrates under the addition of triethylamine in MeOH. The compounds possess an intriguing hetero-octanuclear wheel structure with four Mn(III) and four Ln(III) ions alternatively arranged in a saddle-like ring, where formate ions act as key carboxylate bridges. In the lattice, the molecules stack into columns in a quasi-hexagonal arrangement. Direct current (dc) magnetic susceptibility measurements indicated the depopulation of the Stark components at low temperature and/or very weak antiferromagnetic interactions between magnetic centers. The zero-field alternating current (ac) susceptibility studies revealed that the compounds containing Sm, Tb, and Dy showed frequency-dependent out-of-phase signals, indicating they are single-molecule magnets (SMMs). Magnetization versus applied dc field sweeps on a single crystal of the Dy compound down to 40 mK exhibited hysteresis depending on temperatures and field sweeping rates, further confirming that the Dy compound is a SMM. The magnetization dynamics of the Sm and Y compounds investigated under dc fields revealed that the relaxation of the Sm compound is considered to be dominated by the two-phonon (Orbach) process while the Y compound displays a multiple relaxation process.

  5. Lanthanide triangles sandwiched by tetranuclear copper complexes afford a family of hendecanuclear heterometallic complexes [Ln(III)3Cu(II)8] (Ln = La-Lu): synthesis and magnetostructural studies.

    PubMed

    Iasco, Olga; Novitchi, Ghenadie; Jeanneau, Erwann; Luneau, Dominique

    2013-08-01

    Reaction in ethanol of 3-hydroxymethylen-5-methylsalicylaldoxime (H3L) with CuCl2·2H2O and LnCl3·xH2O [Ln = La (1), Ce (2), Pr (3), Nd (4), Eu (5), Gd (6), Tb (7), Dy (8), Er (9), Yb (10), Lu (11), Ho (12)] allowed the synthesis of a family of hendecanuclear heterometallic copper(II)-lanthanide(III) clusters with general formula [Ln(III)3Cu(II)8(HL)6(μ4-O)2Cl6(H2O)8]Cl3 (1-12). According to the single-crystal X-ray diffraction investigation, the complexes are isomorphous and crystallize in the trigonal R32 group. The hendecanuclear cluster is formed by two tetrahedral μ4-oxo {Cu4} clusters assembled by three lanthanide ions sandwiched in between. Along the family, the separation between the {Cu4} moieties increases linearly from Lu to La in good correlation with ionic radius of the lanthanide ions. A comparative analysis of the magnetic data for the lanthanum (1) and lutetium (11) compounds shows the presence of ferromagnetic and antiferromagnetic interactions within the μ4-oxo {Cu4} moieties. For the gadolinium (6) and terbium (7) compounds, the magnetic interactions between the lanthanide and the copper ions are found to be ferromagnetic. The dysprosium (8) compound exhibits single-molecule magnet behavior.

  6. Small Punch Creep Studies for Optimization of Nitrogen Content in 316LN SS for Enhanced Creep Resistance

    NASA Astrophysics Data System (ADS)

    Mathew, M. D.; Ganesh Kumar, J.; Ganesan, V.; Laha, K.

    2014-02-01

    Small punch creep (SPC) studies have been carried out to evaluate the creep properties of 316LN stainless steel (SS) at 923 K (650 °C) at various stress levels. The results have been compared with uniaxial creep rupture data obtained from conventional creep tests. The minimum deflection rate was found to obey Norton power law. SPC rupture life was correlated with uniaxial creep rupture life. The influence of nitrogen content on the creep rupture properties of 316LN SS was investigated in the range of 0.07 to 0.14 wt pct. SPC rupture life increased and the minimum deflection rate decreased with the increase in nitrogen content. The trends were found to be in agreement with the results obtained from uniaxial creep rupture tests. These studies have established that SPC is a fast and reliable technique to screen creep properties of different experimental heats of materials for optimizing the chemical composition for developing creep-resistant materials.

  7. Extreme compressibility in LnFe(CN)6 coordination framework materials via molecular gears and torsion springs

    NASA Astrophysics Data System (ADS)

    Duyker, Samuel G.; Peterson, Vanessa K.; Kearley, Gordon J.; Studer, Andrew J.; Kepert, Cameron J.

    2016-03-01

    The mechanical flexibility of coordination frameworks can lead to a range of highly anomalous structural behaviours. Here, we demonstrate the extreme compressibility of the LnFe(CN)6 frameworks (Ln = Ho, Lu or Y), which reversibly compress by 20% in volume under the relatively low pressure of 1 GPa, one of the largest known pressure responses for any crystalline material. We delineate in detail the mechanism for this high compressibility, where the LnN6 units act like torsion springs synchronized by rigid Fe(CN)6 units performing the role of gears. The materials also show significant negative linear compressibility via a cam-like effect. The torsional mechanism is fundamentally distinct from the deformation mechanisms prevalent in other flexible solids and relies on competition between locally unstable metal coordination geometries and the constraints of the framework connectivity, a discovery that has implications for the strategic design of new materials with exceptional mechanical properties.

  8. Extreme compressibility in LnFe(CN)6 coordination framework materials via molecular gears and torsion springs.

    PubMed

    Duyker, Samuel G; Peterson, Vanessa K; Kearley, Gordon J; Studer, Andrew J; Kepert, Cameron J

    2016-03-01

    The mechanical flexibility of coordination frameworks can lead to a range of highly anomalous structural behaviours. Here, we demonstrate the extreme compressibility of the LnFe(CN)6 frameworks (Ln = Ho, Lu or Y), which reversibly compress by 20% in volume under the relatively low pressure of 1 GPa, one of the largest known pressure responses for any crystalline material. We delineate in detail the mechanism for this high compressibility, where the LnN6 units act like torsion springs synchronized by rigid Fe(CN)6 units performing the role of gears. The materials also show significant negative linear compressibility via a cam-like effect. The torsional mechanism is fundamentally distinct from the deformation mechanisms prevalent in other flexible solids and relies on competition between locally unstable metal coordination geometries and the constraints of the framework connectivity, a discovery that has implications for the strategic design of new materials with exceptional mechanical properties. PMID:26892560

  9. LN2-free Operation of the MEG Liquid Xenon Calorimeter by using a High-power Pulse Tube Cryocooler

    SciTech Connect

    Haruyama, T.; Kasami, K.; Nishiguchi, H.; Mihara, S.; Mori, T.; Otani, W.; Sawada, R.; Maruno, Y.; Nishitani, T.

    2006-04-27

    A high-power coaxial pulse tube cryocooler, originally developed in KEK and technology-transferred to Iwatani Industrial Gases Corp (IIGC), has been installed in a large liquid xenon calorimeter to evaluate liquid nitrogen-free (LN2-free) operation of the rare {mu}-particle decay experiment (MEG). Features of this pulse tube cryocooler include the cold-end heat exchanger, designed with sufficient surface area to ensure high-power cooling, and a cylindrical regenerator placed inside the pulse tube giving compact design and ease of fabrication. This production-level cryocooler provides a cooling power of {approx}200 W at 165 K, using a 6 kW Gifford-McMahon (GM)-type compressor. The paper describes the detailed configuration of the cryocooler, and the results of the continuous LN2-free operation of the large prototype liquid xenon calorimeter, which ran for more than 40 days without problems.

  10. LN2-free Operation of the MEG Liquid Xenon Calorimeter by using a High-power Pulse Tube Cryocooler

    NASA Astrophysics Data System (ADS)

    Haruyama, T.; Kasami, K.; Nishiguchi, H.; Mihara, S.; Mori, T.; Otani, W.; Sawada, R.; Maruno, Y.; Nishitani, T.

    2006-04-01

    A high-power coaxial pulse tube cryocooler, originally developed in KEK and technology-transferred to Iwatani Industrial Gases Corp (IIGC), has been installed in a large liquid xenon calorimeter to evaluate liquid nitrogen-free (LN2-free) operation of the rare μ-particle decay experiment (MEG). Features of this pulse tube cryocooler include the cold-end heat exchanger, designed with sufficient surface area to ensure high-power cooling, and a cylindrical regenerator placed inside the pulse tube giving compact design and ease of fabrication. This production-level cryocooler provides a cooling power of ˜200 W at 165 K, using a 6 kW Gifford-McMahon (GM)-type compressor. The paper describes the detailed configuration of the cryocooler, and the results of the continuous LN2-free operation of the large prototype liquid xenon calorimeter, which ran for more than 40 days without problems.

  11. High-power and widely tunable mid-infrared optical parametric amplification based on PPMgLN.

    PubMed

    Peng, Yuefeng; Wei, Xingbin; Luo, Xingwang; Nie, Zan; Peng, Jue; Wang, Yong; Shen, Deyuan

    2016-01-01

    We report on a high-power and widely tunable optical parametric amplifier (OPA) based on PPMgLN and pumped by a pulsed 1.064 μm MOPA laser. The operating wavelength of the OPA system is continuously tunable from 2.68 to 3.07 μm by adjusting the temperature of PPMgLN crystals, with average output power varying from 74.6 to 66.7 W for 310 W of pump power, corresponding to an optical-to-optical conversion efficiency of ∼22.8% at 2.68 μm and ∼20.5% at 3.07 μm, respectively. Output beam quality factor (M2) of the OPA was measured to be <4 over the whole tuning range. PMID:26696155

  12. Strigolactones are required for nitric oxide to induce root elongation in response to nitrogen and phosphate deficiencies in rice.

    PubMed

    Sun, Huwei; Bi, Yang; Tao, Jinyuan; Huang, Shuangjie; Hou, Mengmeng; Xue, Ren; Liang, Zhihao; Gu, Pengyuan; Yoneyama, Koichi; Xie, Xiaonan; Shen, Qirong; Xu, Guohua; Zhang, Yali

    2016-07-01

    The response of the root system architecture to nutrient deficiencies is critical for sustainable agriculture. Nitric oxide (NO) is considered a key regulator of root growth, although the mechanisms remain unknown. Phenotypic, cellular and genetic analyses were undertaken in rice to explore the role of NO in regulating root growth and strigolactone (SL) signalling under nitrogen-deficient and phosphate-deficient conditions (LN and LP). LN-induced and LP-induced seminal root elongation paralleled NO production in root tips. NO played an important role in a shared pathway of LN-induced and LP-induced root elongation via increased meristem activity. Interestingly, no responses of root elongation were observed in SL d mutants compared with wild-type plants, although similar NO accumulation was induced by sodium nitroprusside (SNP) application. Application of abamine (the SL inhibitor) reduced seminal root length and pCYCB1;1::GUS expression induced by SNP application in wild type; furthermore, comparison with wild type showed lower SL-signalling genes in nia2 mutants under control and LN treatments and similar under SNP application. Western blot analysis revealed that NO, similar to SL, triggered proteasome-mediated degradation of D53 protein levels. Therefore, we presented a novel signalling pathway in which NO-activated seminal root elongation under LN and LP conditions, with the involvement of SLs. PMID:27194103

  13. Strigolactones are required for nitric oxide to induce root elongation in response to nitrogen and phosphate deficiencies in rice.

    PubMed

    Sun, Huwei; Bi, Yang; Tao, Jinyuan; Huang, Shuangjie; Hou, Mengmeng; Xue, Ren; Liang, Zhihao; Gu, Pengyuan; Yoneyama, Koichi; Xie, Xiaonan; Shen, Qirong; Xu, Guohua; Zhang, Yali

    2016-07-01

    The response of the root system architecture to nutrient deficiencies is critical for sustainable agriculture. Nitric oxide (NO) is considered a key regulator of root growth, although the mechanisms remain unknown. Phenotypic, cellular and genetic analyses were undertaken in rice to explore the role of NO in regulating root growth and strigolactone (SL) signalling under nitrogen-deficient and phosphate-deficient conditions (LN and LP). LN-induced and LP-induced seminal root elongation paralleled NO production in root tips. NO played an important role in a shared pathway of LN-induced and LP-induced root elongation via increased meristem activity. Interestingly, no responses of root elongation were observed in SL d mutants compared with wild-type plants, although similar NO accumulation was induced by sodium nitroprusside (SNP) application. Application of abamine (the SL inhibitor) reduced seminal root length and pCYCB1;1::GUS expression induced by SNP application in wild type; furthermore, comparison with wild type showed lower SL-signalling genes in nia2 mutants under control and LN treatments and similar under SNP application. Western blot analysis revealed that NO, similar to SL, triggered proteasome-mediated degradation of D53 protein levels. Therefore, we presented a novel signalling pathway in which NO-activated seminal root elongation under LN and LP conditions, with the involvement of SLs.

  14. Aqueous Binary Lanthanide(III) Nitrate Ln(NO3)3 Electrolytes Revisited: Extended Pitzer and Bromley Treatments

    SciTech Connect

    Chatterjee, Sayandev; Campbell, Emily L.; Neiner, Doinita; Pence, Natasha; Robinson, Troy; Levitskaia, Tatiana G.

    2015-09-11

    To date, only limited thermodynamic models describing activity coefficients of the aqueous solutions of lanthanide ions are available. This work expands the existing experimental osmotic coefficient data obtained by classical isopiestic technique for the aqueous binary trivalent lanthanide nitrate Ln(NO3)3 solutions using a combination of water activity and vapor pressure osmometry measurements. The combined osmotic coefficient database for each aqueous lanthanide nitrate at 25°C, consisting of literature available data as well as data obtained in this work, was used to test the validity of Pitzer and Bromley thermodynamic models for the accurate prediction of mean molal activity coefficients of the Ln(NO3)3 solutions in wide concentration ranges. The new and improved Pitzer and Bromley parameters were calculated. It was established that the Ln(NO3)3 activity coefficients in the solutions with ionic strength up to 12 mol kg-1 can be estimated by both Pitzer and single-parameter Bromley models, even though the latter provides for more accurate prediction, particularly in the lower ionic strength regime (up to 6 mol kg-1). On the other hand for the concentrated solutions, the extended three-parameter Bromley model can be employed to predict the Ln(NO3)3 activity coefficients with remarkable accuracy. The accuracy of the extended Bromley model in predicting the activity coefficients was greater than ~95% and ~90% for all solutions with the ionic strength up to 12 mol kg-1 and and 20 mol kg-1, respectively. This is the first time that the activity coefficients for concentrated lanthanide solutions have been predicted with such a remarkable accuracy.

  15. Trends in Ln(III) Sorption to Quartz Assessed by Molecular Dynamics Simulations and Laser Induced Flourescence Studies

    SciTech Connect

    Kuta, Jadwiga; Wander, Matthew C F.; Wang, Zheming; Jiang, Siduo; Wall, Nathalie; Clark, Aurora E.

    2011-11-08

    Molecular dynamics simulations were performed to examine trends in trivalent lanthanide [Ln(III)] sorption to quartz surface SiOH0 and SiO- sites across the 4f period. Complementary laser induced fluorescence studies examined Eu(III) sorption to quartz at varying ionic strength such that the surface sorbed species could be extrapolated at zero ionic strength, the conditions under which the simulations are performed. This allowed for direct comparison of the data, enabling a molecular understanding of the surface sorbed species and the role of the ion surface charge density upon the interfacial reactivity. Thus, this combined theoretical and experimental approach aids in the prediction of the fate of trivalent radioactive contaminants at temporary and permanent nuclear waste storage sites. Potential of mean force molecular dynamics, as well as simulations of pre-sorbed Ln(III) species agrees with the spectroscopic study of Eu(III) sorption, indicating that strongly bound inner-sphere complexes are formed upon sorption to an SiO- site. The coordination shell of the ion contains 6-7 waters of hydration and it is predicted that surface OH groups dissociate from the quartz and bind within the inner coordination shell of Eu(III). Molecular simulations predict less-strongly bound inner2 sphere species in early lanthanides and more strongly bound species in late lanthanides, following trends in the ionic radius of the 4f ions. The participation of surface dissociated OHgroups within the inner coordination shell of the Ln(III) ion is, however, consistent across the series studied. Sorption to a fully protonated quartz surface is not predicted to be favorable by any Ln(III), except perhaps Lu.

  16. Cryogenic fracture behavior of 316LN in magnetic fields up to 14.6 T

    SciTech Connect

    Chan, J.W.; Chu, D.; Tseng, C.; Morris, J.W. Jr. |

    1993-07-01

    Some of the proposed magnet case alloys for the International Thermonuclear Experimental Reactor (ITER) are metastable austenitic stainless steels. The case will be subjected to high loads and can be as much as 100 mm thick. Case assembly will probably require thick section welding with its attendant chemical inhomogeneity. Even alloys that are thermally stable with respect to martensitic transformation can, under these conditions of high stresses, cryogenic temperature, and high magnetic fields, undergo transformation. Previous work at 8 T has shown a measurable magnetic field effect on the 4.2K tensile and fracture toughness properties of AISI300 series metastable austenitic stainless steels. Thus, it is important to understand how these alloys will behave under conditions of high magnetic fields and cryogenic temperature, particularly at the higher magnetic fields that will be used in ITER. 4.2K data for 316LN indicates that the change in fracture toughness is not monotonic. It initially decreases and then later increases with applied field.

  17. Corrosion Fatigue Behavior of 316LN SS in Acidified Sodium Chloride Solution at Applied Potential

    NASA Astrophysics Data System (ADS)

    Poonguzhali, A.; Pujar, M. G.; Mallika, C.; Mudali, U. Kamachi

    2015-05-01

    The influence of acidified 1 M NaCl solution by addition of 2 ml/L of HCl on the cyclic plastic deformation of AISI Type 316LN SS containing 0.07 wt.% and 0.22 wt.% N was investigated as a function of the applied potentials. The corrosion fatigue (CF) behavior of stainless steel (SS) was explained vis-a-vis the dislocation behavior, the propensity to form microcracks, and the evolution of the current transients based on the studies carried out at both room-temperature and boiling conditions. CF experiments were conducted using round tensile specimens at a stress ratio of 0.5 and a frequency of 0.1 Hz. Two different kinds of damage mechanisms were observed (I) the damage mechanism in the stable-passive state was correlated with the localization of the anodic dissolution due to a depassivation-repassivation process, whereas (II) the cyclic stress induced pitting corrosion in the metastable pitting state, which resulted in formation of microcracks. The study of the microcracking process and its evolution is a key to the physical mechanism by which the fatigue life of stainless steels would be affected in an aqueous corrosive solution under the applied potential.

  18. LnPO4 nanoparticles doped with Ac-225 and sequestered daughters for targeted alpha therapy.

    PubMed

    McLaughlin, Mark F; Robertson, David; Pevsner, Paul H; Wall, Jonathan S; Mirzadeh, Saed; Kennel, Stephen J

    2014-02-01

    For targeted alpha therapy (TAT) with 225Ac, daughter radioisotopes from the parent emissions should be controlled. Here, we report on a second-generation layered nanoparticle (NP) with improved daughter retention that can mediate TAT of lung tumor colonies. NPs of La3+, Gd3+, and 225Ac3+ ions were coated with additional layers of GdPO4 and then coated with gold via citrate reduction of NaAuCl4. MAb 201b, targeting thrombomodulin in lung endothelium, was added to a polyethylene glycol (dPEG)-COOH linker. The NPs:mAb ratio was quantified by labeling the mAb with 125I. NPs showed 30% injected dose/organ antibody-mediated uptake in the lung, which increased to 47% in mice pretreated with clodronate liposomes to reduce phagocytosis. Retention of daughter 213Bi in lung tissue was more than 70% at one hour and about 90% at 24 hours postinjection. Treatment of mice with lung-targeted 225Ac NP reduced EMT-6 lung colonies relative to cold antibody competition for targeting or phosphate-buffered saline injected controls. We conclude that LnPO4 NPs represent a viable solution to deliver the 225Ac as an in vivo α generator. The NPs successfully retain a large percentage of the daughter products without compromising the tumoricidal properties of the α-radiation.

  19. Efficient Nanosecond Dual-Signal Optical Parametric Generator with a Periodically Phase Reversed PPMgLN

    NASA Astrophysics Data System (ADS)

    Ji, Feng; Li, Xi-Fu; Zhang, Bai-Gang; Zhang, Tie-Li; Wang, Peng; Xu, De-Gang; Yao, Jian-Quan

    2007-11-01

    We report an efficient nanosecond optical parametric generator (OPG) with a periodically-phase-reversed periodically poled MgO:LiNbO3(ppr-PPMgLN), which produces two pairs of signal and idler waves. The OPG is pumped by a 1.064 μm Q-switched Nd:YVO4 laser. When the repetition rate is set at 10 kHz, the maximum average total output power of 570 mW is achieved, including 410 mW of dual-signal radiations and 160 mW of dual-idler radiations. The total conversion efficiency is 32.5%. The tunable dual-signal wavelengths in the range of 1.474-1.518 μm and 1.490-1.539 μm and the dual-idler of 3.826-3.558 μm and 3.726-3.451 μm are obtained by changing the crystal temperature from 30°C to 200°C.

  20. LnPO4 nanoparticles doped with Ac-225 and sequestered daughters for targeted alpha therapy.

    PubMed

    McLaughlin, Mark F; Robertson, David; Pevsner, Paul H; Wall, Jonathan S; Mirzadeh, Saed; Kennel, Stephen J

    2014-02-01

    For targeted alpha therapy (TAT) with 225Ac, daughter radioisotopes from the parent emissions should be controlled. Here, we report on a second-generation layered nanoparticle (NP) with improved daughter retention that can mediate TAT of lung tumor colonies. NPs of La3+, Gd3+, and 225Ac3+ ions were coated with additional layers of GdPO4 and then coated with gold via citrate reduction of NaAuCl4. MAb 201b, targeting thrombomodulin in lung endothelium, was added to a polyethylene glycol (dPEG)-COOH linker. The NPs:mAb ratio was quantified by labeling the mAb with 125I. NPs showed 30% injected dose/organ antibody-mediated uptake in the lung, which increased to 47% in mice pretreated with clodronate liposomes to reduce phagocytosis. Retention of daughter 213Bi in lung tissue was more than 70% at one hour and about 90% at 24 hours postinjection. Treatment of mice with lung-targeted 225Ac NP reduced EMT-6 lung colonies relative to cold antibody competition for targeting or phosphate-buffered saline injected controls. We conclude that LnPO4 NPs represent a viable solution to deliver the 225Ac as an in vivo α generator. The NPs successfully retain a large percentage of the daughter products without compromising the tumoricidal properties of the α-radiation. PMID:24102173

  1. Flux of Nitrogen-13 from L-(N-13)Glutamate in isolated myocardium

    SciTech Connect

    Keen, R.E.; Barrio, J.R.; Krivokapich, J.; Phelps, M.E.

    1985-05-01

    Specific activity of nitrogen-13 containing metabolites in tissue and effluent was determined following an intra-arterial bolus of non-carrier added L-(N-13)glutamate (N-13 GLU) given to isolated rabbit septa under different metabolic states which include pyruvate (2 mM), transaminase inhibition (aminooxy-acetate, AOA, 2 mM), or pyruvate with AOA superimposed on the insulin and glucose perfused septa. Six minutes after the N-13 GLU bolus administration relative tissue specific activities of glutamine, alanine, aspartate, and glutamate were approximately 3:38:52:100, respectively, in the control and pyruvate perfused septa. The lower alanine specific activity when compared with control tissue indicated that alanine output was from a pool separate from GPT alanine pools. Higher glutamate specific activity suggested that its output is from a pool(s) different than the larger intra-cellular glutamate pool(s). All interventions with AOA blocked N-13 flux through transminases altering tissue and effluent relative specific activities with increase in % N-13 and specific activities for glutamine, glutamate, ammonia, and protein concomittant with disappearance of labeled aspartate and alanine. These results indicate that N-13 distribution in myocardium after N-13 GLU administration is mainly controlled by glutamate interaction with reversible transaminases. The differences in reactant (N-13 GLU) and product specific activities are a consequence of channeling between different cytosolic and mitochondrial glutamate microcompartments.

  2. Spin-communication channels between Ln(III) bis-phthalocyanines molecular nanomagnets and a magnetic substrate

    PubMed Central

    Candini, A.; Klar, D.; Marocchi, S.; Corradini, V.; Biagi, R.; De Renzi, V.; del Pennino, U.; Troiani, F.; Bellini, V.; Klyatskaya, S.; Ruben, M.; Kummer, K.; Brookes, N. B.; Huang, H.; Soncini, A.; Wende, H.; Affronte, M.

    2016-01-01

    Learning the art of exploiting the interplay between different units at the atomic scale is a fundamental step in the realization of functional nano-architectures and interfaces. In this context, understanding and controlling the magnetic coupling between molecular centers and their environment is still a challenging task. Here we present a combined experimental-theoretical work on the prototypical case of the bis(phthalocyaninato)-lanthanide(III) (LnPc2) molecular nanomagnets magnetically coupled to a Ni substrate. By means of X-ray magnetic circular dichroism we show how the coupling strength can be tuned by changing the Ln ion. The microscopic parameters of the system are determined by ab-initio calculations and then used in a spin Hamiltonian approach to interpret the experimental data. By this combined approach we identify the features of the spin communication channel: the spin path is first realized by the mediation of the external (5d) electrons of the Ln ion, keeping the characteristic features of the inner 4 f orbitals unaffected, then through the organic ligand, acting as a bridge to the external world. PMID:26907811

  3. Spin-communication channels between Ln(III) bis-phthalocyanines molecular nanomagnets and a magnetic substrate.

    PubMed

    Candini, A; Klar, D; Marocchi, S; Corradini, V; Biagi, R; De Renzi, V; Del Pennino, U; Troiani, F; Bellini, V; Klyatskaya, S; Ruben, M; Kummer, K; Brookes, N B; Huang, H; Soncini, A; Wende, H; Affronte, M

    2016-01-01

    Learning the art of exploiting the interplay between different units at the atomic scale is a fundamental step in the realization of functional nano-architectures and interfaces. In this context, understanding and controlling the magnetic coupling between molecular centers and their environment is still a challenging task. Here we present a combined experimental-theoretical work on the prototypical case of the bis(phthalocyaninato)-lanthanide(III) (LnPc2) molecular nanomagnets magnetically coupled to a Ni substrate. By means of X-ray magnetic circular dichroism we show how the coupling strength can be tuned by changing the Ln ion. The microscopic parameters of the system are determined by ab-initio calculations and then used in a spin Hamiltonian approach to interpret the experimental data. By this combined approach we identify the features of the spin communication channel: the spin path is first realized by the mediation of the external (5d) electrons of the Ln ion, keeping the characteristic features of the inner 4 f orbitals unaffected, then through the organic ligand, acting as a bridge to the external world. PMID:26907811

  4. [Mn(III)4Ln(III)4] calix[4]arene clusters as enhanced magnetic coolers and molecular magnets.

    PubMed

    Karotsis, Georgios; Kennedy, Stuart; Teat, Simon J; Beavers, Christine M; Fowler, Drew A; Morales, Juan J; Evangelisti, Marco; Dalgarno, Scott J; Brechin, Euan K

    2010-09-22

    The use of methylene-bridged calix[4]arenes in 3d/4f chemistry produces a family of clusters of general formula [Mn(III)(4)Ln(III)(4)(OH)(4)(C4)(4)(NO(3))(2)(DMF)(6)(H(2)O)(6)](OH)(2) (where C4 = calix[4]arene; Ln = Gd (1), Tb (2), Dy (3)). The molecular structure describes a square of Ln(III) ions housed within a square of Mn(III) ions. Magnetic studies reveal that 1 has a large number of molecular spin states that are populated even at the lowest investigated temperatures, while the ferromagnetic limit S = 22 is being approached only at the highest applied fields. This, combined with the high magnetic isotropy, makes the complex an excellent magnetic refrigerant for low-temperature applications. Replacement of the isotropic Gd(III) ions with the anisotropic Tb(III) and Dy(III) ions "switches" the magnetic properties of the cluster so that 2 and 3 behave as low-temperature molecular magnets, displaying slow relaxation of the magnetization.

  5. Effect of re-irradiation by neutrons on mechanical properties of un-irradiated/irradiated SS316LN weldments

    NASA Astrophysics Data System (ADS)

    Tsuchiya, K.; Shimizu, M.; Kawamura, H.; Kalinin, G.

    2008-02-01

    Stainless steel of type SS316LN-IG (ITER Grade) is used for the branch pipeline connecting of the module coolant system and for other structures of ITER. One of the most important requirements for the branch pipeline connection is to recover various defects by welding. In the present study, characteristics of irradiated weldments were evaluated. SS316LN-IG specimens irradiated to helium contents of 3 and 10 appm He were prepared by the first neutron irradiation. Thereafter, the SS316LN-IG specimens with three different combinations of un-irradiation and irradiation were welded by a tungsten inert-gas (TIG) welding method. These weldments were re-irradiated at 150 °C up to a fast neutron fluence of about 7.5 × 10 24 n/m 2 ( E > 1 MeV). Tensile tests of the weldments and the base material were carried out at 20 and 150 °C after the re-irradiation. The results of the comparison before and after the re-irradiation showed that tensile properties of all weldment specimens with the different combinations were almost the same as those of the base materials.

  6. 2-D and 3-D phosphotungstate-based TM-Ln heterometallic derivatives constructed from dimeric [Ln({alpha}-PW{sub 11}O{sub 39}){sub 2}]{sup 11-} fragments and copper-organic complex linkers

    SciTech Connect

    Shang, Sensen; Zhao, Junwei; Chen, Lijuan; Li, Yuye; Zhang, Jingli; Li, Yanzhou; Niu, Jingyang

    2012-12-15

    Three organic-inorganic hybrid TM-Ln heterometallic phosphotungstates [Cu(dap){sub 2}(H{sub 2}O)][Cu(dap){sub 2}]{sub 3.5}[La({alpha}-HPW{sub 11}O{sub 39}){sub 2}]{center_dot}6H{sub 2}O (1) [Cu(dap){sub 2}(H{sub 2}O)]{sub 0.5}[Cu(dap){sub 2}]{sub 4}[Nd({alpha}-HPW{sub 11}O{sub 39}){sub 2}]{center_dot}4H{sub 2}O (2) and [Cu(dap){sub 2}(H{sub 2}O)]{sub 2}[Cu(dap){sub 2}]{sub 3.5}[Eu({alpha}-PW{sub 11}O{sub 39}){sub 2}]{center_dot}6H{sub 2}O (3) (dap=1,2-diaminopropane) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, optical diffuse reflectance spectra, powder X-ray diffraction (PXRD), thermogravimetric (TG) analyses and single-crystal X-ray diffraction. Their common features are that 1-3 all consist of asymmetric sandwich-type subunits [Ln({alpha}-PW{sub 11}O{sub 39}){sub 2}]{sup 11-} and [Cu(dap){sub 2}]{sup 2+} bridges. Both 1 and 2 display the 2-D (4,4)-topological sheets whereas 3 exhibits the 3-D 5-connected (4{sup 6}{center_dot}6{sup 4}) topological framework. The magnetic properties of 2 and 3 and the luminescence performance of 3 have been measured. - Graphical Abstract: Three TM-Ln heterometallic phosphotungstates 1-3 have been synthesized and characterized by elemental analyses, IR spectra, optical diffuse reflectance spectra, X-ray diffraction, thermogravimetric analyses magnetic susceptibility and luminescent properties. Highlights: Black-Right-Pointing-Pointer Cu{sup II}-Ln{sup III} heterometallic polyoxometalates. Black-Right-Pointing-Pointer 2-D and 3-D organic-inorganic hybrid phosphotungstates. Black-Right-Pointing-Pointer 2-D and 3-D structures consisting of Cu{sup II}-Ln{sup III} heterometals.

  7. Caspase-activated DNase Is Necessary and Sufficient for Oligonucleosomal DNA Breakdown, but Not for Chromatin Disassembly during Caspase-dependent Apoptosis of LN-18 Glioblastoma Cells*

    PubMed Central

    Sánchez-Osuna, María; Garcia-Belinchón, Mercè; Iglesias-Guimarais, Victoria; Gil-Guiñón, Estel; Casanelles, Elisenda; Yuste, Victor J.

    2014-01-01

    Caspase-dependent apoptosis is a controlled type of cell death characterized by oligonucleosomal DNA breakdown and major nuclear morphological alterations. Other kinds of cell death do not share these highly distinctive traits because caspase-activated DNase (DFF40/CAD) remains inactive. Here, we report that human glioblastoma multiforme-derived LN-18 cells do not hydrolyze DNA into oligonucleosomal fragments after apoptotic insult. Furthermore, their chromatin remains packaged into a single mass, with no signs of nuclear fragmentation. However, ultrastructural analysis reveals that nuclear disassembly occurs, although compacted chromatin does not localize into apoptotic nuclear bodies. Caspases become properly activated, and ICAD, the inhibitor of DFF40/CAD, is correctly processed. Using cell-free in vitro assays, we show that chromatin from isolated nuclei of LN-18 cells is suitable for hydrolysis into oligonuclesomal fragments by staurosporine-pretreated SH-SY5Y cytoplasms. However, staurosporine-pretreated LN-18 cytoplasms do not induce DNA laddering in isolated nuclei from either LN-18 or SH-SY5Y cells because LN-18 cells express lower amounts of DFF40/CAD. DFF40/CAD overexpression makes LN-18 cells fully competent to degrade their DNA into oligonucleosome-sized fragments, and yet they remain unable to arrange their chromatin into nuclear clumps after apoptotic insult. Indeed, isolated nuclei from LN-18 cells were resistant to undergoing apoptotic nuclear morphology in vitro. The use of LN-18 cells has uncovered a previously unsuspected cellular model, whereby a caspase-dependent chromatin package is DFF40/CAD-independent, and DFF40/CAD-mediated double-strand DNA fragmentation does not warrant the distribution of the chromatin into apoptotic nuclear bodies. The studies highlight a not-yet reported DFF40/CAD-independent mechanism driving conformational nuclear changes during caspase-dependent cell death. PMID:24838313

  8. The Murine Dilute Suppressor Gene Dsu Suppresses the Coat-Color Phenotype of Three Pigment Mutations That Alter Melanocyte Morphology, D, Ash and Ln

    PubMed Central

    Moore, K. J.; Swing, D. A.; Rinchik, E. M.; Mucenski, M. L.; Buchberg, A. M.; Copeland, N. G.; Jenkins, N. A.

    1988-01-01

    The murine dilute suppressor gene, dsu, was identified because of its ability to suppress the dilute coat color of mice homozygous for the retrovirally induced allele (d(v)) of the dilute locus (d). dsu is unlinked to the d locus and has recently been shown to be semidominantly inherited. The dilute phenotype of d/d mice is the consequence of abnormal melanocyte morphology. While wild-type melanocytes are dendritic, d/d melanocytes are adendritic. dsu apparently suppresses the dilute phenotype by restoring normal melanocyte morphology. In addition to d, two other loci, ashen (ash) and leaden (ln), have been identified that produce a diluted coat color associated with adendritic melanocytes. Interestingly, d and ash are closely linked on chromosome 9 while dsu and ln are located on chromosome 1. In experiments described here, we present genetic mapping data between ash and d indicating that, despite their identical phenotypes, they are separate genes and are not intragenic complementing alleles of the same locus. We also show that dsu is only loosely linked to ln (approximately 9 cM proximal) and that dsu can suppress, at least partially, the coat color of ln/ln mice and ash/ash mice. The partial suppression of ln and ash coat colors is associated with the partial restoration of normal melanocyte morphology. These studies provide new insights into the mechanism of action of dsu and into the interrelationships between members of a family of pigment genes. PMID:3410303

  9. Complexations of Ln(III) with SnS4H and Sn2S6: Solvothermal syntheses and characterizations of lanthanide coordination polymers with thiostannate and polyamine mixed ligands

    NASA Astrophysics Data System (ADS)

    Tang, Chunying; Lu, Jialin; Han, Jingyu; Liu, Yun; Shen, Yali; Jia, Dingxian

    2015-10-01

    Polymeric lanthanide complexes with thiostannate and polyamine mixed ligands, [Ln(peha)(μ-SnS4H)]n [Ln=La (1a), Nd (1b)] and [{Ln(tepa)(μ-OH)}2(μ-Sn2S6)]nnH2O [Ln=Nd (2a), Sm (2b), Gd (2c), Dy (2d)] (peha=pentaethylenehexamine, tepa=tetraethylenepentamine) were respectively prepared in peha and tepa coordinative solvents by the solvothermal methods. In 1a and 1b, the Ln3+ ions are coordinated by a hexadentate peha ligand forming [Ln(peha)]3+ units. The [SnS4H]3- anion chelates a [Ln(peha)]3+ unit via two S atoms and coordinates to another [Ln(peha)]3+ unit via the third S atom. As a result, the [Ln(peha)]3+ units are connected into coordination polymers [Ln(peha)(μ-SnS4H)]n by an unprecedented tridentate μ-η1,η2-SnS4H bridging ligands. In 2a-2d, the Ln3+ ions are coordinated by a pentadentate tepa ligand, and two [Ln(tepa)]3+ units are joined by two μ-OH bridges to form a binuclear [{Ln(tepa)(μ-OH)}2]4+ unit. Behaving as a bidentate μ-η1, η1-Sn2S6 bridging ligand, the Sn2S6 unit connects [{Ln(tepa)(μ-OH)}2]4+ units into a neutral coordination polymer [{Ln(tepa)(μ-OH)}2(μ-Sn2S6)]n via the trans S atoms. The Ln3+ ions are in distorted monocapped square antiprismatic and bicapped trigonal prismatic environments in [{Ln(peha)(μ-SnS4H)]n and [{Ln(tepa)(μ-OH)}2(μ-Sn2S6)]n, respectively. The denticities of ethylene polyamine play an important role on the formation and complexation of the thiostannate in the presence of lanthanide ions. Compounds 1a-2d show well-defined absorption edges with band gaps between 2.81 and 3.15 eV.

  10. Genetic and proteomic characterization of rpoB mutations and their effect on nematicidal activity in Photorhabdus luminescens LN2.

    PubMed

    Qiu, Xuehong; Yan, Xun; Liu, Mingxing; Han, Richou

    2012-01-01

    Rifampin resistant (Rif(R)) mutants of the insect pathogenic bacterium Photorhabdus luminescens LN2 from entomopathogenic nematode Heterorhabditis indica LN2 were genetically and proteomically characterized. The Rif(R) mutants showed typical phase one characters of Photorhabdus bacteria, and insecticidal activity against Galleria mellonella larvae, but surprisingly influenced their nematicidal activity against axenic infective juveniles (IJs) of H. bacteriophora H06, an incompatible nematode host. 13 out of 34 Rif(R) mutants lost their nematicidal activity against H06 IJs but supported the reproduction of H06 nematodes. 7 nematicidal-producing and 7 non-nematicidal-producing Rif(R) mutants were respectively selected for rpoB sequence analysis. rpoB mutations were found in all 14 Rif(R) mutants. The rpoB (P564L) mutation was found in all 7 mutants which produced nematicidal activity against H06 nematodes, but not in the mutants which supported H06 nematode production. Allelic exchange assays confirmed that the Rif-resistance and the impact on nematicidal activity of LN2 bacteria were conferred by rpoB mutation(s). The non-nematicidal-producing Rif(R) mutant was unable to colonize in the intestines of H06 IJs, but able to colonize in the intestines of its indigenous LN2 IJs. Proteomic analysis revealed different protein expression between wild-type strain and Rif(R) mutants, or between nematicidal-producing and non nematicidal-producing mutants. At least 7 putative proteins including DsbA, HlpA, RhlE, RplC, NamB (a protein from T3SS), and 2 hypothetical proteins (similar to unknown protein YgdH and YggE of Escherichia coli respectively) were probably involved in the nematicidal activity of LN2 bacteria against H06 nematodes. This hypothesis was further confirmed by creating insertion-deletion mutants of three selected corresponding genes (the downregulated rhlE and namB, and upregulated dsbA). These results indicate that the rpoB mutations greatly influence the

  11. Genetic and Proteomic Characterization of rpoB Mutations and Their Effect on Nematicidal Activity in Photorhabdus luminescens LN2

    PubMed Central

    Qiu, Xuehong; Yan, Xun; Liu, Mingxing; Han, Richou

    2012-01-01

    Rifampin resistant (RifR) mutants of the insect pathogenic bacterium Photorhabdus luminescens LN2 from entomopathogenic nematode Heterorhabditis indica LN2 were genetically and proteomically characterized. The RifR mutants showed typical phase one characters of Photorhabdus bacteria, and insecticidal activity against Galleria mellonella larvae, but surprisingly influenced their nematicidal activity against axenic infective juveniles (IJs) of H. bacteriophora H06, an incompatible nematode host. 13 out of 34 RifR mutants lost their nematicidal activity against H06 IJs but supported the reproduction of H06 nematodes. 7 nematicidal-producing and 7 non-nematicidal-producing RifR mutants were respectively selected for rpoB sequence analysis. rpoB mutations were found in all 14 RifR mutants. The rpoB (P564L) mutation was found in all 7 mutants which produced nematicidal activity against H06 nematodes, but not in the mutants which supported H06 nematode production. Allelic exchange assays confirmed that the Rif-resistance and the impact on nematicidal activity of LN2 bacteria were conferred by rpoB mutation(s). The non-nematicidal-producing RifR mutant was unable to colonize in the intestines of H06 IJs, but able to colonize in the intestines of its indigenous LN2 IJs. Proteomic analysis revealed different protein expression between wild-type strain and RifR mutants, or between nematicidal-producing and non nematicidal-producing mutants. At least 7 putative proteins including DsbA, HlpA, RhlE, RplC, NamB (a protein from T3SS), and 2 hypothetical proteins (similar to unknown protein YgdH and YggE of Escherichia coli respectively) were probably involved in the nematicidal activity of LN2 bacteria against H06 nematodes. This hypothesis was further confirmed by creating insertion-deletion mutants of three selected corresponding genes (the downregulated rhlE and namB, and upregualted dsbA). These results indicate that the rpoB mutations greatly influence the symbiotic

  12. Carbonato-bridged Ni(II)2Ln(III)2 (Ln(III) = Gd(III), Tb(III), Dy(III)) complexes generated by atmospheric CO2 fixation and their single-molecule-magnet behavior: [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH or H2O)Ln(III)(NO3)}2]·solvent [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato].

    PubMed

    Sakamoto, Soichiro; Fujinami, Takeshi; Nishi, Koshiro; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Re, Nazzareno

    2013-06-17

    Atmospheric CO2 fixation of [Ni(II)(3-MeOsaltn)(H2O)2]·2.5H2O [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato], Ln(III)(NO3)3·6H2O, and triethylamine occurred in methanol/acetone, giving a first series of carbonato-bridged Ni(II)2Ln(III)2 complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH)Ln(III)(NO3)}2] (1Gd, 1Tb, and 1Dy). When the reaction was carried out in acetonitrile/water, it gave a second series of complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(H2O)Ln(III)(NO3)}2]·2CH3CN·2H2O (2Gd, 2Tb, and 2Dy). For both series, each Ni(II)2Ln(III)2 structure can be described as two di-μ-phenoxo-bridged Ni(II)Ln(III) binuclear units bridged by two carbonato CO3(2-) units to form a carbonato-bridged (μ4-CO3)2{Ni(II)2Ln(III)2} structure. The high-spin Ni(II) ion has octahedral coordination geometry, and the Ln(III) ion is coordinated by O9 donor atoms from Ni(II)(3-MeOsaltn), bidentate NO3(-), and one and two oxygen atoms of two CO3(2-) ions. The NO3(-) ion for the first series roughly lie on Ln-O(methoxy) bonds and are tilted toward the outside, while for the second series, the two oxygen atoms roughly lie on one of the Ln-O(phenoxy) bonds due to the intramolecular hydrogen bond. The temperature-dependent magnetic susceptibilities indicated a ferromagnetic interaction between the Ni(II) and Ln(III) ions (Ln(III) = Gd(III), Tb(III), Dy(III)) for all of the complexes, with a distinctly different magnetic behavior between the two series in the lowest-temperature region due to the Ln(III)-Ln(III) magnetic interaction and/or different magnetic anisotropies of the Tb(III) or Dy(III) ion. Alternating-current susceptibility measurements under the 0 and 1000 Oe direct-current (dc) bias fields showed no magnetic relaxation for the Ni(II)2Gd(III)2 complexes but exhibited an out-of-phase signal for Ni(II)2Tb(III)2 and Ni(II)2Dy(III)2, indicative of slow relaxation of magnetization. The energy barriers, Δ/kB, for the spin flipping were estimated from the Arrhenius

  13. Analyses of Transient and Tertiary Small Punch Creep Deformation of 316LN Stainless Steel

    NASA Astrophysics Data System (ADS)

    Ganesh Kumar, J.; Ganesan, V.; Laha, K.

    2016-09-01

    Creep deformation behavior of 316LN stainless steel (SS) under small punch creep (SPC) and uniaxial creep test has been assessed and compared at 923 K (650 °C). The transient and tertiary creep deformation behaviors have been analyzed according to the equation proposed for SPC deflection, δ = δ0 + δ_{{T}} \\cdot (1 - {{e}}^{ - κ \\cdot t} ) + dot{δ }_{{s}} t + δ3 {{e}}^{{[ {φ ( {t - t_{{r}} } )} ]}} on the basis of Dobes and Cadek equation for uniaxial creep strain. Trends in the variations of (i) rate of exhaustion of transient creep ( κ) with steady-state deflection rate ( dot{δ }_{{s}} ) (ii) ` κ' with time to attain steady-state deflection rate, and (iii) initial creep deflection rate with steady-state deflection rate implied that transient SPC deformation obeyed first-order reaction rate theory. The rate of exhaustion of transient creep ( r') values that were determined from uniaxial creep tests were correlated with those obtained from SPC tests. Master curves representing transient creep deformation in both SPC and uniaxial creep tests have been derived and their near coincidence brings unique equivalence between both the test techniques. The relationships between (i) rate of acceleration of tertiary creep ( φ) and steady-state deflection rate, (ii) ` φ' and time spent in tertiary stage, and (iii) final creep deflection rate and steady-state deflection rate revealed that first-order reaction rate theory governed SPC deformation throughout the tertiary region also. Interrelationship between the transient, secondary, and tertiary creep parameters indicated that the same mechanism prevailed throughout the SPC deformation.

  14. Metabolic fate of L-(N-13) glutamate in normal isolated myocardium

    SciTech Connect

    Keen, R.E.; Krivokapich, J.; Barrio, J.R.; Douglas, A.; Wittmer, S.; Shine, K.; Phelps, M.E.

    1984-01-01

    In the present work nitrogen flux of an amino acid in myocardium is followed via arterial bolus injection of non-carrier added L-(N-13)glutamate (N-13 GLU) into the isolated rabbit septa. Incorporation of nitrogen-13 into (N-13)aspartate (N-13 ASP)(16%) and (N-13)alanine (N-13 ALA)(14%) predominates over (N-13)glutamine (N-13 GLN) (3.2%) as determined by reversed phase HPLC in normal septa 6 min after bolus injection. No N-13 ammonia or N-13 urea is detected. Introduction of the transaminase inhibitor aminooxyacetate (AOA, 2 nM) into perfusate completely blocked transaminase reaction and increased N-13 GLN (7.3%) and free N-13 ammonia (4.0%), probably resulting from glutamate dehydrogenase reaction. Inclusion of 2mM pyruvate in the perfusate resulted in 3 fold increase in N-13 ALA (44%), slight increase in N-13 GLN (5.0%) and significant decrease in N-13 ASP. Addition of 2mM AOA in the presence of pyruvate blocked production of N-13 ASP and N-13 ALA, and increased N-13 GLN slightly (6.0%). All studies had similar residual fractions (50%) except AOA treated septa (23%) indicating decreased metabolic trapping of the N-13 label. In conclusion, nitrogen-13 distribution in tissue is primarily governed by glutamate interaction with transaminases. Although the Michaelis constants of glutamate for GOT (Km = 4 nM, pig heart), GPT (Km = 8.1 mM, beef heart) and glutamine synthetase (Km = 2.5 mM, ovine brain) are similar, the transaminases play a predominant role because of their great abundance in myocardial tissue.

  15. A Comparative Evaluation of the Effect of Low Cycle Fatigue and Creep-Fatigue Interaction on Surface Morphology and Tensile Properties of 316L(N) Stainless Steel

    NASA Astrophysics Data System (ADS)

    Mariappan, K.; Shankar, Vani; Sandhya, R.; Bhaduri, A. K.; Laha, Kinkar

    2016-04-01

    In the present work, the deformation and damage evolution in 316L(N) stainless steel during low cycle fatigue (LCF) and creep-fatigue interaction (CFI) loadings have been compared by evaluating the residual tensile properties. Towards this, LCF and CFI experiments were carried out at constant strain amplitude of ±0.6 pct, strain rate of 3 × 10-3 s-1 and temperature of 873 K (600 °C). During CFI tests, 30 minutes hold period was introduced at peak tensile strain. Experiments were interrupted up to various levels of fatigue life viz. 5, 10, 30, 50, and 60 pct of the total fatigue life ( N f) under both LCF and CFI conditions. The specimens subjected to interrupted fatigue loadings were subsequently monotonically strained at the same strain rate and temperature up to fracture. Optical and scanning electron microscopy and profilometry were conducted on the untested and tested samples to elucidate the damage evolution during the fatigue cycling under both LCF and CFI conditions. The yield strength (YS) increased sharply with the progress of fatigue damage and attained saturation within 10 pct of N f under LCF condition. On the contrary, under CFI loading condition, the YS continuously increased up to 50 pct of N f, with a sharp increase of YS up to 5 pct of N f followed by a more gradual increase up to 50 pct of N f. The difference in the evolution of remnant tensile properties was correlated with the synergistic effects of the underlying deformation and damage processes such as cyclic hardening/softening, oxidation, and creep. The evolution of tensile properties with prior fatigue damage has been correlated with the change in surface roughness and other surface features estimated by surface replica technique and fractography.

  16. Heterobimetallic lanthanide-gold coordination polymers: structure and emissive properties of isomorphous [(n)Bu4N]2[Ln(NO3)4Au(CN)2] 1-D chains.

    PubMed

    Roberts, Ryan J; Li, Xiaobo; Lacey, Tye F; Pan, Zhong; Patterson, Howard H; Leznoff, Daniel B

    2012-06-21

    A new series of lanthanide-containing dicyanoaurate coordination polymers, [(n)Bu(4)N](2)[Ln(NO(3))(4)Au(CN)(2)] (Ln = Nd, Eu, Gd or Tb), were synthesized and structurally characterized. They form an isomorphous series, crystallizing in the space group I2(1)2(1)2(1). The structure is composed of a one dimensional zigzag of Ln-N-C-Au-C-N-Ln chains with no intra- or inter-chain aurophilic interactions. The series is related to and can be described as a reduced dimensionality analogue of the previously studied Ln[Au(CN)(2)](3)·3H(2)O. Unlike the Ln[Au(CN)(2)](3)·3H(2)O series, there is no efficient energy transfer between dicyanoaurate and the lanthanide metal centers in the complexes and they essentially act as two separate emissive chromophores.

  17. Uniform AMoO{sub 4}:Ln (A=Sr{sup 2+}, Ba{sup 2+}; Ln=Eu{sup 3+}, Tb{sup 3+}) submicron particles: Solvothermal synthesis and luminescent properties

    SciTech Connect

    Yang Piaoping; Li Chunxia; Wang Wenxin; Quan Zewei; Gai Shili; Lin Jun

    2009-09-15

    Rare-earth ions (Eu{sup 3+}, Tb{sup 3+}) doped AMoO{sub 4} (A=Sr, Ba) particles with uniform morphologies were successfully prepared through a facile solvothermal process using ethylene glycol (EG) as protecting agent. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FT-IR), photoluminescence (PL) spectra and the kinetic decays were performed to characterize these samples. The XRD results reveal that all the doped samples are of high purity and crystallinity and assigned to the tetragonal scheelite-type structure of the AMoO{sub 4} phase. It has been shown that the as-synthesized SrMoO{sub 4}:Ln and BaMoO{sub 4}:Ln samples show respective uniform peanut-like and oval morphologies with narrow size distribution. The possible growth process of the AMoO{sub 4}:Ln has been investigated in detail. The EG/H{sub 2}O volume ratio, reaction temperature and time have obvious effect on the morphologies and sizes of the as-synthesized products. Upon excitation by ultraviolet radiation, the AMoO{sub 4}:Eu{sup 3+} phosphors show the characteristic {sup 5}D{sub 0}-{sup 7}F{sub 1-4} emission lines of Eu{sup 3+}, while the AMoO{sub 4}:Tb{sup 3+} phosphors exhibit the characteristic {sup 5}D{sub 4}-{sup 7}F{sub 3-6} emission lines of Tb{sup 3+}. These phosphors exhibit potential applications in the fields of fluorescent lamps and light emitting diodes (LEDs). - Graphical abstract: Uniform rare-earth ions (Eu{sup 3+}, Tb{sup 3+}) doped AMoO{sub 4} (A=Sr, Ba) submicron phosphors with tetragonal scheelite-type structure have been prepared through a facile solvothermal process using EG as reaction media. Display Omitted

  18. Towards inert and preorganized d-block-containing receptors for trivalent lanthanides: the synthesis and characterization of triple-helical monometallic Os(II) and bimetallic Os(II)-Ln(III) complexes.

    PubMed

    Riis-Johannessen, Thomas; Dupont, Nathalie; Canard, Gabriel; Bernardinelli, Gérald; Hauser, Andreas; Piguet, Claude

    2008-07-28

    The mononuclear Os(II) complex [Os()(3)](PF(6))(2) ( = 5-methyl(1-methylbenzimidazol-2-yl)pyridine) is an obvious candidate for the design of an inert d-block-based tripodal receptor capable of binding and photosensitizing trivalent lanthanides (Ln(III)). It has thus been prepared and its two enantiomeric meridional (Delta-mer and Lambda-mer) and facial (rac-fac) isomers have been separated by ion-exchange chromatography. The optical isomers have been characterized by CD spectroscopy and assignments of absolute configuration confirmed by an X-ray crystallographic study of Lambda-mer-[Os()(3)](PF(6))(2).1.5MeCN (monoclinic, P2(1), Z = 4). Comparison of the latter structure with that of racemic fac-[Os()(3)](PF(6))(2) (monoclinic, C2/c, Z = 8) and [Os(bipy)(3)](PF(6))(2) (where bipy = 2,2'-bipyridine) shows minimal structural variations, but differences are observed in the photophysical and electrochemical properties of the respective compounds. Luminescence emissions from Os(II) complexes of are typically lower in energy, with shorter lifetimes and lower quantum yields than their bipy analogues, whilst metal-centred oxidation processes are more facile due to the enhanced pi-donor ability of . The key relationships between these parameters are discussed. Finally, though challenged by (i) the low reactivity of many osmium precursors and (ii) the irreversible formation of competing side products, the synthesis and purification of the heterobimetallic triple-stranded helicate HHH-[OsLu()(3)](CF(3)SO(3))(5) has been realised, in which is a segmental ligand containing the same bidentate unit as that found in further connected to a tridentate binding site adapted for complexing Ln(III). Its solid-state structure has been established by X-ray crystallography (triclinic, P1, Z = 2). PMID:18615212

  19. Comparative methyl linoleate and methyl linolenate oxidation in the presence of bovine serum albumin at several lipid/protein ratios.

    PubMed

    Zamora, Rosario; Hidalgo, Francisco J

    2003-07-30

    The oxidation of methyl linoleate (LMe) and methyl linolenate (LnMe) in the presence of bovine serum albumin (BSA) in the dark at 60 degrees C was studied to analyze the role of the type of fatty acid and the protein/lipid ratio on the relative progression of the processes involved when lipid oxidation occurs in the presence of proteins. The disappearance of the fatty acid, the formation of primary and secondary products of lipid peroxidation, the loss of amino acid residues, the production of oxidized lipid/amino acid reaction products, and the development of color and fluorescence were studied as a function of incubation time in protein/lipid samples at 10:1, 6:1, and 3:1 w/w ratios. The incubation of LMe and LnMe in the presence of BSA at 60 degrees C rapidly produced lipid peroxidation and protein damage. Although reaction rates were much faster for LnMe than for LMe, both fatty acids had similar behaviors, and LnMe seemed to be only slightly more reactive than LMe for BSA by producing a higher increase of protein pyrroles in the protein and the development of increased browning and fluorescence. The protein/lipid ratio also influenced the relative progress of the reactions implicated. Thus, a lower protein/lipid ratio increased sample oxidation and protein damage. This also produced an increased browning, in accordance with the mechanisms proposed for browning production by oxidized lipid/protein reactions. On the contrary, browning of extracted lipids increased at higher protein/lipid ratios. This opposite tendency allowed evaluation of the overall significance of the different browning processes implicated in the final colors observed, concluding that color changes observed in BSA/lipid samples were mostly a consequence of oxidized lipid/protein reactions. PMID:14705893

  20. Nanoscale {LnIII(24)ZnII(6)} Triangular Metalloring with Magnetic Refrigerant, Slow Magnetic Relaxation, and Fluorescent Properties.

    PubMed

    Zhang, Li; Zhao, Lang; Zhang, Peng; Wang, Chao; Yuan, Sen-Wen; Tang, Jinkui

    2015-12-01

    The self-assembly of Ln(ClO4)3 · 6H2O and Zn(OAc)2 · 2H2O with pyrazine-2-carboxylic acid (HL) results in the formation of three novel nanosized {LnIII(24)ZnII(6)} triangular metallorings, [Gd24Zn6L24(OAc)22(μ3-OH)30(H2O)14](ClO4)7(OAc) · 2CH3OH · 26H2O (1), [Tb24Zn6L24(OAc)22(μ3-OH)30(CH3O)2(CH3OH)2(H2O)10](ClO4)5(OH) · 6CH3OH · 12H2O (2), and (H3O)[Dy24Zn6L24(OAc)22(μ3-OH)30(H2O)14](ClO4)7(OAc)2 · 4CH3OH · 22H2O (3), having the largest nuclearity among any known Ln/Zn clusters. Magnetic and luminescent studies reveal the special prowess for each lanthanide complex. Magnetic studies reveal that 1 exhibits a significant cryogenic magnetocaloric effect with a maximum -ΔSm (isothermal magnetic entropy change) value of 30.0 J kg(-1) K(-1) at 2.5 K and 7 T and that a slow magnetization relaxation is observed for the dysprosium analogue. In addition, the solid-state photophysical properties of 2 display strong characteristic Tb(III) photoluminescent emission in the visible region, suggesting that Tb(III)-based luminescence is sensitized by the effective energy transfer from the ligand HL to the metal centers. PMID:26600284

  1. Evaluation of DC electric field distribution of PPLP specimen based on the measurement of electrical conductivity in LN2

    NASA Astrophysics Data System (ADS)

    Hwang, Jae-Sang; Seong, Jae-Kyu; Shin, Woo-Ju; Lee, Jong-Geon; Cho, Jeon-Wook; Ryoo, Hee-Suk; Lee, Bang-Wook

    2013-11-01

    High temperature superconducting (HTS) cable has been paid much attention due to its high efficiency and high current transportation capability, and it is also regarded as eco-friendly power cable for the next generation. Especially for DC HTS cable, it has more sustainable and stable properties compared to AC HTS cable due to the absence of AC loss in DC HTS cable. Recently, DC HTS cable has been investigated competitively all over the world, and one of the key components of DC HTS cable to be developed is a cable joint box considering HVDC environment. In order to achieve the optimum insulation design of the joint box, analysis of DC electric field distribution of the joint box is a fundamental process to develop DC HTS cable. Generally, AC electric field distribution depends on relative permittivity of dielectric materials but in case of DC, electrical conductivity of dielectric material is a dominant factor which determines electric field distribution. In this study, in order to evaluate DC electric field characteristics of the joint box for DC HTS cable, polypropylene laminated paper (PPLP) specimen has been prepared and its DC electric field distribution was analyzed based on the measurement of electrical conductivity of PPLP in liquid nitrogen (LN2). Electrical conductivity of PPLP in LN2 has not been reported yet but it should be measured for DC electric field analysis. The experimental works for measuring electrical conductivity of PPLP in LN2 were presented in this paper. Based on the experimental works, DC electric field distribution of PPLP specimen was fully analyzed considering the steady state and the transient state of DC. Consequently, it was possible to determine the electric field distribution characteristics considering different DC applying stages including DC switching on, DC switching off and polarity reversal conditions.

  2. Creep deformation and fracture behavior of types 316 and 316L(N) stainless steels and their weld metals

    NASA Astrophysics Data System (ADS)

    Sasikala, G.; Mannan, S. L.; Mathew, M. D.; Rao, K. Bhanu

    2000-04-01

    The creep properties of a nuclear-grade type 316(L) stainless steel (SS) alloyed with nitrogen (316L(N) SS) and its weld metal were studied at 873 and 923 K in the range of applied stresses from 100 to 335 MPa. The results were compared with those obtained on a nuclear-grade type 316 SS, which is lean in nitrogen. The creep rupture lives of the weld metals were found to be lower than those of the respective base metals by a factor of 5 to 10. Both the base and weld metals of 316L(N) SS exhibited better resistance to creep deformation compared to their 316 SS counterparts at identical test conditions. A power-law relationship between the minimum creep rate and applied stress was found to be obeyed for both the base and weld metals. Both the weld metals generally exhibited lower rupture elongation than the respective base metals; however, at 873 K, the 316 SS base and weld metals had similar rupture elongation at identical applied stresses. Comparison of the rupture lives of the two steels to the ASME curves for the expected minimum stress to rupture for 316 SS base and weld metals showed that, for 316L(N) SS, the specifications for maximum allowable stresses based on data for 316 SS could prove overconservative. The influence of nitrogen on the creep deformation and fracture behavior, especially in terms of its modifying the precipitation kinetics, is discussed in light of the microstructural observations. In welds containing δ ferrite, the kinetics of its transformation and the nature of the transformation products control the deformation and fracture behavior. The influence of nitrogen on the δ ferrite transformation behavior and coarsening kinetics is also discussed, on the basis of extensive characterization by metallographic techniques.

  3. Evolution of Oxidative Continental Weathering

    NASA Astrophysics Data System (ADS)

    Konhauser, Kurt; Lalonde, Stefan

    2014-05-01

    The Great Oxidation Event (GOE) is currently viewed as a protracted process during which atmospheric oxygen levels increased above 10-5 times the present atmospheric level. This value is based on the loss of sulphur isotope mass independent fractionation (S-MIF) from the rock record, beginning at 2.45 Ga and disappearing by 2.32 Ga. However, a number of recent papers have pushed back the timing for oxidative continental weathering, and by extension, the onset of atmospheric oxygenation several hundreds of million years earlier despite the presence of S-MIF (e.g., Crowe et al., 2013). This apparent discrepancy can, in part, be resolved by the suggestion that recycling of older sedimentary sulphur bearing S-MIF might have led to this signal's persistence in the rock record for some time after atmospheric oxygenation (Reinhard et al., 2013). Here we suggest another possibility, that the earliest oxidative weathering reactions occurred in environments at profound redox disequilibrium with the atmosphere, such as biological soil crusts, riverbed and estuarine sediments, and lacustrine microbial mats. We calculate that the rate of O2 production via oxygenic photosynthesis in these terrestrial microbial ecosystems provides largely sufficient oxidizing potential to mobilise sulphate and a number of redox-sensitive trace metals from land to the oceans while the atmosphere itself remained anoxic with its attendant S-MIF signature. These findings reconcile geochemical signatures in the rock record for the earliest oxidative continental weathering with the history of atmospheric sulphur chemistry, and demonstrate the plausible antiquity of a terrestrial biosphere populated by cyanobacteria. Crowe, S.A., Dossing, L.N., Beukes, N.J., Bau, M., Kruger, S.J., Frei, R. & Canfield, D.E. Atmospheric oxygenation three billion years ago. Nature 501, 535-539 (2013). Reinhard, C.T., Planavsky, N.J. & Lyons, T.W. Long-term sedimentary recycling of rare sulphur isotope anomalies. Nature 497

  4. Induction of phenazine biosynthesis in cultures of Pseudomonas aeruginosa by L-N-(3-oxohexanoyl)homoserine lactone.

    PubMed

    Stead, P; Rudd, B A; Bradshaw, H; Noble, D; Dawson, M J

    1996-06-15

    A range of Pseudomonas spp. and other Gram-negative bacteria were screened for induction of antimicrobial activity in response to the autoregulatory factor L-N-(3-oxohexanoyl)homoserine lactone. In one of these, P. aeruginosa ATCC 10145, the production of phenazine metabolites was shown to be inducible in a dose-dependent manner. The production of phenazine-1-carboxamide increased over 50-fold compared to control cultures when supplemented with 200 micrograms/ml of the autoregulator. In addition, the production of an unidentified polar antibacterial substance by this strain increased with autoregulator concentration.

  5. Daily mortality and air pollutants: findings from Köln, Germany.

    PubMed Central

    Spix, C; Wichmann, H E

    1996-01-01

    STUDY OBJECTIVE AND DESIGN: For the APHEA study, the short term effects of air pollutants on human health were investigated in a comparable way in various European cities. Daily mortality was used as one of the health effects indicators. This report aims to demonstrate the steps in epidemiological model building in this type of time series analysis aimed at detecting short term effects under a poisson distribution assumption and shows the tools for decision making. In addition, it assesses the impact of these steps on the pollution effect estimates. SETTING: Köln, Germany, is a city of one million inhabitants. It is densely populated with a warm, humid, unfavourable climate and a high traffic density. In previous studies, smog episodes were found to increase mortality and higher sulphur dioxide (SO2) levels were connected with increases in the number of episodes of croup. PARTICIPANTS, MATERIALS AND METHODS: Daily total mortality was obtained for 1975-85. SO2, total suspended particulates, and nitrogen dioxide (NO2) data were available from two to five stations for the city area, and size fractionated PM7 data from a neighbouring city. The main tools were time series plots of the raw data, predicted and residual data, the partial autocorrelation function and periodogram of the residuals, cross correlations of prefiltered series, plots of categorised influences, chi 2 statistics of influences and sensitivity analyses taking overdispersion and autocorrelation into account. RESULTS AND CONCLUSIONS: With regard to model building, it is concluded that seasonal and epidemic correction are the most important steps. The actual model chosen depends very much on the properties of the data set. For the pollution effect estimates, trend, season, and epidemic corrections are important to avoid overestimation of the effect, while an appropriate short term meterology influence correction model may actually prevent underestimation. When the model leaves very little over

  6. Syntheses, structure and properties of three-dimensional pillared-layer Ag(I)-Ln(III) heterometallic coordination polymers based on mixed isonicotinate and hemimellitate ligands

    SciTech Connect

    Li, Xinfa; Cao, Rong

    2012-12-15

    Three pillared-layer 4d-4f Ag(I)-Ln(III) heterometallic coordination polymers (HCPs), formulated as [Ln{sub 2}Ag(hma){sub 2}(ina)(H{sub 2}O){sub 2}]{sub n} nH{sub 2}O [Ln=La(1), Pr(2), Nd(3); Hina=isonicotinic acid, H{sub 3}hma=hemimellitic acid], have been synthesized under hydrothermal conditions. Single-crystal and powder X-ray diffractions confirm that they are isostructural, which features a three-dimensional (3D) pillared-layer heterometallic structure built upon the strictly alternate arrangement of lanthanide-organic layers and [Ag(ina)] pillars. The layers and pillars are connected to each other by Ln-O and Ag-O coordination bonds. The photoluminescent property of the Nd derivative (3) has also been investigated. - Graphical abstract: Three pillared-layer 4d-4f Ag(I)-Ln(III) heterometallic coordination polymers have been synthesized and structurally characterized. Highlights: Black-Right-Pointing-Pointer Three 3D pillared-layer 4d-4f HCPs were synthesized by hydrothermal reactions. Black-Right-Pointing-Pointer The synergistic coordination strategy was employed. Black-Right-Pointing-Pointer It opens new perspective for the construction of structurally diversified 4d-4f HCPs.

  7. Magnetic and electrical properties of flux grown single crystals of Ln{sub 6}M{sub 4}Al{sub 43} (Ln=Gd, Yb; M=Cr, Mo, W)

    SciTech Connect

    Kangas, Michael J.; Treadwell, LaRico J.; Haldolaarachchige, Neel; McAlpin, Jacob D.; Young, David P.; Chan, Julia Y.

    2013-01-15

    Millimeter-sized single crystals of Ln{sub 6}M{sub 4}Al{sub 43} (Ln=Gd, Yb; M=Cr, Mo, W) were successfully grown with a molten aluminum flux. Synthetic conditions and physical properties for single crystals of all six analogs are discussed. The compounds exhibit metallic resistivity with room temperature values between 0.1 and 0.6 m{Omega}-cm. The Yb analogs are Pauli paramagnets with the Yb ion adopting the nonmagnetic divalent configuration (Yb{sup 2+}). Gd{sub 6}Cr{sub 4}Al{sub 43}, Gd{sub 6}Mo{sub 4}Al{sub 43}, and Gd{sub 6}W{sub 4}Al{sub 43} appear to order antiferromagnetically at 19, 15, and 15 K, respectively. - Graphical abstract: The crystal structure of Yb{sub 6}Cr{sub 4}Al{sub 43}. The light and dark green polyhedra show the chromium sublattice. Highlights: Black-Right-Pointing-Pointer Single crystals up to 0.5 cm in length were grown with a molten aluminum flux. Black-Right-Pointing-Pointer Physical property measurements were conducted on single crystals. Black-Right-Pointing-Pointer Gadolinium analogs appear to order antiferromagnetically with positive {theta}. Black-Right-Pointing-Pointer All analogs show metallic resistivity.

  8. Hydrothermal synthesis and structural characterization of a family of lanthanide tartrates: [Ln 2(C 4H 4O 6) 3(H 2O) 3]·1.5H 2O (Ln = La, Ce, Pr, Nd, Sm)

    NASA Astrophysics Data System (ADS)

    Athar, Muhammad; Li, Guanghua; Shi, Zhan; Chen, Yan; Feng, Shouhua

    2008-12-01

    Coordination polymers containing lanthanides with tartaric acid [Ln 2(C 4H 4O 6) 3(H 2O) 3]·1.5H 2O (Ln = La, Ce, Pr, Nd, Sm and C 4H 4O 6 = D(-) or L(+) tartrate anion) have been synthesized using hydrothermal techniques and characterized by single crystal X-ray diffraction. The compounds are all isotypic with a monoclinic crystal system in the P2 1/ n space group. The asymmetric units of coordination polymers contain two metal centers having different coordination environments. One metal is bonded to four tartrate groups having three D and one L isomers (or three L and one D isomers), whereas the other metal is bonded to five tartrate groups having two D and three L isomers (or two L and three D isomers). Each trivalent metal center is coordinated to nine oxygen atoms that originate from carboxylate and hydroxyl groups of the tartrate anions and water molecules. These new polymers have three-dimensional structures containing open channels that are occupied by non-coordinating water molecules. Thermogravimetric and differential thermal analyses and adsorption of nitrogen have also been studied for these compounds.

  9. Chemical and structural changes in Ln{sub 2}NiO{sub 4+δ} (Ln=La, Pr or Nd) lanthanide nickelates as a function of oxygen partial pressure at high temperature

    SciTech Connect

    Flura, Aurélien; Dru, Sophie; Nicollet, Clément; Vibhu, Vaibhav; Fourcade, Sébastien; Lebraud, Eric; Rougier, Aline; Bassat, Jean-Marc; Grenier, Jean-Claude

    2015-08-15

    The chemical stability of lanthanide nickelates Ln{sub 2}NiO{sub 4+δ} (Ln=La, Pr or Nd) has been studied in the temperature range 25–1300 °C, either in air or at low pO{sub 2} (down to 10{sup −4} atm). Thermal gravimetry analysis (TGA) measurements coupled with X-ray diffraction (XRD) characterization have shown that all compounds retain their K{sub 2}NiF{sub 4}-type structure in these conditions, while remaining over-stoichiometric in oxygen up to 1000 °C. Only Nd{sub 2}NiO{sub 4+δ} starts to decompose into Nd{sub 2}O{sub 3} and NiO above 1000 °C, at pO{sub 2}=10{sup −4} atm. In addition, a careful analysis of the lanthanide nickelates structural features has been performed by in situ XRD, as a function of temperature and pO{sub 2}. For all compounds, a structural transition has been always observed in the temperature range 200–400 °C, in air or at pO{sub 2}=10{sup −4} atm. In addition, their cell volume did not vary upon the variation of the oxygen partial pressure. Therefore, these materials do not exhibit a chemical expansion in these conditions, which is beneficial for a fuel cell application as cathode layers. Additional dilatometry measurements have revealed that a temperature as high as 950 °C for Pr{sub 2}NiO{sub 4+δ} or 1100 °C for La{sub 2}NiO{sub 4+δ} and Nd{sub 2}NiO{sub 4+δ} has to be reached in order to begin the sintering of the material particles, which is of primary importance to obtain an efficient electronic/ionic conduction in the corresponding designed cathode layers. Besides, excellent matching was found between the thermal expansion coefficients of lanthanide nickelates and SOFC electrolytes such as 8wt% yttria stabilized zirconia (8YSZ) or Ce{sub 0.8}Gd{sub 0.2}O{sub 2−δ} (GDC), at least from 400 °C up to 1400 °C in air or up to 1200 °C at pO{sub 2}=10{sup −4} atm. - Graphical abstract: This study reports the good chemical stability of oxygen overstoichiometric Ln2NiO4+δ(Ln = La, Pr or Nd) at high temperatures

  10. Effect of Elevated CO2 Concentration, Elevated Temperature and No Nitrogen Fertilization on Methanogenic Archaeal and Methane-Oxidizing Bacterial Community Structures in Paddy Soil

    PubMed Central

    Liu, Dongyan; Tago, Kanako; Hayatsu, Masahito; Tokida, Takeshi; Sakai, Hidemitsu; Nakamura, Hirofumi; Usui, Yasuhiro; Hasegawa, Toshihiro; Asakawa, Susumu

    2016-01-01

    Elevated concentrations of atmospheric CO2 ([CO2]) enhance the production and emission of methane in paddy fields. In the present study, the effects of elevated [CO2], elevated temperature (ET), and no nitrogen fertilization (LN) on methanogenic archaeal and methane-oxidizing bacterial community structures in a free-air CO2 enrichment (FACE) experimental paddy field were investigated by PCR-DGGE and real-time quantitative PCR. Soil samples were collected from the upper and lower soil layers at the rice panicle initiation (PI) and mid-ripening (MR) stages. The composition of the methanogenic archaeal community in the upper and lower soil layers was not markedly affected by the elevated [CO2], ET, or LN condition. The abundance of the methanogenic archaeal community in the upper and lower soil layers was also not affected by elevated [CO2] or ET, but was significantly increased at the rice PI stage and significantly decreased by LN in the lower soil layer. In contrast, the composition of the methane-oxidizing bacterial community was affected by rice-growing stages in the upper soil layer. The abundance of methane-oxidizing bacteria was significantly decreased by elevated [CO2] and LN in both soil layers at the rice MR stage and by ET in the upper soil layer. The ratio of mcrA/pmoA genes correlated with methane emission from ambient and FACE paddy plots at the PI stage. These results indicate that the decrease observed in the abundance of methane-oxidizing bacteria was related to increased methane emission from the paddy field under the elevated [CO2], ET, and LN conditions. PMID:27600710

  11. Influence of nitrogen-induced grain refinement on mechanical properties of nitrogen alloyed type 316LN stainless steel

    NASA Astrophysics Data System (ADS)

    Kim, Dae Whan

    2012-01-01

    Tensile, fatigue, and creep tests were conducted to investigate the effect of grain refinement by the addition of nitrogen on mechanical properties of nitrogen alloyed type 316LN stainless steel. Grain size was reduced from 100 μm to 47 μm as nitrogen concentration was increased from 0.04% (N04) to 0.10% (N10). When nitrogen concentration was increased, there was a 20% increase in yield stress and a 14% increase in UTS, respectively. Elongation was not significantly changed with increasing nitrogen concentration. As nitrogen concentration was increased, there was a 41% increase in fatigue life and an approximately sixfold increase in the time to rupture. As grain size was reduced from 100 μm to 47 μm, there was an 8% increase in yield stress and a 3% increase in UTS, respectively. Elongation was little changed with decreasing grain size. As grain size was reduced from 100 μm to 47 μm, there was a 9% increase in fatigue life and a 23% increase in the time to rupture. The grain refinement achieved by the addition of nitrogen improved the high temperature mechanical properties of nitrogen alloyed type 316LN stainless steel but was not the main mechanism for improvement of mechanical properties.

  12. Antigenic Protein In Microgravity-Grown Human Mixed Mullerian Tumor (LN1) Cells Preserved In RNA Stabilizing Agent

    NASA Technical Reports Server (NTRS)

    Hammond, Dianne K.; Becker, Jeanne; Holubec, K.; Baker, T. L.; Love, J. E.

    2004-01-01

    Cells treated with RNAlater(TradeMark) have previously been shown to contain antigenic proteins that can be visualized using Western blot analysis. These proteins seem to be stable for several months when stored in RNA stabilizer at 4 C. Antigenic protein can be recovered from cells that have been processed using an Ambion RNAqueous(Registered TradeMark) kit to remove RNA. In this set of experiments, human mixed Mullerian tumor (LN1) cells grown on the International Space Station during Expedition 3 were examined for antigenic stability after removal of RNA. The cells were stored for three months in RNAlater(TradeMark) and RNA was extracted. The RNA filtrate Containing the protein was precipitated, washed, and suspended in buffer containing sodium dodecyl sulfate (SDS). Samples containing equal concentrations of protein were loaded onto SDS-polyacrylamide gels. Proteins were separated by electrophoresis and transferred by Western blot to polyvinylidene fluoride (PVDF) membrane. The Western blots were stained with an enhanced chemiluminescent ECL(Registered TradeMark)Plus detection kit (Amersham) and scanned using a Storm 840 gel image analyzer (Amersham, Molecular Dynamics). ImageQuant(Registered TradeMark)a software was used to quantify the densities of the protein bands. The ground control and flight LN1 cell samples showed a similar staining pattern over time with antibodies to vimentin, glyceraldehyde-3-phosphate dehydrogenase, and epithelial membrane antigens.

  13. Syntheses, crystal structures and properties of series of 4d–4f ln(III)–Ag(I) heterometallic coordination polymers

    SciTech Connect

    Ran, Xing-Rui; Wang, Ning; Xie, Wei-Ping; Xiong, Yan-Ju; Cheng, Qian; Long, Yi; Yue, Shan-Tang; Liu, Ying-Liang

    2015-05-15

    By control of the experimental parameters such as ligands, pH value and reacting temperature, series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction, namely, ([Ln{sup III}Ag{sup I}(na)(ina)(ox)]·2(H{sub 2}O)){sub n} [Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5), Ho(6), Y(7), Yb(8)], have been successfully synthesized under hydrothermal conditions and structurally characterized. All the complexes are characterized by elemental analyses, FT-IR spectroscopy, Powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Furthermore, the luminescence properties of compounds 2 and 4 and the magsnetic properties of complexes 3 and 5 were also investigated in detail. - Graphical abstract: Series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction which are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. - Highlights: • Complexes 1–8 are first built by three kinds of organic ligands based on nicotinic acid and isonicotinic acid. • PCPs 1–8 are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. • The total solvent-accessible volume of PCP 2 comprises 11.6% of the crystal volume after dislodging the free water molecules. • Complexes 2 and 4 exhibit characteristic lanthanide-centered luminescence, while compounds 3 and 5 show antiferromagnetic behaviors.

  14. Nitric oxide release from nitro-fatty acids in Arabidopsis roots

    PubMed Central

    Mata-Pérez, Capilla; Sánchez-Calvo, Beatriz; Begara-Morales, Juan C.; Padilla, María N.; Valderrama, Raquel; Corpas, Francisco J.; Barroso, Juan B.

    2016-01-01

    ABSTRACT In recent years, research on the involvement of nitric oxide (NO) in plant systems has remarkably grown. However, most of the interest in this molecule has been focused on its ability to mediate different post-translational modifications (NO-PTM) in biomolecules, mainly nitration and S-nitrosylation of proteins, and its involvement in physiological and stress situations. Nevertheless, very recently the nitration of other molecules such as fatty acids has commanded increasingly greater attention. In the last February issue of Plant Physiology, we again reported on the endogenous occurrence of nitro-fatty acids (NO2-FAs), specifically nitro-linolenic acid (NO2-Ln), in the model plant Arabidopsis thaliana. The analysis of the presence of this nitro-fatty acid showed that levels of NO2-Ln decreased throughout the plant development with the higher levels detected in seeds and young seedlings of this plant. Furthermore, through a transcriptomic analysis by RNA-seq technology applying NO2-Ln to A. thaliana cell-suspension cultures, we found high induction in the transcriptional expression of several heat-shock proteins (HSPs) and the enzymes ascorbate peroxidase (APX) and methionine sulfoxide reductase (MSR). Based on these findings, the involvement of NO2-Ln in the NO metabolism was analyzed showing a significant NO formation in roots from 7-day-old Arabidopsis thaliana seedlings and standing out that NO generated from NO2-Ln could have an important role at the beginning of plant development. Therefore, these findings highlight the importance of these novel NO-derived molecules in plant systems playing a pivotal role in development and in the antioxidant defense response against different abiotic stress conditions. PMID:26910757

  15. Nitric oxide release from nitro-fatty acids in Arabidopsis roots.

    PubMed

    Mata-Pérez, Capilla; Sánchez-Calvo, Beatriz; Begara-Morales, Juan C; Padilla, María N; Valderrama, Raquel; Corpas, Francisco J; Barroso, Juan B

    2016-01-01

    In recent years, research on the involvement of nitric oxide (NO) in plant systems has remarkably grown. However, most of the interest in this molecule has been focused on its ability to mediate different post-translational modifications (NO-PTM) in biomolecules, mainly nitration and S-nitrosylation of proteins, and its involvement in physiological and stress situations. Nevertheless, very recently the nitration of other molecules such as fatty acids has commanded increasingly greater attention. In the last February issue of Plant Physiology, we again reported on the endogenous occurrence of nitro-fatty acids (NO2-FAs), specifically nitro-linolenic acid (NO2-Ln), in the model plant Arabidopsis thaliana. The analysis of the presence of this nitro-fatty acid showed that levels of NO2-Ln decreased throughout the plant development with the higher levels detected in seeds and young seedlings of this plant. Furthermore, through a transcriptomic analysis by RNA-seq technology applying NO2-Ln to A. thaliana cell-suspension cultures, we found high induction in the transcriptional expression of several heat-shock proteins (HSPs) and the enzymes ascorbate peroxidase (APX) and methionine sulfoxide reductase (MSR). Based on these findings, the involvement of NO2-Ln in the NO metabolism was analyzed showing a significant NO formation in roots from 7-day-old Arabidopsis thaliana seedlings and standing out that NO generated from NO2-Ln could have an important role at the beginning of plant development. Therefore, these findings highlight the importance of these novel NO-derived molecules in plant systems playing a pivotal role in development and in the antioxidant defense response against different abiotic stress conditions. PMID:26910757

  16. Dynamic chiral-at-metal stability of tetrakis(d/l-hfc)Ln(III) complexes capped with an alkali metal cation in solution.

    PubMed

    Lin, Yiji; Zou, Fang; Wan, Shigang; Ouyang, Jie; Lin, Lirong; Zhang, Hui

    2012-06-14

    Chiral tetrakis(β-diketonate) Ln(III) complexes Δ-[NaLa(d-hfc)(4)(CH(3)CN)] (1) and Λ-[NaLa(l-hfc)(4) (CH(3)CN)] (2) (d/l-hfc(-) = 3-heptafluo-robutylryl-(+)/(-)-camphorate) are a pair of enantiomers and crystallize in the same Sohncke space group (P2(1)2(1)2(1)) with dodecahedral (DD) geometry. Typically positive and negative exciton splitting patterns around 320 nm were observed in the solid-state circular dichroism (CD) spectra of complexes 1 and 2, which indicate that their shell configurational chiralities are Δ and Λ, respectively. The apparent bisignate couplets in the solid-state CD spectra of [CsLn(d-hfc)(4)(H(2)O)] [Ln = La (3), Yb (5)] and [CsLn(l-hfc)(4)(H(2)O)] [Ln = La (4), Yb (6)] show that they are a pair of enantiomers and their absolute configurations are denoted Δ and Λ, respectively. The crystallographic data of 5 reveals that its coordination polyhedron is the square antiprism (SAP) geometry and it undergoes a phase transition from triclinic (α phase, P1) to monoclinic (β phase, C2) upon cooling. The difference between the two phases is brought about by the temperature dependent behaviour of the coordination water molecules, but this did not affect the configurational chirality of the Δ-SAP-[Yb(d-hfc)(4)](-) moiety. Furthermore, time-dependent CD, UV-vis and (19)F NMR were applied to study the solution behavior of these complexes. It was found that the chiral-at-metal stability of the three pairs of complexes is different and affected by both the Ln(3+) and M(+) ion size. The results show that the Cs(+) cation can retain the metal center chirality and stablize the structures of [Ln(d/l-hfc)(4)](-) or the dissociated tris(d/l-hfc)Ln(III) species in solution for a longer time than that of the Na(+) cation, and it is important that the Cs(+) ion successfully lock the configurational chirality around the Yb(3+) center of the complex species in solution. This is reasoned by the short Cs(+)···FC, Cs(+)···O-Yb and Cs(+)···Yb(3

  17. Synthesis, crystal structures and luminescent properties of two 4d-4f Ln-Ag heterometallic coordination polymers based on anion template

    SciTech Connect

    Fan, Le-Qing; Chen, Yuan; Wu, Ji-Huai; Huang, Yun-Fang

    2011-04-15

    Two new 4d-4f Ln-Ag heterometallic coordination polymers, {l_brace}[Ln{sub 3}Ag{sub 5}(IN){sub 10}(H{sub 2}O){sub 7}].4(ClO{sub 4}).4(H{sub 2}O){r_brace}{sub n} (Ln=Eu (1) and Sm (2), HIN=isonicotinic acid), have been synthesized under hydrothermal conditions by reactions of Ln{sub 2}O{sub 3}, AgNO{sub 3}, HIN and HClO{sub 4}, and characterized by elemental analysis, IR, thermal analysis and single-crystal X-ray diffraction. It is proved that HClO{sub 4} not only adjusts the pH value of the reaction mixture, but also acts as anion template. The structure determination reveals that 1 and 2 are isostructural and feature a novel two-dimensional (2D) layered hetrometallic structure constructed from one-dimensional Ln-carboxylate chains and pillared Ag(IN){sub 2} units. The 2D layers are further interlinked through Ag...Ag and Ag...O(ClO{sub 4}{sup -}) multiple weak interactions, which form a rare Ag-ClO{sub 4} ribbon in lanthanide-transition metal coordination polymers, to give rise to a three-dimensional supramolecular architecture. Moreover, the luminescent properties of these two compounds have also been investigated at room temperature. -- Graphical abstract: Two new anion-templated 2D 4d-4f Ln-Ag heterometallic coordination polymers based on novel lanthanide-carboxylate chains and pillared Ag(IN){sub 2} units, {l_brace}[Ln{sub 3}Ag{sub 5}(IN){sub 10}(H{sub 2}O){sub 7}].4(ClO{sub 4}).4(H{sub 2}O){r_brace}{sub n} (Ln=Eu (1) and Sm (2), HIN=isonicotinic acid), have been hydrothermally synthesized and structurally characterized. 1 and 2 exhibit good luminescent properties. Display Omitted Research highlights: > Two 2D Eu (Sm)-Ag coordination polymers templated by perchlorate anion have been synthesized. > Polymers consist of novel 1D lanthanide-carboxylate chains. > In both structures, there are rare Ag...Ag and Ag...O(ClO{sub 4}{sup -}) multiple weak interactions. > Both compounds exhibit good luminescent properties.

  18. Two-dimensional 3d-4f heterometallic coordination polymers: syntheses, crystal structures, and magnetic properties of six new Co(II)-Ln(III) compounds.

    PubMed

    Díaz-Gallifa, Pau; Fabelo, Oscar; Pasán, Jorge; Cañadillas-Delgado, Laura; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

    2014-06-16

    Six new heterometallic cobalt(II)-lanthanide(III) complexes of formulas [Ln(bta)(H2O)2]2[Co(H2O)6]·10H2O [Ln = Nd(III) (1) and Eu(III) (2)] and [Ln2Co(bta)2(H2O)8]n·6nH2O [Ln = Eu(III) (3), Sm(III) (4), Gd(III) (5), and Tb(III) (6)] (H4bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized via single-crystal X-ray diffraction. 1 and 2 are isostructural compounds with a structure composed of anionic layers of [Ln(bta)(H2O)2]n(n-) sandwiching mononuclear [Co(H2O)6](2+) cations plus crystallization water molecules, which are interlinked by electrostatic forces and hydrogen bonds, leading to a supramolecular three-dimensional network. 3-6 are also isostructural compounds, and their structure consists of neutral layers of formula [Ln2Co(bta)2(H2O)8]n and crystallization water molecules, which are connected through hydrogen bonds to afford a supramolecular three-dimensional network. Heterometallic chains formed by the regular alternation of two nine-coordinate lanthanide(III) polyhedra [Ln(III)O9] and one compressed cobalt(II) octahedron [Co(II)O6] along the crystallographic c-axis are cross-linked by bta ligands within each layer of 3-6. Magnetic susceptibility measurements on polycrystalline samples for 3-6 have been carried out in the temperature range of 2.0-300 K. The magnetic behavior of these types of Ln(III)-Co(II) complexes, which have been modeled by using matrix dagonalization techniques, reveals the lack of magnetic coupling for 3 and 4, and the occurrence of weak antiferromagnetic interactions within the Gd(III)-Gd(III) (5) and Tb(III)-Tb(III) (6) dinuclear units through the exchange pathway provided by the double oxo(carboxylate) and double syn-syn carboxylate bridges. PMID:24901707

  19. Two-dimensional 3d-4f heterometallic coordination polymers: syntheses, crystal structures, and magnetic properties of six new Co(II)-Ln(III) compounds.

    PubMed

    Díaz-Gallifa, Pau; Fabelo, Oscar; Pasán, Jorge; Cañadillas-Delgado, Laura; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

    2014-06-16

    Six new heterometallic cobalt(II)-lanthanide(III) complexes of formulas [Ln(bta)(H2O)2]2[Co(H2O)6]·10H2O [Ln = Nd(III) (1) and Eu(III) (2)] and [Ln2Co(bta)2(H2O)8]n·6nH2O [Ln = Eu(III) (3), Sm(III) (4), Gd(III) (5), and Tb(III) (6)] (H4bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized via single-crystal X-ray diffraction. 1 and 2 are isostructural compounds with a structure composed of anionic layers of [Ln(bta)(H2O)2]n(n-) sandwiching mononuclear [Co(H2O)6](2+) cations plus crystallization water molecules, which are interlinked by electrostatic forces and hydrogen bonds, leading to a supramolecular three-dimensional network. 3-6 are also isostructural compounds, and their structure consists of neutral layers of formula [Ln2Co(bta)2(H2O)8]n and crystallization water molecules, which are connected through hydrogen bonds to afford a supramolecular three-dimensional network. Heterometallic chains formed by the regular alternation of two nine-coordinate lanthanide(III) polyhedra [Ln(III)O9] and one compressed cobalt(II) octahedron [Co(II)O6] along the crystallographic c-axis are cross-linked by bta ligands within each layer of 3-6. Magnetic susceptibility measurements on polycrystalline samples for 3-6 have been carried out in the temperature range of 2.0-300 K. The magnetic behavior of these types of Ln(III)-Co(II) complexes, which have been modeled by using matrix dagonalization techniques, reveals the lack of magnetic coupling for 3 and 4, and the occurrence of weak antiferromagnetic interactions within the Gd(III)-Gd(III) (5) and Tb(III)-Tb(III) (6) dinuclear units through the exchange pathway provided by the double oxo(carboxylate) and double syn-syn carboxylate bridges.

  20. Complexations of Ln(III) with SnS{sub 4}H and Sn{sub 2}S{sub 6}: Solvothermal syntheses and characterizations of lanthanide coordination polymers with thiostannate and polyamine mixed ligands

    SciTech Connect

    Tang, Chunying; Lu, Jialin; Han, Jingyu; Liu, Yun; Shen, Yali; Jia, Dingxian

    2015-10-15

    Polymeric lanthanide complexes with thiostannate and polyamine mixed ligands, [Ln(peha)(μ–SnS{sub 4}H)]{sub n} [Ln=La (1a), Nd (1b)] and [(Ln(tepa)(μ–OH)){sub 2}(μ–Sn{sub 2}S{sub 6})]{sub n}nH{sub 2}O [Ln=Nd (2a), Sm (2b), Gd (2c), Dy (2d)] (peha=pentaethylenehexamine, tepa=tetraethylenepentamine) were respectively prepared in peha and tepa coordinative solvents by the solvothermal methods. In 1a and 1b, the Ln{sup 3+} ions are coordinated by a hexadentate peha ligand forming [Ln(peha)]{sup 3+} units. The [SnS{sub 4}H]{sup 3−} anion chelates a [Ln(peha)]{sup 3+} unit via two S atoms and coordinates to another [Ln(peha)]{sup 3+} unit via the third S atom. As a result, the [Ln(peha)]{sup 3+} units are connected into coordination polymers [Ln(peha)(μ–SnS{sub 4}H)]{sub n} by an unprecedented tridentate μ–η{sup 1},η{sup 2}–SnS{sub 4}H bridging ligands. In 2a–2d, the Ln{sup 3+} ions are coordinated by a pentadentate tepa ligand, and two [Ln(tepa)]{sup 3+} units are joined by two μ–OH bridges to form a binuclear [(Ln(tepa)(μ–OH)){sub 2}]{sup 4+} unit. Behaving as a bidentate μ–η{sup 1}, η{sup 1}–Sn{sub 2}S{sub 6} bridging ligand, the Sn{sub 2}S{sub 6} unit connects [(Ln(tepa)(μ–OH)){sub 2}]{sup 4+} units into a neutral coordination polymer [(Ln(tepa)(μ–OH)){sub 2}(μ–Sn{sub 2}S{sub 6})]{sub n} via the trans S atoms. The Ln{sup 3+} ions are in distorted monocapped square antiprismatic and bicapped trigonal prismatic environments in [(Ln(peha)(μ–SnS{sub 4}H)]{sub n} and [(Ln(tepa)(μ–OH)){sub 2}(μ–Sn{sub 2}S{sub 6})]{sub n}, respectively. The denticities of ethylene polyamine play an important role on the formation and complexation of the thiostannate in the presence of lanthanide ions. Compounds 1a–2d show well-defined absorption edges with band gaps between 2.81 and 3.15 eV. - Graphical abstract: Lanthanide coordination polymers concerning thiostannate ligands were prepared by the solvothermal methods, and μ{sub 3}

  1. Tetranuclear hetero-metal [Co(II)2Ln(III)2] (Ln = Gd, Tb, Dy, Ho, La) complexes involving carboxylato bridges in a rare μ4-η(2):η(2) mode: synthesis, crystal structures, and magnetic properties.

    PubMed

    Abtab, Sk Md Towsif; Majee, Mithun Chandra; Maity, Manoranjan; Titiš, Ján; Boča, Roman; Chaudhury, Muktimoy

    2014-02-01

    A new family of 3d-4f heterometal 2 × 2 complexes [Co(II)2(L)2(PhCOO)2Ln(III)2(hfac)4] (1-5) (Ln = Gd (compound 1), Tb (compound 2), Dy (compound 3), Ho (compound 4), and La (compound 5)) have been synthesized in moderate yields (48-63%) following a single-pot protocol using stoichiometric amounts (1:1 mol ratio) of [Co(II)(H2L)(PhCOO)2] (H2L = N,N'-dimethyl-N,N'-bis(2-hydroxy-3,5-dimethylbenzyl)ethylenediamine) as a metalloligand and [Ln(III)(hfac)3(H2O)2] (Hhfac = hexafluoroacetylacetone) as a lanthanide precursor compound. Also reported with this series is the Zn-Dy analog [Zn(II)2(L)2(PhCOO)2Dy(III)2(hfac)4] 6 to help us in understanding the magnetic properties of these compounds. The compounds 1-6 are isostructural. Both hexafluoroacetylacetonate and benzoate play crucial roles in these structures as coligands in generating a tetranuclear core of high thermodynamic stability through a self-assembly process. The metal centers are arranged alternately at the four corners of this rhombic core, and the carboxylato oxygen atoms of each benzoate moiety bind all of the four metal centers of this core in a rare μ4-η(2):η(2) bridging mode as confirmed by X-ray crystallography. The magnetic susceptibility and magnetization data confirm a paramagnetic behavior, and no remnant magnetization exists in any of these compounds at vanishing magnetic field. The metal centers are coupled in an antiferromagnetic manner in these compounds. The [Co(II)2Dy(III)2] compound exhibits a slow magnetic relaxation below 6 K, as proven by the AC susceptibility measurements; the activation energy reads U/kB = 8.8 K (τ0 = 2.0 × 10(-7) s) at BDC = 0, and U/kB = 7.8 K (τ0 = 3.9 × 10(-7) s) at BDC = 0.1 T. The [Zn(II)2Dy(III)2] compound also behaves as a single-molecule magnet with U/kB = 47.9 K and τ0 = 2.75 × 10(-7) s.

  2. Preparation and spectroscopic properties of rare-earth (RE) (RE = Sm, Eu, Tb, Dy, Tm)-activated K{sub 2}LnZr(PO{sub 4}){sub 3} (Ln = Y, La, Gd and Lu) phosphate in vacuum ultraviolet region

    SciTech Connect

    Zhang, Zhi-Jun; Lin, Xiao; Zhao, Jing-Tai; Zhang, Guo-Bin

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ► We report the VUV spectroscopic properties of rare-earth ions in K{sub 2}LnZr(PO{sub 4}){sub 3}. ► The O{sup 2−}-Eu{sup 3+} charge transfer bands at about 220 nm have been observed. ► The 4f–5d spin-allowed and spin-forbidden transitions of Tb{sup 3+} have been observed. ► There is energy transfer between the host and rare-earth activators. -- Abstract: Rare earth (RE = Sm, Eu, Tb, Dy and Tm)-activated K{sub 2}LnZr(PO{sub 4}){sub 3} (Ln = Y, La, Gd and Lu) have been synthesized by solid-state reaction method, and their vacuum ultraviolet (VUV) excitation luminescent characteristics have been investigated. The band in the wavelength range of 130–157 nm and the other one range from 155 to 216 nm with the maximum at about 187 nm in the VUV excitation spectra of these compounds are attributed to the host lattice absorption and O–Zr charge transfer transition, respectively. The charge transfer bands (CTB) of O{sup 2−}-Sm{sup 3+}, O{sup 2−}-Dy{sup 3+} and O{sup 2−}-Tm{sup 3+}, in Sm{sup 3+}, Dy{sup 3+} and Tm{sup 3+}-activated samples, have not been obviously observed probably because the 2p electrons of oxygen are tightly bound to the zirconium ion in the host lattice. For Eu{sup 3+}-activated samples, the relatively weak O{sup 2−}-Eu{sup 3+} CTB at about 220 nm is observed. And for Tb{sup 3+}-activated samples, the bands at 223 and 258 nm are related to the 4f-5d spin-allowed and spin-forbidden transitions of Tb{sup 3+}, respectively. It is observed that there is energy transfer between the host lattice and the luminescent activators (e.g. Eu{sup 3+}, Tb{sup 3+}). From the standpoint of luminescent efficiency, color purity and chemical stability, K{sub 2}GdZr(PO{sub 4}){sub 3}:Sm{sup 3+}, Eu{sup 3+}, Tb{sup 3+} are attractive candidates for novel yellow, red, green-emitting PDP phosphors.

  3. Efficient, stable, tunable, and easy to synthesize, handle and recycle luminescent materials: [H2NMe2]3[Ln(III)(2,6-dipicolinolate)3] (Ln = Eu, Tb, or its solid solutions).

    PubMed

    Mooibroek, Tiddo Jonathan; Gamez, Patrick; Pevec, Andrej; Kasunic, Marta; Kozlevcar, Bojan; Fu, Wen-Tian; Reedijk, Jan

    2010-07-28

    Three compounds with the general formulae [H(2)N(Me)(2)](3)[Ln(2,6-dpa)(3)] were prepared from cheap and readily available reactants. Microcrystalline compounds could be isolated in high yields (>80%) by a simple filtration, after only one hour reaction time in refluxing DMF. The Eu and Tb compounds have been structurally characterized by single crystal X-ray diffraction. The compounds have unusual high-absorption coefficients (>95%) and quantum efficiencies (approximately 70%). Furthermore, they are thermally stable up to 250 degrees C and appear to be UV and water tolerant. The emission colour of the final compound can be easily fine-tuned, by varying the Eu:Tb ratio during the preparation.

  4. Crystal structures of [Ln(NO3)3(μ2-bpydo)2], where Ln = Ce, Pr or Nd, and bpydo = 4,4′-bi­pyridine N,N′-dioxide: layered coordination networks containing 44 grids

    PubMed Central

    Stromyer, Michael L.; Lilly, Cassandra P.; Dillner, Adam J.; Knaust, Jacqueline M.

    2016-01-01

    Three isostructural coordination networks of Ce, Pr, and Nd nitrate with 4,4′-bi­pyridine N,N′-dioxide (bpydo) are reported, namely poly[[tris­(nitrato-κ2 O,O′)cerium(III)]-bis­(μ2-4,4′-bi­pyridine N,N′-dioxide-κ2 N:N′)], [Ce(NO3)3(C10H8N2O2)2], poly[[tris­(nitrato-κ2 O,O′)praeseodymium(III)]-bis­(μ2-4,4′-bi­pyridine N,N′-dioxide-κ2 N:N′)], [Pr(NO3)3(C10H8N2O2)2], and poly[[tris(nitrato-κ2 O,O′)neodymium(III)]-bis­(μ2-4,4′-bi­pyridine N,N′-dioxide-κ2 N:N′], [Nd(NO3)3(C10H8N2O2)2]. All three compounds are isostructural to the previously reported La analogue. The asymmetric unit of [Ln(NO3)3(μ2-bpydo)2] contains one lanthanide cation, two bpydo ligands, and three nitrate anions. Both bpydo ligands act as end-to-end μ2-bridges and display nearly ideal cis and gauche conformations, respectively. The bpydo ligands link the ten-coordinate Ln III cations, forming inter­digitating 44 grid-like layers extending parallel to (-101), where inter­digitation of layers is promoted by C—H⋯O inter­actions between nitrate anions and bpydo ligands. The inter­digitated layers are linked to sets of neighboring layers via further C—H⋯O and π–π inter­actions. PMID:26870578

  5. Biological in vitro and in vivo studies of a series of new asymmetrical cationic [99mTc(N)(DTC-Ln)(PNP)]+ complex (DTC-Ln = alicyclic dithiocarbamate and PNP = diphosphinoamine).

    PubMed

    Bolzati, Cristina; Cavazza-Ceccato, Mario; Agostini, Stefania; Refosco, Fiorenzo; Yamamichi, Yoshihiro; Tokunaga, Shinji; Carta, Davide; Salvarese, Nicola; Bernardini, Daniele; Bandoli, Giuliano

    2010-05-19

    (99m)Tc(N)-DBODC5 is a cationic mixed compound under clinical investigation as potential myocardial imaging agent. In spite of this, analogously to the other cationic (99m)Tc-agents, presents a relatively low first-pass extraction. Thus, modification of (99m)Tc(N)-DBODC(5) direct to increase its first-pass extraction keeping unaltered the favorable imaging properties would be desirable. This work describes the synthesis and biological evaluation of a series of novel cationic (99m)Tc-nitrido complexes, of general formula [(99m)TcN(DTC-Ln)(PNP)](+) (DTC-Ln= alicyclic dithiocarbamates; PNP = diphosphinoamine), as potential radiotracers for myocardial perfusion imaging. The synthesis of cationic (99m)Tc-(N)-complexes were accomplished in two steps. Biodistribution studies were performed in rats and compared with the distribution profiles of (99m)Tc(N)-DBODC5 and (99m)Tc-Sestamibi. The metabolisms of the most promising compounds were evaluated by HPLC methods. Biological studies revealed that most of the complexes have a high initial and persistent heart uptake with rapid clearance from nontarget tissues. Among tested compounds, 2 and 12 showed improved heart uptake with respect to the gold standard (99m)Tc-complexes with favorable heart-to-liver and slightly lower heart-to-lung ratios. Chromatographic profiles of (99m)Tc(N)-radioactivity extracted from tissues and fluids were coincident with the native compound evidencing remarkable in vivo stability of these agents. This study shows that the incorporation of alicyclic dithiocarbamate in the [(99m)Tc(N)(PNP)](+) building block yields to a significant increase of the heart uptake at early injection point suggesting that the first-pass extraction fraction of these novel complexes may be increased with respect to the other cationic (99m)Tc-agents keeping almost unaltered the favorable target/nontarget ratios. PMID:20402465

  6. Crystal structures of [Ln(NO3)3(μ2-bpydo)2], where Ln = Ce, Pr or Nd, and bpydo = 4,4'-bi-pyridine N,N'-dioxide: layered coordination networks containing 4(4) grids.

    PubMed

    Stromyer, Michael L; Lilly, Cassandra P; Dillner, Adam J; Knaust, Jacqueline M

    2016-01-01

    Three isostructural coordination networks of Ce, Pr, and Nd nitrate with 4,4'-bi-pyridine N,N'-dioxide (bpydo) are reported, namely poly[[tris-(nitrato-κ(2) O,O')cerium(III)]-bis-(μ2-4,4'-bi-pyridine N,N'-dioxide-κ(2) N:N')], [Ce(NO3)3(C10H8N2O2)2], poly[[tris-(nitrato-κ(2) O,O')praeseodymium(III)]-bis-(μ2-4,4'-bi-pyridine N,N'-dioxide-κ(2) N:N')], [Pr(NO3)3(C10H8N2O2)2], and poly[[tris(nitrato-κ(2) O,O')neodymium(III)]-bis-(μ2-4,4'-bi-pyridine N,N'-dioxide-κ(2) N:N'], [Nd(NO3)3(C10H8N2O2)2]. All three compounds are isostructural to the previously reported La analogue. The asymmetric unit of [Ln(NO3)3(μ2-bpydo)2] contains one lanthanide cation, two bpydo ligands, and three nitrate anions. Both bpydo ligands act as end-to-end μ2-bridges and display nearly ideal cis and gauche conformations, respectively. The bpydo ligands link the ten-coordinate Ln (III) cations, forming inter-digitating 4(4) grid-like layers extending parallel to (-101), where inter-digitation of layers is promoted by C-H⋯O inter-actions between nitrate anions and bpydo ligands. The inter-digitated layers are linked to sets of neighboring layers via further C-H⋯O and π-π inter-actions. PMID:26870578

  7. Manganese Oxide-Coated Carbon Nanotubes As Dual-Modality Lymph Mapping Agents for Photothermal Therapy of Tumor Metastasis.

    PubMed

    Wang, Sheng; Zhang, Qin; Yang, Peng; Yu, Xiangrong; Huang, Li-Yong; Shen, Shun; Cai, Sanjun

    2016-02-17

    Lymph node (LN) status is a major indicator of stage and survival of lung cancer patients. LN dissection is a primary option for lung cancer LN metastasis; however, this strategy elicits adverse effects and great trauma. Therefore, developing a minimally invasive technique to cure LN metastasis of lung cancer is desired. In this study, multiwalled carbon nanotubes (MWNTs) coated with manganese oxide (MnO) and polyethylene glycol (PEG) (namely MWNTs-MnO-PEG) was employed as a lymphatic theranostic agent to diagnose and treat metastatic LNs. After single local injection and lymph drainage were performed, regional LNs were clearly mapped by T1-weighted magnetic resonance (MR) of MnO and dark dye imaging of MWNTs. Meanwhile, metastatic LNs could be simultaneously ablated by near-infrared (NIR) irradiation under the guidance of dual-modality mapping. The excellent result was obtained in mice bearing LNs metastasis models, showing that MWNTs-MnO-PEG as a multifunctional theranostic agent was competent for dual-modality mapping guided photothermal therapy of metastatic LNs.

  8. Energetics of Rare Earth Doped Uranium Oxide Solid Solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Lei

    The physical and chemical properties of UO2 nuclear fuels are affected as fission products accumulate during irradiation. The lanthanides, a main group of fission products, form extensive solid solutions with uranium oxide in the fluorite structure. Thermodynamic studies of such solid solutions had been performed to obtain partial molar free energies of oxygen as a function of dopant concentration and temperature; however, direct measurement of formation enthalpies was hampered by the refractory nature of these oxides. In this work, high temperature oxide melt solution calorimetry was utilized to study the thermochemistry of various rare earth doped uranium oxide LnxU 1-xO2-0.5x+y (Ln = La, Y, Nd) over a wide range of dopant concentrations and oxygen contents. The sintered solid solutions were carefully characterized to determine their phase purity, chemical composition, and uranium oxidation state, with most of the materials in the oxygen excess regime. The enthalpies of formation of LnxU1-xO2-0.5x+y were calculated from the calorimetric data. The oxidation enthalpies of these solid solutions are similar to that of UO2. The formation enthalpies from constituent oxides (LnO1.5, UO2, and UO3) become increasingly negative with addition of dopant cations and appear relatively independent of the uranium oxidation state (oxygen content) when the type and concentration of the dopants are the same. This is valid in the oxygen excess regime; thus an estimation of formation enthalpies of LnxU1-xO2 materials can be made. The formation enthalpies from elements of hyperstoichiometric LnxU1-xO 2-0.5x+y materials obtained from calorimetric measurements are in good agreement with those calculated from free energy data. A direct comparison between the formation enthalpies from calorimetric study and computational research using density functional theory was also performed. The experimental and computational energies of LnxU 1-xO2 (Ln = La, Y, Nd) generally agree within 10 k

  9. Lanthanide mixed-ligand complexes of the [Ln(CAPh)3(Phen)] and [LaxEu1-x(CAPh)3(Phen)] (CAPh = carbacylamidophosphate) type. A comparative study of their spectral properties.

    PubMed

    Litsis, Olena O; Ovchynnikov, Vladimir A; Scherbatskii, Vasyl P; Nedilko, Sergiy G; Sliva, Tatiana Yu; Dyakonenko, Viktoriya V; Shishkin, Oleg V; Davydov, Valentine I; Gawryszewska, Paula; Amirkhanov, Vladimir M

    2015-09-21

    A series of complexes Ln(Pip)3(Phen) (Ln(iii) = La, Ce-Nd, Sm-Lu, Y; HPip (CAPh type ligand) = 2,2,2-trichloro-N-(dipiperidin-1-yl-phosphoryl)acetamide, Phen = 1,10-phenanthroline) has been synthesized. The lanthanum(iii) doped europium(iii) complexes ([LaxEu1-x(Pip)3(Phen)], x = 0.99, 0.95, 0.50) have been obtained by the co-crystallization method. The complexes have been characterized by means of X-ray diffraction, IR, (1)H and (31)P-NMR and absorption spectroscopy. Emission and excitation luminescence spectra were recorded at 295 and 77 K. The lifetime values (τ) for the emission of all europium complexes were determined. The (5)D0 luminescence quantum efficiency is 73-89%. The symmetries of the nearest europium surrounding in pure and doped complexes were evaluated from the Stark splitting of (5)D0-(7)FJ transitions. Crystal structures of [Ln(Pip)3(Phen)] (Ln = Nd (1), Eu (2) and Tb (3)) have been determined. Lattice parameters of the [Ln(Pip)3(Phen)] (Ln = Tb, Yb) and the doped [LaxEu1-x(Pip)3(Phen)] (x = 0.99, 0.95, 0.50) complexes have been measured. The presence of four polymorphs within a number of rare earth elements has been estimated: two in triclinic (Ln1 = La, Nd; Ln2 = Eu), one in the monoclinic (Ln3 = Tb) and one in the rhombic (Ln4 = Tb, Yb) symmetry. Complex 3 can be obtained in two crystal modifications: monoclinic and orthorhombic ones.

  10. Lanthanide mixed-ligand complexes of the [Ln(CAPh)3(Phen)] and [LaxEu1-x(CAPh)3(Phen)] (CAPh = carbacylamidophosphate) type. A comparative study of their spectral properties.

    PubMed

    Litsis, Olena O; Ovchynnikov, Vladimir A; Scherbatskii, Vasyl P; Nedilko, Sergiy G; Sliva, Tatiana Yu; Dyakonenko, Viktoriya V; Shishkin, Oleg V; Davydov, Valentine I; Gawryszewska, Paula; Amirkhanov, Vladimir M

    2015-09-21

    A series of complexes Ln(Pip)3(Phen) (Ln(iii) = La, Ce-Nd, Sm-Lu, Y; HPip (CAPh type ligand) = 2,2,2-trichloro-N-(dipiperidin-1-yl-phosphoryl)acetamide, Phen = 1,10-phenanthroline) has been synthesized. The lanthanum(iii) doped europium(iii) complexes ([LaxEu1-x(Pip)3(Phen)], x = 0.99, 0.95, 0.50) have been obtained by the co-crystallization method. The complexes have been characterized by means of X-ray diffraction, IR, (1)H and (31)P-NMR and absorption spectroscopy. Emission and excitation luminescence spectra were recorded at 295 and 77 K. The lifetime values (τ) for the emission of all europium complexes were determined. The (5)D0 luminescence quantum efficiency is 73-89%. The symmetries of the nearest europium surrounding in pure and doped complexes were evaluated from the Stark splitting of (5)D0-(7)FJ transitions. Crystal structures of [Ln(Pip)3(Phen)] (Ln = Nd (1), Eu (2) and Tb (3)) have been determined. Lattice parameters of the [Ln(Pip)3(Phen)] (Ln = Tb, Yb) and the doped [LaxEu1-x(Pip)3(Phen)] (x = 0.99, 0.95, 0.50) complexes have been measured. The presence of four polymorphs within a number of rare earth elements has been estimated: two in triclinic (Ln1 = La, Nd; Ln2 = Eu), one in the monoclinic (Ln3 = Tb) and one in the rhombic (Ln4 = Tb, Yb) symmetry. Complex 3 can be obtained in two crystal modifications: monoclinic and orthorhombic ones. PMID:26239675

  11. Hybrid luminescence materials assembled by [Ln(DPA)3]3− and mesoporous host through ion-pairing interactions with high quantum efficiencies and long lifetimes

    PubMed Central

    Li, Qing-Feng; Yue, Dan; Lu, Wei; Zhang, Xinlei; Li, Chunyang; Wang, Zhenling

    2015-01-01

    A kind of mesoporous hybrid luminescence material was assembled through the ion exchange method between [Ln(DPA)3]3− and ionic liquid functionalized SBA-15. [Ln(DPA)3]3− was successfully anchored onto positive-charge modified SBA-15 by the strong electrostatic interaction. In [Ln(DPA)3]3−, Ln3+ ions are in 9-fold coordination through six oxygen atoms of carboxyl groups and three nitrogen atoms of pyridine units, leaving no coordination site for water molecules. Therefore the hybrids possess prominent luminescent properties, SBA-15-IMI-Tb(DPA)3 and SBA-15-IMI-Eu(DPA)3 exhibit high quantum yield values of 63% and 79%, and long lifetimes values of 2.38 ms and 2.34 ms, respectively. Especially, SBA-15-IMI-Eu(DPA)3 presents a high color purity, and the red/orange intensity ratio is as high as 7.6. The excellent luminescence properties and ordered mesoporous structures give rise to many potential applications in optical and electronic areas. PMID:25669156

  12. Electrochemical and Thermodynamic Properties of Ln(III) (Ln = Eu, Sm, Dy, Nd) in 1-Butyl-3-Methylimidazolium Bromide Ionic Liquid

    PubMed Central

    Yang, Xiao; He, Ling; Qin, Song; Tao, Guo-Hong; Huang, Ming; Lv, Yi

    2014-01-01

    The electrochemical behavior and thermodynamic properties of Ln(III) (Ln = Eu, Sm, Dy, Nd) were studied in 1-butyl-3-methylimidazolium bromide ionic liquid (BmimBr) at a glassy carbon (GC) electrode in the range of 293–338 K. The electrode reaction of Eu(III) was found to be quasi-reversible by the cyclic voltammetry, the reactions of the other three lanthanide ions were regarded as irreversible systems. An increase of the current intensity was obtained with the temperature increase. At 293 K, the cathodic peak potentials of −0.893 V (Eu(III)), −0.596 V (Sm(III)), −0.637 V (Dy(III)) and −0.641 V (Nd(III)) were found, respectively, to be assigned to the reduction of Ln(III) to Ln(II). The diffusion coefficients (Do), the transfer coefficients (α) of Ln(III) (Ln = Eu, Sm, Dy, Nd) and the charge transfer rate constants (ks) of Eu(III) were estimated. The apparent standard potential (E0*) and the thermodynamic properties of the reduction of Eu(III) to Eu(II) were also investigated. PMID:24752584

  13. Comparison of Cavitation-Erosion Resistance of Carburized and Carburized-Plus-Nitrided 316LN Stainless Steel in Mercury

    SciTech Connect

    Pawel, Steven J

    2007-05-01

    Annealed type 316LN stainless steel in the (1) carburized and the (2) carburized plus nitrided conditions was evaluated for cavitation-erosion resistance in ambient temperature mercury using a vibratory horn method. The results indicated that, relative to the specimens receiving only the carburizing treatment, the specimens that received both surface treatments exhibited substantially greater weight loss, general thinning, and profile development as a function of sonication time - with all observed degradation limited to the nitrided layer. Further, the nitride layer was observed to be susceptible to extensive cracking (occasionally leading to spallation), but the cracking was never observed to penetrate into the carburized layer. These screening test results suggest there is no improvement in cavitation-erosion resistance associated with augmentation of the carburizing treatment with plasma nitriding.

  14. High-repetition-rate dual-signal intracavity optical parametric generator based on periodically-phase-reversal PPMgLN

    NASA Astrophysics Data System (ADS)

    Ji, Feng; Yao, Jianquan; Zheng, Fanghua; Li, Enbang; Zhang, Tieli; Zhao, Pu; Wang, Peng; Zhang, Baigang

    2007-10-01

    A high-repetition-rate dual-signal intracavity optical parametric generator (IOPG) inside a diode-end-pumped acousto-optically (AO) Q-switched Nd:YVO4 laser is presented. The nonlinear material is a periodically-phase-reversal periodically poled MgO-doped lithium niobate (ppr-PPMgLN). At an incident diode pump power of 6.1 W and a Q-switch repetition rate of 20 kHz, an average dual-signal output power of 0.44 W is achieved. The dual-signal wavelengths of 1477 and 1491 nm are obtained at a crystal temperature of 40 °C. The measurements of the beam quality factor of 1.4 and the pulse duration of 77 ns show good spatial and temporal overlaps for the dual-signal radiation.

  15. Assessment of Cavitation-Erosion Resistance of 316LN Stainless Steel Following a Nitro-Carburizing Surface Treatment

    SciTech Connect

    Pawel, Steven J

    2009-11-01

    A nitro-carburizing surface treatment known domestically as the Melonite process was applied to type 316LN stainless steel test pieces and exposed to sonication conditions in mercury using a vibratory horn technique. Cavitation-erosion damage was evaluated for extended exposures and compared to other surface treatments on the same substrate alloy. The results indicate that the Melonite process substantially retards weight loss and crater development for extended periods, but gradually is eroded/destroyed leading to exposure of the substrate and cavitation-erosion behavior similar to untreated specimens. Compared with other surface treatments, cavitation-erosion results indicate that specimens treated with Melonite perform similarly to specimens treated with a simple nitriding process. Neither the simple nitriding nor the Melonite treatment is quite as effective as a previously evaluated low temperature carburizing treatment, the latter being about a factor of three better than Melonite in terms of weight loss during sonication in mercury.

  16. Constitutive modeling of hot horming of austenitic stainless steel 316LN by accounting for recrystallization in the dislocation evolution

    NASA Astrophysics Data System (ADS)

    Kooiker, H.; Perdahcioğlu, E. S.; van den Boogaard, A. H.

    2016-08-01

    Hot compression test data taken from Zhang [1] of metastable austenitic stainless steel AISI 316LN over a range of strain rates and temperatures shows typical dynamic recovery and recrystallization behavior. It is proposed to model this behavior by incorporating not only the hardening and recovery into the Bergstrom dislocation evolution equation, but also the recrystallization. It is shown that the initial mechanical response before recrystallization can be accurately represented by assuming that the mean free path evolves as the microstructure evolves from homogeneously spaced dislocations to cell-pattern. Results show that this novel continuum mechanical model can predict the observed behavior, showing a good match to the experimental data and capturing the transition from recrystallization to (almost) no recrystallization.

  17. Balance of activity between LN(v)s and glutamatergic dorsal clock neurons promotes robust circadian rhythms in Drosophila.

    PubMed

    Collins, Ben; Kane, Elizabeth A; Reeves, David C; Akabas, Myles H; Blau, Justin

    2012-05-24

    Circadian rhythms offer an excellent opportunity to dissect the neural circuits underlying innate behavior because the genes and neurons involved are relatively well understood. We first sought to understand how Drosophila clock neurons interact in the simple circuit that generates circadian rhythms in larval light avoidance. We used genetics to manipulate two groups of clock neurons, increasing or reducing excitability, stopping their molecular clocks, and blocking neurotransmitter release and reception. Our results revealed that lateral neurons (LN(v)s) promote and dorsal clock neurons (DN(1)s) inhibit light avoidance, these neurons probably signal at different times of day, and both signals are required for rhythmic behavior. We found that similar principles apply in the more complex adult circadian circuit that generates locomotor rhythms. Thus, the changing balance in activity between clock neurons with opposing behavioral effects generates robust circadian behavior and probably helps organisms transition between discrete behavioral states, such as sleep and wakefulness.

  18. The interactions between the sterically demanding trimesitylphosphine oxide and trimesityphosphine with scandium and selected lanthanide ions

    NASA Astrophysics Data System (ADS)

    Platt, Andrew W. G.; Singh, Kuldip

    2016-05-01

    The reactions between lanthanide nitrates, Ln(NO3)3 and scandium and lanthanide trifluoromethane sulfonates, Ln(Tf)3 with trimesitylphosphine oxide, Mes3PO show that coordination to the metal ions does not lead to crystalline complexes. Investigation of the reactions by 31-P NMR spectroscopy shows that weak complexes are formed in solution. The crystal structures of Mes3PO·0.5CH3CN (1) and [Mes3PO]3H3O·2CH3CN·Tf (2), formed in the reaction between ScTf3 and Mes3PO, are reported. Trimesitylphosphine, Mes3P, is protonated by scandium and lanthanide trifluoromethane sulfonates and lanthanide nitrates in CD3CN and the structure of [Mes3PH]Cl·HCl·2H2O (3) is reported.

  19. Water-Free Rare Earth-Prussian Blue Type Analogues: Synthesis, Structure, Computational Analysis, and Magnetic Data of {Ln[superscript III](DMF)[subscript 6]Fe[superscript III](CN)[subcsript 6]}[subscript infinity] (Ln = Rare Earths Excluding Pm)

    SciTech Connect

    Wilson, Duane C.; Liu, Shengming; Chen, Xuenian; Meyers, Edward A.; Bao, Xiaoguang; Prosvirin, Andrey V.; Dunbar, Kim R.; Hadad, Christopher M.; Shore, Sheldon G.

    2009-11-04

    Water-free rare earth(III) hexacyanoferrate(III) complexes, {l_brace}Ln(DMF){sub 6}({mu}-CN){sub 2}Fe(CN){sub 4}{r_brace}{sub {infinity}} (DMF = N,N-dimethylformamide; Ln = Sm, 1; Eu, 2; Gd, 3; Tb, 4; Dy, 5; Ho, 6; Er, 7; Tm, 8; Yb, 9; Lu, 10; Y, 11; La, 12; Ce, 13; Pr, 14; Nd, 15), were synthesized in dry DMF through the metathesis reactions of [(18-crown-6)K]{sub 3}Fe(CN){sub 6} with LnX{sub 3}(DMF){sub n} (X = Cl or NO{sub 3}). Anhydrous DMF solutions of LnX{sub 3}(DMF){sub n} were prepared at room temperature from LnCl{sub 3} or LnX{sub 3} {center_dot} nH{sub 2}O under a dynamic vacuum. All compounds were characterized by IR, X-ray powder diffraction (except for 10), and single crystal X-ray diffraction (except for 2, 7, 10). Infrared spectra reveal that a monotonic, linear relationship exists between the ionic radius of the lanthanide and the {nu}{sub {mu}-CN} stretching frequency of 1-10, 12-15 while 11 deviates slightly from the ionic radius relationship. X-ray powder diffraction data are in agreement with powder patterns calculated from single crystal X-ray diffraction results, a useful alternative for bulk sample confirmation when elemental analysis data are difficult to obtain. Eight-coordinate Ln(III) metal centers are observed for all structures. trans-cyanide units of [Fe(CN){sub 6}]{sup 3-} formed isocyanide linkages to Ln(III) resulting in one-dimensional polymeric chains. Structures of compounds 1-9 and 11 are isomorphous, crystallizing in the space group C2/c. Structures of compounds 12-15 are also isomorphous, crystallizing in the space group P2/n. One unique polymeric chain exists in the structures of 1-9 and 11 while two unique polymeric chains exist in structures of 12-15. One of the polymeric chains of 12-15 is similar to that observed for 1-9, 11 while the other is more distorted and has a shorter Ln-Fe distance. Magnetic susceptibility measurements for compounds 3-6, 8, 11 were performed on polycrystalline samples of the compounds.

  20. High thermal sensitivity and the selectable upconversion color of Ln, Yb:Y6O5F8 nanotubes.

    PubMed

    Zaldo, Carlos; Cascales, Concepción

    2014-11-14

    Yb(3+)-sensitized, Ln(3+)(Er(3+), Pr(3+))-doped Y6O5F8 micron-sized bundles of highly crystalline individual nanotubes have been prepared through hydrothermal syntheses at 185 °C. The inhomogeneous broadening observed in their optical spectra is associated with the large distribution of crystal fields around Y(3+)(Ln(3+)) sites in the orthorhombic Pbcm Vernier-type Y6O5F8 host. Based on ratiometric analyses of the thermal evolution of intensities of near-infrared NIR (∼978 nm)-excited green upconversion emissions corresponding to (2)H11/2, (4)S3/2 → (4)I15/2 Er(3+) transitions, the temperature sensing behaviour of Er, Yb:Y6O5F8 was studied. This thermal sensor exhibits a very high sensitivity S = 0.0060 K(-1) at physiological temperatures (22-50 °C), which surpasses the S value found for Er, Yb:β-NaYF4 at these temperatures, and a maximum S = 0.0082 K(-1) at ∼225 °C. Also under NIR diode laser excitation, the color of the upconverted light from codoped Pr, Er, Yb:Y6O5F8 nanotubes can be selected by the control of the Pr(3+) concentration and by the excitation regime and power density. Samples with low Pr(3+) concentration emit green light, and the selection between bluish-green light and white light has been demonstrated with high Pr(3+) concentration (2 mol%), under pulsed or continuous wave excitation, respectively.

  1. High thermal sensitivity and the selectable upconversion color of Ln, Yb:Y6O5F8 nanotubes.

    PubMed

    Zaldo, Carlos; Cascales, Concepción

    2014-11-14

    Yb(3+)-sensitized, Ln(3+)(Er(3+), Pr(3+))-doped Y6O5F8 micron-sized bundles of highly crystalline individual nanotubes have been prepared through hydrothermal syntheses at 185 °C. The inhomogeneous broadening observed in their optical spectra is associated with the large distribution of crystal fields around Y(3+)(Ln(3+)) sites in the orthorhombic Pbcm Vernier-type Y6O5F8 host. Based on ratiometric analyses of the thermal evolution of intensities of near-infrared NIR (∼978 nm)-excited green upconversion emissions corresponding to (2)H11/2, (4)S3/2 → (4)I15/2 Er(3+) transitions, the temperature sensing behaviour of Er, Yb:Y6O5F8 was studied. This thermal sensor exhibits a very high sensitivity S = 0.0060 K(-1) at physiological temperatures (22-50 °C), which surpasses the S value found for Er, Yb:β-NaYF4 at these temperatures, and a maximum S = 0.0082 K(-1) at ∼225 °C. Also under NIR diode laser excitation, the color of the upconverted light from codoped Pr, Er, Yb:Y6O5F8 nanotubes can be selected by the control of the Pr(3+) concentration and by the excitation regime and power density. Samples with low Pr(3+) concentration emit green light, and the selection between bluish-green light and white light has been demonstrated with high Pr(3+) concentration (2 mol%), under pulsed or continuous wave excitation, respectively. PMID:25255864

  2. Functional PEG–PAMAM-Tetraphosphonate Capped NaLnF4 Nanoparticles and their Colloidal Stability in Phosphate Buffer

    PubMed Central

    2015-01-01

    Developing surface coatings for NaLnF4 nanoparticles (NPs) that provide long-term stability in solutions containing competitive ions such as phosphate remains challenging. An amine-functional polyamidoamine tetraphosphonate (NH2-PAMAM-4P) as a multidentate ligand for these NPs has been synthesized and characterized as a ligand for the surface of NaGdF4 and NaTbF4 nanoparticles. A two-step ligand exchange protocol was developed for introduction of the NH2-PAMAM-4P ligand on oleate-capped NaLnF4 NPs. The NPs were first treated with methoxy-poly(ethylene glycol)-monophosphoric acid (Mn = 750) in tetrahydrofuran. The mPEG750-OPO3-capped NPs were stable colloidal solutions in water, where they could be ligand-exchanged with NH2-PAMAM-4P. The surface amine groups on the NPs were available for derivatization to attach methoxy-PEG (Mn = 2000) and biotin-terminated PEG (Mn = 2000) chains. The surface coverage of ligands on the NPs was examined by thermal gravimetric analysis, and by a HABA analysis for biotin-containing NPs. Colloidal stability of the NPs was examined by dynamic light scattering. NaGdF4 and NaTbF4 NPs capped with mPEG2000–PAMAM-4P showed colloidal stability in DI water and in phosphate buffer (10 mM, pH 7.4). A direct comparison with NaTbF4 NPs capped with a mPEG2000-lysine-based tetradentate ligand that we reported previously (Langmuir2012, 28, 12861−1287022906305) showed that both ligands provided long-term stability in phosphate buffer, but that the lysine-based ligand provided better stability in phosphate-buffered saline. PMID:24898128

  3. Modeling of thermal expansion coefficient of perovskite oxide for solid oxide fuel cell cathode

    NASA Astrophysics Data System (ADS)

    Heydari, F.; Maghsoudipour, A.; Alizadeh, M.; Khakpour, Z.; Javaheri, M.

    2015-09-01

    Artificial intelligence models have the capacity to eliminate the need for expensive experimental investigation in various areas of manufacturing processes, including the material science. This study investigates the applicability of adaptive neuro-fuzzy inference system (ANFIS) approach for modeling the performance parameters of thermal expansion coefficient (TEC) of perovskite oxide for solid oxide fuel cell cathode. Oxides (Ln = La, Nd, Sm and M = Fe, Ni, Mn) have been prepared and characterized to study the influence of the different cations on TEC. Experimental results have shown TEC decreases favorably with substitution of Nd3+ and Mn3+ ions in the lattice. Structural parameters of compounds have been determined by X-ray diffraction, and field emission scanning electron microscopy has been used for the morphological study. Comparison results indicated that the ANFIS technique could be employed successfully in modeling thermal expansion coefficient of perovskite oxide for solid oxide fuel cell cathode, and considerable savings in terms of cost and time could be obtained by using ANFIS technique.

  4. Ab initio calculation of excess properties of La{sub 1−x}(Ln,An){sub x}PO{sub 4} solid solutions

    SciTech Connect

    Li, Yan; Kowalski, Piotr M.; Blanca-Romero, Ariadna; Vinograd, Victor; Bosbach, Dirk

    2014-12-15

    We used ab initio computational approach to predict the excess enthalpy of mixing and the corresponding regular/subregular model parameters for La{sub 1−x}Ln{sub x}PO{sub 4} (Ln=Ce,…, Tb) and La{sub 1−x}An{sub x}PO{sub 4} (An=Pu, Am and Cm) monazite-type solid solutions. We found that the regular model interaction parameter W computed for La{sub 1−x}Ln{sub x}PO{sub 4} solid solutions matches the few existing experimental data. Within the lanthanide series W increases quadratically with the volume mismatch between LaPO{sub 4} and LnPO{sub 4} endmembers (ΔV=V{sub LaPO{sub 4}}−V{sub LnPO{sub 4}}), so that W(kJ/mol)=0.618(ΔV(cm{sup 3}/mol)){sup 2}. We demonstrate that this relationship also fits the interaction parameters computed for La{sub 1−x}An{sub x}PO{sub 4} solid solutions. This shows that lanthanides can be used as surrogates for investigation of the thermodynamic mixing properties of actinide-bearing solid solutions. - Highlights: • The excess enthalpies of mixing for monazite-type solid solutions are computed. • The excess enthalpies increase with the endmembers volume mismatch. • The relationship derived for lanthanides is transferable to La{sub 1−x}An{sub x}PO{sub 4} systems.

  5. High-power PPMgLN-based optical parametric oscillator pumped by a linearly polarized, semi-fiber-coupled acousto-optic Q-switched fiber master oscillator power amplifier.

    PubMed

    Chen, Tao; Jiang, Peipei; Yang, Dingzhong; Hu, Chengzhi; Wu, Bo; Shen, Yonghang

    2013-09-01

    We have experimentally demonstrated a periodically poled magnesium-oxide-doped lithium niobate (PPMgLN)-based, fiber-laser-pumped optical parametric oscillator (OPO) generating idler wavelength of 3.82 μm. The pump fiber laser was constructed with a linearly polarized, semi-fiber-coupled acousto-optic Q-switched fiber oscillator and a polarization-maintaining fiber amplifier with pulse duration of 190 ns at the highest output power. The OPO was specifically configured in single-pass, singly resonant linear cavity structure to avoid the damage risk of the pump fiber laser, which is always a serious issue in the fiber-laser-pumped, double-pass, singly oscillating structured OPOs. Under the highest pump power of 25 W, an idler average output power of 3.27 W with one-hour peak-to-peak instability of 5.2% was obtained. The measured M2 factors were 1.98 and 1.44 for horizontal and vertical axis, respectively. The high power stability and good beam quality demonstrated the suitability of such technology for practical application. PMID:24085093

  6. Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

    SciTech Connect

    Zhong, Jie-Cen; Wan, Fang; Sun, Yan-Qiong; Chen, Yi-Ping

    2015-01-15

    A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln{sub 2}(phen){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O){sub 2}]{sub n} (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)]{sub n} (II: Ln=Sm(2a), Eu(2b), Dy(2c), 2-SBA=2-sulfobenzoate, BZA=benzoate) have been hydrothermally synthesized from lanthanide oxide, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, TG analyses and luminescence spectroscopy. Interestingly, SO{sub 4}{sup 2−} anions in I came from the in situ deep oxidation of thiol groups of 2-mercaptonbenzoic acid while 2-sulfobenzoate and benzoate ligands in II from the middle oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. Compounds I are organic–inorganic hybrid lanthanide sulfates, which have rare one-dimensional column-like structures. Complexes II are binuclear lanthanide sulfonate-carboxylates with 2-sulfobenzoate and benzoate as bridges and 1,10-phenanthroline as terminal. Photoluminescence studies reveal that complexes I and II exhibit strong lanthanide characteristic emission bands in the solid state at room temperature. - Graphical abstract: Lanthanide sulfates and lanthanide sulfonate-carboxylates have been hydrothermally synthesized. Interestingly, sulfate anions, 2-sulfobenzoate and benzoate ligands came from the in situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. - Highlights: • In situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. • The organic–inorganic hybrid lanthanide sulfates with one-dimensional column-like structure. • The dinuclear lanthanide sulfonate-carboxylates. • The emission spectra exhibit the characteristic transition of {sup 5}D{sub 0}→{sup 7}F{sub J} (J=0–4) of the Eu(III)

  7. Crystal growth and properties of Ln{sub 2}Ag{sub 1-x}Ga{sub 10-y} (Ln=La, Ce), a disordered variant of the Ce{sub 2}NiGa{sub 10}-structure type

    SciTech Connect

    Menard, Melissa C.; Xiong, Yimin; Karki, Amar B.; Drake, Brenton L.; Adams, Philip W.; Fronczek, Frank R.; Young, David P.; Chan, Julia Y.

    2010-09-15

    We report the flux growth and characterization of Ln{sub 2}Ag{sub 1-x}Ga{sub 10-y} (Ln=La, Ce), a disordered variant of the Ce{sub 2}NiGa{sub 10} structure type. Single crystals of La{sub 2}Ag{sub 1-x}Ga{sub 10-y} (x{approx}0.3; y{approx}0.6) and Ce{sub 2}Ag{sub 1-x}Ga{sub 10-y} (x{approx}0.3; y{approx}0.9) were grown by the self-flux method and characterized using single-crystal X-ray diffraction. Transport measurements of Ce{sub 2}Ag{sub 1-x}Ga{sub 10-y} (x{approx}0.3; y{approx}0.9) reveal metallic behavior with a transition at 3 K. Magnetic measurements indicate antiferromagnetic ordering at 3 K of localized Ce{sup 3+} moments for Ce{sub 2}Ag{sub 1-x}Ga{sub 10-y}. Magnetoresistance is positive with a maximum value of 16% at 9 T. La{sub 2}Ag{sub 1-x}Ga{sub 10-y} exhibits metallic behavior with magnetic susceptibility showing temperature independent paramagnetism. We will compare Ce{sub 2}Ag{sub 1-x}Ga{sub 10-y} (x{approx}0.3; y{approx}0.9) to Ce{sub 2}NiGa{sub 10} to examine the effects of transition metal substitution and to the related Ce(Ag,Ga){sub 4} phase to examine the effects of crystal structure on the physical properties. - Graphical abstract: The figure illustrates the structure of Ce{sub 2}Ag{sub 0.7(1)}Ga{sub 9.1(1)}, which can be described as a distorted variant of the Ce{sub 2}NiGa{sub 10} structure. The distorted gallium segments are best described as variants of CeGa{sub 6} (PuGa{sub 6}-structure type), and the distorted Ce(Ag,Ga){sub 4}-type segments are built of layers of face-sharing tetragonal antiprisms. Here M=Ag+Ga and the shaded atoms are partially occupied.

  8. Enhanced luminescence intensity and color purity of the red emitting LnVO{sub 4}:Eu{sup 3+}@ SiO{sub 2} (Ln = Gd, Y and Gd/Y) powder phosphors

    SciTech Connect

    Rambabu, U.; Han, Sang-Do

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ► Tetragonal phase lanthanide vanadates doped with Eu{sup 3+} were synthesized. ► Luminescence enhancement was done by optimizing the host (Gd,Y) and SiO{sub 2} coatings. ► SiO{sub 2} coating was characterized by SEM-EDAX, FT-IR and PL techniques. ► {sup 5}D{sub 0} → {sup 7}F{sub 2} domination over {sup 5}D{sub 0} → {sup 7}F{sub 1} indicates the absence of an inversion symmetry. ► Y{sub 0.95}VO{sub 4}:Eu{sup 3+}@ SiO{sub 2}(10 vol.%) is found to be a novel enhanced red emitting phosphor. -- Abstract: An attempt was made to enhance the luminescence properties of LnVO{sub 4}:Eu{sup 3+}@ SiO{sub 2} (Ln = Gd, Y and Gd/Y) powder phosphors. Pure phase with tetragonal structure of the produced phosphors was confirmed by XRD profiles. Sub-micron sized phosphors have shown 35% more PL intensity than the bulk, which was further improved 20.22% with SiO{sub 2} shell coating. SiO{sub 2} shell coating was optimized by SEM-EDAX, FT-IR, PL and TEM measurements. Emission intensities of the transition, {sup 5}D{sub 0} → {sup 7}F{sub 2} have dominated {sup 5}D{sub 0} → {sup 7}F{sub 1}, which indicated the lowering of an inverse symmetry in the vicinity of Eu{sup 3+} ions. Luminescence intensity and color purity were enhanced with the host modification by substituting Gd{sup 3+} with Y{sup 3+} sites, followed by SiO{sub 2} coating. Based on the systematic investigations carried out, the phosphor Y{sub 0.95}VO{sub 4}:Eu{sup 3+}{sub 0.05}@ SiO{sub 2} is suggested to be a novel contender for its suitable red emission in certain displays or lighting.

  9. Corrosion Behavior of 316LN and 316 Stainless Steels During Long-term Exposure to Aerated 0.5 M NaCl Using Electrochemical Noise Technique

    NASA Astrophysics Data System (ADS)

    Pujar, M. G.; Parvathavarthini, N.; Jena, Sidhartha S.; Tata, B. V. R.; Dayal, R. K.; Khatak, H. S.

    2008-12-01

    In the present work 316LN as well as 316 stainless steel (SS) coupons each of dimensions (0.025 × 0.018 × 0.006 m3) in well-polished condition were used as two nominal electrodes which were immersed in the aerated solution of 0.5 M NaCl. Correlated current and potential electrochemical noise (EN) signals were collected at 1 Hz sampling frequency for 1 h daily over a period of 30 days. The detrended EN data were used to calculate the noise resistance ( R N) as well as the spectral noise resistance at zero frequency ( R {SN/o}) values and other statistical parameters. To study the nature of pits and distribution of their diameters as well as depths, extensive observations of the pitted and the blank specimens were carried out using Confocal Laser Scanning Microscopy (CLSM). The current and the potential records of the two alloys showed distinct differences in their corrosion behavior. It was observed that within less than 4 h of immersion, 316SS showed signals indicative of unstable pitting and onset of stable pitting was noticed after 48 h of exposure. However, until about 24 h, 316LN showed just the random signals and unstable pitting was observed after 28 h. The signals clearly indicated continuous growth of the stable pits in 316SS as against the repassivation of the unstable pits in 316LN after 7 days exposure. It was observed that R N values showed a continuous decrease in the case of 316SS, but were quite stable in the case of 316LN over the exposure period. Concurrent to these observations it was observed that 316SS specimen was extensively pitted. The frequency distributions of pit diameters as well pit depths were observed to be highest at 10-20 μm and 5-10 μm, respectively. However, pits with as large as 70-80 μm diameter and as deep as 20-25 μm too were observed. No pits were observed in case of 316LN even after 30 days of exposure, an observation that corroborates well with the stable R N values. Thus, in the present investigation, the long

  10. Brush Seals for Cryogenic Applications: Performance, Stage Effects, and Preliminary Wear Results in LN2 and LH2

    NASA Technical Reports Server (NTRS)

    Proctor, Margaret P.; Walker, James F.; Perkins, H. Douglas; Hoopes, Joan F.; Williamson, G. Scott

    1996-01-01

    Brush seals are compliant contacting seals and have significantly lower leakage than labyrinth seals in gas turbine applications. Their long life and low leakage make them candidates for use in rocket engine turbopumps. Brush seals, 50.8 mm (2 in.) in diameter with a nominal 127-micron (0.005-in.) radial interference, were tested in liquid nitrogen (LN2) and liquid hydrogen (LH2) at shaft speeds up to 35,000 and 65,000 rpm, respectively, and at pressure drops up to 1.21 MPa (175 psid) per brush. A labyrinth seal was also tested in liquid nitrogen to provide a baseline. The LN2 leakage rate of a single brush seal with an initial radial shaft interference of 127 micron (0.005 in.) measured one-half to one-third the leakage rate of a 12-tooth labyrinth seal with a radial clearance of 127 micron (0.005 in.). Two brushes spaced 7.21 micron (0.248 in.) apart leaked about one-half as much as a single brush, and two brushes tightly packed together leaked about three-fourths as much as a single brush. The maximum measured groove depth on the Inconel 718 rotor with a surface finish of 0.81 micron (32 microinch) was 25 micron (0.0010 in.) after 4.3 hr of shaft rotation in liquid nitrogen. The Haynes-25 bristles wore approximately 25 to 76 micron (0.001 to 0.003 in.) under the same conditions. Wear results in liquid hydrogen were significantly different. In liquid hydrogen the rotor did not wear, but the bristle material transferred onto the rotor and the initial 127 micron (0.005 in.) radial interference was consumed. Relatively high leakage rates were measured in liquid hydrogen. More testing is required to verify the leakage performance, to validate and calibrate analysis techniques, and to determine the wear mechanisms. Performance, staging effects, and preliminary wear results are presented.

  11. Single-Molecule Magnetism, Enhanced Magnetocaloric Effect, and Toroidal Magnetic Moments in a Family of Ln4 Squares.

    PubMed

    Das, Chinmoy; Vaidya, Shefali; Gupta, Tulika; Frost, Jamie M; Righi, Mattia; Brechin, Euan K; Affronte, Marco; Rajaraman, Gopalan; Shanmugam, Maheswaran

    2015-10-26

    Three cationic [Ln4 ] squares (Ln=lanthanide) were isolated as single crystals and their structures solved as [Dy4 (μ4 -OH)(HL)(H2 L)3 (H2 O)4 ]Cl2 ⋅(CH3 OH)4 ⋅(H2 O)8 (1), [Tb4 (μ4 -OH)(HL)(H2 L)3 (MeOH)4 ]Cl2 ⋅(CH3 OH)4 ⋅(H2 O)4 (2) and [Gd4 (μ4 -OH)(HL)(H2 L)3 (H2 O)2 (MeOH)2 ]Br2 ⋅(CH3 OH)4 ⋅(H2 O)3 (3). The structures are described as hydroxo-centered squares of lanthanide ions, with each edge of the square bridged by a doubly deprotonated H2 L(2-) ligand. Alternating current magnetic susceptibility measurements show frequency-dependent out-of-phase signals with two different thermally assisted relaxation processes for 1, whereas no maxima in χM " appears above 2.0 K for complex 2. For 1, the estimated effective energy barrier for these two relaxation processes is 29 and 100 K. Detailed ab initio studies reveal that complex 1 possesses a toroidal magnetic moment. The ab initio calculated anisotropies of the metal ions in complex 1 were employed to simulate the magnetic susceptibility by using the Lines model (POLY_ANISO) and this procedure yields J1 =+0.01 and J2 =-0.01 cm(-1) for 1 as the two distinct exchange interactions between the Dy(III) ions. Similar parameters are also obtained for complex 1 (and 2) from specific heat measurements. A very weak antiferromagnetic super-exchange interaction (J1 =-0.043 cm(-1) and g=1.99) is observed between the metal centers in 3. The magnetocaloric effect (MCE) was estimated by using field-dependent magnetization and temperature-dependent heat-capacity measurements. An excellent agreement is found for the -ΔSm values extracted from these two measurements for all three complexes. As expected, 3 shows the largest -ΔSm variation (23 J Kg(-1)  K(-1) ) among the three complexes. The negligible magnetic anisotropy of Gd indeed ensures near degeneracy in the (2S+1) ground state microstates, and the weak super-exchange interaction facilitates dense population of low-lying excited states, all of

  12. Single-Molecule Magnetism, Enhanced Magnetocaloric Effect, and Toroidal Magnetic Moments in a Family of Ln4 Squares.

    PubMed

    Das, Chinmoy; Vaidya, Shefali; Gupta, Tulika; Frost, Jamie M; Righi, Mattia; Brechin, Euan K; Affronte, Marco; Rajaraman, Gopalan; Shanmugam, Maheswaran

    2015-10-26

    Three cationic [Ln4 ] squares (Ln=lanthanide) were isolated as single crystals and their structures solved as [Dy4 (μ4 -OH)(HL)(H2 L)3 (H2 O)4 ]Cl2 ⋅(CH3 OH)4 ⋅(H2 O)8 (1), [Tb4 (μ4 -OH)(HL)(H2 L)3 (MeOH)4 ]Cl2 ⋅(CH3 OH)4 ⋅(H2 O)4 (2) and [Gd4 (μ4 -OH)(HL)(H2 L)3 (H2 O)2 (MeOH)2 ]Br2 ⋅(CH3 OH)4 ⋅(H2 O)3 (3). The structures are described as hydroxo-centered squares of lanthanide ions, with each edge of the square bridged by a doubly deprotonated H2 L(2-) ligand. Alternating current magnetic susceptibility measurements show frequency-dependent out-of-phase signals with two different thermally assisted relaxation processes for 1, whereas no maxima in χM " appears above 2.0 K for complex 2. For 1, the estimated effective energy barrier for these two relaxation processes is 29 and 100 K. Detailed ab initio studies reveal that complex 1 possesses a toroidal magnetic moment. The ab initio calculated anisotropies of the metal ions in complex 1 were employed to simulate the magnetic susceptibility by using the Lines model (POLY_ANISO) and this procedure yields J1 =+0.01 and J2 =-0.01 cm(-1) for 1 as the two distinct exchange interactions between the Dy(III) ions. Similar parameters are also obtained for complex 1 (and 2) from specific heat measurements. A very weak antiferromagnetic super-exchange interaction (J1 =-0.043 cm(-1) and g=1.99) is observed between the metal centers in 3. The magnetocaloric effect (MCE) was estimated by using field-dependent magnetization and temperature-dependent heat-capacity measurements. An excellent agreement is found for the -ΔSm values extracted from these two measurements for all three complexes. As expected, 3 shows the largest -ΔSm variation (23 J Kg(-1)  K(-1) ) among the three complexes. The negligible magnetic anisotropy of Gd indeed ensures near degeneracy in the (2S+1) ground state microstates, and the weak super-exchange interaction facilitates dense population of low-lying excited states, all of

  13. Reactions of actinide ions with ethylene oxide.

    PubMed

    Gibson, J K

    2001-03-01

    Naked and oxo-ligated actinide (An) monopositive ions were reacted with ethylene oxide, cyclo-C(2)H(4)O (EtO). Along with An = U, Np, Pu and Am, ions of two lanthanide (Ln) elements, Ln = Tb and Tm, were studied for comparison. Metal and metal oxide ions, M(+), MO(+) and MO(2)(+), were generated by laser ablation and immediately reacted with EtO. Unreacted and product ions were detected by time-of-flight mass spectrometry. It was apparent that the overall reaction cross-sections decreased in the order U(+) > or = Np(+) > Pu(+) > Am(+). A primary reaction channel for each studied metal was the formation of MO(+) from M(+), in accord with the expected exothermicity of oxygen abstraction from EtO. For U, Np and Pu, the dioxides were also major products, indicating OAn(+)--O dissociation energies of at least 350 kJ mol(-1), the energy required for O-atom abstraction from EtO. For Am, Tb and Tm, the dioxides were only very minor products, reflecting the stabilities of the trivalent states and resistance to oxidation to higher valence states; the structures/bonding in these MO(2)(+) are intriguing given that the formal pentavalent bonding state is effectively unattainable. It was demonstrated that EtO, unlike more thermochemically favorable but kinetically restricted O-donors, is effective at achieving facile oxidation of actinide metal ions to the monoxide, and to the dioxide if the second O-abstraction reaction is exothermic. Several intriguing minor products were also identified, most of which incorporate metal--oxygen bonding and are attributed to the oxophilicity of the f-block elements; the contrast to the behavior of first-row d-block transition elements is striking in this regard. Particularly noteworthy was the formation of MH(4)(+) (and MOH(4)(+)), evidently via abstraction of all four H atoms from a single C(2)H(4)O molecule; the structures/bonding in these novel 'hydride' species are indeterminate and warrant further attention.

  14. Facile interchange of 3d and 4f ions in single-molecule magnets: stepwise assembly of [Mn4 ], [Mn3Ln] and [Mn2Ln2 ] cages within calix[4]arene scaffolds.

    PubMed

    Palacios, Maria A; McLellan, Ross; Beavers, Christine M; Teat, Simon J; Weihe, Høgni; Piligkos, Stergios; Dalgarno, Scott J; Brechin, Euan K

    2015-07-27

    The central Mn(II) ions in a series of calix[4]arene-stabilised butterflies can be sequentially replaced with Ln(III) ions, maintaining the structural integrity of the molecule but transforming its magnetic properties. The replacement of Mn(II) for Gd(III) allows for the examination of the transferability of spin-Hamiltonian parameters within the family as well as permitting their reliable determination. The introduction of the 4f ions results in weaker intramolecular magnetic exchange, an increase in the number of low-lying excited states, and an increase in magnetisation relaxation, highlighting the importance of exchange over single-ion anisotropy for the observation of SMM behaviour in this family of complexes. The presence of the [TM(II/III) (TBC[4])(OH)(solvent)] metalloligand (TM=transition metal, TBC=p-tBu-calix[4]arene) suggests that magnetic calix[n]arene building blocks can be employed to encapsulate a range of different "guests" within structurally robust "hosts".

  15. Encapsulation of Ln(III) Ions/Dyes within a Microporous Anionic MOF by Post-synthetic Ionic Exchange Serving as a Ln(III) Ion Probe and Two-Color Luminescent Sensors.

    PubMed

    Zhao, Shu-Na; Song, Xue-Zhi; Zhu, Min; Meng, Xing; Wu, Lan-Lan; Feng, Jing; Song, Shu-Yan; Zhang, Hong-Jie

    2015-06-26

    A new anionic framework {[Me2NH2]0.125[In0.125(H2L)0.25]⋅xDMF}n (1) with one-dimensional (1D) channels along the c axis of about 13.06×13.06 Å(2), was solvothermally synthesized and well characterized. Post-synthetic cation exchange of 1 with Eu(3+), Tb(3+), Dy(3+), Sm(3+) afforded lanthanide(III)-loaded materials, Ln(3+)@1, with different luminescent behavior, indicating that compound 1 could be used as a potential luminescent probe toward different lanthanide(III) ions. Additionally, compound 1 exhibits selective adsorption ability toward cationic dyes. Moreover, the RhB@1 realized the probing of different organic solvent molecules by tuning the energy transfer efficiency between two different emissions, especially for sensing DMF. This work highlights the practical application of luminescent guest@MOFs as sensors, and it paves the way toward other one/multi-color luminescent host-guest systems by rational selection of MOF hosts and guest chromophores with suitable emissive colors and energy levels.

  16. Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides.

    PubMed

    Zhang, Qingnan; Hu, Shu-Xian; Qu, Hui; Su, Jing; Wang, Guanjun; Lu, Jun-Bo; Chen, Mohua; Zhou, Mingfei; Li, Jun

    2016-06-01

    The chemistry of lanthanides (Ln=La-Lu) is dominated by the low-valent +3 or +2 oxidation state because of the chemical inertness of the valence 4f electrons. The highest known oxidation state of the whole lanthanide series is +4 for Ce, Pr, Nd, Tb, and Dy. We report the formation of the lanthanide oxide species PrO4 and PrO2 (+) complexes in the gas phase and in a solid noble-gas matrix. Combined infrared spectroscopic and advanced quantum chemistry studies show that these species have the unprecedented Pr(V) oxidation state, thus demonstrating that the pentavalent state is viable for lanthanide elements in a suitable coordination environment.

  17. Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides.

    PubMed

    Zhang, Qingnan; Hu, Shu-Xian; Qu, Hui; Su, Jing; Wang, Guanjun; Lu, Jun-Bo; Chen, Mohua; Zhou, Mingfei; Li, Jun

    2016-06-01

    The chemistry of lanthanides (Ln=La-Lu) is dominated by the low-valent +3 or +2 oxidation state because of the chemical inertness of the valence 4f electrons. The highest known oxidation state of the whole lanthanide series is +4 for Ce, Pr, Nd, Tb, and Dy. We report the formation of the lanthanide oxide species PrO4 and PrO2 (+) complexes in the gas phase and in a solid noble-gas matrix. Combined infrared spectroscopic and advanced quantum chemistry studies show that these species have the unprecedented Pr(V) oxidation state, thus demonstrating that the pentavalent state is viable for lanthanide elements in a suitable coordination environment. PMID:27100273

  18. Stable luminescent metal-organic frameworks as dual-functional materials to encapsulate ln(3+) ions for white-light emission and to detect nitroaromatic explosives.

    PubMed

    Xie, Wei; Zhang, Shu-Ran; Du, Dong-Ying; Qin, Jun-Sheng; Bao, Shao-Juan; Li, Jing; Su, Zhong-Min; He, Wen-Wen; Fu, Qiang; Lan, Ya-Qian

    2015-04-01

    A stable porous carbazole-based luminescent metal-organic framework, NENU-522, was successfully constructed. It is extremely stable in air and acidic/basic aqueous solutions, which provides the strategy for luminescent material encapsulation of Ln(3+) ions with tunable luminescence for application in light emission. More importantly, Ln(3+)@NENU-522 can emit white light by encapsulating different molar ratios of Eu(3+) and Tb(3+) ions. Additionally, Tb(3+)@NENU-522 is found to be useful as a fluorescent indicator for the qualitative and quantitative detection of nitroaromatic explosives with different numbers of -NO2 groups, and the concentrations of complete quenching are about 2000, 1000, and 80 ppm for nitrobenzene, 1,3-dinitrobenzene, and 2,4,6-trinitrophenol, respectively. Meanwhile, Tb(3+)@NENU-522 displays high selectivity and recyclability in the detection of nitroaromatic explosives. PMID:25768042

  19. Stable luminescent metal-organic frameworks as dual-functional materials to encapsulate ln(3+) ions for white-light emission and to detect nitroaromatic explosives.

    PubMed

    Xie, Wei; Zhang, Shu-Ran; Du, Dong-Ying; Qin, Jun-Sheng; Bao, Shao-Juan; Li, Jing; Su, Zhong-Min; He, Wen-Wen; Fu, Qiang; Lan, Ya-Qian

    2015-04-01

    A stable porous carbazole-based luminescent metal-organic framework, NENU-522, was successfully constructed. It is extremely stable in air and acidic/basic aqueous solutions, which provides the strategy for luminescent material encapsulation of Ln(3+) ions with tunable luminescence for application in light emission. More importantly, Ln(3+)@NENU-522 can emit white light by encapsulating different molar ratios of Eu(3+) and Tb(3+) ions. Additionally, Tb(3+)@NENU-522 is found to be useful as a fluorescent indicator for the qualitative and quantitative detection of nitroaromatic explosives with different numbers of -NO2 groups, and the concentrations of complete quenching are about 2000, 1000, and 80 ppm for nitrobenzene, 1,3-dinitrobenzene, and 2,4,6-trinitrophenol, respectively. Meanwhile, Tb(3+)@NENU-522 displays high selectivity and recyclability in the detection of nitroaromatic explosives.

  20. Electron-stimulated desorption from polished and vacuum fired 316LN stainless steel coated with Ti-Zr-Hf-V

    SciTech Connect

    Malyshev, Oleg B. Valizadeh, Reza; Hogan, Benjamin T.; Hannah, Adrian N.

    2014-11-01

    In this study, two identical 316LN stainless steel tubular samples, which had previously been polished and vacuum-fired and then used for the electron-stimulated desorption (ESD) experiments, were coated with Ti-Zr-Hf-V with different morphologies: columnar and dense. ESD measurement results after nonevaporable getter (NEG) activation to 150, 180, 250, and 350 °C indicated that the values for the ESD yields are significantly (2–20 times) lower than the data from our previous study with similar coatings on nonvacuum-fired samples. Based on these results, the lowest pressure and best long-term performance in particle accelerators will be achieved with a vacuum-fired vacuum chamber coated with dense Ti-Zr-Hf-V coating activated at 180 °C. This is likely due to the following facts: after NEG activation, the hydrogen concentration inside the NEG was lower than in the bulk stainless steel substrate; the NEG coating created a barrier for gas diffusion from the sample bulk to vacuum; the dense NEG coating performed better as a barrier than the columnar NEG coating.

  1. Heterodimetallic [LnLn′] Lanthanide Complexes: Toward a Chemical Design of Two-Qubit Molecular Spin Quantum Gates

    PubMed Central

    2015-01-01

    A major challenge for realizing quantum computation is finding suitable systems to embody quantum bits (qubits) and quantum gates (qugates) in a robust and scalable architecture. An emerging bottom-up approach uses the electronic spins of lanthanides. Universal qugates may then be engineered by arranging in a molecule two interacting and different lanthanide ions. Preparing heterometallic lanthanide species is, however, extremely challenging. We have discovered a method to obtain [LnLn′] complexes with the appropriate requirements. Compound [CeEr] is deemed to represent an ideal situation. Both ions have a doubly degenerate magnetic ground state and can be addressed individually. Their isotopes have mainly zero nuclear spin, which enhances the electronic spin coherence. The analogues [Ce2], [Er2], [CeY], and [LaEr] have also been prepared to assist in showing that [CeEr] meets the qugate requirements, as revealed through magnetic susceptibility, specific heat, and EPR. Molecules could now be used for quantum information processing. PMID:25203521

  2. Effect of an Aging Heat Treatment on the 4 K Fracture and Fatigue Properties of 316LN and Haynes 242

    SciTech Connect

    Walsh, R. P.; Toplosky, V. J.; Han, K.; Miller, J. R.

    2006-03-31

    Since the introduction of the cable-in-conduit conductor (CICC) concept, a variety of alloys have been proposed for fabricating the jacket. The jacket provides primary containment of the liquid helium coolant and is typically also the primary structural component for the magnet coils. These functions create requirements for strength, toughness, fatigue crack resistance, and fabricability. When the CICC uses Nb3Sn superconductor, the conduit alloy must retain good mechanical properties after exposure to the superconductor's reaction heat treatment. Here we present data from cryogenic fracture toughness and fatigue crack growth rate tests on 316LN and a Cr-Mo-Ni base super-alloy (Haynes 242) at 4 K before and after the exposure to the heat treatment. These alloys are presently being considered as candidates for use in the next-generation series connected hybrid magnet for the NHMFL. Both of the alloys are found to have adequate fatigue and fracture properties for the CICC application while the superalloy has distinctly better elastic properties of modulus and thermal expansion.

  3. The Mechanical and material properties of 316LN austenitic stainless steel for the fusion application in cryogenic temperatures

    NASA Astrophysics Data System (ADS)

    Sas, J.; Weiss, K.-P.; Jung, A.

    2015-12-01

    Due to the constant increase of claims for all materials used in superconducting magnets in "magnetic fusion reactors", the article deals with the possibilities of increasing the mechanical properties of austenitic stainless steel tested at cryogenic conditions that ensure the transport of Helium to magnets. The aim of the experimental plan was to increase the mechanical properties of the steel grade 316LN tested at 4.2K from the original value Steel A: YS = 1045 MPa, UTS = 1528 MPa, A = 33% to the value of YS = 1204 MPa,UTS = 1642 MPa, A = 34% and Steel B: YS = 1173 MPa, UTS = 1541 MPa, A = 28% to the value of YS = 1351 MPa, UTS = 1645 MPa, A = 17%. The increase in mechanical properties of the steel grade under examination has been made by means of heat processing in the conditions of annealing: Th1 = 625 ° C / th1 = 696 h. The mechanical properties of steel were evaluated using static tension tests at 4,2 K. The samples were placed in a cryostat filled with liquid helium. Except for the mechanical properties, there were also evaluated structural changes depending on the conditions of heat processing by light optical microscopy and EBSD (Electron Backscatter Diffraction). The increase of steel properties used in low temperatures was achieved by heat processing.

  4. Summary of recommended correlations for ITER-grade type 316L(N) for the ITER materials properties handbook

    SciTech Connect

    Billone, M.C.; Pawel, J.E.

    1996-04-01

    The focus of this effort is the effects of irradiation on the ultimate tensile strengths (UTS), the yield strength (YS), the uniform elongation (UE), the total elongation (TE) and the reduction in area (RA) in the ITER-relevant temperature range of 100-400{degrees}C. For the purpose of this summary, data for European heats of 316 with 0.020.08 wt.% are referred to as E316L(N) data and grouped together. Other heats of 316 and Ti-modified 316 are also included in the data base. For irradiation and postirradiation-test temperatures in the range of 200-400{degrees}C, the common behavior of these heats of stainless steel is a yield strength approaching the ultimate tensile strength approaching 800 MPa, a uniform elongation approaching 0.3%, a total elongation approaching 3-9%, and a high (about 60%) reduction in area as the neutron damage approaches 10 dpa.

  5. Synthesis and Evaluation of Conformationally Restricted N4-Tetradentate Ligands for Implementation in An(III)/Ln(III) Separations

    SciTech Connect

    Mark D. Ogden; G. Patrick Meier; Kenneth L. Nash

    2012-01-01

    The previous literature demonstrates that donor atoms softer than oxygen are effective for separating trivalent lanthanides (Ln(III)) from trivalent actinides (An(III)) (Nash, K.L., in: Gschneider, K.A. Jr., et al. (eds.) Handbook on the Physics and Chemistry of Rare Earths, vol. 18-Lanthanides/Actinides Chemistry, pp. 197-238. Elsevier Science, Amsterdam, 1994). It has also been shown that ligands that 'restrict' their donor groups in a favorable geometry, appropriate to the steric demands of the cation, have an increased binding affinity. A series of tetradentate nitrogen containing ligands have been synthesized with increased steric 'limits'. The pK a values for these ligands have been determined using potentiometric titration methods and the formation of the colored copper(II) complex has been used as a method to determine ligand partitioning between the organic and aqueous phases. The results for the 2-methylpyridyl-substituted amine ligands are encouraging, but the results for the 2-methylpyridyl-substituted diimines indicate that these ligands are unsuitable for implementation in a solvent extraction system due to hydrolysis.

  6. Antigenic Protein In Microgravity-Grown Human Mixed Mullerian Tumor (LN1) Cells Preserved In RNA Stabilizing Agent

    NASA Technical Reports Server (NTRS)

    Hammond, Dianne K.; Becker, Jeanne; Elliott, T. F.; Holubec, K.; Baker, T. L.; Love, J. E.

    2004-01-01

    Cells treated with RNAlater(TradeMark) have previously been shown to contain antigenic proteins that can be visualized using Western blot analysis. These proteins seem to be stable for several months when stored in RNA stabilizer at 4 C. Antigenic protein can be recovered from cells that have been processed using an Ambion RNAqueous(Registered TradeMark) kit to remove RNA. In this set of experiments, human mixed Mullerian tumor (LNI) cells grown on the International Space Station during Expedition 3 were examined for antigenic stability after removal of RNA. The cells were stored for three months in RNAlater(TradeMark) and RNA was extracted. The RNA filtrate containing the protein was precipitated, washed, and suspended in buffer containing sodium dodecyl sulfate (SDS). Samples containing equal concentrations of protein were loaded onto SDS-polyacrylamide gels. Proteins were separated by electrophoresis and transferred by Western blot to polyvinylidene fluoride (PVDF) membrane. The Western blots were stained with an enhanced chemiluminescent ECL(Registered Trademark) Plus detection kit (Amersham) and scanned using a Storm 840 gel image analyzer (Amersham, Molecular Dynamics). ImageQuant(Registered TradeMark) software was used to quantify the densities of the protein bands. The ground control and flight LN1 cell samples showed a similar staining pattern over time with antibodies to vimentin, glyceraldehyde-3-phosphate dehydrogenase, and epithelial membrane antigens.

  7. Corrosion behavior and tensile properties of AISI 316LN stainless steel exposed to flowing sodium at 823 K

    SciTech Connect

    Pillai, S.R.; Barasi, N.S.; Khatak, H.S.; Terrance, A.L.E.; Kale, R.D.; Rajan, M.; Rajan, K.K.

    2000-02-01

    Austenitic stainless steel of the grade AISI 316 LN was exposed to flowing sodium in a loop at 823 K for 6,000 h to examine the corrosion and mass-transfer behavior. The specimens were incorporated in specially designed sample holders in the loop. These were retrieved and examined by various metallurgical techniques. Specimens were also subjected to thermal aging in the same sample holder to aid in separating the consequences of exposure to sodium from those cause by mere thermal effects. Microstructural investigations have revealed that thermal aging caused the precipitation of carbides at the grain boundaries. Exposure to sodium caused the leaching of elements such as chromium and nickel from the specimen. Loss of nickel from the austenite phase promoted the generation of ferrite phase. Microhardness investigation revealed the hardening of the sodium-exposed surface. Analysis using an electron Probe Microanalyzer revealed that the surface of the steel was both carburized and nitrided. Tensile tests indicated that there is no appreciable difference in the yield strength (YS) and ultimate tensile strength (UTS) of the thermally aged and sodium-exposed specimens when compared with the material in the as-received condition. However, the thermally aged and sodium-exposed specimens showed a decrease in the uniform elongation and total elongation at rupture, perhaps due to carburization and nitridation.

  8. Effect of an Aging Heat Treatment on the 4 K Fracture and Fatigue Properties of 316LN and Haynes 242

    NASA Astrophysics Data System (ADS)

    Walsh, R. P.; Toplosky, V. J.; Han, K.; Miller, J. R.

    2006-03-01

    Since the introduction of the cable-in-conduit conductor (CICC) concept, a variety of alloys have been proposed for fabricating the jacket. The jacket provides primary containment of the liquid helium coolant and is typically also the primary structural component for the magnet coils. These functions create requirements for strength, toughness, fatigue crack resistance, and fabricability. When the CICC uses Nb3Sn superconductor, the conduit alloy must retain good mechanical properties after exposure to the superconductor's reaction heat treatment. Here we present data from cryogenic fracture toughness and fatigue crack growth rate tests on 316LN and a Cr-Mo-Ni base super-alloy (Haynes 242) at 4 K before and after the exposure to the heat treatment. These alloys are presently being considered as candidates for use in the next-generation series connected hybrid magnet for the NHMFL. Both of the alloys are found to have adequate fatigue and fracture properties for the CICC application while the superalloy has distinctly better elastic properties of modulus and thermal expansion.

  9. Systematic Study of a Family of Butterfly-Like {M2Ln2} Molecular Magnets (M = Mg(II), Mn(III), Co(II), Ni(II), and Cu(II); Ln = Y(III), Gd(III), Tb(III), Dy(III), Ho(III), and Er(III)).

    PubMed

    Moreno Pineda, Eufemio; Chilton, Nicholas F; Tuna, Floriana; Winpenny, Richard E P; McInnes, Eric J L

    2015-06-15

    A family of 3d-4f [M(II)2Ln(III)2(μ3-OH)2(O2C(t)Bu)10](2-) "butterflies" (where M(II) = Mg, Co, Ni, and Cu; Ln(III) = Y, Gd, Tb, Dy, Ho, and Er) and [Mn(III)2Ln(III)2(μ3-O)2(O2C(t)Bu)10](2-) molecules (where Ln(III) = Y, Gd, Tb, Dy, Ho, and Er) has been synthesized and characterized through single-crystal X-ray diffraction, SQUID magnetometry, and ab initio calculations. All dysprosium- and some erbium-containing tetramers showed frequency-dependent maxima in the out-of-phase component of the susceptibility associated with slow relaxation of magnetization, and hence, they are single-molecule magnets (SMMs). AC susceptibility measurements have shown that the SMM behavior is entirely intrinsic to the Dy and Er sites and the magnitude of the energy barrier is influenced by the interactions between the 4f and the 3d metal. A trend is observed between the strength of the 3d-4f exchange interaction between and the maximum observed in the χ″M(T). PMID:26016421

  10. Uniformly microsized luminescent materials obtained through a solid state reaction of WO{sub 3} with Ln{sup 3+}-exchanged zeolite L at 700 °C

    SciTech Connect

    Wang, Yige; Fang, Yi; Zhang, Wenjun; Zhang, Li; Chen, Yuhuan; Yu, Xiaoyan

    2013-06-01

    Graphical abstract: We have reported the modification of Ln3+/ZL microcrystals by the tungstate-oxygen species via a solid state reaction of WO{sub 3} and Ln{sup 3+}-exchanged zeolite L at 700 °C. Highlights: ► Luminescent materials were obtained from zeolite L crystals. ► The materials show characteristic luminescence of Eu{sup 3+} and Tb{sup 3+} ions. ► The framework of zeolite L crystals has been kept during the annealing process. ► Energy transfer from tungstate-oxygen species to lanthanide was confirmed. - Abstract: In this work, we report the uniformly microsized luminescent materials prepared by a solid state reaction of WO{sub 3} and Ln{sup 3+}-exchanged zeolite L at 700 °C. The obtained materials were investigated by SEM, XRD and photoluminescence spectroscopy. The influence of tungstate-oxygen species on the morphology and luminescence of the materials were discussed in detail. Energy transfer from the tungstate-oxygen species to Eu{sup 3+} and Tb{sup 3+} ions have been demonstrated by the photoluminescence spectra, implying the loading of tungstate-oxygen species into the nanochannels of the crystals and the close proximity of which to Eu{sup 3+} ions.

  11. Lanthanide Metal-Organic Frameworks with Six-Coordinated Ln(III) Ions and Free Functional Organic Sites for Adsorptions and Extensive Catalytic Activities.

    PubMed

    Zhu, Yu; Zhu, Min; Xia, Li; Wu, Yunlong; Hua, Hui; Xie, Jimin

    2016-01-01

    Three chelating-amino-functionalized lanthanide metal-organic frameworks, Y-DDQ, Dy-DDQ and Eu-DDQ, were synthesized with a flexible dicarboxylate ligand based on quinoxaline (H2DDQ = N, N'-dibenzoic acid-2,3-diaminoquinoxaline). The three-dimensional framework is constructed by the H2DDQ linkers connecting the zigzag ladders, showing a net of sra topology. In the structures, one kind of Ln(III) ions metal centers are six-coordinated and thus can potentially behave as open metal sites (OMSs), while the free chelating amino groups can act as free functional organic sites (FOSs). The N2 and Ar adsorption behaviors indicate that these Ln-DDQ exhibits stable microporous frameworks with high surface area after remove of the solvents. Owing to presence of OMSs and FOSs, these MOFs show good ability of CO2, dyes captures and Lewis acid catalyst for cyanosilylation reaction. In view of the existing FOSs in the framework, Pd NPs were immobilized onto the MOFs through graft interactions between free chelating amino groups and metal ions precursor using postsynthetic modification. The well dispersed Pd@Ln-DDQs exhibit efficient and recyclable catalytic reduction of 4-nitrophenol to 4-aminophenol, and they can also act as an excellent catalyst for Suzuki-Miyaura cross-coupling reactions with the exposed Pd NPs. PMID:27431731

  12. Lanthanide Metal-Organic Frameworks with Six-Coordinated Ln(III) Ions and Free Functional Organic Sites for Adsorptions and Extensive Catalytic Activities

    PubMed Central

    Zhu, Yu; Zhu, Min; Xia, Li; Wu, Yunlong; Hua, Hui; Xie, Jimin

    2016-01-01

    Three chelating-amino-functionalized lanthanide metal-organic frameworks, Y-DDQ, Dy-DDQ and Eu-DDQ, were synthesized with a flexible dicarboxylate ligand based on quinoxaline (H2DDQ = N, N′-dibenzoic acid-2,3-diaminoquinoxaline). The three-dimensional framework is constructed by the H2DDQ linkers connecting the zigzag ladders, showing a net of sra topology. In the structures, one kind of Ln(III) ions metal centers are six-coordinated and thus can potentially behave as open metal sites (OMSs), while the free chelating amino groups can act as free functional organic sites (FOSs). The N2 and Ar adsorption behaviors indicate that these Ln-DDQ exhibits stable microporous frameworks with high surface area after remove of the solvents. Owing to presence of OMSs and FOSs, these MOFs show good ability of CO2, dyes captures and Lewis acid catalyst for cyanosilylation reaction. In view of the existing FOSs in the framework, Pd NPs were immobilized onto the MOFs through graft interactions between free chelating amino groups and metal ions precursor using postsynthetic modification. The well dispersed Pd@Ln-DDQs exhibit efficient and recyclable catalytic reduction of 4-nitrophenol to 4-aminophenol, and they can also act as an excellent catalyst for Suzuki-Miyaura cross-coupling reactions with the exposed Pd NPs. PMID:27431731

  13. Lanthanide Metal-Organic Frameworks with Six-Coordinated Ln(III) Ions and Free Functional Organic Sites for Adsorptions and Extensive Catalytic Activities

    NASA Astrophysics Data System (ADS)

    Zhu, Yu; Zhu, Min; Xia, Li; Wu, Yunlong; Hua, Hui; Xie, Jimin

    2016-07-01

    Three chelating-amino-functionalized lanthanide metal-organic frameworks, Y-DDQ, Dy-DDQ and Eu-DDQ, were synthesized with a flexible dicarboxylate ligand based on quinoxaline (H2DDQ = N, N‧-dibenzoic acid-2,3-diaminoquinoxaline). The three-dimensional framework is constructed by the H2DDQ linkers connecting the zigzag ladders, showing a net of sra topology. In the structures, one kind of Ln(III) ions metal centers are six-coordinated and thus can potentially behave as open metal sites (OMSs), while the free chelating amino groups can act as free functional organic sites (FOSs). The N2 and Ar adsorption behaviors indicate that these Ln-DDQ exhibits stable microporous frameworks with high surface area after remove of the solvents. Owing to presence of OMSs and FOSs, these MOFs show good ability of CO2, dyes captures and Lewis acid catalyst for cyanosilylation reaction. In view of the existing FOSs in the framework, Pd NPs were immobilized onto the MOFs through graft interactions between free chelating amino groups and metal ions precursor using postsynthetic modification. The well dispersed Pd@Ln-DDQs exhibit efficient and recyclable catalytic reduction of 4-nitrophenol to 4-aminophenol, and they can also act as an excellent catalyst for Suzuki-Miyaura cross-coupling reactions with the exposed Pd NPs.

  14. Three novel lanthanide metal-organic frameworks (Ln-MOFs) constructed by unsymmetrical aromatic dicarboxylatic tectonics: synthesis, crystal structures and luminescent properties.

    PubMed

    Wu, Ya-Pan; Li, Dong-Sheng; Xia, Wei; Guo, Sha-Sha; Dong, Wen-Wen

    2014-01-01

    Three novel Ln(III)-based coordination polymers, {[Ln2 (2,4-bpda)3 (H2O)x]·yH2O}n (Ln = La (III) (1), x = 2, y = 0, Ce (III) (2), Pr (III) (3), x = 4, y = 1) (2,4-H2bpda = benzophenone-2,4-dicarboxylic acid) have been prepared via a solvothermal method and characterized by elemental analysis, IR, and single-crystal X-ray diffraction techniques. Complex 1 exhibits a 3D complicated framework with a new 2-nodal (3,7)-connected (42·5) (44·51·66·8) topology. Complexes 2 and 3 are isomorphous, and feature a 3D 4-connected (65·8)-CdSO4 network. Moreover, solid-state properties such as thermal stabilities and luminescent properties of 1 and 2 were also investigated. Complex 1 crystallized in a monoclinic space group P21/c with a = 14.800 (3), b = 14.500 (3), c = 18.800 (4) Å, β = 91.00 (3), V = 4033.9 (14) Å3 and Z = 4. Complex 2 crystallized in a monoclinic space group Cc with a = 13.5432 (4), b = 12.9981 (4), c = 25.7567 (11) Å, β = 104.028 (4), V = 1374.16 (7) Å3 and Z = 4. PMID:25215590

  15. The solution structure of Ln (DOTP) 5- complexxes. A comparison of lanthanide-induced paramagnetic shifts with the MMX energy-minimized structure

    NASA Astrophysics Data System (ADS)

    Geraldes, Carlos F. G. C.; Sherry, A. Dean; Kiefer, Garry E.

    Complexes between the trivalent lanthanide ions and the macrocyclic chelate 1,4,7,10-tetraazacyclododecane- N,N',N″,N‴-tetra(methylene phosphonate) (DOTP) have been examined by high-resolution NMR spectroscopy. The proton spectra of the diamagnetic La(DOTP) 5- and Lu(DOTP) 5- complexes provide evidence for very rigid chelate structures with the ethylenediamine-containing chelate rings essentially locked into a single conformation at room temperature. The activation energy for ethylenediamine chelate ring interconversions in these complexes is approximately 100 kJ mol -1, considerably higher than that reported previously for the corresponding Ln(DOTA) - complexes (DOTA is the tetraacetate analog of DOTP). Lanthanide-induced shifts are reported for all 1H, 13C, and 31P nuclei in 11 Ln(DOTP) 5- complexes. The proton spectra of these complexes display unusually large lanthanide-induced shifts, one showing a spectrum in which the 1H resonances span 900 ppm. The contact and pseudocontact contributions to these shifts were separated using Reilley's temperature-independent method and the resulting pseudocontact lanthanide-induced NMR shifts were in excellent agreement with those calculated for a structure derived using MMX molecular modeling methods. The pseudocontact shifts provide evidence for Ln (DOTP) 5- chelates which have virtually identical structures along the lanthanide series, with the possible exception of Tm(DOTP) 5-.

  16. 17β-Estradiol (E-2) administration to male (NZB × SWR)F₁ mice results in increased Id(LN)F₁-reactive memory T-lymphocytes and accelerated glomerulonephritis.

    PubMed

    Feng, F; Silvin, C J; Fiore, N C; Stoll, M L; Price, K E; Shanley, P S; Silverstone, A E; Gavalchin, J

    2012-03-01

    While it has been shown that estradiol treatment accelerates the onset of lupus nephritis with autoantibody production and kidney damage in both male and female lupus-prone mice, the specific mechanism(s) involved are unknown. Our previous work has shown that alterations in Id(LN)F(1)-reactive T cells and Id(LN)F(1)+ antibodies correlated closely with the onset of autoimmune nephritis in female F(1) progeny of SWR and NZB (SNF(1)) mice, supporting a critical role for the Id(LN)F(1) idiotype in the development of disease. Since male SNF(1) mice normally do not develop nephritis, we tested whether administration of 17β-estradiol (E-2) to male SNF(1) mice would increase Id(LN)F(1) IgG levels and autoreactive T cells, and further, induce nephritis. We found that E-2-treated male SNF(1) mice developed nephritis with the same time course and mean survival as normal female SNF(1) mice. Moreover, it appeared that the mechanism involved increased serum Id(LN)F(1)(+)IgG and its deposition in kidney glomeruli, preceded by a striking twofold increase in T-lymphocytes expressing the memory phenotype (CD44(+)CD45RB(lo)) predominantly in the Id(LN)F(1)-reactive T-cell population. In addition, we noted that cells with this phenotype were increased in the nephritic kidneys of treated mice, suggesting a direct involvement of those cells in the renal pathology. E-2 treatment also induced increased numbers of pathogenic Id(LN)F(1)+ antibody-producing B cells and elevated presentation of pathogenic Id(LN)F(1)+ peptide. Taken together, these results suggest a mechanism of E-2-induced acceleration of autoimmune disease in lupus-prone mice may involve expansion of autoreactive idiotypic T and B-cell populations.

  17. Syntheses, Structure, Magnetism, and Optical Properties of the Ordered Interlanthanide Copper Chalcogenides Ln{sub 2}YbCuQ{sub 5} (Ln = La, Ce, Pr, Nd, Sm; Q = S, Se): Evidence for Unusual Magnetic Ordering in Sm{sub 2}YbCuS{sub 5}

    SciTech Connect

    Jin, Geng Bang; Choi, Eun Sang; Guertin, Robert P.; Booth, Corwin H.; Albrecht-Schmitt, Thomas E.

    2010-11-19

    Ln{sub 2}YbCuQ{sub 5} (Ln = La, Ce, Pr, Nd, Sm; Q = S, Se) have been prepared by direct reaction of the elements in Sb{sub 2}Q{sub 3} (Q = S, Se) fluxes at 900 °C. All compounds have been characterized by single-crystal X-ray diffraction methods and they are isotypic. The structure of Ln{sub 2}YbCuQ{sub 5} consists of one-dimensional {sup 1}{sub {infinity}} [YbCuQ{sub 5}]{sup 6-} ribbons extending along the b axis that are connected by larger Ln{sup 3+} ions. Each ribbon is constructed from two single chains of [YbQ{sub 6}] octahedra with one double chain of [CuQ{sub 5}] trigonal bipyramids in the middle. All three chains connect with each other via edge-sharing. There are two crystallographically unique Ln atoms, one octahedral Yb site, and two disordered Cu positions inside of distorted Q{sub 5} trigonal bipyramids. Both Ln atoms are surrounded by eight Q atoms in bicapped trigonal prisms. The magnetic properties of Ln{sub 2}YbCuQ{sub 5} have been characterized using magnetic susceptibility and heat capacity measurements, while their optical properties have been explored using UV-vis-NIR diffuse reflectance spectroscopy. Cesub 2}YbCuSe{sub 5}, La{sub 2}YbCuS{sub 5}, Ce{sub 2}YbCuS{sub 5}, and Pr{sub 2}YbCuS{sub 5} are Curie-Weiss paramagnets. La{sub 2}YbCuSe{sub 5} and Nd{sub 2}YbCuS{sub 5} show evidence for short-range antiferromagnetic ordering at low temperatures. Sm{sub 2}YbCuS{sub 5} shows magnetic ordering at 5.9 K, followed by negative magnetization at low external fields. The band gaps of La{sub 2}YbCuSe{sub 5}, Ce{sub 2}YbCuSe{sub 5}, La{sub 2}YbCuS{sub 5}, Ce{sub 2}YbCuS{sub 5}, Pr{sub 2}YbCuS{sub 5}, Nd{sub 2}YbCuS{sub 5},and Sm{sub 2}YbCuS{sub 5} are 1.15 eV, 1.05 eV, 1.45 eV, 1.37 eV, 1.25 eV, 1.35 eV, and 1.28 eV respectively.

  18. Series of edge-sharing bi-triangle Ln4 clusters with a μ4-NO3- bridge: syntheses, structures, luminescence, and the SMM behavior of the Dy4 analogue.

    PubMed

    Zou, Hua-Hong; Wang, Rong; Chen, Zi-Lu; Liu, Dong-Cheng; Liang, Fu-Pei

    2014-02-14

    A series of Ln4 clusters, [Ln4L2(μ3-OH)2(μ4-NO3)(NO3)4(OCH3)(H2O)]·xMeCN·yMeOH (Ln = Gd (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), L = 2-{[2-(2-hydroxy-ethoxy)-ethylimino]-methyl}-6-methoxyphenol), have been synthesized by the reaction of Ln(NO)3 and a Schiff-base ligand formed in situ. The six complexes display similar structures, with an overall metal core comprising two edge-sharing triangular Ln3 units linked by a μ4-NO3(-) bridge. The luminescence spectrum of complex 2 shows the characteristic emission of the Tb(III) ions. The magnetic susceptibility studies reveal that the Ln(III) ions are very weakly interacting in all six compounds. Frequency dependence of the ac-susceptibility was found for 3, suggesting a typical single-molecule magnet (SMM) behavior with an anisotropic barrier of 28 K.

  19. Magnetism and Raman spectroscopy of the dimeric lanthanide iodates Ln(IO{sub 3}){sub 3} (Ln=Gd, Er) and magnetism of Yb(IO{sub 3}){sub 3}

    SciTech Connect

    Sykora, Richard E. Khalifah, Peter; Assefa, Zerihun; Albrecht-Schmitt, Thomas E.; Haire, Richard G.

    2008-08-15

    Colorless single crystals of Gd(IO{sub 3}){sub 3} or pale pink single crystals of Er(IO{sub 3}){sub 3} have been formed from the reaction of Gd metal with H{sub 5}IO{sub 6} or Er metal with H{sub 5}IO{sub 6} under hydrothermal reaction conditions at 180 deg. C. The structures of both materials adopt the Bi(IO{sub 3}){sub 3} structure type. Crystallographic data are (MoK{alpha}, {lambda}=0.71073 A): Gd(IO{sub 3}){sub 3}, monoclinic, space group P2{sub 1}/n, a=8.7615(3) A, b=5.9081(2) A, c=15.1232(6) A, {beta}=96.980(1){sup o}, V=777.03(5) Z=4, R(F)=1.68% for 119 parameters with 1930 reflections with I>2{sigma}(I); Er(IO{sub 3}){sub 3}, monoclinic, space group P2{sub 1}/n, a=8.6885(7) A, b=5.9538(5) A, c=14.9664(12) A, {beta}=97.054(1){sup o}, V=768.4(1) Z=4, R(F)=2.26% for 119 parameters with 1894 reflections with I>2{sigma}(I). In addition to structural studies, Gd(IO{sub 3}){sub 3}, Er(IO{sub 3}){sub 3}, and the isostructural Yb(IO{sub 3}){sub 3} were also characterized by Raman spectroscopy and magnetic property measurements. The results of the Raman studies indicated that the vibrational profiles are adequately sensitive to distinguish between the structures of the iodates reported here and other lanthanide iodate systems. The magnetic measurements indicate that only in Gd(IO{sub 3}){sub 3} did the 3+ lanthanide ion exhibit its full 7.9 {mu}{sub B} Hund's rule moment; Er{sup 3+} and Yb{sup 3+} exhibited ground state moments and gap energy scales of 8.3 {mu}{sub B}/70 K and 3.8 {mu}{sub B}/160 K, respectively. Er(IO{sub 3}){sub 3} exhibited extremely weak ferromagnetic correlations (+0.4 K), while the magnetic ions in Gd(IO{sub 3}){sub 3} and Yb(IO{sub 3}){sub 3} were fully non-interacting within the resolution of our measurements ({approx}0.2 K). - Graphical abstract: Three f-element iodates Ln(IO{sub 3}){sub 3} (Ln=Gd, Er, Yb), all containing the Bi(IO{sub 3}){sub 3} structure type, were characterized by Raman spectroscopy and magnetic property measurements

  20. Lanthanide N,N'-piperazine-bis(methylenephosphonates) (Ln=La, Ce, Nd) that display flexible frameworks, reversible hydration and cation exchange

    SciTech Connect

    Mowat, John P.S.; Groves, John A.; Wharmby, Michael T.; Miller, Stuart R.; Li Yang; Lightfoot, Philip; Wright, Paul A.

    2009-10-15

    Hydrothermal syntheses of lanthanide bisphosphonate metal organic frameworks comprising the light lanthanides lanthanum, cerium and neodymium and N,N'-piperazine bis(methylenephosphonic acid) (H{sub 2}L(1) and its 2-methyl and 2,5-dimethyl derivatives (H{sub 2}L(2) and H{sub 2}L(3)) gives three new structure types. At elevated starting pH (ca. 5 and above) syntheses give 'type I' materials with all metals and acids of the study (MLnLxH{sub 2}O, M=Na, K, Cs; Ln=La, Ce, Nd; x{approx}4: KCeL(1).4H{sub 2}O, C2/c, a=23.5864(2) A, b=12.1186(2) A, c=5.6613(2) A, beta=93.040(2){sup o}). The framework of structure type I shows considerable flexibility as the ligand is changed, due mainly to rotation around the -N-CH{sub 2}- bond of the linker in response to steric considerations. Type I materials demonstrate cation exchange and dehydration and rehydration behaviour. Upon dehydration of KCeL.4H{sub 2}O, the space group changes to P2{sub 1}/n, a=21.8361(12) A, b=9.3519(4) A, c=5.5629(3) A, beta=96.560(4){sup o}, as a result of a change of the piperazine ring from chair to boat configuration. When syntheses are performed at lower pH, two other structure types crystallise. With the 'non-methyl' ligand 1, type II materials result (LnL(1)H{sub 2}L(1).4.5H{sub 2}O: Ln=La, P-1, a=5.7630(13) A, b=10.213(2) A, c=11.649(2) A, alpha=84.242(2){sup o}, beta=89.051(2){sup o}, gamma=82.876(2){sup o}) in which one half of the ligands coordinate via the piperazine nitrogen atoms. With the 2-methyl ligand, structure type III crystallises (LnHL(2).4H{sub 2}O: Ln=Nd, Ce, P2{sub 1}/c, a=5.7540(9) A, b=14.1259(18) A, c=21.156(5) A, beta=90.14(2){sup o}) due to unfavourable steric interactions of the methyl group in structure type II. - Graphical abstract: The lanthanides La, Ce and Nd give a family of metal organic frameworks based on N,N'-piperazinebismethylenephosphonate ligands: these display reversible dehydration, structural flexibility and cation exchange.

  1. New Cathode Materials for Intermediate Temperature Solid Oxide Fuel Cells

    SciTech Connect

    Allan J. Jacobson

    2005-11-17

    Operation of SOFCs at intermediate temperatures (500-800 C) requires new combinations of electrolyte and electrode materials that will provide both rapid ion transport across the electrolyte and electrode--electrolyte interfaces and efficient electrocatalysis of the oxygen reduction and fuel oxidation reactions. This project concentrates on materials and issues associated with cathode performance that are known to become limiting factors as the operating temperature is reduced. The specific objectives of the proposed research are to develop cathode materials that meet the electrode performance targets of 1.0 W/cm{sup 2} at 0.7 V in combination with YSZ at 700 C and with GDC, LSGM or bismuth oxide based electrolytes at 600 C. The performance targets imply an area specific resistance of {approx}0.5 {Omega}cm{sup 2} for the total cell. The research strategy is to investigate both established classes of materials and new candidates as cathodes, to determine fundamental performance parameters such as bulk diffusion, surface reactivity and interfacial transfer, and to couple these parameters to performance in single cell tests. In this report, the oxygen exchange kinetics of a P2 composition are described in detail. The oxygen exchange kinetics of the oxygen deficient double perovskite LnBaCo{sub 2}O{sub 5.5+{delta}} (Ln=Pr and Nd) have been determined by electrical conductivity relaxation. The high electronic conductivity and rapid diffusion and surface exchange kinetics of PBCO suggest its application as cathode material in intermediate temperature solid oxide fuel cells.

  2. Magnesium Oxide

    MedlinePlus

    ... different reasons. Some people use it as an antacid to relieve heartburn, sour stomach, or acid indigestion. ... stomach.Do not take magnesium oxide as an antacid for longer than 2 weeks unless your doctor ...

  3. Nickel-regulated heart rate variability: The roles of oxidative stress and inflammation

    SciTech Connect

    Chuang, Hsiao-Chi; Hsueh, Tzu-Wei; Chang, Chuen-Chau; Hwang, Jing-Shiang; Chuang, Kai-Jen; Yan, Yuan-Horng; Cheng, Tsun-Jen

    2013-01-15

    Heart rate variability (HRV) has been reported to be a putative marker of cardiac autonomic imbalance caused by exposure to ambient particulate matter (PM). Our objective in this study was to determine the effects on HRV from exposure to nickel, an important chemical component of ambient PM that results in oxidative stress and inflammation. HRV data were collected for 72 h before lung exposure (baseline) and 72 h after intratracheal exposure (response) to nickel sulphate (NiSO{sub 4}; 526 μg) in Wistar Kyoto (WKY) and spontaneously hypertensive (SH) rats. The antioxidant N-acetyl-L-cysteine (NAC) and the anti-inflammatory celecoxib were intraperitoneally injected to examine post-exposure oxidative and inflammatory responses. Self-controlled experiments examined the effects of NiSO{sub 4} exposure on average normal-to-normal intervals (ANN), natural logarithm-transformed standard deviation of the normal-to-normal intervals (LnSDNN) and root mean square of successive differences of adjacent normal-to-normal intervals (LnRMSSD); the resulting data were sequentially analysed using the generalised estimating equation model. HRV effects on NiSO{sub 4}-exposed SH rats were greater than those on NiSO{sub 4}-exposed WKY rats. After adjusted the HRV responses in the WKY rats as control, ANN and LnRMSSD were found to be quadratically increased over 72 h after exposure to NiSO{sub 4}. Both NAC and celecoxib mitigated the NiSO{sub 4}-induced alterations in HRV during the exposure period. The results suggest that concurrent Ni-induced oxidative stress and inflammatory responses play important roles in regulating HRV. These findings help bridge the gap between epidemiological and clinical studies on the plausible mechanisms of the cardiovascular consequences induced by chemical components in ambient PM. -- Highlights: ► To determine the effects on HRV from exposure to nickel. ► ANN and LnRMSSD were found to be quadratically increased after exposure to Ni. ► NAC and

  4. Low-Temperature Sensitization Behavior of Base, Heat-Affected Zone, and Weld Pool in AISI 304LN

    NASA Astrophysics Data System (ADS)

    Singh, Raghuvir; Das, Gautam; Singh, P. K.; Chattoraj, I.

    2009-05-01

    Present investigations were focused on low-temperature sensitization (LTS) behavior of 304LN stainless steels considered from pipes of two different thicknesses. The specimens for the present study were taken from solution-annealed pipes (of varying thicknesses) and welded pipes (including the heat-affected zone (HAZ)). The specimens were subjected to thermal aging at 400 °C and 450 °C for different durations ranging from 125 to 8000 hours, to evaluate their sensitization susceptibility. The aging durations were worked out to simulate the 30-to-100-year life of the studied stainless steel at 300 °C using the Arrheneous equation and considering the activation energy of 150 kJ/mol. The thermally aged specimens were characterized for their degree of sensitization (DOS) and susceptibility to intergranular corrosion (IGC) by double-loop (DL) electrochemical potentiokinetic reactivation (EPR) and by methods given in the ASTM A262 practices A and E. It has been clearly shown that the weld pool is more sensitive to IGC than are the base and the HAZ at both the aging temperatures (LTS), because they showed IGC cracks during the bending subsequent to the boiling in H2SO4-CuSO4 solution. Both the base and the HAZ of the thicker pipe material showed susceptibility to sensitization, as indicated by the increasing DOS and “dual-type” microstructure during electrolytic oxalic acid (EOA) etching; however, they were found safe from IGC for the studied sensitization times. The susceptibility to sensitization and IGC in the weld pool is related to the presence of copious delta ferrite with chromium diffusivity that is accelerated compared to the austenite phase. The time-temperature-sensitization (TTS) curves were prepared accordingly, based on these results.

  5. Study of magnetism in Ni-Cr hardface alloy deposit on 316LN stainless steel using magnetic force microscopy

    NASA Astrophysics Data System (ADS)

    Kishore, G. V. K.; Kumar, Anish; Chakraborty, Gopa; Albert, S. K.; Rao, B. Purna Chandra; Bhaduri, A. K.; Jayakumar, T.

    2015-07-01

    Nickel base Ni-Cr alloy variants are extensively used for hardfacing of austenitic stainless steel components in sodium cooled fast reactors (SFRs) to avoid self-welding and galling. Considerable difference in the compositions and melting points of the substrate and the Ni-Cr alloy results in significant dilution of the hardface deposit from the substrate. Even though, both the deposit and the substrate are non-magnetic, the diluted region exhibits ferromagnetic behavior. The present paper reports a systematic study carried out on the variations in microstructures and magnetic behavior of American Welding Society (AWS) Ni Cr-C deposited layers on 316 LN austenitic stainless steels, using atomic force microscopy (AFM) and magnetic force microscopy (MFM). The phase variations of the oscillations of a Co-Cr alloy coated magnetic field sensitive cantilever is used to quantitatively study the magnetic strength of the evolved microstructure in the diluted region as a function of the distance from the deposit/substrate interface, with the spatial resolution of about 100 nm. The acquired AFM/MFM images and the magnetic property profiles have been correlated with the variations in the chemical compositions in the diluted layers obtained by the energy dispersive spectroscopy (EDS). The study indicates that both the volume fraction of the ferromagnetic phase and its ferromagnetic strength decrease with increasing distance from the deposit/substrate interface. A distinct difference is observed in the ferromagnetic strength in the first few layers and the ferromagnetism is observed only near to the precipitates in the fifth layer. The study provides a better insight of the evolution of ferromagnetism in the diluted layers of Ni-Cr alloy deposits on stainless steel.

  6. PS1 satellite refrigerator heat exchanger: Failure of the LN2 heat exchanger to low pressure helium

    SciTech Connect

    Squires, B.

    1992-11-01

    The PS1 heat exchanger is one of three prototype heat exchangers built by Atomic Welders before Meyer was given the contract to build the Satellite Refrigerator Heat Exchanger components. This heat exchanger was first put into operation in July 1983. In November 1991, this heat exchanger experienced a failure in the shell of heat exchanger 1 causing nitrogen to contaminate the helium in the refrigerator. The resulting contamination plugged heat exchanger 3. The break occurred at a weld that connects a 0.25 inch thick ring to heat exchanger 1. The failure appears to be a fatigue of the shell due to temperature oscillations. The flow rate through the break was measured to be 1.0 scfm for a pressure drop over the crack of 50 psi. An ANSYS analysis of the failure area indicates that the stress would be 83,000 psi if the metal did not yield. This is based on cooling down the shell to 80K from 300K with the shell side helium on the outside of the shell at 300K. This is the largest change in temperature that occurs during operation. During normal operations, the temperature swings are not nearly this large, however temperatures down to 80K are not unusual (LN2 overflowing pot). The highest temperatures are typically 260K. The analysis makes no attempt to estimate the stress concentration factor at this weld but there is no doubt that it is greater than 1. No estimate as to the number of cycles to cause failure was calculated nor any estimate as to the actual number of cycles was made.

  7. Thick-section weldments in 21-6-9 and 316LN stainless steel for fusion energy applications

    NASA Astrophysics Data System (ADS)

    Alexander, D. J.; Goodwin, G. M.

    The Burning Plasma Experiment (BPX), formerly known as the Compact Ignition Tokomak, will be a major advance in the design of a fusion reactor. The successful construction of fusion reactors will require extensive welding of thick-section stainless steel plates. Severe service conditions will be experienced by the structure. Operating temperatures will range from room temperature (300 K) to liquid nitrogen temperature (77 K), and perhaps even lower. The structure will be highly stressed, and subject to sudden impact loads if plasma disruptions occur. This demands a combination of high strength and high toughness from the weldments. Significant portions of the welding will be done in the field, so preweld and postweld heat treatments will be difficult. The thick sections to be welded will require a high deposition rate process, and will result in significant residual stresses in the materials. Inspection of these thick sections in complex geometries will be very difficult. All of these constraints make it essential that the welding procedures and alloys be well understood, and the mechanical properties of the welds and their heat-affected zones must be adequately characterized. The candidate alloy for structural applications in the BPX such as the magnet cases was initially selected as 21-6-9 austenitic stainless steel, and later changed to 316LN stainless steel. This study examined several possible filler materials for thick-section (25 to 50 mm) weldments in these two materials. The tensile and Charpy V-notch properties were measured at room temperature and 77 K. The fracture toughness was measured for promising materials.

  8. Thick-section weldments in 21-6-9 and 316LN stainless steel for fusion energy applications

    SciTech Connect

    Alexander, D.J.; Goodwin, G.M.

    1991-01-01

    The Burning Plasma Experiment (BPX), formerly known as the Compact Ignition Tokomak, will be a major advance in the design of a fusion reactor. The successful construction of fusion reactors will require extensive welding of thick-section stainless steel plates. Severe service conditions will be experienced by the structure. Operating temperatures will range from room temperature (300 K) to liquid nitrogen temperature (77 K), and perhaps even lower. The structure will be highly stressed, and subject to sudden impact loads if plasma disruptions occur. This demands a combination of high strength and high toughness from the weldments. Significant portions of the welding will be done in the field, so preweld and postweld heat treatments will be difficult. The thick sections to be welded will require a high deposition rate process, and will result in significant residual stresses in the materials. Inspection of these thick sections in complex geometries will be very difficult. All of these constraints make it essential that the welding procedures and alloys be well understood, and the mechanical properties of the welds and their heat-affected zones must be adequately characterized. The candidate alloy for structural applications in the BPX such as the magnet cases was initially selected as 21-6-9 austenitic stainless steel, and later changed to 316LN stainless steel. This study examined several possible filler materials for thick-section (25 to 50 mm) weldments in these two materials. The tensile and Charpy V-notch properties were measured at room temperature and 77 K. The fracture toughness was measured for promising materials.

  9. Creep Deformation and Rupture Behavior of Single- and Dual-Pass 316LN Stainless-Steel-Activated TIG Weld Joints

    NASA Astrophysics Data System (ADS)

    Vijayanand, V. D.; Vasudevan, M.; Ganesan, V.; Parameswaran, P.; Laha, K.; Bhaduri, A. K.

    2016-06-01

    Creep deformation and rupture behavior of single-pass and dual-pass 316LN stainless steel (SS) weld joints fabricated by an autogenous activated tungsten inert gas welding process have been assessed by performing metallography, hardness, and conventional and impression creep tests. The fusion zone of the single-pass joint consisted of columnar zones adjacent to base metals with a central equiaxed zone, which have been modified extensively by the thermal cycle of the second pass in the dual-pass joint. The equiaxed zone in the single-pass joint, as well as in the second pass of the dual-pass joint, displayed the lowest hardness in the joints. In the dual-pass joint, the equiaxed zone of the first pass had hardness comparable to the columnar zone. The hardness variations in the joints influenced the creep deformation. The equiaxed and columnar zone in the first pass of the dual-pass joint was more creep resistant than that of the second pass. Both joints possessed lower creep rupture life than the base metal. However, the creep rupture life of the dual-pass joint was about twofolds more than that of the single-pass joint. Creep failure in the single-pass joint occurred in the central equiaxed fusion zone, whereas creep cavitation that originated in the second pass was blocked at the weld pass interface. The additional interface and strength variation between two passes in the dual-pass joint provides more restraint to creep deformation and crack propagation in the fusion zone, resulting in an increase in the creep rupture life of the dual-pass joint over the single-pass joint. Furthermore, the differences in content, morphology, and distribution of delta ferrite in the fusion zone of the joints favors more creep cavitation resistance in the dual-pass joint over the single-pass joint with the enhancement of creep rupture life.

  10. Large-scale synthesis of Lu{sub 2}O{sub 3}:Ln{sup 3+} (Ln{sup 3+} = Eu{sup 3+}, Tb{sup 3+}, Yb{sup 3+}/Er{sup 3+}, Yb{sup 3+}/Tm{sup 3+}, and Yb{sup 3+}/Ho{sup 3+}) microspheres and their photoluminescence properties

    SciTech Connect

    Gao, Yu; Gong, Jian; Fan, Miaomiao; Fang, Qinghong; Wang, Na; Han, Wenchi; Xu, Zhenhe

    2012-12-15

    Graphical abstract: In this work, multicolor and monodisperse Lu{sub 2}O{sub 3}:Ln{sup 3+} (Ln{sup 3+} = Eu{sup 3+}, Tb{sup 3+}, Yb{sup 3+}/Er{sup 3+}, Yb{sup 3+}/Tm{sup 3+}, and Yb{sup 3+}/Ho{sup 3+}) microspheres were prepared by a homogeneous precipitation method followed by a subsequent calcination process. Display Omitted Highlights: ► Lu{sub 2}O{sub 3}:Ln{sup 3+} microspheres were prepared by a precipitation followed by a calcination process. ► Lu{sub 2}O{sub 3}:Eu{sup 3+}/Tb{sup 3+} samples exhibit respective red or green emissions. ► Lu{sub 2}O{sub 3}:Yb{sup 3+}/Er{sup 3+}/Tm{sup 3+}/Ho{sup 3+} exhibit emissions of green, blue, yellow-green, respectively. ► These finding may find potential applications in bioanalysis and field emission displays. -- Abstract: In this work, multicolor and monodisperse Lu{sub 2}O{sub 3}:Ln{sup 3+} (Ln{sup 3+} = Eu{sup 3+}, Tb{sup 3+}, Yb{sup 3+}/Er{sup 3+}, Yb{sup 3+}/Tm{sup 3+}, and Yb{sup 3+}/Ho{sup 3+}) microspheres were prepared by a homogeneous precipitation method followed by a subsequent calcination process. X-ray diffraction (XRD), Fourier transformed infrared (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectra, and cathodoluminescence (CL) spectra were employed to characterize the samples. Upon ultraviolet and low-voltage electron beams excitation, Lu{sub 2}O{sub 3}:Ln{sup 3+} (Ln{sup 3+} = Eu{sup 3+} and Tb{sup 3+}) samples exhibit respective bright red (Eu{sup 3+}, {sup 5}D{sub 0} → {sup 7}F{sub 2}) and green (Tb{sup 3+}, {sup 5}D{sub 4} → {sup 7}F{sub 5}) down-conversion (DC) emissions. Under 980 nm NIR irradiation, Lu{sub 2}O{sub 3}:Ln{sup 3+} (Ln{sup 3+} = Yb{sup 3+}/Er{sup 3+}, Yb{sup 3+}/Tm{sup 3+}, and Yb{sup 3+}/Ho{sup 3+}) exhibit characteristic up-conversion (UC) emissions of green (Er{sup 3+}, {sup 4}S{sub 3/2}, {sup 2}H{sub 11/2} → {sup 4}I{sub 15/2}), blue (Tm{sup 3+}, {sup 1}G{sub 4} → {sup

  11. A chemical test of the principle of critical point universality: The solubility of nickel (II) oxide in isobutyric acid + water near the consolute point

    NASA Astrophysics Data System (ADS)

    Hu, Baichuan; Baird, James K.; Richey, Randi D.; Reddy, Ramana G.

    2011-04-01

    A mixture of isobutyric acid + water has an upper consolute point at 38.8 mass % isobutyric acid and temperature near 26 °C. Nickel (II) oxide dissolves in this mixture by reacting with the acid to produce water and nickel isobutyrate. The solubility of nickel (II) oxide in isobutyric acid + water has been measured as a function of temperature at compositions, 25, 38.8, and 60 mass % isobutyric acid. For values of the temperature, T, which were at least 2 K in excess of the liquid-liquid phase transition temperature, the measured values of the solubility, s, lie on a straight line when plotted in van't Hoff form with ln s versus 1/T. The slope, (∂ln s/∂(1/T)), of the line is negative indicating that the dissolution reaction is endothermic. When the temperature was within 2 K of the phase transition temperature, however, (∂ln s/∂(1/T)) diverged toward negative infinity. The principle of critical point universality predicts that when excess solid nickel (II) oxide is in dissolution equilibrium with liquid isobutyric acid + water, (∂ln s/∂(1/T)) should diverge upon approaching the consolute point along the critical isopleth at 38.8 mass % isobutyric acid. As determined by the sign of the enthalpy of solution, the sign of this divergence is expected to be negative. Not only do our experiments confirm these predictions, but they also show that identical behavior can be observed at both 25 and 60 mass % isobustyric acid, compositions which lie substantially to either side of the critical composition.

  12. Monodisperse and core-shell structured SiO{sub 2}-Lu{sub 2}O{sub 3}:Ln{sup 3+} (Ln=Eu, Tb, Dy, Sm, Er, Ho, and Tm) spherical particles: A facile synthesis and luminescent properties

    SciTech Connect

    Xu, Zhenhe; Feng, Bin; Bian, Shasha; Liu, Tao; Wang, Mingli; Gao, Yu; Sun, Di; Gao, Xin; Sun, Yaguang

    2012-12-15

    The core-shell structured SiO{sub 2}-Lu{sub 2}O{sub 3}:Ln{sup 3+} particles were realized by coating the Lu{sub 2}O{sub 3}:Ln{sup 3+} phosphors onto the surface of non-aggregated, monodisperse and spherical SiO{sub 2} particles by the Pechini sol-gel method. The as-synthesized products were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), energy-dispersive X-ray (EDX) spectra, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photolumiminescence (PL), and low-voltage cathodoluminescence (CL). The results indicate that the 800 Degree-Sign C annealed sample consists of crystalline Lu{sub 2}O{sub 3} shells and amorphous SiO{sub 2} cores, in spherical shape with a narrow size distribution. The as-obtained particles show strong light emission with different colors corresponding to different Ln{sup 3+} ions under ultraviolet-visible light excitation and low-voltage electron beams excitation, which have potential applications in fluorescent lamps and field emission displays. - Graphical Abstract: Representative SEM and TEM images of the core-shell structured SiO{sub 2}-Lu{sub 2}O{sub 3}:Eu{sup 3+} particles; CIE chromaticity diagram showing the emission colors for SiO{sub 2}-Lu{sub 2}O{sub 3}:Ln{sup 3+}; Multicolor emissions of SiO{sub 2}-Lu{sub 2}O{sub 3}:Ln{sup 3+} particles. Highlights: Black-Right-Pointing-Pointer The core-shell particles were realized by coating the phosphors onto the surface of SiO{sub 2} particles. Black-Right-Pointing-Pointer The sample consists of crystalline Lu{sub 2}O{sub 3} shells and amorphous SiO{sub 2} cores. Black-Right-Pointing-Pointer The particles show different light emission colors corresponding to Ln{sup 3+} ions. Black-Right-Pointing-Pointer They have potential applications in fluorescent lamps and field emission displays.

  13. Effects of environment and frequency on the fatigue behavior of the spallation neutron source (SNS) target container material - 316 LN stainless steel

    NASA Astrophysics Data System (ADS)

    Tian, Hongbo

    As the candidate target container material of the new Spallation Neutron Source (SNS) being designed and constructed at the Oak Ridge National Laboratory (ORNL), Type 316 low-carbon nitrogen-added (LN) stainless steel (SS) will operate in an aggressive environment, subjected to intense fluxes of high-energy protons and neutrons while exposed to liquid mercury. The current project is oriented toward materials studies regarding the effects of test environment and frequency on the fatigue behavior of 316 LN SS. In order to study the structural applications of this material and improve the fundamental understanding of the fatigue damage mechanisms, fatigue tests were performed in air and mercury environments at various frequencies and R ratios (R = sigma min/sigmamax, sigmamin and sigmamax are the applied minimum and maximum stresses, respectively). Fatigue data were developed for the structural design and engineering applications of this material. Specifically, high-cycle fatigue tests, fatigue crack-propagation tests, and ultrahigh cycle fatigue tests up to 10 9 cycles were conducted in air and mercury with test frequencies from 10 Hz to 700 Hz. Microstructure characterizations were performed using optical microscopy (OM), scanning-electron microscopy (SEM), and transmission-electron microscopy (TEM). It was found that mercury doesn't seem to have a large impact on the crack-initiation behavior of 316 LN SS. However, the crack-propagation mechanisms in air and mercury are different in some test conditions. Transgranular cracks seem to be the main mechanism in air, and intergranular in mercury. A significant specimen self-heating effect was found during high-cycle faituge. Theoretical calculation was performed to predict temperature responses of the material subjected to cyclic deformation. The predicted cyclic temperature evolution seems to be in good agreement with the experimental results.

  14. Description of ligand field splitting in terms of density functional theory: Split levels of the lowest-lying subterms of the 4f{sup n{minus}1}6s{sup 2} (n=3{endash}14) configurations in lanthanide monofluorides LnF (Ln=Pr{endash}Yb)

    SciTech Connect

    Ren, J.; Whangbo, M.; Dai, D.; Li, L.

    1998-05-01

    The split levels associated with the lowest-lying subterms of the 4f{sup n{minus}1}6s{sup 2} (n=3{endash}14) configurations of lanthanide monofluorides LnF (Ln=Pr{endash}Yb) were calculated by employing the combined ligand field and density functional theory (CLDT) method recently proposed. The 288 calculated split levels are in excellent agreement with experiment and hence shows that the CLDT method can accurately reproduce the low-lying electronic excited states of lanthanide compounds. To quantitatively describe the low-lying electronic states of a lanthanide compound, therefore, the effective ligand potential must include the Coulomb and exchange-correlation potentials of the compound as well as the pseudopotentials of the ligands. {copyright} {ital 1998 American Institute of Physics.}

  15. Oxide Thermoelectrics

    SciTech Connect

    Singh, David J

    2008-01-01

    Thermoelectricity in oxides, especially NaxCoO2 and related materials, is discussed from the point of view of first principles calculations and Boltzmann transport theory. The electronic structure of this material is exceptional in that it has a combination of very narrow bands and strong hybridization between metal d states and ligand p states. As shown within the framework of conventional Boltzmann transport theory, this leads to high Seebeck coefficients even at metallic carrier densities. This suggests a strategy of searching for other narrow band oxides that can be doped metallic with mobile carriers. Some possible avenues for finding such materials are suggested.

  16. Oxidation catalyst

    DOEpatents

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

    The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

  17. Refined separation of combined Fe–Hf from rock matrices for isotope analyses using AG-MP-1M and Ln-Spec chromatographic extraction resins

    PubMed Central

    Cheng, Ting; Nebel, Oliver; Sossi, Paolo A.; Chen, Fukun

    2014-01-01

    A combined procedure for separating Fe and Hf from a single rock digestion is presented. In a two-stage chromatographic extraction process, a purified Fe fraction is first quantitatively separated from the rock matrix using AG-MP-1M resin in HCl. Hafnium is subsequently isolated using a modified version of a commonly applied method using Eichrom LN-Spec resin. Our combined method includes:•Purification of Fe from the rock matrix using HCl, ready for mass spectrometric analysis.•Direct loading of the matrix onto the resin that is used for Hf purification.•Collection of a Fe-free Hf fraction. PMID:26150946

  18. Polarized infra-red and Raman spectra of monoclinic α-KLn(WO 4) 2 single crystals (Ln = Sm—Lu, Y)

    NASA Astrophysics Data System (ADS)

    Hanuza, J.; Macalik, L.

    The polarized i.r. and Raman spectra for single crystals of α-KLn(WO 4) 2 family were measured, where Ln = Y and lanthanides from Sm to Lu. The molecular and crystal structures were analysed in terms of C 2/ c = C62 h (Z = 4) monoclinic unit cell. A comparison of vibrational spectra measured for isomorphic crystals of several RE elements was used to describe the internal and external optic modes. On that basis the hexacoordination of tungsten atoms and polymeric (W 2O 10) n clusters with ? and ? bridge systems were discussed.

  19. Synthesis and structure of a new family of 3d-4f heterometallic compounds Rb7LnFe6O2(PO4)8 (Ln=Sm, Eu, Gd, Dy): Magnetic properties of the Sm-, Gd-, Dy-derivatives

    NASA Astrophysics Data System (ADS)

    Sanjeewa, Liurukara D.; Palmer West, J.; Hwu, Shiou-Jyh

    2012-08-01

    A new family of mixed lanthanide(III) and iron(III) oxo-phosphate phases, Rb7LnFe6O2(PO4)8 (Ln=Sm 1, Eu 2, Gd 3, Dy 4), was isolated by using a high-temperature, solid-state method in molten-salt media. The X-ray single-crystal structure analysis shows that these isomorphic derivatives crystallize in a triclinic space group P-1 (no. 2); Z=1. The 3-D framework of these 3d-4f oxo-phosphates are comprised of LnO6 octahedral, FeO5 trigonal bipyramidal (tbp), and μ3-oxo [Fe4O18] tetrameric units interconnected through PO4 tetrahedra. The preliminary results of the temperature-dependent magnetic susceptibility measurements for selected compounds (1, 3, 4) reveal antiferromagnetic-like behavior. 1 shows a weak antiferromagnetric ordering at TN=˜7 K while others show little evidence of long-range magnetic order down to 2 K. All three compounds have measured magnetic moments significantly smaller than the expected values.

  20. Thallium oxide

    Integrated Risk Information System (IRIS)

    Thallium oxide ; CASRN 1314 - 32 - 5 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic E

  1. Propylene oxide

    Integrated Risk Information System (IRIS)

    Propylene oxide ; CASRN 75 - 56 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Ef

  2. Nitric oxide

    Integrated Risk Information System (IRIS)

    Nitric oxide ; CASRN 10102 - 43 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Ef

  3. Merphos oxide

    Integrated Risk Information System (IRIS)

    Merphos oxide ; CASRN 78 - 48 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effe

  4. Highly efficient extraction and oxidative desulfurization system using Na7H2LaW10O36⋅32 H2O in [bmim]BF4 at room temperature.

    PubMed

    Xu, Junhua; Zhao, Shen; Chen, Wei; Wang, Miao; Song, Yu-Fei

    2012-04-10

    Highly efficient, deep desulfurization of model oil containing dibenzothiophene (DBT), benzothiophene (BT), or 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been achieved under mild conditions by using an extraction and catalytic oxidative desulfurization system (ECODS) in which a lanthanide-containing polyoxometalate Na(7)H(2)LnW(10)O(36)⋅32 H(2)O (LnW(10); Ln = Eu, La) acts as catalyst, [bmim]BF(4) (bmim = 1-butyl-3-methylimidazolium) as extractant, and H(2)O(2) as oxidant. Sulfur removal follows the order DBT>4,6-DMDBT>BT at 30 °C. DBT can be completely oxidized to the corresponding sulfone in 25 min under mild conditions, and the LaW(10)/[bmim]BF(4) system could be recycled for ten times with only slight decrease in activity. Thus, LaW(10) in [bmim]BF(4) is one of the most efficient systems for desulfurization using ionic liquids as extractant reported so far. PMID:22374858

  5. The TMI regenerable solid oxide fuel cell

    NASA Technical Reports Server (NTRS)

    Cable, Thomas L.

    1995-01-01

    Energy storage and production in space requires rugged, reliable hardware which minimizes weight, volume, and maintenance while maximizing power output and usable energy storage. These systems generally consist of photovoltaic solar arrays which operate during sunlight cycles to provide system power and regenerate fuel (hydrogen) via water electrolysis; during dark cycles, hydrogen is converted by the fuel cell into system. The currently preferred configuration uses two separate systems (fuel cell and electrolyzer) in conjunction with photovoltaic cells. Fuel cell/electrolyzer system simplicity, reliability, and power-to-weight and power-to-volume ratios could be greatly improved if both power production (fuel cell) and power storage (electrolysis) functions can be integrated into a single unit. The Technology Management, Inc. (TMI), solid oxide fuel cell-based system offers the opportunity to both integrate fuel cell and electrolyzer functions into one unit and potentially simplify system requirements. Based an the TMI solid oxide fuel cell (SOPC) technology, the TMI integrated fuel cell/electrolyzer utilizes innovative gas storage and operational concepts and operates like a rechargeable 'hydrogen-oxygen battery'. Preliminary research has been completed on improved H2/H2O electrode (SOFC anode/electrolyzer cathode) materials for solid oxide, regenerative fuel cells. Improved H2/H2O electrode materials showed improved cell performance in both fuel cell and electrolysis modes in reversible cell tests. ln reversible fuel cell/electrolyzer mode, regenerative fuel cell efficiencies (ratio of power out (fuel cell mode) to power in (electrolyzer model)) improved from 50 percent (using conventional electrode materials) to over 80 percent. The new materials will allow the TMI SOFC system to operate as both the electrolyzer and fuel cell in a single unit. Preliminary system designs have also been developed which indicate the technical feasibility of using the TMI SOFC

  6. Grain Boundary Effects in Solid Oxide Electrolytes

    NASA Astrophysics Data System (ADS)

    Ng, Mai

    Ion conducting ceramics are essential in applications such as solid oxide fuel cells and oxygen sensors. Traditional 8 mol% yttria-stabilized zirconia (8YSZ) solid oxide electrolytes operate at high temperatures (850°C-1000°C) to achieve high ionic conductivity (> 0.1 Scm-1 at 1000°C) by oxygen ion diffusion via vacancies. Operation at such temperatures requires high temperature electrode materials and shortens device lifetime due to interdiffusion and reactions at electrode/electrolyte interfaces. These concerns drive research in current systems and alternative materials to improve ionic conductivity at reduced operating temperatures. This research considers how grain size and grain boundary phases affect three electrolyte materials with different ion diffusion mechanisms. First, the conductivity of ultra-fine grained two-step sintered and large grained conventional sintered 8YSZ are compared to determine if enhanced ionic conductivity occurs supporting the theory that ion blocking impurities in grain boundaries are diluted with decreasing grain size. Second, apatite-type lanthanide silicates (Ln9.33(SiO4)6O2) which exhibit anisotropic interstitial oxygen diffusion at intermediate temperatures (400°C-800°C) are studied to determine whether grain boundaries detrimentally affect conductivity. Lastly, proton conducting La-monazite (LaPO4) is evaluated to determine the role of Sr-doping (up to 10% substitution of La with Sr) on grain size and conductivity as well as the effect of sintering in air or water vapor on the formation of intergranular phases rich in Sr and P. This research investigates grain boundary effects in three solid oxide electrolyte materials with the goal of understanding how grain boundaries affect ionic conductivity and the atomistic behavior governing these different diffusion mechanisms.

  7. Generation of H2 and CO by solar thermochemical splitting of H2O and CO2 by employing metal oxides

    NASA Astrophysics Data System (ADS)

    Rao, C. N. R.; Dey, Sunita

    2016-10-01

    Generation of H2 and CO by splitting H2O and CO2 respectively constitutes an important aspect of the present-day concerns with energy and environment. The solar thermochemical route making use of metal oxides is a viable means of accomplishing these reduction reactions. The method essentially involves reducing a metal oxide by heating and passing H2O or CO2 over the nonstoichiometric oxide to cause reverse oxidation by abstracting oxygen from H2O or CO2. While ceria, perovskites and other oxides have been investigated for this purpose, recent studies have demonstrated the superior performance of perovskites of the type Ln1-xAxMn1-yMyO3 (Ln=rare earth, A=alkaline earth, M=various +2 and +3 metal ions), in the thermochemical generation of H2 and CO. We present the important results obtained hitherto to point out how the alkaine earth and the Ln ions, specially the radius of the latter, determine the performance of the perovskites. The encouraging results obtained are exemplefied by Y0.5Sr0.5MnO3 which releases 483 μmol/g of O2 at 1673 K and produces 757 μmol/g of CO from CO2 at 1173 K. The production of H2 from H2O is also quite appreciable. Modification of the B site ion of the perovskite also affects the performance. In addition to perovskites, we present the generation of H2 based on the Mn3O4/NaMnO2 cycle briefly.

  8. A new series of lanthanide coordination polymers with 2,2‧-bipyridine and glutaric acid: Synthesis, crystal structures and properties of [Ln(bipy)(glut)(NO3)

    NASA Astrophysics Data System (ADS)

    Wang, Chunguang; Xing, Yongheng; Li, Zhangpeng; Li, Jing; Zeng, Xiaoqing; Ge, Maofa; Niu, Shuyun

    2009-08-01

    A series of new lanthanide coordination polymers, with the formula [Ln(bipy)(glut)(NO 3)] (Ln = Eu ( 1), Tb ( 2), Sm ( 3), Pr ( 4); bipy = 2,2'-bipyridine; H 2glut = glutaric acid), have been synthesized under the hydrothermal condition and characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Structural analyses reveal that all four complexes are isostructural and crystallized in monoclinic system, P2 1/ c space group. For these complexes, the Ln 3+ are all linked through glutaric acid ligands to form 1D chain-like polymeric structures, and bipy and NO3- are coordinated on two sides of the chains. The thermogravimetric analysis of 1 and photoluminescent properties of 1 and 2 are discussed in detail.

  9. Bis-diglycol-amides (Bis-DGA) as new extractants for An(III) and Ln(III) from aqueous high-level wastes issued from the Purex process

    SciTech Connect

    Espartero, A.G.; Murillo, M.T.; Almaraz, M.; Sanchez-Quesada, J.; Iglesias-Sanchez, J.C.; Prados, P.; Segura, M.; Mendoza, J. de

    2008-07-01

    A new family of compounds with two diglycolamide moieties in their molecule have been synthesized and studied as suitable extractants for trivalent actinides (An(III)) and trivalent lanthanides (Ln(III)) present in high-level wastes (HLW) issued from the PUREX process. Although the obtained distribution ratios are comparable with those from TODGA under similar experimental conditions, the bis-DGA compounds showed higher selectivity towards Ln(III). The number of bis-DGA molecules involved in the formation of the dominant complex is two, and it is possible to recover more than 99% of the extracted An and Ln with 0.01 M nitric acid in order to recycle the solvent in subsequent extraction cycles. (authors)

  10. Quasi-Elastic Light Scattering and Dynamic Parameters of the Internal Motion in Superionic Crystals of LNF3 (Ln = La, Ce)

    NASA Astrophysics Data System (ADS)

    Krivorotov, V. F.; Mirzaev, S. Z.; Nuzhdov, G. S.

    2016-07-01

    Low-frequency light scattering in superionic crystals of the LaF3 structural type was studied. The laser light scattering spectra of LnF3 single crystals at 90o scattering geometry were obtained over a wide temperature range. The scattering intensity increased sharply in the temperature range in which the mobility of the fl uoride ions increased. The experimental scattering curves were represented as the sum of three central Lorentz contours. The "narrow" Lorentzian had width Γ1 = 0.8-4.2 cm-1; the "medium" Lorentzian, Γ2 = 4.2-27 cm-1; and the "wide" Lorentzian, Γ3 = 42-96 cm-1. These corresponded to relaxation times τ1 ≈ (0.13-0.67) × 10-11 s, τ2 ≈ (0.20-1.27) × 10-12 s, and τ3 ≈ (0.56-1.27) × 10-13 s that were associated with different types of displacement of fl uoride ions into interstices. The activation energy ΔEd obtained from the temperature dependence of the Lorentz contour width was found to be many times less than the energy Ed determining the dynamic parameters of ion motion in the LnF3 lattice.

  11. Effects of the A-site cation number on the properties of Ln5/8M3/8MnO 3 manganites

    NASA Astrophysics Data System (ADS)

    Collado, J. A.; García-Muñoz, J. L.; Aranda, M. A. G.

    2010-05-01

    The properties of manganites can be tuned by changing the doping level x in Ln1-xM xMnO 3. A second mechanism allows tuning of magnetic and electronic properties, for fixed x values, by varying the average A-cation radius, < r A>. Moreover, for fixed x and < r A> values, the changes in the A-cation size variance, σ2, also modify the ferromagnetic and metal-insulator transition temperatures. Here, we investigate the influence of the number of A-site cations on Ln5/8M3/8MnO 3 manganites, where x, < r A> and σ2 values are kept constant, and in the absence of phase separation phenomena. We have found that the number of cation species at the A site ( N A) has a strong influence on the width of the ferromagnetic and metal-insulator transitions, and a small influence on the average transition temperature. This behavior is opposite to that observed for increasing values of the variance σ2 in manganites, with the same x and < r A> values, where average transition temperatures are strongly reduced.

  12. The role of plasmalogen in the oxidative stability of neutral lipids and phospholipids.

    PubMed

    Wang, Guang; Wang, Tong

    2010-02-24

    The role of ethanolamine plasmalogen extracted from bovine brain (BBEP) in maintaining oxidative stability of bulk soybean oil and liposome made with egg phospholipids (PL) was studied. In a purified soybean oil (PSO), the addition of 200 and 1000 ppm of BBEP promoted lipid oxidation at rates of 0.037 and 0.071 (all rates in ln (PV) h(-1), and PV stands for peroxide value), whereas soy lecithin (SL) added in the same amount showed a trend similar to the PSO blank, which had an oxidation rate of 0.025. The PSO with BBEP was susceptible to cupric ion catalyzed oxidation, in that the oil was oxidized much more quickly than the PSO with SL and cupric ion. In commercial soybean oil (CSO) with the presence of tocopherols, SL at 1000 ppm acted synergistically as an antioxidant with the natural tocopherols, but addition of BBEP accelerated lipid oxidation, as evidenced by the oxidative stability index (OSI) test. In the egg PL liposome, the BBEP caused a fast breakdown of the lipid hydroperoxides and consequently promoted more thiobarbituric acid reactive substance (TBARS) formation. The PL oxidation in the presence of copper in the liposome was not affected by the BBEP, which indicates that the hypothesis of ethanolamine plasmalogen (EthPm) chelating cupric ion as the antioxidation mechanism was not supported. The addition of cumene hydroperoxide to the egg PL liposome promoted lipid oxidation, as indicated by a fast development of PV and TBARS. However, the result with cumene hydroperoxide failed to differentiate the effect of BBEP and SL and their concentration on lipid oxidation. On the basis of the observations from this study, we conclude that EthPm is not an antioxidant but rather a pro-oxidant in a bulk lipid system, and it has no significant antioxidant effect for PL oxidation in the liposome. PMID:20099826

  13. Controllable Assembly of Hierarchical Macroporous-Mesoporous LnFeO₃ and Their Catalytic Performance in the CO + NO Reaction.

    PubMed

    Li, Zhen-Xing; Shi, Fu-Bo; Yan, Chun-Hua

    2015-08-11

    A new synthesis strategy to prepare hierarchical macroporous-mesoporous materials employing poly(ethylene oxide)-poly(phenylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) as a single template and an acid adjusting agent was reported. There is a hierarchical structure including macropores with a size of 50-100 nm and mesopores in the macroporous walls with a size of 3-5 nm. The macroporous walls are composed of rare earth orthoferrite nanoparticles with a size of 5-10 nm. These hierarchically porous materials show high catalytic activities for the CO + NO reaction, and NO can be fully converted to N2 at temperatures as low as 350 °C, indicating their potential in the catalytic conversion of automotive exhaust gas and other catalysis-related fields. This synthesis strategy is a facile method for the preparation of hierarchical porous materials and may give us a guideline for the synthesis of functional materials with further catalytic applications.

  14. Controllable Assembly of Hierarchical Macroporous-Mesoporous LnFeO₃ and Their Catalytic Performance in the CO + NO Reaction.

    PubMed

    Li, Zhen-Xing; Shi, Fu-Bo; Yan, Chun-Hua

    2015-08-11

    A new synthesis strategy to prepare hierarchical macroporous-mesoporous materials employing poly(ethylene oxide)-poly(phenylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) as a single template and an acid adjusting agent was reported. There is a hierarchical structure including macropores with a size of 50-100 nm and mesopores in the macroporous walls with a size of 3-5 nm. The macroporous walls are composed of rare earth orthoferrite nanoparticles with a size of 5-10 nm. These hierarchically porous materials show high catalytic activities for the CO + NO reaction, and NO can be fully converted to N2 at temperatures as low as 350 °C, indicating their potential in the catalytic conversion of automotive exhaust gas and other catalysis-related fields. This synthesis strategy is a facile method for the preparation of hierarchical porous materials and may give us a guideline for the synthesis of functional materials with further catalytic applications. PMID:26196258

  15. Structures and standard molar enthalpies of formation of a series of Ln(III)–Cu(II) heteronuclear compounds with pyrazine-2,3-dicarboxylic acid

    SciTech Connect

    Yang, Qi; Xie, Gang; Wei, Qing; Chen, Sanping Gao, Shengli

    2014-07-01

    Fifteen lanthanide–copper heteronuclear compounds, formulated as [CuLn{sub 2}(pzdc){sub 4}(H{sub 2}O){sub 6}]·xH{sub 2}O (1–6(x=2), 8(x=3), 9–10(x=4)); [CuLn{sub 2}(pzdc){sub 4}(H{sub 2}O){sub 4}]·xH{sub 2}O (7, 12–13, 15(x=4), 14(x=5), 11(x=8)) (Ln(III)=La(1); Ce(2); Pr(3); Nd(4); Sm(5); Eu(6); Gd(7); Tb(8); Dy(9); Ho(10); Er(11); Tm(12); Yb(13); Lu(14); Y(15); H{sub 2}pzdc (C{sub 6}H{sub 4}N{sub 2}O{sub 4})=pyrazine-2,3-dicarboxylic acid) have been hydrothermally synthesized. All compounds were characterized by element analysis, IR spectroscopy, single-crystal X-ray diffraction and thermal analysis. X-ray diffraction analyses confirm that all compounds are isostructural and feature a 3D brick-like framework structure with (4.6{sup 2}){sub 2}(4{sup 2}.6{sup 2}.8{sup 2})(6{sup 3}){sup 2}(6{sup 5}.8){sub 2} topology. Using 1 mol cm{sup −3} HCl(aq) as calorimetric solvent, with an isoperibol solution–reaction calorimeter, the standard molar enthalpies of formation of all compounds were determined by a designed thermochemical cycle. In addition, solid state luminescence properties of compounds 5, 6, 8 and 9 were studied in the solid state. - Graphical abstract: According to Hess' rule, the standard molar enthalpies of formation of Ln–Cu heterometallic coordination compounds were determined by a designed thermochemical cycle. - Highlights: • Fifteen lanthanide–copper heteronuclear isostructural compounds. • Structurally characterization by IR, X-ray diffraction and thermal analysis. • The standard molar enthalpy of formation. • Isoperibol solution–reaction calorimetry.

  16. Luminescent cyanometallates based on phenylpyridine-Ir(III) units: solvatochromism, metallochromism, and energy-transfer in Ir/Ln and Ir/Re complexes.

    PubMed

    Ali, Noorshida Mohd; MacLeod, Voirrey L; Jennison, Petter; Sazanovich, Igor V; Hunter, Christopher A; Weinstein, Julia A; Ward, Michael D

    2012-02-28

    [Ir(ppy)(2)(CN)(2)](-) (ppy = anion of 2-phenylpyridine) and some substituted derivatives have been investigated for their ability to interact with additional metal cations, both in solution and the solid state, via the externally-directed cyanide lone pairs, and to act as energy-donors in the resulting assemblies. [Ir(ppy)(2)(CN)(2)](-) is slightly solvatochromic, showing a blue-shift of the lowest energy absorption manifold in water compared to organic solvents, and the solubilised (t)Bu-substituted analogue [Ir((t)Buppy)(2)(CN)(2)](-) [(t)Buppy = anion of 2-(4-(t)Bu-phenyl)pyridine] is also metallochromic with coordination of the cyanide lone pairs to two M(II) cations in MeCN (M = Ba, Zn) resulting in blue-shifts of the lowest-energy absorption and emission maxima. These effects are however modest because of (i) the presence of only two cyanide groups, and (ii) the fact that the lowest-energy excited state has a substantial (3)LC component and is therefore not purely charge-transfer in nature. Crystallisation of [Ir(ppy)(2)(CN)(2)](-) as its (PPN)(+) salt in the presence of excess of lanthanide(III) salts leads to formation of assemblies based on Ir-CN-Ln bonds, which generate in the solid state either Ir(2)Ln(2)(μ-CN)(4) square assemblies or linear trinuclear species with Ir-CN-Ln-NC-Ir cores. In the Ir(2)Eu(2)(μ-CN)(4) and Ir(2)Nd(2)(μ-CN)(4) complexes the Ir-based emission is substantially quenched due to energy-transfer to lower-lying f-f states of these lanthanide ions. In addition reaction of [Ir(F(2)ppy)(2)(CN)(2)](-) [F(2)ppy = cyclometallating anion of 2-(2,4-difluorophenyl)pyridine] with [Re(phen)(CO)(3)(MeCN)][PF(6)] in solution affords dinuclear IrRe and trinuclear IrRe(2) species in which {Re(phen)(CO)(3)} units are attached to the N-donor termini of one or both of the cyanide groups; these complexes have been structurally characterised and display quantitative Ir→Re energy-transfer, showing luminescence only from the Re(I) terminus on

  17. Crystalline to amorphous phase transition of tin oxide nanocrystals induced by SHI at low temperature

    SciTech Connect

    Kumar, Vijay; Pratap, Deepti; Jain, Anshul; Agarwal, D. C.; Sulania, I.; Tripathi, A.; Chaudhary, R. J.; Chauhan, R. S.

    2012-06-05

    Tin oxide (SnO{sub 2}) thin films were deposited using pulsed laser deposition (PLD) technique on Si substrates. The as-deposited films were irradiated using 100 MeV Ag ions at different fluences ranging from 3x10{sup 13} to 3x10{sup 14} ions/cm{sup 2} at an incidence angle of 75 deg. with respect to surface normal at liquid nitrogen (LN2) temperature. The as-deposited and irradiated films have been characterized using X-ray diffraction (XRD) and atomic force microscopy (AFM) techniques to study the modifications in structural and surface morphological properties. Nanocrystalline film become completely amorphous and nanograins of tin oxide disappeared from the surface as indicated by XRD spectra and AFM micrographs respectively.

  18. PREFACE: Semiconducting oxides Semiconducting oxides

    NASA Astrophysics Data System (ADS)

    Catlow, Richard; Walsh, Aron

    2011-08-01

    Semiconducting oxides are amongst the most widely studied and topical materials in contemporary condensed matter science, with interest being driven both by the fundamental challenges posed by their electronic and magnetic structures and properties, and by the wide range of applications, including those in catalysis and electronic devices. This special section aims to highlight recent developments in the physics of these materials, and to show the link between developing fundamental understanding and key application areas of oxide semiconductors. Several aspects of the physics of this wide and expanding range of materials are explored in this special section. Transparent semiconducting oxides have a growing role in several technologies, but challenges remain in understanding their electronic structure and the physics of charge carriers. A related problem concerns the nature of redox processes and the reactions which interconvert defects and charge carriers—a key issue which may limit the extent to which doping strategies may be used to alter electronic properties. The magnetic structures of the materials pose several challenges, while surface structures and properties are vital in controlling catalytic properties, including photochemical processes. The field profits from and exploits a wide range of contemporary physical techniques—both experimental and theoretical. Indeed, the interplay between experiment and computation is a key aspect of contemporary work. A number of articles describe applications of computational methods whose use, especially in modelling properties of defects in these materials, has a long and successful history. Several papers in this special section relate to work presented at a symposium within the European Materials Research Society (EMRS) meeting held in Warsaw in September 2010, and we are grateful to the EMRS for supporting this symposium. We would also like to thank the editorial staff of Journal of Physics: Condensed Matter for

  19. Syntheses, structures, and magnetic properties of acetato- and diphenolato-bridged 3d-4f binuclear complexes [M(3-MeOsaltn)(MeOH)x(ac)Ln(hfac)2] (M = Zn(II), Cu(II), Ni(II), Co(II); Ln = La(III), Gd(III), Tb(III), Dy(III); 3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato; ac = acetato; hfac = hexafluoroacetylacetonato; x = 0 or 1).

    PubMed

    Towatari, Masaaki; Nishi, Koshiro; Fujinami, Takeshi; Matsumoto, Naohide; Sunatsuki, Yukinari; Kojima, Masaaki; Mochida, Naotaka; Ishida, Takayuki; Re, Nazzareno; Mrozinski, Jerzy

    2013-05-20

    A series of 3d-4f binuclear complexes, [M(3-MeOsaltn)(MeOH)x(ac)Ln(hfac)2] (x = 0 for M = Cu(II), Zn(II); x = 1 for M = Co(II), Ni(II); Ln = Gd(III), Tb(III), Dy(III), La(III)), have been synthesized and characterized, where 3-MeOsaltn, ac, and hfac denote N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, acetato, and hexafluoroacetylacetonato, respectively. The X-ray analyses demonstrated that all the complexes have an acetato- and diphenolato-bridged M(II)-Ln(III) binuclear structure. The Cu(II)-Ln(III) and Zn(II)-Ln(III) complexes are crystallized in an isomorphous triclinic space group P1, where the Cu(II) or Zn(II) ion has square pyramidal coordination geometry with N2O2 donor atoms of 3-MeOsaltn at the equatorial coordination sites and one oxygen atom of the bridging acetato ion at the axial site. The Co(II)-Ln(III) and Ni(II)-Ln(III) complexes are crystallized in an isomorphous monoclinic space group P2(1)/c, where the Co(II) or Ni(II) ion at the high-spin state has an octahedral coordination environment with N2O2 donor atoms of 3-MeOsaltn at the equatorial sites, and one oxygen atom of the bridged acetato and a methanol oxygen atom at the two axial sites. Each Ln(III) ion for all the complexes is coordinated by four oxygen atoms of two phenolato and two methoxy oxygen atoms of "ligand-complex" M(3-MeOsaltn), four oxygen atoms of two hfac(-), and one oxygen atom of the bridging acetato ion; thus, the coordination number is nine. The temperature dependent magnetic susceptibilities from 1.9 to 300 K and the field-dependent magnetization up to 5 T at 1.9 K were measured. Due to the important orbital contributions of the Ln(III) (Tb(III), Dy(III)) and to a lesser extent the M(II) (Ni(II), Co(II)) components, the magnetic interaction between M(II) and Ln(III) ions were investigated by an empirical approach based on a comparison of the magnetic properties of the M(II)-Ln(III), Zn(II)-Ln(III), and M(II)-La(III) complexes. The differences of χ(M)T and M

  20. Luminescence and magnetic properties of novel nanoparticle-sheathed 3D Micro-Architectures of Fe0.5R0.5(MoO4)1.5:Ln3+ (R = Gd3+, La3+), (Ln = Eu, Tb, Dy) for bifunctional application

    NASA Astrophysics Data System (ADS)

    Krishnan, Rajagopalan; Thirumalai, Jagannathan; Kathiravan, Arunkumar

    2015-01-01

    For the first time, we report the successful synthesis of novel nanoparticle-sheathed bipyramid-like and almond-like Fe0.5R0.5(MoO4)1.5:Ln3+ (R = Gd3+, La3+), (Ln = Eu, Tb, Dy) 3D hierarchical microstructures through a simple disodium ethylenediaminetetraacetic acid (Na2EDTA) facilitated hydrothermal method. Interestingly, time-dependent experiments confirm that the assembly-disassembly process is responsible for the formation of self-aggregated 3D architectures via Ostwald ripening phenomena. The resultant products are characterized by x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), photoluminescence (PL), and magnetic measurements. The growth and formation mechanisms of the self-assembled 3D micro structures are discussed in detail. To confirm the presence of all the elements in the microstructure, the energy loss induced by the K, L shell electron ionization is observed in order to map the Fe, Gd, Mo, O, and Eu components. The photo luminescence properties of Fe0.5R0.5(MoO4)1.5 doped with Eu3+, Tb3+, Dy3+ are investigated. The room temperature and low temperature magnetic properties suggest that the interaction between the local-fields introduced by the magnetic Fe3+ ions and the R3+ (La, Gd) ions in the dodecahedral sites determine the magnetism in Fe0.5R0.5(MoO4)1.5:Eu3+. This work provides a new approach to synthesizing the novel Fe0.5R0.5(MoO4)1.5:Ln3+ for bi-functional magnetic and luminescence applications.

  1. Nickel/lanthanide single-molecule magnets: {Ni(3)Ln} "stars" with a ligand derived from the metal-promoted reduction of di-2-pyridyl ketone under solvothermal conditions.

    PubMed

    Efthymiou, Constantinos G; Stamatatos, Theocharis C; Papatriantafyllopoulou, Constantina; Tasiopoulos, Anastasios J; Wernsdorfer, Wolfgang; Perlepes, Spyros P; Christou, George

    2010-11-01

    Unusual {Ni(II)(3)Ln(III)(μ-OR)(6)}(3+) complexes with a "star" topology have been prepared with ligands derived from the metal-promoted reduction of di-2-pyridyl ketone under solvothermal conditions; the Dy(III) member shows weak single-molecule-magnet behavior.

  2. Novel [99mTcIII(PS)2(Ln)] mixed-ligand compounds (PS = phosphino-thiolate; L = dithiocarbamate) useful in design and development of TcIII-based agents: synthesis, in vitro, and ex vivo biodistribution studies.

    PubMed

    Salvarese, Nicola; Morellato, Nicolò; Rosato, Antonio; Meléndez-Alafort, Laura; Refosco, Fiorenzo; Bolzati, Cristina

    2014-11-13

    A general procedure for the preparation of a new class of neutral six-coordinated mixed ligand [(99m)Tc(III)(PS)2(Ln)] compounds (PS = trisalkyl-phosphino-thiolate; Ln = dithiocarbamate) is reported as well as their in vitro stability and the ex vivo tissue distribution studies. [(99m)Tc(PS)2(Ln)] complexes were prepared in high yield in nearly physiologic conditions following a one-pot procedure. For instance, the chemical identity of [(99m)Tc(PSiso)2(L1)] (PSiso = 2-(diisopropylphosphino)ethanethiol; L1 = pyrrolidine dithiocarbamate) was determined by HPLC comparison with the corresponding (99g)Tc-complex. All complexes comprise the stable [(99m)Tc(III)(PS)2](+) moiety, where the remaining two coordination positions are saturated by a dithiocarbamate chelate, also carrying bioactive molecules (e.g., 2-methoxyphenylpiperazine). [(99m)Tc(PS)2(Ln)] complexes were inert toward ligand exchange reactions. No significant in vitro and in vivo biotransformation were observed, underlining their remarkable thermodynamic stability and kinetic inertness. These results could be conveniently utilized to devise a novel class of (99m)Tc(III)-based compounds useful in radiopharmaceutical applications. PMID:25333249

  3. Precipitation in AISI 316L(N) during creep tests at 550 and 600 °C up to 10 years

    NASA Astrophysics Data System (ADS)

    Padilha, A. F.; Escriba, D. M.; Materna-Morris, E.; Rieth, M.; Klimenkov, M.

    2007-05-01

    The precipitation behaviour in the gauge lengths and in the heads of initially solution annealed type 316L(N) austenitic stainless steel specimens tested in creep at 550 and 600 °C for periods of up to 85 000 h has been studied using several metallographic techniques. Three phases were detected: M 23C 6, Laves, and sigma phase. The volume fraction of the precipitated sigma phase was significantly higher than that of carbides and the Laves phase. M 23C 6 carbide precipitation occurred very rapidly and was followed by the sigma and Laves phases formation in the delta ferrite islands. Sigma and Laves phases precipitated at grain boundaries after longer times. Two different mechanisms of sigma phase precipitation have been proposed, one for delta ferrite decomposition and another for grain boundary precipitation. Small quantities of the Laves phase were detected in delta ferrite, at grain boundaries and inside the grains.

  4. 1 W at 531 nm generated in a ppMgO:LN planar waveguide by means of frequency doubling of a DBR tapered diode laser

    NASA Astrophysics Data System (ADS)

    Jedrzejczyk, D.; Feise, D.; Güther, R.; Paschke, K.; Erbert, G.

    2011-03-01

    In this work, we investigate experimentally second-harmonic generation (SHG) in a periodically poled 5 %mol MgO doped LiNbO3 (ppMgO:LN) planar waveguide. As a pump source a 6 mm long distributed Bragg reflector (DBR) tapered diode laser is applied. The laser emits nearly diffraction limited, spectrally single-mode continuous-wave radiation at 1063 nm and is therefore well suited for the SHG process. With the applied lens system in a bench-top experiment a coupling efficiency into the planar waveguide of 73 % is reached. A maximal SH power of 1.07 W is generated at an opto-optical and electro-optical conversion efficiency of 26 % and 8.4 %, respectively. This is, to the best of our knowledge, the highest power level generated in a waveguide structure by means of frequency doubling of diode laser radiation in a single-pass configuration.

  5. Dynamic Mechanical Properties and Fracture Surface Morphologies of Core-Shell Rubber (CSR) Toughened Epoxy at Liquid Nitrogen (Ln2) Temperatures

    NASA Technical Reports Server (NTRS)

    Wang, J.; Magee, D.; Schneider, J. A.

    2009-01-01

    The dynamic mechanical properties and fracture surface morphologies were evaluated for a commercial epoxy resin toughened with two types of core-shell rubber (CSR) toughening agents (Kane Ace(Registered TradeMark) MX130 and MX960). The impact resistance (R) was evaluated by the resulting breaking energy measured in Charpy impact tests conducted on an instrumented drop tower. The resulting fracture surface morphologies were examined using Scanning Electron Microscopy (SEM). Fractographic observations of the CSR toughened epoxy tested at ambient temperature, showed a fracture as characterized by slender dendrite textures with large voids. The increasing number of dendrites and decreasing size of scale-like texture with more CSR particles corresponded with increased R. As the temperature decreased to Liquid Nitrogen (LN 2), the fracture surfaces showed a fracture characterized by a rough, torn texture containing many river markings and deep furrows.

  6. Luminescent properties of Tb-activated rare-earth oxyapatite silicate MLn4Si3O13 (M = Ca, Sr, Ln = La, Gd)

    NASA Astrophysics Data System (ADS)

    Yamane, A.; Kunimoto, T.; Ohmi, K.; Honma, T.; Kobayashi, H.

    2006-09-01

    Rare-earth oxyapatites MLn4Si3O13 (M = Ca, Sr, Ba Ln = La, Gd) have been proposed as a new plasma display panel (PDP) host material to overcome the problems of Zn2SiO4:Mn commercial green phosphor, such as luminance degradation and poor surface charge. Tb-doped MLn4Si3O13 phosphor powders show a green luminescence with the CIE color coordinate (x, y) = (0.337, 0.562). The PL excitation band lies continuously in the wavelength region from 130 to 260 nm. The photoluminescence (PL) peak intensity of SrGd4Si3O13:Tb is comparable with that of Zn2SiO4:Mn. The phosphor is a candidate for a green PDP phosphor for Xe2 excitation.

  7. Effect of Linomide on adhesion molecules, TNF-alpha, nitrogen oxide, and cell adhesion.

    PubMed

    Abdul-Hai, A; Hershkoviz, R; Weiss, L; Lider, O; Slavin, S

    2005-02-01

    Linomide (quinoline-3-carboxamide) is an immunomodulator with anti-inflammatory effects in rodents with autoimmune diseases. Its mode of action still remains to be elucidated. We hypothesized that an investigation of T cell interactions with the extracellular matrix (ECM), composed of glycoproteins such as fibronectin (FN) and laminin (LN), might provide better understanding of their in vivo mode of action in extravascular inflammatory sites. We examined the effect of Linomide on T cell adhesion to intact ECM, and separately to LN, and FN, and on the release and production of tumor necrosis factor (TNFalpha) and nitrogen oxide (NO) in relation to adhesive molecules in non-obese diabetic (NOD) female spleen cells, focusing on intracellular adhesion molecule-1 (ICAM-1) and CD44. NOD female mice that developed spontaneous autoimmune insulitis, which destroys pancreatic islets and subsequently leads to insulin-deficient diabetes mellitus, were studied. Linomide, given in the drinking water or added to tissue cultures in vitro, inhibited the beta1 integrin-mediated adhesion of T cells to ECM, FN and LN, as well as the production and release of TNFalpha and NO, which play a major role in the induction and propagation of T cell-mediated insulitis. In addition, exposure of T cells to Linomide resulted in increased expression of CD44 and ICAM-1 molecules on spleen cells of Linomide-treated mice; such an increase in adhesion molecule expression may lead to more effective arrest of T cell migration in vivo. The regulation of T-cell adhesion, adhesion receptor expression, and inhibition of TNFalpha and NO secretion by Linomide may explain its beneficial role and provide a new tool for suppressing self-reactive T cell-dependent autoimmune diseases. PMID:15652754

  8. Trends in Atomic Parameters for Crystals and Free Ions across the Lanthanide Series: The Case of LaCl3:Ln(3+).

    PubMed

    Yeung, Y Y; Tanner, P A

    2015-06-18

    Analyses of the crystal field energy levels of the series LaCl3:Ln(3+) using a semiempirical Hamiltonian shows that only five ions (Pr, Nd, Pm, Dy, Ho) meet the criteria to avoid overfitting of the atomic part. A new parameter (SNES) has been introduced to represent the strength of the normalized electrostatic repulsion for these ions. This parameter varies linearly (R(2)adj = 0.9994, N = 5) with the reciprocal of the radius of the tripositive lanthanide ion, as expected from the form of repulsive Coulomb interaction. The Slater parameters from the crystal field analyses, F(k)(corr) (i.e., corrected for the effects of the two-particle component of the three-body operator associated with the T(2) parameter), exhibit an exponential variation with the number of electrons, n, in 4f(n). This is explained by reference to the radial part of a hydrogen-like wave function. The ratio of F(k)(corr) with the ab initio free ion Slater parameter F(k)(ab initio) varies linearly with n. Fitted parameters F(k)(corr: free ion) from the free ion data for Pr(3+) and Nd(3+) show that the corresponding ab initio values are between 14 and 27% too high. The spin-orbit coupling constant from crystal field analyses (ζ4f) exhibits a quartic variation with atomic number, and the ratio ζ4f/ζ4f(ab initio) follows an exponential growth model with n. The results serve to confirm the hypothesis that smooth trends can be observed across the Ln(3+) series for the fitted parameters despite the fact that the majority of experimental data is lacking. PMID:25985076

  9. Trends in Atomic Parameters for Crystals and Free Ions across the Lanthanide Series: The Case of LaCl3:Ln(3+).

    PubMed

    Yeung, Y Y; Tanner, P A

    2015-06-18

    Analyses of the crystal field energy levels of the series LaCl3:Ln(3+) using a semiempirical Hamiltonian shows that only five ions (Pr, Nd, Pm, Dy, Ho) meet the criteria to avoid overfitting of the atomic part. A new parameter (SNES) has been introduced to represent the strength of the normalized electrostatic repulsion for these ions. This parameter varies linearly (R(2)adj = 0.9994, N = 5) with the reciprocal of the radius of the tripositive lanthanide ion, as expected from the form of repulsive Coulomb interaction. The Slater parameters from the crystal field analyses, F(k)(corr) (i.e., corrected for the effects of the two-particle component of the three-body operator associated with the T(2) parameter), exhibit an exponential variation with the number of electrons, n, in 4f(n). This is explained by reference to the radial part of a hydrogen-like wave function. The ratio of F(k)(corr) with the ab initio free ion Slater parameter F(k)(ab initio) varies linearly with n. Fitted parameters F(k)(corr: free ion) from the free ion data for Pr(3+) and Nd(3+) show that the corresponding ab initio values are between 14 and 27% too high. The spin-orbit coupling constant from crystal field analyses (ζ4f) exhibits a quartic variation with atomic number, and the ratio ζ4f/ζ4f(ab initio) follows an exponential growth model with n. The results serve to confirm the hypothesis that smooth trends can be observed across the Ln(3+) series for the fitted parameters despite the fact that the majority of experimental data is lacking.

  10. Oxide surfaces.

    PubMed

    Willmott, Phil

    2008-07-01

    Although the history of metal oxides and their surfaces goes back several decades to landmark studies, such as Mott and Peierls' explanation of electrical insulation in materials that are predicted in band theory to be conducting, or the observation by Morin of the superfast metal-to-insulator transition in vanadium dioxide, it is only in the last two decades that the world of condensed matter physics has become increasingly dominated by research into complex metal oxides. This has been driven most notably by an attempt to better understand and describe the fundamental physical processes behind their seemingly endless spectrum of properties, which in turn has also led to the discovery of novel phenomena, most prominently demonstrated by the discovery of high-temperature superconductivity in 1986, colossal magnetoresistance in 1994, and most recently, the formation of a two-dimensional conducting layer at the interface between two band insulators in 2004. One important reason why metal oxides, particularly in the form of thin films, have become such a popular subject for basic condensed matter research is that they offer a uniquely versatile materials base for the development of novel technologies. They owe this versatility both to the many different elemental combinations that lead to structurally similar forms, and also to the fact that in many cases, the strong interaction between the valence electrons means that there is a subtle interplay between structure and magnetic and electronic properties. This aspect has led in recent years to the birth or renaissance of research fields such as spintronics, orbital ordering, and multiferroics. Surfaces and interfaces are especially interesting in these strongly-correlated electron systems, where the rearrangement of electrical charge resulting from a minimization of surface or interfacial energy can have unexpected and often exciting consequences. Indeed, as the drive to miniaturize devices well below the micron size

  11. A flowsheet concept for an Am/Ln separation based on Am{sup VI} solvent extraction

    SciTech Connect

    Mincher, B.J.; Law, J.D.

    2013-07-01

    The separation of Am from the lanthanides and curium is a key step in proposed advanced fuel cycle scenarios. The partitioning and transmutation of Am is desirable to minimize the long-term radiotoxicity of material interred in a future high-level waste repository. However, a separation amenable to process scale-up remains elusive. Higher oxidation states of americium have recently been used to demonstrate solvent extraction-based separations using conventional fuel cycle ligands. Here, the successful partitioning of Am{sup VI} from the bulk of lanthanides and curium using diamyl-amyl-phosphonate (DAAP) extraction is reported. Due to the instability of Am{sup VI} in the organic phase it was readily selectively stripped to a new acidic aqueous phase to provide separation from co-extracted Ce{sup IV}. The use of NaBiO{sub 3} as an oxidant to separate Am from the lanthanides and Cm by solvent extraction has been successfully demonstrated on the bench scale. Based on these results, flowsheet concepts can be designed that result in 96 % Am recovery in the presence of a few percent of the remaining Cm and the lanthanides in two extraction contacts. Preliminary results also indicate that the DAAP extractant is robust toward γ- irradiation under realistic conditions of acidity and dissolved oxygen concentration.

  12. PREFACE: Semiconducting oxides Semiconducting oxides

    NASA Astrophysics Data System (ADS)

    Catlow, Richard; Walsh, Aron

    2011-08-01

    Semiconducting oxides are amongst the most widely studied and topical materials in contemporary condensed matter science, with interest being driven both by the fundamental challenges posed by their electronic and magnetic structures and properties, and by the wide range of applications, including those in catalysis and electronic devices. This special section aims to highlight recent developments in the physics of these materials, and to show the link between developing fundamental understanding and key application areas of oxide semiconductors. Several aspects of the physics of this wide and expanding range of materials are explored in this special section. Transparent semiconducting oxides have a growing role in several technologies, but challenges remain in understanding their electronic structure and the physics of charge carriers. A related problem concerns the nature of redox processes and the reactions which interconvert defects and charge carriers—a key issue which may limit the extent to which doping strategies may be used to alter electronic properties. The magnetic structures of the materials pose several challenges, while surface structures and properties are vital in controlling catalytic properties, including photochemical processes. The field profits from and exploits a wide range of contemporary physical techniques—both experimental and theoretical. Indeed, the interplay between experiment and computation is a key aspect of contemporary work. A number of articles describe applications of computational methods whose use, especially in modelling properties of defects in these materials, has a long and successful history. Several papers in this special section relate to work presented at a symposium within the European Materials Research Society (EMRS) meeting held in Warsaw in September 2010, and we are grateful to the EMRS for supporting this symposium. We would also like to thank the editorial staff of Journal of Physics: Condensed Matter for

  13. Effect of lanthanide on the microstructure and structure of LnMn{sub 0.5}Fe{sub 0.5}O{sub 3} nanoparticles with Ln=La, Pr, Nd, Sm and Gd prepared by the polymer precursor method

    SciTech Connect

    Romero, Mariano; Faccio, Ricardo; Martínez, Javier; Pardo, Helena; Montenegro, Benjamín; Plá Cid, Cristiani Campos; Pasa, André A.; and others

    2015-01-15

    The synthesis of LnMn{sub 0.5}Fe{sub 0.5}O{sub 3} perovskite nanoparticles by the polymer precursor method showed a strong intrinsic dependence with different lanthanides (Ln=La, Pr, Nd, Sm and Gd). The polymerization level reached in the polymer precursor was proportional to the atomic number of lanthanide with exception of samarium, which showed the formation of a different precursor based in a citrate chelate with ethyleneglycol bonded as adduct. The increasing level of polymerization of the polymer precursors showed the formation of large-size perovskite nanoparticles after its calcination. SAXS and TEM analyses suggested that nanoparticles obtained, using this method, have a squared-like microstructure in connection with the polymer precursor microstructure. Structural analysis showed an orthorhombic structure with a slight decline in the Jahn–Teller distortion when the atomic number of lanthanide increases. Mössbauer spectroscopy showed the presence of a majority site in agreement with the Pbnm orthorhombic structure best fitted with Rietveld refinements and in some cases, a more distorted site attributed to local inhomogeneities and oxygen vacancies. - Highlights: • Precursor polymerization level is lower in the presence of lighter lanthanides. • Lighter lanthanide perovskite nanoparticles after calcination are lower-sized. • Nanoparticles obtained by this method have lamellae microstructure. • Jahn–Teller distortion declines for heavier lanthanide perovskites. • Oxygen vacancy phase was observed in lighter lanthanide perovskites.

  14. Tetrathiafulvalene-amido-2-pyridine-N-oxide as efficient charge-transfer antenna ligand for the sensitization of Yb(III) luminescence in a series of lanthanide paramagnetic coordination complexes.

    PubMed

    Pointillart, Fabrice; Cauchy, Thomas; Maury, Olivier; Le Gal, Yann; Golhen, Stéphane; Cador, Olivier; Ouahab, Lahcène

    2010-10-18

    The tetrathiafulvalene-amido-2-pyridine-N-oxide (L) ligand has been employed to coordinate 4f elements. The architecture of the complexes mainly depends on the ionic radii of the lanthanides. Thus, the reaction of L in the same experimental protocol leads to three different molecular structure series. Binuclear [Ln(2)(hfac)(5)(O(2)CPhCl)(L)(3)]·2 H(2)O (hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate anion, O(2)CPhCl(-)=3-chlorobenzoate anion) and mononuclear [Ln(hfac)(3)(L)(2)] complexes were obtained by using rare-earth ions with either large (Ln(III)=Pr, Gd) or small (Ln(III)=Y, Yb) ionic radius, respectively, whereas the use of Tb(III) that possesses an intermediate ionic radius led to the formation of a binuclear complex of formula [Tb(2)(hfac)(4)(O(2)CPhCl)(2)(L)(2)]. Antiferromagnetic interactions have been observed in the three dinuclear compounds by using an extended empirical method. Photophysical properties of the coordination complexes have been studied by solid-state absorption spectroscopy, whereas time-dependent density functional theory (TD-DFT) calculations have been carried out on the diamagnetic Y(III) derivative to build a molecular orbital diagram and to reproduce the absorption spectrum. For the [Yb(hfac)(3)(L)(2)] complex, the excitation at 19,600 cm(-1) of the HOMO→LUMO+1/LUMO+2 charge-transfer transition induces both line-shape emissions in the near-IR spectral range assigned to the (2)F(5/2)→(2)F(7/2) (9860 cm(-1)) ytterbium-centered transition and a residual charge-transfer emission around 13,150 cm(-1). An efficient antenna effect that proceeds through energy transfer from the singlet excited state of the tetrathiafulvalene-amido-2-pyridine-N-oxide chromophore is evidence of the Yb(III) sensitization.

  15. Rational synthesis of multifunctional mixed metal oxides by hydrothermal techniques

    NASA Astrophysics Data System (ADS)

    Stampler, Evan Scott

    Low temperature (<350°C) and pressure (<20 atm) hydrothermal methods have been developed for the synthesis of bismuth copper oxide chalcogenides, hexagonal rare-earth manganites, and silver delafossites with mixed cations on the B-site. These materials are of particular interest because they combine multiple functional properties, such as transparency and conductivity, or magnetism and ferroelectricity, in a single-phase material, thus enabling innovative technological applications. Phase-pure products were achieved by the appropriate combination of starting reagents, pH, and reaction temperature to control the solubility of the reactants. Phase-pure BiCuOS and BiCuOSe have been synthesized in high yield by a single-step hydrothermal reaction at low temperature (250°C) and pressure (< 20 atm). A reaction temperature of 250°C was sufficiently high to solubilize both Bi2O3 ([Bi3+] ≈ 10 -3 M) and Cu2O ([Cu+] ≈ 10-4 M) and stabilize monovalent copper species in solution, yet remains low enough to prevent the oxidation of sulfide and selenide. BiCuOS (Eg = 1.09 eV) and BiCuOSe (Eg = 0.75 eV) have smaller band gaps compared to the p-type transparent conductor LaCuOS (Eg = 3.1 eV) but have significantly higher room temperature conductivities (sigma ≈ 0.08 S cm-1 and 3.3 S cm-1, respectively). The high molar solubility of Mn2O3 ([Mn 3+] ≈ 10-3 M) and the slightly amphoteric character of the late rare-earth sesquioxides were exploited in the hydrothermal synthesis of rare-earth manganites, LnMnO3 (Ln=Ho-Lu and Y). While alkaline conditions were necessary for the solubilization of manganese, a reaction temperature approximately 50°C above the transition temperature of the respective rare-earth trihydroxide (100-300°C) accelerated the transition to the more reactive and soluble rare-earth oxide hydroxide and the subsequent reaction to yield the LnMnO3 phase. The high solubility of Ag2O, [Ag+] ≈ 10 -2.5 M, enabled the synthesis of two new silver delafossite

  16. Phase Relations and Elemental Distributions in the Ceramics of the Pseudo-Binary Systems CaZrTi{sub 2}O{sub 7} - LnAlO{sub 3} (Ln = Eu, Gd)

    SciTech Connect

    Mikhailenko, N.S.; Stefanovsky, S.V.; Ochkin, A.V.; Lapina, M.I.

    2007-07-01

    Zirconolite and perovskite were found to be major and minor phases respectively in the ceramics of the series (1-x) CaZrTi2O{sub 7} - x EuAlO{sub 3} and (1-x) CaZrTi{sub 2}O{sub 7} - x GdAlO{sub 3} (x = 0.25; 0.5; 0.75) produced by cold pressing and sintering at 1400, 1450 and 1500 deg. C. Zirconolite and cubic fianite-type oxide (in the Eu-bearing ceramics) were extra phases. At x = 0.25 major host phase for Eu and Gd is zirconolite accumulating of up to 90% of total Eu and Gd. With increase x value to 0.5 zirconolite remains major host phase for both Eu and Gd and accommodates almost 70% of total Eu{sub 2}O{sub 3} and about 60% of total Gd{sub 2}O{sub 3}. Perovskite becomes major phase for both Eu{sub 2}O{sub 3} and Gd{sub 2}O{sub 3} at x = 0.75 accumulating of about 66% of total Gd{sub 2}O{sub 3}. As follows from SEM/EDS data Eu and Gd contents in the zirconolite may exceed {approx}1 formula units, therefore, zirconolite ceramics may be effective matrices for actinide fraction of HLW where Am and Cm are dominant because their crystal chemical behavior is similar to behavior of Gd. (authors)

  17. Phase Relations and Elemental Distribution Among Co-Existing Phases in the Ceramics of the Pseudobinary System CaZrTi{sub 2}O{sub 7}-LnAlO{sub 3} (Ln= Nd, Sm)

    SciTech Connect

    Mikhailenko, Natalia; Stefanovsky, Sergey

    2007-07-01

    In the ceramics in series (1-x) CaZrTi{sub 2}O{sub 7} - x NdAlO{sub 3} and (1-x) CaZrTi{sub 2}O{sub 7} - x SmAlO{sub 3} (x = 0.25, 0.5 and 0.75) produced by cold pressing and sintering at 1400, 1450 and 1500 deg. C zirconolite was found to be a major phase, perovskite was an extra phase and traces of residual baddeleyite occurred. At x = 0.75 the perovskite was major phase and zirconolite and cubic oxide of fianite or tazheranite type were extra phases. Major Nd and Sm host phase at x = 0.25 was found to be zirconolite (about 65% of total Nd{sub 2}O{sub 3} and 74% of total Sm{sub 2}O{sub 3}). With the x value increasing perovskite becomes major host phase for Nd and Sm accumulating of up to about 92% of total Nd and about 72% of total Sm. As follows from SEM/EDS data Nd and Sm contents in the zirconolite may reach {approx}1 formula unit (fu). (authors)

  18. Lanthanum manganite-based air electrode for solid oxide fuel cells

    DOEpatents

    Ruka, Roswell J.; Kuo, Lewis; Li, Baozhen

    1999-01-01

    An air electrode material for a solid oxide fuel cell is disclosed. The electrode material is based on lanthanum manganite having a perovskite-like crystal structure ABO.sub.3. The A-site of the air electrode material preferably comprises La, Ca, Ce and at least one lanthanide selected from Sm, Gd, Dy, Er, Y and Nd. The B-site of the electrode material comprises Mn with substantially no dopants. The ratio of A:B is preferably slightly above 1. A preferred air electrode composition is of the formula La.sub.w Ca.sub.x Ln.sub.y Ce.sub.z MnO.sub.3, wherein Ln comprises at least one lanthanide selected from Sm, Gd, Dy, Er, Y and Nd, w is from about 0.55 to about 0.56, x is from about 0.255 to about 0.265, y is from about 0.175 to about 0.185, and z is from about 0.005 to about 0.02. The air electrode material possesses advantageous chemical and electrical properties as well as favorable thermal expansion and thermal cycle shrinkage characteristics.

  19. Lanthanum manganite-based air electrode for solid oxide fuel cells

    DOEpatents

    Ruka, R.J.; Kuo, L.; Li, B.

    1999-06-29

    An air electrode material for a solid oxide fuel cell is disclosed. The electrode material is based on lanthanum manganite having a perovskite-like crystal structure ABO[sub 3]. The A-site of the air electrode material preferably comprises La, Ca, Ce and at least one lanthanide selected from Sm, Gd, Dy, Er, Y and Nd. The B-site of the electrode material comprises Mn with substantially no dopants. The ratio of A:B is preferably slightly above 1. A preferred air electrode composition is of the formula La[sub w]Ca[sub x]Ln[sub y]Ce[sub z]MnO[sub 3], wherein Ln comprises at least one lanthanide selected from Sm, Gd, Dy, Er, Y and Nd, w is from about 0.55 to about 0.56, x is from about 0.255 to about 0.265, y is from about 0.175 to about 0.185, and z is from about 0.005 to about 0.02. The air electrode material possesses advantageous chemical and electrical properties as well as favorable thermal expansion and thermal cycle shrinkage characteristics. 10 figs.

  20. Metal–organic frameworks assembled from lanthanide and 2,5-pyridinedicaboxylate with cubane-like [Ln{sub 4}(OH){sub 4}] building units

    SciTech Connect

    Abdelbaky, Mohammed S.M.; Amghouz, Zakariae; Fernández-Zapico, Eva; García-Granda, Santiago; García, José R.

    2015-09-15

    tremendous attention due to the unique characteristic of lanthanide cations, such as variable coordination numbers and geometries which often lead to novel complex structures, and also to their magnetic and photoluminescence properties. Herein, three LOFs formulated as [Ln{sub 4}(OH){sub 4}(25p){sub 4}(H{sub 2}O){sub 3}]·H{sub 2}O (Ln=Y, Yb) and [Y{sub 6}(OH){sub 8}(25p){sub 5}(H{sub 2}O){sub 2}] have been obtained by hydrothermal method and characterized, and the photoluminescence properties of the Eu and Tb doped compounds are discussed. - Highlights: • Three novel LnOFs has been synthesized and characterized. • Crystal structures are based on tetranuclear cuban-like [Ln{sub 4}(OH){sub 4}]{sup 8+} clusters. • 25pYb and 25pY-1 are based on isolated [Ln{sub 4}(OH){sub 4}]{sup 8+} clusters. • 25pY-2 is based on infinite inorganic chains built up from [Y{sub 4}(OH){sub 4}]{sup 8+} clusters. • Photoluminescence studies show strong red and green light emissions.

  1. Atomic-Scale Study Of Complex Cobalt Oxide Using Scanning Transmission Electron Microscope

    NASA Astrophysics Data System (ADS)

    Gulec, Ahmet

    Cobalt oxides offer a rich ?eld for the formation of novel phases, including superconductors and exotic magnetic phases, involving a mixed valence state for cobalt and/or the presence of oxygen vacancies. Having spin states, such as, low spin (LS), high spin (HS), and intermediate spin (IS), cobalt oxides differ from other 3d metal oxides The presence of such spin states make the physics of the cobalt oxides so complicated that it has not yet been completely understood. In order to improve our understanding of the various phase transitions observed in Cobalt oxides and to comprehend the relationship between crystal and electronic structure, both high energy resolution and high spatial resolution are essential. Fortunately, transmission electron microscopy (TEM) is a technique which is capable of ful?lling both of these requirements. In this thesis, I have utilized unique techniques in a scanning transmission electron microscope (STEM) to analyze the atomic-scale structure-property relationship, both at room temperature and through insitu cooling to liquid nitrogen (LN2) temperature. In particular, by using correlated Z-contrast imaging, electron energy loss spectrum (EELS) and electron energy loss magnetic circular dichroism (EMCD), the structure, composition, bonding and magnetic behavior are characterized directly on the atomic scale.

  2. Catalytic effect of metallic oxides on combustion behavior of high ash coal

    SciTech Connect

    X.G. Li; B.G. Ma; L. Xu; Z.T. Luo; K. Wang

    2007-09-15

    By means of thermogravimetric analysis, the catalytic effect of metallic oxides (CuO, Fe{sub 2}O{sub 3}, and ZnO) on the combustion behavior of high-ash coal was investigated under nonisothermal conditions. Experiments were conducted from ambient temperature to 1000{sup o}C at a heating rate of 20{sup o}C{center_dot}min{sup -1}. The ignition temperature, burnout performance, and exothermic behavior were used to evaluate the catalytic effect. Moreover, the kinetics parameters (activation energy and pre-exponential factor) were determined using the Coats-Redfern method. It is indicated that, compared with the combustion characteristics of high-ash coal, the ignition temperature of the samples with metallic oxides decreases by 8-50{sup o}C. Metallic oxides can speed up the combustion rate and burnout of the fixed carbon. The exothermic values of samples incorporating metallic oxides increase by 15-30%, which may be due to the catalytic effect of metallic oxides on fixed carbon combustion. The activation energies of the samples decrease, and there is a linear connection between the activation energies and pre-exponential factors (ln A = 0.2683 x E-12.807). 19 refs., 2 figs., 2 tabs.

  3. Bauhinia purpurea--a new paraffin section marker for Reed-Sternberg cells of Hodgkin's disease. A comparison with Leu-M1 (CD15), LN2 (CD74), peanut agglutinin, and Ber-H2 (CD30).

    PubMed Central

    Sarker, A. B.; Akagi, T.; Jeon, H. J.; Miyake, K.; Murakami, I.; Yoshino, T.; Takahashi, K.; Nose, S.

    1992-01-01

    Thirty-three cases of Hodgkin's disease (thirteen nodular sclerosis, four diffuse, lymphocyte predominance, and sixteen mixed cellularity) were studied with Bauhinia purpurea (BPA), peanut agglutinin (PNA), anti-Leu-M1, LN2, and Ber-H2 by the avidinbiotin-peroxidase complex (ABC) method in paraffin sections. Reed-Sternberg (RS) cells and variants were stained positively with one or more of the reagents in all cases. BPA staining was positive in 32 of 33 cases (97.0%), PNA staining was positive in 23 of 33 cases (69.7%), Leu-M1 was positive in 13 of 33 cases (39.4%), LN2 was positive in 14 of 33 cases (42.4%), and Ber-H2 was positive in 24 of 33 cases (72.7%). Many RS cells were stained moderately to strongly and were readily recognized in 31 cases (96.9%) of BPA+, 10 (43.5%) of PNA+, 8 (61.5%) of Leu-M1+, 6 (42.9%) of LN2+, and 22 (91.7%) of Ber-H2+ cases; in the remaining positive cases, the RS cells were found only after careful searching. Three staining patterns were recognized: paranuclear, diffuse cytoplasmic, and membranous. These three patterns were obtained with all markers except for LN2. LN2 showed diffuse cytoplasmic staining in most of the positive cells, and a few cells showed paranuclear deposits. BPA reactivity was not affected by formalin fixation or paraffin embedding. Except for RS cells, BPA also showed dense cytoplasmic staining reaction with macrophage-histiocytes. Sixty cases of non-Hodgkin's diffuse lymphomas (30 T- and 30 B-cell origin) were also studied. Tumor cells were not stained with BPA, PNA, and Leu-M1, but stained positively with LN2 in six T-cell lymphomas and thirteen B-cell lymphomas, and with Ber-H2 in six T-cell lymphomas and one B-cell lymphoma. In conclusion, to facilitate the detection of RS cells and related variants in paraffin sections, BPA can be accepted as a useful marker due to its high-detection rate, reproducible staining pattern, and resistance to fixatives. Images Figure 1 PMID:1352944

  4. Synthesis, Characterization, and Catalytic Applications of Transition Metal Oxide/Carbonate Nanomaterials

    NASA Astrophysics Data System (ADS)

    Jin, Lei

    2011-12-01

    This thesis contains two parts: 1) Studies of novel synthesis methods and characterization of advanced functional manganese oxide octahedral molecular sieves (OMS) and their applications in Li/Air batteries, solvent free toluene oxidations, and ethane oxydehydrogenation (ODH) in the presence of CO2, recycling the green house gas. 2) Development of unique Ln2O2CO3 (Ln = rare earth) layered materials and ZnO/La2O2CO3 composites as clean energy biofuel catalysts. These parts are separated into five different focused topics included in this thesis. The first topic presents studies of catalytic activities of a single step synthesized gamma-MnO2 octahedral molecular sieve nano fiber in solvent free atmospheric oxidation of toluene with molecular oxygen. Solvent free atmospheric oxidation of toluene is a notoriously difficult liquid phase oxidation process due to the challenge of oxidizing sp³ hybridized carbon in inactive hydrocarbons. The synthesized gamma-MnO2 showed excellent catalytic activity and good selectivity under the mild atmospheric reflux system. Under optimized conditions, a 47.8% conversion of toluene, along with 57% selectivity of benzoic acid and 15% of benzaldehyde were obtained. The effects of reaction time, amount of catalyst and initiator, and the reusability of the catalyst were investigated. The second topic involves developing titanium containing gamma-MnO 2 (TM) hollow spheres as electrocatalysts in Li/Air Batteries. Li/air batteries have recently attracted interest because they have the largest theoretical specific energy (11,972 Wh.kg-1) among all practical electrochemical couples. In this study, unique hollow aspheric materials were prepared for the first time using a one-step synthesis method and fully characterized by various techniques. These prepared materials were found to have excellent electrocatalytic activation as cathode materials in lithium-air batteries with a very high specific capacity (up to 2.3 A.h/g of carbon). The third

  5. Effect of annealing on the structural, optical and emissive properties of SrWO4:Ln3+ (Dy3+, Eu3+ and Sm3+) nanoparticles

    NASA Astrophysics Data System (ADS)

    Maheshwary; Singh, B. P.; Singh, R. A.

    2016-01-01

    Lanthanide ions, Ln3+ (Dy3+, Eu3+ and Sm3+) doped SrWO4 nanoparticles were synthesized using ethylene glycol (EG) as a capping agent as well as reaction medium. The X-ray diffraction (XRD) study reveals that all the Ln3+ (Dy3+, Eu3+ and Sm3+) doped samples are well crystalline in nature with a tetragonal scheelite structure of SrWO4 phase. TG study reveals that the nanophosphors are thermally stable. Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy techniques were used to obtain the information about internal and external vibrational modes present in the SrWO4 structure. Optical properties were investigated using UV-vis and photoluminescence (PL) spectroscopy. The average crystallite size was calculated using Debye-Scherrer's for as-prepared and 800 °C annealed samples and is found to be in the range of ∼35-70 nm. The luminescence intensity of Eu3+ doped SrWO4 nanoparticles under 364 nm excitation wavelength reveals that 5D0 → 7F2 transition at ∼613 nm (red) is more prominent than that of 5D0 → 7F1 transition at ∼590 nm (orange). Also upon excitation by UV radiation, the SrWO4:Dy3+ phosphor shows the yellow and blue transition lines appearing at ∼572 and 484 nm which are the characteristic electronic transitions of 4F9/2-6H13/2 and 4F9/2-6H15/2 emission line of Dy3+, respectively. Also Sm3+ doped SrWO4 nanophosphor shows its characteristic emission lines in the range of 550-720 nm, corresponding to 4G5/2 → 6HJ (J = 5/2, 7/2, 9/2 and 11/2) transitions of Sm3+ ions. The predominant orange red color can be attributed to 4G5/2 → 6H9/2 located at ∼642 nm. This is related to the polarizing effect due to the energy transfer from WO42- to the Eu3+, Dy3+ and Sm3+ sites, respectively. Effect of annealing on the photoluminescence properties of samples has been studied and it was found that luminescence intensity increases up to ∼3 times on heating the samples at 800 °C. This may be due to reduction in non-radiative decay channels

  6. Effect of annealing on the structural, optical and emissive properties of SrWO4:Ln(3+) (Dy(3+), Eu(3+) and Sm(3+)) nanoparticles.

    PubMed

    Maheshwary; Singh, B P; Singh, R A

    2016-01-01

    Lanthanide ions, Ln(3+) (Dy(3+), Eu(3+) and Sm(3+)) doped SrWO4 nanoparticles were synthesized using ethylene glycol (EG) as a capping agent as well as reaction medium. The X-ray diffraction (XRD) study reveals that all the Ln(3+) (Dy(3+), Eu(3+) and Sm(3+)) doped samples are well crystalline in nature with a tetragonal scheelite structure of SrWO4 phase. TG study reveals that the nanophosphors are thermally stable. Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy techniques were used to obtain the information about internal and external vibrational modes present in the SrWO4 structure. Optical properties were investigated using UV-vis and photoluminescence (PL) spectroscopy. The average crystallite size was calculated using Debye-Scherrer's for as-prepared and 800°C annealed samples and is found to be in the range of ∼35-70nm. The luminescence intensity of Eu(3+) doped SrWO4 nanoparticles under 364nm excitation wavelength reveals that (5)D0→(7)F2 transition at ∼613nm (red) is more prominent than that of (5)D0→(7)F1 transition at ∼590nm (orange). Also upon excitation by UV radiation, the SrWO4:Dy(3+) phosphor shows the yellow and blue transition lines appearing at ∼572 and 484nm which are the characteristic electronic transitions of (4)F9/2-(6)H13/2 and (4)F9/2-(6)H15/2 emission line of Dy(3+), respectively. Also Sm(3+) doped SrWO4 nanophosphor shows its characteristic emission lines in the range of 550-720nm, corresponding to (4)G5/2→(6)HJ (J=5/2, 7/2, 9/2 and 11/2) transitions of Sm(3+) ions. The predominant orange red color can be attributed to (4)G5/2→(6)H9/2 located at ∼642nm. This is related to the polarizing effect due to the energy transfer from WO4(2-) to the Eu(3+), Dy(3+) and Sm(3+) sites, respectively. Effect of annealing on the photoluminescence properties of samples has been studied and it was found that luminescence intensity increases up to ∼3 times on heating the samples at 800°C. This may be due to

  7. Oxidation resistance of silicon ceramics

    NASA Technical Reports Server (NTRS)

    Yasutoshi, H.; Hirota, K.

    1984-01-01

    Oxidation resistance, and examples of oxidation of SiC, Si3N4 and sialon are reviewed. A description is given of the oxidation mechanism, including the oxidation product, oxidation reaction and the bubble size. The oxidation reactions are represented graphically. An assessment is made of the oxidation process, and an oxidation example of silicon ceramics is given.

  8. Chemical and electrochemical oxidation of [Rh(β-diketonato)(CO)(P(OCH2)3CCH3)]: an experimental and DFT study.

    PubMed

    Erasmus, Johannes J C; Conradie, Jeanet

    2013-06-28

    An experimental and computational chemistry study of the reactivity of [Rh(β-diketonato)(CO)(P(OCH2)3CCH3)] complexes towards chemical and electrochemical oxidation shows that more electron withdrawing groups on the β-diketonato ligand reduce electron density on the rhodium atom to a larger extent than electron donating groups. This leads to a slower second-order oxidative addition rate, k1, and a higher electrochemical oxidation potential, E(pa)(Rh), linearly related by ln k1 = -11(1) E(pa)(Rh) - 2.3(5). The reactivity of these complexes can be predicted by their DFT calculated HOMO energies: E(HOMO) = -0.34(8)E(pa)(Rh) - 5.04(4) = 0.032(5) ln k1- 4.96(4). k1 of [Rh(β-diketonato)(CO)(P(OCH2)3CCH3)] complexes is slower than that of related [Rh(β-diketonato)(CO)(PPh3)] and [Rh(β-diketonato)(P(OPh)3)2] complexes due to the better π-acceptor ability of the CO-phosphite-rhodium combination than that of CO-PPh3-rhodium or di-phosphite-rhodium. PMID:23632432

  9. Nitric oxide inhibition strategies

    PubMed Central

    Wong, Vivian (Wai Chong); Lerner, Ethan

    2015-01-01

    Nitric oxide is involved in many physiologic processes. There are efforts, described elsewhere in this volume, to deliver nitric oxide to tissues as a therapy. Nitric oxide also contributes to pathophysiologic processes. Inhibiting nitric oxide or its production can thus also be of therapeutic benefit. This article addresses such inhibitory strategies. PMID:26634146

  10. Electrochemical oxidation of cholesterol

    PubMed Central

    2015-01-01

    Summary Indirect cholesterol electrochemical oxidation in the presence of various mediators leads to electrophilic addition to the double bond, oxidation at the allylic position, oxidation of the hydroxy group, or functionalization of the side chain. Recent studies have proven that direct electrochemical oxidation of cholesterol is also possible and affords different products depending on the reaction conditions. PMID:25977713

  11. Thermally exfoliated graphite oxide

    NASA Technical Reports Server (NTRS)

    Prud'Homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Abdala, Ahmed (Inventor)

    2011-01-01

    A modified graphite oxide material contains a thermally exfoliated graphite oxide with a surface area of from about 300 sq m/g to 2600 sq m/g, wherein the thermally exfoliated graphite oxide displays no signature of the original graphite and/or graphite oxide, as determined by X-ray diffraction.

  12. Distinct functions of the laminin β LN domain and collagen IV during cardiac extracellular matrix formation and stabilization of alary muscle attachments revealed by EMS mutagenesis in Drosophila

    PubMed Central

    2014-01-01

    Background The Drosophila heart (dorsal vessel) is a relatively simple tubular organ that serves as a model for several aspects of cardiogenesis. Cardiac morphogenesis, proper heart function and stability require structural components whose identity and ways of assembly are only partially understood. Structural components are also needed to connect the myocardial tube with neighboring cells such as pericardial cells and specialized muscle fibers, the so-called alary muscles. Results Using an EMS mutagenesis screen for cardiac and muscular abnormalities in Drosophila embryos we obtained multiple mutants for two genetically interacting complementation groups that showed similar alary muscle and pericardial cell detachment phenotypes. The molecular lesions underlying these defects were identified as domain-specific point mutations in LamininB1 and Cg25C, encoding the extracellular matrix (ECM) components laminin β and collagen IV α1, respectively. Of particular interest within the LamininB1 group are certain hypomorphic mutants that feature prominent defects in cardiac morphogenesis and cardiac ECM layer formation, but in contrast to amorphic mutants, only mild defects in other tissues. All of these alleles carry clustered missense mutations in the laminin LN domain. The identified Cg25C mutants display weaker and largely temperature-sensitive phenotypes that result from glycine substitutions in different Gly-X-Y repeats of the triple helix-forming domain. While initial basement membrane assembly is not abolished in Cg25C mutants, incorporation of perlecan is impaired and intracellular accumulation of perlecan as well as the collagen IV α2 chain is detected during late embryogenesis. Conclusions Assembly of the cardiac ECM depends primarily on laminin, whereas collagen IV is needed for stabilization. Our data underscore the importance of a correctly assembled ECM particularly for the development of cardiac tissues and their lateral connections. The mutational

  13. U(SMes*)n, (n = 3, 4) and Ln(SMes*)3 (Ln = La, Ce, Pr, Nd): lanthanide(III)/actinide(III) differentiation in agostic interactions and an unprecedented eta3 ligation mode of the arylthiolate ligand, from X-ray diffraction and DFT analysis.

    PubMed

    Roger, Mathieu; Barros, Noémi; Arliguie, Thérèse; Thuéry, Pierre; Maron, Laurent; Ephritikhine, Michel

    2006-07-12

    Reaction of U(NEt(2))(4) with HS-2,4,6-(t)Bu(3)C(6)H(2) (HSMes) gave U(SMes)(3)(NEt(2))(py) (1), whereas similar treatment of U[N(SiMe(3))SiMe(2)CH(2)][N(SiMe(3))(2)](2) afforded U(SMes)[N(SiMe(3))(2)](3) (2) and U(SMes)(3)[N(SiMe(3))(2)]. The first neutral homoleptic uranium(IV) thiolate to have been crystallographically characterized, U(SMes)(4) (4), was isolated from the reaction of U(BH(4))(4) and KSMes. The first homoleptic thiolate complex of uranium(III), U(SMes)(3) (5), was synthesized by protonolysis of U[N(SiMe(3))(2)](3) with HSMes in cyclohexane. The crystal structure of 5 exhibits the novel eta(3) ligation mode for the arylthiolate ligand. Comparison of the crystal structure of 5 with those of the isomorphous lanthanide congeners Ln(SMes)(3) (Ln = La, Ce, Pr, and Nd) indicates that the U-S, U-C(ipso)(), and U-C(ortho)() bond lengths are shorter than the corresponding ones in the 4f-element analogues, when taking into account the variation in the ionic radii of the metals. The distance between the uranium and the carbon atoms involved in the U...H-C epsilon agostic interaction of each thiolate ligand is shorter, by approximately 0.05 A, than that expected from a purely ionic bonding model. The lanthanide(III)/actinide(III) differentiation was analyzed by density functional theory (DFT). The nature of the M-S bond is shown to be ionic strongly polarized at the sulfur for M = U and iono-covalent (i.e. strongly ionic with low orbital interaction), for M = Ln. The strength of the U...H-C epsilon agostic interaction is proposed to be controlled by the maximization of the interaction between U(+) and S(-) under steric constraints. The eta(3) ligation mode of the arylthiolate ligand is also obtained from DFT.

  14. Photo-oxidation catalysts

    DOEpatents

    Pitts, J. Roland; Liu, Ping; Smith, R. Davis

    2009-07-14

    Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

  15. The Enzymatic Oxidation of Graphene Oxide

    PubMed Central

    Kotchey, Gregg P.; Allen, Brett L.; Vedala, Harindra; Yanamala, Naveena; Kapralov, Alexander A.; Tyurina, Yulia Y.; Klein-Seetharaman, Judith; Kagan, Valerian E.; Star, Alexander

    2011-01-01

    Two-dimensional graphitic carbon is a new material with many emerging applications, and studying its chemical properties is an important goal. Here, we reported a new phenomenon – the enzymatic oxidation of a single layer of graphitic carbon by horseradish peroxidase (HRP). In the presence of low concentrations of hydrogen peroxide (~40 µM), HRP catalyzed the oxidation of graphene oxide, which resulted in the formation of holes on its basal plane. During the same period of analysis, HRP failed to oxidize chemically reduced graphene oxide (RGO). The enzymatic oxidation was characterized by Raman, UV-Vis, EPR and FT-IR spectroscopy, TEM, AFM, SDS-PAGE, and GC-MS. Computational docking studies indicated that HRP was preferentially bound to the basal plane rather than the edge for both graphene oxide and RGO. Due to the more dynamic nature of HRP on graphene oxide, the heme active site of HRP was in closer proximity to graphene oxide compared to RGO, thereby facilitating the oxidation of the basal plane of graphene oxide. We also studied the electronic properties of the reduced intermediate product, holey reduced graphene oxide (hRGO), using field-effect transistor (FET) measurements. While RGO exhibited a V-shaped transfer characteristic similar to a single layer of graphene that was attributed to its zero band gap, hRGO demonstrated a p-type semiconducting behavior with a positive shift in the Dirac points. This p-type behavior rendered hRGO, which can be conceptualized as interconnected graphene nanoribbons, as a potentially attractive material for FET sensors. PMID:21344859

  16. Synthesis and magnetic properties of a new family of macrocyclic M(II)3Ln(III) complexes: insights into the effect of subtle chemical modification on single-molecule magnet behavior.

    PubMed

    Feltham, Humphrey L C; Clérac, Rodolphe; Ungur, Liviu; Vieru, Veacheslav; Chibotaru, Liviu F; Powell, Annie K; Brooker, Sally

    2012-10-15

    Thirteen tetranuclear mixed-metal complexes of the hexaimine macrocycle (L(Pr))(6-) have been prepared in a one-pot 3:1:3:3 reaction of copper(II) acetate hydrate, the appropriate lanthanide(III) nitrate hydrate, 1,4-diformyl-2,3-dihydroxybenzene (1), and 1,3-diaminopropane. The resulting family of copper(II)-lanthanide(III) macrocyclic complexes has the general formula Cu(II)(3)Ln(III)(L(Pr))(NO(3))(3)·solvents (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Tb, Ho, Er, Tm, or Yb). X-ray crystal structure determinations carried out on [Cu(3)Ce(L(Pr))(NO(3))(3)(MeOH)(3)] and [Cu(3)Dy(L(Pr))(NO(3))(3)(MeOH)(3)] confirmed that the large Ln(III) ion is bound in the central O(6) site and the three square pyramidal Cu(II) ions in the outer N(2)O(2) sites (apical donor either nitrate anion or methanol molecule) of the Schiff base macrocycle. Only the structurally characterized Cu(3)Tb complex, reported earlier, is a single-molecule magnet (SMM): the other 12 complexes do not exhibit an out-of-phase ac susceptibility signal or hysteresis of magnetization in a dc field. Ab initio calculations allowed us to rationalize the observed magnetic properties, including the significant impact of subtle chemical modification on SMM behavior. Broken-symmetry density functional theory (BS-DFT) calculations show there is a subtle structural balance as to whether the Cu···Cu exchange coupling is ferro- or antiferromagnetic. Of the family of 13 magnetically characterized tetranuclear Cu(II)(3)Ln(III) macrocyclic complexes prepared, only the Tb(III) complex is an SMM: the theoretical reasons for this are discussed.

  17. Assessment of Creep Strain Distribution Across Base Metal of 316LN Austenitic Stainless Steel Weld Joint by an EBSD-Based Parameter

    NASA Astrophysics Data System (ADS)

    Vijayanand, V. D.; Ganesan, V.; Ganesh Kumar, J.; Parameswaran, P.; Naveena; Laha, K.

    2015-11-01

    Electron backscatter diffraction (EBSD) analysis has been used to estimate the accumulated strain in base metal region of 316LN austenitic stainless steel weld joints, creep tested at 923 K (650 °C), and at stresses of 175 and 225 MPa. The variation in strength of weld metal, heat-affected zone (HAZ), and base metal-induced stress and strain gradients across the weld joint under creep exposure. Finite element analysis (FEA) of von-Mises stress distribution across the joint has been carried out on incorporating strength of different constituents of the joint, derived by miniature specimen testing techniques. The FEA simulations revealed preferential accumulation of von-Mises stress in the base metal region near to HAZ. The variation in accumulated plastic strain across the base metal has been estimated using a `crystal deformation' ( C d) parameter which quantifies the orientation spread within a grain. This parameter was obtained by EBSD analysis carried out using a scanning electron microscope. The trend in variation of accumulated plastic strain across the base metal accounted well with the von-Mises stress variation, which causes plastic deformation. The plastic strain in the base metal in both the stress levels was found to accumulate preferentially near to the HAZ and reduced steadily toward the ridge at the end of specimen. Transmission electron microscopic study has been carried out to substantiate the findings of the EBSD investigation.

  18. Modulatory Effects of Curcumin and Tyrphostins (AG494 and AG1478) on Growth Regulation and Viability of LN229 Human Brain Cancer Cells.

    PubMed

    Bojko, Agnieszka; Cierniak, Agnieszka; Adamczyk, Anna; Ligeza, Janusz

    2015-01-01

    In this study we employed curcumin as a potent adjuvant agent in the treatment of human brain cancer involving selective EGFR kinase inhibitors: tyrphostins AG494 and AG1478. Aim of this work was to evaluate the effect of tested compounds on autocrine growth, cell cycle, and viability of LN229 cells, as well as to assess their proapoptotic and genotoxic properties. Our results showed that all tested compounds significantly inhibited autocrine growth of the investigated cell line in a dose dependent manner. However they are characterized by different kinetics of cell growth inhibition. Suppression of growth by the tyrphostins was completely or partially reversible in contrast to curcumin. Curcumin increased the cytostatic and/or cytotoxic potential of AG494 and AG1478. Tyrphostins did not have genotoxic properties regardless of concentration used, whereas curcumin cytotoxic and genotoxic properties were directly proportional to the concentration. Curcumin significantly increased tyrphostins cytotoxicity. The most promising of the obtained results may be the use of curcumin and tyrphostin AG494 in the treatment of cancer cells. Anticancer effect of the mixture was confirmed by increase of cytotoxic effect, decrease of viability, stimulation of apoptotic procesess, irreversible DNA damage, and decrease of the ROS in the culture of glioblastoma cells.

  19. Magnetism and transport properties of layered rare-earth cobaltates Ln{sub 0.3}CoO{sub 2}

    SciTech Connect

    Knížek, K. Novák, P.; Jirák, Z.; Hejtmánek, J.; Maryško, M.; Buršík, J.

    2015-05-07

    The ab-initio (GGA+U) electronic structure calculations of layered cobaltates Ln{sub 0.3}CoO{sub 2} (Ln = La, Pr, Nd) prepared by ionic exchange from Na{sub 0.90}CoO{sub 2} precursors have been performed. The data are used for numerical modeling of Seebeck coefficient within Boltzmann transport theory using BoltzTraP program [G. K. H. Madsen and D. J. Singh, Comput. Phys. Commun. 175, 67 (2006)], as well as for determination of the crystal field split levels of rare-earth ions using a method based on a transformation of Bloch states into the basis of Wannier functions [P. Novák et al., Phys. Rev. B 87, 205139 (2013)]. An overall agreement with observed magnetism and transport properties is obtained. In particular, the high p-type thermopower is well reproduced in a broad temperature range, but instead of theoretical linear decrease down to the lowest temperatures, the real systems exhibit an anomalous change of Seebeck sign, which might be related to the change of bare metallic carriers into the polaronic ones.

  20. High-power multichannel PPMgLN-based optical parametric oscillator pumped by a master oscillation power amplification-structured Q-switched fiber laser.

    PubMed

    Chen, Tao; Wei, Kaihua; Jiang, Peipei; Wu, Bo; Shen, Yonghang

    2012-10-01

    We experimentally demonstrated a compact fiber laser-pumped multichannel PPMgLN-based optical parametric oscillator (OPO) generating total OPO output power of 15.8, 15.2, 14.2, 12.9, and 8.8 W with idler output power of 4.7, 4.3, 4.1, 3.3, and 2.1 W at the wavelength of 3.43, 3.63, 3.72, 3.83, and 3.99 μm, respectively. The OPO was pumped by a fully fiberized polarization maintaining (PM) ytterbium-doped pulsed fiber master oscillation power amplifier (MOPA) operating at 1064 nm at a repetition rate of 65 kHz with effective pump power of 28.7 W. The MOPA system was constructed with an acousto-optic Q-switched fiber laser seed and only one stage PM fiber amplifier without any free space components, which makes the pump system compact and stable in the long-term. Comparisons on efficiencies and signal wavelength shifts between different channels showed that the idler absorption was the main factor preventing high average-power OPO operation with long idler wavelength. PMID:23033106

  1. Effect of Multipass TIG and Activated TIG Welding Process on the Thermo-Mechanical Behavior of 316LN Stainless Steel Weld Joints

    NASA Astrophysics Data System (ADS)

    Ganesh, K. C.; Balasubramanian, K. R.; Vasudevan, M.; Vasantharaja, P.; Chandrasekhar, N.

    2016-04-01

    The primary objective of this work was to develop a finite element model to predict the thermo-mechanical behavior of an activated tungsten inert gas (ATIG)-welded joint. The ATIG-welded joint was fabricated using 10 mm thickness of 316LN stainless steel plates in a single pass. To distinguish the merits of ATIG welding process, it was compared with manual multipass tungsten inert gas (MPTIG)-welded joint. The ATIG-welded joint was fabricated with square butt edge configuration using an activating flux developed in-house. The MPTIG-welded joint was fabricated in thirteen passes with V-groove edge configuration. The finite element model was developed to predict the transient temperature, residual stress, and distortion of the welded joints. Also, microhardness, impact toughness, tensile strength, ferrite measurement, and microstructure were characterized. Since most of the recent publications of ATIG-welded joint was focused on the molten weld pool dynamics, this research work gives an insight on the thermo-mechanical behavior of ATIG-welded joint over MPTIG-welded joint.

  2. General synthesis route to fabricate uniform upconversion luminescent gadolinium oxide hollow spheres.

    PubMed

    Jia, Guang; Zhang, Cuimiao; Ding, Shiwen; Wang, Liyong

    2011-08-01

    Uniform upconversion luminescent gadolinium oxide hollow spheres were successfully synthesized via a homogeneous precipitation method with carbon spheres as template followed by a calcination process. During the annealing process, the carbon spheres template can be effectively removed and the amorphous precursor has converted to crystalline Gd2O3, which can be confirmed by the XRD and TG-DSC analysis. SEM and TEM images indicate that the Gd2O3 hollow spheres with diameters of 300-400 nm are uniform in size and distribution. The rare earth activator ions Ln3+-doped Gd2O3 hollow spheres exhibit intense upconversion luminescence with different colors under 980 nm light excitation, which may find potential applications in the fields such as drug delivery or biological labeling. Moreover, the upconversion luminescent mechanisms of the hollow spherical phosphors were investigated in detail.

  3. Oxidation behavior of a ferritic stainless steel Crofer22 APU with thermal cycling

    NASA Astrophysics Data System (ADS)

    Song, MyoungYoup; Duong, Anh T.; Mumm, Daniel R.

    2013-01-01

    Crofer22 APU specimens were prepared by grinding with grit 80 and 120 SiC grinding papers and were thermally cycled. The variation in oxidation behavior with thermal cycling was then investigated. Observation of microstructure, measurement of area specific resistance (ASR), analysis of the atomic percentages of the elements by EDX, and XRD analysis were performed. XRD patterns showed that the (Cr, Mn)3O4 spinel phase grew on the surface of the Crofer22 APU samples ground with grit 120. For the samples ground with grit 80, the ASR increased as the number of thermal cycles increased. Plots of ln (ASR/T) vs. 1/T for the samples ground with grit 80 after n = 4, 20 and 40 exhibited good linearity, and the apparent activation energies were between 63.7 kJ/mole and 76.3 kJ/mole.

  4. Localized and itinerant states in lanthanide oxides united by GW @ LDA+U.

    PubMed

    Jiang, Hong; Gomez-Abal, Ricardo I; Rinke, Patrick; Scheffler, Matthias

    2009-03-27

    Many-body perturbation theory in the GW approach is applied to lanthanide oxides, using the local-density approximation plus a Hubbard U correction (LDA+U) as the starting point. Good agreement between the G0W0 density of states and experimental spectra is observed for CeO2 and Ce2O3. Unlike the LDA+U method G0W0 exhibits only a weak dependence on U in a physically meaningful range of U values. For the whole lanthanide sesquioxide (Ln2O3) series G0W0 @ LDA+U reproduces the main features found for the optical experimental band gaps. The relative positions of the occupied and unoccupied f states predicted by G0W0 confirm the experimental conjecture derived from phenomenological arguments.

  5. Extraction of phenols from water with tri-octyl phosphine oxide

    SciTech Connect

    MacGlashan, J.D.

    1982-03-01

    Tri-octyl phosphine oxide (TOPO) was examined as an extractant for removing phenol; the dihydric phenols catechol, resorcinol, and hydroquinone; and the trihydric phenols pyrogallol, phloroglucinol, and 1,2,4-benzenetriol from water. Distribution coefficients were measured and results modelled for extractions with different diluents, solvent compositions, temperatures, and extractant-to-solute stoichiometric ratios. Modelling of the results indicates that the extraction mechanism is complicated, with the diluent probably playing an important role. The most effective diluents are those that have some electron-donating ability and are thus able to solvate the solute-TOPO complex, without competing with the solute for the phosphoryl oxygen on TOPO. The distribution coefficients decrease with increasing temperature, and show a linear dependence when plotted as ln(K/sub D/) vs. l/T.

  6. Vascular oxidative stress, nitric oxide and atherosclerosis.

    PubMed

    Li, Huige; Horke, Sven; Förstermann, Ulrich

    2014-11-01

    In the vascular wall, reactive oxygen species (ROS) are produced by several enzyme systems including NADPH oxidase, xanthine oxidase, uncoupled endothelial nitric oxide synthase (eNOS) and the mitochondrial electron transport chain. On the other hand, the vasculature is protected by antioxidant enzyme systems, including superoxide dismutases, catalase, glutathione peroxidases and paraoxonases, which detoxify ROS. Cardiovascular risk factors such as hypercholesterolemia, hypertension, and diabetes mellitus enhance ROS generation, resulting in oxidative stress. This leads to oxidative modification of lipoproteins and phospholipids, mechanisms that contribute to atherogenesis. In addition, oxidation of tetrahydrobiopterin may cause eNOS uncoupling and thus potentiation of oxidative stress and reduction of eNOS-derived NO, which is a protective principle in the vasculature. This review summarizes the latest advances in the role of ROS-producing enzymes, antioxidative enzymes as well as NO synthases in the initiation and development of atherosclerosis.

  7. Electrolytic oxidation of anthracite

    USGS Publications Warehouse

    Senftle, F.E.; Patton, K.M.; Heard, I.

    1981-01-01

    An anthracite slurry can be oxidized only with difficulty by electrolytic methods in which aqueous electrolytes are used if the slurry is confined to the region of the anode by a porous pot or diaphragm. However, it can be easily oxidized if the anthracite itself is used as the anode. No porous pot or diaphragm is needed. Oxidative consumption of the coal to alkali-soluble compounds is found to proceed preferentially at the edges of the aromatic planes. An oxidation model is proposed in which the chief oxidants are molecular and radical species formed by the electrolytic decomposition of water at the coal surface-electrolyte interface. The oxidation reactions proposed account for the opening of the aromatic rings and the subsequent formation of carboxylic acids. The model also explains the observed anisotropic oxidation and the need for the porous pot or diaphragm used in previous studies of the oxidation of coal slurries. ?? 1981.

  8. Zinc oxide overdose

    MedlinePlus

    Zinc oxide is an ingredient in many products. Some of these are certain creams and ointments used ... prevent or treat minor skin burns and irritation. Zinc oxide overdose occurs when someone eats one of ...

  9. Bridged graphite oxide materials

    NASA Technical Reports Server (NTRS)

    Herrera-Alonso, Margarita (Inventor); McAllister, Michael J. (Inventor); Aksay, Ilhan A. (Inventor); Prud'homme, Robert K. (Inventor)

    2010-01-01

    Bridged graphite oxide material comprising graphite sheets bridged by at least one diamine bridging group. The bridged graphite oxide material may be incorporated in polymer composites or used in adsorption media.

  10. Mixed Acid Oxidation

    SciTech Connect

    Pierce, R.A.

    1999-10-26

    Several non-thermal processes have been developed to destroy organic waste compounds using chemicals with high oxidation potentials. These efforts have focused on developing technologies that work at low temperatures, relative to incineration, to overcome many of the regulatory issues associated with obtaining permits for waste incinerators. One such technique with great flexibility is mixed acid oxidation. Mixed acid oxidation, developed at the Savannah River Site, uses a mixture of an oxidant (nitric acid) and a carrier acid (phosphoric acid). The carrier acid acts as a non-volatile holding medium for the somewhat volatile oxidant. The combination of acids allows appreciable amounts of the concentrated oxidant to remain in the carrier acid well above the oxidant''s normal boiling point.

  11. Studies in zirconium oxidation

    NASA Technical Reports Server (NTRS)

    Draley, J. E.; Drunen, C. J.; Levitan, J.

    1968-01-01

    Study provides insight into the oxidation mechanism of zirconium by combining electrical measurements with oxidation data. The measurement of electrical potential across growing scale on zirconium and the determination of conventional weight-change oxidation data were carried out at 550, 700, and 800 degrees C.

  12. Congruently melting complex oxides

    SciTech Connect

    Abrahams, S.C.; Brandle, C.D. Jr.

    1988-04-26

    A device is described comprising: a material including a complex oxide, characterized in that the complex oxide is essentially free of gadolinium scandium gallium garnet, gadolinium gallium garnet and lithium niobate, and the composition of the complex oxide is congruent and differs from stoichiometry by at least 0.1 atomic percent for at least one constituent element.

  13. Effect of cation site-disorder on the structure and magneto-transport properties of Ln5/8M3/8MnO 3 manganites

    NASA Astrophysics Data System (ADS)

    Collado, J. A.; Frontera, C.; García-Muñoz, J. L.; Aranda, M. A. G.

    2005-06-01

    Five members of Ln5/8M3/8MnO 3 series with A-cation size variance ( σ2) ranging between 3×10 -4 and 71×10 -4 Å 2, and the same A-cation size =1.2025 Å, have been synthesized by the ceramic method. The five manganites are single phase and they crystallize in the Pnma perovskite superstructure. The five compositions display ferromagnetic-paramagnetic transitions at temperatures ranging between 130 and 270 K, for the highest and lowest variance sample, respectively. The samples with smaller variances show sharp magnetization transitions and the samples with the larger variances display broad transitions. These transitions have also been studied by differential scanning calorimetry, DSC, and some enthalpy changes are reported. The resistivity study indicates that all samples display the expected metal-to-insulator transitions at temperatures ranging between 140 and 270 K. The samples have been analysed at room temperature by ultra-high-resolution synchrotron powder diffraction and the structural and microstructural features are reported. Furthermore, Nd 5/8Sr 0.255Ca 0.12MnO 3 ( σ2=40×10-4 Å2) and Sm 0.225Nd 0.4Sr 0.308Ca 0.067MnO 3 ( σ2=53×10-4 Å2) samples have also been studied by synchrotron powder diffraction at 140 K, below the transition temperatures. Both samples are found to be single phase above and below the transition by ultra-high-resolution synchrotron powder diffraction. The microstructure of the samples has been investigated through Williamson-Hall plots. Sample broadenings are markedly anisotropic and strongly dominated by microstrains with average values of the Δ d/ d term close to 14×10 -4. A direct correlation is found between the microstrain values and the widths of the magnetization transitions.

  14. Dissolution and oxidation behaviour of various austenitic steels and Ni rich alloys in lead-bismuth eutectic at 520 °C

    NASA Astrophysics Data System (ADS)

    Roy, Marion; Martinelli, Laure; Ginestar, Kevin; Favergeon, Jérôme; Moulin, Gérard

    2016-01-01

    Ten austenitic steels and Ni rich alloys were tested in static lead-bismuth eutectic (LBE) at 520 °C in order to obtain a selection of austenitic steels having promising corrosion behaviour in LBE. A test of 1850 h was carried out with a dissolved oxygen concentration between 10-9 and 5 10-4 g kg-1. The combination of thermodynamic of the studied system and literature results leads to the determination of an expression of the dissolved oxygen content in LBE as a function of temperature: RT(K)ln[O](wt%) = -57584/T(K) -55.876T(K) + 254546 (R is the gas constant in J mol-1 K-1). This relation can be considered as a threshold of oxygen content above which only oxidation is observed on the AISI 316L and AISI 304L austenitic alloys in static LBE between 400 °C and 600 °C. The oxygen content during the test leads to both dissolution and oxidation of the samples during the first 190 h and leads to pure oxidation for the rest of the test. Results of mixed oxidation and dissolution test showed that only four types of corrosion behaviour were observed: usual austenitic steels and Ni rich alloys behaviour including the reference alloy 17Cr-12Ni-2.5Mo (AISI 316LN), the 20Cr-31Ni alloy one, the Si containing alloy one and the Al containing alloy one. According to the proposed criteria of oxidation and dissolution kinetics, silicon rich alloys and aluminum rich alloy presented a promising corrosion behaviour.

  15. Trafficking of a Dual-Modality Magnetic Resonance and Fluorescence Imaging Superparamagnetic Iron Oxide-Based Nanoprobe to Lymph Nodes

    PubMed Central

    Bumb, Ambika; Regino, Celeste A. S.; Egen, Jackson G.; Bernardo, Marcelino; Dobson, Peter J.; Germain, Ronald N.; Choyke, Peter L.; Brechbiel, Martin W.

    2010-01-01

    Purpose To develop and characterize the trafficking of a dual-modal agent that identifies primary draining or sentinel lymph node (LN). Procedure Herein, a dual-reporting silica-coated iron oxide nanoparticle (SCION) is developed. Nude mice were imaged by magnetic resonance (MR) and optical imaging and axillary LNs were harvested for histological analysis. Trafficking through lymphatics was observed with intravital and ex vivo confocal microscopy of popliteal LNs in B6-albino, CD11c-EYFP, and lys-EGFP transgenic mice. Results In vivo, SCION allows visualization of LNs. The particle’s size and surface functionality play a role in its passive migration from the intradermal injection site and its minimal uptake by CD11c+ dendritic cells and CD169+ and lys+ macrophages. Conclusions After injection, SCION passively migrates to LNs without macrophage uptake and then can be used to image LN(s) by MRI and fluorescence. Thus, SCION can potentially be developed for use in sentinel node resections or for intralymphatic drug delivery. PMID:21080233

  16. Thermal properties of rare earth cobalt oxides and of La1- x Gd x CoO3 solid solutions

    NASA Astrophysics Data System (ADS)

    Orlov, Yu. S.; Dudnikov, V. A.; Gorev, M. V.; Vereshchagin, S. N.; Solov'ev, L. A.; Ovchinnikov, S. G.

    2016-05-01

    Powder X-ray diffraction data for the crystal structure, phase composition, and molar specific heat for La1‒ x Gd x CoO3 cobaltites in the temperature range of 300-1000 K have been analyzed. The behavior of the volume thermal expansion coefficient in cobaltites with isovalent doping in the temperature range of 100-1000 K is studied. It is found that the β( T) curve exhibits two peaks at some doping levels. The rate of the change in the occupation number for the high-spin state of cobalt ions is calculated for the compounds under study taking into account the spin-orbit interaction. With the Birch-Murnaghan equation of state, it is demonstrated that the low-temperature peak in the thermal expansion shifts with the growth of the pressure toward higher temperatures and at pressure P ˜ 7 GPa coincides with the second peak. The similarity in the behavior of the thermal expansion coefficient in the La1- x Gd x CoO3 compounds with the isovalent substitution and the undoped LnCoO3 compound (Ln is a lanthanide) is considered. For the whole series of rare earth cobalt oxides, the nature of two specific features in the temperature dependence of the specific heat and thermal expansion is revealed and their relation to the occupation number for the high-spin state of cobalt ions and to the insulator-metal transition is established.

  17. Rhodium oxides in unusual oxidation states

    NASA Astrophysics Data System (ADS)

    Reisner, Barbara Alice

    Mixed valence RhIII/RhIV oxides have been proposed as a promising class of candidate compounds for superconductivity. Unfortunately, it is difficult to stabilize rhodates with a formal oxidation state approaching RhIV, as other techniques used for the synthesis of rhodium. oxides favor the most commonly observed formal oxidation state, RhIII. One technique which has been used to stabilize metal oxides in high formal oxidation states is crystallization from molten hydroxides. This thesis explores the use of molten hydroxides to enhance the reactivity of rhodium oxides in order to synthesize rhodates with high formal oxidation states. K0.5RhO2, Rb0.2RhO2, and CsxRhO2 were synthesized from pure alkali metal hydroxides. All crystallized with a previously unobserved polytype in the alkali metal rhodate system. Due to the low activity of dissolved oxygen species in LiOH and NaOH, LiRhO2 and NaRhO2 cannot be crystallized. The formal oxidation state of rhodium in AxRhO2 (A = K, Rb, Cs) is a function of the alkali metal hydroxide used to synthesize these oxides. These materials exhibit remarkable stability for layered metal oxides containing the heavier alkali metals, but all phases are susceptible to intercalation by water. The synthesis, structural characterization, magnetic susceptibility, and reactivity of these oxides are reported. Sr2RhO4 and a new rhodate were crystallized from a KOH-Sr(OH)2 flux. The synthesis and characterization of these materials is reported. Efforts to substitute platinum for rhodium in Sr 2RhO4 are also discussed. Mixed alkali metal-alkaline earth metal hydroxide fluxes were used to crystallize LiSr3RhO6, and NaSr3RhO 6. The synthesis of LiSr3RhO6 and NaSr3RhO 6 represents the first example of the stabilization of a rhodium oxide with a formal oxidation state approaching RhV. X-ray diffraction, electron beam microprobe analysis, thermogravimetric analysis, potentiometric titrations, X-ray photoelectron spectroscopy, and magnetic susceptibility

  18. All-Oxide Photovoltaics.

    PubMed

    Rühle, Sven; Anderson, Assaf Y; Barad, Hannah-Noa; Kupfer, Benjamin; Bouhadana, Yaniv; Rosh-Hodesh, Eli; Zaban, Arie

    2012-12-20

    Recently, a new field in photovoltaics (PV) has emerged, focusing on solar cells that are entirely based on metal oxide semiconductors. The all-oxide PV approach is very attractive due to the chemical stability, nontoxicity, and abundance of many metal oxides that potentially allow manufacturing under ambient conditions. Already today, metal oxides (MOs) are widely used as components in PV cells such as transparent conducting front electrodes or electron-transport layers, while only very few MOs have been used as light absorbers. In this Perspective, we review recent developments of all-oxide PV systems, which until today were mostly based on Cu2O as an absorber. Furthermore, ferroelectric BiFeO3-based PV systems are discussed, which have recently attracted considerable attention. The performance of all-oxide PV cells is discussed in terms of general PV principles, and directions for progress are proposed, pointing toward the development of novel metal oxide semiconductors using combinatorial methods.

  19. Partial oxidation catalyst

    DOEpatents

    Krumpelt, Michael; Ahmed, Shabbir; Kumar, Romesh; Doshi, Rajiv

    2000-01-01

    A two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion. The dehydrogenation portion is a group VIII metal and the oxide-ion conducting portion is selected from a ceramic oxide crystallizing in the fluorite or perovskite structure. There is also disclosed a method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

  20. ZIRCONIUM OXIDE NANOSTRUCTURES PREPARED BY ANODIC OXIDATION

    SciTech Connect

    Dang, Y. Y.; Bhuiyan, M.S.; Paranthaman, M. P.

    2008-01-01

    Zirconium oxide is an advanced ceramic material highly useful for structural and electrical applications because of its high strength, fracture toughness, chemical and thermal stability, and biocompatibility. If highly-ordered porous zirconium oxide membranes can be successfully formed, this will expand its real-world applications, such as further enhancing solid-oxide fuel cell technology. Recent studies have achieved various morphologies of porous zirconium oxide via anodization, but they have yet to create a porous layer where nanoholes are formed in a highly ordered array. In this study, electrochemical methods were used for zirconium oxide synthesis due to its advantages over other coating techniques, and because the thickness and morphology of the ceramic fi lms can be easily tuned by the electrochemical parameters, such as electrolyte solutions and processing conditions, such as pH, voltage, and duration. The effects of additional steps such as pre-annealing and post-annealing were also examined. Results demonstrate the formation of anodic porous zirconium oxide with diverse morphologies, such as sponge-like layers, porous arrays with nanoholes ranging from 40 to 75 nm, and nanotube layers. X-ray powder diffraction analysis indicates a cubic crystallographic structure in the zirconium oxide. It was noted that increased voltage improved the ability of the membrane to stay adhered to the zirconium substrate, whereas lower voltages caused a propensity for the oxide fi lm to fl ake off. Further studies are needed to defi ne the parameters windows that create these morphologies and to investigate other important characteristics such as ionic conductivity.