12 research outputs found

    Superconductivity in the Nb-Ru-Ge σ\sigma-Phase

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    We show that the previously unreported ternary σ\sigma-phase material Nb20.4_{20.4}Ru5.7_{5.7}Ge3.9_{3.9} is a superconductor with a critical temperature of 2.2 K. Temperature-dependent magnetic susceptibility, resistance, and specific heat measurements were used to characterize the superconducting transition. The Sommerfeld constant γ\gamma for Nb20.4_{20.4}Ru5.7_{5.7}Ge3.9_{3.9} is 91 mJ mol-f.u.−1^{-1}K−2^{-2} and the specific heat anomaly at the superconducting transition, Δ\DeltaC/γ\gammaTc_c, is approximately 1.38. The zero-temperature upper critical field (μ0\mu_0Hc2_{c2}(0)) was estimated to be 2 T by resistance data. Field-dependent magnetization data analysis estimated μ0\mu_0Hc1_{c1}(0) to be 5.5 mT. Thus, the characterization shows Nb20.4_{20.4}Ru5.7_{5.7}Ge3.9_{3.9} to be a type II BCS superconductor. This material appears to be the first reported ternary phase in the Nb-Ru-Ge system, and the fact that there are no previously reported binary Nb-Ru, Nb-Ge, or Ru-Ge σ\sigma-phases shows that all three elements are necessary to stabilize the material. A σ\sigma-phase in the Ta-Ru-Ge system was synthesized but did not display superconductivity above 1.7 K, which suggests that electron count cannot govern the superconductivity observed. Preliminary characterization of a possible superconducting σ\sigma-phase in the Nb-Ru-Ga system is also reported.Comment: 7 pages, 8 figures, 3 table

    Growth, Crystal Structure and Magnetic Characterization of Zn-Stabilized CePtIn4

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    The growth and characterization of CePtIn4, stabilized by 10% Zn substitution for In, is reported. The new material is orthorhombic, space group Cmcm (No. 63), with lattice parameters a = 4.51751(4) {\AA}, b = 16.7570(2) {\AA}, and c = 7.36682(8) {\AA}, and the refined crystal composition has 10% of Zn substituted for In, i.e. the crystals are CePt(In3.6Zn0.1)4. Crystals were grown using a self-flux method: only growths containing Zn yielded CePtIn4 crystals, while Ce3Pt4In13 crystals formed when Zn was not present. Anisotropic temperature-dependent magnetic susceptibilities for single crystals show that Zn-stabilized CePtIn4 orders magnetically at ~1.9 K. High-temperature Curie-Weiss fits indicate an effective moment of ~2.30 muB/ Ce and a directionally averaged Weiss-temperature of approximately - 9 K. Specific heat data shows a peak consistent with the ordering temperature seen in the magnetic susceptibility data. Zn-stabilized CePtIn4 is metallic and displays no superconducting transition down to 0.14 K.Comment: 8 pages, 5 figures, 1 tabl

    Polymerization of Styrene and Cyclization to Macrocyclic Polystyrene in a One-Pot, Two-Step Sequence

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    Dibrominated polystyrene (BrPStBr) was produced by atom transfer radical polymerization (ATRP) at 80 degrees C, using the bifunctional initiator benzal bromide to afford the telechelic precursor. The ATRP reaction was stopped around 40% monomer conversion and directly converted into an radical trap-assisted atom transfer radical coupling (RTA-ATRC) reaction by lowering the temperature to 50 degrees C, and adding the radical trap 2-methyl-2-nitrosopropane (MNP) along with additional catalyst, reducing agent, and ligand to match ATRC-type reaction conditions. In an attempt to induce intramolecular coupling, rather than solely intermolecular coupling and elongation, the total reaction volume was increased by the addition of varying amounts of THF. Cyclization, along with intermolecular coupling and elongation, occurred in all cases, with the extent of ring closure a function of the total reaction volume. The cyclic portion of the coupled product was found to have a (G) value around 0.8 by GPC analysis, consistent with the reduction in hydrodynamic volume of a cyclic polymer compared to its linear analog. Analysis of the sequence by H-1 NMR confirmed that propagation was suppressed nearly completely during the RTA-ATRC phase, with percent monomer conversion remaining constant after the ATRP phase. (C) 2013 Elsevier Ltd. All rights reserved

    One Pot, Two Step Sequence Converting Atom Transfer Radical Polymerization Directly to Radical Trap-Assisted Atom Transfer Radical Coupling

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    Monobrominated polystyrene (PStBr) chains were prepared using standard atom transfer radical polymerization (ATRP) procedures at 80 degrees C in THF, with monomer conversions allowed to proceed to approximately 40%. At this time, additional copper catalyst, reducing agent, and ligand were added to the unpurified reaction mixture, and the reaction was allowed to proceed at 50 degrees C in an atom transfer radical coupling (ATRC) phase. During this phase, polymerization continued to occur as well as coupling; expected due to the substantial amount of residual monomer remaining. This was confirmed using gel permeation chromatography (GPC), which showed increases in molecular weight not matching a simple doubling of the PStBr formed during ATRP, and an increase in monomer conversion after the second phase. When the radical trap 2-methyl-2-nitrosopropane (MNP) was added to the ATRC phase, no further monomer conversion occurred and the resulting product showed a doubling of peak molecular weight (M-p), consistent with a radical trap-assisted ATRC (RTA-ATRC) reaction. (C) 2013 Elsevier Ltd. All rights reserved

    Effect of Trapping Agent and Polystyrene Chain End Functionality on Radical Trap-Assisted Atom Transfer Radical Coupling

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    Coupling reactions were performed to gauge the effect of the inclusion of a radical trap on the success of coupling reactions of monohalogenated polystyrene (PSX) chains in atom transfer radical coupling (ATRC) type reactions. The effect of both the specific radical trap chosen and the structure of the polymer chain end were evaluated by the extent of dimerization observed in a series of analogous coupling reactions. The commonly used radical trap 2-methyl-2-nitrosopropane (MNP) showed the highest amounts of dimerization for PSX (X = Br, Cl) compared to coupling reactions performed in its absence or with a different radical trap. A dinitroxide coupling agent was also studied with the extent of coupling nearly matching the effectiveness of MNP in RTA (Radical trap-assisted)-ATRC reactions, while N-nitroso and electron rich nitroso coupling agents were the least effective. (2,2,6,6-Tetramethyl-piperin-L-yl)oxyl-capped PS (PS-TEMPO), prepared by NMP, was subjected to a coupling sequence conceptually similar to RTA-ATRC, but dimerization was not observed regardless of the choice of radical trap. Kinetic experiments were performed to observe rate changes on the coupling reaction of PSBr as a result of the inclusion of MNP, with substantial rate enhancements found in the RTA-ATRC coupling sequence compared to traditional ATRC
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