Superconductivity in CoSr2(Y1-xCax)Cu2O7+d

The roles of aliovalent Ca(II)-for-Y(III) substitution and high-pressure-oxygen annealing in the process of "superconducterizing" the Co-based layered copper oxide, CoSr2(Y1-xCax)Cu2O7+d (Co-1212), were investigated. The as-air-synthesized samples up to x = 0.4 were found essentially oxygen stoichiometric (-0.03 <= d <= 0.00). These samples, however, were not superconductive, suggesting that the holes created by the divalent-for-trivalent cation substitution are trapped on Co in the charge reservoir. Ultra-high-pressure heat treatment carried out at 5 GPa and 500C for 30 min in the presence of Ag2O2 as an excess oxygen source induced bulk superconductivity in these samples. The highest Tc was obtained for the high-oxygen-pressure treated x = 0.3 sample at ~40 K.Comment: 16 pages, 6 figures, submitted to Solid State Communication

Oxygen non-stoichiometry in Ru-1212 and Ru-1222 magnetosuperconductors

Here we report the results of thermogravimetric (TG) analysis on the oxygen non-stoichiometry of RuSr2GdCu2O8 (Ru-1212) and RuSr2(Gd0.75Ce0.25)2Cu2O10(Ru-1222) samples. With TG annealings carried out in O2 and Ar atmospheres it was found that the oxygen content in Ru-1212 remains less affected upon various annealings, while for Ru-1222 wider-range oxygen-content tuning is possible. When heated in H2/Ar atmosphere the both phases release oxygen upon breaking down to mixtures of metals (Ru and Cu) and binary oxides (CeO2, Gd2O3, and SrO) in two distinct steps around 300 and 450 oC. This reductive decomposition reaction carried out in a thermobalance was utilized in precise oxygen content determination for these phases. It was found that the 100-atm O2-annealed Ru-1212 sample was nearly stoichiometric, while the similarly treated Ru-1222 sample was clearly oxygen deficient. X-ray absorption near-edge (XANES) spectroscopy was applied to estimate the valence of Ru in the samples. In spite of the fact that the Ru-1212 phase was shown to possess less oxygen-deficient RuO2 layer, the valence of Ru as probed with XANES was found to be lower in Ru-1212 than that in Ru-1222.Comment: 11 pages text, 4 pages Figs. To ISS 2002 YOKOHAMA for PHYSICA

Enhanced thermoelectric properties of NaxCoO2 whisker crystals

Single-crystalline whiskers of thermoelectric cobalt oxide, NaxCoO2, have been grown by an unconventional method from potassium-containing compositions, and their transport properties, and chemical compositions were determined. The growth mechanism was analyzed and interpreted by means of thermogravimetric analysis. At 300 K, electrical resistivity r and thermoelectric power S of the whisker are 102 u ohm cm and 83 uV/K, respectively. The power-factor, S2/r, thus is enhanced up to ~ 68 uW/K2 cm.Comment: 8 pages, 4 figures, to appear in Appl. Phys. Let

Experimental results and analysis from the 11 T Nb3Sn DS dipole

FNAL and CERN are developing a 5.5-m-long twin-aperture Nb3Sn dipole suitable for installation in the LHC. A 2-m-long single-aperture demonstrator dipole with 60 mm bore, a nominal field of 11 T at the LHC nominal current of 11.85 kA and 20% margin has been developed and tested. This paper presents the results of quench protection analysis and protection heater study for the Nb3Sn demonstrator dipole. Extrapolations of the results for long magnet and operation in LHC are also presented.Comment: 10 pages, Contribution to WAMSDO 2013: Workshop on Accelerator Magnet, Superconductor, Design and Optimization; 15 - 16 Jan 2013, CERN, Geneva, Switzerlan

Iron and molybdenum valences in double-perovskite (Sr,Nd)2FeMoO6: electron-doping effect

Double perovskite, (Sr1-xNdx)2FeMoO6, was doped with electrons through partial substitution of divalent Sr by trivalent Nd (0 < x < 0.2). The Fe valence and the degree of B-site order were probed by 57Fe Mossbauer spectroscopy. Replacing Sr by Nd increased the fraction of Fe and Mo atoms occupying wrong sites, i.e. antisite disorder. It had very little effect on the Fe valence: a small but visible increase in the isomer shift was seen for the mixed-valent FeII/III atoms occupying the right site indicating a slight movement towards divalency of these atoms, which was more than counterbalanced by the increase in the fraction of antisite Fe atoms with III valence state. It is therefore argued that the bulk of the electron doping is received by antisite Mo atoms, which - being surrounded by six MoV/VI atoms - prefer the lower IV/V valence state. Thus under Nd substitution, the charge-neutrality requirement inflicts a lattice disorder such that low-valent MoIV/V can exist.Comment: 15 pages, 6 figures, to appear in Solid State Commu

Overdoped Cuprates With High Temperature Superconducting Transitions

Evidence for High Tc cuprate superconductivity is found in a region of the phase diagram where non-superconducting Fermi liquid metals are expected. Cu valences estimated independently from both x-ray absorption near-edge structure (XANES) and bond valence sum (BVS) measurements are > 2.3 for structures in the homologous series (Cu0.75Mo0.25)Sr2(Y,Ce)sCu2O5+2s+{\delta} with s = 1, 2, 3, and 4. The s = 1 member, (Cu0.75Mo0.25)Sr2YCu2O7+{\delta}, 0 \leq {\delta} \leq 0.5, is structurally related to YBa2Cu3O7 in which 25% of the basal Cu cations [i.e. those in the chain layer] are replaced by Mo, and the Ba cations are replaced by Sr. After oxidation under high pressure the s = 1 member becomes superconducting with Tc = 88K. The Cu valence is estimated to be ~2.5, well beyond the ~2.3 value for which other High-Tc cuprates are considered to be overdoped Fermi liquids. The increase in valence is attributed to the additional 0.5 oxygen ions added per chain upon oxidation. The record short apical oxygen distance, at odds with current theory, suggests the possibility of a new pairing mechanism but further experiments are urgently needed to obtain more direct evidence. From the structural point of view the members with s \geq 2 are considered to be equivalent to single-layer cuprates. All have Tc ~ 56 K which is significantly higher than expected because they also have higher than expected Cu valences. The XANES-determined valences normalized to give values in the CuO2 layers are 2.24, 2.25, and 2.26 for s = 2, 3, and 4, while the BVS values determined for the valence in the CuO2 layer alone are 2.31-2.34 for the s = 2 and 3 members. No evidence for periodic ordering has been detected by electron diffraction and high resolution imaging studies. The possibility that the charge reservoir layers are able to screen long range coulomb interactions and thus enhance Tc is discussed