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Register a new userMechanism and kinetics of phase formation of cobalt oxyhydrates (Na,K)x(H2O)yCoO2-delta synthesized using aqueous permanganate solution route
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This paper has been withdrawn by the author due to a data error in Fig 5.
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We have first succeefully synthesized the sodium cobalt oxyhydrate superconductors using KMnO4 as a de-intercalating and oxidizing agent. It is a novel route to form the superconductive phase of NaxCoO2.yH2O without resorting to the commonly used Br2/CH3CN solution. The role of the KMnO4 is to de-intercalate the Na+ from the parent compound Na0.7CoO2 and oxidize the Co ion as a result. The higher molar ratio of KMnO4 relative to the sodium content tends to remove more Na+ from the parent compound and results in a slight expansion of the c-axis in the unit cell. The superconducting transition temperature is 4.6-3.8 K for samples treated by the aqueous KMnO4 solution with the molar ratio of KMnO4 relative to the sodium content in the range of 0.3 and 2.29.
We have first used the aquesous KMnO4 solutions to de-intercalate and oxideze gamma-phase of Na0.7CoO2 and successfully form the superconductive phase of cobalt oxyhydrate hydrates (Na,K)xCoO2.yH2O with Tc=3.2-4.6K based on the magnetization measurements. The higher molar ratio of KMnO4/Na used to treat Na0.7CoO2 results in more removal of Na+ and leads to a partial or even complete replacement of K+ for Na+. The low molar ratio of KMnO4/Na forms a superconductive phase with the c-axis ca. 19.6 angstrom, whereas the high molar ratio of KMnO4/Na forms a non-superconductive phase with teh c-axis ca. 13.9 angstrom. The superconductive 19.6 angstrom phase is unstable with respect to the ambient air in terms of losing water molecule from the structure; nevertheless, the dehydration/hydration process is reversible when storing the sample in a chamber with sufficient humidity.
The existence of two phases within one and the same hexagonal lattice of MgB2 compound, differing in Mg and B (in the homogeneity region) and especially in impurity oxygen content, as well as in microstructure, is demonstrated by various techniques. The regions corresponding to these two phases of MgB2 have the sizes of 100-500 {mu}m, and they fill the whole bulk of specimens, alternating with each other. It is suggested that the two-phase state of MgB2 compound is caused by specific features of its formation mechanism (as a result of synthesis at 800-1000{deg}C), including the stages of Mg melting, dissolution of solid boron in it up to the composition of MgB2 and further crystallization of the MgB2 compound from the melt with the formation of dendrite-like structure with corresponding redistribution of main components and impurities.
SrTiO$_{3}$, a quantum paraelectric, becomes a metal with a superconducting instability after removal of an extremely small number of oxygen atoms. It turns into a ferroelectric upon substitution of a tiny fraction of strontium atoms with calcium. The two orders may be accidental neighbors or intimately connected, as in the picture of quantum critical ferroelectricity. Here, we show that in Sr$_{1-x}$Ca$_{x}$TiO$_{3-delta}$ ($0.002<x<0.009$, $delta<0.001$) the ferroelectric order coexists with dilute metallicity and its superconducting instability in a finite window of doping. At a critical carrier density, which scales with the Ca content, a quantum phase transition destroys the ferroelectric order. We detect an upturn in the normal-state scattering and a significant modification of the superconducting dome in the vicinity of this quantum phase transition. The enhancement of the superconducting transition temperature with calcium substitution documents the role played by ferroelectric vicinity in the precocious emergence of superconductivity in this system, restricting possible theoretical scenarios for pairing.
Specific heat, resistivity, susceptibility and Hall coefficient measurements were performed on high-quality single crystalline Na$_{1-delta}$FeAs. This compound is found to undergo three successive phase transitions at around 52, 41, and 23 K, which correspond to structural, magnetic and superconducting transitions, respectively. The Hall effect result indicates the development of energy gap at low temperature due to the occurrence of spin-density-wave instability. Our results provide direct experimental evidence of the magnetic ordering in the nearly stoichiometric NaFeAs.
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