Here we report an unconventional magnetic and transport phenomenon in a layered cobalt oxide, NaxCoO2. Only for x = 0.75, a magnetic transition of the second order was clearly detected at Tm ∼ 22 K where an apparent specific-heat jump, an onset of extremely small spontaneous magnetization, and a kink in resistivity came in. Moreover large positive magnetoresistance effect was observed below Tm. These features of the transition strongly indicate the appearance of an unusual electronic state that may be attributed to the strongly-correlated electrons in Na0.75CoO2.
Electrical resistivity (ρ) and thermoelectric power (S) were measured for NaxCo2O4 samples with various Na contents (x). A highly precise control of Na nonstoichiometry was facilitated by optimizing the synthesis procedure. With increasing x, the absolute value of ρ monotonically decreased, while the value of S increased. For the x=1.5 sample, S reached a value as high as ∼120 μV/K (at 300 K).
A capillary electrophoretic (CE) method for the speciation of Co(II), Co(III), and Cu(II) in electroless copper-plating baths containing ethylenediamine (En) has been developed. The method is based on the selective pre-capillary derivatization of Co(II) with 1,10-phenanthroline (Phen) followed by CE separation of stable [CoPhen(3)](2+), [CoEn(3)](3+), and [CuEn(2)](2+) chelates. The proposed derivatization procedure protects Co(II) from oxidation by dissolved oxygen and enables rapid determination of all three metal species within a single run. The optimized separations were carried out in a fused silica capillary (57 cmx75-microm I.D.) filled with an ethylenediamine sulfate electrolyte (20 mmol L(-1) H(2)SO(4), pH 7.0 with En, applied voltage +30 kV) using direct UV detection at 214 nm. The detection limits for a signal-to-noise ratio of 3 and 10 s, hydrodynamic injections were 5x10(-6) mol L(-1) for Cu(II), 1x10(-6) mol L(-1) for Co(III), and 4x10(-7) mol L(-1) for Co(II). Application of the method to the speciation of Co(II), Co(III), and Cu(II) in copper-plating bath samples is also demonstrated.
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