Characterisation of superconducting Nd123 solid solutions and related phases
The stoichiometry of the Nd1+xBa2-xCu3O7-δ solid solution has been investigated using XRD and EPMA. At 980°C in air, an essentially continuous solid solution forms with limiting compositions xmin = 0.03(1) and xmax = 0.92(2). The solid solution limits are independent of temperature over the range 300 to 1050°C, i.e. stoichiometric Nd123 does not form. Preliminary studies show that annealing in an Ar atmosphere does not affect xmin. Three structurally distinct polymorphs of Nd123ss exist - tetragonal Nd123ss, orthorhombic Nd123ss and orthorhombic Nd123ss. The stability range of each in air has been determined. Quenched samples with 0.03 ≤ x ≤ 0.6 have the tetragonal Nd123ss structure. On oxygenation, samples with 0.03 ≤ x <0.2 are orthorhombic. The orthorhombic-tetragonal phase transition is second order, both with increasing temperature and increasing x. Samples with 0.7-0.9 have the orthorhombic Nd213ss structure at all oxygen contents. Tetragonal Nd123ss is isostructural with tetragonal Y123 and orthorhombic Nd123ss is isostructural with orthorhombic Y123. Orthorhombic Nd213ss has the ideal stoichiometry Nd2BaCu3O7-δ and is based on a 2a x b x 2c superstructure of the Nd123ss structure. The supercell is due to ordering of the Nd and Ba atoms, which leads to ordering of the oxygen atoms. Melting temperatures decrease with x. Two distinct regions of melting behaviour are observed; the first for 0.03 ≤ x ≤ 0.6 with a thermal minimum at x0.4, and the second for 0.7 ≤ x ≤ 0.9. Oxygen contents increase with x. Samples with larger x values have a smaller range of oxygen contents. High pressure oxygen annealing results in a constant Cu valence state of 2.35 for all values of x. Average copper valence states <2 are only obtained readily for x ≤ 0.3. Tc decreases with x and samples become non-superconducting at x0.5. For samples annealed in 1 bar O2, 'double plateau' behaviour is observed.