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The Pr(1+x)Ba(2-x)Cu(3)O(7+/-delta) solid solution was investigated by means of X-ray powder diffraction combined with Rietveld analysis. A Pr123 single phase could be synthesized under Pr-rich conditions by sintering at 950 degreesC in air. The solubility range of Pr(1+x)Ba(2-x)Cu(3)O(7+/-delta) solid solution is 0.08 less than or equal to x less than or equal to 0.80. The structure of Pr(1+x)Ba(2-x)Cu(3)O(7+/-delta) for 0.08 less than or equal to x less than or equal to 0.30 is orthorhombic. The structure transforms into tetragonal for 0.30 less than or equal to x less than or equal to 0.80. To form the Pr123 single phase, the Ba sites in the Pr123 structure must have partial Pr ions, and the least amount is x = 0.08. Ba ions cannot occupy the sites of Pr ions. In the Pr123 structure, Ca ions can replace Pr ions; the highest value is x = 0.4 in the PrBa(2-x)Ca(x)Cu(3)O(7+/-delta) system under our experimental conditions. However, Ca ions cannot replace B a ions. The ionic radius plays a more important role than the chemical properties in the substitution between Pr, Ba and Ca ions in the Pr123 structure.

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