Three series of (R1-xCax)2Ba4Cu7O15-δ (Ca-doped R247; R = Y, Sm, Dy) cuprate superconductors have been synthesized at 990°C and under 26 - 30 bar of oxygen pressure. The effect of Ca2+ doping on the variation of oxygen content, structural chemistry and superconductivity for Ca-doped R247 phases was investigated.The upper limit of substitution of Ca2+ for R in R247 was determined to be 0.10, 0.10, and 0.04, for phases with R = Y, Dy, and Sm, respectively, as indicated by x-ray diffraction (XRD) data. The lattice parameters of Ca-doped R247 phases were found to vary insignificantly or decrease slightly upon Ca doping and these observations were attributed to the possibility of dual substitution of Ca2+ for both R3+ and Ba2+ sites. However, the corresponding orthorhombicity was found to increase or vary insignificantly. Upon Ca2+ doping the sup erconducting transition temperature (T,) of R,247 phases was found to decrease or increase from 93.8 K, 83.4 K and 64.5 K to 90.3 K (x = 0.10), 86.8 K (x = 0.10), and 72.2 K (x = 0.04) for phases with R = Y, Dy, Sm, respectively. Oxygen content or hole concentration (nh) of Ca-doped R247 phases was found to decrease with increasing Ca2+ content, as indicated by the iodometric titration data. The variation of Tc, sites of substitution and oxygen compositions for the title Ca-doped R247 phases will be discussed.
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