Terashita, Hirotoshi

Magnetic, thermodynamic, and structural properties of the manganese oxides La1-xCa xMnO3 are studied. Neutron powder diffraction reveals two distinct crystallographic phases as well as two magnetic (ferromagnetic and antiferromagnetic) phases for 0.08 < x < 0.14. Details of the compositional dependence of the phase fractions is discussed in the context of local ferromagnetism. Comparisons of magnetic and crystallographic properties are made to the analogous electron-doped Ca1- yLayMnO3 (0 < y < 0.20) system. Thermodynamic properties of La1- xCaxMnO 3 (0 < x < 0.54) are investigated for possible applications in magnetic refrigeration. A maximum magnetic entropy change of 5.5 J/kg K and a corresponding temperature change of 2 K are estimated for x = 0.28. The magnetocaloric effect in antiferromagnetic and charge-ordering compounds is found to be small.

Magnetic and electrical properties for La(1-x)Gd(x)0.7Ca(0.3)MnO3 were studied at ambient and high pressure. For x > 0.1 the ferromagnetic saturation moment M is smaller than that expected for complete ferromagnetic alignment of the Mn moments. Gd substitution lowers both the paramagnetic-ferromagnetic transition temperature T(C), the metal-insulator transition temperature T(MI) and dramatically increases the electrical resistivity rho. T(MI) is observed to be significantly lower than T(C) for x > 0.1. The disagreement of T(C) and T(MI) is a result of the A-site ion size difference which causes the coexistence of ferromagnetic La-Ca-Mn-O and antiferromagnetic Gd-Ca-Mn-O phases and leads to the anomalous electrical transport properties. Samples with the largest average A-site ionic radius <rA> show the highest T(C) or T(MI) and are least sensitive to pressure.