Magnetic and Magnetocaloric Properties of Nano- and Polycrystalline Bulk Manganites La0.7Ba(0.3−x)CaxMnO3 (x ≤ 0.25)

Here we report the synthesis and investigation of bulk and nano-sized La0.7Ba0.3−xCaxMnO3 (x = 0, 0.15, 0.2 and 0.25) compounds that are promising candidates for magnetic refrigeration applications. We compare the structural and magnetic properties of bulk and nano-scale polycrystalline La0.7Ba0.3−xCaxMnO3 for potential use in magnetic cooling systems. Solid-state reactions were implemented for bulk materials, while the sol–gel method was used for nano-sized particles. Structurally and morphologically, the samples were investigated by X-ray diffraction (XRD), optical microscopy and transmission electron microscopy (TEM). Oxygen stoichiometry was investigated by iodometry. Bulk compounds exhibit oxygen deficiency, while nano-sized particles show excess oxygen. Critical magnetic behavior was revealed for all samples using the modified Arrott plot (MAP) method and confirmed by the Kouvel–Fisher (KF) method. The bulk polycrystalline compound behavior was better described by the tricritical field model, while the nanocrystalline samples were governed by the mean-field model. Resistivity in bulk material showed a peak at a temperature Tp1 attributed to grain boundary conditions and at Tp2 associated with a Curie temperature of Tc. Parent polycrystalline sample La0.7Ba0.3MnO3 has Tc at 340 K. Substitution of x = 0.15 of Ca brings Tc to 308 K, and x = 0.2 brings it to 279 K. Nanocrystalline samples exhibit a very wide effective temperature range in the magnetocaloric effect, up to 100 K. Bulk compounds exhibit a high and sharp peak in magnetic entropy change, up to 7 J/kgK at 4 T at Tc for x = 0.25. To compare the magnetocaloric performances of the studied compounds, both relative cooling power (RCP) and temperature-averaged entropy change (TEC) figures of merit were used. RCP is comparable for bulk polycrystalline and nano-sized samples of the same substitution level, while TEC shows a large difference between the two systems. The combination of bulk and nanocrystalline materials can contribute to the effectiveness and improvement of magnetocaloric materials.