Synthesis of La_0.5Ca_0.5−x□_xMnO₃ nanocrystalline manganites by sucrose assisted auto combustion route and study of their structural, magnetic and magnetocaloric properties

Perovskite manganite La_0.5Ca_0.5−x□_xMnO₃ (LCMO) nanomaterials were elaborated using the sucrose modified auto combustion method. Rietveld refinements of the X-ray diffraction patterns of the crystalline structure confirm a single-phase orthorhombic state with Pbnm space group (No. 62). The Ca-vacancies were voluntarily created in the LCMO structure in order to study their influence on the magnetic behaviour in the system. The magnetic susceptibility was found to be highly enhanced in the sample with Ca-vacancies. Paramagnetic-to-ferromagnetic phase transition was evidenced in both samples around 254 K. This transition is, characterized by a drastic jump of the susceptibility in the sample with Ca-vacancies. The maximum of entropy change, observed for both compounds at magnetic field of 6 T was 2.30 J kg⁻¹ K⁻¹ and 2.70 J kg⁻¹ K⁻¹ for the parent compound and the lacunar one respectively. The magnetocaloric adiabatic temperature change value calculated by indirect method was 5.6 K and 5.2 K for the non-lacunar and Ca-vacancy compound, respectively. The Ca-lacunar La_0.5Ca_0.5−x□_xMnO₃ (x = 0.05) reported in this work demonstrated overall enhancement of the magnetocaloric effect over the LCMO. The technique used to elaborate LCMO materials was beneficial to enhance the magnetocaloric effect and magnetic behaviour. Therefore, we conclude that this less costly environmentally friendly system can be considered as more advantageous candidate for magnetic refrigeration applications then the commonly Gd-based compounds.