Enhanced magnetocaloric effect in Eu-doped La0.7Ca0.3MnO3 compounds

Orthorhombic La_0.7-xEu_xCa_0.3MnO₃ samples (x = 0.04–0.12) with apparent density of ρ = 3.9–4.1 g/cm³ prepared by solid-state reactions have been studied. The analysis of temperature-dependent magnetization for an applied field H = 500 Oe indicated a decrease of the Curie temperature (T_C) from about 225 K for x = 0.04 through 189 K for x = 0.08–146 K for x = 0.12. The magnetocaloric (MC) study upon analyzing M(H, T) data has revealed that the magnetic entropy change around T_C reaches the maximum (|ΔS_max|), which is dependent on both x and H. For an applied field interval of ΔH = 60 kOe, |ΔS_max| values are about 5.88, 4.93, and 4.71 J/kg?K for x = 0.04, 0.08, and 0.12, respectively. Though |ΔS_max| decreases with increasing x, relative cooling power (RCP) increases remarkably from 383 J/kg for x = 0.04 to about 428 J/kg for x = 0.08 and 0.12. This is related to the widening of the ferromagnetic-paramagnetic transition region when x increases. Particularly, if combining two compounds with x = 0.04 and 0.08 (or 0.12) as refrigerant blocks for MC applications, a cooling device can work in a large temperature range of 145–270 K, corresponding to RCP ≈ 640 J/kg for H = 60 kOe. M(H) analyses around T_C have proved x = 0.04 exhibiting the mixture of first- and second-order phase transitions while x = 0.08 and 0.12 exhibit a second-order nature. The obtained results show potential applications of Eu-doped La_0.7Ca_0.3MnO₃ materials for magnetic refrigeration below room temperature.