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Magnetoelastic Coupling Evidence by Anisotropic Crossed Thermal Expansion in Magnetocaloric RSrCoFeO 6 (R = Sm, Eu) Double Perovskites.

Romualdo S SilvaJoão E RodriguesJavier GainzaFederico Serrano-SánchezLidia MartínezYves HuttelJose Luis MartínezJosé Antonio Alonso
Published in: Inorganic chemistry (2024)
Double perovskite oxides, characterized by their tunable magnetic properties and robust interconnection between the lattice and magnetic degrees of freedom, present an enticing foundation for advanced magnetic refrigeration materials. Herein, we delve into the influence of rare-earth elements on RSrCoFeO 6 (R = Sm, Eu) disordered double perovskites by examining their structural, electronic, magnetic, and magnetocaloric properties. Temperature-dependent synchrotron X-ray diffraction analysis confirmed the stability of the orthorhombic phase ( Pnma ) across a wide temperature range. X-ray photoemission spectroscopy revealed that both Sm and Eu are in the 3+ state, whereas multiple states for Co 2+/3+ and Fe 3+/4+ are identified. The magnetic investigation and magnetocaloric effect (MCE) analysis brought to light the presence of a long-range antiferromagnetic (AFM) order with a second-order phase transition (SOPT) in both samples. The maximum magnetic entropy change Δ S M max was approximately 0.9 J/kg K for both samples at applied field 0-7 T, manifesting prominently above Neel temperatures T N ≈ 93 K (Sm) and 84 K (Eu). Nevertheless, different relative cooling powers (RCP) of 112.6 J/kg (Sm) and 95.5 J/kg (Eu) were observed. A detailed analysis of the temperature-dependent lattice parameters shed light on a distinct magnetocaloric effect across the magnetic transition temperature, unveiling an anisotropic thermal expansion [α V = 1.41 × 10 -5 K -1 (Sm) and α V = 1.54 × 10 -5 K -1 (Eu)] wherein the thermal expansion axial ratio α b Sm /α b Eu = 0.61 became lower with increasing temperature, which suggests that the Eu sample experiences a greater thermal expansion in the b -axis direction. At the atomic bonding level, the evidence for magnetoelastic coupling around the magnetic transition temperatures T N was found through the anomalies along the average Co/Fe-O bond distance, formal valence, octahedral distortion, as well as an anisotropic lattice expansion.
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