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An experimental study of the magnetocaloric effect in tetraaquabis(hydrogen maleato)nickel(II), [Ni(C4H3O4)2(H2O)4] powder sample is presented. The magnetocaloric properties of the studied sample were investigated using specific heat and magnetization measurements in magnetic fields up to 9 T in the temperature range from 0.4 to 50 K. A large conventional magnetocaloric effect was found at a temperature of about 3.5 K, where −ΔSM = 8.5 Jkg−1K−1 and 11.2 Jkg−1K−1 for a magnetic field of 5 T and 7 T, respectively. Assuming a substantial role of the crystal field, the temperature dependence of the magnetic specific heat in a zero magnetic field was compared with an S = 1 model with single-ion anisotropy parameters D and E (axial and rhombic). The best agreement was found for the parameters D/kB = −7.82 K and E/kB = −2.15 K. On the other hand, the experimental temperature dependence of −ΔSM shows higher values compared to the theoretical prediction for the mentioned model, indicating the presence of additional factors in the system, such as an exchange interaction between magnetic ions. The first exchange pathway can be realized through maleic rings between the nearest Ni(II) ions. The second exchange pathway can be realized through water molecules approximately along the a crystallographic axis. Broken-symmetry DFT calculations performed using the computational package ORCA provided the values of ferromagnetic exchange interactions, J1/kB = 1.50 K and J2/kB = 1.44 K (using B3LYP functional). The presence of such ferromagnetic correlations in the studied system may explain the enhanced magnetocaloric effect compared with the model of an anisotropic spin-1 paramagnet. [ABSTRACT FROM AUTHOR]

An experimental study of the rotational magnetocaloric effect in Ni(en)(H2O)4SO4∙2H2O (en = ethylenediamine) single crystal is presented. The study was carried out at temperatures above 2 K and was associated with adiabatic crystal rotation between the easy plane and hard axis in magnetic fields up to 7 T. The magnetocaloric properties of the studied system were investigated by isothermal magnetization measurement. The experimental observations were completed with ab initio calculations of the anisotropy parameters. A large rotational magnetic entropy change ≈12 Jkg−1K−1 and ≈16.9 Jkg−1K−1 was achieved in 5 T and 7 T, respectively. The present study suggests a possible application of this material in low-temperature refrigeration since the adiabatic rotation of the single crystal in 7 T led to a cooldown of the sample from the initial temperature of 4.2 K down to 0.34 K. Finally, theoretical calculations show that S = 1 Ni(II)-based systems with easy-plane anisotropy can have better rotational magnetocaloric properties than costly materials containing rare-earth elements in their chemical structures. [ABSTRACT FROM AUTHOR]

The phase content and sequence, the crystal structure, and the magnetic properties of perovskite solid solutions of the (1-y)BiFeO3-yBiZn0.5Ti0.5O3 series (0.05 ≤ y ≤ 0.90) synthesized under high pressure have been studied. Two perovskite phases, namely the rhombohedral R3c and the tetragonal P4mm, which correspond to the structural types of the end members, BiFeO3 and BiZn0.5Ti0.5O3, respectively, were revealed in the as-synthesized samples. The rhombohedral and the tetragonal phases were found to coexist in the compositional range of 0.30 ≤ y ≤ 0.90. Magnetic properties of the BiFe1-y[Zn0.5Ti0.5]yO3 ceramics with y < 0.30 were measured as a function of temperature. The obtained compositional variations of the normalized unit-cell volume and the Néel temperature of the BiFe1-y[Zn0.5Ti0.5]yO3 perovskites in the range of their rhombohedral phase were compared with the respective dependences for the BiFe1-yB3+ yO3 perovskites (where B3+ = Ga, Co, Mn, Cr, and Sc). The role of the high-pressure synthesis in the formation of the antiferromagnetic states different from the modulated cycloidal one characteristic of the parent BiFeO3 is discussed. [ABSTRACT FROM AUTHOR]