Giant multiple caloric effects in charge transition ferrimagnet.

Caloric effects of solids can provide us with innovative refrigeration systems more efficient and environment-friendly than the widely-used conventional vapor-compression cooling systems. Exploring novel caloric materials is challenging but critically important in developing future technologies. Here we discovered that the quadruple perovskite structure ferrimagnet BiCu3Cr4O12 shows large multiple caloric effects at the first-order charge transition occurring around 190 K. Large latent heat and the corresponding isothermal entropy change, 28.2 J K-1 kg-1, can be utilized by applying both magnetic fields (a magnetocaloric effect) and pressure (a barocaloric effect). Adiabatic temperature changes reach 3.9 K for the 50 kOe magnetic field and 4.8 K for the 4.9 kbar pressure, and thus highly efficient thermal controls are achieved in multiple ways.

Co-Substitution Effect in Room-Temperature Ferromagnetic Oxide Sr3.1Y0.9Co4O10.5.

We investigated the Co substitution effect for the magnetic properties in room-temperature ferromagnetic oxide Sr3.1Y0.9Co4O10.5. The substituted element (Al and Ga) and low-spin state Co3+, which was changed from a high-spin or intermediate-spin state by Al or Ga substitution, reduced the Curie temperature to even 1.5 times lower than the temperature estimated from a simple dilution effect. Al3+ preferentially substituted for intermediate-spin-state Co3+ in the ferrimagnetic CoO6 layer and deteriorated the saturation magnetization of Sr3.1Y0.9Co4O10.5. By contrast, Ga3+ substituted for high-spin-state Co3+ in the CoO6 layer and/or the antiferromagnetic CoO4.25 layer and enhanced the saturation magnetization per Co ion. These results indicate that the magnetic properties of Sr3.1Y0.9Co4O10.5 can be controlled by selectively substituting for Co3+ with different spin states.

Metallurgical Synthesis of Mg2FexSi1-x Hydride: Destabilization of Mg2FeH6 Nanostructured in Templated Mg2Si.

Magnesium-based transition-metal hydrides are attractive hydrogen energy materials because of their relatively high gravimetric and volumetric hydrogen storage capacities combined with low material costs. However, most of them are too stable to release the hydrogen under moderate conditions. Here we synthesize the hydride of Mg2FexSi1-x, which consists of Mg2FeH6 and Mg2Si with the same cubic structure. For silicon-rich hydrides (x < 0.5), mostly the Mg2Si phase is observed by X-ray diffraction, and Mössbauer spectroscopy indicates the formation of an octahedral FeH6 unit. Transmission electron microscopy measurements indicate that Mg2FeH6 domains are nanometer-sized and embedded in a Mg2Si matrix. This synthesized metallographic structure leads to distortion of the Mg2FeH6 lattice, resulting in thermal destabilization. Our results indicate that nanometer-sized magnesium-based transition-metal hydrides can be formed into a matrix-forced organization induced by the hydrogenation of nonequilibrium Mg-Fe-Si composites. In this way, the thermodynamics of hydrogen absorption and desorption can be tuned, which allows for the development of lightweight and inexpensive hydrogen storage materials.

Study of entropic characteristics of strongly correlated systems using VO2 as a model case.

To explain the huge caloric effects often observed in the first-order electronic phase transition in the strongly correlated oxides, the entropic characteristics are investigated in VO2. By evaluating the spin and charge fluctuations based on the local moment model and the Sommerfeld coefficient in the high-temperature rutile phase, it is found that these fluctuations of the high-temperature phase are the main source of the entropic change during the transition. This mode of entropic change is realized by the quenching of these fluctuations owing to the formation of a singlet bonding state in the low-temperature monoclinic phase. By introducing oxygen deficiency, a vagueness in the gap at the Fermi level is confirmed by the transport data, the X-ray photoelectron spectra and also the electronic structure calculated by the first-principles calculations. In this case, the entropic feature at the transition is weakened. Consequently, the large caloric phenomena of the strongly correlated oxides are a result of the conversion of the internal energy gain owing to the orbital selection at the ground state into the free energy gain owing to the spin and charge fluctuations at finite temperature.

Giant barocaloric effect enhanced by the frustration of the antiferromagnetic phase in Mn3GaN.

First-order phase transitions are accompanied by a latent heat. Consequently, manipulating them by means of an external field causes a caloric effect. Although transitions from antiferromagnetic to paramagnetic states are not controlled by a magnetic field, a large barocaloric effect is expected when strong cross-correlations between the volume and magnetic order occur. Here we examine how geometric frustration in itinerant antiferromagnetic compounds can enhance the barocaloric effect. We study the thermodynamic behaviour of the frustrated antiferromagnet Mn3GaN, and report an entropy change of 22.3 J kg(-1) K(-1) that is concomitant with a hydrostatic pressure change of 139 MPa. Furthermore, the calculated value of the adiabatic temperature change reaches 5 K by depressurization of 93 MPa. The giant barocaloric effect in Mn3GaN is caused by a frustration-driven enhancement of the ratio of volume change against the pressure coefficient of the Néel temperature. This mechanism for enhancing the barocaloric effect can form the basis for a new class of materials for solid-state refrigerants.