Search

With the purpose to optimize the functional properties of Heusler alloys for their use in solid-state refrigeration, the characteristics of the martensitic and magnetic transitions undergone by Ni 50 Mn 25- x Ga 25 Cu x ( x = 3-11) alloys have been studied. The results reveal that, for a Cu content of x = 5.5-7.5, a magnetostructural transition between paramagnetic austenite and ferromagnetic martensite takes place. In such a case, magnetic field and stress act in the same sense, lowering the critical combined fields to induce the transformation; moreover, magnetocaloric and elastocaloric effects are both direct, suggesting the use of combined fields to improve the overall refrigeration capacity of the alloy. Within this range of compositions, the measured transformation entropy is increased owing to the magnetic contribution to entropy, showing a maximum at composition x = 6, in which the magnetization jump at the transformation is the largest of the set. At the same time, the temperature hysteresis of the transformation displays a minimum at x = 6, attributed to the optimal lattice compatibility between austenite and martensite. We show that, among this system, the optimal caloric performance is found for the x = 6 composition, which displays high isothermal entropy changes (-36 J·kg -1 ·K -1 under 5 T and -8.5 J·kg -1 ·K -1 under 50 MPa), suitable working temperature (300 K), and low thermal hysteresis (3 K).

Polarized neutron scattering has been used to obtain the magnetic moment at specific crystallographic sites of the austenitic and martensitic phases of two nonstoichiometric Ni-Mn-Ga single crystals with close composition. These alloys have been chosen because they exhibit different structures in the paramagnetic state and inverse positions of the respective martensitic transformation and Curie temperature. The diffraction analysis revealed a remarkable result: Despite the similar alloy composition, the magnetic moments of Mn are quite different for the two alloys at the same crystallographic position. Furthermore, such a difference enabled us to assess that the exchange coupling between Mn atoms switches from ferro- to antiferromagnetic at a distance between 2.92 and 3.32 Å in the martensite. These results are of great importance to guide first principles calculations that, up to now, have not been contrasted with experiments at the atomic level.

The magnetic, magnetocaloric and thermal characteristics have been studied in a Ni(50.3)Mn(20.8)Ga(27.6)V(1.3) ferromagnetic shape memory alloy (FSMA) transforming martensitically at around 40 K. The alloy shows first a transformation from austenite to an intermediate phase and then a partial transformation to an orthorhombic martensite, all the phases being ferromagnetically ordered. The thermomagnetization dependences enabled observation of the magnetocaloric effect in the vicinity of the martensitic transformation (MT). The Debye temperature and the density of states at the Fermi level are equal to θ(D) = (276 ± 4) K and 1.3 states/atom eV , respectively, and scarcely dependent on the magnetic field. The MT exhibited by Ni-Mn-Ga FSMAs at very low temperatures is distinctive in the sense that it is accompanied by a hardly detectable entropy change as a sign of a small driving force. The enhanced stability of the cubic phase and the low driving force of the MT stem from the reduced density of states near the Fermi level.

The proper annealing of Ni(51)Mn(28)Ga(21) ribbon alloy gives rise to an increase of the saturation magnetization and of the magnetic order T(C) (up to 20 K) and martensitic transition T(M) (up to 10 K) temperatures. The combined x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) studies indicate that the annealing treatment drives the alloy to a more ordered structure without significantly affecting the local structure in terms of interatomic distances and bonding geometry. By contrast, the annealing strongly affects the near-edge absorption at the Mn K-edge while no effect is observed at either the Ni or Ga K-edge. These results suggest that annealing leads to a modification of the electronic structure of the Mn atoms while that of Ni and Ga atoms remains unvaried. However, strong XMCD signals are detected at both Ni and Ga K-edges whose amplitude increases after annealing. These results point out that despite the change of the magnetic properties of the system being mainly associated with the modification of the electronic properties of the Mn atoms, both Ni and Ga may play a non-negligible role through the polarization of the conduction band.