Victor A. L'Vov

Ferromagnetic solids acquire nontrivial magnetic and caloric properties when the temperature of the structural phase transition approaches the Curie point. Deciphering magneto-structural transitions, i.e. determining their characteristic temperatures and elucidating the related properties, remains challenging. In the present paper, three types of transformational behaviour of Ni50Mn25-xCuxGa25 (x = 6.25, 6.5, 6.75, 7) and Ni50.5Mn18.5Cu6.5Ga24.5 alloys have been identified, arising from small variations in chemical composition: (i) structural martensitic transformation (MT) in the ferromagnetic phase; (ii) magneto-structural phase transition from paramagnetic austenite to ferromagnetic martensite; (iii) MT in paramagnetic phase. The temperature-dependent values of magnetization, M(T), and of magnetic susceptibility, χ(T), were measured for each alloy. A novel thermodynamic analysis was used to determine the Curie points and MT temperatures. The novelty lies in considering the interplay between structural and magnetic characteristics of the alloys through the impact of the structural transition on the spin-exchange parameter. The theoretical analysis of experimental data revealed that this impact results in a large difference (≥ 50 K) between the Curie temperatures computed for the austenitic and martensitic states of each alloy. The characteristic temperatures, corresponding to the extrema of the dM(T)/dT and χ(T) functions, were calculated. The correlation of these temperatures with the Curie temperatures and the MT temperatures is not straightforward and depends strongly on the type of transformational behaviour (i) ‒ (iii). The proposed approach provides a robust framework for extracting unmeasurable characteristic temperatures from standard magnetization data, applicable to ferromagnetic Heusler systems and other multiferroic ferromagnetic materials.

In the present article, the ferromagnetic shape memory alloys (FSMAs) that undergo structural phase transition of magnetoelastic type from the cubic phase (austenite) to the low-symmetry phase (martensite) are considered. The analytic review of those properties of ferromagnetic shape memory alloys, which are closely related to magnetoelastic coupling, is carried out. The experimentally observed strong impact of structural phase transition on magnetic anisotropy, temperature dependence of magnetization and giant magnetic-field-induced deformation of martensite is explained. The amplification of magnetocaloric response of FSMA by the structural phase transition is analyzed quantitatively. The magnetically induced piezoelectric effect in the piezopolymer/FSMA composite material is considered.

The ferromagnetic resonance (FMR) in the shape memory alloys (SMAs) exhibiting structural cubic-tetragonal phase transition has been studied. The influence of instability and spatial inhomogeneity of crystal lattice on the FMR spectra of twinned ferromagnetic SMAs films has been analyzed using statistical model of ferromagnetic martensite. It has been shown that the abnormally strong temperature dependence of lattice parameters of martensitic film gives a noticeable contribution to the temperature dependence of the resonance value of external magnetic field. The narrowing of the resonance peak, which had been experimentally observed on cooling of the film slightly below the Curie temperature, has been explained. It is argued that the martensitic films are good candidates for the experimental study of local elastic strains influence on the shape of the FMR peak.

In the present work, the magnetization of Ni₅₀Mn_17.5Ga₂₅Cu_7.5 alloy undergoing the first-order phase transition from paramagnetic austenite to ferromagnetic martensite was measured to evaluate the magnetic-field-induced entropy change (MFIEC) and refrigerant capacity (RC) of the alloy. A standard method (SM) of evaluation of MFIEC is based on thermodynamic Maxwell relation. In view of the criticism of SM expressed by some scientists, the alternative method (AM), which is based on thermodynamic relationships for free energy, was proposed recently for the determination of MFIEC. We developed this method and computed MFIEC in two ways—by AM and SM. The values of MFIEC obtained for Ni₅₀Mn_17.5Ga₂₅Cu_7.5 alloy by these methods appeared to be large but very different from each other. Moreover, AM reveals the possibility of both normal and inverse magnetocaloric effects in the adjoining temperature ranges, while SM results only in the normal magnetocaloric effect.

In this paper, our most recent findings on the influence of magnetic order on the main transformational caloric and elastic properties of shape memory alloys (SMAs) are reviewed. It is argued that ferromagnetic order has a strong influence on the temperature interval of martensitic transformation (MT), the characteristics of stress-induced MT, and the shear elastic modulus of SMA. The problem of separation of the magnetic contributions to the entropy change ΔS and heat Q exchanged in the course of martensitic transformation (MT) of SMA is considered in general terms, and theoretical formulas enabling the solution of the problem are presented. As an example, the ΔS and Q values, which were experimentally determined for Ni-Mn-Ga and Ni-Fe-Ga alloys with different Curie temperatures T_C and MT temperatures T_M, are theoretically analyzed. It is shown that for Ni-Mn-Ga martensites with T_M < T_C, the ratio of elastic and magnetic contributions to the entropy change may be greater or smaller than unity, depending on the temperature difference T_C – T_M.

Magnetic and nonmagnetic shape memory alloys (SMAs) exhibit thermoelastic martensitic transformations (MTs) which are hysteretic due to their first‐order nature. According to the thermodynamic Landau theory of phase transitions, which assumes ideal thermoelastic equilibrium at each point of the MT interval, the hysteresis is explained by the different limits of stability for austenite and martensite in the phase diagram. No interactions on the phase boundaries are taken into account. In the real alloys, the hysteresis of MT is related not only to the stability intervals of two phases but also to the processes of nucleation and growth of the resultant phase inside the parent phase. In turn, the features of these processes are related to the heights of energy barriers caused by the incompatibility of austenitic and martensitic lattices, crystal defects and some other physical factors. However, the defects, normally, play a minor role in the width of MT hysteresis if compared to the thermodynamic and crystallographic factors. A reduction of hysteresis of MT in SMAs, being crucial for technology, presents a challenging problem for science. A decrease of hysteresis width of MT was observed recently for the single crystals of ferromagnetic SMAs such Ni–Fe(Co)–Ga and Fe–Pd on approaching of their transformation paths to the critical point in stress–temperature phase diagram. Moreover, the superelastic and shape memory properties characterized by the nearly‐zero hysteresis width were observed in the postcritical transformational regime. Here we show that both the Landau‐type theory of ferroelastic phase transitions and neutron diffraction experiments carried out under axial compression describe the essential features of these properties. We also interpret the experimentally observed anhysteretic phenomena in Ni–Mn–Ga thin films and nanobeam actuators in terms of their postcritical state.