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 Ni₅₀Mn_25−xGa₂₅Cu_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).

Ni-Co-Mn-Ga ferromagnetic shape memory alloys show metamagnetic transition from ferromagnetic austenite to paramagnetic (or weak-magnetic) martensite for a limited range of Co contents. The temperatures of the structural and magnetic transitions depend strongly on composition and atomic order degree, in such a way that combined composition and thermal treatment allows obtaining martensitic transformation (MT) between any magnetic state of austenite and martensite. The entropy change ΔS measured in the magnetostructural transition comprises a magnetic contribution which depends on the type and degree of magnetic order of the related phases. Consequently, both the magnetization jump across the MT (ΔM) and ΔS are composition and atomic order dependent. Both ΔS and ΔM determine the effect of applied magnetic fields on the MT, hence knowledge and understanding of their behavior can help to approach the best conditions for magnetic field induced MT and related effects. In previous papers, we have reported findings regarding the behavior of the transformation entropy in relation to composition and atomic order in Ni_50−xCo_xMn_25+yGa_25−y (x = 3–8, y = 5–7) alloys. In the present paper we will review our recent results, summarizing the key findings and drawing general conclusions regarding the magnetic contribution to ΔS and the effect of different factors on the magnetic and structural properties of these metamagnetic alloys.

Ni_50−x Co _x Mn₃₀Ga₂₀ (x = 6–9) alloys show metamagnetic behaviour, undergoing martensitic transformation (MT) between ferromagnetic austenite and weak magnetic martensite. The temperatures of the structural and magnetic transitions depend on composition and L2₁ order degree, in such a way that combined composition and thermal treatment allows for MT between any magnetic state of austenite and martensite. For these alloys, mutual influence between atomic and magnetic order has been widely studied. However, the type of magnetism of martensite remains unclear. In this work, the magnetic state of martensite in a Ni₄₃Co₇Mn₃₀Ga₂₀ alloy has been studied in detail. Its evolution as a function of post-quench ageing time indicates that improved atomic order enhances the ferromagnetic character of the weakly magnetic martensite. The most important changes occur when austenite switches from paramagnetic to ferromagnetic. The magnetic behavior of martensite is consistent with the presence of ferromagnetic clusters inside a paramagnetic matrix.