Elastic properties and phase stability of shape memory alloys from first-principles theory

Abstract: Ni-Mn-Ga and In-Tl are two examples of shape memory alloys. Their shape memory effect is controlled by the martensitic transformation from the high temperature cubic phase to the low temperature tetragonal phase. Experimentally, it was found that the martensitic transformation, related to the elastic properties, is highly composition-dependent.In order to better understand the phase transition and facilitate the design of new materials with improved shape memory properties, the atomic scale description of the thermophysical properties of these alloys is needed. Therefore, in the presen tthesis, the elastic properties and phase stability of Ni-Mn-Ga and In-Tl shape memory alloys are investigated by the use of first-principles exact muffin-tin orbitals method in combination with the coherent-potential approximation.We present a theoretical description of the equilibrium properties of pure In and standard stoichiometric Ni2MnGa alloy with both cubic and tetragonal structures. In In-Tl alloys, all the calculated composition-dependent thermophysical properties: lattice parameter c/a, tetragonal shear modulus C" = (C11 - C12)/2, energy difference between the austenitic and martensitic phases, as well as electronic structures are shown to be in line with the experimentally observed lowering of the martensitic transition temperature TM with the addition of Tl. For most of the off-stoichiometric Ni2MnGa, the excess atoms of the rich component prefer to occupy the sublattice of the deficient one, except for the Ga-rich alloys, where the excess Ga atoms have strong tendency to take the Mn sublattice irrespective of the Mn occupation. In Ni-Mn-Ga-X (X=Fe, Co, and Cu) quarternary alloys, Fe atom prefers to occupy the Mn and Ni sublattices even in Ga-deficient alloys; Co has strong tendency to occupy the Ni-sublattice in all types of alloys; Cu atoms always occupy the sublattice of the host elements in deficiency. For most of the studied Ni-Mn-Ga and Ni-Mn-Ga-X alloys with stable site-occupations, the shear modulus C" can be considered as a predictor of the composition dependence of TM of the alloys: the alloy with larger C" than that of the perfect Ni2MnGa generally possesses lower TM except for Ni2Mn1+xGa1-x and Ni2Mn1-xGaFex. The failure of C" as a factor of TM in these two types of alloys may be ascribed that the compositiondependentmagnetic interactions and the temperature-dependent C0, which also playan important role on the martensitic transformation in these alloys. Furthermore, wedemonstrate that a proper account of the temperature and composition dependence ofC0 gives us reasonable theoretical TM(x) values in Ni2+xMn1-xGa alloys. Also in this type of Ni-rich and Mn-deficient alloys, by using the Heisenberg model in combination with the mean-field approximation, the abnormal trend of experimental magnetic transition temperature TC(x) with respect to the composition x is shown to be well captured by the theory.