The shape memory alloys are a group of metallic alloys that can return to their original shape when subjected to special conditions of stress or temperature. The samples used in this study were made from Ti, Ni and/or Cu elemental powder with different compositions. The cylindrical shape memory alloys with diameter of 20 mm and height of 4-5 mm were realized in vacuum by uniaxial pressing with 50 MPa at a sintering temperature at 900ºC, in a regime of low-voltage pulses in on/off mode, in 12/2 bursts. In order to increase the alloy homogeneity, the SMA samples were subjected to a post treatment in argon atmosphere. The  neutron diffraction(ND) allowed the identification of main phases of NiTi and NiTiCu microstructures. The majority phase identified by neutron diffraction was B19‘, corresponding to monoclinic structure, but also B2 with cubic structure, and Ni₃Ti and NiTi₂ /(Ni,Cu)Ti₂ precipitates with hexagonal and cubic structures, respectively. These measurements allowed a direct correlation of the microstructure evolution with thermo-electric properties. Measurements at room temperature of resistivity or electrical resistance were determined too. Microstructures identified by diffraction measurements support a correlation of thermal properties with technological process.