Microstructure evolution of nanoprecipitates in half-Heusler TiNiSn alloys

The microstructures of thermoelectric TiNiSn half-Heusler alloys have been studied in detail. For concentration ratios that are slightly rich in Ni, a high density of Heusler-phase nanosized precipitates tended to precipitate within a half-Heusler matrix. The morphology and average size of the Heusler nanoprecipitates were very sensitive to the Ni concentration ratio in the half-Heusler matrix of the alloys. Smaller Heusler nanoprecipitates with coherent ellipsoidal (<5 nm) and disc (<10 nm wide) morphologies tended to precipitate within the matrices of alloys with slightly elevated Ni concentration ratios (Ti:Ni:Sn = 1.0:1.1:1.0). However, much larger coherent discs (<45 nm wide and <5 nm thick), semicoherent platelets (up to 1 μm long and <30 nm thick) and spheres (up to 1 μm wide) were observed in the matrices of the alloys with larger Ni concentration ratios (Ti:Ni:Sn = 1.0:1.2:1.0). Tetragonal structures were observed in the coherent Heusler nanoprecipitates. The formation of such structures was closely associated with the size, morphology and interface coherency of the nanoprecipitates. Moreover, most of the coherent Heusler nanoprecipitates were preferentially oriented parallel to the cubic {0 0 1}_HH orientations. Interfacial defects between the Heusler and half-Heusler phases, as well as lattice point defects, Ni antisites and vacancies, were found to be closely related to the formation of the Heusler nanoprecipitates. A mechanism has been proposed in this study to describe the coarsening of the Heusler nanoprecipitates via the formation of lattice point defects and interfacial defects.