Search

Even though it is widely accepted that the Laves phase is a promising strengthener for chromium-containing stainless steels, there is little information available on its microstructural evolution and growth. Therefore, in this study, we analysed the behaviour of Laves (C14) precipitates in high-Cr ferritic stainless steel, Fe-20Cr-2Mo-0.5Nb (at%), annealed at 1073 K for different time periods. A high density of (Fe,Cr)2(Mo,Nb) precipitates was formed in the α matrix during annealing. Morphological evolution in the Laves phase followed the sequence of spheroidal → faceted ellipsoidal → faceted needle-like → faceted plate-like. The Laves phase is related to the α matrix by two sets of orientation relationships, viz. OR-1: [ 1 ¯ 1 ¯ 2 ] α / [ 1 2 ¯ 10 ] L , [ 111 ] α / [ 0 1 ¯ 10 ] L , and ( 1 ¯ 10 ) α / ( 000 1 ¯ ) L and OR-2: [ 1 1 ¯ 0 ] α / [ 0001 ] L , [ 113 ] α / [ 1 ¯ 1 ¯ 20 ] L , and ( 3 ¯ 3 ¯ 2 ) α / ( 1 1 ¯ 00 ) L . The habit plane of the Laves phase was found to deviate slightly from the ( 3 ¯ 3 ¯ 2 ) α / ( 1 1 ¯ 00 ) L plane. Interfacial defects, namely disconnections (bD, h) and super disconnections (mbD, mh), observed experimentally along the habit plane, were consistent with theoretical results based on OR-2 as the reference coordinate frame. The Burgers vector bD exhibited an edge component b y D (0.1539 nm) parallel to Y / [ 113 ] α / [ 1 ¯ 1 ¯ 20 ] L and a small normal component b z D (0.0747 nm) perpendicular to the terraces; meanwhile, the overlap step height h = d ( 1 1 ¯ 00 ) L . The morphological evolution of Laves precipitates was described based on the lateral motion of disconnections and super disconnections on { 3 ¯ 3 ¯ 2 } α / { 1 1 ¯ 00 } L terraces in the 〈 113 〉 α / 〈 1 ¯ 1 ¯ 20 〉 direction. Arrays of the disconnections (bD, h) were found to be capable of accommodating the misfit strain on { 3 ¯ 3 ¯ 2 } α / { 1 1 ¯ 00 } L terraces.

Half-Heusler compounds are excellent thermoelectric materials. A characteristic of the half-Heusler–type ordered structure is the vacancy site that occupies one-fourth of all the lattice points. Therefore, a half-Heusler ABX phase (where A and B are typically transition metal elements, such as Ti, Zr, and Hf, and X represents a half-metal element such as Sn or Sb) has a crystallographically close relationship with a Heusler AB2X phase in the sense that the vacancy site in the half-Heusler phase is filled with B atoms in the Heusler phase. The thermoelectric properties are improved or affected by point lattice defects related to the vacancy site and the B site, such as the antisite atom B in the vacancy site, vacancies in the B site, and vacancy-site occupancy by quaternary C atoms. A modulated-like nanostructure due to point defects regarding vacancies and Ni atoms is formed for an instance in ZrNiSn alloys even close to the stoichiometric composition. Ni-rich nanoclusters are locally formed by excessive Ni antisite atoms in the vacancy site, which work as precursors of Heusler precipitates (TiNi2Sn, ZrNi2Sn, and so forth). The vacancy-site occupation in ZrNiSn with Co and Ir results in the drastic conversion of thermoelectric properties from n type to p type, and the effective reduction of the lattice thermal conductivity.

The half-Heusler compound ZrNiSn has a quite small solubility for Ni from the stoichiometric composition towards the Ni-rich direction since Ni atoms are not supposed to occupy the vacancy-site. Nevertheless, Co and Ir atoms preferably occupy the vacancy-site of ZrNiSn, which is contrary to the prediction that they would substitute for Ni sites. This implies that the phase stability of the compound gradually changes toward that of the Heusler compound Zr(Ni,M)2Sn (M = Co, Ir). It has been confirmed that there exists a two-phase field between half-Heusler Zr(Ni,Cox)Sn and Heusler Zr(Ni,Co)2Sn. The n-type thermoelectric property of ZrNiSn can be converted to p-type by the addition of Co and Ir within the compositional range of the half-Heusler phase. The occupation of vacancy sites by Co and Ir atoms leads to a drastic reduction in the thermal conductivity owing to the enhancement of phonon scattering. With further Co addition, the Heusler phase Zr(Ni,Co)2Sn alloys show metallic behavior.

Half-Heusler MNiSn (M=Ti, Zr, Hf) compounds are well-known, excellent n-type thermoelectric materials. The n-type Seebeck coefficients of ZrNiSn are reduced because of the precipitation of the metallic Heusler ZrNi2Sn phase. An excellent n-type Seebeck coefficient can be converted to p-type based on the vacancy site occupation by the solute Co atoms in the half-Heusler TiNiSn phase as well as ZrNiSn. The Heusler phase precipitates, including their precursor nano-structure in the half-Heusler matrix and the vacancy site occupation of the half-Heusler phase, are regarded as lattice defects based on the crystallographically and thermodynamically close relationship between half-Heusler and Heusler phases.