Stability and crystal chemistry of the ternary borides M2(Ni21−xMx)B6 (M Ti, Zr, Hf)

• The stability of the borides M2(Ni21−xMx)B6 (M  Ti, Zr, Hf) was studied.
• Refined structural data were used to improve the thermodynamic model of the phase.
• The M solubility range on the 4a site defines the phase compositional boundaries.
• The phase extent is determined by the ability of the 8c polyhedron to expand.
• The 8c polyhedron expands/contracts according to the M/Ni average size in 4a.

A crystallochemical study was undertaken to investigate the structural stability and the compositional extent of the ternary borides M2(Ni21−xMx)B6 (M  Ti, Zr, Hf). This phase often occurs during the production of MB2 joints by means of Ni–B brazing alloys. Samples with the nominal compositions M2Ni21B6 and M3Ni20B6 were synthesized by arc melting and characterized by optical and electron microscopy, and X-ray diffraction. Crystal structure refinements were performed by the Rietveld method. The compositional boundaries of the ternary phases were experimentally determined and found strictly related to the M/Ni size ratio. The stability of this structure is mainly determined by the capability of the structure to expand under the effect of the Ni substitution by the M atom. The CALPHAD modeling of the three M–Ni–B ternary systems in the Ni-rich corner of the phase diagram, performed on the basis of the obtained structural data, shows a good agreement with experimental results.

The structural stability and the compositional extent of the M2(Ni21−xMx)B6 phase (M  Ti, Zr, Hf) has been investigated. Refined structural data were used to improve the CALPHAD modeling of the three M–Ni–B ternary systems in the region close to the ternary phase.Figure optionsDownload as PowerPoint slide