Crystallography of phase transitions in metastable titanium aluminium nitride nanocomposites

The isostructural decomposition of the titanium aluminium nitride supersaturated solid solution crystallising in the face centred cubic (fcc) crystal structure into the titanium-rich fcc-(Ti,Al)N and almost titanium-free fcc-(Al,Ti)N and the transformation of metastable fcc-(Ti,Al)N into the wurtzitic aluminium nitride are discussed from the crystallographic point of view by taking the observed orientation relationships between the adjacent phases into account. It is shown that the isostructural decomposition of fcc-(Ti,Al)N into Ti-rich fcc-(Ti,Al)N and fcc-(Al,Ti)N and the transformation of the metastable fcc-(Ti,Al)N into the thermodynamically stable wurtzitic phase are concurrent processes, which are controlled not only by the thermodynamic stability of the respective compound and by the diffusivity of Al and Ti, but also by the local lattice strains. A part of the local lattice strains is regarded to result from the lattice misfit at the interfaces between the titanium aluminium nitrides having different [Al]/[Ti] concentration ratios and, in the case of the fcc/wurtzite-type interface, also having different crystal structures. The phase transition of the fcc-(Ti,Al)N to the wurtzitic one was predicted to be facilitated by stacking faults. The results of crystallographic considerations were verified experimentally by using in situ high-temperature synchrotron diffraction experiments that were performed on cathodic arc evaporated (Ti,Al)N thin films containing titanium and aluminium in different amounts. •Phase decomposition of metastable (Ti,Al)N was studied in situ at high temperatures.•The fcc-(Ti,Al)N decomposes spinodally and transforms concurrently to w-(Al,Ti)N.•Direct transformation of fcc-(Ti,Al)N into w-(Al,Ti)N is facilitated by stacking faults.•Orientation relationships between individual phases obey the crystal symmetry.•The heteroepitaxy of individual phases causes complex local strain state.