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Phase equilibria in the quaternary system Ti–Cu –Al –N are investigated using XRD, metallography and EDX, yielding the observation of 18 four phase spaces of the 850 °C isotherm. In the ternary boundary systems Ti– Cu–Al and Ti –Al –N, all previously reported phases are confirmed, but several tielines are newly determined. In the system Ti–N, the new ternary phase Ti 3 CuN dominates most phase fields. Based on thermochemical data of the binary boundary systems and the newly investigated or reinvestigated phase equilibria of the ternary boundary systems, a set of Gibbs energies for the solid phases occuring in the quaternary system is derived, which is used in combination with the quaternary experimental data to derive a large section of the isotherm for Ti –Cu –Al –N at 850 °C. The quaternary g-phase (Ti, Cu, Al) 6 N having the composition Ti 3 Cu 2 Al 1 N 0.8  is found to be the only stable quaternary phase of this system. Several η-phases isotypic to Ti 3 Cu 2 Al 1 N 0.8  are synthesized to explore the crystal chemistry effects of substitutions on different crystallographic sites.

Phases and Phase Equilibria in the Quaternary System Ti –Cu–Al –N at 850 °C