The subscale formed during high temperature rapid oxidation of gamma-t
itanium aluminum is revealed by transmission electron microscopy and m
icroanalysis to consist of two phases: one hexagonal with unit cell di
mensions a = 0.58 nm, c = 0.47 nm (+/- 0.005 nm), and a composition cl
ose to Ti6Al3O4; the other simple cubic with a = 0.69 nm (+/-0.005 nm)
and composition Ti3Al2O3, with oxygen concentration known to about 10
% accuracy. The results strongly suggest that the hexagonal phase is a
solid solution of O in Ti3Al, while the cubic phase is a novel ternar
y compound with space group P4(2)32. These subscale phases exhibit som
e tendency for a crystallographic orientation relationship with (110)(
cubic)//(01 (1) over bar 0)(hexagonal) and [0 (1) over bar 1](cubic)/[
(2) over bar 112](hexagonal), and the hexagonal phase is less stable t
han the cubic phase as the distance to the sample surface decreases an
d oxygen level increases.