October 2011
Hydrothermal Oxidation Behavior of Bulk Ti3AlC2
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(4) Comparison of the Hydrothermal Oxidation Behavior
of Ti3AlC2 and Ti3SiC2
Comparing the kinetic data and the thickness and integrity of
oxide layers, it can be concluded that bulk Ti3AlC2 has a better
hydrothermal oxidation resistance than Ti3SiC2. Nevertheless,
similar to Ti3SiC2, the oxide layer formed on Ti3AlC2 is not fully
dense; therefore, linear kinetics is present (Fig. 1) because the
oxide layer cannot provide complete protection for the Ti3AlC2
substrates. The linear kinetics indicates a reaction controlled
oxidation mechanism and the rate of hydrothermal degradation
of Ti3AlC2 is controlled by the reaction between the carbide and
water. In other words, the superior hydrothermal oxidation
resistance of Ti3AlC2 is owing to its intrinsic high resistance
to hydrothermal oxidation, and not because of the presence
of a denser/less permeable oxide layer when comparedwith
Ti3SiC2.20
It is observed that hexagonal Al2O3 plates are formed on the
surfaces after hydrothermal oxidation (Figs. 5(c)–(e)). Ti3AlC2
grains suffering the attack of hydrothermal water break into
layered configuration (Fig. 5(d)). These facts imply that the ox-
idation process is that hydrothermal water attacks the layered
configuration of Ti3AlC2 grains, and extracts aluminum from
grains with the formation of alumina because of the high activity
and fast diffusion of aluminum.34,35 This behavior is also
observed during the hydrothermal oxidation of Ti3SiC2.20 The
extrapolation of literature data to the experimental parameters
of this work showed that the dissolution rate of silica in hydro-
thermal water is very rapid40–42 but that of alumina is extremely
sluggish and can be neglected.43 Obviously the fast dissolution
of silica results in that hydrothermal water easily tears grains
apart and causes the decomposition of Ti3SiC2. In contrast,
the existence of alumina can slow down the decomposition
process of Ti3AlC2. Hence, the critical factor maintaining the
superior structural stability of Ti3AlC2 than Ti3SiC2 is much
higher stability of alumina than silica during hydrothermal
oxidation.
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V. Conclusions
Hydrothermal oxidation of bulk Ti3AlC2 was investigated at
5001–7001C under a hydrostatic pressure of 35 MPa in a con-
tinuous water flow. Titanium and aluminum were selectively
oxidized from Ti3AlC2 during hydrothermal oxidation to form
oxides with the survival of carbon. The reaction obeyed a linear
law. The hydrothermal oxidation rate was slow below and faster
at 7001C accompanied with the formation of cracks in oxides.
The phase transformation from anatase to rutile (two TiO2
modifications) was responsible for the formation of cracks. The
distribution of alumina was uneven in the entire oxide layers,
which was related to the fact that hydrothermal water attacked
the layered configuration of Ti3AlC2 grains and extracted alu-
minum from grains to form alumina. Bulk Ti3AlC2 had better
hydrothermal oxidation resistance than Ti3SiC2. This was re-
lated to the higher stability of alumina than silica in hydrother-
mal water.
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