External oxides of a commercially pure titanium (cpTi), Ti6A14V alloy, and an experimental β-type titanium alloy (Ti 53.4wt%, Nb 29wt%, Ta 13wt%, and Zr 4.6wt%) were characterized after heating to 600, 900, 1150, and 1400°C in contact with three types of investments (alumina cement, magnesia cement, and phosphate-bonded) in air. XRD studies demonstrated that MgO, Li
2TiO
3 and/or Li
2Ti
3O
7 were formed through reactions with the metal and the constituents in the magnesia cement-investment after heating to 900, 1150, and 1400°C. Except for these conditions, TiO
2 (rutile) was only formed on cpTi. For titanium alloys, the other components apart from Ti also formed simple and complex oxides such as Al
2O
3 and Al
2TiO
5 on Ti6Al4V, and Zr
0.25Ti
0.75Nb
2O
7 on the β-type titanium alloy. However, no oxides containing V or Ta were formed. These results suggest that the constituents of titanium alloys reacted with the investment oxides and atmospheric oxygen to form external oxides due to the free energy of oxide formation and the concentration of each element on the metal surface.
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