Oxidation in a regime where diffusion is rapid and pressures are low is addressed. Kinetic effects under these conditions are minimized and a protective oxide film of near-equilibrium composition that is a few nanometers thick may form. Ultrathin oxides have great potential for addressing the corrosion resistance of metals, since they do not always suffer stress-induced cracking upon thermal cycling, and can be reformed under high temperature, oxidizing environments. Ultrathin oxide films ate also preferable to those on a thick oxide scale for electrochemical applications due to their electrical properties. To study the growth of these oxide films, we have developed a high signal x-ray photoelectron spectrometer. The instrument can measure the near-surface composition during growth under oxygen partial pressures of up to 10(-5) mbar and surface temperatures up to 1300 K. Under these conditions, films grow to a level of 3 nm in 1 h. Experiments with Cu-Al alloys show rapid segregation of Al upon oxygen exposure at 875 K, whereas exposures at lower temperatures result in a mixed oxide. With a Ni-Al intermetallic, higher temperatures were needed to preferentially segregate Al. Thermal cycling followed by exposure to chlorine in the same instrument is used as a measure of the degree of corrosion resistance of the oxides in question. (C) 2003 American Vacuum Society.