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P <î _l \ *- % 16 24- \ \ "^' -i . 1 a jcc Aw ^ ''• ' H 1. \ '. i < ''-. -> . _ _ . _ _ . _ • ! ^ ' '** 77 mg in» 10 1 10 o 100 1 l 0' 10 10 PRESSURE Ub/in 2 obs) 10 1000 1 A RADIUS FIG. 24. Development ofporosity in oxide films formed in 400°C steam. Note appearance ofporosity prior to normally accepted weight gain at transition (-30 mgldm2) [22]. The argtunent that these pores or cracks only progress a fraction of the way through the oxide has been made both on mechanical grounds, and on the basis of impedance measurements in aqueous solution.

1) Heated at 1000°C in vac. for l h and quenched. (2) Heated at 880°C in vac. for 72 h and quenched, reheated at 500°C for 6 h. The large amount of isothermal a-phase present in this sample probably results from oxygen absorption during the long anneal at 880°C. 2 mg/dm2. 48 when a proton is discharged by an electron emerging through the oxide film. The site at which this occurs depends on the morphology of the oxide film (Fig. 17). 3 wt%) in the form of a distribution of second-phase particles, the electron current flows primarily at sites where intermetallics partially, or completely, short-circuit the oxide [86].

When a specimen, with an oxide film such as those above, is heated in an environment (vacuum or H2) containing insufficient oxidant to maintain the normal growth of the oxide, the rate of oxygen dissolution in the metal will exceed the rate of formation of new oxide. Under these conditions, the oxide film will slowly dissolve in the metal. This process has been observed (Fig. 37) by following the thinning of interferencecoloured oxide films in the optical microscope [83,84]. On the scale of resolution of this instrument the dissolution process appears to be uniform, provided that the metal core has not become saturated in oxygen [6,84].

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