Growth early stages

A furdrer complication is that in these slowly growing oxide films, tire spread of the oxide across the metal surface is limited in the early stages by nucleation and growth control. The bare patches of metal between the oxide nuclei will clearly be exposed to a higher oxygen potential and new oxide nuclei will grow at a different initial rate than on the existing nuclei. 

Fig. 2. Vapour-grown carbon fiber. showing relatively early stage of growth at the tip the seeded Fe catalytic particle is encapsulated.

The volume ratio (see Section 1.9) for cuprous oxide on copper is 1 7, so that an initially protective film is to be expected. Such a film must grow by a diffusion process and should obey a parabolic law. This has been found to apply for copper in many conditions, but other relationships have been noted. Thus in the very early stages of oxidation a linear growth law has been observed (e.g. at 1 000°C) . 

Logani and Smeltzer " have observed that, for Fe-1.5%Si at 1 000°C in CO/CO2, the initial slow reaction rate was followed by regions of linear behaviour due to the amorphous Si02 film being consumed by the growth of wustite-fayelite nodules during the early stages. These wustite-fayelite... 

In 1929 Pfeil" published a most interesting account of the way layered structures form and the manner in which they influence oxidation rates. From detailed studies of the growth and composition of scales he was able to show clearly how the formation of barrier layers reduced scale formation by hindering outward diffusion of iron through the scale. Naturally, this work had to be largely based on the study of scales of sufficient thickness so that the mechanism of the early stages of oxidation could not be studied in this way. Pfeil analysed the outer, middle and inner layers of scales formed... 

The early stages of cross-flow microfiltration often follow such a pattern. However, the growth of the cake is limited by the cross-flow of the process liquid. There are several ways of accounting for the control of cake growth. A useful method is to rewrite (16.6.1) as ... 

In Mampel s treatment [447] of nucleation and growth reactions, eqn. (7, n = 3) was found to be applicable to intermediate ranges of a, sometimes preceded by power law obedience and followed by a period of first-order behaviour. Transitions from obedience of one kinetic relation to another have been reported in the literature [409,458,459]. Equation (7, n = 3) is close to zero order in the early stages but becomes more strongly deceleratory when a > 0.5. 

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