Diffusion of oxygen

Atmospheric corrosion results from a metal s ambient-temperature reaction, with the earth s atmosphere as the corrosive environment. Atmospheric corrosion is electrochemical in nature, but differs from corrosion in aqueous solutions in that the electrochemical reactions occur under very thin layers of electrolyte on the metal surface. This influences the amount of oxygen present on the metal surface, since diffusion of oxygen from the atmosphere/electrolyte solution interface to the solution/metal interface is rapid. Atmospheric corrosion rates of metals are strongly influenced by moisture, temperature and presence of contaminants (e.g., NaCl, SO2,. ..). Hence, significantly different resistances to atmospheric corrosion are observed depending on the geographical location, whether mral, urban or marine. 

In addition to oxidation itself, gas diffusion into the base metal can be more damaging than the actual loss of metal from the surface. Thus the loss in mechanical properties owing to diffusion of oxygen into niobium makes it more difficult to protect niobium against oxidation damage than molybdenum, even though molybdenum has less resistance to normal oxidation effects than niobium. 

Conversely, in hydroxyl-free vitreous siUca, the oxidation is much slower and is controlled by the diffusion of oxygen through the soHd according to the following reaction ... 

Termination. The conversion of peroxy and alkyl radicals to nonradical species terminates the propagation reactions, thus decreasing the kinetic chain length. Termination reactions (eqs. 7 and 8) are significant when the oxygen concentration is very low, as in polymers with thick cross-sections where the oxidation rate is controlled by the diffusion of oxygen, or in a closed extmder. The combination of alkyl radicals (eq. 7) leads to cross-linking, which causes an undesirable increase in melt viscosity. 

In a study of oxidation resistance over the range 1200—1500°C an activation energy of 276 kj/mol (66 kcal/mol) was determined (60). The rate law is of the form 6 = kT + C the rate-controlling step is probably the diffusion of oxygen inward to the SiC—Si02 interface while CO diffuses outwards. 

Most recent studies (69) on elevated temperature performance of carbon fiber-based composites show that the oxidation resistance and elevated temperature mechanical properties of carbon fiber reinforced composites are complex and not always direcdy related to the oxidation resistance of the fiber. To some extent, the matrix acts as a protective barrier limiting the diffusion of oxygen to the encased fibers. It is therefore critical to maintain interfacial bonding between the fiber and the matrix, and limit any microcracking that may serve as a diffusion path for oxygen intmsion. Since interfacial performance typically deteriorates with higher modulus carbon fibers it is important to balance fiber oxidative stabiHty with interfacial performance. 

For the dilute reactive constituent R which forms the oxide RO , let the thickness of the internal oxidation zone be then for the inward diffusion of oxygen, mole fraction No... 

Firstly, they might be expected to have an effect when corrosion occurs under conditions of active (film-free) anodic dissolution and is not limited by the diffusion of oxygen or some other species in the environment. However, if the rate of active dissolution is controlled by the rate of oxygen diffusion, or if, in general terms, the rate-controlling process does not take place at the metal surface, the effect of crystal defects might be expected to be minimal. 

In natural waters, cold-worked commercial carbon steels of the same composition corrode at more or less the same rate as annealed steels, presumably because the corrosion rate in this case is controlled by the diffusion of oxygen. Unprotected carbon steels are sometimes exposed to natural waters, and it is this latter situation which is of greater practical importance than the behaviour of steels in acids, since steels should never be used in these environments unless they are protected. 

By substituting the appropriate values for viscosity and diffusion at various temperatures, they found that corrosion rates could be calculated which were confirmed by experiment. The corrosion rates represent maxima, and in real systems, corrosion products, scale and fouling would reduce these values often by 50%. The equation was useful in predicting the worst effects of changing the flow and temperature. The method assumes that the corrosion rate is the same as the limiting diffusion of oxygen at least initially this seems correct. 

Dissolved oxygen reduction process Corrosion processes governed by this cathode reaction might be expected to be wholly controlled by concentration polarisation because of the low solubility of oxygen, especially in concentrated salt solution. The effect of temperature increase is complex in that the diffusivity of oxygen molecules increases, but solubility decreases. Data are scarce for these effects but the net mass transport of oxygen should increase with temperature until a maximum is reached (estimated at about 80°C) when the concentration falls as the boiling point is approached. Thus the corrosion rate should attain a maximum at 80°C and then decrease with further increase in temperature. 

Oxygen from the atmosphere, dissolved in the electrolyte solution provides the cathode reactant in the corrosion process. Since the electrolyte solution is in the form of thin films or droplets, diffusion of oxygen from the atmosphere/electrolyte solution interface to the solution/metal interface is rapid. Moreover, convection currents within these thin films of solution may play a part in further decreasing concentration polarisation of this cathodic process . Oxygen may also oxidise soluble corrosion products to less soluble ones which form more or less protective barriers to further corrosion, e.g. the oxidation of ferrous species to the less soluble ferric forms in the rusting of iron and steel. 

The formation of molten M0O3 above 815°C results in a catastrophically accelerating effect due to the following factors (a) the liquid oxide flows off the metal surface, (b) the rate of diffusion of oxygen through the liquid phase is high, and (c) the molten oxide can also act as a flux. 

In the case of alloys having one constituent considerably more reactive to oxygen than the others, conditions of temperature, pressure and atmosphere may be selected in which the reactive element is preferentially oxidised. Price and Thomas used this technique to develop films of the oxides of beryllium, aluminium, etc. on silver-base alloys, and thereby to confer improved tarnish resistance on these alloys. If conditions are so selected that the inward diffusion of oxygen is faster than outward diffusion of the reactive element, the oxide will be formed as small dispersed particles beneath the surface of the alloy. The phenomenon is known as internal oxidation and is of quite common occurrence, usually in association with a continuous surface layer of oxides of the major constituents of the alloy. 

The diffusion of oxygen through polymer films has been examined by a number of workers. Guruviah measured the permeability to oxygen of films cast from five paints (Tabic 14.4) and compared the results with the... 

Table 14.4 Diffusion of oxygen through paint films of thickness 0-1 mm...

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