Graduate Thesis Or Dissertation
 

Sorption by detached organic films and its relation to filiform corrosion

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  • The rate of interaction of carbon dioxide with eight detached organic films commonly used as coatings for metal surfaces was examined. The films studied were lacquers of several different formulations including oleoresinous, phenolic, vinyl, alkyd, epoxy, and hydrocarbon types. The sorption was measured on a McBain type gravimetric adsorption balance fitted with quartz helixes with an extension sensitivity of about one mm. /mg. Rates of sorption were measured at three temperatures, -45.3° C., -63.5° C. and -76.5° C., and at three pressures at each temperature, 461.0 torr, 326.5 torr and 117.5 torr. Theoretical examination of the data lead to the conclusion that the rate controlling mechanism was a diffusion process. Sorption coefficients were calculated from the kinetic data and limiting diffusion coefficients determined by extrapolation to zero CO₂ activity. Values on the order of 10⁻¹² cm.²/sec. were obtained. From these were calculated activation energies for the diffusion process, which were compared to the calculated isosteric heats of sorption. Oxygen sorption isotherms were attempted and no oxygen uptake was detected. A few water vapor rate experiments were performed for comparison with the CO₂ results. The rate of water vapor interaction was found to be two to three orders of magnitude faster than that for CO₂. The eight films studied have been rated as to their relative resistance to filiform corrosion growth. This relative resistance to filiform corrosion was compared with the relative diffusion rate of CO₂. A correlation is suggested, with the films showing faster CO₂ uptake also showing the most resistance. This is in agreement with the observed effect that CO₂ in a corrosion test atmosphere inhibits filiform corrosion growth.
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