Complex oxide conversion coating films

Complex oxide film is formed in a basic solution, whereas the films described earlier are formed in an acidic solution. Complex oxide conversion coating reactions do not contain either hexavalent or trivalent chromium ions. However, the sealing rinse contains much greater quantities of hexavalent and trivalent chromium ions than do the sealing rinses associated with phosphate conversion coatings and chromate conversion coatings. 

Where the corrosion resistance of a coating depends upon its passivity, it is common to follow plating with a conversion coating process to strengthen the passive film. Zinc, cadmium and tin in particular are treated with chromate solutions which thicken their protective oxides and also incorporate in it complex chromates (see Section 1S.3). There are many proprietary processes, especially for zinc and cadmium. Simple immersion processes are used for all three coatings, while electrolytic passivation is us on tinplate lines. Chromate immersion processes are known to benefit copper, brass and silver electrodeposits, and electrolytic chromate treatments improve the performance of nickel and chromium coatings, but they are not used to the extent common for the three first named. 

Conversion coatings, in particular phosphates, have been in existence for over a hundred years and have been extensively used since the 1930s. Conversion coatings can vary widely in thickness from a few nanometres to many micrometres with widely varied chemistry. These films tend to comprise highly complex hydrated metal oxides. Their precise chemistry can be difficult to determine or control as this is a function of many variables such as substrate type, solution composition, pH, temperature and time. 

One concern is that Cr(III) and Al(III) compounds are both capable of forming octahedral complexes, and the introduction of these ions into an aqueous electrolyte will interfere with conversion of the hydrous alumina into the aluminum hydroxide film by bonding to the active film sites. Therefore, similar to their application in hexavalent chromate conversion coatings, fluoride ions are used to remove aluminum oxide and hydroxide films on the substrate surface before forming trivalent chromium conversion coatings. ... 

Chrome baths always contain a source of hexavalent chromium ion (e.g., chromate, dichromate, or chromic acid) and an acid to produce a low pH which usually is in the range of 0-3. A source of fluoride ions is also usually present. These fluoride ions will attack the original (natural) aluminum oxide film, exposing the base metal substrate to the bath solution. Fluoride also prevents the aluminum ions (which are released by the dissolution of the oxide layer) from precipitating by forming complex ions. The fluoride concenfration is critical. If the concentration is too low, a conversion layer will not form because of the failure of the fluoride to attack the natural oxide layer, while too high a concentfa-tion results in poor adherence of the coating due to reaction of the fluoride with the aluminum metal substrate. 

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