R&D GMF Corrosion Resistant Coatings Black Spots White Stain

Dark Spots, Grey Veil and White Corrosion

Zinc does inevitably corrode in moist or wet environment (e.g., in a salt spray test). Only perfectly impermeable coatings (which do not exist in reality) can stop corrosion. Real coatings have pores, cracks, and/or limited permeability for chemical species such as ions or molecules. Hence there is no use in asking when corrosion starts. It starts immediately upon exposure to moist air. The relevant question is: How fast is corrosion in the beginning, and how steep is the increase of the corrosion rate with time. What matters for practical purposes and determines the lifetime of coated parts is the kinetics of corrosion. Considering a coated sample with Zn or Zn alloy coating and chromate or passivate layer, corrosion starts at pores and cracks of the passivate. There is no fundamental difference between layers with or without topcoat. Only the number, size and depth of the pores is different in both cases. Initially, the corrosion rate is essentially determined by the area of Zn exposed to the aggressive atmosphere at the bottom of the pores (cracks). The smaller the pores and the lower their areal density, the smaller the amount of Zn going into solution. Within the
Author: Dr. Roland Vogel, 030/34985-979 Version 6/01

narrow pores, ZnO grows on the metal and precipitation of insoluble Zn salts, mainly ZnO, occurs. These form a barrier layer and inhibit the progress of corrosion by inhibiting access of oxygen and water to the metal surface. However, they do not stop the corrosion process totally. A small but steady flux of Zn ions from the metal side through the barrier layer towards the solution (moisture film) side is established. The chloride applied in salt spray testing increases the solubility of this barrier layer, thereby accelerating the corrosion process. On bright Zn with transparent coating, the surface-grown Zinc Oxide at the bottom of the pores is visible as dark spots in the early phase of corrosion. On black coatings the spots are, of course, not visible. (Surfacegrown ZnO is grey to black, since the oxide contains an excess of Zn. ZnO precipitated from solution has a 1:1 composition of Zn and O and is white). In the salt spray test, the steady flux of Zn ions through the barrier meets a flux of 2 aqueous Cl solution, about 200 ml per m 2+ and hour. As long as the flow of Zn is small 2+ compared to the flow of water, the Zn is
2+ 2+

R&D GMF Corrosion Resistant Coatings Black Spots White Stain

simply washed away and corrosion is invisible on the part. One may now assume a drop of Cl solution 2+ with a small concentration of Zn running over the surface of the part. The drop leaves a rather thick water film behind on its trace. This film has a high surface area. Water evaporates and the film equilibrates with the CO2 of the atmosphere. Due to evaporation the ion concentrations in the film increase. Basic zinc carbonate may precipitate. The precipitate stains the surface and is often called a grey veil. The grey veil is better visible on black than on transparent surfaces. Note that neither dark spots nor grey veil are necessarily indications for failure of corrosion protection. They affect, however, the appearance of parts and therefore are often termed cosmetic corrosion. Cosmetic corrosion may in some cases also result from defects (pores, recesses) in the substrate. Process solution may be encapsulated in such defects when a topcoat is applied. Local corrosion reactions at such inclusions may result and also lead to visible spots. At a later stage of corrosion, the flux of Zn ions becomes so large that the available water is not sufficient to solubilize them. Then voluminous Zn salts precipitate at the centers of corrosion. This is the beginning of white corrosion (formation of voluminous white corrosion products). For passivates with moderate corrosion protection, cosmetic corrosion is rather quickly masked by white corrosion products. For passivates with topcoat, however, the stage of cosmetic corrosion is often visible for many days of salt spray testing and thus is obvious.
2+ -

Author: Dr. Roland Vogel, 030/34985-979 Version 6/01

R&D GMF Corrosion Resistant Coatings Black Spots White Stain

Zinc (cyanide-free alkaline) / Cr(VI)-free thick layer passivate after 72 h of salt spray testing. No corrosion is visible to the bare eye. Dark spots of growing zinc oxide are, however, clearly visible in the optical microscope. (The same can be seen on yellow chromated zinc. It is not specific for Cr(VI)-free passivates).

Zinc-Iron 0.5% (cyanide-free alcaline) / black chromate after 96 h of salt spray testing. No corrosion is visible to the bare eye. Electron microscopy shows precipitated Zn salts blocking the cracks of the chromate layer. Beginning precipitation on top of the chromate layer is visible as well. (vacuum drying in SEM accelerates salt crystallization and makes features more voluminous)

Author: Dr. Roland Vogel, 030/34985-979 Version 6/01