Gaute Svenningsen Department of Materials Technology, 7491 Trondheim, Norway

Introduction
Aluminium alloys are widely used in structures where a high strength to weight ratio is important, such as in the transportation industry. Aluminium has a natural corrosion protection from its oxide layer, but if exposed to aggressive environments it may corrode. Still, if correctly fabricated, constructions of aluminium may be reliable and have long service life. The purpose of this poster is to give a general overview of corrosion mechanisms on aluminium alloys.

Corrosion of Aluminium Alloys

Concentration of elements in particles

Passivity of aluminium

From a purely thermodynamical point of view aluminium is active. However, in oxygen containing environment (air, water), aluminium is rapidly covered with a dense oxide layer [1]. The oxide layer is essentially inert, and prevents corrosion. The thickness of the layer may vary as a function of temperature, environment and alloy elements. Oxide films formed in air at room temperature are 2-3 nm thick on pure aluminium. Heating to 425C may give films up to 20 nm [2]. If the oxide film is damaged, e.g. by a scratch, new oxide will immediately form on the bare metal [3]. This way aluminium is given excellent corrosion protection.

Grain A

les partic Noble

Depleted zone

Grain B

Activ e pa rticle s

Corrosion mechanisms
Oxide destabilisation The following factors may affect the stability of the aluminium oxide and thereby cause corrosion: The oxide is not stable in acidic (pH < 4) or alkaline (pH > 9) environments [1]. Aggressive ions (chlorides, fluorides) may attack the oxide locally. Certain elements (Ga, Tl, In, Sn, Pb) may become incorporated in the oxide and destabilise it [4]. a) Depleted zone dissolved preferentially. b) Active particles dissolved preferentially. Figure 3. Two different intergranular corrosion mechanisms.

Microgalvanic coupling Most commercial alloys contain several types of intermetallic phases. Corrosion on aluminium alloys is essentially a microgalvanic process between these phases and the matrix alloy [4]. While the phases often act as local cathodes because of their Fe content, the surrounding aluminium matrix undergoes localized attack. In addition the following phenomena may become important: An active phase(s) may corrode preferentially. A corroding phase may serve as a sacrificial anode and provide cathodic protection to the surrounding material. Due to the electrochemical reactions at the corroding sites and the cathodes, the composition and pH of the electrolyte adjacent to the reaction sites may become different from the bulk electrolyte. Active components of the matrix alloy and the intermetallic phases may corrode selectively (dealloying), resulting in changed corrosion properties. Figure 4. SEM image of IGC attack on a AA6005 aluminium alloy exposed in acidic NaCl solution. A noble particle remains in the grain boundary zone. Figure 5. Short transverse cross section showing IGC attacks on a AA6005 aluminium alloy exposed in acidic NaCl solution.

The cathode to anode area ratio is also important.

Pitting OH OH ClAl OH I H2 O2 OHAlkaline environment Oxide film Dealloyed layer

Pitting is a highly localized type of corrosion in the presence of aggressive chloride ions. Pits are initiated at weak sites in the oxide by chloride attack [4,5]. Pits propagate according to the reactions Al = Al3+ + 3eAl3+ + 3H2O = Al(OH)3 + 3H+ (1) (2)

while hydrogen evolution and oxygen reduction are the important reduction processes at the intermetallic cathodes, as sketched in figure 1: 2H+ + 2e- = H2 O2 + 2H2O + 4e- = 4OH (3) (4)

As a pit propagates, the environment inside the pit (anode) changes. According to reaction 2 the pH will decrease. To balance the positive charge produced by reaction 1 and 2, chloride ions will migrate into the pit. The resulting HCl formation inside the pit causes accelerated pit propagation. The reduction reaction will cause local alkalinisation around cathodic particles. As previously mentioned aluminium oxide is not stable in such environment, and aluminium around the particles will dissolve (alkaline pits). The active aluminium component of the particles will also dissolve selectively, thereby enriching the particle surface with Fe and increasing its cathodic activity. Etching of the aluminium matrix around the particles may detach the particles from the surface, which may repassivate the alkaline pits. This may also reduce the driving force for the acidic pits causing repassivation of some in the long run. Figure 2 show pitting on an AlMgSi alloy.

H+

Al3+ e-

Intermetallic particle Aluminium matrix Acidic environment

Intergranular corrosion

Intergranular corrosion (IGC) is the selective dissolution of the grain boundary zone, while the bulk grain is not attacked [7]. IGC is also caused by microgalvanic cell action at the grain boundaries. The susceptibility to IGC is known to depend on the alloy composition and thermomechanical processing. Grain boundaries are sites for precipitation and segregation, which makes them physically and chemically different from the matrix. Precipitation of e.g. noble particles at grain boundaries depletes the adjacent zone of these elements, and the depleted zone becomes electrochemically active. The opposite case is also possible; precipitation of active particles at grain boundaries would make the adjacent zone noble. This two cases are illustrated in figure 2. Figures 4 and 5 show examples of intergranular corrosion on an AlMgSi alloy.

Figure 1. Generalised illustration of pitting corrosion on aluminium alloys [3].

Acknowledgement References

This work was supported by the Norwegian Research Council and Hydro Aluminium.

1. Pourbaix, M., Atlas of electrochemical equilibria in aqueous solutions, NACE Cebelcor, Huston, 1974. 2. Shimizu, K.; Furneaux, R. C.; Thompson, G. E.; Wood, G. C.; Gotoh, A. and Kobayashi, K., On the nature of easy paths for the diffusion of oxygen in thermal oxide films on aluminium, Oxidation of aluminium, 35 (5/6):427-439, 1991. 3. Davis, J. R. et. al, editor, Metals Handbook, volume 13, pages 104-122 and 583-609. ninth edition, ASM International, Ohio, 1987. 4. Nisancioglu, K., Corrosion of aluminium alloys. Proceedings of ICAA3, volume 3, pages 239-259. Trondheim, 1992. NTH and SINTEF. 5. Scamans, G. M.; Hunter, J. A.; Holroyd, N. J. H.. Corrosion of Aluminum - a New Approach, Proceedings of 8th International Light Metals Congress, pages 699-705. Leoben-Wien, 1987. 6. Shreir, L. L., editor, Corrosion, volume 1, pages 1:1-1:51, 1:131-1:191 and 4:1-4:32. Newnes-Butterworths, London, 1979. Figure 2. Cross section of pitting attack on AA6082 aluminium alloy after exposure to marine atmosphere for 6 months. The dark spots are intermetallic particles. 7. Hatch, J. E., editor. Aluminium - Properties and physical metallurgy, pages 242-264. ASM, Ohio, 1984.