CHAPTER

Atmospheric corrosion
H.1
Chapter outline
1.1 Historical background ..................................................................................................................541
1.2 Knowledge base of aluminium weathering ..................................................................................... 542
1.3 The nature of atmospheric corrosion ............................................................................................. 542
References ..........................................................................................................................................543

Due to its excellent resistance to atmospheric corrosion, the use of aluminium in construction, civil
engineering, electrical power transmission lines [1] and transport has increased considerably since
1930. Nowadays, aluminium is the second most common metal, after steel, to be exposed to weath-
ering, in all climates and geographic zones.

1.1 Historical background

The resistance of aluminium to atmospheric corrosion has been a very important issue, and, since the
early 1930s, has attracted a great deal of attention from corrosion experts working with the major
aluminium producers in Europe and North America. The first tests of aluminium alloys in outdoor
corrosion testing stations were performed in the United States in 1931 by ASTM [2].
Atmospheric corrosion has been the subject of many publications.1 The first was by E. Wilson, who
reported results of observations made on electrical cables exposed in London over 24 years, beginning
in 1902 [3]. Since 1945, many national and international conferences in Europe and in the United
States have been devoted to the atmospheric corrosion of aluminium (as well as that of other common
metals and alloys such as steel, copper, etc.).
From the very beginning of the industrial history of aluminium, several outdoor applications were
accomplished, some of which are still in place including the Eros statue, erected in 1893 on the top of
the monument dedicated to the memory of Lord Shaftesbury at Piccadilly Circus in London [4] and the
roof of the San Gioacchino Church in Rome, build in 1898 (see Chapter H.5). Other achievements,
mainly in the building sector, were to follow during the 1920s and 1930s both in Europe and in the
United States. The widespread use of aluminium began in the 1950s in the building sector e cladding,
curtain walls, roofing sheet, metallic fittings e as well as for public utilities: street signs, road signs,
street equipment, etc. These applications use both cast and wrought (flat-rolled and extruded) products.

1
Over 400 publications are referenced in Chemical Abstracts, from the first volume (1907) to volume 124 (1997).
Corrosion of Aluminium. https://doi.org/10.1016/B978-0-08-099925-8.00039-9
Copyright © 2020 Elsevier Ltd. All rights reserved.
541
542 Chapter H.1 Atmospheric corrosion

These products can be used without any protection or can be protected by anodizing, painting,
lacquering, etc.

1.2 Knowledge base of aluminium weathering

Our present knowledge of the resistance of aluminium to atmospheric corrosion has solid foundations,
based on two complementary approaches:
➢ Testing in outdoor corrosion testing stations in Europe and the United States (where most, and the
oldest, of these stations can be found), often for a very long time: 10, 20 years, and sometimes even
longer, and under three classic atmospheric conditions: marine, industrial and rural [5];
➢ Experience with applications over several decades e some of the oldest and most prestigious have
been reported by aluminium producers and transformers.
Our understanding of the atmospheric corrosion of metals is based on theoretical foundations that
are a special case of corrosion of metals and alloys. Before discussing the specific aspects of
aluminium, they need to be recalled here.

1.3 The nature of atmospheric corrosion

Atmospheric corrosion is the attack of a metal (or an alloy) by the atmospheric environment to which it
is exposed. This corrosion is caused by the simultaneous attack by rainwater or condensed water,
oxygen contained in the air and atmospheric pollutants.
The first theoretical explanation of atmospheric corrosion of metals was given by Vernon [6] and
Hudson [7] starting in 1923 and was completed later by Rozenfeld in the 1960s [8] and by Graedel for
aluminium in the 1980s [9]. Vernon introduced the concept of the critical degree of moisture, the
threshold below which practically no corrosion will occur. The value of this threshold depends on
several factors such as the nature and concentration of atmospheric pollutants and the metal’s surface
condition.
Atmospheric corrosion is a special type of corrosion because the electrolyte is represented by a thin
film of moisture whose thickness does not exceed a few hundred micrometres. On the surface of a
metal, very thin water films are probably in an intermediate state between the perfectly ‘free’ liquid
state and the solid state. Water adsorbed on the surface of a metal is organized according to a structure
close to the tridymite structure of one of the crystalline forms of ice. Cohesion with the metal is due to
hydrogen bonding [10].
According to Cheng [11], who studied the influence of thin electrolyte layers on the reduction of
oxygen on AA2024-T3 in a 3 wt.% sodium chloride solution, for the following electrolyte thicknesses:
➢ At >200 mm, the oxygen reduction current is of the same order of magnitude as in a bulk solution;
➢ Over a range of 200e100 mm, the oxygen reduction current is inversely proportional to the thickness
of the electrolyte layer and the thickness constitutes the rate-determining step for the oxygen process;
➢ Over a range of 100e58 mm, the oxygen reduction current is slightly decreased probably due to the
formation of aluminium hydroxide, which blocks the site for oxygen reduction, or even to a change
in oxygen diffusion mode due to the thinness of the electrolyte layer.
 References 543

3.0x10–4
60 Pm
2.5x10–4 110 Pm
170 Pm
300 Pm

1/Rct / (:–1.cm–2)
2.0x10–4
500 Pm
1.5x10–4 bulk solution

1.0x10–4

5.0x10–5

0.0

1 10 100
Time (h)

FIGURE H.1.1
Variation of corrosion rate with time as a function of different electrolyte layer thicknesses.
From Zhou et al. [12].

On AA7075-T6, Zhou [12] obtained similar results with thin layers of 1M Na2SO4 electrolyte
solutions (Fig. H.1.1); the thickness of 300 mm is a threshold below which the corrosion rate depends
strongly on the thickness of the electrolyte film. In these thin films, the diffusion of corrosion products
and Al3þ ions is much more difficult than in the bulk solution.
It can be assumed that such a film is always saturated with oxygen, and that diffusion is not
hindered. This type of corrosion may be intermittent, because it stops when the metal surface is no
longer wet. When immersed in water or in a salt solution, the metal is in permanent contact with the
electrolyte, but the corrosion may be slowed down by the weak diffusion of oxygen to cathodic sites.

References
[1] Hérenguel J. Examen de câbles conducteurs en Almelec et en aluminium-acier déposés après 15 à 25 ans de
service. 1947. p. 357e60. Revue de l’Aluminium.
[2] Ailor WH. ASTM Atmospheric corrosion testing: 1906 to 1976. ASTM STP 646 atmospheric factors
affecting the corrosion of engineering metals. 1978. p. 129e51.
[3] Wilson E. The corrosion products and mechanical properties of certain light aluminum alloys as affected by
atmospheric exposure. Proceedings of the Physical Society of London 1926;30:15e25.
[4] Sutton RS, Selligmann R. An aluminium statue of 1893: Gilbert’s Eros. Journal of the Institute of Metals
1938;60:67e74.
[5] Dix EH, Mears RB. In: The Resistance of Aluminium Base Alloys to Atmospheric Exposure. Symposium
Atmospheric Exposure Tests on Non-ferrous Metal, vol. 67. ASTM STP; 1946. p. 57e75.
[6] Vernon WH. First experimental report to the atmospheric corrosion research committee. Transactions of the
Faraday Society 1923-24;19:839e934.
[7] Hudson JC. The effects of two years atmospheric exposure on the breaking load of hard drawn non-ferrous
wires. Journal of the Institute of Metals 1930;44.
544 Chapter H.1 Atmospheric corrosion

[8] Rozenfeld IL. Atmospheric corrosion of metals. Houston: NACE; 1972. English language Edition translated
by BH Tytell.
[9] Graedel TE. Corrosion mechanisms for aluminium exposed to the atmosphere. Journal of the Electro-
chemical Society 1989;136(4):204Ce12C.
[10] Baroux B. La corrosion des métaux e passivité et corrosion localisée. Dunod 2014:21.
[11] Cheng YL, Zhang Z, Cao FH, Li JF, Zhang JQ, Wang JM, Cao CN. A study of the corrosion of aluminum
alloy 2024-T3 under thin electrolyte layers. Corrosion Science 2004;46(7):1649e67.
[12] Zhou HR, Li XG, Ma J, Dong CF, Huang YZ. Dependence of the corrosion behavior of aluminum alloy 7075
on the thin electrolyte layers. Materials Science and Engineering B 2009;162(1):1e8.