13 Corrosion and Corrosion Protection of

Magnesium
P. Kurze, AHC-Oberflchentechnik GmbH & Co. OHG, Kerpen

13.1 Introduction
Magnesium is very ignoble (normal potential 2.34 volts). It forms thin passive layers in
air and water.

13.2 Corrosion Types

All corrosion types affecting magnesium alloys can be reduced to electrochemical processes. A high corrosion trend is predicted due to the high electron negative potential of Mg.

13.2.1 Passivation Behaviour

In pure or alkaline water, Mg forms passivating crystalline films of Mg(OH)2 on the surface
[1]. The following chemical reaction will then take place:
Mg + 2OH Mg(OH)2 + 2e
2H2O + 2e 2OH + H2
This passive layer is not stable in aqueous solutions with pH < 10. This is because there
are high compression stresses within the layer (geometrical mismatches with respect to the
Mg lattice), which cause cracks. Thus, the magnesium is exposed and corrosion begins.
The hydrogen liberated during corrosion then causes a further detachment of the passivating layer. The layer is very stable in pure alkaline aqueous solutions with pH > 10.5
(striking difference compared to aluminium), since the cracks are sealed with Mg(OH)2
(curing).
In aqueous solutions containing chloride, sulfide, or carbonate ions, among others
(except fluoride ions), the passivating layer of Mg(OH)2 is destroyed and magnesium goes
into solution:
Mg + 2H+ Mg2+ + H2
Unprotected magnesium is often exposed to this type of corrosion, e.g. by exhaust
gases, acid rain, salts, etc.
The corrosion attacks the whole passivating layer equally. The corrosion rate of magnesium is two orders of magnitude greater in solutions containing chloride or sulfide ions
than in pure distilled water. Hydrogen formation is the main cathodic reaction in this
corrosion mechanism.
Passive layers can also be specifically generated in aqueous solutions. Chromate films
are well-known in this regard since they act in a self-curing manner on magnesium and
Magnesium Alloys and Technology. Edited by K.U. Kainer
Copyright 2003 WILEY-VCH Verlag GmbH & Co. KG aA, Weinheim
ISBN: 3-527-30570-X

Corrosion Types

219

form a good bonding basis for organic coatings, although they are physiologically questionable. Systematic electrochemical tests with regard to replacing chromate led to dilute
aqueous solutions containing cerium permanganate or -vanadate, but not the phosphate and
fluoride ions described in the literature.

13.2.2 Pitting Corrosion

The origin of pitting lies in inhomogeneous crystal structures such as Mg17Al12 precipitations. They show a higher standard voltage (more noble) and form an electrolysis junction
with the surrounding matrix. This galvanic corrosion generates hole-like corrosion prints
and is therefore not pitting corrosion in the common sense (no potential for pitting in
passive area).

13.2.3 Stress Corrosion Cracking

With magnesium alloys, stress corrosion cracking occurs when inner or outer tensile
stresses are combined with a corrosive medium (chloride-, sulfide-, chlorate-containing
solutions). This leads to brittleness at the tip of the crack, because the hydrogen evolved
during the corrosion process is absorbed.

13.2.4 Galvanic Corrosion

The basic requirements for galvanic corrosion are the formation of a galvanic element. This
corrosion mode is very frequently encountered for two reasons:
a) The Mg alloys always contain more noble components, such as heavy metals, especially Fe, Cu, Ni
b) There is hardly any technical application in which magnesium does not come into
contact with other more noble metals, often steel.
As regards point a)
Galvanic corrosion becomes very excessive with magnesium alloys containing noble
metals (alloying components or impurities) such as heavy metals, especially iron, copper,
or nickel, which thus have an electrical contact with the matrix. When aqueous media affect
the alloys, hydrogen is formed with a slight overpotential. The whole process is supported
by specific anions (e.g. chloride, sulfide). High-purity Mg alloys were developed to prevent
this process. They are much more corrosion-resistant in chloride-containing aqueous media
than the older versions with high contents of Fe, Cu, and Ni. HP alloys contain minimal
amounts of these heavy metals. Table 1 summarizes the compositions of the most common
ET alloys.

220

Corrosion and Corrosion Protection of Magnesium

Table 1:

Figure 1:

Compositions of magnesium die-castings

Corrosion tests on magnesium die-casting alloys

Figure 1 lists some corrosion tests (comparison of old/new, comparison with GDAlSi9Cu3) carried out on magnesium cast alloys in a salt spray (DIN 50021-SS) [2].
As can be seen from the figure, the corrosion rate of AZ91 (old version), for example, is
19 times faster in the salt-spray test than that of AZ91 HP.
As regards point b)
The two metals in electrical contact with each other have different potentials. The
higher the difference, the more the ignoble metal Mg (anode) will dissolve. It will dissolve
in the electrolyte accumulated at the contact point.
The following precautionary measures logically stem from the model for galvanic
corrosion:
In a dry atmosphere, no galvanic protection is necessary for magnesium (no electrolyte)

Corrosion Protection Measures

221

When there is high corrosion potential (electrolyte at the contact point), the following
measures are proposed:
The electrical contact between magnesium and other metallic materials should be
prevented by insulation. There can be no direct contact to copper, nickel, iron, or
stainless steel.
Al/Mg alloys (AlMg2.5, AlMg4.5Mn, AlMgSi1), or those containing zinc, tin, or
cadmium, exhibit only little galvanic corrosion of magnesium. Contact corrosion
when using steel and aluminum screws can easily be prevented by using HARTCOAT covered washers. HART-COAT coated aluminum screws are also serviceable (insulation).
Avoidance of accumulations of electrolyte at the contact areas

13.3 Corrosion Protection Measures

Currently, three main protection measures are in use:

13.3.1 Improving the Purity of Mg Alloys

The aim here is to prevent galvanic corrosion. Section 13.2 gives more information on this.
The heavy metal content needs to be lowered even further.

13.3.2 Addition of Specific Alloying Elements

The addition of special alloying elements is intended to prevent galvanic processes on a
micro-scale and to form a superior cover coating.
The classic alloying elements except for Al can hardly improve magnesiums
corrosion resistance. At up to 10%, Al has no effect on the Mg matrix.
A specific addition of rare earth elements such as Nd, La, and Ce has a positive
influence on the corrosion behaviour of the corresponding magnesium alloy. The electrochemical standard potentials of rare earths are, without exception, close to that of magnesium. In this way, galvanic corrosion is prevented. An example of such a material is WE54
(5% Y, 3.5% Nd and other RE, 0.5% Zr), which is heat resistant up to 300 C and shows
excellent corrosion resistance (in Cl-containing aqueous solution) [3].
An improvement should be seen if the Mg alloy attains a higher level of homogeneity
by suitable freezing. In that way, additional passivation effects will occur, which lower the
corrosion current density by two to three orders of magnitude. The synergistic effects with
multiply alloyed Mg materials have hardly been studied, even though they are of tremendous potential.

13.3.3 Surface Treatment of Magnesium

Some important preliminary remarks need to be made for this part:
1. Even the best surface protection is useless for a non-HP quality material.
2. The casting skin of Mg die-castings is the closest packed area.

222

Corrosion and Corrosion Protection of Magnesium

Removing the skin by acid cleaning or mechanical treatment, and then applying a
surface protection results in much worse corrosion rates than with the untouched
casting skin.
3. The surface protection is less effective on a porous casting than on a dense one.
4. The surface cannot be compacted by abrasive blasting (glass pearls, corundum particles) as with aluminum, as it would be rendered impure by the blasting medium.
Figure 2 shows possible methods for a surface treatment of magnesium materials.

 
   



  

   



 

 
 
 

 
 


 




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Figure 2:

Possible methods for a surface treatment of magnesium materials

Anodic treatment is a widely used process for magnesium. Table 2 lists the most
common methods for the anodic oxidation of magnesium.
The MAGOXID-COAT process was developed by the AHC company [4] and is
described in more detail in [58]. The surface is covered with a ceramic layer by a
plasmatic reaction of the electrolyte; the whole process is run by partial anodes. It is a gas
solid reaction in the electrolyte.

Corrosion Protection Measures

Table 2:

223

Processes for the anodic oxidation of magnesium and its alloys

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Figure 3 shows the reaction mechanism of the MAGOXID-COAT coating, which is

separated into four constituent parts.

Figure 3:

Reaction mechanism of the MAGOXID-COAT coating

The layers formed by the MAGOXID-COAT process are of an oxidizing nature; they
are ceramic-like, white layers, which contain a large amount of highly resistant spinels, e.g.
MgAl2O4. Colored MAGOXID-COAT layers are also available, e.g. black. Figure 4
shows a schematic of a MAGOXID-COAT layer. It should be mentioned that the layer
consists of two parts, a pore-free and a porous oxide ceramic layer. The pore-free layer
prevents corrosion, while the porous layer serves as a basis for painting or proofing, e.g.
with PTFE.

224

Corrosion and Corrosion Protection of Magnesium

Figure 4:

Schematic model of the set-up of a MAGOXIDCOAT layer

Table 3 lists the properties of MAGOXID-COAT layers.

Table 3:

Properties of MAGOXID-COAT layers (thickness 25 m)

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The corrosion resistance of the MAGOXID-COAT layer can be further improved for
special applications. Special processes, reaching a corrosion resistance of up to 3000 h,
additionally seal the layer. Table 4 lists potential fields of application for a MAGOXIDCOAT layer.

Literature
Table 4:

225

Applications of MAGOXID-COAT layers


 
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13.4 Literature
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Ferrando, W.A.: Review of Corrosion and Corrosion Control of Magnesium Alloys

and Composites, J. Mat. Eng. 11 (1989), 299-313.
Olsen, A.L.: Oberflchenbehandlung und Korrosionsschutz von Magnesiumguteilen, Hydro Magnesium, Norwegen, 1993.
Frazier, E.W. et al.: Advanced Lightweight Alloys for Aerospace Applications,
JOM May 1989, 22-26.
EP 8 910 423.
Olbertz, B., Haug, A.T.: Oberflchenschutz fr Magnesiumwerkstoffe, Metalloberfl., 43 (1989) 4, 174-178.
Kurze, P.: Electrochemical Coatings of Magnesium Alloys, Tagungsmaterial der
DGM Magnesium Alloys and Their Applications, Garmisch-Partenkirchen, April
1992.
Kurze, P.: Magnesiumlegierungen elektrochemisch beschichten, Metalloberfl. 48
(1994) 2, 104-105.
Kurze, P., Banerjee, D.: Eine neue anodische Beschichtung zur Verbesserung der
Korrosions- und Verschleibestndigkeit von Magnesiumwerkstoffen, GieereiPraxis 11/12 (1996), 211-217.