Corrosion Science 45 (2003) 27412755

www.elsevier.com/locate/corsci

A corrosion study of the main constituent

phases of AZ91 magnesium alloys
S. Mathieu, C. Rapin, J. Steinmetz *, P. Steinmetz
Laboratoire de Chimie du Solide Min
eralUMR CNRS 7555, Universit
e Henri Poincare-Nancy I,
BP 239, 54506 Vandoeuvre-les-Nancy, France
Received 30 April 2002; accepted 31 March 2003

Abstract
The dierent constituents of an AZ91 alloy (a; b, and MnAl phases) were synthesized and
their corrosion resistance was studied by electrochemistry in ASTM D1384 water, pH 8.3. The
pure phases were characterised through the corrosion potential, the polarisation resistance,
and polarisation curves, then systematically coupled to assess the galvanic corrosion occurring
in the AZ91 alloy. The aluminium content of the oxide lm was obtained by X-ray photoelectron spectroscopy measurements. The corrosion rate of the a solid solution alloys depends
closely on their Al content. Aluminium enhances the corrosion resistance of the a-phase
through the formation of an Al enriched supercial layer. The b-phase is 150 mV nobler than
the a-phase, but their corrosion rates are similar. The galvanic currents are low (below 20
lA cm
2 ) whatever the implemented couples and close to the corrosion current previously
measured for the AZ91 alloys.

2003 Elsevier Ltd. All rights reserved.
Keywords: Magnesium (A); Aluminium (A); Alloys (A); Polarization (B); Galvanic corrosion

1. Introduction
Magnesium-based alloys exhibit an attractive combination of low density and high
strength/weight ratio associated with good castability and workability. Thus they
oer substitutes to ferrous alloys and aluminium in automotive and aeronautical
applications [1,2]. Among the magnesium alloys, AZ91D (9 wt.% Al, 1 wt.% Zn or

Corresponding author. Tel.: +33-383-91-24-44; fax: +33-383-91-21-66.

E-mail address: jean.steinmetz@lcsm.uhp-nancy.fr (J. Steinmetz).

0010-938X/$ - see front matter
2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0010-938X(03)00109-4

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S. Mathieu et al. / Corrosion Science 45 (2003) 27412755

8.2 at.% Al, 0.4 at.% Zn) is one of those having the best mechanical properties/
corrosion resistance balance and the present study is a continuation of a previous
one devoted to the inuence of the elaboration process of the AZ91D alloy
on its corrosion behaviour in corrosive environments [3]. It was demonstrated
that the corrosion resistance of AZ91D elaborated through the semi-solid process (SSP) was somewhat higher than that of the same alloy manufactured by highpressure die casting (DC). As the SSP process induces strong modications of
the alloy microstructure, in terms of distribution, composition and volume fraction
of the constituting phases, the better corrosion resistance of the alloys was attributed, in part, to the high aluminium content of the a-phase (2.7 at.%), (the a-phase
from the DC process only contains 1.6 at.%). Unfortunately this explanation is not
supported by some investigations on the corrosion behaviour of the main phases of
the AZ91 alloys, a and b, and particularly on their galvanic coupling [4,5], since the
higher the aluminium content of the a-solid-solution alloy, the higher the galvanic
current between the progressively Al-enriched a-phase and Mg17 Al12 (b) [3,4];
according to [3], the galvanic corrosion current density between a and b can even be
as high as 5 mA/cm2 . So the present electrochemical investigations were undertaken
so as to better determine the role of aluminium in the corrosion behaviour of the
dierent phases of the AZ91 alloy, a, b, and the minority MnAl phase. The three
pure phases were characterised through the corrosion potential, Ecorr , the polarisation resistance, Rp , the corrosion current density, icorr , and polarisation curves
successively. The individual phases were then coupled to simulate the AZ91 alloy
corrosion.

2. Experimental methods
The constituting phases (Table 1) of the AZ91D alloys were synthesized from
coarse grains (>4 mesh) of high purity elements (Table 2), melted under argon by
high frequency inductive heating (Celes 50 kW, 300 kHz). The argon atmosphere was
puried using a Messer getter 1 and its pressure was maintained at 60 kPa to avoid
the magnesium volatilisation. Oxidation of the metal powders was prevented thanks
to a rapid increase of temperature. Once both aluminium and magnesium were alloyed, the ingots were cooled. A second melting was required for a better homogenisation. Afterwards, the ingots were annealed in an alumina vessel for one day at
400 C, then rapidly cooled by water quenching. The samples were quantitatively
analysed using an automated electron probe microanalyser (SX50 CAMECA) and a
PAP correction program [6]. The results are summarised in Table 1. In order to
electrochemically investigate the phases, ingots of a were cut in small plates
(12 12 2 mm3 ), whereas the very brittle b and MnAl alloys, broken in coarse
grains, were embedded in an epoxy resin, then polished on two parallel faces.

Messer griesheim Gmbh product: oxisorb , ref: 79239797.

S. Mathieu et al. / Corrosion Science 45 (2003) 27412755

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Table 1
Chemical composition of the synthesized alloys (WDS analysis)

Samples

Mg (at.%)

Al (at.%)

a3Al
a5Al
a9Al
a5Al0.5Zn
b (Mg17 Al12 )
b-1Zn
MnAl

96.90
94.80
91.43
94.31
57.19
57.63

3.10
5.20
8.57
5.24
42.81
41.25
59.94

Mn (at.%)

Zn (at.%)

40.06

0.45

1.12

Solid-solution; below the detection threshold.

Table 2
Analysis of the element powders used to synthesize the AZ91 constitutive phases (in wt.%, particle size > 4
mesh)
Mg
Al

Purity

Al

Mg

Mn

Zn

Si

Fe

Cu

Ni

99.98%
99.99%

0.003
Balance

Balance
0.0005

0.004
0.002

0.001

0.0005

0.003
0.001

0.001
0.001

0.001

The electrochemical tests were conducted in a at sample cell, tted with the fairly
corrosive ASTM D 1384-87 2 water [7], and using a three-electrode tting in which
the working electrode is facing the counter electrode (Fig. 1). The counter electrode
was made with platinum or with the b or MnAl phases in the case of the galvanic
couplings. A saturated calomel electrode (SCE) was used as reference. Before each
electrochemical experiment, the surface area of the working electrode was carefully
determined. Polishing was carried out on samples with SiC paper up to 4000 grit
before starting measurements. The experiments were done at least two times and the
solutions were neither deaerated nor stirred. The electrochemical parameters of each
phase were obtained by successively measuring the open circuit potential, then the
polarisation resistance and nally, a potentiodynamic scan was recorded. The polarisation resistance (Rp ) was determined using the Stern Geary method by scanning
the potential at a rate of 0.166 mV/s over the range of Ecorr
10 to Ecorr 10 mV.
The potentiodynamic scans were recorded in two areas:
(i) the anodic, from the corrosion potential (Ecorr ) up to a potential such that the
current density did not exceed the pre-set value of 1 mA/cm2 ,
(ii) the cathodic, from Ecorr to Ecorr
500 mV. All curves were recorded with a 0.166
mV/s scan rate. The IR mode was selected in the scan set-up in order to take into
account the uncompensated resistance.

ASTM D 1384-87 water contains 148 mg l
1 of Na2 SO4 , 138 mg l
1 of NaHCO3 and 165 mg l
1 of
NaCl. The initial pH of the electrolyte is equal to 8.3.

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S. Mathieu et al. / Corrosion Science 45 (2003) 27412755

Fig. 1. Electrochemical cell (medium: ASTM D1384 water; pH 8.3).

Concerning the galvanic corrosion test, between a and b or MnAl, a at sample of

a-phase was disposed in the bottom of the cell, the watertightness of which was
obtained using a viton ring. Electrodes of b or MnAl were placed opposite to a, at
about 2 cm. All the Sb =Sa or SMnAl =Sa area ratios were chosen to approximately
reproduce those of the alloys, manufactured by SSP or DC [3,8]. Both coupling
potential and galvanic current were recorded for a 12 h period. All electrochemical
measurements were carried out using an EG&G model 263 potentiostat and with the
EG & G M352 software.
X-ray photoelectron spectroscopy (XPS) was performed using an Al source (Ka :
1486.6 eV). Before each measurement, surface contamination was removed by
sputtering with argon ions.
2.1. Corrosion behaviour of the phases in ASTM D1384 water
2.1.1. a-phases
Four compositions of the a-solid-solution were tested, noted a3Al, a5Al, a9Al,
and a5Al0.5Zn respectively (Table 1). In the D1384 ASTM medium (pH 8.3), the a
corrosion potential is always higher than that of pure magnesium, whatever the Al
content. Moreover, it increases linearly with the aluminium level (Fig. 2, Table 3),
contrary to what is stated in the literature [4,5]. The polarisation resistance (Rp ), or
the corrosion current density (Icorr ), also depends on the aluminium content. On the
other hand, the eect of Zn on Ecorr and Icorr is very slight. Based on the anodic and
cathodic I f E curves (Figs. 3 and 4), the corrosion appears to be controlled by
the anodic process.
A parallel can also be drawn between these results and the pH values measured
after 12 h immersion of the dierent a-phases in the ASTM solution, initially having
a pH of 8.3. In this set of experiments, the nal pH value can be considered as a
corrosion indicator (Table 4), and it conrms the benecial eect of aluminium
additions on the corrosion resistance of the a-phases. These latter were also tested in
a 0.1 M HCO

3 medium, in which Mg is not passivated [9]. After 3 h immersion in

S. Mathieu et al. / Corrosion Science 45 (2003) 27412755

2745

-1.35
-1.4
-1.45
-1.5
-1.55
at% Al

-1.6
0

Fig. 2. Corrosion potential of the a-phases as a function of the Al content in the solid solution (in ASTM
D1384 water; initial pH 8.3).

Table 3
Corrosion potential and polarisation resistance of the pure phases after 3 h immersion in ASTM D1384
water (initial pH 8.3)
Phases

Ecorr

Rp (kX cm2 )

Mg
a3Al
a5Al
a9Al
a5Al0.5Zn
b (Mg17 Al12 )
b-1Zn
MnAl

)1.55
)1.49
)1.45
)1.40
)1.43
)1.31
)1.24
)1.28

3.4
7.4
12
13.5
11
19
12
25

1.E-02

1.E-03

1.E-04

1.E-05

1.E-06

1.E-07
-1.6

-1.4

-1.2

-1

-0.8

Fig. 3. Anodic I f E curves of the a-phases: a3Al (), a5Al (), a5Al0.5Zn (n), a9Al (e) and of pure
magnesium (n), recorded after 3 h immersion in ASTM D1384 water (initial pH 8.3).

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S. Mathieu et al. / Corrosion Science 45 (2003) 27412755

1.E-03

1.E-04

1.E-05

1.E-06

1.E-07
-1.8

-1.7

-1.6

-1.5

-1.4

Fig. 4. Cathodic I f E curves of the a-phases: a3Al (), a5Al (), a5Al0.5Zn (n), a9Al (e) and of
pure magnesium (n), recorded after 3 h immersion in ASTM D1384 water (initial pH 8.3).

Table 4
Final pH of ASTM D1384 water solutions (initial pH 8.3) resulting of the immersion of the materials for
12 h
Phase

Final pH

Mg
SSP AZ91D
a3Al
a5Al
a9Al
a5Al0.5Zn
b
b-1Zn
MnAl

10.5
9.5
9.85
9.2
9.4
9.1
8.75
8.75
8.45

this solution, pure magnesium retains a metallic aspect, even though the three Almodied alloys (3%, 5%, 9% Al) are covered by a discontinuous dark coating. The
corresponding Ecorr values reveal their better corrosion resistance (Fig. 5).
XPS measurements were carried out on each sample after 12 h immersion in
ASTM water so as to estimate the composition of the oxide scale. The thin surface
lm contains Mg, C, O and Al. The Al/Mg atomic ratio was higher in the lm (17%)
than in the bulk, especially for the a-phases containing 5 and 9 at.% Al (Fig. 6).
2.1.2. b-phase
The corrosion potential of the Mg17 Al12 phase is 150 mV higher than that of the
a9Al phase. However, the Icorr (or Rp ) is quite similar (Table 3). The main dierence

S. Mathieu et al. / Corrosion Science 45 (2003) 27412755

2747

-1.75
-1.85
-1.95
at% Al

-2.05
0

Fig. 5. Corrosion potential of the a-solid-solution as a function of the Al content, in NaHCO3 0.1 M
(initial pH 8.3).

18.0%
17.0%
16.0%
15.0%
14.0%
13.0%
12.0%
11.0%
10.0%
0

Fig. 6. XPS measurements: Al/Mg atomic ratio of the supercial part of the corrosion layer as a function
of the Al concentration in the a-solid-solution.

can be observed on Fig. 7, corresponding to the anodic part of the polarisation

curve, which exhibits a passivation plateau of about 600 mV. Addition of Zn weakly
increases Ecorr and bc (Fig. 8), without great modication of either breakdown potential or Rp . As for the a-phase study, XPS experiments were performed to characterise the composition of the corrosion layer. C, O, Mg and Al were detected at
the surface of the b samples immersed for 12 h in the ASTM solution. Carbonates
are associated with hydroxides in MgAl compounds, for which the Al/Mg ratio was
close to 1/3, independently of the zinc content. This ratio (Table 5) is lower than in
the alloy (0.41), but much higher than in the corrosion layer growing on the Al-rich
a-phase (0.17).
In order to evaluate the electrochemical behaviour of the b-phase over a large
range of pH, the ASTM solution was modied by addition of H2 SO4 or NaOH. The
pH was automatically maintained throughout the experiment duration (3 h). Ecorr
and Rp were measured at pH values increasing from 4 to 12 (Table 6). These

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S. Mathieu et al. / Corrosion Science 45 (2003) 27412755

1.E-02

1.E-03

1.E-04

1.E-05

1.E-06
-1.4

-1.2

-1

-0.8

-0.6

-0.4

-0.2

Fig. 7. Anodic I f E curves of b (h) and b-1Zn (n), recorded after 3 h immersion in ASTM D1384
water (initial pH 8.3).
1.E-03

1.E-04

1.E-05

1.E-06
-1.6

-1.5

-1.4

-1.3

-1.2

Fig. 8. Cathodic I f E curves of b (h) and b-1Zn (n), recorded after 3 h immersion in ASTM D1384
water (initial pH 8.3).

parameters exhibit two maxima, at pH 6 and 12 respectively (Table 6); on the other
hand, both corrosion potential and polarisation resistance of the a3Al compound are
unchanged up to pH 10, then increase strongly up to pH 12.
2.1.3. MnAl phase
The fast passivation in air of this intermetallic compound required taking some
precautions when measuring its Ecorr at pH 8.3. The MnAl electrode was quickly

S. Mathieu et al. / Corrosion Science 45 (2003) 27412755

2749

Table 5
XPS measurements: Al/Mg atomic ratio of the surface layer
Al/Mg atomic ratio

In the bulk

In the corrosion layer

a9Al
b
b-Zn

0.1
0.41
0.41

0.17
0.36
0.32

Table 6
Corrosion potential and polarisation resistance of a3Al and b as a function of pH in ASTM D1384 water
after 3 h immersion
a3Al
b-phase

pH

8.3

10

12

Ecorr
Rp
Ecorr
Rp

)1.57
6.2
)1.17
20

)1.55
7.0
)1.10
65

)1.49
7.4
)1.25
19

)1.53
5.4
)1.41
7

)1.35
33
)1.20
35

immersed in the cell after polishing, before the electrochemical measurements were
performed. Both Ecorr and Rp appear to be slightly higher than those of Zn-free
(Table 3), and a large passivation plateau of about 1 V is observed on the polarisation curve. Finally the XPS analyses revealed that the corrosion layer is mainly
constituted of an aluminium hydroxide.
2.2. Galvanic couples
Figs. 9 and 10 show the evolution of both galvanic potential and current obtained
for the couples between Zn-free b and Mg (or a0Al), a3Al, a5Al, a9Al respectively,
with a Sb =Sa area ratio close to 0.12, and for 12 h immersion. In each experiment, the
galvanic potential follows approximately a parabolic growth up to 6 h, then remains
stable. Its values increase with the Al content in a from )1.47 up to )1.34 V/ECS,
according to the corrosion potential of the corresponding phases. On the contrary,
the galvanic currents decrease with Al content, but level o for compositions beyond
5% Al. On the other hand, Zn in a-phase (a5Al0.5Zn) has no inuence on the galvanic corrosion (Table 7). The galvanic potential is somewhat enhanced when the
couples (Sb =Sa close to 0.12) are performed with the Zn containing b-phase, which is
in better agreement with the composition of the b detected in the AZ91 alloys. At the
same time, the associated galvanic currents are approximately doubled. However, if
zinc is present in both a and b, i.e. if the a5Al0.5Zn/b-1Zn couple is tested, the resulting galvanic current is signicantly reduced.
Very low galvanic currents were recorded between a and the MnAl phase (Table
8). The highest value, obtained with a3Al, does not exceed 1.5 lA and certainly is
overestimated since the SMnAl =Sa area ratio is higher than in the AZ91D alloy (0.07
and less than 0.002 respectively). One again, Al in the a-phase decreases the galvanic
current (Table 8).

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S. Mathieu et al. / Corrosion Science 45 (2003) 27412755

-1.3
- 9 at% Al

-1.35

- 5 at% Al

-1.4
- 3 at% Al

-1.45

- Mg

-1.5

-1.55
0

10

12

Fig. 9. Evolution of the galvanic potential corresponding to the coupling between the a-solid-solution
containing 0, 3, 5 and 9 at.% Al and the b-phase; Sb =Sa 12:4% (Sa 0:5 cm
2 ).

12

10

6
- Mg
4

- 3 at%Al

- 9 at%Al
- 5 at%Al

0
0

10

12

Fig. 10. Evolution of the galvanic current corresponding to the coupling between the a-solid-solution
containing 0, 3, 5 and 9 at.% Al and the b-phase; Sb =Sa 12:4% (Sa 0:5 cm
2 ).

3. Discussion
The most signicant result of the present corrosion study, performed in the ASTM
D1384 medium on the dierent phases of the AZ91D magnesium alloy, concerns the
benecial eect of aluminium additions on Ecorr and Rp of a, the main constituent of
the AZ91D magnesium alloy. Indeed, their values increase from )1.55 V (3.4
kX cm2 ) for pure magnesium up to )1.40 V (13.2 kX cm2 ) for the a-phase containing

S. Mathieu et al. / Corrosion Science 45 (2003) 27412755

2751

Table 7
Galvanic couplings between a and b in ASTM D1384 water
Phases

b-1Zn

Sb =Sa

12.4%

11.7%

Mg

E
I

)1.46
5.0

a3Al

E
I

)1.43
3.7

)1.40
10.4

a5Al

E
I

)1.36
1.3

)1.34
4.6

a5Al0.5Zn

E
I

)1.36
1.3

)1.30
2.2

a9Al

E
I

)1.34
1.6

)1.31
3.0

E: galvanic potential; I: galvanic current; Sa 0:5 cm
2 .

Table 8
Galvanic couplings between a and MnAl in ASTM D1384 water
Phases

MnAl
7.4%

SMnAl =Sa
a3Al

E
I

)1.45
1.5

a5Al

E
I

)1.38
0.9

a5Al0.5Zn

E
I

)1.37
0.6

a9Al

E
I

)1.36
0.7

E: galvanic potential; I: galvanic current; Sa 0:5 cm
2 .

9 at.% Al. The corrosion appears to be under anodic control, and the origin of the
corrosion resistance of the Al-rich a-phase may be found in the growth of a thin
mixed hydroxide carbonate layer, better stabilised in a more concentrated hydrogen
carbonate medium, and containing Mg, C, O and Al, as detected by XPS. The aluminium content is higher in the corrosion product than in the substrate since the
Al/Mg ratio reaches 17% for a5Al, and the lm composition could have the
[Mg:85 Al:15 (OH)2 ]:15 [(CO3 ).075 ]:15
m H2 O formula, in agreement with previous results [10,11]. The formula is consistent with that of a brucite-like layered double
hydroxide (LDH). In this structure some Mg2 cations of the brucite are substituted
by Al3 ions, introducing a charge deciency in the layers that is neutralized by
anions in the interlayer region. The water molecules and carbonate ions form largely
disordered intermediate layers (Fig. 11) [12].

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S. Mathieu et al. / Corrosion Science 45 (2003) 27412755

Layer of

[Mg1-xAlx(OH)2]x+

Interlayer of [(CO3)x/2]x-, mH2O

Layer of

[Mg1-xAlx(OH)2]x+
Fig. 11. Structure of the hydrotalcite phase.

Our corrosion results are not consistent with those of Lunder or Lee [4,5], obtained in 5% or 3.5% NaCl solution, and at pH values close to 10.5 and 7 respectively. In their investigations, Ecorr is much less dependent on the Al content and for
Lee et al. [5], the higher the aluminium content, the lower the Rp value. Moreover, if
we compare the corrosion rates of solid-solution alloys of similar composition, for
example a9Al in deaerated 3.5% NaCl solution at pH 7 [5], and a9Al in the
ASTM medium at pH 8.3, the former is much more corroded than a9Al (0.03
and 13.2 kX cm2 respectively). However it could be expected that the chloride-rich
medium improves the formation of a hydroxy-carbonate-chloride compound less
protective than the chloride-free LDH, taking into account the well known anion
exchange capabilities of such a layered structure [13,14].
The b-phase, although more noble than a9Al by about 150 mV and exhibiting a
wide passivation plateau, is corroded at a rate close to those of the a-phases. XPS
measurements performed on the b-phase immersed for 12 h into the ASTM
D1384 water revealed that the corrosion layer is constituted of a magnesium
aluminium hydroxide carbonate, with a formula which could correspond to
[Mg:75 Al:25 (OH)2 ]:25 [(CO3 ):125 ]:25
. nH2 O. The aluminium enrichment of the corrosion layer explains the evolution versus pH of the Rp values of the b-phase immersed for 3 h in the corrosive medium (Table 6). From pH 46, Ecorr and Rp increase
according to the aluminium hydroxide stability domain [15]. For higher pH (610),
the Mg/Al ratio in the LDH structure increases due to the dissolution of aluminium
into the medium, which could explain both Rp and Ecorr decrease. Finally for pH 12,
the brucite layer induces a new improvement of the corrosion resistance. Comparatively an Al-poor a-phase, a3Al, for example, maintains Rp values approximately
constant between pH 4 and 10, before an increase at pH 12 due to the protection by
brucite. A similar experiment was performed by Lunder et al. in deaerated 5% NaCl
solutions of various pH [4]. According to these authors, the b-phase would combine
the passive protection of magnesium in alkaline and that of aluminium in neutral
solutions; it corrodes less and less in the pH range 414, and without any anomaly in
the 610 pH domain, in spite of a maximum in the Ecorr values. The presence of
chloride-modied LDH phases can be considered [10], perhaps provoking a
smoothing of the high corrosion rates. For example, at the same pH (8.5), b is approximately forty times more corroded in the 5% NaCl solution than in the ASTM

S. Mathieu et al. / Corrosion Science 45 (2003) 27412755

2753

water (0.4 and 0.01 mg cm
2 day
1 respectively). At the same pH in a 3.5% NaCl
medium, Lee et al. measured still higher corrosion rates, but below those of their less
resistant aluminium-containing a-solid-solution alloys [5].
Concerning the galvanic corrosion between the dierent phases, an increase of
aluminium in the a-phase reduces the coupling current whatever the phase. Contrary
to some literature results [4,5], the galvanic corrosion is not enhanced when the Al
content is raised. Moreover, all the current values are low. They are similar to those
of the pure phases and do not exceed 20 lA/cm2 , a value to compare to that of 11
lA/cm2 recorded for the SSP AZ91 alloy. These results are in good agreement with
those predicted by the superposition of the individual I f E anodic curves of the
a-phase and the individual cathodic curves of b (Fig. 12). The presence of zinc in
the a-phase does not modify either the galvanic potential or the current. Since in the
two-phase alloy zinc was never detected in the a-phase, the corrosion rates of SSP
and DC alloys can be discussed on looking at the results of the couples Zn-free a=b
(with and without Zn). These results demonstrate that the SSP alloy, for which the aphase contains at least 3 wt.% Al, should be systematically more corrosion resistant
than the DC alloy (a-phase contains only 1.8 wt.% Al). The couples between aphases and the b-1Zn phase show that zinc in the b-phase increases the derived
galvanic current by a factor of 2.5. As Zn is essentially located in the b-phase of the
AZ91 alloy, whatever the elaboration mode, the couplings are unfavourable.
However, the galvanic current values do not exceed 20 lA/cm2 in the ASTM D1384
water, for a Sb =Sa ratio probably above the corresponding surface ratio in the AZ91
alloys. Concerning the MnAl/a phase couplings, the galvanic currents are low.
Consequently due to the small fraction of MnAl in the commercial AZ91 alloys

1.E-03

1.E-04

1Zn
1.E-05

1.E-06

1.E-07
-1.6

-1.5

-1.4

-1.3

-1.2

-1.1

Fig. 12. Theoretic couplings between the b and b1Zn-phases and the a-solid-solutions: a3Al (), a5Al
(s), a5Al0.5Zn (j), a9Al (e) and pure magnesium (n) after 3 h of immersion in ASTM D1384 water
(initial pH 8.3; Sb =Sa 12:4%, Sa 0:5 cm
2 ).

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S. Mathieu et al. / Corrosion Science 45 (2003) 27412755

(0.2%), the contribution of this phase in the overall corrosion mechanism could be
very limited, in the presence or not of iron, and even if localised galvanic corrosion
can be observed around the intermetallic precipitates [8].
To summarise, it seems that in a fairly corrosive medium, additions of Al in the aphase contribute to decreasing the galvanic corrosion rate between the two main
constituents of the AZ91 alloys, much less corroded than in a chloride-rich medium.
In this latter case, the preferential dissolution of the a-phase provokes a b-phase
supercial enrichment [16]. However the corrosion rate of this phase remains high
and no protective barrier can be formed.

4. Conclusions
1. In ASTM D1384 water, at a pH of 8.3, the corrosion resistance of the Al-containing a-solid-solution alloys strongly depends on the Al content. Ecorr increases with
Al whereas icorr decreases. Aluminium contributes to the enhancement of the protection of the a-phases through a supercial layer of a carbonate hydroxide of
magnesium and aluminium.
2. The Mg17 Al12 phase, also called b, is not much more corrosion resistant than the
a-phase. Nevertheless, its corrosion potential is higher by 150 mV than that of the
a 9 at.% Al phase. Its chemical behaviour is pH dependent.
3. The galvanic corrosion currents are low whatever the implemented couples and
close to the corrosion current measured on the SSP AZ91 alloy. They decrease
with increasing aluminium content in the a-phase when a is coupled either with
b or with MnAl. Finally the galvanic current of the a=b is doubled if the b-phase
contains zinc, and this is the case in the AZ91 two-phase alloys.
4. This work seems to demonstrate that the SSP (thixomolding), which leads
to aluminium-rich a-phases, would be a way to reduce the AZ91 alloy corrosion.

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