Corrosion Science 42 (2000) 14331455

Evaluation of microstructural eects on

corrosion behaviour of AZ91D magnesium
alloy
Rajan Ambat*, Naing Naing Aung, W. Zhou
School of Mechanical and Production Engineering, Nanyang Technological University, Nanyang Avenue,
Singapore 639798, Singapore
Received 3 September 1999; accepted 13 November 1999

Abstract
The eect of microconstituents on the corrosion and electrochemical behaviour of
AZ91D alloy prepared by die-casting and ingot casting route has been investigated in 3.5%
NaCl solution at pH 7.25. The experimental techniques used include constant immersion
technique, in-situ corrosion monitoring, and potentiodynamic polarisation experiments.
Surface examination and analytical studies were carried out using optical and scanning
electron microscopy, EDX and XRD. The corrosion behaviour of microconstituents namely
primary a, eutectic a and b phases was signicantly dierent. Coring of aluminum showed
inuence on corrosion behaviour more signicantly in ingot material. Areas with
aluminium concentration less than about 8% were found to be prone to corrosion attack
compared with either those with higher amount of aluminium or b phase. Die-cast material
with smaller grain size and ne b phase oered marginally lower corrosion rate and better
passivation compared with the ingot. In die-cast and ingot, hydrogen evolution took place
preferentially on b phase. XRD pattern of non-corroded and corroded surface revealed the
removal of b phase from alloy surface during corrosion. The corrosion products for ingot
consisted of Mg(OH)2 with small amounts b phase, magnesium-aluminium oxide and
MgH2 while for die-cast, the product showed a highly amorphous structure. 7 2000
Elsevier Science Ltd. All rights reserved.
Keywords: Magnesium alloys; AZ91D; Ingot; Die-cast; Microstructure; Corrosion

* Corresponding author. Tel.: +65-790-4963; fax: +65-791-1857.

E-mail address: marajan@ntu.edu.sg (R. Ambat).
0010-938X/00/$ - see front matter 7 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 0 - 9 3 8 X ( 9 9 ) 0 0 1 4 3 - 2

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R. Ambat et al. / Corrosion Science 42 (2000) 14331455

1. Introduction
The need for weight reduction, particularly in portable microelectronics,
telecommunication, aerospace and automobile sector has stimulated engineers to
be more adventurous in their choice of materials. Magnesium and its alloys,
with one quarter of the density of steel and only two thirds that of aluminium,
and a strength to weight ratio that far exceeds either, fulls the role admirably
as an `ultra light' alloy. In the microelectronics industry, magnesium alloys have
become promising materials for many components in hand phone, CVD/DVD
chassis, computer disk drives and camera casings. The ultra lightness of these
alloys is also attractive for transport industry where weight saving pays many
dividends.
Although a wide variety of applications can be envisaged for Mg alloys, the
use at present is limited mainly due to inferior corrosion properties. The
standard electrochemical potential of magnesium is 2.4 V (NHE), even
though in aqueous solutions it shows a potential of 1.5 V due to the
formation of Mg(OH)2 lm. Consequently, magnesium dissolves rapidly in
aqueous solutions by evolving hydrogen below pH 11.0, the equilibrium pH
value for Mg(OH)2. As a result, researchers all over the world has shown much
interest to study the corrosion behaviour of Mg alloys and to develop protective
measures.
Magnesium alloys with Al and Zn have (mainly AZ91 series) found wide spread
application in the automobile sector [1,2]. The spectrum includes several
applications like steering wheel, dashboard mounting bracket, gearbox housing
and chassis [2]. Corrosion resistance is one of the prerequisites for all these
applications.
The corrosion behaviour of cast magnesiumaluminium alloys could depend
considerably on microstructure (presence of b phase and coring) and the
environment to which it is exposed. Microstructural features vary with the method
of processing that gives rise to dierent corrosion behaviours. Even though few
studies have been reported [35] earlier on the eect of microstructure on the
corrosion and electrochemical behaviour of AZ91 alloy, a considerable amount of
ambiguity still exists. More importantly, coring during solidication that leads to
unequal distribution of aluminium and zinc in the microstructure on corrosion
behaviour is not understood properly. Further, in most of these studies, the
interpretation on the eect of several microconstituents is based more on
electrochemical data. The present investigation is concentrated on studying the
eect of microconstituents on corrosion behaviour of AZ91D alloy prepared by
die-casting and ingot casting route by a combination of surface morphology and
analytical studies. This includes constant immersion experiments, in-situ corrosion
analysis, and surface morphology studies by optical and scanning electron
microscopy and analytical studies by EDX and XRD. The electrochemical
parameters for the alloys were deduced by potentiodynamic polarization
experiments.

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1435

2. Experimental method
2.1. Material
The AZ91D die-cast material (die-cast) was available in the cylindrical rod form
with a diameter of 010 mm. Circular specimens of thickness 2 mm were sliced out
from the rod. For ingot material (ingot), a specimen size of 1 cm  1 cm  2 mm
was used for all the experiments. The chemical composition of the alloy is given in
Table 1.
2.2. Constant immersion testing
For constant immersion testing, the specimens were polished successively on
ner grades of emery papers up to 1000 level. All the specimens were initially
cleaned using the procedure of ASTM standard G-I-72 [6]. The polished and
preweighed specimens were exposed to the solution (150 ml, 3.5% NaCl) for
various intervals of time. Final cleaning of the specimen at the end of the
experiment was done by dipping it in a solution of 15% CrO3 + 1% AgCrO4 in
100 ml of water at boiling condition. An acetone washing followed this. The
weight loss was measured after each experiment and the corrosion rate was
calculated in millimeters per year. In each case duplicate experiments were
conducted and showed that the results fall within the expected error.
2.3. Electrochemical testing
Electrochemical polarisation experiments were carried out using an Auto Lab
Corrosion measurement system. Electrodes for this purpose were prepared by
connecting a wire to one side of the sample and covering with cold setting resin.
The opposite surface of the specimen was exposed to the solution. The exposed
area was about 1 cm2. The specimens were given a metallographic polishing prior
to each experiment, followed by washing with distilled water and acetone. A
polarisation test was carried out in a corrosion cell containing 150 ml of 3.5%
NaCl using a standard three electrode conguration: saturated colomel as a
reference with a platinum electrode as counter and the sample as the working
electrode. Specimens were immersed in the test solution and a polarization scan
was carried out towards more noble values at a rate of 1 mV s1, after allowing a
steady state potential to develop.

Table 1
Chemical composition of the AZ91D alloy (in wt%)
Al
9.1

Mn
0.17

Ni
0.001

Cu
0.001

Zn
0.64

Ca
< 0.01

Si
< 0.01

K
< 0.01

Fe
< 0.001

Mg
Bal

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2.4. In-situ corrosion observation

Usually a humid atmosphere causes the formation of tiny water droplets on the
surface of materials. In marine atmospheres, these droplets contain a signicant
amount of chloride ions. Several electrochemical cells nucleate and propagate
within this tiny droplet. In the present investigation, a droplet of 3.5% NaCl was
put on the surface of the material and the corrosion phenomena within this tiny
droplet was monitored continuously through a ZEISS model optical microscope.
The features at the surface of the specimen were recorded as a function of time.
The passivation behaviour was also studied by scratching technique.
2.5. Surface morphology analytical work
The microstructure and surface morphology of the corroded surface were
characterized using optical (ZEISS Model) and Scanning electron microscope
(JEOL Model No. 5600LV). Concentration proling of Al and Zn in the material
was carried out using EDX facility (Oxford Model) attached to the scanning
electron microscope. X-ray diraction technique (Philips, Model No. PW1830)
was used for analysing corroded surface and corrosion products.
2.6. Corrosive media
A solution of 3.5% NaCl with a pH of 7.25 was used for all the experiment. All
the experiments were conducted at room temperature. The solution was prepared
using A.R. grade NaCl in distilled water.
3. Experimental results
3.1. Microstructure
Fig. 1 shows the microstructure of the die-cast and ingot. The microstructure
consisted of primary a, eutectic a and b phase (marked in the gure). Die-cast
showed much ner grains and b phases. A considerable amount of porosity could
be observed on die-cast. On the other hand, ingot showed coarse grain structure
with bigger b particles.
3.2. Constant immersion studies
The variation of corrosion rate as a function of exposure time for AZ91D diecast and ingot is given in Figs. 2 and 3. The ingot showed an initial decrease in
corrosion rate followed by an increase upto 6 days of exposure. However, in the
case of die-cast, the corrosion rate showed a steady decrease with exposure time
except for 24 h exposure where it showed a slight upward trend. The corrosion
rate for ingot was slightly higher than die-cast at all exposure times.

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1437

Figs. 2 and 3 also show the typical surface features of the corroded surface after
exposure. Corrosion started initially at localised sites, preferentially in both cases
on primary a phase (more details given later). For ingot material this is clearly
visible on the surface while these features are not so clear for die-cast probably
due to ne grain size. The localised attack invaded the entire surface with
continued exposure to give a general corrosion pattern (after 6 days of exposure)
with several b particles remained on the surface unaected while the entire matrix
was dissolved. The degree of attack revealed the aggressiveness of the corrosive
medium.

Fig. 1. Microstructures of AZ91D alloy (a) ingot and (b) die-cast.

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R. Ambat et al. / Corrosion Science 42 (2000) 14331455

Fig. 2. Corrosion rate for AZ91D ingot as a function of exposure time.

In Fig. 4 a comparison is made between the corrosion of ingot and die-cast

materials at three dierent pH conditions. At 7.25 pH condition, the plot also
gives the dierence in corrosion rate in distilled water and in 3.5% NaCl solution.
The importance of these three pH conditions is as follows. At 2.0 pH, as it is

Fig. 3. Corrosion rate for AZ91D die-cast as a function of exposure time.

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1439

evident from the EhpH diagram for magnesium and aluminium [7], these
elements are not stable. At 7.25 pH, magnesium is unstable (so that it can
corrode) but aluminium is passive and at 12.0 pH, aluminium is active while
magnesium is passive. The corrosion rates for the materials in these three
solutions showed that the acidic solutions are very aggressive while the highly
alkaline solutions oer better corrosion protection. An increase in pH from 2.0 to
7.25 decreased the corrosion rate by 10 times and the rates were almost similar for
die-cast and ingot. The addition of 3.5% NaCl had increased the corrosion rate
by about four times both for ingot and die-cast.
To understand the eect of microconstituents in greater detail, several
specimens were immersed in 3.5% NaCl solution for a very short interval of time
(starting from few seconds to 15 min) and observed under SEM. Selected
micrographs are given in Fig. 5. For ingot, in general, the corrosion was initiated
on primary a phase while the eutectic a and b phases were completely protected,
although few areas were observed with severe corrosion at the b interface leading
to undermining of the same. Die-cast showed (Fig. 5(d)) a cellular type of network
after corrosion. It can be clearly seen that the corrosion was preferentially started
at the grain interior surrounded by b phase. Corrosion was found to be very
severe at these locations leading to deep pits in contrast to ingot where the
corrosion attack was more spread out.

Fig. 4. Corrosion rate for ingot and die-cast at three dierent pH conditions.

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3.3. In-situ corrosion observation

The anodic and cathodic activity under a droplet of 3.5% NaCl on the surface
of the die-cast and ingot was recorded using an optical microscope. These
experiments were done on etched (so that the microstructural features can be
clearly seen) and unetched surfaces. Figs. 6 and 7 show some of the sequential
pictures taken during in-situ observation of corrosion on etched surfaces. In all
the cases, as can be seen from the pictures, hydrogen evolution started
immediately after the solution was dropped (see arrows in Figs. 6(b) and 7(b)).
However, these nucleation sites were concentrated to a few places, rather than on
entire b surface. As shown in Fig. 6, for ingot, at a few locations hydrogen
evolution was so severe that the bubbles were coalesced and there was vigorous
reaction underneath (see arrow in Fig. 6(c)). Similar sites were found on die-cast
though the pictures shown (Fig. 7) did not have these. The activity was sustained
at these sites for a few minutes with the expulsion of corrosion product that was

Fig. 5. Scanning electron micrographs showing the eect of microconstituents on corrosion behaviour
of AZ91D ingot and die-cast material in 3.5% NaCl solution. (a), (b) and (c) ingot: (a) 5 min exposure,
(b) 15 min exposure, (c) 15 min exposure, back scattered image showing corrosion free areas near to b
phase and (d) die-cast after 15 min, exposure; back scattered image showing b network and corrosion
with in the grain.

R. Ambat et al. / Corrosion Science 42 (2000) 14331455

1441

visible in the neighbouring areas (see arrows in Fig. 6(d) and (e)). On die-cast, the
activity at these sites was subsided much faster than that on ingot. It is also
important to note that this type of vigorous hydrogen evolution did not happen at
all hydrogen evolution sites. Larger pits were observed in these areas after
cleaning the surface (Fig. 6(f)). Fig. 7(f) shows corrosion at the waterair interface

Fig. 6. In-situ corrosion observation of AZ91D ingot: micro-corrosion features as a function of time.
(a) 0 min, (b) 3 min, (c) 10 min, (d) 22 min, (e) 30 min and (f) surface after cleaning.

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R. Ambat et al. / Corrosion Science 42 (2000) 14331455

for die-cast. These areas have undergone severe corrosion compared to the surface
inside the drop. A similar behaviour was observed for ingot.
In general, the unetched surface was found to be less active compared to the
etched one. For the unetched surface, the surface of the specimens tarnished with
time due to corrosion. For ingot, corrosion was initiated at primary a phase.

Fig. 7. In-situ corrosion observation of AZ91D die-cast: micro-corrosion features as a function of time.
(a) 0 min, (b) 3 min, (c) 10 min, (d) 30 min, (e) surface after cleaning and (f) corrosion at the
boundary.

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1443

In another experiment, after a specic interval of time, the surface of the

specimen under the droplet was scratched with a thin glass rod. This broke the
oxide lm that was covering the surface of the alloy. For ingot, the repassivation
of these areas took a long time while on die-cast; these scratches were repassivated
quickly.
3.4. Aluminium and zinc concentration proling using EDX
It was suspected that the dierence in corrosion behaviour with in the a phase
is due to the variation in aluminium content. In order to understand this in detail
concentration proling of Al and Zn was carried out at several locations starting

Fig. 8. Concentration proles for Al and Zn along the line shown in the micrographs for AZ91D ingot.

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R. Ambat et al. / Corrosion Science 42 (2000) 14331455

from b phase to interior of the microstructure using EDX. Figs. 8 and 9 gives the
concentration prole of the elements along the lines shown in micrographs. It has
to be remembered that the EDX analysis gives the concentration of the element
not exactly on the surface, but with in the interacting volume of the electron
beam. It is possible that, in such cases, interference from features below the
surface. To take care of this fact, a number of measurements were carried out at
dierent locations (Fig. 8) and the interpretation is based on majority of the data.
In general, for ingot, it can be seen that the b phase and the neighbouring areas
(probably eutectic a phase) consisted of higher percentage of aluminium and zinc,
and the concentration decreases as we move away from the b phase. The width of
this aluminium rich region (>8%) adjacent to the b phase varied at dierent sites.
The concentration of aluminium typically varied between 035% at the b phase to
086% near or with in the primary a phase. In highly corroded region of the
microstructure (probably primary a found to have an aluminium concentration
R86% with negligible amount of zinc. In Fig. 8, curve (C ) represents the
concentration prole of aluminium between two b phases in a specimen exposed
to corrosive environment for 5 min. Comparing the prole with the micrograph, it
is clear that the corrosion was nucleated at areas where the concentration of
aluminium was less than 8%. Analysis of the EDX results led to the conclusion
that the composition of the b phase is 1 Mg17 Al11 Zn0.5. The concentration
proles for a non-corroded and corroded sample was similar.
In the case of die-cast (Fig. 9), the pattern was slightly dierent due to the

Fig. 9. Concentration proles for Al and Zn along the lines shown in the micrographs for AZ91D diecast.

R. Ambat et al. / Corrosion Science 42 (2000) 14331455

1445

neness of the microstructure. The EDX measurement was dicult on this

material due to interference from bottom as the b phase was very thin. Adjacent
to b phase, only a very thin layer was found with higher amount of aluminium.

3.5. X-ray diraction studies

XRD patterns (Fig. 10 (a) and (b)) were taken at same area of the specimen
before and after corrosion to get an idea about the amount of b phase removed
from the surface due to corrosion. The corrosion products were removed before
subjecting the specimen to XRD.
The surface of the unexposed alloys showed mainly peaks corresponding to Mg
and b phase (Fig. 10(a)(i) and (b)(i)). After exposing to the corrosive media the
intensity of the peaks corresponding b phase was lowered showing the
undermining of many b phases (Fig. 10(a)(ii) and (b)(ii)). For ingot, the peaks for
b phase was more intense compared to that of die-cast. One to one comparison of
intensities of all the peaks corresponding to b phase before and after corrosion
revealed that for ingot, the intensity has come down by an average of 8% while
for die-cast the value was only about 2%. Keeping in mind that it was all
occurring at the surface and dierence in the size of b phases, the amounts are
quite high for both materials.
X-ray diractogram of the corrosion product (Fig. 11(a)) for ingot, extracted
from the corrosive medium showed the presence of Mg(OH)2, b phase, MgH2 and
a mixed oxide of magnesium and aluminium. The JCPDS card showed that the
MgO:Al2O3 ratio of this mixed oxide is 1:2.5 [8].
However, it is interesting to note that the corrosion product analysis of die-cast
in the same corrosive media revealed an amorphous structure for corrosion
product (Fig. 11(b)). Two broad peaks can be seen in the diractogram probably
due to Mg(OH)2 and the mixed oxide mentioned above.

3.6. Potentiodynamic polarisation

The potentiodynamic polarisation curves for AZ91D die-cast and ingot in 3.5%
NaCl solution is shown in Fig. 12. Both materials did not show any passivity in
this solution. Table 1 shows the Ecorr, tafel slope and Icorr values for the materials.
The die-cast is found to be slightly cathodic to ingot cast. Tafel slope is same for
both alloys whereas the Icorr is higher for die-cast compared to that of ingot. The
cathodic part of the curve reveals that the cathodic currents were much higher for
die-cast at all potentials. On the other hand, ingot was more active anodically.
The surface of the specimen after polarisation studies showed surface features
similar to that in Fig. 5, except for ingot; some attack was found on eutectic a
phase.

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R. Ambat et al. / Corrosion Science 42 (2000) 14331455

Fig. 10. X-ray diractogram of alloy surface: (a) ingot: (i) before corrosion and (ii) same area after
exposure to 3.5% NaCl for 6 days, (b) die-cast: (i) before corrosion and (ii) same area after exposure to
3.5% NaCl for 6 days.

R. Ambat et al. / Corrosion Science 42 (2000) 14331455

Fig. 10 (continued)

1447

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R. Ambat et al. / Corrosion Science 42 (2000) 14331455

Fig. 11. X-ray diractogram of corrosion product in 3.5% NaCl after exposure for 6 days: (i) ingot
and (ii) die-cast.

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1449

4. Discussion
The phase diagram for MgAl system is characterised by three microstructural
constituents in the cast microstructure [9]. These are: primary a, eutectic a and b
phase. These three microconstituents can be clearly seen in the microstructure
given in Fig. 1(a). Macroscopically the a phase looks homogeneous, however
microscopically it is heterogeneous due to coring during solidication. As a result,
primary a contain much less aluminium compared to that of eutectic a and b
phase. The width of this zone depends on solidication rate [9]. The b phase
reported to have more cathodic potential than that of a matrix [4]. That way in
AZ91 alloys, the size and spatial distribution of b phase together with the coring
makes the alloy surface electrochemically heterogeneous. The corrosion behaviour
of the material thus depends on how these microconstituents interact when it is
exposed to aqueous environment. The above said parameters changes with
processing route, gives rise to dierent corrosion behaviours for materials
prepared by dierent processing routes.
The results presented above reveal considerable inuence of this microstructural
heterogeneity especially the volume fraction and nature of b phase, and coring
(leading to unequal distribution of aluminium and zinc) on corrosion behaviour of
cast AZ91D alloy. A detailed discussion of the results is given below.

Fig. 12. Potentiodynamic polarisation curves for AZ91D ingot and die-cast in 3.5% NaCl solution.

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4.1. Eect of corrosive environment

A solution of 3.5% NaCl was found to be an aggressive environment for the
present alloys (Table 2). The drastic increase in corrosion rate (4 times) observed
for die-cast and ingot in 3.5% NaCl solution (Fig. 4) may be interpreted as due to
the participation of chloride ions in the dissolution reaction. Chloride ions are
aggressive for both magnesium and aluminium. The adsorption of chloride ions to
magnesium surface, transforms Mg(OH)2 to easily soluble MgCl2 [10]. The critical
concentration of chloride ions required for pitting in uninhibited NaCl was
reported to be about 0.002 to 0.02 M NaCl [10]. This value increases with increase
in pH of the solution.
The eect of pH on the corrosion behaviour is in agreement with the EhpH
diagram of magnesium [7]. In highly alkaline solution, the corrosion rate for diecast and ingot was found to be comparatively low due to the stability of Mg(OH)2
lm. The eect of these parameters was also found to depend on the
microstructure. A more detailed paper on this subject will be published separately.
4.2. Eect of microconstitutents on corrosion behaviour
4.2.1. b phase
For both materials, b phase showed maximum resistance to corrosion
environment. This phase did not undergo corrosion in 3.5% NaCl except that it
was undermined due to corrosion at the interface. However, the inuence of this
phase on the overall corrosion behaviour was dierent in ingot and die-cast
because of the dierence in morphology. The lower corrosion rate and better
passivation of die-cast owes to ne distribution of b phase. Earlier investigations
on the corrosion behaviour of AZ91 alloys proved that the b phase could play a
dual role in the dissolution behaviour [3]. It can act as either a galvanic cathode
or a kinetic barrier to dissolution [3]. Lunder et al. [4] reported that the corrosion
potential of b phase in 5% NaCl saturated with Mg(OH)2 is about 490 and 420
mV cathodic to pure Mg and AZ91 alloy, respectively. Since this phase is highly
cathodic to the a phase, hydrogen evolution preferentially takes place on b phase
to make it an eective cathode. This has been observed in the present study
during in-situ corrosion observation. On the other hand if the a grains are ne
and b fraction is not too low, the oxide lm formed on b phase is nearly
continuous [3]. It has been reported that [4,11] the lm formed on b phase is more
stable because of the presence of higher amount of aluminium. The continuous
Table 2
Icorr, Ecorr and bc values for die-cast and ingot in 3.5% NaCl solution
Material

Icorr (mA cm2)

Ecorr (mV)

bc (mV)

Die-cast
Ingot

0.0063
0.011

1461.0
1441.5

169
182

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1451

stable oxide lm acts as barrier so that the dissolution of a phase is inhibited. For
this to occur the interparticle distance between b phase should not be too large. In
die-cast this was possible due to the close net work of b phase. On the other hand,
in ingot, the interparticle distance was very high so that such a networking was
impossible. In contrast, the undermining of b phase occurred due to the corrosion
of a phase (more detailed discussion given later) leads to reduction of b fraction
on the surface which in turn causes an increase in corrosion rate. This is exactly
what was observed in the case of ingot above an exposure time of 6 h (Fig. 2).
The XRD data (Fig. 10(a)) also showed that the undermining of b phase from the
surface of this material was quite high. On the other hand on die-cast, b
undermining was found to be comparatively low (Fig. 10(b)), the fraction of b on
surface increased with time, nally leading to a network of b phases that reduces
the corrosion rate with exposure time. Fig. 5(d) shows the b network in die-cast in
and around the corroded area.
In-situ corrosion studies further conrm this fact where the corrosion sites were
subsided much faster on die-cast compared to that on ingot. Scratching of the
surface also showed better passivation of die-cast. The reason for this may be
same as that explained before.
Corrosion product collected from the solution for ingot showed presence of b
phase (Fig. 11(a)). As the XRD analysis was carried out on corrosion product
collected after 6 days of exposure, the result indicated the stability of b phase in
aqueous solutions. b phase is reported to be stable in a wide pH range (414) [4].
The corrosion potential of this phase is close to pure Al in neutral and mildly
acidic solutions where as in highly acidic conditions, it approaches to the value for
Mg [4]. Corrosion properties of this phase are reported [4] to be superior to either
of its components in mildly alkaline environments.
4.2.2. a phase: eect of coring
The morphology of the corroded surface given in Fig. 5 together with EDX
analysis given in Figs. 8 and 9 convincingly proved that apart from the presence b
phase, coring play a bigger role in corrosion behaviour. This is especially true in
the case of ingot due to a wider width of zone with higher aluminium content
(Fig. 8). In this material, corrosion was nucleated at regions with aluminium
content R86%. The eect of aluminium on the corrosion behaviour of Mg
alloys has also been subject of many investigations [3,5,1113]. It has been
generally agreed that the presence of aluminium was benecial in improving the
corrosion behaviour of magnesium. Later, it was found that for eective
protection an optimum level of aluminium was required. Lunder et al. [4] reported
that this quantity was about 8% where as Warner et al. [12] using TEM studies
on rapidly solidied ribbons of composition Mg-9%Al, arrived at the conclusion
that it is >5%. Hehmann et al. [13] studied corrosion behaviour of rapidly
solidied splates and ribbons with aluminium concentration varying between 9
and 62.3 wt%. They observed a decrease in the corrosion rate and Ecorr, from 9.6
to 23.4 wt% Al in aerated 0.01 M sodium chloride solution. But none of these

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studies reported the eect of the concentration dierence of aluminium in the

microstructure near to the b phase on corrosion behaviour of MgAl alloys.
The present study shows that the concentration of aluminium decreases (Fig. 8)
as we go away from the b phase, to a value of 06% with in the primary a matrix.
As explained earlier in the section on results, for ingot the variation was found to
be in the range of 035% on b surface to 06% in the primary a phase. Comparing
this concentration prole with the corrosion morphology (Fig. 5), it is clear that
the region preferentially corroded was the one with less than 8% aluminium. The
value is in agreement with the value reported by Lunder et al. [4]. This shows that
whether it is in a single-phase alloy or multiphase alloy, the amount of aluminium
needed for considerable protection is more than 8%. In multiphase alloys,
variation of concentration of aluminium with in the microstructure leads to
corrosion of regions where aluminium content is less than 8%.
An analysis of the aluminium concentration in ingot near the b phase at various
locations led to the conclusion that (Fig. 8) the width of the region with higher
amount of aluminium (>8%) varies from point to point. As shown in Fig. 8, it
can be as high as 80100 mm to few microns. For ingot, at several locations
corrosion was initiated just adjacent to b boundary nally leading undermining of
this phase. It is believed that, these are the regions where aluminium
concentration just adjacent to b phase was <8%. However, it is important to

Fig. 13. Ecorr values for MgAl alloys as a function of Al and Zn concentration. (Values from Refs. [4]
and [11]: Lunder et al.: in 5% NaCl saturated with Mg(OH)2 and Daloz et al.: in ASTM D1384 water).

R. Ambat et al. / Corrosion Science 42 (2000) 14331455

1453

note that with exposure time or at lower pH conditions [14], the regions with
aluminium content >8% was also corroded.
In the case of die-cast a similar feature can be seen on careful observation
(Fig. 9). As explained earlier, concentration proling was diclt due to
interference. The width of the region surrounding this phase with higher
aluminium content was found to be comparatively small. Fig. 5(d) revealed that
the corrosion was preferentially started within the grain surrounded by the b
phase nally leading to a cellular structure with a network of undissolved b phase.
Fig. 13 shows the Ecorr values for MgAl alloys as a function of Al and Zn
content reported in the literature. Increasing aluminium content in the material
shifted the potential towards anodic side. A comparison of EDX result (Fig. 8)
with Fig. 13 reveals that a variation in the electrochemical potential could be
expected with in the a phase with regions of higher Al content showing higher
anodic potentials. The corrosion results showed an opposite trend. The reason for
this behaviour is not clear. However, as shown in Fig. 13, the presence of Zn may
alter the situation. In the present study aluminium rich regions found to have a
higher amount of zinc (Figs. 8 and 9). Daloz et al. [11] reported that in MgAl
alloys, presence of Zn inuences the Ecorr of both matrix and precipitate and had
a benecial eects on the corrosion resistance of the alloys.
4.3. Corrosion behaviour of ingot cast vs. die-cast
Overall comparison of the results reveal that, die-cast was marginally less
corrosive than ingot. However, a comparison of the corrosion features in
Fig. 5(a)(d) reveal deep pitting on die-cast. It was found that these areas (grain
interior) contain comparatively less quantity of aluminium (Fig. 9). In the case of
ingot, the corrosion was spread out in the comparatively large primary a phase.
The eutectic a phase in die-cast was more corrosion resistant due to its higher
aluminium content even though it was very narrow compared to that in ingot.
The lower aluminium content of eutectic a phase in ingot compared to die-cast
makes it susceptible to corrosion at longer exposure times that led to undermining
of b phase which was found to be high for ingot material from XRD data.
Electrochemically die-cast was found to be more cathodic due to the presence of
higher area fraction of b at the surface (Fig. 12). The potential of an alloy is
determined by the potential of the constituent phases and the area fraction
covered by each phase [15]. As explained earlier, the b phase is highly cathodic to
a phase in Mg alloys, so that the presence of a higher fraction of b phase on the
surface shifts the potential towards more cathodic side. The more cathodic current
density at all potentials may also be due to the same factor. The anodic and
cathodic tafel slope remained the same for both materials, showing that the
electrochemical reactions are the same.
XRD data showed that the quantity of b phase removed from the surface due
to corrosion was high in ingot (8%) (Fig. 10(a) and (b)). However, the 2%
reduction in b phase on the surface for die-cast can be substantial considering the
size of b phase in this material. The nature of corrosion products was found to be

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R. Ambat et al. / Corrosion Science 42 (2000) 14331455

dierent for ingot and die-cast (Fig. 11(a) and (b)). For ingot, the compounds
identied are fairly in agreement with that reported in the literature. Earlier
studies have reported the presence of Mg(OH)2 and MgH2 in the corrosion
product of Mg and Mg alloys [1620] even though none of the studies have
reported the presence of a mixed oxide of aluminium and magnesium, and the
presence of b phase. The reason for the amorphous structure for product for diecast is not clear. This needs further investigation. However our work on the
analysis of corrosion product formed in dierent environments points to the fact
that the presence of more aluminium oxide in the product leads to the above
mentioned result [14].
As mentioned earlier, on both materials at a few sites hydrogen evolution was
very vigorous and severe corrosion was found underneath. This may be the
location where AlFeMn phases may be found. Lunder et al. [4] also reported a
similar phenomena in AZ91 alloy in 5% NaCl. The AlFeMn phases act as a good
cathode for hydrogen evolution.
In summary, the corrosion behaviour of cast AZ91 alloy depends signicantly
on the size and distribution of b phase and distribution of aluminium and zinc
with in the microstructure. Although a close network of b phase provides a
barrier to dissolution, an optimum level of aluminium and zinc is essential to
ensure more corrosion resistance for the a phase. Further, a higher aluminium
content adjacent to b phase reduces the undermining of the same that help in
improving the corrosion resistance.

5. Conclusions
1. AZ91D die-cast showed higher corrosion resistance and better passivation than
AZ91D ingot due to ne grain structure and b phase. Electrochemically die-cast
was found to be more cathodic to ingot.
2. Size and morphology of b phase and coring were found to have signicant
inuence on corrosion behavior of AZ91D alloy. In both materials, corrosion
initiated at areas where aluminium concentration was less than 8%. Hydrogen
evolution took place preferentially on b phase but only at few locations.
3. XRD pattern showed a higher percentage of b undermining on ingot. XRD
data also showed the presence of undermined b phase in corrosion product (for
ingot) in addition to Mg(OH)2 and small quantities of magnesium-aluminium
oxide and MgH2. The corrosion product for die-cast was found to be more
amorphous.

Acknowledgements
The authors would like to thank Dr. Qiu Jian Hai of NTU for his help in

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1455

conducting the electrochemical experiments and Drs. B.H. Hu and Ian Pinwill of
Gintic for providing the magnesium alloys. Financial assistance from Nanyang
Technological University through research grant RG79/98 is gratefully
acknowledged.
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