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Corrosion Science 49 (2007) 11101130

www.elsevier.com/locate/corsci

Corrosion characterisation of aluminamagnesium


metal matrix composites
A. Bakkar

a,c

, V. Neubert

a,b,

Institut fuer Materialpruefung und WerkstoVtechnik, Dr Neubert GmbH, Freiberger Strasse 1,


D-38678 Clausthal-Zellerfeld, Germany
b
Zentrum fuer FunktionswerkstoVe GmbH, Sachsenweg 8, D-38678 Clausthal-Zellerfeld, Germany
c
Department of Metallurgy and Materials Engineering, Suez Canal University, P.O. Box 43721, Suez, Egypt
Received 21 October 2005; accepted 7 July 2006
Available online 18 September 2006

Abstract
Alumina magnesium metal matrix composites are a precious alternative for aerospace and automotive applications because of their high stiVness-to-weight ratio. A considerable deal of investigations had been devoted to their processing and mechanical properties, while the corrosion behaviour
is still uncertain. In this study, the corrosion behaviour of Al2O3 Wbres strengthened magnesium
AS41 composite, in aqueous solutions containing various concentrations of NaCl at diVerent pH
values, was studied and compared with the behaviour of pure AS41 magnesium matrix alloy using
electrochemical techniques, hydrogen evolution test, optical microscopy, and scanning electron
microscopy (SEM) coupled with EDX and WDX capabilities. The results showed that the corrosion
behaviour of the composite was comparable to its pure matrix alloy, yet a reduction in the corrosion
resistance was observed in the composite at higher chloride concentrations. The corrosion mechanism involved, as well as the corrosion characteristics, was extensively discussed in terms of the eVect
of Al2O3 Wbres. Also, an appropriate model describing the corrosion mechanism was proposed.
2006 Elsevier Ltd. All rights reserved.
Keywords: A. Mg; A. Al2O3; A. MMC; C. Microstructure; C. Corrosion mechanism; C. Interfacial reaction

*
Corresponding author. Address: Institut fuer Materialpruefung und WerkstoVtechnik, Dr Neubert GmbH,
Freiberger Strasse 1, D-38678 Clausthal-Zellerfeld, Germany. Tel.: +49 5323 989 890; fax: +49 5323 989 899.
E-mail address: volkmar.neubert@tu-clausthal.de (V. Neubert).

0010-938X/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2006.07.002

A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

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1. Introduction
Magnesium metal matrix composites (Mg MMCs) are of great value for applications in
the automotive, aircraft and aerospace industries because they have high strength and high
stiVness with lower density compared with the structure materials. Alumina (Al2O3) Wbres
magnesium composites are of particular consideration to be used where high stiVness/
weight ratio is required. Ferrando [1] reported that the Al2O3/Mg composites are prime
candidates for applications in aircraft engines, power transmission housings and rotating
shafts, and, thereby, were suggested to be used in helicopter transmission components.
Although addition of an appropriate reinforcement into a magnesium alloy matrix
results in a composite material with highly improved physical and mechanical properties,
signiWcant deterioration in the corrosion resistance can arise. Hihara [2] listed the possible
reasons that deteriorate the corrosion resistance of the MMCs to be: (1) galvanic coupling
of the reinforcement constituent and matrix alloy; (2) formation of an interfacial phase
between the reinforcement and matrix; and (3) microstructural changes and processing
contaminants resulted from manufacture of the MMC.
In contrast to the extensive research into development of the physical and mechanical
properties of the Mg MMCs, few studies have been devoted to their corrosion behaviour.
Also, research ascertained the corrosion behaviour of Al2O3/Mg MMCs can be considered
rather sparse compared with research on that of C/Mg and SiC/Mg MMCs.
Hall [3] investigated the corrosion of C-Wbres/Al-containing Mg MMCs in laboratory
atmosphere and speculated that the driving force for attack is the galvanic corrosion
resulted from matrix/Wbres coupling. Yet the interfacial compound Al4C3, formed during
the fabrication process, evidenced the susceptibility to attack. Trzaskoma [4] reported the
severe degradation of the graphite Wbres/magnesium composites in aqueous chloride environments. The author conWrmed the important role of galvanic interaction in the aqueous
corrosion rather than the rapid reaction of magnesium with the solution.
Hihara and Kondepudi [5,6] investigated the galvanic corrosion behaviour of SiC/
pure Mg and SiC/ZE41A-Mg MMCs in oxygenated and de-aerated nitrate, sulphate and
chloride solutions. The reinforcement constituent SiC monoWlament (MF) was made
of a carbon core coated by a carbon-rich SiC layer. The results showed the evidence of
highly galvanic corrosion rates in the existence of oxygen. In order to mitigate the galvanic coupling eVect, the authors suggested replacing the SiC MF by pure SiC particles,
which was assumed to have the same electrochemical behaviour of hot-pressed SiC.
Compared with pure Mg, a better corrosion resistance was observed with ZE41A alloy as
a matrix.
Nunez-Lopez et al. [7] evaluated the corrosion rate of 12%SiCp/ZC71-Mg composite
using the salt spray test to be three times higher than that of its matrix, due to the formation of less protective corrosion products. The authors neglected eVect of the either
galvanic coupling between the matrix alloy and SiC or formation of reactive matrix/SiCinterphases. In a successive study using an especially prepared high purity SiCp/Mg MMC,
the same authors [8] proved the absence of microgalvanic corrosion in the vicinity of SiC
particles.
Zucchi et al. [9] examined the corrosion behaviour of SiCp/AZ80A and SiCp/ZK60A
magnesium metal matrix composites in sodium sulphate and sodium chloride solutions.
Immersion data and electrochemical test results indicated higher corrosion rates dictated
by the composite surfaces, where a stable protective hydroxide Wlm was diYcult to form.

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A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

Hihara and Latanision [10] summarised shortly the published literature in the corrosion
behaviour of Al2O3/Mg MMCs. According to the available studies, corrosion rates of the
composite was higher than that of the alloy in the most cases. The authors mentioned, also,
that the possibility of galvanic corrosion between magnesium and precipitates or an interphase formed by the presence of Al2O3 was still under controversy. Chan et al. [11] found
that the 20% Al2O3/AZ91C Mg MMCs exhibited much more susceptibility to corrosion in
chloride-containing solutions compared with the matrix alloy. The corrosion current
density (Icorr) of the composite was approximately equal to that of the matrix alloy in low
chloride-concentration alkaline solutions. When the chloride concentration was increased
up to 3.5% NaCl, the Icorr of the composite was recorded to be about three times higher
than that of the matrix. Free immersion test, for three days in a 3.5% NaCl alkaline solution, ranked the corrosion rate of the composite to be seven times faster than that of the
matrix alloy.
However, there is no published systematic study, to date, disclosing the mechanism by
which the accelerated corrosion occurred in Al2O3/Mg MMCs. Therefor, the present
research aimed to study the corrosion behaviour of Al2O3/Mg MMCs, ascertaining the
eVect of alumina on the corrosion potential, corrosion rate and corrosion morphology, in
addition to the mechanism involved in the corrosion process. A composite based on AS41Mg alloy reinforced with 20 vol% alumina (SaYl) Wbres, compared with its pure matrix
alloy, was used for this purpose.
2. Experimental procedures
2.1. Composite preparation
The composite product was fabricated using the squeeze casting route. The equipment
used can be described as in Fig. 1. The SaYl-alumina-Wbres preform was heated up to
1000 C, and placed into the mould, which was also preheated up to about 200 C. The
matrix alloy, heated up to 800 C in a crucible protected by inert gas (2 l/min Ar + 0.5 l/min
SF6), was successively poured into the mould. A dovetail ram (20 cm), located directly
above the die, was soon lowered onto the molten cast with a pressure of 8 MPa for 15 s.
This pressure was then increased up to 14 MPa and maintained for 90 s. Then, the pressure
was allowed to fall back to zero, and the ram was raised. Another ram located in the bottom of the die was then raised up, bringing with it the Wnal cast. Table 1 shows the typical
composition of the both matrix alloy and alumina Wbres.
2.2. Materials and sample preparation
The Wnal cast product was in the shape of disc with a diameter of 200 mm and a height
of 40 mm. Contained in this disc was the MMC block with dimensions of 120
120 35 mm, see Fig. 2. The SaYl-alumina Wbres (20 vol%) were distributed quasi-isotropically in the horizontal plane. Specimens were cut into small blocks 15 15 7 mm3. Each
specimen was successively wet ground on all faces. For electrochemical tests at pH D 12,
the specimens were soldered to copper wires on one side and mounted in epoxy, and suspended in the electrolyte, exposing a free test surface of 15 15 mm2. For all electrochemical tests and hydrogen evolution measurements, a fresh surface was obtained by grinding
using 1200 grit SiC paper and ethanol, as a lubricant and cooler. Finally, the specimens

A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

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Fig. 1. A schematic illustration of the squeeze casting process.


Table 1
Typical chemical composition (wt%) of both magnesium matrix alloy (AS41) and alumina (SaYl) Wbres
AS41
SaYl

Al
4.998

Si
0.93

Mn
0.357

Zn
0.0555

Fe
0.0014

Al2O3
95.00

Ni
0.0006

Cu
<0.0002
SiO2
4.16

Pb
<0.002

Sn
0.0053

Zr
<0.010

Mg
Bal.

Others
0.84

were ultrasonically cleaned with several rinses of ethanol and immediately examined. Three
specimens were replicated for each experimentation at 25 C 1.
2.3. Electrochemical experimentation
Potentiodynamic polarisation experiments were carried out using the model Wenking
LB 94L (Auto Range) Laboratory Potentiostat and controlled by a suitable computer.
For electrochemical measurements in alkaline solutions, pH D 12, the specimen was
immersed in the solution for 15 min prior to polarisation, by which time a stable potential
(open circuit potential OCP) was monitored. With reference to saturated calomel electrode (SCE), the polarisation was obtained by scanning from 500 mV more negative than

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A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

MMC
Alloy

Fibre preform

Final cast product

Fig. 2. A schematic diagram showing the Wnal cast fabricated by squeeze casting containing the metal matrix
composite (MMC) within it.

the OCP at a rate of 20 mV/min. The corrosion current density (Icorr) was determined by
the extrapolation of Tafel lines of the cathodic curves using the software program CPCDAU 41. The pH was adjusted to 12 by adding NaOH.
For electrochemical measurements in neutral pH solutions, the same procedure was followed by potentiodynamic polarisation using the Avesta cell [12]. Exposed area of the
specimen to the solution was circular with a 5-mm-diameter.
2.4. Hydrogen evolution test
The specimen was put on a glass seat in a beaker, open to air, containing 1200 ml of pH
9.3 borax-buVered 3% NaCl solution. To collect the hydrogen evolved, a burette with a
funnel end was placed over the specimen, which ensured the collection of all hydrogen
from the specimen surface. The hydrogen volume, which is equal to the displaced test solution in the burette, was gradually recorded.
2.5. Microstructure analysis
Optical microscopy and scanning electron microscopy SEM SX 100 Electron Probe
Microanalyser, equipped with EDX and WDX capabilities were used to characterise the
microstructure of the specimens, as-received and after corrosion tests.
3. Results
3.1. Microstructure
The microstructure of as-fabricated samples, before corrosion testing, is illustrated in
Figs. 3 and 4. In addition to the primary phases Mg17Al12, Mg2Si, and Mn-rich phase
common to be found in the AS-Mg alloys [13,14], formation of extensive zones of high
aluminium content (9 wt% Al), marked HA, was evident around the SaYl-alumina
Wbres (F). The aluminium content (3 wt% Al) in the matrix, labelled LA, was similar to
that detected in the original pure matrix alloy. These high Al-content zones (HA) were considered to result from the interfacial reaction:
3Mg(L) C Al2O3(S) D 3MgO(S) C 2Al(L)

A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

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Fig. 3. SEM micrograph of as-cast AS41 Mg matrix alloy showing the contained phases.

At Wrst, there was doubt that the high Al-content zones (HA) resulted from the interfacial reaction, because it was assumed that the interfacial phases were very thin. However, it
has been reported that the above reaction is thermodynamically possible [15,16]. Also,
extensive reaction has been conWrmed, particularly, when the Wbres are exposed to the
magnesium melt for a rather long time. Moreover, severe Wbre/matrix interaction has been
reported to the extent that the Wbres reacted completely with magnesium, but this was pronounced owing to the particular circumstances [16,17].
As the SaYl Wbres contain about 4 wt% SiO2, Table 1, there could be another reaction at
the Wbre/matrix interface as well [15,16]:
4Mg(L) C SiO2(S) D Mg2Si(S) C 2MgO(S)
The reaction products (Mg2Si + MgO) have been reported to be concentrated at the
interface. This is most likely the reason for non-existence of HA zones on occasional sites
at the interface, Fig. 4. However, large segregated Mg2Si particles have been recognised in
matrices based on AZ61 and AZ91 alloys in vicinity of the SaYl Wbres [16]. In the present
study, Mg2Si phase showed a tendency to segregate at the Wbres, but it cannot be veriWed as
the result of the interfacial reaction because the original alloy contains the silicide phase.
A similar inclination of Mg2Si to precipitate at carbon Wbres has been observed in C/AS41
Mg MMC [14,18].
3.2. Electrochemical measurements
3.2.1. Polarisation in Cl-containing alkaline solution
The potentiodynamic polarisation at conditions in which Mg is passive, pH D 12, in a
100 ppm NaCl solution was applied for the comparison between corrosion behaviour of
the both alloy and composite, Fig. 5(a). As it has been previously found by the authors
[13,19] that, for comparing corrosion of various Mg alloys in a such alkaline electrolyte,
the most feasible parameter was the pitting potential (Ep). It can be seen that the presence

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A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

Fig. 4. (a) SEM micrograph of as-cast SaYl/AS41 Mg MMC showing two types of matrix structures; low Alcontent matrix (LA) and high Al-content matrix (HA) around SaYl Wbres (F), and the original phases of AS41
alloy; Mg17Al12 (), Mg2Si (S), and Mn-rich phase (M). (b) Higher magniWcation of micrograph (a).

of SaYl-alumina Wbres reduced the Ep to less noble values, which were more than 400 mV
less than that of the matrix alloy, Table 2. The polarisation of the normal plane of composite, the plane in which the most of Wbres are normal to the surface to be tested, showed a
slight increase in the Ep towards the noble direction, compared with the horizontal plane.
3.2.2. Polarisation in Cl-free alkaline solution
The potentiodynamic polarisation curves that were monitored for chloride-free alkaline
solutions, pH D 12, were almost identical, Fig. 5(b). The pitting potential (Ep) values did
not show much variation with adding SaYl-alumina Wbres, Table 2.

A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

2500

1500

2000

1000

1500

500

AS41 Mg alloy
Al2O3/AS41 Mg MMC
(h orizontal plane)
Al2O3/AS41 Mg MMC
(n ormal plane)

0
-500
-1000

Potential (mV vs. SCE)

Potential (mV vs. SCE)

2000

1000
AS41 Mg alloy
Al2O3/AS41 Mg MMC
(horizontal plane)
Al2O3/AS41 Mg MMC
(normal plane)

500
0
-500
-1000

-1500
-2000
-5
10

1117

-1500

-4

-3

10

10

-2

10

-1

10

10

10

-2000
-5
10

-4

-3

10

10

-2

10

-1

10

10

10

Current density (mA/cm )

Current density (mA/cm )

Fig. 5. Potentiodynamic polarisation diagrams for alloy and composite specimens in pH 12 sodium hydroxide
solution: (a) with 100 ppm NaCl, (b) chloride-free.
Table 2
Electrochemical parameters obtained from polarisation curves for Al2O3/AS41 Mg composite and its pure matrix
alloy in pH 12 sodium hydroxide solution
Parameter

CP (mVSCE)
Ecorr (mVSCE)
Icorr (A/cm2)
Ep (mVSCE)
Ipass (A/cm2)

100 NaCl solution, pH D 12

Cl-free solution, pH D 12

Alloy

Composite
parallel

Composite
normal

Alloy

Composite
parallel

Composite
normal

1419 56
1349 26
0.957 0.011
1587 58
2.4 0.08

1327 23
1324 5
1.286 0.06
1080 85
1.87 0.15

1334 25
1316 30
1.376 0.212
1177 14
1.37 0.35

1432 30
1313 22
1.075 0.009
2085 15
2.55 0.12

1327 10
1281 11
0.966 0.04
1953 19
2.06 0.32

1316 14
1273 17
0.903 0.034
2037 10
1.75 0.22

3.2.3. Morphology of pitting corrosion


The topography of composite specimen potentiodynamically polarised in 100 ppm
NaCl alkaline solution up to 1050 mV (vs. SCE) and at that potential followed by potentiostatic polarisation for 3 h is revealed in Fig. 6. Actually, the pitting was reached after 2 h,
but the specimen was polarised after pitting for 1 h more until the pitting was visible. It is
clear that the pitting sites had no evident tendency to be in the proximity of the Wbres. The
deep pits, marked by white arrows, which had initiated in earlier times, appeared with the
same intensity and depth near and far away from the Wbres. The shallow pits pointed out
by dashed arrows, were not only found near the Wbres, but also farther within the matrix
alloy. Moreover, similar shallow pitting was depicted adjacent to Mg2Si phase, represented
by black arrow. Finally, it can be stated that the pitting localisation was independent on
the Wbres sites.
In chloride-free solution, the Al2O3/Mg composite surface was not signiWcantly aVected by
potentiostatic polarisation at 1050 mV for 3 h after potentiodynamic polarisation. Fig. 7 shows

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A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

Fig. 6. SEM micrograph of corroded surface after 3 h polarisation at 1050 mV in pH 12 sodium hydroxide solution containing 100 ppm NaCl, showing the pitting sites represented by arrows.

Fig. 7. SEM micrograph of composite surface polarised for 3 h at 1050 mV in chloride-free pH 12 sodium hydroxide solution.

the absence of any localised attack within the magnesium matrix alloy, which corroded uniformly under the passive behaviour.
3.2.4. Polarisation in neutral conditions
The corrosion characteristics of the alloy and composite, which were obtained by potentiodynamic polarisation in neutral aqueous solutions containing 0.03, 0.3, 1.0 and 3.0 wt%
NaCl are shown in Fig. 8 and Table 3.
In 0.03 wt% NaCl (300 ppm NaCl) solution, the polarisation curves showed a quasi-passive behaviour, where the anodic current increased gradually with increasing potential
until a value from which a relatively sharp increase of the current occurred. This value,

A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

-800

-800

0.3 % NaCl

-1000

-1000

-1200

-1200

Potential (mV vs. SCE)

Potential (mV vs. SCE)

0.03 % NaCl

-1400

-1600
AS41 alloy
Saf/AS41 MMC
(horizontal plane)
Saf/AS41 MMC
(normal plane)

-1800

-4

-3

10

-2

10

-1400

-1600

-1800

-2000
-4
10

-2000
-1

10

10

AS41 alloy
Saf/AS41 MMC
(horizontal plane)
Saf/AS41 MMC
(normal plane)
-3

10

1.0 % NaCl

10

3.0 % NaCl
-1000

-1200

-1200

Potential (mV vs. SCE)

Potential (mV vs. SCE)

10

-800

-1000

-1400

-1600

-2000
-3
10

-1

10

Current density (mA/cm )

-800

-1800

-2

10

Current density (mA/cm )

1119

AS41 alloy
Saf/AS41 MMC
(horizontal plane)
Saf/AS41 MMC
(normal plane)
-2

10

-1

10

-1400

-1600

-1800

10
2

Current density (mA/cm )

10

-2000
-3
10

AS41 alloy
Saf/AS41 MMC
(horizontal plane)
Saf/AS41 MMC
(normal plane)
-2

10

-1

10

10

10
2

Current density (mA/cm )

Fig. 8. Potentiodynamic polarisation diagrams for alloy and composite specimens in neutral 0.03, 0.3, 1.0 and
3.0 wt% NaCl solutions.

pointed out by the arrows in Fig. 8(a), was considered to be the breakdown potential
(Ebreak) of the quasi-passive Wlm of Mg(OH)2. The eVect of alumina Wbres in reducing the
breakdown resistance of the Mg composite by shifting the Ebreak into the active direction
was evident. By increasing the NaCl concentration to 0.3 wt%, the quasi-passive behaviour
disappeared in the curves displayed by the composites, but the alloy still exhibited a limited
quasi-passivation range of about 100 mV beyond the Ecorr, Fig. 8(b).
In concentrated NaCl solutions (1.0 and 3.0 wt% NaCl), the polarisation behaviour for
all of the materials investigated were almost the same. The curves indicated no protective
Wlm formation or its breakdown, if formed, at the corrosion potentials (Ecorr), which were
approximately equal. However, a possible parameter for comparison purposes was only

OCP
(mVSCE)
Ecorr
(mVSCE)
Icorr
(A/cm2)
Ebreak
(mVSCE)
Ibreak
(A/cm2)

Composite
parallel

Composite
normal

Composite
parallel

Composite
normal

Composite
parallel

Composite
normal

13.13 7.05 4.47 2.26

7.38 0.92 16.07 3.19

8.16
1.14

12.523
4.118

12.817
3.377

26.327
6.343

22.963
5.605

16.313
1.801

4.688
0.776

1.537
1.069
1.216
4.313
0.522
0.119
0.185
0.281
1094 53 1261 61 1224 11 1373 9

4.884
0.169

1509 4 1519 6 1528 9

Alloy

1423 33 1402 21 1406 24 1466 10 1437 10 1453 14 1465 16 1481 11 1478 8

Alloy

1447 23 1483 27 1534 13 1472 9 1489 7 1524 6 1511 11 1513 10 1552 7 1540 4 1536 12

Alloy

3% NaCl

1495 7

Composite
normal

1% NaCl

Composite
parallel

0.3% NaCl

Alloy

Parameter 0.03% NaCl

Table 3
Electrochemical parameters obtained from polarisation curves for Al2O3/AS41 Mg composite and its pure matrix alloy in neutral NaCl solutions

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1121

the corrosion current density (Icorr). The increase in the Icorr of the composite material was
evident to be around 1.5 times of that of the matrix alloy, Table 3.
3.2.5. Corrosion morphology
The morphology of corroded surfaces after polarisation was examined by optical
microscopy. The results showed that the most representative surfaces were after polarisation in 0.03 wt% (300 ppm) NaCl solution, Fig. 9. The corroded surface of the alloy specimen polarised up to 900 mV, Fig. 9(a) and (b), depicts the cellular corrosion type. This
type has been reported to occur in MgAl alloys as a development of Wliform corrosion
[20]. Even though the corroded surface morphology in Fig 9(b) might presume intergranular corrosion to occur, earlier corroded surface polarised only up to 800 mV, Fig. 9(c),
conWrmed the cellular corrosion type that evolved from initial Wliform corrosion sites.
It has been reported that the intergranular corrosion is improbable to occur in Mg alloys,
because the grain boundary is perpetually cathodic to the grain body [20,21]. However, Wliform corrosion has been typically documented for MgAl alloys [2022], thereby indicating the protective character of the oxide/hydroxide Wlm formed naturally on the surface, as
will be demonstrated in the discussion section.
The corrosion attack in the composite specimens was highly localised and the propagation of pits appeared to be restricted by the alumina Wbres, Fig. 9(d) and (e). Closed view,
Fig. 9(f), proved the absence of preferential corrosion at the alumina/matrix interface. On
the contrary, the Wbres were maintained surrounded by non-corroded matrix alloy.
3.2.6. Corrosion resistance vs. plane direction
All polarisation tests in chloride-containing solutions, both neutral and alkaline,
showed that the normal plane of the composite (the plane in which the most of Wbres are
normal to the surface) had a slightly more corrosion resistance than the horizontal plane.
The volume fraction, or rather the area fraction, of the alumina Wbres was measured in the
two directions (horizontal and normal planes) and found to be equal, about 20%. However, this total area of Wbres is mostly dispensed as rectangles in the horizontal plane, and
as circles in the normal plane. In other words, the same area fraction is displayed by a
larger number of circular Wbres in the normal plane, compared with the number of rectangular Wbres in the horizontal plane. Consequently, the total speciWc interfacial surface is
larger in the normal plane, and so the arising HA zones are enlarged. This is, most likely,
the reason for the slightly higher corrosion resistance of the normal plane than that of the
horizontal one.
3.3. Hydrogen evolution test data
Fig. 10 shows the typical results of H2-evolution measured on both alloy and composite
after 50 h, 100 h, and 144 h immersion in pH 9.3 borax-buVered 3% NaCl solution.
Comparing between the measured H2-evolution values leads to an apparent result that the
composite had slightly lower H2-evolution rates than the alloy. However, it must be taken
into account that: (1) the composite material contains about 20 vol% Al2O3 Wbres, and (2)
the Wbres are inert, where they did not contribute any H2-evolution when they were
immersed in the test solutions for more than 200 h. Based on these considerations, a proper
conversion was required to express the realistic H2-evolution per the actual reactive unit
area (cm2) of the matrix alloy in which the Wbres are embedded. As the volume fraction of

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A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

Fig. 9. Corrosion surfaces following potentiodynamic polarisation in 0.03% NaCl solution for: (a) AS41-Mg
alloy, polarised up to 900 mV, showing the overall corrosion morphology, (b) higher magniWcation of (a), (c)
AS41-Mg alloy, polarised up to 800 mV, showing the initial Wliform corrosion sites, (d) Al2O3/AS41-Mg composite, polarised up to 900 mV, showing the overall pitting morphology, (e) higher magniWcation of (d),
showing the local pitting, and (f) normal plane of Al2O3/AS41-Mg composite, polarised up to 900 mV, showing the resistance of matrix around the Wbres F to attack.

Al2O3 in the matrix is 0.2, this conversion was obtained by dividing the measured H2-evolution value by 0.8 of the all surface area of composite specimen.
Following the hydrogen evolution as a function of time, Fig. 11, it can be seen that, by
comparing the alloy and composite, the variation of H2-evolution with time was diVerent.

Hydrogen evolution (ml/cm )

A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

1123

50 h
100 h
144 h

5
4
3
2
1
0
Alloy

Composite
Composite
(as measured values) (as rectified values)

Fig. 10. Hydrogen evolution values measured on Al2O3/AS41 composite and its pure matrix alloy, in addition to
rectiWed values for the composite that exerted by the realistic reactive surface area, after diVerent immersion times
in pH 9.3 borax-buVered 3% NaCl solution.

For the alloy, the H2-evolution increased rapidly at the start of the test (stage I) and then
gradually with a lowest rate (stage II), but changed to an almost constant rate at a later
stage (stage III). The gradual decrease in rate (stage II) may have been due to the formation of a quasi-passive Wlm from the corrosion products. However, the composite showed a
sharp increase in H2-evolution rate at earlier times (stage I), followed by an increasing, but
lower, rate at the later stage (stage III), with absence of the stage II. This implies that the
quasi-passive Wlm did not form or was destroyed as soon as it was formed. The appearance
of the specimens, H2-evolution tested for 50 h and 100 h, Fig. 12, conWrmed the explanation
of the H2-evolution rate diagram shown in Fig. 11. The surface of composite had pitting at
times earlier than that of the alloy.
Representative cross-section through corroded surface of the MMC is revealed in
Fig. 13. The right part of the micrograph depicts a regular Wlm of corrosion products
formed on the surface. This regular corrosion Wlm was associated with deep localised
attack. Evidently, the deep attack developed at the expense of low aluminium zones
LA and was restricted by the high Al zones HA which may also be attacked in later
stages. Alumina Wbres protruded from the surface maintaining their original angular
shape, but, in highly attacked regions, they undermined and could be observed in the
corrosion products precipitated beneath the specimen, by the optical microscope. In conclusion, there was no preferential corrosion of the matrix where the Wbres were relatively
agglomerated, and the deep attack penetrated into the matrix, particularly through the
LA zones.
4. Discussion
4.1. The role of alumina on the microstructure
Comparing the microstructure of the composite with that of the alloy, Figs. 3 and 4, it is
obvious that, except for the reWning of Mg2Si script, the Wbres have no eVect on the parent

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A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

Hydrogen evolution (ml/cm )

II

III

10

20

30

40

50

60

70

80

90 100

70

80

90 100

Hydrogen evolution (ml/cm )

Time (h)

III

10

20

30

40

50

60

Time (h)
Fig. 11. Hydrogen evolution as a function of time measured on: (a) AS41 Mg alloy, and (b) Al2O3/AS41 Mg composite, immersed in pH 9.3 borax-buVered 3% NaCl solution.

phases. However, the high Al zones (HA), containing 9 wt% Al are resultant from the interfacial reaction during fabrication. It is impossible that these zones (about 33 vol%) resulted
from segregation of Al from the parent alloy which contains only 4 wt% Al. The high Al
zones (HA) resulted from the interfacial reaction aforementioned above in Section 3.1.
This interfacial reaction has been reported in many references [15,16,2326].
It is believed that the interfacial reaction occurred during inWltration of the Mg alloy
(800 C) into the alumina Wbres preform preheated up to 1000 C. The subsequent squeezing by means of hydraulic dies, which act as a heat soak, results in a pseudo rapid solidiWcation, thereby rendering HA zones segregated close to the Wbres. The extended HA zones
contain only 9 wt% Al, i.e. only 6 wt% Al more than the matrix. Also, the previous work
conWrmed the extensive interfacial reaction between the alumina Wbres and the magnesium
melt. Rehman et al. [15] reported that the reinforcement of pure magnesium (CP Mg) with
25% alumina Wbres showed extensive lamellar eutectic of -Mg and -Mg17Al12. The bulk
analysis of eutectic had 3036 wt% Al. On the other hand, MgO was reported to form on
the alumina Wbres as very Wne particulates [2326]. In the present study, it was diYcult to
detect the MgO by SEM due, possibly, to the coarse interaction volume diameter produced

A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

1125

Fig. 12. Photographs of the specimens following immersion for 50 h and 100 h, in pH 9.3 borax-buVered 3% NaCl
solution.

by the electron beam. Rehman et al. [15], however, introduced TEM image with corresponding elemental concentration proWle across the interface within 1 m. Also, the MgO,
revealed in other investigations [2326] against the alumina Wbres, was detected using
Auger spectra, which is known to have high surface sensitivity.
Finally, it can be stated that the interfacial reaction is a valid phenomenon according to
the present and previous work, but the extent of the reaction depends on the fabrication
processing, type of alumina Wbre, Mg matrix alloy, temperature of the Mg melt, and temperature of the preheated Wbres.
4.2. The role of alumina on the corrosion resistance
Magnesium is an active metal, and forms MgO at its surface when is exposed to the
atmosphere at room temperature. In the presence of moisture or aqueous environments,
the magnesium oxide is converted into magnesium hydroxide Mg(OH)2 which is stable only
at high pH values. However, the corrosion potential of magnesium in aqueous solutions

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A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

Fig. 13. SEM cross-sectional micrograph of Al2O3/AS41 Mg composite following 144 h immersion in pH 9.3
borax-buVered 3% NaCl solution.

was observed to be almost 1 V more noble than the standard potential of 2.37 V vs. NHE.
This implies that the Mg corrodes with formation of a fairly protective Wlm. Higher pH
values (>8.5), according to Pourbaix diagram, promotes stability of this Wlm to dominate
as a consistent passive Mg(OH)2 layer at pH 7 11.5. This passivation layer is destroyed in
the presence of several anions, such as chloride, sulphate and nitrate [27].
Regarding the corrosion behaviour of Mg MMCs, a particular concern must be paid to
the principle reasons aVecting the corrosion resistance of MMCs as postulated by Hihara
[2] in the introduction section. Galvanic corrosion is the primary prospect when the active
magnesium is coupled with a relatively noble material. The conductivity of the inert constituent plays an important role, and thereby Hihara and Latanision [10] stated that the galvanic corrosion is unlikely to take place between the Mg matrix and alumina Wbres since
Al2O3 is an insulator. Comparing the Ecorr of both alloy and composite recorded in the one
same solution, Tables 2 and 3, there was no signiWcantly evident diVerence. This substantiates primarily the expected non-existence of galvanic eVect between the MMC constituents.
4.3. Corrosion mechanism
Understanding the electrochemical behaviour of magnesium-based materials is imperative to ascertain their corrosion mechanism. Magnesium reacts with water, forming its
hydroxide and hydrogen, through the following reactions [20,22]:
Anodic reaction:
Mg ) Mg2 C C 2e and/or
Mg(s) C 2(OH) ) Mg(OH)2(s) C 2e
Cathodic reaction:
2H C C 2e ) H2(g) and/or
2H2O C 2e ) H2(g) C 2(OH)

A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

1127

The overall reaction is: Mg(s) + 2H2O ) Mg(OH)2(s) + H2(g).


Stability of the hydroxide Wlm is strongly inXuenced by the alloying elements and microstructure. Aluminium, the most customarily metal alloyed with magnesium, strongly
aVects the developed corrosion products and the evolved interfacial Wlms. Makar and
Kruger [28] aYrmed that the MgAl surfaces form a layered structure embracing an MgO/
MgAl oxide when exposed to the atmosphere, and thereby, ascribed the higher resistance
to breakdown of the passive Wlm formed on MgAl alloys in pH 10 chloride-containing
aqueous solutions to the beneWcial eVect of aluminium. Song et al. [29] proposed, based on
XPS studies on pure  and  phases (main constituents of MgAl alloys), a surface Wlm
model illustrating the electrochemical corrosion behaviour of the AZ91 Mg alloy. This
model showed that the surface Wlm on the  phase comprises three layers: one inner
enriched in Al, a middle containing mainly MgO, and the outer layer consisting of
Mg(OH)2. In contrast, the  phase developed a Mg/Al hydroxide on the Mg/Al oxide interface. Neubert and Bakkar [13] indicated that the corrosion progress of the AS41 Mg alloy
is determined by the stability of the corrosion products, which is improved by higher aluminium and silicon concentrations.
Consequently, based on these previous studies and on the microscopic and analytical
observations, a model explaining the corrosion mechanism of the studied Al2O3/Mg MMC

Fig. 14. Schematic representative model showing the corrosion mechanism of Al2O3/Mg MMC.

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A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

can be represented as shown in Fig. 14. From microstructure evidence, two Mg matrices
can be distinguished: the original Mg matrix, that contains the typical Al content of about
3 wt%, and the high aluminium zones (HA) extending around Al2O3 Wbres, which contain
about 9 wt% Al.
On the surface of the original Mg matrix, as a result of exposure to air, a MgO Wlm
formed. Because of the high aYnity of Al for O, Al2O3 compound is also expected to form.
XPS data reported, by Nordlien et al. [30] on oxide Wlm formed naturally on pure Mg as a
result of exposure to air indicated that a mixture of Mg, MgO, and Mg(OH)2 is formed.
Therefore, the surface Wlm on Mg matrix was represented to be Al-containing MgO/
Mg(OH)2 layer as shown in Fig. 14. When this surface is exposed to the aqueous solution,
Mg and/or MgO react with water forming a thick layer of Mg(OH)2. As the corrosion process continues, a barrier of Al-containing MgO/Mg(OH)2 layer, which is believed to control the corrosion performance, is formed. However, this layer is partially protective and it
is occasionally destroyed, especially in the presence of Cl ions. The destroyed points are
nucleation sites for pitting.
On the other hand, high aluminium (HA) zones have an initial air-formed Wlm enriched
in Al to the extent it may contain Al2O3. Nordlien et al. [31,32] have reported that this Wlm
is a mixture of Al2O3, MgO and Mg(OH)2. It is amorphous and dense, and responsible for
the passivity in aqueous environments. Thus, the initial Wlm on the HA zones is represented
as Al2O3/MgO-Mg(OH)2, which develops an outer layer, assumed to be Al-rich Mg(OH)2
as a result of exposure to the aqueous solution.
When the MMC is exposed to a corrosive environment, the Mg matrix has an anodic
behaviour compared with the adjacent (HA) zones, which hypothetically act as cathodic
sites. So, the corrosion of the composite initiates preferentially on the matrix near to (HA)
zones, with the formation of localised pits, which become deeper with time. The pit is
developed by the anodic reaction, producing Mg2+ ions which diVuse outwards from the
metal surface. Chloride ions migrate inwards into the pit, to maintain electroneutrality. As
corrosion advances, the pit grows larger and wider and undermines the partially protective
Wlm on the Mg matrix rather than the passive Wlm on the HA zones. At the same time, the
pit deepens at the expense of the Mg matrix avoiding the HA zones. The sites, in the vicinity of the alumina Wbres where HA zones are non-existent, are also susceptible to the initiation of pitting due to the discontinuity of the protective oxidehydroxide layer at the Wbre/
matrix interface.
5. Conclusions
1. Electrochemical test results and free immersion test data showed that the Al2O3/AS41
Mg MMC possessed a corrosion behaviour comparable to its pure matrix alloy.
2. The corrosion potential did not vary greatly or show a deWnite trend in relation to the
presence of Al2O3 Wbres. However, an increase in the degree of corrosion was attributed
to the presence of Al2O3.
3. No evidence of galvanic corrosion between the Wbres and matrix was observed, and neither was preferential corrosion at the Wbre/matrix interface. In contrast, the higher aluminium zones in proximity of the Wbres, that resulted from the interfacial reactions,
showed higher corrosion resistance than the original matrix.
4. In terms of the formation and stability of partially protective Wlms on magnesiumbased alloys, the corrosion mechanism involved was stated to be a localised type

A. Bakkar, V. Neubert / Corrosion Science 49 (2007) 11101130

1129

arising in low Al zones and induced by the resultant high Al zones which act as cathodic
sites.
5. In recommendation: The results substantiated the absence of both direct galvanic eVect
and interfacial attack attributable to the Al2O3 Wbres. Therefore, it is promising to
develop highly corrosion resistant MMCs based on Al2O3/Mg, by controlling the fabrication process and utilising corrosion resistant grades of the matrix alloy.
Acknowledgements
The authors would like to express their thanks to Mr. E. Herrmann for SEM investigations and to Mr. B. Brinkhaus for the metallographic preparation of specimens. Also
thanks are due to the Egyptian Ministry of High Education for partial funding provided to
Dr. A. Bakkar.
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