Electrochimica Acta 88 (2013) 129134

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Electrochemical behavior of a discontinuously A6092/SiC/17.5p metal matrix

composite in chloride containing solution
Abdel Salam Hamdy a, , Feras Alfosail b , Zuhair Gasem b
a
b

Central Metallurgical Research and Development Institute, Cairo, Egypt

Center of Research Excellence in Corrosion, King Fahd University of Petroleum & Minerals, Dhahran, Saudi Arabia

a r t i c l e

i n f o

Article history:
Received 6 October 2012
Received in revised form 18 October 2012
Accepted 18 October 2012
Available online 26 October 2012
Keywords:
Corrosion assessment
Silicon carbide
Aluminum matrix composite
Automotive and aerospace materials
Electrochemical impedance spectroscopy

a b s t r a c t
Aluminum alloys are used widely in automotive and aerospace industries. The demand for weight savings
materials of superior mechanical, thermal and electrical properties has focused attention on aluminum
metal matrix composites (AMMCs). AMMCs have been applied in areas that can cost-effectively capitalize on improvements in specic stiffness, specic strength, fatigue resistance, wear resistance, and
coefcient of thermal expansion. However, AMMCs typically have lower damage tolerance properties
than their unreinforced counterparts, and hence the extent of application in primary structures has been
limited. In this paper, the corrosion resistance of ALCOA peak-aged Al6092/SiC/17.5p composite has been
evaluated by recording of impedance spectra during immersion over one week in an air-exposed 3.5%
NaCl. Results conrmed the occurrence of galvanic, crevice, intergranular corrosion and pitting attack due
to the inhomogeneous structure of the composite which is the main reason behind enhancing the corrosion susceptibility. This paper formulates a complex hypothesis concerning the corrosion mechanisms
of A6092/SiC/17.5p metal matrix composite in chloride containing solution as a function of time. A fourstage corrosion mechanism has been proposed to explain the sequence and the reasons of occurrence of
each corrosion form.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Aluminum alloys are used widely in the aerospace, automotive
and architectural industries. The increased demand for improved
mechanical, electrical and physical performance and weight savings has focused attention on a number of advanced materials, such
as nano-structured materials, ceramics and composites.
A composite material consists of two main constituents: a
matrix and reinforcement materials. Composite materials are a
rapidly growing class of tailor-making materials. They can be classied, based on the matrix, to include organic matrix composites,
ceramic matrix composites and metal matrix composites [1].
Metal matrix composites are the most common class of composites used in aerospace and automotive industries and can be
dened by the type of metal matrix, type of reinforcement, and
reinforcement geometry. According to the type of metal matrix,
most metallic systems such as Al, Br, Fe, Mg, Ti, have been explored.
However, aluminum is the most commonly used in practical.

Corresponding author at: Central Metallurgical Research and Development

Institute, Cairo, 5 Egypt. Tel.: +20 2 1061607279; fax: +20 2 25010 639.
E-mail address: asalam85@yahoo.com (A.S. Hamdy).
0013-4686/$ see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2012.10.079

According to type of the reinforcement materials, the reinforcements can be ceramics such as Al2 O3 , SiC, B4 C, TiC, graphite to
provide a very benecial combination of stiffness, strength, and
relatively low density. Or, in some cases, metallic materials such as
tungsten or steel bers can be used as reinforcements.
According to the geometry of the reinforcement materials, the
reinforcement can be in the form of continuous ber, chopped ber
or whisker, and particulate. Typically, the selection of the reinforcement morphology is determined by the required property/cost
combination. Generally, the reinforcements in the particulates
geometry provide a comparatively more moderate but isotropic
increase in properties, and are typically available at the lowest cost
[2].
Aluminum composite, AMMCs, materials are formed by the
addition of a second phase, generally a ceramic material, to an
aluminum matrix. AMMCs are used extensively in aerospace,
automotive and military applications due to various reasons including weight reduction, corrosion and wear resistance, erosion
resistance, high-temperature performance, thermal and acoustical
insulation, electrical performance and life cycle cost reductions [1].
Military aircraft as well as ground vehicles and tactical weapons
employ composite materials in order to provide better mobility due
to weight reductions offered. Many of the aircraft structure applications require a combination of adequate strength, damage tolerance

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A.S. Hamdy et al. / Electrochimica Acta 88 (2013) 129134

Table 1
The chemical composition of aluminum alloy 6092.
Elements

Si

Fe

Cu

Mg

Zn

Al

Composition (wt%)

0.8

0.3

1.0

1.2

0.25

Balance

and corrosion resistance. MMCs typically have lower damage tolerance properties than their unreinforced counterparts, and hence
the extent of application in primary structures has been limited.
However, MMCs have been selected for some aircraft structures,
such as F-16 aircraft, Airbus, and the Eurocopter rotor sleeve [2].
Aluminum-based, particulate-reinforced AMMCs have been the
most popular due to their low density and isotropic properties
[3]. Although the incorporation of a second phase into a matrix
material can enhance the physical and mechanical properties of an
MMC, such an addition could also signicantly change its corrosion
behavior [46].
Several particulate such as alumina, graphite, SiC, have been
used as reinforcements for AMMCs. However, SiC is one of the most
common reinforcements used in Al-based MMCs [6]. SiC-AMMCs
were used to replace aluminum tubes in the catamaran Stars and
Stripes88 resulting in 20% weight savings in comparison to monolithic aluminum [7].
In contrast to aluminum alloys, relatively little is known about
the corrosion behavior of aluminum MMC and the role of the reinforcement in the corrosion process. Some researchers reported that
the corrosion resistance of composite materials decreases in NaCl
solution [17]. However, another research group investigated the
corrosion behavior of Al 6092/17.5 SiC(p) and reported that the
material offered a good resistance to corrosion in 3.5% NaCl as
measured by weight loss, salt spray chamber and electrochemical studies [8]. Therefore, the objective of this work is to provide a
better understanding about the electrochemical corrosion behavior
of A6092/SiC/17.5p metal matrix composite in 3.5% NaCl solution using EIS techniques. Surface examination will be performed
by scanning electron microscopy (SEM), visual inspection, optical
micrography, and energy dispersive X-ray (EDS) analyses before
and after immersion in NaCl corrosive solution.

were cut into 60 mm 30 mm and 3 mm thickness. Aluminum

samples were mechanically ground using SiC paper starting
from coarse to ne with grades of 240, 320, 400, and 600 using
metallographic techniques. Samples were degreased with acetone,
washed with distilled water and dried for 5 min at 55 C. Table 1
summarizes the chemical composition of aluminum alloy 6092.
3. Testing methods
3.1. Electrochemical impedance spectroscopy
Electrochemical impedance spectroscopy measurements were
carried out in aerated 3.5% sodium chloride (NaCl) solution at room
temperature for up to seven days. The exposed surface area was
2.30 cm2 and all data were normalized to 1 cm2 .
A three-electrode set-up was used with impedance spectra
being recorded at the corrosion potential ECorr . A saturated calomel
reference electrode (SCE) was used as the reference electrode. It
was coupled to a graphite rod serving as a counter electrode. EIS
was performed between 0.01 Hz and 65 kHz frequency range using
a frequency response analyzer GAMRY Instruments Reference 3000
ac/dc potentiostat. The amplitude of the sinusoidal voltage signal
was 10 mV.
3.2. SEMenergy-dispersive spectrometry
SEM images were obtained using a digital scanning electron
microscope Model JEOL JSM 6460 Oxford Instruments, Japan, was
used to examine the corrosion products after immersion. Microprobe analysis was performed using Oxford Instrument INCA
energy dispersive spectrometry, EDS.
3.3. Surface morphology
Corrosion morphology was examined with a metallographic
microscope LEICA DMR with a Quips programming window, LEICA
Imaging Systems Ltd., Cambridge, UK.

2. Experimental

4. Results and discussion

2.1. Materials and surface preparation

4.1. Surface examinations

Aluminum alloy 6092 reinforced with 17.5 vol% SiC T6 metal

matrix composite was supplied as sheets from ALCOA. Samples

4.1.1. Visual inspection and optical microscopic examination

Microscopic examination of the as-polished virgin composite samples before corrosion revealed presence of many surface
defects. The surface roughness was very high as shown in Fig. 1.

Fig. 1. Optical microscopic images of the composite samples before corrosion. (The
macrograph shows the surface defects and high surface roughness of the virgin
composite samples before corrosion.)

Fig. 2. Macro-image of virgin composite samples after one week in NaCl solution.

A.S. Hamdy et al. / Electrochimica Acta 88 (2013) 129134

Visual inspection and macrographs of the as-polished after

seven days of immersion in 3.5% NaCl solution showed severe pitting and crevice corrosion (Fig. 2). The average number of pits
formed on the surface of the as-polished samples was 10 pit/cm2 .
It was noticed that pits of different sizes are distributed randomly
at the surface. Some of them are tiny; while others are large, deep
or wide.
4.1.2. SEMEDS micrographs
Surface examination using SEM micrograph of the as-polished
virgin composite samples before corrosion revealed the presence
of many surface defects, high surface roughness and intermetallic
precipitates (Fig. 3a) to be the preferred sites for initiation of pits
[8].
Localized corrosion initiated on a A6092-T6/SiC/17.5p in an
air-exposed 3.5 wt% NaCl solution. Scanning electron microscopy

131

indicated that corrosion mainly initiated around SiC reinforcement

particles. After seven days of immersion in corrosive NaCl, two
forms of corrosion have been identied; namely pitting corrosion
and intergranular corrosion attack (Fig. 3b and c).
Bavarian et al. [9] found that the corrosion of AMMC-25%SiCp
was observed only when the breakdown of passive lm occurred,
which exposed active aluminum and noble SiC particles to the corrosive environment and initiated a galvanic corrosion. Ding and
Hihara [10] reported that although it is not necessary for Cl to
be present for corrosion initiation and propagation, the presence of
Cl accelerated the corrosion process. Accordingly, we suggest that
galvanic corrosion might be formed in the early stage of exposure
to corrosive NaCl solution or even before the exposure to chloride
solution (Fig. 4) due to the sharp difference in the potential between
SiC particles (act as cathode) and the aluminum matrix (acts as
anode).

Fig. 3. SEMEDS of the composite samples before and after one week in NaCl solution.

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A.S. Hamdy et al. / Electrochimica Acta 88 (2013) 129134

Fig. 4. Schematic representation (not to scale) showing the proposed mechanism of corrosion at the interface between Al6092 alloy matrix and SiC particle.

Galvanic corrosion was not the only mechanism proposed for

corrosion of composite materials in chloride media. Other two possible mechanisms have been proposed [7,11]. The rst one was
suggested by Hihara et al. [7] and is based on crevice formation at
the reinforcementmatrix interface either by debonding or some
other mechanism. The second mechanism is hypothesized that
a thin layer of Al4 C3 formed at the SiCAl interface during the
processing of the Al/SiC MMC as reported by Iseki et al. [11]. In
the presence of water or moisture, Al4 C3 readily hydrolyzes and
can induce crevices at the AlSiC interfaces:
Al4 C3 + 12H2 O = 4Al(OH)3 + 3CH4

(11)

The schematic diagram in Fig. 4 illustrates the possible formation of Al4 C3 interphase at the Al/SiC interface and the hydrolysis of
Al4 C3 is likely the cause of a preferential dissolution of the interface
between the alloy matrix and the SiC reinforcing particles.

5. Electrochemical impedance spectroscopy

A series of electrochemical experiments was performed on
samples of A6092/SiC/17.5p in order to investigate potential
applications for these promising materials in automotive and
aircraft industries in presence of a corrosive chloride medium. The

A.S. Hamdy et al. / Electrochimica Acta 88 (2013) 129134

133

Fig. 5. Electrochemical impedance spectroscopy of aluminum metal matrix composite over one week immersion in corrosive NaCl solution.

corrosion resistance of the AMMC material has been evaluated by

recording of impedance spectra during immersion in 3.5% NaCl
over one week.
Ongoing research by our team showed that the cathodic current density for oxygen reduction in 3.5% NaCl increased, which

was attributed to electrochemically active interfaces between the

matrix and the reinforcement particles. The observed reduction
in corrosion protection was believed to result from corrosionsusceptible interfaces formed between the reinforcement particles
and the matrix [12].

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According to Nyquist plots (Fig. 5a), the corrosion started too

early where a small tail representing the diffusion process was
observed in the impedance spectra recorded after only 30 min
of immersion in corrosive NaCl solution. This result is in agreement with the previous observations by Hihara and his coworkers
[7,10] who noticed that the corrosion initiation and propagation of
the AMMC started even before exposure to chloride media. They
attributed such behavior to the galvanic action between SiC reinforcements and the aluminum matrix.
Accordingly, we suggest that the whole corrosion process has
been done, as a function of time, and passed with four stages. The
rst and early stage of corrosion was galvanic corrosion due to galvanic action between the inert SiC reinforcements (act as cathode)
and the aluminum matrix (acts as anode) in presence of moisture. Then, crevice corrosion is the second stage of corrosion to
take place due to the presence of the deposits (corrosion products resulted from the galvanic corrosion in the rst stage) and
the inert SiC reinforcements themselves. This hypothesis matches
with the mechanism proposed by Iseki et al. [11] in which a thin
layer of Al4 C3 formed at the SiCAl interface during the processing
which can be hydrolyzed to form crevice corrosion at the AlSiC
interfaces.
The third stage is the initiation and propagation of pitting
corrosion due to the differential aeration and formation of microelectrochemical cells at the materials surface. This stage of pitting
corrosion formation has been attributed to nucleation of precipitates at matrixreinforcement interfaces in the composite material
[13,14].
Parallel to this stage, a fourth stage in which intergranular corrosion can also occur through the electrochemical dissolution of
the active elements (such as Al and other minor alloying elements)
after relatively long immersion time in NaCl leaving the surface
cracked as mud-like structure. Moreover, increasing the corrosion
around the SiC particulates can result in debonding of these particles from the surface leaving hole similar to pitting (Figs. 3c and 4).
As expected, the surface resistance of the AMMC to localized
corrosion decreased with increasing the exposure time in NaCl.
The measured surface resistance after 30 min, one day and one
week of immersion in NaCl solution was 15 103 , 7.1 103 , and
5.8 103  cm2 respectively. This result conrms the previous
observations by SEM, optical microscope and visual inspection
where the number and size of pits increased by increasing the
immersion time in corrosive NaCl.
The resistance and () angle spectra in Bode plots (Fig. 5b
and c) provide further explanation of these observations where
the samples exposed to corrosive NaCl solution for short time
(30 min) showed the highest polarization resistance (Rp ) compared
with those exposed for longer immersion times (one day and one
week). The Rp values were 20 103  cm2 , 10 103  cm2 and
7 103  cm2 for the samples immersed in NaCl for 30 min, one day
and one week, respectively. These results conrm our hypothesis
about the four-stage mechanism of AMMC corrosion in corrosive
chloride solution.
6. Conclusions
A four-stage mechanism for corrosion of A6092/SiC/17.5p
metal matrix composite in NaCl solution has been proposed. The

mechanism suggested that the time of immersion in corrosive

media has a detrimental effect on the type of corrosion formed. It
was hypothesized that galvanic corrosion is naturally occurred at
the surface in presence of moisture due to galvanic action between
SiC reinforcements (act as cathode) and the aluminum matrix (acts
as anode). Crevice corrosion was formed in the second stage due
to the deposition of a thin layer of Al4 C3 at the SiCAl interface and
the formed corrosion products due to the galvanic corrosion in the
rst stage. In the third stage, pitting corrosion was enhanced due
to the differential aeration and formation of micro-electrochemical
cells at the materials surface in addition to the nucleation of precipitates at matrixreinforcement interfaces. In the fourth stage,
intergranular corrosion could also take place as a result of the
electrochemical dissolution of the active alloying elements segregated at the grain boundaries.
Increasing the exposure time in NaCl solution increases the corrosion around the SiC particulates and can result in debonding some
of these particles leaving hole at the surface.
The proposed four-stage mechanism provides new insights
towards a better understanding of the practical electrochemical behavior of A6092/SiC/17.5p metal matrix composite in Cl
containing media and hence, designing suitable coatings for
corrosion protection which is the main objective of our next
articles.
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