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Corrosion Science 44 (2002) 917925

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Corrosion behaviour of garnet particulate


reinforced LM13 Al alloy MMCs
K.H.W. Seah a,*, M. Krishna b, V.T. Vijayalakshmi c, J. Uchil d
a

Department of Mechanical and Production Engineering, National University of Singapore, 10 Kent


Ridge Crescent, Singapore 119260, Singapore
b
Department of Mechanical Engineering, R.V. College of Engineering, Bangalore-560059, India
c
Department of Chemistry, N.M.K.R.V. College for Women, Jayanagar, Bangalore-560011, India
d
Department of Material Science, Mangalore University, Mangalagangothri, Karnataka, India
Received 22 May 2000; accepted 23 May 2001

Abstract
This paper describes a study of the corrosion characteristics of LM13 Al alloy-based
composites reinforced with various amounts of garnet particulates. The weight loss method
was used and the corrodent was 1 M HCl solution at room temperature. The durations of the
tests ranged from 24 to 96 h. Corrosion tests were performed on the unreinforced matrix alloy
as well as on the various composites in both heat-treated and as-cast conditions. In each test,
the corrosion rates of the unreinforced matrix alloy and the composites were found to decrease
with duration of exposure to the corrodent. Solution heat treatment at 525C followed by
articial aging at 175C was found to improve the corrosion resistance of every specimen
tested. Corrosion resistance was also found to improve with increase in garnet content. An
attempt is made in the paper to explain these phenomena. 2002 Elsevier Science Ltd. All
rights reserved.
Keywords: LM13; Aluminium alloy; Garnet; Corrosion; Metal matrix composite

1. Introduction
Metal matrix composites (MMCs) oer designers many benets as they are
particularly suited for applications requiring good strength at high temperature,
good structural rigidity, dimensional stability, and light weight [15]. The trend is

Corresponding author. Tel.: +65-772-2212; fax: +65-772-1459.


E-mail address: mpeskh@nus.edu.sg (K.H.W. Seah).

0010-938X/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 0 - 9 3 8 X ( 0 1 ) 0 0 0 9 9 - 3

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towards safe usage of the MMC parts in the automobile engine, which work particularly at high temperature and pressure environments [6,7]. Particulate reinforced
MMCs have been the most popular MMCs over the last two decades. Of these,
ceramic reinforced Al-based MMCs are the most common. Although the incorporation of a second phase into a matrix material can enhance the physical and mechanical properties of the latter, it could also signicantly change the corrosion
behaviour.
Particulate reinforced Al-based MMCs nd potential applications in several
thermal environments, especially in automobile engine parts such as drive shafts,
cylinders, pistons, and brake rotors. Al-based MMCs which are used in automobile
engine parts normally encounter acidic environments containing chloride, sulphiate
and nitrate radicals, in addition to exhaust gases like CO2 , CO and NOx . MMCs
used at high temperatures should have good mechanical properties and resistance to
chemical degradation in air and acidic environments [8]. For high-temperature applications, it is essential to have a thorough understanding of the corrosion behaviour of the aluminium composites. Published data [911] indicate that the addition of
SiC particles do not appear to improve corrosion resistance on some aluminium
alloys because pits were found to be more numerous on the composites than on the
unreinforced alloys although they were comparatively smaller and shallower than
those on the unreinforced alloy. Gonzalez et al. [12] reported that the presence of SiC
particles does not give rise to signicant galvanic corrosion and no active phases are
formed at the matrix/particle interface. Nevertheless, the present study is aimed at
characterising the corrosion behaviour of LM13 Al alloy and the eect of reinforcing
it with garnet particles in both the as-cast and the heat-treated conditions.

2. Experimental procedure
2.1. Constituent materials of composites
The matrix alloy used for the composites is LM13 Al alloy, a material suitable for
mass production of lightweight castings which can either be sand-cast or die-cast.
The chemical composition of the LM13 alloy is given in Table 1.
Garnet, the reinforcement material, is abundantly available in the earth and has
a Mohrs hardness of 6.57.0 which is nearly equal to that of SiC. It is composed
of alumino-silicates of calcium, having the chemical formula Ca2 Al2 (SiO4 )3 and is
chemically inert at elevated temperatures. It does not have a sharp melting point
although it softens at temperatures of 11401280C.

Table 1
Chemical composition of matrix LM13 alloy by weight percentage
Mg

Si

Fe

Cu

Ti

Pb

Zn

Mn

Sn

Ni

Al

0.81.5

1012

1.0

0.71.5

0.2

0.1

0.5

0.5

0.1

1.5

balance

K.H.W. Seah et al. / Corrosion Science 44 (2002) 917925

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2.2. Preparation of the composites


The liquid metallurgy technique was adopted to prepare the LM13-based composites. In this technique, a measured quantity of preheated garnet particulates was
slowly added into the vortex created in the molten matrix alloy by stirring it with an
alumina-coated steel impeller in an inert gas atmosphere. The coating of alumina is
necessary in order to prevent the migration of ferrous ions from the stirrer to the
matrix alloy melt. The melt containing the reinforcement was then poured into the
lower half of the die (permanent mould) and the top half was brought down to apply
pressure on the melt as it solidied. The unreinforced matrix material was cast in the
same manner, except that no garnet particulates were added. LM13-based composites containing 2%, 4% and 6% by weight respectively of garnet particulates were
fabricated and tested, and their properties were compared with those of the unreinforced matrix alloy.
2.3. Specimen preparation
Cylindrical specimens of diameter 20 mm and height 20 mm were machined from
castings of the composite and the base alloy. Before corrosion testing, the specimen
surfaces were ground with 1000 grit silicon carbide paper and then polished using 3
lm diamond paste to obtain a good surface nish. The specimens were then washed
in distilled water, followed by acetone, and then allowed to dry thoroughly.
2.4. Heat treatment and aging
To study the eect of articial aging on the composites, some of the as-cast test
specimens were subjected to solution heat treatment at 525C for 48 h, quenched in
water at 80C and then aged at 175C for 4, 8 and 12 h, respectively.
2.5. Corrosion testing
The corrosion tests were static immersion tests conducted at room temperature
using the conventional weight loss method to an accuracy of 0.1 mg. Each specimen
was rst weighed before being immersed in 200 ml of 1 M HCl solution and later
taken out after 24, 48, 72, and 96 h respectively. HCl solution was selected as the
corrodent for accelerated results since the corrosion studies reported in this paper are
comparative ones. After each corrosion test, the specimen was immersed in Clarks
solution for 10 min and gently cleaned with a soft brush to remove adhered scales.
Clarks solution is a standard mixture containing potassium chloride, potassium
phthalate, potassium phosphate, boric acid and sodium hydroxide [13]. After drying
thoroughly, the specimens were weighed again. The weight loss was measured and
converted into corrosion rate expressed in mils penetration per year (mpy). The
corroded surfaces were studied using scanning electron microscopy (SEM).

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K.H.W. Seah et al. / Corrosion Science 44 (2002) 917925

3. Results and discussion


3.1. Microscopy
Fig. 1(a) shows that the unreinforced matrix alloy has a very thin discontinuous
layer on the surface with small dendrites growing. The photographic image is dependent principally on the mean atomic number of the dierent phases present in the
matrix alloy. Thus, the aluminium-rich regions are bright whereas the other elements
(Mg, Si, Fe, Cu, etc.) turn out dark in the optical microscope.
A typical photomicrograph of the transverse section of an as-cast MMC specimen
containing 6% by weight of garnet is shown in Fig. 1(b). The distribution of particulates appears to be reasonably homogenous, although there was a tendency for
the particulates to be aligned more in the longitudinal direction.

Fig. 1. (a) Photomicrograph showing dendritic structure of unreinforced LM13 alloy. (b) Microstructure
of LM13-based MMC reinforced with 6% garnet.

K.H.W. Seah et al. / Corrosion Science 44 (2002) 917925

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Table 2
Corrosion rate of as-cast and heat-treated LM13 alloy and MMCs for dierent durations of exposure to
HCl solution
Aging time (h)

Garnet content (wt.%)

Corrosion rate (mpy)


After 24 h
exposure

After 48 h
exposure

After 72 h
exposure

After 96 h
exposure

0
2
4
6

10.93
10.80
9.15
8.66

5.64
5.52
5.07
4.68

4.12
4.02
3.52
3.55

3.21
3.11
3.06
3.00

0
2
4
6

7.97
7.47
7.18
6.60

4.47
4.24
4.20
4.47

3.25
3.16
2.82
2.79

2.97
2.83
2.41
2.31

0
2
4
6

7.72
7.38
6.16
6.40

3.65
3.63
3.60
3.58

2.88
2.83
2.72
2.91

2.30
2.12
2.11
2.10

12

0
2
4
6

7.68
7.09
5.99
5.79

3.98
3.10
3.37
3.35

2.83
2.56
2.67
2.69

2.22
2.02
2.01
1.95

3.2. Eect of duration of exposure to corrodent


Table 2 shows the results of all the corrosion tests conducted on the unreinforced
matrix alloy and on the MMCs in the as-cast and heat-treated conditions in 1 M HCl
solution. These results are represented graphically in Figs. 2 and 3. Each result
tabulated is an average obtained from six identical tests. In each case, the error bars
(not shown) are 35% from the mean value.
Fig. 2 shows plots of the corrosion rate (in mpy) of the as-cast unreinforced
matrix alloy and composites in HCl solution against exposure time (in hours), as well
as for the same materials aged for 4, 8 and 12 h respectively. It can be seen that in
every case, there is a decrease in corrosion rate with increase in duration of exposure
to the corrodent, implying that the corrosion resistance of the materials tested increases as the exposure time is increased. Visible inspection showed that there were
no hydrogen bubbles clinging onto the surface of the test specimens. The phenomenon of monotonically decreasing corrosion rate with respect to time indicates some
passivation of the matrix alloy. De Salazar et al. [14], in their study of aluminareinforced Al-based MMCs, observed that a protective black lm is formed on the
surface consisting of hydrogen hydroxy chloride, which apparently retards the corrosion. Castle et al. [15], who studied SiC particulate reinforced Al-based MMCs,
believe that the black lm formed on the surface consists of an aluminium hydroxide
compound which protects the bulk material from further corrosion in the acid
medium. The exact chemical nature of such a protective lm is still not fully

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K.H.W. Seah et al. / Corrosion Science 44 (2002) 917925

Fig. 2. Graphs of corrosion rates of LM13 alloy and MMCs vs. exposure time in 1 M HCl solution for
various durations of aging.

understood. However, it can be seen in each graph that as duration of exposure is


increased, the benecial eect on corrosion resistance levels o, probably due to the
protective layer reaching a steady state with time.
3.3. Eect of heat treatment
Fig. 3 is a plot of corrosion rate after 24 h exposure time against the duration of
aging for the unreinforced matrix alloy and the MMCs. It can be seen that aging for
4, 8, and 12 h (at 175C) signicantly improves the corrosion resistance of every
specimen tested. Solution heat treatment and aging is used to improve material
strength for precipitation-hardening alloys. It can be seen that aging for 4 h causes

K.H.W. Seah et al. / Corrosion Science 44 (2002) 917925

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Fig. 3. Eect of articial aging on corrosion rate of LM13 alloy and MMCs after 24 h of exposure in 1 M
HCl solution.

the corrosion rate to drop by about one-third. One possibility is that the articial
aging has enhanced the protective layer of aluminium oxide described above, conferring greater corrosion resistance to the corrodent which is seen in all the specimens, unreinforced as well as reinforced, no matter what the garnet content is.
As aging duration is increased beyond 4 h, the benecial eect on corrosion resistance apparently levels o, probably due to the protective layer of aluminium oxide
reaching a steady state with time during aging, which was done after the specimen
had been machined.
3.4. Eect of garnet content
From Table 2 and Fig. 2, it is apparent that for materials in both the as-cast and
aged conditions, there is a trend of decreasing corrosion rate with increase in garnet
content, especially for shorter exposure times. For long exposure times, however, this
eect is less pronounced.
The corrosion rate of the unreinforced matrix alloy is higher than those of the
composites because in the former, there is no reinforcement phase and the matrix
alloy does not have much corrosion resistance to the acid medium. Garnet, being a
ceramic, remains inert and is itself unaected by the acidic medium during the tests.
The inert garnet particulates are also not expected to aect electrochemically the
corrosion mechanism of the composite. Nevertheless, the results show an improvement in corrosion resistance as the garnet content is increased in the composite,
indicating that the garnet particulates do inuence the corrosion characteristics of
the composites albeit not electrochemically. Sharma et al. [16] obtained similar

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K.H.W. Seah et al. / Corrosion Science 44 (2002) 917925

results in short glass ber reinforced ZA-27 aluminium alloy composites, observing
that the corrosion resistance increases with increase in reinforcement content.
Wu Jianxin et al. [17] in their work on corrosion of SiC particulate reinforced Albased MMCs state that this corrosion behaviour is not aected to a signicant extent
by the presence of the SiC, although these particulates denitely play a subsidiary
role as physical barriers to MMC corrosion. According to them, particulates act as
inert physical barriers to the initiation and development of pitting corrosion, modifying the microstructure of the matrix material and hence improving the corrosion
resistance of the MMC.
Another reason for the decrease in the corrosion rate could be the formation of a
magnesium inter-metallic layer adjacent to the particle during fabrication of the
specimen as discussed by Trzaskoma [9]. McIntyre et al. [18], in their research on
MMCs, showed that the magnesium inter-metallic compounds are more active than
the alloy matrix causing more pitting in the particle/matrix interfaces because of the
higher magnesium content in such regions. These electrochemically active crevices
act as sacricial anodes and protect the rest of the matrix, restricting pit formation
and propagation to only these crevices [19]. Further evidence of the formation of a
magnesium layer can be found in another paper by Sharma [20].

4. Conclusions
In the present study of garnet particulate reinforced LM13 Al alloy MMCs,
corrosion resistances of the unreinforced matrix alloy and the composites were found
to improve with duration of exposure to the corrodent. Solution heat treatment at
525C followed by articial aging at 175C was found to improve the corrosion
resistance of every specimen tested. The improvement in corrosion resistance due to
these two factors is attributed to a protective layer formed on the surface of the
material. Corrosion resistance was also found to improve with increase in garnet
content, probably due to the garnet particles acting as physical barriers to the corrosion process.

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