Materials and Corrosion 2005, 56, No.
1 Magnesium alloys in commercial engine coolants
Corrosion of magnesium alloys in commercial
engine coolants
A number of magnesium alloys show promise as engine block
materials. However, a critical issue for the automotive industry
is corrosion of the engine block by the coolant and this could limit
the use of magnesium engine blocks. This work assesses the corro-
sion performance of conventional magnesium alloy AZ91D and a
recently developed engine block magnesium alloy AM-SC1 in sev-
eral commercial coolants. Immersion testing, hydrogen evolution
measurement, galvanic current monitoring and the standard
ASTM D1384 test were employed to reveal the corrosion perfor-
mance of the magnesium alloys subjected to the coolants. The re-
sults show that the tested commercial coolants are corrosive to the
magnesium alloys in terms of general and galvanic corrosion. The
two magnesium alloys exhibited slightly different corrosion resist-
ance to the coolants with AZ91D being more corrosion resistant
1 Introduction
There is growing interest in magnesium alloys in the auto-
motive industry and a magnesium engine block has the poten-
tial to significantly reduce the weight of an automobile, and
thus its fuel consumption and environmental pollution levels.
A new magnesium alloy AM-SC1 has been recently devel-
oped for this purpose [1, 2].
In automobile engines, coolant corrosion is an important
issue and considerable research has been conducted with re-
gard to coolant corrosion and inhibition [3 – 8] and various
brands of coolants have been developed and are commercially
available in the market for aluminium and cast iron engine
blocks. The main composition of the commercial coolants
is 30 vol.%
70vol.% ethylene glycol, and the added inhibi-
tors normally include molybdate, phosphate, borate, nitrate,
nitrite, tolyltriazole, benzoate and silicate. In addition,
some organic acid-based long life coolants have recently
emerged in the market, which contain organic acid carboxy-
late ions [9 – 11] as the main inhibitors.
It should be stressed that to date all inventions in coolants
and inhibitors are based on their ability to protect the tradi-
tional engine materials, such as cast iron, aluminium, copper,
steel and lead-tin solder. It is still unclear whether the existing
commercial coolants and inhibitors can be used for a non-tra-
ditional engine material, such as magnesium alloys. There is
no publication on the corrosivity of these coolants to magne-
sium alloys, except some limited results in an ASM hand book
[12], indicating that magnesium is suitable for exposure to any
* G. Song, D. H. StJohn,
CRC for Cast Metals Manufacturing (CAST), Division of Mate-
rials, School of Engineering, The University of Queensland,
Brisbane, QLD 4072 (Australia)
F 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
15
G. Song and D. H. StJohn
than AM-SC1. The corrosivity varied from coolant to coolant. Gen-
erally speaking, an organic-acid based long life coolant was less
corrosive to the magnesium alloys than a traditional coolant.
Among the studied commercial coolants, Toyota long life coolant
appeared to be the most promising one. In addition, it was found
that potassium fluoride effectively inhibited corrosion of the ma-
gnesium alloys in the studied commercial coolants. Both general
and galvanic corrosion rates were significantly decreased by addi-
tion of KF, and there were no evident side effects on the other en-
gine block materials, such as copper, solder, brass, steel and alumi-
nium alloys, in terms of their corrosion performance. The ASTM D
1384 test further confirmed these results and suggested that Toyota
long life coolant with 1%wt KF addition is a promising coolant for
magnesium engine blocks.
concentration of ethylene glycol, but inhibitors may be re-
quired for warranted service. Recently, Song and StJohn
[13] investigated the corrosion behaviour of pure magnesium
in ethylene glycol solutions and pointed out that the ethylene
glycol solutions were in fact corrosive to pure magnesium.
This implies that magnesium alloys may suffer unacceptable
corrosion attack in the commercial coolants.
Theoretically, most inhibitors only selectively inhibit the
corrosion of certain metals. It is unlikely that the inhibitors
added to the commercial coolants will protect magnesium al-
loys from corrosion, because protection of magnesium alloys
was not considered in developing these commercial coolants.
Some companies have realised the difficulty of using the ex-
isting coolants for magnesium alloys and are developing new
coolants with new inhibitors for magnesium alloys [14].
It is a normal approach as shown in some patents [14], to
develop a new brand of coolant for magnesium alloys by start-
ing with screening inhibitors in ethylene glycol. This approach
will lead to numerous standard tests for various coolant prop-
erties and performance being used where going from an initial
ethylene glycol and inhibitor recipe to a final coolant product.
The aim of this paper is to directly identify a suitable com-
mercial coolant and an inhibitor for magnesium alloys through
assessing the corrosion performance of magnesium alloys in
existing commercial coolants. The reason for directly screen-
ing commercial coolants for magnesium alloys is that all the
commercial coolants have passed various performance and
property tests, including their corrosivity to all the traditional
engine materials, such as aluminium alloys, steel, copper,
brass, solder, etc. These performance and property require-
ments, including corrosivity to the traditional materials, are
also critical to a new coolant for magnesium engine blocks,
as some of these traditional materials will be used in the con-
struction of magnesium engines. Therefore, as long as a cool-
ant is measured to be non-corrosive to magnesium alloys, it is
likely to meet the other essential requirements of a normal
DOI: 10.1002/maco.200403803
16 Song and StJohn
engine coolant, and does not need to be tested again for those
essential performance and properties or its corrosivity to the
traditional materials. Moreover, in selection of inhibitors for
magnesium alloys, only those inhibitors that are effective for
magnesium alloys should be considered, as there are already
inhibitors in the commercial coolants for the other engine
block materials.
2 Experimental
2.1 Specimens
Magnesium alloys AM-SC1 and AZ91D as well as alumi-
nium alloy AlSi9Cu3 were tested in this study. AM-SC1 is a
new alloy with rare earth elements, zinc and zirconium as the
main alloying elements, which was developed as an engine
block material [1, 2]. AZ91D is one of the most common ma-
gnesium alloys, containing Al and Zn as its primary alloying
elements. AZ91D could be used for components attached to
the magnesium engine block such as a water pump housing.
AlSi9Cu3 is one of the current aluminium engine block alloys
and due to the copper content represents the worst case alu-
minium material in terms of corrosion resistance that is likely
to be in contact with a magnesium engine block.
In immersion tests, the alloys were cut into small coupons
with dimensions 1  1  1 cm. For electrochemical tests, the
coupons were made into electrodes with only one surface
1  1 cm unsealed as the working area. These alloys were
also cut into plates 2  5  0.2 cm, the same size as the metal
plates used in the ASTM D 1384 standard for the standard
tests.
2.2 Coolants
Table 1 lists commercial coolants used in this study.
MBL and CTL are traditional coolants and LLC-T and
LLC-F are representatives of modern organic acid-based
long life coolants. LLG is a traditional coolant with some or-
ganic inhibitors.
To separately measure the effect of a fluoride inhibitor, dif-
ferent weight percentages of potassium fluoride, KF, were
added into the above coolants.
Table 1. Commercial coolants used
Abbreviation Commercial name
MBL Mobil coolant 33 plus
CTL Castrol
LLG Tectaloy Green
Long life glycol
LLC-T Long life coolant (Red), Genuine
Toyota part
LLC-F Long life anti freeze/anti boil concentrate
(Red), Genuine Ford part
Materials and Corrosion 2005, 56, No. 1
2.3 Testing methods
In the following tests, all the potentials referred to
are relative to the silver/silver chloride electrode.
2.3.1 Immersion, hydrogen collection and weight loss
measurement
Before immersion, the specimens were polished with up to
1200# emery paper, cleaned with distilled water and acetone,
dried and weighed for the original weight (w0), and then tied
with a fine PVC string and hung in 800 ml tall form beakers
that contained 500 ml of coolant. Immersion tests were con-
ducted at controlled temperatures. The duration of immersion
was 2 weeks. At the same time, hydrogen evolved from the
magnesium specimens was collected. The method of collect-
ing hydrogen to estimate the corrosion rate of a magnesium
alloy has been illustrated by Song et al [15, 16] and will
not be repeated here. After immersion, the loose corrosion
products on the specimen surfaces were removed with a brush.
The corrosion products that could not be brushed off were re-
moved by immersing these magnesium specimens in a chro-
mic solution (200 g/L CrO3 þ 10 g/L AgNO3) for 5
10 mi-
nutes. The specimens were subsequently washed in deminer-
alised water, dried and weighed again to obtain the final
weight (w1). The weight loss caused by corrosion in the cool-
ant was then calculated (w0-w1).
The weight loss results of the immersion tests represent the
general corrosion performance of the specimens. There is no
specific criterion for an acceptable corrosion rate for magne-
sium alloys in coolants. However, according to ASTM D4340,
a rate of weight loss greater than 1 mg/cm2/week for an alu-
minium alloy should be rejected. Considering that the same
volume loss caused by corrosion should be used as the criter-
ion for the acceptance of a magnesium alloy, 0.67 mg/cm2/
week was therefore regarded as an acceptable threshold for
magnesium alloys.
2.3.2 Galvanic current measurement
Magnesium and aluminium electrodes were immersed in a
beaker of the coolant, face to face with a fixed distance (2 cm)
between them. The galvanic current between these two elec-
trodes was then monitored. For magnesium alloys, the accep-
Details as per described on the product
Pre-mixed, ready-to-use, precise blend of 33% ethylene glycol with
inhibitors
Pre-mixed, ready-to-use, precise blend of 33% ethylene glycol with
inhibitors
Pre-mixed concentrated ethylene glycol, diluted to 33% ethylene
glylcol with demineralised water in this study.
934 ml/L ethylene glycol and 10 mg/kg denatonium benzoate.
1:1 diluted with demineralised water for use
950 mg/L ethylene glycol and 10 ppm denatonium benzoate as a
bittering agent.
1:1 diluted with demineralised water for use
Materials and Corrosion 2005, 56, No. 1
table threshold of corrosion rate of 0.67 mg/cm2/week corre-
sponds to a current density of 8.8 lA/cm2. Therefore, 8.8 lA/
cm2 will be regarded as an acceptable galvanic current density
threshold for magnesium in this test.
2.3.3 Polarisation curve
Polarisation curves of the specimens were measured in an
electrolytic cell containing about 500 mL of the coolant. The
electrodes were polished and cleaned prior to measurement in
the same way as specified in the immersion, hydrogen collec-
tion and weight-loss measurements. A piece of platinum net
was used as a counter electrode in the cell. The potential scan-
ning rate was 10 mV/min.
2.3.4 ASTM D1384
ASTM D1384 was designed to simulate the coolant circuit
in an engine assembly. In this study, it was slightly modified
with a magnesium plate and used to confirm the results ob-
tained from the immersion and galvanic current measure-
ments. Commercially made coupon bundles as per described
in ASTM D1384 were purchased and used in this study. The
steel plate in the standard bundle was replaced by a magne-
sium alloy plate. This is because steel is in the most severe
galvanic corrosion position in the bundle. When the magne-
sium alloy plate is fixed there, it will be in contact with a steel
spacer and adjacent to brass and iron plates. The detailed test-
ing procedures followed the standard specification.
3 Results and discussion
3.1 The performance of AM-SC1 in the selected coolants
Although the corrosion rates are different for each of the
selected coolants, the corrosion behaviour of AM-SC1 is si-
milar in various coolants. The corrosion rates of AM-SC1 are
summarised in Table 2. The general corrosion rates were mea-
sured after two weeks of immersion, and the galvanic currents
were determined after the currents became stable usually after
about 4 hours of immersion.
Table 2 shows that none of the studied commercial coolants
has acceptable corrosivity to AM-SC1 if the general and gal-
vanic corrosion rates at room and high temperatures are con-
sidered. This indicates that an engine block made of AM-SC1
Table 2. Corrosion performance of AM-SC1 in various coolants
coolants General corrosion at 25 8C General corrosion at 95 8C
(mg/cm2/week) (mg/cm2/week)
MBL 12
13
0.5
CTL 8
9
0.4
LLG 1.5
2 1.5
1.8
LLC-F 1.2
1.7 0.8
1.1
LLC-T 0.12
0.17 0.15
0.25
Magnesium alloys in commercial engine coolants 17
alloy will suffer from either general or galvanic or combined
corrosion attack all the time no matter whether the vehicle is
running or not if the selected commercial coolants are used.
In Table 2 there are also some promising results. The cor-
rosivity of LLC-T and LLC-F is very close to the acceptable
threshold. These two coolants could be modified to meet the
corrosivity requirements for AM-SC1 alloy.
3.2 Inhibitive effect of KF
It has been demonstrated [13] that fluorides can react with
magnesium and form a low solubility MgF2 film on pure ma-
gnesium, which effectively inhibits the corrosion of pure ma-
gnesium in ethylene glycol solutions. Since the matrix of ma-
gnesium alloys is similar to pure magnesium in crystal struc-
ture and ethylene glycol is the major component of commer-
cial coolants, magnesium alloys are expected to be well pro-
tected from corrosion attack by fluorides in commercial cool-
ants. This expectation is examined as follows.
In this study, KF was added as an inhibitor in the commer-
cial coolants to reduce the corrosivity of these coolants to ma-
gnesium alloys. For example, the inhibitive effect of KF on the
general corrosion of AM-SC1 in MBL at room temperature is
illustrated in Fig. 1 which shows that the general corrosion
rate of AM-SC1 decreases as the concentration of KF in-
creases. When the concentration of KF is greater than 1%
wt, the corrosion rate becomes lower than the corrosion
Fig. 1. Dependence of the general corrosion rate of AM-SC1 on the
concentration of KF in MBL coolant for two weeks
Galvanic corrosion in Galvanic corrosion in
contact with AlSi9Cu3 contact with AlSi9Cu3
at 25 8C at 95 8C
(lA/cm2) (lA/cm2)

800
60

30

1
100

10
40
18 Song and StJohn
Fig. 2. Galvanic currents between AM-SC1 and aluminium alloy
AlSi9Cu3 in MBL coolant with and without 1%wt KF as inhibitor
at different temperatures
rate threshold of 0.67 mg/cm2/week. However, for galvanic
corrosion at high temperature, this inhibitor does not work
so well. Fig. 2 shows the galvanic currents between AM-
SC1 and AlSi9Cu3 in MBL with 1%wt KF as inhibitor at
room temperature and 95 8C. The galvanic corrosion rate
was still higher than the acceptable threshold after 1%wt
KF was added into the coolant.
Similar general and galvanic corrosion tests were carried
out for the other coolants with and without KF as an inhibitor.
The results are summarised in Table 3.
Through a comparison between Table 3 and Table 2, it can
be seen that KF generally has an inhibitive effect in all the
studied coolants. It seems that LLC-Fþ1%wt KF has accep-
table corrosivity to AM-SC1 alloy and LLC-Tþ1%wt KF is
also close to the acceptable level based on the results in Ta-
ble 3. They were chosen as promising coolant candidates
based on the results presented in Table 2 and Table 3.
The likely mechanism of the inhibitive effect of KF on AM-
SC1 is probably similar to that for pure magnesium in fluoride
containing ethylene glycol solutions, i.e. fluorides react with
the magnesium in the matrix of AM-SC1, forming a low so-
lubility magnesium fluoride product which deposits on the al-
loy surface and prevents further corrosion attack to the alloy.
3.3 Health and environment concerns of KF
According to the Australian National Pollutant Inventory
Database [17], fluorides are present throughout the environ-
ment at low levels and are not harmful. Small amounts of so-
dium fluoride in fact can help prevent tooth decay. However,
high levels of fluoride or hydrogen fluoride gas are hazardous
Table 3. Corrosion performance of AM-SC1 in various coolants with 1%wt KF as inhibitor
1%wt KF in General corrosion at 25 8C General corrosion at 95 8C
coolants (mg/cm2/week) (mg/cm2/week)
MBL
0.5
0.5
CTL 0.08
0.19 0.18
1
LLG
0.16
1.9
LLC-F 0.14
0.17 0.07
0.1
LLC-T 0.06
0.11 0.06
0.09
Materials and Corrosion 2005, 56, No. 1
to health. Hydrogen fluoride exists as a particle in the air if
released to the atmosphere and it dissolves when mixed
with water. Insufficient data are available to predict the
short-term or long term effects of hydrogen fluoride to aquatic
life, plants, birds or land animals. Concentrated hydrogen
fluoride is very corrosive and would badly burn exposed
plants, birds or land animals. Small quantities of hydrogen
fluoride can be neutralised by the natural alkalinity in aquatic
systems.
In a coolant system, the health and environmental hazards
of fluoride should be lower. This is because:
l The cooling system is a closed cyclic device and coolant
will not be released into the environment under normal op-
erating conditions. The chance of humans being directly ex-
posed to the fluoride in a coolant is extremely rare.
l Current commercial coolants need to be recycled and are
not allowed to be disposed into the environment directly
after use. Thus the fluoride will also be recycled together
with the coolants.
l Even though fluoride has slightly higher health and envir-
onmental hazard ratings than ethylene glycol, its concentra-
tion in a coolant as an inhibitor is much lower than the con-
centration of ethylene glycol in the coolant. Thus the hazard
due to the fluoride may not necessarily be higher than ethy-
lene glycol in this case.
l Most coolants are slightly alkaline, thus it is unlikely that a
significant amount of hydrogen fluoride will be generated
from KF in these solutions. Therefore, the formation of hy-
drogen fluoride in coolants should not be a significant ha-
zard.
Therefore, if KF is added to coolants to prevent the corro-
sion of magnesium alloys, the health and environmental issues
may not be a major concern.
3.4 Performance of AZ91D in the selected coolants
AZ91D may be used to make some parts of a magnesium
engine, e.g. a water pump housing. Hence, it is of importance
to examine whether this metal can survive in a proposed cool-
ant, and, if not, whether KF as an inhibitor can also effectively
inhibit its corrosion in the coolant.
Fig. 3 and Fig. 4 display the general corrosion rates of
AZ91D alloy in the two most promising coolants with and
without KF as an inhibitor at room and high temperatures.
The general corrosion rates of AZ91D ingot in these two cool-
ants were lower than the acceptable threshold even without
KF as an inhibitor. The addition of KF further reduced the
general corrosion rate. These imply that LLC-T and LLC-F
can effectively inhibit the general corrosion of AZ91D alloy.
Galvanic corrosion at 25 8C Galvanic corrosion at 95 8C
(lA/cm2) (lA/cm2)
2
3
20

25

30

1
4

5
18
Materials and Corrosion 2005, 56, No. 1 Magnesium alloys in commercial engine coolants 19

Fig. 3. General corrosion rates of AZ91D in LLC-T coolant with

and without 1%wt KF at room temperature and 95 8C

Fig. 5. Galvanic currents between AZ91D and AlSi9Cu3 in LLC-T

coolant with and without KF at room temperature and 95 8C

Fig. 4. General corrosion rates of AZ91D in LLC-F coolant with

and without 1%wt KF at room temperature and 95 8C

The weight gains as displayed in the figures may be experi-

mental errors. There are several possible causes: 1) Some of
the corrosion product was not completely removed. 2) Chro-
mic products may have deposited on the magnesium surface
from the chromic acid solution during the corrosion product
removal process. 3) Magnesium reacted with the coolants or
inhibitors to form passive films or layers on the surface, which Fig. 6. Galvanic currents between AZ91D and AlSi9Cu3 in LLC-F
could not be easily removed in the chromic solution. coolant with and without KF at room temperature and 95 8C
The galvanic corrosion rates of AZ91D in these coolants are
slightly higher than the acceptable threshold at 95 8C (see
Fig. 5 and Fig. 6). The addition of 1% wt KF at this tempera-
ture reduced the galvanic current very close to 8.8 lA/cm2
in LLC-T, but in LLC-F it was still much higher than the
threshold. Therefore, LLC-T appears to be slightly better
than LLC-F.

3.5 Performance of aluminium alloy AlSi9Cu3 in coolants

In a magnesium engine, some parts are likely to be made

from aluminium alloys. Therefore, the corrosivity of coolants
to an aluminium alloy is also important. As an aluminium al-
loy is a traditional engine material, most existing commercial
coolants should not be corrosive to aluminium alloys. If KF
needs to be added into commercial coolants to reduce their
corrosivity to magnesium alloys, it is important to know
whether the addition of KF will affect the corrosivity of these
commercial coolants to aluminium alloys. Fig. 7. Polarisation curves of AlSi9Cu3 in MBL and LLC-T cool-
Measurement of polarisation curves was employed to in- ants with and without 1%wt KF at 25 8C
vestigate the influence of KF on the corrosion performance
of AlSi9Cu3 at room temperature. The polarisation curves
of AlSi9Cu3 in MBL and LLC-T coolants are displayed in polarisation current became lower. These results suggest that
Fig. 7. In the MBL coolant, the anodic polarisation current KF is not detrimental to AlSi9Cu3 in LLC-T in terms of its
was slightly increased but the cathodic polarisation current general and galvanic corrosion performance. The influence of
decreased by addition of KF. In LLC-T, KF had no significant KF on AlSi9Cu3 and other engine materials at a high tempera-
influence on the anodic polarisation curve whilst the cathodic ture are demonstrated in the following ASTM D1384 tests.
20 Song and StJohn Materials and Corrosion 2005, 56, No. 1

3.6 ASTM D1384 verification

The configurations of the above immersion, galvanic cur-

rent and polarisation curve measurements are very simple
compared with a real coolant system. Hence, the above results
need to be further confirmed by the ASTM standard test.
Fig. 8 and Fig. 9 are two examples of the results of ASTM
D 1384 testing, which show that MBL and LLC-Tþ1%wt KF
are not corrosive to copper, solder, brass, steel and aluminium.
However, the weight loss rate of AM-SC1 in MBL is higher
than 0.67 mg/cm2/week, indicating that AM-SC1 will not be
able to survive in the MBL coolant. This confirms the results
presented earlier. In LLC-T + 1%wt KF, the corrosion rate of Fig. 8. Weight loss rates of various standard metals and AM-SC1
AM-SC1 was lower than the threshold. Fig. 10 and Fig. 11 in MBL coolant by ASTM D1384 test
show the surfaces of the tested coupons. It is clearly shown
that AM-SC1 was more severely corroded by the MBL cool-
ant than in the LLC-T coolant þ1%wt KF while the other ma-
terials were still intact in both coolants. These two examples
suggest the acceptability of LLC-Tþ1%wt KF for use in an
AM-SC1 engine block.
The ASTM D1384 test was also conducted for AM-SC1,
ingot AZ91D and diecast AZ91D in the other coolants with
or without KF addition. The results are listed in Table 4.
These results (Table 4) show that the corrosion rates of AM-
SC1, ingot AZ91D and diecast AZ91D all decreased after KF
was added to the LLC-T coolant. The corrosion rates of AM- Fig. 9. Weight loss rates of various standard metals and AM-SC1
SC1, ingot AZ91D and diecast AZ91D are all acceptable in in LLCþ1%wt KF by ASTM D1384 test
LLC-T, even without KF as an inhibitor. Apart from those
listed in the table, the other metals such as copper, brass, steel,
solder and aluminium alloys, have all been measured to have a 3.7 Alloy influence
very low corrosion rate in these coolants, which means that the
addition of KF does not affect the corrosion rates of these me- It is noticed from Table 3 that AZ91D, particularly diecast,
tals. The significance of these findings is that LLC-T may be a is more corrosion resistant than AM-SC1 in the tested cool-
suitable coolant for magnesium engine blocks, and KF can be ants. A similar conclusion can be drawn by comparing the re-
added to further reduce the corrosivity of the coolant. sults listed in Table 2 with those shown in Fig. 3, Fig. 4, Fig. 5

Table 4. ASTM D 1384 testing results

# Coolant þ KF Magnesium alloy Weight loss rate (mg/cm2/week)

1 MBL AM-SC1 3.767

2 MBL Ingot AZ91D 0.129
3 LLC-T AM-SC1 0.845
4 LLC-Tþ0.2% wt KF AM-SC1 0.525
5 LLC-Tþ0.5% wt KF AM-SC1 0.157
6 LLC-Tþ1% wt KF AM-SC1 0.131
7 LLC-Tþ2% wt KF AM-SC1 0.078
8 LLC-T Ingot AZ91D 0.277
9 LLC-Tþ0.2% wt KF Ingot AZ91D 0.798
10 LLC-Tþ0.5% wt KF Ingot AZ91D  0.046*
11 LLC-Tþ1% wt KF Ingot AZ91D  0.091*
12 LLC-T Diecast AZ91D 0.565
13 LLC-Tþ0.5% wt KF Diecast AZ91D 0.151
14 LLC-Tþ1% wt KF Diecast AZ91D 0.139
* The weight gains (#10 and 11) could be experimental errors caused by some reaction products deposited from the corrosion product
removal solution or a passive film/layer formed in the coolants.
Materials and Corrosion 2005, 56, No. 1 Magnesium alloys in commercial engine coolants 21

and Fig. 6. It is understandable that different magnesium al-

loys have different corrosion behaviours. Magnesium alloys
can normally be classified into two groups. The first group
of alloys has aluminium as a primary alloying element and
the alloys in the second group usually contain rare earth ele-
ments, zinc and zirconium as a grain refiner (and do not con-
tain aluminium). These two groups of alloys have different
corrosion behaviours in a salt solution [18]. In this study,
AZ91D is a typical aluminium containing alloy of the first
group, and AM-SC1 belongs to the second group and their Fig. 10. Corrosion morphologies of metals after ASTM D1384 test
corrosion performance should not be the same. The higher in MBL coolant
corrosion resistance of AZ91D could be due to the aluminium.
Since these coolants are non-corrosive to aluminium alloys,
which is a basic requirement of an existing commercial cool-
ant, the coolants could also have a certain degree of inhibitive
effect on an aluminium containing alloy such as AZ91D.

3.8 The effect of temperature

In a traditional coolant, the traditional engine materials of-

ten corrode faster at a higher temperature. However, for ma-
Fig. 11. Corrosion morphologies of metals after ASTM D1384 test
gnesium alloys, it does not appear to be the case. in LLC-Tþ1%wt KF
For example, MBL is more corrosive to AM-SC1 at room
temperature than at the high temperature of 95 8C. The aver-
age general corrosion rate of AM-SC1 immersed in MBL
(Fig. 12) decreases as temperature increased. When the tem-
perature was lower than 85 8C, the general corrosion rate be-
came unacceptable. The typical hydrogen evolution curves in-
dicating the corroded amount of AM-SC1 are displayed in
Fig. 13. It shows that the corrosion rate of AM-SC1 at a higher
temperature increased dramatically at the very beginning,
then slowed down quickly with time becoming stable after
a half-hour. However, at room temperature, the corroded
amount of AM-SC1 slowly increased, and the increasing trend
continued for a couple of hours until it achieved a certain sta-
ble high level. These results suggest that AM-SC1 became
passive with time, and at a higher temperature the “passivat-
ing” process was much faster. This could be due to the forma-
tion of a certain type of film on the surface and the film for-
mation process is faster at higher temperatures. XPS analysis
of the specimen after immersion in the MBL coolant revealed
that the corrosion products on the magnesium surface were
mainly magnesium silicates. Silicate is one of the important
inhibitors in the MBL coolant. Fig. 12. Average weight loss rates of AM-SC1 immersed in MBL
The effect of temperature on the corrosion behaviour of coolant for 2 weeks
AM-SC1 in MBL was further demonstrated by an immersion
test at alternating temperatures. Two groups of specimens
were immersed in the MBL coolant at initial temperatures
of 25 8C and 95 8C. The coolants was cyclically heated up
and cooled down between these two temperatures. This to
some extent simulated the operating temperature change of
the coolant in a car during running and parking. Fig. 14 shows
the amounts of evolved hydrogen from these two groups of
samples. It can be seen that the initial temperature had a de-
cisive effect on the corrosion of AM-SC1. When the initial
temperature was 25 8C, almost all the measured hydrogen
was generated during this initial period. Once the temperature
was increased to 95 8C the specimen surface appeared to be
passivated, and no further hydrogen evolution occurred in
the following temperature cycles. If the initial temperature
was 95 8C, AM-SC1 appeared to be passivated at the begin-
ning. The hydrogen evolution slowed down in the first few
minutes. After that, no significant hydrogen evolution was de- Fig. 13. Typical hydrogen evolution curves of AM-SC1 in MBL
tected in the following temperature cycles. This further con- coolant
22 Song and StJohn
firms that a film was formed on the surface of the alloy at high
temperature and the formed passive film was stable under the
subsequent cyclic temperature conditions.
The prolonged temperature effect on corrosion resistance
due to the formation of a passive film on the surface of the
specimen is of great practical significance. It signifies that
the more frequently a vehicle is used and more miles done,
the lower the risk of corrosion will be to a magnesium engine
block.
In organic acid-based long life coolants, such as LLC-T and
LLC-F, the influence of temperature on corrosion is different.
A higher temperature appeared to increase the general and
galvanic corrosivity to AM-SC1. The different temperature
dependence of the corrosivity between the organic acid-based
long life coolants and the traditional coolants could result
from the different corrosion inhibition mechanisms of the in-
hibitors in the coolants. It seems that the inhibitive effect of
the organic acid in the long life coolants becomes less signif-
icant at a higher temperature. A possible reason is illustrated
in the next section.
3.9 Influence of the type of coolant
As mentioned earlier, the two groups of coolants, traditional
and long life, may have different mechanisms of inhibiting the
corrosion of magnesium alloys. In fact, it is quite normal that
magnesium alloys have different corrosion and inhibition be-
haviours in different coolants due to the differences in their
compositions. The critical component of a coolant is its inhi-
bitors. Different inhibitors can lead to different inhibition per-
formance.
The traditional coolants usually contain molybdate, phos-
phate, borate, nitrate, nitrite, silicate, etc, as inhibitors. These
inorganic inhibitors tend to react with metals to form salt films
(phase films) depositing on the metal surfaces. A high tem-
perature sometimes is favourable to the formation of these
phase films due to the change of solubility of the salts with
temperature. Hence, it is postulated by the authors that in
the traditional coolants, a better inhibitive effect sometimes
achieved at a higher temperature might be attributed to
such a kind of salt film formed on the magnesium surface.
Since not many magnesium salts have low solubility, the cor-
rosion of magnesium alloys can not be inhibited to a very low
level in the coolants because of insufficient magnesium salts
Materials and Corrosion 2005, 56, No. 1
Fig. 14. Hydrogen production from
AM-SC1 in MBL coolant to a cyclic
temperature variation
deposited on the magnesium alloys. This postulation needs to
be further experimentally examined in future studies.
In the organic acid-based long life coolants, carboxylate
ions will determine the inhibition performance. Theoretically,
an organic species is likely to be adsorbed on a metal surface.
The adsorbed organic species more or less can act as an in-
hibitor and the inhibition degree depends on the coverage
of the adsorptive film on the metal. It has been reported
that [14] some carboxylate ions are effective inhibitors for ma-
gnesium alloys in ethylene glycol solutions. Thus, the low cor-
rosivity of LLC-T and LLC-F to AM-SC1 can be simply as-
cribed to the adsorption of carboxylate ions on the alloy sur-
face, and the adsorbed carboxylate ions form a nearly contin-
uous adsorptive film and effectively retard the corrosion of the
alloy. Normally, an adsorbed species is likely to be desorbed at
a high temperature. This explains the decreased inhibitive ef-
fect of LLC-T and LLC-F on the galvanic corrosion of AM-
SC1 at a high temperature.
Moreover, with the different inhibition mechanisms be-
tween the traditional coolants (e.g. MBL) and the organic
acid-based long life coolants (e.g. LLC-T and LLC-F), the dif-
ferent degrees of the inhibitive effect of KF in these two
groups of coolants can also be explained. In the traditional
coolants, as MgF2 has much lower solubility than the magne-
sium salts resulting from the reactions between magnesium
with the inhibitors in the traditional coolants, fluoride may
preferentially form a protective MgF2 film replacing other re-
latively soluble salt films (e.g. magnesium silicate) on the ma-
gnesium surface. Hence, the corrosion rate of AM-SC1 in
MBL is likely to be significantly reduced by the addition
of KF. In contrast in an organic acid-based long life coolant,
it is likely that a good adsorptive carboxylate film that might
have already formed on the magnesium surface prevents the
reaction of fluorides with magnesium. Therefore, the inhibi-
tive effect on AM-SC1 by KF in LLC-T or LLC-F is less sig-
nificant.
4 Summary
Based on the above investigation, the following conclu-
sions can be made:
1. The studied commercial coolants are corrosive to magne-
sium alloys. Corrosion attack can occur at room and higher
temperatures.
Materials and Corrosion 2005, 56, No. 1
2. AZ91D is more corrosion resistant than AM-SC1 in the stu-
died coolants
3. The corrosivity of different commercial coolants also var-
ies. Generally speaking, the organic acid-based long life
coolants are relatively less corrosive to the magnesium al-
loys than the traditional coolants.
4. KF is an effective inhibitor for the magnesium alloys sub-
jected to the studied commercial coolants. It can reduce the
general and galvanic corrosion rates at room temperature
and high temperature. It has no detrimental effect on the
other engine block materials in terms of their corrosion per-
formance.
5. The corrosion rates of the magnesium alloys in the Toyota
long life coolant are acceptable. The addition of KF into this
coolant can further reduce the corrosion rate such that it
essentially prevents corrosion. In addition, Ford long life
coolant is also a promising coolant for the magnesium al-
loys studied.
5 Acknowledgment
The study was supported by the CRC for Cast Metals Man-
ufacturing (CAST). CAST was established under and is sup-
ported by the Australian Government’s Cooperative Research
Centres Program (CRC). The authors thank Mr. Zhiming Shi,
Miss Jay-Ellen Grimmett and Mr. Gary Cleeland who parti-
cipated in the experimental work in this study. The authors
also acknowledge the support and interest of Dr. Malcolm
Frost from Australian Magnesium Corporation in this study.
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(Received: April 26, 2004) W 3803