Corrosion of Refractory Aggregates by Molten Aluminum

Saied AFSHAR and Claude ALLAIRE

CIREP/CRNF, Dept. of Eng. Physics & Materials Engng.,
Ecole Polytechnique of Montreal (CRIQ campus),
8475 Christophe Colomb Street,
Montreal, Quebec, H2M 2N9
Abstract:
The use of a non-wetting additive is not always a sufficient solution to improve the
corrosion resistance of refractories against molten aluminum. Once in contact with liquid
aluminum, the coarse refractory aggregates, which do not benefit from the non-wetting
additives in the matrix, may be corroded. In some cases, the corrosion of aggregates
promotes the corrosion of the surrounding matrix, even in the presence of a non-wetting
agent. The present study evaluates the corrosion resistance of some fifteen different types
of aggregates commonly used in monolithic refractories and analyses their effect within a
non-wetting matrix. Based on the present experimental results, the selection of
aluminosilicate aggregates that improve the corrosion resistance of castables to aluminum
alloys can be made according to their chemical composition.
Introduction:
Because of their low cost and their good thermal and mechanical properties,
aluminosilicate refractories have been widely used in the various processes involved in
aluminum production. In particular, in the aluminum cast-houses, the aluminosilicate
castables are often employed for the lining of the holding and melting furnaces. These
materials can be roughly described as a mixture of aggregates, having different
composition and size, and fine reactive powders, composed mainly of alumina, silica and
calcium oxide. Once mixed with the necessary amount of water and dried, the castables
should be fired at an appropriate temperature to acquire the required properties. During
firing, the fine particles of refractory react together to form the new solid phases which
act as a continuous cement between the aggregates and constitute a rigid matrix
surrounding each aggregate. This provides the refractory with the desirable properties to
resist to the thermomechanical abuses during furnace operation.
However, many types of aluminosilicate castables, especially those containing a
significant amount of free silica and/or impurities such as the alkalis, exhibit poor
corrosion resistance in contact with molten aluminum. To solve this problem, in the last
decade, the refractory producers have developed new technologies and products for the
furnaces used in aluminum industry. The most common solution brought to this field is
the use of some additives making the refractory non- wettable by aluminum.
To better identify the factors involved in the chemical reactions of refractory with molten
aluminum, the corrosion resistance of samples, made only from the fine particles of a low
cement castable, has been recently examined via a laboratory corrosion test
1
. The
advantage of such method is to minimize the eventual effect of the coarse aggregates and
to better appreciate the chemical stability of the refractory matrix in contact with the
liquid aluminum. Previous works have been investigated on the corrosion of
aluminosilicate materials, where effort has been focused on the role of non-wetting
agents on the protection mechanism of refractory matrix
1-4
. In fact, due to the usual
firing temperatures of castables, the coarse aggregates of refractory are generally not
subjected to significant phase transformations and, consequently, cannot benefit from the
effect of most non-wetting additives
1
. Therefore, through a direct contact with liquid
aluminum, the aggregates can be corroded and, under some conditions, this corrosion
may affect the matrix of refractory even in the presence of a non-wetting agent.
The purpose of the present work was to evaluate the corrosion resistance of different
types of aggregate usually employed in aluminosilicate low cement castables. The
general aspects of corrosion as well as the effects of different factors such as
microstructure, size and chemical composition of aggregates on their surrounding
refractory matrix were investigated. Three categories of aluminosilicate aggregates,
according to their corrosion behavior are presented here.
Experimental procedures:
Materials:
Three series of aggregates denoted A, B, and C were used to evaluate their corrosion
resistance to aluminum attack. Series A consisted of four categories of aggregates
selected from an aluminosilicate low cement castable according to their color. These
aggregates are designated as A-White, A-Yellow, A-Gray, and A-Black in the text.
Series B corresponded to the samples prepared from the aggregates classified in series A.
The sample preparation consisted of grinding the aggregates of each category of series A.
In order to obtain an identical shape for all the samples, the resulting powders were then
dry-pressed at room temperature and fired at 1200
0
C for 5 hours. The series B samples
were designated, by referring to the original materials, as B-White, B-Yellow, B-Gray,
and B-Black. It should be noted that the chemical composition of the starting materials
must not be affected by the preparation procedure used for series B samples. Using the
same procedure, some other samples were prepared from a commercial high purity silica
powders (designated as B-Silica).
Series C covered 11 types of aggregates, which currently are used in monolithic
refractories. They are designated as C-a to C-k and, similarly to series A, were used as
received. The chemical compositions of all the aggregates are listed in Table I.
Preparation of samples:
To facilitate the handling of the samples and also to evaluate the potential effect of
corroded aggregates on the corrosion of the refractory matrix, the aggregates were
mounted in a relatively inert material. The latter was obtained from the fine particles of a
low cement castable containing BaSO
4
as a non-wetting. The previous works
1,4
have
demonstrated that the samples made from these refractory fine components (see Table II
for chemical composition) present a good corrosion resistance to molten aluminum, when
the pre-firing temperature is less than 1050
0
C.
The preparation details of the tested samples were as follows: The fine components (less
than 500 m in size) of the above castable, referred here to as refractory matrix, were
first mixed with about 10 wt.% water and casted on a vibrating table. To ensure a good
adherence, the aggregates were inserted in the refractory matrix immediately after
casting. This was done in order to expose only one face of the aggregates to the molten
alloy during the corrosion test (Figure 1).
All samples were dried for 24 hours in air, then heated for about 10 hours in an oven at
110
0
C and finally fired at 1000
0
C for 5 hours. As mentioned earlier, this firing
temperature preserves the good performance of non-wetting agent to protect the
refractory matrix during the corrosion test.
Corrosion test:
The corrosion resistance of the samples to aluminum attack was evaluated using a
corrosion immersion test procedure
5
(Figure 2). In this test, an inert crucible was charged
with 2 identical samples and 2 kg commercial grade aluminum (99.9% purity). Then it
was heated from room temperature to 850
0
C, at a rate of 120
0
C/h, in a vertical furnace.
One hundred grams of magnesium were added to the liquid metal at about 700-800
0
C to
obtain a nominal Al-5 wt.% Mg alloy. The tests were carried out over a four-day period
with a daily addition of 40 g magnesium to maintain a constant composition of alloy
during the test.
After carried out the test, samples were taken out of the liquid metal and allowed to cool
slowly to room temperature. Visual examination of corrosion was performed on a central
cross section of the tested samples.
Results and Discussion:
Corrosion aspect:
In general, the affected area by molten aluminum in a refractory material is visible by
naked eye due to its black appearance. Sometimes, the affected zone is just limited to a
discolored (black) layer of refractory contacting molten aluminum, without any
significant change in the microstructure of material. The term corrosion or corroded
area is employed here when a deep modification in the original texture of the sample is
detected, for example, under optical microscope examination. In this case, the corroded
area appears as a composite material, composed mainly of small grains of corundum
surrounded by an interconnected metallic network. Therefore, a simple electric resistance
measurement may often permit to determine rapidly whether the affected zone was
subjected to metal penetration (i.e. to corrosion) or not.
Figure 3 shows three different aspects of samples after the corrosion test. In Figure 3-a,
virtually no trace of corrosion is observed neither in the aggregate nor in the surrounding
refractory matrix. In Figure 3-b, corrosion is only observed in the aggregate contacting
the molten metal. While, in the last case (Figure 3-c), corrosion is obvious in both the
aggregate and the refractory matrix. Considering the fact that the refractory matrix
remained intact during the corrosion tests for the two first cases, it seems reasonable to
think that the observed corrosion in the refractory matrix, in the latter case, has been
initiated from the corrosion of the aggregates. This observation confirms the previous
results
1
indicating that, in some cases, the corrosion of aggregates within a refractory
castable may lead to the corrosion of their surrounding matrix.
Microstructure effect:
Figure 4 illustrates the corrosion aspect of the series A samples and their equivalent in the
series B. Among the series A samples, only the A-White resisted perfectly to aluminum
attack. For the samples A-Yellow and A-Gray, the aggregates are, respectively, partially
and deeply corroded but their refractory matrix are only locally discolored. The worst
case is A-Black sample, when both aggregate and matrix are heavily corroded.
The main objective of series B samples preparation was to obtain a regular shape and
especially an identical size for all the aggregate samples. This should make the
quantitative comparison of the corrosion results much easier. However, the laboratory
prepared aggregates visibly presented a much better corrosion resistance compared to the
series A samples. Microscopic examination of samples revealed that only a slight layer
(about 100 m thick) of corrosion has been produced in B-Black aggregate, whereas the
black area on the top of B-Gray aggregate, as well as in the refractory matrix,
corresponds more to a discoloration than a corrosion process.
Although, the chemical compositions of materials are the same for both series A and B
(see Table I), the difference in their corrosion behaviors should be related to their
difference in microstructure due to the laboratory procedure employed for the series B
samples preparation. Figure 5 shows the microstructure of A- and B-Yellow samples. The
microstructure of B-Yellow seems to be more homogeneous and apparently contains less
large pores compared to A-Yellow sample. These results imply that, in some cases, the
densification of an aluminosilicate material may significantly decrease the kinetics of
corrosion.
Size effect:
As mentioned earlier, the corrosion of aggregates may extend to their surrounding
refractory matrix during the laboratory corrosion test. This behavior can be explained by
the fact that the corrosion products of some aggregates should, at least in the corroded
region, modify the chemical composition of the alloy, making it more aggressive with
regards to the refractory matrix. In such a case, the degree of contamination of the metal
should be proportional to the volume of the corroded aggregate. Moreover, the extent of
affected region of the refractory matrix should depend on the size of the aggregates
involved during the corrosion.
Figure 6 illustrates the size effect of two poor corrosion resistant aggregates (B-Silica and
C-j) on the corrosion aspect of the samples. For both types of aggregates, the surface area
of the affected refractory matrix (dark region) appears larger for the big aggregates than
for the smaller ones.
A similar interpretation can be made on the corrosion aspect of some low cement
castables. Figure 7 shows the cross sections of two aluminosilicate castables, containing a
non-wetting agent, after the Alcan immersion test
5
. For these experiences, the 5.08 x
2.54 x 2.54 cm samples have been cut from the fired cast material, in order to have 3
cross sections and 3 original surfaces for the corrosion test. Thus, the specific area of
aggregates contacting the metal bath, as well as the volume of aggregates subjected to
corrosion, is quite larger for the cross sections than for the original surfaces. This may
explain the more significant corrosion took place on the cut surfaces of the refractory
samples.
Chemical composition effect:
The results of the immersion tests for the C series samples are presented in Figure 8. In
these series, only samples C-a and C-b exhibited great resistance to aluminum alloy
attack during the corrosion tests. These samples contain more than 99 wt.% of alumina
(see Table I), which may explain the excellent corrosion resistance of such materials. For
the C-c samples, despite their high alumina content (more than 90 wt.%), a thin corroded
layer with a thickness up to a few hundred microns is observed in some aggregates. This
suggests that the high content of alumina in a refractory material is not always a
dominant parameter to prevent the corrosion by aluminum. The presence of some oxides,
such as alkalis, even at low quantity, may favorably contribute to the metal attack
1,2,4,6
.
This is the case for C-d and C-e samples which were totally corroded, most probably due
to their greater alkali content compared to the C-c aggregates. The same argument can be
made to explain the more severe corrosion produced in the C-i in comparison with the C-
h (partially corroded), despite the lower alumina content of the latter.
Table III puts together two chemical composition parameters, determined from Table I,
and corrosion aspect of aluminosilicate samples of series A and C. To better illustrate the
chemical composition effect of the aggregates on the corrosion behavior of the samples,
the above results are reported by a graph. On this graph, the ratio values of major
reducible oxides, such as SiO
2
, Fe
2
O
3
and TiO
2
(see Table IV), over the Al
2
O
3
content of
the aggregates are reported on the Y-axis. The X-axis present the alkaline oxides (Na
2
O +
K
2
O) content of the aggregates. According to the above considerations, the corrosion
results of the tested aggregates (series A and C) are shown in Figure 9.
From such representation, three zones, separated by two approximate boundaries, can be
distinguished: For the low values of (SiO
2
+Fe
2
O
3
+TiO
2
)/Al
2
O
3
ratio and alkali content
(zone I: both less than 0.3), aggregates should exhibit a good corrosion resistance. For
high values of these parameters (zone III: both more than 0.5), aggregates can be
corroded and their corrosion may extend to the refractory matrix. Between these two
zones, there is an intermediate zone (zone II), where the aggregates can be subjected to a
corrosion process but this corrosion act does not seem to affect the rest of refractory.
It should be noted that the boundaries between these different zones could be shifted
forward the higher values in X and/or Y axis, by improving the microstructure of
aggregates, for example through the densification procedures used for series B sample
preparation.
It is clear that, for aluminum furnaces application, the aggregates situated in the zone III
are not desirable, considering the fact that the extension of their corrosion to the
refractory may decrease the service life of the furnace lining.
Acknowledgements:
The authors are very grateful to Narco Canada Inc., Alcan International Ltd. and the
Centre Qubcois de Recherche et de Dveloppement de l'Aluminium (CQRDA) for
their financial contribution during the realization of this work.
References:
1. S. Afshar, and C. Allaire, The Corrosion of Refractories by Molten Aluminum,
JOM, 48 [5], pp 23-27 (1996).
2. M. Allahverdi, C. Allaire, and S. Afshar, Effect of BaSO
4
, CaF
2
, and AlF
3
as well as
Na
2
O on the Aluminosilicates having a mullite like composition, Journal of the
Canadian Ceramic Society, 66 [3], pp 223-230 (1997).
3. M. Allahverdi, S. Afshar, and C. Allaire, Corrosion Resistance of Aluminosilicate
Ceramics to Molten Al - 5% Mg Alloy, Advances in Refractories for the
Metallurgical Industries II, CIM Proceedings, d. par M. Rigaud et C. Allaire, pp.
295-303, aot (1996).
4. M. Allahverdi, S. Afshar, and C. Allaire, Additives and the Corrosion Resistance of
Aluminosilicate Refractories in Molten Al-5 Mg, JOM, pp. 30-34, February (1998).
5. C. Allaire, Refractories for the Lining of Holding and Melting Furnaces, Advances
in Production and Fabrication of Light Metals and Metal Matrix Composites, d. par
M.M. Avedesian et al., CIM Proceedings, pp. 163-174 (1992).
6. C. Allaire and P. Desclaux, Effect of Alkaline and of a Reducing Atmosphere on the
Corrosion of Refractories by Molten Aluminum, Journal of the American Ceramic
Society, 74 [11], pp 2781-2785 (1991).
Table I: Chemical composition (in wt.%) of the aggregates.
Material SiO
2
Al
2
O
3
Fe
2
O
3
TiO
2
CaO MgO Na
2
O K
2
O
A, B-White 28.9 67.1 0.93 2.56 <0.02 <0.05 <0.10 0.10
A, B-Yellow 32.7 62.0 2.25 2.69 <0.02 0.06 <0.10 0.05
A, B-Gray 35.5 60.5 1.76 2.40 <0.02 <0.05 <0.10 0.06
A, B-Black 30.6 50.8 17.2 2.08 <0.02 <0.05 <0.10 0.12
B-Silica 99 --- --- --- --- --- --- ---
C-a 0.15 99.5 0.03 --- 0.04 0.02 0.20 0.01
C-b 0.05 99.6 0.08 --- 0.04 0.02 0.16 ---
C-c 2.85 90.1 0.80 3.75 0.09 0.35 0.01 0.49
C-d 5.21 86.6 1.02 4.13 0.11 0.44 0.06 0.83
C-e 4.76 86.0 2.21 3.72 0.21 0.40 0.06 0.64
C-f 49.7 45.1 0.80 1.82 0.12 0.23 0.01 0.40
C-g 36.5 58.2 1.27 2.54 0.14 0.29 <0.01 0.10
C-h 27.3 66.6 1.25 3.13 0.11 0.27 0.02 0.08
C-i 24.6 73.7 0.24 0.05 0.09 0.23 0.21 0.01
C-j 38.2 58.9 0.97 0.16 0.09 0.18 <0.10 0.31
C-k 0.35 73.7 0.05 --- 0.20 25.4 0.30 ---
Table II: Chemical composition (in wt.%) of the refractory matrix.
SiO
2
Al
2
O
3
Fe
2
O
3
TiO
2
CaO MgO Na
2
O K
2
O ZrO
2
Ba
24.2 54.7 0.21 0.70 2.80 0.05 0.23 0.14 6.72 4.1
Table III: Corrosion test results on series A and C aluminosilicate samples.
Sample (SiO
2
+Fe
2
O
3
+TiO
2
)
Al
2
O
3
Alkalis (wt.%)
Na
2
O+K
2
O
Aggregate Surrounding
refractory matrix
A-White 0.48 0.15 Not corroded Not corroded
A-Yellow 0.61 0.1 Partially corroded corroded
A-Gray o.65 0.11 corroded corroded
A-Black 0.98 0.17 corroded corroded
C-a 0.002 0.21 Not corroded Not corroded
C-b 0.001 0.16 Not corroded Not corroded
C-c 0.08 0.5 Partially corroded Not corroded
C-d 0.12 0.89 corroded Not corroded
C-e 0.12 0.7 corroded corroded
C-f 1.16 0.41 corroded corroded
C-g 0.69 0.1 corroded Not corroded
C-h 0.47 0.1 Partially corroded Not corroded
C-i 0.34 0.22 corroded Not corroded
C-j 0.67 0.36 corroded corroded
Note: Not Corroded = no trace of corrosion is observed.
Partially corroded = corrosion zone in the aggregate is less than about 1 mm.
Corroded = significant corrosion is observed (more than 1 mm thick).
Table IV: Free enthalpy of some of the oxides in refractory materials.
Oxides 660
o
C 850
o
C 1000
o
C
CaO -256 -249 -242
MgO -143 -233 -226
BaO -225 -215 -208
Al
2
O
3
-220 -210 -203
TiO
2
-177 -167 -162
SiO
2
-153 -160 -167
FeO -98 -92 -87
Note: Oxides listed below aluminum oxide can be easily reduced by molten aluminum
unlike the others.
Figure 1: Configuration of the sample.
Figure 2: Corrosion immersion test.
28 mm
20 mm
Refractory
matrix
Aggregate
Al-5%Mg
Samples
Figure 3: Different corrosion aspects of tested samples.
a) A-White ; b) C-g ; c) C-j
Figure 4: Comparison of samples in series A (left) and B (right).
From top to bottom, White, Yellow, Gray and Black aggregates,
respectively.
Magnification: 200
Figure 5: Optical micrographs taken from the samples A-Yellow (top) and B-
Yellow (bottom).
Figure 6: Size effect of aggregates on the corrosion of samples.
Top: small (left) and large (right) B-Silica aggregates ;
Bottom: small (left) and large (rigth) C-j aggregates.
---- Cut surfaces
Figure 7: Cross section of two low cement castables, containing a non-wetting agent,
after the corrosion immersion test. The sample on the top shows no corrosion
of the refractory matrix enhanced by the corrosion of the exposed aggregates
(on the cut surfaces) unlike the sample at the bottom.
Figure 8: Corrosion aspects of series C samples.
Figure 9: Effect of the chemical composition of the aggregates on the corrosion
behavior of the samples.
0
0,2
0,4
0,6
0,8
1
1,2
1,4
0 0,2 0,4 0,6 0,8 1
Na
2
O + K
2
O (% poids)
(
S
i
O
2

+

F
e
2
O
3

+

T
i
O
2
)

/

A
l
2
O
3
None corroded aggregates
Partially corroded aggregates
Totally corroded aggregates
Aggregates and refractory matrix corroded
zone I
zone II
zone III
zone I