Influence of Magnesium-Aluminum Spinel on the

Directed Oxidation of Molten Aluminum Alloys

Manfred Sindel, Nahum A. Travitzky,* and Nils Claussen*
Advanced Ceramics Group, Technische Universitat Hamburg-Harburg, 2100 Hamburg 90,
Federal Republic of Germany

The directed oxidation of some molten aluminum alloys was 11. Experimental Procedure
studied. Alloys containing Si, Zn, and Mg are readily
converted into A1,03/AI composites with the characteristic The compositions of the four different A1 alloys used are
directed metal oxidation process (DIMOX) metal-channel given in Table I. Alloy A contains Si and Zn, alloy B only Si,
structure. No reaction took place when alloys without Mg alloy C only Zn, and alloy D contains Mg, Si, and Zn. Alloy A
were used. However, when Mg-free melts containing Si and was prepared by alloying B with pure Zn (99.99%). The spinel
Zn were in contact with bulk spinel (MgAlZO4),the typical was reaction-sintered from a stoichiometric mixture of MgOt
reaction product grew from the metal pool, although with- and A12O3' at 1600°C for 1 h. The porous body (50% porosity)
out formation of the spinel starter layer which was thought was analyzed by XRD to be Mg-A1 spinel. A disk of spinel, 1
to he a prerequisite for DIMOX growth. Furthermore, the to 2 mm thick, was mechanically fixed to the bottom of an
growth front was more planar than when Mg-containing al- alumina crucible.* The alloys were machined into cylinders of
loys were used. [Key words: oxidation, aluminum, magne- 1-cm height and placed on top of the spinel. Experiments
sium, alloys, spinels.] with alloy D were done without spinel. The reactions were
czrried out in an electrically heated box furnace at 1050" or
1150°Cin ambient atmosphere for 8 to 12 h, with heating rates
I. Introduction of 10 K/min. After reaction, the specimens were cut and ex-
amined by means of optical and scanning electron mi-
T HE directed oxidation of molten A1 alloys by a vapor-
phase oxidant through the directed metal oxidation
process (DIMOX*) can be utilized to produce metal/oxide
croscopy, EDS, and XRD. The chemical composition of the
residual metal phase of alloy A after reaction was analyzed by
composites.' The process is schematically shown in Fig. 1. atomic emission spectroscopy to determine the equilibrium
The growth depends crucially on certain dopants. Additions concentration of Mg. The kinetics of reaction were studied by
of both Mg and Si promote the oxidation process, whereas a TGA in ambient atmosphere using heating rates of 10 K/rnin.
single dopant is ineffective.' According to Nagelberg: the for- The crucibles for the TGA experiments were 99.7% alumina
mation of a continuous MgO layer on top of the growing with Si02 (0.12%) and MgO (0.08%) as the main impurities.
oxide controls the oxygen uptake by the diffusion of Mg ions
through this layer. Mg results from the dissociation of MgO at
its interface with the liquid metal. The atomic oxygen dis- 'Article 5866, Merck, Darmstadt, FRG.
solves in the alloy and diffuses to the alumina surface, react- 'CT3000 SG, Alcoa Deutschland GmbH, Frankfurt, FRG.
ing with A1 to form a-AI2O3.The role of Si is to improve the
wetting of the oxide by the liquid alloy.3 An increase of the
oxidation rate was obtained with small additions of Zn (cZn = Vapor Phase Oxidant
0.2 wt%) to Mg-containing A1 alloys (cMg< 0.2 ~ t % )Also, .~
reactions between molten A1 alloys and refractory oxides play
an important role in the oxidation process. Lindsay et d 5
studied the reaction between different A1-Mg alloys and alu- Metal Channels
mina, periclase (MgO), and Mg-A1 spinel (MgAI20,). No re-
action between the alloy and periclase or spinel was observed.
However, alumina bricks led to the formation of periclase
and spinel. Recently it was shown that the reaction between
pure A1 and spinel resulted in the formation of a-A1203and
Mg at 80O"C6 ,Reaction
There is, however, no consistent analysis of the reaction Product
between A1 and spinel and its influence on the oxidation rate
of A1 alloys. In the present work, the influence of bulk spinel
in contact with molten A1 alloys on the oxidation behavior
with particular respect to the formation of the DIMOX-type*
structure is discussed.

D. Clark-contributing editor

R e f r a c t o r y Container
Manuscript No. 197803. Received January 30, 1990; approved April 2,
1990. Fig. 1. Scheme of directed metal melt oxi-
Supported by ALCANINT, Montreal, Canada. dation process.' The oxide is growing on
*Member, American Ceramic Society. top of the parent metal, containing capil-
*DIMOX is a registered trademark of Lanxide Co., Newark, DE. laries for metal transport.

2615
2616 Journal of the American Ceramic Society - Sindel et al. Vol. 73, No. 9

Table I. Composition of the Alloys Used

Composition (wt%)
Alloy Mg Si Zn cu Ti Fe Mn Cr
A* 0.001 4.5 12.5 0.001 0.007 0.15 0.002 0.002
Bt 0.001 5.0 0.004 0.001 0.007 0.16 0.002 0.002
Ct 0.025 0.03 1.02 0.001 0.011 0.15 0.002 0.001
D* 0.3-0.5 8.5-9 9.5-10 0.01 0.05 0.15 0.02 n.d.
A§ 0.1 3.8 10.81 n.d.” n.d. n.d. n.d. n.d.
*Source was alloy B + Zn (99.99%). ‘Supplied by VAW Research, Bonn, FRG. k F 9 0 , Alusuisse, Rheinfelden,
FRG. ‘Alloy A after reaction with spinel. k d . is not determined.

111. Results and Discussion tion of Mg, assuming a coefficient of activity of 1, is small
(cMg= 0.13 at.%, cMMg= [ ~ X ~ ( - A G ~ / / R T ) ]This
” ~ ) .value is in
(1) Influence of Alloy Composition on Oxidation Behavior accordance with the experimental result.
Pure Al, alloy A, alloy B, alloy C, and alloy B or alloy C, in
contact with spinel formed passivating oxide layers at 1050°C; (3) Interface MetallComposite and Growth Surface
hence no directed oxide growth took place. On top of alloy A The alloy which initially contained Mg (alloy D) formed a
when exposed to spinel, however, an oxide product is formed layer of Mg-AI spinel between the metal and the growth
which is comparable to the product of alloy D at 1050°C in a product Al alloy/A1203. Originally the spinel layer was as-
spinel-free environment. Figure 2 shows cross sections of the sumed to be necessary to form the channel system that would
crucibles after reaction. No significant difference can be ob- start the characteristic A1203growth product,’ especially be-
served between the microstructures of the reaction products cause an epitaxial relationship exists between (111) [110] of
(Fig. 3). The structure consists of a-AI2O3penetrated by a spinel and (0001) [1100] of a-Alz03(the misfit is 3.85%). How-
channel system of alloy which forms a metal/ceramic com- ever, no Mg spinel was detected by XRD and no Mg could be
posite of the DIMOX type. Even though there is also a small found by EDS analysis at the metal/growth product interface
reaction zone between either alloy B or C and spinel (Fig. 4), when alloy A had reacted with spinel (Fig. 7). According to
no matrix growth occurred, because alloy C lacks the neces- these experiments, the presence of Mg-AI spinel at this inter-
sary Si, and, in the case of alloy B, the primary oxide layer phase cannot be responsible for the formation of the typical
could probably not be broken because of the absence of Zn composite structure of the growth product but may act as a
with its high vapor pressure (bp 907”C).7 supply for the Mg in the alloy during the growth of the
product. Nagelberg2 reported that the top layer is a continu-
(2) Reaction between Alloy A and Spinel
The reaction between alloy A and spinel at a temperature
of 1050°C decreased the Mg concentration in the spinel plate
near the metal/spinel interface, as detected by EDS analysis
(Fig. 5). At 1150°C a notable reaction zone exists between
alloy and spinel at this interphase. The structure of this Mg-
depleted layer is similar to that of the grown product itself
(Fig. 6). Chemical analysis (AES) proved the presence of Mg
in the residual metal phase (cMg= 0.11 ? 0.05 at.%) after the
reaction between alloy A and spinel at 1150°C. Therefore,
spinel is suggested to be decomposed according to the redox
reaction
3MgA1204(~)+ 2Al(l) 4A1203(s) + 3Mg(l) (1)
The standard Gibbs energy of this reaction is highly positive
(ACY423 = 237 kJ,7 and the calculated equilibrium concentra-

Fig. 2. Cross sections of crucibles after reaction:

(A) alloy C (see Table I) exposed to spinel formed a pas-
sivating oxide on the Al; (B) alloy A exposed to spinel
results in directed growth of oxide on top of the parent
metal phase; (C) alloy D in spinel-free environment re-
acts, forming a similar product.
Fig. 3. Optical micrographs of oxide products formed
(A) by alloy A exposed to spinel and (B) by alloy D in
spinel-free environment. The white phase is metal and
the dark phase is alumina formed by the oxidation.
September 1990 Influence of Magnesium-Aluminum Spinel on the Directed Oxidation of Molten Aluminum Alloys
Fig. 4. Optical micrograph of the reaction zone he-
tween alloy C and spinel.
Fig. 5. SEM micrograph and EDS line profile of section
of the spinel plate after reaction with alloy A. The inter-
face metal/spinel was at the left side. The EDS line pro-
file of Mg shows a continuous increase of intensity from
the interface to the center (reaction temperature 105WC).
Fig. 6. SEM micrograph of a section of spinel after re-
action with alloy A at 1150°C. The structure is similar to
the composite structure grown into free space. The dark
phase is A1 alloy, the white phase is alumina. The continu-
ous phase at the bottom is unreacted spinel.
ous MgO layer and controls the oxygen ~ p t a k eIn
. ~contrast to
this, the present investigation did not reveal a continuous
layer. The morphology of the surface structure, however,
may have changed during cooling from the reaction tempera-
ture. The surface structure consists of small spherical shapes
2617
Fig. 7. SEM micrograph of the original interface he-
tween alloy A (in contact with spinel) and the oxide
product grown on top of it after completed conversion.
At this interface, no Mg could be detected by EDS analy-
sis and no spinel was found by XRD, in contrast to alloys
containing Mg and Si from t h e beginning, such as
alloy D.
F i g . 8. S E M m i c r o g r a p h s of g r o w t h s u r f a c e s :
(A) surface of alloy A exposed to spinel; (B) after com-
pleted reaction, Zn is oxidized on top of the composite
and the ZnO plates are vertical to the surface.
which are sometimes covered by a smooth continuous phase
(Fig. 8(A)). The elemental distribution is inhomogeneous.
XRD analysis of the grown surface showed the presence of
crystalline ZnO, MgO, Alz03,Si, and Al. Surfaces of alloy A
growth products are similar to those of the alloy D product
2618 Journal of the American Ceramic Society - Sindel el al. Vol. 73, No. 9

but seem to be macroscopically more planar. If the alloy is Table 11. Rate of Weight Gain of the Directed
reacted to the very end, the surface is different (Fig. 8(B)) Growth of Oxide
from the typical growth surfaces. Platelike particles, rich in Rate at 1050°C Rate at 1150°C
Zn, are homogeneously distributed at the surface. XRD analy- Allov (XIO-’ ma/s) ( XIO-’ mds)
sis showed high ZnO phase content, and the Mg content was A/spineI 1.12 1.45
low compared to the other surfaces, as analyzed by EDS. D 0.77 1.07
(4) Kinetics of Oxidation Process
The growth rate of the product is constant at a given reac- molten alloy is somewhere in contact with bulk MgA1204;
tion temperature. Figure 9 shows the weight gain versus time i.e., the reaction between alloy and spinel supplies sufficient
for alloy A exposed to spinel. At constant temperature Mg (-0.11 at.% in the case of an A1 alloy with 4.5 wt% Si and
(T = l0500C), the curve rises linearly, and the weight gain 12.5 wt% Zn).
stops after complete conversion or channel clogging due to Si (2) The spinel layer at the interface alloy/growth product
precipitations. A similar curve was obtained for the oxidation which forms during oxidation of Al-Mg-Si(-Zn) alloys is no
of alloy D. The growth rate increases with increasing tempera- prerequisite for the growth of the characteristic DIMOX com-
ture (Table 11). The growth rate of alloy A in contact with posite product. The MgA1204 buffer just forms whenever a
spinel is of the same magnitude as that of alloy D. However, critical Mg content (>0.11 at.%) in the alloy is exceeded.
the rate is increased by a factor of -1.4 for both temperatures (3) The oxide product surface grown from an Al-Si-Zn
1050”and 1150°C. This difference can be due to different reac- alloy is more planar than when the usual Mg-containing al-
tion surface areas. loys are used.

IV. Conclusions References

‘M. S. Newkirk, A.W. Urquhart, H. R. Zwicker, and E. Breval, “Forma-
(1) Mg-free A1 alloys containing Si and Zn can also be tion of LanxideTMCeramic Composite Materials,”J. Mater. Res., l, 81 (1986).
used to initiate the directed oxide growth as long as the 2A.S. Nagelberg, “Effect of Alloy Composition on the Growth Rate of
A1203/AI Composites”; presented at the 90th Annual Meeting of the Ameri-
can Ceramic Society, Cincinnati, OH, May, 1988 (Engineering Ceramics Di-
vision, Paper No. 107-C-88).
1000
’W. D. Kingery, “Metal-Ceramic Interactions: IV, Absolute Measurement
of Metal-Ceramic Interfacial Energy and the Interfacial Adsorption of Sili-
con from Iron-Silicon Alloys,” J. Am. Cerarn. Soc., 37 [2] 42-45 (1954).
000 .sz ‘M. Richard and R. Emery, “Liquid Aluminum Alloys: Oxidation and
Reactivity with Refractories” (in Fr.), Fonderie (Paris), [373] 389-96 (1977).
b30 p
OJ
5J. G. Lindsay, W.T. Bakker, and E.W. Dewing, “Chemical Resistance of
Refractories to Al and AI-Mg Alloys,” J. Am. Ceram. Soc., 47 [2] 90-94
2 (1964).
LOO t
‘D. A. Weirauch, “Interfacial Phenomena Involving Liquid Metals and
Solid Oxides in the Mg-A1-0 System,” J. Mater. Res., 3 [4] 729-39 (1988).
200 ’0. Kubaschewski and C. B. Alcock, Metallurgical Thermochemistry,
5th ed. Pergamon Press, Oxford, U.K., 1979.
0 ‘N. Claussen and A.W. Urquhart, “Formation of Ceramic Composites by
0 200 LOO 600 800 1000 the Directed Oxidation of Molten Metals”; to be published in Concise Ency-
Time (mml clopedia of Advanced Ceramic Materials. Edited by R. J. Brook. Pergamon
Press, Oxford, U.K.
Fig. 9. Thermal balance curve of oxidation behavior 9M. S. Newkirk, H . D. Lesher, D. R. White, C. R . Kennedy, A.W.
of alloy A exposed to spinel at 1050°C showing the Urquhart, and T . D. Claar, “Preparation of LanxideTMCeramic Matrix
typical time-linear weight gain for the directed metal Composites: Matrix Formation by the Directed Oxidation of Molten
melt oxidation at constant temperature. Metals,” Ceram. Eng. Sci. Proc., 8 17-81 879-85 (1988). 0