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Institute of Metallurgy and Materials Science, PAS, 25 Reymonta St., Cracow, POLAND
Al drop
MgAl2O4
Point
1
2
3
4
5
6
Mg
14
2
2
2
13
Al
at.%
38
55
54
100
46
36
O
48
48
44
52
51
Phases
MgAl2O4
Al(Mg); Al2O3
Al(Mg); Al2O3
Al
Al(Mg); Al2O3
MgAl2O4
Fig. 2. SEM images and EDS analysis of cross-sectioned Al/MgAl2O4(111) couple (1000C, 60 min).
For Al/MgO couples produced at 900 or 1000C, the RPR is heterogeneous and composed of
two layers schematically shown in Fig. 3. SEM+EDS analysis (Fig. 4) evidenced that the 1st
layer, formed at the drop-side interface, is composed of large crystals with a strong directional
alignment. Its structure presents two mutually interpenetrating and continuous networks,
similar to that already reported in Al/MgAl2O4 couples [12]. The 2nd layer, formed at the
substrate-side interface, looks to be more dense with less visible grain boundaries. Similar
two-layered structure of RPR was reported recently in Al/SiO2 and Al/mullite couples [11]
but their EDS analysis did not show any variations in chemistry despite well distinguished
differences in the structure of these layers. Therefore, it was concluded that the layered
structure is caused by optical effect due to dissimilar dispersion of the phases formed in two
layers. In order to verify the same effect in Al/MgAl2O4 couple, its detailed EDS analysis was
also done (Fig. 4). It showed that the 1st layer is built of Al2O3 crystals separated by metallic
channels filled with Al containing up to 4 at.% Mg. However, Mg was not detected in the
drop, and this fact can be explained by rapid evaporation under dynamic vacuum at high
temperature. EDS analysis of the 2nd layer suggests that it consists of fine MgAl2O4
precipitates surrounded by metal enriched in Mg, since Mg content in this layer is twice
higher than that of pure spinel.
1st layer
2
nd
Al drop
layer
MgO
Al drop
Al drop
1
First layer
RPR
Second layer
5
3
Point
1
2
3
4
5
6
Stand.
Mg
4
4
43
46
52
17
Al
at.%
100
52
52
18
13
5
38
O
44
42
40
41
43
45
Phase
Al
Al2O3+Al(Mg)
Al2O3+Al(Mg)
Mg(Al)+MgAl2O4
Mg(Al)+MgAl2O4
MgO
MgAl2O4
Fig. 4. SEM images and EDS analysis of cross-sectioned Al/MgO(100) couple (1000C, 60 min).
For Al/MgO couple, TEM examinations showed a good agreement with SEM+EDS analysis
since in the 1st layer, Al2O3 and Al(Mg) phases were identified (Fig. 5), while the 2nd layer
was composed mainly of MgAl2O4 phase (Fig. 6). Based on available literature data [13-17]
and our observations that are similar for all crystallographic orientations of oxide substrates,
the following two mechanisms of the formation of C4 structure can be proposed according to
two reaction paths (Table 1) schematically shown in Fig. 7, taking into account the
thermodynamically unstable interfaces, marked by double backslash (//), particularly in the
initial Al//MgO contact system.
For the first path, the phase transformation starts from the redox reaction (1). Under applied
conditions (high dynamic vacuum and high temperature), the freshly formed Mg evaporates
and its continuous removal from the reaction front takes place by working turbomolecular
pump resulting in the shift of reaction (1) towards the formation of Al2O3. For this reaction,
the calculated modified Pilling-Bedworth' ratio (PBR* [7]) indicates that the solid product
formed (Al2O3) has a 24.15% less molar volume than initial oxide (MgO), thus creating
cracking in the Al2O3 layer and the formation of the network of channels. Since at 1000 C
liquid Al wets Al2O3, the channels are filled with liquid metal to form a ceramic-metal
network. These channels play an important role in rapid transfer of Al and Mg to and from the
reaction front, respectively. Moreover, the wider are the channels, the larger are Al 2O3
crystals, as it is evidenced by structural studies. Consequently, after reaction (1), the initial
Al/MgO interface is replaced by two interfaces, i.e. stable Al/Al 2O3 and unstable
Al2O3//MgO.
HAADF Detector
Al dorp
Counts
AlK
CK
First layer
b)
a)
Energy (keV)
Counts
Counts
AlK
OK
CK
CK
c)
Energy (keV)
d)
Energy (keV)
Fig. 5. TEM image (a) and EDS analysis (b-d) of the drop-side interface in Al/MgO(100) couple
(1000C, 60 min): solidified drop (b) and RPR (c-d) in Al/MgO couple.
HAADF Detector
First layer
Counts
2
3
CK
OK
Second layer
a)
b)
Energy (keV)
AlK
Counts
Counts
CK
AlK
OK
MgK
CK
c)
Energy (keV)
d)
Energy (keV)
Fig. 6. TEM image (a) and EDS analysis (b-d) of 1st (b-c) and 2nd (d) layers of RPR in Al/MgO(100)
couple (1000C, 60 min).
Next, Al2O3 and MgO, being in contact, react with each other to form spinel MgAl 2O4 according
to reaction (2) accompanied with ~6% volume increase, thus facilitating the densification of RPR
by narrowing or even disappearance of the channels generated at the 1st stage. Finally, the RPR
consists of two layers with different structure and composition of the thermodynamically stable
interfaces such as Al/Al2O3, Al2O3/MgAl2O4 and MgAl2O4/MgO.
Table 1. The proposed two paths of reactions in Al/MgO system.
Sequence of interfaces
Reactions
PBR*
Al/Al2O3//MgO
Al/Al2O3/MgAl2O4/MgO
2Al+3MgOAl2O3+3Mg
(1)
-24.15%
Al2O3+MgOMgAl2O4
(2)
+5.99%
Al//MgAl2O4/MgO
Al/Al2O3/MgAl2O4/MgO
2Al+4MgOMgAl2O4+3Mg
(3)
-13.28%
2Al+3MgAl2O44Al2O3+3Mg (4)
-12.60%
Stage I
PBR*=-24.15%
Stage I
PBR*=-13.28%
Stage II
PBR*=+5.99%
Stage II
PBR*=-12.60%
Stage III
Increasing thickness
of layers
Stage III
Increasing thickness
of layers
a)
b)
Fig. 7. Scheme of phase transformations in Al/MgO by 1st path (a) and 2nd path (b) of reactions.
For the 2nd possible path of reactions, the interaction starts from the formation of MgAl2O4
by redox reaction (3) while freshly formed Mg diffuses into the Al drop and evaporates from its
surface, creating favorable conditions for reaction (3) accompanied with 13.28% volume decrease
and the formation of discontinuities in the reactively formed layer of MgAl 2O4. Among the two
interfaces formed (Al//MgAl2O4 and MgAl2O4/MgO), only MgAl2O4/MgO is
thermodynamically stable. Therefore, at the next stage, the reaction (4) takes place leading to
an additional 12.6% volume decrease accompanied with continuous evaporation of the freshly
formed Mg.It is important that in the 2nd path of reactions, the required conditions for creating
the C4 structure are fully satisfied only at the second stage because liquid Al does not wet
MgAl2O4 while wetting in Al/MgAl2O4 couple takes place when the wettable reaction product
Al2O3 is formed at the interface, as reported in [12]. Taking into account this fact as well as
the structural observations showing more dense structure of the 2nd layer, one may conclude
that the 1st path of reactions is preferable. It should also be noted that the above mentioned
two factors (Mg evaporation and volume decrease) play an important role not only in the
formation and growth of the RPR of C4 structure but also in the appearance of an interesting
phenomenon called substrate surface whiskering [12], observed during high-temperature
wettability studies of both Al/MgO [15] and Al/MgAl2O4 [12] systems.
Our TEM examinations evidenced that in both cases, the structure and chemistry of whiskers
are similar to those of the corresponding single crystal substrates and no new reaction
products were detected within each separated whisker. Moreover, the detailed observations of
real-time movies clearly showed that high-temperature substrate whiskering is caused by
substrate cracking and detachment of thin whisker-like crystals from the mother oxide
substrate. It presents experimental evidence of the important primary role of high stresses
created in the substrate due to volume decrease accompanying the redox reactions in the
examined systems.
Summary
OM, SEM and TEM observations coupled with EDS analysis of interfaces formed between
molten aluminium and MgO and MgAl2O4 single crystals at 800-1000C proved the redox
reactions leading to the formation of reaction product region. For Al/MgAl2O4 couples, it
presents one single layer composed of separate Al2O3 particles surrounded with Al(Mg)
phase. In Al/MgO couples, independently of substrate crystallographic orientation, the RPR is
composed of two layers, where the 1st layer has a structure similar to that recorded in the
Al/MgAl2O4 couples, while its 2nd layer is composed of MgAl2O4 with small amount of the
narrow Mg(Al) channels. Two paths of possible reactions have been proposed taking into
account the thermodynamic stability of particular contact systems (interfaces) formed at each
step of the interaction. Structural analysis suggests that the following sequence of phase and
interface
transformations
is
preferable
Al//MgO
Al/Al2O3//MgO