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Structural Characterization of Reaction Product Region in Al/MgO

and Al/MgAl2O4 Systems


Rafal Nowak1,a, Natalia Sobczak1,2,b, Edmund Sienicki2,c, Jerzy Morgiel3,d
1

Foundry Research Institute, 73 Zakopianska St., Cracow, POLAND


2

Motor Transport Institute, 80 Jagiellonska St., Warsaw, POLAND

Institute of Metallurgy and Materials Science, PAS, 25 Reymonta St., Cracow, POLAND

rnowak@iod.krakow.pl, natalie@iod.krakow.pl, zlg@its.waw.pl, nmmorgiel@imim-pan.krakow.pl

Keywords: single crystals, MgO, MgAl2O4, redox reaction


ABSTRACT
The reaction product region, formed between molten aluminium and MgO and MgAl2O4
single crystals of three different crystallographic orientations, was investigated by scanning
electron microscopy (SEM) and transmission electron microscopy (TEM) coupled with X-ray
energy dispersive spectrometry (EDS). The Al/MgO and Al/MgAl2O4 couples were produced
under ultra high vacuum at 800, 900 and 1000C. The observations proved the redox reactions
of Al with both MgO and MgAl2O4. Independently of crystallographic orientation of initial
oxide single crystals, the reaction product region (RPR) was formed and it was built of oxide
particles surrounded by continuous metallic phase. For Al/MgO couples, the RPR was
composed of two layers, where in the first layer, the oxide phase was Al2O3 while in the
second layer, the MgAl2O4 was identified. In the case of Al/MgAl2O4 couples, a single layer
was distinguished and only the Al2O3 phase was recognized.
Introduction
Information on interaction in Al/MgO and Al/MgAl2O4 systems is of practical importance for
understanding the reasons of degradation of MgO-rich refractories by Al-rich melts and for
selecting suitable conditions for synthesis of metal-ceramic composites or for joining oxides
to ceramics.
This paper is focused on the analysis of structure, chemistry and phase composition of
reactively formed interfacial regions in Al/MgO and Al/MgAl2O4 couples in order to identify
the type of possible reactions and accompanying processes taking place at high temperatures.
Experimental Procedure
The Al/MgO and Al/MgAl2O4 couples were produced during the sessile drop wettability tests
by heating of Al (99,999%) sample on MgO or MgAl2O4 single crystal substrates at 800, 900
and 1000C for 60 or 120 minutes in a vacuum of 510 -6 mbar [1,2]. MgO crystals were
produced by arc melting while MgAl2O4 by Czochralski method (MTI Corp., USA) [3]. The
substrates were polished by the producer up to a roughness of 8 . Structure and chemistry
characterization of reaction product region in the solidified, cross-sectioned and mechanically
polished Al/MgO and Al/MgAl2O4 couples was carried out by optical microscopy (OM) and
scanning electron microscopy (JOEL 3036) coupled with energy dispersive X-ray
spectrometry (EDS). Preparation of the thin foils for TEM was performed applying Quanta
3D (Fei). TEM lamellas from the particular location were obtained by Focused Ion Beam
(FIB) technique. The TEM examinations were carried out using TECNAI G2 FEG super
TWIN (200 kV) microscope equipped with High Angle Angular Dark Field (HAADF)
detector and integrated with EDAX energy dispersive X-ray spectroscopy system.

Results and discussion


OM observations of cross-sectioned Al/MgAl2O4 couples revealed one layer of continuous
reaction product region (RPR) formed inside the substrate under Al drop, particularly well
distinguished in polarized light and showing a heterogeneous structure composed of small
ceramic precipitates surrounded by thin metallic channels (Fig. 1), typical for C4 (CoContinuous-Ceramic-Composite) structure reported in other reactive Al/MeO systems [4-11].
SEM+EDS analyses of RPR evidenced the presence of alumina and Al(Mg) phases (Fig. 2).

Fig. 1. Optical microscopy images of cross-sectioned Al/MgAl2O4(111) couple (1000C, 60 min).


Al drop

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

Fig. 3. Scheme of layered structure of reactive product region in Al/MgO couples.

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

EDX HAADF Detector Point 1

Counts

AlK

CK

First layer

b)

a)

Energy (keV)

EDX HAADF Detector Point 2

EDX HAADF Detector Point 3


AlK

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

EDX HAADF Detector Point 1


AlK

Counts

2
3

CK

OK

Second layer

a)

b)

Energy (keV)

EDX HAADF Detector Point 3

EDX HAADF Detector Point 2

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*

First path of reactions


Al//MgO

Al/Al2O3//MgO

Al/Al2O3/MgAl2O4/MgO

2Al+3MgOAl2O3+3Mg

(1)

-24.15%

Al2O3+MgOMgAl2O4

(2)

+5.99%

Second path of reactions


Al//MgO

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

Al/Al2O3/MgAl2O4/MgO. Volume decrease and Mg evaporation are two phenomena


accompanying high-temperature interaction between liquid Al and MgO or MgAl2O4 that play
a key role in the formation of interpenetrating (C4) structure of reactively formed interfacial
layers as well as in the substrate surface whiskering observed during wettability studies.
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