Materials Science and Engineering A337 (2002) 134
/139

www.elsevier.com/locate/msea

The influence of oxygen impurities on the formation of AlN
Al /

composites by infiltration of molten Al
Mg /

S. Swaminathan, B. Srinivasa Rao *,1, V. Jayaram

Department of Metallurgy, Indian Institute of Science, Bangalore 560012, India

Received 14 August 2001; received in revised form 17 December 2001

Abstract

The influence of residual oxygen in nitrogen on the formation of AlN
/Al matrix by reactive infiltration has been investigated.
Increasing the oxygen content from 10 ppm upwards decreased the nitride content in the matrix from 64 to 6%. Based on the
analysis of the availability of oxygen at the Al-melt/gas interface, three distinct scenarios have been proposed: (i) at lowest values,
oxygen does not interfere with either infiltration or nitridation reaction; (ii) at intermediate values, nitridation is suppressed,
however infiltration continues; and (iii) at a critical upper value, the melt passivates without any infiltration. This phenomenon
offers control of the AlN/Al ratio in the matrix and the possibility of creation of microstructural gradients by the appropriate choice
of gas mixtures. # 2002 Elsevier Science B.V. All rights reserved.

Keywords: Infiltration; Residual oxygen; Nitridation; AlN

1. Introduction from 95% in N2
/0.7% H2 (0.1 ppm oxygen), to 16%

The formation of ceramic particulate composites with
AlN
/Al matrices with interesting mechanical and
thermal applications is made possible by the nitridation
and simultaneous infiltration of molten Al alloys into a
preform. It is known that during the process of
nitridation of Al
/Mg alloys the degree of conversion
of Al to AlN is a strong function of temperature and
alloy composition. Two different types of experiments
have been conducted. In the first, alloys have been
exposed to nitrogen containing atmospheres in the
absence of a preform. The increase in AlN content at
1000 8C with Mg in the range 1
/10% and with the
Mg:Si ratio has been determined [1]. In addition, it was
pointed out that the degree of conversion also depended
on oxygen impurities in static atmosphere. For Al
/
2Mg
/0.8Si, the fractional conversion to AlN diminished
* Corresponding author. Present address: Technische Universität
Darmstadt, FB Materialwissenschaft, FG Nichtmetallisch-
Anorganischewerkstoffe, Petersen Straße 23, 64287 Darmstadt,
Germany. Tel.: 49-6151-16-6318; fax: 49-6151-16-6314
E-mail address: bsrao@ceramics.tu-darmstadt.de (B. Srinivasa
Rao).
1
Presently a Humboldt Fellow.
0921-5093/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 1 - 5 0 9 3 ( 0 2 ) 0 0 0 0 2 - 3
with pure nitrogen (3 ppm oxygen), while oxygen
contents of
/1% brought the level of nitridation to
:/3% and lower [1]. In contrast, the practically more
useful situation is when the alloy is simultaneously
infiltrating into a ceramic preform, such as alumina
[2
/6]. Here, it has been shown that Mg plays a key role
in reducing the oxygen partial pressure to enable the
alloy to infiltrate by capillary action. While alloyed Mg
content is important, in this regard, it was also shown
[5,6] that gettering the incoming nitrogen with a molten
Al
/Mg alloy was even more effective in ensuring that
passivation of the infiltration did not occur. This
phenomenon applies in the low temperature regime
(850
/950 8C) in which the extent of nitridation is small
and equally at higher temperatures at which AlN
becomes a significant phase. At the same time, it has
been shown that the transition temperature from metal-
rich to ceramic-rich composites increases slightly when
commercial nitrogen is used instead of a nitrogen
/
hydrogen mixture.
The purpose of the present paper is to report a much
more substantial variation in nitride content that may be
achieved during infiltration by introducing oxygen
impurities and to examine the possible reasons for this
sensitive behaviour.
 S. Swaminathan et al. / Materials Science and Engineering A337 (2002) 134
/139
2. Experimental procedure
Fused alumina particulate of 53 mm size were used as
the dispersion into which infiltration was carried out.
Preforms of the dimensions 80 /40 /5 mm were made
by cold pressing in a steel die by applying a pressure of
:/10 tons. These cold compacts were heated at 3 8C
min 1 to 800 8C to avoid cracking of the preform
during binder removal. After 800 8C the preforms were
heated to 1600 8C and held for 1 h in order to obtain
sufficient mechanical strength for handling purposes.
Commercial purity aluminium and magnesium were
used to prepare Al
/2 wt.% Mg and Al
/5 wt.% Mg
alloys. Aluminium was melted in air in a clay graphite
crucible at a temperature of :/750 8C and the melt was
degassed by using hexachloroethane before and after
magnesium was added to the melt. Magnesium was
wrapped in aluminium foil in order to minimise
evaporative losses. An excess of 10% (over and above
the desired value) of magnesium was added to compen-
sate for any residual evaporation. The alloys were cast
into plates and homogenised at a temperature of 400 8C
for 24 h and cut to the final size for infiltration. Alloy
composition was determined using atomic absorption
spectroscopy and inductively coupled plasma spectro-
scopy (ICP). Mg contents in these alloys were found to
be 1.95 and 5.01% for the Al
/2Mg and Al
/5Mg,
respectively. Alumina trays of dimensions 84 /42 /30
mm were used as crucibles. The insides of the crucibles
were lined with graphite foil in order to facilitate easy
removal of the composite and residual metal after the
experiment.
Infiltration experiments were carried out in a high
temperature tube furnace (Barnstead Thermolyne). The
dimensions of the composites fabricated were 80 /40 /
5 mm. Alumina preforms were kept on the top of the
Al
/2Mg alloy billets in the alumina crucible. The in-
coming gas was passed over an alloy of Al
/5Mg that
acted as an oxygen getter before the gas reached the
melt-preform assembly. The getter was located in the
900
/950 8C temperature zone of the same tube. The
effectiveness of the getter could be gauged by the
formation of MgO whiskers on the wall of the furnace
tube, downstream of the getter. However, no measure-
ments were made of the oxygen partial pressure. The
tube was evacuated to a pressure of 0.05 mbar and then
back-filled with N2
/2% H2 (10 ppm oxygen) or com-
mercial nitrogen (5000 ppm oxygen) before the start of
experiment. Gas was passed at a rate of 250 ml min 1
throughout the experiment at a pressure slightly above
one atmosphere and bubbled out through a column of
oil before being vented to the atmosphere. The furnace
was heated at a rate of 4 8C min 1 to 975 8C and held
there for 3 h to ensure complete infiltration of the
preform.
135
After infiltration the crucibles were cut longitudinally
with a high speed precision saw using a diamond-
wafering blade for optical metallography. The sectioned
samples were polished using standard metallographic
procedures to 1 mm diamond finish. The polished
samples were examined under an optical microscope to
determine the distribution of various phases in the
composite. For scanning electron microscopy, the
polished samples were etched with concentrated Keller’s
reagent in order to remove Al and the samples were
coated with gold in order to make the surface electrically
conducting. The matrix hardness was measured by a
SHIMADZU HMV-2000 tester at test loads of 100 g
and a hold period of 10 s. Care was taken to ensure that
the indentation fell within the matrix and that there was
no interference with adjacent particles. An average of
ten to 15 readings was taken as a measure of the
representative hardness of the matrix.
The volume fraction of AlN present in the composite
was determined by decomposing it with sodium hydrox-
ide solution to evolve ammonia which is quantitatively
analysed by titrating against a strong acid.
3. Results and discussion
The microstructures of the composites fabricated at
975 8C are shown in Figs. 1 and 2. As shown in Table 1,
the first three runs, all carried out in N2
/2% H2,
indicated wide scatter in the AlN content which was,
however, consistent with the microstructures (Fig. 1)
and hardnesses. It was also noted that the microstruc-
tures were uniform throughout the composite and that
the infiltration was therefore reproducible across the
section and along the length. It transpired that in the
first two experiments in which the AlN content was as
low as 6%, that the O-rings that sealed the tube furnace
had given way during previous experiments. Degrada-
tion of the seals was evident when attempts were made,
unsuccessfully, to fully evacuate the system after these
two runs. During subsequent runs, the seals were
replaced more frequently and, accordingly, the AlN
content obtained increased to 64.5% (No. 3 in Table 1).
The experiment was repeated for reproducibility at the
same temperature with a new seal and a nitride content
of 62 vol.% was obtained. Consequently, this value is
expected to be representative of the maximum achiev-
able at that temperature with N2
/2% H2. The AlN
/Al
matrix in the above cases is divided into two parts: a
portion adjacent to the particle surfaces that is rich in
AlN (Al/AlN in Fig. 1B,C) and the inter-particulate
region that contains metal pockets as shown in Fig. 1(B)
and Fig. 2(B). The relative microstructural scales may be
seen more clearly in the etched scanning electron
micrographs in Fig. 2. The hardness of the metal
136 S. Swaminathan et al. / Materials Science and Engineering A337 (2002) 134
/139
Fig. 1. Microstructures of the samples processed at 975 8C depicting
the influence of different amounts of oxygen impurities on the amount
of AlN formed in the matrix. (A) 6% AlN; AlN is mostly dispersed as
isolated particles in Al-alloy matrix as indicated with an arrow. (B)
34% AlN; formation of AlN around the Al2O3 particles and starts
extending into the inter-particle pores is the dominant feature at this
volume fraction. However, large metal channels can still be seen
(marked with M; white in colour). (C) 64.5% AlN; almost all of the
inter-particle regions are covered with AlN (dark in colour) inter-
spersed with fine Al-alloy channels (white in colour).
pockets changes little, suggesting that its nitride content
is minimal.
The mechanisms of alloy infiltration and nitridation
are, at this time, not fully understood. However, certain
physical features of the process have been established
[7,8]. The melt tends to preferentially climb along
alumina particle surfaces and commences nitriding out-
wards from the surface along an irregular front into the
inter-particle pores. It is possible for residual porosity in
the portions infiltrated earlier (far below the maximum
extent of melt penetration), to then become isolated
from the nitrogen diffusing in from the outside. These
regions then fill up with advancing alloy without
reacting significantly with nitrogen and lead to the large
metal-rich pockets that are seen in Figs. 1 and 2. Thus,
the appearance of the microstructure is completely
consistent with experiments [7,8] that are carried out
as a function of temperature (after ensuring the absence
of air leaks) in the range 950
/1100 8C in which the total
amount of AlN increases, both by the expansion of the
composite Al/AlN zone adjacent to the particulate at the
expense of the alloy pockets as well as by an increase in
the fraction of AlN within these regions. The amount of
oxygen leaked into the system in the present instance is
not known. However, to confirm its role, an experiment
was conducted at 975 8C with commercial purity
nitrogen, which has a residual oxygen content of :/
5000 ppm and which yielded a composite with a nitride
content of 29 vol.% (Fig. 1) that is close to the result of
one of the earlier runs in N2
/2% H2, which is known to
have been performed with a leaking seal (Table 1, No.
2). Thus, the behaviour with decreasing oxygen is
similar to that displayed with increasing temperature,
i.e. an increase in the nitride content of the composite.
In order to understand the role of oxygen, the
suggested mechanisms of nitrogen uptake by the melt
are now briefly reviewed. It has been suggested [9] that
nitridation proceeds by a two-step reaction, beginning
with the nitridation of Mg in the vapour phase to
Mg3N2, followed by reduction to AlN by the advancing
melt. This sequence is similar to that which is now
accepted for directed melt oxidation, in which MgO or
MgAl2O4 plays a similar intermediate role. However,
the presence of Mg3N2 at the composite surface has not
yet been established. It has been shown [10] that if the
oxides are suppressed by adequate gettering, that AlN is
more stable than Mg3N2 in the alloys of interest.
However, this balance could be overturned if the Mg
activity was substantially increased in the vapour phase,
thereby making it more available for reaction with the
incoming gas. At this point in time, this issue is
unresolved, i.e. does nitrogen combine directly with
aluminium in the melt or via an intermediate compound.
What has been believed, however, is that residual
oxygen levels need to be sufficiently lowered so that
oxides (MgO or MgAl2O4) do not form and terminate
 S. Swaminathan et al. / Materials Science and Engineering A337 (2002) 134
/139 137

in some of the runs, the oxygen levels are sufficiently low

that infiltration is still able to occur. Thus, one of the
key presumptions in our prior understanding of the
pressureless infiltration of Al-alloys, i.e. the need to
maintain extremely low oxygen partial pressures, needs
to be modified. Now one has to interpret these results in
a framework that allows minute amounts of oxygen to
permit capillary advance of the metal at rates that are
not significantly altered, but effectively poisons the
nitridation reaction, even though, for all practical
purposes, the partial pressure of nitrogen is one atmo-
sphere and that of oxygen is several orders of magnitude
lower.
We now examine the issues relating to the thermo-
dynamics and rate of oxygen transport in this system. It
has been pointed out [1] that the oxygen partial
pressures under which AlN is stabilised in preference
to Al2O3 are extremely low and in the vicinity of 10 20
atmosphere. At these pressures, the number of oxygen
molecules available within the entire preform would be
only / unity. This value becomes even lower if one
assumes that Mg vapour from the getter is in equili-
brium with MgO and oxygen. Similar or lower numbers
are obtained when examining the competition between
other equilibria, e.g. those involving MgO and Mg3N2.
Thus, it is likely that thermodynamic considerations do
not play as important a role as the availability of the
appropriate gas molecules to enable a particular equili-
brium to be achieved. In particular, it is likely that while
experiments carried out in closed systems might con-
ceivably approach such equilibria, the situation in
flowing gas, which is the practically relevant one for
Fig. 2. SEM photographs after etching of the samples. (A) 6% AlN
and (B) 64.5% AlN in the matrix. AlN formed around the Al2O3 the fabrication of matrices that contain AlN, is certain
particles, fine metal channels and a metal pocket (marked with P) that to be dominated by kinetic availability. To analyse the
has been etched away can be seen clearly in the case of 64.5% AlN problem of oxygen arrival at the melt-atmosphere
sample. interface, it is assumed that the flux is determined by
the partial pressure difference between the interface and
the infiltration. (The system may then choose to grow an the outside of the preform. In addition, the ratio of the
oxide/metal composite, as in directed melt oxidation, oxygen flux to the rate at which the melt advances
[11] if the temperature and oxygen partial pressures are through the preform determines the net uptake of
sufficiently high.) The results presented here show that oxygen by the alloy. We assume that whether the
there is an additional degree of complexity in the surface is passivated or not can be defined with respect
infiltration. Despite the reduced extent of nitridation to two limits of oxygen content. The lower limit is one at
which the bulk level of oxygen in the melt, enhanced by
Table 1 surface segregation, can lead to strong binding between
Hardness of and AlN content in the matrix Al and O atoms, thereby preventing any nitrogen
S. No. Gas AlN (vol.%) Hardness (GPa) uptake. Beyond the upper limit, precipitation of oxides
takes place. Between the lower and upper limits,
Nitride region Metal pockets infiltration is possible, but with a gradual decrease in
1. a
N2
/2%H2 6
/ 0.6890.06 the extent of nitridation, i.e. the composite becomes
2.a N2
/2%H2 34 3.890.6 0.790.07 progressively metal rich as the oxygen content rises.
3. N2
/2%H2 64.5 6.491.1 0.890.2 Let Jg be the flux of oxygen arriving at the surface of
4. Repeat of 3 62.0 melt, D Dc /Dx , where Dc is the concentration difference
5. N2b 29.0
between furnace atmosphere and melt surface, D is the
a
In the presence of oxygen impurities. gas phase diffusivity and Dx is the preform thickness.
b
Contains 0.5% oxygen. Assume that melt surface is at 0, i.e. everything that
138 S. Swaminathan et al. / Materials Science and Engineering A337 (2002) 134
/139
arrives there is instantaneously adsorbed. Then Dc /
cfurnace /P /RT, where P is the partial pressure of
oxygen in furnace. Let us suppose that poisoning occurs
when the average O:Al ratio exceeds f. For this to
happen, before the interface moves up by one mono-
layer, the number of oxygen atoms arriving per unit area
must exceed f or fN moles oxygen per area, where N is
the number of moles of aluminium per unit area. Thus,
the limiting flux is given by: Jt /fN , where t is the time
taken for melt to move up a layer /y /vm, where y is the
height of one monolayer and vm is the speed of
infiltration.
Therefore, the limiting value of pressure is given by:
DP=(RTDx) (vm fN)=y
or
P (fNRTvm Dx)=(Dy)
At 1248 K, Dx is the preform thickness :/0.01 m and
D /104 m2 s 1 [12], with oxygen ions of 0.28 nm
diameter and an experimentally observed infiltration
rate of :/2 mm h1:
y 2:810 10 m
vm 0:002=3600 5:610 7 m s 1
Let oxygen adsorb as a close-packed array with a
spacing of 0.28 nm. The number of moles of oxygen
atoms per unit area is {(2.8)2(0.866)(10 20)(6)
(1023)} 1 /2.45 /105 and the number of molecules
per unit area is N /105 per m2.
Since the oxygen ion radius (0.14 nm) and aluminium
atom radius are the same, the number of moles of each
per unit area is the same for normalisation, assuming
that Al is close-packed at 1248 K.
P f f(10 5 )(10375)(5:610 7 )(0:01)g=f(2:810 10 )
 (10 4 )g
: 210 4 f Pascals
It seems likely that the critical oxygen concentration
that can be tolerated before all infiltration ceases is the
solubility limit, beyond which spinel or alumina would
be precipitated. Thus, the limit for poisoning of nitrida-
tion is expected to be lower than this solubility limit. It
will be even further lowered, if surface segregation is
present. Some evidence is available in the literature to
support the argument that the Al melt is partially
covered with oxygen before Al2O3 precipitates out.
Goumiri and Joud [13] studied the initial stages of
oxidation and its effect on the surface tension of Al by
auger electron spectroscopy. It was reported that the
surface tension of Al decreases strongly at initial
oxidation and stays rather constant for coverage up to
one monolayer. The decrease in the surface tension of
the melt was attributed to the formation of oxide islands
up to approximately saturation coverage. There was no
description of the steps involved before Al2O3 precipi-
tates out. Stucki et al. [14] studied the initial oxidation of
Al. When a solid Al is exposed to oxygen, there is
chemisorption up to 20 Langmuirs and then the oxide
peaks start to appear in the auger signal. In contrast,
when the liquid is exposed, there was no chemisorption,
but the oxygen appears to go into the solution until 1000
Langmuirs and then the oxide signal appears directly.
This tells us that liquid Al can dissolve more oxygen
than solid Al, however, there was no indication of what
happens at the melt surface after the melt is saturated
with oxygen and before Al2O3 starts to precipitate.
An estimate of the solubility of O in pure Al is 10 6
[15]. Thus, if we use f /106, then we get P /0.02 Pa
and assuming a total pressure of 1 atm or 105 Pa, the
oxygen level is 2/107 Pa or 0.2 ppm. In the absence
of more detailed information on solubilities or the actual
partial pressures prevailing, it is difficult to be more
quantitative. The above estimate is intended to demon-
strate that partial pressures much higher than those
predicted from thermodynamic equilibrium can be
tolerated, given the kinetic constraints when infiltration
is proceeding simultaneously.
Evidence supporting the inhibiting effect of O2 on
AlN growth comes from the literature on the growth of
group-III nitride single crystals (AlN, GaN and InN) by
dissolution of nitrogen in the melts (Al, Ga and In)
under high nitrogen pressure [16]. Quantum mechanical
calculations have provided some insight into the me-
chanisms of nitrogen dissolution into these metals [17].
It was shown that the adsorption of N2 on the surface of
Al melt leads to the dissociation of N2 molecule. The
energy barrier for this dissociation is around 3.2 eV,
which is less than half of the dissociation energy of N2,
which is 9.8 eV. In contrast, O2 dissociates and then
adsorbs onto the melt surface without any energy
barrier. This points to the fact that the growth of defect
free AlN or GaN is difficult since any oxygen in the
processing environment dissolves in the melt very easily.
In the similar way, it is expected that the presence of
oxygen impurities during the infiltration of Al
/Mg into
Al2O3 preform inhibit the growth of AlN mainly by
adsorption onto the Al melt surface. Strictly speaking,
one has to consider the effect of Mg on the adsorption
of O2 onto the surface of Al melt since Al
/2% Mg is
used for infiltration. At this moment, it is unclear
whether Mg helps or hinders the formation of AlN.
However, its role in keeping the melt surface free of any
passivating oxides, such as alumina or spinel, is well
studied [5,6].
From the above analysis, one can then envisage three
distinct scenarios of infiltration that are delineated by
the arrival rate of oxygen at the interface. At the lowest
values, oxygen dissolves in the melt in small amounts
and does not interfere with either infiltration or the
reaction between Al and N2. At intermediate values,
 S. Swaminathan et al. / Materials Science and Engineering A337 (2002) 134
/139
local regions of the surface experience a sufficiently high
oxygen content (possibly enhanced by surface segrega-
tion), such that Al and O atoms preferentially bind to
one another. Thus, nitride formation is suppressed but
infiltration is not seriously affected, thus leading to a
metal-rich composite. At a critical upper value of
oxygen content, the surface passivates through the
formation of a monolayer of spinel or MgO. Infiltration
of metal now ceases entirely and the reaction front has
to advance by mechanisms which are closer to those
encountered in directed melt oxidation [11,18
/20].
4. Conclusions
The residual oxygen in the N2 strongly influences the
amount of AlN formed during the infiltration of Al
/Mg
alloys into Al2O3 preforms in N2. The amount of AlN
increases with decreasing residual oxygen content. Oxy-
gen appears to inhibit the reaction between Al and N2,
mainly due to the relative ease with which it is adsorbed
on to Al. The control of ceramic to metal ratio and the
creation of microstructural gradients may now be more
readily accomplished through the use of appropriate gas
mixtures of N2 and O2 compared to the alternative,
slower method of cycling the process temperature.
Acknowledgements
Financial support for this work has been provided by
the Volkswagen Foundation, Germany.
139
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