Composites: Part A 41 (2010) 1511–1515

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Influence of atmosphere and carbon contamination on activated pressureless

infiltration of alumina–steel composites
M. Bahraini a, E. Schlenther b, J. Kriegesmann b, T. Graule a, J. Kuebler a,*
a
Empa, Swiss Federal Laboratories for Materials Testing and Research, Laboratory for High Performance Ceramics, Ueberlandstrasse 129, 8600 Duebendorf, Switzerland
b
Fachhochschule Koblenz, Rheinstrasse 56, 56203 Höhr-Grenzhausen, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Al2O3/steel metal–matrix composites (MMCs) were fabricated by activated pressureless infiltration at
Received 15 February 2010 atmospheric pressure in different gas atmospheres; N2, Ar and Ar–5%H2. The infiltration quality was eval-
Accepted 25 June 2010 uated with examination of the microstructure, infiltrated area and remaining porosity. The atmosphere
with the best infiltration quality was chosen for improvement of infiltration by varying infiltration
parameters such as temperature, holding time and heating and cooling rates. Further improvement
Keywords: was achieved by addition of Si or SiO2 powder to the preform in order to reduce the effect of the residual
A. Metal–matrix composites (MMC)
carbon. The results show that the activated melt infiltration can be successfully done at atmospheric
E. Liquid metal infiltration
Inert atmosphere
pressure in inert gas.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction MMCs have been successfully produced also by incorporation of

Activated pressureless melt infiltration of metal–matrix com-
posites (MMCs) has been performed for fabrication of several me-
tal–ceramic composites such as SiC/Al and Al–Si [1], SiC/bronze
and AlN/cast iron [2], Al2O3/Fe-based and Al2O3/Ni-based alloys
[3] and ZrO2/steel [4]. These composites have been the subject of
research mainly for wear applications. In general, pressureless
infiltration offers an industrially preferred route as infiltration
can be done without application of an external pressure. However,
capillary forces have to be used to promote infiltration. Therefore,
poor wettability of ceramics by liquid metal has to be overcome,
e.g. by introducing an activator. Several methods have been devel-
oped based on modifying the matrix or the reinforcement to
achieve wetting, e.g.:
– chemical reaction between the metal matrix and infiltration
atmosphere [5,6],
– chemical reaction between the reinforcement and the metal
matrix [7,8],
– coating ceramic particles [9] and
– addition of reactive alloying elements in the metal matrix
[10,11].
The introduction of the reactive transition metals such as Ti and
Cr is well known for improving wettability of ceramic materials
with liquid metals in active brazing [12]. Al2O3/Fe-based alloy
* Corresponding author. Tel.: +41 44 8234223; fax: +41 44 8234150.
E-mail address: jakob.kuebler@empa.ch (J. Kuebler).
Ti particles as an activator element in the Al2O3 preform [3]. They
have been used, e.g. for metal forming tools, exhibiting a good wear
resistance. Infiltration was performed by penetration of the molten
metal through the pores of a self-standing porous ceramic body,
called a preform, containing alumina particles activated with Ti
particles. The process has been performed under relatively high
vacuum (approx. 1.4  102 Pa). Vacuum is needed to avoid chem-
ical reaction of the activator with the environment that oxidizes
the activator. The above mentioned vacuum level is industrially
not favorable for mass production of MMCs, therefore infiltration
under atmospheric pressure and in an inert gas is a desirable
alternative.
In this work, we present the results of activated pressureless
infiltration of Al2O3/steel under atmospheric pressure in inert (Ar,
N2) or slightly reductive (Ar–5%H2) gas. The atmosphere with the
best infiltration result has been further investigated to improve
and optimize the infiltration quality.
2. Experimental procedures
Al2O3 powder, Alodur WSK 120 with an average particle size of
160 lm (Treibacher GmbH, Laufenburg, Germany) was used for the
preparation of the preforms. The characteristics of the powder are
described in [3]. Elemental titanium (99.23% purity, 325 mesh,
d10 = 16 lm, d50 = 33 lm, d90 = 62 lm) was used as activator (TLS
Technik GmbH, Bitterfeld, Germany). The steel X38CrMoV5-1 pur-
chased from Böhler & Co., AG, Wallisellen, Switzerland with a melt-
ing point of 1490 °C was used as the metal matrix. Composition of
steel is given in [3].

1359-835X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2010.06.013
1512 M. Bahraini et al. / Composites: Part A 41 (2010) 1511–1515
A mixture of Al2O3 powder containing 20 wt.% elemental tita-
nium and 6 wt.% Si or SiO2 together with 2 wt.% of organic binder,
carboxymethylcellulose basis, was used for the preparation of
ceramic green bodies. Samples with dimensions of 22 mm diame-
ter and 10 mm height were prepared by uniaxial pressing of gran-
ulates under an applied pressure of 30 MPa. The green bodies were
subsequently dried in a drying oven for 24 h at 70 °C and finally
debinded at 450 °C in air for 2 h to obtain preforms ready for infil-
tration. The Volume fraction of porosity within the preforms was
0.42 with an average pore diameter of 33 lm for Al2O3–20
wt.%Ti–6 wt.%Si. The pore size distribution of the preforms was
measured with Hg-porosimetry (POROTEC Pascal 140 and 440,
POROTEC, Italy) and the porosity was quantified by He-pycnome-
try (Micromeritics AccuPyc 1330, Micromeritics, USA). Residual
carbon within the preforms after debinding was measured by dry
combustion method using ELTRA CS 800 carbon/sulfur determina-
tor (ELTRA GmbH, Neuss, Germany).
Infiltrations were conducted in an alumina tube furnace (CTF 17/
300, Carbolite GmbH, Germany) under atmospheric pressure and at
a temperature of 1600 °C (about 100 °C higher than the melting
point of the metal) or 1700 °C for 2 or 4 h with heating and cooling
rates of 5 K/min under flowing gas. One infiltration has been run at
1700 °C for 2 h with heating and cooling rates of 10 K/min.
Preliminary infiltrations were done under different atmo-
spheres N2 (purity > 99.5%), Ar (purity > 99.998%) and Ar–5%H2 at
temperature of 1600 °C for 2 h with heating and cooling rates of
5 K/min. Afterwards Ar which provided the best infiltration quality
was chosen and the influence of the infiltration parameters such as
infiltration temperature, time and heating/cooling rate on infiltra-
tion quality were investigated.
In some preforms Si (avg. diameter 16 lm, ICRA, Italy) and SiO2
(avg. diameter 8 lm, Sihelco AG, Birsfelden, Switzerland) were
added for elimination or reduction of the residual carbon from
the binder burn out in the preform.
The microstructure of the preforms and MMCs were investi-
gated with SEM VEGA Plus 5136 MM (Tescan, Czech Republic)
and SEM XL 30 ESEM FEG (Philips, Netherlands) equipped with
EDX (EDAX GENSIS, USA). X-ray diffraction (XRD) was conducted
using PANanalytical, X’Pert Pro diffractometer.
Porosity content in the MMCs were measured by image analysis
of micrographs covering the complete vertical cross section for a
qualitative comparison of a given sample with a reference sample
(MMC produced from packed alumina and Ti powder without bin-
der). For this purpose a light microscope Leica Wild M3Z Combi-ste-
reo (Leica Microsystems, Wetzlar, Germany) was used and the
images with 256 grey level were analyzed with the software Gatan
DigitalMicrograph 3.4. (Gatan Inc., Pleasanton, USA). Several micro-
graphs were taken with the same magnification covering the com-
plete vertical cross section of a MMC. No prior smoothing or shape
correction operations were carried out on the images. The pores
were detected on the images by manual thresholding based on the
best visual impression. The analyses have been done on all samples
with the same operator, equipment and analysis parameters.
3. Results and discussion
3.1. Microstructure
In activated pressureless infiltration homogeneity of the pre-
form is of prime importance for a successful infiltration. It has been
found that the distance between Ti particles plays a key role for
infiltration according to the mechanism proposed by Vasic et al.
[13]. According to this mechanism metal vapor condensates onto
Ti particles. These particles/metal condensate islands within the
preform grow and build up wetting bridges which act as the driv-
ing force for activated infiltration. Therefore, microstructure of the
preform was examined for the homogeneity of the preform. Fig. 1
shows a typical micrograph of a preform containing Al2O3, 20
wt.%Ti and 6 wt.%Si particles homogeneously distributed within
the whole preform.
Microstructure of infiltrated preforms has been examined for
porosity and reaction phases, Fig. 2. In all cases, EDX analysis of
the metal matrix shows the presence of Al in the metal matrix as
a result of dissolution of the Al2O3 particles by molten metal. In
general, the Ti-rich phases, appeared in grey color and indicated
by R in Fig. 2, contain Ti, O, C according to EDX analysis which indi-
cates the formation of Ti-rich phases of TiOx and TiC. It has been
shown previously [14] that the formation of Ti reaction products,
especially with the presence of carbon in the infiltration environ-
ment can block infiltration channels and hinder the infiltration
progress. This has been verified in this work by infiltration of a
packed powder preform containing a dry mixture of Al2O3 and Ti
without binder in order to prevent any residual carbon in the pre-
form. The mixture was packed into an alumina crucible by tapping
and infiltrated with steel under argon flowing gas. The microstruc-
ture of this MMC, Fig. 3, shows much lower and more homoge-
neous distribution of Ti-rich phases in comparison with the
microstructure of MMCs containing 2 wt.% of organic binder.
3.2. Influence of atmosphere and carbon
At first some preliminary experiments in different atmospheres
(N2, Ar and Ar–5%H2) have been done. Infiltration in N2 was not
successful due to the formation of TiN. This has been proved by
XRD of the non infiltrated powder preform which showed the pres-
ence of TiN together with TiO and TiC which inactivate Ti particles.
Infiltration in Ar and Ar–5%H2 showed in both cases that the
preforms were only partially infiltrated. XRD analysis of the un-
infiltrated powder shows the presence of TiO, TiC, Ti and C.
Based on infiltration behavior in N2 and the reducing atmo-
sphere of Ar–5%H2 showing no infiltration in the former and no
preferable result in comparison with Ar in the latter, Ar was chosen
as the infiltration atmosphere for optimization of infiltration
parameters in order to improve the infiltration quality. The effect
of infiltration time, temperature and heating and cooling rate on
infiltration quality were studied afterwards.
In order to eliminate the effect of residual carbon from debind-
ing, an infiltration was performed with a preform which was pre-
pared by mixing Al2O3 powder with Ti particles without binder
(Fig. 4, No. 1).
It has been observed that increasing the infiltration time from 2
to 4 h improves the infiltration quality (Fig. 4, Nos. 2 and 3). How-
200 µm
Fig. 1. Microstructure of Al2O3 WSK 120 preform containing 20 wt.%Ti and 6 wt.%Si
homogeneously distributed in the whole preform.
 M. Bahraini et al. / Composites: Part A 41 (2010) 1511–1515 1513

(a) (b)
R

R
P
M
P

M
200 µm 200 µm

(c) M (d)
M
R
R

P
P
200 µm 200 µ
µm
m

Fig. 2. SEM images of Al2O3/steel MMC infiltrated under Ar, at 1700 °C for 4 h, all from downstream near the infiltration front with (a) 2 wt.%Si, (b) 2 wt.%SiO2, (c) 6 wt.%Si and
(d) 6 wt.%SiO2. The continuous R phases in (a) and (b) are where infiltration is stopped.

comparison with the MMC made of the preform with binder and
infiltrated under the same condition. Therefore, this MMC was ta-
ken as a reference for further improvement of infiltration quality.
Unfortunately, green bodies without binder cannot be produced
M industrially for MMC production. In industrial processes a green
body with an adequate strength is essential, e.g. for machining to
a desired shape and dimensions before infiltration. Therefore, the
presence of binder for providing an acceptable strength value is
indispensable. In order to reduce the effect of residual carbon as
a result of the debinding process, Si and SiO2 were added sepa-
rately to the green bodies. The aim was to enable reaction of car-
bon with these components to form volatile phases. As Si
P particles are covered with a natural oxide layer, both Si and SiO2,
200 µm R react with carbon to produce volatile SiO and CO:

Fig. 3. SEM image of Al2O3/steel MMC, packed Al2O3 + Ti with no binder infiltrated
under Ar, at 1600 °C for 4 h. M: metal matrix, P: alumina particles, R: Ti-rich phases.
ever, an increase of infiltration time over 4 h did not show further
improvement in the infiltration quality.
The increase of the infiltration temperature from 1600 °C to
1700 °C revealed improvement in infiltration quality by reducing
porosity, Fig. 4, No. 4.
It was expected that an effect of heating and cooling rate on the
formation of reaction products could be observed. This should
affect directly the infiltration quality, more specifically this should
influence the level of remaining porosity. For example, by increas-
ing heating/cooling rate the contact time between molten metal
and ceramic/reactive particles can be reduced. Therefore, the
heating and cooling rate was increased from 5 K/min to 10 K/min.
However, no enhancement in infiltration quality was observed.
The result of infiltration under argon atmosphere given in Fig. 4,
No. 1 shows a significant improvement in infiltration quality in
SiO2 þ C ! SiO þ CO ð1Þ
This reaction is the overall result of the two following reactions
[15]:
SiO2 þ 3C ! SiC þ 2CO ð2Þ
2SiO2 þ SiC ! 3SiO þ CO ð3Þ
At first a total amount of 6 wt.%Si or SiO2 were added to the mix-
ture of Al2O3 and 20 wt.%Ti and infiltration was performed at 1600 °C
and 1700 °C for 4 h. The result revealed an improved infiltration
quality of the preforms in Ar as it is shown in Fig. 4, Nos. 5–8. How-
ever, significantly more porosity was observed at 1600 °C than at
1700 °C (Table 1, Nos. 5–8). The best result was obtained for the sam-
ple which contained 6 wt.% of Si and was infiltrated at 1700 °C for 4 h
(Table 1 and Fig. 4, No. 7). This infiltration was comparable to the ref-
erence MMC from packed powder without binder (Fig. 4, No. 1).
The presence of Si reaction products was investigated in above
MMCs by SEM and EDX analysis, however no SiC or other Si reaction
1514 M. Bahraini et al. / Composites: Part A 41 (2010) 1511–1515

1 2 3

4 5 6

7 8 9
Infiltration direction

22 mm
10
Fig. 4. MMC complete vertical cross sections containing 0, 2 and 6 wt.%Si or SiO2 in Argon and with the parameters in Table 1. MMC No. 1 is from packed preform containing
no binder or Si/SiO2. Numbers 1–9 corresponds to the sample numbers in Table 1.

Table 1
Infiltration parameters for Al2O3–20 wt.%Ti containing 0, 2 and 6 wt.%Si and SiO2 in Argon.
Infiltration No. 1 was performed with a packed mixture of Al2O3–20 wt.%Ti without binder. Porosity
of samples 2–4 is not given, as they were not completely infiltrated.

No. Si/SiO2 (wt.%) T (°C) Time (h) Porosity (%)

1 Packed preform-no 1600 4 3
binder-0 wt.%Si/SiO2
2 0 1600 2 –
3 0 1600 4 –
4 0 1700 4 –
5 6 wt.%Si 1600 4 12
6 6 wt.%SiO2 1600 4 12
7 6 wt.%Si 1700 4 3
8 6 wt.%SiO2 1700 4 6
9 2 wt.%Si 1700 4 12
10 2 wt.%SiO2 1700 4 18

products could be detected showing that the major part of the reac-
tion products has been volatile or under the detection limit of the
measurements. EDX analysis of grey reaction phases shows only
the presence of Ti, O and C. Quantitative EDX analysis of the metal
matrix revealed more Si in the metal matrix in comparison with
the base steel. This shows that dissolution of Si in the Fe-based alloy
took place too, and therefore the Si content in the matrix increased
from 1.2 wt.% to 2.2 wt.%. Therefore, the enhancement of infiltration
may be argued as a reduction of surface tension of steel by addition of
Si as it has been shown that surface tension of Fe decreases with
increasing Si content in Fe alloys [16,17].
In a final step two infiltrations with reduced amount of Si or
SiO2, 2 wt.%, have been performed at 1700 °C for 4 h. The infiltra-
tion results show that this quantity is not high enough to diminish
the effect of residual carbon. Comparison of the microstructures of
MMCs containing 2 wt.% Si or SiO2 with MMCs containing 6 wt.% Si
or SiO2, show that Ti-rich phases have formed a continuous layer at
the infiltration front of MMCs with 2 wt.% Si or SiO2, Fig. 2a and b.
This was not observed in MMCs containing 6 wt.% Si or SiO2, Fig. 2c
and d, indicating that not all of residual carbon was eliminated
with only 2 wt.% Si or SiO2. In addition, the porosity contents in
the MMCs arise again considerably (Table 1 and Fig. 4, Nos. 9
and 10). Knowing that Ti particles are not melted at the infiltration
temperature, it is supposed that smaller Ti particles are trans-
ported with molten metal flow in infiltration direction. The trans-
portation of Ti particles with the molten metal and formation of Ti
reaction phases (especially with carbon) in infiltration direction
end up with the formation of a continuous reaction layer at the
infiltration front that might stop the infiltration progress or locally
close infiltration channels and produce porous areas. As it is shown
in this study the negative effect of residual carbon on infiltration
quality can be well reduced by addition of Si or SiO2 to performs.
4. Conclusion
The following conclusions are derived from the results reported
in this work:
– Activated pressureless infiltration can be done under atmo-
spheric pressure in inert argon atmosphere.
 M. Bahraini et al. / Composites: Part A 41 (2010) 1511–1515
– The residual carbon in the preforms as a result of debinding
plays a key role in infiltration quality. Carbon reacts with Ti
and together with the reaction of Ti and O forms Ti-rich phases
(TiC and TiOx), which leads to inactivation of Ti particles. More-
over, transportation of Ti with metal flow in infiltration direc-
tion can accumulate these phases that eventually block the
infiltration channels or cause formation of porosity and stop
the metal advance in the preform.
– Addition of 6 wt.% Si or SiO2 to the preforms could reduce the
effect of carbon by forming volatile reaction products and pro-
vide an acceptable infiltration quality in infiltration under Ar
in atmospheric pressure. The best quality has been obtained
with the preforms containing 6 wt.%Si, infiltrated at 1700 °C
for 4 h with heating and cooling rate of 5 K.
Acknowledgements
The authors would like to thank E. Pieper and F. Alvarez for assis-
tance at the Empa work shop and M. Zgraggen and S. Truellinger for
support to use the SEM-EDX equipment at Empa, Laboratory for
Corrosion and Materials Integrity.
References
[1] Kajikawa Y, Nukami T, Flemings MC. Pressureless infiltration of aluminum
metal–matrix composites. Metall Mater Trans A 1995;26:2155.
[2] Krauss G, Kuebler J, Trentini E. Preparation and properties of pressureless
infiltrated SiC and AlN particulate reinforced metal ceramic composites based
on bronze and iron alloys. Mater Sci Eng A 2002;337:315.
1515
[3] Lemster K, Graule T, Kuebler J. Processing and microstructure of metal matrix
composites prepared by pressureless Ti-activated infiltration using Fe-base
and Ni-base alloys. Mater Sci Eng A 2005;393:229.
[4] Wittig D, Glauche A, Aneziris CG, Minghetti T, Schelle C, Graule T, et al.
Activated pressureless melt infiltration of zirconia-based metal matrix
composites. Mater Sci Eng A 2008;448:580.
[5] Newkirk MS, Urguarht AW, Zwicker HR, Breval E. Formation of lanxide ceramic
composite materials. J Mater Res 1986;1:81.
[6] Aghajanian MK, Rocazella MA, Burke JT, Keck SD. The fabrication of metal
matrix composites by a pressureless infiltration technique. J Mater Sci
1991;26:447.
[7] Du WF, Watanabe T. High-toughness B4 C–AlB12 composites prepared by Al
infiltration. J Eur Ceram Soc 1997;17:879.
[8] Janghorban K. Processing of ceramic matrix SiC–Al composites. J Mater Process
Technol 1993;38:361.
[9] Rohatgi PK. Pressure infiltration technique for synthesis of aluminum fly ash
particulate composite. Mater Sci Eng 1998;A244:22.
[10] Gonzalez EJ, Trumble KP. Spontaneous infiltration of alumina by copper–
oxygen alloys. J Am Ceram Soc 1996;79:114.
[11] Travitzky NA, Shlayen A. Microstructure and mechanical properties of Al2O3/
Cu–O composites fabricated by pressureless infiltration technique. Mater Sci
Eng A 1998;244:154.
[12] Li JG. Wetting of ceramic materials by liquid silicon, aluminum and metallic
melts containing titanium and other reactive elements – a review. Ceram Int
1994;20:391.
[13] Vasic S. Activation mechanism and kinetic study of Fe-based alloy infiltration
into porous Al2O3/Ti preforms. Department für Geowissenschaften-
Mineralogie und Petrographie. PhD thesis. Freiburg: Universität Freiburg-CH;
2008.
[14] Bahraini M, Minghetti T, Zoellig M, Schubert J, Berroth K, Schelle C, et al.
Activated pressureless infiltration of metal matrix composites with graded
activator content. Composites Part A 2009;40(10):1566.
[15] Miller PD, Lee JG, Cutler IB. The reduction of silica with carbon and silicon
carbide. J Am Ceram Soc 1979;62:147.
[16] Dumay C, Cramb AW. Density and interfacial-tension of liquid Fe–Si alloys.
Metall Mater Trans B – Process Metall Mater Process Sci 1995;26:173.
[17] Dzhemilev NK, Popel SI, Tsarevskii BV. Isotherm of the density and surface
energy of iron-silicon melts. Phys Mater Metallogr 1964;18:77.