Scripta Materialia 54 (2006) 1875–1878

www.actamat-journals.com

The role of the chemical reaction in the infiltration

of porous carbon by NiSi alloys
V. Bougiouri a, R. Voytovych a, N. Rojo-Calderon b, J. Narciso b, N. Eustathopoulos a,*

a
LTPCM-UMR CNRS No. 5614, 1130 rue de la piscine, 38420 Saint Martin d’Hères Cedex, France
b
Lab. de Materiales Avanzados, Dep. de Quimica Inorgànica, Univ. de Alicante, Ap.99, 03080 Alicante, Spain

Received 19 January 2006; accepted 10 February 2006

Available online 3 March 2006

Abstract

The infiltration of porous carbon by NiSi alloys is studied using the sessile drop technique in high vacuum. The role of the NiSi-car-
bon reaction in infiltration is determined and discussed. The experimental infiltration results are used to determine which process—
viscous flow or the reaction at the infiltration front—limits the infiltration rate.
Ó 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Infiltration; Interfaces; Wetting; Ni alloys; Graphite; Reactivity

1. Introduction of rapid infiltration followed by the reaction between Si

Infiltration of molten metals into solid preforms or pow-
der is a successful technique for processing metal matrix
composites. A molten metal can penetrate into the pore
channels either spontaneously, through the action of a cap-
illary pressure created when the liquid wets the solid, or by
the assistance of an external force such as an applied addi-
tional pressure [1,2]. Liquid silicon and Si-rich alloys are
known to wet carbon [3,4] and they can therefore sponta-
neously infiltrate a carbon preform. Moreover, infiltrated
Si reacts with carbon to form SiC. Reactive infiltration is
used to process the so-called ‘‘reaction bonded silicon car-
bide’’ [5] or SiC/alloy composites [6,7].
The kinetics of infiltration of Si [8,9] and Si–Me alloys
[10,6] into porous carbon preforms has been studied by a
number of authors. However, the mechanism of reactive
infiltration in the above systems, especially the role of the
reaction on infiltration, is not yet well understood. As a
general rule reactive infiltration is described as consisting
*
Corresponding author.
E-mail address: nikos@ltpcm.inpg.fr (N. Eustathopoulos).
and C to form SiC. The rate of infiltration is assumed to
be controlled by the viscous resistance of the liquid and
the infiltration depth z to vary with time t parabolically,
according to Washburn’s equation [11]:
r cos h
z2 ¼ reff t; ð1Þ
2g
where r and g are the surface tension and the viscosity of
the liquid, h the equilibrium contact angle of the liquid
on the solid and reff an effective pore radius, characteristic
of the preform [8]. According to previous studies, the only
effect of the reaction of SiC formation on the infiltration
kinetics is to decrease the pore radius [8,9]. The wetting
of carbon by liquid Si at the infiltration front was assumed
implicitly to be independent of the SiC formation reaction.
However, in recent works on the wetting of smooth vitre-
ous carbon or graphite substrates by liquid Si or Si con-
taining alloys, it has been shown that the spreading rate
in this type of system depends on and is even controlled
by the SiC formation reaction at the interface. Indeed,
the wetting of carbon substrates by Si-containing alloys re-
sults from the formation at the interface of SiC which is
wetted by Si alloys [12,4]. From these results it appears

1359-6462/$ - see front matter Ó 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2006.02.015
1876 V. Bougiouri et al. / Scripta Materialia 54 (2006) 1875–1878
questionable to assume that the infiltration of porous car-
bon by Si and Si alloys is controlled by viscous resistance.
The aim of the present study is to determine the role of
the chemical reaction during infiltration of Si alloys into
porous carbon and to verify the validity of Eq. (1) for this
type of system. One difficulty which arises when reactive
infiltration is being analyzed using Eq. (1) is that reff is
not constant in time. For this reason the selected alloy must
minimize the thickening of the SiC layer occurring behind
the infiltration front as a result of the reaction. NiSi alloy
appeared to be a good candidate since Si activity in this
alloy may be considerably decreased in comparison with
pure Si. Furthermore, the experimental temperature, which
also affects reactivity, can be lowered significantly due to
the presence of deep eutectics in the NiSi binary phase dia-
gram. In addition, the reactivity in the liquid NiSi/C system
is known. Indeed, Rado et al. [13] showed that at tempera-
tures in the 1100–1300 °C range and with alloys containing
more than 36 at.% Si, Si reacts with carbon to form SiC
(hereafter this type of alloy will be referred to as reactive),
while with less Si, the alloys are non-reactive: in this case,
the only reactivity is a limited carbon dissolution in the
alloy. Finally, it should be noted that the wetting of reactive
NiSi alloys on carbon (i.e., spreading kinetics and final con-
tact angle) is very similar to the wetting of pure Si [14].
In the present work, the role of the chemical reaction in
the infiltration of porous carbon by NiSi alloys was evi-
denced by comparing the infiltration capabilities of one
reactive and one non-reactive NiSi alloy containing
47 at.% and 21 at.% of Si, respectively.
2. Experimental
The porous graphite preforms used in this study were
processed from needle coke as filler and coal-tar pitch as
binder. Filler and binder were ground to the particle size
required. This allows better control of the packing charac-
teristics and optimizes the density and porosity of the final
product. Filler and binder were blended in the proper pro-
portion into a homogeneous mix where each filler particle
was coated with the binder. This homogeneous mix was
shaped or formed into preforms, green preforms, through
isostatic molding, where external pressure was applied
from all directions, resulting in a material with a great uni-
formity, isotropic properties and generally with few defects.
The obtained preforms were carbonized up to 1200 °C in
inert atmosphere, where the volatile material was removed.
Subsequently, the preforms were graphitized up to 2500 °C
in an inert atmosphere too [15].
The final porous graphite had a density of 1.45 g/cm3
and a purity of 99.7%, the remaining 0.3% being hydrogen.
The material had an open porosity of 30% and a closed
porosity of 2.7%. The degree of graphitization found by
X-ray analysis was 92%. The pore size distribution deter-
mined by mercury porosimetry and image analysis showed
90% of the pore radii being in the 0.5–8 lm range (see also
Section 3) with a median value rmed = 3.3 ± 0.2 lm.
Table 1
Physicochemical properties of NiSi (47 at.% Si) alloy at 1270 °C and of
polyethylene glycol (PEG) at room temperature. The contact angle is on
carbon substrates
Contact Surface tension Viscosity
angle (°) (mJ/m2) (mPa s)
NiSi 30 [14] 1150 [16] 5.0 [17]
PEG 15a 43.7 [18] 63.8 [18]
a
Measured by the sessile drop technique.
400
300
2
z , mm
200
2
100
0
0 1000 2000 3000
t, s
Fig. 1. Squared infiltration distance (z2) as a function of time t measured
for PEG for determining the parameter reff of the carbon preform by
means of Eq. (1).
As shown by several authors (see, for instance Ref. [8]),
the effective radius reff in Eq. (1) may be significantly lower
than rmed. In the present study, reff of the porous carbon pre-
forms was obtained by measuring the infiltration kinetics of
an auxiliary, low-temperature, non-reactive liquid (polyeth-
ylene glycol (PEG)) with known values of surface tension r,
viscosity g and contact angle h (Table 1). Using these values
and the slope of the straight line expressing the squared
infiltration depth as a function of time (Fig. 1), reff was
found to be 0.3 lm. The infiltration experiments with the
selected NiSi alloys were performed using the classical ses-
sile drop technique. NiSi droplets of about 500 mg were
placed on the porous carbon substrate in a vacuum furnace
and then heated to the experimental temperature (1270 °C)
under high vacuum (104 Pa). The NiSi droplets containing
21.0 at.% and 47.0 at.% of Si were prepared prior to the
infiltration experiment by melting pure Ni (99.997 wt.%)
and Si (99.9995 wt.%) on pure alumina substrates in high
vacuum. The furnace was equipped with windows enabling
the process to be filmed by a video camera (25 frames/s) and
the change in time of the contact angle h, drop base radius
and drop volume to be monitored in situ. Knowing the ini-
tial volume of the drop, it was possible to determine the
volume of infiltrated liquid at any moment.
3. Results
A first experiment was performed with the alloy contain-
ing 21 at.% Si. A few minutes after melting, a steady non-
wetting contact angle hf = 118 ± 3° was established. This
remained constant for 30 min. The same is true for the
 V. Bougiouri et al. / Scripta Materialia 54 (2006) 1875–1878
drop base radius R and the drop volume V. Fig. 2(a) pre-
sents the SEM micrographs of the cross-section of the drop
in contact with the porous graphite substrate. No infiltra-
tion of the alloy into the pores of the graphite preform
was observed. As expected, no new compound was formed
at the interface. All that occurred was some dissolution of
graphite into the alloy (Fig. 2(b)).
A second experiment, performed with the alloy contain-
ing 47 at.% Si, exhibited a completely different behavior.
The alloy was shown to wet the porous carbon well. The
contact angle after 1 h hold was h = 40° (Fig. 3(a)). About
40% of the initial drop volume was found to have infil-
Fig. 2. SEM micrographs of non-reactive NiSi (21 at.% Si)/graphite
couple after 30 min at 1270 °C: (a) a general view of the sectioned sample;
(b) alloy/carbon interface.
Fig. 3. SEM micrographs of reactive NiSi (47 at.% Si)/graphite couple
after 66 min at 1270 °C: (a) a general view of the sectioned sample; (b) an
area of the infiltrated zone.
1877
1
Cumulative frequency
0.8
0.6
0.4
0.2
0
0 10 20 30
d, µm
Fig. 4. Cumulative frequencies of pores diameter d obtained from image
analysis: before (s) and after infiltration (j).
trated into the porous carbon substrate, giving an infiltra-
tion depth of 2.0 ± 0.05 mm in the middle of the drop. A
closer look at the infiltration zone showed that all the
graphite particles were covered by a thin SiC layer
(Fig. 3(b)). In addition, SiC in the form of faceted crystals
was also observed inside the alloy. However, as expected,
the reaction was not extensive.
Quantitative evaluation of the pore size distribution was
performed by image analysis applied to the micrographs of
the infiltrated zone transformed into binary white-and-
black images. The images were processed in such a way
that SiC formed at the alloy/carbon interface was consid-
ered either as a ceramic phase together with the non-
reacted carbon or as a metallic phase together with the
Ni–Si alloy. By combining these two types of results, it
was also possible to compute the size distribution before
infiltration, assuming a constant thickness of the reaction
product along the interface (Fig. 4). The plot shows that,
after infiltration, the median radius of the pores decreased
from 3.7 lm to 3.0 lm, i.e., by less than 20%.
4. Discussion
From the experiments performed with the non-reactive
(Fig. 2) and reactive (Fig. 3) alloys it may be concluded
that the chemical reaction is a necessary condition for infil-
tration in this system. Without SiC formation at the inter-
face, no wetting and consequently no infiltration of the
liquid alloy into the pores is possible. Therefore, the flow
of liquid alloy in the porous carbon is coupled with the rate
of formation of SiC at the infiltration front.
According to this scheme, infiltration will be limited by
the slowest of the two processes, viscous flow or reaction. If
infiltration is governed by viscous flow, the experimental
infiltration distance will be close to that predicted by Eq.
(1). The time to infiltrate the graphite preform to 2 mm,
calculated by Eq. (1), using the value of the parameter reff
determined with PEG (see Section 2) and physico-chemical
properties of the NiSi alloy given in Table 1, is about 0.6 s.
This is four orders of magnitude smaller than the experi-
mental time (4000 s). It is evident that this difference can
1878 V. Bougiouri et al. / Scripta Materialia 54 (2006) 1875–1878
Fig. 5. Schematic presentation of the coupled processes of reaction and of
liquid flow at the infiltration front (the SiC layer is in black).
not be explained by the observed pores size decrease, by
about 20%, due to the thickening of SiC behind the triple
line. This result implies that infiltration in the system is
not governed by viscous flow but by the rate of growth
of SiC parallel to the pore walls at the moving Cgr-alloy-
vacuum triple line (Fig. 5).
In reaction-limited infiltration, two stages may still con-
trol the process: either long-range diffusion of Si from the
alloy bulk to the infiltration front or the local reaction pro-
cess at the triple line. This question, as well as the detailed
kinetics of infiltration in the system, will be addressed in an
upcoming publication.
5. Conclusions
The infiltration of a non-reactive and a reactive NiSi
alloy (containing 21 at.% and 47 at.% of Si, respectively)
into graphite porous preforms was studied at 1270 °C
under high vacuum using the sessile drop configuration.
The chemical reaction in the system to form SiC was shown
to be a necessary condition for wetting and spontaneous
infiltration; neither wetting nor infiltration was observed
in the non-reactive couple.
The infiltration rate in the reactive couple was found to
be several orders of magnitude lower than the rate pre-
dicted for infiltration limited by viscous flow. This result
strongly suggests that the infiltration process is not con-
trolled by viscous flow but by the reaction at the infiltration
front. The role of Si long-range diffusion and of the local
process at the triple line on this reaction will be addressed
in an upcoming publication.
Acknowledgements
The authors are very grateful to Mr. J.-M. Missiaen for
assistance with image analysis. N. Rojo-Calderon and J.
Narciso also acknowledge partial support from the Spanish
‘‘Ministerio de Educaciyn y Ciencid’’ (grant MAT2004-
03139).
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