Journal of Materials Processing Technology 119 (2001) 324±328

The wettability of SiC particles by molten aluminium alloy

J. Hashim*, L. Looney, M.S.J. Hashmi
Materials Processing Research Centre, Dublin City University, Dublin, Ireland

Abstract

A critical step in the processing of cast, particle reinforced, metal matrix composites (MMCs) is the incorporation of the ceramic particles
into the molten matrix alloy. Therefore, in a foundry MMC fabrication method, wettability of the reinforcement particles by the matrix alloy
is one aspect of the process that must be optimised. In general, the reinforcement ceramic particles are very dif®cult to wet by a liquid
metal. Information about this phenomenon is also dif®cult to obtain as it is widely dispersed throughout the literature.
This paper presents a review of available information on factors which contribute to poor wetting between ceramic phases, and liquid
metals. It particularly focuses on aluminium, a common MMC matrix material. Research on methods which can be used to improve this
wettability is also detailed. This paper aims to bridge an existing information gap between the fundamentals of the wetting of solid particles,
and the practice of the preparation of cast MMCs. # 2001 Elsevier Science B.V. All rights reserved.

Keywords: MMC processing; Composite casting; Wettability

1. Introduction tative studies have been conducted, and many fundamental

Casting of metal matrix composites (MMCs) is an attrac-
tive processing method for these advanced materials since it
is relatively inexpensive, and offers a wide variety of
material and processing condition options. Generally, these
composites consists of a metal matrix, which is melted
during casting, and discontinuous ceramic reinforcement
which is added to the molten matrix material. Good wetting
between the solid ceramic phase and the liquid metal matrix
is an essential condition for the generation of a satisfactory
bond between these two during casting [1]. The mechanical
properties of MMCs are controlled to a large extent by the
structure and properties of this reinforcement±metal inter-
face [2±5]. It is believed that a strong interface permits
transfer and distribution of load from the matrix to the
reinforcement, resulting in an increased elastic modulus
and strength. From metallurgical consideration the desired
interfacial region in a composite relies on several factors [6]:
1. An intimate contact between the reinforcement and the
matrix to established satisfactory wetting of the
reinforcement by the matrix.
2. A very low rate of chemical reaction at the interface, and
little or no inter-diffusion between the component
phases, so that the reinforcement is not degraded.
In spite of the importance of wettability in the manufac-
ture of composites by casting, seven relatively few quanti-
*
Corresponding author.
questions remain unanswered.
2. Wettability
Wettability can be de®ned as the ability of a liquid to
spread on a solid surface, and represents the extent of
intimate contact between a liquid and a solid. It can be
described by the angle of contact between a drop of liquid
resting on a solid substrate, as shown in Fig. 1. The contact
angle at equilibrium, y, is determined by the following
equation, often referred to as the Young±Dupre equation [7]:
gsv ˆ gsl ‡ glv cos y (1)
where gsv is the specific energy of the solid±vapor interface,
gsl the specific energy of the liquid±solid interface, and glv
the specific energy of liquid±vapor interface. Each specific
energy is an energy per unit area, or surface tension force.
When a liquid drop is put on a solid substrate, it will
replace a portion of the solid±vapor interface by a liquid±
solid and a liquid±vapor interface. The spreading of liquid
will occur only if this results in a decrease in the free energy
of the system. The bonding force between the liquid and the
solid phase, i.e. the work of adhesion, Wa, is de®ned as [7]
Wa ˆ glv ‡ gsv gsl (2)
Combining Eqs. (1) and (2) give
Wa ˆ glv …1 ‡ cos y† (3)

0924-0136/01/$ ± see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 4 - 0 1 3 6 ( 0 1 ) 0 0 9 7 5 - X
 J. Hashim et al. / Journal of Materials Processing Technology 119 (2001) 324±328 325

below 9008C, and Eustathopoulos et al. [12] showed that this

Fig. 1. Sessile drop test for contact angle measurement [1].
Therefore the bonding force between the liquid and solid
phase can be expressed in terms of the contact angle, and
surface tension of the liquid.
The magnitude of the contact angle will describe the
wettability:
1. y ˆ 0, for perfect wetting.
2. y ˆ 180, no wetting, and for
3. 0 < y < 180, there will be partially wetting.
This means that a low contact angle is indicative of good
wettability. A liquid is said to wet solid surface when
cos y > 0, i.e. when gsv > gsl . According to Delannay
et al. [8], in a vacuum, the driving force for wetting is
affected by only two factors: the surface tension of the liquid
and the strength of the solid±liquid interaction at the inter-
face.
Usually, wetting properties are measured by the sessile
drop technique, which is based on the measurement of
the work of adhesion, and is generally carried out in the
temperature range 400±20008C [7,9,10]. This technique
involves placing a drop of liquid metal on a solid substrate
(Fig. 1). To measure the dihedral angles, the system is
rapidly cooled in order to freeze the equilibrium shapes.
In measuring the contact angle y, great care must be exerted
to tightly control several important parameters including the
composition and surface ®nish of the solid, the purity of the
melt, and the composition and pressure of the vapour phase.
All these can exert a signi®cant in¯uence on y. Such control
is often dif®cult to achieve, and the literature contains many
contradictions and inaccuracies attributable to error in
experimental conditions.
particular phenomenon is due to the presence of an alumi-
nium oxide layer, which prevents direct contact of alumi-
nium and, in this case, carbon. As a rule, the wettability of
covalent carbides such as SiC and B4C follows the same
dependence on the nature of the metal as the wettability of
carbon.
It has been observed that a ceramic particle surface is
normally covered with a gas layer [13]. Zhou and Xu [14]
have proposed that this gas layer may be the main reason for
their poor wettability. The layer prevents molten matrix
material from coming into contact with the surface of
individual particles and additionally, when the particle
concentration in a melt reaches a critical level, the gas
layers can form a bridge, leading to total rejection of
particles from the melt [15]. Hence it is essential that gasses
from the surface of particles are desorbed prior to composite
synthesis, or alternatively that gas layers are broken by
mechanical means. Depending on the density of the ceramic
material, completely wet particles may tend to sink to the
bottom, rather than ¯oat to the surface of a melt.
The wetting or contact angle of various ceramic phases by
liquid aluminium, as measured using the sessile drop tech-
nique, are summarised in Table 1. It shows that in general the
value of contact angle decreases with an increase in alumi-
nium liquid temperature, i.e. wettability is improved at a
higher temperature, normally above 9008C.
Properties of the particle surface also affect wettability,
which can be reduced by adsorbed contaminants on the
ceramic substrate. The wetting of SiC by metals is often
hindered by the presence of a layer of silicon oxide on the
solid surface. As a result, a sharp transition from non-
wetting to wetting is observed at a certain threshold tem-
perature [22]. This transition temperature is determined by
the kinetics of diffusion of the metal through the oxide layer.
The attainment of complete wetting becomes more dif®-
cult to achieve as particle size decreases. This is due to the
increase of surface energy required for the metal surface to
deform to a small radius as the particle begins to penetrate
through it. The smaller particles are also more dif®cult to
Table 1
Contact angles between liquid aluminium and various ceramic materials

Ceramic Temperature Angle, y (8) Vacuum Reference

phase (8C) (Torr)
3. Factors which reduce wettability SiC 900 150 2:7  10 4
[15]
5
1100 34 1:5  10 [16]
Generally, the presence of oxide ®lms on a melt surface 1100 42 2:7  10 4
[17]
leads to non-wetting by molten alloys of reinforcement B4C 900 135 5
10  10 6
[18]
particles. This oxide layer creates a resistance to reinforce- 1100 120 10 5  10 6
[18]
ment particle penetration of a molten matrix, especially 1100 119 1:5  10 4 [19]
when the particles are added from the top of a cast. Alu- Al2O3 900 90 2:6  10 5
[19]
minium has high oxygen af®nity, e.g. at 4008C, a 50 nm 900 120 10 5 [20]
5
thick layer is formed on aluminium alloy in 4 h [11]. It is 1100 70 2:6  10 [19]
therefore very dif®cult to avoid oxide formation in alumi- 1100 80 10 4 [20]
1100 83 10 5 [21]
nium-based systems. Wetting is not usually observed at all
326 J. Hashim et al. / Journal of Materials Processing Technology 119 (2001) 324±328
disperse because of their inherently greater surface area.
These ®nely divided powders show an increasing tendency
to agglomerate or clump together as particle size decreases.
4. Methods to promote wettability
Several approaches have been taken to promote wetting of
reinforcement particles with a molten matrix alloy [7,23,24].
These include:
1. the addition of alloying elements to the matrix alloy,
2. coating of the ceramic particles, and
3. treatment of the ceramic particles.
The principles upon which approaches to improve wetting
are based are: to increase the surface energy of the solid,
decrease the surface tension of the liquid alloy, or decrease
the solid±liquid interfacial energy at the particle±matrix
interface [25,26].
4.1. Addition of alloying elements
The composites produced by liquid metallurgy techniques
generally show excellent bonding between ceramic and
molten matrix when reactive elements are added to induce
wettability [27]. For example, the addition of magnesium,
calcium, titanium, or zirconium to the melt may promote
wetting by reducing the surface tension of the melt, decreas-
ing the solid±liquid interfacial energy of the melt, or indu-
cing wettability by chemical reaction.
It has been found that for aluminium-based composites,
magnesium has a greater effect in incorporating reinforce-
ment particles in the melt and improving their distribution,
than other elements tested including: cerium [28,29], lantha-
num, zirconium, and titanium [29], bismuth, lead, zinc, and
copper [30]. The addition of magnesium to molten alumi-
nium has been found to be successful in promoting wetting
of alumina [27,31], and indeed it is thought that magnesium
is suitable in aluminium with most reinforcements [32,33].
Magnesium is a powerful surfactant. The addition of
magnesium to an aluminium melt improves wetting because
of the lower surface tension of magnesium (0.599 N m 1)
compared with that of aluminium (0.760 N m 1) or alumi-
nium±11.8 wt.% Si (0.817 N m 1) [36]. The addition of
3 wt.% magnesium to aluminium reduces its surface tension
from 0.760 to 0.620 N m 1 at 7208C. The reduction is very
sharp for the initial 1 wt.% magnesium addition, e.g. with
1 wt.% magnesium, the surface energy of an aluminium
alloy has been found to drop from 860 to 650 dyn cm 1
[36,37]. In the work of Sukumaran et al. [36] they concluded
that the addition of magnesium is necessary during the
synthesis of A356±SiC particle composites by a stir casting
route, and found the optimum addition of magnesium for
obtaining the best distribution and maximum mechanical
properties to be around 1 wt.%. The addition of magnesium
lower than the optimum value results in the formation of
agglomerates of reinforcement particles and their non-uni-
form dispersion in the melt.
Magnesium can also reduce the solid±liquid interfacial
energy by aiding the reaction at the surface of the rein-
forcement particles and forming new compounds at the
interface. Very small quantities of reactive elements may
be quite effective in improving wetting since they can
segregate either to the melt surface or at the melt±particle
interface (simultaneously reducing the reactive element
content in the matrix). Levi et al. [33] found that the
incorporation, wetting and bonding of the reinforcement
can be achieved by alloying aluminium with an element
which can interact chemically with the reinforcement to
produce a new phase at the interface which is readily wetted.
In the case of an Al±Mg alloy based composite, they suggest
that bonding was achieved through the formation of a
MgAl2O4 layer, by reaction between the reinforcement
and the magnesium in the aluminium liquid.
Magnesium is also a powerful scavenger of oxygen; it
reacts with the oxygen present on the surface of particles,
thinning the gas layer, and thus improving wetting and
reducing the agglomeration tendency. A composite which
was prepared by the liquid metal processing technique with
80±100 mm size silicon carbide particles in a 356 alloy
matrix, showed that the addition of magnesium helped in
thinning the gas layer, which was present over the silicon
carbide particles [34].
It can be concluded that the presence of magnesium in an
aluminium alloy matrix during composites fabrication, not
only strengthens the matrix, but also scavenges the oxygen
from the surface of the particle, leading to an increase in the
surface energy of the particles. However, caution must be
exercised in adding magnesium because the presence of
excess magnesium in an aluminium melt will alter the
microstructure of the matrix alloy by forming low-melting
constituents, which deteriorate mechanical properties. The
addition of 3.0 wt.% magnesium to an A356 alloy for
example leads to the formation of a Mg5Al8 phase, having
a low melting point of 4508C [35]. In addition, Korolkov
[35] has warned that the addition of magnesium to molten
aluminium will reduces its casting ¯uidity.
4.2. Particle treatment
Heat treatment of particles before dispersion in the melt
aids their transfer by causing description of adsorbed gases
from the particle surface. Agarwala and Dixit [30] observed
the importance of preheating in the incorporation of graphite
particles in an aluminium alloy. There was no retention when
the graphite particles were not preheated, whereas the
particles were retained when preheated. Heating silicon
carbide particles to 9008C assists in removing surface
impurities, desorption of gases, and altering the surface
composition due to the formation of an oxide layer on the
surface [38]. The ability of this particle oxide layer to
improve the wettability of SiC particles by an alloy melt
 J. Hashim et al. / Journal of Materials Processing Technology 119 (2001) 324±328
has been suggested by several investigators [39,40], and its
action is distinctly different from that of a melt oxide layer
which is a barrier to wetting. The addition of preheated
alumina particles in an Al±Mg melt has also been found to
improve the wetting of alumina [41,42].
A clean surface provides a better opportunity for melt±
particle interaction, and thus enhances wetting. Ultrasonic
techniques, various etching techniques and heating in sui-
table atmosphere can be used to clean the particle surface [7].
The silica layer grown naturally or arti®cially on the surface
of SiC particles used in aluminium-based matrix composites
is supposed to have two functions: to protect the SiC from
aluminium attack and the formation of Al4C3, and to improve
wettability by aluminium which would result from the
reaction between aluminium and the SiO2 layer [10].
4.3. Particle coating
In general, the surface of non-metallic particles are dif®-
cult to wet by a liquid metal. Wetting has been achieved,
however, by ®rst coating the particles with a wettable metal.
This is because the liquid metals almost always wet solid
metals, and wettability is highest in the case of mutual
solubility or formation of inter-metallic compounds. In®l-
tration is thus made easier by desorption of a metallic
coating on the surface of the reinforcing solid [8]. Coating
are applied in a variety of ways including chemical vapour
deposition (CVD), several forms of plasma vapour deposi-
tion (PVD), electroplating, cementation, plasma spraying
[43] and by sol±gel processes [44].
Nickel and copper are wet well by many alloys, and these
metals have been used as a coating material. Silver, copper
and chromium coatings have also been proposed [14,45±47].
However, nickel is the most frequently used metal for
coating reinforcement particles used with aluminium-based
composites [44,45,48,49]. It is important to note that the
interaction of coatings with a liquid metal during in®ltration
or stirring, and the in¯uence of this on the solidi®cation
microstructure and the mechanical properties of a composite
are not well understood.
4.4. Other methods
A mechanical force can usually be used to overcome
surface tension and improve wettability. However, in the
experimental work of Zhou and Xu [14], it was found that
mechanical stirring cannot solve poor wettability when the
matrix alloy is in a completely liquid state. Stirring in a
semi-solid state did help to promote wettability between SiC
particles and Al±Si and Al±Mg alloys.
Ultrasonic vibration was applied to liquid MMC proces-
sing to improve apparent wettability of Al2O3 particles with
molten aluminium. Prior to the ultrasound-assisted proces-
sing, it was found that the application of ultrasonic vibration
made the contact angle of the system change from non-
wetting to a wetting system [15].
327
Mixing time is one of the important variables which is
often not adequately recognised or reported. Many of the
metal±ceramic systems of commercial interest are made
wettable by promoting interfacial reaction. Since the pro-
cesses which effect the interfacial energy balance progress
with time, the contact angle, y, is often a function of time.
Therefore if the processing time is short, the particles may
appear non-wet, but with an increase in time these particles
become wettable. Near-linear decreases of wetting angle
with time for the SiC/Al system were observed at 980 and
9008C by Kohler [17] and Halverson et al. [18]. Brennan and
Pask [19] reported that there is a linear time dependence of
wetting angle in the Al2O3/Al system. Similar time depen-
dence of contact angle may also be observed for coated
particles if the coating is soluble in the melt. The processing
time should be controlled so that the coating does not
dissolve completely [13].
5. Conclusions
Both chemical and mechanical factors in¯uence the wett-
ability of ceramic reinforcement particles by molten metal in
MMC solidi®cation processing. The chemical nature of the
interface determines not only wetting but also the strength
and stability of the interface. Good wetting leads to a strong
bond between reinforcement particles and the matrix. How-
ever, contamination, the presence of a gas layer, or the
formation of an oxide layer on the melt can be detrimental
to wettability.
Three main wettability enhancement methods include
adding some surface-active elements such as magnesium
into the matrix, coating or oxidising the ceramic particles or
cleaning the particles, for example by pre-heat treatment.
These can make mixing and retention of the ceramic par-
ticles easier. The applications of mechanical stirring when
the slurry is in semi-solid state, or the application of ultra-
sonic vibration have also had a bene®cial effect on wett-
ability.
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