COMPOSITES

SCIENCE AND
TECHNOLOGY
Composites Science and Technology 64 (2004) 18431854
www.elsevier.com/locate/compscitech

Oxidation treatments for SiC particles used as reinforcement

in aluminium matrix composites
a,*
A. Ure~
na , E.E. Mart
nez b, P. Rodrigo a, L. Gil a

a
Dpto. Tecnolog
a Qu
mica, Ambiental y de los Materiales, Escuela Superior de Ciencias Experimentales y Tecnolog
a,
Universidad Rey Juan Carlos, 28933 M
ostoles, Madrid, Spain
b
Instituto de Metalurgia, Facultad de Ingenier
a, Universidad Aut
onoma de San Luis Potos
, San Luis Potos
, S.L.P. CP 78210, Mexico

Received 10 October 2003; received in revised form 26 January 2004; accepted 27 January 2004
Available online 11 March 2004

Abstract

The present research is centred on the application of oxidation treatments to SiC particles to improve the casting processability of
AlSiC composites by means of a chemical interface control. If a continuous SiO2 layer is generated on the particle surface, the
reinforcement particles can be incorporated in a molten aluminium matrix, and the degrading reaction of Al4 C3 formation is re-
placed by other interfacial reactions which improve wettability, avoid particle consumption and increase interface strength. This
work presents an optimisation study of the oxidation treatment conditions for SiC particles to obtain continuous adherent coatings
which act as active barriers. The inuence of particle sizes and treatment temperatures on the oxidation kinetics and barrier structure
were evaluated. The capability of the protective barriers developed in the interfacial control was analysed by means of reactivity tests
with molten aluminium, in comparison with unprotected particles. Both eects on local reactivity and mechanical interface prop-
erties were studied.
2004 Elsevier Ltd. All rights reserved.

Keywords: Aluminium matrix composites; A. Coating; B. Interfacial strength

1. Introduction niques and dry mixing procedures to deposit oxide ag-

Reactivity between molten aluminium and SiC par-
ticles in composites during their liquid phase manufac-
ture has important detrimental eects, such as reducing
reinforcement and interfacial strengths and increasing
corrosion susceptibility [14]. To avoid AlSiC interface
reactions during melt processing without limiting the
composition and microstructure of the resulting com-
posite, a possible solution is to interpose a diusion
barrier between the SiC and the reactive matrix. Both
metallic [5] and ceramic barriers [6,7] have been tested
by other authors using dierent coating methods such as
electroless or cementation for metallic coatings, and
thermochemical treatments (oxidation), solgel tech-
*
Corresponding author. Tel.: +34-91-394-4181; fax: +34-91-664-
7490.
E-mail address: a.urena@escet.urjc.es (A. Ure~
na).
gregates on the surface of the SiC particles.
For the selection of an optimum coating, several
functions must be considered. Although, its main role
may be to act as a protective barrier (e.g. diusion bar-
rier) to prevent the formation of Al4 C3 by reaction be-
tween molten Al and SiC; the selected coating should
favours the contact between the solid ceramic reinforce-
ments and the molten aluminium matrix during com-
posite fabrication following a casting procedure. It could
be possible if the coating favours a reactive wetting be-
cause the free energy produced by the reaction between a
liquid and a solid in the interface results in a transient
decrease in liquid/solid interfacial energy and in contact
angle, according to the model proposed by Aksay et al.
[8]. This is desirable because another problem which
limits casting manufacturing of AlSiC composites is the
low wetting of ceramic particles by molten aluminium.
A third desirable characteristic of the selected coating
might be its ability to generate a high strength bond

0266-3538/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2004.01.010
1844 A. Ure~na et al. / Composites Science and Technology 64 (2004) 18431854
between the reinforcement and the matrix, without
forming brittle reaction compounds which could limit
the mechanical behaviour of the resulting composite.
In the present study, the authors have evaluated the
application of a continuous layer of SiO2 on the surfaces
of the SiC particles. It has been proved by other authors
that the presence of silica favour reactive wetting be-
tween molten aluminium and SiC substrates [9]. Oxi-
dising heat treatment of the SiC particles was used as a
coating method to produce the silica reactive layers. The
research was centred on optimisation of the coating
conditions applied to the SiC particles and their ability
to control the interface reactions and properties occur-
ring when the aluminium matrix is melted under similar
conditions to those used for liquid processing of com-
posites (rheocasting, stircasting, compocasting, etc).
This purpose was achieved by kinetic studies of the
oxidation of SiC particles by means of dierential
thermogravimetry (DTG). The continuity of the coat-
ings produced was studied by scanning electron mi-
croscopy (SEM) and their structures were determined by
X-ray diractometry (XRD) and transmission electron
microscopy (TEM). The ability of the developed barriers
to control the interface reactivity was evaluated by
means of microstructural studies, using SEM-EDX, in
specimens of aluminium composites constituted with
protected SiC particles and subjected to reaction tests
which simulate a casting procedure. Similar treatments
were applied to composites with unprotected reinforce-
ments for comparative purposes.
Vickers indentation was used as an indirect method
for the determination of inuence of the oxidation
treatment on the interfacial strength of the matrix-re-
inforcement interfaces.
2. Experimental procedure
2.1. Materials
The SiC particles used in this study were supplied, in
three dierent denominations, by Navarro S.A. Their
sizes and chemical compositions are described in Tables
1 and 2 respectively. Measurements of the particles
specic surfaces were made using a BET technique
(adsorption/desorption of N2 in the solid surface).
Table 1
Chemical composition of SiC particles
Denomination Chemical composition (wt%)
Free C SiC SiO2 + Si
F-360 0.05 99.75 0.02
F-500 0.06 99.59 0.16
F-800 0.28 99.14 0.62
Table 2
Sizes of as-received SiC particles
Denomination Particle size (lm)
6% 50% 97%
F-360 14.7 26.2 42.7
F-500 7.2 15.3 27.2
F-800 3.0 8.6 18.2
Commercially pure (99.7%) aluminium powders, fabri-
cated by gas atomisation, with a mean diameter of
16 lm were used to form the composite matrix.
2.2. Coating procedure
SiC particles were coated with a silicon oxide lm
obtained by direct oxidation in an air-furnace at 1200 C
with holding times of 2 and 8 h and heating and cooling
rates of 5 C/min. To determine these optimum condi-
tions, prior kinetic studies of the SiC particle oxidation
were carried out using dierential thermogravimetry
(DTG) tests in a Setaram Thermoanalyser (mod. Se-
tys16/18). Both DTG continuous heating from room
temperature to 1530 C at a heating rate of 10 C/min
and an air ow of 200 cm3 /min, and isothermal DTG
tests at 1200 C for 8 h, were applied. The initial weight
of the tested samples was 500 mg being the balance
resolution
0.4 lg. The thickness of the oxide coatings
was calculated from gravimetric measurements after
DTG tests, although direct measurements were made by
TEM in particles oxidised in the air furnace.
The original state of particle surfaces and their
modication after protection treatment were evaluated
by SEM. In addition, oxidised particles were mounted in
a low contraction resin to preserve the coating on the
SiC surface and observed by SEM in cross-section using
backscattered electron images (BSE) to analyse the
continuity and homogeneity of the oxide layer. After-
ward, these specimens were thinned mechanically and by
ion-milling for direct measurement of the coating
thickness by TEM.
The evolution of the oxide coating constitution and
chemical composition during the oxidation treatment
was monitored by XRD, and their structures were
characterised by means of electron microdiraction in
TEM. For this purpose, both as-received particles and
Fe2 O3 Al2 O3 CaO
0.05 0.03 0.02
0.04 0.01 0.02
0.10 0.01 0.01
 A. Ure~na et al. / Composites Science and Technology 64 (2004) 18431854
oxidised particles were prepared by milling in an agatha
mortar followed by dispersion in high vacuum evapo-
rated carbon lms on a copper grid.
2.3. Reactivity tests
Interfacial reaction tests were carried out using cold
compacted mixtures of aluminium powders with 30%
volume of SiC particles. The SiC and Al powders were
pressed into disks of 15 mm diameter and 5 mm thick-
ness. Compaction was carried out using a pressure of
2.85 MPa. Both specimens, with as-received SiC parti-
cles and with pre-oxidised particles (SiCoxd ), were pre-
pared to compare the interfacial reactivity, under similar
melting conditions, in dierent surface particle states.
The interfacial reaction tests consisted of melting the
composites under high vacuum (>104 Pa) at 900 C
and holding times of 20 and 60 min. Such high reaction
temperature was chosen because of the interest to eval-
uate the capabilities of the proposed coating in extreme
manufacturing conditions, where matrix-reinforcement
reactivity is thermodynamically and kinetically very
favoured.
Both interface reaction grade and wetting behaviour
in the molten AlSiC and AlSiCoxd composites were
microstructurally evaluated by SEM and the changes of
chemical composition at SiC/Al interfaces were deter-
mined by EDS microanalysis. Both were prepared using
conventional metallographic techniques for aluminium
matrix composites: grinding with SiC paper up to 600
grade and polishing with diamond paste of decreasing
particle size (3, 1 and 0.1 lm). To prevent degradation of
any Al4 C3 formed by the action of water, all prior sur-
face preparation was carried out using ethylene-glycol as
the lubricant. SEM studies were carried out with a Jeol
6400 SEM equipped with EDX analysis.
2.4. Matrix-reinforcement interface characterization
The eect of the chemical interface reactions on the
SiC surfaces and the inuence of the protecting barrier
on it was analysed from SEM observation of the ceramic
particles, once these were extracted from the aluminium
matrix. This was achieved by electrolytic dissolution of
the tested composites in a solution of HNO3 (30 vol.%)
in methanol followed by ltration of the solid residue.
The method used to determine the interfacial strength
of the tested composites was an indirect one based on the
Vickers indentation, which has been proposed by several
authors to determine the fracture toughness of ceramic
materials [1012]. For example, Shetty [12] has proposed
a model to determine the critical stress intensity factor
s 5
(KIC ) in brittle materials such as TiB2 cermets by mea-
suring the length of the cracks generated from the Vickers
mark vertices, according to the following equation:
1845
s 1=2
KIC bHP=4aE ; 1
where P is the applied load, H the calculated
Vickers hardness, E the Young modulus, b a geo-
metric constant having a value of 0.089 for the Vickers
indentation, and a is the crack length. The application
of Shetty model to the local characterization of tough-
ness in embrittled interfacial zones can be acceptable,
especially for comparative purposes as it has been ap-
plied in present papers. Values of KIC s
for the dierent
generated interfaces were determined, analysing the
crack propagation behaviour in both coated and un-
coated interfaces. For it, Vickers indentations were
made with loads of 0.25 and 1 N, both inside the SiC
particles and in the aluminium matrix located in the
vicinity of the reinforcement/matrix interfaces.
3. Results
3.1. Characterisation of protecting barriers
The three types of as-received SiC particles had as-
pect ratios in the range of 1:21:5, showing the typical
sharp edges with evident signs of fracture characterised
by the formation of serrated surfaces. Their specic
surfaces measured by BET method decreased with in-
creasing average particle size, as is shown in Fig. 1.
DTG tests carried out with the three kinds of parti-
cles in oxidant atmosphere up to 1530 C, showed that
SiC oxidation was activated at temperatures above 1000
C, reaching the maximum oxidation rate at close to
1200 C, except for the lower sizes (F-800) for which the
oxidation rate increases further reaching its maximum at
1300 C (Fig. 2). The gain in weight corresponds with a
passive oxidation with formation of SiO2 . Considering
the volume relation between SiO2 formed and SiC
consumed (VSiO2 =VSiC ) due to the oxidation, it is ap-
proximately 1.8. Therefore the oxide coating can cover
1.0
Specific surface (m2/g)
0.8
0.6
0.4
0.2
10 15 20 25 30
Particle size (m)
Fig. 1. Specic surfaces of SiC particles vs. average sizes.
1846 A. Ure~na et al. / Composites Science and Technology 64 (2004) 18431854

0.030 10

9 F-800
0.025
8
Weight percent/time

0.020 7

Gain (weight ptc)

F-800
6 F-500
0.015
F-360
5

0.010 4
F-360
3
F-500
0.005
2

0.000 1

0
-0.005
0 200 400 600 800 1000 1200 1400 1600 -1
0 200 400 600 800 1000 1200 1400 1600
Temperature (C)
(a) Temperature (C)
Fig. 2. Oxidation rate of the SiC particles vs. temperature.
200

the SiC surface having protective eects. The maximum F-360

rates obtained imply the formation of a continuous 150

oxide layer which protects and inhibits the SiC surface

Film thickness (nm)

against further oxidation. For these reason, oxidation 100
rate decreases from this maximum. Smaller particles F-500

present greater active surface and therefore higher gains

F-800
of weight, but the critical oxide thickness which controls 50

the oxidation reaction is reached later.

Fig. 3(a) and (b) show that the weight of the particles
0
during oxidation and the average coating thickness,
calculated considering that the weight gain is due to the 0 200 400 600 800 1000 1200 1400 1600
conversion of SiC to SiO2 by direct oxidation and using (b) Temperature (C)
the Eq. (2) given by Guy Ervin [13], increased with
Fig. 3. (a) Weight gain of the SiC particles during DTG analysis, for a
temperature.
heating rate of 10 C/min. (b) Calculated thickness of the oxidation
MSiC barriers vs. oxidation temperature.
t DW =100  S ; 2
MSiO2  MSiC  qSiC
where t is the thickness of the oxidized lm, S the specic 100
surface of SiC particles (cm2 /g), q the SiC density (3.22 F-360
90
g/cm)3 , DW the weight gain (%), being MSiC and MSiO2
the molecular masses of SiC and silica, respectively. 80 F-800
F-500
These data conrm that although oxidation treat-
Thickness (nm)

70

ment is activated in particles with smaller sizes, it is 60

more eective as a coating process for the particles with 50
average size of 26.2 lm. The isothermal DTG tests
40
carried out at the selected coating temperature (1200 C)
obtained for each type of SiC particles during the 30

coating treatment showed that maximum average 20

thickness of 93 nm could be achieved in F-360 SiC 10
particles after 8 h of coating treatment and was 55 nm 0 2 4 6 8

after only 2 h of treatment (Fig. 4). Time (h)

After application of these oxidation conditions (1200
C for 2 and 8 h) to the as-received SiC particles in an air
furnace, their surfaces were covered by an apparently
continuous coating, which extended even to the fracture
serrations (Fig. 5(a)), although occasional points of
cracking or local disruptions of the oxide barrier were
detected (Fig. 5(b)).
Cross-section observation of the protected particles
using BSE images (Fig. 6) showed that the barriers can
Fig. 4. Calculated thickness of the oxidation barriers produced at
1200 C vs. oxidation time.
continuously cover the particle and are of even thick-
ness. This was directly measured by TEM for the F-360
SiC particles treated in an air furnace for 8 h at 1200 C;
obtained values were in the range 150250 nm, higher
than average values calculated from DTG tests. Lower
 A. Ure~na et al. / Composites Science and Technology 64 (2004) 18431854 1847

(a-cristobalite), which amount increased with the pro-

longation of the oxidation time (Fig. 7). However, to
conrm the crystalline nature of the oxide, TEM ob-
servations were carried out. These showed that protec-
tion barriers are constituted mainly by amorphous silica,
although there is always a certain amount of a-cristo-
balite, being greater in particles oxidised for longer
times. Fig. 8(a) shows a TEM image of a barrier which
has been extracted from the SiC surface after particle
milling; it is constituted mostly by glassy silica, although
there are some points (Fig. 8(b)) where a-cristobalite
was identied by electron microdiraction.

3.2. Eect of coating on wetting behaviour and interface

reactivity

The eect of the oxidation barrier to control both

wetting behaviour and interface reactivity in mol-
ten aluminium was mainly evaluated using protected

3500

(c)
SiC

2000

1500

Fig. 5. (a) SEM image of the oxidised SiC particles and (b) detail of the
1000 SiC
disruption of the oxide barrier at the SiC fracture marks. SiC SiC
SiC
500 SiC
SiO2 SiC
SiC SiC SiC SiC
0
3500
Relative Intensity

(b)
3000

2500

SiC
2000

1500
SiC

1000
SiC SiC
SiC
500 SiC SiC
SiO2 SiC SiC SiC
SiC
0
3500

(a)
3000
SiC

2500

2000
Fig. 6. Backscattered electron image of coated SiC particles showing
surface oxide barrier. 1500
SiC
1000 SiC SiC SiC
values obtained from DTG data can be inuenced by SiC
500 SiC
the presence of a distribution of particle size in each SiC SiC
SiC SiC
sample of powders tested (Table 2) and because of the 0
0 20 40 60 80
possible formation of defects or discontinuities in the
Angle (2 )
oxidised coatings.
In relation to the barrier composition and structure, Fig. 7. DRX patterns of SiC particles: (a) as-received, (b) oxidised at
XRD tests showed the formation of crystalline SiO2 1200 C for 2 h and (c) oxidised at 1200 C for 8 h.
1848 A. Ure~na et al. / Composites Science and Technology 64 (2004) 18431854
Fig. 8. TEM images of the SiO2 coatings showing vitreous zones (a)
and crystalline zones (b), identied by electron diraction as a-cris-
tobalite.
particles of the higher average size (F-360), as their be-
haviour was more homogeneous during coating treat-
ment. Nevertheless, comparative test studies were
carried out using both coated particles of smaller sizes
and unprotected SiC particles.
3.2.1. Reactivity tests in unprotected SiC particles
Fig. 9(a) shows the typical microstructure of an Al/
SiC composite constituted by F-360 unprotected parti-
cles after a reaction test (900 C for 20 min). Micro-
structural observations show that SiC particles are
homogeneously distributed in the aluminium matrix,
Fig. 9. (a) Microstructure of an AlSiC composite obtained after a
reaction test (900 C, 20 min) with unprotected particles. (b) Solidied
aluminium drops on SiC particle surfaces.
and there is high continuity at the Al/SiC interfaces with
a low proportion of faults of contact or voids produced
by a pour wetting between the molten aluminium and
the silicon carbide particles. Both microstructural
characteristics are signs of a proper wettability between
both composite components, although some points
where there is no wetting can be seen in Fig. 9(a) (ar-
rowed). SEM observation inside these gaps at higher
magnications (Fig. 9(b)) showed the presence of alu-
minium drops solidied on SiC surfaces, with evidence
of the formation of high wetting angles between both
surfaces.
Another characteristic of Al/SiC composites after
reaction tests is the formation of a continuous reaction
layer at the metalceramic interface. This was detected
in reactivity tests carried out at 900 C for 20 min
(Fig. 9(a)), and was especially evident when melting time
was prolonged for 60 min (Fig. 10(a)). Microanalytical
studies of these reaction compounds (Fig. 10(b)) showed
the formation of Al4 C3 caused by the reaction between
molten aluminium and SiC. This reaction is produced by
a dissolutionprecipitation mechanism [14]; SiC is dis-
solved by molten Al which becomes saturated in carbon,
precipitating the Al4 C3 in the form of tabular aggregates
which penetrate the SiC. Some of these points of pref-
 A. Ure~na et al. / Composites Science and Technology 64 (2004) 18431854
Fig. 10. (a) Eect of the interface reaction between an unprotected SiC
particle and molten aluminium after a reaction test at 900 C/60 min.
(b) EDS microanalysis of the interfacial reaction product.
erential dissolution of SiC particles are marked with
arrows in Fig. 10(a); in some zones (marked A), the
hexagonal morphology presented by the reaction prod-
ucts is evident.
Elimination of the aluminium matrix by electrolytic
etching revealed the characteristics of the dissolution
eect produced on the SiC particles by the molten alu-
minium. Firstly, the interface reaction was not homo-
geneous around the particles; there were some zones of
preferential etching (A) and others where the original
SiC surface was preserved (B), as shown in Fig. 11(a).
This dierence in behaviour among zones may be at-
tributed to the lower reactivity of certain planes of SiC
(i.e. carbon faces of a-SiC) [15], also taking in account
the polycrystalline nature of the SiC particles. This
heterogeneity of behaviour with respect to the surface
reactivity of the particles also determines that surfaces
1849
Fig. 11. (a) Preferential etching of the SiC surfaces by dissolution in
molten aluminium. (b) Detail at higher magnication.
with lower reactivity present poorer wetting behaviour,
limiting the time of contact with the molten aluminium.
A study in depth of the reaction zones (Fig. 11(b))
showed points of local dissolution of the SiC forming
hexagonally symmetric steps or terraces. These points
would coincide with the formation zones of tabular
Al4 C3 crystals which had been eliminated by the acid
etching.
3.2.2. Reactivity tests in protected SiC particles
SEM study of reaction test specimens constituted by
Al and coated SiC particles (Al/SiCoxd composites)
conrmed both the control of interface reactivity and
the improvement of wetting behaviour. Fig. 12(a) shows
an Al/SiCoxd composite (with particles oxidised at 1200
C for 2 h) melted at 900 C for 20 min. There is a high
level of continuity (proper wetting behaviour) and the
interface reactivity in this specimen is clearly lower than
in the one tested in the same conditions but using un-
protected particles; although there is evident formation
of a continuous reaction layer, this is narrower and the
points of penetration inside the particle are less nu-
merous. EDS microanalysis of this interphase showed
that the reaction compounds were mainly constituted by
Al, Si and O, although variable C contents were detected
(Fig. 12(b)).
1850 A. Ure~na et al. / Composites Science and Technology 64 (2004) 18431854

Fig. 13. Detail of the interface reaction layer formed between pre-
oxidised SiC (1200 C, 2 h) and molten aluminium at 900 C, 60 min.

1000

Al
(a)
800

Al
SiC
600

400

Al
SiC
SiC
200
Relative Intensity

SiC

SiC
SiC
4 3
SiC

Al C
Si

Si

Si
0
1000

(b)
800
Al

600
Fig. 12. (a) SEM microstructure of an AlSiC obtained after a reaction
test (900 C, 20 min) with protected particles after oxidation at 1200 C
for 2 h. (b) EDS microanalysis of the interfacial reaction product. 400
Al

200
4 3
SiC Al C
4 3
SiC
SiC
Al C

Al
SiC

TEM and HREM observations of these reaction

SiC
4 3
Al C
Si

Si

layers carried out for present authors [16] have made 0

possible to propose a mechanism for the interfacial re-
action which considers the reaction between molten
aluminium and SiO2 to form an alumina-silicate glassy
phase. The consumption of the SiO2 barrier favours a
preferential dissolution of SiC particles by the glassy
phase AlSiO and its subsequent C-enrichment. Other
interfacial reaction between matrix and coating are also
possible with formation of Al2 O3 and Si, products which
have been also detected, although in low proportions, in
the manufactured composites.
For longer times of contact with the molten alumin-
ium (60 min), the penetration zones inside the particles
increases, as shown in Fig. 13. However, no generalised
formation of the characteristic tabular crystals of Al4 C3
was detected. This was conrmed by XRD comparison
20 40 60 80
Angle ()
Fig. 14. DRX patterns of SiCAl reaction tests at 900 C, 20 min for:
(a) particles oxidised at 1200 C, 2 h (b) unprotected particles.
of the tested specimens with unprotected composites
tested in the same melting conditions (Fig. 14).
Penetration of the reaction layer must be originated
by consumption of the oxide coating and can be re-
tarded by increasing the coating thickness. For this
reason, specimens constituted by SiC particles oxidised
at 1200 C for 8 h did not present those points of local
penetration, even after 60 min of contact with molten
aluminium at 900 C (Fig. 15).
 A. Ure~na et al. / Composites Science and Technology 64 (2004) 18431854
Fig. 15. Interface between an oxidised SiC particle (1200 C, 8 h) and
molten aluminium (900 C, 60 min) without local penetration of the
reaction layer.
To determine the morphologic characteristics of the
layer formed by reaction between the SiO2 barrier and
the molten aluminium and its possible interaction with
the SiC surface, Al/SiCoxd composites were electrolyti-
cally dissolved to extract the protected reinforcement.
Fig. 16 shows one of the protected SiC particles with the
most oxidant conditions (1200 C, 8 h), which was in
contact with molten aluminium at 900 C for 60 min.
The SiC surface is covered by a reaction layer with a
homogeneous and continuous appearance. However,
there are also signs that the reaction layer has been
locally disrupted (marked with A), probably during l-
tration to extract it from the aluminium matrix. The
exposed inner surface is constituted by SiC, which pre-
sents its original structure with no signs of dissolution,
demonstrating the eectiveness of the SiO2 barrier.
Fig. 16. SiC coated particle extracted by matrix dissolution from an
AlSiC reaction test specimen showing a zone (marked A) where the
reaction layer is disrupted.
1851
3.3. Inuence of particle size on the eectiveness of
protection
Additional studies were carried out with similar
protection conditions and reaction tests but using F-500
SiC particles (15 lm). The most striking observation was
that although the specic surface of the ceramic phase
had increased, there was adequate wettability, which
means that the SiO2 barrier reacts with molten alumin-
ium, decreasing the interface free energy and increasing
the adhesion work. However the formation of tabular
Al4 C3 crystals in a higher proportion than in composites
with protected F-360 SiC was detected. In general, it was
observed that particles of smaller size usually presented
a higher proportion of Al4 C3 , which means that, for the
tested conditions, the coating treatment is less eective
when specic surface of the reinforcement increases, due
to the thinner coating produced and the higher proba-
bility to generate discontinuities in the barrier.
3.4. Eect of the oxidation treatment on the interfacial
strength
Fig. 17(a) shows the Vickers mark on an unprotected
SiC particle with a load of 0.25 N. Notice the crack
formation from the mark vertices which grow towards
Fig. 17. (a) Crack propagation along the matrix/particle in Al/SiCp
composite. (b) Detail of matrix embrittlement.
1852 A. Ure~na et al. / Composites Science and Technology 64 (2004) 18431854

the Al/SiC interface, with lengths close to 40 lm in some

vertices. However, the most striking feature is that the
particle fractured when the load was applied, generating
interfacial push-down. Observation at higher magni-
cation (Fig. 17(b)) shows that beside of the interfacial
disjoint produced by the application of the Vickers in-
dentation on the SiC particle; there is also a massive
microcraking inside the metallic matrix which surrounds
the tested particle. This matrix embrittlement in and
around the altered reinforcements is associated with the
formation of Al4 C3 and Si as a consequence of the in-
terface reaction between Al and the unprotected SiC.
This kind of behaviour contrasts with what happens
when the Vickers indentation is made on a SiC particle
which has been previously protected with a SiO2 active
barrier. One of these particles is shown fractured by a Fig. 19. Vickers indentation marks in proximity to unprotected SiC
particles.
1 N indentation in Fig. 18. Although there is interfacial
push-down, there is no propagation of secondary cracks
in the nearest aluminium matrix.
Nevertheless, the evidence of mechanically suitable
behaviour of the composites manufactured with pro-
tected SiC particles is clearest when the Vickers inden-
tations are made in the matrix but in proximity to both
kinds of particle. The micrographs in Fig. 19 show two
indentations of 0.25 and 1 N (marked A and B respec-
tively) made close to an unprotected particle. From
mark A, a crack propagates toward the SiC/Al interface,
which originates the interfacial failure. Two cracks, 10
and 30 lm long, run from the vertices of mark B, made
inside the altered aluminium matrix.
Analysis of crack propagation in proximity to pro-
tected particles shows absence of interfacial failure and
of cracking in the matrix close to the Al/SiC interface in Fig. 20. Vickers indentation marks in proximity to protected SiC
all cases (Fig. 20). Another interesting observation is the particles.
irregular shape of most of the Vickers marks made in
proximity to protected particles. The semi-diagonals of larger than the others, which probes the lower hardness
these marks inside the matrix close to the interface are of this zone.

4. Discussion

Previous results have shown that the application of

Fig. 18. Fracture of a protected SiC particle after an indentation test.
controlled oxidation to SiC particles is an eective
method for protecting them against degradation by
molten aluminium during casting. The proposed coating
oers another additional benet related to the im-
provement of processability by casting route, which is
increased wetting in the tested conditions.
SEM-EDX studies have demonstrated that, at the
tested temperature (900 C), SiO2 coating reacts with the
molten aluminium to form a continuous reaction layer
constituted mainly by an AlSiO compound. This
chemical reaction is thermodynamically favoured hav-
ing a negative value of its Gibbs free energy and hence
produced decrease in solid/liquid interfacial (metal
ceramic) energy. Laurent et al. [9] have shown that the
 A. Ure~na et al. / Composites Science and Technology 64 (2004) 18431854
wetting angles in reactive oxide/metal systems can be
obtained from the following relationship:
 
Dcsl DGr
cos h cos h0  ; 3
clv
where: h0 is the wetting angle in the absence of reaction;
Dcsl takes into account the variation in solid-liquid in-
terfacial energy (csl  c0sl ) due to the replacement of ce-
ramic-metal interface (e.g. SiCAl) by a double interface
(e.g. SiCSiO2 Al); clv is the surface energy of the
molten Al; and DGr is the Gibbs free energy of the in-
terfacial reaction between the coating and the molten
aluminium and h is the resulting contact angle, which
measures the wetting behaviour.
Because the coating is largely amorphous and con-
tinuously envelops the SiC particle, the interface reac-
tion occurs homogeneously around it. This implies that
the improvement of wetting is not localised at points of
preferential interface reactivity, such as occurs with the
formation of Al4 C3 by reaction between molten Al and
unprotected SiC, but aects all coated surfaces.
It was observed that increasing the oxidation time at
1200 C favours the formation of crystalline phase
(a-cristobalite) in the protective coating. Although the
results did not show that the presence of this phase could
be detrimental to the protective role of the barrier, the
important change in volume associated with this crystal-
lisation could cause it to crack by generating internal
stresses. In spite of this, when the oxidation time was in-
creased from 2 to 8 h at 1200 C, the protection coating
obtained in F-360 SiC particles prevented the interface
reaction from penetrating the reinforcement, even in the
more extreme conditions (900 C, 1 h). This means that
although partial transformation of amorphous silica to
cristobalite could generate local discontinuities at the
barrier, the increase in thickness produced by prolonging
the oxidation treatment enhances its protective eect by
preventing complete consumption.
Although the study of the eectiveness of the pro-
tection coating focussed on the coarser particles (F-360),
it was found that the experimental oxidation conditions
were insucient to protect smaller particles. SEM
observation showed that although coated F-500 SiC
particles presented suitable wettability by molten alu-
minium, the proportion of tabular Al4 C3 crystals pro-
duced by direct reaction between SiC and Al increased.
This means that the increase in the specic surface of
these particles (0.4 m2 /g for F-500 vs. 0.2 m2 /g for F-
360) not only reduces the thickness of the oxide layer but
in the tested oxidation conditions could also generate
more defects and discontinuities in it.
To complete the study of the eectiveness of the studied
treatments, it was proved that its presence avoid the
problems of embrittlement caused by the direct reaction
between molten aluminium and SiC particles. The values
for the critical stress intensity factors measured by ap-
1853
Table 3
Critical stress intensity factors measured applying the Shetty model
Zone H P a E s
KIC
(g) (lm) (GPa) (MPa m1=2 )
SiC particle 2574 25 6.54a 470 2.0
Altered matrix 100.5 100 8.20b 69 1.9
a
Average value.
b
Maximum measured value.
plying Eq. (1) are summarized in Table 3. The most in-
s
teresting nding is the low KIC in some regions of the
matrix close to the reaction interface in unprotected
particles, where the minimum values determined (1.9
MPa m1=2 ) may be more than one order of magnitude less
s
than the typical KIC of pure aluminium. This is explained
by the high proportion of brittle phases (Al4 C3 and Si)
that form in these altered zones. This located precipitation
was not observed working with protected particles, and
even a local matrix softening around particles was de-
tected. This eect could be explained by the diusion of
some impurities present in the aluminium (Cu, Fe) toward
the active barrier, where they are stopped by the reactions
occurring inside this interface [16].
5. Conclusions
(1) Oxidation of SiC particles for 28 h at 1200 C gen-
erates a continuous homogeneous coating which
acts as a reaction barrier preventing degradation
of the particles by molten aluminium.
(2) Coatings developed by SiC oxidation consist of a mix-
ture of amorphous silica and a-cristobalite, increasing
the proportion of the crystalline phase when time of
treatment at oxidation temperature is prolonged.
(3) The kinetic of SiC particle oxidation is inuenced by
their sizes and specic surfaces. Maximum oxidation
rates were obtained at temperatures in the range of
12001300 C, being this temperature higher for
the smallest particles (F-800). Higher coating thick-
ness is obtained in coarser particles (F-360 of 26.2
lm mean size) and the maximum oxidation rate
for this size occurs approximately at 1200 C.
(4) The oxide barrier enhances the wetting behaviour of
the particles protected by molten aluminium at 900
C by means of an interface reaction between the
SiO2 and the Al, which occurs all around the parti-
cle, producing a continuous reaction layer and
reducing the interface free energy.
(5) Consumption of SiO2 barrier produces preferential
dissolution of the SiC particle but not formation of
Al4 C3 by direct reaction between Al and the particles.
(6) The formation of Al4 C3 in molten composites with
protected SiC particles is associated with faults or
discontinuities in the barrier and is more generalised
1854 A. Ure~na et al. / Composites Science and Technology 64 (2004) 18431854
when composites of lower particles sizes (<15 lm)
are tested.
(7) The new interphase generated by reaction between
aluminium matrix and SiO2 coating has a proper
mechanical behaviour, avoiding the embrittlement
eect of the direct reaction with the SiC particle
and favouring a light matrix softening around the
reinforcements.
Acknowledgements
The authors wish to thank to the Ministerio de
Ciencia y Tecnolog
a (MICYT) for the nancial support
given to this research (Project MAT2000-1646-C02-01).
We also wish to thank Navarro S.A. for supplying the
SiC particles.
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