Composites Part B 81 (2015) 141e148

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Microstructure evolution and tribological properties for new

AlSi9Cu3/5%GrCu composite
Petru Moldovan a, Ioana Csaki a, *, Gabriela Popescu a, Mariana Lucaci b,
Magdalena Lungu b, Mihai Butu a
a
University Politehnica Bucharest, Splaiul Indepentei 313, Bucharest, Romania
b
ICPE-CA, Bucharest, Romania

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

Article history: A metallic matrix composite, with AlSi9Cu3 matrix reinforced with 5% copper coated graphite (GrCu) was
Received 1 April 2015 processed in semi solid state by centrifugal casting. This technique allows the uniform controlled dis-
Received in revised form tribution of the reinforcing material to provide improved tribological properties in certain area. The
10 June 2015
graphite particles were copper coated for a better embedding in the matrix. The microstructure evolution
Accepted 9 July 2015
Available online 17 July 2015
revealed compounds containing Mn, Si and Mg in the matrix alloy and the final composite and controlled
distribution of the copper coated graphite as reinforcing material. The hardness measurement showed
48% improvement towards the matrix alloy and the Young modulus showed 27% improvement. The
Keywords:
A. Metal-matrix composites (MMCs)
friction coefficient and wear rate obtained revealed a very good and promising behavior of the composite
B. Wear processed in semi solid state for ball bearings ring application.
D. Surface analysis © 2015 Elsevier Ltd. All rights reserved.
D. Mechanical testing
Semi solid state processing

1. Introduction demanding low density, elevated thermal conductivity, low coef-

Aluminum matrix composites (AMC) were obtained by incor-
porating inorganic hard particles in the aluminum alloys melt,
increasing the elastic modulus, mechanical strength and creep
resistance for AMC [1]. The excellent mechanical properties of these
alloys and comparatively low cost make them an attractive option
for lightweight composite materials fabrication. A large number of
fabrication techniques are available now to manufacture metal
matrix composite materials according to the reinforcement type:
compo-casting, liquid metal infiltration, squeeze casting, spray co-
deposition [2].
Infiltration of porous ceramic preform by liquid metals is one of
the most convenient routes to manufacture metal matrix com-
posite with high volume fraction of the ceramic reinforcement. This
technique allows obtaining near net shapes composite with uni-
form distribution of the reinforcement and high dimensional sta-
bility. Most of the research efforts on Al/SiC composite with SiC high
volume fraction have been directed toward applications
* Corresponding author. Tel.: þ40 21 402 94 32; fax: þ40 21 318 10 17.
E-mail address: ioana.apostolescu@upb.ro (I. Csaki).
ficient of thermal expansion and high modulus [3e6].
Engineers, nowadays, are looking to create the extreme best
from the best, maximizing optimization as possible. These de-
velopments of low cost metal matrix composites reinforced with
graphite particles were major innovations in the field of materials
in the past few decades. Aluminum alloys reinforced with ceramic
particles exhibit mechanical properties superior to unreinforced
aluminum alloys and hence are candidate for engineering appli-
cations [7].
Graphite as particulates has long been recognized as a high e
strength, low-density material. Aluminum graphite particulate
MMCs produced by solidification techniques represent a class of
inexpensive application such as automotive components, faucets
and bearings. These MMCs are explored due to their superior
technological properties such as the low friction coefficient, a low
wear rate, higher wear resistance, high seizure resistance, high
damping capacity and good machinability. Several processes
involving incorporating graphite particles in aluminum alloys have
been developed. While powder metallurgy is a powerful method to
produce such composite, in mass scale production of small parts,
the liquid processing techniques are attracting much attention
because their inherent production advantages. The most econom-
ical production of such composites is by stir casting but this

http://dx.doi.org/10.1016/j.compositesb.2015.07.006
1359-8368/© 2015 Elsevier Ltd. All rights reserved.
142 P. Moldovan et al. / Composites Part B 81 (2015) 141e148

Table 1
Chemical composition for AlSi9Cu3 alloy used as matrix.
Si Cu Fe Mg Mn Al
9783 4068 0.478 0.167 0.091 85,02
technique is associated with apparent non-wettability of graphite
by liquid aluminum alloys and density differences between two
materials. As a result, the introduction and retention of graphite
particles in liquid aluminum is extremely difficult.
With the discovery of shear thinning and the thixotropic
behavior of partially solidified alloys under vigorous agitation, a
new era in forming technology begun, namely semi-solid metal
processing. This technology promises significant advantages:
improved die filling, less air entrapment and less oxide inclusions
due to the higher viscosity compared with fully liquid melts, longer
die life, shorter solidification time, reduced cycle time and there-
fore higher productivity due to lower heat content and lower
process temperature and reduced shrinkage and thus near net
shape or even net shape production due to partially solidified slurry
[9]. This technique, semi solid processing was successfully used for
obtaining composite materials.
The composite obtained for this study were processed in semi
solid state due to the above mentioned advantages. The composite
with AlSi9Cu3 matrix composite, reinforced with graphite particles
was obtained by semi solid processing and presents a series of
advantages as: better conductivity, lower density (less than 2.7 g/
cm3), working temperature till 350  C, very good casting properties,
better tribological and mechanical properties. For graphite wetta-
bility improving the graphite reinforcing particles was coated with
a thin copper layer. The choice for AlSi9Cu3 as matrix is justified by
the good tribological behavior of this alloy and graphite is added to
improve even more these tribological properties. Although the
graphite is a non-load bearing constituent, a strong particle/matrix
interface helps graphite particles embed themselves into the ma-
trix properly. An improvement in interfacial bonding between the
graphite and aluminum matrix under pressure during solidification
has been reported [8].
2. Materials and method
Raw materials used are AlSi9Cu3 alloy, graphite and copper
powder and AlSr10 as master alloy. AlSr10 master alloy was added
to grain refine the silicon from matrix alloy for obtaining the best
structure enhancing good properties. The copper coated graphite
represented 5% (wt%). Two major categories exist for semi-solid
materials slurry processes production. The first group comprises
all processes in which slurries are produced directly from the liquid
phase. The second category of semi solid materials processing e
Others thixo e route e deals with solid feedstock that was agitated during
balance
solidification and exhibits a rosette e like structure. After this step
the material is reheated into the freezing range in order to form a
non-dendrite, globular structure of the primary phase.
We chose to elaborate AlSi9Cu3/GrCu the first route, we heated
the material and we added the graphite coated particles using
vortex technique. The semi solid material was formed directly from
the liquid phase. The composite was cast using centrifugal casting
technique.
The graphite particles were coated with a thin copper layer. The
procedure used to coat graphite particles was cementation. The
final particles were obtained C50:Cu50.
The graphite powder used had a dimension lower than 20 mm
and was reduced in hydrogen current for 1 h and then cleaned by
washing it with ethylic alcohol to remove any grease trace. To
accelerate the reduction reaction for copper on the graphite parti-
cles and to ensure a good uniformity for the coated layer the
powder was treated to activate its particles. The graphite powder
was immersed in antimony chlorine solution and activate with
silver nitride solution. In the first stage the antimony ions are
absorbed on the graphite surface as materials islands of few hun-
dred nanometers. A catalyst was essential for the coating and the
choice was silver nitride solution. The antimony ions adsorbed
provide the position and electrons for the silver ion adsorbed. The
colloidal silver particles thus formed represent the active agent
nucleating form non electrolytic bath. The copper coating on the
graphite surface was realized from a copper sulfate solution in the
presence of formaldehyde as reducing agent. The cementation
process end was detected by the solution losing color and graphite
particles turning red color. The graphite particles were separated
from solution by filtration and washed with distilled water till a
neutral PH. The obtained powder was dried in the furnace and
treated in hydrogen current at 350  C for 1 h to reduce the oxide
formation. The final powder has a reddish color.
The copper coated graphite (GrCu) particles were introduced in
the AlSi9Cu3 melted alloy. The semi solid state was formed and the
particles were highly agitated using a stirrer. The composite in semi
solid state was centrifugally cast in order to obtain a controlled
distribution of the graphite particles. The temperature interval for
centrifugal casting was 530e580  C and the rate was 300 rot/min.
The composite was cast in the ball bearing ring shape and the
samples from inner and outer part of the ring were analyzed. The
copper coating improved the graphite particles introducing in the
melt by increasing the particles wettability and the centrifugal
casting influenced the distribution of the graphite particles towards
the inside ring part.

Fig. 1. Microstructure of AlSi9Cu3 matrix with Si segregated particles (C3 e medium grey plates), AlCuFe (C1) and Al(FeMn)CuSi (C2) compounds (a) and mapping of the elements
images (b).
 P. Moldovan et al. / Composites Part B 81 (2015) 141e148 143

Fig. 2. Power spectra emitted by AlCuFe (C1) compound in AlSi9Cu3 matrix alloy (a) and Al(FeMn)CuSi (C2) compound in AlSi9Cu3 matrix alloy (b).

The samples obtained were analyzed using a QUANTA INSPECT F
with EDS analyze system. The samples were encapsulated, bright
finished and etched with Keller reactive to underline the com-
pounds formed. Nanoindentation was realized using nano-
mechanical universal tester with a Berkovich tip. The applied
measuring routine was the fast hardness measurement with a
maximum load of 50 mN. The indentation hardness was derived
from the load displacement curves by means of the method of
Oliver and Pharr [10].
3. Results and discussions
interdendritic space compounds containing Al, Cu and Fe (C1) with
Chinese letter aspect can be observed. In Fig. 1 compounds as
Al(FeMn)CuSi (C2) could be observed. In Fig. 2 the EDS analyses of
compounds AlCuFe (C1) and Al(FeMn)CuSi (C2) are shown.
The copper coated graphite particles were analyzed using and
electronic microscope. In Fig. 3 the diffraction pattern of copper
coated graphite is shown and the optical microstructure of the
copper coated graphite (GrCu) is shown in Fig. 4.
After composite processing, the sample microstructure was
investigated. The samples were taken both from the inner and

3.1. Microstructure analyses

The AlSi9Cu3 alloy as matrix was studied, before processing the

composite materials, from microstructure point of view.
The chemical composition for the alloys used is shown in
Table 1.
The melting range of this alloy is between 521 and 582  C,
allowing the semi-solid state formation and a better particle
introduction in the melt. This alloy is placed in a ternary AleSieCu
system and the ternary compounds apparition is avoided. The
equilibrium phases are CuAl2 and Si. Using back scattering images
and EDS analyses we observed that the main phase was Al based
solid solution at the solubility limit with a certain super saturation
level in Cu. The eutectic segregated Si particles (C3, grey color)
could be observed in Fig. 1, in interdendritic space. Also, in the

Fig. 4. Microstructure of copper coated graphite particles, used as reinforcement in

AlSi9Cu3/GrCu composite.

Fig. 5. Macrostructure of the samples (ball bearing ring shape, cut in half) and the
section plane. Area A is the outer part of the ring and Area B is the inner part of the ring
Fig. 3. Diffraction pattern for copper coated graphite particles. and the section plan is underlined.
144 P. Moldovan et al. / Composites Part B 81 (2015) 141e148

Fig. 6. Microstructure of the sample B (inner part of the ball bearing ring) from AlSi9Cu3/GrCu revealing very fine Si eutectic and compounds with Al, Cu and Mg a) and EDS analyses
results for the sample in area B.

Fig. 7. Mapping of the elements present in AlSi9Cu3/GrCu underlining a uniform distribution of graphite.
 P. Moldovan et al. / Composites Part B 81 (2015) 141e148 145

Fig. 8. Microstructure in zone A for the composite AlSi9Cu3/GrCu a) and the EDS analyses results b).

Fig. 9. Mapping for the AlSi9Cu3/GrCu composite elements revealing the graphite particles agglomeration and uneven distribution.
146 P. Moldovan et al. / Composites Part B 81 (2015) 141e148

Table 2 outer part of the ring. The macrostructure of the ring is shown in
Mean value for microhardness in inner and outer part of the ball Fig. 5 to underline the places where the samples were taken.
bearing ring composite AlSi9Cu3/GrCu.
The inner part (area B) and the outer part (area A) are very
HV inner part (area B) 191.59 HV different from microscopic point of view. The studied areas (A and
HV outer part (area A) 156.10 HV B) contained compounds with Al, Cu and Fe as the original matrix
alloy.
The microstructure study revealed even more differences.
The microstructure is shown in Fig. 6 is from the inner part of
Table 3
Results for friction coefficient and wear rate for the sample from Area B, inner part of the ring. The EDS analyses results are shown in Fig. 7. The com-
the ball bearing ring. pound AlCuMg could be observed (light grey area), Si segregated
particles in interdendrite space (medium grey) and copper coated
Inner part of the ball bearing ring
graphite particles (dark). Mapping of the elements present in the
Average friction coefficient Wear rate [mm3/Nm]
AlSi9Cu3/GrCu composite, in the inner part of the ring, is shown in
Fn [N] Fn [N]
Fig. 8.
Sample 1 2 3 1 2 3 In interdendrite space compounds as AlFeSi as needle are pre-
Area B 0.508 0.593 0.628 10.05*104 13.22*104 17.18*104
sent and island compound containing Al, Cu and Mg appears. The
dark particles are copper coated graphite that presents a quite
uniform distribution within the matrix.

Fig. 10. Vickers microhardness profile variation for the sample in outer and inner part from the ball bearing ring AlSi9Cu3/GrCu composite; b. reference measurement.
 P. Moldovan et al. / Composites Part B 81 (2015) 141e148 147

In Fig. 8 the samples from the outer part are shown. The
microstructure reveals Si eutectic, compounds Al, Fe and Si and
Al, Cu and Mg compounds. The graphite particles are agglomer-
ated in some areas but the distribution is quite uneven in this
area.
The mapping for the elements present in outer part of the
AlSi9Cu3/GrCu composite ball bearing ring is shown in Fig. 9.
The structure obtained in the outer part of the ring is fine sug-
gesting a high cooling rate.
The mean value for elastic modulus obtained was 93.663 GPa
representing an improvement with 27% in comparison with the
matrix alloy.
The good values obtained for hardness could be explained by the
uniform distribution of the graphite particles in the inner part. The
hardness value in the inner part is higher than the value in the
outer part of the ring. The reinforcing materials were uniform
distributed in the inner part due to the fabrication technique. This
technique allowed us to obtain the graphite on the inner part of the
ball bearing ring, the one subjected to high wear rate.

3.2. Microhardness results and discussion 3.3. Tribological measurements

The Vickers microhardness for the base alloy, AlSi9Cu3 is
118 HV. The fracture resistance has a value near 220 MPa, the
fracture elongation is 1% and the elasticity modulus is 73 GPa.
After composite processing the microhardness mean value re-
sults are shown in Table 2.
The profile of hardness variation is shown in Fig. 10.
The tribological measurements were realized with a tribometer
with the steel substrate. The graphite particles shear under wear
conditions and create a graphite surfaces reducing the friction co-
efficient and wear rate Table 3.
The profile of the test realized with a load of 1, 2 and 3 N are
shown in Fig. 11.

Fig. 11. The profile curve for the wear tests realized at 1N (a), 2N (b) and 3N (c).
148 P. Moldovan et al. / Composites Part B 81 (2015) 141e148
The friction coefficient and wear rate increased with the in-
crease of the load suggesting that the copper coated graphite par-
ticles in the matrix perform wear in an adhesive manner and
increased the friction coefficient values. Thus explains the
increasing wear rate with the increase of the load. The AlSi9Cu3/
GrCu composite material would provide a smooth, tough surface for
the crank to rotate, with excellent wear resistance and possessing
self-lubricating properties at significantly less weight compared to
copperelead or copperegraphite components. Practically com-
posite as AlSi9Cu3/GrCu could be extended to other applications in
the power train, including cam shaft journals, rocker arms, oil and
water pump bearings and wrist pins.
4. Conclusions
The distribution particles, copper coated graphite, were well
incorporated and controlled distributed in the matrix due to the
elaboration technique used. The copper coating tremendously
improved the graphite wettability being well incorporated in the
particles.
The impurities in the matrix determined the compound with
Chinese letter shape formation, compound found in the final
composite also.
The microstructure study, EDS analyze results and elements
mapping revealed the reinforcing particles were uniformly
distributed in the inner part of the AlSi9Cu3/GRCu composite ball
bearing ring and only few graphite particles were found in the
outer part of the ring.
The elastic modulus of the inner part of the sample
increased with 27% and the HV hardness value was improved
with 48% for the inner part of the ring and 32% for the outer
part of the ring, underling the strong effect of copper coated
graphite particles.
The tribological measurement indicated a value of 0.632 for
friction coefficient and the wear rate results indicated a good
behavior for this material in wear application.
Acknowledgments
This work is supported by the Grant Romanian EEA Financial
Mechanism Committee 2009e2014 and Iceland as Donor Stat.
Bilateral Agreement Program IcelandeRomania „Research within
priority sectors”- Contract 16 SEE/30.06.2014 and by the Ministry of
Education e Executive Unit for Financing Education higher,
Research and Development and Innovation (UEFISCDI) with Part-
nerships in priority areas e PN II Program, under the Contract
no.270/2014.
References
[1] Nehrkorn Sissy, Ha €ndel Manja, Dietrich Dagmar, Podlesak Harry,
Nickel Daniela, Wielage Bernhard, et al. A hardnessemicrostructure correla-
tion study of anodised powder-metallurgical AleCu alloy composites. Surf
Coat Tech 2014. http://dx.doi.org/10.1016/j.surfcoat.2014.01.028.
[2] Vijaya Ramnath B, Elanchezhian C, Jaivignesh M, Rajesh S, Parswajinan C,
Siddique Ahmed Ghias A. Evaluation of mechanical properties of Aluminium
alloy-Alumina-Boron Carbide metal matrix composites. Mater Des 2014.
http://dx.doi.org/10.1016/j.matdes.2014.01.068.
[3] Hunt Jr WH, Premkumar MK. Novel materials for electronic packaging and
thermal management. JOM July 1992:8e10.
[4] Zweben C. Metal matrix composites for electronic packaging. JOM July 1992:
15e23.
[5] Lee HS, Lee CS, Loc JR. Pressure infiltration casting process and thermal
properties of high volume fraction SiCp/Al composite for electronic packaging.
Alum Trans 2000;3:1e6.
[6] Montoyae Davila M, Pech e Canul MA, Pech Canul MI. Effect of bi and tri-
modal size distribution on the superficial hardness of Al/SiCp composite
prepared by pressureless infiltration. Powder Technol 2007;176:66e71.
[7] Saravanan SD, Senthil Kumar M. Effect of mechanical properties on rice husk
ash reinforced aluminum alloys (AlSi10Mg) matrix composites. Procedia Eng
2013;64:1505e13.
[8] Baker N, Tzamtzmis S, Dhindaw BK, Patel J, Hari Babu N, Fan Z. Processing of
aluminum- graphite metal matrix composite by advance shear technology.
JMEPEG 2009;18:1230e40. http://dx.doi.org/10.1007/s11665e009e9362e5.
[9] Uggowitze P Jr., Uhlenhaut DI. ThixofOrming: semi-solid metal processing,
metallurgical aspects of SSM processing. ISBN: 978-3-527-32204-6.
[10] Kan Q, Yah W, Kang G, Sun Q. Oliver e Pharr indentation method in deter-
mining elastic moduli of shape memory alloys e a phase transformable ma-
terial. J Mech Phys Solids 2013;61:2015e33.