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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
University Politehnica Bucharest, Splaiul Indepentei 313, Bucharest, Romania
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
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-

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

1359-8368/© 2015 Elsevier Ltd. All rights reserved.
142 P. Moldovan et al. / Composites Part B 81 (2015) 141e148

Table 1 all processes in which slurries are produced directly from the liquid
Chemical composition for AlSi9Cu3 alloy used as matrix. phase. The second category of semi solid materials processing e
Si Cu Fe Mg Mn Al Others thixo e route e deals with solid feedstock that was agitated during
9783 4068 0.478 0.167 0.091 85,02 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
technique is associated with apparent non-wettability of graphite
the material and we added the graphite coated particles using
by liquid aluminum alloys and density differences between two
vortex technique. The semi solid material was formed directly from
materials. As a result, the introduction and retention of graphite
the liquid phase. The composite was cast using centrifugal casting
particles in liquid aluminum is extremely difficult.
With the discovery of shear thinning and the thixotropic
The graphite particles were coated with a thin copper layer. The
behavior of partially solidified alloys under vigorous agitation, a
procedure used to coat graphite particles was cementation. The
new era in forming technology begun, namely semi-solid metal
final particles were obtained C50:Cu50.
processing. This technology promises significant advantages:
The graphite powder used had a dimension lower than 20 mm
improved die filling, less air entrapment and less oxide inclusions
and was reduced in hydrogen current for 1 h and then cleaned by
due to the higher viscosity compared with fully liquid melts, longer
washing it with ethylic alcohol to remove any grease trace. To
die life, shorter solidification time, reduced cycle time and there-
accelerate the reduction reaction for copper on the graphite parti-
fore higher productivity due to lower heat content and lower
cles and to ensure a good uniformity for the coated layer the
process temperature and reduced shrinkage and thus near net
powder was treated to activate its particles. The graphite powder
shape or even net shape production due to partially solidified slurry
was immersed in antimony chlorine solution and activate with
[9]. This technique, semi solid processing was successfully used for
silver nitride solution. In the first stage the antimony ions are
obtaining composite materials.
absorbed on the graphite surface as materials islands of few hun-
The composite obtained for this study were processed in semi
dred nanometers. A catalyst was essential for the coating and the
solid state due to the above mentioned advantages. The composite
choice was silver nitride solution. The antimony ions adsorbed
with AlSi9Cu3 matrix composite, reinforced with graphite particles
provide the position and electrons for the silver ion adsorbed. The
was obtained by semi solid processing and presents a series of
colloidal silver particles thus formed represent the active agent
advantages as: better conductivity, lower density (less than 2.7 g/
nucleating form non electrolytic bath. The copper coating on the
cm3), working temperature till 350  C, very good casting properties,
graphite surface was realized from a copper sulfate solution in the
better tribological and mechanical properties. For graphite wetta-
presence of formaldehyde as reducing agent. The cementation
bility improving the graphite reinforcing particles was coated with
process end was detected by the solution losing color and graphite
a thin copper layer. The choice for AlSi9Cu3 as matrix is justified by
particles turning red color. The graphite particles were separated
the good tribological behavior of this alloy and graphite is added to
from solution by filtration and washed with distilled water till a
improve even more these tribological properties. Although the
neutral PH. The obtained powder was dried in the furnace and
graphite is a non-load bearing constituent, a strong particle/matrix
treated in hydrogen current at 350  C for 1 h to reduce the oxide
interface helps graphite particles embed themselves into the ma-
formation. The final powder has a reddish color.
trix properly. An improvement in interfacial bonding between the
The copper coated graphite (GrCu) particles were introduced in
graphite and aluminum matrix under pressure during solidification
the AlSi9Cu3 melted alloy. The semi solid state was formed and the
has been reported [8].
particles were highly agitated using a stirrer. The composite in semi
solid state was centrifugally cast in order to obtain a controlled
2. Materials and method distribution of the graphite particles. The temperature interval for
centrifugal casting was 530e580  C and the rate was 300 rot/min.
Raw materials used are AlSi9Cu3 alloy, graphite and copper The composite was cast in the ball bearing ring shape and the
powder and AlSr10 as master alloy. AlSr10 master alloy was added samples from inner and outer part of the ring were analyzed. The
to grain refine the silicon from matrix alloy for obtaining the best copper coating improved the graphite particles introducing in the
structure enhancing good properties. The copper coated graphite melt by increasing the particles wettability and the centrifugal
represented 5% (wt%). Two major categories exist for semi-solid casting influenced the distribution of the graphite particles towards
materials slurry processes production. The first group comprises 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 interdendritic space compounds containing Al, Cu and Fe (C1) with
with EDS analyze system. The samples were encapsulated, bright Chinese letter aspect can be observed. In Fig. 1 compounds as
finished and etched with Keller reactive to underline the com- Al(FeMn)CuSi (C2) could be observed. In Fig. 2 the EDS analyses of
pounds formed. Nanoindentation was realized using nano- compounds AlCuFe (C1) and Al(FeMn)CuSi (C2) are shown.
mechanical universal tester with a Berkovich tip. The applied The copper coated graphite particles were analyzed using and
measuring routine was the fast hardness measurement with a electronic microscope. In Fig. 3 the diffraction pattern of copper
maximum load of 50 mN. The indentation hardness was derived coated graphite is shown and the optical microstructure of the
from the load displacement curves by means of the method of copper coated graphite (GrCu) is shown in Fig. 4.
Oliver and Pharr [10]. After composite processing, the sample microstructure was
investigated. The samples were taken both from the inner and
3. Results and discussions

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
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 The mean value for elastic modulus obtained was 93.663 GPa
microstructure reveals Si eutectic, compounds Al, Fe and Si and representing an improvement with 27% in comparison with the
Al, Cu and Mg compounds. The graphite particles are agglomer- matrix alloy.
ated in some areas but the distribution is quite uneven in this The good values obtained for hardness could be explained by the
area. uniform distribution of the graphite particles in the inner part. The
The mapping for the elements present in outer part of the hardness value in the inner part is higher than the value in the
AlSi9Cu3/GrCu composite ball bearing ring is shown in Fig. 9. outer part of the ring. The reinforcing materials were uniform
The structure obtained in the outer part of the ring is fine sug- distributed in the inner part due to the fabrication technique. This
gesting a high cooling rate. 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 The tribological measurements were realized with a tribometer
118 HV. The fracture resistance has a value near 220 MPa, the with the steel substrate. The graphite particles shear under wear
fracture elongation is 1% and the elasticity modulus is 73 GPa. conditions and create a graphite surfaces reducing the friction co-
After composite processing the microhardness mean value re- efficient and wear rate Table 3.
sults are shown in Table 2. The profile of the test realized with a load of 1, 2 and 3 N are
The profile of hardness variation is shown in Fig. 10. 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- Acknowledgments
crease of the load suggesting that the copper coated graphite par-
ticles in the matrix perform wear in an adhesive manner and This work is supported by the Grant Romanian EEA Financial
increased the friction coefficient values. Thus explains the Mechanism Committee 2009e2014 and Iceland as Donor Stat.
increasing wear rate with the increase of the load. The AlSi9Cu3/ Bilateral Agreement Program IcelandeRomania „Research within
GrCu composite material would provide a smooth, tough surface for priority sectors”- Contract 16 SEE/30.06.2014 and by the Ministry of
the crank to rotate, with excellent wear resistance and possessing Education e Executive Unit for Financing Education higher,
self-lubricating properties at significantly less weight compared to Research and Development and Innovation (UEFISCDI) with Part-
copperelead or copperegraphite components. Practically com- nerships in priority areas e PN II Program, under the Contract
posite as AlSi9Cu3/GrCu could be extended to other applications in no.270/2014.
the power train, including cam shaft journals, rocker arms, oil and
water pump bearings and wrist pins.
4. Conclusions
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