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Tribology International 37 (2004) 4550

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Effect of copper content on the mechanical and sliding wear


properties of monotectoid-based zinc-aluminium-copper alloys
Temel Savaskan , Ali Pasa Hekimoglu, Gencaga Purcek
Mechanical Engineering Department, Karadeniz Technical University, 61080 Trabzon, Turkey
Received 15 July 2002; received in revised form 24 March 2003; accepted 12 June 2003

Abstract
One binary zinc-aluminium monotectoid and five ternary zinc-aluminium-copper alloys were produced by permanent mould
casting. Their wear properties were examined using a block-on-ring test machine. Hardness, tensile strength and percentage elongation of the alloys were also determined and microhardness of aluminium-rich a phase was measured.
It was observed that the hardness of the alloys increased continuously with increasing copper content up to 5%. Their tensile
strength also increased with increasing copper content up to 2%, but above this level the strength decreased as the copper content
increased further. Microhardness of the aluminium-rich a phase was also affected by the copper content in a manner similar to
that of the tensile strength. It was found that the wear loss of the alloys decreased with increasing copper content and reached a
minimum at 2% Cu for a sliding distance of 700 km. However, the coefficient of friction and temperature due to frictional heating
were found to be generally less for the copper containing alloys than the one without the element. The effect of copper on the
wear behaviour of the alloys was explained in terms of their microstructure, hardness, tensile strength, percentage elongation and
microhardness of the a phase.
2003 Elsevier Ltd. All rights reserved.
Keywords: Zinc-aluminium-copper alloys; Sliding wear; Mechanical properties; Microstructure

1. Introduction
The hardness and strength of binary zinc-aluminium
alloys are not adequate for most of the engineering applications, but they form the basis of a number of commercial alloys including ZAMAK, ALZEN and ZA families
[14]. These alloys are mainly based on zinc-aluminium
eutectic, eutectoid or monotectoid compositions. The
zinc-aluminium monotectoid alloys were found to have
higher strength and wear resistance than either eutectic
or eutectoid alloys [4,5]. It has been shown that the
addition of alloying elements including copper, silicon,
magnesium and nickel can improve the mechanical and
tribological properties of zinc-aluminium alloys [58].
Copper was found to be the most effective alloying
addition towards improving mechanical and tribological

Corresponding author. Tel.: +90 462 377 2919; fax: +90 462
325 5526.
E-mail address: savaskan@ktu.edu.tr (T. Savaskan).

0301-679X/$ - see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0301-679X(03)00113-0

properties of these alloys [5,914]. However, the effects


of copper content on friction and wear properties of these
alloys have not been fully established. It is therefore the
purpose of this work to investigate the effect of copper
on the friction and wear properties of monotectoid-based
zinc-aluminium-copper alloys and to determine the optimum copper content.

2. Experimental procedure
2.1. Preparation and testing of alloys
One binary Zn-40Al and five ternary Zn-40Al-1Cu,
Zn-40Al-2Cu, Zn-40Al-3Cu, Zn-40Al-4Cu, Zn-40Al5Cu alloys were produced from high purity zinc
(99.9%), commercially pure aluminium (99.7%) and
electrolytic copper (99.9%). The alloys were melted in
a crucible using an electrical furnace and poured at a
temperature of approximately 630 C into a steel mould
at room temperature. The moulds had a conical shape

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T. Savaskan et al. / Tribology International 37 (2004) 4550

with a length of 180 mm, a bottom diameter of 57 mm


and a top diameter of 70 mm. The chemical compositions of the alloys were determined by atomic absorption analysis. Metallographic samples were prepared
using standard metallographic techniques, etched with
5% nital and examined by optical and scanning electron microscopy.
The density of the alloys was determined by measuring their volume and mass. Tensile tests were performed
on round specimens having a diameter of 8 mm and a
gauge length of 40 mm at a strain rate of 4.5 103
s1. Three specimens were used to determine the tensile
strength of each alloy. Brinell hardness of the alloys was
measured using a load of 62.5 kgf and a 2.5 mm diameter ball as an indenter. Vickers microhardness of the
alloys was also measured at a load of 5 gf. The macro
hardness and microhardness of the alloys were determined by taking an average of five and ten readings
respectively.

force by the normal load. The temperature of the specimens was monitored during the tests by inserting a copper-nickel thermocouple in a hole made at a distance of
2 mm from the rubbing surface.
Each wear specimen was ultrasonically cleaned and
weighed before the wear test using a balance with an
accuracy of 0.01 mg. The ring was cleaned with
organic solvents to remove traces of oil or other surface
contaminants before each test. The sample was removed
after an interval of 20 h corresponding to a sliding distance of 140 km, cleaned in solvents and weighed to
determine the mass loss. This procedure was repeated
for each sample for 100 h, which corresponds to a total
sliding distance of 700 km. The measured values of mass
loss for all the specimens tested were converted into volume loss using the measured density of the alloys. The
wear surfaces of the samples tested for 100 h were examined using a scanning electron microscope (SEM) with
secondary electron emission mode.

2.2. Friction and wear testing


The friction and wear tests were carried out using a
block-on-ring type test machine, the schematic diagram
of which is shown in Fig. 1. The machine consists of a
ring, a block (specimen) and its mounting system, a
loading system and friction force and temperature measuring systems. The ring having a diameter of 149.750
0.010 mm was fabricated using an SAE 4140 steel
(0.41% C, 0.90% Cr, 0.14% Mo, 0.90% Mn, 0.20% Si
and remainder Fe) and hardened to 55 1 HRC. Specimens 10 15 35 mm in size were prepared from the
alloy castings. One end of the samples was machined
with a 149.750 0.010 mm diameter cutter to conform
to the surface of the ring. Friction and wear tests were
performed at a constant pressure of 7.2 MPa (539 N)
and a sliding speed of 1.95 m.s1 (248 rev.min1). The
sliding surface was continuously lubricated with SAE
20W/50 oil at a flow rate of 1 ml.h1. The friction force
was determined using a load cell and the coefficient of
friction of the alloys calculated by dividing the friction

3. Results
3.1. Chemical composition and microstructure
The chemical compositions and density of the alloys
are given in Table 1. It can be seen from this table that
the density of the alloys increased with the increasing
content of copper.
The microstructure of the Zn-40Al alloy consisted of
aluminium-rich a dendrites and interdendritic zinc-rich
h phases as shown in Fig. 2(a). Addition of copper
resulted in the formation of copper-rich intermetallic e
(CuZn4) phase in the interdendritic regions of the alloys.
This can be seen in the microstructures of the alloys containing 3 and 5% copper, Fig. 2(b) and (c). The number
and size of the e phase particles increased with the copper content of the alloys.

Table 1
Chemical compositions and density of the alloys
Alloy

Fig. 1.

Schematic diagram of the block-on-ring test apparatus.

Zn-40Al
Zn-40Al-1Cu
Zn-40Al-2Cu
Zn-40Al-3Cu
Zn-40Al-4Cu
Zn-40Al-5Cu

Chemical composition (wt. %)

Zn

Al

Cu

59.4
59.7
55.8
56.7
56.0
55.2

40.6
39.2
42.2
40.4
40.1
39.9

1.1
2.0
2.9
3.9
4.9

Density
(kgm3)

4198
4213
4219
4274
4287
4318

T. Savas kan et al. / Tribology International 37 (2004) 4550

47

Fig. 3. This figure also includes the plot of microhardness of a phase versus copper content of the alloys. It
can be seen from the figure that the macro hardness of
the alloys increased almost continuously with increasing
copper content. The tensile strength of the alloys also
increased with increasing copper content but only up to
2% above which the strength decreased as the copper
content increased. The trend shown by the microhardness of a phase was similar to that of the tensile strength
of the alloys.
4.1. Friction and wear test results
The friction coefficient of the alloys as a function of
sliding distance is shown in Fig. 4. It can be seen from
the figure that the friction coefficient of all the alloys
reached a steady state after showing a sharp decrease
during the initial sliding period. The plots of temperature
versus sliding distance were found to be similar to those
of the friction coefficient versus sliding distance for all
the alloys (Fig. 4). The friction coefficient obtained at
steady state reduced initially with increasing copper content, attained the minimum at 1% Cu, and then tended
to increase at still higher contents of copper (Fig. 3).
The plots of wear loss versus sliding distance for the
alloys are shown in Fig. 5. It can be seen from the figure
that the wear loss for most of the alloys increased with
sliding distance. The copper-free alloy was most sensitive to the changing distance. The wear loss of the copper containing alloys was less than that for the copperfree alloy in general. Moreover, the wear loss decreased
with increasing copper content attaining the minimum at
2% Cu.
Wear surfaces of the samples were characterised by
scratches, grooves and smearing as seen in Fig. 6(a)(c).
As the copper content increased, the scratches became
coarser but their number decreased.

5. Discussion

Fig. 2. Microstructures of the alloys: (a) Zn-40Al, (b) Zn-40Al-3Cu


and (c) Zn-40Al-5Cu.

4. Mechanical properties
Variation of hardness, tensile strength and percentage
elongation of the alloys with copper content is shown in

The microstructure of the binary monotectoid alloy


(Zn-40Al) consisted of aluminium-rich a dendrites and
zinc-rich h phase in the interdendritic regions, Fig. 2 (a).
Addition of copper produced copper-rich e phase particles, but had no effect on the dendritic structure of the
alloys as shown in Fig. 2(b) and (c). It was observed
that the e phase was formed in the interdendritic region
of the alloys containing more than 2% Cu. This type of
microstructure seems to be ideal for bearing materials
which usually have two phases, one of which is hard
and the other one soft [4]. In zinc-aluminium-copper
alloys, the aluminium-rich a phase having a face-centred
cubic (fcc) crystal structure exhibits excellent ductility
[5,6,1517]. The zinc-rich h phase having an hexagonalclose-packed (hcp) crystal structure with a large c/a ratio

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Fig. 3. Effect of copper content on the microhardness of the a phase, and hardness, tensile strength, percentage elongation, friction coefficient
and wear loss of monotectoid-based Zn-Al-Cu alloys. The wear loss data were obtained after a sliding distance of 700 km.

Fig. 4. Friction coefficient and temperature versus sliding distance


plots for the alloys.

Fig. 5. Plots of wear loss versus sliding distance for the alloys tested.

than the ideal can give rise to good smearing characteristics or even allow certain materials to act as solid lubricants [6,18]. The e phase which has a hexagonal crystal
structure acts as a load-bearing phase, produces hardening effects and offers wear resistance in the alloys
[9,11,19].
It was found that the hardness of the alloys increased
almost continuously with increasing copper content up

to 5% (Fig. 3). However their tensile strength increased


with increasing copper content only up to 2% above
which the property decreased as the copper content
increased (Fig. 3). The increase obtained in both hardness and tensile strength of the alloys results from the
solid solution strengthening [20]. However the decrease
observed in the tensile strength of the alloys containing
more than 2% Cu may be explained in terms of microstructure. It is known that when the copper content of
the zinc-aluminium-copper alloys exceeds a certain level
(12%), the copper-rich e phase forms in the interdendritic region of the alloys [21,22]. Since e is a hard phase
its formation increases the overall hardness of the alloys
(Fig. 3). However, formation of the e phase results in a
reduction of the copper content of the a phase which is
the matrix of the alloys and hence reduces the effect of
solid solution strengthening [22,23]. This can be seen
from the change in microhardness of a phase with copper content, Fig. 3. In addition, formation of e phase may
also increase the cracking tendency of the alloys [5,24
27]. As a result, the tensile strength of the alloys containing more than 2% Cu decreases with increasing copper
content, while their hardness increases almost continuously with increasing copper content.
It was found that the tensile strength of the alloys
increased, but their volume loss due to wear decreased
with increasing copper content up to 2%. Above this
level, the tensile strength decreased but the volume loss
showed an increase (Fig. 3). However the hardness of
these alloys continuously increased with increasing copper content (Fig. 3). This may be related to the effect of
copper content on the hardness and tensile strength of
the alloys. It is known [28,29] that the wear loss is
inversely proportional to their hardness and tensile
strength. This means that as the hardness and strength
of the alloys increase their wear loss should decrease.
Since the hardness and tensile strength of these alloys
increase with increasing copper content up to 2%, the
wear loss decreased with increasing copper content up
to this level. However above this level, the positive

T. Savas kan et al. / Tribology International 37 (2004) 4550

49

effect (i.e. reduced wear rate) of increased hardness was


outweighed by the negative influence (high wear rate)
of decreasing strength. This is probably why when the
copper content exceeded 2%, marginal increase in wear
loss was observed in the alloys. This indicates that the
hardness and tensile strength of monotectoid-based zincaluminium-copper alloys have a strong effect on their
wear resistance.
Wear surfaces of the alloys tested were characterised
by smearing and scratches. As the copper content
increased, the scratches became coarser but their number
decreased. This may be related to the removal of hard
e phase particles from the surface of the wear samples
and abrasion thereof. Coarser e phase in higher copper
containing alloys led to the formation of coarser grooves.
These observations suggest that adhesion, smearing and
abrasion take place during wear of zinc-aluminiumcopper alloys.

6. Conclusions
1. When the copper content reached 2%, copper-rich
intermetallic e phase formed in the interdendritic
regions of monotectoid-based zinc-aluminium-copper alloys.
2. Hardness of monotectoid-based zinc-aluminium-copper alloys increased continuously with increasing copper content. Microhardness of a phase and tensile
strength of the alloys also increased with increasing
copper content but only up to 2%, above which
they decreased.
3. The wear loss of monotectoid-based zinc-aluminiumcopper alloys decreased with increasing copper content up to 2%, above which the property showed an
increase. Therefore the highest strength and wear
resistance can be obtained with the monotectoidbased alloy containing 2% Cu.
4. The friction coefficient and temperature due to frictional heating were generally less for the copper containing alloys than the one without the element.
5. Tensile strength and hardness are very effective
towards controlling the wear behaviour of monotectoid-based zinc-aluminium-copper alloys, but
microhardness of a phase has the strongest influence
on their wear resistance.
6. Wear surfaces of monotectoid-based zinc-aluminiumcopper alloys were characterized by smearing and
scratches.
Fig. 6. Wear surfaces of Zn-40Al (a), Zn-40Al-3Cu (b) and Zn-40Al5Cu (c) alloys tested for a sliding distance of 700 km.

Acknowledgements
The authors would like to thank Dr. C. Duran for
chemical analysis of the alloys and all the technicians in
the Materials Division of the Mechanical Engineering

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T. Savas kan et al. / Tribology International 37 (2004) 4550

Department of Karadeniz Technical University for


their assistance.
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