Materials Science & Engineering A 603 (2014) 5257

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Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

Microstructure and mechanical properties of Zn15Al-based ternary

and quaternary alloys
Temel Savakan n, Ali Paa Hekimolu
Mechanical Engineering Department, Karadeniz Technical University, Kanuni Campus, 61080 Trabzon, Turkey

art ic l e i nf o a b s t r a c t

Article history: One binary Zn15Al, ve ternary Zn15AlCu and six quaternary Zn15Al3CuSi alloys were prepared
Received 31 January 2014 by permanent mold casting. Their microstructures and mechanical properties were investigated using
Received in revised form metallography and hardness, tensile, compression and impact tests. The microstructure of the binary Zn
12 February 2014
15Al alloy consisted of dendrites and and phases. The microstructure of ternary Zn15AlCu alloys
Accepted 15 February 2014
Available online 22 February 2014
containing more than 2% Cu revealed (CuZn4) particles in addition to the phases present in the binary
alloy and the quaternary Zn15Al3CuSi alloys exhibited silicon particles in addition to the phases
Keywords: present in the ternary alloys. The hardness and compressive strength of these alloys increased
ZnAl-based alloys continuously with increasing copper and silicon contents. Their tensile strength also increased with
Microstructure
increasing copper and silicon contents, but above 3% Cu and 1% Si the trend reversed. However, total
Hardening
percent elongation and impact energy of the ternary and quaternary alloys decreased with increasing
Mechanical properties
Hardness measurement copper and silicon contents. T6 heat treatment further increased the hardness and tensile strength of
Electron microscopy ternary Zn15Al3Cu and quaternary Zn15Al3Cu1Si alloys by altering their microstructures.
Mechanical test results obtained from the experimental alloys were discussed in terms of their chemical
compositions and microstructures. It was concluded that ternary Zn15Al3Cu and quaternary Zn15Al
3Cu1Si alloys can be successfully substituted for some non-ferrous commercial alloys including ZAMAK
and ZA alloys, bronzes and brasses in engineering applications.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction
The ZnAl-based commercial alloys called ZAMAK 2, 3, 5 and
7 were rst introduced in the late 1920s. These alloys have been used
in production of different structural and decorative parts for mainly
automotive, electrical and electronic industries and general purpose
machinery and equipment [1,2]. Extensive research was carried out
by a number of German workers on ZnAl-based alloys containing
small amounts of copper during Second World War to replace
traditional bearing materials including white metals and bronzes
[35]. As a result of these investigations ALZEN 305 and ALZEN 501
commercial alloys were developed. Later work on the ZnAl-based
alloys resulted in the development of ZA-8, ZA-12 and ZA-27
commercial alloys [1,2,5]. Further studies on these alloys have shown
that they have some advantages over traditional bearing materials.
These advantages can be stated as excellent uidity, good castability,
high damping capacity, good surface qualities, low friction coefcient,
n
Corresponding author. Tel.: 90 462 377 2919; fax: 90 462 377 3336.
E-mail address: savaskan@ktu.edu.tr (T. Savakan).
high wear resistance in dry and lubricated conditions and lower
production cost [6-11].
Addition of copper and/or silicon was found to be very useful
to increase hardness, strength and wear resistance of ZnAl alloys
[1217]. As a result of extensive research on the near eutectoid and
monotectoid ZnAl based alloys, new ternary (Zn27Al2Cu, Zn
40Al2Cu and Zn40Al2Si) and quaternary (Zn40Al2Cu2Si and
Zn60Al2Cu2Si) alloys have been developed [1217]. All of these
alloys have been shown to have higher strength and wear resistance
than the conventional bearing materials including SAE 660 and SAE
65 bronzes [1821]. However, the effects of copper additions on the
structure and mechanical properties of the ZnAl alloys containing
less than 25% Al have not been investigated in a systematic manner
and no work has been carried out to determine the inuence
of silicon additions on the structure and properties of these alloys.
A recent study carried out on the binary alloys the chemical composi-
tions of which lie between eutectic and eutectoid points showed that
Zn15Al alloy is a suitable choice for the base of new ternary or
quaternary alloys as far as their strength and ductility are concerned
[22]. According to the results of this work it would be more benecial
to try to develop Zn15Al-based new ternary and quaternary alloys
containing copper or both copper and silicon. Therefore, the purpose

http://dx.doi.org/10.1016/j.msea.2014.02.047
0921-5093 & 2014 Elsevier B.V. All rights reserved.
 T. Savakan, A.P. Hekimolu / Materials Science & Engineering A 603 (2014) 5257 53

of this work was to investigate the effect of copper and silicon contents Table 1
on the microstructure and mechanical properties of ternary Zn15Al Chemical compositions of the alloys investigated.
Cu and quaternary Zn15AlCuSi alloys and determine the most
Alloy Chemical composition (wt%)
suitable alloy compositions for engineering applications.
Zn Al Cu Si

2. Experimental procedures Zn15Al 85.1 14.9

Zn15Al1Cu 84.2 14.9 0.9
Zn15Al2Cu 82.9 15.0 2.1
2.1. Alloy preparation and microstructure Zn15Al3Cu 81.9 15.2 2.9
Zn15Al4Cu 81.3 14.8 3.9
One binary Zn15Al alloy and ve ternary Zn15AlCu alloys and Zn15Al5Cu 80.4 14.8 4.8
six quaternary Zn15Al3CuSi alloys were prepared using commer- Zn15Al3Cu0.5Si 81.3 15.1 3.0 0.6
Zn15Al3Cu1Si 81.3 14.9 2.9 0.9
cially pure aluminum (99.7%), high purity zinc (99.9%) and electro- Zn15Al3Cu1.5Si 80.4 14.9 3.1 1.6
lytic copper (99.9%). An Al20Si master alloy was used to produce Zn15Al3Cu2Si 80.0 15.0 2.9 2.1
the quaternary alloys. They were melted in an electric furnace and Zn15Al3Cu2.5Si 79.6 14.8 3.0 2.6
poured at a temperature of approximately 550 1C into a steel mold Zn15Al3Cu3Si 78.9 15.2 2.8 3.1
which had a conical shape. The chemical compositions of the alloys
were determined by atomic absorption analysis method. Zn15Al
3Cu and Zn15Al3Cu1Si alloys which exhibited the highest tensile
strength among the ternary and quaternary alloys were subjected to
T6 heat treatment. This treatment was performed by solutionizing
the alloys at a temperature of 330 1C followed by cold water quen-
ching and articial ageing at 180 1C until the highest hardness was
obtained. The ageing time for this treatment was determined as for
210 s. Samples for metallographic examinations were prepared using
standard techniques and examined with a scanning electron micro-
scope (SEM) using secondary electron mode and energy dispersive
X-ray analysis (EDS) procedure.

2.2. Physical and mechanical tests

The densities of the alloys were measured according to Archi-

medes principle. The hardness of the alloys and microhardness of
their phases were measured using Rockwell hardness F and Vickers
test procedures, respectively. The microhardness measurements
were performed under a load of 10 g. Impact energy values of the
alloys were determined with the samples which had the dimensions
of 10 mm  10 mm  55 mm using Charpy impact test machine.
The tensile and compressive tests were performed with the alloy
samples having the diameter and gauge length of 8 mm  40 mm
and 10 mm  10 mm, respectively at a strain rate of 6.25  10  3 s  1.
At least, three measurements were taken to determine the density,
hardness, microhardness, tensile strength, impact energy, compres-
sive strength and total percent elongation of each alloy.

3. Results

3.1. Microstructure

Chemical compositions of the alloys examined in this work are
given in Table 1. The binary (Zn15Al) and ternary (Zn15AlCu)
alloys are marked on the binary AlZn phase diagram [2325] and
350 1C isothermal section of the ternary AlZnCu alloy system [26],
Fig. 1a and b. The microstructure of Zn15Al alloy consisted of
proeutectic dendrites and and phases, Fig. 2. Copper additions
less than 2% had no signicant effect on the microstructure of this
alloy, but when the copper content exceeded this level (CuZn4)
phase formed in the interdendritic regions as seen in Fig. 3ac.
Quaternary Zn15Al3CuSi alloys revealed silicon particles in addi-
tion to the phases present in the ternary alloys, Fig. 4ac. Two types
of silicon particles were observed in these alloys. They appeared to be
as small needles and large particles with sharp edges. T6 heat
treatment modied the dendritic microstructure of Zn15Al3Cu
alloy and produced a microstructure consisting of partially decom-
posed phase and primary and eutectic and particles, Fig. 5a.
Fig. 1. (a) The binary AlZn phase diagram [2325] and (b) isothermal section of
the ternary AlZnCu alloy system at 350 1C [26].
After T6 heat treatment quaternary Zn15Al3Cu1Si alloy exhibited
primary and eutectic Si particles in addition to the phases observed
in ternary Zn15Al3Cu alloy, Fig. 5b.
3.2. Mechanical tests results
The hardness and compressive strength of the ternary Zn15AlCu
and quaternary Zn15Al3CuSi alloys increased continuously with
increasing copper and silicon contents, Figs. 6 and 7. The tensile
strength of these alloys also increased with increasing copper and
silicon contents, but the trend reversed above 3% Cu and 1% Si
respectively, Figs. 6 and 7. However, their total percent elongation
and impact energy decreased as the copper and silicon contents
54 T. Savakan, A.P. Hekimolu / Materials Science & Engineering A 603 (2014) 5257

Fig. 2. Microstructure of Zn15Al alloy.

increased as shown in Figs. 6 and 7. T6 heat treatment further

increased the hardness and strength of Zn15Al3Cu and Zn15Al
3Cu1Si alloys which exhibited the highest tensile strength among the
ternary and quaternary alloys without changing their total percent
elongation considerably. The hardness, tensile strength and total
percent elongation of these alloys are given in Table 2.
The curves showing the variations in microhardness of den-
drites and interdendritic regions of the ternary alloys as a function of
copper content are given in Fig. 8. The microhardness of both the
dendrites and interdendritic regions increased with increasing cop-
per content, but the microhardness of dendrites reached almost a
constant level above 3% Cu. However, no considerable change was
observed in microhardness of the dendrites and interdendritic
regions of the quaternary alloys with silicon content.

4. Discussion

The microstructure of binary Zn15Al alloy consisted of proeu-

tectic dendrites and a mixture of and phases, Fig. 2. Formation
of the lamellar structure in this alloy results from transformation of
phase into and phases by eutectoid reaction on cooling after
solidication. During solidication of these alloys proeutectic
dendrites form rst and the remaining liquid transforms into
mixture by the eutectic reaction [27]. On cooling to room tempera-
ture the proeutectic phase decomposes into a phase mixture of
and which appears to be in the form of lamellae [27]. The phase
mixture between the zinc-rich and lamellar areas represents the
decomposition products of the eutectic .
Copper additions less than 3% had no signicant effect on the
microstructure of this alloy, but when the copper content exceeded
2% (CuZn4) phase formed in the interdendritic regions as seen
Fig. 3ac. The size and volume fraction of the particles in the Fig. 3. Microstructures of (a) Zn15Al1Cu, (b) Zn15Al3Cu and (c) Zn15Al5Cu
microstructure of the alloys increased with increasing copper con- alloys.
tent, Fig. 3b and c. These observations can be explained in terms of
solid solubility of copper in dendrites of the alloys. The maximum
solid solubility of copper in dendrites of the alloys investigated was microstructures in ternary ZnAlSi and quaternary ZnAlCuSi
found to be approximately 3%. Therefore, when the copper content of alloys was explained in terms of their solidication behavior
the alloys exceeds 2%, phase is expected to form. [14,17].
The solid solubility of silicon in zinc-aluminum matrix of the The hardness and compressive strength of the ternary alloys
alloys at room temperature is virtually zero [28]. Therefore, silicon increased continuously with increasing copper content, Fig. 6. Tensile
solidies as pure silicon particles in the microstructure of the strength of the alloys and the microhardness of dendrites also
quaternary Zn15Al3CuSi alloys. Two types of silicon particles increased with increasing copper content up to 3%, but above this
appear in the microstructure of these alloys, Fig. 4ac. These are level the trend for the tensile strength reversed and the microhard-
eutectic and primary silicon particles. The number and volume ness of dendrites remained almost the same, Figs. 6 and 8. These
fraction of the primary silicon particles increased with increasing observations can be explained in terms of solid solution hardening
silicon content of the alloys, Fig. 4ac. Formation of this type of and formation of relatively hard and brittle intermetallic phase in
 T. Savakan, A.P. Hekimolu / Materials Science & Engineering A 603 (2014) 5257
Fig. 4. Microstructures of (a) Zn15Al3Cu0.5Si, (b) Zn15Al3Cu1Si and (c) Zn
15Al3Cu3Si alloys.
these alloys. The maximum solid solubility of copper in aluminum-
rich dendrites of the ternary alloys was found to be around 3%.
Dissolution of copper in dendrites results in an increase in both
hardness and strength of these alloys due to the solid solution
hardening [12,29,30]. However, when the copper content of the
alloys reaches 3%, the phase forms and the size and volume fraction
of it increases as the copper content increases. Since is a hard and
brittle intermetallic phase, the tensile strength of the alloys would be
expected to decrease while the microhardness of dendrites
remains the same, but their hardness and compressive strength
increase continuously with increasing copper content [12,13]. The
55
Fig. 5. Microstructures of T6 heat treated (a) Zn15Al3Cu and (b) Zn15Al3Cu
1Si alloys.
decrease in the total percent elongation and impact energy for these
alloys with increasing copper content can also be related to solid
solution hardening and the formation of phase in the interdendritic
regions. It is well known that as the solid solubility in the alloys
increases the strength of the alloys increases, but their total percent
elongation decreases [12,13,15,29,30]. In addition, hard and brittle
particles can reduce the total percent elongation and impact energy
of the alloys by weakening the interdendritic regions and giving rise
to cracking tendency [18,22].
The hardness and compressive strength of the quaternary alloys
increased continuously with increasing silicon content, Fig. 7. Their
tensile strength also increased with increasing silicon content, but
when the silicon content exceeded 1% the trend reversed, Fig. 7. The
continuous increase in hardness and compressive strength of the
quaternary alloys results from the formation of hard and brittle silicon
particles and increase in their volume fraction, Fig. 4ac. The change in
tensile strength of the alloys with silicon content can be related to the
formation of different types of silicon particles in their microstructures
[14,17]. It was observed that both ne eutectic and large primary
silicon particles formed in the alloys. However, when the silicon
content exceeded 1%, only the amount of primary silicon particles
increased in the microstructure of these alloys. Fine eutectic silicon
particles showed a more homogeneous distribution with lower inter-
particle spacing compared to the primary silicon particles, Fig. 4ac.
On the other hand hard and brittle primary silicon particles increase
the hardness and compressive strength of the alloys, but give rise to
brittleness by increasing their cracking tendency. Therefore, tensile
strength of the alloys is expected to increase with increasing silicon
56 T. Savakan, A.P. Hekimolu / Materials Science & Engineering A 603 (2014) 5257

Fig. 6. The change of hardness, tensile and compressive strengths, total percent elongation and impact energy of Zn15AlCu alloys as a function of copper content.

Fig. 7. The change of hardness, tensile and compressive strengths, total percent elongation and impact energy of Zn15Al3CuSi alloys as a function of silicon content.

Table 2
The hardness, tensile strength, total percent elongation and specic strength of Zn15Al3Cu and Zn15Al3Cu1Si alloys.

Alloy Hardness (RSD-F) Tensile strength (MPa) Specic strength (kN m/kg) Total percent elongation (%)

As-cast T6 heat treated As-cast T6 heat treated As-cast T6 heat treated As-cast T6 heat treated

Zn15Al3Cu 83 95 304 406 52.9 70.6 3.1 3.0

Zn15Al3Cu1Si 87 99 314 413 55.1 72.5 1.9 2.0

content up to 1% and then decrease above this level due to dispersion
hardening and brittleness, respectively. The decrease in the total
percent elongation and impact energy of the quaternary alloys with
increasing silicon content may also be related to the increase in
cracking tendency or brittleness caused by primary silicon particles.
T6 heat treatment further increased the hardness and tensile
strength of Zn15Al3Cu and Zn15Al3Cu1Si alloys. This can be
attributed to age hardening of supersaturated solid solutions
which results from the precipitation of new phases [31].
Zn15Al3Cu and Zn15Al3Cu1Si alloys in the as-cast con-
dition exhibited the highest tensile strength among the ternary
and quaternary alloys, respectively. Their tensile and specic
strengths (Table 2) were found to be higher than those of ZAMAK
3 (283 MPa and 42.9 kN m/kg), ZAMAK 5 (328 MPa and 49.7 kN m/
kg), ZAMAK 7 (283 MPa and 42.9 kN m/kg), ZA-8 (238 MPa and
37.7 kN m/kg), SAE 40 brass (255 MPa and 28.9 kN m/kg) and SAE
65 bronze (286 MPa and 36.8 kN m/kg), comparable to those of
ZA-12 alloy (325 MPa and 54.6 kN m/kg), but lower than those of
ZA-27 alloy (426 MPa and 85.2 kN m/kg) [1,32]. After T6 heat
treatment the tensile strengths of the Zn15Al3Cu and Zn15Al
3Cu1Si alloys exceeded those of ZA-12 alloy. The total percent
elongation of these alloys (3% and 2%) were observed to be higher
than that of ZA-8 alloy (12%), more or less the same as those of
ZA-12 and ZA-27 alloys (13% and 36%), but lower than those of
the other engineering alloys mentioned above [1,32]. These
observations indicate that ternary Zn15Al3Cu and quaternary
Zn15Al3Cu1Si alloys can successfully be substituted for some
commercial alloys including ZAMAK and ZA alloys, bronzes and
brasses in engineering applications.
5. Conclusions
(1) The microstructure of the binary Zn-15 alloy consists of
dendrites and aluminum-rich and zinc-rich phases. Addi-
tion of small amounts of copper has no signicant effect on the
microstructural appearance of this alloy. However, when the
 T. Savakan, A.P. Hekimolu / Materials Science & Engineering A 603 (2014) 5257
Fig. 8. The change of microhardness of phase and eutectic mixture ( ) of Zn
15AlCu alloys as a function of copper content.
copper content of the Zn15Al-based alloys exceeds 2%,
(CuZn4) phase forms in their interdendritic regions.
(2) Microstructures of Zn15Al3CuSi alloys reveal both eutectic
and primary silicon particles, and the number and volume
fraction of the latter increase with increasing silicon content.
(3) The hardness and compressive strength of the ternary
Zn15AlCu and quaternary Zn15Al3CuSi alloys increase
continuously with both increasing copper and silicon contents.
Their tensile strength also increases with increasing copper
and silicon contents, but the trend reverses above 3% Cu and
1% Si, respectively. The decrease in tensile strength of the
ternary and quaternary alloys results from the formation of
phase and increase in the amount of large primary silicon
particles, respectively.
(4) T6 heat treatment increases the hardness and tensile strength
of Zn15Al3Cu and Zn15Al3Cu1Si alloys without affecting
their ductility considerably.
(5) Formation of phase and silicon particles causes brittleness in
the Zn15Albased ternary and quaternary alloys by increas-
ing their cracking tendency. Therefore, total percent elonga-
tion and impact energy of the alloys decrease with increasing
copper and silicon contents.
(6) Evaluation of microstructural and mechanical test results sug-
gests that it would be benecial to keep the copper and silicon
contents of the ternary Zn15AlCu and quaternary Zn15Al
3CuSi alloys around 3% and 1%, respectively. Therefore, ternary
Zn15Al3Cu and quaternary Zn15Al3Cu1Si alloys can be
recommended for engineering applications where the specic
strength is considered to be a signicant factor.
57
Acknowledgment
This work was supported by the Karadeniz Technical University
under a research contract (No. 2008.112.03.2). The authors would
like to thank Prof. Dr. Servet Timur in Metallurgy and Materials
Engineering Department of Istanbul Technical University for per-
forming the chemical analysis of the alloys.
References
[1] F.E. Goodwin, A.L. Ponikvar, Engineering Properties of Zinc Alloys, third ed.,
International Lead Zinc Research Organization, Research Triangle Park, NC,
USA, 1989.
[2] P.E. Philip, A. Schweitzer, Metallic Materials: Physical, Mechanical, and Corro-
sion Properties, Marcel Dekker Inc., USA, 2003.
[3] P.P. Lee, T. Savakan, E. Laufer, Wear 117 (1987) 7989.
[4] R.J. Marczak, R. Ciach, in: Proceedings of the 1st European Tribology Congress,
London, 1973, pp. 223227.
[5] E. Gervais, H. Levert, M.L. Bess, Trans. Am. Foundrym. Soc. 88 (1980) 183194.
[6] T. Calayag, D. Ferres, in: Proceedings of the SAE Annual Conference, Paper No.
820643, SAE, 1983.
[7] T. Calayag, Min. Eng. 35 (1983) 727728.
[8] S. Murphy, T. Savakan, Wear 98 (1984) 151161.
[9] A.F. Skenazi, J. Pelerin, D. Coutsouradis, B. Magnus, M. Meeus, Metallwis-
senschaft Tech. 37 (1983) 898902.
[10] P. Delneuville, Wear 105 (1985) 283292.
[11] E. Gervais, R.J. Barnhurst, C.A. Loong, J. Met. 37 (1985) 4347.
[12] T. Savakan, G. Purek, A.P. Hekimolu, Tribol. Lett. 15 (2003) 257263.
[13] T. Savakan, A.P. Hekimolu, G. Prek, Tribol. Int. 37 (2004) 4550.
[14] T. Savakan, O. Bican, Mater. Sci. Eng. A 404 (2005) 259269.
[15] Y. Alemda, T. Savakan, Tribol. Int. 42 (2009) 176182.
[16] Y. Alemda, T. Savakan, Tribol. Lett. 29 (2008) 221227.
[17] T. Savakan, A. Aydner, Wear 257 (2004) 377388.
[18] T. Savakan, O. Bican, Y. Alemda, J. Mater. Sci. 44 (2009) 19691976.
[19] T. Savakan, Y. Alemda, Mater. Sci. Eng. A 496 (2008) 517523.
[20] T. Savakan, Z. Azakl, Wear 264 (2008) 920928.
[21] T. Savakan, O. Bican, Tribol. Lett. 40 (2010) 327336.
[22] A.P. Hekimolu, PhD Dissertation, Karadeniz Technical University, 2013.
[23] A.A. Presnyakov, Y.A. Gorban, V.V. Chrevyakova, Russ. J. Phys. Chem. 35 (1961)
632633.
[24] H. Auer, K.E. Mann, Z. Metallkd. 28 (1936) 323326.
[25] G.M. Kuznetsov, A.D. Barsukov, G.B. Krivosheeva, Russ. Metall. 5 (1986)
195198.
[26] S. Murphy, Z. Metallkd. 71 (1980) 96102.
[27] B. Duric, I. Bobic, R. Nikolic, M. Jovanovic, J. Min. Metall. B 37 (2001) 4755.
[28] E.A. Brandes (Ed.), Smithells Metals Reference Book, sixth ed.,Butterworth,
London, England, 1983.
[29] G.E. Dieter, Mechanical Metallurgy, McGraw-Hill Book Company, New York,
USA, 1976.
[30] M.F. Ashby, D.R.H. Jones, Engineering Materials, Pergamon Press, Oxford,
England, 1983.
[31] W.D. Callister, Materials Science and Engineering, seventh ed., John Wiley &
Sons, Inc., New York, USA, 2007.
[32] ASM International Handbook Committee, ASM Handbook Volume 2: Proper-
ties and Selection: Nonferrous Alloys and Special-Purpose Materials, ASM
International, tenth ed., Materials Park, OH, USA, 1990.