Wear, 98 (1984) 151 - 161 151

COMPARATIVE WEAR BEHAVIOUR OF Zn-AI-BASED ALLOYS IN

AN AUTOMOTIVE ENGINE APPLICATION

SAMUEL MURPHY
Department of Mechanical and Production Engineering, University of Aston in Birming-
ham, Birmingham B4 7ET (Gt. Britain)

TEMEL SAVASKAN
Technical University of NOVQ Scotia, Halifax, Nova Scotia B3J 2X4 (Canada)

(Received August 2,1984; accepted October 15,1984)

Summary

Three Zn-Al-based ternary alloys containing copper or silicon were

produced by casting. Their structures were investigated in the as-cast and
heat-treated conditions.
In an automotive application, a comparison was made of the wear be-
haviour of these alloys with that of cast iron and phosphor bronze. It was
shown that the monotectoid Zn-Al-based alloy containing silicon was com-
parable with or superior to these traditional alloys.

1. Introduction

Zn-Al alloys containing small amounts of copper and/or silicon are

gaining commercial importance as bearing materials. Marczak and Ciach [l]
reported that zinc-based alloys containing approximately 40% Al and 2% Cu
exhibited good tribological properties. These properties were attributed to
a favourable multiphase structure produced by heat treatment and the
formation of aluminium and zinc oxides on bearing surfaces. Alumina is
hard and hence gives good wear resistance, whereas zinc oxide is much
softer and has a hexagonal crystal structure which allows it to act as a
lubricant under near-seizure conditions.
Comparative tests of Zn-38%Al-2%Cu alloy against a Cu-30%Pb alloy
showed that the Zn-Al-based alloy had better seizure resistance at loads less
than 175 N [l]. Good running-in properties and excellent embeddability
were also demonstrated for these bearings. Maximum bearing loads for the
zinc-based alloy in clean or contaminated oils were found to lie between
those for Al-lO%Sn and bearing bronze, both of which are high performance
bearing alloys.

0043-1648/84/$3.00 @ Elsevier Sequoia/Printed in The Netherlands

152

The Alzen alloys as developed by Voest AG. [2] consist of a zinc base
containing 27% - 70% Al, 0% - 5% Cu and 0% - 5% Si. Of this range of al-
loys, that containing 32% Al and 5% Cu (Alzen 305) has been manufactured
in Gt. Britain. Experience with this alloy showed that it may be substituted
for bronzes in a wide range of applications. Although particularly successful
in poorly lubricated conditions, especially where seizure could have serious
consequences, it may also be used in well-lubricated applications [ 31.
A similar zinc-based alloy with 27% Al, 2% Cu and 0.015% Mg has been
developed in recent years and has been shown to have good wear resistance
[4] and a tensile strength substantially higher than that of ordinary cast
aluminium alloys [ 51. Although superior to bronze under low speed and high
loading conditions, the maximum operating temperature was said to be no
more than 120 “C [6].
One serious problem which may arise with these alloys is a gradual
irreversible expansion which occurs over a period of time at ambient or
slightly elevated temperatures. It has been shown that this is due to the
conversion of copper-rich metastable phases formed during casting to the
equilibrium phases [7 - 91. A stabilizing heat treatment may be used to
accelerate these changes so that they are essentially completed prior to
machining.
No previous work appears to have been published on the wear proper-
ties of Zn-Al-Si alloys. It is therefore the purpose of this paper to report on
the comparative wear performance of Zn-Al-Cu and Zn-Al-% alloys and
to compare the results with those for grey cast iron and phosphor bronze
LPBl.

2. Experimental details
Two Zn-Al-Cu alloys and one Zn-Al-Si alloy were produced by chill
casting into permanent moulds. The compositions of the alloys were deter-
mined by wet chemical analysis and are listed in Table 1.
The alloys were tested in the as-cast (A) and heat-treated (B) condi-
tions. Heat-treated alloys were prepared by homogenization at 350 “C! for
48 h followed by quenching in cold water and aging at 150 “C for 2 h. Tem-
perature variations during the heat treatments were limited to +2 “C.

TABLE 1
Chemical composition of the zinc-based alloys

Alloy number Composition (wt.%)

Zn Al cu Si

lA, 1B 69.9 27.1 3.0

2A, 2B 60.1 38.0 1.9
3A, 3B 56.0 35.6 8.4
 153

To perform the wear test, the cast iron valve rockers of an 850 cm3
overhead valve four-cylinder water-cooled engine were bored out and
bushed with the experimental alloys and fitted to a high mileage works
test car. This application was chosen because a variety of materials could be
tested together under closely similar conditions. For comparison purposes,
one of the eight rockers was fitted with a phosphor bronze bush, and an-
other was left unbushed as standard so that the BS 1452 grade 14 cast iron
ran directly against the steel rocker shaft.
Accurately machined bushes were produced from the experimental
alloys, press fitted into the rockers and reamed to the same size and dimen-
sional tolerance as the standard cast iron rocker bearing. Each rocker was
stamped with an identification number so that it could be replaced in the
same position on the rocker shaft. The rockers operated on a hollow steel
shaft made from BS 970 080A47 steel, which had been induction hardened
to produce a surface hardness of 60 HRC, then ground to a centre-line
average finish of 0.64 - 0.81 pm. An individual rocker is shown in Fig. l(a),
and the rocker assembly in Fig. l(b).

(a)

(b)
Fig. 1. (a) Cast iron valve rocker fitted with bearing bush in experimental zinc-based
alloy; (b) rocker assembly ready for fitting to engine of wear test vehicle.
154

A copious flow of SAE 20/50 lubricating oil to BS 1905 [lo] was

pressure fed into the hollow shaft and thence through small drilled holes to
the bearing surface of each rocker. The lubricant temperature did not
exceed 100 “C.
After the vehicle had covered a certain distance, the rocker assembly
was removed and dismantled. Each rocker complete with its bush was ultra-
sonically cleaned and weighed, so that the weight loss due to wear could be
determined. This wear included a very small amount of wear of the rocker
tips due to contact with the valve stems, which was assumed to be negligible.
After weighing, the r,ockers were refitted to the shaft in exactly the same
order and replaced on the vehicle to continue the test. The procedure was
repeated until the vehicle had covered a total of 32 761 km. After the final
weighing, the bushes were removed from the rockers, the density was mea-
sured and the bearing surfaces were inspected.

3. Results and discussion

3.1. Microstructure
Specimens for optical microscopy were prepared using standard metal-
lographic techniques, followed by etching in 2% Nital. The structures of the
Zn-Al-based alloys are shown in Figs. 2 - 4.
The as-cast structure of alloy 1A consisted of aluminium-rich dendrites
with zinc-rich interdendritic phases which included the metastable E phase
CuZn,. The heavily cored structure is shown in Fig. 2(a). Solution treatment
produced a homogeneous f.c.c. solid solution, which on quenching and aging
decomposed into a fine mixture of zinc (n phase) and aluminium (a phase)
grains (Fig. 2(b)).
Figure 3(a) shows the as-cast structure of alloy 2A. This was essentially
the same as alloy 1A except that there was a greater volume fraction of the
dendritic material resulting from the higher aluminium content. Heat treat-
ment produced fine precipitates of zinc and the E phase dispersed within the
large grains (Fig. 3(b)).
Alloy 3A exhibited a three-phase structure which consisted of a cored
aluminium-rich matrix, an interdendritic zinc-rich phase and both large and
small particles of silicon (Fig. 4(a)). Heat treatment had no discernable
effect on the silicon but produced a matrix with a similar microstructure to
that of alloy 2B.
The hardnesses and densities of the as-cast and heat-treated alloys,
cast iron and phosphor bronze are listed in Table 2.

3.2. Wear behaviour

The measured mass losses for the eight materials are listed together
with the distance covered by the test vehicle in Table 3. Zn-Al alloys may
have densities very different from those of conventional alloys. Since in
bushing applications the life is determined by the development of excessive
 155

(b)
Fig. 2. (a) As-cast microstructure of alloy IA showing heavy coring and interdendritic
eutectic; (b) microstructure after solution treatment and aging showing fine eutectoid
mixture of zinc and aluminium grains.

clearance between the journal and the bearing bush, the volume loss is a
more significant parameter than the mass loss. For this reason the measured
mass loss was converted to volume loss by dividing by the measured density
of the bush. The volume loss is plotted as a function of distance travelled by
the vehicle in Fig. 5.
Phosphor bronze and cast iron differed in their wear behaviour in that
the phosphor bronze showed a near-linear relationship between distance and
volume loss. Cast iron, in contrast, showed a rapid initial rate of wear up to
8000 - 10 000 km and thereafter a very low wear rate of approxima~ly
5 X lo-* cm3 km-‘.
The near-eutectoid zinc-based alloy 1A in the as-cast condition had a
very rapid wear rate, which decreased slightly after 5000 km but increased
again after 10 000 km to produce an overall average of 111 X 10e8 cm3 km-‘.
156

(a)

tb)
Fig. 3. (a) As-cast microstructure of alloy 2A showing effect of higher aluminium con-
tent; (b) microstructure of alloy 2B showing effect of solution treatment and aging.

In the heat-treated condition the behaviour was strikingly different; ahoy 1B

showed a considerably smaller initial wear rate followed by a gradual reduc-
tion to 12 X 10e8 cm3 km-‘.
The monotectoid copper-containing alloy 2A showed an almost linear
wear rate of 40 X 10-s cm3 km- *. In the heat-treated condition (alloy 2B)
a slightly more rapid initial wear was followed by a somewhat lower wear
rate of 33 X lo-’ cm3 km- ‘. The overall wear was somewhat greater than
that for the as-cast alloy.
The monotectoid ahoy containing silicon in the as-cast condition had
a low initial wear rate which decreased after 10000 km to 16 X lo-’ cm3
km-- ‘. The heat-treated alloy of the same composition showed very similar
behaviour, but with lower wear rates. The steady state wear rate after
10 000 km was the lowest of the %-Al-based alloys at 8 X lo-’ cm3 km-‘.
 157

(a)

(b)
Fig. 4. (a) As-cast microstructure of alloy 3A showing cored matrix of aluminium den-
drites and particles of silicon; (b) fine more uniform structure with silicon particles
resulting from heat treatment of alloy 3B.

These results show that the eutectoid-based alloy containing copper had
an exceptionally high wear rate in the as-cast condition but if heat treated
to produce a uniform fine-grained structure it achieved a very low wear rate
after the initial running-in period, even though the hardness was much lower.
The reason for this dramatic improvement in wear resistance with
heat treatment is not fully understood, but it may be linked with the volume
expansion produced in alloys which contain copper during aging [4 - 61.
Solution treatment is known to reduce the magnitude of the volume change
and to accelerate greatly the approach to equilibrium on subsequent aging,
so that the heat treatment given to the alloy 1B would be expected to
complete largely the expansion before testing. It is clear from Fig. 5 that for
alloy 1A the sharp increase in wear rate at 10 000 km is superimposed on
158

TABLE 2
Measured hardness and density of the bearing bushes
-
Alloy Hardness (HV) Density (kg rn-’ )

1A 95 5037
1B 13 5046
2A 94 4401
2B 62 4444
3A 104 3999
3B 66 3994
Cast iron 250 7257
Phosphor bronze 155 8876

TABLE 3
Mass loss of the rockers as a function of distance covered by the test vehicle

Alloy Mass loss (mg) for the following distances covered by test vehicle

2706 km 6214 km 10398 km 18554 km 32761 km

Cast iron 33.2 40.7 45.8 48.3 53.6

Phosphor bronze 1.9 9.3 17.7 30.6 49.5
1A 43.8 54.3 60.9 122.8 183.0
1B 23.7 35.4 46.5 44.9 59.5
2A 3.1 12.1 18.4 33.3 56.5
2B 5.4 22.8 32.9 34.7 64.7
3A 6.6 17.4 22.4 22.6 36.6
3B 3.6 8.1 10.7 13.3 18.2

a smooth curve which had levelled off at that point. If an average speed for
the test vehicle of 80 km h-’ is assumed, then the increase in wear rate ap-
peared after about 125 h, which is consistent with the kinetics of precipi-
tation-induced expansion in aged as-cast alloys [ 7, 81. Since the outward ex-
pansion of the bush was constrained by the cast iron rocker in which it was
housed, the normal increase in clearance due to wear would be more than
compensated by the inward expansion of the bush due to aging. The result-
ing high load on the bush would cause the observed high wear rate. There
was no detectable difference in the surface finish of the bush at the end of
the test compared with the others, but in view of the known seizure re-
sistance of Zn-Al alloys this was not unexpected.
The monotectoid-based alloy containing copper showed similar wear
behaviour to that of phosphor bronze but with substantially higher wear
rates. This alloy was only marginally softer than alloy 1 in the as-cast state
and much softer in the heat-treated state, yet it had appreciably higher wear
rates in both cases, which may be attributed to the lower copper content. In
this alloy a little interdendritic zinc was present as a eutectic phase in the
 159

DISTANCE RUN (km)

Fig. 5. Calculated volume loss of rocker bushes as a function of distance travelled by the
test vehicle: A, alloy 1A; A, alloy 1B; 0, alloy 2A; 0, alloy 2B; 0, alloy 3A; l, alloy 3B;
+, cast iron; x , phosphor bronze.

as-cast structure owing to extensive coring during solidification (Fig. 3(a)).

This was completely removed after solution treatment (Fig. 3(b)), and the
resulting softer material was more susceptible to wear, giving higher intrinsic
wear rates for the heat-treated alloy 2B compared with alloy 2A. In addition,
the low copper high aluminium material was subject to a much reduced
volume expansion on aging, so that the wear behaviour of the as-cast alloy
was not impaired. In combination, these factors may explain the different
response of the wear behaviour to heat treatment compared with alloy 1.
Alloy 3 had a Zn:Al ratio almost identical with that of alloy 2, and
similar metallurgical structures in both the as-cast and the heat-treated con-
ditions, yet both initial and steady state wear rates were very much lower.
Since the only substantial difference was in the nature of the hard load-
bearing particles, it appears that the substitution of silicon for copper had
produced this improvement. This conclusion is at variance with the sug-
gestion of Marczak and Ciach that the wear behaviour is determined by the
matrix chemistry [ 11.
There are no metastable transitional phases involving silicon in Zn-Al-S
alloys, and thus the dimensional changes on aging are very minor. Unlike
copper-containing alloys, the volume fraction of a hard load-bearing phase
such as silicon can be increased without entailing problems with dimen-
sional instability in service. In the case of alloy 3, a relatively large volume
fraction of silicon had produced good bearing properties together with a
substantial reduction in density compared with the equivalent copper-
containing alloy.
160

This does not imply that heat treatment is unnecessary, and the results
show that the wear rates of the as-cast alloy were higher than those of the
heat-treated alloy. Examination of the bore of the bush made from alloy 3A
at the end of the test showed a great deal of surface cracking and some loss
of material by spalling. The bush made from alloy 2A showed no sign of
this degradation, suggesting that copper in the alloy may reduce the sus-
ceptibility to this type of failure. It is possible that combinations of copper
and silicon may produce better wear behaviour than silicon by itself, and
this is being investigated.
In production vehicles, the cast iron of the rocker arm is run directly
against the steel rocker shaft. As far as wear resistance is concerned this is
an excellent arrangement because, once the initial running-in has been
completed at 10 000 km, the wear rate for this combination is the lowest
of all. However, the initial wear rate is high, and distances in excess of
130 000 km would have to be covered before the total volume loss fell below
that of alloy 3B.
The cost of producing and fitting bushes to rockers is substantial and a
better method of utilization of the zinc-based alloy would be to produce
the whole rocker as a casting in that material, which would allow both the
good wear behaviour and the low density to be exploited.

4. Conclusions

(1) The wear rate of a monotectoid Zn-Al-based alloy ~ont~ning

silicon has been found to be comparable with or superior to that of cast
iron and phosphor bronze in this application.
(2) The excellent wear behaviour of this alloy is attributed to the
presence of discrete silicon particles in the %-Al matrix.
(3) As-cast versions of the silicon-containing alloy have inferior wear
behaviour owing to cracking and spalling of the bearing surface during
service.
(4) Low copper mono~ctoid alloys have relatively poor wear resis-
tance .
(5) Eutectoid-based alloys containing copper have a very high wear rate,
which may be reduced to an acceptable level by heat treatment.

Acknowledgments

The authors would like to thank the Reliant Motor Company of Tam-
worth, Staffs., for their generous cooperation, and especially for the provi-
sion of test facilities for carrying out this work.
 161

References

1 R. J. Marczak and R. Ciach, Proc. 1st Eur. Tribology Congr., London, 1973, Institu-
tion of Mechanical Engineers, London, pp. 223 - 227.
2 A. Kaye, Internal Rep., September 1973 (Fry’s Diecasting Ltd.).
3 G. Pascoe, 1st Int. Conf. on ZA Alloys, Sutton Coldfield, 1983.
4 R. Barnhurst, 1st Int. Conf. on ZA Alloys, Sutton Coldfield, 1983.
5 M. J. Barber and P. E. Jones, Foundry Trade J., (January 1980) 114 - 124,131.
6 K. J. Altofer, Met. Prog., (November 1982) 29 - 31.
7 S. Murphy, T. Savaskan and J. K. Wheeldon, Casting and Foundry Technology
Int. Congr. on Metallurgical Engineering, University of Aston, Birmingham, 1981,
Paper 7.
8 N. Mykura, Y. H. Zhu and S. Murphy, Phase transformations in solids, Materials Re-
search Society Symp. Proc., Vol. 21, Elsevier, New York, 1984, pp. 841 - 846.
9 K. Lohberg, 2. Metallkd., 74 (1983) 456 - 457.
10 Engine lubricating oils (detergent types), Br. Stand. BS 1905, 1965 (British Standards
Institute).