Abstract

According to market data, about 15% of world zinc consumption is devoted

to the production of zinc-base alloys that are used for manufacturing
automotive parts, electronic/electrical systems and also, water taps and
sanitary fittings, household articles, fashion goods, etc. These alloys are
characterized by low melting points and high fluidity that make them
suitable for foundry applications. Typically, they are processed by hot
chamber high-pressure die-casting where can be cast to thicknesses as
low as 0.13 mm. The die-cast zinc alloys possess an attractive combination
of mechanical properties, permitting them to be applied in a wide variety of
functional applications. However, depending on the alloying elements and
purposes, some zinc alloys can be processed also by cold chamber die-
casting, gravity, or sand casting as well as spin casting and slush casting.
In this paper, a detailed overview of the current knowledge in the
relationships between processing, microstructure and mechanical
properties of zinc-base alloys will be described. In detail, the evolution of
the microstructure, the dimensional stability and aging phenomena are
described. Furthermore, a thorough discussion on mechanical properties,
as such as hardness, tensile, creep, and wear properties of zinc-base
alloys is presented.
Keywords:
zinc alloys; zamak; ZA; aging
1. Introduction
Zinc is the fourth metal in the world, after iron, aluminum and copper. In
2018, the global zinc supply increased up to 13.4 Mt with a global demand
of 13.77 Mt [1]. Significant amounts of zinc are also recycled and
secondary zinc production is estimated in the order of 20–40% of global
consumption [2]. However, because of the strict limitation on impurities in
die-casting composition standards, almost all zinc die-casting alloys are
prepared from primary zinc production.
In general, about a half of the consumed zinc finds its application in the
galvanizing steel, preventing corrosion [3]. Other important applications
involve the use of zinc for other coatings, or as alloying element in brasses,
bronzes, aluminum, and magnesium alloys. Zinc is exploited also as oxide
in chemical, pharmaceutical, cosmetics, paint, rubber, and agricultural
industries. Recently, zinc has been investigated as a promising alternative
to iron and magnesium as new biodegradable metal [4]. However, about
15% of world zinc is used as base metal for the production of zinc-base
alloys [5]. Some of them are available on the market as wrought alloys, in
the form of flat-rolled, wire-drawn, and extruded and forged products. They
are applied in the construction field for the production of roofing,
downspouts, gutters, flashlight reflectors, parts for lamps, etc. Lately, a new
zinc alloy for extrusion and forging has been also developed

Figure 1. Examples of cast zinc-base alloys products.

 2 Alloys and Manufacturing Technologies

Nowadays there are more than 25 alloys used in foundry and the most
commercially relevant are specified in international standards (e.g., EN
12844) [5]. In Table 1, the chemical compositions of the most frequently
applied alloys are reported, according to the ASTM B86 standard [13].

Aluminum has an appreciable solubility in zinc. It is added because it

creates a eutectic phase at 381 °C and 6% of Al (Figure 2) that increases
the alloy fluidity and reduces melting temperature, making the alloys
particularly suitable for foundry. It also enhances mechanical properties
[5,10]. Moreover, the eutectoid alloy has been found to exhibit exceptional
elongation at room temperature, i.e., superplastic behavior [15].
3. Microstructures
As already reported, zinc casting alloys always contain aluminum as
main alloying element. Hence, in agreement with Zn-Al phase diagram
(Figure 2), they could be distinguished in three categories: hypoeutectic
(e.g., Zamak), hypereutectic (e.g., ZA12, ZEP), and hypereutectoid alloys
(e.g., ZA27, Alzen 305).
The hypoeutectic alloys are the most widely used in industrial
applications, as they correspond to the hot-camber die-casting alloys,
commercially known as Zamak. The hyper-eutectic/eutectoid ones are
more devoted to cold chamber process or gravity and sand casting,
covering a more restricted market. The corresponding microstructures are
therefore different, depending also on the specific cooling rate related to
the foundry process.
In Figure 3a, the metallographic analysis of a Zamak 5 die-cast part
after Nital 2% etching is reported as an example of the hypoeutectic alloys.
Primary Zn-rich η dendrites (white) surrounded by the η + β eutectic can be
distinguished. The microstructure at higher magnification (Figure 3b)
reveals that the eutectoid consists of platelets of Al-rich phase dispersed in
Zn-rich one. As shown by the scanning electron microscope with energy
dispersive spectroscopy microanalysis (SEM-EDS), Cu is mainly retained
in solid solution in the primary phase. In case of alloy containing Cu in
percentage higher than 2%, like for instance in Zamak 2, also Cu-rich ε-
phase (CuZn4) can be easily found [21].
4. Performance of Zinc Alloys
4.1. Tensile Properties and Hardness
The mechanical properties of zinc alloys mainly depend at on two
factors: the casting conditions and the alloy chemical composition.
Concerning the first point, each foundry process is characterized by
specific solidification/cooling rates that are responsible of the final part
microstructure. In particular, high pressure die-casting (D) is expected to
promote rapid solidification and cooling, giving rise to a fine microstructure,
meanwhile sand (S) or gravity (G) casting are characterized by slower
cooling rates which determines a coarser microstructure [24]. As a result, a
sound die-cast part should show higher mechanical properties than a
gravity or sand cast one. This can be clearly noticed when comparing the
data available in the literature and summarized in Table 2.

.
4.2. Effect of Aging
Zinc alloys experience a remarkable reduction of mechanical properties
with time at room temperature. This drop in performance, called aging, is
well documented in the literature [12,39,40]. After one year of maintenance
at room temperature, Zn alloys can experience a reduction in tensile
strength in the order of 5–15%, depending on the alloy composition and
specimen thickness (i.e., cooling rate/microstructure) [17,40].
Susceptibility to this phenomenon results from the non-equilibrium
solidification and cooling conditions typical of cast products, which induce
subsequent solid-state transformations towards more stable configurations.
These reactions take place extremely slowly at room temperature and at
higher rates as the temperature is increased [8]. In fact, Zn alloys age
already at low temperature as diffusion at room temperature is rather high
due to the low melting point of zinc [41].
Very thin castings, having a fine microstructure due to the fast cooling,
are characterized by the smallest diffusion distances. It follows that the
reduction in tensile strength with time is the fastest for the thinnest
castings. Moreover, depending on the alloy chemical composition and
casting thickness, a maximum strength can be detected after some days of
natural ageing, which is related to the growth and dissolution of copper-rich
ε phase [41].
To stabilize the properties of zinc alloys, artificial aging treatments at
65–105 °C have been frequently proposed [12,39,40,41]. Artificial aging for
24 h at 85 °C is shown to lead only to a partial decrease in performance. In
fact, the results in terms of mechanical properties are not comparable to
those after natural aging for one year. Additionally, artificial aging at this
temperature does not match the extent of natural aging seen in thin
samples because of the longer diffusion distances in thicker ones.
On the contrary, it was demonstrated for some zinc alloys that 24 h
aging at 105 °C results almost in the same changes in properties that
would take place in one year at room temperature, assessing a consistent
relationship between natural and artificial aging. Furthermore, mechanical
tests performed maintaining specimens at this temperature for different
times showed that the maximum drop in properties occurs in the first 24 h,
while they are almost stable for longer soaking times [42].
It has to be noted that some of these reactions are accompanied by
volumetric changes, resulting also in a slight but measurable dimensional
instability of Zn-Al castings (most of all in those containing Cu). This
determines first an expansion or a shrinkage and then an expansion.
4.3. Wear and Cavitation Resistance
Wear resistance is particularly important for Zn-base alloys due to the
specific application fields of these materials, ranging from fashion and
decorative (buckles, chain and belts, zippers, etc.) to automotive industry
(small gears, gear racks, pulleys, gearboxes, etc.). In addition, as
mentioned above, Zn alloys are often used for bearings production to
replace Cu-base alloys.
.
It has to be reminded that wear resistance is not an intrinsic property of
the material, as it depends on the considered tribological system and the
used test conditions. Therefore, a comparison of the wear behavior of
alloys tested under different conditions (i.e., different applied load, sliding
distance, with or without lubrication, etc.) is not reliable. However, different
authors agree about general findings. A common point is that the
microstructural features discussed in Paragraph 3 play a major role in
determining wear performance of Zn-Al alloys. Considering for instance
those with low Al content, hypo-eutectic Zamak 2 and Zamak 3 alloys were
studied in comparison with Zn alloys with higher levels of Cu and/or Al
[51,52]. In general, the low hardness of Zamak 3 alloy (due to the primary
Zn-rich η-phase) results in higher friction coefficient and wear rate than the
other alloys when tested against steel counter-part in dry conditions [51].
On the other hand, Zamak 2 alloy is harder, due to the higher Cu content,
but it is reported to exhibit worse wear resistance in comparison with alloys
with higher Al content alloys (i.e., ZnAl15Cu1 and ZA27). This is likely due
to a limited oxide formation on the wear track, especially in the first stages
of the test, as shown as an example in Figure 7. On the contrary, the oxide
formed on the wear track of ZnAl15Cu1 (ZEP) and ZA27 alloys seems able
to protect the surface from damage. However, also Zamak 2 experiences a
pronounced oxidation of the track by increasing the sliding distance (i.e., up
to 1000 m) [52]. In all the alloys, scratches aligned with the sliding direction
can be seen, as a result of the abrasive wear damage.
4.4. Creep
The mechanism of creep (time and temperature dependent
deformation/plastic flow under a constant applied load) for Zn-Al alloys has
been widely debated during the years. Indeed, because of their low melting
points, this phenomenon is particularly relevant for this family of alloys and
it is one of the reason for their limited applications for structural
components, especially if exposed above 100 °C.
In general, three stages can be defined for the creep behavior of zinc
alloys. The primary creep is dominated by strain hardening phenomena
and is characterized by a decreasing in strain rate with time. During
secondary creep, the strain rate is mainly constant since strain hardening
effects are compensated by recovery phenomena. Finally, the tertiary
creep, which leads to failure, sees a steep increase in strain rate due to a
general softening of the matrix and reduction in the load bearing cross
section.
Important parameters for designers are the time to set strain (e.g., time
to 1% strain) and the stress to produce a set strain in a set time (e.g.,
stress needed to produce 0.2% strain in 100,000 h). Early studies on creep
behavior of Zn-Al alloys allowed the identification of a relationship among
creep elongation time, stress, and temperature by means of an empirical
equation, that could be fit to the behavior of various Zn-Al alloys [68,69].
According to these findings, the creep elongation can be described by a
simple empirical equation like
f(ε) = A t σn exp(−Q/RT),
(1)
where A is a constant (function of alloy composition and structure), t is
the time, σ is the nominal stress, n is the stress exponent, Q is the effective
activation energy for creep, R is the gas constant, T is the absolute
temperature of the test, and f(ε) an undefined function of the creep strain ε.
The stress exponent n usually lies between 4 and 7 and it can be
calculated experimentally from the power law function as the slope of the
creep line (i.e., plotting the strain rate as a function of stress), while the
activation energy Q can be determined performing the creep tests over a
range of temperatures. For Zn alloys n is frequently found between 3.33
and 5 [40,68] while Q results about 94 kJ/mol for Zamak alloys and in the
range 102–112 kJ/mol for ZA8, ZA12, and ZA27 [70,71]. A more detailed
literature review about Q and n values for Zn alloys can be found in [71].
4.5. Corrosion Resistance
Similarly to mechanical properties, also corrosion resistance of Zn
alloys is linked to the microstructure, the chemical composition and the
level of impurities. About the last, Pb, Sn, and Cd are known to cause
intergranular corrosion in Zn-Al alloys and to reduce physical and
mechanical properties. For this reason, their level must be maintained
within the limits specified in ASTM B86 standard and small amount of Mg is
added to inhibit the phenomenon [5].
Concerning the main alloying elements, Cu has been found to have a
beneficial effect on the atmospheric corrosion resistance. Also Al improves
the corrosion resistance. In fact, the corrosion rate of the ZA alloys in water
was demonstrated to increase below pH 6.0 and above pH 11.5,
meanwhile for ZA27 it resulted one-third that of other Zn-Al alloys [8,86].
This because the corrosion attack appears mainly concentrated on the Zn-
rich phase, whose amount is reduced by increasing the Al content. It is
worth noting that for hypo-eutectic Zn-Al alloys, Ares et al. detected a
decrease of corrosion resistance as the concentration of aluminum
increases and that close to the eutectic composition this resistance
depends on the microstructure [87].
Other authors investigated the role of the microstructure on corrosion
behavior of Zn-Al alloys, analyzing the influence of coarse and fine
columnar/equiaxed structures and of secondary dendrite arm spacing.
Concerning the grain size of pure Zn, Osorio et al. demonstrated a better
corrosion resistance of coarse structures than with fine grains in both
columnar and equiaxed structures [88,89]. Moreover, for hypo-eutectic Zn-
Al alloys, whose grain boundaries and inter-dendritic regions contain Al-rich
phase in the lamellar eutectic mixture, it was found that a finer dendritic
structure shows higher corrosion resistance than a coarser one. On the
opposite, for hyper-eutectic Zn-Al alloys, coarser dendritic structures seem
to improve the corrosion resistance because of the eutectoid
decomposition [90].
Hence, it is general accepted that conventional Zn-Al alloys show good
corrosion resistance in different environments and that their behavior is
strongly affected by the solidification and cooling conditions (i.e., secondary
dendrite arm spacing, grain size, and solute redistribution). However, many
attempts have been performed to further improve this property by means of
alternative alloy chemical compositions as such as Zn-Al alloys reinforced
by different types of particles (zircon, graphite, fiber-glass, fly-ash, etc.) or
with addition of Ag, Si, or rare earth elements.
For instance, Sharma et al. [91] investigated the corrosion performance
of ZA27 reinforced ith zircon particles, finding that the corrosion rate in 1 N
HCl decreases with the zircon content. The effect of graphite particle
addition in ZA27 on corrosion resistance in 1 M HCl and in SAE 40 oil was
studied by Seah et al. [92]. They showed that the composite corrodes in
HCl, meanwhile in oil the corrosion resistance is enhanced. Also the
addition of glass fibers to ZA27 resulted in an improvement of corrosion
resistance [93]. Similar results were obtained by reinforcing ZA27 by fly-ash
or Al2O3, what resulted was the improvement of resistance to uniform
corrosion of the alloy [94].
Regarding the addition of alloying elements, tests performed on Zn-22
wt. % Al modified with silver showed that the corrosion behavior in saline
solution is only weakly dependent on the Ag concentration [95]. On the
contrary, the addition of REE appeared to improve the corrosion resistance
of the ZnAl40Cu3 alloy, meanwhile that of Si seemed not to affect the
behavior of the alloy [96].
Other papers dealing with corrosion resistance of modified Zn-Al alloys
are available in the literature, however until now all these modification of
standard Zn-Al alloys have not found real industrial applications.
5. Summary
In the present paper, an overview of the properties of Zn alloys is
provided, paying particular attention to the identification of the correlation
between microstructure and performance. In particular, after a first
summary of commercial alloys and relative manufacturing processes,
microstructural properties are described. In this regard, the discussion is
focused on the Zn-Al and Zn-Cu systems, which are the most widely used.
Subsequently, various aspects are described, as such as tensile properties,
wear resistance, creep behavior, and corrosion resistance. A paragraph is
also dedicated to the discussion of the effect of natural aging on material
properties since Zn alloys are especially sensitive to this phenomenon. The
general aim of the present discussion of properties of Zn-based alloy is to
allow the reader to better understand the specific applications suitable for
this family of alloys.

Author Contributions
Conceptualization, A.P.; analysis, A.P. and M.T.; writing—original draft
preparation, A.P. and M.T.; writing—review, F.G.; editing A.P., M.T. and
F.G. All authors have read and agreed to the published version of the
manuscript.

Funding
This research received no external funding.

Acknowledgments
The authors would like to thank Didier Rollez and Lorenzo Montesano
for the precious support.

Conflicts of Interest
The authors declare no conflict of interest.
CONCLUSION :-
Zinc alloys are promising biodegradable metals due to their desirable
corrosion characteristics and good biocompatibility. Zn has a corrosion rate
intermediate to that of Mg and Fe, produces a compact corrosion product,
and exhibits no gas evolution during degradation. It is therefore expected
that Zn will continue to attract research attention. Some important
conclusions on the corrosion behavior of Zn are as follows:

1. ZnO and Zn(OH)2 are the primary corrosion films formed on Zn. Other
corrosion products may form and can have significant implications for Zn
corrosion. Studies have particularly identified the importance of zinc
phosphate as a corrosion-regulator and biocompatibility-promoter.

2. Both in vitro and in vivo experiments have been used for estimating
Zn biocorrosion rates. The gold standard of biocorrosion testing is in
vivo experiments. In vitro corrosion tests specific to biodegradable metals
still need to be developed and standardized to allow useful comparisons
between the results of different studies.

3. The reported in vivo corrosion rate of pure Zn is between 10 and

50 µm/year, and meets the ideal corrosion rate of about 20 µm/year
for cardiovascular applications. Zn-based orthopedic devices also perform
satisfactorily.

4. The corrosion of Zn inside the body occurs in stages, with the associated
corrosion mechanisms evolving in response to physiological changes
occurring around the implant.

5. Alloying elements and the fabrication route influence the Zn biocorrosion

behavior by inducing changes in the microstructure.

6. Other factors such as surface condition, pH, type of physiological fluid,

and implant location also influence the corrosion behavior of biodegradable
Zn.
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