Corrosion Science 53 (2011) 409417

Contents lists available at ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

The effect of T4 heat treatment on the microstructure and corrosion behaviour

of Zn27Al1.5Cu0.02Mg alloy
Biljana Bobic a,, Jelena Bajat b, Zagorka Acimovic-Pavlovic b, Marko Rakin b, Ilija Bobic c
a

IHIS R&D Center, Batajnicki put 23, 11080 Zemun, Serbia

Faculty of Technology and Metallurgy, Karnegijeva 4, 11120 Belgrade, Serbia
c
INN Vinca, University of Belgrade, Mike Petrovica Alasa 12-14, 11001 Belgrade, Serbia
b

a r t i c l e

i n f o

Article history:
Received 3 March 2010
Accepted 22 September 2010
Available online 29 September 2010
Keywords:
A. Zinc
A. Alloy
B. Weight loss
B. Polarization
B. SEM

a b s t r a c t
The effect of heat treatment on the microstructure and corrosion behaviour of Zn27Al1.5Cu0.02Mg alloy
was examined. The alloy was prepared by melting and casting route and then thermally processed (T4
regime). Corrosion behaviour of the as-cast and heat treated alloy was studied in 3.5 wt.% NaCl solution
using immersion method and electrochemical polarization measurements. The applied heat treatment
affected the alloy microstructure and resulted in increased ductility and higher corrosion resistance of
the heat treated alloy. Electrochemical measurements of the corrosion rate at the free corrosion potential
are in agreement with the results obtained using the weight loss method.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
Zn27Al1.5Cu0.02Mg alloy (ZA27 alloy in the further text) belongs to a group of zinc alloys with increased content of aluminium
(ZA alloys). The alloy has been of used in technological applications
for several decades. ZA27 alloy with a nominal aluminium content
of 27 wt.% has the highest strength and the lowest density of the
ZA alloys [1]. The alloy has been shown to possess favorable combination of physical, mechanical and technological characteristics
(low melting point, high strength, exceptional castability, easy
machinability, high corrosion resistance, as well as excellent bearing and wear resistance properties) [1,2]. ZA27 alloy has been used
for pressure die castings and gravity castings wherever very high
strength is required: in automobile engine mounts and drive trains,
general hardware, agricultural equipment, domestic and garden
appliances and heavy duty hand and work tools [3,4]. The alloy
has been also used in bearings and bushing applications as a
replacement for bronze bearings because of its lower cost and
equivalent or superior bearing performances [5].
During past two decades a few different approaches have been
taken in order to improve physical, mechanical, tribological and
corrosion properties of ZA27 alloy at room temperature: (a) addition of elements like Ni, Ti and Sr [6,7], Mn [8] or Mg and rare
earths [9]; (b) using different heat treatment regimes [6,1012]
and thermomechanical treatments [13,14]; (c) improvements in
Corresponding author. Tel.: +381 11 316 8154; fax: +381 11 194 991.
E-mail address: biljanabobic@gmail.com (B. Bobic).
0010-938X/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2010.09.051

the alloy manufacturing techniques e.g. the use of thixoforming

[15,16] or unidirectional solidication [1719]; (d) production of
composites with Al2O3 [20], SiC [21], ZrO2 [22] and graphite particles [23] or glass bres [24].
Mechanical properties of ZA27 alloy can be inuenced by thermal processing. It was reported [12] that ductility and structural
stability of Zn25Al3Cu alloy were markedly improved by applying
T4 heat treatment. It was also shown that T4 regime had a benecial effect on the tribological characteristics of the commercial
ZA27 alloy [11], although it resulted in a minor reduction in hardness and tensile strength. In addition, T4 heat treatment is relatively cheap and easy to perform, thus providing time and energy
savings. Upon exposure to the corrosive environment many thermally processed alloys are subjected to drastic changes. Possible
effects of used heat treatments on the alloy performance in a corrosive medium are essential for a complete understanding of the
alloy corrosion behavior [25]. The inuence of metallic microstructure on the corrosion performance of zinc and zinc alloys has been
recently evaluated in dependence on the applied thermal treatment [26]. Determination of mass loss during eld trials and
immersion tests and anodic polarization studies were used for corrosion behaviour assessment [26].
Corrosion characteristics of the as-cast ZA27 alloy have been
previously studied and reported in [27,28]. Aluminium presence
in the alloy has a favourable effect on its corrosion behaviour
[27,28]. The alloy exhibits high corrosion resistance in the atmospheric conditions, natural waters, soil etc. because of zinc ability
to form a protective layer of corrosion products at the surface

410

B. Bobic et al. / Corrosion Science 53 (2011) 409417

[25,27], consisting mainly of zinc oxide [29], zinc hydroxide, simonkolleite or their mixtures [30], or of various basic salts, depending
on the corrosive media [30,31]. The most common form of
corrosion encountered by ZA27 alloy in a variety of natural environments is general (uniform) corrosion [27]. This enables evaluation of the alloy mass loss pere unit surface area that is evaluation
of corrosion rate. Neutral chloride solutions open to air have been
mostly used in corrosion studies of zinc [26,32,33], zinc coatings
[30,34,35] and zincalloy coatings [32] because the chloride ion
is present in many corrosion environments and because of great
inuence of dissolved oxygen on the kinetics and mechanism in
the corrosion of zinc. Potentiodynamic polarization measurements
[26,29,30,3234], EIS technique [29,30,35] and weight loss method
[26,29] have been mostly applied. Weight loss method and electrochemical polarization measurements have been recently applied in
corrosion studies of ZA27 alloy [7]. It was shown that results of
electrochemical measurements were not in agreement with direct
weight loss measurements [7].
Thermally processed (T4) ZA27 alloy is characterized by a good
combination of tribological and mechanical properties [11] with
ductility double of the as-cast alloy [12] and can be used in producing machine parts where high ductility is required. However, there
have been no results reported so far concerning the effect of T4
heat treatment on the corrosion performance of the ZA27 casting
alloy. In view of the above, the aim of this work was to examine
the inuence of T4 heat treatment on the corrosion behaviour of
ZA27 alloy. An attempt was also made to establish the correlation
between the microstructural parameters of the as-cast and heat
treated ZA27 alloys and their corrosion properties.
Weight loss method and electrochemical polarization measurements were used within this work to assess the corrosion behaviour of ZA27 alloy. LPR tests and Tafel plots have been frequently
used in corrosion studies to evaluate the rate of uniform corrosion
[25,36,37]. LPR tests provide the value of polarization resistance Rp
enabling the corrosion rate calculation based on the SternGeary
equation [38] while Tafel plots alow direct measurements of the
corrosion current by extrapolating the linear portions of anodic
and cathodic Tafel plots back to their intersection. Tafel slopes
can be obtained from examination of appropriate portions of the
polarization curve [25,36,39]. Although this method has been
widely used it is encountered by many restrictions [25,37]. Recently, many studies have been done to investigate the application
of potentiodynamic polarization measurements in evaluation of
corrosion rate [4045]. The results obtained by solution analysis
[44,45] or, more frequently, by the weight loss method have been
used as a criterion to investigate the accuracy of Tafel method
[26,41,45]. The same approach was applied within this work.
2. Experimental
2.1. Materials and heat treatment
Experiments were performed using zincaluminium alloy
Zn27Al1.5Cu0.02Mg. Chemical composition of the alloy is given
in Table 1 that is in accordance with EN standard [46].
The alloy was prepared by conventional melting and casting
route in Department of Materials Science, INN Vinca. Schematic
presentation of the casting assembly used was given in [47]. The
alloy casting was performed at 570 C in the steel mold preheated

Table 1
Chemical composition of Zn27Al15Cu0.02Mg alloy.
Element

Al

Cu

Mg

Fe

Sn

Cd

Pb

Zn

wt.%

26.3

1.54

0.018

0.062

0.002

0.005

0.004

Balance

up to 100 C. Prismatic castings (20  30  120 mm) were machine

cut and samples for corrosion studies (20  30  6 mm) and microstructural examinations (8  8  30 mm) were obtained. The samples were subjected to heat treatment (T4 regime: solutionizing at
370 C for 3 h followed by water quenching and natural aging).
The hardness test was conducted in accordance with ASTM E10
[48] using Brinell hardness tester with a ball indenter of 2.5 mm
diameter and a load of 62.5 kg. The load was applied for 30 s.
The test was performed at room temperature on specimens with
28 mm in diameter and 10 mm in height. Five hardness readings
were taken for each specimen at different locations. The average
hardness value was 124 HB for the as-cast ZA27 alloy and 130
HB for the heat treated alloy.
2.2. Corrosion tests
The immersion test and electrochemical polarization measurements were used to access the corrosion behaviour of ZA27 alloy.
Corrosion rates of the as-cast and heat treated alloy were determined by the weight loss method, linear polarization resistance
(LPR) test and using Tafel plots. All tests were performed in an
approximately neutral NaCl solution (pH = 6.7) in contact with
air. The chloride concentration of the test solution (3.5 wt.% NaCl)
is the same as in natural seawater.
2.2.1. Immersion test
The samples were exposed in stagnant 3.5 wt.% NaCl solution at
room temperature. They were vertically immersed in the test solution. Samples preparation and exposure procedure were performed
in accordance with ASTM G31 [49]. As-cast and heat treated samples (20  30  6 mm) were at rst dry ground using a grinding
machine, and then wet ground using progressively ner abrasive
SiC paper (240, 360, 600 and 800 grit), washed in warm running
water, rinsed with acetone and dried in the air. After weighing,
the samples were exposed (in triplicate) to the test solution. The
period of exposure was 1 month.
After exposure samples were removed from the test solution
and rinsed with distilled water. Corrosion products were removed
from the samples surface by chemical cleaning according to ASTM
G1 [50]. The samples were then reweighed to determine their mass
loss during exposure to NaCl solution.
2.2.2. Electrochemical polarization measurements
Polarization measurements were carried out at room temperature using a cell for at specimens with a contact area of 1 cm2 between working electrode and electrolyte (3.5 wt.% NaCl, pH = 6.7).
The cell contained the platinum electrode as a counter electrode
and the saturated calomel electrode (SCE) as a reference electrode.
All the potentials were referred to the SCE. Working electrode (ascast and heat treated sample of ZA27 alloy, respectively) was
washed with acetone and distilled water before the polarization
test. The open circuit potential (OCP) of working electrodes was
monitored 3060 min prior to application of electrochemical techniques. Polarization tests were conducted using Gamry Reference
600 Potentiostat and three measurements were performed for each
sample, with good reproducibility.
In the LPR test each working electrode was potentiodynamically
polarized in the potential range between 15 and +15 mV (from
cathodic to anodic) [51] over the respective open circuit potential
(OCP) using a computer controlled potentiostat. Prior to each LPR
sweep, test electrodes were permitted to stabilise for approximately 3060 min in the solution to make sure that steady state
has been reached. Each electrode was then cathodically polarised
from its OCP by 15 mV, which was immediately followed by a
cathodic sweep over a 30 mV range at the 0.2 mV s1 sweep rate.
The electrode was then returned to open circuit potential.

B. Bobic et al. / Corrosion Science 53 (2011) 409417

411

After each LPR test Tafel plots were obtained by starting the potential scan from a cathodic potential and increasing the potential
towards the anodic side [35,44,45] at a scan rate of 0.2 mV s1.
Each electrode was potentiodynamically polarized in the potential
range 0.250 V over the respective OCP.
2.3. Microstructure and surface morphology characterization
Microstructure and surface morphology of the as-cast and heat
treated samples of ZA27 alloy were examined before the immersion test and after 1 month of exposure in the test solution. The
samples were analyzed by optical microscopy (OM) and scanning
electron microscopy (SEM) combined with energy dispersive spectrometry (EDS). SEM/EDS and X-ray diffraction method (XRD) were
used to characterize corrosion products of both ZA27 alloys. Carl
Zeiss optical microscope and JEOL JSM 5800 scanning electron
microscope coupled with Oxford Link ISIS energy dispersive spectrometer were used. XRD patterns were obtained using Siemens
model D500 X-ray diffractometer.
The samples for microstructure studies were rinsed with acetone and dried in the air before their exposure to test solution
(3.5 wt.% NaCl). After exposure, surface of the samples was ground
and polished. Wet grinding was performed on progressively ner
abrasive paper (240, 360, 600 and 800 grit SiC), while polishing
was done using polishing cloth and diamond paste (up to 2 lm
particles size). After washing in distilled water and drying with
warm owing air, the samples were etched in 9% v/v nitric acid
to reveal the microstructure, while polished samples were subjected to SEM and SEM/EDS analysis.
3. Results and discussion
3.1. Corrosion studies

Fig. 1. LPR plots of ZA27 alloy in 3.5 wt.% NaCl. (a) ZA27 as-cast, (b) ZA27 heat
treated.

3.1.1. Immersion test

After 1 month of exposure to 3.5% NaCl solution corrosion products were removed from the surface of the samples. It could be noticed that corrosion had occured uniformly over the surface of the
exposed as-cast and heat treated samples. The average corrosion
rate CR, in mm year1, was calculated on the basis of the samples
mass loss during immersion test [50]:

KW
CR
AT D

where B is a parameter dependent on the values of anodic ba and

cathodic Tafel slope bc:

Accordingly

3.1.2. Electrochemical polarization measurements

3.1.2.1. LPR test. Polarization curves in a small potential range near
to OCP were obtained in the LPR test for both as-cast and heat treated ZA27 alloy. Polarization resistance Rp was determined from the
slope of iR corrected experimental curve (dE/dj) at the corrosion
potential Ecorr (Fig. 1a and b).
It can be seen that applied heat treatment resulted in increased
value of Rp. Polarization resistance can be converted to corrosion
current density jcorr using the SternGeary equation [38]:

B
Rp

ba  bc
2:303  ba bc

jcorr

where K is a constant [49], W is sample mass loss in grams, A is sample area in cm2, T is time of exposure in hours and D is density of
ZA27 alloy in g cm3.
The calculated values of average penetration rate were
0.118 mm year1 for the as-cast and 0.095 mm year1 for the heat
treated ZA27 alloy. The result obtained for the as-cast alloy is in
good agreement with the result reported in [52].

jcorr

ba  bc
2:303  ba bc  Rp

This expression was derived on the assumption that both anodic and cathodic reactions were charge-transfer controlled and
that ohmic drop iR was negligible [25]. For a process that is controlled by diffusion of the cathode reactant (transport control)
and in which the anodic process is under activation control the
modied SternGeary equation applies [25]:

jcorr

ba
2:303  Rp

It can be noticed from Tafel plots in Fig. 2a and b that anodic

reaction is activation controlled alloy (ZA27) dissolution with anodic Tafel slope ba = 40 mV dec1, while the cathodic reaction is under diffusion control of oxygen reduction. Accordingly, the Eq. (5)
was used to calculate corrosion current density. The calculated values were 8 lA cm2 for the as-cast and 7.15 lA cm2 for the heat
treated ZA27 alloy, which is in a very good agreement with the
results reported [7].
3.1.2.2. Tafel plots. Polarization curves for the as-cast and heat treated ZA27 alloys were recorded in the potential range 0.250 V with
respect to OCP. The curves were corrected for the ohmic drop iR.
Corrected polarization curves are presented in Fig. 2a and b.

412

B. Bobic et al. / Corrosion Science 53 (2011) 409417

applied heat treatment of ZA27 alloy resulted in the alloy of greater

corrosion stability.
The weight loss method has been considered as the most accurate
method in determining corrosion rate of metal materials liable to
general (uniform) corrosion and has been widely used as a criterion
to investigate the accuracy of electrochemical polarization tests
[26,41,45]. With regard to this values of jcorr obtained in the LPR test
(Section 3.1.2.1.) and by using Tafel plots (Section 3.1.2.2.) were converted into penetration rate CR and compared with the results of
immersion test. Corrosion current density jcorr, in lA cm2, and corrosion rate CR expressed in mm year1 are related by the following
equation [39]:

CR K i 

Fig. 2. Tafel plots of ZA27 alloy corrected for iR drop. (a) ZA27 as-cast, (b) ZA27 heat
treated.

The anodic polarization curves show a considerable increase in

current density for a small increase in polarization indicating active alloy dissolution during anodic polarization. Such behaviour
is typical of Zn dissolution in natrium chloride solution [35]. The
curves exhibit Tafel behaviour over about 1.5 current decade which
means that the anodic reaction for both ZA27 alloys is activation
controlled with anodic Tafel slope ba = 40 mV dec1. This value corresponds closely to values reported in literature for the anodic dissolution of zinc [34,52]. The anodic Tafel slope ba = 40 mV dec1
was used to calculate corrosion current density in the LPR test
according to the Eq. (5) (Section 3.1.2.1).
The cathodic polarization curves show highly polarized behaviour, i.e., only a small increase in current density was obtained
for a signicant increase in polarization. This is indicative of cathodic reaction under diffusion control [25,39,53]. Low solubility of
oxygen (about 103 mol dm3) [25] in the test solution limits the
transport of oxygen to the electrode surface and the cathodic reaction is under dominant diffusion control of oxygen reduction.
When the reaction rate is entirely controlled by the rate of mass
transport it no longer depends on potential [36,53]. Accordingly,
the value of the cathodic Tafel slope bc ? 1 [29,53].
Considering that the cathodic reaction is under diffusion control. The corrosion current densities for the as-cast and heat treated ZA27 alloys were determined by extrapolation of the anodic
Tafel lines to the corrosion potential Ecorr (Fig. 2a and b). The value
of corrosion current density for the as-cast ZA27 alloy as
14 lA cm2 whereas T4 heat treatment resulted in the alloy with
somewhat lower corrosion current density (6.6 lA cm2), pointing
to its higher corrosion resistance.
The results obtained by using Tafel plots are in accordance with
the results obtained in LPR test, where it was also shown that

jcorr
 Ew
D

where Ki is a constant [39], EW is equivalent weight of ZA27 alloy

and D is as in Eq. (1).
Corrosion rates obtained by the weight loss method and by
electrochemical polarization measurements are expressed as penetration rates and presented in Fig. 3.
It can be seen that lower values of corrosion rate were obtained
for the heat treated alloy in relation to the as-cast alloy which
means that applied heat treatment resulted in increased corrosion
stability of ZA27 alloy. In addition, the results of polarization measurements are in a very good agreement with the results of weight
loss measurements, excluding the result obtained by using Tafel
plot (ZA27 alloy as-cast). This could be possibly explained by the
irreversible changes of the electrode surface at higher polarizations
[54] which conrms that corrosion rate estimations based on Tafel
extrapolation should be compared to weight loss measurements
whenever possible [45].
The value of corrosion rate for each ZA27 alloy can be expressed
as an average of the values obtained by the weight loss method and
by electrochemical measurements. Comparing these average values of the corrosion rate one can reveal that corrosion rate of the
heat treated alloy is about 30% lower than that of the as-cast alloy.
Although this effect is not remarkable it should not be neglected.

3.2. Microstructures
Corrosion behaviour of ZA27 alloy is determined by the alloy
microstructure, that is by chemical composition and distribution
of the alloy constituents (phases) [7,17,19].

Fig. 3. Corrosion rates of ZA27 alloy. (A) weight loss method, (B) linear polarization
resistance test, (C) Tafel plots.

B. Bobic et al. / Corrosion Science 53 (2011) 409417

3.2.1. ZA27 alloy, as-cast

The alloy was casted in metal mold (Section 2.1.) and hence
subjected to rapid cooling. Solidication of the alloy in these conditions resulted in the alloy with dendritic microstructure. Microstructure of the as-cast ZA27 alloy is shown in Fig. 4ac. Inclusions
can be noticed in the alloy sample (Fig. 4a) while porosity was not
observed at this level of examination.
Non-metallic inclusions in ZA27 alloy might be oxides of Al, Zn,
Cu, Mg or intermetallic compounds like CuZn4, AlCu, Al4Cu, AlMg,
Mg2Zn11 [6,55] and FeAl3 [55]. The inclusions arise because of various physicalchemical effects that occur during melting and solidication of an alloy [55].
General appearance of the alloy microstructure after etching is
shown in Fig. 4b. Dendrites are complex (Fig. 4b and c), consisting
of a core (a phase) and a periphery (a mixture of a phase and hexagonal g phase). g phase is located into interdendritic regions.
According to the aluminiumzinc phase diagram [1] solidication of ZA27 alloy in the equilibrium conditions starts with the
appearance of a phase particles at 493 C. At 443 C the peritectic
reaction occurs: L + a = b. This b phase is unstable at lower temperatures and at about 320 C a phase emerges. The rest of b phase
decomposes at 275 C (eutectoid temperature) according to the
following relation: b = a + g (phase mixture). Considering that mutual solubility of zinc and aluminium is insignicant, it could be expected that a ne mixture of aluminium and zinc would be created
during equilibrium solidication. However, in a real casting process regardless of the procedure applied, the solidication rate of
ZA27 alloy is much higher and the time for peritectic reaction to
occur is signicantly reduced. ZA27 alloy solidies dendritically
therefore. Particles of a phase react partially with the melt creating
high-temperature b phase that solidies on the surface of a particles. Upon further cooling b phase transforms at eutectoid temperature into a phase mixture (a + g), which makes the periphery of
dendrites (Fig. 4b and c).
Variations in chemical composition of microconstituents in the
as-cast sample of ZA27 alloy are shown in Fig. 4d. SEM/EDS analysis
was performed along the L line (Fig. 4c). The line of analysis starts
from the core of a dendrite goes through its periphery and interdendritic phase, passes the periphery of a second dendrite, and ends in
the core of the second dendrite. It can be seen (Fig. 4d) that dendritic
cores are rich in aluminium; interdendritic phase is rich in zinc,
while the composition of the dendritic periphery is approximately
equal to the chemical composition of ZA27 alloy. Variations in copper concentration (low in the dendritic core and very high in the
interdendritic phase) indicate presence of intermetallic compound
CuZn4 (e-phase) in the interdendritic regions. It was reported that
presence of e phase had a benecial effect on mechanical and wear
properties of Zn25Al3Cu alloy, particularly after certain heat treatment regimes [11]. Oxygen presence points to the existence of an
oxide/hydroxide lm at the alloy surface [30,31,42].
The effect of corrosion on the microstructure of the as-cast sample after one month exposure in the test solution is shown in
Fig. 5ad. It can be seen that corrosion has started on the edge of
the sample and around inclusions (Fig. 5a), like it was reported earlier [56]. It was noticed [25] that corrosion or zinc and zinc alloys in
salt solutions usually started at places where defects (scratches,
abrasion) or impurities were present. Chemical composition of
inclusions and their chemical and physical characteristics, as well
as their distribution and quantity are dependent on the chemical
composition of an alloy, smelting method and solidication regime
[55]. Accordingly, an investigation of the inclusions effect on the
alloy corrosion behaviour is rather complex and has to be treated
from the standpoint of metal solidication theory related to the
method of the alloy processing (in liquid state), but that was beyond the scope of this work. Corrosion behaviour of the as-cast
and heat treated ZA27 alloy was examined assuming that chemical

413

Fig. 4. Microstructure of as-cast ZA27 alloy. (a) OM, polished, (b) OM, etched, (c)
SEM, polished; DC, dendritic core; DP, dendritic periphery; IDS, interdendritic
space; (d) EDS, variations of chemical composition along the L line (Fig. 4c).

composition of inclusions and their amount were unaffected by the

applied thermal treatment. Chemical composition of ZA27 alloy

414

B. Bobic et al. / Corrosion Science 53 (2011) 409417

Corrosion processes around inclusions in the as-cast sample

mainly take place laterally over the sample surface, which can be
also seen on the etched sample (Fig. 5b). Destruction of g phase
and a + g phase mixture regions occur during the corrosion progress (Fig. 5b). Microcracks can be observed (B) at higher magnication, besides the corrosion products on the sample surface and
around some inclusions (A) (Fig. 5c). The microcracks are sites
of more intensive corrosion [56]. Besides the microcracks
propagation along the a/a + g phase boundary, transcrystalline
microcracks can be also seen (Fig. 5d) probably as a result of
machining process during the sample preparation.

3.2.2. ZA27 alloy, heat treated

Microstructures of the heat treated ZA27 alloy are shown in
Fig. 6ac.
After thermal processing the microstructure of ZA27 alloy has
remained dendritic although a signicant morphological change

Fig. 5. Microstructure of as-cast ZA27 alloy after exposure in 3.5 wt.% NaCl. (a) OM,
polished, b) OM, etched, (c) SEM, polished; A, inclusions, B, microcrack, (d) SEM,
polished.

has remained identical after thermal processing although a significant morphological change took place.

Fig. 6. Microstructure of heat treated ZA27 alloy. (a) OM, polished, (b) OM, etched,
(c) SEM, polished.

B. Bobic et al. / Corrosion Science 53 (2011) 409417

415

took place (Fig. 6b and c) as a result of T4 heat treatment. Solutionizing time (3 h) was not enough for a complete homogenization of
the alloy to take place i.e., for a complete destruction of dendritic
cores and interdendritic g phase. The regions of a + g phase mixture were extended while dendritic cores (a phase region) and
interdendritic regions (g phase) were reduced (Fig. 6c). A decrease
in size of dendritic cores (a phase) and rounding off their edges
happened, as well as the separation of individual dendritic cores
into several smaller segments. Smaller dendritic cores were transformed into a + g phase mixture. During heating at 370 C for 3 h,
there was an expansion of b phase at the expense of supersaturated
a and g phases. After cooling, the newly created b phase was transformed into a + g phase mixture. According to our results [12] the
lattice parameter of a phase in the heat treated alloy was reduced
comparing to the lattice parameter of a phase in the as-cast alloy
as a consequence of zinc diffusion from the metastable a phase. Besides, it was shown by quantitative metallographic analysis [47]
that volume fraction of a + g phase mixture was increased while
both volume fractions of a and g phase were reduced in the heat
treated ZA27 alloy in relation to the as-cast alloy.
T4 heat treatment that was applied within this work differs
from the heat treatment regime prescribed by standard where furnace cooling instead of water quenching was prescribed [46]. It
was shown [12] that structure coarsening and appearance of T0
phase (Al4Cu3Zn2) took place during furnace cooling of ZA27 alloy.
The presence of T0 phase in the alloy structure was also conrmed
in [57]. This phase is brittle and thus has a bad effect on the alloy
ductility. The appearance of T0 phase in the heat treated samples of
ZA27 alloy was avoided within this work by using T4 regime,
which resulted in increased ductility of the heat treated alloy as
was reported in [12].
The effect of corrosion on the microstructure of the heat treated
sample is shown in Fig. 7ad. Corrosion attack is observed on the
sample edge (area of mechanical damage) and around some inclusions (Fig. 7a). The corrosion has taken place in the region of a + g
phase mixture and in the interdendritic g phase (Fig. 7b). Bright islands of a phase are surrounded by dark corrosion products. Corroded areas are shown in Fig. 7c and d. The arrows in Fig. 7c
indicate corrosion progress through the region of a + g phase mixture as well as through the interdendritic g phase. Zinc-rich corrosion products are mainly needle-like and rosette-shaped crystals
(Fig. 7d). The appearance of microcracks in the heat treated samples was not observed after 1 month of exposure in corrosion environment which indicates increased ductility and thus, greater
corrosion stability of the heat treated alloy.
3.3. Surface appearance of test samples after electrochemical tests
Surface appearance of the as-cast and heat treated sample of
ZA27 alloy after electrochemical polarization measurements is presented in Fig. 8a and b. It is noticeable that the layer of corrosion
products on the sample surface is quite thin (A), so that the alloy
microconstituents can be observed through this layer, e.g., white
traces of g phase are visible.
According to the results of EDS analysis in point (surface area
A and B, Fig. 8a and b) an increase in oxygen amount can be observed, which indicates formation of oxides and hydroxides during
corrosion process. This effect was more pronounced in the heat
treated sample (Fig. 8c).
3.4. Corrosion products
After 1 month exposure to quiescent NaCl solution the surface
of test samples was covered with white powdered corrosion
products. A part of the corrosion products that had been detached
from the samples surface was precipitated in the test solution.

Fig. 7. Microstructure of heat treated ZA27 alloy after exposure in 3.5 wt.% NaCl. (a)
OM, polished, (b) OM, etched, (c and d) SEM, polished.

Corrosion products were collected by ltration of the test solution

and dried before subjected to XRD analysis. Characteristic XRD pat-

416

B. Bobic et al. / Corrosion Science 53 (2011) 409417

Fig. 9. XRD patterns of ZA27 alloy corrosion products. (a) ZA27 as-cast, (b) ZA27
heat treated.1 Zn(OH)2, 2 Mg(OH)2, 3 ZnO.

Fig. 8. Surface appearance of test samples after electrochemical tests. (a) SEM, ZA27
as-cast, (b) SEM, ZA27 heat treated, (c) oxygen amount in the samples of ZA27 alloy;
A, corroded area; B, non corroded area.

terns are presented in Fig. 9a and b. It can be seen that corrosion

products of ZA27 alloy are composed mainly of Zn(OH)2 and ZnO,
as it was reported in [31]. According to the intensities of reexion
it can be concluded that corrosion products of the as-cast alloy
contain a larger amount of Zn(OH)2 and a smaller amount of ZnO
compared to the heat treated ZA27 alloy.
Corrosion products of aluminium were not detected by XRD
analysis after 1 month exposure of the as-cast and heat treated
ZA27 alloys to NaCl solution, possibly because the time of exposure
was too short for crystallized corrosion products to be formed. It
was reported that in the initial stage of seawater corrosion of
ZnAl alloy coating (2230 wt.% Al) the gelatinous deposit of
Al(OH)3 was rst produced on the coating surface and that with
lengthening of immersion time corrosion products tended to increase in crystallinity and grain size [58]. After 3, 6, 12 and

18 months exposure to seawater corrosion products were typical

nanometer microcrystals, containing mainly Zn4CO3(OH)6H2O,
Zn5(OH)8Cl2 and Zn6Al2CO3(OH)164H2O [58].
Based on all the results presented it could be concluded that applied heat treatment (T4) affected the ZA27 alloy microstructure,
as well as its corrosion stability. The alloy morphology was changed so that the regions of a + g phase mixture were extended
while dendritic cores (a phase region) and interdendritic regions
(g phase) were reduced (Fig. 6c). After T4 heat treatment microcracks were not observed in thermally processed ZA27 alloy
(Fig. 6a). Also, the appearance of microcracks in the heat treated
samples was not noticed after one month exposure to NaCl solution (Fig. 7). This indicates an increase in ductility and thus, greater
corrosion stability of the heat treated alloy. Corrosion products of
the heat treated ZA27 alloy contain a larger amount of ZnO compared to the as-cast alloy like it was shown by XRD analysis
(Fig. 9a and b). All these resulted in greater Rp values (Fig. 1a and
b) and lower jcorr values (Figs. 2 and 3) of the heat treated ZA27 alloy, namely in reduced corrosion rate. These results allow us to
conclude that T4 heat treatment of ZA27 alloy has a small benecial effect on its corrosion stability and that was the aim of this
work.
4. Conclusions
On the basis of the results presented the following conclusions
can be made:

B. Bobic et al. / Corrosion Science 53 (2011) 409417

1. T4 heat treatment affected the microstructure and corrosion

resistance of ZA27 alloy.
2. The alloy structure remained dendritic after T4 heat treatment
and corrosion process takes place through g phase and a + g
phase mixture.
3. T4 heat treatment has a small benecial effect on the corrosion
resistance of ZA27 alloy.
4. Increased ductility and favourable corrosion properties of the
heat treated ZA27 alloy indicate its potential use in manufacturing machine parts like gears and worm gears.
5. Electrochemical measurements of corrosion rate, based on the
corrosion current at free corrosion potential, are in good agreement with the results obtained by the weight loss method.
Acknowledgements
This work was nancially supported by the Ministry of Sciences
and Environmental Protection of the Republic of Serbia through the
projects TR 19061 and TR 14005B. The authors are gratefully
acknowledged to RAR foundry Batajnica, for providing the master
alloy for performance of the research.
References
[1] E. Gervais, R.J. Barnhurst, C.A. Loong, An analysis of selected properties of ZA
alloys, JOM 11 (1985) 4347.
[2] E.J. Kubel Jr., Expanding horizons for ZA alloys, Adv. Metal Prog. 7 (1987) 51
57.
[3] H. Chendler, Heat Treaters Guide: practices and procedures for nonferrous
alloys, ASM International, 1996.
[4] ASM Handbook, Properties and selection: nonferrous alloys and specialpurpose materials, vol. 02, ASM International 1990.
[5] P.P. Lee, T. Savasakan, E. Laufer, Wear resistance and microstructure of ZnAl
Si and ZnAlCu alloys, Wear 117 (1987) 7989.
[6] P. Choudhury, K. Das, S. Das, Evolution of as-cast and heat-treated
microstructure of a commercial bearing alloy, Mater. Sci. Eng., A 398 (2005)
332343.
[7] P. Choudhury, S. Das, Effect of microstructure on the corrosion behavior of a
zincaluminium alloy, J. Mater. Sci. 40 (2005) 805807.
[8] C. Dominguez, M.V. Moreno Lopez, D. Rios-Jara, The inuence of manganese on
the microstructure and the strength of a ZA27 alloy, J. Mater. Sci. 37 (2002)
51235127.
[9] T.J. Chen, Y. Hao, Y. Sun, Y.D. Li, Effects of Mg and RE additions on the semisolid microstructure of a zinc alloy ZA27, Sci. Technol. Adv. Mater. 4 (2003)
495502.
[10] M.T. Jovanovic, I. Bobic, B. Djuric, N. Grahovac, N. Ilic, Microstructural and
sliding wear behavior of a heat-treated zinc-based alloy, Tribol. Lett. 3 (2007)
173184.
[11] M. Babic, A. Vencl, S. Mitrovic, I. Bobic, Inuence of T4 heat treatment on
tribological behavior of ZA27 alloy under lubricated sliding condition, Tribol.
Lett. 2 (2009) 125134.
[12] I. Bobic, B. Djuric, M.T. Jovanovic, S. Zec, Improvement of ductility of a cast Zn
25Al3Cu alloy, Mater. Charact. 29 (1992) 277283.
[13] H. Aashuri, Globular structure of ZA27 alloy by thermomechanical and semisolid treatment, Mater. Sci. Eng., A 391 (2005) 7785.
[14] T.J. Chen, Y. Hao, J. Sun, Microstructural evolution of previously deformed
ZA27 alloy during partial remelting, Mater. Sci. Eng., A 337 (2002) 7381.
[15] T.J. Chen, Y. Hao, Y.D. Li, Effects of processing parameters on microstructure of
thixoformed ZA27 alloy, Mater. Des. 28 (2007) 12791287.
[16] T.J. Chen, Y. Hao, J. Sun, Y.D. Li, Phenomenological observations on
thixoformability of a zinc alloy ZA27 and the resulting microstructures,
Mater. Sci. Eng., A 396 (2005) 213222.
[17] W.R. Osorio, C.M. Freire, A. Garcia, The effect of the dendritic microstructure on
the corrosion resistance of ZnAl alloys, J. Alloys Compd. 397 (2005) 179191.
[18] G.A. Santos, C.M. Neto, W.R. Osorio, A. Garcia, Design of mechanical properties
of a ZA27 alloy based on microstructure dendritic array spacing, Mater. Des. 28
(2007) 24252430.
[19] A.E. Ares, L.M. Grassa, S.F. Gueijman, C.E. Schvezov, Correlation between
thermal parameters, structures, dendritic spacing and corrosion behavior of
ZnAl alloys with columnar to equiaxed transition, J. Cryst. Growth 310 (2008)
13551361.
[20] I. Bobic, M.T. Jovanovic, N. Ilic, Microstructure and strength of ZA27 based
composites reinforced with Al2O3 particles, Mater.Lett. 57 (2003) 16831688.
[21] Z.Q. Li, B.Y. Wu, S.Y. Zhang, Pretreatment process of SiC particles and
fabrication technology of SiC particulate reinforced ZnAl alloy matrix
composite, Mater. Sci. Technol. 17 (2001) 954960.

417

[22] S.C. Sharma, D.R. Somashekar, B.M. Satish, A note on the corrosion
characterization of ZA-27/zircon particulate composites in acidic medium, J.
Mater. Process. Technol. 118 (2001) 6264.
[23] S.C. Sharma, B.M. Girish, R. Kamath, B.M. Satish, Graphite particles reinforced
ZA-27 alloy composite materials for journal bearing applications, Wear 219
(1998) 162168.
[24] S.C. Sharma, B.M. Girish, B.M. Satish, R. Kamath, Mechanical properties of ascast and heat-treated ZA-27 alloy/short glass ber composites, J. Mater. Eng.
Perform. 7 (1998) 9399.
[25] L.L. Shreir, R.A. Jarman, G.T. Burstein (Eds.), Corrosion, third ed., Butterworth,
Heinemann, Oxford, 2000.
[26] T.H. Muster, W.D. Ganther, I.S. Cole, The inuence of microstructure on surface
phenomena: rolled zinc, Corros. Sci. 49 (2007) 20372058.
[27] F.C. Porter, Corrosion Resistance of Zinc and Zinc Alloys, in: P.A. Schweitzer
(Ed.), Marcell Dekker, New York, 1994.
[28] R.J. Barnhurst, S. Belisle, Corrosion properties of Zamak and ZA alloys, Noranda
Report, 1992.
[29] V. Barranco, S. Feliu Jr., S. Feliu, EIS study of the corrosion behaviour of zincbased coatings on steel in quiescent 3% NaCl solution. Part 1: directly exposed
coatings, Corros. Sci. 46 (2004) 22032220.
[30] Y. Hamlaoui, F. Pedraza, L. Tifouti, Comparative study by electrochemical
impedance spectroscopy (EIS) on the corrosion resistance of industrial and
laboratory zinc coatings, Am. J. Appl. Sci. 4 (2007) 430438.
[31] T.H. Muster, I.S. Cole, The protective nature of passivation lms on zinc:
surface charge, Corros.Sci. 46 (2004) 23192333.
[32] H. Dafydd, D.A. Worsley, H.N. McMurray, The kinetics and mechanism of
cathodic oxygen reduction on zinc and zincaluminium alloy galvanized
coating, Corros. Sci. 47 (2005) 30063018.
[33] K. Aramaki, The inhibition effects of cation inhibitors on corrosion of zinc in
aerated 0.5 M NaCl, Corros. Sci. 51 (2009) 10431054.
[34] C. van den Bos, H.C. Schnitger, X. Zhang, A. Hovestad, H. Terryn, J.H.W. de Wit,
Inuence of alloying elements on the corrosion resistance of rolled zinc sheet,
Corros. Sci. 48 (2006) 14831499.
[35] S.T. Vagge, V.S. Raja, R.G. Narayanan, Effect of deformation on the
electrochemical behavior of hot-dip galvanized steel sheets, Appl. Surf. Sci.
253 (2007) 84158421.
[36] P.A. Schweitzer, Fundamentals of corrosion, Mechanisms, Causes and
Preventive Methods, CRC Press, Taylor & Francis Group, Boca Raton, 2010.
[37] P. Marcus, F. Mansfeld, Analytical Methods in Corrosion Science and
Engineering, CRC Press, Taylor & Francis Group, Boca Raton, 2006.
[38] M. Stern, A.L. Geary, J. Electrochem. Soc. 104 (1957) 56.
[39] R.G. Kelly, J.R. Scully, D.W. Shoesmith, R.G. Buchheit, Electrochemical
Techniques in Corrosion Science and Engineering, Marcell Dekker, Inc., 2002.
[40] F. Mansfeld, Tafel slopes and corrosion rates obtained in the pre-Tafel region of
polarization curves, Corros. Sci. 47 (2005) 31783186.
[41] E. McCafferty, Validation of corrosion rates measured by the Tafel
extrapolation method, Corros. Sci. 47 (2005) 32023215.
[42] H.J. Flitt, D.P. Schweinsberg, Synthesis, matching and deconstruction of
polarization curves for the active corrosion of zinc in aerated near-neutral
NaCl solutions, Corros. Sci. 52 (2010) 19051914.
[43] H.J. Flitt, D.P. Schweinsberg, Evaluation of corrosion rate from polarisation
curves not exhibiting a Tafel region, Corros. Sci. 47 (2005) 30343052.
[44] M.A. Amin, K.F. Khaled, S.A. Fadl-Allah, Testing validity of the Tafel
extrapolation method for monitoring corrosion of cold rolled steel in HCl
solutions Experimental and theoretical studies, Corros. Sci. 52 (2010) 140
151.
[45] E. Poorqasemi, O. Abootalebi, M. Peikari, F. Haqdar, Investigating accuracy of
the Tafel extrapolation method in HCl solutions, Corros. Sci. 51 (2009) 1043
1054.
[46] BS EN 12844:1999 Zinc and zinc alloys. Castings. Specications.
[47] I. Bobic, PhD Thesis, Belgrade, 2003.
[48] ASTM E1008 Standard Test Method for Brinell Hardness of Metallic Materials.
[49] ASTM G3172 (2004) Standard Practice for Laboratory Immersion Corrosion
Testing of Metals.
[50] ASTM G103 Standard Practice for Preparing, Cleaning and Evaluating
Corrosion Test Specimens.
[51] K.R. Baldwin, M.J. Robinson, C.J.E. Smith, Corrosion rate measurements of
electrodeposited zincnickel alloy coatings, Corros. Sci. 36 (1994) 1115
1131.
[52] X.G. Zhang, Corrosion and Electrochemistry of Zinc, Plenum Press, New York,
1996.
[53] D. Landolt, Corrosion and Surface Chemistry of Metals, rst ed., EPFL Press,
2007.
[54] G. Rocchini, The determination of Tafel slopes by an integral method, Corros.
Sci. 36 (1994) 113125.
[55] ASM Handbook, Metallography and Microstructures, vol. 9, ASM International,
2004.
[56] R.J.H. Wanhill, T. Hattenberg, Corrosion-Induced Cracking of Model Train Zinc
Aluminium Die Castings, NLR-TP-2005-205, (2005).
[57] S. Murphy, T. Savaskan, Metallography of zinc-25% Al based alloys in the as
cast and aged conditions, Prakt. Metallogr. 24 (1987) 204221.
[58] Y. Li, Formation of nano-crystalline corrosion products on ZnAl alloy coating
exposed to seawater, Corros. Sci. 43 (2001) 17931800.