Current Applied Physics 19 (2019) 582–598

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Current Applied Physics

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

Near-eutectic Zn-Mg alloys: Interrelations of solidification thermal T

parameters, microstructure length scale and tensile/corrosion properties
Talita A. Vidaa, Crystopher Britob, Thiago S. Limaa, José E. Spinellic, Noé Cheunga,∗,
Amauri Garciaa
a
Department of Manufacturing and Materials Engineering, University of Campinas, UNICAMP, 13083–860, Campinas, SP, Brazil
b
Campus of São João da Boa Vista, São Paulo State University - UNESP, 13876-750, São João da Boa Vista, SP, Brazil
c
Department of Materials Engineering, Federal University of São Carlos, UFSCar, 13565-905, São Carlos, SP, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: Zn-Mg alloys are considered to have potential application in bone implants, since both metals are biocompatible
Zn-Mg alloys and have biodegradable characteristics. Adding Mg to Zn can boost mechanical and corrosion resistances.
Directional solidification However, the literature is very limited on quantifying the interrelation of solidification parameters, micro-
Microstructure structural features and mechanical/corrosion properties of Zn-Mg alloys. The present study examines the in-
Tensile properties
terrelations of alloy Mg content, macrosegregation effects, morphology and scale of the matrix and eutectic
Corrosion
phases, nature of intermetallics and tensile and corrosion properties of near-eutectic Zn-Mg alloys. The alloys
samples are obtained by unsteady-state directional solidification resulting in a wide range of solidification
thermal parameters and microstructures. We examine microstructural features of both dendritic and complex
regular eutectic phases. It is shown that the eutectic exhibits a bimodal pattern with neighboring areas of coarse
and fine lamellae. Experimental growth laws relating the primary, secondary and eutectic spacings to the so-
lidification cooling rate and growth rate are proposed. Hall-Petch type equations are derived expressing tensile
strength and elongation to dendritic and eutectic spacings. Electrochemical parameters determined by polar-
ization curves during corrosion tests and SEM analyses of corroded areas have shown that the alloy having an
essentially eutectic microstructure is associated with better corrosion resistance.

1. Introduction promising for applications in painted zinc-magnesium coatings on steel

Several investigations underlined Zn as a promising bio-absorbable
material because of its non-toxicity and inherent benefits to the human
body [1–4]. The potential for build-up biocompatible corrosion layers
together with superior mechanical strength and castability describes
the Zn-Mg family of alloys [5]. This explains why these materials may
become so attractive for clinical bone implants. Load-bearing applica-
tions with biocompatible Zn-Mg alloys are among those considered as
highly innovative [6–8]. Since Mg is nearly exclusively present in the
form of Zn-Mg intermetallics (i.e., Mg2Zn11 and MgZn2), an increase in
mechanical strength does not seem surprising. Therefore, Mg emerges
as a natural alloying element that could provide superior mechanical
properties [9–14], while preserving the biocompatibility. However,
systematic studies correlating microstructural features and mechanical/
corrosion properties of Zn-Mg alloys are still scarce in the literature.
The addition of Mg to Zn coatings is reported to improve the cor-
rosion properties [15–17]. The excellent level of protection is also very
sheets. The corrosion resistance of these covered sheets exceeded by far
that of the unalloyed zinc coatings, as well as that of many other alloy
coatings. These encouraging results open a perspective to reduce
coating thickness and maybe even to omit pre-treatments [18]. As
stated by Prosek et al. [19], advanced coatings can provide a barrier
and galvanic protection to steel parts applied in automotive, building,
and other industries, improving durability and aesthetic properties of
final products.
It seems unexpected that Mg-containing Zn alloys could display
better corrosion properties, as Mg is much less noble than Zn [19]. As a
matter of fact, Mg added to the alloys is mostly expended for the growth
of Zn-Mg intermetallics during the liquid-to-solid transformation stage.
Therefore, the role of the Zn-Mg intermetallic particles on the protec-
tion mechanisms defining the corrosion behavior is critical, as outlined
in previous investigations [18,20]. The corrosive action starts exactly at
the intermetallics in Zn-Mg alloys [20]. Despite the most recent studies
of specific mechanisms, the effects of Zn-Mg intermetallics on the

∗
Corresponding author.
E-mail address: cheung@fem.unicamp.br (N. Cheung).

https://doi.org/10.1016/j.cap.2019.02.013
Received 8 December 2018; Received in revised form 14 January 2019; Accepted 19 February 2019
Available online 28 February 2019
1567-1739/ © 2019 Korean Physical Society. Published by Elsevier B.V. All rights reserved.
T.A. Vida, et al. Current Applied Physics 19 (2019) 582–598

corrosion behavior have not yet been fully comprehended [21–24].

According to Yao et al. [1], bulk parts of a specific Mg-Zn alloy may
have a very different microstructure as compared to that of surface
coatings of the same composition. This is due to the different cooling
rates associated with processing of bulk alloys and coatings. As such,
the corrosion properties may be affected accordingly. The effect of the
imposed cooling rate during casting in the microstructural array and
consequently in the final application properties is thoroughly docu-
mented [25,26]. Therefore, the solidification cooling rate may have an
important impact on the resulting properties of the Zn-Mg alloys, e.g.,
on mechanical strength and electrochemical behavior.
Many of the experimental researches on Zn-Mg alloys reported a
qualitative description of the resulting microstructure [1,22,27,28].
Although it is known that solidification thermal parameters, such as the
growth rate and the cooling rate, define the development of the as-cast
microstructure, these studies have not focused on the correlations be-
tween thermal and microstructure parameters. The literature on
quantifying the morphology, size, distribution of microstructural fea-
tures and mechanical properties related to the solidification thermal
parameters of Zn-Mg alloys [29,30] is very limited.
The length scales of the phases forming the microstructure of me-
tallic alloys, that is, cellular, dendritic and interphase spacings, are Fig. 1. Partial Zn-Mg phase diagram. The vertical dotted lines indicate the
known to play significant roles in the improvement of mechanical and compositions of interest in the present investigation.
chemical properties. The solidification thermal parameters influence
these microstructural spacings, porosity, segregation patterns, mor- Table 1
phology, size and dissemination of second phases, therefore affecting Chemical composition (wt.%) of metals used to prepare the alloys.
the final properties - physical [31], mechanical and corrosion properties
Element Zn Mg Mn Cr Fe Al Pb Si
[32,33] - of as-cast alloys. Several studies reported that the micro-
structural refinement is generally positive to mechanical properties, Zn balance – – – 0.015 – 0.012 0.003
since a more homogeneous distribution of second/intermetallic phases Mg 0.01 balance 0.01 0.01 0.01 0.11 – –
throughout the alloy matrix makes obstruction to the motion of dis-
locations more efficient [26,34–36].
Kubasek and Vojtech [37] investigated the effects of Mg on the cooling) or imposing slow cooling by controlling the sample in a fur-
tensile mechanical properties of Zn-Mg alloys (1.0, 1.5 and 3.0 wt-pct nace. The microstructures revealed small spiral segments in the fast-
Mg) by pouring the molten alloys into a non-preheated steel mold. A cooled samples, with the presence of various eutectic colonies. These
qualitative description of the resulting microstructures was reported. colonies prevented the spirals from reaching a sufficient size of several
Higher ultimate tensile strengths of 153 MPa and 147 MPa were ob- turns. At the slowest cooling rates, the eutectic phases were distributed
tained for the 1.0 and 1.5 wt% Mg-containing alloys, while ductility in a typical spheroidized shape.
was quite low in both cases, i.e., 1.5% and 0.4%, respectively. The Zn- In a previous study, some of the present authors analyzed the mi-
3wt.%Mg alloy was characterized by extremely lower strength and crostructural development of dilute hypoeutectic Zn-Mg alloys along a
ductility - values of 28 MPa and 0.2%, respectively. wide range of cooling rates during transient directional solidification
As alloys of the Zn-Mg system exhibits a skewed couple zone [38], a [42]. A plate-like cellular matrix has been shown to characterize the
variety of microstructures including dendritic arrangements and eu- microstructure of Zn-0.3 wt%Mg and Zn-0.5 wt%Mg alloys for high
tectics, can be formed with an increase in the growth rate. Akdeniz and cooling rates (higher than 9.5 and 24 K/s, respectively) followed by a
Wood [38] have described the extent to which a specific microstructure granular/dendritic transition with a decrease in the solidification
is present in rapidly solidified Zn-Mg alloys by establishing a very cooling rate. The increase in the alloy Mg content to 1.2 wt% was
complete growth rate-composition map. The coupled zone was shown shown to induce a matrix morphology formed by equiaxed dendritic
to shift from a symmetry position. Thus, it skews towards the facet- grains along the entire length of the directionally solidified (DS)
forming Mg2Zn11 side of the phase diagram, i.e., towards the hyper- casting. A low fraction eutectic mixture was shown to be located along
eutectic side. This means that for eutectic and hypereutectic alloys, the intercellular regions/grain boundaries. The evolution of the inter-
there seem to exist critical growth rates beyond which eutectic solidi- cellular spacing, λc (0.3 and 0.5 wt%Mg alloys), and of the secondary
fication is not possible for a eutectic composition, with eutectic struc- dendritic arm spacings, λ2 (1.2 wt%Mg alloy) as a function of solidifi-
tures prevailing for hypereutectic chemistries. cation thermal parameters, such as the growth rate (VL) and the cooling
The growth of complex regular eutectics involves a group of eu- rate (Ṫ ), have been established by experimental growth laws, given by:
λc = 21VL−1/2; λc = 39 Ṫ −1/4 and λ2 = 13VL−2/3; λ2 = 28.5 Ṫ −1/3,
tectics where one phase has a high entropy of fusion while the other, a
where λc,2 [μm]; VL [mm/s] and Ṫ [K/s]. With the increase in the Mg
low entropy of fusion. Here, metallic systems such as Pb-Bi [39], Sn-Bi
alloy content, the volume fraction of the eutectic mixture also increases,
[40], Bi-Ca [39] and Zn-Mg [27] are examples of this kind of growth.
and, therefore, the role of the eutectic phase in determining mechanical
Two types of regions generally characterize the complex eutectic
and chemical properties becomes more significant. However, the stu-
structures: zones of a regular repeating pattern and other zones of
dies on the nature and morphology of the phases forming the eutectic
random orientation (irregular). Some authors reported other type of
mixture under transient solidification conditions, the length scale of the
structures forming the eutectic in Zn-Mg alloys [41]. Fullman and Wood
eutectic and their effects on the resulting properties are still missing in
[41], for instance, reported structures in which the two phases com-
the literature.
posing the eutectic Zn-3wt%Mg alloy appear as intertwined spirals in
The present study aims to investigate the influences of growth rate/
the examined cross sections. A wide range of cooling rates was obtained
cooling rate and segregation effects on the morphology and length scale
by varying the casting conditions. These conditions were associated
of both the Zn-rich matrix and eutectic mixture during unsteady-state
with either generating a casting onto a large cold brass block (i.e., fast

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Fig. 2. Schematic representations: (a) of the water-cooled upward directional solidification system and (b) of the procedures for extraction of the samples for
corrosion and tensile tests along the length of the directionally solidified (DS) Zn-Mg alloys castings.
unidirectional solidification of Zn-Mg near-eutectic compositions (hy-
poeutectic and hypereutectic). Additionally, experimental correlations
between the microstructural spacings and tensile and corrosion prop-
erties are investigated.
2. Experimental procedure
2.1. Zn-Mg alloys
The near-eutectic nominal compositions of the alloys investigated in
this work are: Zn-2.2 wt%Mg (hypoeutectic) and Zn-3.15 wt%Mg (hy-
pereutectic), as indicated by vertical dotted lines in the phase diagram
of Fig. 1, which was calculated by a computational thermodynamics
software, assuming equilibrium cooling conditions. The metals used to
prepare these alloys were supplied by TED Indústria e Comércio de
Metais and their compositions are shown in Table 1.
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Current Applied Physics 19 (2019) 582–598
The alloys were melted in a Silicon Carbide crucible (coated with an
alumina layer to avoid contamination) using an electric-resistance
furnace under protective argon atmosphere. For this purpose, Zn was
first melted up to a temperature of 550 °C and then elemental Mg pieces
were added to the melt. The molten alloy was then stirred, using a
stainless steel bar coated with alumina, not only to guarantee that Mg
was completely molten but also to homogenize the bath. The alloy was
then poured into the casting chamber of the directional solidification
apparatus that was subjected to a forced argon gas flow to avoid both
oxidation and loss of Zn and Mg. The casting chamber consisted of a
stainless steel mold having an internal diameter of 55 mm, a height of
150 mm, and a wall thickness of 5 mm. Its inner surface was covered
with a layer of insulating alumina to minimize heat losses. The bottom
part of the mold was closed with a thin (3 mm) disc of carbon steel.
Both near-eutectic Zn-Mg alloys were re-melted in situ by controlling
the power of the radial electrical wiring of the solidification system.
T.A. Vida, et al. Current Applied Physics 19 (2019) 582–598

microstructures are associated with high cooling rates and vice-versa.

2.3. Metallography

Samples for metallography were extracted from several positions

along the length of the DS Zn-Mg alloys castings. Longitudinal and
transverse samples referring to various positions were separately
identified, mounted, polished, etched with an etching solution (Nital 10
pct reagent) for 7 s, and then examined using an optical microscope.
The overall microstructure of each investigated sample was observed
using an Olympus inverted metallurgical microscope (model 41GX).
Length-scales of the eutectic mixture were characterized by the lamellar
spacing referring to either coarse regions or finer arrays forming the
eutectic mixture. Length-scales of dendrites were determined by the
spacing between the primary equiaxed dendrites and between the
secondary dendrite arm branches.
The primary (λ1) and secondary dendritic arm (λ2) spacings were
measured from the optical images of the solidified samples on long-
itudinal sections of the castings (about 40 independent readings for
each selected position, with the average taken to be the local spacing).
The coarse and fine eutectic spacings (λ eut) were measured on trans-
verse sections of the SEM images. The SEM images were obtained by the
use of a ZEISS scanning electron microscope-SEM (ZEISS-EVO-MA15),
equipped with an energy dispersive spectroscope-EDS (OXFORD-X-
MAX).
Some samples of each DS alloy casting were selected and subjected
to X-ray diffraction (XRD) analyses. The patterns were obtained by an
XRD diffractometer with a 2-theta range from 20 to 90°
(Bragg–Brentano reflection geometry with CuKα radiation;
λ = 1.5418 Å), by comparing the XRD patterns with crystallographic
data from the Inorganic Crystal Structure Database –ICSD [44] to de-
termine all the phases forming the microstructures. Samples for mac-
rosegregation analyses were extracted along the different positions
from the cooled surface of the DS castings and measured by a fluores-
cence spectrometer (XRF), Shimadzu EDX-720 model, to estimate local
average concentrations on a 100 mm2 probe.

2.4. Mechanical and corrosion tests

The procedures used to obtain the samples for mechanical and

Fig. 3. Experimental cooling curves obtained for different thermocouple posi-
tions along the length of the DS castings: (a) Zn-2.2 wt% Mg alloy; (b) Zn-
corrosion tests from the DS Zn-Mg castings can be seen in Fig. 2b. In the
3.15 wt% Mg alloy. TL is the alloy liquidus temperature. case of electrochemical tests, two samples of each alloy casting were
tested. Samples showing very distinct microstructures between each
other were chosen to permit the investigation of the effects of micro-
2.2. Upward directional solidification system
structure on the corrosion behavior.
The electrochemical corrosion tests were performed in a 0.06 M
The solidification experiments were carried out in a water-cooled
NaCl solution using an Autolab (PGSTAT 128N) potentiostat/galvano-
system, shown in Fig. 2a, which was designed to promote directional
stat. The electrochemical cell used for the test was a three-electrode
solidification under transient heat flow conditions. The details of the
cell, where an Ag/AgCl (saturated KCl) electrode was the reference
experimental casting apparatus have been described in a previous study
electrode, the counter-electrode was a platinum wire, and the working
[43]. The molten alloy is re-melted inside the solidification system.
electrode was the sample under study. The exposed area of the samples
When the melt temperature reached 10% above the alloy liquidus
was 0.5 cm2. All the tests were done in aerated conditions at room
temperature, the furnace windings were disconnected. At the same
temperature. All electrochemical measurements were conducted in
time, the external water flow at the bottom of the container began to
triplicate. Before obtaining the polarization curves the evolution of the
cool down, thus permitting the onset of solidification.
open circuit potential (OCP) was recorded for 15 min. A potential step
The solidification system allows for the placing of several fine K-
of 0.1 V with respect to the corrosion potential was applied, starting the
type thermocouples along the length of the casting. Eight (8) thermo-
sweep in the anodic direction at a polarization scan rate of 0.16 mV/s
couples have been strategically spaced between each other until 70 mm
until reaching a limit current density value of 0.25 mA/cm2.
from the cooled bottom of the casting. The frequency of temperature
Each position along the length of the DS castings chosen for ex-
data acquisition was 5 Hz. Postmortem examination regarding the exact
tracting tensile tests samples allowed three specimens to be machined
positions of the thermocouple tips from the cooled bottom of the
to determine the average tensile strength and ductility properties and
castings was carried out. A broad range of solidification microstructures
their standard deviations. Several specimens referring to various posi-
can be obtained from the bottom to the top of the directionally solidi-
tions from the water-cooled bottom of the Zn-Mg castings were sub-
fied (DS) casting. This is due to the decreasing profiles of cooling rates
jected to tensile tests using a MTS 810 machine according to specifi-
(Ṫ ) along the length of the DS Zn-Mg alloys castings. Finer
cations of the ASTM Standard E 8M/04 at a strain rate of 3 × 10−3 s−1.

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T.A. Vida, et al.
Fig. 4. (a) Position (P) from the cooled surface of the DS castings vs. time (t) of passage of the liquidus isotherm and (b) growth rate; (c) cooling rate and (d)
temperature gradient as a function of P.
3. Results and discussion
3.1. Cooling rate, growth rate, and macrosegregation
Fig. 3 depicts the cooling curves representing the local thermal
evolution, i.e. temperature vs. time at 8 different positions along the
length of the castings during directional solidification of the Zn-2.2 wt%
Mg (Fig. 3a) and the Zn-3.15 wt% Mg (Fig. 3b) alloys. These tempera-
ture-time data allowed us to determine representative solidification
thermal parameters, that is the solidification cooling rate (Ṫ ) and the
growth rate (VL).
Fitting functions representing a plot of position of each thermo-
couple (P) versus time (t) related to the passage of the liquidus isotherm
from the bottom to the top of each alloy casting have been determined,
as shown in Fig. 4a. The growth rates were then calculated by the time-
derivative of these functions and are shown in Fig. 4b. The VL profile
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Current Applied Physics 19 (2019) 582–598
along the length of the DS castings is slightly higher for the Zn-2.2 wt%
Mg alloy. The experimental temperature data nearby the liquidus tem-
perature in Fig. 3a and b were used to determine the coefficients of a
5th-order polynomial, by the least square method, with a view to
generating T = f(t) functions. The derivative of these functions with
respect to time yielded cooling rate (Ṫ ) functions: Ṫ = f(t). The ex-
perimentally determined time related to the liquidus front passing by
each thermocouple is then inserted into the Ṫ = f(t) function, thus
allowing Ṫ to be calculated. The Ṫ values along the length of both DS
castings are shown in Fig. 4c as a function of P. It can be seen that a
quite expressive range of cooling rates can be observed from the bottom
to the top of the castings, which varied from about 25 K/s for positions
close to the cooled surface to less than 2 K/s near the top of the castings.
Such significant range of cooling rates in a single casting experiment is
expected to be associated with corresponding expressive variation in
the scale of representative phases of the microstructure along the length
T.A. Vida, et al. Current Applied Physics 19 (2019) 582–598

Fig. 5. Mg profile as a function of solidification cooling rate along the length of
the DS castings for Zn-2.2 wt% Mg and Zn-3.15 wt% Mg alloys.
of the DS castings. The temperature gradient (GL) has also been de-
termined (Fig. 4c) by inserting the experimental values of both Ṫ and VL
in the expression that relates both thermal parameters during direc-
tional solidification, given by Ṫ = GLVL [45].
To analyze the eventual macrosegregation profiles along the length
of the DS castings, the experimental Mg concentration has been de-
termined and is shown in Fig. 5 as a function of the local solidification
cooling rate. For both examined alloys, the experimental points are
quite close to the alloys nominal compositions (represented by the solid
lines). However, in both profiles the Mg content exhibits a slight but
progressive increase with the decrease in cooling rate (that is, from the
bottom to the top of the DS castings). Mg is rejected at the solidification
interface, therefore enriching the liquid ahead of this interface. Since
Mg is much lighter than Zn, this liquid will be lighter than the open
liquid in the DS casting and it will tend to move upwards, thus inducing
the Mg profiles of Fig. 5. As correlations between microstructure fea-
tures and cooling rates are envisaged in the following sections of this
study, the Mg content has been plotted in Fig. 5 as a function of soli-
dification cooling rates along the length of the DS castings, thus per-
mitting to include local deviations of the nominal composition of each
alloy in the analyses.

Fig. 6. (a) Macrostructure and (b) typical optical microstructures of the Zn-2.2 wt% Mg alloy at three different positions (P) along the length of the DS casting. The
local thermal parameters VL and Ṫ , as well as the scale of the primary dendritic arm spacing (λ1) are also indicated at the right side of the microstructures.

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T.A. Vida, et al.
Fig. 7. (a) Macrostructure and (b) typical optical microstructures of the Zn-3.15 wt% Mg alloy at three different positions (P) along the length of the DS casting. The
local thermal parameters VL and Ṫ , as well as the scale of the lamellar eutectic spacing (λeut) are also indicated at the right side of the microstructures.
3.2. Macrostructure and microstructure
The macrostructures of the DS alloys castings are shown on the left
side of Fig. 6a and Fig. 7a for the Zn-2.2 wt% Mg and Zn-3.15 wt% Mg
alloys, respectively. It can be seen that both alloys castings are char-
acterized by fine equiaxed grains distributed from the bottom to the top
of the castings without any evidence of columnar regions. A previous
study on dilute Zn-Mg alloys (0.3 and 0.5 wt% Mg) [42] reported the
occurrence of columnar areas close to the bottom of DS castings, as-
sociated with high solidification cooling rates, which is one of the
factors inducing the development of columnar macrostructures [46].
However, a recent investigation has shown that intermetallic (IMC)
Zn2Mg particles act as potent sites for heterogeneous nucleation [47],
and, as will be shown later in this section, the Zn2Mg IMC is present in
the microstructure of both alloys examined in the present study. This
can be the cause of the copious nucleation inducing the presence of fine
equiaxed grains throughout the entire DS castings.
Fig. 6b shows typical optical microstructures at different positions
along the Zn-2.2 wt% Mg alloy casting, which are characterized by a
matrix formed by a Zn-rich phase (α-Zn), having an equiaxed dendritic
morphology, with interdendritic regions constituted by the eutectic
mixture of lamellar morphology as shown by SEM images in Fig. 8. The
measured primary dendritic arm spacing (λ1), taken as the diameter of
the equiaxed grain [48], is also indicated in Fig. 6b with the local
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Current Applied Physics 19 (2019) 582–598
solidification thermal parameters VL and Ṫ . It is worth noting the re-
markable effect of increasing values of Ṫ on the refinement of the
dendritic microstructure.
Optical microstructures of the DS Zn-3.15 wt% Mg alloy casting are
shown in Fig. 7b, for three different positions along the length of the
casting. They are characterized by a competitive mixture of stable (α-
Zn + Zn11Mg2) and metastable (α-Zn + Zn2Mg) eutectic mixtures of
lamellar morphology, where the local spacing between adjacent la-
mellae (λeut) and local solidification thermal parameters are also in-
dicated. According to Liu and Jones [49], both intermetallics forming
the eutectic mixtures are equilibrium phases; however, the eutectic
reaction forming the Zn2Mg phase only occurs under non-equilibrium
conditions.
Detailed optical (left side) and SEM (right side) images of the eu-
tectic mixture along different positions in the DS castings of both Zn-
2.2 wt% Mg and Zn-3.15 wt% Mg alloys are shown in Figs. 8 and 9
respectively. The eutectic is formed by a bimodal lamellar eutectic
morphology characterized by neighboring areas of coarse (CL) and fine
(FL) lamellae. Similar occurrence of fine and coarse eutectic structures
has been reported recently for the complex eutectic growth of ternary
Sn-Bi– (Cu; Ag) alloys [40], in which such combined structure has been
attributed to the thermal instabilities typical of transient solidification,
i.e., conditions that are similar to those of the present study.
Spiral structures can also be clearly observed in Figs. 8 and 9 (both
T.A. Vida, et al. Current Applied Physics 19 (2019) 582–598

Fig. 8. Optical microstructures (left) and highlighted SEM-BSE mode (right) images showing typical lamellar morphologies of the eutectic mixture at three different
positions (P) along the length of the DS Zn-2.2 wt% Mg alloy casting, in which arrows indicate regions of different scales of lamellar spacings; CL: coarse lamellae and
FL: fine lamellae.

for P = 70). According to Chalmers [50], the spiral structure, found by
Fullman and Wood [41], is a discontinuous type of eutectic that may be
formed when there exists a significantly strong growth anisotropy. The
Zn-Mg eutectic is formed by two complex regular structures, in which
the spiral morphology has been reported to be formed by the me-
tastable α-Zn + Zn2Mg mixture [49,51]. In a SEM image at the right
side of Fig. 9 (P = 70), a hexagonal idiomorphic phase can also be
observed, which is quite similar to those reported to occur in Zn-3.4 wt
%Mg alloy samples cast into a wedge-section copper mold and identi-
fied as the Zn2Mg phase [49]. In Fig. 9, P = 4 (optical image – left side),
an equiaxed α-Zn dendritic grain can also be observed, despite the
nominal composition of the alloy (3.15 wt%Mg) being located above

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Fig. 9. Optical microstructures (left) and highlighted SEM-BSE mode (right) images showing typical lamellar morphologies of the eutectic mixture at three different
positions (P) along the length of the DS Zn-3.15 wt% Mg alloy casting, in which arrows indicate regions of different scales of lamellar spacings; CL: coarse lamellae
and FL: fine lamellae.

the eutectic composition. This can be explained by the macrosegrega-
tion profile exhibited in Fig. 5. The sample P = 4 is associated with the
highest solidification cooling rate, i.e. the only sample associated with a
local composition slightly below the eutectic one that induces the
presence of a small fraction of equiaxed α-Zn grains in the alloy mi-
crostructure.
X-ray diffraction (XRD) patterns permitted to identify the Zn11Mg2
and Zn2Mg intermetallics all along the length of both DS castings
(Fig. 10). The precipitation of Zn2Mg IMCs seems to come from the non-
equilibrium solidification conditions associated with the present ex-
periments. Yao et al. [52] in a study on hot-dipped Zn-1; 2; 3 and 4 wt%
Mg coatings, i.e., under non-equilibrium solidification, also reported

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Fig. 10. XRD patterns (Bragg–Brentano reflection geometry with CuKα radiation, λ = 1.5418 Å) at three different positions (P) in the DS castings referring to
different solidification cooling rates. The XRD patterns were compared with crystallographic data from the Inorganic Crystal Structure Database –ICSD [44].

Fig. 11. Solidification paths of: a) Zn-2.2 wt%Mg and b) Zn-3.15 wt%Mg alloys simulated by the Thermo-Calc software based on the non-equilibrium Scheil–Gulliver
model (Continuous line) and considering equilibrium conditions (Dotted line) showing the precipitation of phases during solidification.

the occurrence of a lamellar (α-Zn + Zn2Mg) eutectic, based on XRD
and energy dispersive spectroscopy (EDS) analyses.
The following sequence of precipitation of phases under equilibrium
conditions has been calculated by the ThermoCalc software in Fig. 11:
for the Zn-2.2 wt%Mg alloy, 19.7% of molar solid fraction of Zn is
formed from the open liquid; and subsequently, a eutectic reaction
forming the Zn+Zn11Mg2 mixture occurs until solidification comple-
tion at 367.2 °C. On the other hand, for the same alloy, under non-
equilibrium conditions, and considering the Scheil–Gulliver model, the
amount of molar solid fraction of Zn is quite near the previous value,
18.3%, and the eutectic mixture is formed in a temperature interval
from 368.15 °C to 367.2 °C. Similarly, for the Zn-3.15 wt%Mg alloy,
12.2% of solid fraction of Zn11Mg2 is formed from the open liquid; after
that, the same eutectic reaction occurs. Similarly, for non-equilibrium
conditions, the amount of molar solid fraction of Zn11Mg2, predicted by
the Scheil-Gulliver model, is quite near the previous value, 11.8%, and

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T.A. Vida, et al. Current Applied Physics 19 (2019) 582–598

Fig. 12. Dendritic arm spacings as a function of solidification cooling rate and growth rate: (a) λ1 vs. Ṫ ; (b) λ1 vs. VL; (C) λ2 vs. Ṫ and (d) λ2 vs. VL. R2 is the coefficient
of determination.

Table 2 the eutectic mixture is formed in a narrower temperature interval from

Thermophysical properties of the Zn–2.2 wt%Mg alloy. 367.5 °C to 367.2 °C. It can be realized that the cooling conditions that
Properties Zn-2.2 wt%Mg Symbol (Units) were imposed during the solidification experiments of the present study
are more severe than the non-equilibrium conditions assumed by the
Partition coefficient 0.036 k0 (−) Scheil-Gulliver model, since the metastable (α-Zn + Zn2Mg) eutectic
Solute diffusivity [49] 2.04 × 10−3 D (mm2/s) mixture has been formed, as aforementioned. To the best knowledge of
Gibbs–Thomson coefficient [56] 3.3 × 10−5 Γ (K mm)
Liquidus temperature 651 TL (K)
the authors, the ThermoCalc is no able to elaborate solidification paths
Liquidus slope 18.77 mL (K/wt.%Mg) for the range of cooling conditions inherent of the present work ex-
Nominal Composition 2.2 C0 (wt.%Mg) periments.
BK constant [55] 3.6 × 10−2 G0ε (Kmm−1)
BK parameter a1 [55] 75 (-)
3.3. Solidification thermal parameters and microstructural spacings
BK parameter a2 [55] 6 (-)
Solidification range 11 ΔT (K)
Experimental growth laws relating the primary and secondary
dendritic arm spacings (λ1 and λ2, respectively) to VL and Ṫ have been
determined from the experimental results measured along the length of

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Fig. 13. Lamellar eutectic spacing as a function of solidification cooling rate and growth rate: (a) λeut vs. Ṫ ; (b) λeut vs. VL. R2 is the coefficient of determination.

the DS Zn-2.2 wt% Mg alloy casting (Fig. 12). Power functions with
−1/4 and −1/2 exponents characterize the evolution of λ1 with Ṫ and
VL, as shown in Fig. 12a and b respectively. These exponents diverge
from those reported for columnar cellular/dendritic growth during
transient directional solidification of binary alloys, which have been
reported to be in the ranges of −0.5 to −0.55 and −1.0 to −1.1 for Ṫ
and VL respectively [53]. Experimental investigations on the evolution
of the scale of dendritic spacings with solidification thermal parameters
during equiaxed solidification are rare in the literature; however, a
recent study on equiaxed directional solidification of hypoeutectic Mg-
Zn alloys has reported the same exponents as we found in the present
study for λ1 vs. Ṫ and VL [26], i.e., it seems that the unconstrained
growth of equiaxed dendrites is related to different experimental ex-
ponents when compared with those that are typical of columnar
growth. The experimental scatter of dendritic spacings has also been
compared with theoretical predictions of the Hunt-Lu (H-L) [54] and
Bouchard-Kirkaldy [55] models, which are represented by the fol-
lowing equations:
Hunt-Lu:
λ1′ = 0.07798 V′ (a−0.75) (V′ − G′)0,75 G′ − 0.6028
where
a= −1.131 − 0.1555 log10 (G′) − 0.007589[log10 (G′)]2
λ1 ΔT G Γk V Γk
λ1′ = , G′ = L 2 0 and V′ = L 0
Γk 0 ΔT DΔT
where Γ is the Gibbs-Thomson coefficient, k0 is the solute partition
coefficient, D is the liquid solute diffusivity, ΔT is the difference be-
tween the equilibrium liquidus and solidus temperatures. This model
evaluates the lower and upper limits of the spacings within which an
array can be stable, and proposes that the upper limit should be twice
the lower one.
Bouchard-Kirkaldy (BK):
1/2
16C01/2 G0 εΓD ⎞
λ1 = a1 ⎜⎛ ⎟
where Co is the solute composition, mL is the slope of the liquidus line,
TF is the fusion temperature of the solvent, and a1 and a2 are the pri-
mary and secondary dendrite-calibrating factors, which are suggested
by the authors [55] to account for uncertainties such as those involving
contribution of the values of thermophysical properties used in calcu-
lations, solid diffusion/coring for λ1, ripening for λ2, etc. G0ε is defined
by the authors as a characteristic parameter associated with the ratio of
liquid and solid diffusivities. The thermophysical properties used in the
calculations with both models are shown in Table 2.
The comparison between experimental λ1 values and those pre-
dicted by the theoretical models is shown in Fig. 12a. I t can be seen
that both models underestimate significantly the experimental scatter
and that they do not predict the related slopes, which is a significant
feature of theoretical growth models.
Power functions with −1/3 and −2/3 exponents characterize the
evolution of λ2 with Ṫ and VL, as shown in Fig. 12c and d respectively.
The −2/3 exponent (λ2 vs. VL) agrees with that of the BK theoretical
growth model (Eq. (5)) and with reports of experimentally derived
growth equations [53]. Taking into account that Ṫ = constant VL2
[45], the replacement of VL2 by Ṫ /constant in Eq. (5) will provide a
(1) functional relationship λ2 = f (Ṫ )−1/3, which has the same dependence
exhibited by the corresponding experimental equation of Fig. 12c. It
can be seen in Fig. 12d that the slopes of the experimentally derived
(2) growth law and that of the BK model are the same; however, the pre-
dictions are far from the experimental scatter. It is worth noting that the
used calibrating factor a2 = 6 has been suggested by Bouchard and
(3)
Kirkaldy based on a range of values experimentally derived for Al-
based, Sn-Pb and Fe-C alloys [55]. However, they have emphasized the
need to calibrate the experiments for other alloy systems. In order to
permit better fit to be provided between theoretical and experimental
results of hypoeutectic Zn-Mg alloys, the present λ2 experimental re-
sults of the Zn-2.2 wt%Mg alloy have been used to determine a new
calibrating factor a2 for the BK model, that is a2 = 16.
The scatters of experimental lamellar eutectic spacings (λeut) of both
experimentally examined Zn-Mg alloys are shown in Fig. 13a and
Fig. 13b, as a function of Ṫ and VL respectively, where they are sepa-

⎝ (1 − k 0) mL GL VL ⎠ (4) rated by the scale of the observed lamellae (coarse and fine). It can be
seen that −1/4 and −1/2 exponents respectively characterize the
1
3 2 present experimental power laws and that single experimental growth
4 Γ ⎛ D ⎞ ⎞⎟
λ2 = 2 π a2 ⎛⎜ 2
⎜ ⎟ laws can encompass the experimental spacings of both alloys. These
⎝ C0 (1 − k 0) TF ⎝ VL ⎠ ⎠ (5)

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T.A. Vida, et al.
Fig. 14. Comparison of present experimental growth laws relating spacings to
the cooling rate and data from Bridgman growth from the literature [49]: (a)
secondary dendritic spacings and (b) lamellar eutectic spacing.
exponents are the same as in the classical Jackson-Hunt equation for the
growth of regular lamellar eutectics [57].
Other experimental λ2 and λeut data from the literature [49] re-
garding the steady-state growth (Bridgman type directional solidifica-
tion) of near eutectic Zn-Mg alloys over a VL range 0.001–8 mm/s and
at a temperature gradient of 15 K/mm, have been plotted in Fig. 14a
and b respectively, as a function of the solidification cooling rate. These
data are compared with the experimental growth laws derived in the
present study for unsteady-state solidification (Figs. 12c and 13a re-
spectively), where a good agreement can be observed indicating that
these laws are also able to encompass the evolution of these spacings in
the steady-state regime.
3.4. Microstructural features vs tensile and corrosion properties
The evolution of experimental tensile properties as a function of the
secondary dendritic arm spacing along the length of the DS Zn-2.2 wt%
Mg alloy casting is shown in Fig. 15: (a) ultimate tensile strength (σu)
and (b) elongation-to-fracture (δ). Hall-Petch type correlations have
been determined representing the experimental scatters. The Hall-Petch
equation has been originally proposed to demonstrate the dependence
of the yield strength on the inverse square root of grain size. Recently,
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Current Applied Physics 19 (2019) 582–598
other properties such as the ultimate tensile strength and elongation
[58], hardness [33] and wear volume [59], have their correlation been
based on Hall-Petch type equations, as a function of microstructural
features such as primary and secondary dendrite arm spacings and in-
terphase spacing.
It can be seen in Fig. 15 that both σu and δ increase with the de-
crease in λ2 (increase in λ2−1/2), i.e., higher values of such properties
are related to more refined microstructures. With smaller values of λ2
the eutectic mixture is more homogeneously distributed throughout the
microstructure, and the finer the dispersion of the eutectic intermetallic
particles (IMCs) is, the more efficient they will serve as barriers for
dislocation motions. This has permitted the ultimate tensile strength to
increase from about 170 to 230 MPa along the experimental range of
λ2. A slight increase in ductility, represented by the elongation to
fracture from 2% to about 7% can also be observed in Fig. 15b, which
seems to be also associated with the higher dispersion of IMCs of more
refined dendritic microstructures.
With the increase in the alloy Mg content from 2.2 wt% Mg to
3.15 wt% Mg, the resulting microstructure has been shown to be es-
sentially characterized by the eutectic mixture. In this case, the tensile
properties have been plotted as a function of the eutectic lamellar
spacing, λeut, as shown in Fig. 15 (c) and (d) for σu and δ respectively.
With the small increase in the alloy Mg content, the σu results of the Zn-
3.15 wt% Mg alloy increased in the range of 180 MPa–280 MPa with the
decrease in λeut, i.e., the increase in the eutectic fraction induced higher
σu for refined microstructures when compared with the corresponding
values of the Zn-2.2 wt% Mg alloy. In contrast, the ductility range is
shown to be the same for both alloys examined (δ from 2% to about
7%).
To compare both corrosion and mechanical resistances, two samples
collected from high and low cooling rates regions of the DS castings
have been subjected to corrosion tests, thus allowing us to evaluate the
influence of the scale of representative phases of the microstructure.
The electrochemical behavior of the Zn-2.2 wt% Mg and Zn-3.15 wt%
Mg samples was assessed by experimental potentiodynamic polariza-
tion curves, shown in Fig. 16a and b respectively. The corrosion po-
tential (Ecorr) has been measured by determining the voltage differences
between each sample immersed in the electrolyte and the Ag/AgCl
reference electrode. Ecorr and current density (icorr) have been de-
termined by Tafel's extrapolation, using both cathodic and anodic
branches of the polarization curves. Ecorr points out the electrochemical
activity in terms of general corrosion, and icorr designates the corrosion
rate. The resistance to general corrosion is intensified with the decrease
in current density and when the corrosion potential begins to be less
negative, that is, becomes nobler. The breakdown potential (Ebreak) has
been determined by the sudden change in slope of the anodic branch,
and it represents the critical pitting potential. In a comparative analysis,
when Ebreak represents a more active potential this can be related to
higher predisposition to pitting.
A comparison between the results of samples P_20 mm and P_4 mm
(Zn-2,2%Mg alloy) is shown in Fig. 16a, where it can be seen that the
corrosion potential of sample P_20 mm is displaced towards the more
active side (Ecorr = −952 mV: about 14 mV towards the more active
potential) and that the corresponding icorr is about six times higher than
that of P_4 mm. The following results are associated with the sample
P_4 mm: icorr = 0,17 ± 0,03 μA cm−2; Ecorr = −938 mV (vs. Ag/AgCl)
and Ebreak = −912 mV (vs. Ag/AgCl). When the corrosion potential
attains −912 mV (vs. Ag/AgCl), icorr increases rapidly, as shown in
Fig. 16a. This is related to Ebreak and is generally associated with the
partial rupture of oxide films, formation of corrosion-by-products or
even intermediate species. Consequently, chloride ions can penetrate
reaching the alloy microstructure. This also happened to the sample
P_20 mm, however, at a more active potential. A combined analysis of
Figs. 5 and 6b permits to conclude that the sample P_4 mm (Ṫ
= 13.8 K/s) has a local composition that is lower than the alloy nom-
inal composition (2.2 wt %Mg), whereas the local composition of
T.A. Vida, et al.
Fig. 15. –Ultimate tensile strength (a) and elongation (b) as a function of the secondary dendritic arm spacing along the length of the DS Zn-2.2 wt% Mg alloy casting;
Ultimate tensile strength (c) and elongation (d) as a function of the eutectic lamellar spacing along the length of the DS Zn-3.15 wt% Mg alloy casting. R2 is the
coefficient of determination.
sample P_20 mm is about 2.2 wt% Mg. This means that the sample
P_20 mm has a higher eutectic fraction as compared to that of sample
P_2 mm. The microstructural arrangement α-Zn matrix/eutectic forms a
galvanic couple where the cathodic/anodic areas ratio depends on the
eutectic fraction. The higher the eutectic fraction the lower such areas
ratio affecting the potentiodynamic parameters leading to a deleterious
effect on the corrosion resistance.
The Zn-3.15 wt%Mg alloy samples exhibited a different corrosion
behavior, as shown in Fig. 16b. A comparison between the results of the
two examined samples shows that the corrosion potential of the sample
P_4 mm (Ecorr = −918 mV) is displaced towards the nobler side com-
pared with that of the sample P_30 mm (Ecorr = −950 mV). However,
its corresponding icorr (0,18 ± 0,03 μA cm−2) is higher than that of the
sample P_30 mm (0,11 ± 0,03 μA cm−2). Despite the nobler corrosion
potential of the sample P_4 mm, the lower icorr of the sample P_30 mm
gives indications of better corrosion resistance. These results are in-
trinsically associated with the morphology of the alloy microstructure,
which is determined by the solidification cooling rate and macro-
segregation. The combined analysis of Figs. 5 and 7b permits to
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Current Applied Physics 19 (2019) 582–598
conclude that the sample P_4 mm (highest cooling rate of Fig. 5) has a
local composition that is lower than the eutectic one; thus, its micro-
structure is formed by a eutectic matrix having a certain distribution of
α-Zn dendritic equiaxed grains (Fig. 7b). The cathodic character of the
Zn-rich phase seems to have contributed to the increase in Ecorr,
whereas a slight increase in icorr occurred through a mechanism similar
to the one described previously for the Zn-2.2%Mg alloy samples.
It is worth noting that many variables affect the electrochemical
parameters determined by the polarization curves: nominal composi-
tion of the alloys, local composition of each sample (deviations from the
nominal composition caused by macrosegregation effects), volume
fraction of phases forming the microstructure, and nature, scale and
distribution of the phases (affected by the solidification cooling rate). In
order to conduct general comparative analyses, these parameters have
been synthesized in Table 3 for each examined alloy sample, in which
the corrosion resistance (CR) has been taken as the inverse of the cur-
rent density. It can be observed slight variations in Ecorr, whereas higher
differences can be observed in both icorr values and in the profiles of the
polarization curves of Fig. 16a and b. Considering the samples that were
T.A. Vida, et al. Current Applied Physics 19 (2019) 582–598

Fig. 16. Potentiodynamic polarization curves and SEM images (BSE) after corrosion tests of samples extracted from two regions of the DS castings associated with
quite different solidification cooling rates: (a) Zn-2.2 wt% Mg and (b) Zn-3.15 wt% Mg alloys.

596
T.A. Vida, et al.
Table 3
Summary of experimental results of potentiodynamic polarization tests, tensile tests, cooling rates and microstructural features such as λ1, λ2, λeut, and Mg content of
the Zn-2.2 wt%Mg and Zn-3.15 wt%Mg alloys.
Alloy Sample (mm) Cooling rate (K/s) λ1 (μm) λ2 (μm) λeut (μm)b
Zn-2.2 wt%Mg P_4 13.8 88 5.5 0.51
P_20 3.9 138.5 8.6 0.65
Zn-3.15 wt%Mg P_4 13 – – 0.63
P_30 0.9 – – 0.87
a
Measurement of potential vs. Ag/AgCl at 25 °C; *P is the position from the cooled surface of the casting.
b
Mean value between coarse and fine eutectic spacings.
not affected by macrosegregation effects (P_20/Zn-2.2 wt%Mg and
P_30/Zn-3.15 wt%Mg) as shown in Table 3, it can be seen that the alloy
with higher Mg content can be associated with higher CR.
The formation of galvanic couples in the examined alloys can occur
between the α-Zn matrix and the eutectic phase or even between the
phases forming the eutectic mixture. The phases forming the micro-
structures of the examined alloys have been described in sub-section
3.2, i.e. α-Zn; eutectic (α-Zn + Zn11Mg2; α-Zn+ Zn2Mg). According to
these phases the following galvanic couples can be formed: Zn-2,2%Mg
alloy: α-Zn dendrites [cathodic area] + eutectic mixture (α-
Zn + IMCs) [anodic area]; Zn-3.15%Mg alloy: eutectic α-Zn [cathodic
area] + eutectic IMCs [anodic area]. Krieg et al. [21] reported corro-
sion potentials for Zn and the Zn2Mg IMC of −770 mV(SHE) and
−782 mV(SHE) respectively, for corrosion tests carried out in a 0.1M
NaCl solution.
SEM images depicting the morphology of the Zn-2.2 wt%Mg alloy
samples after the corrosion tests are shown in Fig. 16a. As expected, the
Zn-rich areas appear preserved, whereas selective corrosion occurred
on lamellar eutectic areas, i.e., pitting corrosion is localized over the
eutectic areas. As the Zn-3.15 wt%Mg alloy is formed essentially by a
eutectic microstructure, the corrosion action had a more generalized
character since both IMCs forming the competitive eutectic mixture
have deteriorated (Fig. 16b). Considering both examined alloys, the Zn-
3.15 wt%Mg alloy exhibited better corrosion resistance. This seems to
be associated with the formation of corrosion-by-products due to the
essentially eutectic fraction of this alloy, since Mg in aqueous en-
vironments forms a partially protective surface film constituted by MgO
and Mg(OH)2, which can slow down the corrosion process [60,61].
When considering both properties listed in Table 3 (tensile strength and
corrosion resistance) to select the alloy having combined best values of
σu and CR, it can be seen that the sample P_4 mm of the Zn-3.15 wt%
Mg alloy is the best choice, i.e. this alloy solidified at a cooling rate of
13 K/s and is associated with a fine eutectic spacing, as shown in
Fig. 7b.
4. Conclusions –
• The macrostructures along the length of the DS castings of both
examined Zn-Mg alloys were characterized by fine equiaxed grains
distributed from the bottom to the top. The microstructure of the Zn-
2.2 wt% Mg alloy is constituted by a Zn-rich matrix (α-Zn), having
an equiaxed dendritic morphology with interdendritic regions con-
stituted by a competitive mixture of stable (α-Zn + Zn11Mg2) and
metastable (α-Zn + Zn2Mg) eutectic mixtures of lamellar mor-
phology, whereas the microstructure of the Zn-3.15 wt% Mg alloy is
essentially eutectic along the entire DS casting. The eutectic mixture
was shown to be formed by a bimodal lamellar morphology char-
acterized by neighboring areas of coarse and fine lamellae. Spiral
structures have also been formed in the eutectic areas of both ex-
amined alloys.
• Experimental growth laws describing the evolution of primary and
secondary dendritic arm spacings with both the growth rate and the
cooling rate along the length of the DS Zn-2.2 wt% Mg alloy casting
have been proposed. The theoretical models of Hunt-Lu and
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Current Applied Physics 19 (2019) 582–598
Mg (%) σU (MPa) δ (%) Ecorra (mV) Ebreak (mV) icorr (μA/cm2) CR (cm2/μA)
1.9 217 4.9 −938 −912 0.17 5.88
2.1 194 3.1 −952 −921 1.04 0.96
2.6 259 4.9 −918 −899 0.18 5.55
3.1 193 2.1 −950 −905 0.11 9.09
Bouchard-Kirkaldy were shown to significantly underestimate the
dendritic experimental scatters.
For both alloys castings, the growth of lamellar eutectics complied
with the classical Jackson–Hunt relationship for growth of eutectic
systems, with the lamellar spacing being related to the growth and
cooling rates by −1/2 and −1/4 power functions, respectively.
The derived experimental growth laws λ2 vs. Ṫ and λeut vs. Ṫ were
also shown to be able to encompass the evolution of these spacings in
the Bridgman steady-state growth of near-eutectic Zn-Mg alloys.
• Hall-Petch type correlations relating the evolution of the ultimate
tensile strength and elongation to fracture with λ2 (Zn-2.2 wt% Mg
alloy) and λeut (Zn-3.15 wt% Mg alloy) have been proposed.
• Considering both examined alloys, the Zn-3.15 wt%Mg alloy was
shown to exhibit better corrosion resistance, which was attributed to
the formation of corrosion-by-products due to the essentially eu-
tectic microstructure, since Mg in aqueous environments forms a
partially protective surface film constituted by MgO and Mg(OH)2,
which can slow down the corrosion process. When considering both
tensile strength and corrosion resistance to select the alloy having
best values of combined properties, it was shown that the Zn-3.15 wt
% Mg alloy solidified at a higher cooling rate (13 K/s) and asso-
ciated with a fine eutectic spacing is the best choice.
Acknowledgements
The authors are grateful to FAPESP- São Paulo Research
Foundation, Brazil (grants: 2014/50502-5 and 2017/16058-9), Capes-
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, Brazil
(Funding Code 001) and CNPq- National Council for Scientific and
Technological Development (grant 406239/2018-5) for their financial
support. The authors would like to thank the Brazilian Nanotechnology
National Laboratory – LNNano for allowing us to use its facilities.
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