You are on page 1of 11

Journal of Alloys and Compounds 673 (2016) 220e230

Contents lists available at ScienceDirect

Journal of Alloys and Compounds


journal homepage: http://www.elsevier.com/locate/jalcom

Cellular/dendritic arrays and intermetallic phases affecting corrosion


and mechanical resistances of an AleMgeSi alloy
 Cheung a,
Crystopher Brito a, Talita Vida a, Emmanuelle Freitas a, Noe
 Eduardo Spinelli b, *, Amauri Garcia a
Jose
a
University of Campinas e UNICAMP, Department of Manufacturing and Materials Engineering, 13083-860 Campinas, SP, Brazil
b ~o Carlos e UFSCar, Department of Materials Engineering, 13565-905 Sa
Federal University of Sa ~o Carlos, SP, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Outdoor applications of AleMgeSi alloys have been specified due to their very good corrosion resistance
Received 2 January 2016 when compared with those of other aluminum alloys. Nevertheless, these alloys still have corrosion
Received in revised form problems. One of the interests consists in characterizing the microstructure evolution, which is supposed
6 February 2016
to have important role on the final properties. In many aluminum alloys, the effects of intermetallics on
Accepted 18 February 2016
Available online 21 February 2016
both the corrosion and mechanical behavior is of industrial interest. Particularly concerning AleMgeSi
alloys, hardly anything is known about the influence of the Mg2Si phase. This work aims to encompass
such analyses on an Al-3.0 wt% Mg-1.0 wt% Si alloy directionally solidified under a wide range of cooling
Keywords:
AleMgeSi alloy
rates. Experimental results include primary dendritic and cellular spacings, nature and distribution of
Solidification intermetallics associated with corrosion potential, pitting potential, current density, ultimate tensile
Microstructure strength and elongation. A high-cooling rate cellular region has been identified, followed by a dendritic
Mechanical properties region that occurred for cooling rates lower than 0.8 K/s. The cellular spacing varied from about 16 mm to
Corrosion resistance 38 mm whereas the primary dendritic arm spacing varied from 120 mm to 270 mm. The a-Al cellular
region is shown to be characterized by finely dispersed Mg2Si and Fe-bearing particles, which allowed
better mechanical properties (strength and elongation) and better corrosion resistance to be attained.
Both mechanical strength and corrosion resistance (for 0.15 M and 0.5 M NaCl electrolytes) is shown to
be unaffected by the scale of l1 within the dendritic region.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction 15 mm). As reported, such configuration improves the corrosion


resistance mainly due to the galvanic protection of both Al2Cu and
The presence of secondary phases in aluminum and its alloys is Si phases. Studies addressing the effects of different morphologies
well known for inducing pitting corrosion. Such microstructural and distributions of Mg2Si and AlFeSi intermetallic particles on the
features may be formed during casting and subsequent thermo- corrosion resistance of AleMgeSi alloys are scarce in the literature,
mechanical processing [1e4]. The morphology, chemical compo- in particular, investigations dealing with the effects of morphology
sition and distribution of second phases along the a-Al phase affect and scale of the a-Al phase on the corrosion resistance of ternary
the corrosion of Al alloys. Birbilis and Buchheit [2] affirmed that AleMgeSi alloys [5,6].
from a localized corrosion perspective, the dominant feature of AleMgeSi alloys are well known by their high specific stiffness,
alloy microstructures is the distribution of second-phases/ good formability, recycling potential, good corrosion resistance and
intermetallic particles. According to Osorio et al. [4] finely and good weldability [7]. All these features indicate that these alloys
homogeneously distributed Al2Cu and needle-like Si particles may may be considered as strong candidates for the manufacture of
be obtained along the microstructure of AleSieCu alloys, associ- components for the automotive and transport sectors [6,8]. Despite
ated with an Al-rich dendritic matrix characterized by very fine the adequate corrosion resistance obtained in Al alloys, character-
secondary dendrite arm spacings (ranging between 5 mm and ized by their passive behavior, several problems associated with
localized corrosion action are still faced [7]. The influences of
microstructure features of AleMgeSi alloys such as, growth mor-
* Corresponding author. phologies of the phases forming the microstructure, scale of
E-mail address: spinelli@ufscar.br (J.E. Spinelli).

http://dx.doi.org/10.1016/j.jallcom.2016.02.161
0925-8388/© 2016 Elsevier B.V. All rights reserved.
C. Brito et al. / Journal of Alloys and Compounds 673 (2016) 220e230 221

Table 1
Chemical composition (wt.%) of metals used to prepare the alloys.

Element Al Mg Si Cu Fe Zn Ni Sn Mn

Al balance 0.01 0.03 0.01 0.03 0.01 e e e


Mg 6.98 balance 0.14 0.115 0.001 0.63 0.001 0.005 0.14
Si 0.11 e balance e 0.32 e 0.01 e e

dendritic/cellular spacings, distribution of eutectic mixtures, and aqueous solutions except for pitting corrosion due to some reactive
their effects on the mechanical properties (ductility, strength) are species, such as chloride [14]. The pitting susceptibility can be
still to be determined. However, besides the mechanical properties, related to the presence in the alloy microstructure of dissimilar
the effect of microstructural features on the corrosion resistance is intermetallic phases (IMCs), which exposed on the surface of the
also an important issue to be considered in engineering applica- alloy, create local corrosion cells [15]. Therefore, IMCs such as Al2Cu
tions. Cellular and dendritic growth in Al alloys may be affected by and Al3Fe, leads to the formation of local electrochemical cells
the alloy composition and cooling rate during solidification. Some between them and the Al-rich phase, that act as pitting corrosion
recent studies have pointed out the effect of microstructure, and initiation sites. A number of aspects can be associated with corro-
particularly of the morphology and scale of the Al-rich matrix on sion by pitting in Al alloys, for example, the type of concentration of
the resulting mechanical properties [9,10]. A study by Goulart et al. aggressive ion, the pH of the media, the temperature or the struc-
[11] gives an interesting example of the role of intermetallics on the tural characteristics of the oxide passive film [14]. In the case of
resulting mechanical properties of as-solidified Al-based alloys. AleMgeSi alloys, IMCs and grain boundaries are seen as the main
These authors examined AleFe alloys and demonstrated that the corrosion initiation sites and most of these IMCs enhance the
tensile strength increases with increasing alloy Fe content and with corrosion rate due to their cathodic activity [7,16].
a more homogeneous distribution of fiber-like Al6Fe intermetallics. The Fe-containing intermetallics are considered more noble
For coarser microstructural cellular arrangements, the Al6Fe fibers when compared with the Al-rich matrix, and the MgSi precipitates
remain more concentrated in the intercellular regions provoking a show ambivalent electrochemical behavior. Zeng et al. [5] showed
deleterious effect on the mechanical properties due to the brittle that the corrosion potential of the Al-rich matrix in an AleMgeSi
nature of these fibers. On the other hand, when Al3Fe particles are alloy, for tests carried out in a 3.5% NaCl solution, is around 0.9 V
present in the alloy microstructure, it is expected that they nega- (vs SCE: saturated calomel electrode), the potential for Mg2Si is
tively influence the ductility level, since their plate-like about 1.2 V while Si refers to about 0.5 V. The most negative
morphology is more susceptible to induce microcracks than the potential is that of Mg2Si, which is then considered more suscep-
fibrous Al6Fe phase [12]. For a dilute Ale0.5 wt.% Fe alloy, it has tible to corrosion than the other two phases. During corrosion,
been reported that coarse cells tend to improve the corrosion Mg2Si has an anodic behavior with respect to the Al-rich phase,
resistance mainly due to the reduction in cellular boundaries. In promoting anodic dissolution and surface corrosion. However, Zeng
contrast, for the quasi-eutectic Ale1.5 wt.% Fe alloy, an opposite et al. [5] observed that this behavior changes during the corrosion
trend was shown to occur, with fine cells providing better corrosion process, when active Mg is preferentially dissolved in a later stage,
resistance than coarse ones. This has been attributed to the more resulting in an enrichment of Si. This may shift the MgSi potential
extensive distribution of the intermetallic Al6Fe particles that is towards the positive direction, becoming more cathodic. As a
associated with finer cells, due to the protective effect provided by consequence, anodic dissolution of the Al-rich matrix occurs in the
the more noble Al6Fe particles that envelope the Al-rich phase in periphery of adjacent MgSi particles.
the eutectic mixture [13]. Based on the aforementioned findings, it would be interesting to
Al-based alloys are usually passive and corrosion resistant in identify the weak points where corrosion starts in AleMgeSi alloys,
in particular characterizing microstructural features that induce
corrosion action. Furthermore, it is essential to examine the effects
of electrolyte concentration on the corrosion resistance of these
alloys. While the active phases in AleCu alloys have been well
examined [4], the behavior of phases forming the microstructure of
AleMgeSi alloys has received little attention in the literature. In
contrast, research studies with Mg-based alloys systems focusing
on mechanical properties and corrosion resistance are available in
the literature [17,18].
The present work aims, to evaluate the effects of the
morphology (cellular; dendritic) and scale of the Al-rich matrix,
nature and distribution of intermetallics and electrolyte concen-
tration on the resulting electrochemical corrosion resistance of an
Ale3 wt.% Mge1 wt.% Si alloy, based on results of potentiodynamic
polarization curves. Samples extracted along the length of a
directionally solidified (DS) alloy casting will be subjected to both
corrosion tests in naturally stagnant 0.06 M, 0.15 M and 0.5 M NaCl
solutions at 25 (±2)  C and tensile tests. Interrelations emphasizing
the correlation between microstructural features and mechanical
and corrosion resistances are envisaged.

Fig. 1. Overall schemes showing the relative positions from where specimens were
extracted for corrosion (left side) and tensile (right side) tests along the length of the
DS Al-3 wt% Mg-1 wt% Si alloy casting.
222 C. Brito et al. / Journal of Alloys and Compounds 673 (2016) 220e230

stainless steel mold containing the alloy was transferred to the


directional solidification apparatus where it was remelted under
continuous flow of argon at the top of the casting. Details con-
cerning the solidification apparatus can be found in a previous
study [19].
The temperature to start the transient directional solidification
of the alloy has been defined as around 20  C above the alloy liq-
uidus temperature (TL ¼ 640  C). In order to start cooling, the
electric heaters were disconnected, and the water flow at the bot-
tom part of the mold was started. Three directional solidification
experiments were carried out with the same parameters so that
enough number of specimens could be extracted for microstruc-
tural characterization, corrosion and tensile tests and to ensure
reproducibility of experimental results. With a view to determining
the cooling rate during solidification, eight (8) fine type K ther-
mocouples (0.2 mm diameter wire) were placed in the geometrical
center of the cylindrical mold cavity along its length. All the ther-
mocouples were connected by coaxial cables to a data logger
interfaced with a computer, capable of automatically record tem-
perature data at a frequency of 5 Hz.
Optical microscopy was performed using an Olympus Inverted
Metallurgical Microscope (model 41GX). The primary dendritic arm
spacing (l1) and cell spacing (lc) were measured from optical im-
ages referring to several cross sections along the Al-3 wt% Mg-1 wt
% Si alloy casting. The triangle method [20] was used in order to
perform the measurements of the microstructural spacing. At least
30 measurements were performed for each selected position along
the length of the castings. In order to determine all the phases
forming the microstructure two samples associated with different
cooling rates (at positions 5 mm and 50 mm from metal/mold
interface, respectively 9.9 and 0.56 K/s) were selected for X-ray
Diffraction (XRD) analyses. The patterns were obtained by a XRD
diffractometer with a 2-theta range from 20 to 90 , Cu-Ka radiation
with a wavelength of 0.15406 nm. Intermetallic compounds (IMCs)
were characterized by SEM micrographs and microanalysis using a
ZEISS Scanning Electron Microscope e (ZEISS-EVO-MA15), equip-
ped with an Energy Dispersive Spectrometer e EDS (OXFORDeX-
MAX).
An electrochemical cell with a three-electrode configuration
was used to perform the corrosion tests, one being the silver/silver
chloride (Ag/AgCl) as reference electrode, platinum wire as the
counter electrode and the working electrode was the test material,
the Al-3 wt% Mg-1 wt% Si alloy. The alloy samples were firstly
ground up to a 1200 grit SiC finish, followed by distilled water
washing and air drying before all potentiodynamic polarization
corrosion tests. The linear polarization tests were performed using
a potentiostat/galvanostat model Autolab (PGSTAT 128N), with a
sample surface area of 0.2 cm2 put in contact against the naturally
aerated and stagnant electrolyte at 25  C. For these tests different
sodium chloride concentrations in solution: 0.06; 0.15 and 0.5 M
were adopted. Triplicate tests were performed with samples
Fig. 2. Computations performed with the Thermo-Calc software (database TTAL5): (a)
extracted from each position selected along the length of the
(Ale1%Si)eMg phase diagram and (b) Solidification path of the Al-3.0 wt% Mg-1.0 wt%
Si alloy considering an impurity level of 0.15 wt% Fe. directionally solidified (DS) casting. Before the linear polarization
test, the samples were subjected to measurements at open circuit
potential (OCP) for 2400 s, and then the linear polarization tests
2. Experimental procedure were conducted at a scan rate of 0.167 mV/s from 0.200
to þ0.250 mV vs. OCP. The corrosion current density values (icorr)
The Al-3 wt% Mg-1 wt% Si alloy was prepared from commer- were calculated in different samples exposed to different electro-
cially pure (c.p.) metals (the composition of each metal used to lyte concentrations by using the Tafel extrapolation method. The
prepare the alloys is shown in Table 1). The alloy was melted in a samples for corrosion tests were extracted from cross sections
refractory crucible in a muffle furnace heated by Kanthal-A1 along the length of the DS casting, as depicted in Fig. 1. The
heating elements, under argon atmosphere. Al was melted first corrosion tests were carried out in samples extracted from four
and, after the liquid achieving 750  C, the elemental Mg and Si different regions from the cooled surface of the DS casting, i.e. two
pieces were added to the melt, mixed well and allowed to remelt samples corresponding to the Al-rich matrix with a cellular
further for three times to guarantee homogenization. Secondly, a morphology (5 mm and 25 mm) and two other samples with the
C. Brito et al. / Journal of Alloys and Compounds 673 (2016) 220e230 223

Fig. 3. Directionally solidified macrostructure of the ternary Al-3 wt%Mg-1 wt%Si alloy with indications of the four (4) relative positions chosen for corrosion analyses and their
corresponding microstructures.

Al-rich matrix having a dendritic array (50 mm and 90 mm). solid fraction from 80% to 82%). At the end, a ternary (a-
Transverse specimens for tensile tests were extracted from Al þ Mg2Si þ AlFe) eutectic mixture is formed, which corresponds
different positions along the length of the DS casting (see Fig. 1). to the final 18% of solid fraction, according to this calculation. This is
These specimens were prepared according to specifications of the fairly in agreement with the observations reported by Kumar et al.
ASTM Standard E 8 M/04 and tested in a MTS 810 machine at a [22], who identified on impure AleMg alloys as-cast strip, the
strain rate of about 3  103 s1. In order to ensure reproducibility growth of a-Al, and Fe-bearing intermetallics by a three-
of the tensile results, three specimens were tested for each selected dimensional analysis of the extracted particles.
position to determine ultimate tensile strength and elongation-to-
fracture.
3.2. Macrostructure, microstructure and solidification thermal
parameters
3. Results and discussion
Fig. 3 shows the resulting columnar macrostructure that pre-
3.1. Computational thermodynamics calculations vailed along the longitudinal section of the AleMgeSi alloy DS
casting, associated with typical microstructures of both cellular and
In order to establish the possible microstructural phases dendritic regions. The average values of cellular (lc) and of primary
evolving along the DS Al-3 wt% Mg-1 wt% Si alloy casting, com- dendritic (l1) spacings are about 16 mm, 38 mm, 120 mm and
putations have been performed by a computational thermody- 270 mm at 5 mm, 25 mm, 50 mm and 90 mm from the cooled
namics software (Thermo-Calc). Iron impurity on the level of surface of the casting, respectively. A well-defined growth of cells is
0.15 wt% Fe was considered on the solidification path of the alloy so clearly observed for regions close to the casting surface, which are
that partial precipitations provoked by the presence of Fe could be associated with higher cooling rates (higher than 2 K/s) and higher
taken into account during solidification. The presence of trace thermal gradients. Hence, such microstructures can be character-
amounts of Fe was determined by X-ray fluorescence spectrometry ized as high cooling rates/high thermal gradients cells [21]. An in-
(XRF) as reported in a recent study [21]. Fig. 2 shows the (Ale1% termediate region is characterized by a gradual morphological
Si)eMg phase diagram with a view to emphasizing the possible transition from cells to dendrites. With the decrease in cooling rate
equilibrium phases from liquid-to-solid for the referred nominal to about 0.8 K/s, dendrites start to prevail. The slower cooling
alloy composition. On the other hand, the solidification path of the conditions associated with this dendritic region is due to the in-
Al-3 wt% Mg-1 wt% Si-0.15 wt% Fe chemistry is shown in Fig. 2b. In crease in the thermal resistance of the solidified shell with distance
this case, the a-Al phase is formed until approximately 80% of solid from the cooled surface towards the top of the casting.
fraction, followed by the precipitation of the Mg2Si phase (~2% of The samples selected for corrosion and mechanical tests were
224 C. Brito et al. / Journal of Alloys and Compounds 673 (2016) 220e230

extracted from positions in the casting with well-defined micro-


structural morphologies, and dissimilar microstructural spacings.
The experimental correlation between cooling rate ðTÞ, _ thermal
gradient (GL) and microstructural spacings (lc, l1) determined
along the AleMgeSi alloy casting length may be seen in Fig. 4,
encompassing both cellular and dendritic regions. It can be noted
that the cooling rate decreases continuously with the increase in
distance (P) from the cooled surface of the DS casting. In contrast, lc
and l1 tend to increase as the cooling rate decreases. It is worth
noting the sudden increase from lc of 38 mm at the final portion of
cellular region to l1 of about120 mm at the beginning of the region
of dendritic morphology. Rosa et al. [23] also reported a sudden
increase in the dendritic spacing of PbeSb alloys with respect to
intercellular spacings during transient directional solidification,
however, after a transition region from low velocities cells to
dendrites, i.e. with the increase in the cooling rate.
The MgeSi and AlFe(SiMg) intermetallics have been identified
within the interdendritic and intercellular regions by XRD spectra
[21], SEM images and EDS microprobe. Both binary (a-Al þ Mg2Si)
and refined ternary (a-Al þ Mg2Si þ AlFe(Si)) eutectic mixtures
were observed concurrently all along the alloy casting. With a view
to assessing the compositions of the intermetallic particles and of
the a-Al phase along the DS alloy, samples were also subjected to
SEM-EDS analyses, as shown in Fig. 5, i.e., point #1: the primary Al-
rich phase; and points #2 and #3: ternary and binary eutectic
mixtures, respectively. These EDS results refer to two different re-
gions with prevalence of cells for P ¼ 5 mm and dendrites for
P ¼ 50 mm. According to point #1, Mg is the main element
dispersed within the a-Al phase. Instead, the compositions asso-
Fig. 4. Experimental scatters and fitted curves for the DS Al-3wt%Mg-1wt%Si alloy
ciated with point #2 of both regions evaluated may be character-
casting: (a) thermal gradient and cooling rate and (b) microstructural spacings (l1, lc). ized by the occurrence of Al, Mg, Si and Fe with prevalence of Al and
R2 is the coefficient of determination. Mg. The results referring to point #3 indicate Mg, Si and Al ele-
ments, which is in consonance with the phases identified in the

Fig. 5. SEM micrographs of the Al-3.0 wt% Mg-1.0 wt%Si alloy. Points 1, 2 and 3 indicate local wt% concentration of Al/Mg/Si/Fe obtained by SEM-EDS microprobe analyses. P is the
position from the cooled surface of the casting.
C. Brito et al. / Journal of Alloys and Compounds 673 (2016) 220e230 225

samples was evaluated through the experimental potentiodynamic


polarization curves shown in Fig. 6. The corrosion potential (Ecorr) is
readily measured by determining the voltage difference between
the alloy sample immersed in the electrolyte environment and the
reference electrode Ag/AgCl. In Fig. 6 both Ecorr and icorr are deter-
mined by Tafel's extrapolation, using both cathodic and anodic
branches of the polarization curves. Ecorr indicates the electro-
chemical activity in terms of general corrosion, and icorr indicates
the corrosion rate (The resistance to general corrosion increases
when icorr decreases and when Ecorr becomes less negative, i.e,
more noble). The pitting potential (Epit) is determined by scanning
the anodic branch of the polarization curve until a large increase in
current is observed. This point defines Epit characterizing the
beginning of localized corrosion. The breakdown potential (ET)
values indicated in Fig. 6 correspond to the potential associated
with the dissolution of the passive film, which is formed by oxides
or even by corrosion products.
The chosen samples allowed the effects of both morphology
(cells or dendrites) and scale of the microstructure of the Al-rich
matrix on the corrosion resistance to be assessed. Also, the influ-
ence of the electrolyte concentration on the pitting corrosion may
be valued in Fig. 6. It is very clear that either Ecorr or Epit values may
vary not only with the sample microstructure but also with the
electrolyte concentration. All the experimental values of the
aforementioned parameters, as well as icorr may be found in Table 2.
In general, increase in the electrolyte concentration may affect
slightly Ecorr. In the case of the samples having dendritic
morphology, i.e., P ¼ 50 mm and 90 mm, Ecorr increases as the
solution concentration increases, for example, varying
from 676 mV to 802 mV for P ¼ 90 mm. However, expressive
changes have been realized concerning Epit values and by
comparing the experimental polarization curves. This is because
with the increase in the electrolyte concentration, Epit increases for
any condition examined. Such tendency may not depend on a-Al
morphology as well as on the size of the microstructure. Similar
corrosion behavior associated with the electrolyte concentration
has also been reported in previous investigations considering
diverse Al-alloys and corrosion tests conditions [14,24e26].
If only an individual electrolyte concentration is examined in
Fig. 6, it can be seen that Epit may also be affected by: microstruc-
tural spacing, a-Al morphology and second-phase size, proportion
and distribution, which characterize each sample during corrosion
tests. This means that different microstructural features may affect
the alloy electrochemical behavior. Therefore, it will be possible to
identify microstructural features that are conducive to better
corrosion resistance.
Considering the results associated with the electrolyte of high-
est NaCl content (0.5 M NaCl at 25  C), significant differences of Ecorr
values can be noted for the different regions with different
microstructural morphologies, i.e., cellular and dendritic arrange-
ments. A corrosion potential of 688 mV was obtained for a sample
Fig. 6. Potentiodynamic polarization curves of samples extracted from 4 different
of cellular structure (P ¼ 25 mm) and a higher value of 773 mV for
positions from the cooled surface of the DS AleMgeSi alloy casting for: (a) 0.06 M a sample with a dendritic structure (P ¼ 50 mm). For corrosion tests
NaCl, (b) 0.15 M NaCl and (c) 0.5 M NaCl electrolyte solutions. with higher NaCl concentration, for positions farther from the
cooled surface of the casting (50 and 90 mm), beyond more active
eutectic a-Al þ Mg2Si. It is essential to remark that spatial resolu- corrosion potentials, trends of surface passivation seem to happen
tion of SEM-EDS is governed by the penetration and spreading of with high level of steadiness for P ¼ 50 mm at icorr of 15.9 mA/cm2.
the electron beam in the specimen, which for quantitative analysis As reported by Doli c et al. [15], the susceptibility for pitting
may cause deviations depending on the size of the region of formation in as-cast 5083 AleMg based alloy subjected to an
interest. electrolyte concentration of 0.01 M NaCl may be related to the
presence of IMCs that are disseminated all along the a-Al phase.
3.3. Electrochemical corrosion behavior (0.06 M; 0.15 M and 0.5 M Such particles lead to the formation of local electrochemical cells
NaCl solutions) between them and the aluminum-rich matrix. The quoted inves-
tigation showed that aluminum dissolution is favorably localized
The electrochemical behavior of the Al-3 wt% Mg-1 wt% Si alloy along the boundaries between the intermetallic particles Al6 (Fe,
226 C. Brito et al. / Journal of Alloys and Compounds 673 (2016) 220e230

Table 2
Summary of experimental results of potentiodynamic polarization tests at different electrolyte concentrations, cooling rates and microstructural features such as l1, lc and
proportions of phases of the Al-3.0 wt% Mg-1.0 wt% Si alloy.

Al-3 wt% Mg- Cooling rate l1 lc AlFeSi Mg2Si Ecorr (mV) Epit/ET (mV) icorr (mA/cm2) CR (cm2/mA)
1 wt% Si (K/s) (mm) (mm) proportion (%) proportion (%)

NaCl solution e e e e e 0.06 M 0.15 M 0.5 M 0.06 M 0.15 M 0.5 M 0.06 M 0.15 M 0.5 M 0.06 M 0.15 M 0.5 M

P5 (cells) 9.9 e 16.2 29.7 70.3 654 681 688 528 549 626 0.0346 0.103 0.103 28.90 9.71 9.71
P25 (cells) 2.5 e 37.6 23.8 76.2 726 681 688 578 603 688 0.432 0.103 0.103 2.31 9.71 9.71
P50 (dendrites) 0.80 120.0 e 17.6 82.4 650 761 773 461 630 773/ 0.069 0.112 0.447 14.49 8.93 2.24
691
P90 (dendrites) 0.45 270.0 e 28.8 71.2 676 702 802 639/ 630 802/ 0.245 0.110 0.287 4.08 9.09 3.48
578 691

*Measurement of potential vs. Ag/AgCl at 25  C; *P is the position from the cooled surface of the casting.

experimental polarization curves can provide a better observation


concerning the occurrence of localized corrosion. For Ecorr
of 654 mV, icorr of 0.0346 mA cm2 is observed associated with
P ¼ 5 mm, where the microstructure is constituted by more refined
cells than at P ¼ 25 mm (726 mV/0.432 mA cm2). In contrast, for
Ecorr ¼ 650 mV, icorr ¼ 0.069 mA cm2 is observed for P ¼ 50 mm,
where the microstructure is constituted by more refined dendrites
than those found at P ¼ 90 mm (676 mV/0.245 mA cm2). The
Mg2Si intermetallic particles are finer at P ¼ 5 mm considering the
cellular region and at P ¼ 50 mm if considered the dendritic region.
Mg2Si is constituent of both binary and ternary eutectic mixtures
and, according to Fig. 7, such particles exist in higher proportion
than AleFeeSi type IMCs along the DS AleMgeSi alloy casting.
Fig. 7 shows the area fractions with decreasing cooling rates. Mg2Si
particles are characterized by less noble potential than pure Al
[5,27], which reveals the anodic character of this phase when
compared with a-Al. Thus, local corrosion action tends to be
increased due to Mg2Si [28,29]. Also, Mg2Si may act as a protective
Fig. 7. Proportions of the main types of intermetallic phases: Mg2Si and AleSieFe (Mg) layer due to its active character. In contrast, Fe-bearing interme-
with the decrease in cooling rate along the length of the DS Al-3.0 wt%Mg-1.0 wt%Si
tallic particles are recognized by its cathodic nature with respect to
alloy casting.
the a-Al phase.
This seems to explain the better electrochemical behavior of
finer cellular and dendritic arrays, owing to lower current densities
and more positive corrosion potential when compared with coarser
microstructures. The fineness of the intermetallic particles (regions
closer to the cooled bottom of the DS casting) may be intimately
associated with the higher solidification thermal parameters of
such regions during solidification (see Fig. 4a). The as-cast micro-
structure array has distinct anode/cathode area ratios along the
length of the DS casting. This is related to the local microstructure,
more particularly with the way the IMC particles are distributed
throughout the microstructure, i.e. with the interconnectivity level
of the more noble phase. Considering separately each morphology
of the Al-rich matrix (cells and dendrites), this suggests that icorr
increases with the increase in distance from the cooled surface of
the casting. The corrosion process may be highly affected by pro-
portion and distribution of the IMCs [27,30]. Refined microstruc-
tures propitiate a more extensive distribution of second phases
along intercellular or interdendritic regions. This seems to provoke
a less intense process regarding pitting corrosion. On the other
Fig. 8. Comparison of Epit for different positions along the length of the DS Al-3.0 wt%
hand, coarser Mg2Si particles may be associated with increase in
Mg-1.0 wt% Si alloy casting for electrolytes of three distinct NaCl concentrations.
the kinetics of pit formation.
In general, by examining Fig. 7 and the phase proportions ob-
Mn) and the a-Al phase. The higher incidence of pits is shown to tained for different cooling rates, i.e., P ¼ 5 mm z 9.9 K/s,
occur for regions with high density of IMCs. It is stated that the Al6 P ¼ 25 mm z 2.5 K/s, P ¼ 50 mm z 0.8 K/s and
(Fe, Mn) phase acts as a cathode, which induces anodic dissolution P ¼ 90 mm z 0.45 K/s, it can be inferred that only slight differences
of the surrounding matrix where pits nucleate. in the fractions associated with these positions can be perceived.
As shown in Fig. 6a, the more dilute electrolyte is associated Such positions are those from where the samples for corrosion tests
with a less severe and more gradual corrosion action. Such were extracted. Thus, it seems that the electrochemical behavior
C. Brito et al. / Journal of Alloys and Compounds 673 (2016) 220e230 227

in the literature for other metallic systems [31e34].


The intermetallic phases may contribute to surface heteroge-
neities on the AlMgSi samples. Such heterogeneities may induce
the formation of local micro-galvanic couples in the presence of an
electrolyte, affecting the whole corrosion process [35]. The direct
consequence is the occurrence of micro-defects on the formed film
of Al2O3, which induces a difference in potential between these
particles and the Al-rich matrix. These defects and the galvanic
couples AleMg may be the responsible not only for nucleation but
also for the growth of pits when the alloy is in contact with the NaCl
electrolyte.
The pitting potential (Epit) evolution as a function of different
electrolyte concentrations for all positions examined along the
length of the DS Al-3.0wt%Mg-1.0wt%Si alloy casting can be seen in
Fig. 8. In general, it can be noted that Epit becomes more negative
with the increase in the electrolyte concentration. This means that
the anodic activity over the samples becomes more intense.

3.4. Tensile strength and corrosion resistance vs. microstructural


spacings

In order to permit a combined analysis of corrosion and me-


chanical resistances to be attained, tensile tests were also per-
formed. Fig. 9a depicts some typical stressestrain curves of the
alloy specimens considering the same positions in the casting
monitored by corrosion tests. Also, experimental interrelations
between elongation (d) and l1/2 1,c and between ultimate tensile
strength (su) and l1/2
1,c were derived and can be observed in Fig. 9b
and c, respectively. The tensile parameters determined are: UTS or
su (ultimate tensile strength) of 178 MPa, 151 MPa, 133 MPa and
130 MPa and elongation (d) of 20%, 6%, 3.5% and 1.6% corresponding
to the positions 5 mm, 25 mm, 50 mm and 90 mm from the cooled
surface of the casting, respectively. The dependences of strength
and ductility on lC and l1 have been experimentally established by
Hall-Petch type relationships. In general, it can be seen in Fig. 9 that
su and d increase with the decrease in l1,c. In the case of the den-
dritic region, the elongation is essentially constant with l1. The
tensile strength and elongation corresponding to P ¼ 5 mm in the
cellular region are the highest of all samples examined, which
seems to be associated with a more homogeneous distribution of
the hard Mg2Si and AlFeSi(Mg) IMCs [36,37]. With the reduction in
the microstructural spacing, the as-cast structure becomes cleaner
and sounder and these qualities are important contributors to
improved strength. A more homogeneous distribution of the
eutectic mixture that occurs for smaller spacings, contribute for the
increase in strength and ductility. Lower strength and ductility may
be associated with regions with coarse microstructures. The vari-
ation of these properties is mainly associated with the micro-
structural spacing and tends to decrease with increasing l1,c. For
example, su is maintained essentially constant within the dendritic
region, despite the increase in the relative fraction of AlFeSi with
decreasing cooling rates (and hence with increasing l1). According
to Table 2 and Fig. 7 the proportion of the AlFeSi phase varies from
17.6% to 28.8% with the increase in l1 from 120 mm to 270 mm.
The concurrent evaluation of key requirements such as me-
Fig. 9. (a) Stress-strain curves from directionally solidified AleMgeSi alloy specimens chanical strength and corrosion resistance are shown in Figs. 10 and
extracted from P ¼ 5 mm, 25 mm, 50 mm and 90 mm from the cooled surface of the DS 11. The microstructural spacing was found to strongly affect such
casting; Evolutions of elongation (b) and ultimate tensile strength (c) with the square properties. Representative SEM microstructures of each examined
root of primary dendritic and cellular spacings. position have been inserted in Fig. 10. If considered the more
concentrated electrolytes, i.e., 0.15 M and 0.5 M, similar in-
terrelations between corrosion resistance (CR: represented by the
concerning tests in a 0.06 M NaCl solution is mainly affected by the
inverse of icorr) and l1,c may be noted. Therefore, a constant elec-
size and phases distribution, which are features deeply related to
trochemical behavior is seen for the cellular region in both cases
the solidification thermal parameters and the scale of microstruc-
with higher corrosion resistance values than those determined for
tural spacings such as l1 and lc. Similar interrelations are reported
the dendritic positions. The corrosion resistance increases slightly
228 C. Brito et al. / Journal of Alloys and Compounds 673 (2016) 220e230

Fig. 10. Ultimate tensile strength (su) and corrosion resistance (CR) as a function of l1,c. CR values were obtained for three electrolyte concentrations. Representative SEM mi-
crostructures of the four (4) positions examined.

for higher values of l1. The particular behavior obtained for higher resistance vs. microstructural spacing to be established. The results
NaCl concentrations is due to the simultaneous occurrence of shown in Figs. 10 and 11 are of fundamental interest so that a
localized and general corrosion processes, which could contribute balance between strength and corrosion resistance could be
for distinct profiles of corrosion resistance than those associated attained in the search of a better behavior of ternary AleMgeSi
with the dilute electrolyte (0.06 M). alloy components.
The combination of more aggressive conditions promoted by The corrosion tests performed in the 0.06 M NaCl solution al-
concentrated electrolytes and more extensive distribution of the lows a proper analysis of the effects promoted by the galvanic
AlFeSi and Mg2Si intermetallics phases on the cellular side of the microcells between the a-Al matrix and AlFeSi/Mg2Si intermetallics
samples may be the reason why such particular behavior occurred. phases. Further, the influence of the distribution of these particles
However, in the dendritic side of the samples, very low corrosion within the intercellular and/or the interdendritic regions on the
resistance values may be observed, which proves that the exposure galvanic behavior can be taken into account. Fig. 11 shows typical
of the Al-3.0 wt% Mg-1.0 wt% Si alloy in more aggressive medium SEM images of AleMgeSi alloys samples after the corrosion tests in
(0.5 M NaCl, for instance) do not permit a correlation corrosion a 0.06 M NaCl solution at room temperature. For instance, the
C. Brito et al. / Journal of Alloys and Compounds 673 (2016) 220e230 229

Fig. 11. Typical SEM images after corrosion test in a NaCl solution (0.06 M) of Al-3.0 wt.% Mg-1.0 wt% Si alloy samples at positions (P) from the cooled surface of the DS casting: (a)
5 mm, (b) 25 mm, (c) 50 mm and (d) 90 mm.

electrochemical behavior of the sample P ¼ 90 mm (dendritic: microstructures. The fineness of the intermetallic particles was
l1 ¼ 270 mm) may be highly associated with the growth of the shown to be intimately associated with the higher cooling rate/
AlFeSi phase in form of needles, since such phase is considered thermal gradients of regions closer to the cooled bottom of the
nobler than a-Al. As a consequence, the local dissolution of the Al- DS casting. The as-cast microstructure array has distinct anode/
rich matrix is facilitated as highlighted by white outlines in Fig. 11d. cathode area ratios along the length of the DS casting. Refined
Coarser AlFeSi needles, found in the sample at P ¼ 90 mm, make the microstructures were shown to be associated with more
sample surface more heterogeneous and, as consequence, may extensive distribution of second phases along intercellular or
enable the formation of galvanic cells type aAl/AlFeSi. The SEM interdendritic regions, thus leading to a less intense process
images in Fig. 11 show the damage caused by localized corrosive regarding pitting corrosion. On the other hand, coarser Mg2Si
attack in the microstructure, which resulted in the preferential particles were shown to increase the kinetics of pit formation.
corrosion of the a-Al phase. Extensive corroded areas in Fig. 11 are 4. HallePetch type equations have been proposed relating su and
indicated by white dot arrows. d to l1,c. It was shown that in general, su and d increase with the
decrease in l1,c. In the case of the dendritic region, the elonga-
tion is essentially constant with l1. The tensile strength and
4. Conclusions elongation corresponding to P ¼ 5 mm in the cellular region are
the highest of all samples examined, associated with a more
The following conclusions can be drawn from the present homogeneous distribution of the hard Mg2Si and AlFeSi(Mg)
experimental study: IMCs.
5. The concurrent evaluation of key requirements such as me-
1. The DS AleMgeSi alloy casting was shown to be characterized chanical strength and corrosion resistance was provided by a
by an Al-rich matrix of both cellular (high cooling rates/high combined experimental plot of such properties as a function of
thermal gradients cells) and dendritic microstructural mor- l1,c. The microstructural spacing was found to strongly affect
phologies. The cellular (lc) and primary dendritic (l1) spacings such properties.
varied from 16 mm, 38 mm, 120 mm and 270 mm at 5 mm, 25 mm,
50 mm and 90 mm from the cooled surface of the casting,
respectively.
2. Mg2Si and AlFe(SiMg) intermetallics have been identified within
the interdendritic and intercellular regions. Mg2Si is a constit- Acknowledgments
uent of both binary and ternary eutectic mixtures and, such
particles were shown to exist in higher proportion than The authors acknowledge the financial support provided by
AleFeeSi type IMCs along the length of the casting. ~o Paulo Research Foundation, Brazil (grants 2012/08494-
FAPESP- Sa
3. Better electrochemical behavior was observed for finer cellular 0, 2013/23396-7, 2013/15478-3, 2014/50502-5 and 2014/25809-0),
and dendritic arrays, owing to lower current densities and more CNPq (The Brazilian Research Council) and CAPES-COFECUB (grant
positive corrosion potential when compared with coarser 857/15).
230 C. Brito et al. / Journal of Alloys and Compounds 673 (2016) 220e230

References [18] S. Zhao, Q. Peng, H. Li, B. Liu, Effects of super-high pressure on microstruc-
tures, nano-mechanical behaviors and corrosion properties of MgeAl alloys,
J. Alloys Comp. 584 (2014) 56e62.
[1] T. Dorin, N. Stanford, N. . Birbilis, R.K. Gupta, Influence of cooling rate on the
[19] M.V. Cante , J.E. Spinelli, I.L. Ferreira, N. Cheung, A. Garcia, Microstructural
microstructure and corrosion behavior of AleFe alloys, Corros. Sci. 100 (2015)
development in AlNi alloys directionally solidified under snsteady-state
396e403.
conditions, Metall. Mater. Trans. A 39 (2008) 1712e1726.
[2] N. Birbilis, R.G. Buchheit, Electrochemical characteristics of intermetallic
[20] M. Gunduz, E. Çardili, Directional solidification of aluminiumecopper alloys,
phases in aluminum alloys. An experimental survey and discussion,
Mater. Sci. Eng. A 327 (2002) 167e185.
J. Electrochem. Soc. 152 (2005) B140eB151.
[21] C. Brito, G. Reinhart, H. Nguyen-Thi, N. Mangelinck-Noe €l, N. Cheung,
[3] V. Proton, J. Alexis, E. Andrieu, J. Delfosse, A. Deschamps, F. De Geuser,
J.E. Spinelli, A. Garcia, High cooling rate cells, dendrites, microstructural
M.C. Lafont, C. Blanc, The influence of artificial ageing on the corrosion
spacings and microhardness in a directionally solidified Al-Mg-Si alloy,
behaviour of a 2050 aluminiumecopperelithium alloy, Corros. Sci. 80 (2014)
J. Alloys Comp. 636 (2015) 145e149.
494e502.
rio, D.J. Moutinho, L.C. Peixoto, I.L. Ferreira, A. Garcia, Macro- [22] S. Kumar, N.H. Babu, G.M. Scamans, Z. Fan, K.A.Q. O'Reilly, Twin-roll casting of
[4] W.R. Oso
Al-Mg alloy with high added impurity content, Metall. Mater. Trans. A 45
segregation and microstructure dendritic array affecting the electrochemical
(2014) 2842e2854.
behaviour of ternary AleCueSi alloys, Electrochim. Acta 56 (2011)
[23] D.M. Rosa, J.E. Spinelli, I.L. Ferreira, A. Garcia, Cellular/dendritic transition and
8412e8421.
microstructure evolution during transient directional solidification of Pb-Sb
[5] F. Zeng, Z. Wei, J. Li, Ch Li, X. Tan, Z. Zhang, Z. Zheng, Corrosion mechanism
alloys, Metall. Mater. Trans. A 39A (2008) 2161e2174.
associated with Mg2Si and Si particles in AleMgeSi alloys, T. Nonferr. Metal.
[24] Y. Wang, G. Cheng, W. Wu, Q. Qiao, Y. Li, X. Li, Effect of pH and chloride on the
Soc. 21 (2011) 2559e2567.
micro-mechanism of pitting corrosion for high strength pipeline steel in
[6] Z. Li, C. Li, Z. Gao, Y. Liu, X. Liu, Q. Guo, L. Yu, H. Li, Corrosion behavior of
aerated NaCl solutions, Appl. Surf. Sci. 349 (2015) 746e756.
AleMg2Si alloys with/without addition of AleP master alloy, Mater. Charact.
[25] Z. Szklarska-Smialowska, Pitting corrosion of aluminum, Corros. Sci. 41 (1999)
110 (2015) 170e174.
1743e1767.
[7] F. Eckermann, T. Suter, P.J. Uggowitzer, A. Afseth, P. Schmutz, The influence of
[26] J. Malina, J. Radosevi c, Influence of NaCl concentration on pitting corrosion of
MgSi particle reactivity and dissolution processes on corrosion in AleMgeSi
extruded Al-Mg-Si alloy AA6060, Zastita Mater. 56 (2015) 47e51.
alloys, Electrochim. Acta 54 (2008) 844e855.
[27] Y. Wu, H. Liao, Corrosion behavior of extruded near eutectic Al-Si-Mg and
[8] W.S. Miller, L. Zhuang, J. Bottema, A. Wittebrood, P. De Smet, A. Haszler,
6063 alloys, J. Mater. Sci. Technol. 29 (2013) 380e386.
A. Vieregge, Recent development in aluminium alloys for the automotive in-
[28] K.A. Yasakau, M.L. Zheludkevich, S.V. Lamaka, M.G.S. Ferreira, Role of inter-
dustry, Mater. Sci. Eng. A 280 (2000) 37e49.
rio, A. Garcia, Mechanical properties as a metallic phases in localized corrosion of AA5083, Electrochim. Acta 52 (2007)
[9] P.R. Goulart, J.E. Spinelli, W.R. Oso
7651e7659.
function of microstructure and solidification thermal variables of AleSi cast-
[29] R. Arrabal, B. Mingo, A. Pardo, M. Mohedano, E. Matykina, I. Rodriguez, Pitting
ings, Mater. Sci. Eng. A 421 (2006) 245e253.
 rio, L.C. Peixoto, L.R. Garcia, N. Mangelinck-Noel, A. Garcia, Micro- corrosion of rheocast A356 aluminium alloy in 3.5 wt.% NaCl, Solut. Corros. Sci.
[10] W.R. Oso
73 (2013) 342e355.
structure and mechanical properties of Sn-Bi, Sn-Ag and Sn-Zn lead-free
[30] H. Ahlatci, Production and corrosion behaviours of the Ale12SieXMg alloys
solder alloys, J. Alloys Comp. 572 (2013) 97e106.
containing in situ Mg2Si particles, J. Alloys Comp. 503 (2010) 122e126.
[11] P.R. Goulart, J.E. Spinelli, N. Cheung, A. Garcia, The effects of cell spacing and
[31] W.R. Oso rio, E.S. Freitas, J.E. Spinelli, M.V. Cante , Assessment of electro-
distribution of intermetallic fibers on the mechanical properties of hypo-
chemical and mechanical behavior of hot-extruded powders and as-cast
eutectic Al-Fe alloys, Mater. Chem. Phys. 119 (2010) 272e278.
samples of Al-Ni alloys, Int. J. Electrochem. Sci. 7 (2012) 9946e9971.
[12] P.R. Goulart, V.B. Lazarine, C.V. Leal, J.E. Spinelli, N. Cheung, A. Garcia, Inves-
[32] E.S. Freitas, W.R. Oso rio, J.E. Spinelli, A. Garcia, Mechanical and corrosion re-
tigation of intermetallics in hypoeutectic Al-Fe alloys by dissolution of the Al
sistances of a Sne0.7 wt.%Cu lead-free solder alloy, Microelectron. Reliab. 54
matrix, Intermetallics 17 (2009) 753e761.
(2014) 1392e1400.
[13] W.R. Osorio, P.R. Goulart, L.C. Peixoto, A. Garcia, Electrochemical corrosion
[33] W.R. Oso  rio, M.V. Cante , C. Brito, E.S. Freitas, A. Garcia, Electrochemical
parameters of as-cast Al-Fe alloys in a NaCl solution, Corr. Sci. 52 (2010)
behavior of an Al-Fe-Ni alloy affected by nano-sized intermetallic particles,
2979e2993.
Corros 71 (2015) 510e522.
[14] B. Zaid, D. Saidi, A. Benzaid, S. Hadji, Effects of pH and chloride concentration
[34] W.R. Oso rio, A. Cremasco, P.N. Andrade, A. Garcia, R. Caram, Electrochemical
on pitting corrosion of AA6061 aluminum alloy, Corros. Sci. 50 (2008)
behavior of centrifuged cast and heat treated Ti-Cu alloys for medical appli-
1841e1847.
cations, Electrochim. Acta 55 (2010) 759e770.
[15] N. Dolic, J. Malina, A. Begi c Hadzipasi
c, Pit Nucleation on as-cast aluminium
[35] R.A. Rodríguez-Diaz, J. Uruchurtu-Chavarín, A.M. Cotero-Villegas, S. Valdez,
alloy AW-5083 in 0.01M NaCl, J. Min. Metall. Sect. B 47B (2011) 79e87.
J.A. Juarez-Islas, Corrosion behavior of AlMgSi alloy in aqueous saline solution,
[16] C. Meng, D. Zhang, H. Cui, L. Zhuang, J. Zhang, Mechanical properties, inter-
Int. J. Electrochem. Sci. 10 (2015) 1792e1808.
granular corrosion behavior and microstructure of Zn modified AleMg alloys,
[36] K. Kondoh, H. Oginuma, A. Kimura, S. Matsukawa, T. Aizawa, In-situ synthesis
J. Alloys Comp. 617 (2014) 925e932.
of Mg2Si intermetallics via powder metallurgy process, Mater. Trans. 44
[17] S. Seetharaman, C. Blawert, B.M. Ng, W.L.E. Wong, C.S. Goh, N. Hort, M. Gupta,
(2003) 981e985.
Effect of erbium modification on the microstructure, mechanical and corro-
[37] L.F. Mondolfo, Aluminium Alloys: Structure and Properties, Butterworths,
sion characteristics of binary MgeAl alloys, J. Alloys Comp. 648 (2015)
London, 1979.
759e770.