J Mater Sci

Metals
METALS

Texture-governed electrochemical corrosion behaviour

of AA 6082 alloy
Jiayi Wang1, Zhenli Mi1,* , Haitao Jiang1, and Runze Wang2

1
Institute of Engineering Technology, University of Science and Technology Beijing, Beijing 100083, People’s Republic of China
2
School of Materials Science and Engineering, Beihang University, Beijing 100083, People’s Republic of China

Received: 13 October 2018 ABSTRACT

Accepted: 27 December 2018 The variations of through-thickness corrosion behaviour with the b-fibre evo-
lution of hot-rolled AA 6082 alloy at the sub-surface layer (SL), quarter layer and
Ó Springer Science+Business middle layer (ML) in 3.5 wt% NaCl solution were mainly investigated by EIS,
Media, LLC, part of Springer potentiodynamic polarization, SEM, XRD and 3D-MLM. Results showed that
Nature 2019 the strong b-fibre (rolling) and shear orientation formed at ML and SL,
respectively. Compared to ML, charge transfer resistance increased, whereas
double-layer capacitance was reduced at SL. From ML to SL, corrosion current
density decreased and corrosion potential and pitting potential rose succes-
sively. Moreover, the deepened pits occurred at ML. Based on the surface
energy of Al in the order (111) \ (100) \ (110)/high-index planes, the worse
corrosion resistance at ML with strong b-fibre orientation stemmed from the
high surface energy. As a consequence, the available shear textures are benefi-
cial to improving the corrosion resistance. This provides a new design strategy
to enhance the corrosion resistance for the commercial Al alloys.

Introduction (0001) revealed an enhanced corrosion resistance

compared with the prismatic plane (01–10) and
The changes in crystallographic orientation state (11–20) orientation [1–10]. Similarly, crystal orienta-
originated from the processing technologies and tion can also affect the corrosion properties for the Ti
further influence the mechanical and chemical prop- and Ti alloys markedly [11–13]. For instance, the
erties of the metallic materials. Thereinto, the corro- more optimized corrosion parameters will be gained
sion behaviour affected by the orientation and texture in the hydrostatic-extrusion HCP pure Ti (a Ti) with
has been an intriguing research subject gradually close-packed (0001) planes rather than the prismatic
over the past decade. To data, the orientation- or plane (10–10) [11]. It could be indicated above that
texture- controlled corrosion phenomena have been the basal plane (0001) orientation will improve the
detected in varied metallic materials. Many reports corrosion resistance, regardless in Mg and a Ti,
have demonstrated that the hexagonal-close-packed implying that the corrosion resistance is orientation
(HCP) Mg and Mg alloys oriented in the basal plane dependent. Additionally, in a large-deformation

Address correspondence to E-mail: [email protected]

https://doi.org/10.1007/s10853-018-03303-9
 J Mater Sci

body-centred-cubic (BCC) b Ti alloy (TNTZO), the using electrochemical impedance spectroscopy (EIS)
medium close-packed planes {100} and {111} planes and potentiodynamic polarization. By using scanning
exhibited greater resistance against dissolution than electron microscope (SEM), X-ray diffraction (XRD)
the random high-index planes [13]. As to face-cen- and 3D measuring laser microscope (3D-MLM), the
tred-cubic (FCC) Al and its alloys, the corrosion corrosion products and morphologies were recorded
behaviour displays an aeolotropism along various and analysed. Such a revelation of the nexus between
crystal orientations [14, 15]. Furthermore, Beck and the intensified b-fibre orientations and electrochemi-
Funk [16] found that the roughness r of Al grains cal properties can offer new possibilities to under-
etched in 1 mol/L NaOH increased in the order of stand the corrosion behaviour.
(111) \ (100) \ (110)/high-index planes in AlMg1
sheet. They considered that it lies in the increasing
surface energy c for Al, i.e. (111) \ (100) \ (110)/ Experiment procedures
high-index planes. The similar theoretically calcu-
lated results of Al surface energy were obtained Materials preparation
elsewhere [17, 18]. Besides, the varied corrosion
phenomena stemmed from the specific orientations The as-received material (100-mm cube) used in our
have been also observed in the binary Fe–26Al alloy rolling process was cut from the centre of a cylin-
[19], stainless steel [20–22], Ni and Ni alloy [23, 24] drical as-cast AA 6082 alloy ingot
and Cu [25, 26]. Thus, it is worthwhile to further (* U 500 9 500 mm in size). Such a sample location
investigate to understand the corrosion behaviour avoided the macro-segregation in the as-received
dominated by crystal orientations. material. The chemical composition of this alloy is
The b-fibre textures are usually presented in the listed in Table 1. The hot rolling process was carried
rolled FCC metals, in which the conventional typical out by using a laboratory scale rolling mill with two
rolling textures are mainly comprised of copper (Cu) 270-mm-diameter rolls that were kept at room tem-
{112} h111i, S {123} h634i and brass (B) {011} h211i. The perature (RT) * 23 °C. The constant rolling speed
orientation density of b-fibre textures will be varied was 1 m min-1. The whole preparation technology is
dramatically with the increasing rolling reduction schematically illustrated in Fig. 1a. The as-received
ratios [27–32] and along through-thickness direction alloy was heated to 570 °C and maintained this
form surface to centre [33–38] for the rolled Al and Al temperature for 8 h, and then cooled down to RT in a
alloy sheets. Conversely, due to the relatively high resistance furnace to achieve the homogenization
friction, the shear textures will generate at the rolling (process I in Fig. 1a). After the alloy was reheated up
surface, which contain the Rotated Cube (Rt-C) {001} to 470 °C reaching the entrance temperature (process
h110i texture and minor h111ikND fibre (c-fibre) II in Fig. 1a), the multi-pass hot rolling was per-
[34, 36–38]. On the other hand, the corrosion beha- formed until its final thickness reduced to 20 mm (i.e.
viour of Al alloys has been investigated widely. In an 80% final reduction). In order to keep the constant
general, the previous studies aimed at the corrosion entrance temperature, the alloy sheet was preheated
properties of Al alloys mainly focused on the differ- to 470 °C and held for 15 min during the intervals of
ent phase structures, e.g. grain size, precipitates, each pass (process III in Fig. 1a). During rolling, the
grain boundary [39–46] and corrosion conditions anti-wear hydraulic oil (L-HM #46) was used as a
[47–50]. Besides, a few reports merely pointed out the lubricant to reduce the sliding friction resistance at
effect of single crystal plane or certain texture on the the contact surface between the rolls and the alloy
corrosion behaviour [14–16, 51]. They hardly took the sheet. Ultimately, the final-rolling alloy sheet was
combined influence of multiple textures into consid- cooled to RT in air.
eration, such as b-fibre and shear textures.
Table 1 Chemical composition (wt%) of the AA 6082 alloy in
In this work, the through-thickness b-fibre and
this work
shear textures were achieved in the hot-rolled AA
6082 alloy sheet and characterized by orientation Alloy Mg Mn Cr Si Fe Cu Ti Al
distribution function (ODF). Furthermore, the elec-
AA 6082 0.73 0.44 0.15 0.99 0.36 0.083 0.052 Bal.
trochemical corrosion properties varied with the
intensified b-fibre textures were investigated in detail
J Mater Sci

electrode and reference electrode, respectively. The

electrode specimen with 1 cm2 exposed surface
and * 4 mm thickness was sampled by using spark
cutting at the sub-surface layer (SL), quarter layer
(QL) and middle layer (ML) on the RD/TD plane in
the through-thickness hot-rolled AA 6082 alloy sheet,
as shown in Fig. 1b. And then the electrode specimen
was contacted with the copper wire and embedded in
resin to obtain the working electrode. As defined
previously, the sampled positions in the sheet along
the through-thickness direction can be depicted by a
parameter S using the formula as follows [33, 34, 37]:
S ¼ 2Dt=t0 ð1Þ
where Dt is the distance from sampled position to the
middle of the sheet and t0 is the sheet thickness (ac-
curate 20 mm). In this work, the exposed surface was
ground by SiC papers from #400 to #2000 finished.
The grind caused a thickness decrease of * 0.5 mm
to expose the immersion surface of the electrode
specimen with the various b-fibre textures (preferred
shear orientation formed at SL). So the parameter S of
SL, QL and ML were 0.95, 0.5 and 0, respectively.
Figure 1 a The schematic diagram of hot rolling processes of the The open-circuit potential (OCP) was stabilized
AA 6082 alloy sheets (FC, furnace cooling; AC, air cooling).
during 3600-s immersion. Subsequently, EIS mea-
Therein, the technology processes are (I) the homogenization
surement was carried out in the frequency range of
treatment, (II) the preheating treatment and (III) the multi-pass hot
100 kHz–0.01 Hz using a sinusoidal voltage ampli-
rolling, respectively. b The exposed surfaces sampled at the sub-
surface layer (SL), quarter layer (QL) and middle layer (ML) of tude of 5 mV at each OCP. The EIS was fitted and
the hot-rolled AA 6082 alloy sheet used in electrochemical calculated by ZsimpWin 3.10 software. After EIS
measurements (RD rolling direction, ND normal direction, TD measurement, the potentiodynamic polarization
transverse direction). measurement was proceeded in the voltage range of
- 0.9–0.6 V during 1800 s duration at each OCP as
Electrochemical measurements well. In other words, the scanning rate was * 0.833
mV/s. The corrosion parameters of polarization
The electrochemical measurements were completed curves were fitted and calculated using EC-Lab
in a three-electrode cell system in a glass beaker using V10.40 software, including the corrosion potential
RST5100 electrochemical workstation (Chengdu (Ecorr), corrosion current density (icorr), Tafel slope of
Centome Ltd. Company, China). The electrochemical anodic (ba) and cathodic (bc) values. Furthermore,
impedance spectroscopy (EIS) and potentiodynamic pitting potential (Epit) values were observed and
polarization measurements were conducted to obtained further from the polarization curves.
investigate the corrosion behaviour of the through- To ensure the repeatability of electrochemical
thickness hot-rolled AA 6082 alloy. The various lay- measurements, three specimens were retested for
ers of the alloy specimens with the trending b-fibre each control groups.
textures were immersed in 3.5 wt% (0.62 mol/L)
NaCl aqueous solution at * 23 °C. The NaCl solu- XRD measurements
tion contained naturally dissolved O2 was mixed by
analytical reagent grade NaCl and deionized water at The texture, phase composition and residual stress
a near neutral pH value. The working electrode was measurements of the varied layers (i.e. SL, QL and
hot-rolled AA 6082 alloy. The Pt foil and saturated ML) were conducted with a Bruker D8 Advance
calomel electrode (SCE) were utilized as the counter diffractometer, operating at 40 kV and 40 mA, using
 J Mater Sci

a Cu Ka radiation (k = 1.5418 Å). For texture mea- Vickers microhardness tests

surements, the {111}, {200} and {220} incomplete pole
figures (0°–70°) were measured and used to calculate The Vickers microhardness (HV) of the varied layers
the orientation distribution function (ODF) in TexE- was measured using an HV-1000 hardness tester
val software, and the ODF maps were analysed in under a 200-g load at a dwell time of 15 s. To ensure
TexTools software. It should be indicated that the the accuracy, five hardness data were tested to cal-
reference direction of the pole figure measurement culate the average values for each sample.
was parallel to the rolling direction (RD) of the sheet.
Additionally, the XRD patterns of phase composi-
tions (i.e. hot-rolled AA 6082 alloy and its corrosion Results and discussion
products immersed in NaCl solution) were tested in
the diffraction angle (2h) range between 10° and 90° Variations of electrochemical corrosion
at a scanning speed of * 5.8°/min with an increment behaviour
of * 0.02°. The biaxial residual stress (longitudinal
OCP analysis
direction) measurements were conducted with a
range of 4° between 135.5° and 139.5° corresponding The OCP evolution of various layers of the hot-rolled
to {422} crystallographic reflection of a-Al, as well as AA 6082 alloy in 3.5 wt% NaCl solution is shown in
a step size * 0.02° per 1.2 s. The diffractograms were Fig. 2. The OCP of each layer can all reach and keep a
tested for five tilt angles w at 0°, 18°, 27°, 33°, 36° and closely steady value within the whole immersion
45°, respectively. The residual stresses were calcu- duration. The OCPs shifted towards the more noble
lated and fitted by the sin2w method. The XRD pat- values in the order of OCP, ML \ OCP, QL \ OCP, SL,
terns and residual stresses were analysed using Jade i.e. (- 1004.3 ± 16.7), (- 889.5 ± 23.4) and
6.5 software. (- 832.9 ± 12.7) mV versus SCE. This suggests that
the equilibrium potential versus redox reactions
Surface characterization taken place on the electrode surface declined fol-
lowing the order of SL [ QL [ ML.
The microstructures of the varied layers in AA 6082
alloy were observed with an optical microscope (OM,
EIS analysis
ZEISSAX10). The OM samples were ground using
SiC papers from #400 to #2000 finished, mechanically
Figure 3a and b presents the EIS Nyquist and Bode
polished and etched with a Keller’s reagent contain-
plots of SL, QL and ML in hot-rolled AA 6082 alloy
ing 10-ml HF, 15-ml HCl, 25-ml HNO3 and 95-ml
after 1-h immersion at OCP in 3.5 wt% NaCl solution
H2O. The values of mean grain size were calculated
from the measured values for over 400 grains using
the linear intercept method on the ImagePlus soft-
ware for each layer. Upon the OM micrographs, the -800

calculated value of grain size is equal to dRD þd

2
TD
(dRD
-850
and dTD represent the grain diameter along RD and
E (mV vs. SCE)

TD, respectively). -900

Before removing the corrosion products, the two- -950

dimensional corroded surface was photographed and
the element distribution maps were recorded by -1000

employing a scanning electron microscopy (SEM, FEI

-1050
Quanta 450FEG) configured with an energy-disper-
sive spectrometer (EDS), operating at 20-kV acceler- -1100 SL QL ML

ation voltage. After removing the corrosion products

0 500 1000 1500 2000 2500 3000 3500
using an alcohol wipe, the three-dimensional height
t (s)
map of the corroded surface was measured with 3D
measuring laser microscope (3D-MLM, Olympus Figure 2 Typical OCP curves of various layers in hot-rolled AA
OLS4100) using a semiconductor laser (k = 408 nm). 6082 alloy in 3.5 wt% NaCl solution.
J Mater Sci

at RT. All the Nyquist plots displayed the similar and the relaxation reaction, as well as the surface
shape, which consisted of two depressed capacitive activation adsorption of corrosion products [52, 53]. It
arcs in the first quadrant and a depressed inductive can be seen that the radius of the impedance loop of
arc in the fourth quadrant. The capacitive arcs at high SL was much larger than those of QL and ML, which
frequencies indicate that the oxide film (air-formed) manifests that the SL exposed surface reveals a better
existed on the alloy surface. Next, the capacitive arcs protection function against the corrosion, conversely
in the medium-frequency region might be stemmed poorer at ML. In EIS Bode plots (Fig. 3b), there was
from the metastable/stable pitting corrosion beha- the capacitive behaviour in the high-frequency region
viour. Moreover, the inductive arcs at low frequen- (100 kHz * 1000 Hz); furthermore, the crest value of
cies were related to the surface activity of electrode phase angle (h) was below 40° and the impedance
magnitude (|Z|) was tiny and less than 0.1 kX cm2.
This signifies that the air-formed oxide film was even
(a) thin and incomplete on the alloy surface. In the
medium frequencies between 1000 and 1 Hz, the hmax
was merely about 65°, which was far smaller than
90°. In addition, the crest width of h was even nar-
rower, implying that the oxide film formed during
the 1-h immersion also was not dense and intact. For
the alloy surface covered with the insufficient oxide
film, the corrosion resistance could be mainly deter-
mined on the charge transfer process. At the fre-
quency of * 0.1 Hz, |Z| reached a maximum value
for all layers. Thereafter, when f \ f|Z| ? max, |Z|
turned to decrease and h shifted to the positive val-
ues. This accounts for the presence of inductive
(b) behaviour at low frequency.
To analyse the electrochemical behaviour on the
exposed surface of AA 6082 alloy, a suitable equiva-
lent circuit, R(Q(R(Q(R(LR))))), in Fig. 3c was ascer-
tained to fit the EIS plots. Rs is the solution resistance;
Rf and Cf represent resistance and capacitance of the
oxide film (air-formed); Rct and Cdl are the charge
transfer resistance and double-layer capacitance; L
and RL stand for the inductance and the adsorption
resistance of corrosion product, respectively. Q rep-
resents the constant phase angle element (CPE) used
to replace the pure capacitor to depict the non-ideal
capacitance behaviour. CPE can be defined by the
admittance Y as follows [51, 54, 55]:
(c)
YCPE ¼ Y0 ðjxÞn ð2Þ

where Y0 is a constant for CPE (X-1 cm2 sn), j repre-

sents the imaginary number (j2 = - 1), x is the AC
angular frequency (rad s-1) and n stands for a CPE
exponent, which is in an adjustable region of
0.5 B n B 1. When n = 1, the CPE serves as an ideal
capacitor. And the impedance of CPE, ZCPE, is equal
Figure 3 Typical EIS plots of varied layers in hot-rolled AA
6082 alloy after 1-h immersion in 3.5 wt% NaCl solution at the to 1/YCPE [54, 56, 57]. On the other hand, the equiv-
OCP: a Nyquist plots and b Bode plots. c The equivalent circuit alent capacitance C can be calculated on the basic of
used to fit EIS plots.
 J Mater Sci

CPE parameters via the following formula Further, the changes in surface energy with the var-
[54, 56–58]: ious textures on SL, QL and ML exposed surface have

1=ni been discussed in ‘‘Effects of texture evolution on
Ci ¼ Y0 R1n
i
i
ð3Þ corrosion behaviour’’ section below.

where the resistance Ri is the one paralleled to Potentiodynamic polarization analysis

capacitance Ci in the equivalent circuit. As a result,
using the equivalent circuit, the fitted and calculated Figure 4 presents the potentiodynamic polarization
EIS data are obtained and listed in Table 2. It can be curves of SL, QL and ML in the hot-rolled AA 6082
seen that Rs values were basically same, suggesting alloy after 1-h immersion (OCP reached stable) in
that the immersion conditions were practically 3.5 wt% NaCl solution. It can be distinctly observed
invariant. The fitting data values of Rf declined from that the cathodic and anodic braches were of a similar
(155.5 ± 11.9) X cm2 of ML to (67.62 ± 6.9) X cm2 of sharp. The anodic branch did not clearly show a
SL, but there was an ascent of their Cf from primary passivation current density (ipp). Yet it can
(0.2004 ± 0.012) to (1.092 ± 0.059) lF cm-2. This may be noted that SL exposed surface reached the passi-
be caused by the drop of surface energy, leading to vation state form the activation state at the lower ipp
the lack of air-formed oxide film and the increase in than others. This manifests that the passive film will
activation area on SL exposed surface. However, form on SL exposed surface more easily to inhibit the
from ML, QL to SL, the fitting values of Rct were corrosion in NaCl solution. When the polarized
(2.652 ± 0.15), (3.004 ± 0.13) and (5.861 ± 0.16) potential rose and exceeded the pitting potential, Epit,
kX cm2, respectively, which increased by * 54.75%. the exposed surface of the alloy reached the
Meanwhile, the fitting values of Cdl dropped down to transpassive state, and then the polarized current
(29.45 ± 2.8) lF cm-2 of SL from (57.29 ± 1.95) density rapidly increased. The corrosion parameters
lF cm-2 of ML, which was a reduction of * 48.59%. fitted from potentiodynamic polarization curves are
These mean that ML exposed surface is of the higher listed in Table 3. It can be seen that Ecorr and Epit
surface energy and more susceptible to attack of Cl– became more noble values in the order ML \ QL \
and OH– than SL exposed surface. The corrosion SL, i.e. the increase of * 145.5 and 154.7 mV versus
resistance is improved on the SL exposed surface SCE, respectively, implying that SL exposed surface
compared to that of ML in the NaCl solution. Besides, has the less surface activity and the low susceptibility
the increase in both L and RL from ML to SL perhaps to pitting, compared to ML. Meanwhile, a relatively
stemmed from the decrease in activated-adsorption greater decrease has occurred in icorr from
corrosion products after the relaxation reaction took (3.073 ± 0.12) lA cm-2 of ML to (0.8523 ± 0.05)
place on the corroded surface of AA 6082 alloy. lA cm-2 of SL, i.e. a drop of * 72.26%. Thus, the SL

Table 2 Fitting results of EIS

plots for the varied layers in Varied layers of the hot-rolled AA6082 alloy sheet
the hot-rolled AA 6082 alloy ML QL SL
after 1-h immersion in
3.5 wt% NaCl solution Rs (X cm2) 53.37 ± 4.6 51.77 ± 4.4 61.23 ± 3.8
Yf 9 10-6 (X-1 cm2 sn) 3.827 ± 0.074 4.990 ± 0.13 6.426 ± 0.27
nf 0.7157 ± 0.01 0.7593 ± 0.01 0.8138 ± 0.01
Rf (X cm2) 155.5 ± 11.9 103.5 ± 7.2 67.62 ± 6.9
Cf (lF cm-2) 0.2004 ± 0.012 0.4532 ± 0.029 1.092 ± 0.059
Ydl 9 10-5 (X-1 cm2 sn) 6.076 ± 0.27 3.814 ± 0.13 3.034 ± 0.20
ndl 0.9690 ± 0.01 0.9697 ± 0.02 0.9829 ± 0.02
Rct (kX cm2) 2.652 ± 0.15 3.004 ± 0.13 5.861 ± 0.16
Cdl (lF cm-2) 57.29 ± 1.95 35.64 ± 2.5 29.45 ± 2.8
L 9 104 (H cm-2) 2.382 ± 0.49 3.371 ± 0.28 4.317 ± 0.49
RL (kX cm2) 4.774 ± 0.32 8.737 ± 0.22 14.14 ± 0.38
The scatter bands of standard deviations were calculated by the data from three retested specimens
J Mater Sci

-300 Characterization and analysis of immersed

-400 surfaces and polarized corrosion products
-500
Element distribution on the immersed surface of AA 6082
-600 alloy in NaCl solution
Epit
E mV vs. SCE

-700

-800
To ascertain the pitting sites and corrosion products
more precisely, the ML corroded surface undergone a
-900
strengthening anodic reactions (after potentiody-
-1000 namic polarization) was observed by SEM. Based on
SL
-1100 QL the gradually deteriorative corrosion resistance from
ML
-1200 SL to ML, severe-corroded ML was selected to
highlight the corrosion processes of the exposed
-1300
-9 -8 -7 -6 -5 -4 -3 -2 -1 0 surface. Figure 5 exhibits a ubiquitous polarized
2
log i A/cm corrosion surface morphology (Fig. 5a) and its cor-
responding EDS elementary maps (Fig. 5b–i) for an
Figure 4 Typical potentiodynamic polarization curves of varied
AA 6082 alloy immersed in NaCl solution. The grain
layers in hot-rolled AA 6082 alloy after 1-h immersion in 3.5 wt%
boundary (GB) that segmented three grains (#1, #2
NaCl solution at the OCP.
and #3 in Fig. 5a) was observed under the adsorption
exposed surface of hot-rolled AA 6082 alloy can resist layer of corrosion products in EDS maps (Fig. 5b, c, h,
corrosion better than other two in NaCl solution. i), where the obvious boundary segregation of Si, Fe
From the aforementioned EIS results, the decrease in and Mn elements was presented. As shown in
icorr might be relative to the greater Rct on SL and icorr Fig. 5a, the serious pitting corrosion did not occur at
will normally determine the corrosion rate, i.e. the GB site (marked by yellow dashed lines) but inside
smaller icorr is, the slower anodic reactions take place the grain #3. Therefore, the OH- (from the cathodic
on the exposed surface. On the other hand, the reaction of Eq. 5) and Cl– ions will not attack the GB
increase in anodic Tafel slopes ba means that ML will site selectively (or first). In addition, Mg, Cr, etc.
undergo a faster process to reach the passivation alloying elements distributed inside a-Al matrix or
state, implying that the thinner and incomplete pas- formed intermetallic compounds in hot-rolled AA
sive film will form on ML during an immersion in the 6082 alloy, rather than producing the boundary
NaCl solution, compared to the others. For AA 6082 segregation.
alloy, the anodic reactions and polarization products
will be investigated and discussed in detail below. Corrosion products of AA 6082 alloy immersed in NaCl
In brief, as seen from the results of OCP, EIS and solution
potentiodynamic polarization measurements, it has
As shown in Fig. 6, the immersed surface and pitting
been obviously testified that SL exposed surface of
area topographies were observed using SEM and the
hot-rolled AA 6082 alloy has a superior corrosion
chemical composition of corrosion products was
resistance, but ML is worse.
indicated by EDS spectra. It can be found that cor-
rosion product covered on the exposed surface was
mainly Al2O3, and a small amount of the oxides
contained Mg and Ti, etc. alloying elements. The

Table 3 Corrosion parameters

of varied layers in hot-rolled Layer Ecorr (mVSCE) Epit (mVSCE) icorr (lA cm-2) ba (mV/decade) bc (mV/decade)
AA 6082 alloy after 1-h
SL - 873.4 ± 18.3 - 562.2 ± 16.4 0.8523 ± 0.05 367.7 ± 20.4 - 142.3 ± 15.9
immersion in 3.5 wt% NaCl
QL - 923.6 ± 21.5 - 631.7 ± 14.7 1.677 ± 0.08 521.2 ± 16.6 - 139.8 ± 11.3
solution
ML - 1018.9 ± 19.1 - 716.9 ± 13.0 3.073 ± 0.12 649.2 ± 11.8 - 150.2 ± 9.4
The scatter bands of standard deviations were calculated by the data from three retested specimens
 J Mater Sci

Figure 5 a SEM image of the

Al Si Mg
ML immersed surface of hot-
rolled AA 6082 alloy and
corresponding EDS maps of
the element distribution: b Al,
c Si, d Mg, e O, f Cl, g Cr,
h Mn, i Fe, after the (b) (c) (d)
potentiodynamic polarization
(a) O
measurement in 3.5 wt% NaCl
solution.
Grain #2
GB
GB (e)
Pit
Cl

Grain #1
Grain #3
50 μm
(f)

Fe Mn Cr

(i) (h) (g)

major corrosion reactions took place during the dis- Al3þ þ 2Cl þ 2OH ! Al(OH)2 Cl ð8Þ
2
solution of the bare a-Al matrix (see the EDS spectra
of Fig. 6a1, d1) are involved as the following chemi- Besides, the extra reactions as the formation pro-
cal equations [51, 55, 59, 60]: cesses of the traces of corrosion products could occur
Alðs:Þ ! Al3þ  on AA 6082 alloy surface in NaCl solution.
ðsol:Þ þ 3e ½Anodic reaction ð4Þ
Mgðs:Þ þ 2H2 O ! MgðOHÞ2 ðads:Þ þ 4Hþ
ðsol:Þ
2H2 O þ O2 þ 4e ! 4OH ½Cathodic reaction ð5Þ
þ 4e ½6; 62 ð9Þ

Al3þ þ 3OH ! AlðOHÞ3 ðads:Þ
ðsol:Þ
  Tiðs:Þ þ H2 O ! TiO2 ðads:Þ þ 4Hþ 
ðsol:Þ þ 4e ½63; 64
! Al2 O3  H2 O Formation of corrosion product
ð10Þ
ð6Þ
Apart from Mg(OH)2 and TiO2, the residual NaCl
Therein, due to the immersion in the NaCl solution will adsorb on the surface of some corrosion products
containing naturally dissolved O2, the oxygen existed due to the detected peaks of Na elements in EDS
in the electrolyte, so that Eq. (5) took place during the spectra.
cathodic reaction. In NaCl solution, the Cl– ions will In Fig. 6b, the edge and interior of a pitting domain
attack a-Al matrix lacked surface oxide film to form both presented the similar corrosion products (as
the aluminium chloride and oxychloride compound, indicated by EDS spectra of Fig. 6b1, b2). It demon-
dissolving the alloy via the chemical reactions below strates that the same dissolution reactions will take
[55, 59, 61]: place during the nucleation and development of pits
Al3þ þ 4Cl ! AlCl
4 ð7Þ on the exposed surface of AA 6082 alloy. As seen
from the EDS spectra of Fig. 6c1, c2, the composition
of corrosion products around the emerging pit hole
J Mater Sci

(a) (b)

EDS Spot b2
EDS Spot a2

EDS Spot b1
EDS Spot a3

EDS Spot a1

20 μm 20 μm

(a1) (a2) (a3) (b1) (b2)

(c) (d)

EDS Spot c1
EDS Spot d1

EDS Spot d2

EDS Spot c2

EDS Spot d3
5 μm 1 μm

(c1) (c2) (d1) (d2) (d3)

Figure 6 Typical SEM images and EDS spectra of each morphology, c emerging pit hole and d the enlarged image in
corresponding spot on the ML corrosion surface: a the exposed the blue rectangle of c, after the potentiodynamic polarization
surface and the adsorbed corrosion products, b pitting measurement in 3.5 wt% NaCl solution.

(Fig. 6c) was approximately similar to the developed where a lot of micro-sized corrosion phase particles
corrosion pits. Figure 6d reveals the enlarged area (such as EDS spot d2 of Fig. 6) that were possibly
(blue rectangle in Fig. 6c) in an emerging pit hole, composed of Al2O3, Mg(OH)2 and SiO2 [65, 66]
 J Mater Sci

formed and adsorbed on the bare and corroded a-Al

matrix (labelled EDS spot d1 in Fig. 6). Furthermore,
the beach-like corrosion phase (EDS spectrum of
Fig. 6d3) covered at the edge of emerging pit hole
was of the almost identical composition as the cor-
rosion phase particles. It can be conjectured that the
reason why the exposed surface of AA 6082 alloy will
be dissolved and form corrosion pits is that the cor-
rosion phase particles produced on the a-Al matrix
fall off and drift into the corresponding solution
system. This causes the initiation of pitting corrosion
and rough exposed surface.

Characterization of corrosion topography

Figure 7 shows the representative 3D-MLM images

of SL, QL and ML in hot-rolled AA 6082 alloy sheet
after the potentiodynamic polarization measurement
in 3.5 wt% NaCl solution and removal of the corro-
sion products. The results pointed out that the max-
imum depth of corrosion pit gradually increased in
the order of DSL \ DQL \ DML, which were mea-
sured as 55.07, 76.27 and 84.31 lm, respectively. That
is, the maximum depth of corrosion pit at ML gave
rise to * 29.24 lm, surging * 53.10%, compared to
SL. This suggests that SL has a superior corrosion
resistance to suppress the deepening development of
corrosion pits, whereas ML is weaker. Based on the
results of EIS and potentiodynamic polarization
measurement, the increasing depth of corrosion pits
is mainly blamed for the decrease in Rct but the rise in
icorr on the exposed surface at ML in the hot-rolled
AA 6082 alloy.

Effects of texture evolution on corrosion

behaviour
Figure 7 Typical 3D-MLM images of the exposed surfaces at:
a SL, b QL and c ML in hot-rolled AA 6082 alloy after the
Microstructure analysis of varied layers
potentiodynamic polarization measurement in 3.5 wt% NaCl
solution.
The typical OM micrographs of hot-rolled
microstructures of SL, QL and ML in AA 6082 alloy
the three layers. Figure 8e presents the XRD patterns
sheet are shown in Fig. 8a–c. The values of the mean
of varied layers in hot-rolled AA 6082 alloy. The
grain size calculated from the OM images, the Vick-
major precipitates, AlFeSi (JCPDS No. 20-0030),
ers microhardness and the longitudinal residual
Al13Fe4 (JCPDS No. 47-1420), Al6Mn (JCPDS No.
stress are plotted in Fig. 8d, respectively. It can be
44-1195), Mg2Si (JCPDS No. 35-0773) and FeCr
observed that there were few variations basically for
(JCPDS No. 41-1466) existed in the a-Al (JCPDS No.
the Vickers microhardness [(46.22 ± 1.90),
04-0787) matrix. Meanwhile, the intensity of each
(47.28 ± 1.17) and (46.8 ± 1.41) HV200 g], the mean
peak of precipitates (except the overlapped peaks
grain size (99.35, 101.25 and 98.64 lm) and longitu-
with a-Al) was nearly equal at SL, QL and ML. It
dinal residual stress (15.18, 17.58 and 16.28 Mpa) at
means that an unchanged volume fraction of
J Mater Sci

(a) (b) (c)

(d) (e)

Figure 8 Typical OM micrographs of a SL, b QL and c ML in the to the thickness parameter S. e Typical XRD patterns of varied
hot-rolled AA 6082 alloy sheet. d Comparison plots of Vickers layers in the hot-rolled AA 6082 alloy sheet.
microhardness, mean grain size and residual stress corresponding

precipitates can be determined in the through-thick- and ML (u1 and U were less than * ± 15° from idea
ness hot-rolled AA 6082 alloy sheet. position of b-fibre in the subset of Euler space
In a word, it is judged that the variation of corro- [34, 35]). The b-fibre can more conveniently display
sion resistance did not stem from changes in the grain the evolution of texture components (i.e. a series
size, hardness and residual stress, as well as was orientation from Cu {211} h111i via S {123} h643i
almost independent of the existence of precipitates on towards B {011} h211i mainly) occurred in the ODFs
the exposed surface in this work. (Fig. 10). As shown in Fig. 9a, it is clear that the ori-
entation densities of the whole b-fibre increased
Changes in corrosion behaviour with evolution of b-fibre remarkably from SL via QL to ML. For the SL spec-
and shear orientation imen, the orientation densities were all lower than 1.6
and within a smaller difference * ± 0.35 for each
As mentioned previously, the rolling texture will texture component along the b-fibre. At QL, near Cu
always form in the rolled FCC aluminium alloy sheet, and B orientation had the relatively low orientation
which is embodied in a dramatically increasing ori- density of * 2.47 and * 2.90, respectively, whereas
entation density of b-fibre textures. An enhanced b- near {103} h231i orientation attained the maximum
fibre texture from surface to centre in a hot-rolled orientation density of * 4.0. Noticeably, in the case
6xxx series Al alloy (Al–Mg–Si system) has been of ML specimen, there was an obvious increase near
already found in the study of Wang et al. [33]. In our {101} h232i orientation with the density of * 6.76,
work, a similar case was presented in the hot-rolled implying that ratio of near {101} h232i orientation
AA 6082 alloy sheet. Figure 9 illustrates the maxi- content will be greater at ML in the hot-rolled AA
mum orientation densities (Fig. 9a) and Euler angle 6082 alloy sheet. Viewed vertically, the typical Cu, S
(u1 and U) positions (Fig. 9b) versus the corre- and B orientations of ML were about 3.15, 3.78 and
sponding Euler angle u2 along the b-fibre at SL, QL 4.08 times than those of SL, respectively. The overall
 J Mater Sci

(a) 6082 alloy. So the exposed surface of ML specimen

with a higher-orientation-density b-fibre, especially
near B orientation, had a smaller Rct during the
immersion of EIS measurement in NaCl solution. In
contrast, the Rct was greater on the exposed surface of
SL specimen with the weaker b-fibre orientations.
Similarly, a study on the relationship between the
orientation and electrical conductivity (r) found that
an Al–Mg–Si alloy with main recrystallization tex-
tures of B and Goss {110} h001i obtained a slightly
increasing r [67]. As a result, based on R µ 1/r (due
to R µ q and q = 1/r, q represents electrical resis-
tivity), preferred b-fibre orientation will play a role in
the diminishing of Rct of ML specimen to some
extent.
(b) As shown from the ODF maps in Fig. 10, for the
varied layers in hot-rolled AA 6082 alloy, the typical
shear and b-fibre (rolling) textures occurred in the
ODF sections of u2 = 45°, 65° and 90° have been
marked with symbols, respectively. As expected, the
shear textures formed at SL (Fig. 10a) were deter-
mined as Rotated Cube (Rt-C) {001} h110i, E {111}
h110i and {221} h210i texture with maximum orien-
tation densities of 3.63, 3.18 and 3.10, respectively.
However, the textures along b-fibre orientation were
absent at SL (see the black dashed-line region in
Fig. 10a). In other words, compared to shear orien-
tations, the orientation densities of b-fibre were quite
low. In Fig. 10b, at QL apart away * 5 mm below
SL, obviously, almost no grain was situated along the
shear orientation. And the orientation densities con-
Figure 9 a The maximum orientation densities and b Euler angle
centrated towards the near b-fibre, in which *
(u1, U) positions along the b-fibre at varied layers in hot-rolled
Cu, * S, and * B textures were visible. Meanwhile,
AA 6082 alloy sheet.
two extra textures, i.e. {213} h142i and {102} h251i
orientation densities of QL were moderate. So the texture with maximum orientation densities of 3.33
increase rate of B orientation was more rapid along and 3.54, respectively, coexisted with main near b-
the through-thickness direction when AA 6082 alloy fibre textures. For ML, the orientation densities of b-
was subjected to a hot rolling. The cause for the fibre textures were dramatically enhanced and sited
changes in corrosion behaviour can be revealed by the idea positions, as shown in the red solid-line
the aforementioned synergy evolution of b-fibre and region of Fig. 10c. The * {110} h223i texture can be
shear textures on the exposed surface. found in the ODF section of u2 = 45° in Fig. 10c due
After eliminating influencing factors on the corro- to the symmetry, which also existed in the ODF sec-
sion resistance above: (1) GB sites will not be attacked tion of u2 = 85° along b-fibre, as indicated in Fig. 9a
by caustic ions (e.g. Cl- and OH-) preferentially (or above. Moreover, * {213} h142i texture with maxi-
first); (2) the nearly unchanged grain size, hardness, mum orientation densities of 4.71 also formed at ML.
residual stress and amount of precipitates on the By comparing the texture evolution between SL, QL
exposed surface of SL, QL and ML specimen, it can and ML, it is basically clear that the overall shear
be unravelled that the strong b-fibre orientation will orientations at SL will rotate towards b-fibre orien-
result in a deteriorated corrosion resistance for AA tations at ML via a transition of near b-fibre of QL in
the hot-rolled AA 6082 alloy.
J Mater Sci

Figure 10 Typical ODF

sections (u2 = 45°, 65° and
90°) involving typical shear
and b-fibre texture evolution Absent β-fibre
at: a SL, b QL and c ML, in (a)
hot-rolled AA 6082 alloy.

(b)
Near β-fibre

(c)
β-fibre

: Rt-C {001}<110> : Cu {211}<111> : {213}<142>

: E {111}<110> : S {123}<634> : {102}<251>

: {221}<210> : B {011}<211> : {110}<223>
Shear texture Rolling texture

In conclusion, associated with the electrochemical Summary

results above discussed, such a deteriorative corro-
sion resistance is undoubtedly resulted from the Utilizing a multi-pass hot rolling, the shear textures,
strong orientation densities of b-fibre textures. On the near b-fibre and b-fibre textures were formed in the
other hand, SL specimen, at which b-fibre textures AA 6082 alloy at SL, QL and ML, respectively. The
were absent, displayed the enhanced shear textures. corrosion behaviour of the exposed surface with the
That is to say, during immersion in 3.5 wt% NaCl specific orientations has been investigated with EIS

solution, there were vast {111} RD=TD and {100} RD=TD and potentiodynamic polarization in 3.5 wt% NaCl
crystal planes on the exposed surface at SL specimen, solution. It was found that the corrosion resistance
was orientation dependent: the exposed surface with
whereas {110} RD=TD , {211} RD=TD and other high-in-
dex crystal planes predominantly existed on the shear orientation (i.e. preferred {100} RD=TD and

exposed surface at ML and QL specimen with b-fibre {111} RD=TD crystal planes) had an improved corro-
textures. As is well known, the surface energy is sion resistance than that with the b-fibre orientation

increased in the sequence: {111} \ {100} \ {110}/ (i.e. preferred {110} RD=TD , {211} RD=TD and other
high-index crystal planes, for the FCC Al [16–18]. high-index crystal planes). EIS results showed that
Therefore, the improved corrosion resistance on the for SL, Rct increased by * 33.87% but Cdl reduced
SL with shear textures can be actually attributed to by * 70.12%, compared to ML. Potentiodynamic
the low surface energy. polarization showed icorr decreased by * 73.19%
 J Mater Sci

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