Materials Science & Engineering A 773 (2020) 138865

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Materials Science & Engineering A

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

Microstructure, mechanical behavior and stress corrosion cracking

susceptibility in ultrafine-grained Al-Cu alloy
Diogo Pedrino Braga a, *, Danielle Cristina Camilo Magalha
~es b, Andrea Madeira Kliauga b,
b b
Carlos Alberto Della Rovere , Vitor Luiz Sordi
a
Postgraduate Program in Materials Science and Engineering at the Federal University of S~
ao Carlos - PPGCEM/UFSCar, Rod. Washington Luís, km 235, SP-310, S~
ao
Carlos, SP, Brazil
b
Materials Engineering Department, Federal University of S~
ao Carlos – UFSCar, Rod. Washington Luís, km 235, SP-310, S~ao Carlos, SP, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Equal-channel angular pressing (ECAP) is capable of improving the mechanical properties of many aluminum
Aluminum alloys alloys by means of intense grain refinement. Meanwhile, a general relationship between grain size and stress
Severe plastic deformation corrosion cracking (SCC) resistance is not yet established, since the introduction of microstructural heteroge­
Microstructure
neities affects, in many ways, the localized corrosion susceptibility. This work evaluates the simultaneous impact
Mechanical strength
of ECAP processing on microstructure, mechanical strength and SCC resistance of an Al-4wt.%Cu alloy, in
Stress corrosion cracking
comparison with a commercially pure aluminum. Microstructure was observed by optical and electronic mi­
croscopy, while mechanical response was evaluated by hardness measurements and tensile tests. SCC resistance
was evaluated by slow strain rate tests and by constant load tests performed in an aqueous solution with 3.5 wt.%
NaCl. ECAP promoted grain refinement, breakdown/redistribution of coarse secondary phase particles and
contributed to reduce the local chemical heterogeneity. Consequently, mechanical properties and SCC resistance
were simultaneously improved.

1. Introduction susceptibility may be changed, mainly in aggressive environments.

The primary damage mechanism affecting many aluminum alloys in
Aluminum alloys are among the most versatile and used materials for an aggressive medium, such as halide containing environments, is
several technological purposes, mainly due to the good combination of pitting corrosion. Despite the protective oxide layer on the surface of Al
intermediate-to-high mechanical strength with low density, good alloys, imperfections and service conditions may contribute to acceler­
formability and high corrosion resistance [1,2]. It is known that me­ ating dissolution of the metal. Previous studies on the relationships
chanical strength and corrosion properties can be modified by an between ultrafine grain size and corrosion behavior of Al alloys have
appropriate microstructure design. Intense grain refinement, down to suggested that as grain size decreases, corrosion rate also decreases
the sub-micrometric scale (<1 μm) through Severe Plastic Deformation mainly due to higher grain boundary density and the breakdown of
(SPD), has been shown to be an effective strategy to improve mechanical secondary phase particles bellow to a critical size [14–16]. Other studies
properties [3–6]. Among the SPD techniques, Equal-Channel Angular on UFG-Al alloys containing intermetallic particles have shown a
Pressing (ECAP) is an efficient tool to produce Ultrafine-Grained (UFG) decrease in the density of observed pits, due to changes in size and/or
materials by means of intense shear plastic deformation [7]. Early in­ redistribution of particles promoted by SPD processing [17–19]. More­
vestigations have shown that ECAP is very effective in refining micro­ over, Brunner and co-authors [20] have found that by increasing the
structure and improving mechanical properties of aluminum alloys number of ECAP passes in AA2024 alloy, a redistribution of copper
[8–11]. Moreover, ECAP may introduce a number of microstructural occurs throughout the matrix, which results in grain boundary desen­
heterogeneities, namely: highly deformed areas; fragmentation and sitization and a transition of the dominant corrosion propagation mode,
redistribution of intermetallic particles; crystallographic texture; and from intergranular to pitting corrosion.
high internal stresses [12,13]. Therefore, localized corrosion In particular, a combination of stress concentration and an

* Corresponding author.
E-mail address: [email protected] (D.P. Braga).

https://doi.org/10.1016/j.msea.2019.138865
Received 6 August 2019; Received in revised form 5 November 2019; Accepted 22 December 2019
Available online 23 December 2019
0921-5093/© 2019 Elsevier B.V. All rights reserved.
D.P. Braga et al. Materials Science & Engineering A 773 (2020) 138865

Table 1 causing the preferential anodic dissolution of the adjacent Al matrix and
Chemical composition (wt.%) of the AA1050 and Al-4wt%Cu alloys. induce crack nucleation [32–34]. This study was based on Slow Strain
Alloy Al Cu Fe Si Ti Rate (SSR) and Constant Load (CL) tensile tests in air and in a 3.5 wt.%
Sodium Chloride (NaCl) solution. Microstructural changes, mechanical
AA1050 Bal. 0.002 0.28 0.09 0.03
Al-4wt.%Cu Bal. 4.10 0.07 0.05 0.03 response and fracture surface analysis were discussed to address the
combined effects of grain refinement, particles size/distribution and
local chemical heterogeneity on the SCC susceptibility.
aggressive environment makes Al alloys more susceptible to the Stress
Corrosion Cracking (SCC) phenomena, for which hydrogen embrittle­ 2. Experimental procedure
ment and anodic dissolution have been indicated as the main mecha­
nisms [21–23]. Slow Strain Rate (SSR) tensile tests combined with Two materials were employed in this work: a commercially pure
polarization measurements in Al-Mg alloys indicated that susceptibility aluminum AA1050, produced by a twin roll caster, and an experimental
to SCC decreased after grain refinement by ECAP [24]. However, the alloy Al-4wt.%Cu produced in Lab scale as detailed in Ref. [35]. Table 1
effect of grain refinement on the SCC susceptibility remains controver­ describes the chemical compositions of both alloys, determined by op­
sial in the literature: while some investigations reported a decrease tical emission spectroscopy. Samples for ECAP processing, with di­
[25–27], others indicated that SCC may be increased in UFG materials mensions of 70.0 � 25.0 � 7.0 mm, were prepared as follow:
[28,29]. In addition, there is a lack of detailed studies to evaluate the
influence of SPD processing on the SCC resistance of Al alloys, especially i) AA1050 ─ the samples were machined from the as-received plate,
addressing the combined effects of grain size refinement and particle having the ECAP pressing direction parallel to the original rolling
fragmentation/redistribution in precipitation-hardenable alloys. direction. Before processing, an annealing treatment was performed
Recently, a comprehensive review on this subject [30] concluded that at 350 � C for 1 h followed by water cooling;
the existing literature is definitely insufficient to find the trend of impact ii) Al-4wt%Cu ─ sections of 15.0 mm thickness were cut from a 100 mm
of UFG formation on SCC. diameter ingot, then hot rolled at 530 � C, down to 7.0 mm thickness,
The present work analyses the relationship between intense grain from which ECAP samples were machined. Before processing, a so­
refinement and SCC behavior of an ECAP processed Al-4wt.%Cu alloy. A lution treatment was performed at 530 � C, for 3 h, followed by slow
commercially pure aluminum (AA1050), which is expected to be non- cooling in a furnace to provide a coarse dispersion of Al2Cu particles.
susceptible to SCC [31], was employed for comparative purposes. The
Cu-rich particles present in the Al-4wt.%Cu may act as cathodic sites, An ECAP die was properly designed to process samples extracted

Fig. 1. (a) Samples for ECAP processing and specimens for tensile and SCC tests; (b) dimensional details of the notched specimen; (c) SCC set-up used for SSR tests;
and (d) view of a SCC specimen inside the mini chamber.

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D.P. Braga et al. Materials Science & Engineering A 773 (2020) 138865

from sheet materials, having the internal and concordance angles, Φ ¼ perform SCC experiments at a Slow Strain Rate (SSR) and at a Constant
120� and Ψ ¼ 25� , respectively, which result in an Equivalent Strain Load (CL), in air and in aqueous solution with 3.5 wt.% NaCl. In both
(εeq) equal to 0.67 per pass. A pressing speed of 10 mm/min was applied cases, the aqueous environment was provided by a polycarbonate mini
and a MoS2 lubricant was used to minimize friction between the die and chamber (see Fig. 1b), specially designed to cover only the gauge length
samples. Specimens from both alloys were ECAP processed up to eight of the specimens, preventing the contact of the grabs and other system
passes, following route A, which means no rotation of the samples be­ components with the electrolyte. The SSR tests were performed in an
tween the passes [7]. The non-deformed initial state was identified as 0x Instron machine, with a constant anvil speed, equivalent to an initial
and the ECAP processed samples were named 1x, 2x, … etc. with the strain rate equal to 1.0 � 10 6 s 1. The CL tests were performed in a
numeral indicating the number of passes. dead weight creep machine, starting with a constant load equivalent to
Microstructures of 0x and ECAP processed samples were analyzed by 70% of the respective yield stress (σy) and maintained under this con­
Optical Microscopy (OM) on samples taken from the Y plane (perpen­ dition up to 20 days for AA1050, and up to 10 days for Al-4wt.%Cu.
dicular to the y direction in Fig. 1), for both alloys. The samples were When fractures did not occur in this period, the load was increased to
prepared by conventional polishing. Afterwards, microstructural fea­ 80%σy and then 90%σy, up to 60 days for the former and up to 30 days
tures were observed under polarized light, in anodized samples prepared for the later alloy, according to the ASTM G-64 and ASTM G-47 pro­
with Barker’s reagent (2 vol.% HBF4 aqueous solution), using 20 V for 5 cedures for AA1050 and Al-4wt.%Cu, respectively [36,37].
min. In order to characterize morphology, size, distribution and chem­
ical composition of secondary phase particles, selected samples of the Al- 3. Results and discussion
4wt.%Cu alloy were submitted to a more detailed microstructural
analysis. For this purpose, Scanning Electron Microscopy (SEM) analyses 3.1. Microstructural evolution
were performed in the Y plane, by using a Phillips XL-30 FEG micro­
scope, with an Energy-dispersive X-ray Spectroscopy (EDX) device, The microstructures of the non-deformed (0x) and ECAP processed
operated at 25 kV. For Transmission Electron Microscopy (TEM), thin (8x) samples of both alloys are shown in Fig. 2. As expected, the mi­
foils were prepared from the ECAPed sheets, using a twin-jet electro crographs from the 0x condition show coarse recrystallized grains, with
polisher and a solution of 34 mL HClO4, 50 mL butyl glycol, 350 mL average sizes of 149 � 2 μm and 465 � 2 μm, for AA1050 (Fig. 2a) and
ethanol and 60 mL distilled water, with an operating voltage of 20 V, at Al-4wt.%Cu (Fig. 2c), respectively. In the initial annealed condition,
room temperature. Observations were made in a TEM FEI TECNAI G2 AA1050 shows coarse intermetallic particles disperse in the matrix,
(LaB6 filament) microscope operated at 200 kV with the foil surface since at the present levels of temperature the solubility of Fe in Al are
parallel to the Y plane. In addition, to determine the crystallographic virtually null [38]. In the furnace cooled Al-4wt.%Cu, coarse interme­
mapping, an ASTAR device in TEM was used to obtain an automated tallic phases originating from segregations during the casting process
crystallographic orientation mapping. Vickers Hardness (HV) measure­ appear in the grain boundaries together with a coarse dispersion of
ments were taken on the Y plane for both alloys, using a Heckert-HPO Al2Cu particles [34]. After ECAP (Fig. 2b and Fig. 2d), both micro­
3000 tester, under a load of 5 kgf maintained during 15 s. structures show an intense grain refinement, with the grains deformed
Conventional tensile tests were performed in a 5500 Instron ma­ and oriented along shear bands, as expected when following route A in
chine, using non-notched specimens with geometry and dimensions ECAP [39,40] and new fine grains from a continuous dynamic recrys­
indicated in Fig. 1, except for the notch. The initial strain rate was equal tallization process, which are not clearly visible at this level of
to 1.0 � 10 3 s 1 and three specimens were tested for each condition. magnification.
Notched specimens, with the dimensions shown in Fig. 1c, were used to The intermetallic particles play an important role in SCC, once this

Fig. 2. Typical microstructures observed by OM (polarized light in anodized samples), before and after ECAP processing: (a) AA1050 – 0x; (b) AA1050 – 8x; (c) Al-
4wt.%Cu – 0x and (d) Al-4wt.%Cu – 8x.

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D.P. Braga et al. Materials Science & Engineering A 773 (2020) 138865

Fig. 3. Al-4wt%Cu alloy, before (0x – left column) and after (8x – right column) ECAP processing. SEM micrographs (a, b, c, d) and EDX mapping of copper (e, f).

kind of microstructural heterogeneity and their neighborhoods are deformation bands, but remained mainly at the grain boundaries. By
preferential areas to anodic dissolution and induces crack nucleation using SEM analysis, it was observed that the fraction of area covered by
[32,33]. For a better characterization of the constituent phases, SEM and such constituents remained approximately constant before (0x) and
EDX analyses were performed to determine copper atom distribution in after (8x) ECAP processing, close to 1.2 � 0.2%. On the other hand, the
the Al-4wt.%Cu alloy, as presented in Fig. 3 for 0x and 8x samples. average particle area was reduced from 18 � 2 μm2 in the sample 0x to
In Fig. 3a and Fig. 3c, coarse intermetallic phases are localized 3.9 � 0.6 μm2 in the sample 8x. Coarse constituent phases, especially the
preferentially at the grain boundaries of the Al-4wt.%Cu alloy, before insoluble ones, normally make no substantial contribution to the me­
ECAP processing. Most of these constituent phases have typical chanical strength, however they can influence the corrosion resistance
morphology of eutectic structures, which arise from casting and are due to electrochemical potential differences with the aluminum matrix.
insoluble during heat treatment. From Fig. 3b and Fig. 3d, it can be Thus, a finer and more homogenous distribution of such intermetallic
observed that SPD by ECAP promoted fragmentation and redistribution particles promoted by ECAP processing may contribute to decreasing the
of the coarse intermetallic phases, which were aligned along the localized corrosion rate, provided that their size is below some critical

Fig. 4. (a) TEM bright field image of the Al-4wt%Cu after 8x ECAP passes, and (b) respective orientation mapping with high angle grain boundaries in red. (For
interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article).

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D.P. Braga et al. Materials Science & Engineering A 773 (2020) 138865

Table 2
Effect of ECAP processing on the engineering tensile properties.
Sample εeq σy (MPa) σu (MPa) εf (%) εu (%)
AA1050 - 0x - 72 � 3 100 � 3 43 � 1 22 � 2
AA1050 - 1x 0.7 139 � 2 153 � 4 7.9 � 0.3 1.6 � 0.3
AA1050 - 4x 2.6 146 � 4 167 � 1 9.2 � 0.1 2.6 � 0.2
AA1050 - 8x 5.3 155 � 2 173 � 1 22 � 1 2.5 � 0.3

Al-4wt.%Cu - 0x - 66 � 3 203 � 9 21 � 1 18 � 1
Al-4wt.%Cu - 1x 0.7 276 � 4 281 � 5 2.6 � 0.3 0.9 � 0.3
Al-4wt.%Cu - 4x 2.6 363 � 5 368 � 5 2.6 � 0.2 1.1 � 0.2
Al-4wt.%Cu - 8x 5.3 408 � 6 414 � 8 6.8 � 0.3 1.5 � 0.3

Note: εeq ¼ equivalent strain; σy ¼ yield stress; σu ¼ ultimate tensile stress; εf ¼

elongation to failure; εu ¼ uniform elongation.

ECAP, in which a crystallographic texture is expected due to the

deformation systems activated during processing [5,7,8].

3.2. Mechanical response after ECAP

Fig. 5 shows a marked increase in hardness after the first ECAP pass
Fig. 5. Effect of ECAP equivalent strain on the Vickers hardness evolution of
and a trend towards stabilization after the third pass. This tendency of
the AA1050 and Al-4wt%Cu alloys.
hardness saturation is a characteristic of severely deformed materials,
limit which prevents them from operating as local cathodes [18,41]. In which can be related to recovery and dynamic recrystallization pro­
Fig. 3e and Fig. 3f, EDX element maps clearly indicate the presence of cesses and to the formation of high angle boundaries, as pointed out in
copper in the coarse particles. In copper-containing aluminum alloys, previous works [36]. The increase in hardness promoted by ECAP pro­
eutectic structures containing Al, Cu, Fe and Si are likely to be a mixture cessing in the AA1050 alloy was approximately 40% compared with the
of Al12Fe3Si, Al7Cu2Fe and Al6(Fe,Cu) [31]. Moreover, in a previous initial state, while for Al-4wt.%Cu alloy this increase reached 80%. The
work [35], performed on this same Al-4wt.%Cu alloy, it was observed higher hardening effect observed in the second alloy is due to the
that Al2Cu is the main soluble precipitate responsible for increasing the presence of precipitates and intermetallic particles. The work-hardening
hardness and mechanical strength after aging and that it can be found behavior of an Al-4wt.%Cu alloy was previously evaluated by means of
either as fine precipitates or coarse particles close to the grain bound­ controlled post-deformation aging treatments [35]. In the present work,
aries, which act as sites for its nucleation. On the other hand, Fig. 3f all the samples were ECAP-processed in the solutionized state, without
indicates a better distribution of copper throughout the Al matrix, as any subsequent treatment. However, in the copper-containing alloy,
previously reported by Brunner et al. [20], which may affect the static and dynamic precipitation may have occurred, respectively, in the
corrosion resistance as commented further below. slow furnace cooling from the solution temperature and during ECAP
Since the OM and SEM images were not clear enough to resolve the processing.
grain subdivisions formed after ECAP, TEM and orientation mapping Typical curves from conventional tensile tests, performed on ECAP
analysis are presented in Fig. 4a and Fig. 4b, for the sample 8x of Al-4wt. processed samples, are shown in Fig. 6 and the corresponding engi­
%Cu. An intense grain refinement can be seen, with elongated grains neering tensile properties are presented in Table 2. Elastic deformations
along deformation bands in the shear direction and an average grain size were removed from the curves, since the subsequent analysis will be
equal to 0.7 � 0.1 μm, with an aspect ratio near to 4:1. It can also be restricted to the uniform plastic deformation of the specimen. A sup­
observed that inside the grains there are plenty of subgrain structures, i. plementary file is available containing representative raw data,
e., low-angle grain boundaries and high dislocation density inside the including elastic regions.
grains. These features are typical for materials processed by route A in AA1050 alloy shows a significant increase in tensile strength after
the first pass (1x), while elongation to failure is strongly reduced, if
compared to 0x. On the other hand, at higher deformation levels (4x and
8x), strength and elongation increase simultaneously, a typical behavior
of SPD ultrafine-grained materials [42]. Meanwhile, the ECAP processed
samples showed a high proportion of non-uniform (after necking)
elongation and a small work-hardening capacity (see the small values of
uniform elongation, εu, in Table 2), as often observed in highly deformed
materials [7,34,43]. Again, the strengthening effect promoted by ECAP
processing is more evident in the Al-4wt.%Cu alloy due to the presence
of secondary phase particles: after eight passes (8x), yield stress and
ultimate tensile stress increased, respectively, 500% and 100%
compared to the 0x condition. As for the AA1050 alloy, these figures
were 100% and 70%, respectively (see Table 2).
The plastic deformation behavior of the processed alloys was
analyzed from true stress versus true strain tensile curves, in terms of the
Hollomon model (σ ¼ k.εn) strain-hardening parameters [44] and the
Kocks-Mecking (K-M) hardening/recovery rates [45]. As shown by Chu
and Morris [46], the strain hardening rate can be described by equation
(1):
dσ
Fig. 6. Representative tensile curves for different numbers of ECAP passes. θ¼ ¼ θ0 Kσ (1)
dε
Initial strain rate equal to 1 � 10 3 s 1.

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D.P. Braga et al. Materials Science & Engineering A 773 (2020) 138865

Table 3
Hollomon strain-hardening parameters and K-M recovery rates.
Sample n k (MPa) K θo (MPa)
-[dθ/d(σ-σo)]

AA1050 - 0x 0.149 � 0.01 164 �7 6.4 415

AA1050 - 1x 0.02 � 0.01 189 �9 773 6681
AA1050 - 4x 0.03 � 0.01 215 �7 401 8374
AA1050 - 8x 0.03 � 0.01 225 �3 351 9030

Al-4wt.%Cu - 0x 0.18 � 0.01 378 � 13 22 4574

Al-4wt.%Cu - 1x 0.031 � 0.002 340 �4 237 9493
Al-4wt.%Cu - 4x 0.034 � 0.001 458 �8 194 12654
Al-4wt.%Cu - 8x 0.034 � 0.001 515 � 10 116 9285

Note: (n, k) ¼ Hollomon parameters; (K, θ0) ¼ K-M parameters.

(σ-σo), where σo is close to the yield stress, at the very beginning of the
uniform plastic regime. The K-M parameters, thus determined, are
shown in Table 3, together with the Hollomon parameters for all the
tested conditions.
The effect of ECAP processing on the strain-hardening n-exponent
can be summarized as follows: i) a marked loss of uniform deformation
capacity occurs in the first pass, which is quantified by a drastic
reduction in n-values, if compared with the 0x condition; ii) with the
subsequent passes, the uniform elongation (and consequently the n-

Fig. 7. Representative Kocks-Mecking plots after ECAP for: (a) AA1050; (b) Al-
4wt%Cu; and (c) a comparison between the two alloys before and after ECAP
processing. Dashed lines in (a) and (b) represent the recovery rates (K, in
Eq. (1)).

where, the hardening rates, θ ¼ (dσ/dε), can be obtained from the

tangent lines of the “true stress x plastic true strain” curves, in the uniform
deformation region. According to this model, two operational parame­
ters can be defined from the curves θ versus σ (or K-M plots): i) θo, which
expresses the maximum hardening rate, is a measure of accumulated
dislocations, related to the athermal hardening; ii) K ¼ -dθ/dσ, which is
the slope of the curve θ versus σ, represents the dynamic recovery rate.
Fig. 7 shows the K-M plots constructed with the “true stress vs plastic
true strain” data taken from the tensile tests shown in Fig. 6. The curves
exhibit an initial transient where the work hardening (θ) drops to levels
appropriate to a well-developed plastic state, called stage III, in which Fig. 8. Slow strain rate tensile tests performed on notched specimens, in air and
Eq. (1) was applied. Note that the x-axis was plotted as the difference in a 3.5 wt.% NaCl environment: (a) AA1050; (b) Al-4wt.%Cu. Initial strain rate
equal to 1 � 10 6 s 1.

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Table 4
Results from slow strain rate (SSR) tensile tests performed with notched specimens.
Condition σy (MPa) σu (MPa) εf (%) εu (%) Time to failure (h)

AA1050 - 0x Air 77 � 2 110 � 3 17 � 1 9.5 � 0.3 59 � 2

3.5 wt% NaCl 75 � 3 111 � 8 17 � 1 9.2 � 0.3 59 � 3

AA1050 - 8x Air 171 � 4 207 � 7 11 � 1 3.6 � 0.2 63 � 2

3.5 wt% NaCl 170 � 4 194 � 13 10 � 1 3.8 � 0.1 60 � 4

Al-4wt.%Cu - 0x Air 133 � 1 273 � 5 7.1 � 0.1 6.7 � 0.2 34 � 2

3.5 wt% NaCl 99 � 2 236 � 8 7.0 � 0.2 6.5 � 0.3 30 � 3

Al-4wt.%Cu - 8x Air 436 � 2 533 � 13 2.6 � 0.2 1.9 � 0.1 27 � 2

3.5 wt% NaCl 414 � 4 481 � 21 1.8 � 0.1 1.4 � 0.1 24 � 4
6
Note: εeq ¼ equivalent strain, σy ¼ yield stress; σu ¼ ultimate tensile stress; εf ¼ elongation to failure; εu ¼ uniform elongation. Initial strain rate equal to 1.0 � 10 s 1.

values) tend to increase, but still one order of magnitude smaller than occurred in both 0x and 8x samples. However, the mechanism by which
the initial condition; iii) highly deformed samples show a tendency to long-term SCC occurred in AA1050 needs to be further investigated.
increase the non-uniform concentrated (post-necking) deformation. Regarding the effect of ECAP-processing, CL tests were not conclu­
As for the dynamic recovery rate, represented by the parameter K ¼ sive for AA1050, since the results of 0x and 8x samples were similar
-dθ/d(σ-σo), Fig. 7 clearly shows that ECAP sharply accentuated this within the dispersion range. Concerning Al-4wt.%Cu, the results suggest
phenomenon compared with the non-deformed (0x) samples. However, that ECAP caused some improvement in the SCC resistance, since in the
in Table 3, it can be observed that after the first pass, the K values tend to processed samples (8x), fractures were detected only for tests performed
decrease with the increase in the number of passes, which is in agree­ at 80%σy, compared to 70%σy for the 0x samples. The present number of
ment with that observed for the strain-hardening n-exponent. Such an tests is certainly not sufficient for a statistical interpretation, but if one
effect is less evident in the case of the Al-4wt.%Cu alloy. The lower re­
covery rates (K-values) observed for the Al-4wt.%Cu alloy can be
explained by the presence of Al2Cu secondary particles. Previous works
have shown that the precipitates tend to hinder the movement of dis­
locations, thus reducing the rate at which storage and/or annihilation
occurs [47,48].

3.3. Stress corrosion cracking

Fig. 8 shows the engineering stress-strain curves from SCC tests

performed at a Slow Strain Rate (SSR), with notched specimens, in air
and in a 3.5 wt.% NaCl environment. The corresponding tensile prop­
erties are shown in Table 4. In Fig. 8a, the presence of a saline envi­
ronment apparently did not affect the response of the AA1050 alloy to
SCC at SSR for both the 0x and the 8x samples. The small differences
among the curves are within the dispersion range of the results, as can be
seen in Table 4. As for the Al-4wt.%Cu samples, shown in Fig. 8b, the
ultimate tensile stress at SSR was reduced in the NaCl environment,
indicating that the presence of copper in this alloy impaired the SCC
resistance. The Al-4wt.%Cu non-deformed sample (0x) was more
affected by the aggressive environment than the processed one (8x): in
the former, yield stress and ultimate tensile stress were reduced,
respectively, by 25% and 14%, while these losses were 5% and 10% in
the latter. A similar tendency of reduction of the elongation values in the
saline environment was also observed, although these variations were
close to the dispersion limits. Despite any uncertainty involved in this
kind of comparison, it is clear that ECAP processing did not impair the
SCC resistance in SSR tests. On the contrary, the present results suggest
that the breakdown and redistribution of coarse particles had a positive
effect on this resistance.
In long-term Constant Load (CL) tests, performed with notched
specimens in a 3.5 wt.% NaCl solution, fractures occurred below the
respective yield stress for both alloys, both solutionized and ECAP-
processed condition. Fig. 9 shows results of CL tests, performed with
initial stresses corresponding to 70%, 80% and 90% of the respective σy.
In the AA1050 alloy (Fig. 9a), specimens fractured only at a stress as
high as 90% of σy, while for Al-4wt.%Cu fractures were detected at 70%
and 80% of the yield stress, which is clear evidence that the copper-
containing alloy is more susceptible to SCC than the commercially
pure aluminum. On the other hand, it was demonstrated that AA1050,
although less sensitive, is not immune to SCC after long times of expo­ Fig. 9. Constant load tensile tests performed on notched specimens, in air and
sure to an NaCl environment, since at a stress equal to 90%σy, fractures in a 3.5 wt% NaCl environment: (a) AA1050; (b) Al-4wt.%Cu.

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D.P. Braga et al. Materials Science & Engineering A 773 (2020) 138865

Fig. 10. Fracture surface after constant load tensile tests performed on notched specimens in a 3.5 wt.% NaCl environment. Yellow arrows indicate brittle fracture
areas, red arrows ductile fracture areas and green arrows corrosion cracks. (For interpretation of the references to colour in this figure legend, the reader is referred to
the Web version of this article).

considers the significant improvement in mechanical strength promoted 4. Conclusions

by ECAP, a similar resistance to SCC is a positive result. Moreover, SCC
of UFG materials have been investigated mostly by SSR tensile tests [19, For the two alloys studied here, a detailed mechanical and micro­
22], while long-term experiments remain very scarce in the literature structural characterization showed that ECAP promoted: i) an intense
[29]. In the present study, the Cu-containing alloy was purposely pre­ grain refinement, down to the sub-micron scale; ii) a remarkable in­
pared and slow cooled from the solution temperature to introduce coarse crease in hardness and tensile strength with a decrease in uniform
intermetallic phases, of which adjacent areas favorable for anodic deformation capacity; iii) a sharp increase in the dynamic recovery rate
dissolution and crack nucleation are expected. Thus, the fracture surface in tensile tests — all in line with most literature.
was observed by MEV in specimens summited to long-term CL tests in In the Al-4wt.%Cu alloy, ECAP processing caused the fragmentation
aqueous solution with 3.5 wt.% NaCl. of coarse precipitates and undissolved phases initially present at the
Fig. 10 shows details of the fracture surface of CL-tested specimens, grain boundaries. The fragmented particles were redistributed along the
taken from regions close to the notches. In AA1050 – 0x, despite the deformation bands, with a more homogeneous distribution of Cu in their
lower number of coarse secondary phase particles, cracks can be neighborhood.
observed in such regions, which cause the material to fracture under a In SSR tensile tests, SCC was detected only in the Al-4wt.%Cu alloy.
stress of 90% of σy. After ECAP, cracks in AA1050 became less evident Meanwhile, in CL tests, fractures occurred under stresses lower than the
but no significant difference was observed in the SCC resistance, yield stress in both alloys. Although less sensitive, AA1050 was not
compared to 0x. Regarding Al-4wt.%Cu, the images in Fig. 10 suggest immune to SCC under long-term CL testing.
that the SCC process occurred, assisted by anodic dissolution in the In the Al-4wt.%Cu alloy, ECAP processing reduced the SCC suscep­
neighborhood of intermetallic phases, preferentially located at the grain tibility, which was attributed to the breakdown and redistribution of
boundaries. Moreover, the reduction in grain size, fragmentation and secondary phase/intermetallic particles and to a grain boundary
redistribution of particles promoted by ECAP reduced the localized desensitization effect caused by a better chemical homogeneity. As for
corrosion susceptibility. AA1050, no significant effects of ECAP processing were observed on the
Despite some controversies, the literature suggests that an response to SCC tests.
improvement in the corrosion resistance of UFG Al alloys may be It was demonstrated that, in Al copper-containing alloys, grain size
attributed to: acts together with size/distribution of particles and local electro­
chemical heterogeneity to define the resulting SCC resistance, and that
i) the higher grain boundary density, which would favor passivation these factors can be modified — and possibly controlled — by ECAP
[16,25]; processing.
ii) the breakdown of secondary phase particles bellow to a critical size,
which would difficult their operation as local cathodes [16–18]. Data availability

Additionally, the SPD processing may affect the local electro­ The raw/processed data required to reproduce these findings cannot
chemical homogeneity by impairing the local chemical microstructure be fully shared at this time due to technical or time limitations. Repre­
of the secondary phase/intermetallic particles. In the present case, EDX sentative raw/processed data from tensile tests are available as a sup­
mapping (see Fig. 3) clearly shows a more homogeneous distribution of plementary file.
Cu in the Al matrix after ECAP processing (8x sample), which may have
resulted in a grain boundary desensitization effect [20] and, conse­ Declaration of competing interest
quently, contributed to reduce the SCC susceptibility. In this sense, a
direct relation between grain refinement and corrosion resistance seems The authors declare that they have no known competing financial
to be an assessment rather elementary, and this may be the reason why interests or personal relationships that could have appeared to influence
literature is often contradictory on this subject. the work reported in this paper.

8
D.P. Braga et al. Materials Science & Engineering A 773 (2020) 138865

Acknowledgements [19] K.D. Ralston, J.G. Brunner, S. Virtanen, N. Birbilis, Effect of processing on grain
size and corrosion of AA 2024-T3, Corrosion 67 (2011), https://doi.org/10.5006/
1.3647762, 105001-105001-10.
We gratefully acknowledge the financial support of the Sa~o Paulo [20] J.G. Brunner, N. Birbilis, K.D. Ralston, S. Virtanen, Impact of ultrafine-grained
Research Foundation – FAPESP (Grant number 2016/10997-0), the microstructure on the corrosion of aluminum alloy AA2024, Corros. Sci. 57 (2012)
National Council for Scientific and Technological Development - CNPq, 209–214, https://doi.org/10.1016/j.corsci.2011.12.016.
[21] G.R. Argade, N. Kumar, R.S. Mishra, Stress corrosion cracking susceptibility of
Brazil (Grant number 449009/2014-9) and the Coordination for the ultrafine Al-Mg-Sc alloy, Mater. Sci. Eng. A565 (2013) 80–89, https://doi.org/
Improvement of Higher Education Personnel – CAPES, Brazil - Finance 10.1016/j.msea.2012.11.066.
Code 001 and the Graduate Program in Materials Science and Engi­ [22] J.L. Searles, P.I. Gouma, R.G. Buccheit, Stress corrosion cracking of sensitized
AA5083 (Al-4.5Mg-1.0Mn), Metall. Mater. Trans. A 32 (2001) 2859–2867, https://
neering of the Federal University of Sa
~o Carlos. doi.org/10.1007/s11661-001-1036-3.
[23] R.H. Jones, D.R. Baer, M.J. Danielson, J.S. Vetrano, Role of Mg in the stress
Appendix A. Supplementary data corrosion cracking of an Al-Mg alloy, Metall. Mater. Trans. A 32 (2001)
1669–1711, https://doi.org/10.1007/s11661-001-0148-0.
[24] H. Nakano, S. Oue, S. Taguchi, S. Kobayashi, Z. Horita, Stress-corrosion cracking
Supplementary data to this article can be found online at https://doi. property of aluminum-magnesium alloy processed by Equal-Channel Angular
org/10.1016/j.msea.2019.138865. Pressing, Int. J. Corros. 2012 (2012), https://doi.org/10.1155/2012/543212,
543212.
[25] D. Song, A.B. Ma, J.H. Jiang, P.H. Lin, D.H. Yang, Corrosion behavior of ultra-fine
References grained Industrial pure Al fabricated by ECAP, Trans. Nonferrous Metals Soc. China
19 (2009) 1065–1070, https://doi.org/10.1016/S1003-6326(08)60407-0.
[1] E.A. Starke, J.T. Staley, Application of modern aluminum alloys to aircraft, Prog. [26] M.K. Chung, Y.S. Choi, J.G. Kim, Y.M. Kim, J.C. Lee, Effect of the number of ECAP
Aerosp. Sci. 32 (1996) 131–172, https://doi.org/10.1016/0376-0421(95)00004-6. pass time on the electrochemical properties of 1050 Al alloys, Mater. Sci. Eng. A
[2] J. Hirsch, Recent development in aluminum for automotive applications, 366 (2004) 282–291, https://doi.org/10.1016/j.msea.2003.08.056.
T. Nonferrous Met. Soc. 24 (2014) 1995–2002, https://doi.org/10.1016/S1003- [27] E. Akiyama, Z. Zhang, Y. Watanabe, K. Tsuzaki, Effects of severe plastic
6326(14)63305-7. deformation on the corrosion behavior of aluminum alloys, J. Solid State
[3] P. Vishnu, R. Raj Mohan, E. Krishna Sangeethaa, S. Raghuraman, R. Venkatraman, Electrochem. 13 (2009) 277–282, https://doi.org/10.1007/s10008-007-0496-9.
A review on processing of aluminium and its alloys through Equal Channel Angular [28] W.R. Os� orio, C.M. Freire, A. Garcia, The role of macrostructural morphology and
Pressing die, Mater. Today Proc. (2019), https://doi.org/10.1016/j. grain size on the corrosion resistance of Zn and Al castings, Mater. Sci. Eng. A 402
matpr.2019.04.223. (2005) 22–32, https://doi.org/10.1016/j.msea.2005.02.094.
[4] T.G. Langdon, Twenty-five years of ultrafine-grained materials: achieving [29] D. Song, A.B. Ma, J.H. Jiang, P.H. Lin, F.M. Lu, L.Y. Zhang, Significantly changed
exceptional properties through grain refinement, Acta Mater. 61 (2013) intergranular corrosion and exfoliation corrosion behavior of the ultra-fine grained
7035–7059, https://doi.org/10.1016/j.actamat.2013.08.018. Al–5 mass% Cu alloy fabricated by ECAP, Mater. Corros. 64 (2013) 1015–1023,
[5] Y. Estrin, A. Vinogradov, Extreme grain refinement by severe plastic deformation: a https://doi.org/10.1002/maco.201206874.
wealth of challenging science, Acta Mater. 61 (2013) 782–817, https://doi.org/ [30] H. Miyamoto, Corrosion of ultrafine grained materials by severe plastic
10.1016/j.actamat.2012.10.038. deformation, an overview, Mater. Trans. 57 (No. 5) (2016) 559–572, https://doi.
[6] T.G. Langdon, The processing of ultrafine-grained materials through the org/10.2320/matertrans.M2015452.
application of severe plastic deformation, J. Mater. Sci. 42 (2007) 3388–3397, [31] E.H. Hollingsworth, H.Y. Hunsicker, Corrosion of Aluminum and Aluminum Alloys.
https://doi.org/10.1007/s10853-006-1475-8. Corrosion. 13, ASM International (American Society For Metals), Ohio, USA, 1990.
[7] R.Z. Valiev, T.G. Langdon, Principles of equal-channel angular pressing as a [32] S.C. Wang, M.J. Starink, Review of precipitation in Al-Cu-Mg(-Li) alloys, Int.
processing tool for grain refinement, Prog. Mater. Sci. 51 (2006) 881–981, https:// Mater. Rev. 50 (2005) 193–215, https://doi.org/10.1179/174328005X14357.
doi.org/10.1016/j.pmatsci.2006.02.003. [33] M. Navaser, M. Atapour, Effect of friction stir processing on pitting corrosion and
[8] A.M. Kliauga, V.L. Sordi, N.S. De Vincentis, R.E. Bolmaro, N. Schell, H.- intergranular attack of 7075 aluminum alloy, J. Mater. Sci. Technol. 33 (2017)
G. Brokmeier, Severe plastic deformation by equal channel angular pressing and 155–165, https://doi.org/10.1016/j.jmst.2016.07.008.
rolling: the influence of the deformation path on strain distribution, Adv. Eng. [34] R. Goswami, S. Lynch, N.J.H. Holroyd, S.P. Knight, R.L. Holtz, Evolution of grain
Mater. 20 (2018), https://doi.org/10.1002/adem.201700055, 1700055. boundary precipitates in Al 7075 alloy upon aging and correlation with stress
[9] Y. Dulan, L. Tang, G. Xu, Y. Deng, Z. Yin, Microstructure and mechanical properties corrosion cracking behavior, Metall. Mater. Trans. A 44 (3) (2012) 1268–1278,
of 7005 aluminum alloy processed by room temperature ECAP and subsequent https://doi.org/10.1007/s11661-012-1413-0.
annealing, J. Alloy. Comp. 664 (2016) 518–529, https://doi.org/10.1016/j. [35] E.F. Prados, V.L. Sordi, M. Ferrante, The effect of Al2Cu precipitates on the
jallcom.2016.01.022. microstructural evolution, tensile strength, ductility and work-hardening
[10] Y.Y.J. Chen, Y.C. Chai, H.J. Roven, S.S. Gireesh, Y.D. Yu, J. Hjelen, Microstructure behaviour of Al-4wt%Cu alloy processed by equal channel angular pressing, Acta
and properties of Al-xMg alloys processed by room temperature ECAP, Mater. Sci. Mater. 61 (2013) 115–125, https://doi.org/10.1016/j.actamat.2012.09.038.
Eng. A 545 (2012) 139–147, https://doi.org/10.1016/j.msea.2012.03.012. [36] ASTM International (American Society For Testing And Materials), G64-99:
[11] E. El-Danaf, Mechanical properties and microstructure evolution of 1050 Standard Classification of Resistance to Stress-Corrosion Cracking of Heat-
aluminum severely deformed by ECAP to 16 passes, Mater. Sci. Eng. A 487 (2008) Treatable Aluminum Alloys, 2013. USA.
189–200, https://doi.org/10.1016/j.msea.2007.10.013. [37] ASTM International (American Society For Testing And Materials), G47-98:
[12] S.G. Chowdhury, C. Xu, T.G. Langdon, Texture evolution in an aluminum alloy Standard Test Method for Determining Susceptibility to Stress-Corrosion Cracking
processed by ECAP with concurrent precipitate fragmentation, Mater. Sci. Eng. of 2XXX and 7XXX Aluminum Alloy Products, 2011. USA.
A473 (2008) 219–225, https://doi.org/10.1016/j.msea.2007.05.052. [38] X. Li, A. Scherf, M. Heilmaier, F. Stein, The Al-Rich part of the Fe-Al phase diagram,
[13] T.G. de Sousa, V.L. Sordi, L.P. Brand~ ao, Dislocation density and texture in copper J. Phase Equilibria Diffusion 37 (2016) 162–173, https://doi.org/10.1007/s11669-
deformed by cold rolling and ECAP, Mater. Res. 21 (1) (2018), e20170515, https:// 015-0446-7.
doi.org/10.1590/1980-5373-mr-2017-0515. [39] K. Nakashima, Z. Horita, M. Nemoto, T.G. Langdon, Influence of channel angle on
[14] K.D. Ralston, D. Fabijanic, N. Birbilis, Effect of grain size on corrosion of high the development of ultrafine grains in Equal-Channel Angular Pressing, Acta
purity aluminium, Electrochim. Acta 56 (2011) 1729–1736, https://doi.org/ Mater. 46 (1998) 1589–1599, https://doi.org/10.1016/S1359-6454(97)00355-8.
10.1016/j.electacta.2010.09.023. [40] M.C.V. Vega, R.E. Bolmaro, M. Ferrante, V.L. Sordi, A.M. Kliauga, The influence of
[15] E. Kus, Z. Lee, S. Nutt, F. Mansfeld, A comparison of the behavior of nanocrystalline deformation path on strain characteristics of AA1050 aluminum processed by
and conventional Al 5083 samples, Corrosion 62 (2006) 152–161, https://doi.org/ equal-channel angular pressing followed by rolling, Mater. Sci. Eng. A 646 (2015)
10.5006/1.3278260. 154–162, https://doi.org/10.1016/j.msea.2015.07.083.
[16] E. Sikora, X.J. Wei, B.A. Shaw, Corrosion behavior of nanocrystalline buld [41] K.D. Ralston, N. Birbilis, Effect of grain size on corrosion: a review, Corros. Sci. 66
Al–Mg–based alloys, Corrosion 60 (2004) 387–398, https://doi.org/10.5006/ (2010), https://doi.org/10.5006/1.3462912, 075005-075005-13.
1.3287748. [42] B. Verlinden, Severe plastic deformation of metals, Metalurgija – J. Metall. 11
[17] I.J. Son, H. Nakano, S. Oue, S. Kobayashi, H. Fukushima, Z. Horita, Pitting (2005) 65–182, https://doi.org/10.30544/380.
corrosion resistance of ultra-fine grained aluminium processed by Severe Plastic [43] A.A. Mendes Filho, E.F. Prados, G.T. Valio, J.B. Rubert, V.L. Sordi, M. Ferrante,
Deformation, Mater. Trans. 69 (2006) 892–898, https://doi.org/10.2320/ Severe plastic deformation by equal cannel angular pressing: product quality and
jinstmet.69.892. operational details, Mater. Res. 14 (2011) 335–339, https://doi.org/10.1590/
[18] M.K. Chung, Y.S. Choi, J.G. Kim, Y.M. Kim, J.C. Lee, Effect of the number of ECAP S1516-14392011005000045.
pass time on the electrochemical properties of 1050 Al alloys, Mater. Sci. Eng. A [44] ASTM International (American Society for Testing and Materials), E646: Standard
366 (2004) 282–291, https://doi.org/10.1016/j.msea.2003.08.056. Test Tensile Strain-Hardening Exponents (n-values) of Metallic Sheet Materials,
2007. USA.

9
D.P. Braga et al. Materials Science & Engineering A 773 (2020) 138865

[45] U.F. Kocks, H. Mecking, Physics and phenomenology of strain hardening: the FCC properties, Mater. Sci. Eng. A 368 (2004) 205–211, https://doi.org/10.1016/j.
case, Prog. Mater. Sci. 48 (2003) 171–273, https://doi.org/10.1016/S0079-6425 msea.2003.10.311.
(02)00003-8. [48] L.M. Cheng, W.J. Poole, J.D. Embury, D.J. Lloyd, The influence of precipitation on
[46] D. Chu, J.W. Morris, The influence of microstructure on work hardening in the work-hardening behavior of the aluminum alloys AA6111 and AA7030, Metall.
aluminum, Acta Mater. 44 (1996) 2599–2610, https://doi.org/10.1016/1359- Mater. Trans. A 34 (2003) 2473–2481, https://doi.org/10.1007/s11661-003-
6454(95)00403-3. 0007-2.
[47] M. Tiryakio�glu, J. Campbell, J.T. Staley, Evaluating structural integrity of cast
Al–7% Si–Mg alloys via work hardening characteristics: 1. concept of target

10