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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci
Laboratoire Science et Ingnierie des Matriaux et Procds (SIMAP), Grenoble INP, UJF, CNRS, 38402 Saint Martin d, Hres, France
Rio Tinto Alcan Centre de Recherches de Voreppe, BP 27, 38341 Voreppe Cedex, France
a r t i c l e
i n f o
Article history:
Received 10 June 2010
Accepted 8 January 2011
Available online 18 January 2011
Keywords:
A. Aluminium
B. Galvanostatic
C. Exfoliation corrosion
C. Hydrogen absorption
a b s t r a c t
Electrochemical approaches are used to investigate the exfoliation corrosion (EFC) of a 7XXX series aluminium alloy that has undergone different tempering treatments. EFC was produced under an articial
crevice at open circuit potential in neutral chloride solutions, and is found to be associated to current
and potential transients. EFC was also produced under galvanostatic control conditions. Observations
made through Scanning Electron Microscopy (SEM) suggest that these transients result from the progression of inter-granular cracks. Last, over-ageing heat treatments that are known to decrease both metal
hardness and EFC sensitivity were found to decrease the number of transients.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
Aluminium alloys with an elongated grain structure parallel to
the plate surface are known [1] to be sensitive to exfoliation corrosion. High strength 2XXX and 7XXX series alloys used in aircraft
are particularly sensitive to this form of inter-granular corrosion
[2], which is considered to be a major cause of airframe degradation [3]. For instance, it has been shown that EFC above a certain
critical level could signicantly decrease fatigue life [4]. The resistance of such alloys to EFC is generally increased through over-ageing treatments, which unfortunately, signicantly decrease the
mechanical strength [1].
In the last decade, the effect of heat treatment on the corrosion
behaviour of aluminium alloys has been extensively studied as evidenced by the works on liform corrosion [58]. More recently the
effect of temper on localised corrosion kinetics of 7XXX alloys has
been studied using the foil penetration technique [9], which presents the advantage of measuring corrosion rates under various
experimental conditions. Some electrochemical transients were
observed that the authors attributed to the selective grain attack
combined with inter-granular corrosion, both controlled by the
alloying elements content [10,11]. Having this in mind, we intended in this paper to investigate the inuence of tempering on
the EFC behaviour of some new 7XXX aluminium alloys.
The mechanisms of EFC generally involve some type of mechanical wedging stresses, created by the precipitation of aluminium
chloride/oxy-chloride complexes, which have higher molar volumes than that of aluminium [12]. This precipitation occurs along
grain boundaries and may cause the surface grains to lift up [13].
Other possible mechanisms, such as stresses caused by hydrogen
bubbles or hydrogen embrittlement are barely taken into consideration, despite the fact that hydrogen originating from the cathodic
reaction in an acidic electrolyte can be absorbed by the aluminium
matrix, inducing then a degradation of its mechanical properties
[1417]. Therefore, the question arises whether hydrogen generated by the cathodic reaction may also contribute to EFC through
the mechanisms described in the literature [18,19].
In terms of experimentation, various procedures have been proposed to assess the susceptibility of aluminium alloys to EFC. Alloy
and aircraft manufacturers commonly use tests such as those set
forth in ASTM G66, ASTM G85, and ASTM G34 (the so-called EXCO,
i.e. exfoliation corrosion, test) [2023]. However, most of these
tests, although widely accepted, yield only qualitative results.
The EXCO test, for instance, is based on the visual examination of
a surface corroded in an acidic medium. Thus, a method that would
provide a quantitative assessment of EFC sensitivity would be
useful to optimise alloys and tempering and to predict lifetimes
[11,24].
This study is an attempt to better understand the EFC mechanisms at work in 7XXX aluminium alloys with different heat
treatment histories, including the standard industrial tempers T6
(used to maximise metal hardness) and T76 (used to improve
EFC resistance). It examines the electrochemical transients
observed in chloride-based electrolytes at open circuit potential
(OCP), or under galvanostatic, and in some cases under potentiostatic conditions. OCP measurements are advantageous in that they
135C
15C/min
As received:
6h at 120C
12h
24h
48h
96h
T6
~130h
T76
Fig. 1. Ageing heat treatments used in the present study: various durations all at
135 C, following an initial 6-h ageing phase at 120 C. The T6 and T76 tempers
correspond, respectively, to 12 and 96 h at 135 C, and will be the focus of this
paper.
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Fig. 2. Diagram of the two specimens taken from the sheet of metal. The arrows indicate the surfaces tested during the galvanostatic experiments. The acronyms L/LT and ST/
LT stand for longitudinal/long-transverse and short-transverse/long-transverse.
im
(a)
(b)
ZRA
Crevice
sample
V1
PMMA support
V2
Fig. 3. (a) Diagram of the experimental setup with two working electrodes (subscripts 1 and 2) connected through a low resistance ammeter (ZRA). im is the measured
current through the ammeter and V1 = V2 = V is the measured potential; (b) a diagram of the screw/wing system of the articial crevice assembly.
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-708
-709
V(t)
-710
4
-711
incubation time
I(t)
Potential (mV/SCE)
Intensity (A)
equal to that obtained at the end of the EXCO test [2629] and also
corresponds to that of the crack tip solution measured during the
environmentally-assisted cracking of alloy AA7050 [30]. Preliminarily experiments were conducted to optimise the applied current
IG, in order to reduce experimental time and achieve noticeable
exfoliation corrosion morphologies. The IG value of 2.5 mA was
subsequently used for all experimentation.
3. Results
3.1. Open circuit testing
-712
0
-713
0
20
40
Time (h)
60
Fig. 4. Current and potential transients occurring during the OCP measurements of
the T6 specimen in the 1 M NaCl, 0.25 M NaNO3 electrolyte. Exfoliation corrosion
occurs after 20 h of incubation.
Fig. 5. SEM image of the T6 specimen with the articial crevice assembly, after 48 h
of immersion in the 1 M NaCl, 0.25 M NaNO3 electrolyte at open circuit potential.
used was based on that of the OCP measurements and was supplemented by 0.033 M AlCl3 in order to buffer the variation of Al3+ cations and to hold the pH stable at 3.2. This value is approximately
Fig. 6. SEM images of the early stages of exfoliation corrosion on the T6 specimen obtained during the OCP tests. Blisters generally take the form of protuberances as shown
in the close-ups.
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Potential (mV/SCE)
(a) -600
-640
T6
-680
T76
-720
0
12
Time (h)
(b)
Potential (mV/SCE)
-620
3 min
T6
Fig. 9. Potential recorded during the galvanostatic experiments carried out for heat
treatments ranging from peak-aged temper T6 to over-aged temper T76. The details
for the heat treatments are shown in Fig. 1.
-640
-660
4000
T76
8000
8100
8200
8300
Time (s)
8400
8500
Fig. 7. (a) Evolution of the measured potential during the galvanostatic experiments for both the T6 and T76 specimens. Note the large uctuations in potential
for the T6 specimen, as illustrated in close-up (b).
3.2
Intensity (mA)
2.8
-620 mV/SCE, T6
2.4
1.5 min
3.42
Time (h)
3000
2000
1000
0
10
100
Overaging time (h)
Fig. 10. Impact of the ageing time on the total number of transients greater than
2 mV (threshold) recorded during the 24 h galvanostatic experiment.
3.38
Cumulative transients
-680
3.44
Fig. 8. Transient current recorded during the potentiostatic tests for the T6 and T76
samples.
After the galvanostatic treatment, the specimens were immersed for 24 h in a large volume of pure water before being observed with SEM. Fig. 11 shows the cross sections of the T6 and
T76 specimens after 90 min of galvanostatic testing. The corrosion
morphologies are signicantly different; they are quite localised
for the T6 temper specimen, and more uniform for the T76 temper
specimen. The corrosion is deeper for the T6 specimen: 100 lm
below the surface of the sample, compared to 50 lm for the T76
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Fig. 11. (a) FEG-SEM images of a cross section of the T6 sample after 3/2 h of galvanostatic testing, evidencing long inter-granular cracks with non-dissolved precipitates
(indicated by arrows) revealed using the chemical contrast imaging mode; (b) FEG-SEM images of a cross section of the T76 sample after 3/2 h of the same test, evidencing
more diffuse inter and inter-sub-granular corrosion.
(b) 3000
(a)
a)
T6
2400
1800
1200
T76
600
10
20
30
Time (h)
40
50
Fig. 12. (a) Illustration of the corrosion depths measured on the cross sections of both the T6 and T76 samples for statistical analysis of EFC kinetics. (b) Variation of the mean
value as a function of time.
though there were less events than in the longitudinal tests (L/LT
plane). SEM images of the cross section reveal band-like corrosion
zones with some long inter-granular cracks (200300 lm) that extend far into the unaffected metal (Fig. 13). Moreover, when these
samples were aged under air (50% humidity ratio) after the test,
cracks still propagated in the rolling direction until they crossed
the whole sample after 15 days, as shown in Fig. 14a. Fractographic
investigations (Fig. 14b, and images at a higher magnication in
Fig. 14c and d) show that the damage consists of mostly brittle, inter-granular cracks with no evident corrosion attack.
4. Discussion
Our results show that the appearance of exfoliation corrosion,
either under OCP conditions underneath an articial crevice or under galvanostatic or potentiostatic control, systematically correlates with the presence of well-dened voltage or current
transients. The magnitude of these transients, as well as their
amplitude, is shown to be a major parameter that parallels improved EFC susceptibility when prolonging heat treatment beyond
T6. For the future, this type of measurement opens the door to the
quantitative evaluation of EFC susceptibility for a wide range of alloys and corrosion media. However, it is rst necessary to understand the mechanisms giving rise to these transients and their
relation to exfoliation events.
Fig. 13. SEM images of a cross section (on the L/ST plane) of the T6 sample after a
brief period (6 h) of transverse galvanostatic testing. Note the band-like form of the
selective dissolution along grain boundaries.
1399
mely fast once grain boundary strength is exceeded, creating sudden contact between the electrolyte and the fresh metallic surface,
promoting in turn the dissolution of the aluminium matrix. Such
an elementary crack advancing step is expected to be at the origin
of the transients, e.g. the intense electrochemical activity observed
during the galvanostatic measurements. The transients can be
regarded as the triggering response of the experimental setup to
a crack occurrence, and the gradual return of the potential to a
steady state value as the result of the formation of aluminium chloride/oxy-chloride complexes [35,36] on the bare surface thereby
limiting the anodic dissolution kinetics.
The question remains as to whether the stresses causing these
cracks are due to the volumic effect of solid corrosion products.
No such corrosion products were observed in the experiments
reported here, thus suggesting the possibility of a hydrogen effect.
In the acidic medium formed in a corrosion zone due to the
hydrolysis of the aluminium cations, Al dissolution is likely
accompanied by hydrogen emissions, depending on the local pH
and potential at the bottom of the corroding zone [37]. Hydrogen
bubbling was, in fact, clearly visible during and after each test.
The molecular recombination of these hydrogen atoms at or near
grain boundaries is assumed to generate enough pressure to induce crack initiation. This scenario would be consistent with the
fact that very long and extremely thin cracks are observed far
from the corrosion location (in locations where it is highly unlikely that uplifting mechanical stresses due to corrosion products
would be have much effect). However, most importantly, it would
be consistent with the observation that similar cracks are
observed when corrosion proceeds along the long direction of
the grains normal to the surface of the sample, in which case no
signicant external stress is exerted on the grain boundaries by
the corrosion products. Lastly, if a hydrogen evolution reaction
is behind the local stress producing the cracks, it is signicant that
the presence of a crevice, known to produce local acidication,
was found to favour EFC initiation in a nearly neutral electrolyte
under open circuit conditions.
Fig. 14. (a) Images of a cross section of the T6 sample after 6 h of transverse galvanostatic testing followed by 30 days under air (50% humidity ratio), showing the extension
of thin cracks throughout the entire sample; (b) shows the fractograph after fracturing the sample in (a); (c) and (d) are magnications of (b).
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Acknowledgements
C. Henon (Alcan), T. Warner (Alcan) and M. Reboul (SIMAP) are
warmly thanked for stimulating discussions.
References
[1] R. Develay, Traitements thermiques des alliages daluminium in Techniques
de lingnieur, M1290, M1291.