Corrosion Science 52 (2010) 2489–2497

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

The behaviour of second phase particles during anodizing of aluminium alloys

M. Saenz de Miera, M. Curioni *, P. Skeldon, G.E. Thompson
Corrosion and Protection Centre, School of Materials, The University of Manchester, P.O. Box 88, Manchester, M60 1QD, UK

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

Article history: Several model second phase particles and a practical alloy (AA7075-T6) have been anodized in chromic
Received 28 January 2010 and sulphuric acid to disclose the relation between particle composition, electrolyte nature and oxidation
Accepted 31 March 2010 behaviour. Generally, magnesium-containing second phases are readily oxidized, because the presence of
Available online 8 April 2010
sufficient magnesium hinders the formation of a stable oxide, while copper- and iron-containing particles
oxidize at reduced rates and support a relatively stable oxide. At low potential, in chromic acid, the oxi-
Keywords: dation rate of magnesium-containing particles is reduced, due to passivation induced by chromate
A. Aluminium
anions. Conversely, for particles containing only copper and/or iron, chromate anions increase the oxida-
A. Intermetallics
B. SEM
tion rate.
B. TEM Ó 2010 Elsevier Ltd. All rights reserved.
C. Anodic films
C. Oxide coatings

1. Introduction chromate species to provide corrosion inhibition to the aluminium

High strength aerospace aluminium alloys are engineered for a
combination of mechanical properties achieved by tailoring the
metallurgical microstructure through addition of copper and zinc
as primary alloying elements, and suitable heat treatment. How-
ever, such alloys are susceptible to localized corrosion through
microgalvanic coupling between the different metallurgical phases
developed. Local electrochemical studies [1–3] on various alloys
indicate that second phase particles containing only elements no-
bler than aluminium are generally cathodic compared with the
surrounding matrix and constitute preferential sites for corrosion
initiation [4]. Second phase particles that also contain magnesium
are generally anodic with respect to the matrix, but their behaviour
may be affected by the electrolyte pH [5]. In neutral or acidic, chlo-
ride-containing electrolytes, Al–Cu–Mg-containing particles may
undergo preferential dissolution or de-alloying [6]. Following
de-alloying, copper-rich residues, generated on the alloy surface,
provide active sites for the cathodic reaction [6,7].
In order to reduce corrosion susceptibility, the alloy is generally
anodized in acidic electrolytes and, subsequently, painted with an
inhibitor-loaded primer and a polymeric topcoat. Concerning the
anodizing process, chromic acid anodizing (CAA) has proven to
be highly effective in generating porous oxide films with outstand-
ing anticorrosion properties [8–10], which are also suited as a base
layer for both paints and adhesives [11,12]. The outstanding anti-
corrosion performance following CAA is due to the capability of
* Corresponding author. Tel.: +44 1613065971; fax: +44 1613064865.
E-mail address: michele.curioni@manchester.ac.uk (M. Curioni).
alloy at anodic and/or cathodic sites [13,14]. When chromate ions
are available in the vicinity of the alloy surface, they form a protec-
tive film, which heals defects present after surface treatment
[15–17]. Additionally, chromate and dichromate oxyanions reduce
the zeta potential of the anodic aluminium oxide film, restricting
chloride adsorption and associated weakening of the Al–O bonds
[18]. Further, unlike sulphuric or phosphoric acid based anodizing
baths, CAA does not impact significantly on the fatigue life of the
aerospace components [19].
Localized phenomena that occur during anodizing, at and in
the zone of influence of second phase particles, are important con-
tributions to the performance of the filmed alloy [20] and have
been investigated widely. Guminski et al. [21] generated various
large second phase particles by slow cooling of appropriate binary
alloys and investigated their anodizing behaviour in oxalic acid.
They found that Mg2Si, CuAl2, b-AlMg and CrAl7 particles oxidized
faster than the surrounding alloy matrix, while FeAl3 particles oxi-
dized at a similar rate and TiAl3, NiAl3 and MnAl6 particles oxidize
at reduced rate. Similar studies were performed by Cote et al. dur-
ing potentiostatic anodizing in sulphuric acid [22], disclosing that
MnAl6 particles were relatively inert and were sometime occluded
in the oxide, while FeAl3 particles oxidized approximately at the
same rate as the matrix, and CuAl2 and AlZnMg particles oxidized
faster than the matrix. Keller et al. found that CrAl7 and b-AlFeSi
particles oxidized at approximately the same rate as the matrix
when anodized galvanostatically in sulphuric acid [23,24]. Frati-
la-Apachitei et al. [25] studied the behaviour Al–Fe, Al–Fe–Si
and Al–Cu containing particles produced in cast Al 99.80 wt.%,
Al–10 wt.% Si and Al–10 wt.% Si–3 wt.% Cu alloys during anodizing

0010-938X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2010.03.029
2490 M. Saenz de Miera et al. / Corrosion Science 52 (2010) 2489–2497
in relatively concentrated sulphuric acid at 0 °C. They found that
oxygen evolution accompanied the anodizing process [26] and
that Al–Fe and Al–Fe–Si containing particles were relatively inert
and protruded into or were occluded in the oxide; Al–Cu contain-
ing particles oxidized preferentially to produce flawed oxides [26].
Brown et al. [27] investigated the anodizing behaviour of the
Al3Ni second phase in phosphoric acid, observing major changes
in the film morphology on the second phase particle, compared
with the surrounding matrix, and oxygen evolution. Dim-
ogenontakis et al. related oxygen evolution observed during anod-
izing of an AA2024-T3 alloy in borate solutions with localized
phenomena occurring on second phase particles. More recent
studies [28–30] on aerospace alloys indicated that second phase
particles oxidized at a higher or lower rates than the matrix,
depending on the anodizing potential, the particle composition
and the electrolyte nature. Specifically, Al–Cu–Mg-containing par-
ticles were selectively dissolved by relatively small anodic polari-
zation in sulphuric acid electrolytes [30] , but additions to the
anodizing electrolyte, such as tartaric acid, significantly influenced
this process [29]. Conversely, Al–Cu and Al–Cu–Fe-containing
particles, were relatively inert compared with the matrix at low
potential, but oxidized preferentially when the alloy was polar-
ized above 5–6 V(SCE) [28,30].
Table 1
Nominal composition of AA7075-T6 alloy in weight %.
Alloy Zn Cu Mg
7075-T6 5.1–6.1 1.2–2.0 2.1–2.9
Fig. 1. Scanning electron micrographs of the AA7075-T6 alloy (a, c and e) after etching/desmutting and (b, d and f) after anodizing in 0.4 M sulphuric acid for 90 s at
5 mA cm 2 (e and f are reported from Ref. [13]). Elemental analyses of second phase particles are given in Table 2.
If a porous anodic oxide is formed above a second phase
particle, it is generally less regular than the film generated under
similar conditions on relatively pure aluminium due to the for-
mation of flaws within the oxide [31] associated with oxygen
evolution within the barrier layer during anodizing [32–34].
For this reason, the anodic oxides generated on second phase
particles generally provide reduced protection compared with
oxides formed on the surrounding matrix. From the previous, it
is evident that, for successful implementation of protective anod-
izing treatments, knowledge of the anodic oxidation behaviour of
second phase particles with respect to the surrounding alloy
matrix is critical as well as understanding of the properties of
the oxides covering the second phases. In the present study,
the surface microstructural modifications induced by anodizing
model and practical alloys in two different anodizing electrolytes
have been studied. Specifically, the effect of the anodizing
electrolyte on the electrochemical and filming behaviour of the
second phase particles was investigated by anodizing model sec-
ond phase particles obtained by magnetron sputtering, while
variations of the distribution and surface area of second phase
particles present on the surface of a practical alloy (AA7075-
T6) were examined by field emission gun-scanning electron
microscopy (FEG-SEM).
Cr Fe Si Mn Ti Other
0.18–0.28 0.50 0.40 0.30 0.20 0.5Zr + Ti
 M. Saenz de Miera et al. / Corrosion Science 52 (2010) 2489–2497 2491

2. Experimental NaOH solution for 120 s at 313 K and subsequently desmutted in

4.7 M HNO3 for 15 s at room temperature. Anodizing of the
Aluminium AA7075-T6 alloy specimens, of nominal composi- AA7075-T6 specimens was undertaken at 5 mA cm 2 , in stirred
tion given in Table 1, were ultrasonically degreased for 3 min in 0.4 M sulphuric acid at 295 K (pH 1.51) or in 0.25 M chromic acid
acetone and subsequently for 3 min in ethanol (90 vol.%). After electrolyte at 313 K (pH 1.128) for 90 s in a 2-electrode cell with
degreasing, the specimens were individually etched in 20 g l 1 a large platinum mesh counter electrode. Following anodizing,
the specimens were rinsed and dried. The current density of
5 mA cm 2 ensured the generation of a well-developed porous
Table 2
anodic oxide in both electrolytes and enabled qualitative compar-
Elemental analyses of second phase particles after etching/desmutting (AE) and after
anodizing (AA) in sulphuric acid (particles 1–10) and in chromic acid (particles 11–18). ison of the anodizing behaviour. Field emission gun-scanning elec-
tron microscopy (Phillips XL-30 FEG-SEM) observation, with
IMC # Cu (at.%) Fe (at.%) Mg (at.%) Si (at.%) O (at.%)
energy dispersive X-ray analysis (EDX), was carried out on selected
AE AA AE AA AE AA AE AA AE AA areas of the alloy specimens prior to and after anodizing to evalu-
1 3.6 0.8 14.0 4.6 1.3 0.7 2.8 1.6 – 57.5 ate the changes in morphology and composition of the second
2 25.1 – – – 25.4 – – – – – phase material located at the alloy surface.
3 4.3 1.2 16.3 5.4 2.2 0.9 – – – 58.4
In order to simulate the behaviour of selected second phase
4 4.4 1.7 16.3 7.1 2.5 1.2 – – – 50.0
5 3.5 1.8 11.6 5.0 1.7 1.8 – – – 35.5
particles, macroscopic model specimens of specific compositions
6 3.2 1.7 14.2 6.2 2.4 1.2 – – – 49.7 were prepared by magnetron sputtering, as described elsewhere
7 30.2 – 16.4 – – – – – – – [28]; such specimens are termed model second phase particles.
8 30.0 – – – 16.1 – – – – – The selected compositions of the model second phase particles,
9 2.2 0.8 11.1 4.7 – – 1.8 0.9 – 57.5
determined by EDX and RBS analyses, are Al–30 at.% Cu, Al–17 at.%
10 – – – – 1.5 – 32.3 29.1 42.3 53.4
11 13.2 – 7.0 – – – – – – – Cu–7 at.% Fe, Al–25 at.% Cu–25 at.% Mg, Al–28 at.% Fe, Al–25 at.%
12 3.5 – 14.8 – 0.9 – – – 18.3 – Mg and Al–7 at.% Fe. A sputtered Al–5 at.% Cu alloy, representative
13* 1.1 1.8 14.3 13.2 0.9 – 4.1 3.9 – 12.7 of a copper-containing aluminium matrix, was also prepared. The
14 1.9 1.4 14.6 11.0 – – 4.2 3.0 – 25.8
first three model second phase particles are designated Al2Cu, Al7-
15 23.4 – – – 18.9 – – – 7.3 –
16 2.8 0.9 14.8 3.2 1.3 – – – – 63.9
Cu2Fe and Al2CuMg, respectively. Anodizing of the model second
17 – – – – 1.4 1.3 24.6 25.1 44.7 47.8 phases was undertaken under the conditions previously detailed
18 2.9 1.5 18.7 9.6 – – – – – 33.7 as well as potentiodynamically at 297 K, employing a Solartron
1280 potentiostat and a 3-electrode cell, with a potential scan from

Fig. 2. Scanning electron micrographs of the AA7075-T6 alloy after etching/desmutting in 20 g/l NaOH for 2 min followed by 15 s in 4.7 M HNO3. Elemental analyses of
second phase particles are given in Table 2.
2492 M. Saenz de Miera et al. / Corrosion Science 52 (2010) 2489–2497
0.4 V below the open circuit potential (OCP) to 12 V vs saturated
calomel electrode (SCE). When commercial or model aluminium al-
loys are anodized under potentiodynamic conditions, potential
dependent and time dependent processes may overlap [35], result-
ing in current responses dependent on the sweep rate [30,35]. In or-
der to identify the characteristic potentials associated with
generation, modification, or disruption of oxide layers, low sweep
rates are generally preferred because processes displaying some
time dependence can proceed in a near-to-equilibrium condition,
and the direct relationship between current and potential can be re-
vealed. However, in the present work, the thickness of the model al-
loy layer was of a few hundred nanometers, due to the limited
thicknesses of the alloy films produced by magnetron sputtering.
Therefore, based on previous works [28,30,35] and preliminary
tests, a sweep rate of 2 V min 1 was selected for all the experiments
since it was sufficiently low to obtain reliable responses and suffi-
ciently high to guarantee an appropriate potential scan prior to con-
sumption of the sputtered layer due to the anodic current. Cross-
sections of selected galvanostatically anodized specimens, pre-
pared by ultramicrotome to a nominal thickness of 15 nm, were
examined in a JEOL 2000 FX II transmission electron microscope.
Compositions of model second phase particles and anodic oxides
were determined by RBS using 1.7 MeV He4+ ions supplied by the
Van de Graaff accelerator of the University of Paris. The ion beam
was incident normal to the specimen surface, with scattered ions
detected at 165° to the direction of the incident beam. The RBS data
were interpreted using the RUMP program [36].
Fig. 3. Scanning electron micrographs of the AA7075-T6 alloy after anodizing in 0.25 M chromic acid at 5 mA cm
particles are given in Table 2.
3. Results
3.1. Modification of the surface microstructure after anodizing
Characterization of second phase particles present in the
AA7075-T6 alloy after etching and desmutting was undertaken
by FEG-SEM, with the typical surface shown in Fig. 1(a, c and e).
From energy dispersive X-ray analysis (EDX), on average (Table
2), 52% of the revealed particles contained copper and iron, 42%
contained copper and magnesium and 7% displayed a composition
close to silicon oxide (SiO2). The modification of the surface micro-
structure after anodizing in sulphuric acid is evident in Fig. 1(b, d
and f), with the following general observations: all Al–Cu–Mg-con-
taining particles, such as particles 2, 7 and 8, were removed by
anodizing in sulphuric acid (independent of their size); coarse
Al–Cu–Fe-containing particles (e.g. particles 1 and 4–6) remained
on the surface, although with reduced dimensions. After sulphuric
acid anodizing, the surface area of the second phases particles was
reduced to approximately 55% of their original area and the num-
ber of particles was reduced by about 53%. Before chromic acid
anodizing (Fig. 2), the second phase particles revealed on the spec-
imen surface again included Al–Cu–Fe-containing particles (64%),
Al–Cu–Mg-containing particles (34%) and silicon oxide particles
(2%). The reduction in second phase surface area after CAA was
about 80%, with approximately 82% of particles being removed
(Fig. 3). The behaviour in the two electrolytes is now investigated
further by study of the model second phase particles.
2
for 90 s at 313 K. Elemental analyses of second phase
 M. Saenz de Miera et al. / Corrosion Science 52 (2010) 2489–2497
Fig. 4. Potentiodynamic polarization curves (scan rate: 2 V min 1) for model Al2Cu,
Al7Cu2Fe, Al–28 at.% Fe and Al–7 at.% Fe second phase particles during anodic
oxidation in 0.25 M chromic acid (CAA) at 313 K and in 0.4 M sulphuric acid (SAA)
at 297 K to 12 V(SCE).
Fig. 5. Potentiodynamic polarization curves (scan rate: 2 V min 1) for model Al–
5 at.% Cu, Al2CuMg and Al–25 at.% Mg second phase particles during anodic
oxidation in 0.25 M chromic acid (CAA) at 313 K and in 0.4 M sulphuric acid (SAA)
at 297 K to 12 V(SCE).
3.2. Potentiodynamic polarization behaviour
Potentiodynamic polarization curves of model second phase
particles, prepared by magnetron sputtering to give compositions
close to those identified in Table 2, namely Al2Cu, Al–28 at.% Fe,
Al7Cu2Fe, Al–25 at.% Mg, Al2CuMg and Al–5 at.% Cu, recorded in
0.25 M chromic acid at 313 K and 0.4 M sulphuric acid at 297 K,
are presented in Figs. 4 and 5. In both figures, the potentiodynamic
behaviour of a magnetron sputtered Al–5 at.% Cu alloy is reported
as representative of an alloy matrix containing copper as an alloy-
ing element in solid solution. It is revealed immediately that all the
model second phase particles display significantly higher anodic
currents compared with the alloy matrix. As revealed in Fig. 4,
the oxidation behaviour of the model second phases containing
copper and/or iron was similar in chromic and sulphuric acids.
Generally, the current densities were slightly higher for anodizing
in chromic acid, with the difference between the values decreasing
as the relative content of iron increased in the second phase parti-
2493
Fig. 6. Transmission electron micrographs of anodized model (a) Al2Cu, (b)
Al7Cu2Fe and (c) Al–28Fe second phase particles in 0.4 M sulphuric acid (SAA) at
5 mA cm 2 for 90 s at 295 K.
cle. Conversely, the anodic oxidation behaviour of the magnesium-
containing model second phases was affected significantly by the
anodizing electrolyte, as evident from Fig. 5. Specifically, for the
sulphuric acid electrolyte, the anodic current increased approxi-
mately linearly with potential from the OCP until the sputtered
layer was fully consumed. Conversely, for chromic acid anodizing,
a relatively low anodic current was measured for an extended po-
tential region above the OCP and, subsequently, the current in-
creased rapidly to values higher than those revealed for the
alloys anodized in sulphuric acid electrolyte.
3.3. Transmission electron microscopy
Transmission electron micrographs of ultramicrotomed sec-
tions of the Al2Cu, Al7Cu2Fe and Al–28 at.% Fe model second phases
after galvanostatic anodizing at 5 mA cm 2 in sulphuric acid for
2494 M. Saenz de Miera et al. / Corrosion Science 52 (2010) 2489–2497

2
Fig. 7. Transmission electron micrographs of anodized model (a) Al2Cu, (b) Al7Cu2Fe and (c) Al–28Fe second phase particles in 0.25 M chromic acid (CAA) at 5 mA cm for
90 s at 313 K.

90 s displayed thin anodic films of relatively uniform thickness,

with an internal sponge-like appearance; fine pores passing per-
pendicularly to the alloy surfaces were not readily resolved
(Fig. 6). The anodic films appeared to be more compact as the rel-
ative content of iron in the model second phase particles increased.
Further, disruption of the anodic film and detachment of the film
from the Al2Cu substrate were frequently observed during TEM
observations. It is thus probable that oxygen gas generation and
evolution proceeding during anodizing weakened the oxide
through generation of lateral porosity and subsequent film rupture
and loss of oxide fragments to the anodizing electrolyte. The anodic
films developed on the selected model second phase particles after
anodizing in 0.25 M chromic acid at 313 K were similar to those
generated in sulphuric acid (Fig. 7). However, the anodic oxides
were generally thinner than those formed during sulphuric acid
for the same charge passed. The anodic film thicknesses developed
on the model Al2Cu, Al7Cu2Fe and Al–28 at.% Fe particles were
respectively 33, 29 and 60 nm for anodizing in chromic acid
and 67, 68 and 75 nm for anodizing in sulphuric acid.

3.4. Rutherford backscattering spectroscopy

Fig. 8. Experimental (dots) and simulated (solid line) RBS spectra of a model Al2Cu
second phase particles before (red spectrum) and after (blue spectrum) anodizing in
Rutherford backscattering spectroscopy (RBS) was undertaken 0.4 M sulphuric acid at 295 K. (For interpretation of the references to color in this
on the as-deposited model Al2Cu and Al7Cu2Fe second phases figure legend, the reader is referred to the web version of this paper.)
 M. Saenz de Miera et al. / Corrosion Science 52 (2010) 2489–2497
Table 3
TEM and RBS analyses of model Al2Cu and Al7Cu2Fe model second phase particles after anodizing at 5 mA cm
(CA) at 313 K.
Model alloy Average Charge used Charge Charge due to
TEM for film due to oxygen
thickness formation losses (%)a generation (%)a
(nm) (%)a
SA CA SA CA SA CA SA CA
Al2Cu 67 33 12 4 12 13 76 83
Al7Cu2Fe 68 29 15 9 3 8 82 83
All values are within an accuracy of 5%.
a 2
Percentage with respect to the total charge at 90 s of anodizing, QT = 0.45 C cm
and after anodizing in chromic acid and sulphuric acid electrolytes,
with typical spectra for as-deposited and anodized Al2Cu alloys
shown in Fig. 8. Relevant information calculated from fitting of
the RBS spectra are presented in Table 3. Thus, from RBS, the com-
position and thickness of the model second phase particles, ex-
pressed as atoms cm 2 of aluminium, copper and/or iron, are
obtained before and after anodizing. Subtraction of the previous
values gives the number of atoms cm 2 that are oxidized from me-
tal to cations. RBS also provides the number of cations that consti-
tute the anodic film material; subtracting the number of oxidized
atoms cm 2 from metal to cations and those that comprise the
anodic film gives the losses to the anodizing electrolyte. Such cal-
culations quantify the charge densities consumed by the various
electrode reactions, e.g. anodic film formation, losses to the elec-
trolyte and oxygen generation (Table 3).
As revealed in Table 3, the charge used in forming the anodic
films on the Al2Cu and Al7Cu2Fe model second phase particles by
chromic acid anodizing (CAA) was less (4% and 9%, respectively)
than for anodizing in sulphuric acid (12% and 15%, respectively).
Additionally, there was a higher presence of Cu–O units in the
anodic films formed in CAA compared with the films formed in sul-
phuric acid. Further, typical concentrations of SO24 ions incorpo-
rated into the anodic films developed on all model second phases
were in the range 16–19 wt.%. The previous values are greater than
the levels reported in films formed on high purity aluminium, i.e.
12–14 wt.% sulphate [37], probably due to residual electrolyte
within the relatively disordered film morphology.
4. Discussion
During anodizing of a practical alloy, a protective porous oxide
film is generated above the alloy matrix and the second phase par-
ticles variously present on the alloy surface respond individually to
the electrochemical conditions. This may result in the formation of
a chemically and morphologically modified oxide film above and in
the zone of influence of the specific second phase. The oxidation
behaviour depends on the composition of the second phase parti-
cle and on the electrolyte. Specifically, second phase particles with
high contents of metals with cations that migrate faster than alu-
minium cations across the oxide under the field (for example, Mg
or Li) and are highly soluble in the acidic anodizing electrolyte tend
to form an oxide with very poor adhesion to the metal and voids at
the metal/film interface [38]. In the case of the model second
phases, high amounts of magnesium results in a highly flawed
mixed oxide [38]. Further such an oxide may also be dissolved in
the anodizing electrolyte due to the high solubility of magnesium
oxide in acidic environment if the amount of magnesium cations
is sufficient to prevent the formation of a continuous alumina net-
work. Therefore, locally, the metal can be exposed directly to the
anodizing electrolyte and the high potential available results in a
high rate of consumption.
2495
2
in 0.4 M sulphuric acid (SA) at 295 K and in 0.25 M chromic acid
Density of Film stoichiometry Al2O3
xAl2(SO4)3
yCuO
zFe2O3
anodic films
(g cm3)
SA CA SA CA
1.5 1.0 Al2O3
0.1Al2(SO4)3
0.01CuO Al2O3
2.1 2.2 Al2O3
0.08Al2(SO4)3
0.01CuO
0.07Fe2O3 Al2O3
0.24CuO
0.08Fe2O3
.
Conversely, for the second phase containing metals capable of
forming an adherent oxide with reduced solubility in the anodizing
electrolyte, the rate of consumption of the second phase depends
on the properties of the anodic oxide. The simultaneous oxidation
of aluminium and copper or iron, results in an anodic oxide con-
taining Al–O units together with Cu–O and Fe–O units that display
modified electrical properties. Specifically, an anodic oxide with
high content of non-aluminium atoms can be locally generated
where the oxidation of the copper or irons, enriched at the alloy-
oxide interface, take place. Due to the semi-conductive properties
of Fe–O and Cu–O units, preferential paths for the direct discharge
of the electrons of the oxygen anions are available. Therefore, a
proportion of the inward-migrating oxygen anions lose their elec-
trons and form atomic oxygen within the barrier layer of the por-
ous anodic film. Subsequently, the atomic oxygen combines to
form oxygen gas that generates a gas-filled void, with the develop-
ing oxygen gas pressure eventually increasing to levels sufficient to
rupture the oxide. The rupture of the oxide provides a path for
electrolyte penetration in close proximity of the underlying alloy.
At this location, the high electric field present across the residual
oxide promotes accelerated local growth that progresses until a
new oxygen-filled void is generated and the process is cyclically re-
peated. Overall, this process results in accelerated second phase
particle consumption compared with conditions where a relatively
pure aluminium oxide is generated. According to this view, it is
possible to explain the relatively high anodic current observed
for the oxidation of the model Al2Cu second phase. In this case,
the high amount of copper produces a film which supports vigor-
ous oxygen gas generation and evolution within the oxide, as con-
firmed by the calculations form the RBS data. Oxygen evolution
ruptures the oxide, contributing to the limited film thickness and
to the sponge-like morphology observed by transmission electron
microscopy. As the relative content of copper is reduced and the
relative content of iron is increased, the process of electron dis-
charge is less favoured and, therefore, less oxygen evolution takes
place. This results in a reduced anodic current and in a transition to
a more defined porous oxide morphology, where a barrier layer can
be distinguished from the material constituting the cell walls.
The conclusions drawn for the model second phases are con-
firmed by the anodizing experiments on the practical alloy. Thus,
the magnesium-containing second phase particle are the most
reactive to the anodizing condition and were fully oxidized in both
electrolytes, independent of their initial size. Conversely, the cop-
per/iron-containing second phases, supporting an oxide that was
chemically stable in the anodizing electrolyte, yet cyclically dis-
rupted by oxygen generation and evolution during anodizing, were
partially or completely oxidized depending of their initial size.
From the previous, it is possible to understand the effect of the
electrolyte on the oxidation behaviour of the various second phase
particles. Specifically, variation in the behaviour due to electrolyte
composition is more marked for second phase particles that do not
support a stable oxide film. In this case, due to incomplete alumina
2496 M. Saenz de Miera et al. / Corrosion Science 52 (2010) 2489–2497
film formation, the electrolyte is in direct contact with the metal
and determines the dissolution behaviour. From the potentiody-
namic experiments, it is evident that active dissolution of the
magnesium-containing intermetallics proceeds at all potentials
during polarization in sulphuric acid. Conversely, in chromic acid
electrolyte, reduction of chromate may occur on the surface during
the early stages of immersion and, consequently, a protective outer
layer is formed, below which a passive film develops readily during
the potentiodynamic polarization, since it does not contact the
electrolyte. However, at relatively high potential, the chromate-
containing passive layer on the second phase surface is disrupted
under the high electric field and cannot prevent the active dissolu-
tion, as evident from the potentiodynamic polarization behaviour.
For second phase particles supporting a stable oxide, the effect of
the anodizing electrolyte is less marked. This is due to the more
complex oxidation regime, which involves formation of oxide
and oxygen generation within it, leading to local rupture. There-
fore, there is no direct contact between the oxidising surface and
the anodizing electrolyte and, consequently, the interaction is lim-
ited. However, from observation of the practical alloy, where the
reduction in intermetallic size and number is more marked after
CAA than SAA, and consideration of the potentiodynamic polariza-
tion behaviour, where the currents recorded for polarization in the
chromic acid electrolyte are generally higher than those recorded
in the sulphuric acid electrolyte, it can be concluded that for
second phases supporting a relatively stable oxide film chromic
acid increases the oxidation rate and, therefore, acts as a mild oxi-
dation promoter.
From the practical viewpoint, the nature of the electrolyte is not
critical in determining the oxidation behaviour of magnesium-con-
taining second phases on conventional alloys because the applied
voltage in industrial processes is generally sufficiently high to trig-
ger their preferential dissolution during the very early stages of
anodizing. Conversely, the capability of chromate to promote the
oxidation of copper and/or iron-containing second phases is bene-
ficial to the anticorrosion performance because it reduces the num-
ber and extent of potentially active cathodic sites present on the
alloy surface after anodizing. For this reason, the capability of pro-
moting second phases oxidation should be maintained by candi-
date environmentally-friendly electrolytes.
5. Conclusions
The behaviour of model and real second phase particles present
in a pretreated alloy and the relationship between second phase
composition, electrolyte nature and oxidation behaviour have been
investigated. Concerning the composition, magnesium-containing
second phases, are more readily oxidized compared with second
phases containing only aluminium and copper and/or iron. This
was attributed to the absence of a stable oxide above the magne-
sium-containing second phases which results in direct metal disso-
lution. Further, the oxidation behaviour of second phases
supporting stable oxides was related to the oxide properties. Spe-
cifically, the rate of second phase particle consumption increased
with copper content due to increase of oxygen evolution and asso-
ciated cyclic disruption of the anodic oxide. Concerning the effect
of the electrolyte, the presence of a passivating ion, such as chro-
mate, significantly affects the oxidation behaviour of the magne-
sium-containing second phase particles, by producing an
extended passive region prior to the onset of active dissolution.
Conversely, for the second phases containing only copper and iron,
the effect of the electrolyte composition was less marked. This is
attributed to the presence of a stable oxide film between the sec-
ond phase and the electrolyte which prevents direct contact be-
tween the chromate species and the oxidising metal.
Acknowledgement
EPSRC is acknowledged for provision of financial support
through the LATEST Portolio Partnership.
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