Electrochimica Acta 49 (2004) 1675–1685

The role of chromate in filiform corrosion inhibition夽

J. Vander Kloet, W. Schmidt, A.W. Hassel∗ , M. Stratmann
Max-Planck-Institut für Eisenforschung GmbH, Max-Planck-Strasse 1, 40237 Düsseldorf, Germany
Dedicated to Professor J.W. Schultze on the occasion of his 65th birthday and retirement from the Heinrich-Heine University in Düsseldorf.

Abstract

This paper is part of a study on filiform corrosion (FFC) on aluminum alloy 2024-T3 and focuses on the surface characterization of corroded
samples. Untreated samples were used as well as samples which had undergone pretreatments including polishing, surface etching and
chromated conversion coatings (CCC). These samples were coated with both pigmented and non-pigmented epoxy-based coatings. Scanning
electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS)
analysis were used to investigate the nature of the surface as well as optical images to gauge the rate of FFC advancement. FFC corrosion rates
decreased on samples which had received a surface etching pretreatment and a chromate conversion coating. Pigmented coatings reduced the
rate of FFC further and led to two different types of corrosion surface morphology. On pretreated samples, the corrosion appeared deeper and
pit-like, possibly due to an enhanced polymer-substrate bond. On untreated samples, widespread FFC developed. SEM and EDX analysis
of various intermetallic particles (IMPs) on all samples, inside and outside of corroded regions, revealed that Cr from pigments was found
deposited on Cu-containing intermetallics in corroded areas while Fe/Mn-containing particles were free from all pigment traces. These results
suggest that the Cr deposition on Cu particles hinders the cathodic reduction of oxygen necessary for FFC advancement. For this reason,
the coating pigments proved, under FFC conditions, to be a more effective inhibitor than the Cr originating from a chromate conversion
coating.
© 2003 Elsevier Ltd. All rights reserved.

Keywords: Aluminum alloy 2024-T3; Filiform corrosion (FFC); Chromate conversion coatings (CCC); Chromate pigments; Intermetallic particles

1. Introduction
Filiform corrosion (FFC) is a thread-like, superficial cor-
rosion which advances on metal surfaces under coatings [1].
The filiform filament contains two major features: (1) a head
containing both a local anode and a local cathode and (2) a
tail. The FFC propagates by an anodic undermining of the
surface which arises due a differential aeration cell within
the filiform head [2]. Oxygen is reduced at the local cath-
ode (back of FFC head) while the metal dissolution takes
place at the local anode (front of FFC head). On aluminum
alloys, the coupling of intermetallic particles (IMPs) to the
Al substrate leads to differences in potential and therefore
the IMPs may act as local cathodes.
The appearance of FFC arises due to a complicated mix-
ture of several factors including: high relative humidity [3],
coating defects where salts may come into contact with ex-
夽 PII of original article S0013-4686(02)00829-0.
∗ Corresponding author. Tel.: +49-211-6792-464;
fax: +49-211-6792-218.
posed metal [1], the presence of IMPs [4,5], the presence of
oxygen [6] and the permeability of the coating to allow for
water diffusion to the active head [6,7]. Furthermore, surface
processing, including rolling and annealing, plays a critical
role in the surface composition and structure which in turn,
greatly affected the alloy susceptibility to FFC [8,9].
Surface pretreatments, such as chromate conversion coat-
ings (CCC) can reduce the extent of FFC. Conversion coat-
ings form as a result of Cr(VI) reduction to Cr(III) while
the aluminum substrate oxidizes in the presence of fluoride
[10]. However, the final oxide retains a small amount of
unreacted Cr(VI) [11]. The mechanism of corrosion protec-
tion by CCC films has been attributed to several factors in-
cluding the inhibition of oxygen reduction kinetics [12], an
increase in film resistance [13] and the presence of Cr(VI)
in the film. The latter may serve as a reservoir to be re-
duced when the aluminum surface is exposed via film cracks
or defects, thereby regenerating the protective oxide film
[10]. However, analytical analysis of corroded AA2024-T3
CCC treated samples have shown that the oxide thickness
and Cr(VI):Cr(III) surface concentration ratio decrease and

0013-4686/$ – see front matter © 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0013-4686(03)00256-1
1676 J.V. Kloet et al. / Electrochimica Acta 49 (2004) 1675–1685
a change in coordination occurs for Cr6+ from hexagonal to
tetrahedral [10,14]. This suggests that in the presence of a
corrosive environment, the effectiveness of the CCC to pre-
vent FFC may be reduced.
Other investigations have indicated that coating adhesion
on CCC treated samples plays an important role in prevent-
ing FFC. A slower growing, deeper FFC morphology on
CCC treated aluminum alloy samples has been attributed to
good wet coating adhesion [15]. A lift angle method has
been used to quantify the mechanical lifting and quality of
the coating adhesion. In this work it was shown that the coat-
ing adhesion was enhanced due to the presence of a CCC,
which also led to deeper, less superficial surface corrosion
[9].
Apart from CCC films, another source of chromate is
coating pigments, specifically SrCrO4 . These pigments are
slightly soluble in water which enables them to diffuse to-
wards active corrosion sites [16]. As far as the authors of
this paper are aware, there are no references in the litera-
ture of FFC studies under pigmented coatings with SrCrO4 .
However, several studies using other pigments have revealed
interesting results. The rate of FFC on aluminum alloys
containing iron or iron and manganese was significantly
lower under pigmented coatings. Impedance measurements
revealed a lower porosity in pigmented coatings which sug-
gests a reduced path for oxygen or water [17]. Furthermore,
a critical pigment volume concentration (CPVC) is needed
to reduce the coating permeability sufficiently such that the
pathway for oxygen and water is hindered [18]. Several al-
loys composed from combinations of Al, Mg, Si and Cu
were coated with a polyurethane coating containing TiO2
pigments. Following the initiation of FFC, the alloy with the
deepest surface attack was the Al–Cu–Mg sample. In the
absence of pigments, the corrosion depth was similar on all
alloy samples [19].
Other corrosion studies with SrCrO4 , either in an artifi-
cial acid rain solution or in an epoxy coating, demonstrated
that these pigments suppress the cathodic reaction on zinc
galvanized steel metal surfaces and increase the metal resis-
tance to electron transfer [20,21]. Furthermore, solution pH
was shown to play an important role as SrCrO4 pigments
leach from coatings only at low pH values, possibly due to
the breakdown of the polymer network structure in the pres-
ence of acid [20].
The intermetallics play an important role as the cathodic
sites for oxygen reduction in the FFC mechanism. The reac-
tion of these intermetallics under corrosion conditions and
in the presence of corrosion inhibitors such as chromate is a
topic of recent research. AES depth profiles have shown that
Cr coating thicknesses originating from a chromate–NaCl
solution are much greater on S-phase particles (Al, Cu, Mg)
than on (Cu,Fe,Mn)Al particles at both low and neutral pH
[22]. Dealloying of S-phase particles was predominant in
NaCl solution at pH 3 while at pH 6, the attack to the matrix
was enhanced. Dealloying was retarded in the presence of
solution chromate. No dealloying occurred on (Cu,Fe,Mn)Al
particles [22]. Potentiostatic dissolution measurements of
synthesized alloy intermetallics containing combinations of
aluminum, iron, manganese and silicon in alkaline solu-
tion indicated that dealloying leading to an Fe surface en-
richment occurs to a greater degree if Mn is absent [23].
Higher manganese concentrations provide better corrosion
resistance since the increased dissolved Mn shifts the matrix
potential cathodically while the increased Mn:Fe ratio in the
IMPs shifts their potential anodically, leading to an overall
lower potential difference between matrix and intermetallics
[24]. The role of aqueous chromate in arresting intermetallic
dealloying of Cu-containing particles is of particular interest
to this work. This paper presents a comparison between the
mobility of chromate originating from a conversion coating
or pigments on samples which have undergone FFC. In an-
other work, surface characterization prior to corrosion has
been studied [25].
2. Experimental
The aluminum alloy samples used throughout this re-
search were AA2024-T3. The alloy composition is given in
Table 1. The AA2024-T3 samples were ground and polished
to 1 ␮m using an ethanol-based diamond paste. These sam-
ples, along with unpolished specimens, were then treated
with Sanchem 500/1000 or with Sanchem 500/1000 and
Alodine 1200S solutions [26]. The Sanchem 500/1000 solu-
tions were used to remove the IMPs from the alloy surface.
Alodine 1200S is a chromating solution, which produces a
CCC on aluminum surfaces. The contents of these solutions
are given in Table 2. Detailed application descriptions can
be found elsewhere [26]. Table 3 lists all samples, which
were investigated.
Aluminum alloy 2024-T3 samples used for filiform inves-
tigations are listed in Table 3 along with the pre-treatments
and the applied coating conditions. All samples were coated
with a mixture of an epoxy polymer (Epon 828, Shell Chem-
ical Co.) and a polyamide curing agent (Epi-cure 3140, Shell
Chemical Co.). When desired, the pigments, 5% SrCrO4 ,
were mixed with the coating compounds. All pre-treatments
and coatings were carried out to model industrial practices
[26].
FFC was initiated by introducing a defect through the
polymer coating on all samples. In this case, a flat, circular
depression was cut through the coating and extended only
negligibly into the substrate itself. A drop of 1.0 M HCl
was placed in the defects and the samples were then stored
at 86% relative humidity until either FFC or other types of
corrosion appeared.
In order to analyze the corroded alloy surface once FFC
had occurred, the coating and corrosion products were re-
moved. The former by ultrasonicating the sample in a chlo-
roform bath for 5 min and the latter by ultrasonicating in a
water–ethanol–triazol–H3 PO4 solution for 5 min. XPS sur-
face analysis revealed negligible traces of phosphorous or
 J.V. Kloet et al. / Electrochimica Acta 49 (2004) 1675–1685 1677

Table 1
Composition (in %) of aluminum alloy 2024-T3
Cu Mg Fe Si Zn Ti Cr Other

AA2024-T3 4.35 1.50 0.50 0.50 0.25 0.15 0.10 0.20

Table 2 element distributions on the sample surfaces. The primary

Contents of pre-treatment solutions ion source was a gallium gun operated at 25 kV. All sam-
Solution Contents ples were pre-sputtered to remove atmospheric depositions
Sanchem 500 Phosphate cleaner with no silicate
and the acquisition time was 6 min.
Sanchem 1000 Sodium bromate in nitric acid
Alodine 1200S Chromic acid ∼60%
Sodium fluoride ∼5–10% 3. Results and discussion
Zirconium potassium ∼5–10%
Potassium fluoroborate ∼30%
Potassium ferrocyanide ∼10–15%
3.1. Optical microscopy

The optical images of samples 1–3, 7–9 (Table 3) follow-

chloride and, therefore, it can be concluded that neither so- ing 35 days of exposure to chloride in a humid environment
lution affected surface analysis significantly by the intro- are shown in Fig. 1a–f. In all six images, the coatings are in-
duction of new contaminants. Since FFC growth rates vary tact. From these images, two things are immediately obvious.
depending on the samples, these removal procedures were Firstly, all samples without pigmented coatings (Fig. 1a–c)
carried out at different times, ranging from 46 to 208 days exhibited typical FFC attack, with more or less long, thin,
storage following FFC initiation. uniform filaments with dark active heads. The growth rates
The techniques used in the analysis of the samples men- for FFC on these samples are shown in Fig. 2. Clearly, the
tioned in Table 3 were optical microscopy, scanning elec- FFC advancement rate decreases as more pre-treatments are
tron microscopy (SEM), X-ray photoelectron spectroscopy applied, but is not completely eliminated.
(XPS) and time-of-flight secondary ion mass spectroscopy Secondly, although minor corrosion attack was observed
(TOF-SIMS). With the exception of the optical images on samples with pigmented coatings (Fig. 1d–f), this attack
recorded, nearly all other measurements presented here does not appear to be FFC, but a blistering effect under-
were those determined for polished samples. The decreased neath the coating. A relatively large amount of corrosion
surface roughness of these samples enabled easier analysis is evident in sample 7 (Fig. 1d). In subsequent trials, both
with the aforementioned techniques. samples 7 and 10 showed significantly more attack when
SEM (CamScan 4, Elektronenoptik, Germany) provided compared with the other samples with pigmented coatings.
detailed images of the surface morphology and, through en- These visual results suggest that corrosion protection is en-
ergy dispersive X-ray (EDX) analysis, IMP compositions hanced not only by a pigmented coating, but rather by such
before and after the various surface pre-treatments as well a coating in combination with Sanchem or with Sanchem
as in and around corroded regions. XPS (Quantum 2000, and CCC pre-treatments.
PHI, USA) measurements provided information on surface
chemical quantities. The source used was monochromated 3.2. SEM
Al. TOF-SIMS (Trift II, PHI, USA) was used to determine
SEM analysis was also performed for both polished and
unpolished samples and the results were nearly identical. In
Table 3
the following sections, the SEM results and discussion will
Samples used in the investigation of FFC on AA2024-T3
be focused on polished samples (4–6, 10–12, epoxy coatings
Samples Polished Sanchem Alodine Pigments removed):
1
2 X
a) with/without pigmented coatings;
3 X X b) with Sanchem pre-treatments with/without pigmented
4 X coatings and;
5 X X c) with Sanchem and CCC pretreatments with/without pig-
6 X X X mented coatings.
7 X
8 X X
9 X X X 3.2.1. No pre-treatments, pigmented coatings
10 X X The corrosion seen on samples 7 and 10 was previously
11 X X X described as blister-like (Section 1). Upon removal of the
12 X X X X
coating and corrosion products from these samples, two
1678 J.V. Kloet et al. / Electrochimica Acta 49 (2004) 1675–1685
Fig. 1. (a–f) Visual results of FFC on unpolished, samples (coating intact) after 35 days storage (a: Sample 1, b: Sample 2, c: Sample 3, d: Sample 7,
e: Sample 8, f: Sample 9) size: 3×3 cm.
types of corrosion were observed. The first was a deeper
form of corrosion found close to the defect and the other was
a shallow, wide-spread corrosion front seen better with the
naked eye than under a microscope. It is also possible that
this corrosion front was simply a jumble of FFC filaments.
In Fig. 3a, a potential FFC head is shown. In SE detec-
tor mode (Fig. 3a), three topographical regions are easily
recognizable: heavily corroded regions (A), lightly corroded
Fig. 2. FFC filament growth rates on samples without pigmented coatings;
a value of ‘20’ indicates a growth rate too fast to be determined by this
method (sample numbers are indicated in their corresponding bars).
regions (B) and uncorroded surfaces (C). In Fig. 3b–d, SEM
image enlargements of the various regions are shown. Since
the dividing boundaries between these regions became in-
distinguishable in BSE detector mode (necessary for EDX
analysis), these boundaries have been drawn onto the images
(Fig. 3b and d). The spots analyzed by EDX are marked in
Fig. 3b–d and the corresponding compositions are provided
in Tables 4 and 5. Spots 1–8, 9–23 and 24–31 correspond
to regions C, B and A, respectively. The EDX results have
led to some interesting observations.
Aluminum and copper were found in all locations since
EDX detected a small amount of the surrounding substrate
matrix in addition to the intermetallic or particle examined.
Small quantities of copper are soluble in aluminum during
the alloying process and are therefore expected also in sub-
strate analysis (spots 22 and 29).
Chloride and Cr were always associated together with
intermetallics containing primarily copper (spots 9, 13–15,
18, 21, 24–26, 28, 30–31). In addition, concentrations of
both elements were higher in regions which were more
heavily corroded (region A, spots 24–26, 30, 31) and the
appearance of Sr at these locations suggests a massive set-
tling of pigment molecules on these IMPs. However, the
resulting Cr coating on these particles is insufficient to
completely inhibit the onset of corrosion. This is best seen
 J.V. Kloet et al. / Electrochimica Acta 49 (2004) 1675–1685 1679

Fig. 3. (a) SEM image of FFC head on Sample 10, approximately 1 cm from defect (SE detector reveals 3 regions: A: heavily corroded regions, B:
lightly corroded regions, C: uncorroded areas). (b) Border between regions B and C (BSE detector). (c) Enlargement from b (BSE detector). (d) Border
between regions A and B (BSE detector, not an excerpt from a).

around particles such as those in spots 14 and 15 where dis-
solution of the Al matrix around the intermetallic is clearly
demonstrated despite the finding of Cr on the particle.
On the other hand, within lightly or heavily corroded ar-
eas, Cr or Sr deposition on intermetallics containing signif-
icant amounts of Mn, Fe and Cu (spots 4, 10, 11, 12, 16,
17, 19, 20, 23 and 27) either did not occur or was too low
in concentration to be detected with EDX. All intermetallics
outside the corroded area (region C) showed no traces of Cr.
3.2.2. Sanchem pre-treated, pigmented coatings
As shown in Section 1, samples 8 and 11 exhibited only
minor corrosion attack. Removal of the pigmented coating
from these samples proved to be very difficult. Following
as much as 1 h exposure to chloroform, only small coating
fragments were removable from regions close to the defect
where corrosion had occurred. This can be clearly seen in
Fig. 4a.
Fig. 4b–d are enlargements of various regions in Fig. 4a.
In both Fig. 4b and c, the alloy surface appears to have been
pushed upwards from below. This may indicate a ‘tunneling’
of the active corrosion [9]. This characteristic was found pre-
dominantly on samples (8, 9, 11, 12) which had a Sanchem
pre-treatment and a pigmented coating. It appears as though
this combination has led to a strengthened polymer–substrate
bond which had, at certain locations, caused the advancing
corrosion to submerge. The corrosion, in general, appears to
attack the substrate much deeper than FFC.
1680 J.V. Kloet et al. / Electrochimica Acta 49 (2004) 1675–1685

Table 4 removed and the corrosion was relatively deep. This deeper,
EDX analysis of spots labeled in Fig. 3b and c pitting-type of corrosion seen in samples 8, 9, 11 and 12
Spot Cl Cr Al Cu Mn Mg Fe Si Sr has also been noted in previous FFC studies of CCC treated
1 0 0 75.0 17.8 1.8 0 5.4 0 0
aluminum alloys where the wet coating adhesion was shown
2 0 0 62.3 22.6 0 15.2 0 0 0 to be very good [15].
3 0 0 79.4 10.6 0 10.0 0 0 0 The chemical analysis of different spots on these samples
4 0 0 79.5 13.9 1.2 0 4.3 0 0 was similar to that described previously in that little to no
5 0 0 77.4 15.3 0 5.1 0 0 0 Cr was deposited onto the intermetallics.
6 0 0 71.5 14.3 0 14.2 0 0 0
7 0 0 83.5 12.0 0.9 0 3.6 0 0
8 0 0 87.4 7.6 0 4.8 0 0 0 3.2.4. No pre-treatments, non-pigmented coatings
9 1.6 2.4 72.4 19.4 1.3 0 2.3 0 0 FFC on samples 1 and 4 proceeded quickly and was very
10 0 0 73.2 16.0 2.9 0 7.9 0 0 shallow as seen in Fig. 5. The EDX analysis of the spots
11 0 0 76.0 12.9 2.7 0 6.7 1.6 0 marked in Fig. 5 is presented in Table 6. In general, there was
12 0 0 82.6 7.9 2.3 0 5.3 1.9 0
13 1.3 3.3 63.8 30.3 0 0 0 0 0
little to no chemical difference between the intermetallics
14 2.4 4.3 74.4 18.1 0 0 ∗ 0 found within or surrounding the FFC filaments. However,
15 0.6 2.0 67.8 28.0 0 0 0 0 0 from this data, it is clearly evident that at least two types of
16 0 0 84.6 10.8 1.2 0 3.5 0 0 metal mixtures were found in the AA2024-T3 alloy: Cu–Mg
17 0 0 74.3 14.1 2.3 0 6.0 2.1 0 and Cu–Mn–Fe. The existence of these two types of inter-
18 0.7 2.2 75.0 18.3 0.8 0 1.5 0 0
19 0 0 80.7 13.8 1.5 0 4.1 0 0
metallics has been confirmed by SEM/EDX investigations
20 0 0 88.0 8.8 0.8 0 2.4 0 0 [27,28].
∗ <0.5%
3.2.5. Sanchem pre-treated, non-pigmented coatings
Fig. 4d and e are enlarged images of shallow ‘stepping The FFC filaments on samples 2 and 5 were very faint
stones’ found in an otherwise uncorroded region. This oc- and easier to observe with the naked eye than with the mi-
currence is somewhat of a mystery, but was seen on a num- croscope. Almost no topographical or chemical differences
ber of other samples as well (1, 4 and 8). The ‘stepping were observed and most particles contained Fe and Mn, as
stones’ bear a remarkable resemblance to the attack of the seen in other Sanchem pretreated samples.
matrix surrounding S-phase (Al–Cu–Mg) particles in aque-
ous NaCl at neutral pH values [22]. 3.2.6. Sanchem and CCC pre-treated, non-pigmented
Chemical analysis showed that most of the large coatings
Cu-containing particles had been removed and that remain- As seen in Fig. 2, FFC was significantly reduced on sam-
ing intermetallics contained predominantly Fe and Mn. ples with Sanchem and CCC pre-treatments (samples 3 and
Insignificant quantities of Cr (no Sr or Cl) were found with 6). The FFC filaments which did appear advanced slowly,
these particles, as explained in the previous section. This but remained shallow. Fig. 6a–d illustrate the topography of
highlights the importance of the Sanchem pretreatment as sample 6 while Table 7 lists the chemical analysis of se-
a method to remove the Cu-containing IMPs which render lected points. Two interesting points arise upon examination
the surface active. of this analysis. First, chromate is primarily located on un-
corroded regions within and outside of the FFC filaments
3.2.3. Sanchem and CCC pre-treated, pigmented coatings (spots 1, 3, 4, 5, 7 and 11). Second, little to no chromate
As described in the previous section, the SEM images was found on exposed intermetallics following FFC (spots
for samples 9 and 12 showed that coatings were not easily 6, 8–10). Topographically, samples 3 and 6 appear different
compared with other samples with shallow FFC. The ap-
Table 5 pearance of corroded ‘pockets’ of approximately equal size
EDX analysis of spots labeled in Fig. 3d and depth supports previous work which described FFC ad-
Spot Cl Cr Al Cu Mn Mg Fe Sr vancement on CCC treated samples as an undermining of
the chrome-oxide layer [9,29]. In those investigations, the
21 3.3 4.6 61.7 30.0 0 0 0 0
22 0 0 96.8 1.8 * 1.1 0 0 chrome-oxide layer was shown to be disbanded with the or-
23 0 0 82.3 12.7 0.9 0 4.0 0 ganic coating. Although no chemical analysis of the coating
24 10.1 14.8 31.5 35.5 0 0 0 4.9 underside was carried out in this work, the surface topog-
25 8.7 11.3 12.5 64.9 0 0 0.5 1.1 raphy and EDX analysis strongly suggest that an oxide un-
26 39.5 19.3 39.5 13.8 0.5 0 0 4.2
∗ dermining has taken place.
27 0 91.9 5.4 0.6 0.9 1.1 0
28 3.7 3.9 80.2 10.8 0.6 0 0 0.5
29 0 0 97.5 2.2 * 0 0 0 3.3. XPS
30 22.5 22.8 38.5 9.4 0.5 0 0 4.0
31 8.2 8.3 44.9 33.8 * 0 0.6 2.1 Of the samples which produced FFC (samples 1–6), two
∗ <0.5% were chosen for XPS analysis: samples 3 and 5. Following a
 J.V. Kloet et al. / Electrochimica Acta 49 (2004) 1675–1685 1681

Fig. 4. (a–e) Corrosion on sample 11 after 208 days storage at 86% RH.
1682 J.V. Kloet et al. / Electrochimica Acta 49 (2004) 1675–1685

Table 7
EDX analysis of spots labeled in Fig. 6c and d
Spot Cl Cr Al Cu Mn Mg Fe

1 0 1.7 88.7 6.8 0.5 0.8 1.2

2 0 1.0 94.9 2.7 * 0.8 0
3 0 1.6 95.1 2.0 * 0.8 *
4 0 1.5 95.1 1.9 * 0.9 0
5 0 * 96.1 2.6 * 0.8 0
6 0 1.4 95.5 1.6 * 1.0 0
7 0 0 92.9 5.4 * 1.0 *
8 0 0 89.2 8.0 0.6 0 2.2
9 0 0 86.5 9.8 0.8 0 3.0
10 0 1.5 95.3 1.9 * 1.0 0
11 0 0 95.4 3.1 * 1.2 0

mating. Iron was also observed in appreciable quantities in

Fig. 5. Corrosion on sample 4 after 46 days storage at 86% RH. the intact region since the chromating solution contains fer-
rocyanide.
The chloride concentrations on both samples, in all loca-
brief sputter time (12 s, corresponding to a 0.5 nm SiO2 stan- tions, were negligible.
dard) to remove microscopic depositions which may have
occurred upon atmospheric exposure, at least two spots were
3.4. TOF-SIMS
analyzed on each of these samples. The percentages of Cr,
Cu, Fe and Al in these two samples are compared in Fig. 7.
TOF-SIMS ion distributions for sample 6 (coating re-
For both samples 3 and 5, analysis of regions in the active
moved, corrosion products present) are shown in Fig. 8a.
FFC head and on the uncorroded surface was carried out.
The images are intended to be used only as evidence for ion
As seen in Fig. 7, the Al–Cu–Fe ratio is relatively constant,
distributions and should not be compared for the purpose of
regardless of whether measurements were taken inside or
drawing conclusions about ion concentrations.
outside of the FFC filament. These results are in agreement
From the images in Fig. 8a, it is readily apparent that
with those presented in the last section which showed little
chloride is found within the active FFC head. TOF-SIMS
chemical difference in the EDX analysis between corroded
high sensitivity to halogens was useful in identifying the
and uncorroded regions.
presence of chloride in an active FFC head, thereby pro-
Fig. 7 also illustrates that, following the advancement of
viding further confirmation for the mechanism of FFC
FFC, no Cr remained on the surface of sample 3. Nearly
advancement. The aluminum ion distribution shows that
all Cu found was located in the head region since the chro-
the most intense Al signal came from the exposed alloy
mate coating on uncorroded areas effectively covered other
surface beneath the FFC filaments. Similarly, the Cr ion
Cu particles. However, small amounts of Cu were observed
distribution illustrates the partial removal of the CCC from
where the chromate coating was intact. This is in agreement
the alloy surface under FFC. These results are in agreement
with previous studies [30,31] which reported the appearance
with the EDX chemical analysis presented previously which
of a Cr–Al–Cu mixture on the alloy surface following chro-
showed the partial removal of the CCC as a result of FFC.
The fluoride enrichment in the FFC filament also suggests
Table 6 an incorporation of this CCC component in the corrosion
EDX analysis of spots labeled in Fig. 5 products.
Spot Cl Cr Al Cu Mn Mg Fe An interesting discovery was found in the FFC tail region
1 0 0 81.0 13.1 1.4 0 4.5
of sample 5 where a Cu and Cl grid-type pattern appeared
2 0 0 72.9 15.9 2.8 0 8.4 (Fig. 8b). SKPFM analysis of this pattern revealed the Cu/Cl
3 * 0 69.0 29.9 0 0.7 0 stripes to be shallow ‘troughs’ with a negligible potential
4 0 0 67.1 32.5 0 * 0 difference to the surrounding ‘plateaus’. The occurrence of
5 0 0 96.8 1.9 * 1.0 0 such Cu-/Cl-containing ‘troughs’ may indicate that remnants
6 0 0 97.0 1.8 * 1.1 0
7 0 0 87.9 8.2 1.3 0 2.7
of corrosion products were retained. The appearance of this
8 0 0 83.8 11.9 0.9 0 3.4 ‘grid’ pattern can not be explained at this time. This feature
9 0 0 79.4 15.0 1.3 0 4.3 did not appear in all FFC filaments on sample 8 or on all
10 0 0 82.1 9.1 2.6 0 6.2 other samples. Typically, this corrosion type was seen on
11 0 0 82.6 9.5 2.5 0 5.4 polished samples on which wide (1–3 mm) FFC filaments
12 0 0 96.7 1.9 * 1.2 0
developed.
 J.V. Kloet et al. / Electrochimica Acta 49 (2004) 1675–1685 1683

Fig. 6. (a–d) FFC on sample 6 after 46 days storage at 86% RH.

Fig. 7. XPS chemical analysis of samples 3 and 5 at various locations following 12 s sputter (0.5 nm SiO2 ).
1684 J.V. Kloet et al. / Electrochimica Acta 49 (2004) 1675–1685
Fig. 8. TOF-SIMS ion distributions (300×300 ␮m, 1 min sputter, 5 min acquisition time) of (a) a FFC head on sample 6 (coating removed, corrosion
products present) (b) a FFC tail on sample 5 (coating and corrosion products removed).
4. Discussion and conclusions
The visual images of FFC on AA2024-T3 with and with-
out various pre-treatments showed corrosion protection was
enhanced by either a pigmented coating on a Sanchem pre-
treated sample or by a pigmented coating on a Sanchem and
CCC pre-treated sample. As seen with SEM, the corrosion
which does occur on these samples is slow in advancing and
deeper in appearance. One contributing factor to this deeper
form of corrosion may be a strengthened polymer–substrate
bonding which could have led to a longer contact time
between a small surface area and the corrosive solution.
The corrosion on untreated samples under pigmented
coatings also developed slowly, but was more superficial (i.e.
FFC) in comparison to the above mentioned samples. The
role pigments play in the inhibition of FFC can be best under-
stood in terms of the FFC mechanism on aluminum alloys.
The basic reactions describing the dissolution of the Al
substrate (Eq. (1)) and the reduction of oxygen (Eq. (2))
over certain IMPs are given below.
Al → Al3+ + 3e−
O2 + 2H2 O + 4e− → 4OH−
As mentioned previously, the IMPs formed in the alloy-
ing process may exhibit a different potential compared to
the Al matrix. An extensive list of corrosion potentials for
Al alloy intermetallics revealed that, compared with the Al
matrix, Al–Cu compounds generally have a more positive
potential while Al–Cu–Mg and Al–Fe–Mn phases have a
more negative potential in aqueous NaCl solutions of vary-
ing molarity [32]. This characterization is broad and such
factors as dealloying or the dynamic conditions of a corro-
sive environment may lead to potential changes within or
with respect to the surrounding matrix.
Chromate-containing inhibitors, whether in the form of a
conversion coating or as coating pigments, inhibit the anodic
dissolution of the Al substrate in an acidic environment by
building a combination of Cr and Al oxides through the
following reaction [11]:
+
Cr 2 O2−
7 + 2Al + 2H + H2 O → 2CrOOH ↓ +2AlOOH ↓
(3)
Once the chrome oxide covers the surface, further contact
between the corrosive solution and the Al is blocked and the
surface is effectively protected from further dissolution.
The finding of Cr and Cl exclusively on Al–Cu particles
suggests that dealloying of the Cu-containing intermetallics
upon contact with the corrosive solution present in a filiform
filament has taken place. It has already been established that
the pH of the an active filiform head ranges between 1 and
3 [6] and, under these conditions, the dealloying of S-phase
particles (Al, Cu, Mg) led to the selective dissolution of
Al and a surface enrichment of Cu [22]. This dealloying
could be interrupted in the presence of aquous Na2 CrO4
[22]. The experimental evidence presented here regarding
intermetallics found in active filiform filaments also sug-
gests that SrCrO4 pigments can halt the dealloying process
in and around S-phase particles. In all likelihood, this is
(1) accomplished through the reduction of Cr(VI) to Cr(III) as
(2) described in Eq. (3).
Once a Cr oxide layer has formed on the intermetallics, a
barrier to oxygen reduction (Eq. (2)) is formed. An inhibi-
tion of the cathodic reaction has previously been observed
during the delamination of galvanized steel coated with
PVB coatings containing SrCrO4 pigments [33]. Polariza-
tion curves of AA2024-T3 in NaCl solutions have also
demonstrated a reduction in cathodic kinetics when Cr was
present. It was suggested that reduction of Cr(VI) to Cr(III)
passivates the cathodic intermetallic by reducing their ac-
tivity [34]. Evidence of this Cr oxide barrier on cathodic
Al–Cu particles has been presented here through SEM im-
agery and EDX analysis. The chemical structure of the Cr
barrier could not be confirmed with XPS due to the small
spot size of the particles.
The SEM images have also clearly shown characteristic
matrix dissolution in the immediate region surrounding the
 J.V. Kloet et al. / Electrochimica Acta 49 (2004) 1675–1685
S-phase particles. This suggests that the pigment Cr is un-
able to completely inhibit the anodic reaction and also gives
further evidence for newly exposed particle surfaces arising
from substrate dissolution under corroding conditions. This
implies that a delay time exists between the exposure of a
new surface and the deposition of Cr.
Furthermore, it is seen from the large number of Fe-
and Mn-containing intermetallics remaining in the corrosion
path that these particles play a negligible role in advancing
FFC. This is in agreement with their anodic potential to the
Al substrate and is evidenced by the lack of matrix dissolu-
tion in the particle region.
CCC reduced, but did not eliminate, FFC when no pig-
mented coating was present. The CCC remained intact
where no FFC had occurred. There were no observations
made to indicate that Cr deposition from CCC occurs on
intermetallics, which may have played a role in FFC ad-
vancement. Rather, as recorded in the literature, the CCC on
intermetallics is sufficiently thin; that under little exposure
to a corrosive environment, the galvanic coupling between
IMPs and the aluminum matrix may be re-established and
FFC can proceed.
The results from this work have clearly revealed the higher
mobility of Cr-containing pigments as compared with the
Cr originating from a CCC. This ability to deposit from the
bulk coating demonstrated that SrCrO4 pigments effectively
slowed the corrosion advancement by forming an effective
barrier to the reduction of oxygen and therefore the galvanic
coupling between IMP and substrate.
XPS and TOF-SIMS supported the EDX chemical anal-
ysis by providing the same chemical information, but on a
larger scale.
Acknowledgements
The authors wish to acknowledge G. Frankel (Ohio State
University) for his organization and coordination of the
MURI project of which this work is a part. Special thanks
are extended to R. Granata of Florida Atlantic University
(Seatech) for sample preparation and M. Rohwerder for
many useful discussions.
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