Corrosion Science 47 (2005) 341–354

www.elsevier.com/locate/corsci

Chromate conversion coatings

on aluminium–copper alloys
Y. Liu a, P. Skeldon a,*, G.E. Thompson a,
H. Habazaki b, K. Shimizu c
a
Corrosion and Protection Centre, University of Manchester, Institute of Science and Technology,
P.O. Box 88, Manchester M60 IQD, UK
b
Graduate Engineering School, Hokkaido University, N13 W8, Kita-ku,
Sapporo 060-8628, Japan
c
University Chemical Laboratory, Keio University, 4-1-1 Hiyoshi, Yokohama 223, Japan

Received 12 June 2003; accepted 11 June 2004

Available online 11 September 2004

Abstract

The study compares the formation of chromate/fluoride conversion coatings, composed

mainly of amorphous hydrated chromia, on model, solid-solution, binary Al–Cu alloys, of
a range of compositions, and on 2014-T6 aluminium alloy. The model alloys, produced by
magnetron sputtering, reveal the importance of copper in limiting the thickness of the coatings
by promoting loss of coating material. This occurs at an earlier time in the treatment with
increasing copper content of the alloy. The coating loss follows closely upon the achievement
of the required level of copper enrichment for incorporation of copper into the coating, with a
thin alumina film beneath the hydrated chromia sustaining the enrichment process. The coat-
ing on the 2014-T6 alloy is of non-uniform thickness, with much thinner coating developing at
copper-rich second phases, consistent with the results of model alloys.

2004 Elsevier Ltd. All rights reserved.

Keywords: Aluminium; Copper; Alloys; 2014 alloy; Conversion coating; Chromate

*
Corresponding author. Tel.: +44 161 200 4872; fax: +44 161 200 4865.
E-mail address: p.skeldon@umist.ac.uk (P. Skeldon).

0010-938X/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2004.06.005
342 Y. Liu et al. / Corrosion Science 47 (2005) 341–354

1. Introduction

Chromate conversion coatings are employed to protect aluminium alloys against

corrosion and as base layers for promoting adhesion of organic coatings. The coat-
ings form by reduction of chromate ions, leading to the development of hydrated
Cr2O3, which provides barrier protection and further protects due to residual chro-
mate ions that are corrosion inhibitors [1–6]. The initial coating is amorphous, and
ageing in air is important to develop its protective properties [6]. In the initial stages
of coating development, the coating material is produced locally at cathodic sites
associated with particular microstructural features of the substrate [7–9]. Later,
the coating covers the surface generally and develops in thickness up to a few mi-
crons. The anodic reaction, oxidation of aluminium, results in a thin, residual alu-
mina layer at the base of the coating [9]. This layer is continuously thinned by
fluoride ions in the bath, such that a high rate of reaction is maintained and the re-
quired coating thickness is developed within a few minutes [9].
With aluminium alloys, second phase materials are important in corrosion and
protection processes, since the composition of the surface is locally altered; thus, dif-
fering electrochemical responses are expected across the surface [10–14]. Recent
work of the authors has considered the effects of alloying elements on conversion
coating of aluminium in chromate/fluoride solution [15]. This has revealed a reduc-
tion in the rate of thinning of the aluminium substrate with the addition of either
copper or gold, and the loss of coating material about the time that the alloying ele-
ment enters the growing coating. The loss of coating was suggested to follow the
incorporation of nano-particles of copper or gold, with subsequent generation of
hydrogen possibly involved. Key to the behaviour is the fact that copper and gold
are first enriched in the alloy, with oxidation of only aluminium taking place, which
is also established from anodizing of aluminium alloys [16–18]. Only later can copper
and gold be incorporated into the coating, following sufficient enrichment of the
alloy [17]. The typical thickness of the enriched alloy layers is a few nanometres.
In the present study, the previous work is extended to a range of binary Al–Cu al-
loys, with compositions relevant to matrix and second phase regions of copper-con-
taining commercial alloys. Comparison is also made with 2014-T6 alloy in which
copper is a key alloying element. The expectation from a previous work [15] is that
the loss of coating material occurs at an earlier time in the coating process with
increasing concentration of copper in the alloy, since enrichment of copper in the
alloy is more rapid and hence, also its incorporation into the coating. Thinner coat-
ings are thus anticipated on copper-rich second phase than on matrix regions of alloy.

2. Experimental

Al–1.6at.%Cu, Al–3.5at.%Cu and Al–30at.%Cu alloys were deposited by magne-

tron sputtering following the previous procedures [15]. The first two alloys were
deposited on to substrates of electropolished aluminium, the last on to electropo-
lished and subsequently anodized aluminium. The 2014-T6 alloy (nominal composi-
 Y. Liu et al. / Corrosion Science 47 (2005) 341–354 343

tion 0.5–1.2% Si, 0.7% Fe, 3.9–5.0% Cu, 0.4–1.2% Mn, 0.2–0.8% Mg, 0.1% Cr,
0.25% Zn, 0.15% Ti by wt), in the form of a sheet of thickness 1 mm, was ground
on wet SiC paper to 4000 grit, then polished to a 1 lm diamond finish. Residual con-
taminants were removed by further polishing on a cotton cloth wetted by deionized
water. Conversion coatings were produced by immersion of specimens for selected
times in a solution consisting of 3.5 g Na2Cr2O7, 4 g CrO3, and 0.8 g NaF in 1 l of
deionized water at 293 K. The pH of the solution was about 1.8. Coated specimens
were rinsed in deionized water, dried in cool air and stored in a desiccator. The
potential–time behaviour was determined during conversion treatment of the Al–
3.5at.%Cu alloy, using a saturated calomel electrode (SCE). Potentials are later
expressed with respect to SCE.
Coatings were analysed by Rutherford backscattering spectroscopy (RBS), using
either 1.53 or 1.86 MeV He+ ions, supplied by the Van de Graaff accelerator of the
University of Paris. The diameter of the ion beam was 1 mm. Data were interpreted
by the RUMP program [19]. Electron-transparent sections of specimens were pre-
pared by ultramicrotomy, with nominal thickness 10 nm, and examined by transmis-
sion electron microscopy (TEM) in a JEOL 2000 FX II instrument equipped with
energy-dispersive X-ray (EDX) analysis facilities. Topographies of the coated
2014-T6 alloy were investigated by atomic force microscopy (AFM), using a Nano-
scope III instrument, and field emission gun scanning electron microscopy (FEG-
SEM), using a Philips XL 30 instrument. EDX analyses of specimen surfaces
employed an Amray 1810 scanning electron microscope operating at 10 keV.

3. Results

3.1. Rutherford backscattering spectroscopy

The previous work of the authors has quantified the chromium contents and
thickness of the conversion coatings on an Al–2.3at.%Cu alloy for various times
of treatment [15]. The present Al–1.6at.%Cu and Al–3.5at.%Cu alloys revealed rates
of coating growth broadly similar to that found previously. Here, interest is focused
on the role of copper on the integrity of the coating. Figs. 1–4 present key RBS spec-
tra for the various materials. The initial sputtering-deposited alloys were of uniform
composition, as exemplified by the Al–1.6at.%Cu alloy (Fig. 1(a)). Following con-
version treatment of the alloy for times up to 6 min, the coating thickened progres-
sively, but at a reducing rate, as evident from the widths of the peaks due to
chromium species in the coatings (Fig. 1(b)). Significantly, the leading edges of sig-
nals for copper and aluminium are displaced to relatively low energy indicating that
the coatings are largely free of copper and aluminium species. Following treatment
for 12 min, the coating is reduced in thickness and hence, the displacement of the alu-
minium edge is less than for a thicker coating. Further, a peak due to enrichment of
copper near the surface of the specimen is now evident (Fig. 1(c)). The enrichment
corresponds to about 6.4 · 1015 Cu atoms cm 2. All spectra can be fitted well with
a coating composition Cr2O3 Æ nH2O (n  2), as found also for the later alloys and
344 Y. Liu et al. / Corrosion Science 47 (2005) 341–354

Fig. 1. Experimental and simulated (solid line) RBS spectra for Al–1.6at.%Cu alloy in the sputtering-
deposited condition (a) and following conversion coating in a chromate/fluoride bath for (b) 6 min and (c)
12 min. The bars mark the positions of chromium and copper at the surface of the specimen. The arrow
indicates the enrichment of copper near the alloy/coating interface.
 Y. Liu et al. / Corrosion Science 47 (2005) 341–354 345

Fig. 2. Experimental and simulated (solid line) RBS spectra for sputtering-deposited Al–3.5at.%Cu alloy
following conversion coating in a chromate/fluoride bath for (a) 3 min and (b) 6 min. The bars mark the
positions of chromium and copper at the surface of the specimen. The arrow indicates the enrichment of
copper near the alloy/coating interface.

in previous work [15]. Similarly, loss of coating material occurred for the Al–
3.5at.%Cu alloy, but for shorter treatment times, between 3 and 6 min (Fig. 2(a)
and (b)). The enrichment of copper, evident after coating loss, was about
1.3 · 1016 Cu atoms cm 2. The typical thickness of conversion coatings just before
the reduction in coating thickness, as determined by TEM [15], was in the range
100–200 nm.
346 Y. Liu et al. / Corrosion Science 47 (2005) 341–354

Fig. 3. RBS spectra for sputtering-deposited Al–30at.%Cu alloy following conversion coating in a
chromate/fluoride bath for (a) 6 min (dotted line) and (b) 24 min (solid line).

For both the previous alloys, the thickness of the alloy layer decreases throughout
the coating process. The thinning is evident particularly from the width of the copper
signal. The decreasing widths indicate average thinning rates of about 8.1 and
7.6 nm min 1 for the Al–1.6at.%Cu and Al–3.5at.%Cu alloys respectively, corre-
sponding to treatments from 0 to 6 min.
For the Al–30at.%Cu alloy, the initial coating material was typically about 5–7 nm
thick, such that the shift in the copper and aluminium edges was only slight for coating
times up to 6 min (Fig. 3). No signal for oxygen could be resolved due to limited coat-
ing thickness. Following treatment for 24 min, the edge for aluminium retreated and
became less sharp (Fig. 3), which TEM reveals later is associated with nano-porosity.
The high concentration of copper in the alloy and similarity of atomic masses pre-
vented resolution of contributions of chromium in the coating and copper in the alloy
and coating. Similarly, the extent of thinning of the alloy could not be determined. An
oxygen peak was now evident corresponding roughly to 2 · 1017 O atoms cm 2.
The RBS spectra for the commercial alloy disclosed thickening of the coating for
treatment times up to 5 min (Fig. 4(a)). After treatment for 10 min, the coating thick-
ness had reduced significantly, with a small peak due to enrichment of copper in the
surface regions to about 6 · 1015 Cu atoms cm 2 (Fig. 4(b)). The spectra also re-
vealed an apparent presence of aluminium and copper in the coating prior to the loss
of coating material, with signals being evident corresponding to the presence of these
elements near the specimen surface. However, later results indicate that the near-sur-
face concentrations of copper and aluminium probably arise due to the thin coatings
on the second phase. The copper and aluminium signals suggest that about 15% of
the surface had relatively thin coating material.

3.2. Potential–time behaviour

The potential changes during conversion coating treatment were recorded for the
Al–3.5at.%Cu alloy. Upon immersion of the alloy, the potential fell rapidly to about
 Y. Liu et al. / Corrosion Science 47 (2005) 341–354 347

Fig. 4. Experimental and simulated (solid line) RBS spectra for 2014-T6 alloy following conversion
coating in a chromate/fluoride bath for (a) 5 min and (b) 10 min. The bars mark the positions of chromium
and copper at the surface of the specimen. The arrow indicates the enrichment of copper near the alloy/
coating interface.

0.60 V, then recovered to about 0.55 V in approximately 10 s, followed by a more

gradual increase to about 0.50 V in 75 s (Fig. 5). The subsequent thickening of the
coating is associated with cycling of the potential, usually in the range 0.59 to
0.45 V, with a period of 7–13 s. Typically after 285 s, the cycling ceases, and the
potential remains relatively constant in the range 0.54 to 0.52 V. EDX analyses
348 Y. Liu et al. / Corrosion Science 47 (2005) 341–354

Fig. 5. Potential–time behaviour for sputtering-deposited Al–3.5at.%Cu alloy during conversion coating
in a chromate/fluoride bath.

of specimens on either side of the transition from cyclic to steady behaviour indi-
cated thinning of the coating, with atomic ratios of chromium to aluminium of about
0.10 and 0.03 for treatment times of 3 and 24 min respectively.

3.3. Atomic force, scanning electron and transmission electron microscopies

AFM images of the conversion-coated 2014-T6 alloy, following treatment for

5 min, revealed a relatively uniform coating, with a nodular texture, over most of
the surface (Fig. 6). However, the coating thickness appeared much less at regions
of large second phase particles, identified by EDX as AlMgCuSi, AlFeMnSiCu
and CuAl2 phases, with step heights at the boundary between the second phase
and adjacent regions of about 130 nm. Following an increased time of treatment,
6.5 min, FEG-SEM disclosed regions of the surface from which most of the original
coating material had been lost, and adjacent regions with original material still pre-
sent (Fig. 7).
Results of TEM examination of a conversion-coated dilute Al–Cu alloy have been
reported earlier [15]. In brief, the initial coating is similar to that on high purity alu-
minium, while copper is enriched in the alloy. After loss of coating material, the sub-
sequently developed coating contains copper species, with the appearance of the
coating material being modified. Here attention is focused on the Al–30at.%Cu
alloy. The alloy, following treatment for 1 min, supports a coating of thickness about
5–7 nm (Fig. 8(a)). By 6 min treatment, localized intrusions, apparently containing
coating material, penetrate the alloy (Fig. 8(b)). The intrusions are about 10 nm wide
and about 20 nm deep. These become more extensive with increasing time of treat-
ment. Eventually, a continuous outer layer develops, with a modified texture com-
pared with that of the unaffected underlying alloy (Fig. 8(c)). The thickness of the
 Y. Liu et al. / Corrosion Science 47 (2005) 341–354 349

Fig. 6. AFM image of 2014-T6 alloy following conversion coating in a chromate/fluoride bath for 5 min.

Fig. 7. Scanning electron micrograph of 2014-T6 alloy following conversion coating in a chromate/
fluoride bath for 6.5 min.

layer increases with increase in the treatment time, for instance from about 90 to
120 nm between 12 and 24 min. The modified layer has a vermicular appearance,
and contains crystalline material, giving diffraction contrast, interlaced with material
similar to that of the conversion coating. In transforming from the initial, uniform
alloy, of thickness about 220 nm, to the final two-layered morphology, the total
thickness of the substrate and coating is approximately constant, to within an
accuracy of 20 nm. EDX analyses reveal increased signals from chromium, oxygen
350 Y. Liu et al. / Corrosion Science 47 (2005) 341–354

Fig. 8. Transmission electron micrographs for sputtering-deposited Al–30at.%Cu alloy following

conversion coating in a chromate/fluoride bath for (a) 1 min, (b) 6 min and (c) 12 min.
 Y. Liu et al. / Corrosion Science 47 (2005) 341–354 351

Fig. 9. EDX analyses of (a) the inner layer and (b) the outer layer of sputtering-deposited Al–30at.%Cu
alloy following conversion coating in a chromate/fluoride bath for 12 min. The nickel signal originates
from the use of a nickel grid.

and copper in the outer layer, while the underlying alloy disclosed relatively more
aluminium, but no significant amount of chromium, the small signal from the latter
element arising from spreading of the electron beam (Fig. 9(a) and (b)).

4. Discussion

4.1. Al–1.6at.%Cu and Al–3.5at.%Cu alloys

The formation of the conversion coating on the Al–1.6at.%Cu and Al–3.5at.%Cu

alloys follows the pattern found in a previous study of binary aluminium alloys [15].
352 Y. Liu et al. / Corrosion Science 47 (2005) 341–354

The initial coating growth develops with oxidation of aluminium only, while copper
enriches in the alloy. The copper is eventually incorporated into the coating and the
coating thickness then reduces over the general surface of the specimen, with the sub-
sequently formed coating being relatively thin. The loss of coating material affects
the potential–time behaviour, occurring about the same time that cycling of the
potential terminates, with EDX analyses confirming a reduced presence of chromium
in the subsequent period of relatively steady potential. Based on the results for ano-
dizing Al–Cu alloys, enrichments of copper to about 6 · 1015 Cu atoms cm 2 are re-
quired in order for copper to be incorporated into alumina films in the two present
alloys [16,17]. From the measured thinning rates of the substrates during conversion
treatment [15], such enrichments are expected to be generated following treatment
times of about 7.6 and 3.7 min, which are in reasonable agreement with the measured
times for the loss of coating material.
In the case of Al–Au alloys, loss of coating material follows enrichment of gold in
the alloy and the subsequent generation of gold nano-particles [15]. Such behaviour
suggests that coating material detaches close to the coating/alloy interface, leading to
loss of the outer part of the coating. Additionally, nano-particles of copper may
form during treatments of Al–Cu alloys, possibly by occlusion of copper-rich regions
in the enriched alloy layer, since the potential during conversion treatment, typically
in the range 0.45 to 0.59 V, is lower than the equilibrium potential for Cu/Cu2+ by
about 0.5–0.6 V [20]. The mechanism of detachment may relate to physical disrup-
tion of the coating material due to the presence of the nano-particles, or to associ-
ated secondary processes, such as generation of hydrogen. Copper ions generated
through oxidation of copper nano-particles may also play a role. At this stage, fur-
ther work is needed to identify the precise reason for the loss of the coating material.

4.2. Al–30at.%Cu alloy

With the Al–30at.%Cu alloy, a thin chromia-based coating forms initially, leading
to enrichment of copper in the alloy immediately beneath the coating. The enrich-
ment will occur with oxidation of no more than a few nanometres of alloy, with a
significant contribution being made by the formation of the air-formed oxide. Thus,
copper is incorporated into the coating at a relatively early stage in the coating pro-
cess and a thick coating does not develop for reasons already considered. However,
the planar alloy/coating interface is unstable with further time of treatment, and
local intrusions of coating material develop, possibly at grains boundaries in the
alloy. The instability may arise due to local influences of copper nano-particles
and hydrogen generation affecting the coating and the solution within pores, such
that the anodic reaction is focused at more favourable sites. It is also possible that
the sputtering-deposited alloy has undergone some compositional changes due to
ageing at room temperature, possibly with generation of relatively copper-rich and
copper-lean regions. Whatever the precise cause of the instability, the alloy is perme-
ated by intrusions, which undercut the remaining overlying alloy. When fully estab-
lished, the permeated structure appears to be self-sustaining, such that the alloy at
longer coating times consists of two layers, of roughly uniform thickness, comprising
 Y. Liu et al. / Corrosion Science 47 (2005) 341–354 353

an inner layer of original alloy and an outer layer of transformed alloy. RBS and
EDX analyses indicate that the outer layer contains chromium, oxygen and copper
but is relatively depleted of aluminium. The depletion of aluminium can be explained
by the action of fluoride ions on any residual alumina.

4.3. 2014-T6 alloy

The behaviour of the commercial alloy reflects the variations in the composition
of the substrate between the matrix and second phase regions. The large precipitates
evident in the AFM image are AlMgCuSi, AlFeMnSiCu and CuAl2 phases, which
contain amounts of copper from 10 at.% to 33 at.%, including levels similar to those
of the Al–30at.%Cu model alloy. The copper content of the matrix per se is relatively
low compared with the average composition of the alloy, since for the T6 alloy tem-
per the copper is mainly in the strengthening phases. Thus, fine, copper-rich,
strengthening precipitates are present between the large precipitates. Relatively thin
and thick coatings form initially on the large second phase and adjacent regions
respectively reflecting differences in copper contents. There may also be some influ-
ences of iron and manganese, although these elements enrich less strongly than cop-
per [16]. The later loss of coating material from the surface more generally may
follow copper enrichment in the aluminium matrix phase. Further, the concentration
of copper in the fine strengthening phases would also assist relatively early incorpo-
ration of copper into the coating.

5. Conclusions

1. Chromate/fluoride conversion coatings formed on solid-solution binary Al–Cu

alloys initially thicken forming a copper-free coating, while copper enriches in
the alloy to the required level for its incorporation into the coating. The incorpo-
ration of copper leads to an associated loss of coating material. Subsequent thick-
ening of the coating is limited, since further incorporation of copper can take
place immediately. The loss of coating material occurs at an earlier stage of the
treatment for more concentrated alloys since the required enrichment of copper
can be achieved more rapidly.
2. Conversion coating of commercial 2014-T6 alloy results in regions of relatively
thin and thick coating material reflecting mainly the local distributions of copper
and the influence of copper on the development of the coating layer.

Acknowledgments

The authors are grateful to the Engineering and Physical Sciences Research Coun-
cil for support of this work. They also wish to thank Dr. C. Ortega, Groupe de Phy-
siques des Solides, for provision of time on the Van de Graaff accelerator of the
354 Y. Liu et al. / Corrosion Science 47 (2005) 341–354

Universités de Paris VI et VII (work partially supported by Centre National de la

Recherche Scientifique (GDR86)).

References

[1] J. Zhao, L. Xia, A. Sehgal, D. Lu, R.L. McCreery, G. Frankel, Surf. Coatings Technol. 140 (2001)
51.
[2] P. Campestrini, S. Böhm, T. Schram, H. Terryn, J.H.W. de Wit, Thin Solid Films 410 (2002) 76.
[3] L. Xia, E. Akiyama, G. Frankel, R. McCreery, J. Electrochem. Soc. 147 (2000) 2556.
[4] J. Zhao, G. Frankel, R.L. McCreery, J. Electrochem. Soc. 145 (1998) 2258.
[5] M.W. Kendig, A.J. Davenport, H.S. Isaacs, Corros. Sci. 34 (1993) 4.
[6] Y.-J. Tan, S. Bailey, B. Kinsella, Corros. Sci. 44 (2002) 1277.
[7] G.M. Brown, K. Shimizu, K. Kobayashi, G.E. Thompson, G.C. Wood, Corros. Sci. 33 (1992) 1371.
[8] G.M. Brown, K. Shimizu, K. Kobayashi, G.E. Thompson, G.C. Wood, Corros. Sci. 34 (1993) 1045.
[9] G.M. Brown, K. Shimizu, K. Kobayashi, G.E. Thompson, G.C. Wood, Corros. Sci. 35 (1993) 253.
[10] Y. Liu, G.E. Thompson, P. Skeldon, C.J.E. Smith, K. Shimizu, Aluminium Surface Science and
Technology (ASST II), Manchester, May 2000, 2000, p. 479.
[11] M. Jaime Vasquez, G.P. Halada, C.R. Clayton, Electrochim. Acta 47 (2002) 3105.
[12] L. Juffs, A.E. Hughes, S. Furman, P.J.K. Paterson, Corros. Sci. 44 (2002) 1755.
[13] W.R. McGovern, P. Schmutz, R.G. Buchheit, R.L. McCreery, J. Electrochem. Soc. 147 (2000) 4494.
[14] P.L. Hagans, C.M. Haas, Surf. Interface Anal. 21 (1994) 65.
[15] Y. Liu, P. Skeldon, G.E. Thompson, K. Shimizu, H. Habazaki, Corros. Sci. 46 (2004) 297.
[16] H. Habazaki, K. Shimizu, P. Skeldon, G.E. Thompson, G.C. Wood, X. Zhou, Trans. Inst. Met.
Finishing 75 (1997) 18.
[17] H. Habazaki, M.A. Paez, K. Shimizu, P. Skeldon, G.E. Thompson, G.C. Wood, X. Zhou, Corros.
Sci. 38 (1996) 1033.
[18] H. Habazaki, K. Shimizu, P. Skeldon, G.E. Thompson, G.C. Wood, X. Zhou, J. Phys. D 30 (1997)
1833.
[19] L.R. Doolittle, Nucl. Instrum. Meth. B 9 (1985) 344.
[20] M. Pourbaix, Atlas of Electrochemical Equilibria in Aqueous Solutions, National Association of
Corrosion Engineers, Houston, TX, 1974.