Surface and Coatings Technology 140 Ž2001.

58᎐66

Role of hexavalent chromium in the inhibition of corrosion

of aluminum alloys

M. KendigU , S. Jeanjaquet, R. Addison, J. Waldrop

Rockwell Science Center, LLC, 1049 Camino dos Rios, Thousand Oaks, CA 91360, USA

Abstract

Selection of alternatives to hexavalent chromium for inhibitors and inhibiting films for Al and its alloys requires a clear
understanding of how hexavalent chromium inhibits corrosion. To this end, the following hypotheses have been proposed:
residual chromate in conversion coatings provides self healing; hydrated CrŽIII. oxide films are uniquely inert and hydrophobic;
oxyanions of CrŽVI. rapidly passivate secondary phases in the highly unstable Cu-rich aluminum alloys; and adsorption of
hexavalent chromium on passive aluminum oxide makes it less susceptible to chloride attack. Evidence supporting these
hypotheses come from X-ray spectroscopic analysis ŽXANES. of conversion coatings on aluminum, characterization of CrŽVI.
oxyanion adsorption on anodized aluminum via a piezo᎐electrokinetic ŽPEK. method, and the electrochemical current vs. voltage
response model intermetallic compounds. 䊚 2001 Published by Elsevier Science B.V. All rights reserved.

Keywords: XANES; Piezo-electrokinetic intermetallics; Zeta potential; AFM; Benzotriazole; Hexavalent chromium; Inhibition; Aluminum alloys

1. Introduction 䢇 hydrated chromiumŽIII. oxides films are particularly

Identification of non-chromate corrosion inhibitors
for aluminum and its alloys requires a clear under-
standing of the mechanism by which hexavalent
chromium compounds inhibit and form protective films
on aluminum and its alloys. To this end, widely stated
hypotheses are now under scrutiny in this laboratory
and other laboratories throughout the world. These
hypotheses are the following:
䢇 corrosion-inhibiting conversion coatings Žor chemi-
cal films. contain mobile residual hexavalent
chromium making the films ‘self-healing’;
U
Corresponding author. Tel.: q1-805-373-4241; fax: q1-805-373-
4383.
E-mail address: mwkendig@rsc.rockwell.com ŽM. Kendig..
inert, hydrophobic and stable over a broad pH
range;
䢇 oxyanions of hexavalent chromium efficiently and
rapidly passivate active secondary phases in Al al-
loys, particularly those found in the difficult to
protect high-strength aluminum alloys;
䢇 oxyanions of hexavalent chromium Žchromate and
dichromate. rapidly and electrochemically react with
Al surfaces to inhibit cathodic reactions; and
䢇 oxyanions of hexavalent chromium lower the zeta
potential of anodic Al oxide films to discourage
chloride adsorption.
A detailed and thorough review of historical and
ongoing efforts aimed at proving or disproving these
hypotheses is beyond the scope of this paper. However,
we present selected recent results to demonstrate the
validity of several of them.

0257-8972r01r$ - see front matter 䊚 2001 Published by Elsevier Science B.V. All rights reserved.
PII: S 0 2 5 7 - 8 9 7 2 Ž 0 1 . 0 1 0 9 9 - 4
 M. Kendig et al. r Surface and Coatings Technology 140 (2001) 58᎐66 59

2. The role of chromate in conversion coatings of

aluminum and its alloys

The formation of chromate conversion coatings on

aluminum and its alloys involves the reduction of the
oxy chromium species:

6eyq 8 Hqq Cr2 O 72yª 2 Cr Ž OH. 3 q H 2 O Ž1.

by the consequent oxidation of Al,

2Aly 6eyª 2Al 3q. Ž2. Fig. 2. XANES for chromate conversion coating on Al 2024-T3 after
different processing times.
Conversion coatings usually contain fluoride and var-
ious accelerators for destabilizing the aluminum oxide
ble to corrosion as a result of the activity of the
in favor of the formation of the stable chromiumŽIII.
Cu-bearing intermetallic phases. These phases can be
oxy-hydroxide film. In addition to existing as a stable,
very active or provide a source for generating Cu-rich
insulating, hydrophobic CrŽIII. oxide barrier, the film
cathodes w6x. The fact that hexavalent chromium
contains residual hexavalent chromium as shown by
reagents readily passivate these surfaces can be at-
X-ray absorption, near-edge spectroscopy ŽXANES. w1x.
tributed to the rapid passivation of these phases by
Fig. 1 shows XANES spectra for CrŽ0., CrŽIII. and
oxy-chromium ŽVI. anions. For example, Waldrop and
CrŽVI. compounds. The CrŽVI. and CrŽIII. spectra are
Kendig w7x have recently shown that chromate selec-
both shifted to higher energies relative to the CrŽ0.
tively reacts with the highly cathodic Cu᎐Mn phases
spectrum, but a very sharp pre-edge peak characterizes
present in Al 2024-T3 as shown by atomic force micro-
the CrŽVI. compounds. Spectra taken for chromate
scopy ŽAFM. in Fig. 4. Additional evidence for the
conversion coatings formed after different processing
rapid passivation of the intermetallic phases by CrŽVI.
times in an Alodine 1200S solution show predominately
compounds comes from electrochemical analysis of
CrŽIII. oxy-hydroxides, but also by way of the pre-edge
model intermetallics.
peak, considerable levels of residual, unreacted CrŽVI.
ŽFig. 2.. Furthermore, the CrŽVI. is relatively labile in Model intermetallic phases have been found quite
useful for demonstrating the rapid passivation of these
that it shows a significant decrease during exposure to
phases by oxy-chromium ŽVI. anions in neutral and
an electrolytic environment ŽFig. 3.. These data and
near neutral chloride-containing environments. Both
results from the work of others w2᎐4x provide data for
sigma phase ŽCu,Mg.Al 2 and theta phase CuAl 2 poly-
the self-repair mechanism by chromate conversion
crystalline compounds having relatively large crystals of
coatings. Recently our colleagues at Ohio State Univer-
the intermetallic have been prepared. Fig. 5 shows a
sity have confirmed that the residual hexavalent
micrograph of the as-prepared sigma phase material.
chromium species in conversion coatings inhibit corro-
sion w5x.
Pure Al is widely recognized generally to exhibit
good corrosion resistance in neutral chloride contain-
ing environments. However, certain alloys, the Cu-rich
2000 series Al alloys in particular, are highly suscepti-

Fig. 3. The time dependence for the total Cr and ratio of CrŽVI. to
total Cr of a chromate conversion coating on Al 3003-H14 as a
Fig. 1. XANES for chromium compounds of valency 0, 3 and 6. function of time of exposure to air-equilibrated 0.5 M NaCl.
60 M. Kendig et al. r Surface and Coatings Technology 140 (2001) 58᎐66

results occur. At y800 mV the theta phase remains

cathodically active in 0.01 M NaCl. The sigma phase
rapidly dissolves anodically in 0.01 M NaCl at this
potential. Both phases readily passivate in the presence
of chromate ŽFigs. 8 and 9..
Electrochemical impedance analysis could be per-
formed with meaningful results only for the samples in
the chromate containing electrolytes since they exhib-
ited a stable, steady state behavior. The resulting single
time constant spectra allowed calculation of a polariza-
tion resistance and an apparent parallel capacitance. In
the y500 to y800 mV region, the polarization resis-
tance remains in the vicinity of 10 k ⍀ ⭈ cm2 for the
sigma phase and 20᎐50 k ⍀ ⭈ cm2 for the theta phase.
For both cases, the capacitance was on the order of
10᎐30 ␮Frcm2 , typical value for a double layer capaci-
tance. The magnitude of the capacitance suggests that
Fig. 4. AFM image of a polished Al 2024-T3 surface after short
the passivating films are very thin, and are not three-
exposure to a chromate solution Žintermetallic A is a Cu᎐Fe᎐Mn dimensional insulating layers. The resistances when
aluminide.. scaled appropriately, can account for the observed re-
sistance of a chromated 2024-T3 material. This asser-
tion assumes that all electrochemical depolarization
The material contains by design impurities that allow defining corrosion resistance occurs at the sigma phase
the formation of a more-or-less crack-free sample. With intermetallics. Since this phase comprises 4% of the
the proper heat treatment, relatively large single crys- total surface of the alloy, the range of the observed
tals with diameters of several hundred microns can be corrosion resistance for the alloy will equal Ž20᎐50 k ⍀
formed Žsee Fig. 5.. Samples with attached conducting cm2 .r0.04. This translates to values between 0.5 and
leads are potted in epoxy, polished to 1 ␮m with 1.25 M⍀ ⭈ cm2 as typically observed for chromated Al
diamond paste and electro-polished at y30⬚C in 20 2024-T3 exposed to 0.5 M NaCl.
vro nitric acidrmethanol for 15 s at 18 V. Following an These results show that oxy-chromium ŽVI. species
ultrasonic methanol rinse, the sample is masked under actively react by an adsorption rather than a precipita-
a microscope with an electroplater’s mask to expose
only one of the larger grains. Hence single-crystal,
model intermetallic electrodes are formed. Elec-
trochemical experiments were performed on these ma-
terials using a 0.01-M NaCl electrolyte with or without
the presence of oxy-chromium ŽVI. anions. Two solu-
tions of 0.01 M NaCl containing chromate and dichro-
mate, respectively, are mixed in an appropriate propor-
tion to obtain the desired pH, typically 7. The analyti-
cal CrŽVI. concentrations for these solutions are typi-
cally maintained at 0.01 M. These solutions are re-
ferred to as 0.01 F oxy chromium ŽVI. solutions.
The high and erratic currents that flow under poten-
tiostatic control at y500 mV vs. SCE Ža typical open
circuit potential for the 2024-T3 alloy. confirm that
both the theta phase and sigma phase materials in 0.01
M NaCl are rather unstable ŽFigs. 6 and 7.. The theta
phase becomes a very good cathode, reducing oxygen at
a current density of 0.02 mArcm2 at steady state, while
the sigma phase rapidly dissolves anodically after a
brief initial cathodic transient ŽFigs. 6 and 7, respec-
tively.. However, with the addition of 0.01 F CrŽVI.,
both materials passivate and give currents considerably Fig. 5. Scanning electron micrograph of the model sigma phase
less than 1 ␮Arcm2 . At y800 mV vs. SCE, similar material.
 M. Kendig et al. r Surface and Coatings Technology 140 (2001) 58᎐66 61

Fig. 6. Potentiostatic current transient observed at y500 mV vs. SCE for theta phase CuAl 2 in 0.01 M NaCl with and without 0.01 F
oxy-chromium ŽVI. anion concentration.

tion mechanism to passivate the active intermetallic
phases. Inhibitors such as cerium salts that depend on
a precipitation mechanism do not exhibit the same
passivation as does the chromate at 0.01 M activity
levels. In fact, Ce 3q species when compared to chro-
mate at comparable concentrations and pH actually
exhibit acceleration of corrosion ŽFig. 10.. Dilute levels
of Ce 3q released by pigments or conversion coatings
would be highly unlikely to have much of a beneficial
influence on the Cu-rich Al alloys. Like the chromate,
the Znrbenzotriazole ŽZnrBTA. also exhibits good
inhibition as shown by the low steady-state currents in
Fig. 10.
These results confirm several of the hypotheses

Fig. 7. Potentiostatic current transient observed at y500 mV vs. SCE for sigma phase ŽCu, Mg.Al 2 in 0.01 M NaCl with and without 0.01 F
oxy-chromium ŽVI. anion concentration.
62 M. Kendig et al. r Surface and Coatings Technology 140 (2001) 58᎐66

Fig. 8. Potentiostatic current transient observed at y800 mV vs. SCE for theta phase CuAl 2 in 0.01 M NaCl with and without 0.01 F
oxy-chromium ŽVI. anion concentration.

concerning the presence of hexavalent chromium com-
pounds as an active species in a self-repairing film, and
the ability of relatively low levels of hexavalent
chromium oxy anions to passivate electrochemically
active phases in difficult-to-protect alloys.
3. Ionic structure of anodized aluminum
Recent evidence shows that chromate also preserves
the integrity of aluminum oxide as a result of its ability
to alter surface charge. A piezo᎐electrokinetic ŽPEK.

Fig. 9. Potentiostatic current transient observed at y800 mV vs. SCE for sigma phase ŽCu,Mg.Al 2 in 0.01 M NaCl with and without 0.01 F
oxy-chromium ŽVI. anion concentration.
 M. Kendig et al. r Surface and Coatings Technology 140 (2001) 58᎐66 63

Fig. 10. Potentiostatic current transients observed at y800 mV for theta phase CuAl 2 in chloride solutions containing different inhibiting
species.

analysis demonstrates how hexavalent oxy chromium
ŽVI. anions alter the surface charge of the porous
aluminum oxide of anodized aluminum.
The PEK experiments have been designed to ex-
amine the hypothesis that the chromate wCrŽVI. oxy-an-
ionsx, in general, and chromate seals in particular,
impart a negative zeta potential on the surface of
aluminum. As such, they discourage the adsorption of
chloride ions which subsequently weaken the Al᎐O
bonds in favor of the soluble acidic chloro-complex.
This hypothesis has been proposed by Sato w8x for the
chromate and molybdate inhibition of ferrous materials
and by Natishan, McCafferty and Hubler to explain the
role of alloying elements in inhibiting the pitting of Al
w9x. The PEK experiment can determine the relative
magnitude and sign of the surface charge on the oxide
surfaces within micropores of the anodized aluminum.
This method was first described by Bernstein and White
w10x in a model for the piezo᎐electrokinetic ŽPEK.
response of anodized aluminum. According to their

Fig. 11. Schematic of the piezo᎐electrokinetic test cell. Test sample is held between the water couplant and a water film contacting a counter
electrode. The anodized surface is oriented toward the counter electrode.
64 M. Kendig et al. r Surface and Coatings Technology 140 (2001) 58᎐66
model, the normalized piezo᎐acoustic response has the
following form:
Voutru Ž 0 . s ␲ nR 2 ␴␥r Ž 2 ␻1r2 ␧ pore ␣1r2 ␮1r2 .
where ␴ s surface charge, ␥ s Debye length Žconstant
with constant ionic strength and dielectric constant.,
␧ s dielectric constant of the fluid in the pore, ␣ s the
fluid’s compressability, ␻ s angular frequency of the
acoustic signal, R s the pore diameter, and ␮ s fluid’s
viscosity. The surface charge, s, is related to the zeta
potential, or the potential at the plane of shear, by the
following equation:
␴ s D␨r Ž 4 ␲ ␥ . ,
where D is the diffusion coefficient and ␨ is the zeta
potential, potential at the plane of shear.
4. Experimental details for the PEK experiments
The device used in this laboratory to perform the
PEK experiment is schematically shown in Fig. 11. Fig.
12 shows a timing diagram for the acoustic and elec-
trokinetic responses that occur. Every time an incident
or reflected acoustic wave impinges on the
samplerwater interface it generates a PEK signal. Al
1100 alloy was used for the PEK experiment. The
samples were polished to a 1-␮m finish and then
anodized in 10 wro H 2 SO4 at 34 " 1⬚C, and a current
density of 16 mArcm2 . The samples were introduced to
the bath ‘hot lead’. Anodization was carried out for 0.5
h. After anodization, the samples were thoroughly
rinsed with deionized water, dried with a blast of nitro-
gen gas, and stored in a desiccator.
The PEK response was very sensitive to wetting of
both surfaces of the specimen and slightly dependent
on the gap. All measurements were made after com-
plete specimen wetting was confirmed by observation of
the signal. For the pH dependence, measurements were
made at a constant gap of 1 mm. PEK signals were
obtained from more than five identically anodized sam-
ples in order to determine sample-to-sample variation.
The PEK signals were observed as a function of time to
assure that there was no systematic temporal variation.
The electrolyte used for these experiments was 0.01
M NaNO3 or a chromate solution formed from sodium
chromate and sodium dichromate, each adjusted in
concentration to give the same conductivity as the
0.01-M NaNO3 . Hence, all solutions had nearly the
same ionic strength. The pH of the nitrate solution was
adjusted by adding small quantities of acid or base. The
0.01-M NaNO3 solution gave a pH of 5.8 as a result of
equilibration with carbon dioxide from the air. In order
Ž3.
Ž4.
Fig. 12. Timing diagram for the PEK and acoustic signals.
to maintain a constant pH between 4 and 8, 0.001 M
hydrazine was added as a buffer. For pH 9, a 0.001-M
solution of ammonium hydroxiderammonium chloride
served as the buffer. In the case of the chromate
electrolytes, the mixture of chromate and dichromate
served as an effective buffer. No variation in pH of the
chromate solutions was observed. All solutions had the
same conductivity, as did the 0.01-M NaNO3 , to main-
tain as closely as possible, a constant ionic strength.
Initial experiments entailed firstly observing the PEK
for an anodized sample in a nitrate solution followed
by ultrasonic rinsing of the sample in deionized water,
making the measurement in the neutral chromate solu-
tion, rinsing again and then repeating the PEK obser-
vation in the nominally neutral sodium nitrate. These
measurements were made as a function of time, but
showed virtually no drift in signal level ŽFig. 13.. The
replacement of the nitrate solution with the chromate
solution lowers the normalized PEK signal by almost a
factor of 10. This effect is partly reversible since revert-
ing to the nitrate solution brought the PEK signal back
to nearly the same level.
5. Results for PEK of anodized aluminum
The pH dependence of the PEK signals for the
anodized Al 1100 is summarized in Fig. 14. For some of
the data points in Fig. 14, a scaled waveform has been
superimposed to illustrate the phase and, hence, justify
the assignment of the sign to the signal. The PEK
signal for the sample in the nitrate solution remains
high and of the same phase over the accessible pH
 M. Kendig et al. r Surface and Coatings Technology 140 (2001) 58᎐66
Fig. 13. PEK signal levels as a function of time for anodized Al 1100
samples in the presence of nitrate or chromate.
range Ž4᎐9.. Higher pHs were not evaluated since the
oxide becomes unstable to dissolution above pH 9.
In contrast to the nitrate solutions, the PEK re-
sponse in the CrŽVI. oxy-anion electrolytes made from
mixtures of dichromate and chromate so as to set the
pH, is considerably lower. Furthermore, between pH 7
and 9, the signal changes phase Žas indicated by the
respective waveforms superimposed on Fig. 14.. The
change in phase with pH is taken as a change in sign.
Furthermore, the sign can be determined by the fol-
lowing arguments: Ž1. the PEK signal is proportional to
the zeta potential ␨ Žaccording to Eqs. Ž3. and Ž4..; Ž2. ␨
for pHs below the pH of zero charge Žpzc. is positive,
but negative above the pzc; and Ž3. if the phase re-
verses with an increase in pH then the sign changes
from positive to negative. Therefore, we have assigned
a sign to the PEK signals in Fig. 4. Interpolation
between the two points where the phase changes allows
Fig. 14. PEK signal amplitudes as a function of pH for the nitrate
and CrŽVI. oxy-anion media. Insets show signal waveforms.
65
estimation of a pH of zero charge Žpzc. for the anodized
surface in the oxy CrŽVI. medium to be 8.4.
Considering the results for the nitrate solution, the
pzc appears to be significantly above pH 9 Žsee Fig. 14..
This result, it must be noted, is not entirely consistent
with the colloid literature which reports pzc for various
oxides of aluminum to be considerably lower in the
vicinity of pH 9 Žw11,12x.. While we find our result to be
puzzling, we do not consider it to be in error. Although
the details of the Bernstein and White model may not
be entirely correct, a change in phase for the PEK
signal indicates a change in sign of the zeta potential.
Furthermore, the results of this work clearly show that
a reversal in phase occurs for the samples in the CrŽVI.
environment between pH 7 and 9, but no change in
phase is observed up to pH 9 for the anodized sample
in the nitrate solutions. We can only hypothesize that
the anodization process generates considerably higher
positive charge on the surfaces within the porous anodic
oxide such that the oxide within the pores has a much
higher zeta potential than the highly dispersed alumina
colloids. The highly dispersed colloids are typically used
in the other determinations of the zeta potential. Most
importantly, the results presented here show that chro-
mate reversibly reduces this charge and lowers the pzc.
This implies that the adsorption of chromate on
anodized aluminum films discourages the adsorption of
detrimental anions such as chloride.
6. Summary of PEK results
The PEK results show that chromate significantly
lowers the surface charge Žzeta potential. within the
porous anodized layer on sulfuric acid anodized
aluminum. The results suggest that the apparent pH of
zero charge for the anodized aluminum Ž) 11. is higher
than dispersed alumina, but is reduced to between 8.2
and 8.4 in the presence of CrŽVI. oxy-anions as com-
pared to the non-chromate nitrate environment.
7. Summary
These results validate the following hypotheses re-
garding corrosion inhibition by hexavalent chromium:
䢇 chromate conversion coatings contain residual hex-
avalent chromium that renders the film an active
inhibitor in addition to being a good environmental
barrier;
䢇 hexavalent chromium oxy-anionic species rapidly
inhibit cathodic reactions of Cu-containing
aluminides by a rapid adsorption process; and
䢇 hexavalent chromium compounds adsorb on
aluminum oxides so as to minimize the otherwise
66 M. Kendig et al. r Surface and Coatings Technology 140 (2001) 58᎐66

positive surface charge, which makes the films less
susceptible to adsorption of chloride.
Acknowledgements
The authors are grateful for the financial support
from AFOSR contract F49620-96-0479 and from the
Rockwell Science Center.
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