Corrosion Engineering, Science and Technology

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Cerium-based conversion coatings on aluminium

alloys: a process review

T G Harvey

To cite this article: T G Harvey (2013) Cerium-based conversion coatings on aluminium

alloys: a process review, Corrosion Engineering, Science and Technology, 48:4, 248-269, DOI:
10.1179/1743278213Y.0000000089

To link to this article: http://dx.doi.org/10.1179/1743278213Y.0000000089

Published online: 18 Nov 2013.

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 REVIEW
Cerium-based conversion coatings on
aluminium alloys: a process review
T. G. Harvey*
Rare earths are among the most promising options for replacing chromate conversion coatings on
aluminium. In nearly three decades of research, several hundred papers have been published in
the area, the bulk of which has never been reviewed. This paper reviews the literature on rare
earth coating processes, with particular emphasis on those based on cerium. It is concluded that
several process areas are poorly understood, some of which are critical to further progress in the
field. These include the development of industrially suitable pretreatments, technologies for
coating non-aerospace alloys and seals to enhance corrosion performance and paint adhesion.
Keywords: Review, Aluminium, Cerium, Rare earth, Conversion, Coating

Introduction
The replacement of chromate conversion coatings on
aluminium is a perennial topic. Chromate is an outstanding
corrosion preventative for aluminium.1 It works extremely
well as a soluble inhibitor in cooling water systems,2 as an
inhibiting pigment in paints2–5 and as a component in
deoxidisers2,4,6 and anodised coatings.2,4,7 Most importantly,
in the context of this review, chromate is a near ideal
conversion coating,1,2,6 as it provides outstanding co-
rrosion resistance4,8–14 and paint adhesion,10,14–17 ease of
application,8,9,11–13,18–21 self-healing6,8,9,11,14,18,19,21 and elec-
trical conductivity.18,19,21–23 It works rapidly14 at room
temperature14 on a wide variety of metals and alloys24 while
requiring a minimum of maintenance.10 Indeed, given this
combination of excellent properties and versatility, it
seems unlikely that there will be a single replacement for
chromate.1,25,26 However, chromate is carcinogenic1,11,18,19,27–29
and has been listed in the USA as one of the Environmental
Protection Agency’s most toxic substances,5,18,19,28 with a
view to it being progressively phased out.1,5,12–14,30–32 An
enormous amount of work has been carried out on
chromate, and there are a number of excellent reviews that
cover chromate chemistry and practice.6,14,33–35
An enormous amount of data on potential chromate
replacements for aluminium has also been published.1
This is not only because of the importance of the topic
but also because of the breadth of the replacement
chemistries available for aluminium. These include
molybdate,1,11,26,30,36,37 permanganate,6,11,26,36–38 refrac-
tory metal oxyfluorides (mainly Ti/Zr, but also Hf, Nb
and Ta),6,11,26,36–40 phosphates,1,26 silanes,6,26,36,37,39,41,42
sol–gels,1,6,11 self-assembling monolayers,6,26,39–42 con-
ducting polymers,1,6,11,30 cobalt based coatings,6,24,26,38,43
hydrotalcites6,11,26,38 and rare earths.1,6,11,26,30,36–42
CSIRO Materials Science and Engineering, Private Bag 33, Clayton South
MDC, Clayton, Vic. 3169, Australia
*Corresponding author, email tim.harvey@csiro.au
Rare earths are among the most promising options for
replacing chromate conversion coatings,5,23,29,44 but
although the literature on the topic runs to several
hundred articles, the bulk of it has never been review-
ed. For example, the reviews of Seon,45 Cohen,46
Ramanathan,47 Hinton,2,36,37,48 Henderson et al.38 and
Ryan49 briefly cover rare earths but are confined almost
entirely to the early (pre-1991) papers of Hinton et al.
In addition, a number of excellent reviews on chro-
mate replacements have subsequently appeared in
which rare earth coatings appear as part of the
discussion,1,5,6,11,26,30 but as they only represent one
option among many, the coverage is necessarily limited.
The review by Bethencourt et al.50 is probably the most
comprehensive, but is quite dated now. Some of the best
information on rare earth conversion coatings is found
not in reviews but in the primary literature. For
instance, an excellent summary of the development of
the cerium coating process is found in the introduction
of the paper by Campestrini et al.,51 and probably the
most useful background material on the process is found
in the introduction of the paper of Palomino et al.52 and
in the discussion in the paper by Buchheit et al.53 From
the view of process conditions, the best coverage is
found in papers by Chemetall41,42 and in the review by
Buchheit and Hughes,6 although these are still limited in
their coverage of the published literature.
Given these considerations and the fact that rare earth
coatings are beginning to find commercial application as
chromate replacements,40–42 it was considered that a
process based review of rare earth coatings on alumi-
nium would be useful.
This review only covers rare earth conversion coating
processes and excludes sol–gel processes54,55 and, more
importantly, oxide growth processes in which rare earths
are incorporated.6,53,56–59 Oxide growth processes are
surprisingly common in the chromate replacement
literature and include the Commonwealth Scientific
and Industrial Research Organisation’s (CSIRO)
Sirox process,60–63 Mansfeld’s Stainless Aluminium
process,56,64 the Hughes Chrome Free Conversion

ß 2013 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 15 November 2012; accepted 11 February 2013
248 Corrosion Engineering, Science and Technology 2013 VOL 48 NO 4 DOI 10.1179/1743278213Y.0000000089

1 Abbreviated outline of the structure of this review
Coating process,65,66 the General Motors Boehmite
process,67 the Miller (Lockheed) process68–71 and
others.21,72–76 Oxide growth processes are generally
distinguished by a high temperature step (.80uC),
which thickens the surface oxide, and by the absence
of an oxidant. Conversion coating processes are, by
comparison, generally run at temperatures ,50uC in the
presence of an oxidant and result in the deposition of
hydrated or mixed oxide surfaces.57,77 Thus, the
chemistries are sufficiently distinct that it was felt that
oxide growth required separate treatment.
With regard to conversion coatings however, several of
the rare earths have been found to act as cathodic
inhibitors, including Ce,20,78–86 Sm,78 La,20,78,79,82–89
Nd,20,79–81 Pr,20,79–81 Y,80,81 Gd90 and Tb.90 Ce is generally
the most active91,92 and is, in particular, more active than
La82,85,88,90–93(except on pure Al),83 Y93 and Pr.91 The
corrosion resistance usually follows the sequence:
Ce.Nd.Pr.Y.La.20,79–81 With the exception of La,
Corrosion Engineering, Science and Technology
Harvey Cerium-based conversion coatings on aluminium alloys
the other rare earths are effectively ruled out of widespread
commercial use due to cost considerations, but La not only
is less active than Ce82,91 but also shows poor adhesion as a
coating as well.82 Thus, the term rare earth in this review
may be considered to mean cerium unless otherwise
specified.
General process outline
There are a number of papers in the literature, which
include a general process outline for the cerium coating
of aluminium, including process conditions and methods
of quality control.6,41,42 In common with other coating
processes,35 cerium coatings require at least one
pretreatment step (and usually more), a coating step,
and, if maximum corrosion resistance is needed, a
sealing step. An outline of the structure of the paper is
shown in Fig. 1. This section examines the individual
process steps in detail.
2013 VOL 48 NO 4 249
Harvey Cerium-based conversion coatings on aluminium alloys
Alloys treated
The alloys that have been most widely investigated
with regard to rare earth coating are the aero-
space alloys1 AA 202410,17,31–33,38,51,58–60,77,94–135 and
AA 7075.8,12,13,31,32,77,79,102,105,112,114,122,126,131–133,136–149 Other
alloys studied include AA 2618,57 AA 3004,150,151
AA 3102,67 AA 5005,42,121,122,150–154 AA 5052,155 AA
5083,78,156–171 AA 5754,122 AA 6009,122 AA 6060,40,42
AA 6061,57,121,150,151,172–174 AA 6063,122,152–154,175,176
AA 6082,177 AA 7020,178 AA 7475,10,77,126
AA 8090 82,91,102
and LC4 (7xxx series).179 Evaporated
Al has also been tested,155 as have cast alloys86 and metal
matrix composites (MMCs), whose corrosion sensitivity
is enhanced by the composite reinforcement.89,180,181
Metal matrix composites that have been coated with
cerium compounds include AA 6061–10%Al2O3,21
AA 6061–SiC,182,183 aluminium borate whisker rein-
forced AA 6061,23,29,174 carbon reinforced
184,185
AA 6061, TiB2–Al176,186 and SiC–Al.89,180,187–190
There is usually a distinction drawn between conver-
sion coatings on aerospace aluminium alloys and those
on other alloys because of the harsh testing requirements
for the former121 and the fact that they are, generally,
the most corrosion prone.191 While aerospace alloys are
the most widely studied (in terms of chromate replace-
ment),1 it must be remembered that non-aerospace
alloys comprise the bulk of aluminium use in the world.
For instance, AA 5xxx and 6xxx alloys are used in
automotive applications,122 and AA 5005, AA 6061 and
AA 6063 are used in architecture as extruded profiles.122
Furthermore, even aerospace alloys are often used in the
clad form rather than the bare alloy11 with AA 2xxx
alloys clad with pure Al,11,35 while AA 7xxx alloys use
an Al–Zn alloy.192 In both cases, the clad layer acts as a
barrier and as a sacrificial coating,191,192 but these
present their own problems insofar as rare earth
coatings are concerned. For example, putting Ce coat-
ings on AA 1150 is claimed to be extremely difficult and
completely impossible on pure Al,177 and AA 6061 does
not develop any appreciable colour under conditions
which coat AA 2618 easily.57 These issues have, it
should be noted, been addressed by other workers (see
the section on ‘Effect of Additives’), but it must be
emphasised that, while coating aerospace alloys is
important and has been intensively studied, the ability
to coat non-aerospace alloys is not only more important
but also more difficult. These aspects of coating
development will be covered in later sections.
Pretreatment
It is normal practice with aluminium alloys to lightly
etch the surface before chromate coating.96 In a similar
way, cerium processes also require pretreatment, as
cerium will generally not deposit on an as received
surface, even on an active alloy like AA 2024,51 and the
surface must normally be stripped back before coating
can take place. Surface preparation also influences both
the degree of Ce deposition58,96,102 and the coating
performance,132,147 particularly on different alloys.41,42
The work in Australia by CSIRO and the Defence
Science and Technology Organisation (DSTO) with
Boeing in the early 1990s was based on the view that
rare earth coatings could be improved by altering the
pretreatment,121 an idea that was later extended in work
with BAE Systems77,126,193 and Lockheed-Martin.194
250 Corrosion Engineering, Science and Technology 2013 VOL 48
The group at the Defence Evaluation and Research
Agency (DERA) in the UK also took this approach.96
Overall, however, relatively little work has been
carried out on the effect of pretreatment on Ce coatings,
and the conditions required for uniform deposition are
still uncertain.105 It has been pointed out that, of the
several groups who have been working on cerium
coatings, all use fairly standard degreasing and deoxida-
tion steps as pretreatments.118 More exotic surface
treatments, such as plasma, have been investigated,132
but with little success to date. It is not clear, however,
that these would achieve acceptance over existing
pretreatments without offering significant process or
performance advantages.
Useful pretreatments involve, at the very least,
physical abrasion, but more commonly include steps
such as alkaline cleaning and etching or deoxidation as
well. These steps will now be examined in order.
Abrasion
The simplest method of pretreatment is physical
abrasion, using alumina or silicon carbide paper,
followed by rinsing and degreasing, usually with
acetone, ethanol or isopropanol. Cerium coatings have
been shown to form on a variety of abraded or polished
alloy surfaces,15,21,59,78,82,89,102,106,140,159,164,167–169,179,195–200
although the coatings tend to form extremely slowly,95,102
as, with a few exceptions,59,102,168,169,179 abrasion has
generally been used as preparation for unaccelerated coating
processes (immersion in CeCl3 solution) (see the section on
‘Non-accelerated immersion coating’).
Other workers have used abrasion or polishing before
chemical pretreatments such as NaOH23,29,104 or acid
pickling steps98,119,128,173,176 or both,135 but, with the
possible exception of repair processes, abrasion is
suitable only for small samples and cannot reasonably
be expected to form the basis of industrial applications,
despite claims to the contrary.169
Alkaline cleaning
Alkaline cleaning is normally a standard requirement in
any pretreatment regime, but in the case of rare earth
coatings, there is some disagreement in the literature as
to whether alkaline cleaning should serve as the only
pretreatment that is required.
Quite early on, it was claimed that significant
improvements in corrosion performance were obtained
when the samples were only degreased and not
deoxidised.20,81,201–203 Indeed, Mansfeld concluded from
his observations that the surface oxide was necessary for
the formation of a resistant Ce coating.20,81,201–203 This
was not a case of simply leaving the native oxide intact,
as studies had found that coatings applied to AA 6061
from different suppliers showed poor reproducibility,80
which was attributed to non-uniform surface oxides and
various surface defects.80
The group at the University of Missouri-Rolla
(UMR) have reported the formation of satisfactory Ce
coatings on AA 7075 by electrolytic deposition,144
spray109,110,148 and immersion, using alkaline cleaning
as the only pretreatment.144,147,148 This did not work
with AA 2024,132 although alkaline cleaning has been
noted to have relatively little effect on the surface of
AA 2024.51 The UMR claimed that including a deox-
idation step overetched the surface and affected the rate
of deposition and performance of the coating,145–147 and
NO 4

as acceptable coatings could be deposited without the
use of any additional process steps,144 it appears that
efforts to incorporate them were abandoned, at least
temporarily (see the section on ‘Base etching’).
Non-etching alkaline cleaners will alter the surface pH
of the sample and remove grease or other organic
contaminants, but cannot remove inorganic contami-
nants from the surface. Thus, such elements as Mg, Zn
and Fe will remain,204 and the cleaner may leave
contaminants such as silicates that are present to inhibit
surface etching.121,204 The CSIRO/DSTO group have
used a variety of commercial alkaline cleaners in their
studies. Initially, Brulin 815 DG (60uC, 15 min) was
favoured for degreasing, followed by Henkel Ridoline 53
(65uC, 4 min) for alkaline cleaning, with deoxidation
and coating following after that.121,124 It was found that
abrasion could be substituted for the Brulin step,128
although, ultimately, both abrasion and Brulin steps
were removed entirely. This pretreatment was later
replaced by a simple solvent wipe (acetone) followed by
the Gibson Process 204B (a silicated alkaline cleaner).126
This pretreatment was replaced in turn by immersion in
Henkel/Turco 4215 NC-LT, a cleaner that others have
also found to be effective.149,205
These examples serve to illustrate that even the simple
issue of surface cleaning may be quite complicated. In
contrast to the UMR’s minimalist approach, for
instance, Mansfeld’s pretreatments were quite complex,
incorporating abrasion (600 grit), detergent degrease,
rinse, air dry, hot hexane soak, rinse, air dry, sonication
in acetone, rinse, air dry,80 plus another detergent
degrease, rinse and air dry.81 This might be followed
with a deoxidation step, rinse and heat in air at 100uC
for 24 h at high humidity.81,206 These complex pretreat-
ments were transferred to subsequent work on oxide
growth processes,27,207 with further developments sim-
plifying the degreasing stages somewhat, but substitut-
ing in up to three consecutive deoxidation steps
instead.207,208
Acid/base pickling
Aluminium pretreatments usually use caustic etch to
remove surface oxide and deformed layers, often
followed by a deoxidation (desmutting) step in nitric
acid or similar.97 This is not universally followed in the
published studies of cerium coatings. For instance,
Trolho et al. noted, without any detail, that acid
pickling pretreatments could be used alone or in
combination with alkaline pretreatments42 and that the
use of alkaline pretreatments alone could often eliminate
pitting that might otherwise occur.42 Hamdy et al.
claimed, also without any details, that pickling greatly
improved corrosion resistance.21 Palomino et al. tested a
range of different basic and acidic pretreatments and
found that they resulted in different Ce levels on the
surface.58
For this reason, base/acid etching treatments will be
examined both separately and as sequential steps. As
noted previously, there is surprisingly little information
available on the effect of acid or base etching on
subsequent coating steps or on the performance of the
coatings. Authors appear to favour particular recipes,
either their own or borrowed from others, but it cannot
be said that there is much published scientific support
for the choices that are made. For this reason, most of
the details in the following sections simply list the
Corrosion Engineering, Science and Technology
Harvey Cerium-based conversion coatings on aluminium alloys
choices that have been made. For the purposes of this
discussion, pretreatment steps using oxidising acids
(e.g. nitric) are covered in a separate section on
‘Deoxidation’.
Acid etching
Pickling or acid etching of light metals with non-
oxidising acids is not widely used in pretreatments for
cerium coating. While this will generally increase the
rate of coating deposition, it does so by exposing
subsurface (often Cu rich) smut, which then accelerates
the cathodic deposition. (Base etching, of course,
acts in the same manner.) The problem with smut
is that it is only loosely held to the
surface,17,51,52,58,98,115,130,177,209,210 and the subsequent
cerium coatings are usually poorly or non-adherent.29,51
Acids used as pretreatments include HF,174 H2SO4–
HF177 and H2SO4–H3PO4.51 It may be noted however
that H2SO4–H3PO4 does not affect either the electro-
chemical nature of intermetallics or the extent of their
galvanic coupling to the matrix.98 Surprisingly, a
number of authors recognise that non-oxidising acids
(e.g. HOAc58 and H2SO4)111,114,118,211 accelerate coating
by forming surface smut, but choose to do so any-
way.116,141,205 In once instance, it has been claimed that
H2SO4 gave better corrosion performance on AA 7075
than chromate deoxidation.141
Base etching
The problem with base etching on its own is essentially
the same as etching in a non-oxidising acid: it will ex-
pose smut. The consequent acceleration of the coat-
ing deposition rate is, or should be, outweighed by
the fact that the smut is only loosely held to the
surface,17,51,52,58,98,115,130,177,209,210 and any resulting
coating will be poorly adherent or non-adherent.29,51
As with acid etching (see previous section), this fact is
often dealt with by the simple expedient of not
measuring coating adhesion, although poor adhesion
has been noted on base treated AA 202458 and
aluminium–borate whisker reinforced AA 6061.29 Base
etching has been used as a Ce coating pretreatment on
AA 5083,156,157,171 AA 6082,177 aluminium borate whis-
ker reinforced AA 606123,29 and even the aerospace
alloys (AA 2xxx/ AA 7xxx series),58,105 although sub-
sequent coatings on AA 2024 showed poor corrosion
performance.105 Mild base (0?3%NaOH, 1 min) does not
have any significant effect on the original surface
features of AA 2024.210 Decroly claimed that any
etching sequence on a low Cu alloy (eg AA 6056) should
end with an alkaline step because the resulting non-
insulating alumina gel layer is necessary for rapid
deposition of Ce.177 Similarly, it was claimed by
Chemetall (although in this case, without any support-
ing experimental detail) that use of alkaline pretreat-
ments alone could eliminate the pitting that might
otherwise occur.42
Recently, the principal proponents for basic pretreat-
ments have been UMR, as a means of accelerating their
spray coating process on AA 7075114,137,139,212,213 with
either NaOH139,213 or sodium carbonate.212,213 Basic
pretreatment was found to increase coating deposition
(after one spray cycle) from ,30 nm to as much as
250 nm.212 Sodium hydroxide was claimed to result in a
more protective layer than carbonate.213 Sodium carbo-
nate, on the other hand, gave the most uniform coatings
2013 VOL 48 NO 4 251
Harvey Cerium-based conversion coatings on aluminium alloys
and reduced subsurface cracking, but despite giving
thinner coatings than sodium hydroxide,212 it gave
higher impedence in both the sealed and the unsealed
state.212 Cerium coated carbonate pretreated panels
were reported to have survived for 48 h in neutral salt
spray (NSS), which was on a par with NaOH.212
Base then acid etching
Occasionally, researchers have used a combination of
base etching (usually in NaOH), followed by acid
treatment. There are essentially two varieties of this.
The first involves the use of non-oxidising acid(s),
such as Bondagard (H2SO4–H3PO4–HF)57,115 or acetic
acid17,52,58,130 or HCl.135 As noted in the two previous
sections, this leaves loosely held intermetallic smut on
the surface.17,51,52,58,98,115,130,177,209,210 Palomino et al.
tested different acid/base pretreatments and found that
they resulted in different Ce levels on the surface,58 but
there was no mention of the error margins in these
results or how adherent the coatings were.
The second version of base/acid etching involves the
use of oxidising acids and in particular nitric acid.
Rangel et al. found that, on AA 2024, this resulted in
dissolution of the matrix, local attack on intermetallics
and redistribution of Cu, formation of an alumina layer,
dealloying, redox processes associated with Cu(0)/(I)/(II)
and, on coating, the rapid formation of uniform Ce
containing layers.94,95 Significantly, however, it did not
result in any improvement in the corrosion resistance of
the coating.103 The coatings showed slightly higher
resistance when the base used was more dilute (0?03
versus 0?3%).94 On AA 2024, NaOH/nitric pretreatment
resulted in the surface oxide film going from an irregular
10–13 nm compact layer (as rolled) to a bilayered film
with a compact inner layer (3 nm) and an amorphous,
possibly hydrated, outer layer (to a total of 10 nm).210
Chromic acid has been used instead of nitric acid, but
the latter is preferred for desmutting (removal of
intermetallics).95,210 On AA 2024, chromic acid treat-
ment results in a 3 nm compact layer overlaid by
an open porous film (30 nm).210 Others have noted
that Cr containing pretreatments tend to result
in slow, uneven Ce coatings127,128 and poor corrosion
performance.127,141
There may be an argument for including additives in a
base/acid etch treatment. For example, Davenport et al.
found that S phase particles (which have a deleterious
effect on corrosion resistance) are unaffected by
sequential treatment with NaOH and nitric acid, while
AlCuFeMn (the other main constituent particles, which
are the preferential sites for fatigue crack initiation) are
only roughened by the treatment.97 The addition of
CeCl3 to the nitric acid only had a slight effect on
AlCuFeMn, but the S phase particles were completely
removed, leaving rounded holes.97 The treatment with
added CeCl3 also improved the corrosion performance97
and appears to inhibit accumulation of Cu on the
surface.97,214 Cu accumulation is apparently indepen-
dent of NaOH etching time if it is followed by nitric,
suggesting that the electroactive Cu is associated with
intermetallics rather than the matrix.97 This doped base/
acid pretreatment formed the basis of a patented surface
treatment process,215,216 although it may be that the
active agent in this case was, in fact, the chloride rather
than the rare earth.
252 Corrosion Engineering, Science and Technology 2013 VOL
Deoxidation
As received alloy surfaces typically display a build-up of
alloying components, particularly Mg,122,132,211 and
commercial pretreatments normally remove several
micrometres from the surface210 to leave an oxide layer
of relatively uniform thickness and composition.210 As
noted earlier, simply etching the surface of Al alloys
leaves insoluble residue or smut, which dulls the surface
and results in poor adhesion of plating or coating
films.51,209 The formation of deoxidised, smut free
surfaces for coating is, then, extremely important,121
and the choice of deoxidiser can have an important
positive127,128 or negative145,217 influence on coating
performance. The removal of smut is encompassed
within the term ‘deoxidation’.51,209
The most common method of deoxidation of alumi-
nium alloys is the use of acidified chromate or chromic
acid solutions.
Chromate deoxidation. The use of chromate deoxida-
tion was not uncommon early in the development of the
various Ce coating processes and has continued to this
day. Initially, it made sense to use a well understood
pretreatment when investigating a coating process that
was not well understood. In addition, some research
groups (e.g. CSIRO/DSTO, UMR) undertook extended
studies funded by aerospace companies (e.g. Boeing,
BAE Systems, Lockheed-Martin), whose processes,
including pretreatments, are all but set in stone, and it
made sense to introduce as few changes as possible. On
the basis of the available data, however, chromate
deoxidation is not a good choice as a pretreatment. The
earliest instance of chromate deoxidation was when
Mansfeld modified the Hinton CeCl3 immersion process
by applying commercial Cr based deoxidisers (Parker-
Amchem Deox 7/17) to AA 7075, AA 6061 and graphite
AA 6061 MMC.20,81,172,201–203,217,218 The CSIRO/DSTO
group also utilised chromate deoxidation (Parker-
Amchem/Henkel Deoxidizer 4/6/7/17) during the
1990s59,119,127,128 and later,77,126,129 but it was concluded
that, particularly on aerospace aluminium, chromate
deoxidation gave poorer protective and coating results
than other deoxidisers.120,123,127,128 More recently, the
group at UMR also used chromate deoxidation (Parker-
Amchem/Henkel Deoxidizer 7/11) before electrodeposi-
tion or immersion coating,12,13,31,32,131,141,219–221 although,
again, chromate did not appear to be a good choice. For
instance, they tested Henkel no. 7 made up with H2SO4141
but found that a dilute H2SO4 treatment149 gave superior
results.141
It is considered likely that chromate left on the
surface222 interferes with Ce deposition, which results in
coatings that are uneven and incomplete,127,128 resulting
in poor performance.127 This was a view also taken by
the group at UMR, who similarly found disappointing
NSS performance (48 h) with Cr deoxidised panels.141
Non-chromate deoxidation. A necessary part of devel-
oping a chromate free coating process is the develop-
ment of non-chromate pretreatments, and particularly
deoxidisers, in parallel with non-chromate coating
systems. Although there are a variety of non-chromate
deoxidiser chemistries available,4 there has been rela-
tively little work carried out on the use of non-chromate
deoxiders with Ce coatings. A number of resear-
chers have used nitric acid94,95,97,105,185,210 or mixtures
containing nitric acid,101 although, on AA 2024, S phase
48 NO 4

particles are unaffected by nitric acid, and AlCuFeMn
are only roughened.97 In addition, on aerospace alloys
(AA 2xxx and AA 7xxx), nitric generates thin (approxi-
mately 2–4 nm) Cu/Zn enriched alloy layers.105 The
addition of HF to HNO3 on the other hand has been
found to drastically affect the microstructure of
AA 2024, removing surface smut and etching the surface
around the intermetallics, many of which drop out
during treatment, leaving large pits in the surface.51 A
certain number of intermetallics, nevertheless, remain
and continue to generate galvanic couples with the Al
matrix of the order of a few hundred millivolts.51 There
are several non-chromate deoxidisers available from
commercial sources.4 Thus, Fe-based Henkel/Turco
Smut-Go NC-B has been tested on AA 2024126,223,224
and AA 7075/7475,126,225 and bromate-based Sanchem
1000 has been tested on AA 2024/7075/7475.126,225 The
Sanchem deoxidiser gave better results on AA 2024 than
the Henkel/Turco product, and results for AA 2024
were superior to the results on AA 7075, which were
similar for both pretreatments.194 Neither deoxidiser
performed well on AA 7475.194
Two groups have studied cerium containing deox-
idisers: CSIRO/DSTO, who devised low etch rate
deoxidiser (LERD) and high etch rate deoxidiser
(HERD),120,123 and DERA, who used a Ce containing
deoxidiser as part of their rare earth coating studies.96
Both groups found that the presence of cerium appeared
to have a beneficial effect on the coatings, although the
reasons for this are not understood and Ce-based
deoxidisers have not achieved wide ranging application,
either scientific or commerical.
The invention of LERD [0?5M H2SO4 and 0?05M
Ce(IV)]120,123 was based on the proposition that as
chromate based deoxidation provided a good base for
chromate coatings and a poor base for Ce coatings, then
a Ce based deoxidiser might promote the growth of Ce
coatings.121 This simplistic approach worked rather
well.77,113,120,121,123–126,128 The use of LERD markedly
improved the performance of Ce coatings121,128 and gave
good NSS results when used at up to 50uC, although
room temperature operation was also satisfactory.120,123
A range of modifications to the basic LERD formula
were tested, but without much improvement,120,123 and
all that could be readily concluded was that shorter
deoxidation times required longer coating times.120,123
As might be expected from the name (LERD), the etch
rate is low by comparison with other commercially
available Cr free deoxidisers.126 It has been tested on
AA 2024/7075/747577,126,225 and gave excellent results
on AA 2024, good results on AA 7075 and poor results
(like everything else) on AA 7475. An early summary of
what was understood about the mechanism of rare earth
deoxidation may be found in the literature, along with
tentative suggestions as to how this might facilitate the
deposition of Ce.124 The CSIRO/DSTO group also
invented a second Ce containing deoxidiser, known as
HERD,120,123 whose composition [0?05M Ce(IV), 0?5M
H2SO4, 1?3M HNO3, 0?04M F, plus optional oxidant]
could be described as approximating a Ce analogue of a
chromate deoxidiser. The presence of fluoride results in
much higher etch rates, and the optional oxidant (H2O2
or persulphate) effectively removes copper that is
otherwise redeposited over the surface during etching.226
Surprisingly, on AA 2024, it shows a tendency to leave a
Corrosion Engineering, Science and Technology
Harvey Cerium-based conversion coatings on aluminium alloys
large proportion of the intermetallics behind.51,226 As a
result, HERD has not been used much with Ce
coatings,60 and there has been little follow up on its use.
A group at DERA investigated a variety of acidic
pretreatments, several of which were doped with Ce.96
One Ce containing pretreatment in particular gave good
results, but it is difficult to determine the effect of the Ce,
as there were no data covering a non-Ce control.96 A
parallel experiment showed that in one case, addition of
Ce to the pretreatment made no difference to the coating
performance, while adding less Ce actually improved the
coating.96 [It is not, incidentally, advisable to combine
both fluoride and Ce(III) in the one solution as these
experiments did, as CeF3 will be precipitated.227]
Post-deoxidation treatment
There have been relatively few examples of post-
deoxidation treatments before coating.
Rangel et al. examined the effect of adding a known
corrosion inhibitor (benzotriazole) after deoxidation but
found that it resulted in poorer coating morphology and
longer deposition times, suggesting that redeposited Cu,
rather than intermetallics, plays the most critical role in
Ce formation.95
The group at UMR found that a boiling water
pretreatment increased the rate of coating deposition,
but it also led to a substantial amount of film cracking,
which they believed was the reason for poor NSS
performance.147 The use of a boiling solution of
phosphate as a pretreatment, by contrast, did not result
in any increase in coating deposition and gave even
poorer performance.147 The group at DERA published
an unusual process that deposited a mixed Ce/La layer
onto a regrown oxide surface on AA 2024 via a hot
water treatment.96 This was reported to have given very
good corrosion performance and paint adhesion.96
Rungta patented a method whereby boehmite was
grown on the surface in ethanolamine solutions (80uC,
4 min) and before immersion in Ce(III) (57uC,
15 min).67 The UMR also tried a pretreatment variant
by reimmersing their panels in the alkaline cleaner after
acid etching (in H2SO4).116 It was not clear, however, if
there was any effect. Yu et al. used a fairly standard
coating system (Ce/H2O2) to put a coating on an
anodised layer over AA 202499,100 and AA 6061/
SiCp.183 While they claimed similar performance to Cr
sealed anodised coatings,100 it took 2 h to generate a
coating,99,100,183 which would be prohibitive for com-
mercial applications.
Jaworowski and Kryzman immersed AA 6061 in a
solution of amonia/tungstate (at pH 11–12) and then in
Ce nitrate (pH 3?5–3?6). This formed a layer of
Ce2(WO4)3 about 1–1?5 mm in thickness, which was
claimed to result in an order of magnitude decrease in
corrosion rate.228
Coating processes
The elements of an ideal non-chromate coating process
would include the following:
(i) it should be inexpensive177 with similar costs to
Cr229
(ii) it should require no more steps than Cr
processes177,229
(iii) it should require similar processing time to
Cr177,229
(iv) it should use non-toxic chemicals229
2013 VOL 48 NO 4 253
Harvey Cerium-based conversion coatings on aluminium alloys
(v) it should require bath temperatures ,60uC,229
with room temperature operation preferable177
(vi) it should have a robust and reliable bath
chemistry229
(vii) it should produce a coating with an identifiable
colour229
(viii) it should be applicable to a wide range of Al
alloys.229
Cerium based conversion coatings can be applied to
aluminium alloys by electrolytic deposition,53,148,188
spray,148 swabbing10,148 and immersion processes.53,148,188
Immersion processes may be further divided into those that
are unaccelerated188 and those that are accelerated either
thermally188 or chemically.151,122 These deposition processes
will now be examined.
Electrolytic deposition
Electrolytic deposition is a potentially useful procedure
in that it actively drives the coating process across the
whole alloy surface, unlike, for example, immersion
coating, which can result in coatings mainly over
cathodically active sites89 (see the section on ‘Where
the coating forms’). In addition, it should combine mild
operating conditions (temperature, pressure) and gen-
erate pure coatings with controllable thickness.190
Theoretically, electrolytic deposition should also provide
better corrosion protection.89 The problem is that, to
date, no one has managed to successfully implement
these potential advantages.
The first examples of electrodeposition of cerium onto
aluminium appear in the 1980s, where Hinton et al.
deposited pale gold coatings onto AA 7075 from
aqueous 2-butoxythanol containing Ce nitrate.136,230,231
Small additions of water were required for the process to
work. Potentials of 20–50 V (100–150 s) were optimal,
and exceeding levels of 3%Ce nitrate or 3% added water
resulted in cracked, powdery coatings of poor quality.136
It was eventually concluded that the coatings lacked
durability due to a variety of discontinuities, including
blistering232 and cracking232 and perforations caused by
hydrogen evolution.36,231 Poor adhesion was also an
issue.231 It was eventually concluded that the process
was inconvenient232 and that the high voltages required
for operation with the organic solvent would make scale
up difficult for commercial application.36 Hinton’s
group abandoned electrolytic deposition in favour of
immersion coating (see the section on ‘Accelerated
immersion coating’), although other groups took up
the challenge of the electrodeposition route some years
later.
The group at UMR, for instance, spent considerable
time examining electrolytic deposition on aerospace
alloys12,13,31,142,221,233 while under contract to Boeing.
Curiously though, this effort was later described
as a mere preliminary to developing an immersion
process.147 The conditions of their electrolytic deposi-
tion process in its final state have been described in the
literature144 and incorporated cerium nitrate, nitric acid,
gelatine and hydrogen peroxide.148 The coating was
subsequently sealed with hot phosphate.144,148 Variables
such as pH, additive concentration, coating time,
potential and current density were examined.144 It was
found that too high a solution temperature (.40uC) led
to poor coatings,234 and efforts to raise this limit using
organic additives were not successful.144 It was claimed
that Ce7O12 was deposited by the electrolytic process,
254 Corrosion Engineering, Science and Technology 2013 VOL
which then converted to Ce(III) phosphate during the
sealing step.148 There were mixed signals as to the
success of the process. It was claimed at one point to be
an order of magnitude faster than immersion coating,148
which is difficult to understand as most immersion
processes generally require a few minutes at most (see
the section on ‘Effect of coating time’). It was also
described as producing good surface coverage and
coatings,144 although the same paper concluded
that the process was more expensive than immersion
coating144 and could not be adapted to repair
processes.144 In addition, the coating reproducibility of
this patented process233,234 was poor32,144 due to the
organic additive that reduced corrosion performance
and primer adhesion.144 Work then seemed to have
been discontinued in favour of a largely conventional
immersion process,144,146 as it offered better ease of
application.146 Recently, however, UMR has published
more work in the area.118
Other researchers have also used electrolytic deposi-
tion on a variety of alloys, including AA 2024,115
3A21,235 A360/A361/A380–SiCp,89,187,188,190 A36186
and LC4,179 with improvements in corrosion resistance
noted.179,187,188 In an interesting paper, Tang et al.
recently reported an electrolytic method that drove the
coating process through a solution soaked sponge.294
The coatings were comparatively thick (3–4 mm) and
corrosion resistant, although they required some base/
acid pretreatments before application.294
Spray coating
The group at UMR has also expended consider-
able effort on the development of a spray coating
process for aerospace alloys, largely because of
the ease of application.146 The general process entails
spraying samples (AA 2024/AA 7075) with a CeCl3–
H2O2–gelatine mixture at pH 2?1 for between 5 and 20
spray/drain cycles (50uC), rinsing, drying (rt, 24 h) and
sealing in sodium phosphate (85uC, pH 4?5,
5 min).108–112,114,118,137,139,148,205,211,213 Cerium nitrate
was tested as a Ce source but was found to be ineffective
in the spray process,139 and although the use of chloride
resulted in subcoating cracking, it also provided a far
more corrosion resistant coating.139 The composition of
the spray solution has varied slightly over the years,116
although the components remain the same and the main
area of development appears to have been in the area of
the pretreatment, as this was found to be a critical
factor affecting deposition rate, thickness and coat-
ing performance.109 Initially, a minimalist approach
was taken, with alkaline cleaning being the only
pretreatment used.108–110 This was then upgraded to
include the use of a sulphuric acid etch (tested on both
AA 2024 and AA 7075, but preferred only for
AA 2024)111,112,114,116,118,211 or base etch (later the
preferred treatment for AA 7075).112,114,213 This, not
surprisingly, resulted in a considerable improvement in
the coating rate, as the acid treatment exposed Cu rich
intermetallics,111,112,114,211 more commonly known as
smut. While this increased the coating thickness and
significantly improved the corrosion resistance,111,112
there must be deleterious effects on the coating
adhesion. It was claimed that Ce7O12 was deposited by
the spray treatment, which then converted to Ce(III)
phosphate during the sealing step.148 Some self-healing
has been observed taking place in defects, which was
48 NO 4

apparently not due to either the Ce or the phosphate
seal.236 It is not clear, however, that the authors
excluded the possibility of the soluble gelatine in the
coating migrating into the defects.
It is difficult to draw conclusions about the future of
spray processes. If immersion is a problem that spray
processing is intended to circumvent, then it faces the
problem that the required pretreatments all use immer-
sion. In addition, the spray coating compositions
published to date all use high chloride solutions and
non-standard pretreatments and require long coating
times due to the necessity to carry out multiple spray/
drain cycles.211 High chloride means that all process
tanks and lines must be specially lined to prevent
corrosion. These factors, along with the unfamiliarity of
non-standard pretreatments, may result in slow take up
by industry. As noted earlier, the pretreatments being
used to reduce coating times suggest that the coatings
will have poor adhesion. Moreover, it has been our
experience that spray processing results in rapid decom-
position of the peroxide accelerator, which raises the
cost of operation significantly,194 although this has not
been discussed in the literature to our knowledge. There
may be solutions to these problems, but it would appear
that spray deposition of Ce coatings has a number of
hurdles facing it before it can be considered for
mainstream application.
Swabbing
In-service coating repair processes are all but indispensible
in applications such as aerospace, but have largely been
ignored in the literature, probably because they exclude
the more common coating methods. Immersion is not
appropriate for obvious reasons, nor is electrolytic
deposition144 (although a recent electrolytic process by
Tang et al.,294 inaccurately described as a ‘brushing’
process, may be), and spray treatments have not been used
in this application as yet. Application of Ce coatings as a
gel has been suggested,237 although it has never been
implemented. Swabbing would seem the best option for
implementing a non-chromate repair process, although it
is almost completely absent from the literature. A single
Ce based swab repair process has been reported.10
Surprisingly, no standard tests appear to exist to measure
the integrity of a repair process. In the absence of such a
test, two were devised involving scoring and cross-
hatching repaired areas and comparison with a control
area after 720 h NSS exposure and 5000 h outdoor
exposure.10 Using these tests, Ce repairs were found to
perform as well as chromate.10 A significant obstacle to the
implementation of any non-chromate process is devising a
suitably wide ranging and satisfactory demonstration that
the new process can replace the old without introducing
new problems. This is certainly true of Ce coatings, and
particularly in the aerospace industry, which is very
conservative in introducing new processes where failure
can be catastrophic. Swab/repair processes are, poten-
tially, one means of demonstrating satisfactory in service
performance on small non-critical areas of an airframe
and could build confidence in the application of non-
chromate coatings on a larger scale.10 To the best of the
author’s knowledge, this challenge has yet to be taken up.
Immersion coating
In examining immersion processes, it becomes apparent
that there are two quite different coating regimes. The
Corrosion Engineering, Science and Technology
Harvey Cerium-based conversion coatings on aluminium alloys
first is an unaccelerated process entailing room tem-
perature immersion in solutions of Ce salts for long
periods (days to weeks) at neutral pH140,195,238 and
which is generally restricted to the more active
aluminium alloys. The second is an accelerated process,
entailing immersion in acidified, oxidising Ce solutions
for short periods (minutes),232,239 sometimes with
additives to enable satisfactory coatings to form. Both
the accelerated and non-accelerated processes originated
in work by Hinton and his colleagues.195,232
Non-accelerated immersion coating
The first (non-accelerated) immersion process stemmed
from experiments in 1984 onwards by Hinton et al. when
studies of various rare earths196,197,238 on steel,197,240
zinc197,241 and AA 7075 140,195,238 showed that immer-
sion in low levels of Ce(III) salts produced corrosion
inhibition. In addition, crevice corrosion, stress corro-
sion crack initiation, corrosion initiated fatigue failure
and stress corrosion crack propagation were also
reduced on AA 7075.238 While the initial focus was on
corrosion inhibition, the development of faint yellow
coatings in cerium solutions was noted a number of
times in early papers,231,238 and cerium had been
specifically chosen for testing because it formed an
insoluble hydroxide.195,196 It was subsequently shown
that a compact film of cerium oxides/hydroxides had
formed.79
Mansfeld et al. subsequently applied Hinton’s
process to AA 606120,80,81,172,201–203,217,218,242 and
MMCs20,201–203,217,218 and found that it behaved similarly
to chromate.217 Indeed, it was concluded that cerium
chloride passivation was a viable alternative to chromate
on Al alloys,20,81,201–203,218 although its potency varied not
only among different alloys (e.g. AA 6061 and AA 7075)
but also between different alloy tempers (e.g. AA 7075-T6
and AA 7075-T73).202,203,217,217 (It is not widely appre-
ciated, however, that the performance of chromate
coatings also varies considerably between alloys,77 so this
may be less of an issue than it might seem at first.243) Other
authors have applied this process to pure Al,83 AA 2014,84
AA 2024,106,198,199 AA 5083,78,161,164,166,167 AA 6061,88
AA 8090,82 AA 6061z10%Al2O3,21,244 AA 6061z
8%SiC, A3xx.x/SiCp187 and SiCp/5A06.180
85
The extended coating times for the non-accelerated
process have long been understood to be impracti-
cal,64,140,195,197,217 and later authors have confirmed
this.161,164,167,188,190,244 Coating times of 1,244 5,164,167
6,199 7,83–85,88,202,203,218,242,245 3078,80,82,202,203,217 or even
60 days21 are encountered in the literature. [Shorter
times (15–60 min) have also been used in combination
with higher temperatures.89,166,168,180 This was the basis
for a patent application,246 although Ce is not incorpo-
rated into the surface layer,166 which means that it is not
a true conversion coating process.]
Not surprisingly, it has been confirmed that the
deposition process is a progressive one.161 On AA 2024,
the most significant deposition was initially on dealloyed
CuMgAl2 intermetallics, then on AlCuFeMn and then
lastly on the bulk matrix,106 while on AA 5083, Ce only
deposits on the intermetallics, and not on the matrix at
all.167 On AA 5083, it was found that the layers given by
non-accelerated immersion and those deposited electro-
chemically were very similar by SEM.164 During the
corrosion of AA 5083 in aqueous NaCl, crystallographic
pitting takes place during the first day, then alkaline
2013 VOL 48 NO 4 255
Harvey Cerium-based conversion coatings on aluminium alloys
pitting subsequently commences.165 A side effect of the
Ce coating is that it delays the formation of a passive
layer, which prevents the formation of crystallographic
pits.165 Furthermore, Ce hinders alkaline pitting by
precipitating not only before attack starts but also while
attack is in progress.165 It has been reported that
pickling the samples before immersion led to greatly
improved corrosion resistance, although no supporting
experimental details or results were provided.21
In summary, the non-accelerated coating process is
essentially of historical interest only due to the long
coating times involved. For any practical purpose, an
accelerated process must be used, and it is to these that
we now turn our attention.
Accelerated immersion coating
As outlined in the previous section, simple immersion in
aqueous CeCl3 will slowly deposit a coating on more
active aluminium alloys (e.g. AA 2xxx/7xxx), but the
coating times are prohibitive for any commercial
application. On less reactive alloys (e.g. AA 1xxx/3xxx/
5xxx/6xxx or any clad alloy), a coating will only form
extremely slowly or not at all.129 For example, condi-
tions that will coat AA 2618 quite satisfactorily will not
generate any coating on AA 6061.57 Thus, some form of
acceleration is required in both cases, with the aerospace
alloys requiring somewhat less encouragement,129
despite claims to the contrary.102
A coating bath for a typical accelerated immersion
process consists of at least the following principal
components:41,42
(i) a Ce(III) salt
(ii) an acid to adjust the pH
(iii) an oxidiser (usually hydrogen peroxide).
A range of other materials may also be included. There
is, as a result, a wide range of bath components
and compositions that have been described in the
literature.58 These and other related matters are
discussed below.
Effect of anions. Chloride seems to be the most
favoured Ce source.174 Indeed, Decroly and Petitjean
claimed that chloride was essential to the coating
reaction,177 a determination noted by others as
well.114,174,190 Even so, Hardin et al. have patented a
low chloride process using Cu acceleration to forestall
corrosion of stainless steel processing lines.153 Conde
et al., by contrast, massively increased the amount of
chloride in an attempt to accelerate coating formation
on AA 8090,102 although the coating rate remained slow
(requiring up to 30 min), and the process failed
completely on AA 2024 and AA 7075.102
Sulphate is poorer at coating than chloride,173 being
slightly inhibitive to the coating process.177 Nitrate,
however, is strongly inhibitive to the coating
reaction114,177 and gives slow coating rates.118
Although nitrate does give more uniform coatings on
some alloys (e.g. AA 5083), they are reported to be less
corrosion resistant.157 This effect is complicated by the
passivation effect of nitrate on aluminium, as small
amounts of chloride appear to be necessary to activate
the surface247–249 and chloride has been shown
(on AA 7075) to be much more active for coating
formation than nitrate.139 Despite this, a number of
studies have used nitrate as their cerium
source.44,94,95,99,100,103,114,134,135,144,168–170,174,176,183,249 It
should be noted that although fluoride96,135,185 and
256 Corrosion Engineering, Science and Technology 2013 VOL 48
phosphate171 have been added to coating solutions
containing Ce(III) (for instance either as a salt or for
pH control as HF or H3PO4), both anions will result in
rapid and quantitative precipitation of the correspond-
ing Ce salt. For this reason, the practice should be
discouraged.
Effect of pH. Bath pH is one of the most critical
coating parameters and needs to be strictly controlled.
For architectural applications, for instance, the pH
needs to be maintained between 1?9 and 2?241,42 as,
outside these limits, the quality of the coating can
deteriorate dramatically42 and give a less corrosion
resistant coating.120,123 Other workers have also con-
firmed this general region as providing satisfactory
results.57,98,174,186 Fortunately, this degree of pH control
is not difficult.42 Lower pH values give better solution
stability, but generally slow the deposition rate,177
although the coatings are often quite uniform in
appearance.120,123 Higher pH values give faster deposi-
tion rates but at the expense of making the coating
solutions less stable177 and can result in the formation of
non-adherent, powdery coatings as well.120,123 This will
vary with the alloy. For example, coatings will form on
AA 2024 above pH 1?6,51 while AA 7075 gives
better corrosion results around pH 2?5121,232 and
noticeably lower coverage around pH 1?9.121 Although
higher pHs (.3) have been recommended in the
literature,99,100,102,169,171,177,183,185 this is generally inad-
visable, as coating solutions containing H2O2 become
unstable and precipitate Ce above pH 3.157,190 The
presence of Al3z ions increases the pH at which Ce
precipitates.247 As noted in the previous section, HF185
or H3PO4171 should not be used to modify the pH of any
solution containing Ce(III) (such as in the coating step),
as they will result in the precipitation of the correspond-
ing Ce salt.
Effect of oxidant. The most widely used oxidant
(accelerator) is acidified hydrogen peroxide, a discovery
made by Hinton et al. in the late 1980s.232 They had
postulated that the deposition of Ce coatings from
solution was due to the oxidation of Ce(III) by hydrogen
peroxide produced by the reduction of oxygen at
cathodic sites.241 The slowness of H2O2 generation in
solution offered an explanation as to why the yellow
coatings formed so slowly. Thus, it was reasoned, that
the addition of hydrogen peroxide to the acidic coating
solution should accelerate the coating formation. This
insight resulted in a 1988 patent,232 now abandoned,
which decreased the coating time required by between
four and five orders of magnitude, from weeks to
minutes.121 As virtually all subsequent work in the area
has depended on this concept, it can fairly be described
as the second of the two most critical process discoveries
in the field. Apart from accelerating the coating
kinetics,95,137,250 H2O2 also increases adhesion and
corrosion performance.239 Its effectiveness, ease of use,
ease of handling and the fact that its decomposition
products (water and oxygen) are harmless make H2O2
the oxidant of choice. Excellent discussions of the
chemistry of H2O2 in the coating process may be found
in the literature.122,247 It has been found that, in the Ce
coating reaction, H2O2 acts as a complexing agent, an
oxidant, a crystallisation inhibitor and a source of OH2
ions, resulting in precipitation (coating) reactions.125
The peroxide accelerated cerium coating process has
NO 4

become known generically as ‘cerating’,27,50,81,121,127,251–254
by analogy with chromating, despite the fact
that there are no oxyanions of Ce involved.6 Other
oxidants (e.g. NaClO4, KMnO4) have been
used44,91,114,137,141,145,147,149,173,174,176,190,237,255 but have
failed to gain much attention, in part because they have
been found to be less effective.114,143 Despite claims to the
contrary,190 peroxide acceleration is indispensible for
coating both non-aerospace170,173 and clad alloys, and, as
rare earth coatings on non-aerospace alloys are much
slower to form,121 some additional form of acceleration,
either thermal or chemical, is usually required (see the
sections on ‘Effect of temperature’ and ‘Effect of
additives’).
Effect of coating time. Coating times are dependent on
the alloy being treated (whether aerospace or non-
aerospace), the cerium source (chloride or nitrate), the
coating temperature, the reactant concentrations and the
pretreatments used. Coating times for aerospace alloys
(AA 2xxx/7xxx), regardless of temperature, are typically
of the order of 1–5 min,38,77,113 although longer times
(10124,130,144–15 min141,145) are also encountered. Non-
aerospace alloys typically take slightly longer (e.g.
20 min for AA 6063),176 although shorter periods have
been recorded as well (e.g. 5 min for AA 6082).177 These
differences, as noted previously, are process dependent.
The record for a peroxide accelerated process must be
held by Yu et al. for their double conversion coating on
AA 2024,101,256 which takes 2 h for the first step and
1?5 h for the second!101,256
Finer divisions have been observed during the coating
period. For instance, Hughes et al. discerned a variable
induction period during coating, where the alumina
thickens and cerium deposits on intermetallics and along
rolling marks, and a subsequent period where Ce coated
the general surface.77,122,124 Up to 20 s, there was no
change in surface composition, then Si was removed and
amorphous Al oxide growth occurred over the first 20–
50 s.124 Gas evolution is initially vigorous but slows as
coating proceeds124 and, against the commonly accepted
mechanism, appears to be oxygen.119,121 This may be
due to H2O2 decomposition.
Effect of temperature. Not surprisingly, increased
temperature generally leads to an increase in the coating
rate. For example, at room temperature, an acceptable
coating may require several days to form on some
alloys,166,190 while at 50uC, an hour or less may be
sufficient.166,190 A range of coating temperatures can be
found in the literature (e.g. 25,98 30,23,29,99,100,174 25–
35,101,256 45,113,152,154 60,96 80174,176 and 90uC168,207),
with the choice depending largely on the Ce salt being
used (chloride or nitrate), the alloy being treated and
whether an oxidant is present. The preferred operating
range for a commercial peroxide based process for
coating AA 5005 is ambient to 50uC.41,42
Despite its apparent importance, the effect of tem-
perature on corrosion performance has not been system-
atically explored in the literature. Hot (50uC) Ce nitrate
on AA 5083 gives coatings with corrosion performance
similar to room temperature coatings,166 although this
greatly improved at 75uC168 and decreased again when
the coating temperature was increased to 90uC.168
Dabala et al. found that corrosion resistance improved
on AA 5083 when the coating temperature was raised
from 20 to 35uC, but they also found that there was little
Corrosion Engineering, Science and Technology
Harvey Cerium-based conversion coatings on aluminium alloys
improvement when increased to 50uC.156,157 On
AA 2024, elevated temperatures have been reported to
give more uniform coatings, but the corrosion resistance
is not as good as coatings formed at ambient.120,123
Increased temperatures were also found to lead to
localised attack on the surface.190
There is at least one patent application that claims the
invention of heating the acidified H2O2 solutions for
accelerating the coating process,246 although a number
of other publications also mention the use of heated
coating solutions.38,119–122,127,128,150–153,257 In general,
however, elevated reaction temperatures are to be
discouraged with peroxide accelerated solutions, as
H2O2 starts decomposing rapidly at or .50uC. This is
further accelerated if there are any active metals present
(e.g. Fe/Cu), and the peroxide replenishment required
can make the coating process commercially unviable.194
Effect of additives. Coating times on some alloys
are excessive even with H2O2 acceleration (e.g. 120
min99–101,184,185,256), and the ease of coating differs
considerably among the less active alloys (e.g.
AA 6061.AA 3004.AA 5005150,151). It becomes
apparent that with such alloys, some form of additional
acceleration is required.
Surprisingly, it has been claimed that there are
relatively few reports on the use of additives with the
Ce coating process,174 although an examination of the
literature will show that this is not the case.
Transition metals and other accelerators. The purpose
of accelerators is, essentially, to activate the surface by
the deposition of nanocathodes across the metal.151,258
The first deliberate additions of accelerators were made
by Hughes et al.150 As cerium preferentially coated Cu
rich intermetallics in aerospace alloys such as AA 2024,
it was reasoned that the addition of Cu to the coating
solution might accelerate the coating formation on less
reactive alloys. Thus, transition metals were found to
accelerate coatings on non-aerospace alloys (AA 3004/
5005/6061) and to improve the coating quality (in
particular, the adhesion). This was ultimately the subject
of a US patent.151 There were considered to be two types
of additives, which were divided into those that form
peroxo species (e.g. Ti, Zr, V and Mo) and those that
did not (e.g. ZnCl2, CuCl2, MnCl2 and FeCl3). These
could be added as either simple inorganic salts
or as complexed compounds, with synergistic activity
being observed in the case of such mixtures as
Ti(peroxo)–Cu(glycinate).122 These additives reduced
coating times to a third or even a tenth of the original
process,121,150,151 although the added Cu lowered the
corrosion resistance of the coating.177 The other weak-
ness of this approach proved to be that Cu catalysed the
decomposition of the H2O2, thus adding a significant
process cost.152,154 (Ce, by contrast, does not decompose
peroxide.249) A subsequent development by CSIRO was
the use of bismuth complexes as accelerators for the less
active alloys.152,154,258 These complexes accelerate
the coating rate but do so without accelerating the
decomposition of the peroxide in solution152,154 and are
sufficiently mild that they can also be used on aerospace
alloys without producing powdery coatings.60 Typical
conditions use 50–150 mmol Ce, 300–600 mmol
H2O2 and 50–300 mmol bismuth accelerator, with
typical coating times of a few minutes to produce
coating weights on AA 5xxx/ AA 6xxx alloys of
2013 VOL 48 NO 4 257
Harvey Cerium-based conversion coatings on aluminium alloys
,500 mg m22.152,154 These catalysts are the basis of a
process that was commercialised by Chemetall for
architectural aluminium.41,42 Strontium chloride and
ammonium vanadate have been tested on AA 6063, and
both were claimed to increase the coating thickness
and the corrosion resistance, although SrCl2 was
regarded the better of the two,174,176 as vanadate
reduced the compactness and adhesion of the layer.174
Wang et al. claimed the use of ZnCl2 with acidified H2O2
to accelerate coatings on AA 2024.104 Zn is not,
however, present in a catalytic amount as might be
expected, being of the same order as Ce (15 versus
25 mmol). This result is puzzling, as cerium normally
deposits quite easily on AA 2024, although at pH 3, the
solution acidity may be too low for effective coating to
occur. On AA 6082, low levels of CuCl2 were found to
give faster coating and better adhesion,177 although this
idea was probably covered in a earlier patent.151 Other
transition metals (Fe/Sn/Mn/Co) were also tried,
but without success,177 as FeCl3 and SnCl2 imme-
diately hydrolysed, while Mn and Co had no effect
whatsoever.177
Gelatine (coating modifier). The group at UMR
has long included gelatine in their coating
formulations.33,137,144,255 It was claimed to improve
coating uniformity255 and adhesion144 by reducing both
the grain size145 and the cracking in the coating,145,148,205,259
which was thought in turn to improve the corrosion
performance.144,205,255 This did not work on AA 2024,
however,255 and appeared to reduce coating rate.205 In
addition, the amount of gelatine had to be controlled or
subsequent sealing steps could be impeded.205 The
situation is somewhat confused by the fact that some
gelatine containing coatings are still referred to as being
highly cracked,33 that some cracked coatings still
performed quite well118 and that complete elimination
of cracking did not, in any case, result in good corrosion
performance.33 Only one other group has reported using
gelatine in their coatings.171
Boric acid (‘stabiliser’). Boric acid has been used by a
number of authors58,99,100,130,183 as a ’stabiliser’,176,184,185
although it has not been made clear in any of these papers
what exactly is being stabilised, or how, or how well boric
acid achieves this function.
Factor assessments. Only a few groups have under-
taken broad examinations of multiple factors associated
with the coating process. Taylor and Hughes undertook
an early Plackett–Burmann investigation of process
variables.229 This enabled substantial improvements in
performance and the elimination of one of the pretreat-
ment steps then in use.229 Decroly and Petitjean tested
the effect of different Ce salts, pH, time, H2O2
concentration, buffers, catalysts and surfactant on
coatings on AA 6082.177 They found that coating could
be accelerated by increasing peroxide or pH levels.177
Sun et al. carried out an orthogonal experiment covering
three composition factors, four different levels and
two accelerants (strontium chloride and ammonium
vanadate). Coating thickness was most affected by
solution temperature.oxidiser concentration.Ce con-
centration, although for best corrosion performance, the
order was Ce concentration.oxidiser concentration.
solution temperature.176 It was found that increasing
the solution temperature reduced the density of the
coating.44 Pardo et al. investigated the effect of stirring,
258 Corrosion Engineering, Science and Technology 2013 VOL 48
degreasing, pH, Ce concentration, H2O2 concentration,
anion type, coating time and temperature on A3xx.x/
A3xx.x-SiCp alloys.190 They (like Decroly and
Petitjean177) noted that deposition increased with pH,
but solution stability decreased.190 They found 50uC
optimal for coating, using 2000 ppm CeCl3 for
10 min.190 Dabala et al. coated AA 5083 over a range
of conditions [CeCl3 (10–20 g L21), H2O2 (100 mL L21)
at pH 2 for 2–10 min and 18–50uC156] and found that
the corrosion resistance improved from 20 to 35uC,
although there was little subsequent improvement at
50uC.156,157 Using cyclic voltammetry, it was found that
(at 50uC) corrosion performance improved up to 10 min
coating time and decreased thereafter.156 Increasing Ce
concentration produced no improvement in perfor-
mance.156 Later, Dabala et al.157found that for CeCl3,
corrosion resistance increased with temperature (rt to
50uC) (which was less marked if nitrate was used
instead), time (2–10 min, decreased thereafter),
increased pH (1–3) and lower H2O2 concentration
(100–200 g L21), while changing the Ce concentration
had little effect over the range studied (20–40 g L21).
Higher temperatures gave ‘no sensible effects’.157 They
concluded that the optimum conditions for coating
AA 5083 were CeCl3 (20 g L21), H2O2 (33 vol.-%)
(100 mL L21), pH 2, 50uC, 10 min.157 These are within
the ranges suggested also by Chemetall researchers.41,42
Recently, an interesting comparison has appeared on
the effect of the various coating conditions published by
five different research groups.118 It was found that
nitrate coating (e.g. Zhang, de Frutos and Rangel) gave
little etching but gave low coating rates. The formula-
tion used by CSIRO/DSTO gave very light etching and
very good coatings, but it was concluded, somewhat
surprisingly, that the pretreatment used might adversely
affect deposition rate, coating thickness or corrosion
protection.118 Published data, however, would suggest
that it does not.77
Coating formation
How the coating forms
Hinton and his colleagues, in their first papers on Ce
corrosion inhibition, proposed that local pH increases
occurred at cathodic sites as a result of O2 reduction, which
resulted in the precipitation of Ce oxide, thus reducing the
cathodic current and therefore the overall corrosion
rate.79,195,196,231,238 This was not unexpected,260 and cerium
had been specifically chosen for testing because it formed an
insoluble hydroxide.195,196 The mechanism was reiterated in
later papers59,127,128 and was confirmed, or simply repeated,
by many later researchers.9,15,19,21,23,33,41,42,53,58,59,80,91,92,
113,114,119,121,139,143,144,157,159,160,162,168,170,173,174,198,256,260–265
In
fact, the mechanism accepted today is essentially the same
as that proposed by Hinton et al. in 1985,52 although it may
have had an antecedent in the work of Da Fonte et al.266–268
It may also be noted that, while all the rare earths will
precipitate given a high enough pH, only two of them,
cerium and europium, have oxidation couples [Ce(III)–(IV)
and Eu(II)–(III)], which are stable in aqueous solution.227
As aqueous Eu(III) is reduced to Eu(II) by aluminium and
Eu(OH)2 is water soluble,227 Ce is the only rare earth that
can involve a change in oxidation state and form a water
insoluble hydroxide/oxide on aluminium.
While Ce in the coatings has been found in a
few preparations to be mostly or completely in the
NO 4

Ce(IV) state,119,186 mixtures of (III/IV) are far more
common.23,29,57,59,104,135,140,141,146,147,175,176,185,248,256,269 In
fact, the Ce(III/IV) ratio varies considerably,155 and the
higher oxidation state appears to be due to the effect of air
oxidation256 during either formation or subsequent
aging.270 In fact, the group at UMR showed that, in the
presence of air, a yellow Ce coating forms on AA 7075,
while under argon, a colourless, translucent gel forms.143
Davo and de Damborenea have also observed the
formation of a transparent Ce layer with little or no
Ce(IV).82
The question remained51 as to whether the pH increase
precipitated Ce(III), which was then oxidised to Ce(IV)
(the four-electron mechanism),155 or the oxidation pre-
ceded the precipitation (the two-electron mechanism).263
There was evidence that Ce(III) was precipitated first or,
under anaerobic conditions, that Ce(IV) was favoured if
oxygen or H2O2 was present.263 The latter mechanism is
now accepted,41,42,271,272 although this may depend on the
metal being coated.272 The solution chemistry during the
formation of Ce coatings has probably been most clearly
articulated in the work of Hardin and Hughes.122 To that
point, the role of peroxide, known to be critical in the
process, had not been described well. The presence of
peroxide in the coatings was later confirmed by Raman
surface studies.125
Where the coating forms
It is generally accepted that cathodic intermetallics
are significant contributors to coating nuclea-
tion,15,51,53,58,59,77,86,89,92,102,106,114,119,122,124,128,159,160,162,169,
198,260,264,265
descriptions of which may be found in the
literature.11,82,98,121,262,273–275 Intermetallics vary in their
electrochemical character53,59,197,260 and hence in H2O2
reducing efficiency, and this can further vary during the
corrosion process.95,106,264 Thus, there is a hierarchy of
cathodically active sites on the surface,106,260 and, as the
most active sites become passivated, the next most active
sites can take over. It should be noted, however, that no
coating will occur over an as-received metal surface, even
over intermetallics that will cause Cr to deposit, so the
cathodic nature of the intermetallics is not in itself a
sufficient condition to generate a Ce layer,51,98 and the view
that intermetallics are the chief contributor to the
formation of Ce coatings is not universally held.52,98,168
Indeed, it has been pointed out that the coating can also
form along a range of electrochemically active areas,
such as grain boundaries,1,82,241 oxides, contaminants,
surface variations made during manufacture (such as
rolling marks),1,59,122,124 preferentially etched areas form-
ed during coating, hardening precipitates at grain
boundaries121 as well as on smut left by incomplete surface
etching.51 Significantly, enrichment of copper by replating
on the surface has been observed92,95,98,124,262 and is
thought by some to play a significant role in coating the
matrix of aerospace alloys.17,58,98,122,124,247 Indeed, it is this
lack of distributed cathodic sites through Cu enrichment
that is claimed to inhibit generalised coating from
occurring on non-aerospace alloys.51 This has prompted
extensive research into accelerators to promote coating on
non-aerospace alloys (see the section on ‘Effect of
additives’).
What the coating is...
Physically. Cerium coatings are generally light
yellow to golden in colour6,134 and form as either
Corrosion Engineering, Science and Technology
Harvey Cerium-based conversion coatings on aluminium alloys
amorphous44,174,256 or nanocrystalline145,174 gel271,276,277
spheres or nodules,29,77,102,104,145,174,176,184,185,256 which
agglomerate into a continuous film44,102,184,256 even-
tually covering the entire matrix.174,185 The spheres/
nodules are, of course, Ce rich29,147,149,174,176,185 (and are
occasionally claimed to contain a small amount of
Al176,185) and can vary from 5 to 500 nm in
size,141,145,147,149,185 with the thickness increasing with
time77 to several micrometres.185 Li et al. observed
microscopic crystalline units over the surface, which
then act as the active centres for the deposition of the
bulk of the coating over the surface.271,276,277 The
processes of nucleation and growth are comparatively
slow.271,276,277 A consistent physical feature of the
coatings is a morphology similar to cracked or dried
mud.12,13,17,23,29,50–52,57–59,104,115,117,119,124,130,135,144,149,
156,157,161,174,181,184–186,231,252,259,278,279
These cracks have
long been understood to form due to drying of the
gel,17,51,58,115,119,124,135,144,161,174,181,231,279 which cannot
only happen in the vacuum of an SEM, but
has also been observed to occur in air under an optical
microscope.144 Occasionally, however, this surface
cracking is still credited to process variations rather
than to, for example, the use of the SEM, which has
been used to observe and characterise the cracking. The
cracking has long been blamed for poor corrosion
performance of the coatings117,144,186,259 and has been
claimed to be a weakness of the process,17,89,141,147,174
although in fact, few cracks go through to the metal
surface.52 It has been claimed that cracks form only over
intermetallics containing Fe, Cr or Mn,156 although this
is disputed.52 In addition, some cracked coatings have
been shown to perform quite well,118,280 and complete
elimination of cracking does not result in good
corrosion performance in any case.33 It should be
pointed out that chromate coatings also exhibit this
type of cracking.14
In summary, however, the effect and importance of
the surface morphology on Ce coating performance is
not well understood.
Chemically. The Ce coatings have been described as
mixed Al–Ce layers41,42,57,128 or as layers composed of
mixed Ce rich and Al rich areas.59,104,124,157 Some
workers have found that the coatings contain no Al at
all.149,155 Others find evidence of a bilayered coating.
Early Auger studies showed a top 100140,238–200 nm196
layer of principally Ce oxide, with another 100 nm of
mixed Ce–Al oxide.140,196,238 Later workers found a
hydrated aluminium oxide layer overlaid by a Ce rich
layer 0?1–0?2 mm thick77,122,124,127,128,140,247 that was
thought to indicate a two-stage coating process invol-
ving oxide growth followed by Ce deposition.77,247 Some
of these differences may be caused by non-uniform Ce
layers or to irregularities in the Ce/Al interface due to
surface roughness.115 The Ce component of the coating
was initially described as a mixture of CeO2, Ce(OH)4,
and Ce(OH)3140 or just CeO2 (fluorite),140 but the
situation appears to be more complicated than this.
Pourbaix diagrams are usually invoked to explain the
precipitation of the various cerium containing phases on
the surface, and a number of updated Pourbaix
diagrams have been published.124,143,169,281 There are
difficulties however in identifying solution species with
titrated species,125,169 and Pourbaix diagrams (even
covering such useful areas as the Ce–H2O–H2O2/O2
2013 VOL 48 NO 4 259
Harvey Cerium-based conversion coatings on aluminium alloys
system)281 are equilibrium diagrams, and there is the
possibility that the Ce containing species may be a non-
equilibrium cerium peroxo complex122,125 or a dimeric
species.282 Other candidates that have been suggested
include CeO2 (fluorite),124,140 CeO2.2H2O,114 hydrated
Ce oxide,139 mixtures of CeO2, Ce2O3, Ce(OH)3,183,199
Ce(III/IV) hydroxides,270 Ce2O3, CeO2, Ce(OH)3,
Ce(OH)4 plus hydrates,175 Ce(III/IV) oxide and carbo-
nate104 and Ce hydroxide and carbonate and Ce peroxy
or Ce peroxycarbonate species.59 Some researchers
have simply stated their view that the orange colour
of the coating is diagnostic of a simple Ce(IV)
species.115,169,177,241 The problem is that X-ray diffrac-
tion has shown that the coating is not consistent with
hydrated CeO2 or hydroxide or indeed any other known
oxidic form of Ce,249 so it is difficult to be confident
about these identifications. Although it was claimed that
electrolytic and spray coatings were Ce7O12,148 it has
been found that immersion coatings do not match any
known Ce oxide or hydroxide [CeO2, Ce7O12, Ce6O11,
Ce(OH)3].145,147,148,184,185 Raman spectroscopy has con-
firmed that peroxo (O2{ 2 ) is present on the surface and
would seem to support the suggestion that the coating
contains Ce(OH)x(OOH)y species.113,125 The presence of
a peroxo species is supported by thermogravimetric
analysis, which shows a large loss of O2 at 100uC.247 A
progressive loss of colour has been noted in the coating
with time,125,144 which has been attributed to hydroxide
transforming to oxide144 or degradation of surface
peroxo species.125 The latter suggestion is supported by
the fact that the coating colour may be restored if the
panel is dipped briefly into a dilute solution of hydrogen
peroxide. Ce peroxo compounds are not unknown in the
literature,283 and some are surprisingly stable.284
If the coating is, in fact, based on a peroxo species, it
would go some way to explaining why the characterisa-
tion data have not been matched to Ce oxides or
hydroxides. It should be borne in mind that the coating
may, instead, consist of mixed crystalline and amor-
phous phases and that surface species (i.e. peroxide) may
not be typical of the bulk of the coating. In any case, the
issue of coating composition cannot be said to be settled.
Post-treatments
Air drying
The simplest post-treatment after a water based coating
deposition process is air drying, and most published
processes incorporate a drying step, either implicitly or
explicitly. The variation in the conditions used is
interesting, but of greater interest is that there seems
to be little or no published evidence for any drying step
at all and the conditions reported in the literature appear
to be more or less arbitrary. Thus, reports of drying at
ambient (24 h),33,110,111,117,137,149,205,213 50uC (30 min),98
60uC,94 50–100uC,180 60–120uC41,42,190 and 160uC
(10 min)67 are encountered. Pardo et al. claimed an
optimum drying temperature of 105uC,89 but this is not
particularly helpful, as nothing was tested below this
temperature.190 Also unhelpful are references to drying
in an ‘air furnace’103 in ‘hot air’102 or at up to 500uC
(!).190
Two points may be made. The first is that while
500uC190 will certainly convert any amorphous Ce oxy/
hydroxide to an oxide layer, it will also destroy the
temper of a wrought alloy, distorting it and spalling off
260 Corrosion Engineering, Science and Technology 2013 VOL
the layer in the process.285,286 So, this is not recom-
mended. In the case of AA 2024, exceeding even 120uC
is inadvisable.286 The second point is that most of the
drying conditions reported for cerium are well in excess
of what chromate coatings are capable of withstanding,
without irreversibly compromising the corrosion protec-
tion of the coating (,60uC).6,35,287,288
Thus, while there is nothing necessarily wrong with
heating Ce coatings to dry them, as Ce, like Cr, deposits
as a gel, there appears to be little or no supporting data
for recommending it either.
Sealing the coating surface
It has long been known that the corrosion protection
provided by bare Ce coatings is not sufficient to
withstand the rigors of NSS testing.127 In order to
increase the durability of the coating, it is necessary
to seal the coating.177 A variety of methods have
appeared in the literature for doing this.
Hot water
The least complicated sealing process is hot water
immersion. The group at UMR has looked at immersing
coated samples in boiling water12,13,141 to decrease the
amount of water in the coating and to thicken the oxide
layer on the Al.12,13 The coatings changed from orange
to olive in colour and were claimed to be improved.12,13
Sealing in hot water (over an electrolytically deposited
coating) did not improve corrosion performance
however,144 nor did the inclusion of the organic
additives polyethylene imine or triethylene tetramine.144
In fact, SEM analysis suggests that hot water treatment
either significantly disrupts the coating144,145 or removes
it entirely.147 This probably explains why hot water
sealing is no longer being pursued as a sealing step.
Silicate
Silicate is a known corrosion inhibitor24 and has been
used for several decades for sealing surface coatings.266
It has been most widely used on Ce coatings by the
group at CSIRO/DSTO, who found that it provided
significant improvements in NSS resistance.121,122,128 It
appears to have been used first at room temperature (as
10% KSil) for 5120,123–10 min127,128 with an immediate
post-seal rinse. This formed a 0?4 mm silicate layer that
contained no Ce127,128 and allowed NSS performance of
up to 336 h without pitting.127,128 It was thought that
silicate might react with metal through flaws in the Ce
coating, thus improving its performance.127,128 The same
papers also mentioned allowing silicate to dry overnight
before rinsing, a process that was adopted in later
experiments,77 but for which no experimental results or
rationale has been provided.127,128 Silicate immersion
(10% KSil/10 min) at 80uC, dried overnight and then
rinsed, could provide impressive NSS performance77 (see
section on ‘Salt spray results (CSIRO/DSTO)’). Silicate
was tested with a variety of dopants (including glycerol,
vanadate, permanganate), but these provided no
improvement over silicate alone.120,123 While it can
provide excellent corrosion resistance, silicate suffers
from a significant drawback in that it absorbs carbon
dioxide from the air, and so the bath chemistry (and
hence the performance) constantly changes,6 particu-
larly at higher temperatures. This issue has not been
satisfactorily resolved.
48 NO 4

Phosphate
Given the widespread use of phosphate coatings for
corrosion prevention on metals such as Fe and Zn and
the insolubility of cerium phosphate, it was perhaps
natural that treatment of a cerium containing layer with
phosphate would suggest itself. This idea was originated
by CSIRO in the early 1990s under work funded by
Boeing289 and was developed further by the group at
UMR, under a later collaboration with Boeing. In fact,
UMR and others171,173,235 use phosphate sealing to the
present day. The simplicity of the phosphate sealing
and the stability of the solution have much to com-
mend them, and it markedly improves the corrosion
performance.145,147,173 Initially, immersion in 2?5%
sodium phosphate at or near boiling at pH 4?5–7 was
preferred.12,13,31,131,141,142,144,147,148,221,233 Data (SEM)
showed that this significantly disrupted the coating
layer144,145 or even removed it entirely.147 The treatment
conditions were altered to 85uC for 5 min145,148 and were
later standardised to immersion in sodium phosphate
(2?5%, 85uC, 10 min, as either NaH2PO4139,212 or
Na3PO4 adjusted to pH 4 with H3PO4)213 and dried in
air for 24 h.33,110,111,117,137,205,213 The treatment converts
the surface to Ce(III) phosphate148 after being predo-
minantly Ce(IV).145,147 Transmission electron micro-
scopy found the CePO4 layer is typically 200 nm thick
with a grain size of 5–10 nm.110 The microstructure of
the coating changes significantly144 after phosphate
treatment (from spherical nodules to random needles
which grow together),237 and the particle size increases
slightly.145 It has not been reported to date, but such a
microstructure should improve adhesion to paint layers,
although at the expense of reduced effectiveness as a
barrier film. Phosphate has been claimed to decrease the
degree of cracking in the coating,117,205,235,237 which has
been cited as an explanation for it resulting in increased
corrosion performance, but since the complete elimina-
tion of cracking does not result in good corrosion
performance,33 this can hardly be correct. Ammonium
phosphate (NH4H2PO4) has also been used,33 as has
Na3PO4235 and NaHPO4,173 but pyro- or polyphosphate
is apparently unsuitable, as they do not form phosphate
on the surface, although they do reduce cracking of the
layer.33 It may also be noted that it is not simply the
presence of the phosphate which is important, as sealing
without the presence of the cerium results in corrosion
performance equivalent to a bare panel.33
Other sealing methods
Considering the importance of post-coating sealing in
overcoming corrosion performance problems, it is
surprising that, with the exceptions of silicate and
phosphate, there appear to have been few other
chemistries reported in the literature. The CSIRO/
DSTO group tested polyacrylic acid (with or without
doping with dichromate or titanium isopropoxide), an
aminosilane, nickel sulphate or a mixture of magnesium
and nickel sulphates.120,123 None of these showed any
improvement over silicate.120,123 Palomino et al. tested a
silane as a post-layer treatment and found that it
increased the impedance by an order of magnitude over
Ce alone.17 A post-treatment by benzotriazole was
claimed to provide a beneficial effect on the impedance
of the Ce layer,52 although no experimental details were
provided as to how this was carried out. Another
Corrosion Engineering, Science and Technology
Harvey Cerium-based conversion coatings on aluminium alloys
process put an anodised layer onto AA 2024 after Ce
coating.290
Performance data
In any coating application, there are a variety of
performance requirements that must be met. For
example, Boeing’s requirements included excellent NSS
corrosion resistance and paint adhesion (dry, immer-
sion, humidity, impact).229 The results for a number of
these performance tests have been published and are
summarised below.
Corrosion performance
Salt spray
Neutral salt spray testing is simultaneously the Holy
Grail and the hair-shirt for the non-chromate coating
researcher. It is the Holy Grail in that consistently
passing 168–336 h in NSS on three different alloys is the
ultimate test of chromate replacements4,16 (and even,
occasionally, of chromate itself).8 It is the hair shirt in
that no one appears to have consistently managed to
achieve this,4,16,30 and the requirement has essentially
skewed more than two decades of research.10 Indeed, it
has been argued that the performance requirements for
coatings in the aerospace industry refer to the perfor-
mance characteristics of chromate rather than the actual
requirements of the product.10
There are proprietary standards for NSS that are
quoted in the literature (e.g. BAC 5719),16,122,128 but
NSS is essentially defined by three widely quoted
standards: ASTM B-117,12,13,32,33,38,74,75,77,96,102,109,121,
122,127,141,142,144–147,149,168,169,188,213,233
MIL-C-
8170612,13,33,109,122,141,147 and MIL-C-5541.12,13,141,146,147
While there are well recognised shortcomings with NSS
as a testing procedure,8,10,17,56,291,292 there are also some
serious shortcomings in the Ce coating literature as to
how these standards have been quoted and applied,
despite the frequency with which they are cited. For
example, ASTM B-117293 only provides a procedure for
carrying out NSS testing and does not provide pass/
fail criteria. Therefore, coatings cannot ‘pass’ B-117 as
has been claimed on occasion.8,32,102,110,168 Two groups
have published well defined ranking systems, which
they devised for describing NSS results,74,75,96,121,127,128
although these are not widely used. MIL-C-81706288 and
MIL-C-5541287 do, however, provide pass/fail criteria for
NSS testing. The former is the most demanding, requiring
five AA 2024/AA 7075 100630 panels survive 336 h of
NSS exposure with no corrosion whatsoever.35,288 MIL-
C-5541E requires five 100630 panels survive 168 h of
NSS exposure with no more than 5 pits on a single panel
and no more than 15 pits over the five panels.35,287 (The
Boeing corrosion specification BAC 5719 is, incidentally,
intermediate between the two, requiring no more than
three visible pits after 168 h.)229 There are two research
groups that have made particular efforts towards passing
NSS testing. It is perhaps no surprise that both have
worked with aerospace companies.
Salt spray results (CSIRO/DSTO)
The CSIRO/DSTO group, working with Boeing (1991–
1994), initially ran bench scale experiments, then moved
to small scale process lines (using 20 L tanks and later
40 L tanks229) to allow preparation of 100630 panels
2013 VOL 48 NO 4 261
Harvey Cerium-based conversion coatings on aluminium alloys
and to ensure reproducibility. Reproducibility, however,
remained an issue even in the 40 L line.121 Testing at
CSIRO/DSTO and Boeing demonstrated better than
168 h for both AA 2024/AA 7075 panels,121,127 largely
based on the LERD pretreatment.127 Subsequently,
336 h (AA 2024) was reached,38,128,229 without pitting
using room temperature silicate as a seal.128 Later, on
the 20 L line, AA 2024-T3 again reached 336 h122 and
AA 7075-T6 reached 300 h.122
As noted earlier, chromate deoxidation before
cerium coating was found to result in poor NSS per-
formance (80 versus 336 h using LERD).127 This was
attributed to the nature of etching and the surface left
behind127 or to the presence of Cr left on the sur-
face after deoxidation,128 a fact confirmed later by
UMR.141
During later work with BAE Systems (1999–2001),
CSIRO/DSTO set up an automated dual process line
with 60 L tanks. This achieved NSS results on AA 2024
of up to 960 h (easily exceeding the 700 h reached on
chromate control panels), but the performance was
lower on AA 7075 (288 versus 1300 h with Cr) and
AA 7475 (72 versus 120 h with Cr).77 Apart from the
significant, and still unexplained, differences between
alloys, it may be noted that the 960 h result was
extraordinary (with five panels all exceeding 800 h),
although during this period, 336 h on AA 2024 was an
unexceptional result.194 The inability to reach 336 h with
AA 7075, in spite of earlier work achieving this mark, is
probably due to the changing chemistry of the seal (see
the section on ‘Silicate’) and the use for this work of hot,
rather than room temperature, silicate, which worked
better with AA 2024.
Salt spray results (UMR)
The group at UMR, working variously with electro-
deposition, immersion and spray coatings, have claimed
impressive corrosion performance for their samples over
the years. Thus, AA 7075 has been reported to have
reached 336 h in NSS,8,12,31,32,141,144–147,149,212,213,221,233
and spray coatings on AA 2024 have been reported to
have reached between 168118,205 and 336 h.110,280 These
are impressive results, but it must be noted that the
MIL specs require test panels of a specific size (1006
30), and the smaller panel sizes UMR
use8,33,108–110,141,142,144,145,147–149,205 do not comply with
this requirement. For example, their early work used
30660 panels,8,12,13,144 but more recently, 10630 panels
appear to have become standard,145 and these are not
compliant with the standards.33,110,144,205 As with the
CSIRO/DSTO work, there are indications of reprodu-
cibility issues with the UMR cerium coatings, with
ambiguous references to panels meeting the MIL
specifications.8,12,13,31,131,144 This is also apparent in
the varying percentages of panels that are claimed to
pass 336 h in NSS (e.g. 20,144 50,149 70,212,213 80147 and
85%144,145).
Salt spray results (others)
Other workers have also used NSS as part of their
testing procedures. Tang et al. reported that an
unsealed, electrolytically deposited Ce coating on
AA 2024 could last 120 h in NSS before the first pit
formed.294 An uncoated panel showed severe widespread
pitting after only 24 h.294 Bethencourt et al. claimed that
their cerium coatings could allow AA 5083 to last for
262 Corrosion Engineering, Science and Technology 2013 VOL 48
168 h in NSS with no corrosion;168,169 however, the
panels tested were surprisingly small (,10610).168,169
Conde et al. found that Ce coated AA 8090 was not
damaged after 168 h of exposure.102 AA 8090 is a fairly
corrosion resistant alloy, however, requiring ,96 h in
NSS before showing signs of corrosion.102 AA 2024, by
contrast, will show pitting from NSS exposure in
,10 h.229
Other corrosion tests
Weight loss
Hinton et al. used weight loss measurements
(ASTM G1-1972) and found that Nd, Pr and Ce all
reduced the corrosion of AA 7075 by more than a factor
of 10,79 a figure confirmed for Ce by later workers.295
The order of inhibition effectiveness was found to be
NdyPr.Ce.La.Y.79 Electrolytically deposited Ce
coatings were also found to lower the weight loss by a
factor of 10.136 Hu et al. also used weight loss
experiments (immersion in 3?5%NaCl) to demonstrate
that Ce coatings significantly reduced the degree of
corrosion over an untreated panel.23 Pardo et al. used
immersion in 3?5%NaCl to determine that La coatings
(either immersion or electrolytically deposited)
decreased the degree of pitting attack and delayed the
growth of the corrosion layer.89
Outdoor exposure
Outdoor exposure testing of a Ce coating on AA 2024
passed 35 days, which was more than enough to destroy
a bare panel, although Cr lasted over 50 days.127,128
Immersion testing
Mansfeld found that Ce coated AA 7075 did not begin
pitting in NaCl for over 3 weeks, while as-received
panels pitted in a matter of hours.202,203,218,245 Similarly,
Ce coated AA 6061 took between 30202 and 90
days201 to pit as opposed to 24 h for untreated
samples.201–203,218 The group at UMR have also used
immersion to assess their coatings, claiming that if a
coating remains stable after a day’s immersion in
Prohesion solution,12,13,142 then the coating will pass
336 h in NSS.31,32 This is an unusual and interesting
claim, but one that does not appear to have been
followed up.
Electrochemistry
A large number of electrochemical studies have
been carried out on cerium inhibited alumi-
nium.15,20,23,58,80,81,109,134,140,156,157,159–162,164–170,172,195,196,
201–203,205,206,217–219,231,238,245,296
Electrochemical measure-
ments are sometimes favoured as a substitute for NSS
testing as they are quicker,112,173 are less labour intensive,
cost less are capital intensive and give useful information
that a simple pass/fail NSS corrosion test will not. The
problem is that the latter remains the industry standard
and despite claims that electrochemical impedance
spectroscopy (EIS) can be used to predict NSS
results,33,38,297 the data do not seem to be conclusive
and electrochemical failure mechanisms (particularly
those of EIS) have not been convincingly linked to those
of NSS,112 at least on a deterministic basis.292 Most
electrochemical studies have simply provided the con-
firmation that the coatings provide corrosion protec-
tion12,13,134,296 or have quantified the relative degree of
electrochemical protection57,104,157 and how this develops
NO 4

over time.82,94,95,199 Thus, Ce coatings have been variously
claimed to be much better than Cr,31 slightly better than
Cr,176 about the same as Cr81 or worse than Cr,38,57 which
may say as much about the variability in coating
preparations as anything else. There is, however, near
universal acceptance that Ce provides a considerable
improvement over the corrosion resistance of the bare
metal 12,15,79–81,101,102,104,127,128 even in the absence of a
seal.127,128 Polarisation studies have repeatedly shown that
Ce does not operate as a barrier coating but suppresses the
cathodic oxygen reduction,12,23,79,82,102,104,121,128,136,140,221
although there have been isolated claims of the anodic
reaction also being affected.12,13,211 Polarisation experi-
ments indicate that Ce affects the corrosion potential, but
not the pitting potential,58 although this is elsewhere
claimed to be dependent on the peroxide concentration
during the coating.29 The CSIRO/DSTO group also
found that the Ce coatings were not self-healing. A
polarisation test on bare metal in a solution in which a
coated specimen had been immersed for several hours
showed that there was no leaching of a soluble Ce
species,128 a finding confirmed by Dabala et al. from the
return branches of the polarisation curves.157 Palomino
et al. did find that, by immersing a Ce coated sample in a
0?5M NaCl solution with a polished, uncoated panel, Ce
slowly deposited on the intermetallics of the uncoated
panel over 72 h.52 The evidence for self-healing in Ce
coatings is not particularly strong at this point, although
Ce(III) release from hydrotalcites,53 bentonite298 and
nanoparticles130 has been observed.
Electrical conductivity
A fundamental property of class 3 coatings under MIL-
C-81706/5541E is electrical conductivity.35,288 The
CSIRO/DSTO found that Ce coatings failed electrical
conductivity testing on AA 2024/7075/7475 in the sealed
condition and for all conditions (sealed and unsealed)
after NSS.77 Davo and de Damborenea also found that a
non-accelerated coating showed very low conductivity.82
It would appear, then, on the basis of the limited evidence
available, that electrical conductivity is a property of
chromate6 that Ce coatings are unable to duplicate.
Performance under paint
Filiform corrosion
Filiform corrosion is the primary corrosion mechanism
for organic coated aluminium and is a major obstacle
for the increased use of Al in the architectural and
automotive industries.40 In filiform corrosion, thread-
like corrosion attacks (filaments) spread under the
organic coating causing adhesion loss and degradation
of the visual appearance.40 Despite its objectionable
appearance, filiform corrosion is only an aesthetic issue
and has little effect on the metal’s properties.299 Early
on, Mansfeld et al. found that a non-accelerated Ce
coating under epoxy did not prevent the formation of
filiform corrosion on AA 6061.172 This appears to have
been less of a problem with accelerated coatings, with
filiform results equivalent to Cr being published soon
after,121 and Hughes et al. made the point that Ce
coatings under either powdercoat and e-coat on a range
of alloys generally performed as well as chromate (in
architectural applications) and zinc phosphate (in
automotive applications).122 In another study, Ce coat-
ings were found to produce excellent filiform inhibition
on a range of 12 different aluminium alloys, with results
Corrosion Engineering, Science and Technology
Harvey Cerium-based conversion coatings on aluminium alloys
in most cases as good as or better than chromate.133
Knudsen et al. assessed a number of non-chromate
conversion coatings (Ce, Ti/Zr, anodising, self-assem-
bling monolayer, phosphate) on AA 6060-T640 and
demonstrated that, with a good quality polyester
powdercoat, the filiform results for Ce were as good as
those for anodising and superior to Cr.40 Chemetall
published data to show that, for AA 5005 and AA 6060,
the performance of Ce coatings under powder coat is as
good as chromate in cross-hatch, ESS creepage (1008 h),
copper accelerated acetic acid salt spray (CASS)
creepage (240 h) and filiform tests (1008 h),42 and, on
the basis of this data, Qualicoat and GSB approval tests
were initiated for the Cerate process in 2002.42 Later
work by Hughes et al. found that, in general, the extent
of filament filiform corrosion on AA 2024 was similar to
that of chromate (according to DIN 65472), but the
maximum depth of attack in the filaments was higher in
the Ce coated samples.129 When this was repeated with
bismuth accelerated coatings on AA 2024-T3, the
filament lengths were shorter than Cr.60 Near Cu–Ni
fasteners, Ce performed similarly to Cr coated samples,
although it did not perform as well as Cr near Cu
fasteners.60
Corrosion tests
The CSIRO and Chemetall carried out tests on painted
AA 6063 and found results comparable to chromate
after exposure to 1000–2000 h of acetic acid enhanced
salt spray and 1000 h of CASS.152,154 The CSIRO/
DSTO group also carried out tests (720 h NSS and
5000 h temperate/tropical outdoor exposure) on scribed,
repaired, painted AA 2024/7475 surfaces.10 In outdoor
exposure testing, the results for repairs using a Ce
formulation were as good as those for standard
chromate. While the data were slightly poorer for
cerium than chromate on NSS tests, this was dependent
on the alloy and certainly showed that this prototype
process performed well against a commercial chromate
repair.
The group at UMR found that their electrolytically
deposited cerium coating passed 2000 h NSS exposure
under e-coat on AA 7075 and AA 2024,13,31,32 under
polyaniline (scribed) on AA 7075142 and under epoxy on
AA 7075.142
Adhesion
Although it may be argued that the corrosion perfor-
mance of Ce coatings has never consistently matched
that of Cr(VI),44 Ce performs well in adhesion tests,
although there are not as much data available in the
literature as there is for corrosion.
There are several varieties of adhesion testing avail-
able. The most straightforward is a simple dry adhesion
(tape) test150,151,249 to determine if the Ce coating will
adhere to the metal when the tape is pulled off. The
CSIRO/DSTO group routinely uses this test as a form of
quality control on their coatings. Tang et al. have also
used this test.294
More complex paint adhesion tests are harder to carry
out in terms of both equipment and the expertise
required to run and interpret the results, but they are, in
general, more informative. Early tests by CSIRO/
DSTO229 showed that Ce coatings had extremely good
dry and wet adhesion when painted and showed no
blistering or loss of paint adhesion after 30 days
2013 VOL 48 NO 4 263
Harvey Cerium-based conversion coatings on aluminium alloys
exposure to condensing humidity.229 Adhesion of
scribed panels before and after 7 days immersion in
water and impact resistance was also good.229 Later tests
found Ce coatings passed dry adhesion testing on
AA 2024 but failed wet adhesion,121 and, surprisingly,
sealing the coating had relatively little effect on the
results.121 The coatings could also pass condensing
humidity tests, although not consistently,121 and impact
resistance and cross-hatch humidity test results were
similar to Cr.121 Later again, dry/wet paint adhesion
tests were passed on both unsealed coating and silicate
sealed coating on AA 2024/7075/7475,77 and PATTI
adhesion testing showed it was equivalent or better than
Cr on AA 2024/7075 and only slightly poorer on
AA 7475.77 Chemetall found that paint adhesion
(cross-hatch, ESS creepage, CASS creepage and filiform
creepage) of powder coated cerium coated AA 5005
panels and AA 6060 profiles were equivalent to chro-
mate coatings on the same substrates.41,42 Adhesion
testing (ISO 4624 pull-off) with a good quality powder
showed that Ce was behind only Cr and Ti/Zr, while
with a poor quality powder, it gave results equal of
anodised samples and inferior to Cr, but better than all
the other non-Cr options tested.40 The DERA has
published some excellent adhesion data on their coatings
(carried out according to BS EN24624), which not only
showed that the adhesion for rare earth coatings with
chromated and non-chromated primers was adequate,
but also described the adhesion failure modes.96 This
paper illustrates the amount of useful detail that can be
obtained from a well executed adhesion test.
Summary
Although much of the discussion in preceding sections
has been related to aspects of Ce coating performance,
performance on its own is not the sum of the benefits or
the liabilities of a process. (If it were, of course, there
would be no reason at all to replace chromate.) In an
effort to address this problem, a quality function
deployment (QFD) assessment was applied to aerospace
conversion coating processes, taking into account issues
of time, operation, repair, as well as process, capital and
operational costs.193 The weightings were decided after
extensive discussions with commercial, technical and
production staff, using real data as far as possible. This
assessment showed that Ce coatings were very compe-
titive with chromate.193
The advantages and disadvantages of Ce coating
processes have been listed by Chemetall researchers41,42
and others. The advantages include the following:
(i) it is free of both chromate and fluoride
(ii) bath control is straightforward (pH, peroxide
and cerium concentration)
(iii) bath replenishment is straightforward
(iv) the layer thickness increases with time
(v) the coating weight can be determined by
dissolution or X-ray fluorescence
(vi) it can provide excellent paint adhesion and good
corrosion performance (sealed or under paint)
(vii) resulting waste water is easily treated with
standard NaOH/lime treatment
(viii) it provides a visible (coloured) conversion layer
to allow for easy assessment by production
staff24,122
(ix) it has low environmental impact57
264 Corrosion Engineering, Science and Technology 2013 VOL
(x) the components and byproducts have low
toxicity.20,31,32,50,187,188,238
The disadvantages of cerium coatings41,42 include the
following:
(i) the coating operation is often carried out at
mildly elevated temperatures (up to 50uC)
(ii) poor or variable NSS performance in the
unsealed condition
(iii) uncertainty about how coating performance is
affected by different pretreatments
(iv) certain metals that dissolve into solution during
coating (particularly Fe and Cu) result in
catalytic decomposition of the peroxide. This
can become an unsustainable cost unless the
process is controlled
(v) the low pH and chloride content of the coating
solution requires the use of resistant materials
(polymer coating, acid resistant metals etc.) for
the coating bath,42 which can inhibit its use as a
drop-in replacement for other processes
(vi) Ce is not as effective as Cr(VI), as it does not
inhibit oxygen reduction to the same degree or
with the same speed.107
Conclusions
Cerium coatings, remain a promising option for
chromate replacement on aluminium alloys, although
there are areas that need development. These include the
following.
1. Pretreatments. The effect of pretreatments on
cerium coatings is not well understood, and some of
the pretreatments favoured in the literature would not
be suitable in an industrial context.
2. Coating non-aerospace alloys. Putting cerium
coatings on aerospace alloys is relatively easy, but
generating coatings on non-aerospace alloys or the
cladding on aerospace alloys remains a significant issue,
particularly as these less reactive alloys represent the
bulk of the potential market. Patented solutions exist,
but relatively little has been published to allow these
methods to be assessed.
3. Post-coating seals. Post-coating seals need further
development for applications where unpainted corrosion
resistance is critical. The two most widely used sealing
processes show either inadequate corrosion resistance
(phosphate) or inconsistent bath chemistry (silicate).
Potential alternatives, however, are not obvious.
Progress in these areas will make cerium an easier
option for replacing chromate as the conversion coating
of choice on aluminium alloys.
Acknowledgements
The author would like to thank Dr A. E. (Tony) Hughes
for his encouragement to write this review and Drs A. E.
Hughes, T. Markley and T. Muster (all of CSIRO) for
their comments on the manuscript. The author also
wishes to thank his colleague S. Hardin (CSIRO) for
many helpful discussions and insights over the years in
the area of chemistry generally and in the chemistry of
rare earths in particular.
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