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T G Harvey
Download by: [Visvesvaraya Technological University - VTu] Date: 10 February 2017, At: 19:37
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 Rare earths are among the most promising options for
replacing chromate conversion coatings,5,23,29,44 but
The replacement of chromate conversion coatings on although the literature on the topic runs to several
aluminium is a perennial topic. Chromate is an outstanding hundred articles, the bulk of it has never been review-
corrosion preventative for aluminium.1 It works extremely ed. For example, the reviews of Seon,45 Cohen,46
well as a soluble inhibitor in cooling water systems,2 as an Ramanathan,47 Hinton,2,36,37,48 Henderson et al.38 and
inhibiting pigment in paints2–5 and as a component in Ryan49 briefly cover rare earths but are confined almost
deoxidisers2,4,6 and anodised coatings.2,4,7 Most importantly, entirely to the early (pre-1991) papers of Hinton et al.
in the context of this review, chromate is a near ideal In addition, a number of excellent reviews on chro-
conversion coating,1,2,6 as it provides outstanding co- mate replacements have subsequently appeared in
rrosion resistance4,8–14 and paint adhesion,10,14–17 ease of which rare earth coatings appear as part of the
application,8,9,11–13,18–21 self-healing6,8,9,11,14,18,19,21 and elec- discussion,1,5,6,11,26,30 but as they only represent one
trical conductivity.18,19,21–23 It works rapidly14 at room option among many, the coverage is necessarily limited.
temperature14 on a wide variety of metals and alloys24 while The review by Bethencourt et al.50 is probably the most
requiring a minimum of maintenance.10 Indeed, given this comprehensive, but is quite dated now. Some of the best
combination of excellent properties and versatility, it information on rare earth conversion coatings is found
seems unlikely that there will be a single replacement for not in reviews but in the primary literature. For
chromate.1,25,26 However, chromate is carcinogenic1,11,18,19,27–29 instance, an excellent summary of the development of
and has been listed in the USA as one of the Environmental the cerium coating process is found in the introduction
Protection Agency’s most toxic substances,5,18,19,28 with a of the paper by Campestrini et al.,51 and probably the
view to it being progressively phased out.1,5,12–14,30–32 An most useful background material on the process is found
enormous amount of work has been carried out on in the introduction of the paper of Palomino et al.52 and
chromate, and there are a number of excellent reviews that in the discussion in the paper by Buchheit et al.53 From
cover chromate chemistry and practice.6,14,33–35 the view of process conditions, the best coverage is
An enormous amount of data on potential chromate found in papers by Chemetall41,42 and in the review by
replacements for aluminium has also been published.1 Buchheit and Hughes,6 although these are still limited in
This is not only because of the importance of the topic their coverage of the published literature.
but also because of the breadth of the replacement Given these considerations and the fact that rare earth
chemistries available for aluminium. These include coatings are beginning to find commercial application as
molybdate,1,11,26,30,36,37 permanganate,6,11,26,36–38 refrac- chromate replacements,40–42 it was considered that a
tory metal oxyfluorides (mainly Ti/Zr, but also Hf, Nb process based review of rare earth coatings on alumi-
and Ta),6,11,26,36–40 phosphates,1,26 silanes,6,26,36,37,39,41,42 nium would be useful.
sol–gels,1,6,11 self-assembling monolayers,6,26,39–42 con- This review only covers rare earth conversion coating
ducting polymers,1,6,11,30 cobalt based coatings,6,24,26,38,43 processes and excludes sol–gel processes54,55 and, more
hydrotalcites6,11,26,38 and rare earths.1,6,11,26,30,36–42 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
CSIRO Materials Science and Engineering, Private Bag 33, Clayton South and Industrial Research Organisation’s (CSIRO)
MDC, Clayton, Vic. 3169, Australia Sirox process,60–63 Mansfeld’s Stainless Aluminium
*Corresponding author, email tim.harvey@csiro.au process,56,64 the Hughes Chrome Free Conversion
Coating process,65,66 the General Motors Boehmite the other rare earths are effectively ruled out of widespread
process,67 the Miller (Lockheed) process68–71 and commercial use due to cost considerations, but La not only
others.21,72–76 Oxide growth processes are generally is less active than Ce82,91 but also shows poor adhesion as a
distinguished by a high temperature step (.80uC), coating as well.82 Thus, the term rare earth in this review
which thickens the surface oxide, and by the absence may be considered to mean cerium unless otherwise
of an oxidant. Conversion coating processes are, by specified.
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
General process outline
chemistries are sufficiently distinct that it was felt that There are a number of papers in the literature, which
oxide growth required separate treatment. include a general process outline for the cerium coating
With regard to conversion coatings however, several of of aluminium, including process conditions and methods
the rare earths have been found to act as cathodic of quality control.6,41,42 In common with other coating
inhibitors, including Ce,20,78–86 Sm,78 La,20,78,79,82–89 processes,35 cerium coatings require at least one
Nd,20,79–81 Pr,20,79–81 Y,80,81 Gd90 and Tb.90 Ce is generally pretreatment step (and usually more), a coating step,
the most active91,92 and is, in particular, more active than and, if maximum corrosion resistance is needed, a
La82,85,88,90–93(except on pure Al),83 Y93 and Pr.91 The sealing step. An outline of the structure of the paper is
corrosion resistance usually follows the sequence: shown in Fig. 1. This section examines the individual
Ce.Nd.Pr.Y.La.20,79–81 With the exception of La, process steps in detail.
as acceptable coatings could be deposited without the choices that have been made. For the purposes of this
use of any additional process steps,144 it appears that discussion, pretreatment steps using oxidising acids
efforts to incorporate them were abandoned, at least (e.g. nitric) are covered in a separate section on
temporarily (see the section on ‘Base etching’). ‘Deoxidation’.
Non-etching alkaline cleaners will alter the surface pH
of the sample and remove grease or other organic Acid etching
contaminants, but cannot remove inorganic contami- Pickling or acid etching of light metals with non-
nants from the surface. Thus, such elements as Mg, Zn oxidising acids is not widely used in pretreatments for
and Fe will remain,204 and the cleaner may leave cerium coating. While this will generally increase the
contaminants such as silicates that are present to inhibit rate of coating deposition, it does so by exposing
surface etching.121,204 The CSIRO/DSTO group have subsurface (often Cu rich) smut, which then accelerates
used a variety of commercial alkaline cleaners in their the cathodic deposition. (Base etching, of course,
studies. Initially, Brulin 815 DG (60uC, 15 min) was acts in the same manner.) The problem with smut
favoured for degreasing, followed by Henkel Ridoline 53 is that it is only loosely held to the
(65uC, 4 min) for alkaline cleaning, with deoxidation surface,17,51,52,58,98,115,130,177,209,210 and the subsequent
and coating following after that.121,124 It was found that cerium coatings are usually poorly or non-adherent.29,51
abrasion could be substituted for the Brulin step,128 Acids used as pretreatments include HF,174 H2SO4–
although, ultimately, both abrasion and Brulin steps HF177 and H2SO4–H3PO4.51 It may be noted however
were removed entirely. This pretreatment was later that H2SO4–H3PO4 does not affect either the electro-
replaced by a simple solvent wipe (acetone) followed by chemical nature of intermetallics or the extent of their
the Gibson Process 204B (a silicated alkaline cleaner).126 galvanic coupling to the matrix.98 Surprisingly, a
This pretreatment was replaced in turn by immersion in number of authors recognise that non-oxidising acids
Henkel/Turco 4215 NC-LT, a cleaner that others have (e.g. HOAc58 and H2SO4)111,114,118,211 accelerate coating
also found to be effective.149,205 by forming surface smut, but choose to do so any-
These examples serve to illustrate that even the simple way.116,141,205 In once instance, it has been claimed that
issue of surface cleaning may be quite complicated. In H2SO4 gave better corrosion performance on AA 7075
contrast to the UMR’s minimalist approach, for than chromate deoxidation.141
instance, Mansfeld’s pretreatments were quite complex,
Base etching
incorporating abrasion (600 grit), detergent degrease,
rinse, air dry, hot hexane soak, rinse, air dry, sonication The problem with base etching on its own is essentially
in acetone, rinse, air dry,80 plus another detergent the same as etching in a non-oxidising acid: it will ex-
degrease, rinse and air dry.81 This might be followed pose smut. The consequent acceleration of the coat-
with a deoxidation step, rinse and heat in air at 100uC ing deposition rate is, or should be, outweighed by
for 24 h at high humidity.81,206 These complex pretreat- the fact that the smut is only loosely held to the
ments were transferred to subsequent work on oxide surface,17,51,52,58,98,115,130,177,209,210 and any resulting
growth processes,27,207 with further developments sim- coating will be poorly adherent or non-adherent.29,51
plifying the degreasing stages somewhat, but substitut- As with acid etching (see previous section), this fact is
ing in up to three consecutive deoxidation steps often dealt with by the simple expedient of not
instead.207,208 measuring coating adhesion, although poor adhesion
has been noted on base treated AA 202458 and
Acid/base pickling aluminium–borate whisker reinforced AA 6061.29 Base
Aluminium pretreatments usually use caustic etch to etching has been used as a Ce coating pretreatment on
remove surface oxide and deformed layers, often AA 5083,156,157,171 AA 6082,177 aluminium borate whis-
followed by a deoxidation (desmutting) step in nitric ker reinforced AA 606123,29 and even the aerospace
acid or similar.97 This is not universally followed in the alloys (AA 2xxx/ AA 7xxx series),58,105 although sub-
published studies of cerium coatings. For instance, sequent coatings on AA 2024 showed poor corrosion
Trolho et al. noted, without any detail, that acid performance.105 Mild base (0?3%NaOH, 1 min) does not
pickling pretreatments could be used alone or in have any significant effect on the original surface
combination with alkaline pretreatments42 and that the features of AA 2024.210 Decroly claimed that any
use of alkaline pretreatments alone could often eliminate etching sequence on a low Cu alloy (eg AA 6056) should
pitting that might otherwise occur.42 Hamdy et al. end with an alkaline step because the resulting non-
claimed, also without any details, that pickling greatly insulating alumina gel layer is necessary for rapid
improved corrosion resistance.21 Palomino et al. tested a deposition of Ce.177 Similarly, it was claimed by
range of different basic and acidic pretreatments and Chemetall (although in this case, without any support-
found that they resulted in different Ce levels on the ing experimental detail) that use of alkaline pretreat-
surface.58 ments alone could eliminate the pitting that might
For this reason, base/acid etching treatments will be otherwise occur.42
examined both separately and as sequential steps. As Recently, the principal proponents for basic pretreat-
noted previously, there is surprisingly little information ments have been UMR, as a means of accelerating their
available on the effect of acid or base etching on spray coating process on AA 7075114,137,139,212,213 with
subsequent coating steps or on the performance of the either NaOH139,213 or sodium carbonate.212,213 Basic
coatings. Authors appear to favour particular recipes, pretreatment was found to increase coating deposition
either their own or borrowed from others, but it cannot (after one spray cycle) from ,30 nm to as much as
be said that there is much published scientific support 250 nm.212 Sodium hydroxide was claimed to result in a
for the choices that are made. For this reason, most of more protective layer than carbonate.213 Sodium carbo-
the details in the following sections simply list the nate, on the other hand, gave the most uniform coatings
particles are unaffected by nitric acid, and AlCuFeMn large proportion of the intermetallics behind.51,226 As a
are only roughened.97 In addition, on aerospace alloys result, HERD has not been used much with Ce
(AA 2xxx and AA 7xxx), nitric generates thin (approxi- coatings,60 and there has been little follow up on its use.
mately 2–4 nm) Cu/Zn enriched alloy layers.105 The A group at DERA investigated a variety of acidic
addition of HF to HNO3 on the other hand has been pretreatments, several of which were doped with Ce.96
found to drastically affect the microstructure of One Ce containing pretreatment in particular gave good
AA 2024, removing surface smut and etching the surface results, but it is difficult to determine the effect of the Ce,
around the intermetallics, many of which drop out as there were no data covering a non-Ce control.96 A
during treatment, leaving large pits in the surface.51 A parallel experiment showed that in one case, addition of
certain number of intermetallics, nevertheless, remain Ce to the pretreatment made no difference to the coating
and continue to generate galvanic couples with the Al performance, while adding less Ce actually improved the
matrix of the order of a few hundred millivolts.51 There coating.96 [It is not, incidentally, advisable to combine
are several non-chromate deoxidisers available from both fluoride and Ce(III) in the one solution as these
commercial sources.4 Thus, Fe-based Henkel/Turco experiments did, as CeF3 will be precipitated.227]
Smut-Go NC-B has been tested on AA 2024126,223,224
Post-deoxidation treatment
and AA 7075/7475,126,225 and bromate-based Sanchem
1000 has been tested on AA 2024/7075/7475.126,225 The There have been relatively few examples of post-
Sanchem deoxidiser gave better results on AA 2024 than deoxidation treatments before coating.
the Henkel/Turco product, and results for AA 2024 Rangel et al. examined the effect of adding a known
were superior to the results on AA 7075, which were corrosion inhibitor (benzotriazole) after deoxidation but
similar for both pretreatments.194 Neither deoxidiser found that it resulted in poorer coating morphology and
performed well on AA 7475.194 longer deposition times, suggesting that redeposited Cu,
rather than intermetallics, plays the most critical role in
Two groups have studied cerium containing deox-
Ce formation.95
idisers: CSIRO/DSTO, who devised low etch rate
The group at UMR found that a boiling water
deoxidiser (LERD) and high etch rate deoxidiser
pretreatment increased the rate of coating deposition,
(HERD),120,123 and DERA, who used a Ce containing
but it also led to a substantial amount of film cracking,
deoxidiser as part of their rare earth coating studies.96
which they believed was the reason for poor NSS
Both groups found that the presence of cerium appeared
performance.147 The use of a boiling solution of
to have a beneficial effect on the coatings, although the
phosphate as a pretreatment, by contrast, did not result
reasons for this are not understood and Ce-based
in any increase in coating deposition and gave even
deoxidisers have not achieved wide ranging application,
poorer performance.147 The group at DERA published
either scientific or commerical.
an unusual process that deposited a mixed Ce/La layer
The invention of LERD [0?5M H2SO4 and 0?05M onto a regrown oxide surface on AA 2024 via a hot
Ce(IV)]120,123 was based on the proposition that as water treatment.96 This was reported to have given very
chromate based deoxidation provided a good base for good corrosion performance and paint adhesion.96
chromate coatings and a poor base for Ce coatings, then Rungta patented a method whereby boehmite was
a Ce based deoxidiser might promote the growth of Ce grown on the surface in ethanolamine solutions (80uC,
coatings.121 This simplistic approach worked rather 4 min) and before immersion in Ce(III) (57uC,
well.77,113,120,121,123–126,128 The use of LERD markedly 15 min).67 The UMR also tried a pretreatment variant
improved the performance of Ce coatings121,128 and gave by reimmersing their panels in the alkaline cleaner after
good NSS results when used at up to 50uC, although acid etching (in H2SO4).116 It was not clear, however, if
room temperature operation was also satisfactory.120,123 there was any effect. Yu et al. used a fairly standard
A range of modifications to the basic LERD formula coating system (Ce/H2O2) to put a coating on an
were tested, but without much improvement,120,123 and anodised layer over AA 202499,100 and AA 6061/
all that could be readily concluded was that shorter SiCp.183 While they claimed similar performance to Cr
deoxidation times required longer coating times.120,123 sealed anodised coatings,100 it took 2 h to generate a
As might be expected from the name (LERD), the etch coating,99,100,183 which would be prohibitive for com-
rate is low by comparison with other commercially mercial applications.
available Cr free deoxidisers.126 It has been tested on Jaworowski and Kryzman immersed AA 6061 in a
AA 2024/7075/747577,126,225 and gave excellent results solution of amonia/tungstate (at pH 11–12) and then in
on AA 2024, good results on AA 7075 and poor results Ce nitrate (pH 3?5–3?6). This formed a layer of
(like everything else) on AA 7475. An early summary of Ce2(WO4)3 about 1–1?5 mm in thickness, which was
what was understood about the mechanism of rare earth claimed to result in an order of magnitude decrease in
deoxidation may be found in the literature, along with corrosion rate.228
tentative suggestions as to how this might facilitate the
deposition of Ce.124 The CSIRO/DSTO group also Coating processes
invented a second Ce containing deoxidiser, known as The elements of an ideal non-chromate coating process
HERD,120,123 whose composition [0?05M Ce(IV), 0?5M would include the following:
H2SO4, 1?3M HNO3, 0?04M F, plus optional oxidant] (i) it should be inexpensive177 with similar costs to
could be described as approximating a Ce analogue of a Cr229
chromate deoxidiser. The presence of fluoride results in (ii) it should require no more steps than Cr
much higher etch rates, and the optional oxidant (H2O2 processes177,229
or persulphate) effectively removes copper that is (iii) it should require similar processing time to
otherwise redeposited over the surface during etching.226 Cr177,229
Surprisingly, on AA 2024, it shows a tendency to leave a (iv) it should use non-toxic chemicals229
(v) it should require bath temperatures ,60uC,229 which then converted to Ce(III) phosphate during the
with room temperature operation preferable177 sealing step.148 There were mixed signals as to the
(vi) it should have a robust and reliable bath success of the process. It was claimed at one point to be
chemistry229 an order of magnitude faster than immersion coating,148
(vii) it should produce a coating with an identifiable which is difficult to understand as most immersion
colour229 processes generally require a few minutes at most (see
(viii) it should be applicable to a wide range of Al the section on ‘Effect of coating time’). It was also
alloys.229 described as producing good surface coverage and
Cerium based conversion coatings can be applied to coatings,144 although the same paper concluded
aluminium alloys by electrolytic deposition,53,148,188 that the process was more expensive than immersion
spray,148 swabbing10,148 and immersion processes.53,148,188 coating144 and could not be adapted to repair
Immersion processes may be further divided into those that processes.144 In addition, the coating reproducibility of
are unaccelerated188 and those that are accelerated either this patented process233,234 was poor32,144 due to the
thermally188 or chemically.151,122 These deposition processes organic additive that reduced corrosion performance
will now be examined. and primer adhesion.144 Work then seemed to have
been discontinued in favour of a largely conventional
Electrolytic deposition
immersion process,144,146 as it offered better ease of
Electrolytic deposition is a potentially useful procedure application.146 Recently, however, UMR has published
in that it actively drives the coating process across the more work in the area.118
whole alloy surface, unlike, for example, immersion Other researchers have also used electrolytic deposi-
coating, which can result in coatings mainly over tion on a variety of alloys, including AA 2024,115
cathodically active sites89 (see the section on ‘Where 3A21,235 A360/A361/A380–SiCp,89,187,188,190 A36186
the coating forms’). In addition, it should combine mild and LC4,179 with improvements in corrosion resistance
operating conditions (temperature, pressure) and gen- noted.179,187,188 In an interesting paper, Tang et al.
erate pure coatings with controllable thickness.190 recently reported an electrolytic method that drove the
Theoretically, electrolytic deposition should also provide coating process through a solution soaked sponge.294
better corrosion protection.89 The problem is that, to The coatings were comparatively thick (3–4 mm) and
date, no one has managed to successfully implement corrosion resistant, although they required some base/
these potential advantages. acid pretreatments before application.294
The first examples of electrodeposition of cerium onto
aluminium appear in the 1980s, where Hinton et al. Spray coating
deposited pale gold coatings onto AA 7075 from The group at UMR has also expended consider-
aqueous 2-butoxythanol containing Ce nitrate.136,230,231 able effort on the development of a spray coating
Small additions of water were required for the process to process for aerospace alloys, largely because of
work. Potentials of 20–50 V (100–150 s) were optimal, the ease of application.146 The general process entails
and exceeding levels of 3%Ce nitrate or 3% added water spraying samples (AA 2024/AA 7075) with a CeCl3–
resulted in cracked, powdery coatings of poor quality.136 H2O2–gelatine mixture at pH 2?1 for between 5 and 20
It was eventually concluded that the coatings lacked spray/drain cycles (50uC), rinsing, drying (rt, 24 h) and
durability due to a variety of discontinuities, including sealing in sodium phosphate (85uC, pH 4?5,
blistering232 and cracking232 and perforations caused by 5 min).108–112,114,118,137,139,148,205,211,213 Cerium nitrate
hydrogen evolution.36,231 Poor adhesion was also an was tested as a Ce source but was found to be ineffective
issue.231 It was eventually concluded that the process in the spray process,139 and although the use of chloride
was inconvenient232 and that the high voltages required resulted in subcoating cracking, it also provided a far
for operation with the organic solvent would make scale more corrosion resistant coating.139 The composition of
up difficult for commercial application.36 Hinton’s the spray solution has varied slightly over the years,116
group abandoned electrolytic deposition in favour of although the components remain the same and the main
immersion coating (see the section on ‘Accelerated area of development appears to have been in the area of
immersion coating’), although other groups took up the pretreatment, as this was found to be a critical
the challenge of the electrodeposition route some years factor affecting deposition rate, thickness and coat-
later. ing performance.109 Initially, a minimalist approach
The group at UMR, for instance, spent considerable was taken, with alkaline cleaning being the only
time examining electrolytic deposition on aerospace pretreatment used.108–110 This was then upgraded to
alloys12,13,31,142,221,233 while under contract to Boeing. include the use of a sulphuric acid etch (tested on both
Curiously though, this effort was later described AA 2024 and AA 7075, but preferred only for
as a mere preliminary to developing an immersion AA 2024)111,112,114,116,118,211 or base etch (later the
process.147 The conditions of their electrolytic deposi- preferred treatment for AA 7075).112,114,213 This, not
tion process in its final state have been described in the surprisingly, resulted in a considerable improvement in
literature144 and incorporated cerium nitrate, nitric acid, the coating rate, as the acid treatment exposed Cu rich
gelatine and hydrogen peroxide.148 The coating was intermetallics,111,112,114,211 more commonly known as
subsequently sealed with hot phosphate.144,148 Variables smut. While this increased the coating thickness and
such as pH, additive concentration, coating time, significantly improved the corrosion resistance,111,112
potential and current density were examined.144 It was there must be deleterious effects on the coating
found that too high a solution temperature (.40uC) led adhesion. It was claimed that Ce7O12 was deposited by
to poor coatings,234 and efforts to raise this limit using the spray treatment, which then converted to Ce(III)
organic additives were not successful.144 It was claimed phosphate during the sealing step.148 Some self-healing
that Ce7O12 was deposited by the electrolytic process, has been observed taking place in defects, which was
apparently not due to either the Ce or the phosphate first is an unaccelerated process entailing room tem-
seal.236 It is not clear, however, that the authors perature immersion in solutions of Ce salts for long
excluded the possibility of the soluble gelatine in the periods (days to weeks) at neutral pH140,195,238 and
coating migrating into the defects. which is generally restricted to the more active
It is difficult to draw conclusions about the future of aluminium alloys. The second is an accelerated process,
spray processes. If immersion is a problem that spray entailing immersion in acidified, oxidising Ce solutions
processing is intended to circumvent, then it faces the for short periods (minutes),232,239 sometimes with
problem that the required pretreatments all use immer- additives to enable satisfactory coatings to form. Both
sion. In addition, the spray coating compositions the accelerated and non-accelerated processes originated
published to date all use high chloride solutions and in work by Hinton and his colleagues.195,232
non-standard pretreatments and require long coating
Non-accelerated immersion coating
times due to the necessity to carry out multiple spray/
drain cycles.211 High chloride means that all process The first (non-accelerated) immersion process stemmed
tanks and lines must be specially lined to prevent from experiments in 1984 onwards by Hinton et al. when
corrosion. These factors, along with the unfamiliarity of studies of various rare earths196,197,238 on steel,197,240
non-standard pretreatments, may result in slow take up zinc197,241 and AA 7075 140,195,238 showed that immer-
by industry. As noted earlier, the pretreatments being sion in low levels of Ce(III) salts produced corrosion
used to reduce coating times suggest that the coatings inhibition. In addition, crevice corrosion, stress corro-
will have poor adhesion. Moreover, it has been our sion crack initiation, corrosion initiated fatigue failure
experience that spray processing results in rapid decom- and stress corrosion crack propagation were also
position of the peroxide accelerator, which raises the reduced on AA 7075.238 While the initial focus was on
cost of operation significantly,194 although this has not corrosion inhibition, the development of faint yellow
been discussed in the literature to our knowledge. There coatings in cerium solutions was noted a number of
may be solutions to these problems, but it would appear times in early papers,231,238 and cerium had been
that spray deposition of Ce coatings has a number of specifically chosen for testing because it formed an
hurdles facing it before it can be considered for insoluble hydroxide.195,196 It was subsequently shown
mainstream application. that a compact film of cerium oxides/hydroxides had
formed.79
Swabbing Mansfeld et al. subsequently applied Hinton’s
In-service coating repair processes are all but indispensible process to AA 606120,80,81,172,201–203,217,218,242 and
in applications such as aerospace, but have largely been MMCs20,201–203,217,218 and found that it behaved similarly
ignored in the literature, probably because they exclude to chromate.217 Indeed, it was concluded that cerium
the more common coating methods. Immersion is not chloride passivation was a viable alternative to chromate
appropriate for obvious reasons, nor is electrolytic on Al alloys,20,81,201–203,218 although its potency varied not
deposition144 (although a recent electrolytic process by only among different alloys (e.g. AA 6061 and AA 7075)
Tang et al.,294 inaccurately described as a ‘brushing’ but also between different alloy tempers (e.g. AA 7075-T6
process, may be), and spray treatments have not been used and AA 7075-T73).202,203,217,217 (It is not widely appre-
in this application as yet. Application of Ce coatings as a ciated, however, that the performance of chromate
gel has been suggested,237 although it has never been coatings also varies considerably between alloys,77 so this
implemented. Swabbing would seem the best option for may be less of an issue than it might seem at first.243) Other
implementing a non-chromate repair process, although it authors have applied this process to pure Al,83 AA 2014,84
is almost completely absent from the literature. A single AA 2024,106,198,199 AA 5083,78,161,164,166,167 AA 6061,88
Ce based swab repair process has been reported.10 AA 8090,82 AA 6061z10%Al2O3,21,244 AA 6061z
Surprisingly, no standard tests appear to exist to measure 8%SiC, A3xx.x/SiCp187 and SiCp/5A06.180
85
the integrity of a repair process. In the absence of such a The extended coating times for the non-accelerated
test, two were devised involving scoring and cross- process have long been understood to be impracti-
hatching repaired areas and comparison with a control cal,64,140,195,197,217 and later authors have confirmed
area after 720 h NSS exposure and 5000 h outdoor this.161,164,167,188,190,244 Coating times of 1,244 5,164,167
exposure.10 Using these tests, Ce repairs were found to 6,199 7,83–85,88,202,203,218,242,245 3078,80,82,202,203,217 or even
perform as well as chromate.10 A significant obstacle to the 60 days21 are encountered in the literature. [Shorter
implementation of any non-chromate process is devising a times (15–60 min) have also been used in combination
suitably wide ranging and satisfactory demonstration that with higher temperatures.89,166,168,180 This was the basis
the new process can replace the old without introducing for a patent application,246 although Ce is not incorpo-
new problems. This is certainly true of Ce coatings, and rated into the surface layer,166 which means that it is not
particularly in the aerospace industry, which is very a true conversion coating process.]
conservative in introducing new processes where failure Not surprisingly, it has been confirmed that the
can be catastrophic. Swab/repair processes are, poten- deposition process is a progressive one.161 On AA 2024,
tially, one means of demonstrating satisfactory in service the most significant deposition was initially on dealloyed
performance on small non-critical areas of an airframe CuMgAl2 intermetallics, then on AlCuFeMn and then
and could build confidence in the application of non- lastly on the bulk matrix,106 while on AA 5083, Ce only
chromate coatings on a larger scale.10 To the best of the deposits on the intermetallics, and not on the matrix at
author’s knowledge, this challenge has yet to be taken up. all.167 On AA 5083, it was found that the layers given by
non-accelerated immersion and those deposited electro-
Immersion coating chemically were very similar by SEM.164 During the
In examining immersion processes, it becomes apparent corrosion of AA 5083 in aqueous NaCl, crystallographic
that there are two quite different coating regimes. The pitting takes place during the first day, then alkaline
pitting subsequently commences.165 A side effect of the phosphate171 have been added to coating solutions
Ce coating is that it delays the formation of a passive containing Ce(III) (for instance either as a salt or for
layer, which prevents the formation of crystallographic pH control as HF or H3PO4), both anions will result in
pits.165 Furthermore, Ce hinders alkaline pitting by rapid and quantitative precipitation of the correspond-
precipitating not only before attack starts but also while ing Ce salt. For this reason, the practice should be
attack is in progress.165 It has been reported that discouraged.
pickling the samples before immersion led to greatly Effect of pH. Bath pH is one of the most critical
improved corrosion resistance, although no supporting coating parameters and needs to be strictly controlled.
experimental details or results were provided.21 For architectural applications, for instance, the pH
In summary, the non-accelerated coating process is needs to be maintained between 1?9 and 2?241,42 as,
essentially of historical interest only due to the long outside these limits, the quality of the coating can
coating times involved. For any practical purpose, an deteriorate dramatically42 and give a less corrosion
accelerated process must be used, and it is to these that resistant coating.120,123 Other workers have also con-
we now turn our attention. firmed this general region as providing satisfactory
Accelerated immersion coating results.57,98,174,186 Fortunately, this degree of pH control
is not difficult.42 Lower pH values give better solution
As outlined in the previous section, simple immersion in
stability, but generally slow the deposition rate,177
aqueous CeCl3 will slowly deposit a coating on more
although the coatings are often quite uniform in
active aluminium alloys (e.g. AA 2xxx/7xxx), but the
appearance.120,123 Higher pH values give faster deposi-
coating times are prohibitive for any commercial
tion rates but at the expense of making the coating
application. On less reactive alloys (e.g. AA 1xxx/3xxx/
solutions less stable177 and can result in the formation of
5xxx/6xxx or any clad alloy), a coating will only form
non-adherent, powdery coatings as well.120,123 This will
extremely slowly or not at all.129 For example, condi-
vary with the alloy. For example, coatings will form on
tions that will coat AA 2618 quite satisfactorily will not
generate any coating on AA 6061.57 Thus, some form of AA 2024 above pH 1?6,51 while AA 7075 gives
acceleration is required in both cases, with the aerospace better corrosion results around pH 2?5121,232 and
alloys requiring somewhat less encouragement,129 noticeably lower coverage around pH 1?9.121 Although
despite claims to the contrary.102 higher pHs (.3) have been recommended in the
A coating bath for a typical accelerated immersion literature,99,100,102,169,171,177,183,185 this is generally inad-
process consists of at least the following principal visable, as coating solutions containing H2O2 become
components:41,42 unstable and precipitate Ce above pH 3.157,190 The
(i) a Ce(III) salt presence of Al3z ions increases the pH at which Ce
(ii) an acid to adjust the pH precipitates.247 As noted in the previous section, HF185
(iii) an oxidiser (usually hydrogen peroxide). or H3PO4171 should not be used to modify the pH of any
A range of other materials may also be included. There solution containing Ce(III) (such as in the coating step),
is, as a result, a wide range of bath components as they will result in the precipitation of the correspond-
and compositions that have been described in the ing Ce salt.
literature.58 These and other related matters are Effect of oxidant. The most widely used oxidant
discussed below. (accelerator) is acidified hydrogen peroxide, a discovery
Effect of anions. Chloride seems to be the most made by Hinton et al. in the late 1980s.232 They had
favoured Ce source.174 Indeed, Decroly and Petitjean postulated that the deposition of Ce coatings from
claimed that chloride was essential to the coating solution was due to the oxidation of Ce(III) by hydrogen
reaction,177 a determination noted by others as peroxide produced by the reduction of oxygen at
well.114,174,190 Even so, Hardin et al. have patented a cathodic sites.241 The slowness of H2O2 generation in
low chloride process using Cu acceleration to forestall solution offered an explanation as to why the yellow
corrosion of stainless steel processing lines.153 Conde coatings formed so slowly. Thus, it was reasoned, that
et al., by contrast, massively increased the amount of the addition of hydrogen peroxide to the acidic coating
chloride in an attempt to accelerate coating formation solution should accelerate the coating formation. This
on AA 8090,102 although the coating rate remained slow insight resulted in a 1988 patent,232 now abandoned,
(requiring up to 30 min), and the process failed which decreased the coating time required by between
completely on AA 2024 and AA 7075.102 four and five orders of magnitude, from weeks to
Sulphate is poorer at coating than chloride,173 being minutes.121 As virtually all subsequent work in the area
slightly inhibitive to the coating process.177 Nitrate, has depended on this concept, it can fairly be described
however, is strongly inhibitive to the coating as the second of the two most critical process discoveries
reaction114,177 and gives slow coating rates.118 in the field. Apart from accelerating the coating
Although nitrate does give more uniform coatings on kinetics,95,137,250 H2O2 also increases adhesion and
some alloys (e.g. AA 5083), they are reported to be less corrosion performance.239 Its effectiveness, ease of use,
corrosion resistant.157 This effect is complicated by the ease of handling and the fact that its decomposition
passivation effect of nitrate on aluminium, as small products (water and oxygen) are harmless make H2O2
amounts of chloride appear to be necessary to activate the oxidant of choice. Excellent discussions of the
the surface247–249 and chloride has been shown chemistry of H2O2 in the coating process may be found
(on AA 7075) to be much more active for coating in the literature.122,247 It has been found that, in the Ce
formation than nitrate.139 Despite this, a number of coating reaction, H2O2 acts as a complexing agent, an
studies have used nitrate as their cerium oxidant, a crystallisation inhibitor and a source of OH2
source.44,94,95,99,100,103,114,134,135,144,168–170,174,176,183,249 It ions, resulting in precipitation (coating) reactions.125
should be noted that although fluoride96,135,185 and The peroxide accelerated cerium coating process has
,500 mg m22.152,154 These catalysts are the basis of a degreasing, pH, Ce concentration, H2O2 concentration,
process that was commercialised by Chemetall for anion type, coating time and temperature on A3xx.x/
architectural aluminium.41,42 Strontium chloride and A3xx.x-SiCp alloys.190 They (like Decroly and
ammonium vanadate have been tested on AA 6063, and Petitjean177) noted that deposition increased with pH,
both were claimed to increase the coating thickness but solution stability decreased.190 They found 50uC
and the corrosion resistance, although SrCl2 was optimal for coating, using 2000 ppm CeCl3 for
regarded the better of the two,174,176 as vanadate 10 min.190 Dabala et al. coated AA 5083 over a range
reduced the compactness and adhesion of the layer.174 of conditions [CeCl3 (10–20 g L21), H2O2 (100 mL L21)
Wang et al. claimed the use of ZnCl2 with acidified H2O2 at pH 2 for 2–10 min and 18–50uC156] and found that
to accelerate coatings on AA 2024.104 Zn is not, the corrosion resistance improved from 20 to 35uC,
however, present in a catalytic amount as might be although there was little subsequent improvement at
expected, being of the same order as Ce (15 versus 50uC.156,157 Using cyclic voltammetry, it was found that
25 mmol). This result is puzzling, as cerium normally (at 50uC) corrosion performance improved up to 10 min
deposits quite easily on AA 2024, although at pH 3, the coating time and decreased thereafter.156 Increasing Ce
solution acidity may be too low for effective coating to concentration produced no improvement in perfor-
occur. On AA 6082, low levels of CuCl2 were found to mance.156 Later, Dabala et al.157found that for CeCl3,
give faster coating and better adhesion,177 although this corrosion resistance increased with temperature (rt to
idea was probably covered in a earlier patent.151 Other 50uC) (which was less marked if nitrate was used
transition metals (Fe/Sn/Mn/Co) were also tried, instead), time (2–10 min, decreased thereafter),
but without success,177 as FeCl3 and SnCl2 imme- increased pH (1–3) and lower H2O2 concentration
diately hydrolysed, while Mn and Co had no effect (100–200 g L21), while changing the Ce concentration
whatsoever.177 had little effect over the range studied (20–40 g L21).
Gelatine (coating modifier). The group at UMR Higher temperatures gave ‘no sensible effects’.157 They
has long included gelatine in their coating concluded that the optimum conditions for coating
formulations.33,137,144,255 It was claimed to improve AA 5083 were CeCl3 (20 g L21), H2O2 (33 vol.-%)
coating uniformity255 and adhesion144 by reducing both (100 mL L21), pH 2, 50uC, 10 min.157 These are within
the grain size145 and the cracking in the coating,145,148,205,259 the ranges suggested also by Chemetall researchers.41,42
which was thought in turn to improve the corrosion Recently, an interesting comparison has appeared on
performance.144,205,255 This did not work on AA 2024, the effect of the various coating conditions published by
however,255 and appeared to reduce coating rate.205 In five different research groups.118 It was found that
addition, the amount of gelatine had to be controlled or nitrate coating (e.g. Zhang, de Frutos and Rangel) gave
subsequent sealing steps could be impeded.205 The little etching but gave low coating rates. The formula-
situation is somewhat confused by the fact that some tion used by CSIRO/DSTO gave very light etching and
gelatine containing coatings are still referred to as being very good coatings, but it was concluded, somewhat
highly cracked,33 that some cracked coatings still surprisingly, that the pretreatment used might adversely
performed quite well118 and that complete elimination affect deposition rate, coating thickness or corrosion
of cracking did not, in any case, result in good corrosion protection.118 Published data, however, would suggest
performance.33 Only one other group has reported using that it does not.77
gelatine in their coatings.171
Coating formation
Boric acid (‘stabiliser’). Boric acid has been used by a
number of authors58,99,100,130,183 as a ’stabiliser’,176,184,185 How the coating forms
although it has not been made clear in any of these papers Hinton and his colleagues, in their first papers on Ce
what exactly is being stabilised, or how, or how well boric corrosion inhibition, proposed that local pH increases
acid achieves this function. occurred at cathodic sites as a result of O2 reduction, which
Factor assessments. Only a few groups have under- resulted in the precipitation of Ce oxide, thus reducing the
taken broad examinations of multiple factors associated cathodic current and therefore the overall corrosion
with the coating process. Taylor and Hughes undertook rate.79,195,196,231,238 This was not unexpected,260 and cerium
an early Plackett–Burmann investigation of process had been specifically chosen for testing because it formed an
variables.229 This enabled substantial improvements in insoluble hydroxide.195,196 The mechanism was reiterated in
performance and the elimination of one of the pretreat- later papers59,127,128 and was confirmed, or simply repeated,
ment steps then in use.229 Decroly and Petitjean tested 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
the effect of different Ce salts, pH, time, H2O2 In
concentration, buffers, catalysts and surfactant on fact, the mechanism accepted today is essentially the same
coatings on AA 6082.177 They found that coating could as that proposed by Hinton et al. in 1985,52 although it may
be accelerated by increasing peroxide or pH levels.177 have had an antecedent in the work of Da Fonte et al.266–268
Sun et al. carried out an orthogonal experiment covering It may also be noted that, while all the rare earths will
three composition factors, four different levels and precipitate given a high enough pH, only two of them,
two accelerants (strontium chloride and ammonium cerium and europium, have oxidation couples [Ce(III)–(IV)
vanadate). Coating thickness was most affected by and Eu(II)–(III)], which are stable in aqueous solution.227
solution temperature.oxidiser concentration.Ce con- As aqueous Eu(III) is reduced to Eu(II) by aluminium and
centration, although for best corrosion performance, the Eu(OH)2 is water soluble,227 Ce is the only rare earth that
order was Ce concentration.oxidiser concentration. can involve a change in oxidation state and form a water
solution temperature.176 It was found that increasing insoluble hydroxide/oxide on aluminium.
the solution temperature reduced the density of the While Ce in the coatings has been found in a
coating.44 Pardo et al. investigated the effect of stirring, few preparations to be mostly or completely in the
Ce(IV) state,119,186 mixtures of (III/IV) are far more amorphous44,174,256 or nanocrystalline145,174 gel271,276,277
common.23,29,57,59,104,135,140,141,146,147,175,176,185,248,256,269 In spheres or nodules,29,77,102,104,145,174,176,184,185,256 which
fact, the Ce(III/IV) ratio varies considerably,155 and the agglomerate into a continuous film44,102,184,256 even-
higher oxidation state appears to be due to the effect of air tually covering the entire matrix.174,185 The spheres/
oxidation256 during either formation or subsequent nodules are, of course, Ce rich29,147,149,174,176,185 (and are
aging.270 In fact, the group at UMR showed that, in the occasionally claimed to contain a small amount of
presence of air, a yellow Ce coating forms on AA 7075, Al176,185) and can vary from 5 to 500 nm in
while under argon, a colourless, translucent gel forms.143 size,141,145,147,149,185 with the thickness increasing with
Davo and de Damborenea have also observed the time77 to several micrometres.185 Li et al. observed
formation of a transparent Ce layer with little or no microscopic crystalline units over the surface, which
Ce(IV).82 then act as the active centres for the deposition of the
The question remained51 as to whether the pH increase bulk of the coating over the surface.271,276,277 The
precipitated Ce(III), which was then oxidised to Ce(IV) processes of nucleation and growth are comparatively
(the four-electron mechanism),155 or the oxidation pre- slow.271,276,277 A consistent physical feature of the
ceded the precipitation (the two-electron mechanism).263 coatings is a morphology similar to cracked or dried
There was evidence that Ce(III) was precipitated first or, mud.12,13,17,23,29,50–52,57–59,104,115,117,119,124,130,135,144,149,
under anaerobic conditions, that Ce(IV) was favoured if 156,157,161,174,181,184–186,231,252,259,278,279
These cracks have
oxygen or H2O2 was present.263 The latter mechanism is long been understood to form due to drying of the
now accepted,41,42,271,272 although this may depend on the gel,17,51,58,115,119,124,135,144,161,174,181,231,279 which cannot
metal being coated.272 The solution chemistry during the only happen in the vacuum of an SEM, but
formation of Ce coatings has probably been most clearly has also been observed to occur in air under an optical
articulated in the work of Hardin and Hughes.122 To that microscope.144 Occasionally, however, this surface
point, the role of peroxide, known to be critical in the cracking is still credited to process variations rather
process, had not been described well. The presence of than to, for example, the use of the SEM, which has
peroxide in the coatings was later confirmed by Raman been used to observe and characterise the cracking. The
surface studies.125 cracking has long been blamed for poor corrosion
Where the coating forms performance of the coatings117,144,186,259 and has been
claimed to be a weakness of the process,17,89,141,147,174
It is generally accepted that cathodic intermetallics
although in fact, few cracks go through to the metal
are significant contributors to coating nuclea-
surface.52 It has been claimed that cracks form only over
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 intermetallics containing Fe, Cr or Mn,156 although this
descriptions of which may be found in the
is disputed.52 In addition, some cracked coatings have
literature.11,82,98,121,262,273–275 Intermetallics vary in their
been shown to perform quite well,118,280 and complete
electrochemical character53,59,197,260 and hence in H2O2
elimination of cracking does not result in good
reducing efficiency, and this can further vary during the
corrosion performance in any case.33 It should be
corrosion process.95,106,264 Thus, there is a hierarchy of
pointed out that chromate coatings also exhibit this
cathodically active sites on the surface,106,260 and, as the
type of cracking.14
most active sites become passivated, the next most active
In summary, however, the effect and importance of
sites can take over. It should be noted, however, that no
coating will occur over an as-received metal surface, even the surface morphology on Ce coating performance is
over intermetallics that will cause Cr to deposit, so the not well understood.
cathodic nature of the intermetallics is not in itself a Chemically. The Ce coatings have been described as
sufficient condition to generate a Ce layer,51,98 and the view mixed Al–Ce layers41,42,57,128 or as layers composed of
that intermetallics are the chief contributor to the mixed Ce rich and Al rich areas.59,104,124,157 Some
formation of Ce coatings is not universally held.52,98,168 workers have found that the coatings contain no Al at
Indeed, it has been pointed out that the coating can also all.149,155 Others find evidence of a bilayered coating.
form along a range of electrochemically active areas, Early Auger studies showed a top 100140,238–200 nm196
such as grain boundaries,1,82,241 oxides, contaminants, layer of principally Ce oxide, with another 100 nm of
surface variations made during manufacture (such as mixed Ce–Al oxide.140,196,238 Later workers found a
rolling marks),1,59,122,124 preferentially etched areas form- hydrated aluminium oxide layer overlaid by a Ce rich
ed during coating, hardening precipitates at grain layer 0?1–0?2 mm thick77,122,124,127,128,140,247 that was
boundaries121 as well as on smut left by incomplete surface thought to indicate a two-stage coating process invol-
etching.51 Significantly, enrichment of copper by replating ving oxide growth followed by Ce deposition.77,247 Some
on the surface has been observed92,95,98,124,262 and is of these differences may be caused by non-uniform Ce
thought by some to play a significant role in coating the layers or to irregularities in the Ce/Al interface due to
matrix of aerospace alloys.17,58,98,122,124,247 Indeed, it is this surface roughness.115 The Ce component of the coating
lack of distributed cathodic sites through Cu enrichment was initially described as a mixture of CeO2, Ce(OH)4,
that is claimed to inhibit generalised coating from and Ce(OH)3140 or just CeO2 (fluorite),140 but the
occurring on non-aerospace alloys.51 This has prompted situation appears to be more complicated than this.
extensive research into accelerators to promote coating on Pourbaix diagrams are usually invoked to explain the
non-aerospace alloys (see the section on ‘Effect of precipitation of the various cerium containing phases on
additives’). the surface, and a number of updated Pourbaix
diagrams have been published.124,143,169,281 There are
What the coating is... difficulties however in identifying solution species with
Physically. Cerium coatings are generally light titrated species,125,169 and Pourbaix diagrams (even
yellow to golden in colour6,134 and form as either covering such useful areas as the Ce–H2O–H2O2/O2
system)281 are equilibrium diagrams, and there is the the layer in the process.285,286 So, this is not recom-
possibility that the Ce containing species may be a non- mended. In the case of AA 2024, exceeding even 120uC
equilibrium cerium peroxo complex122,125 or a dimeric is inadvisable.286 The second point is that most of the
species.282 Other candidates that have been suggested drying conditions reported for cerium are well in excess
include CeO2 (fluorite),124,140 CeO2.2H2O,114 hydrated of what chromate coatings are capable of withstanding,
Ce oxide,139 mixtures of CeO2, Ce2O3, Ce(OH)3,183,199 without irreversibly compromising the corrosion protec-
Ce(III/IV) hydroxides,270 Ce2O3, CeO2, Ce(OH)3, tion of the coating (,60uC).6,35,287,288
Ce(OH)4 plus hydrates,175 Ce(III/IV) oxide and carbo- Thus, while there is nothing necessarily wrong with
nate104 and Ce hydroxide and carbonate and Ce peroxy heating Ce coatings to dry them, as Ce, like Cr, deposits
or Ce peroxycarbonate species.59 Some researchers as a gel, there appears to be little or no supporting data
have simply stated their view that the orange colour for recommending it either.
of the coating is diagnostic of a simple Ce(IV)
species.115,169,177,241 The problem is that X-ray diffrac- Sealing the coating surface
tion has shown that the coating is not consistent with It has long been known that the corrosion protection
hydrated CeO2 or hydroxide or indeed any other known provided by bare Ce coatings is not sufficient to
oxidic form of Ce,249 so it is difficult to be confident withstand the rigors of NSS testing.127 In order to
about these identifications. Although it was claimed that increase the durability of the coating, it is necessary
electrolytic and spray coatings were Ce7O12,148 it has to seal the coating.177 A variety of methods have
been found that immersion coatings do not match any appeared in the literature for doing this.
known Ce oxide or hydroxide [CeO2, Ce7O12, Ce6O11,
Ce(OH)3].145,147,148,184,185 Raman spectroscopy has con- Hot water
firmed that peroxo (O2{ 2 ) is present on the surface and The least complicated sealing process is hot water
would seem to support the suggestion that the coating immersion. The group at UMR has looked at immersing
contains Ce(OH)x(OOH)y species.113,125 The presence of coated samples in boiling water12,13,141 to decrease the
a peroxo species is supported by thermogravimetric amount of water in the coating and to thicken the oxide
analysis, which shows a large loss of O2 at 100uC.247 A layer on the Al.12,13 The coatings changed from orange
progressive loss of colour has been noted in the coating to olive in colour and were claimed to be improved.12,13
with time,125,144 which has been attributed to hydroxide Sealing in hot water (over an electrolytically deposited
transforming to oxide144 or degradation of surface coating) did not improve corrosion performance
peroxo species.125 The latter suggestion is supported by however,144 nor did the inclusion of the organic
the fact that the coating colour may be restored if the additives polyethylene imine or triethylene tetramine.144
panel is dipped briefly into a dilute solution of hydrogen In fact, SEM analysis suggests that hot water treatment
peroxide. Ce peroxo compounds are not unknown in the either significantly disrupts the coating144,145 or removes
literature,283 and some are surprisingly stable.284 it entirely.147 This probably explains why hot water
If the coating is, in fact, based on a peroxo species, it sealing is no longer being pursued as a sealing step.
would go some way to explaining why the characterisa-
tion data have not been matched to Ce oxides or Silicate
hydroxides. It should be borne in mind that the coating Silicate is a known corrosion inhibitor24 and has been
may, instead, consist of mixed crystalline and amor- used for several decades for sealing surface coatings.266
phous phases and that surface species (i.e. peroxide) may It has been most widely used on Ce coatings by the
not be typical of the bulk of the coating. In any case, the group at CSIRO/DSTO, who found that it provided
issue of coating composition cannot be said to be settled. significant improvements in NSS resistance.121,122,128 It
appears to have been used first at room temperature (as
Post-treatments 10% KSil) for 5120,123–10 min127,128 with an immediate
Air drying post-seal rinse. This formed a 0?4 mm silicate layer that
The simplest post-treatment after a water based coating contained no Ce127,128 and allowed NSS performance of
deposition process is air drying, and most published up to 336 h without pitting.127,128 It was thought that
processes incorporate a drying step, either implicitly or silicate might react with metal through flaws in the Ce
explicitly. The variation in the conditions used is coating, thus improving its performance.127,128 The same
interesting, but of greater interest is that there seems papers also mentioned allowing silicate to dry overnight
to be little or no published evidence for any drying step before rinsing, a process that was adopted in later
at all and the conditions reported in the literature appear experiments,77 but for which no experimental results or
to be more or less arbitrary. Thus, reports of drying at rationale has been provided.127,128 Silicate immersion
ambient (24 h),33,110,111,117,137,149,205,213 50uC (30 min),98 (10% KSil/10 min) at 80uC, dried overnight and then
60uC,94 50–100uC,180 60–120uC41,42,190 and 160uC rinsed, could provide impressive NSS performance77 (see
(10 min)67 are encountered. Pardo et al. claimed an section on ‘Salt spray results (CSIRO/DSTO)’). Silicate
optimum drying temperature of 105uC,89 but this is not was tested with a variety of dopants (including glycerol,
particularly helpful, as nothing was tested below this vanadate, permanganate), but these provided no
temperature.190 Also unhelpful are references to drying improvement over silicate alone.120,123 While it can
in an ‘air furnace’103 in ‘hot air’102 or at up to 500uC provide excellent corrosion resistance, silicate suffers
(!).190 from a significant drawback in that it absorbs carbon
Two points may be made. The first is that while dioxide from the air, and so the bath chemistry (and
500uC190 will certainly convert any amorphous Ce oxy/ hence the performance) constantly changes,6 particu-
hydroxide to an oxide layer, it will also destroy the larly at higher temperatures. This issue has not been
temper of a wrought alloy, distorting it and spalling off satisfactorily resolved.
and to ensure reproducibility. Reproducibility, however, 168 h in NSS with no corrosion;168,169 however, the
remained an issue even in the 40 L line.121 Testing at panels tested were surprisingly small (,10610).168,169
CSIRO/DSTO and Boeing demonstrated better than Conde et al. found that Ce coated AA 8090 was not
168 h for both AA 2024/AA 7075 panels,121,127 largely damaged after 168 h of exposure.102 AA 8090 is a fairly
based on the LERD pretreatment.127 Subsequently, corrosion resistant alloy, however, requiring ,96 h in
336 h (AA 2024) was reached,38,128,229 without pitting NSS before showing signs of corrosion.102 AA 2024, by
using room temperature silicate as a seal.128 Later, on contrast, will show pitting from NSS exposure in
the 20 L line, AA 2024-T3 again reached 336 h122 and ,10 h.229
AA 7075-T6 reached 300 h.122
As noted earlier, chromate deoxidation before Other corrosion tests
cerium coating was found to result in poor NSS per- Weight loss
formance (80 versus 336 h using LERD).127 This was Hinton et al. used weight loss measurements
attributed to the nature of etching and the surface left (ASTM G1-1972) and found that Nd, Pr and Ce all
behind127 or to the presence of Cr left on the sur- reduced the corrosion of AA 7075 by more than a factor
face after deoxidation,128 a fact confirmed later by of 10,79 a figure confirmed for Ce by later workers.295
UMR.141 The order of inhibition effectiveness was found to be
During later work with BAE Systems (1999–2001), NdyPr.Ce.La.Y.79 Electrolytically deposited Ce
CSIRO/DSTO set up an automated dual process line coatings were also found to lower the weight loss by a
with 60 L tanks. This achieved NSS results on AA 2024 factor of 10.136 Hu et al. also used weight loss
of up to 960 h (easily exceeding the 700 h reached on experiments (immersion in 3?5%NaCl) to demonstrate
chromate control panels), but the performance was that Ce coatings significantly reduced the degree of
lower on AA 7075 (288 versus 1300 h with Cr) and corrosion over an untreated panel.23 Pardo et al. used
AA 7475 (72 versus 120 h with Cr).77 Apart from the immersion in 3?5%NaCl to determine that La coatings
significant, and still unexplained, differences between (either immersion or electrolytically deposited)
alloys, it may be noted that the 960 h result was decreased the degree of pitting attack and delayed the
extraordinary (with five panels all exceeding 800 h), growth of the corrosion layer.89
although during this period, 336 h on AA 2024 was an
unexceptional result.194 The inability to reach 336 h with Outdoor exposure
AA 7075, in spite of earlier work achieving this mark, is Outdoor exposure testing of a Ce coating on AA 2024
probably due to the changing chemistry of the seal (see passed 35 days, which was more than enough to destroy
the section on ‘Silicate’) and the use for this work of hot, a bare panel, although Cr lasted over 50 days.127,128
rather than room temperature, silicate, which worked
better with AA 2024. Immersion testing
Mansfeld found that Ce coated AA 7075 did not begin
Salt spray results (UMR) pitting in NaCl for over 3 weeks, while as-received
The group at UMR, working variously with electro- panels pitted in a matter of hours.202,203,218,245 Similarly,
deposition, immersion and spray coatings, have claimed Ce coated AA 6061 took between 30202 and 90
impressive corrosion performance for their samples over days201 to pit as opposed to 24 h for untreated
the years. Thus, AA 7075 has been reported to have samples.201–203,218 The group at UMR have also used
reached 336 h in NSS,8,12,31,32,141,144–147,149,212,213,221,233 immersion to assess their coatings, claiming that if a
and spray coatings on AA 2024 have been reported to coating remains stable after a day’s immersion in
have reached between 168118,205 and 336 h.110,280 These Prohesion solution,12,13,142 then the coating will pass
are impressive results, but it must be noted that the 336 h in NSS.31,32 This is an unusual and interesting
MIL specs require test panels of a specific size (1006 claim, but one that does not appear to have been
30), and the smaller panel sizes UMR followed up.
use8,33,108–110,141,142,144,145,147–149,205 do not comply with
this requirement. For example, their early work used Electrochemistry
30660 panels,8,12,13,144 but more recently, 10630 panels A large number of electrochemical studies have
appear to have become standard,145 and these are not been carried out on cerium inhibited alumi-
compliant with the standards.33,110,144,205 As with the 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
CSIRO/DSTO work, there are indications of reprodu- Electrochemical measure-
cibility issues with the UMR cerium coatings, with ments are sometimes favoured as a substitute for NSS
ambiguous references to panels meeting the MIL testing as they are quicker,112,173 are less labour intensive,
specifications.8,12,13,31,131,144 This is also apparent in cost less are capital intensive and give useful information
the varying percentages of panels that are claimed to that a simple pass/fail NSS corrosion test will not. The
pass 336 h in NSS (e.g. 20,144 50,149 70,212,213 80147 and problem is that the latter remains the industry standard
85%144,145). and despite claims that electrochemical impedance
spectroscopy (EIS) can be used to predict NSS
Salt spray results (others) results,33,38,297 the data do not seem to be conclusive
Other workers have also used NSS as part of their and electrochemical failure mechanisms (particularly
testing procedures. Tang et al. reported that an those of EIS) have not been convincingly linked to those
unsealed, electrolytically deposited Ce coating on of NSS,112 at least on a deterministic basis.292 Most
AA 2024 could last 120 h in NSS before the first pit electrochemical studies have simply provided the con-
formed.294 An uncoated panel showed severe widespread firmation that the coatings provide corrosion protec-
pitting after only 24 h.294 Bethencourt et al. claimed that tion12,13,134,296 or have quantified the relative degree of
their cerium coatings could allow AA 5083 to last for electrochemical protection57,104,157 and how this develops
over time.82,94,95,199 Thus, Ce coatings have been variously in most cases as good as or better than chromate.133
claimed to be much better than Cr,31 slightly better than Knudsen et al. assessed a number of non-chromate
Cr,176 about the same as Cr81 or worse than Cr,38,57 which conversion coatings (Ce, Ti/Zr, anodising, self-assem-
may say as much about the variability in coating bling monolayer, phosphate) on AA 6060-T640 and
preparations as anything else. There is, however, near demonstrated that, with a good quality polyester
universal acceptance that Ce provides a considerable powdercoat, the filiform results for Ce were as good as
improvement over the corrosion resistance of the bare those for anodising and superior to Cr.40 Chemetall
metal 12,15,79–81,101,102,104,127,128 even in the absence of a published data to show that, for AA 5005 and AA 6060,
seal.127,128 Polarisation studies have repeatedly shown that the performance of Ce coatings under powder coat is as
Ce does not operate as a barrier coating but suppresses the good as chromate in cross-hatch, ESS creepage (1008 h),
cathodic oxygen reduction,12,23,79,82,102,104,121,128,136,140,221 copper accelerated acetic acid salt spray (CASS)
although there have been isolated claims of the anodic creepage (240 h) and filiform tests (1008 h),42 and, on
reaction also being affected.12,13,211 Polarisation experi- the basis of this data, Qualicoat and GSB approval tests
ments indicate that Ce affects the corrosion potential, but were initiated for the Cerate process in 2002.42 Later
not the pitting potential,58 although this is elsewhere work by Hughes et al. found that, in general, the extent
claimed to be dependent on the peroxide concentration of filament filiform corrosion on AA 2024 was similar to
during the coating.29 The CSIRO/DSTO group also that of chromate (according to DIN 65472), but the
found that the Ce coatings were not self-healing. A maximum depth of attack in the filaments was higher in
polarisation test on bare metal in a solution in which a the Ce coated samples.129 When this was repeated with
coated specimen had been immersed for several hours bismuth accelerated coatings on AA 2024-T3, the
showed that there was no leaching of a soluble Ce filament lengths were shorter than Cr.60 Near Cu–Ni
species,128 a finding confirmed by Dabala et al. from the fasteners, Ce performed similarly to Cr coated samples,
return branches of the polarisation curves.157 Palomino although it did not perform as well as Cr near Cu
et al. did find that, by immersing a Ce coated sample in a fasteners.60
0?5M NaCl solution with a polished, uncoated panel, Ce
slowly deposited on the intermetallics of the uncoated Corrosion tests
panel over 72 h.52 The evidence for self-healing in Ce The CSIRO and Chemetall carried out tests on painted
coatings is not particularly strong at this point, although AA 6063 and found results comparable to chromate
Ce(III) release from hydrotalcites,53 bentonite298 and after exposure to 1000–2000 h of acetic acid enhanced
nanoparticles130 has been observed. salt spray and 1000 h of CASS.152,154 The CSIRO/
DSTO group also carried out tests (720 h NSS and
Electrical conductivity 5000 h temperate/tropical outdoor exposure) on scribed,
A fundamental property of class 3 coatings under MIL- repaired, painted AA 2024/7475 surfaces.10 In outdoor
C-81706/5541E is electrical conductivity.35,288 The exposure testing, the results for repairs using a Ce
CSIRO/DSTO found that Ce coatings failed electrical formulation were as good as those for standard
conductivity testing on AA 2024/7075/7475 in the sealed chromate. While the data were slightly poorer for
condition and for all conditions (sealed and unsealed) cerium than chromate on NSS tests, this was dependent
after NSS.77 Davo and de Damborenea also found that a on the alloy and certainly showed that this prototype
non-accelerated coating showed very low conductivity.82 process performed well against a commercial chromate
It would appear, then, on the basis of the limited evidence repair.
available, that electrical conductivity is a property of The group at UMR found that their electrolytically
chromate6 that Ce coatings are unable to duplicate. deposited cerium coating passed 2000 h NSS exposure
under e-coat on AA 7075 and AA 2024,13,31,32 under
Performance under paint
polyaniline (scribed) on AA 7075142 and under epoxy on
Filiform corrosion AA 7075.142
Filiform corrosion is the primary corrosion mechanism
for organic coated aluminium and is a major obstacle Adhesion
for the increased use of Al in the architectural and Although it may be argued that the corrosion perfor-
automotive industries.40 In filiform corrosion, thread- mance of Ce coatings has never consistently matched
like corrosion attacks (filaments) spread under the that of Cr(VI),44 Ce performs well in adhesion tests,
organic coating causing adhesion loss and degradation although there are not as much data available in the
of the visual appearance.40 Despite its objectionable literature as there is for corrosion.
appearance, filiform corrosion is only an aesthetic issue There are several varieties of adhesion testing avail-
and has little effect on the metal’s properties.299 Early able. The most straightforward is a simple dry adhesion
on, Mansfeld et al. found that a non-accelerated Ce (tape) test150,151,249 to determine if the Ce coating will
coating under epoxy did not prevent the formation of adhere to the metal when the tape is pulled off. The
filiform corrosion on AA 6061.172 This appears to have CSIRO/DSTO group routinely uses this test as a form of
been less of a problem with accelerated coatings, with quality control on their coatings. Tang et al. have also
filiform results equivalent to Cr being published soon used this test.294
after,121 and Hughes et al. made the point that Ce More complex paint adhesion tests are harder to carry
coatings under either powdercoat and e-coat on a range out in terms of both equipment and the expertise
of alloys generally performed as well as chromate (in required to run and interpret the results, but they are, in
architectural applications) and zinc phosphate (in general, more informative. Early tests by CSIRO/
automotive applications).122 In another study, Ce coat- DSTO229 showed that Ce coatings had extremely good
ings were found to produce excellent filiform inhibition dry and wet adhesion when painted and showed no
on a range of 12 different aluminium alloys, with results blistering or loss of paint adhesion after 30 days
exposure to condensing humidity.229 Adhesion of (x) the components and byproducts have low
scribed panels before and after 7 days immersion in toxicity.20,31,32,50,187,188,238
water and impact resistance was also good.229 Later tests The disadvantages of cerium coatings41,42 include the
found Ce coatings passed dry adhesion testing on following:
AA 2024 but failed wet adhesion,121 and, surprisingly, (i) the coating operation is often carried out at
sealing the coating had relatively little effect on the mildly elevated temperatures (up to 50uC)
results.121 The coatings could also pass condensing (ii) poor or variable NSS performance in the
humidity tests, although not consistently,121 and impact unsealed condition
resistance and cross-hatch humidity test results were (iii) uncertainty about how coating performance is
similar to Cr.121 Later again, dry/wet paint adhesion affected by different pretreatments
tests were passed on both unsealed coating and silicate (iv) certain metals that dissolve into solution during
sealed coating on AA 2024/7075/7475,77 and PATTI coating (particularly Fe and Cu) result in
adhesion testing showed it was equivalent or better than catalytic decomposition of the peroxide. This
Cr on AA 2024/7075 and only slightly poorer on can become an unsustainable cost unless the
AA 7475.77 Chemetall found that paint adhesion process is controlled
(cross-hatch, ESS creepage, CASS creepage and filiform (v) the low pH and chloride content of the coating
creepage) of powder coated cerium coated AA 5005 solution requires the use of resistant materials
panels and AA 6060 profiles were equivalent to chro- (polymer coating, acid resistant metals etc.) for
mate coatings on the same substrates.41,42 Adhesion the coating bath,42 which can inhibit its use as a
testing (ISO 4624 pull-off) with a good quality powder drop-in replacement for other processes
showed that Ce was behind only Cr and Ti/Zr, while (vi) Ce is not as effective as Cr(VI), as it does not
with a poor quality powder, it gave results equal of inhibit oxygen reduction to the same degree or
anodised samples and inferior to Cr, but better than all with the same speed.107
the other non-Cr options tested.40 The DERA has
published some excellent adhesion data on their coatings Conclusions
(carried out according to BS EN24624), which not only
showed that the adhesion for rare earth coatings with Cerium coatings, remain a promising option for
chromated and non-chromated primers was adequate, chromate replacement on aluminium alloys, although
but also described the adhesion failure modes.96 This there are areas that need development. These include the
paper illustrates the amount of useful detail that can be following.
obtained from a well executed adhesion test. 1. Pretreatments. The effect of pretreatments on
cerium coatings is not well understood, and some of
the pretreatments favoured in the literature would not
Summary be suitable in an industrial context.
Although much of the discussion in preceding sections 2. Coating non-aerospace alloys. Putting cerium
has been related to aspects of Ce coating performance, coatings on aerospace alloys is relatively easy, but
performance on its own is not the sum of the benefits or generating coatings on non-aerospace alloys or the
the liabilities of a process. (If it were, of course, there cladding on aerospace alloys remains a significant issue,
would be no reason at all to replace chromate.) In an particularly as these less reactive alloys represent the
effort to address this problem, a quality function bulk of the potential market. Patented solutions exist,
deployment (QFD) assessment was applied to aerospace but relatively little has been published to allow these
conversion coating processes, taking into account issues methods to be assessed.
of time, operation, repair, as well as process, capital and 3. Post-coating seals. Post-coating seals need further
operational costs.193 The weightings were decided after development for applications where unpainted corrosion
extensive discussions with commercial, technical and resistance is critical. The two most widely used sealing
production staff, using real data as far as possible. This processes show either inadequate corrosion resistance
assessment showed that Ce coatings were very compe- (phosphate) or inconsistent bath chemistry (silicate).
titive with chromate.193 Potential alternatives, however, are not obvious.
The advantages and disadvantages of Ce coating Progress in these areas will make cerium an easier
processes have been listed by Chemetall researchers41,42 option for replacing chromate as the conversion coating
and others. The advantages include the following: of choice on aluminium alloys.
(i) it is free of both chromate and fluoride
(ii) bath control is straightforward (pH, peroxide Acknowledgements
and cerium concentration)
(iii) bath replenishment is straightforward The author would like to thank Dr A. E. (Tony) Hughes
(iv) the layer thickness increases with time for his encouragement to write this review and Drs A. E.
(v) the coating weight can be determined by Hughes, T. Markley and T. Muster (all of CSIRO) for
dissolution or X-ray fluorescence their comments on the manuscript. The author also
(vi) it can provide excellent paint adhesion and good wishes to thank his colleague S. Hardin (CSIRO) for
corrosion performance (sealed or under paint) many helpful discussions and insights over the years in
(vii) resulting waste water is easily treated with the area of chemistry generally and in the chemistry of
standard NaOH/lime treatment rare earths in particular.
(viii) it provides a visible (coloured) conversion layer
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