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February 2008
Assessment of Chemical
Conversion Coatings for the
Protection of Aluminium Alloys
B.D. Dunn
Product Assurance and Safety Department, ESA/ESTEC,
The Netherlands
Contents
Introduction 5
1.1 Project Background and Objectives 5
1.2 State of the art 6
1.2.1 Commercially Available Chemical Conversion
Coatings ... 6
1.2.2 Review of Published Papers 9
2 ExperimentalPhase ... 17
2.1 Materials, preparation of specimens, and treatments 17
2.2 Evaluation of the aluminium alloys samples 17
2.2.1 Surface roughness 17
2.2.2 Surface electrical resistivity 18
2.2.3 Thermal cycling tests 18
2.2.4 Salt spray tests ... ... 18
2.2.5 Scanning electron microscopy and energy dispersive
X-ray spectrometry (SEM/EDS) 19
2.2.6 Chemical conversion coatings procedure 19
3 Results / Discussion... 21
3.1 Visual inspection 21
3.1.1 'As received' ... 21
3.1.2 'As produced' 21
3.1.3 After thermal cycling tests 21
3.1.4 After salt spray tests 21
3.1.5 After thermal cycling + salt spray tests , 21
3.2 Surface roughness. 29
3.3 Surface electrical resistivity measurements 30
3.4 Surface morphology analysis - Scanning electron microscopy.. 31
3.4.1 After cleaning with Novaclean AI86 31
3.4.2 After chemical conversion coating treatments 32
3.4.3 After thermal cycling tests 39
3.4.4 After salt spray tests 43
3.4.5 After thermal cycling plus salt spray tests 47
3.4.6 Comparison and correlation between Aluminium
alloys and techniques performed 51
4 Conclusions 57
5 References 59
4 ESA STM-276
Abstract
The most common conversion coating (CCC) currently used for improving
the corrosion resistance of aluminium and its alloys that are used in the
construction of ESA spacecraft is Alodine 1200 manufactured by Henkel.
This commercial product is a chromium (VI)-based chemical conversion
coating. However, due to the environmental impact of hexavalent chromate,
and recent EU regulations enforcing prohibition of the use of certain
hazardous substances in electrical and electronic equipment, there is a great
need for chrome (VI)-free anti-corrosion coatings.
The aim ofthis work was the study of commercially-available alternatives to
chromium (V I)-based treatments. They should assure the same level of
performance in terms of corrosion resistance, thermal and electrical
properties. The objective of this study was to perform an assessment of
commercially existing chemical conversion coatings for the protection of
aluminium alloys that are to be used in the hardware of ESA space vehicles.
In this study, the aluminium alloys A17075, Al22l9 and Al5083 were used
as substrates for evaluation of the chemical conversion coatings.
Among various chemical conversion coating systems, three alternative
conversion coating pretreatments were selected for evaluation: Alodine
5700, Nabutan STI/310 and Iridite NCP. The chromium (VI) conversion
coating Alodine 1200 was used as the reference.
The quality assessment of conversion coatings was evaluated by optical and
scanning electron microscopy. Coated samples were characterised by salt
spray exposure in order to simulate ground storage conditions; thermal
cycling under vacuum, which simulates an in-orbit space environment; and
electrical resistivity, as spacecraft sub-systems are electrically grounded to
one another.
ESA STM-276 5
1 Introduction
It should be noted that the low strength aluminium alloys (5000 and 6000
series) are permitted to have a final finish of chromate conversion coating.
However, ESA prescribes in ECSS-Q-70-71 ('Data for the selection of space
materials and processes'), that the high strength alloys (2000 and 7000
series) shall have a further painted finish applied to the chromate pre-
treatment, or alternatively be anodised.
resistance to varying extents. The use of acid cleaning after the alkaline
etching allowed a significant improvement of the aluminium surface
chemistry, and consequently the filiform corrosion resistance. The best
behaviour was obtained by chromate or fluorotitanate conversion coatings
after an alkaline plus acid chemical cleaning.
Zhao et at. [27] studied the effects of chromate conversion coatings (CCC)
and chromate in solution on the corrosion behaviour of AA2024-T3, and
pure AI. The influence of the chromate on pit growth was studied by the thin
film pit-growth technique. The release and migration of chromate from
CCCs and the comparison of the CCCs chemistry with various synthetic
mixed oxides composed of Al (III), Cr (III) and Cr (VI) species, was
investigated by Raman spectroscopy. The effect of released chromate was
also studied by electrochemical methods. Using an artificial scratch cell,
chromate released from CCCs was seen to migrate to, and protect, a nearby
uncoated area. However, experiments investigating the effect of chromate in
solution on the anodic dissolution kinetics under potentiostatic control
indicated that large chromate concentrations were needed in order that an
effect can be seen.
John Bibber [28] published an overview of non-hexavalent chromium
conversion coatings that could provide excellent corrosion resistance and
paint adhesion characteristics when used with aluminium and its alloys,
compared with the chromium-based conversion treatment. The four main
types of conversion coatings in common use are based upon:
I) The formation of a chromium hydroxide and/or chromium oxide film;
2) The production of a precipitated heavy metal phosphate or oxide film;
3) The use of various synthetic polymers, with or without heavy metal
phosphates or oxides; and
4) The formation of a manganese oxide/aluminium oxide film by use of
permanganates.
The author concluded that the manganese oxides produced by the
heptavalent-manganese-based system are by far the most closely related to
the chromium oxides and hydroxides in terms of their respective chemistries.
Thus, the aluminium oxide/manganese oxide film, as produced by the
heptavalent-manganese conversion coating system, is the alternative pre-
treatment most closely matching the actual CCC in terms of actual chemistry
and performance.
NCAP ('Non-Chromate Aluminum Pretreatment Project') [4] has
undertaken a project to validate, and implement, multiple chromate-free
aluminium pretreatment alternatives. The researchers concluded that all
alternatives tested showed acceptable performance. From the evaluated
chemical coatings, the only pretreatments that came close to matching the
technical performance, cost and flexibility of chromates are those based on
trivalent chromium (Navair TCP). Furthermore, the Alodine 5200/5700
pretreatment performed similarly to TCP in most painted systems, but not in
unpainted applications. In general, although none of the other selected pre-
treatments can compete with the overall performance of these two
pretreatments, many could be selected for specific coating system
applications, and achieve the desired performance.
Cerium-based Al and AI-alloy pre-treatments have been proven as efficient,
environmentally-clean alternatives to the environmentally-undesirable
Cr (VI) compounds. Thus, full immersion in cerium salt solutions allows an
identical corrosion protection level to that of chromate-based treatments. A
ESA STM-276 13
major drawback is that treatment time is too long for industrial applications
[29].
Bethencourt et al. [30] proposed accelerated methods for obtaining cerium-
rich conversion coatings on aluminium-magnesium alloys (AI5083). The
films developed have been characterised by SEM and EDS. These studies
revealed that the coatings have a mixed or heterogeneous nature, being
composed of a layer of alumina covering the matrix, together with islands of
cerium formed over the cathodic intermetallics present on the alloy surface.
Furthermore, electrochemical studies indicate that the protection level
provided by these coatings is several orders of magnitude higher than
achieved with other treatments, such as chromate-based treatment.
Work by Arnott et at. [3 I] has shown that cerium-based coating deposition
relies on electrochemical interactions between the aluminium matrix and
intermetallic inclusions that make up structural aluminium alloys.
Fahrenholtz et al. [32] studied the performance of a cerium-based conversion
coating formed by spontaneous reaction between a water-based solution
containing CeCh and aluminium alloy 7075-T6 substrates. This study has
shown that the cerium conversion coating morphology and salt fog
performance were affected by the type of pre-treatment of the panel prior to
coating. The best pre-treatment consisted of desmutting, degreasing, and
acid activation.
Rivera et al. [33] developed an improved process for the spontaneous
deposition of cerium oxide conversion coatings for corrosion protection of
aluminium alloy 7075- T6, by a spontaneous dip-immersion process that
resulted in improved salt fog corrosion performance. The role of substrate
surface preparation and post-treatment was discussed in terms of the surface
morphology, thickness and performance of coatings on aluminium alloy
7075-T6.
Decroly et al. [34] investigated a chromate conversion coating alternative
treatment (cerium salt-based conversion) that could meet all the
requirements for industrial application. The corrosion protection properties
of this Ce conversion coating were investigated by cathodic and anodic
polarisation measurements and by electrochemical impedance spectroscopy
(EIS). However, although the coatings formed presented interesting
properties, their performances did not match those of chromate conversion
coatings.
The cerium-based chemical conversion coating is an effective method to
improve the resistance to localised corrosion of the aluminium borate
whisker reinforced AA6061 composite (AI1sB4033w/606IAI). Hu et al. [35,
36] reported a cerium conversion coating formed by an immersion process
that resulted in improved salt spray corrosion performance. The CeCh
concentration in the test solution has been shown to have a significant
influence on the corrosion behaviour, and surface morphologies of the
coated samples.
The electrochemical behaviour of a Ce conversion coating formed on Al
alloy 2024- T3 covered with a Cu-rich smut has been studied by Palomino et
al. [37]. The microstructural characterisation has shown that the precipitation
of the Ce conversion layer seems to occur homogeneously in the presence of
the Cu-rich smut originating a uniform coating. Moreover, it has been
confirmed that the dry-mud structure of this kind of conversion layer is just a
superficial phenomenon, with only a few cracks attaining the metallic
substrate) most likely due to stress relieving. Electrochemical results and
SEM/EDS characterisation have evidenced the self-healing properties of the
14 ESA STM-276
2 Experimental Phase
Alloys AI Cu Mg Mn Fe Zn Cr Si Ti
AI7075 Bal. 1.2-2.0 2.1-2.9 0-0.3 0-0.5 5.1-6.1 0.2-0.4 0-0.4 0-0.2
AI5083 Bal. 0-0.1 4.0-4.9 0.4-1.0 0-0.4 0-0.25 0.05-0.25 0-0.4 0-0.15
To assure that the metal surface was free from oil, grease and other foreign
matter before the treatment, an appropriate cleaner was used. Because of its
availability, Novaclean A186 was used. This is a cold degreaser for
aluminium used in immersion processes, combining degreasing and
deoxidising characteristics.
Surface roughness X X X X -
Thermal cycling* - - X -
* The thermal profile corresponds to a standardised profile of -50C and +1 OOC,with dwell times of 15 min,
at cooling/heating rates of 10C/min;
p = (R x S) /l
where:
p = surface electrical resistivity (Q m);
R = electrical resistance of a uniform specimen of the material (Q);
S = cross-sectional area of the specimen (m2);
I = length of the specimen (m).
Drying
3 Results / Discussion
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For the Al7075 alloy, there is a decrease in roughness for all treatments;
there is a decrease in roughness with the coating application as well as with
the thermal cycling.
For the Al 5083 alloy the influence of the different surface conditions is the
smallest, but it follows the same tendency as the AL 7075 alloy: a decrease
tendency in roughness with coating application and thermal cycling.
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cleaning but the coating deposition strongly increases the surface roughness,
which decreases again with the thermal cycling.
In summary, thermal cycling always decreases surface roughness. This
feature can be related to a dehydration of the surface layer. Treatment
application also decreases roughness, except for A12219, for which this
treatment makes roughness values higher than those obtained in the 'as
received' condition.
The behaviour described is essentially the same for the two perpendicular
directions.
In general, the Al2219 test panels show a higher surface roughness than the
other two aluminium alloys. It should be noted that the conversion coating
treatments Alodine 1200 and Iridite NCP provide a higher average surface
roughness, except for the Al7075 samples, where those coated with Alodine
5700 and Nabutan showed higher values.
The surface roughness measurements after the salt spray tests were only
performed on the test panels treated with the Alodine 1200S and on samples
of A15083, since that in general the surface of samples presented visible
evidence of corrosion to allow the measurement of the roughness. In those
samples measured it can be seen that there is no significant differences
between the roughness values obtained after salt spray tests.
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54 ESA STM-276
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ESA STM-276 55
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ESA STM-276 57
4 Conclusions
Chemical cleaning of the as-received sheet samples in Novaclean Al86
has been seen to decrease the surface roughness of all alloys (AI7075,
Al2219 and AI5083).
The coating supplier recommended processes were applied. Only
Alodine 1200S was observed to be defect-free after its application. The
other coatings contained some defects. For Alodine 5700, even
immersion time variations did not exclude defects (except for the 30-
second immersion).
Only the Alodine 1200S samples (for all alloys) survived thermal
cycling; the other conversion coatings were seen to partially spall-off.
The electrical resistivities of all samples were very similar, even after
thermal cycling.
Only the Alodine 1200S samples (for all alloys) can be considered to
have survived the salt spray test. The other coatings (A Iodine 5700,
lridite NCP and Nabutan STi/310) did not provide adequate corrosion
protection.
For A15083, chromium free coatings seem to have promising corrosion
behaviour.
Only Alodine 1200S provided a compact finish. The other coatings
tended to spall-off and are considered to be a severe source for
contamination in any given spacecraft application.
It is recommended that corrosion protection schemes for ESA
spacecraft continue to utilise Alodine 1200S, as the other (hexavalent
chromium-free) coatings did not provide suitable protection.
ESA STM-276 59
5 References
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-
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60 ESA STM-276
[19] G.M. Brown and KJ. Kobayashi, "Nucleation and growth ofa
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[33] B.F. Rivera, B.Y. Johnson, MJ. O'Keefe and W.G. Fahrenholtz,
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ESA STM-276 61