ADVANCED SURFACE TREATMENT…

Advanced plasma electrolytic oxidation treatment for

protection of light weight materials and structures in
a space environment
S. Shrestha1 and B. D. Dunn2
(1)
Keronite International Ltd, Cambridge CB21 6GP, United Kingdom, Email: [Link]@[Link]
(2)
European Space Agency, NL-2201AZ Noordwijk ZH, The Netherlands, Email: [Link]@[Link]

INTRODUCTION The recommended black anodising uses Nickel

Light weight materials such as aluminium alloys are sulphide or Cobalt sulphide as an inorganic black dye
extensively used in spacecraft components. Protection [1]. These chemicals are considered to have
of these materials in a space environment presents environmental and health concerns. Even conventional
enormous challenge due to stringent requirements e.g. hard anodising techniques are not fully
resistance to corrosion prior to launch, wear, cold environmentally friendly because of the use of strong
welding and fretting impacts, stability in vacuum, acids and their disposal issues. Moreover, there is a
resistance to severe thermal shocks, UV degradation, limitation with the hard anodising process in achieving
debris formation or outgassing. Other requirements black finishes on certain aluminium alloys. Thus, there
include stable thermo-optical and high dielectric exists a strong need to identify new coating processes
characteristics. that can meet the requirements of recent environmental
legislation and a continual drive for better coating
Equipment on-board the manned habitats of the performance.
International Space Station (Fig.1) can experience
humidity levels up to 70% RH and also that spacecraft PLASMA ELECTROLYTIC OXIDATION
and equipment often have to be stored on earth for Plasma electrolytic oxidation is one of relatively new
considerable periods of time and that during storage / environmentally safe electrolytic coating processes,
launch and return to earth they are often exposed to applicable to light metals and their alloys and
corrosive environments. Also, the repetitive represents a rapidly developing sector in surface
mechanical contacting of aluminium alloys in vacuum engineering. The process involves the use of higher
can lead to seizure by cold welding. voltages than in anodising and the electrolyte usually
consists of low concentration alkaline solutions and all
variants of this process are considered to be
environmentally friendly. The process results in the
formation of a ceramic layer that offers protection to
the base alloy in terms of corrosion, wear and offers
other functional characteristics including thermo-
optical, dielectric, thermal barrier, low friction
coefficient and also can be used as pre-treatment for
topcoat paints and other metal/ceramics to create
composite coatings. A number of processes are being
offered by research laboratories and commercial
companies around the world. These available processes
differ in terms of coating deposition rate and thickness
limit, applied voltage, electrolyte type, electrolyte life,
phase formation, process speed and scalability etc. The
Fig.1 International Space Station (ISS). Courtesy of process has demonstrated significant interest in
European Space Agency offering improved surface treatment to Mg and Al
alloys and as a replacement for conventional acid based
Poor corrosion, wear and other functional processes such as DOW and other chemical processes
characteristics of high strength aluminium alloys are that contain hexavalent chrome, and including
well known, and as such, these alloys are always used anodising processes.
with protective surface coatings which include
chromating, metal spraying, paints, anodising.

Conventional black-anodised coatings with organic

dyes used as spacecraft thermal control materials are
considered not to have stable thermo-optical properties
after environmental exposures in a space environment.

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Table 1 Typical process parameters during Keronite PEO and hard anodising of AA7075 alloy
Coating Aluminium Pre-treatment Electrolyte Total Typical Nominal Voltage Process Coating Surface
process alloy salt thickness Coating temp formation appearance
content pH (µm) rate (V) (°C) method
(%) (μm/min)
Keronite Proprietary
(AC) Degrease alkaline free Plasma Grey to
7075 only of Cr, V or <4 7-12 15-60 1-4 200 - 12 to oxidation Charcoal
other heavy 900 30 black
metals
Hard Degrease and
Anodising 7075 chemical Sulphuric 10 - 20 <3 < 60 0.8 - 1 45 - 50 -10 to Oxidation Bluish
(DC) clean in acid H2SO4 0 without Black
alkaline plasma
solution

The Keronite® is an advanced surface technology based COATING CHARACTERISTICS

on plasma electrolytic oxidation. It is an An SEM image of an as-prepared surface of the
environmentally friendly and safe process for the Keronite layer is shown in Fig.3a which depicts an
preparation of corrosion and wear resistant black finish abundance of spherical and irregular shaped particles-
[2] ceramic layers on aluminium alloys that has seen like structures that were formed during the PEO
increasing interest over recent years in aerospace, process. An as-prepared surface of the hard-anodised
defence, optical instruments and general industrial layer is shown in Fig.3b which shows several voids and
applications. The Keronite process employs a low micro-porosity on the coating surface. In addition, the
concentration alkaline / neutral solution that is free of surface clearly shows parallel lines that form vertical
heavy metals with salt concentration < 4%. Unlike through thickness cracks.
Keronite, most commonly used sulphuric acid hard
anodising uses 10-20 vol. % of acid concentration. a) Keronite b) Hard anodised
Some parameters for the Keronite PEO and sulphuric
acid hard anodising processes are given in Table 1.

Fig.2 Plasma discharge around a component immersed

in electrolyte Fig.3 SEM images showing a sharp edge/corner of the
coating on AA7075: a) good and uniform coating
Coating of aluminium alloys using the Keronite plasma retention with the Keronite layer; and b) wide-opening
electrolytic oxidation (PEO) process involves creation cracks with the hard anodised layer[3].
of a plasma discharge around a component immersed
in an electrolyte (Fig.2). The mechanism of oxide layer a) b)
formation during the Keronite PEO process represents Hard anodised
complex combinations of oxide growth with Keronite
subsequent fusing, re-crystallisation of the oxide film
and also involves partial substrate metal dissolution at
microscopic levels. While the Keronite PEO process
can be considered very aggressive due to extensive
plasma discharges on the surface and oxide eruptions at
very high local pressures (believed to be several GPa)
but these discrete processes occur at microscopic levels
and the treated component including the working
surface receive no heat affected zones or distortion.
The process temperature and the component are Fig.4 Optical micrographs of: a) Keronite coating
typically in the range of 12-30°C. The resulting showing a uniform coating coverage and good edge
oxidation of the alloy surface can also include some retention; and b) hard anodised coating showing
elemental co-deposition from the electrolyte, creating a extensive V-shaped through thickness columnar cracks
ceramic layer that contains both crystalline and extending down to the substrate on the edge.
amorphous phases.

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Table 2 Characteristics of Keronite PEO coatings on aluminium alloys.
Coating Alloy Colour Rough Poro- Phase Hard- 1Corro- Solar Thermal Reflec- UV Vacuum TSR
type -ness sity composi- ness sion absorp- emit- tance resis- outgass- -196 to
tion resis- tance tance (%) tance ing +100°C
(Ra, (%) (HV) tance, (αS) (εn) (TML%)
µm) (hrs)
Keronite 2219 Grey to 1-1.6 <5 Crystalline 1200- > 360 0.88 - 0.71- Yes
black charcoal alumina 1550 0.89 0.75 - Pass -
Type 1 black

Keronite 7075 Grey to <1 <2 Crystalline 1600- > 360 0.81- 0.70- Yes
black charcoal alumina 1650 0.83 0.72 - Pass < 0.1
Type 1 black

Keronite 6082 charcoal 1-1.5 30-50 Amor- 500- > 1000 0.94 0.84 0.1 Pass - Yes
new black black phous 1200
Type 2 alumina
1
– ASTM B117; TSR – thermal shock resistance, UV resistance – grey scale rating ≥ 4.

A typical cross section of the Keronite layer on and NiCr plated AA7075 against an anodised AA7075
AA7075 alloy at the outer corner / edge is shown in are similar. An aluminium alloy without a coating
Fig.4a. The Keronite layer, although, has some micro- resulted in extremely high adhesion after fretting. The
scale porosity as would be expected from the PEO Keronite coating surface against itself displayed a
process but the coating can be considered relatively higher adhesion than against a steel surface by about
dense. A typical cross section of the hard-anodised three times. Despite low adhesion values displayed by
layer on AA7075 alloy at the outer corner is shown in the Keronite and hard anodised coatings against steel
Fig.4b which shows the presence of extensive ‘V- surfaces, the Keronite coating displayed superiority
shaped’ columnar cracks. These cracks are seen over the anodised coasting. The Keronite coating
through the entire coating thickness and extend down shows no sign of surface damage, whereas, the
to the underlying substrate, and in several areas even anodised coating displayed extensive cracking and
expose the bare metal substrate. Some general chipping of the coating surface in a fretting
characteristics of the Keronite coating on three environment. The differences in the damage
different aluminium alloys are given in Table 2. mechanisms between the Keronite and anodised
coating surfaces are shown in Fig.6.
108 AA2219+Keronite / AISI 52100
0,14
0,12
329 AA2219+Keronite / AA2219+Keronite 0,12
Friction Coefficient

0,10 0,08
242 AA7075+Anodised / SS15-5PH
0,08
0,06
0,06
100 AA7075+NiCr pl. / AA7075+Anodised 0,04
0,04

AA7075 / AA7075 7330 0,02

0,00
0 1000 2000 3000 4000 5000 6000 1000 mbar 1 mbar 10e-2 mbar 10e-4 mbar

Adhesion force, mN Pressure

Fig. 7 Friction coefficient of Keronite + MoS2

Fig.5. Adhesion measured during fretting tests [2]. composite coating after extreme wear tests in a
cryogenic environment. Courtesy: Instituto de
250 250
a) b) Astrofísica de Canarias

While the friction coefficient of Keronite to Keronite

has been reported relatively high about 0.5-0.6 [2], this
can be substantially reduced to an extremely low value
of about 0.04 by impregnating the porosity in the
coating with solid lubricants e.g. MoS2 (Fig.7).
Recently, Instituto de Astrofísica de Canarias (IAC)
and Keronite have undertaken a co-operative research
Fig.6. Surface after fretting test of: a) Keronite coating
on cryogenic plain sliding bearings. Keronite + MoS2
(no visible damage) and b) anodised coating (showing
composite coating has been developed as a tribological
extensive surface cracks) [2]
surface with a low sliding friction coefficient,
maximum resistance to wear, minimum debris
The Keronite ceramic surface after fretting tests in
generation, vacuum compatibility, resistance to thermal
vacuum was shown to have very low adhesion as
shock and thermal conductivity better than plastics.
shown in Fig.5 which shows that adhesion values of
the Keronite coated AA2219 against a 52100 steel ball

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Keronite PEO coatings on Cu containing aluminium Keronite coated parts including sun sensors (Fig.12-
alloys such as 2219 and 7075 can be prepared black 13).
and these have been extensively studied by the
European Space Agency as thermal control coatings.
Recently there has been growing interest by industries
on black finish coatings on other aluminium alloys. In
this regard, Keronite International Ltd. has recently
developed an industrial scale PEO process capable of
producing a charcoal black finish on most wrought and
some cast aluminium alloys. Unlike the process
discussed above, this new process converts the
aluminium alloys into a black finish and the resulting
surface characteristics and properties are not dependent
on the substrate alloy composition [4]. A typical SEM
image of this new black Keronite surface is shown in
Fig.8.

New black Keronite

Fig. 10 Keronite + MoS2 composite coating on EMIR

GRISM cryostat wheel bearing currently used for
space observation. The coating has been extensively
evaluated for wear resistance, debris formation, stick-
slip behaviour, ultra-low friction. Courtesy: Instituto
de Astrofísica de Canarias

Fig. 8 SEM image of new black Keronite on AA6060

alloy showing coating surface morphology with crater-
like porosity.

Fig. 9 Reflectance from the surface of a Keronite black

sample, measured at 25°C with a fixed angle of
incidence of 30 degrees [5]. Fig. 11 Barrel for satellites treated with new black
Keronite. The black Keronite coating has recently been
This coating surface has very low reflectance of about extensively tested in humidity, vibration, debris
<0.1% (Fig.9). This reflectance value is less than formation, low optical reflectivity tests and as a sub-
reported reflectance values for super black Ni-P layer for adhesive bonding. Courtesy: Cilas Marseille
coating and significantly less than that for black
sulphuric acid anodised coating and black paints. CNES, ESA, the University of Southampton and
ONERA have participated in a cooperative effort to
APPLICATIONS develop a test-bed called the Material Exposure and
Keronite coatings have been extensively evaluated by Degradation Experiment (MEDET) to be launched in
ESA for spacecraft material applications as thermal December 2007. Keronite coated thermal control
control coatings. More studies have been made by micro-calorimeters are mounted on the MEDET flight
Instituto de Astrofísica de Canarias, Spain for hardware (Fig.14) that will be located on the external
cryogenic bearing applications (Fig.10) and by Cilas payload facility of ESA’s Columbus Laboratory on the
Marseille for satellites (Fig.11) with extremely good International Space Station.
results. Several other studies for various space and
aerospace applications are currently underway on

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corrosion and wear. In addition, the use of
conventional paints and electrolytic surface
modifications offer only limited surface enhancement.

Plasma electrolytic oxidation is an emerging surface

technology and has received growing research and
industrial interests in the last decade due to its
environmentally friendliness and extremely good
surface properties which are often unachievable by
other coating routes [5-7]. While PEO has become an
acceptable surface modification platform for light
metal alloys, further industry support and research will
be required to optimise the process to suit individual
industry standards and requirements and make this
Fig. 12 Fine sun sensor (FSS) Baffle treated with black novel surface modification process economically more
Keronite. viable and globally acceptable.

REFERENCES
1. ESA PSS-01-703, Issue 1, October 1982, The
black anodising of aluminium with inorganic dyes,
ESTEC, Noordwijk, The Netherlands.
2. S. Shrestha, A. Merstallinger, D. Sickert and B.D.
Dunn, Some preliminary evaluations of black coating
on aluminium AA2219 alloy produced by plasma
electrolytic oxidation (PEO) process for space
applications’, Proc. 9th Intl. Symposium on Materials
in a Space Environment, 16-20 June 2003, The
Netherlands, p.57-65.
3. S. Shrestha, P. Shashkov and B. D. Dunn:
Microstructural and thermo-optical properties of black
Keronite PEO coating on aluminium alloy AA7075 for
Fig. 13 Coarse sun sensor (CSS) Housing treated with spacecraft materials applications, Proc. ‘10th Intl.
black Keronite. Symposium on Materials in a Space Environment’,
Collioure, France, 19-23 June 2006 (ESA SP-616).
4. S. Shrestha, S. Hutchins, O. Dunkin, J. Curran and
R. Wagner, Recent Developments in Black Finish
Coatings on Aluminium Alloys by Keronite® Plasma
Electrolytic Oxidation, Intl. Automotive Body
Keronite coated
micro-calorimeter Congress, Design Engineering, Materials &
Manufacturing, Vol. 8-10, p.196-203.
5. L. R. Krishna, A. Sudha Purnima and G.
Sundararajan, A comparative of tribological behaviour
of microarc oxidation and hard anodised coatings,
Wear 2006, in Press.
6. P. A. Dearnley, J. Gummersbach, H. Weiss, A.A.
Ogwu, T. J. Davies, The sliding wear resistance and
frictional characteristics of surface modified
aluminium alloys under extreme pressure, Wear, 225–
229, (1999) p.127-134.
7. J. A. Curran and T. W. Clyne, Thermo-physical
properties of plasma electrolytic oxide coatings on
aluminium, Surface & Coatings Technology 199
(2005) p.168-176.

Fig. 14 Keronite coated micro-calorimeter part Copyright© 2007, Keronite Plc

mounted on the MEDET system for the International
Space Station. Courtesy: MEDET Project.

CLOSURE
Aluminium alloys represent attractive materials for
spacecraft structures but they have been only
selectively used to-date for mechanical parts, the key
reasons for this, being the inherent problems with

SURFACE WORLD B NOVEMBER 2007